JP2003054947A - Zinc oxide-based fine particle and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide zinc oxide-based fine particles which have excellent transparency, shielding properties to ultraviolet rays and shielding properties to infrared rays including heat rays and have electric conductivity as well, and to provide its use. SOLUTION: The fine particles contain at least one kind of added elements selected from the group IIIB metallic elements and the group IVB metallic elements and zinc as metallic components. The content of zinc is 80 to 99.9% expressed in terms of the ratio of the number of zinc atoms to the total number of the metallic components atoms. Metallic oxide coprecipitated bodies exhibiting zinc oxide crystallinity in X-ray diffraction patterns are at least used as the main components.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is mainly composed of zinc.
The present invention relates to zinc oxide-based fine particles containing a Group IIIB metal element and / or a Group IVB metal element as an accessory component, and the use thereof.

[0002]

2. Description of the Related Art In recent years, glass products used for clean room windows, cathode ray tubes, floors, wall materials, clothes, etc., resin products such as films, fibers, etc., have an antistatic treatment for preventing the adhesion of dust and dirt The need for is increasing. Conventionally, as a method of imparting conductivity to an insulator such as a resin, a method of dispersing a conductive agent in an insulator such as a resin, or forming a conductive layer on a substrate using a coating material containing the conductive agent dispersed therein There is a method. Examples of the conductive agent include metal particles such as nickel (Ni), copper (Cu), and aluminum (Al); metal oxide particles obtained by reducing metal oxides represented by titanium black; and heterogeneous elements. White conductive metal oxides (tin oxide,
Indium oxide-based and zinc oxide-based) metal oxide-based fine particles; carbon-based fine particles such as carbon black and graphite; organic conductive agents represented by nonionic, anionic, cationic and amphoteric surfactants are known. ing.

Of these, organic conductive agents have a conductive mechanism based on ionicity, so that the conductivity is highly dependent on humidity and not effective in low humidity, and those having a low molecular weight bleed. There is a problem that performance deteriorates with time due to out. On the other hand, metal-based, metal oxide-based, and carbon-based conductive agents are superior to organic-based conductive agents in that they have substantially no humidity dependence because their conductive mechanism is based on electron conduction. However, the metal oxide-based conductive agent and the carbon-based conductive agent obtained by the reduction treatment of titanium black or the like have a hue of black or a color close to black, and also strongly reflect visible light in the metal-based fine particles, so that the substrate Alternatively, it is extremely difficult to maintain the transparency of the matrix, and the application is also limited.

On the other hand, white conductive fine particles such as antimony-doped tin oxide and tin-doped indium oxide are films obtained by coating ink or paint containing these fine particles already dispersed, or the fine particles. It is known that in a film or the like obtained by dispersing the above powder in a resin, antistatic conductivity can be imparted without substantially impairing the hue of the substrate and matrix. Further, by a vapor phase method such as sputtering, those oxide films formed on a glass or plastic film have high conductivity, therefore, liquid crystal displays, transparent electrodes and word processors for flat displays such as electroluminescence displays, It is used as an electrode material for touch panels of electronic games and the like, an antistatic film and the like. However, tin oxide-based and indium oxide-based raw materials are extremely expensive, and the gas phase method cannot be said to be a versatile conductive method because it requires an expensive apparatus.

By the way, in recent years, in glass products such as window glass and resin products such as polyester-based and (meth) acrylic-based films and sheets, coating and internal addition do not impair the transparency and hue of the substrate. , UV: UV-B (280-320 nm, UV-A (320
˜400 nm) and a material that effectively shields heat rays is required. Conventionally, as a material having an ultraviolet blocking effect, organic UV absorbers such as benzotriazole and benzophenone are known, and inorganic UV absorbers such as titanium oxide, zinc oxide and cerium oxide are known. It does not have a heat ray blocking effect.

As the heat ray blocking agent, anthraquinone type,
Polymethine-based, cyanine-based, aminium- and diimonium-based organic dyes having absorption in the infrared region, and the above-described conductive tin oxide-based and indium oxide-based dyes are known. It cannot be effectively blocked. It is known that the mica coated with the titanium oxide thin film absorbs ultraviolet rays by the titanium oxide thin film and scatters electromagnetic waves in the heat ray region to some extent based on the fact that the fine particles have a multi-layered structure. Therefore, it cannot be said that it is a fine particle material that can sufficiently meet the above-mentioned needs.

Therefore, it is conceivable to use a UV ray blocking agent and a heat ray blocking agent together, but the organic dye (heat ray blocking agent) is absorbed due to its absorption even in the visible portion, or coloring is inevitable, or the heat ray absorbing region is narrow. However, the tin oxide type and the indium oxide type are disadvantageous in economical efficiency because they are expensive as described above. On the other hand, zinc oxide optically absorbs both the A wave and the B wave of ultraviolet light and has no selective absorption of visible light. Therefore, zinc oxide is a thin film in which ultrafine particles of zinc oxide are highly dispersed, or a gas phase. The homogeneous zinc oxide thin film obtained by the method becomes a transparent ultraviolet absorbing film. Further, by doping zinc oxide with a trivalent or tetravalent metal element, conductivity is imparted, and in some cases, heat ray shielding property is imparted.

Conventionally, zinc oxide fine particles, so-called zinc white, are
(1) Method of vapor phase oxidation of zinc vapor (French method, American method), or (2) Reaction of zinc salt with alkali metal carbonate in aqueous solution, washing with water, drying to obtain zinc carbonate powder, and then air It is manufactured by a method of pyrolyzing in. The zinc oxide obtained by the method (1) is said to have a submicron particle size, but since it is strongly secondary agglomerated in the manufacturing process, it requires a great deal of mechanical effort to disperse it in a paint or resin. However, a homogeneous dispersion state cannot be obtained. The method of (2) is (1)
A finer particle size (primary particle size) of 0.1 μm or less can be obtained as compared with the above method, but the cohesive force between the primary particles is strong and the effect based on the fine particle size cannot be sufficiently obtained. . Furthermore, it is impossible to obtain zinc oxide fine particles in which the morphology such as the particle diameter, particle shape, surface state and dispersion / aggregation state of the primary particles is strictly controlled according to the purpose of use by these methods. The current situation.

In recent years, as a material capable of absorbing ultraviolet rays, which is excellent in weather resistance and heat resistance and has excellent transparency in the visible region, that is, a so-called transparent / ultraviolet absorber, the particle size is substantially 0.
Development of zinc oxide fine particles of 1 μm or less is desired. As a method for producing such fine particles, in addition to (3) vapor phase oxidation of zinc vapor, (4) hydrolysis method of alkaline solution of zinc salt (JP-A-4-164813 and JP-A-4-357114). JP-A No. 2-311314) and the like, a method of further oxidizing the zinc sulfide obtained through autoclave treatment using a mixed solution of an acidic salt of zinc and ammonium acetate and hydrogen sulfide as a starting material. A law has been proposed. The fine particles obtained by the method (3) are strongly secondary-aggregated powders, and are blended with plastic moldings such as fibers, plates, films, or paints for the purpose of imparting ultraviolet absorbing ability or improving weather resistance. However, even if it is made to have good transparency, it cannot be obtained. Further, for the purpose of imparting ultraviolet absorbing ability to glass, plastic film and the like, even if these powders are dispersed in a suitable solvent and a binder resin is mixed if necessary, a coating agent may be applied to these transparent substrates. However, there is a problem that only a film having insufficient transparency and homogeneity can be obtained. In the method (4), since the manufacturing process is complicated, the obtained ultrafine particles must be expensive. As described above, a method for producing zinc oxide fine particles which can exhibit the functions and characteristics of the fine particles sufficiently and is highly versatile has not been known so far. Moreover, although all of the zinc oxide fine particles obtained by these conventional production methods have the ability to absorb ultraviolet rays, they cannot block (near) infrared rays.

On the other hand, for example, it is described that a zinc oxide film obtained by doping aluminum (Al) into zinc oxide by a vapor phase method has high conductivity and heat ray shielding ability (south). Utsuji, Applied Physics, Volume 61, Volume 1
No. 2, '92). However, this is an impractical manufacturing method, and since the ultraviolet absorption edge is shifted to the short wavelength side, the shielding property against A wave is not sufficient. In addition, zinc oxide, silicon (Si), germanium (Ge), zirconium (Z
r) etc. as a solid solution (Japanese Patent Publication No. 5-6766), zinc oxide such as boron (B), scandium (Sc), yttrium (Y), indium (In), thallium (Tl), etc.
IIB group element is solid-dissolved (Japanese Patent Publication No. 3-20111), and aluminum (Al) is dissolved in zinc oxide (Japanese Patent Publication No.
-929), it has been proposed to obtain a transparent zinc oxide film excellent in conductivity and infrared reflectivity, but all of them are vapor phase methods such as a sputtering method, and thus are highly versatile manufacturing methods. I don't get it.

As a method for making the zinc oxide film conductive, in addition to the above, in a method for producing a zinc oxide thin film utilizing a thermal decomposition method of a salt of zinc, heat treatment is finally performed at a high temperature in a reducing atmosphere, or a dopant is zinc. There is also known a method in which a salt solution is allowed to exist and finally subjected to high temperature treatment (for example, JP-A-1-301515). However, it is not known that the heat ray shielding property can be obtained by this method. As a method for making the conductive zinc oxide powder conductive, further, a method of firing the zinc oxide powder at a high temperature in a reducing atmosphere, a method of mixing a zinc oxide powder with a dopant such as aluminum oxide and firing at a high temperature in a reducing atmosphere are generally used. It is known that the former method has a limitation in making it electrically conductive, and in either method, it is not possible to obtain fine particles, particularly fine ultrafine particles of 0.1 μm or less, due to exposure at high temperature. .

The specific surface area diameter obtained by the specific manufacturing method is 0.1 μm or less, and the volume resistivity in a specific pressurized state is 10.
A transparent conductive film forming composition containing a conductive zinc oxide fine powder activated by aluminum (Al) of ⁴ Ωcm or less is known (JP-A-1-153769). But,
Since the zinc oxide powder is fired at a high temperature when it is produced, even if the specific surface area diameter is 0.1 μm or less, the dispersed particle diameter in the paint is larger, so the composition (paint) obtained by this method is applied. It can be inferred that the resulting film has a limited transparency. Even with this method, the heat ray shielding property is not known.

[0013]

SUMMARY OF THE INVENTION Therefore, the present invention is based on zinc oxide, which has an excellent ultraviolet ray shielding property, and is provided with heat ray shielding property and conductivity, and it is easy to obtain transparency. The first object is to provide zinc-based fine particles. The present applicant has already found and applied a method for producing zinc oxide fine particles by a consistent wet process, in which the morphology such as particle size and particle shape, the dispersibility, etc. are controlled and the productivity is excellent (Patent application Flat 6-2398
9). Therefore, it is a second object to provide a method for producing the above-described zinc oxide type fine particles of the present invention with high productivity.

Further, by containing the zinc oxide type fine particles of the present invention, a coating having excellent transparency, capable of blocking infrared rays such as ultraviolet rays and heat rays, and having controlled conductivity such as antistatic property. The third object is to provide a composition, a coated product, a resin composition, a resin molded product, paper, and a cosmetic.

[0015]

The zinc oxide type microparticles of the present invention have at least one additive element selected from the group consisting of IIIB group metal elements and IVB group metal elements and zinc as a metal component, The content of zinc is 80 to 99.9% in terms of the ratio of the number of zinc atoms to the total number of atoms of the metal component, and a metal oxide exhibiting zinc oxide (Zn0) crystallinity as seen from X-ray diffraction. It is a zinc oxide-based fine particle containing at least a coprecipitate as a main constituent. Here, the crystal form of zinc oxide is not particularly limited, and for example, hexagonal crystal (wurtzite structure),
A cubic crystal (salt type structure), a cubic crystal face-centered structure, and the like are known, and any one showing an X-ray diffraction pattern may be used. In the zinc oxide-based fine particles of the present invention, the zinc content of the metal oxide coprecipitate is 80 to 99.9%, preferably 90 to 99.5, expressed as the ratio of the number of zinc atoms to the total number of metal components. %. If it is less than the above range, it becomes difficult to form fine particles having a controlled uniformity of particle shape, particle diameter, higher order structure, etc., and if it exceeds the above range, the function as a coprecipitate, that is, the infrared ray shielding property including heat rays becomes insufficient.

The zinc oxide type fine particles referred to in the present invention are, for example, silane coupling agents, aluminum coupling agents and other coupling agents or organosiloxanes, chelate compounds and other organic compounds, as long as they are as described above. The metal compound is a fine particle formed by bonding to the surface of the zinc oxide crystal or forming a coating layer on the surface, an inorganic acid such as a halogen element, a sulfate group, a nitrate group, or an organic compound such as a fatty acid, an alcohol, an amine, etc. And / or particles contained on the surface are also included in the zinc oxide-based fine particles of the present invention.
At least one additive element selected from the group consisting of Group IIIB metal elements and Group IVB metal elements and a metal element other than zinc are alkali metals and alkaline earth metals in a solid solution in ZnO crystals, etc. It is not preferable to exist in the form of, and the group IIIB metal element that constitutes the coprecipitate
The total number of atoms of at least one additional element selected from the group consisting of Group IVB metal elements is preferably 1/10 or less, more preferably 1/100 or less.

In the zinc oxide type fine particles of the present invention, the group IIIB metal element as an additional element constituting the metal oxide coprecipitate is, for example, boron, aluminum (Al), gallium (Ga), indium (In) or thallium. At least one selected from (Tl), and the group IVB metal element is, for example, silicon (Si) or germanium (G).
e), at least one selected from tin (Sn) and lead (Pb), among which indium and / or aluminum is most preferable. The zinc oxide-based fine particles according to the present invention include a state in which they exist as single particles composed of the metal oxide coprecipitate, a case in which a plurality of these single particles exist, and a single particle is a polymer. There is a composite with. The above three cases will be described below.

In the first case, the zinc oxide type fine particles consist of only a single particle of a metal oxide coprecipitate. In this case, the size of a single particle is 0.001 to 0.001 as the average particle size when viewed in the shortest part.
It is preferably in the range of 0.1, and 0.001 to 0.
More preferably, it is in the range of 05 μm. Further, the zinc oxide-based fine particles of the present invention, as described above, the surface composition of the zinc oxide crystals and fine particles is not particularly limited,
Zinc oxide-based fine particles of the present invention include those in which metal oxide crystals as the main component are exposed and those in which a surface layer made of an organic compound or an inorganic compound is formed on the surface. Hereinafter, such fine particles are referred to as surface modification fine particles, the surface layer is referred to as a surface modification layer, and a substance used for forming the surface modification layer is referred to as a surface modification agent. However, simply referring to zinc oxide type fine particles, surface modified fine particles are also included.

The above-mentioned single particles composed of a metal oxide coprecipitate and fine particles formed by aggregating a plurality of single particles include surface-modified fine particles, and the single particles are compounded with a polymer. It can be said that the fine particles are one form of the surface-modified fine particles. In the present invention, the particle size (including the average particle size and the number average particle size) means the particle size of the shortest part of the particle unless otherwise specified, and the particle size of the shortest part is the center of the particle. Means the shortest diameter. For example, if the shape of the fine particles is: spherical, it means the diameter of the sphere, if it is elliptical, it means the shortest of the longest and longest, and if it is cubic, rectangular parallelepiped, or pyramidal, it is cubic. , Rectangular parallelepiped, means the shortest length passing through the center of the triangular pyramid, and if it is needle-like, columnar, rod-like, or tubular, means the length passing through the center measured in the direction perpendicular to the length direction, In the case of a flaky shape such as a flaky shape or a (hexagonal) plate shape, it means the shortest length (= thickness) through the center in the direction perpendicular to the plate surface direction, that is, the thickness direction.

However, for particles such as particles and spheres, the longest diameter is preferably in the same range as the shortest diameter. For anisotropically shaped particles (flakes, needles, etc.), the longest diameter is 0.002μ.
The range of m or more and less than 0.5 μm is preferable. In the present invention, the shape of the metal oxide coprecipitate / zinc oxide-based fine particles is arbitrary. Examples thereof include flaky shapes such as scales and (hexagonal) plate shapes; needle shapes, columnar shapes, rod shapes, tubular shapes; granular shapes such as cubic shapes and pyramid shapes; and spherical shapes. Second
In the case of, the zinc oxide-based fine particles are secondary particles obtained by assembling the above-mentioned single particles as primary particles and collecting these primary particles.
In this case, the secondary particles may be hollow particles having only the outer shell. When it is hollow, it has excellent light diffusion and transmission properties. In this case, the relationship between the size of the single particle and the size of the zinc oxide-based fine particles, which is an aggregate thereof, is that the ratio of the particle diameter of the shortest part of the single particle to the particle diameter of the shortest particle is 1 /.
It is preferably 10 or less.

In the third case, the zinc oxide type fine particles are obtained by combining the single particles with a polymer. In this case, the form of the composite includes a form that behaves as a single particle, a form that behaves as a secondary particle, and any of them may be used. For example, first, the (A) polymer is the single particle. There is a form in which one surface and / or the surface of the aggregate of a plurality of the single particles are coated, and next,
There is a form in which the (B) polymer bonds the single particles to each other, and finally, the (C) polymer constitutes a matrix, and the single particles are not aggregated in the matrix and / or the single particles are formed. There is a form in which a plurality of particles are dispersed. In this case as well, the single particle and the polymer may be in a hollow shape in which only the outer shell portion is constituted, and the hollow shape is excellent in light diffusion and transmission as in the second case. is there. In this case, the content of the polymer is not particularly limited, but is in the range of 1 to 90% by weight based on the total amount of the single particles and the polymer.

In the third case, the polymer used for the composite is an acrylic resin-based polymer, an alkyd resin-based polymer, an amino resin-based polymer, a vinyl resin-based polymer, an epoxy resin-based polymer, a polyamide resin-based polymer, a polyimide resin. -Based polymers, polyurethane resin-based polymers, polyester resin-based polymers, phenol resin-based polymers, organopolysiloxane-based polymers, acrylic silicone resin-based polymers, polyalkylene glycols, etc., as well as polyolefin-based polymers such as polyethylene and polypropylene, polystyrene-based polymers, etc. Thermoplastic or thermosetting resin; synthetic rubber or natural rubber such as ethylene-propylene copolymer rubber, polybutadiene rubber, acrylonitrile-butadiene rubber; polysiloxane group-containing poly There is over.

Also in the second and third cases above, except where the polymer-composite particles behave essentially as a single particle (where the particle is a surface-modified single particle). The shape of the zinc oxide-based fine particles is preferably spherical or ellipsoidal. It is preferable that the surface be rich in unevenness regardless of the outer shape of the particles. This is because if the surface has irregularities, light scattering on the particle surface acts synergistically to improve the light scattering performance. In both the second case and the third case, the average particle diameter of the zinc oxide-based fine particles is
Although not particularly limited, it is usually in the range of 0.001 to 10 μm. For example, in the case of the third (A), 0.001 to 0.1 μm is preferable in terms of high transparency, and in the case of a hollow body shape, 0.1 to 5 μm in terms of high light diffusion / transmission ability.
m is preferred. In the second and third cases, when the zinc oxide-based fine particles are hollow bodies, the shape of the fine particles is preferably spherical or ellipsoidal. The reason is that the light diffusion and transmission properties are high.

In the surface-modified fine particles of the present invention, the surface-modified layer may have any composition of inorganic, organic, and inorganic-organic composite composition, and the surface of a single particle composed of a metal oxide coprecipitate. Or a surface modifier may be discontinuously present. Moreover, the ratio and thickness of the surface modification layer in the fine particles are not particularly limited. However, from the viewpoint of the effect of modification by the surface modification layer and economical efficiency, metal oxides (zinc and IIIB
The weight ratio of the surface modification layer to the oxide containing a Group IV or Group IVB metal as a metal component is preferably 0.01 to 1. Further, the average particle size and shape of the surface-modified fine particles are not particularly limited. However, the transparent UV
In applications where transparency is important, such as infrared cut films, in order to fully exhibit transparency, the particle size is fine and extremely high dispersion in coating compositions, resin compositions, etc. Since it is required to have
The average particle size is 0.005 to 0.1 μm, preferably 0.1.
It is necessary to be 005 to 0.05 μm, and the surface-modified fine particles of the present invention can exhibit its performance in any application where such performance is required.

The zinc oxide type fine particles of the present invention may be used as a dispersion formed by dispersing in a solvent. This solvent dispersion is also included in the present invention. The solvent dispersion contains at least zinc oxide-based fine particles and a solvent, and the zinc oxide-based fine particles have a metal oxide content of 2 to 2 based on the total amount of the dispersion.
It is dispersed and contained in a solvent at a ratio of 70% by weight. As the solvent, water, alcohols, ketones, aliphatic and aromatic carboxylic acid esters, ethers,
Ether esters, aliphatic and aromatic hydrocarbons,
Besides halogenated hydrocarbons, there are mineral oils, vegetable oils, wax oils, silicone oils and the like. Further, these solvents may contain other components, for example, an organic binder or an inorganic binder used as a binder for paints. Examples of the organic binder include (meth) acrylic, vinyl chloride, vinylidene chloride, silicone, melamine, urethane, styrene, alkyd, phenol, epoxy, polyester, etc. Curable resin; UV-curable acrylic resin, UV-curable acrylic silicone resin or other UV-curable resin; ethylene-propylene copolymer rubber,
There are synthetic rubbers and natural rubbers such as polybutadiene rubber and acrylonitrile-butadiene rubber, and examples of the above-mentioned inorganic binders include silica sol, alkali silicates, silicon alkoxides and phosphates.

From the viewpoint of versatility, preferred solvents are alcohols, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons, aromatic and aliphatic compounds having a boiling point of 40 to 250 ° C. under normal pressure. It is one or more mixed solvents selected from carboxylic acid esters, ketones, (cyclic) ethers, ether esters, and water. Furthermore, methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol. Methyl ether acetate, ethylene glycol ethyl ether acetate,
Ethylene glycol butyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methyl-3-methoxybutanol, 3 -Methyl-3-methoxybutyl acetate, toluene, xylene, benzene, cyclohexane, n-hexane, ethyl acetate, propyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, water, and one selected from the group consisting of Alternatively, a solvent dispersion containing at least two kinds of mixed solvents can be used in various coating systems. , Especially preferable.

The zinc oxide type fine particles of the present invention can be used as a plasticizer dispersion obtained by dispersing them in a plasticizer of a resin or a solution containing a plasticizer. This plasticizer dispersion is also included in the present invention. The plasticizer dispersion contains at least zinc oxide-based fine particles and a plasticizer, and based on the total amount of the dispersion,
The total weight of the zinc oxide-based fine particles and the plasticizer is 50 to 100.
It means that the weight ratio of the zinc oxide fine particles to the plasticizer is 0.01 to 5 by weight. The balance is, for example, a resin and / or solvent component. What is a plasticizer?
It includes all known plasticizers for resins such as phthalic acid esters (dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-phthalate).
Octyl, di-2-ethylhexyl phthalate, isononyl phthalate, octyldecyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, etc.), fatty acid monobasic acid ester (butyl oleate, glycerin monooleate, etc.), fatty acid diester Basic acid esters (dibutyl adipate, di-n-hexyl adipate, di-2-ethylhexyl adipate, adipic acid esters such as alkyl 610; sebacic acid esters such as dibutyl sebacate, di-2-ethylhexyl sebacate; azelaine Azelaic acid ester such as di-2-ethylhexyl acid ester),
Phosphate ester (tributyl phosphate, tri-2-phosphate)
Ethylhexyl, triphenyl phosphate, tricresyl phosphate, etc.), dihydric alcohol esters (diethylene glycol dibenzoate, triethylene glycol di-2)
-Ethyl butyrate, etc., oxyacid esters (methyl acetylricinoleate, butyl acetylricinoleate,
_{Butylphthalyl} butyl glycolate, acetyl citrate tributyl, etc.), chlorinated paraffin (C ₂₅ H _{45 Cl 17)}
Etc.), polyester plasticizers (polypropylene glycol adipate, 1,3-butylene glycol adipate, etc., having an average molecular weight of 1,000 to 15,000, dibasic acids such as adipic acid, phthalic acid, azelaic acid, sebacic acid, and glycols, Co-condensation polymers with glycerins and monobasic acids, etc.), epoxy-based plasticizers (alkyl epoxystearate, epoxy triglycerides, etc.),
Others (stearic acid plasticizer; chlorinated biphenyl, 2
-Nitrobiphenyl, dinonylnaphthalene; o-toluenesulfone ethylamide, show brain, methyl abietic acid, etc.) and the like, and any one kind or two or more kinds are used.

Above all, from the group consisting of phthalic acid ester plasticizers, fatty acid monobasic acid ester plasticizers, fatty acid dibasic acid ester plasticizers, phosphoric acid ester plasticizers, polyester plasticizers, epoxy plasticizers. At least one selected is preferable because it has high compatibility with a resin, particularly a vinyl chloride resin. The above-mentioned plasticizer dispersion has the zinc oxide-based fine particle-containing resin composition of the present invention for the purpose of improving the processability of a polymer substance or imparting flexibility, which is the original purpose of the plasticizer. It can be used as a raw material for fine particles when producing an article, a molded article, a coating composition or a coated article. That is, a vinyl chloride resin containing zinc oxide fine particles, a polyvinylidene chloride resin, a methacrylic acid resin, an acetate cellulose type, a nitrocellulose type, a polystyrene type, a vinyl acetate resin type, a polyvinyl butyral type resin composition, etc. When producing a molded product such as a sheet or film formed by processing the above, or a coating composition using these resin components as a binder component and a coated article formed by forming the coating composition into a film, fine particles and a plasticizer It can be used as part or all of the raw material. Also,
The plasticizer dispersion containing a phosphate ester-based plasticizer can impart flame retardancy to the above-mentioned resin molded product or coated product at the same time.

Further, conventionally, a polyester film,
Polycarbonate resin, methacrylic resin film or sheet, plate, diethylene glycol bisallyl carbonate lens, etc. have been developed or used for the purpose of improving surface hardness, abrasion resistance, etc., or surface hardness equivalent to or close to glass, A so-called hard coat agent that gives a film having scratch resistance, or a material synthesized by the inventors for the same purpose (for example, the mixture (x) of Example II-11 described later) is used as a binder component. It can also be used as a dispersion medium component such as a solvent or a vehicle. Moreover, since the fine particles of the present invention have a metal oxide crystal as a main component, it is possible to easily obtain a film which is transparent and blocks ultraviolet rays and infrared rays and has excellent abrasion resistance by combining with these hard coating agents. You can

The method for producing zinc oxide type fine particles according to the present invention will be described below. The method for producing zinc oxide-based fine particles according to the present invention comprises a zinc source and a monocarboxylic acid in a medium containing at least an alcohol and at least one selected from the group consisting of Group IIIB metal elements and Group IVB metal elements. 100 ° C in the presence of a compound containing one additional element
This is a method of generating fine particles by maintaining the above temperature. In this case, for example, the group IIIB metal element is exemplified as described above, and indium and / or aluminum is preferable among these additive elements.

The method for producing the zinc oxide type fine particles of the present invention is specifically, for example, the first step containing a zinc source and a monocarboxylic acid.
A first step of preparing a mixture, a second step of preparing the second mixture by mixing the first mixture with a medium containing at least alcohol, and the second mixture being heated to a temperature of 100 ° C. or higher. And a third step of holding, wherein in any one of the first, second and third steps, the first and / or second mixture contains a Group IIIB metal element and a Group IVB metal element. A compound containing at least one additional element selected from the group consisting of is added and mixed. At this time, the compound containing the additional element may be added alone, or may be dissolved in a medium containing at least alcohol and added. In the first step, it is preferable that the zinc source is dissolved in a mixed solvent in which monocarboxylic acid is dissolved in water.

In the method for producing zinc oxide type fine particles according to the present invention, a mixture prepared by mixing a zinc source and a monocarboxylic acid with water is added to and mixed with a medium which is heated to 100 ° C. or higher and which is composed of at least alcohol. Therefore, it is preferable to include a step of removing at least a part of the water and / or the monocarboxylic acid by evaporation. The zinc source and the monocarboxylic acid are preferably used by dissolving them in water, but they prevent the crystallinity of the fine particles from being impaired, and
This is because it is preferable to remove water or monocarboxylic acid out of the system as much as possible in order to prevent the subsequent aggregation and obtain the uniformity of the size and shape of the fine particles. Although fine particles may be produced during the addition of the mixture to the heating medium, the fine particles are usually produced by keeping the reaction system at a temperature of 100 ° C. or higher after that. During this period, water and monocarboxylic acid are usually removed by evaporation.

In the method for producing zinc oxide type fine particles of the present invention, the zinc source is, for example, at least one selected from the group consisting of zinc oxide, zinc hydroxide and zinc acetate. In the method for producing zinc oxide based fine particles of the present invention, the monocarboxylic acid is
A saturated fatty acid having a boiling point of 200 ° C. or lower under normal pressure is preferable. In the method for producing zinc oxide type fine particles of the present invention, at least one selected from the group consisting of a Group IIIB metal element and a Group IVB metal element in a medium containing at least an alcohol, a zinc source and a monocarboxylic acid. When a compound containing the additional element is kept at a temperature of 100 ° C. or higher in the presence of the compound, a polymer is allowed to coexist in this system, or a carboxyl group, an amino group, a quaternary ammonio group, an amide group, an imide bond is present in the molecule. , Alcoholic and / or phenolic hydroxyl group, carboxylic acid ester bond, urethane group, urethane bond, ureido group, ureylene bond, isocyanate group, epoxy group, phosphoric acid group, metal hydroxyl group, metal alkoxy group and sulfonic acid group An additive compound having at least one atomic group selected from the group of 1 or 2 or more and having a molecular weight of less than 1000; Or is exist, or the coexistence of carbon dioxide and / or carbonate source, which may or coexist lactic acid source.

The surface-modified fine particles are produced by mixing the zinc oxide-based fine particles obtained by an arbitrary production method with a surface-modifying agent under appropriate conditions. The method) is not particularly limited, and the type and amount of the surface modifier and the surface modification method may be appropriately selected depending on the purpose of the surface modification. The compounds shown in the above-mentioned, especially the compounds having a polymer or a specific atomic group, can effectively act as so-called surface modifiers that control the surface of fine particles. According to the method of the present invention, there is an advantage that the morphology, size, higher-order structure and the like of the fine particles can be controlled and the composition and properties of the fine particle surface can be controlled.

However, for the purpose of modifying the surface to improve the dispersibility in a hydrocarbon solvent having a low polarity, the affinity with a resin, or the like, or the secondary agglomerated fine particles are dispersed into a single particle. When surface modification is performed for the purpose of
The method is not particularly limited. When the system is kept at a temperature of 100 ° C. or higher, when a polymer is allowed to coexist, zinc oxide type fine particles in which single particles are combined with the polymer are obtained.
Depending on the type of polymer, for example, after producing a dispersion of zinc oxide-based fine particles not complexed with the polymer,
Although it is possible to form a complex by adding a polymer at a temperature of 100 ° C. or higher or a temperature of 100 ° C. or lower, in order to obtain fine particles having a controlled higher-order structure such as hollow fine particles, The above-mentioned “method of allowing a polymer to coexist when the system is maintained at a temperature of 100 ° C. or higher” is effective, and the method can simultaneously form a single particle composed of a metal oxide coprecipitate and form a composite. It is an economical manufacturing method. Suitable polymers used in this case include the above-mentioned acrylic resin-based polymers, alkyd resin-based polymers, amino resin-based polymers, vinyl resin-based polymers, epoxy resin-based polymers, polyamide resin-based polymers, polyimide resin-based polymers, polyurethanes. In addition to resin-based polymers, polyester resin-based polymers, phenolic resin-based polymers, organopolysiloxane-based polymers, acrylic silicone resin-based polymers, polyalkylene glycols, etc. Thermosetting resins; synthetic rubbers such as ethylene-propylene copolymer rubber, polybutadiene rubber, acrylonitrile-butadiene rubber and natural rubber; and polysiloxane group-containing polymers.

When the system is maintained at a temperature of 100 ° C. or higher,
When the compound having the specific functional group described above and / or the polymer described above coexists, the surface-modified fine particles in which the particle size and shape of single particles and the particle size, shape, and higher order structure of fine particles are controlled. Can be manufactured. System at 100 ℃
When carbon dioxide and / or a carbonic acid source is allowed to coexist when the temperature is maintained at the above temperature, the water dispersibility is excellent, and fine (0.
It is easy to obtain fine particles of less than 05 μm. In this case, the carbonic acid source can be replaced by using (basic) zinc carbonate as a part of the zinc raw material. However,
A suitable amount of the carbonic acid source is 0.1 to 20 mol% with respect to zinc. This is because if the amount is too large, the crystallization of zinc oxide may be hindered, and the heat treatment temperature needs to be increased. As the carbonic acid source, for example, ammonium carbonate,
Compounds that generate carbonate ions or carbon dioxide gas by heating such as ammonium hydrogen carbonate and urea; yttrium carbonate, cadmium carbonate, silver carbonate, samarium carbonate, zirconium carbonate, cerium carbonate, thallium carbonate,
Metal carbonates such as lead carbonate and bismuth carbonate, basic zinc carbonate, basic cobalt carbonate (1I), basic copper carbonate (II),
Examples include basic carbonates of metals such as basic lead (II) carbonate and basic nickel (II) carbonate, which may be used alone or in combination of two or more.

One effective method for obtaining zinc oxide type fine particles in the form of secondary particles formed by aggregating single particles composed of a metal oxide coprecipitate is
An example is a method in which a lactic acid source is allowed to coexist when the system is maintained at a temperature of 100 ° C. or higher. The lactic acid source used in the present invention is
Lactic acid; ammonium lactate, sodium lactate, lithium lactate, calcium lactate, magnesium lactate, zinc lactate, aluminum lactate, manganese lactate, iron lactate, nickel lactate, silver lactate, and other metal lactates; methyl lactate, ethyl lactate,
Lactic acid ester compounds such as n-butyl lactate that can generate lactic acid by hydrolysis and the like, and any one of them may be used alone, or two or more thereof may be used in combination.

The uses of the zinc oxide type fine particles of the present invention will be described below. The zinc oxide-based fine particles of the present invention protect the contents from ultraviolet rays, prevent discoloration / alteration / deterioration of various materials such as printed matter due to ultraviolet rays, block ultraviolet rays for the purpose of protecting the human body from ultraviolet rays, and Various fields that need to block infrared rays for the purpose of suppressing indoor temperature rise, keeping the room warm during heating, etc., as well as prevention of electrostatic damage, antistatic properties such as giving conductivity to plastic, paper, cloth, etc., It is useful in various fields that require conductivity,
Various dispersions, coating compositions, coated products, resin compositions, resin moldings, papers, cosmetics, etc. containing the fine particles exhibit one or more of these functions.

For example, various packaging films used for food packaging, pharmaceutical packaging, cosmetic packaging, electronic material packaging, etc.
Protective film for containers, agricultural films, greenhouse films, building materials, automobiles, etc., adhesive films that can be used for window materials for buildings, automobiles, high-temperature furnaces, adhesive films or paints, clothing such as clothes and hats Effectively blocking ultraviolet rays and infrared rays by using the zinc oxide type fine particles of the present invention for textile products excellent in coolness or heat retention, protective film materials for eyeglass lenses such as sunglasses, umbrellas, sunroofs, cosmetics, etc. You can At the same time, antistatic property can be imparted. Further, the zinc oxide type fine particles of the present invention can be incorporated into a coating material, a film or the like useful for a bar coater material such as a stealth bar coater. Furthermore, windows for vehicles such as clean rooms and automobiles, clothing, various CRTs, LCDs
Films, films and papers containing the zinc oxide based fine particles of the present invention for antistatic of screens of various displays, touch panels, etc., and conductivity of electrostatic recording papers such as recording papers for facsimiles. It can be used in various forms.

The zinc oxide type fine particles of the present invention are used as a component of a coating material for forming a transparent conductive film used in solar cells, various displays, touch panels, optical elements, optical sensors, etc., or sintered for sputtering. It is also useful as body raw material fine particles. The coating composition of the present invention comprises the zinc oxide-based fine particles of the present invention and a binder component capable of forming a coating film that binds the zinc oxide-based fine particles to the zinc oxide based on the total weight of the solid contents of both. 0.1 to 99% by weight of fine particles, the binder component 1
.About.99.9% by weight. in this case,
The total solid content of the zinc oxide type fine particles and the binder component may be 1 to 80% by weight, and the balance may be a solvent.

The coated article of the present invention comprises an arbitrary substrate and a coating film formed on the surface of the substrate. This coating film combines the zinc oxide type fine particles of the present invention with the zinc oxide type fine particles. The binder component and the total weight of these two,
The zinc oxide fine particles are contained in an amount of 0.1 to 99% by weight and the binder component is 1 to 99.9% by weight.
Usually, it comprises one substrate selected from the group consisting of a resin molded product, glass and paper and a coating film formed on the surface thereof, and this coating film is the same as the zinc oxide type fine particles of the present invention. ,
A binder component that binds the zinc oxide-based fine particles,
The zinc oxide fine particles are contained in an amount of 0.1 to 99% by weight, and the binder components 1 to 99.9, based on the total weight of both of them.
It is included in a weight percentage. In this case, the resin molded product is, for example, at least one selected from the group consisting of plates, sheets, films and fibers.

The resin composition of the present invention comprises the zinc oxide type fine particles of the present invention and a resin capable of forming a continuous phase in which the zinc oxide type fine particles are dispersed, based on the total weight of the solid contents of both. The zinc oxide based fine particles are contained in an amount of 0.1 to 99% by weight and the resin is contained in an amount of 1 to 99.9% by weight. The resin molded product of the present invention is obtained by molding the resin composition of the present invention into any shape selected from the group consisting of plates, sheets, films and fibers. The paper of the present invention comprises a paper-made pulp and the zinc oxide-based fine particles of the present invention dispersed in the pulp, and the amount of the zinc oxide-based fine particles is 0.01 to 5 relative to the pulp.
It is 0% by weight. The cosmetic of the present invention contains 0.1% by weight or more of the zinc oxide-based fine particles of the present invention.

In the present invention, the size of a single particle of fine particles (0.05 μm or less, preferably 0.02 μm or less),
Surface composition, dispersed state (average particle size in dispersed state is 0.1
μm or less, preferably 0.05 μm or less) is used, and the composition in the coating composition is
Alternatively, by selecting the composition of the resin composition, a coated product provided with a transparent film or a transparent resin molded product can be obtained. The “transparent” in the present invention is defined as follows. As for the coated product, the visible light transmittance of the coated product obtained by forming the coating composition containing the zinc oxide-based fine particles of the present invention on the substrate (visible light transmittance is the total light ray for visible light). The difference between the transmittance (the same applies hereinafter) and the visible light transmittance of the substrate is 10% or less: −10% ≦ (visible light transmittance of the substrate) − (visible light transmittance of the coated product) ≦ 10% Preferably 5% or less: -5% ≤ (Visible light transmittance of base material)-(Visible light transmittance of coated product) ≤ 5% Particularly preferably 3% or less: -3% ≤ (of base material) Visible light transmittance)-(visible light transmittance of coated product) ≤ 3%, and the difference between the haze of the coated product (haze is the haze for visible light; the same applies hereinafter) and the haze of the substrate. 10,
% Or less: −10% ≦ (haze of coated product) − (haze of base material) ≦ 1
0% preferably 3% or less: -3% ≤ (haze of coated product)-(haze of substrate) ≤ 3% particularly preferably 1% or less: -1% ≤ (haze of coated product)-(group The haze of the material is ≦ 1%.

In addition to the above, when the substrate is a plate, sheet, film-shaped resin molded product or glass, the coated product has a visible light transmittance of 80% or more and a haze of 10%.
% Or less, more preferably 85% or more in visible light transmittance and 5% or less in haze. The resin composition and the molded product are produced in the same manner except that the molded product obtained by molding the resin composition containing the zinc oxide-based fine particles of the present invention has a visible light transmittance and does not contain the fine particles. The difference from the visible light transmittance of the molded product is 10% or less: -10% ≤ (visible light transmittance of the molded product without fine particles)-
(Visible light transmittance of molded article containing fine particles) ≤10%, preferably 5% or less: -5% ≤ (visible light transmittance of molded article without fine particles)-(visible light transmittance of molded article containing fine particles) ≤5 % Particularly preferably 3% or less: −3% ≦ (visible light transmittance of molded product without fine particles) − (visible light transmittance of molded product containing fine particles) ≦ 3%, and haze and fine particles of molded product containing fine particles The difference from the haze of the molded product without any particles is 10% or less: -10% ≤ (haze of molded product containing fine particles)-(haze of molded product without fine particles) ≤ 10% Preferably 3% or less: -3% ≤ (Haze of molded article containing fine particles)-(Haze of molded article without fine particles) ≤ 3% Particularly preferably 1% or less: -1% ≤ (Haze of molded article containing fine particles)-(Haze of molded article without fine particles) ≦ 1%. Moreover, the visible light transmittance of the molded article containing fine particles is 8
Those having 0% or more and a haze of 10% or less, and more preferably having a visible light transmittance of 85% or more and a haze of 5% or less are useful as a resin molded article having excellent transparency, and are easily used in the present invention. can get.

[0045]

BEST MODE FOR CARRYING OUT THE INVENTION In the zinc oxide type fine particles of the present invention, when the metal oxide coprecipitate is a single particle, the single particle may be uniformly dispersed throughout, but May be aggregated. In particular, when the single particles are aggregated as the primary particles to form the outer shell of the secondary particles, the secondary particles have a multi-layer structure, so that the light scattering on the surface of the secondary particles (this is , Which corresponds to the scattering of light on the surface of conventional inorganic transparent fine particles), as well as the scattering of light on the surface of primary particles in secondary particles and the interface between the outer shell and the inner shell in secondary particles. Scattering of light occurs, and exhibits high diffusivity while having high light transmittance. The thickness of the outer shell formed by aggregating the single particles is not particularly limited, but is preferably 0.1 to 0. 0 with respect to the value of the number average particle diameter of the secondary particles.
It is 4. If it is less than the above range, the mechanical strength of the zinc oxide based fine particles may be lowered, and if it is more than the above range, the above effect due to having a multilayer structure may not be sufficiently exhibited.

The shape and size of the primary particles are not particularly limited, but they must be smaller than the secondary particles. For example, the secondary particles have a particle size of 0.1 to 10 μm (preferably 0.1 μm).
1 to 2 μm), the primary particles have a number average particle size of 0.001 to 0.1 μm.
1/10 to 1/100 of the number average particle diameter of secondary particles
00. If the number average particle diameter of the primary particles is less than the above range, the ultraviolet shielding ability of the zinc oxide based fine particles may be reduced, and if it exceeds the above range, the light transmittance may be reduced. If the ratio of the number average particle diameter of the primary particles to the number average particle diameter of the secondary particles is less than the above range, the ultraviolet shielding ability of the secondary particles may be reduced, and if the ratio exceeds the above range, the secondary particles are practically used. There is a possibility that it may not have sufficient mechanical strength or that the aggregation effect may not be sufficiently exerted.

When the secondary particles have a large number of pores between the primary particles and when they are hollow, they function as porous fine particles or microcapsules, for example, oil absorption ability, moisture absorption ability, harmful metal ions. Adsorption capacity, absorption and separation of toxic gases and odors, removal, collection function; heat and sound insulation function such as heat insulation and sound insulation (insulation filler, sound insulation filler); metal ions, enzymes, bacteria It has immobilizing functions such as immobilization (catalyst carrier, chromatographic packing, etc.); lightweight; sustained release function of liquids and fragrances held inside. The zinc oxide type fine particles of the present invention (composite particles) in which a single particle and a polymer are combined will be described. First, there is a particle in which a single particle composed of a metal oxide coprecipitate is combined with a polymer to behave substantially as a single particle. This includes surface-modified fine particles in which the polymer forms a surface-modified layer. In this case, individual surface-modified fine particles having an average particle size of 0.1 μm or less, preferably 0.05 μm or less are particularly useful for obtaining a coated product having a transparent coating film or a transparent resin molded product. is there.
Next, when the single particles aggregate and localize to form the outer shell, the polymer is contained only in the outer shell, only in the inner shell, or in both the outer shell and the inner shell. May be. However, it is preferable that the polymer is also contained only in the outer shell and the zinc oxide-based fine particles are hollow. When the zinc oxide-based fine particles are hollow, the light diffusion function is higher. In this case, the shape and size of the primary particles are not particularly limited, but they must be smaller than the composite particles.
For example, when the composite particles have a number average particle size of 0.1 to 10 μm (preferably 0.1 to 2 μm), 1
The number average particle diameter of the secondary particles is 0.001 to 0.1 μm, and is 1/10 to 1/1 with respect to the number average particle diameter of the composite particles.
It is 0000. If the number average particle diameter of the primary particles is less than the above range, the ultraviolet shielding ability of the zinc oxide based fine particles may be reduced, and if it exceeds the above range, the light transmittance may be reduced. If the ratio of the number average particle diameter of the primary particles to the number average particle diameter of the composite particles is less than the above range, the ultraviolet shielding ability of the composite particles may be reduced, and if it exceeds the above range, the composite particles are practically sufficient. There is a possibility that it may not have mechanical strength or the combined effect may not be fully exerted. Polymer exists in outer shell and primary particles (single particles)
Alternatively, when the surface layer of the secondary particles is covered, the zinc oxide based fine particles have excellent dispersibility, and the binding property with the matrix polymer in the composition is further enhanced.

The polymer contained in the zinc oxide type fine particles of the present invention is not particularly limited, but for example, it has a weight average molecular weight of 1,000 to 1,000,000 and is generally an oligomer,
Also included are those referred to as prepolymers and the like. Such a polymer easily dissolves in the mixture (n), the mixture (m), or in the heating process for precipitating the zinc oxide-based fine particles, or easily emulsifies or suspends in a state as fine as possible. It is easy to obtain zinc oxide type fine particles having a uniform particle size (the variation coefficient of the particle size is 30% or less) and having a uniform particle shape. Polymers contained in the zinc oxide-based fine particles of the present invention include, for example, the following (1) to (1
It is at least one resin selected from the resin group of 4).
When these resins are used, for example, zinc oxide type fine particles having an average particle size of 0.001 to 10 μm are easily obtained.

(1) Acrylic resin-based polymer Homopolymer / copolymer of (meth) acrylic monomer such as acrylic acid ester / methacrylic acid ester;
Maleic acid ester, itaconic acid ester-based monomer,
Vinyl-based monomers such as styrene, p-chlorostyrene, vinyltoluene, vinyl acetate, vinyl chloride, vinylmethyl ether, vinyl butyral, olefins such as ethylene and propylene, dienes such as butadiene, trienes, etc. (meth) acrylic Thermoplastic acrylic resin such as a copolymer of a polymerizable monomer having no functional group other than the system monomer and the (meth) acrylic monomer, a modified product thereof, a derivative thereof (such as one having a substituent introduced), etc. , Acrylic acid, methacrylic acid, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, hydroxyalkyl ester of (meth) acrylic acid, glycidyl ester of (meth) acrylic acid, aminoalkyl ester of (meth) acrylic acid, etc. A polymerizable monomer having A polymerizable monomer having a functional group; serial copolymer of (meth) acrylic monomer
A thermosetting acrylic resin such as a copolymer of the (meth) acrylic monomer and a polymerizable monomer having no functional group, a modified product thereof, a derivative thereof (having a substituent introduced, a functional group of Etc.), and UV-curable acrylic resin.

(2) Alkyd resin type polymer phthalic anhydride, isophthalic acid, terephthalic acid, benzoic acid, rosin, adipic acid, maleic anhydride, succinic acid,
Polybasic acids such as sebacic acid, fumaric acid anhydride, trimellitic acid, pyromellitic acid, and ethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol, glycerin, trimethylolethane,
Pentaerythritol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polycondensation products with polyhydric alcohols such as hydrogenated bisphenol A (oil-free alkyd resin); Modified products (alkyd resins) modified by, for example, natural resins such as rosin, synthetic resins such as phenolic resins, epoxy resins, urethane resins, silicone resins, amino resins, etc., above (1) Modified products modified with the listed monomers (rosin modified alkyd resin, phenol modified alkyd resin, epoxy modified alkyd resin, styrenated alkyd resin, acrylated alkyd resin, urethane modified alkyd resin, silicone modified alkyd resin, amino resin Modified alkyd resins such as modified alkyd resins); the polycondensates, the alkyd resins, derivatives of the modified alkyd resins (neutralized some or all of functional groups such as carboxyl groups, introduced with substituents, etc.) ).

(3) Amino resin polymer melamine formaldehyde resin, butylated melamine resin, methylated melamine resin, benzoguanamine resin and other melamine resins; urea formaldehyde resin, butylated urea resin, butylated urea melamine resin and other urea resins;
Amino resin-modified alkyd resin obtained by modifying the alkyd resin of (2) above by a co-condensation reaction using a melamine resin or urea resin; Methylol melamine, addition product of methylol melamine initial condensation product and polyhydric alcohol, condensation product of melamine or urea and polyhydric amine, butylated melamine with hydrophilic group introduced, benzoguanamine with hydrophilic group introduced, etc. Amino resin) etc.

(4) Vinyl resin type polymers Homopolymers / copolymers of vinyl type monomers such as vinyl chloride, vinyl acetate, vinyl propionate, vinylidene chloride, vinyl butyral, styrene, p-chlorostyrene, vinyltoluene, etc. Vinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer, modified ethylene-vinyl acetate copolymer, polyvinyl butyral, polyvinyl alcohol, polystyrene, etc.); vinyl monomers and ethylene. Copolymers of olefins such as propylene, dienes such as butadiene, and other unsaturated monomers such as trienes; copolymers of vinyl-based monomers with the (meth) acrylic-based monomers and / or other unsaturated monomers Polymers; derivatives of those polymers.

(5) Epoxy resin type polymer Bisphenol A type epoxy resin, phenoxy resin (high molecular weight of bisphenol A type epoxy resin (molecular weight ≧ 3
10,000) type resin), phenol novolac type epoxy resin, orthocresol novolac type epoxy resin,
Glycidyl ether type epoxy resin such as bisphenol A novolac type epoxy resin, brominated phenol novolac type epoxy resin, tetraphenylolethane type epoxy resin; glycidyl ester type epoxy resin; glycidyl amine type epoxy resin; epoxidized polybutadiene; these epoxy resins A compound having active hydrogen such as an amino group, a carboxyl group, an amide group, a thiol group and / or a (pre) polymer (aliphatic (poly) amine, aromatic (poly)) capable of undergoing a crosslinking reaction with an epoxy group.
Polymers reacted with amines, diethylaminopropylamine, alicyclic amines, polymercaptans, etc.).

(6) Polyamide resin-based polymer Nylon resin (for example, nylon 66) obtained by polycondensation of diamine and dicarboxylic acid, nylon resin (for example, nylon 6) obtained by ring-opening polymerization of lactam, and polycondensation of amino acid The resulting polypeptide (eg, polyglycine, poly (α-L-alanine))
Etc.), a polyamine amide that may have an amino group, obtained by dehydration condensation of a polycarboxylic acid typified by polymerized fatty acid (dimer acid) that is a polymer of vegetable oil fatty acid and a polyamine such as ethylenediamine / diethylenepolyamine. Derivatives etc.

(7) Polyimide resin type polymer Polycondensation reaction of dianhydride of tetracarboxylic acid such as pyromellitic anhydride and aromatic diamine, bismaleimide such as bishexamethylenemaleimide and biscyclopentadienyl compound Diels-Alder with 2,5-dimethyl-3,4-diphenylcyclopentadienone (Di
les-Alder) Polyimide polymer obtained by polymerization reaction. (8) Polyurethane resin-based polymer Any resin having a urethane bond in the molecule may be used, for example, alkyd resin in which dibasic acid is replaced with diisocyanate; (meth) acryl having hydroxyl group such as methacrylic acid hydroxyester. A polymer obtained by reacting an acrylic polymer obtained by polymerizing a monomer containing a base monomer with an isocyanate compound; a polymer obtained by reacting a polyester polymer consisting of a dibasic acid and excess polyhydric alcohol with an isocyanate compound; Polymer prepared by reacting isocyanate compound with polyalkylene glycol obtained by addition-polymerizing propylene oxide or ethylene oxide with alcohol; Polymer prepared by reacting isocyanate compound with epoxy resin having hydroxyl group; Moisture curable polyurethane resin , Heat-curable polyurethane resin, catalyst-curable polyurethane resin, and other polyurethane resins that have been conventionally used for paints; phenylglycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer / phenylglycidyl ether acrylate isophorone diisocyanate urethane prepolymer / phenylglycidyl Ether Acrylate Tolylene Diisocyanate Urethane Prepolymer / Glycerin Dimethacrylate Hexamethylene Diisocyanate Urethane Prepolymer / Glycerin Dimethacrylate Isophorone Diisocyanate Urethane Prepolymer / Pentaerythritol Triacrylate Hexamethylene Diisocyanate Urethane Prepolymer / Pentaerythritol Triacrylate Isophorone Diyl Cyanate urethane prepolymer / pentaerythritol triacrylate tolylene diisocyanate Urethane prepolymer and other prepolymers containing urethane bonds and having a polymerizable double bond, homopolymers / copolymers of these prepolymers, prepolymers thereof Polymers and other polymerizable monomers (for example, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylic monomers such as (meth) acrylamide; maleic acid, maleic acid ester, styrene, Styrene-based monomers such as p-chlorostyrene and vinyltoluene; olefins such as ethylene and propylene; dienes and trienes such as butadiene; vinyl acetate, vinyl chloride, vinyl methyl ether, vinyl alcohol, vinyl butyra. Vinyl monomers such as Le)
Copolymers with; urethane acrylate polymers obtained by reacting polyisocyanates such as hexamethylene diisocyanate and toluylene diisocyanate with (meth) acrylic acid or (meth) acrylic acid oligomers.

(9) Polyester resin type polymers such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol and other aliphatic glycols, hydroquinone, resorcin, etc. At least one glycol selected from the group consisting of aromatic diols, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, and aromatic dicarboxylic acids such as (anhydrous) phthalic acid / isophthalic acid / terephthalic acid / naphthalenedicarboxylic acid, adipine Aliphatic dicarboxylic acid such as acid and sebacic acid,
Obtained by polycondensation with at least one dicarboxylic acid selected from the group consisting of alicyclic dicarboxylic acids such as cyclohexane-1,4-dicarboxylic acid and unsaturated dicarboxylic acids such as (anhydrous) maleic acid and fumaric acid. A saturated or unsaturated polyester polymer; a polymer obtained by polymerizing an unsaturated polyester with a polymerizable monomer such as styrene or (meth) acrylic acid ester.

(10) Phenol resin-based polymer Phenol, alkyl-substituted phenol, allyl-substituted phenol, bisphenol A, and other phenol resins generally obtained by polycondensing formaldehyde with formaldehyde, and a phenol resin generally referred to as a resol type, and Derivatives obtained by modifying or substituting these phenolic resins. (11) Organopolysiloxane-based polymer A polymer having a siloxane bond as a skeleton and an organic group containing a carbon atom directly bonded to a silicon atom in the siloxane bond (eg, an alkyl group) (eg, polydimethylsiloxane, polymethyl) Polyalkylsiloxanes such as phenylsiloxane); those in which some of the organic groups in these polymers are bonded to silicon atoms via oxygen atoms, modified silicones in which some of the organic groups in these polymers have been modified (eg, , Alkyd modified silicone, epoxy modified silicone, polyester modified silicone, acrylic modified silicone, urethane modified silicone, etc.).

(12) Acrylic Silicone Resin Polymer An organosilicon compound having a polymerizable double bond such as methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane is copolymerized with an unsaturated monomer such as an acrylic monomer. The resulting polymer (for example, an acrylic copolymer containing an alkoxysilyl group) and the like. (13) Fluororesin-based polymers Fluorinated ethylene, vinylidene fluoride, vinyl fluoride, etc., homopolymers / copolymers of fluorine-containing polymerizable monomers, fluorine-containing polymerizable monomers, other vinyl-based, Copolymers with olefin-based and acrylic-based polymerizable monomers.

(14) Other resin-based polymers Xylene resin, petroleum resin, ketone resin, liquid polybutadiene, rosin-modified maleic acid resin, coumarone resin, and other conventionally known resins, and derivatives of these resins. Preferred polymers are those having one or more polar atomic groups. When this polymer and a single particle composed of a metal oxide coprecipitate are combined, they have excellent chemical stability such as solvent resistance and chemical resistance (when the fine particles are hollow particles or aggregate particles, etc. Is excellent in mechanical properties such as compressive strength) and fine (average particle size 0.001).
~ 0.1 μm) Single particles are easily obtained, and zinc oxide type fine particles having a uniform particle size (the variation coefficient of the particle size is 30% or less) and having a uniform particle shape are easily obtained. Preferred polar atomic groups are carboxyl group, amino group (primary amino group, secondary amino group, tertiary amino group, imino group, imino bond), quaternary ammonio group, amide group, imide bond, hydroxyl group (alcoholic , Phenolic), carboxylic acid ester bond, urethane group, urethane bond, ureido group, ureylene bond, isocyanate group, epoxy group, phosphoric acid group, metal hydroxyl group, metal alkoxy group and sulfonic acid group. Is one.

Examples of the polymer having one or more carboxyl groups include (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid and 2- (meth).
Homopolymers / copolymers of carboxyl group-containing polymerizable monomers such as acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and maleic acid; the carboxyl group-containing polymerizable monomer and (meth) acrylic acid ester・ (Meth) acrylamide ・
(Meth) acrylic monomers such as (meth) acrylonitrile, substituted (meth) acrylic monomers such as α-chloromethyl methacrylate, maleic acid esters, styrene monomers such as styrene / p-chlorostyrene / vinyltoluene, ethylene・ Olefins such as propylene,
Diene or triene such as butadiene, vinyl acetate
Copolymers with vinyl monomers such as vinyl chloride, vinyl methyl ether, vinyl butyral, vinyl alcohol, etc., and copolymers with polymerizable monomers such as vinyltrimethoxysilane, methacryloxytrimethoxysilane etc .; alkyd resin type Among polymers and polyester resin-based polymers, a polymer having a carboxyl group at the terminal or side chain; a carboxyl group at the terminal and / or side chain such as polydimethylsiloxane having carboxypropyl at the terminal or side chain Examples thereof include carboxyl-modified organopolysiloxane-based polymers.

Polymers having one or more amino groups and / or quaternary ammonio groups include primary amino groups,
Any polymer having at least one selected from the group consisting of a secondary amino group, a tertiary amino group, an imino group, an imino bond and a quaternary ammonio group may be used, and examples thereof include dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate. , 4-vinylpyridine, p-
Homopolymers / copolymers of aminostyrene, imino group, ammonio group-containing polymerizable monomers such as aminostyrene, 3-vinylaniline, 4-vinylimidazole, vinylpyrrole, and dimethyldiallylammonium chloride; ) Acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, (meth) acrylonitrile and other (meth) acrylic monomers, α-chloromethyl methacrylate and other (meth) acrylic monomer substitution products, maleic acid, maleic acid Acid ester, styrene
Styrene-based monomers such as p-chlorostyrene / vinyltoluene, olefins such as ethylene / propylene, dienes or trienes such as butadiene, vinyl-based monomers such as vinyl acetate / vinyl chloride / vinyl methyl ether / vinyl butyral / vinyl alcohol, Copolymer with a polymerizable monomer such as a polymerizable organosilicon compound such as vinyltrimethoxysilane / methacryloxytrimethoxysilane; a polymer having an amino group in the polyamide resin-based polymer; the amino resin-based polymer; Amino-modified organopolysiloxane-based polymers having amino groups at the terminal and / or side chains, such as polydimethylsiloxane having a dimethylamino group or aminopropyl group in the side chain; polyethyleneimine,
Polymers of alkyleneimines such as polypropyleneimine;
Polymers such as pyrrolidine and piperidine; polydiallylammonium halides; ionene compounds; chitosan;
Examples thereof include porphines such as tetramethylporphine and tetraphenylporphine.

Examples of the polymer having one or more amide groups include homopolymers and copolymers of amide group-containing polymerizable monomers such as (meth) acrylamide and 2-acrylamido-2-methylpropanesulfonic acid; And a (meth) acrylic acid / (meth) acrylic acid ester / (meth) acrylonitrile etc., (meth) acrylic monomer substitution product such as α-chloromethyl methacrylate, maleic acid, Maleic acid esters, styrene-based monomers such as styrene / p-chlorostyrene / vinyltoluene, olefins such as ethylene / propylene, dienes or trienes such as butadiene, vinyl acetate / vinyl chloride / vinyl methyl ether / vinyl butyral / vinyl alcohol. Vinyl monomers such as vinyl Copolymer with a polymerizable monomer such as a polymerizable organosilicon compound such as trimethoxysilane / methacryloxytrimethoxysilane; the above polyamide resin-based polymer; an amide-modified organopolysiloxane having an amide group at the terminal and / or side chain Examples include polymer-based polymers.

Examples of the polymer having one or more imide bonds include the above-mentioned polyimide resin polymers and the like. Examples of the polymer having one or more alcoholic hydroxyl groups include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerin dimethacrylate, glycerol monomethacrylate, 3-chloro-2-hydroxypropyl methacrylate, 2-acryloyloxyethyl-
2-hydroxyethylphthalic acid, pentaerythritol triacrylate, 2-hydroxy-3-phenoxypropyl acrylate, bisphenol A-diepoxy-
(Meth) acrylic acid adducts, homopolymers / copolymers of hydroxyl group-containing polymerizable monomers such as vinyl alcohol; these monomers, and (meth) acrylic acid / (meth) acrylic acid ester / (meth) acrylonitrile / ( (Meth) acryl-based monomers such as (meth) acrylamide, (meth) acryl-based monomer substitution products such as α-chloromethyl methacrylate, maleic acid, maleic acid ester, styrene-based monomers such as styrene / p-chlorostyrene / vinyltoluene , Olefins such as ethylene and propylene, dienes and trienes such as butadiene, vinyl-based monomers such as vinyl acetate, vinyl chloride, vinyl methyl ether, vinyl butyral, and polymerizable organics such as vinyltrimethoxysilane and methacryloxytrimethoxysilane. Polymerizability of silicon compounds Copolymer with Nomer; Cellulose-based Polymers such as Hydroxypropyl Cellulose / Methyl Cellulose / Hydroxyethyl Methyl Cellulose; Polyamide Resin-based Polymers Obtained by Condensation Reaction of Polyamines with Polybasic Acids such as Aliphatic Dicarboxylic Acids; Examples thereof include polydimethylsiloxane which is hydroxypropyl, polydimethyl-hydroxyalkylene oxide methylsiloxane, and other organopolysiloxane polymers having an alcoholic hydroxyl group at the terminal and / or side chain.

Examples of the polymer having one or more phenolic hydroxyl groups include the above-mentioned phenol resin-based polymers. Examples of the polymer having one or more carboxylic acid ester bonds include, for example, methyl methacrylate / ethyl methacrylate / butyl methacrylate / isobutyl methacrylate / isoamyl acrylate / 2-ethylhexyl methacrylate / isodecyl methacrylate / n-lauryl (meth) acrylate /
Benzyl acrylate / tridecyl methacrylate / n
-Stearyl (meth) acrylate, isooctyl acrylate, isostearyl methacrylate, behenyl methacrylate, butoxyethyl acrylate, methoxydiethylene glycol methacrylate, n-butoxyethyl methacrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol acrylate, methoxypolyethylene glycol methacrylate.
Cyclohexyl methacrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,
6-hexanediol dimethacrylate / trimethylolpropane tri (meth) acrylate / glycerin dimethacrylate / trifluoroethyl methacrylate / pentaerythritol triacrylate / pentaerythritol tetraacrylate / dipentaerythritol hexaacrylate / neopentyl glycol acrylic benzoate ester / 3 -(Meth) acrylic acid esters such as acryloyloxyglycerin monomethacrylate / propylene oxide modified bisphenol A diacrylate / hydrogenated dicyclopentadienyl diacrylate / perfluorooctylethyl acrylate, methyl maleate
Homopolymers / copolymers of maleic acid esters such as butyl maleate, vinyl acetate, and carboxylic acid ester-containing polymerizable monomers such as methacryloxypropyltrimethoxysilane; these monomers and other monomers ((meth) acrylic) Acid / (meth) acrylonitrile / (meth)
(Meth) acrylic monomers such as acrylamide, maleic acid, styrene monomers such as styrene / p-chlorostyrene / vinyltoluene, olefins such as ethylene / propylene, dienes or trienes such as butadiene, vinyl chloride / vinyl methyl ether Copolymers with vinyl monomers such as vinyl alcohol and vinyl butyral, and polymerizable monomers such as polymerizable organosilicon compounds such as vinyltrimethoxysilane; the above polyester resin polymers; polydimethylsiloxanes such as acetoxy and stearyloxy at the ends. Examples thereof include organopolysiloxane-based polymers having an ester bond at the terminal and / or side chain.

Examples of the polymer having one or more urethane groups and / or urethane bonds include the polyurethane resin-based polymers mentioned above. Examples of the polymer having one or more ureido groups and / or ureylene bonds include polyurea obtained by a polycondensation reaction of nonamethylenediamine and urea. Examples of the polymer having one or more isocyanate groups include polymethylene polyphenyl polyisocyanate; polyol-modified isocyanate; polyfunctional aromatic or polyfunctional aliphatic isocyanate compounds such as hexamethylene diisocyanate and toluylene diisocyanate, amino groups, Obtained by reacting with a (pre) polymer containing a functional group having active hydrogen such as a carboxyl group and a hydroxyl group (a part of the isocyanate group contained in the isocyanate compound is reacted with a functional group having active hydrogen) Examples thereof include polymers.

Examples of the polymer having one or more epoxy groups include glycidyl methacrylate and N-.
Homopolymers / copolymers of epoxy group-containing polymerizable monomers such as epoxy group-containing (meth) acrylic monomers such as [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide; Monomers, which do not react with epoxy groups in the polymerization process, for example, (meth) acrylic monomers such as (meth) acrylic acid esters, (meth) acrylic monomer substitution products such as α-methyl chloromethacrylate, maleic acid esters,
Styrene-based monomers such as styrene / p-chlorostyrene / vinyltoluene, olefins such as ethylene / propylene, dienes or trienes such as butadiene, vinyl acetate / vinyl chloride / vinyl methyl ether / vinyl butyral / vinyl alcohol, etc. Monomers, copolymers with polymerizable monomers such as polymerizable organosilicon compounds such as vinyltrimethoxysilane and methacryloxytrimethoxysilane; the above epoxy resin-based polymers; polydimethylsiloxane having glycidoxypropyl at the end, poly Examples thereof include organopolysiloxane-based polymers having a glycidoxy group at the terminal and / or side chain such as glycidoxypropylmethylsiloxane and polyglycidoxypropylmethyl-dimethylsiloxane copolymer.

Examples of the polymer having one or more phosphoric acid groups include phosphorus such as mono (2-methacryloyloxyethyl) acid phosphate, mono (2-acryloyloxyethyl) acid phosphate and 2-acryloyloxyethyl acid phosphate. Homopolymers / copolymers of acid group-containing polymerizable monomers; these monomers and (meth) acrylic monomers such as (meth) acrylic acid / (meth) acrylic acid ester / (meth) acrylonitrile / (meth) acrylamide , (Meth) acrylic monomer substitution products such as α-chloromethyl methacrylate, maleic acid, maleic acid ester, styrene / p-
Styrene-based monomers such as chlorostyrene and vinyltoluene, olefins such as ethylene and propylene, dienes and trienes such as butadiene, vinyl-based monomers such as vinyl acetate, vinyl chloride, vinyl methyl ether, vinyl alcohol, vinyl butyral, and vinyl triene. Examples thereof include copolymers with polymerizable monomers such as polymerizable organic silicon compounds such as methoxysilane and methacryloxytrimethoxysilane.

Examples of the polymer having one or more metal hydroxyl groups and / or metal alkoxy groups include a silicon compound having a polymerizable double bond such as methacryloxypropyltrimethoxysilane, and (meth) acrylic acid. ( (Meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide and other (meth) acrylic monomers, α-chloromethacrylate and other (meth) acrylic monomer substitution products, maleic acid, maleic acid ester, styrene Styrene-based monomers such as p-chlorostyrene / vinyltoluene, olefins such as ethylene / propylene, dienes or trienes such as butadiene, vinyl-based monomers such as vinyl acetate / vinyl chloride / vinyl methyl ether, vinyltrimethoxysilane / methacryloxy. Copolymers with polymerizable monomers such as polymerizable organosilicon compounds such as remethoxysilane; and polymers obtained by (partly) hydrolyzing the alkoxysilyl groups in these copolymers; polydimethyl having silanol at the end Siloxane, silanol-terminated polydiphenylsiloxane, silanol-terminated polydimethyl-diphenylsiloxane, silanol-containing organopolysiloxanes such as polytetramethyl-p-silphenylene siloxane; (N-trimethoxysilylpropyl) polyethylene Imines, (N-trimethoxysilylpropyl) -o-polyethylene oxide urethane, triethoxysilyl modified poly (1,2-butadiene) and polymers obtained by (partial) hydrolysis of alkoxysilyl groups in these polymers; Acry Examples include silicone resin-based polymers.

Furthermore, examples of the polymer having one or more metal hydroxyl groups and / or metal alkoxy groups include polysiloxane group-containing polymers. The polysiloxane group referred to in the present invention is composed of two or more Si atoms linearly or branchedly linked by a siloxane bond (Si-O-Si), and has at least 1 bonded to the Si atom.
A polysiloxane chain having at least one group selected from the group consisting of an alkoxy group, a hydroxyl group, or an acyloxy group capable of forming a hydroxyl group by hydrolysis, and an acetoxy group (hereinafter referred to as X group). The polysiloxane group-containing polymer is defined as a polymer which has at least one polysiloxane group in one molecule and which is a complex of an arbitrary polymer (hereinafter referred to as polymer P) and a polysiloxane group. The molecular weight of the polysiloxane group-containing polymer is not particularly limited as long as the number average molecular weight is 1,000 or more. Further, there is no particular limitation on the molecular weight of the polysiloxane group and the polymer (P) in the polymer. The number of polysiloxane groups is at least one per one molecule of the polysiloxane group-containing polymer, and is not particularly limited, but for example, in order to form fine particles dispersed at a single particle level (ultrafine particles), 1 to 3 is preferable. . When it is present in excess of 3, the polymer acts as a coagulant, and it is difficult to form fine particles dispersed at the single particle level. To obtain aggregate fine particles or hollow fine particles, a polymer having a large amount of polysiloxane groups per molecule of the polysiloxane group-containing polymer may be used.

The polysiloxane group may be an alkyl group which may be substituted, in addition to the X group directly bonded to the Si atom,
It may have at least one group selected from an aryl group, an aralkyl group, a cycloalkyl group, an acyl group, or a hydrogen atom. The composition of the polymer P is not particularly limited, but usually, the polymers of (1) to (14) described above are
It is illustrated. The composite form of the polymer P and the polysiloxane group is arbitrary. For example, a polymer P having a main chain and a polysiloxane group bonded thereto, or a polymer P having a main chain having the polymer P bonded thereto. Existing, polysiloxane chains and polymer P are alternately bonded,
Examples thereof include those having a linear structure or a ring structure. Any form is effective for the purpose of synthesizing zinc oxide type fine particles complexed with a polymer.

As a method for synthesizing such a polysiloxane group-containing polysiloxane, for example, an organopolysiloxane having a hydrosilyl group (polymer P) and a polysiloxane having a polymerizable group such as C = C (polymerizable polysiloxane) can be used. ) Is a composite of an organopolysiloxane and a polysiloxane using a hydrosilylation reaction, and is synthesized by copolymerizing a polymerizable polysiloxane and a (meth) acrylic or vinyl-based polymerizable monomer. The method, which utilizes the reaction with a functional group capable of forming a bond by the reaction with the X group described above, in which a polymer (P) having an alcoholic hydroxyl group, a carboxyl group, a metal alkoxy group and the like coexist with a polysiloxane group. Then, the polymer (P) and the polysiloxane group become Si--
Examples thereof include a method of forming a composite through an O—C bond and a Si—OCO bond. Among them, the method (1) is a method in which the composition of the polymer (P) can be selected relatively arbitrarily, so that the polar parameter of the polymer can be controlled arbitrarily, and the polysiloxane group is formed by the Si—C bond. It is preferable since it is a method having a structure in which it is directly or indirectly bound to, having excellent thermal stability and solvent resistance, and being excellent in economic efficiency.

The method and the polysiloxane group-containing polymer obtained by the method are described in JP-A-6-22845.
It is described in detail in No. 7 as a silicon-containing polymer. The polymerizable polysiloxane is obtained, for example, by a cohydrolysis condensation reaction of a polymerizable silane compound and a non-polymerizable silane compound. The polymerizable silane compound is γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltriethoxysilane. Methoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxyethoxypropyltrimethoxysilane, γ-methacryloxypropylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, 1-hexenyltrimethoxysilane Methoxysilane, 1-octenyltrimethoxysilane, vinyloxypropyltrimethoxysilane, 3-vinylphenyltrimethoxysilane, 3- (vinylbenzylaminopropyl) ) A silane compound having a polymerizable group, such as trimethoxysilane.

The non-polymerizable silane compound is, for example, tetrafunctional silane monomer such as tetraalkoxysilane such as tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane; methyltrimethoxysilane, isopropyltrimethoxy. Silane,
Alkyltrialkoxysilanes such as octyltrimethoxysilane, aryltrialkoxysilanes such as phenyltrimethoxysilane, phenyltrihydroxysilane,
Trifunctional silane monomer such as aminoethylaminopropyltriethoxysilane, mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldihydroxysilane, etc. And a bifunctional silane monomer, etc.

Examples of the polymer having one or more sulfonic acid groups include sulfonic acid group-containing polymerizable monomers such as acrylamidomethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and sodium salts thereof. Polymers / copolymers; these monomers and (meth) acrylic monomers such as (meth) acrylic acid / (meth) acrylic acid ester / (meth) acrylonitrile / (meth) acrylamide; α-chloromethyl methacrylate (Meth) acrylic monomer substitution product, maleic acid, maleic acid ester, styrene p-
Styrene-based monomers such as chlorostyrene and vinyltoluene, olefins such as ethylene and propylene, dienes and trienes such as butadiene, vinyl-based monomers such as vinyl acetate, vinyl chloride, vinyl methyl ether, vinyl alcohol, vinyl butyral, and vinyl triene. Copolymers with polymerizable monomers such as polymerizable organosilicon compounds such as methoxysilane and methacryloxytrimethoxysilane;
Examples thereof include sulfonic acid group-containing polymers obtained by reacting a styrene-based polymer with a sulfonating agent such as concentrated sulfuric acid, chlorosulfonic acid and sulfuric anhydride.

Examples of polymers having other polar atomic groups include poly-N-formylethyleneimine and poly-N-acetylethyleneimine obtained by ring-opening polymerization of oxazoline, 2-methyloxazoline and the like. (2-) ring-opening compounds of cyclic imino ethers such as substituted oxazoline and / or (2-substituted) oxazine; opening of cyclic imino ethers and lactones like an alternating copolymer of oxazoline and β-propiolactone Among polymers having at least one functional group, such as ring copolymers, polymers having a structure used for a chelate resin having a coordination group (functional group) capable of coordinating a metal ion (for example, polyvinyl alcohol, polyvinyltriene). Acrylic methane, polyvinyl methacryloylacetone, poly (4
-Hydroxystyrene), pyrogallol phenol formaldehyde resin, salicylic acid formaldehyde resin,
Polyvinyl salicylic acid, polyacrylic acid, polymethacrylic acid, polyitaconic acid, aminophenol formaldehyde resin, poly (8-hydroxy-5-vinylquinoline), polyvinylamine, polyethyleneimine, poly (4-aminostyrene), poly (3-vinyl) (Aniline), poly (4-vinylpyridine), poly (4-vinylbipyridine), poly (4-vinylimidazole), polyvinylpyrrole, polyglycine, poly (α-L-alanine), etc.) with metal ions partially Or a polymer formed by adsorption coordination with all coordination groups (functional groups); carboxyl groups, sulfonic acid groups, etc., of metal salts such as alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and calcium Examples include shaped polymers and the like.

Among the polymers exemplified in the above (1) to (14), (meth) acrylic type, styrene type, vinyl type,
At least one main chain selected from the group consisting of copolymerization type, alkyd type, polyester type, and polyamide type, and a group consisting of carboxyl group, amino group, amide group, silanol group, and alkoxysilyl group. A polymer having at least one polar atomic group, a composite particle with the above-mentioned polysiloxane group-containing polymer, or surface-modified fine particles is preferable because it is particularly excellent in affinity and dispersibility for a resin. In the surface-modified fine particles of the present invention, the composition of the surface-modified layer may be any of an inorganic material, an organic material, and an inorganic-organic composite composition. It is appropriately selected depending on the purpose of use of the fine particles.

When the fine particles of the present invention are used in a coating composition or a resin composition, it is preferable that the fine particles have high dispersibility in these compositions, while the surface modification layer and the bulk metal oxide. A well-balanced surface modification layer has an inorganic-organic composite composition from the viewpoints of the adhesiveness with a single particle composed of a coprecipitate, and the chemical and thermal stability of the surface modification layer and fine particles. Is preferred. The surface-modified layer of the surface-modified fine particles may be one that forms a continuous layer in which the surface of a single particle composed of a metal oxide coprecipitate is completely covered, or one in which the surface-modifying agent is discontinuously present. Moreover, the ratio and thickness of the surface modification layer in the fine particles are not particularly limited.

As the surface modification layer, a metal oxide coating film of silica, titania or the like, a layer in which metalloxane chains of polysiloxane or the like are cross-linked with each other or singly bonded to the surface by a Zn--O--M bond or the like, an organic compound However, the organic compound layer and the like formed by adsorption, hydrogen bond, or chemical bond such as Zn—O—C are exemplified. Dispersion improving effect for solvents, resins, etc. by surface modifiers, chemical resistance such as deterioration due to acid or alkali, deterioration due to carbon dioxide gas, gas resistance improving effect, heat-resistant oxidation resistance (resistance to oxidation during high temperature exposure, It suffices that any modification effect such as an effect of improving (crystal growth preventing property), an effect of reducing or improving catalytic activity is substantially exhibited.

However, the surface modification layer is preferably present on the surface as uniformly as possible in order to fully exert its modification effect, and metal oxides (zinc and Group IIIB,
The ratio of the surface modification layer to the oxide containing a Group IVB metal as a metal component is preferably 0.01 to 1 in weight ratio. Even if the weight ratio exceeds 1, the surface modification effect is saturated, which is economically disadvantageous. From the perspective of modifier effect and economy
A particularly preferred weight ratio is 0.02-0.5. Further, the average particle size and shape of the surface-modified fine particles are not particularly limited. However, in applications where transparency is important, such as the transparent UV and infrared cut films described below,
In order to sufficiently exhibit transparency, the particle size is fine, and since extremely high dispersibility in a coating composition, a resin composition, etc. is required, the average particle size is 0.1 μm or less,
Further, it is particularly important that the surface-modified fine particles have a particle size of 0.05 μm or less.

The surface modifier is not limited in its composition, molecular weight and the like. The above-mentioned polymers (polymers that are allowed to coexist in the system when the system is maintained at a temperature of 100 ° C. or more in the method for producing zinc oxide-based fine particles of the present invention), and the above-mentioned or later-specified specific compounds used for the purpose of controlling the particle size, etc. It is possible to use an additive compound having a functional group (an additive compound which is allowed to coexist in this system when the system is maintained at a temperature of 100 ° C. or higher in the method for producing zinc oxide based fine particles of the present invention). However, as described above, for the purpose of use in a coating composition, a resin composition, etc., the surface modification layer is preferably an inorganic-organic composite composition. Polymers containing siloxane groups are preferred.

A preferred embodiment of the polysiloxane group-containing polymer, which is particularly preferred as the surface modifier, is described below. The molecular weight of the polysiloxane group-containing polymer is not particularly limited as long as the number average molecular weight is 1,000 or more,
From the viewpoint that the fine particles do not aggregate in a solvent or a resin and are excellent in high dispersibility, it is preferably 1,000 or more and 1,000,000 or less, and more preferably 2,000 or more and 100,000 or less. There are no particular restrictions on the molecular weight of the polysiloxane group or polymer (P) in the polymer. However, the number of Si atoms contained in the polysiloxane group is preferably 4 or more on average per polysiloxane group, and 11 or more, from the viewpoint of high reactivity, binding force or affinity between the polymer and the surface of the fine particles. More preferable. The polysiloxane group is
The number of the polysiloxane group-containing polymer is at least 1 per molecule, and 1 to 3 is preferable in order to obtain fine particles dispersed at a single particle level (ultrafine particles). When present in excess of 3, the polymer acts as a coagulant,
It is difficult to obtain fine particles dispersed at the single particle level.

The production method of the present invention will be described in detail below. In the production method of the present invention, for example, a mixture (m) obtained by dissolving or dispersing the above zinc source and a monocarboxylic acid in a medium containing at least an alcohol is used as a group IIIB metal element and an IV group.
A compound containing at least one additive element (hereinafter sometimes referred to as “metal (M)” selected from the group consisting of Group B metal elements (this compound is a metal such as a simple metal or an alloy) In the following, 100 ° C. in the coexistence of “metal (M) compound”.
By maintaining at the above temperature, the crystallinity of the metal oxide containing 80 to 99.9% zinc and 0.1 to 20% metal (M) in terms of the ratio of the number of atoms to the total number of atoms of the metal element. This is a manufacturing method in which zinc oxide type fine particles composed of a precipitate are deposited.

By heating the mixture (m) containing the monocarboxylic acid and the alcohol, the zinc source is converted into crystalline zinc oxide by X-ray diffraction, and at this time, the metal (M The coexistence of the compound makes it possible to obtain a dispersion containing the zinc oxide-based fine particles of the present invention. At that time, if any one of the three components of the zinc source, the monocarboxylic acid, and the alcohol is missing as a starting material, the precipitation reaction of zinc oxide crystals does not occur, and if the metal (M) does not exist, the present invention No such zinc oxide-based fine particles can be obtained. The zinc used in the present invention is supplied from at least one zinc source selected from the group consisting of metallic zinc and zinc compounds. The zinc source is not particularly limited, but includes metallic zinc (zinc dust), zinc oxide (zinc white, etc.), zinc hydroxide, basic zinc carbonate, and optionally a mono- or di-carboxylic acid salt (for example, At least one selected from the group consisting of zinc acetate, zinc octylate, zinc stearate, zinc oxalate, zinc lactate, zinc tartrate and zinc naphthenate) is preferable. When these zinc sources are used, the desalting step is unnecessary, and the number of steps is smaller than when zinc chloride, zinc nitrate or zinc sulfate, which requires the desalting step, is used.

Among them, at least one zinc source selected from the group consisting of metallic zinc (zinc dust), zinc oxide (zinc white), zinc hydroxide, basic zinc carbonate and zinc acetate is inexpensive and easy to handle. It is preferable because it is easy. Zinc oxide,
At least one zinc source selected from the group consisting of zinc hydroxide and zinc acetate is substantially free of impurities that hinder the reaction of forming zinc oxide crystals during the heating process, and the crystals It is more preferable because the size and shape of the fine particles can be easily controlled. Zinc oxide and / or zinc hydroxide are not only inexpensively available, but also the type of monocarboxylic acid can be arbitrarily selected, and by using these raw materials, fine particles whose shape or particle diameter is controlled can be obtained particularly. It is particularly preferable because it is easy.

The amount of the zinc source is, for example, 0.1 to 95% by weight, preferably 0.5 to 50% by weight, and more preferably 0.5 to 50% by weight, calculated as ZnO, based on the total amount of the zinc source, the monocarboxylic acid and the medium. Is 1 to 30% by weight. If it is less than the above range, the productivity may be lowered, and if it is more than the above range, secondary agglomeration of fine particles is likely to occur, and fine particles having good dispersibility and uniform particle size distribution may be difficult to obtain. The monocarboxylic acid used in the present invention is a compound having only one carboxyl group in the molecule. Specific examples of the compound include saturated fatty acids (saturated monocarboxylic acids) such as formic acid, acetic acid, propionic acid, isobutyric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, and stearic acid; acrylic acid, methacrylic acid. , Unsaturated fatty acids (unsaturated monocarboxylic acids) such as crotonic acid, oleic acid and linolenic acid; cyclic saturated monocarboxylic acids such as cyclohexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, phenylacetic acid and toluic acid; The above-mentioned monocarboxylic acid anhydrides such as acetic anhydride; halogen-containing monocarboxylic acids such as trifluoroacetic acid, monochloroacetic acid and o-chlorobenzoic acid; and lactic acid. Any of these compounds may be used alone, or two or more compounds may be used in combination.

The preferred monocarboxylic acid is 20 at 1 atm.
It is a saturated fatty acid having a boiling point of 0 ° C or lower. Specifically, formic acid, acetic acid, propionic acid, butyric acid, and isobutyric acid are preferable. The reason is that it is easy to control the content of the monocarboxylic acid in the reaction system during the heating process from the preparation process of the mixture, and thus it is easy to strictly control the precipitation reaction of zinc oxide crystals. The saturated fatty acid is preferably used in the range of 60 to 100 mol%, more preferably 80 to 100 mol% based on the total amount of monocarboxylic acid. If the amount is less than the above range, the crystallinity of zinc oxide in the obtained fine particles may be low.

The monocarboxylic acid also includes a monocarboxylic acid salt of zinc such as zinc acetate, and when the zinc salt is used, it is not always necessary to separately add the monocarboxylic acid as a raw material. The amount of the monocarboxylic acid used (or charged) in the production method of the present invention is, for example, 0.5 to 50, and preferably 2.2 to 10, in terms of molar ratio with respect to the amount of Zn atoms in the zinc source. Economical within the above range,
It is preferable in terms of the ease of forming fine particles, the ease of obtaining fine particles that are less likely to aggregate, and have excellent dispersibility. If it is less than the above range, it may be difficult to obtain zinc oxide type fine particles having good ZnO crystallinity or fine particles having a high uniformity in shape and particle diameter, and if it exceeds the above range, not only the economical efficiency is deteriorated but also the fine particles having good dispersibility are obtained. Can be difficult to obtain.

Alcohols used in the present invention include aliphatic monohydric alcohols (methanol, ethanol, isopropyl alcohol, n-butanol, t-butyl alcohol, stearyl alcohol, etc.) and aliphatic unsaturated monohydric alcohols (allyl alcohol, chloro alcohol). Chill alcohol, propargyl alcohol, etc.), alicyclic monohydric alcohol (cyclopentanol, cyclohexanol, etc.), aromatic monohydric alcohol (benzyl alcohol, cinnamyl alcohol, methylphenylcarbinol, etc.), heterocyclic monohydric Monohydric alcohols such as alcohols (furfuryl alcohol, etc.); alkylene glycols (ethylene glycol, propylene glycol, trimethylene glycol, 1,4
-Butanediol, 1,5-pentanediol, 1,6
-Hexanediol, 1,8-octanediol, 1,
10-decanediol, pinacol, diethylene glycol, triethylene glycol, etc., aliphatic glycols having an aromatic ring (hydrobenzoin, benzpinacol, phthalyl alcohol, etc.), alicyclic glycols (cyclopentane-1,2-diol) , Cyclohexane-
1,2-diol, cyclohexane-1,4-diol, etc.), glycols such as polyoxyalkylene glycol (polyethylene glycol, polypropylene glycol, etc.); ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol monomethyl ether, Monoethers and monoesters of the above glycols such as ethylene glycol monoacetate; aromatic diols such as hydroquinone, resorcinol, 2,2-bis (4-hydroxyphenyl) propane and their monoethers and monoesters; glycerin and the like 3 Examples thereof include polyhydric alcohols and their monoethers, monoesters, diethers and diesters. Any one of these alcohols may be used alone, or two or more may be used in combination.

The amount of alcohol in the medium consisting of at least alcohol is not particularly limited, but in order to carry out the reaction for producing zinc oxide type fine particles in a short time, the molar ratio of alcohol to Zn atoms derived from the zinc source is, for example, 1-100, preferably 5-80, more preferably 1
0 to 50. When it is less than the above range, it is difficult to obtain zinc oxide type fine particles having good ZnO crystallinity, or dispersibility,
It may be difficult to obtain fine particles excellent in uniformity of shape and particle diameter, and if it exceeds the above range, it may be economically disadvantageous. The medium is a medium consisting only of the alcohol, a mixed solvent of the alcohol and water, a mixed solvent of the alcohol and an organic solvent other than alcohol, such as ketones, esters, aromatic hydrocarbons, ethers and the like. The ratio of the alcohol to the other solvent is 5 to 100% by weight, preferably 40 to 40% by weight of the charging (using) agent used for preparing the mixture (m).
It is 100% by weight, more preferably 60 to 100% by weight. If the amount of alcohol is less than the above range, fine particles having good crystallinity, shape / particle size uniformity, and dispersibility may be difficult to obtain.

The metal (M) compound used in the production method of the present invention includes, for example, metal (M) such as metal simple substance and alloy; oxide; hydroxide; (basic) carbonate and nitrate. Inorganic salts such as halides such as sulfates, chlorides and fluorides; carboxylates such as acetates, propionates, butyrates and laurates; metal alkoxides; β-diketones, hydroxycarboxylic acids, ketoesters , All compounds containing trivalent or tetravalent metal (A), such as metal chelate compounds with keto alcohol, amino alcohol, glycol, quinoline, etc .; multiple valences such as In, Tl, etc. are possible In the case of a metal element, at least one compound selected from the group consisting of compounds containing a low-valent metal that can finally change to trivalent or tetravalent in the process of forming fine particles (this Gobutsu is a concept including a metal such as an elemental metal or an alloy) is used.

When aluminum is used as the Group IIIB metal element, examples of compounds containing aluminum include aluminum, aluminum hydroxide, aluminum oxide, aluminum chloride, aluminum fluoride, aluminum nitrate, aluminum sulfate, and basic acetic acid. Aluminum, aluminum trisacetylacetonate, aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, acetoalkoxy aluminum diisopropylate, aluminum laurate, aluminum stearate, diisopropoxyaluminum. Stearate, ethyl acetoacetate aluminum diisopropylate, etc. are used.

When boron is used as the group IIIB metal element, examples of compounds containing boron include boron trioxide, boric acid, boron oxalate, boron trifluoride diethyl ether complex, boron trifluoride monoethylamine complex, and trimethyl. Borate,
Triethyl borate, triethoxy borane, tri-n-
Butyl borate is used. When gallium is used as the group IIIB metal element, examples of compounds containing gallium include gallium, gallium hydroxide, gallium oxide, gallium (III) chloride, gallium (III) bromide,
Gallium (III) nitrate, gallium (III) sulfate, ammonium gallium sulfate, triethoxygallium, tri-n-butoxygallium and the like are used.

When indium is used as the group IIIB metal element, examples of the compound containing indium include indium, indium (III) oxide, indium (III) hydroxide, indium (III) sulfate, and indium chloride (I).
II), indium (III) fluoride, indium iodide (II
I), indium isopropoxide, indium acetate (II
I), triethoxyindium, tri-n-butoxyindium and the like are used. When thallium is used as the Group IIIB metal element, examples of compounds containing thallium include thallium, thallium (I) oxide, thallium (III) oxide, basic thallium (I) hydroxide, and thallium (I) chloride. , Thallium (I) iodide, thallium (I) nitrate, thallium (I) sulfate, thallium hydrogen (I) sulfate, thallium (I) basic sulfate, thallium acetate (I), thallium formate (I), malonic acid Thallium (I), thallium (III) chloride, thallium (III) nitrate, thallium carbonate (III), thallium sulfate (III), thallium hydrogen sulfate (III), etc. are used.

When silicon is used as the group IVB metal element, examples of compounds containing silicon include silicon, silicon oxide, tetraalkoxysilane such as tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane, and methyltrimethoxysilane. , Trimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, III-glycidoxypropyltrimethoxysilane, III- (II-aminoethylaminopropyl) trimethoxysilane, phenyltrimethoxysilane, Alkylalkoxysilanes such as diethoxydimethylsilane, trimethylethoxysilane and hydroxyethyltriethoxysilane, phenyltrimethoxysilane, benzyltriethoxysilane, γ-aminopropyltriethoxysilane Silane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxy Silicon alkoxide compounds such as silane coupling agents such as silane and stearyltrimethoxysilane; 4
Chlorosilanes such as silicon chloride, trichlorosilane and methyltrichlorosilane; acetoxysilanes such as triacetoxysilane are used.

When germanium is used as the Group IVB metal element, examples of compounds containing germanium include germanium, germanium (IV) oxide, germanium (IV) chloride, germanium (IV) iodide, germanium (IV) acetate. , Germanium (IV) chloride bibilidyl complex, β-
Carboxyethyl germanium sesquioxide, germanium (IV) ethoxide and the like are used. When tin is used as the group IVB metal element, examples of compounds containing tin include tin, tin (IV) oxide, tin (IV) chloride, tin (IV) acetate, and di-n-butyltin (IV) dichloride. , Di-n-butyltin (IV) dilaurate, di-n-butyltin (IV) maleate (polymer), di-n-butyltin (IV) oxide, di-n-methyltin (IV) dichloride, di-
n-octyltin (IV) maleate (polymer), di-n-octyltin (IV) oxide, diphenyltin (IV) dichloride, mono-n-butyltin (IV) oxide, tetra-n-butyltin (IV), tin oxalate (II), tri-n-
Butyltin (IV) acetate, tributyltin ethoxide, trimethyltin chloride, triphenyltin acetate, triphenyltin (IV) hydroxide, tetraethoxytin, tetra-n-butoxytin and the like are used.

When lead is used as the IVB group metal element, lead-containing compounds such as lead and lead acetate (I
V), lead (IV) chloride, lead (IV) fluoride, lead (IV) oxide, lead (I) oxide
I + IV), lead (II) oxalate, etc. are used. The metal (M) oxide or hydroxide may be in the form of powder, but an aqueous sol of colloidal metal oxide and / or metal hydroxide such as alumina sol or silica sol, or alcohol sol may also be used. The production method of the present invention has, for example, the following steps I to III as essential steps, and
The metal (M) compound can be added in any one or two or more of the steps I, II and III.

(I) A first step for preparing a mixture (n) consisting of a zinc source and a monocarboxylic acid. (II) A second step of preparing the mixture (m) in which the zinc source and the monocarboxylic acid are dissolved or dispersed in the medium containing at least the alcohol by mixing the mixture (n) with the medium containing at least the alcohol. (III) By maintaining the mixture (m) at a temperature of 100 ° C. or higher, the ratio of the number of atoms to the total number of metal elements is 80 to 99.9% zinc and 0.1 to 20% metal (M).
A third step of depositing zinc oxide-based fine particles composed of a crystalline coprecipitate of a metal oxide containing and.

In the production method of the present invention, step I is preferably a step of producing a mixture (n) further containing water. By this step, the mixture (n) in the form of solution is easily obtained. The zinc source, the monocarboxylic acid and water may be added in any order. For example, the mixture (n) is prepared by dissolving the zinc source in the mixed solvent of the monocarboxylic acid and water.
In the manufacturing method of the present invention, the step II and the step III are performed at 100 ° C.
It is preferable that the step (a) is carried out by adding the mixture (n) to a medium containing at least alcohol and maintained at the above temperature. By this step, the mixture (m) is easily made. When the mixture (n) composed of the zinc source and the monocarboxylic acid, or composed of these and the metal (M) compound is added to the medium composed of at least alcohol, the mixture (n) is preferably a solution. . When the mixture (n) is a solution, the zinc source and the monocarboxylic acid, or these and the metal (M) compound are compatible with each other, or are dissolved in a solvent having a high compatibility with them. Is desirable. As a solvent used for that purpose, a zinc source and a monocarboxylic acid, or these and a metal (M) compound can be easily dissolved at a temperature of from room temperature to about 100 ° C., and the solvent also forms a phase with the medium. From the viewpoint of high solubility, water, alcohols, ketones and esters are preferable. The alcohols mentioned here include all of the above-mentioned alcohols.

One or more zinc oxide precursors (the precursors may contain a metal (M)) in the course of conversion of the zinc source into X-ray diffractometrically crystalline zinc oxide. However, it may not be included). For example, the case where zinc oxide or the like is used as the zinc source can be mentioned. The zinc oxide precursor means an ion or compound state containing at least a zinc atom other than zinc oxide, such as zinc (hydrate) ion (Zn2 +), zinc polynuclear hydroxide ion, and zinc acetylacetone. Β-dicarbonyl compound or a compound having a chelate-forming ability such as lactic acid, ethylene glycol, ethanolamine, etc., in which some or all of the above ions are chelated, (basic) zinc acetate, (basic) ) Zinc salicylate, (basic)
The case where it exists as a (basic) carboxylic acid salt such as zinc lactate and the like can be mentioned. A case where a part or all of the precursor is present as a complex composition such as a complex salt with a monocarboxylic acid and / or alcohol is also included.

In the process of converting the zinc source and the metal (M) compound used as raw materials in the mixture (m) into zinc oxide type fine particles, the monocarboxylic acid present in the mixture (m) changes. Not, or part or all of the monocarboxylic acid causes an esterification reaction with part or all of the alcohol in the mixture (m) to form an ester compound. The mixture (m) may be any one obtained by mixing four components of the zinc source, the monocarboxylic acid, the alcohol, and the metal (M) compound as essential components, and if necessary, , Components other than the four components such as water, ketones, esters, (cyclo) paraffins, ethers, organic solvents such as aromatic compounds, components such as additives described below, or zinc and metal (M) Other metal components than the above, for example, inorganic salts such as metal acetates, nitrates and chlorides, and organic metal alkoxides such as metal alkoxides may be contained. However, the alkali metal and the alkaline earth metal may reduce the heat ray cutting function and conductivity of the fine particles, and it is preferable that the number is 1/10 or less of the number of atoms of the metal (M) in the mixture (m), It is more preferably 1/100 or less. Also,
Water and an organic solvent are usually contained as solvent components.

The state of existence of the above four components and the form of existence of each component in the mixture (m) are not particularly limited. For example, as an example of the presence state of the zinc source, the zinc source and / or the metal (M) compound is directly dissolved in the zinc oxide precursor using alcohol and / or the water and the organic solvent as solvent components. It may be in a changed and dissolved state or in a colloidal state, an emulsified state or a suspended state. Therefore, the state of the mixture (m) is not particularly limited, and there is no problem even if it is in the form of liquid, sol, emulsion or suspension. The mixture (m) is prepared by mixing the respective components within the above range. The preparation method is not particularly limited.

Particularly, the average particle size of single particles is 0.001 to
In order to obtain a dispersion of zinc oxide-based fine particles controlled in the range of 10 μm, the first mixture (n) consisting of the zinc source and monocarboxylic acid is added to an alcohol-containing solution with heating to obtain a mixture. It is preferable to prepare (m) because practical productivity can be obtained. The preparation method at this time will be described below. As a method of adding the mixture (n), for example, a method of adding and mixing the mixture (n) at once,
Alternatively, a method of mixing the mixture (n) by dropping it on or in the alcohol-containing solution, a method of spraying the mixture (n), or the like can be adopted.

Further, the addition and mixing of the mixture (n) was carried out under normal pressure,
It may be carried out under pressure or under reduced pressure, but it is preferably carried out under normal pressure in view of manufacturing cost. When adding and mixing under normal pressure, when it is desired to obtain a zinc oxide-based fine particle dispersion that is highly uniform in particle size, shape, etc., and whose dispersed / aggregated state is controlled, alcohol-containing during mixing and addition. 6 solution
It is preferable to maintain the temperature of 0 ° C. or higher, especially 60 ° C. or higher and 300 ° C. or lower. When the temperature of the alcohol-containing solution at the time of addition and mixing is less than 60 ° C., the viscosity of the mixture (m) may sharply increase during or after the addition and mixing, and the mixture may become a gel. In such a case, stirring is not possible and uniform mixing cannot be achieved, or when the next step, that is, heating, causes a problem such as insufficient heat transfer and temperature distribution, crystallinity, It is difficult to obtain zinc oxide-based fine particles having a uniform particle diameter and particle shape, and it is difficult to obtain only aggregates. Such a problem is related to the zinc concentration in the mixture (m) and is more likely to occur when the zinc concentration is higher. Therefore, the lower limit temperature of these optimum temperatures differs depending on the pressure of the system, and when performing under reduced pressure or increased pressure, it is necessary to appropriately select the temperature of the alcoholic solvent according to the pressure. As described above, when the mixture (n) is added while heating the alcohol-containing solution, a part of the monocarboxylic acid and / or a part of the alcohol in the mixture (m) is distilled out of the system by evaporation. Sometimes it's gone,
The thus obtained product is also included in the mixture (m).

The raw material composition for preparing the mixture (n) is not particularly limited, but the amount of the zinc source used as the raw material of the mixture (n) is Z based on the total amount of the mixture (n).
It is in the range of 1 to 90% by weight in terms of nO, and the amount of the monocarboxylic acid used as a raw material of the mixture (n) is 0.5 to 5 in terms of molar ratio to Zn atoms in the zinc source.
It is preferably in the range of 0 times the mole. The mixture (m) is obtained by adding and mixing the mixture (n) prepared as above to the alcohol-containing solution. When the mixture (n) is added and mixed, the mixture (n) may be at room temperature or in a heated state. Also,
During the addition and mixing, it is particularly preferable that the alcohol-containing solution is stirred for the purpose of obtaining uniform mixing.

At this time, the content of alcohol contained in the alcohol-containing solution is not particularly limited, but in order to carry out the zinc oxide type fine particle formation reaction during heating in a short time, a mixture of alcohols (m 1) represented by a molar ratio to Zn atoms derived from the zinc source contained in 1).
A 100-fold molar range is preferred. The concentration of alcohol in the alcohol-containing solution is usually in the range of 5 to 100% by weight based on the total amount of the solution. Further, as a method for producing the zinc oxide type fine particles of the present invention, a zinc source, a monocarboxylic acid and an alcohol are required without the above steps (I) and (II) (without forming the mixture (n)). A mixture (m) containing water and containing a zinc source and a monocarboxylic acid dissolved or dispersed therein is prepared.
Is maintained at a temperature of 100 ° C. or higher in the same manner as in the step (III), the ratio of the number of atoms to the total number of metal elements is 80 to 99.9% for zinc and 0.1 to 0.1% for the metal (M). 20
Another method of precipitating zinc oxide-based fine particles composed of a crystalline co-precipitate of a metal oxide containing 10% by weight can also be used. In this alternative method, during the preparation of the mixture (m) or thereafter at 100 ° C.
It is preferable to go through the state of a solution in which the zinc source and the monocarboxylic acid are uniformly dissolved in the process of depositing any of the fine particles in the above heat treatment, and in order to obtain a homogeneous solution mixture (m) For example, a method such as heating is adopted. The metal (M) compound may be added and mixed when the mixture (m) is prepared, or may be separately added during the heat treatment at 100 ° C. or higher. When added during this heat treatment, for example, a method may be employed in which the metal (M) compound is dissolved in a solvent system in which it can be (heated) dissolved, and then the resulting solution is added. In the case of the above-mentioned alternative method, the raw material composition for preparing the mixture (m) is not particularly limited, but the amount of the zinc source used as the raw material of the mixture (m) is relative to the total amount of the mixture (m). Is in the range of 1 to 20% by weight in terms of ZnO, and the amount of the monocarboxylic acid used as the raw material of the mixture (m) is 0.5 to 10 times the molar ratio with respect to Zn atoms in the zinc source. It is preferably in the range of. Further, the content of alcohol is such that the total weight of alcohol is Z contained in the mixture (m).
The weight ratio of n atom to ZnO equivalent weight is preferably 10 to 50 times.

Mixture (m) obtained as described above
By heating, the dispersion containing zinc oxide-based fine particles can be obtained in good yield. The heating temperature is not particularly limited, and it goes without saying that the heating temperature is not lower than the temperature at which crystalline zinc oxide precipitates, but the particle size, shape, dispersion / aggregation state, etc. of the zinc oxide-based fine particles to be finally obtained. The heating temperature and the heating time must be selected from a comprehensive point of view including the initial composition of the mixture (m) and the various parameters described above, which is not uniquely determined depending on the morphology. In particular, the average particle size of single particles is 0.001 to 1
In order to obtain a dispersion of zinc oxide-based fine particles controlled in the range of 0 μm with practical productivity, it is preferable to carry out at a heating temperature of 100 ° C. or higher, particularly 100 ° C. or higher and 300 ° C. or lower.

In this case, for example, the mixture (n) is mixed with 10
When the mixture (m) is obtained by adding and mixing to an alcohol-containing solution maintained at a temperature of 0 ° C. or higher, the temperature may be maintained as it is, or after heating or cooling to a predetermined temperature, heating is performed. May be processed. Moreover, when the mixture (n) is obtained by adding and mixing the mixture (n) to alcohol at a temperature lower than 100 ° C., the temperature may be raised to 100 ° C. or higher and then heat treatment may be performed. Setting the heating temperature of the mixture (m) to 100 ° C. or higher strictly controls the composition of the reaction system, including the rate and amount of evaporation and removal of excess or unnecessary components, in order to obtain zinc oxide-based fine particles. Therefore, there is an advantage that it is easy to control the particle diameter and the like of the resulting fine particles.

In addition, in the heating process for obtaining the dispersion, a component other than the above components, that is, an alcohol, the ester compound produced by heating, or a part of the solvent component present in the mixture as necessary, or All may be removed by evaporation. The heating time is not particularly limited, but is usually preferably about 0.1 to 30 hours in order to complete the reaction. When water is allowed to exist in the mixture (m), the free water concentration in the dispersion is preferably 5% by weight in order to be converted into zinc oxide type fine particles in the heating process. It is preferable to carry out the distillation until the content becomes not more than%, more preferably not more than 1% by weight. The reason is that if the water concentration exceeds this range, the crystallinity of the zinc oxide-based fine particles becomes low and the above-mentioned function cannot be sufficiently exhibited depending on the type of other components such as alcohol contained in the dispersion. Because there is.

As the (final) composition in the produced zinc oxide type fine particle dispersion, the amount of the monocarboxylic acid is based on the total amount of zinc atoms contained in the produced dispersion. It is preferably 0.5 times or less mol. The reason is that if it exceeds 0.5 times by mole, the crystallinity of the zinc oxide-based fine particles is lowered and the function as zinc oxide may not be sufficiently exhibited. Therefore, when the amount of the monocarboxylic acid present in the mixture (m) exceeds 0.5 times the total amount of zinc atoms contained in the produced dispersion in terms of zinc atoms, heating is performed. In the process
At least the excess needs to be distilled off. Of course, even if the above ratio is 0.5 times or less, the distillation may be carried out in the process of heating.

In the case where the above-mentioned single particles are used as primary particles and secondary particles formed by aggregating the primary particles are obtained, it is effective to make a lactic acid source coexist when the temperature is kept at 100 ° C. or higher. Is. The source of lactic acid is lactic acid; ammonium lactate, sodium lactate, lithium lactate, calcium lactate, magnesium lactate, zinc lactate, aluminum lactate, manganese lactate,
Metal lactates such as iron lactate, nickel lactate, and silver lactate; lactic acid ester compounds that can generate lactic acid by hydrolysis such as methyl lactate, ethyl lactate, and n-butyl lactate, and any one of them alone. May be used, or
You may use 2 or more together.

The amount of the lactic acid source used is not particularly limited, but the molar ratio to zinc in the mixture (m) is, for example, 0.001 to 0.4. Below the range, zinc oxide crystals cannot be obtained because the coexisting effect of lactic acid is insufficient. On the other hand, above the range, the precipitation reaction of zinc oxide crystals is difficult to occur, and it is difficult to obtain the target fine particles. In order to obtain fine particles having a uniform particle shape, the molar ratio of lactic acid to zinc is preferably in the range of 0.001 to 0.2, and in order to obtain fine particles having a uniform particle diameter and good dispersibility, the ratio to zinc is The molar ratio of lactic acid is 0.001
0.1 is preferred.

The addition of the lactic acid source is as follows, for example. When lactic acid (CH ₃ CH (OH) COOH) and / or lactic acid ester is used, the above steps I, I
I, III (Hereinafter, Step III is
(Including the step corresponding to), or any time selected from between I and II, and a method of directly adding, or
A method of adding a solution dissolved in a solvent (eg alcohol) can be adopted. The latter addition method is preferable especially when the lactic acid source is added in step III because lactic acid easily diffuses quickly. When a metal lactate is used, it may be at any time selected from the above Steps I, II, III, or between I and II, and preferably in Step I with or without a zinc source (n). ) Dissolved in.
For example, a zinc source powder and a metal lactate powder are added to and mixed with a solution containing a monocarboxylic acid and stirred to prepare a uniform solution. At this time, the dissolution rate of each powder,
Stirring while heating to increase the solubility is preferably adopted because a high-concentration solution can be obtained in a short time.

When lactic acid is dissolved or dispersed in the medium, the zinc oxide crystals grow anisotropically to form flaky zinc oxide crystals, and these flaky zinc oxide crystals have their tips facing outward. A dispersion containing zinc oxide-based fine particles having a crowded surface may be obtained. At this time, when the molar ratio of lactic acid to zinc is in the range of 0.001 to 0.4, the produced single particles are flaky (anisotropic shape), for example, the long and short (1.0 to 5.0). Major axis /
Minor axis), flatness of 2 to 200 (major axis / thickness), major axis 5
The thickness is 1000 nm, which is preferable because of excellent light diffusion and transmission. The major axis is the longest of the triaxial diameters measured for the particles, and the thickness is the lesser of the width and height of the triaxial diameters (particle diameter at the shortest part). .

The polymer used in the production method of the present invention is the same as that described for the polymer contained in the zinc oxide type fine particles of the present invention. The amount of the polymer used is not particularly limited, but is a weight ratio of the amount of zinc atoms in the zinc source (that is, in the second mixture) to the amount converted to zinc oxide, for example, in the range of 0.01 to 2.0. Done. If it is less than the above range, it is difficult to obtain composite particles, and if it is more than the above range, the precipitation reaction of zinc oxide crystals may be difficult to occur, so that it is difficult to obtain the intended zinc oxide-based fine particles. In order to obtain zinc oxide-based fine particles having the above-mentioned multi-layered structure among the composite particles and having a uniform particle shape and particle size and good dispersibility, it depends on the type of polymer and other reaction conditions, The amount is preferably a weight ratio of 0.05 to 0.5 with respect to the above zinc oxide equivalent amount.

In the production method of the present invention, the polymer is added in any one of the above steps or in two or more steps. The addition of the polymer is performed at any time before the zinc oxide based fine particles are deposited. For example, a method of adding and mixing to the mixture (n) or adding and mixing to the mixture (m) is exemplified. In the production method of the present invention, the polymer may be added in any of the above steps as long as it is a stage before the zinc oxide based fine particles are formed. The polymer can spread rapidly into the reaction system,
It is preferably dissolved in the alcohol used in the medium in advance or dissolved in any solvent and added to the reaction system. The solvent used for dissolving the polymer is not particularly limited as long as it is a liquid capable of dissolving the polymer, and examples thereof include alcohols (described above), aliphatic and aromatic carboxylic acids, aliphatic and aromatic carboxylic acid esters. , Ketones, ethers, ether esters, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons and other organic solvents; water; mineral oils; vegetable oils; wax oils; at least one selected from the group consisting of silicone oils Is one.

The mixture (m) may be any one obtained by mixing four components of zinc, monocarboxylic acid, alcohol and metal (M) as essential components, and it is a stage before the formation of zinc oxide type fine particles. The polymer is added at. The mixture (m) containing the polymer is heated to 100 ° C. or higher, preferably 100 to 300 ° C., more preferably 150 to 200 ° C. for 0.1 to 30 hours, preferably 0.5 to
By maintaining for 10 hours, the zinc oxide-based fine particles of the present invention according to the kind of raw material and composition ratio can be obtained as zinc oxide-based crystal-polymer composite particles with practical productivity. That is, the zinc dissolved or dispersed in the medium is converted into crystalline zinc oxide by X-ray diffraction when the second mixture is maintained at the temperature within the above range for the time within the above range. . Since the polymer is also dissolved or dispersed in the medium, nuclei of zinc oxide crystals are deposited, and the polymer is complexed in the process of crystallization, so that a dispersion containing zinc oxide-polymer composite particles is obtained. can get. Type of polymer used, type of raw material such as alcohol contained in the medium, composition of raw material, reaction liquid composition and temperature when composite particles are formed based on temperature history until composite particles are formed, etc. It is possible to control the internal structure of the composite particles, the particle shape / particle size, the particle size of the single particles (metal oxide coprecipitate) contained, and the like by controlling the.

In the production method of the present invention, a metal oxide coprecipitate and a polymer are contained in a content of 0.0 by heating at a temperature of 100 ° C. or higher in the presence of the above-mentioned polymer.
1 to 80% by weight of zinc oxide based fine particles having a number average particle diameter of 01 to 10 μm and a coefficient of variation of particle diameter of 30% or less.
A dispersion containing the alcohol and / or the ester compound and / or the organic solvent as a solvent is obtained. Furthermore, for the purpose of controlling the particle size, particle shape, dispersion state or higher-order structure of single particles of the finally obtained zinc oxide-based fine particles, and / or the polarity or composition of the fine particle surface, a specific additive is added. It is also possible to coexist in the heating process. The addition timing of the additive is not particularly limited, and it may be either a step of preparing the mixture (m) or the mixture (n) or a step of heat treatment, and is appropriately selected depending on the purpose and the kind of the additive. For example, when added immediately before or after the zinc oxide crystals are precipitated, the effect of the additive can be sufficiently exhibited, which is often preferable.

In particular, in order to obtain zinc oxide type fine particles which are highly uniform in particle diameter and particle shape of a single particle, a carboxyl group, amino group, imino group, amide group,
Amide bond, imide group, imide bond, ureido group, ureylene bond, isocyanato group, sulfonic acid group, sulfuric acid group,
A compound having one or two or more atomic groups selected from the group consisting of a phosphoric acid group, a metal hydroxyl group, a metal alkoxy group, an epoxy group, a urethane group, a urethane bond, and an ester bond, and having a molecular weight of less than 1000, and / Alternatively, it is preferable that a so-called chelating agent (polydentate ligand) that forms a chelate compound by being multidentately coordinated with zinc ions is used as an additive and is allowed to coexist during the heat treatment.

Examples of the additive include long-chain saturated fatty acids such as caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and the above-mentioned carboxyl group-containing compounds and their ester compounds; monoethanolamine, Alcohols having primary, secondary, and tertiary amino groups such as diethanolamine and N, N-dimethylethanolamine, tetramethylammonium hydroxide, n
-Quaternary ammonium salt such as hexadecyltrimethylammonium hydroxide, 6-aminocaproic acid, N, N
-Amino acids such as bis (octylaminoethyl) glycine, p-aminobenzoic acid, aspartic acid and glutamic acid, amino (di) carboxylic acids and their esters or anhydrides, 2-hydroxypyridine, pyridine-2,6
-Pyridine derivatives such as dicarboxylic acids, amino group-containing compounds such as aliphatic amines such as octadecylamine and stearylamine; amides such as dimethylformamide, dimethylacetamide, benzamide, oxamide and oxamic acid; acid imides such as succinimide and phthalimide, Imino (di) carboxylic acids such as imino (di) acetic acid, imino group-containing compounds such as imino ethers; dicarboxylic acid ureides such as parabanic acid, alloxan, barbituric acid and dialuric acid, ureido acids such as oxalic acid and malonuric acid, uric acid And the like, β-aldehyde acid ureides such as uracil, ureido group-containing compounds and derivatives such as α-oxyacid ureido such as 5-methylhydantoin; urethane compounds such as ethyl carbamate and their N-nitrosides, N- Chlorasse Derivatives such as chilled compounds; tolylene diisocyanate, diisocyanyl diphenylmethane, hexamethylene diisocyanate, isobutyl isocyanate, phenyl isocyanate, and other isocyanato group-containing compounds; 1,2-epoxycyclohexene, 1,8-cineole, ethylene Glycol diglycidyl ether, 1,
Aliphatic diglycidyl ethers such as 6-hexanediol diglycidyl ether, polyglycidyl ethers such as glycerol triglycidyl ether, pentaerythritol tetraglycidyl ether, and aliphatic and aromatic diglycidyl esters such as adipic acid diglycidyl ester In addition to the above, compounds containing an epoxy group such as resorcin diglycidyl ether, bisphenol A diglycidyl ether, oligomers having an epoxy group as a functional group; isopropyl triisostearoyl titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tetra Octyl bis (ditridecyl phosphite) titanate, isopropyl tri (N-
Titanate coupling agents such as aminoethylaminoethyl) titanate, methyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, III-glycidoxypropyltrimethoxysilane, III- (II- Aminoethylaminopropyl) trimethoxysilane, phenyltrimethoxysilane, diethoxydimethylsilane, trimethylethoxysilane, hydroxyethyltriethoxysilane, and other alkylalkoxysilanes, phenyltrimethoxysilane, benzyltriethoxysilane, γ-aminopropyltriethoxy. Silane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-meth Lucaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane,
Silane coupling agents such as stearyltrimethoxysilane, aluminum-based coupling agents such as acetoalkoxyaluminum diisopropylate, aluminum laurate, aluminum stearate, diisopropoxyaluminum stearate, ethyl acetoacetate aluminum diisopropylate, etc. Various coupling agents and partial hydrolysates thereof; other than the above-mentioned coupling agents, for example, tetraethoxytitanium, tetrabutoxytitanium, diethyldiethoxytitanium, tetrabutoxytitanium, tetramethoxyzirconium, tetrabutoxyzirconium, hexaethoxy. Tungsten, J-
n-butoxy manganese, diisopropoxy cobalt, diethoxy nickel, di-n-butoxy nickel, triethoxy lanthanum, triethoxy yttrium, diethoxy copper, di-n-butoxy copper, pentaethoxy niobium, penta-n-butoxy niobium, Pentaethoxy tantalum,
Specific examples of organometallic compounds containing a metal hydroxyl group and / or a metal alkoxy group represented by metal alkoxides such as penta-n-butoxytantalum, triethoxyiron, tri-n-butoxyiron and the like, derivatives thereof, and derivatives thereof Is a condensate such as (partial) hydrolyzate obtained by (partially) hydrolyzing and / or condensing a mixture of these organometallic compounds; trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris ( 2-chloroethyl) phosphate, phosphoric acid ester such as (polyoxyethylene) bis [bis (2-chloroethyl) phosphate], methyl acid phosphate, propyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, vinyl ester -2-Ethylhexyl phosphate, diisodecyl phosphate and other acidic phosphoric acid esters, trimethyl phosphite and other phosphite esters, dimethyldithiophosphoric acid, diisopropyldithiophosphoric acid and other thiophosphoric acid ester organic phosphorus compounds; at least primary amino in the molecule Group, secondary amino group, tertiary amino group, 4
Organopolysiloxanes having a molecular weight of less than 1000 and containing the above-mentioned atomic groups such as amino groups such as primary ammonio groups, carboxyl groups, sulfonic acid groups, phosphoric acid groups, hydroxyl groups and epoxy groups; sodium lauryl sulfate, dodecylbenzenesulfonic acid ( Sodium), sodium polyoxyethylene lauryl ether sulfate, sodium dialkylsulfosuccinate, calcium stearate and other anionic surfactants, polyoxyethylene lauryl ether, polyoxyethylene alkyl amine, polyethylene glycol monolaurate, glycerol monostearate, etc. Nonionic surfactants; cationic surfactants such as lauryldimethylamine and stearyltrimethylammonium chloride; amphoteric fields such as laurylbetaine and stearylamine acetate. Active agent, various surfactants or the like having the above-mentioned atomic group are exemplified.

Further, as a so-called chelating agent (polydentate ligand) which forms a chelate compound by polydentate coordination with zinc ion, β-diketones such as acetylacetone, ethyl acetoacetate, benzoylacetone, ethylenediamine, Dimethylglyoxime, benzyldioxime, cyclohexane1,2-dionedioxime, dithizone, oxine, glycine, glycolic acid, oxalic acid, catechol, dipyridyl, 1,10-phenanthroline,
α-hydroxypropionic acid, monoethanolamine,
Examples include diethanolamine and ethylene glycol. As mentioned above, depending on the type of additive and the amount added,
The size and shape of a single particle of the obtained zinc oxide based fine particles,
The dispersion state, higher-order structure, surface polarity, surface composition, etc. of single particles are greatly different. For example, when a compound having a hydrophilic main chain such as methoxypoly (oxyethylene) monoglycolic acid is used as an additive, the size and shape of the primary particles are uniform, and the primary particles are compatible with polar solvents such as water. Zinc oxide-based fine particles having excellent dispersibility can be obtained. On the other hand, when a compound having a highly hydrophobic or lipophilic main chain such as alkyltrialkoxysilane and octadecylamine is used as an additive, Thus, it is possible to obtain zinc oxide type fine particles having a uniform shape and excellent in dispersibility of primary particles in a low polar solvent such as toluene or a nonpolar solvent.

Needless to say, the size and shape of the single particle, the dispersed state and higher-order structure of the single particle, the surface polarity, the surface composition and the like can be controlled by the above-mentioned polymer and surface modifier. The addition amount of the above-mentioned additive is not particularly limited, but it is usually preferably 0.1% or more and 80% or less in terms of the weight ratio of the additive to zinc oxide contained in the zinc oxide-based fine particle dispersion. If it is less than 0.1%, the effect of adding the additive is not substantially observed, while if it exceeds 80%, zinc oxide type fine particles may not be obtained in some cases. The above-mentioned additives can be used alone or as a mixture, and the addition method is not particularly limited, and may be appropriately selected depending on the kind of the additive, the addition timing and the like. For example, when the additive is added during heating, a method of adding the additive directly or by dissolving and / or diluting it in an arbitrary solvent such as alcohol is exemplified. The latter method is an additive in the reaction system. Is preferable because it easily diffuses quickly and the effect of addition is sufficiently exhibited.

The method for producing the surface-modified fine particles will be described. The surface-modified fine particles are produced by mixing the zinc oxide-based fine particles obtained by an arbitrary production method with a surface-modifying agent under appropriate conditions, and the surface-modifying agent and the surface-modifying method are not particularly limited. Depending on the purpose, the type of surface modifier,
The amount and the surface modification method may be appropriately selected. But,
In order for each fine particle to be surface-modified uniformly and for the surface modification layer in each fine particle to be homogeneous, zinc oxide-based fine particles are dispersed in a solvent, and with sufficient stirring,
A surface modifier is preferably added and mixed. Therefore,
Preferably, in the method for producing zinc oxide-based fine particles of the present invention, a dispersion of zinc oxide-based fine particles is produced once by the method of allowing a surface modifier to coexist in the process of producing the fine particles or according to the production method of the present invention. A method in which a surface modifier is added and mixed later as a post-treatment is preferable. Examples of the latter method include adding and mixing an appropriate amount of a surface modifier selected according to the purpose of use to a dispersion liquid in which single particles having an average particle diameter of 0.1 μm or less are dispersed or to a dispersion liquid in which secondary aggregation has occurred. Then
A method of obtaining surface-modified fine particles whose surface is modified by stirring at a temperature of 100 ° C. or higher or a temperature of 100 ° C. or lower for about 0.5 to 24 hours is usually mentioned.

The surface modifier may be the same as or different from the above-mentioned polymers and additives, and may be used in combination with these polymers and additives. Further, two or more kinds of surface modifiers may be added sequentially or simultaneously. As the surface modifier, in addition to the above-mentioned polymers and additives, for example,
Methyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, III-glycidoxypropyltrimethoxysilane, III- (II-aminoethylaminopropyl) trimethoxysilane, phenyltrimethoxysilane, Alkylalkoxysilanes such as diethoxydimethylsilane, trimethylethoxysilane and hydroxyethyltriethoxysilane, phenyltrimethoxysilane, benzyltriethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrisilane. Methoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Silane coupling agents such as chloropropyltrimethoxysilane and stearyltrimethoxysilane, acetoalkoxyaluminum diisopropylate, aluminum laurate, aluminum stearate, diisopropoxyaluminum stearate, ethylacetoacetate aluminum diisopropylate, etc. Examples include aluminum-based coupling agents.

The amount of the surface-modifying agent added to the fine particles is not particularly limited. However, when the purpose is surface modification, in order to fully exert the modifying effect, the metal oxide (zinc and IIIB The weight ratio of the surface modifier to the oxide containing a metal of Group IV or Group IVB as a metal component is 0.01.
It is preferably -1. Even if the weight ratio exceeds 1, the surface modification effect is saturated, which is economically disadvantageous. Also,
From the viewpoint of modification effect and economical efficiency, a particularly preferable weight ratio is:
It is 0.02-0.5. Next, in the above-mentioned present invention, particularly, the average particle size of single particles is 0.001 to 0.1 μm.
Regarding the preferred embodiment for obtaining zinc oxide-based fine particles controlled in the range of m, among the above production conditions, the following conditions (I) to (IV) are particularly mentioned, and preferably (I) to It is to carry out under the condition that two or three of (IV) are satisfied, and more preferably, all of (I) to (IV) are satisfied.

As the zinc source (I), those containing, as a main component, at least one selected from the group consisting of zinc oxide, zinc hydroxide and zinc acetate among the above zinc or its compounds, and particularly preferably oxidized It is mainly composed of zinc and / or zinc hydroxide. The reason for this is that zinc oxide, zinc hydroxide, and zinc acetate do not substantially contain impurities that hinder the reaction of forming zinc oxide-based fine particles in the heating process, so that they are 0.001 to 0.1 μm. This is because it is easy to strictly control the particle size in a fine region. Among them, zinc oxide and zinc hydroxide are not only inexpensively available, but also the type of carboxyl group-containing compound can be arbitrarily selected. This is because it is particularly easy to obtain fine particles having the above-mentioned particle diameter range by using the above raw material.

(II) The monocarboxylic acid is a saturated fatty acid having a boiling point of 200 ° C. or less at normal pressure. Specifically, formic acid, acetic acid, propionic acid, butyric acid, and isobutyric acid are preferable, and acetic acid is particularly preferable. The reason is that it is easy to control the content of the carboxyl group in the reaction system during the heating process from the preparation process of the mixture, and thus it is easy to strictly control the particle size in a fine region. Further, it is preferable to use the saturated fatty acid in a ratio of 80 mol% or more in the total amount of the monocarboxylic acid. Further, the content of the monocarboxylic acid is not particularly limited as long as it is within the above range, but the content of the monocarboxylic acid in the mixture (n) is based on the Zn atom in the zinc oxide. The molar ratio of 2.2 to 10 times is particularly preferable in that fine particles with suppressed secondary aggregation and excellent dispersibility can be obtained.

(III) The mixture (m) was prepared by mixing the zinc source and the monocarboxylic acid, and optionally the zinc source, the monocarboxylic acid and the metal (M) compound. The mixture (n) is added dropwise continuously or intermittently to the alcohol-containing solution maintained at a temperature of 100 ° C. or higher, preferably 100 ° C. or higher and 300 ° C. or lower. In this case, the mixture (n) is preferably in a liquid state, and when the zinc source and the monocarboxylic acid further include a metal (M) compound, the zinc source, the monocarboxylic acid and the metal (M) compound are It is desirable that they are dissolved in a solvent that is compatible or highly compatible with them. As a solvent used for that purpose, water and alcohols can be easily dissolved in a zinc source and a monocarboxylic acid described below by heating from room temperature to about 100 ° C., and have high compatibility with an alcoholic solvent. , Ketones and esters are preferred. The alcohols mentioned here include all of the above-mentioned alcohols.

(IV) The heating temperature of the mixture (m) is 10
0 ° C or higher and 300 ° C or lower, particularly preferably 150 ° C or higher and 3
It is to be performed at 00 ° C or lower. When the mixture (m) is heated to precipitate ZnO crystals and the fine particles of the present invention are produced, the ZnO conversion concentration with respect to the mixture (m) is 0.5 wt% or more and 20 wt% or less, further 2.0 wt% or more. 1
When the amount is less than 0 wt%, it is preferable that the average particle size of the primary particles is in the range of 0.001 to 0.1 μm because fine particles in which secondary aggregation is suppressed are easily obtained. Furthermore, in the zinc oxide type fine particles having an average particle size in the range of 0.001 to 0.1 μm, the particle size and shape are controlled to be more uniform.
An effective method for controlling the surface state such as hydrophobicity and controlling the dispersion / aggregation state will be described below. Even in the preferable method for producing zinc oxide-based fine particles having an average particle diameter of 0.001 to 0.1 μm, the shape of particles, the state of dispersion of particles and the high particle diameter can be improved by using the additives as described above. It is possible to obtain zinc oxide-based fine particles in which the secondary structure and surface polarity are controlled. In addition, in the case of obtaining zinc oxide type fine particles in which the primary particles have a uniform particle size distribution and the average particle size is substantially within the above range and secondary aggregation is suppressed, zinc or a compound thereof used as a raw material Containing at least one selected from the group consisting of zinc oxide, zinc hydroxide and zinc acetate as a main component, and basic zinc carbonate and /
Alternatively, a method in which a zinc salt of a monocarboxylic acid having a boiling point at atmospheric pressure higher than the heating temperature is used as an accessory component is preferably used. The ratio of the sub ingredient to the main ingredient is usually 0.01% or more by atomic ratio of zinc in the ingredient 2
It is 0% or less. If the proportion is less than 0.01%, the combined effect of subcomponents is insufficient, while if it exceeds 20%, zinc oxide with high crystallinity may not be obtained.

As another method for obtaining zinc oxide type fine particles having a uniform shape and particle size distribution and excellent dispersibility, a method of coexisting carbonate ions and / or CO2 in the heat treatment process is also effective. For example, carbon dioxide gas is intermittently or continuously supplied into the mixture (m) before and / or during the zinc oxide formation reaction in the heat treatment process, urea, ammonium (hydrogen) carbonate, basic Examples thereof include a method of adding a compound such as zinc carbonate which produces carbon dioxide or carbonate ions under heating conditions. In addition to the above-described preferred production method, the surface is modified with the above-mentioned surface modifier to give an average particle diameter of 0.0
It is possible to obtain fine particles having a particle size distribution of 01 to 0.1 μm, which are controlled in shape and have a uniform particle size distribution, and which have extremely excellent affinity and dispersibility for various solvent systems, coating systems, and resin systems. In particular, by using a preferable surface modifier, a fine particle (ultrafine particle) dispersion having an average particle size of 0.05 μm or less, which is excellent in dispersibility of a single particle, is obtained, and by processing this according to the method described below, Various solvent dispersions, coating compositions, and resin compositions can be produced economically and easily without impairing the finely dispersed state of fine particles.

Among the production methods of the present invention, particularly according to the above-mentioned production conditions, the particle shape, the surface state, the dispersed / aggregated state and the like are controlled in the range of 0.001 to 0.1 μm in average particle diameter. When the zinc oxide concentration is in the range of 1 to 80% by weight, a dispersion of zinc oxide based fine particles using an alcohol and / or the ester compound and / or an organic solvent as a solvent can be obtained. The zinc oxide-based fine particle dispersion obtained in the present invention may be used as it is, but if necessary, it may be used in a zinc oxide-based fine particle powder, a coating containing zinc oxide-based fine particles, or another solvent by solvent substitution. It can be easily converted into a dispersion in which zinc oxide type fine particles are dispersed.

As a method for obtaining the powder of zinc oxide type fine particles obtained in the present invention, the fine particles are separated by subjecting the dispersion to a commonly used method such as filtration, centrifugation or solvent evaporation, and then dried. Alternatively, a firing method may be employed. Among them, the powderization method by the solvent evaporation method using the vacuum flash evaporation device after performing the concentration operation of the dispersion as needed is a method in which the secondary aggregation of fine particles, which tends to occur in the drying process, is suppressed. Therefore, it is preferable as a method for pulverizing zinc oxide based fine particles having excellent dispersibility. As a method for obtaining a dispersion in which zinc oxide based fine particles are dispersed in a solvent different from the dispersion containing the zinc oxide based fine particles obtained in the present invention, the powder obtained after pulverization according to the method described above is used. After mixing with water or other solvent to be replaced, a known method of dispersing by mechanical energy such as a ball mill, sand mill, ultrasonic homogenizer or heating the dispersion to evaporate or distill part or all of the solvent in the dispersion While
A so-called heating solvent substitution method in which a solvent to be replaced is mixed can be adopted. The solvent component constituting the dispersion is not particularly limited, and alcohols, aliphatic and aromatic carboxylic acid esters, ketones, ethers, ether esters, aliphatic and aromatic hydrocarbons, halogenated carbonized Examples include organic solvents such as hydrogen, water, mineral oils, vegetable oils, wax oils, silicone oils and the like, which may be appropriately selected according to the purpose of use. Preferred solvent components are as described above.

As for the method for obtaining the plasticizer dispersion containing the zinc oxide type fine particles obtained in the present invention, as in the case of the above-mentioned solvent dispersion, fine particles once pulverized are mixed with a plasticizer or a plasticizer. After adding and mixing to a solution containing an agent, dispersing by mechanical energy, or a method of mixing a dispersion of fine particles with a plasticizer or a solution containing a plasticizer and evaporating and distilling off the solvent component by heating. Can be adopted. In addition, when the plasticizer dispersion is produced, the resin component is mixed with the fine particle dispersion or the plasticizer in advance to coexist, thereby producing a compound with the fine particles, the plasticizer and the resin. You can also do it.

The zinc oxide type fine particles of the present invention and the zinc oxide type fine particles obtained by the production method of the present invention can be used in various industrial applications or industrial applications, for example, as a composition containing at least one of them. A resin composition constituting a film, a sheet, a fiber, a resin plate, glass, a paper, a cosmetic, etc. for increasing the added value of a film, a sheet, a fiber, a resin plate, etc .; a film, a fiber, a resin plate, a glass, a paper At least one kind of the zinc oxide-based fine particles of the present invention and the zinc oxide-based fine particles obtained by the production method of the present invention is added to a coating composition applied to the above; [1] Coating composition and coated article of the present invention The coating composition of the present invention is at least one selected from the group consisting of the zinc oxide type fine particles of the present invention and the zinc oxide type fine particles obtained by the production method of the present invention. And a binder component capable of forming a film that binds the zinc oxide-based fine particles.
The amounts of the zinc oxide-based fine particles and the binder component are 0.1 to 99% by weight of the fine particles and 1 to 99.9% by weight of the binder component with respect to the total solid content of both of them.

The coated article of the present invention comprises one substrate selected from the group consisting of resin molded articles, glass and paper, and a coating film formed on the surface (for example, one side or both sides) of the substrate. ing. The coating film contains at least one selected from the group consisting of the zinc oxide based fine particles of the present invention and / or the zinc oxide based fine particles obtained by the production method of the present invention, and a binder component that binds the zinc oxide based fine particles. . The amount of the zinc oxide-based fine particles and the binder component is 0.1 to 99% by weight of the fine particles, based on the total weight of the solid contents of the both.
The content of the binder component is 1 to 99.9% by weight. The form of the resin molded product is, for example, at least one selected from the group consisting of plates, sheets, films and fibers. The base material may be a transparent base material or a semitransparent base material.

If the amount of the fine particles exceeds the above range, there is a problem that the adhesion of the coating film to the substrate, the scratch resistance, the abrasion resistance, etc. of the coating film are insufficient. There is a problem that is insufficient. In the coating composition of the present invention, the total amount of the zinc oxide-based fine particles and the binder component is, for example, in the range of 1 to 80% by weight, based on the total amount of the coating composition. It is selected appropriately. The balance of the coating composition is a solvent that disperses the fine particles and dissolves or disperses the binder component, and an additive such as a pigment used depending on the purpose of use of the coating composition.

The binder component that can be used in the coating composition is not particularly limited, and examples thereof include (meth) acrylic resins and
Vinyl chloride-based, vinylidene chloride-based, silicone-based, melamine-based, urethane-based, styrene-based, alkyd-based, phenol-based, epoxy-based, polyester-based thermoplastic or thermosetting synthetic resins; UV-curable acrylic resin, UV-curable UV curable resin such as acrylic silicone resin; organic binder such as synthetic rubber or natural rubber such as ethylene-propylene copolymer rubber, polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, silica sol, alkali silicate, silicon Alkoxides and their hydrolysis-condensation products, inorganic binders such as phosphates and the like can be used. These binder components are appropriately selected according to the intended use such as heat resistance and scratch resistance of a film obtained by coating and drying a coating composition on a substrate and the purpose of use such as the type of substrate.
One is used alone, or two or more are used as a mixture.

Also, conventionally, a polyester film,
Polycarbonate resin, methacrylic resin film or sheet, plate, diethylene glycol bisallyl carbonate lens, etc. have been developed or used for the purpose of improving surface hardness, abrasion resistance, etc., or surface hardness equivalent to or close to glass, A material called a so-called hard coat agent that gives a film having scratch resistance, or a material synthesized by the present inventors for the same purpose (for example, the mixture (x) of Example II-11 described later) is used. It can also be used as a binder component, a dispersion medium component such as a solvent or a vehicle, for dispersing the fine particles of the present invention.

Examples of the hard coating agent include UV-curable acrylic resin-based, heat-curable and moisture-curable silicone-based (polysiloxane-based), all of which are effective binders in the present invention. It can be adopted as an ingredient. Moreover, since the fine particles of the present invention have a metal oxide crystal as a main component, it is possible to easily obtain a film which is transparent and blocks ultraviolet rays and infrared rays and has excellent abrasion resistance by combining with these hard coating agents. You can As the silicone-based hard coating agent, usually, tetraalkoxysilane (tetrafunctional silane compound) such as tetramethoxysilane and tetraethoxysilane, and trifunctional silane compound such as methyltrimethoxysilane and phenyltrimethoxysilane are main raw materials. And these monomers or (co)
The hydrolysis / condensation product is dissolved in a solvent such as alcohol or exists in a sol state. Also in the present invention, a hard coat coating composition can be synthesized by mixing such a solution or sol with zinc oxide-based fine particles.
However, in consideration of the type of the substrate, the desired surface hardness, the flexibility, etc., colloidal silica is used as the tetrafunctional silane compound, or a normal silane cup such as γ-glycidoxypropyltrimethoxysilane is used. Compounds collectively called a ring agent can be added.

In the coating composition of the present invention, the binder component may be dissolved, emulsified or suspended in a solvent. The solvent of the binder component is appropriately selected according to the purpose of use of the coating composition, the type of binder, and the like. For example, alcohols, aliphatic and aromatic carboxylic acid esters,
Organic solvents such as ketones, ethers, ether esters, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons; water; mineral oil, vegetable oil, wax oil, silicone oil, etc. It may be appropriately selected according to
Moreover, you may mix and use 2 or more in arbitrary ratios as needed. As the solvent of the binder component, the solvent of the above dispersion of the fine particles of the present invention can be used.

Polyvinylidene chloride type, vinylidene chloride-
When a vinyl chloride copolymer is used as the binder component,
When polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylidene chloride, etc., which has excellent water vapor barrier properties, is used as a binder component, a coating film with excellent barrier properties against gases such as oxygen and carbon dioxide (coating) Product) is obtained. These coated products, particularly coated films, are extremely useful in food packaging and the like as a film having a high gas barrier ability while having the ultraviolet ray and infrared ray shielding ability originally possessed by the zinc oxide-based fine particles of the present invention. Is. The method for producing the coating composition of the present invention is not particularly limited. For example, a method of adding and mixing fine particles of the present invention and / or powder of fine particles obtained by the production method of the present invention in a solvent containing a binder component, a method of including a dispersion of fine particles in a solvent and a binder component. A method of mixing with a solvent, a method of adding a binder component to a dispersion in which fine particles are dispersed in a solvent and mixing, and the like can be adopted. The dispersion method is not particularly limited, and for example, a stirrer, a ball mill,
A conventionally known method using a sand mill, an ultrasonic homogenizer or the like can be adopted.

In the coating composition of the present invention, a binder component or a solvent containing a binder component is directly added to a solvent dispersion of zinc oxide type fine particles and / or a dispersion such as a plasticizer dispersion obtained by the above-mentioned production method. It can also be obtained by adding and mixing. According to the method for producing a coating composition described above, a coating composition containing at least fine particles, a binder component and a solvent can be obtained. The obtained coating composition is an arbitrary substrate, for example, a plastic film or sheet such as polyester film; fibers such as natural fibers and synthetic fibers; transparent such as vinyl chloride resin, polycarbonate resin, acrylic resin, polyethylene terephthalate resin, or the like. A film containing zinc oxide-based fine particles can be formed by applying and drying it on a semitransparent synthetic resin plate; glass; paper or the like.

In order to form the film, heating may be performed at a temperature not higher than the deformation temperature of the substrate, if necessary. Heating is performed, for example, by using an inorganic binder such as a silicon alkoxide as the binder component and sufficiently promoting the condensation reaction between the molecules of the binder component to form a tough film, or the binder component as a thermosetting resin. To form a cured film by sufficiently advancing the curing reaction of the thermosetting resin, or a resin and an isocyanate having two or more active hydrogen atoms such as polyether and / or polyester in at least part of the binder component. This is because the crosslinking reaction can be efficiently performed when the crosslinking reaction is performed, such as when a polyurethane film is finally formed using a crosslinking agent such as.

The binder component in the coated article of the present invention is a film formed by drying or dry curing (dry crosslinking) the above organic and / or inorganic binder. The method of applying the coating composition of the present invention is not particularly limited, and a conventionally known method such as a dipping method, a spray method, a screen printing method, a roll coater method or a flow coating method is adopted. The coating film formed from the coating composition of the present invention as described above, and the coated article of the present invention obtained as described above, the zinc oxide fine particles according to the present invention are dispersed in the binder component. Are included. Therefore, the coating film and the coated article have a function reflecting the characteristics of the fine particles, that is, (1) an ultraviolet ray cutting ability and (2) an infrared ray cutting ability (near infrared ray = heat ray and far infrared ray). (3) to provide a coated article with controlled conductivity, and further, if ultrafine particles, transmit visible light (= transparency)
A fine particle having a multilayer structure such as a hollow body can form a film having excellent light diffusivity.

The zinc oxide type fine particles of the present invention are
Since O is a main component, the antibacterial property is excellent, and the coated product obtained also has the antibacterial property. All particles of the fine particles of the present invention have the same shape and have a number average particle diameter of 0.1 to 0.1.
When the particle diameter variation coefficient is 30% or less at 10 μm,
A coating film formed from the coating composition of the present invention and a coated article of the present invention have at least the above-mentioned properties (1) to (3), and have a slip property and an anti-blocking property without impairing the surface flatness. Will have. [2] Resin composition and resin molded article of the present invention The resin composition of the present invention is at least one selected from the group consisting of the zinc oxide based fine particles of the present invention and the zinc oxide based fine particles obtained by the production method of the present invention. And a resin capable of forming a continuous phase in which the zinc oxide based fine particles are dispersed. The amount of the zinc oxide based fine particles and the resin is 0.1 to 99% by weight of the fine particles and the resin 1 to 99.
It is 9% by weight, preferably 0.1 to 50% by weight of fine particles and 50 to 99.9% by weight of resin.

If the amount of fine particles exceeds the above range, a molded product having no problem in mechanical strength may not be obtained,
If it is less than the above range, there is a problem that the compounding effect of the fine particles cannot be sufficiently exhibited. The resin molded product of the present invention is obtained by molding the resin composition of the present invention into a shape selected from the group consisting of plates, sheets, films and fibers. The type of resin that can be used in the resin composition and the resin molded product of the present invention is not particularly limited, but is appropriately selected according to the purpose of use. Examples of the resin include polyolefin resins such as polyethylene and polypropylene; polystyrene resins; vinyl chloride resins; vinylidene chloride resins; polyvinyl alcohol; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polyamide resins; polyimide resins; polymethyl (meth) acrylate. (Meth) acrylic resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, polycarbonate resin, etc.
Thermoplastic or thermosetting resin such as epoxy resin, ethylene-propylene copolymer rubber, polybutadiene rubber, styrene-butadiene rubber, synthetic rubber such as acrylonitrile-butadiene rubber or natural rubber is exemplified.
Any one of them may be used alone, or two or more may be used in combination.

The method for producing the resin composition of the present invention is not particularly limited. Although the target resin composition can be obtained by mixing and dispersing the fine particles of the present invention in a resin,
For example, when melt-kneading a resin in pellet form or powder form, a master batch method of adding and mixing powder of fine particles,
A conventionally known method such as a method in which fine particles are mixed and dispersed in a solution in which a resin is dissolved and then the solvent is removed can be adopted. Alternatively, a method of mixing and dispersing fine particles in the process of producing a resin, for example, when the resin is a polyester resin, the fine particles are produced at any time during the polyester production process, that is, in the transesterification reaction to the polymerization reaction. It is also possible to employ a method of adding and mixing a dispersion obtained by dispersing the powder, preferably fine particles, in glycol, which is a polyester raw material.
Further, when it is necessary to improve the processability at the time of molding or to impart flexibility, one or more plasticizers,
And / or one or more kinds of the above-mentioned fine particle plasticizer dispersion of the present invention can be added. The addition amount of each is appropriately selected according to the type of resin, processing conditions, purpose of use, and the like. When the plasticizer is contained, the content (total) of the plasticizer is usually 2 to 70% by weight based on the total amount of the resin composition or the resin molded product. 2% by weight
If it is less than 70% by weight, the effect of adding the plasticizer is difficult to obtain, and if it exceeds 70% by weight, stable physical properties as a molded product may not be obtained.

Further, the resin composition and the molded product of the present invention may be used, if necessary, in the known heat stabilizer, antioxidant,
Various resin additives such as light stabilizers, fungicides, dyes, pigments, antistatic agents, and ultraviolet absorbers can be contained in usual amounts. According to the above method, a resin composition in which the fine particles of the present invention are dispersed and contained in a resin can be obtained. The resin composition may be in the form of a usual molding material such as pellet. By molding the obtained resin composition into a plate shape, a sheet shape, a film shape, a fiber shape or the like, a resin molded product containing the fine particles of the present invention and having the following functions can be obtained. (1) It has at least ultraviolet ray cutting ability and (2) infrared ray cutting ability (near infrared ray = heat ray and far infrared ray), and (3) gives a resin molded article with controlled conductivity, and Transparency to visible light (= transparency)
A fine particle having a multi-layer structure such as a hollow body can form a resin molded article having excellent light diffusion.

When the resin is a polyvinylidene chloride-based or vinylidene chloride-vinyl chloride copolymer, it has excellent water vapor barrier properties, and polyvinyl alcohol,
In the case of ethylene-vinyl alcohol copolymer, polyvinylidene chloride type, stretched nylon, etc., they exhibit an excellent barrier property against gases such as oxygen and carbon dioxide. In particular, a film containing the resin as a resin component is extremely useful in food packaging and the like as a film having a high gas barrier ability while having an ultraviolet ray and infrared ray shielding ability originally possessed by the zinc oxide based fine particles of the present invention. is there. Moreover, since the zinc oxide based fine particles of the present invention have ZnO as a main component,
It also has excellent antibacterial properties, and the obtained resin molded product also has antibacterial properties.

When all the fine particles of the present invention have the same shape and the number average particle diameter is 0.1 to 10 μm and the particle diameter variation coefficient is 30% or less, the resin molded article of the present invention is
It has a slip property and an anti-blocking property without impairing the surface flatness. The molded product is formed into a film, in particular, a film stretched by a stretching operation or the like, whereby irregularities due to the presence of fine particles are formed. When the fine particles obtained according to the preferred embodiment of the present invention are contained, since the particle size distribution of the fine particles is uniform and highly dispersed, the unevenness of the film surface becomes uniform and fine and extremely flat. The film is excellent but also excellent in slipperiness and anti-blocking property. For example, the polyester film thus obtained is useful as a base film for magnetic tape, a packaging film, a capacitor film, and the like.

The method for obtaining a molded product having a desired shape from the resin composition of the present invention is not particularly limited, and a conventionally known method can be adopted as it is. An example will be described below. When it is desired to obtain a polycarbonate resin plate in which fine particles of the present invention are dispersed and contained, for example, a composition in which fine particles are uniformly mixed in a resin by melt-kneading a polycarbonate resin pellet or powder and a powder of a predetermined amount of fine particles Then, a method is adopted in which the obtained product is continuously or once pelletized and then processed into a flat or curved plate by injection molding, extrusion molding, compression molding, or the like. Of course, it is also possible to form the flat-plate shaped body into an arbitrary shape such as a corrugated plate shape by further post-processing. A resin plate such as an acrylic resin plate, a vinyl chloride resin plate, or a polyester resin plate can be obtained in the same manner.

When it is desired to obtain fibers such as nylon fibers and polyester fibers containing the fine particles dispersed therein according to the present invention and films such as polyolefin films, polyamide films and polyester films, for example, fine particle powders and resin pellets or powders are used. After obtaining a composition in which fine particles are uniformly mixed in the resin by melt-kneading, continuously or once pelletized as is, a conventionally known fiberizing method such as melt spinning, or a sheet shape by extrusion molding After the above-mentioned molding, if necessary, a uniaxially or biaxially stretching operation may be performed by a conventionally known method for producing a (stretched) film.

The resin molded article of the present invention also includes a laminated film or sheet containing one or more layers containing the fine particles of the present invention, such as packaging films for food packaging and heat insulating films. It can be used as a gas barrier film. The laminated film / sheet may be produced, for example, by laminating the above-described film / sheet containing the fine particles of the present invention with another film / sheet by a heat fusion method or a method using an adhesive (layer). And a method of applying the above-mentioned coating composition of the present invention to a film or sheet, and the like. In addition, as another method: -When a film or sheet as a base material or another functional film / sheet is formed by an extrusion molding method,
Powder of fine particles of the present invention and resin pellets or resin powder,
Alternatively, a method of obtaining a laminated film / sheet by co-extruding a resin pellet or resin powder containing the fine particles of the present invention in advance as a raw material is also included. At that time, the equipment used is a multilayer film
Any conventionally known extruder used for producing a sheet can be used.

In order to obtain the polyester fiber or the polyester film in which the fine particles are dispersed and contained according to the present invention, the following other conventionally known methods can be adopted. That is, as a method for obtaining a polyester fiber, fine particles, for example, 0.1 to
A polyester polymer in which fine particles are dispersed and contained in the polyester is obtained by adding and mixing a dispersion obtained by dispersing in glycol in a proportion of 50% by weight to complete the polymerization reaction of the polyester. The method of melt spinning may be adopted.

On the other hand, in order to obtain a polyester film, a polyester polymer in which fine particles are dispersed and contained in a polyester is obtained in the same manner and then extruded into a sheet by extrusion molding, and then uniaxially or biaxially if necessary. A method of performing stretching treatment in the axial direction can be adopted. [3] Paper of the Present Invention The paper of the present invention is composed of paper pulp, a zinc oxide-based fine particle of the present invention dispersed in the pulp, and a zinc oxide-based fine particle obtained by the production method of the present invention. And at least one selected. The amount of zinc oxide-based fine particles is 0.01 to 50% by weight, preferably 0.1 to 20% by weight, based on the pulp. Below the range, there is a problem that the effect of adding fine particles is insufficient, and above the range, there is a problem that the mechanical properties of the paper are deteriorated.

The paper may be any one containing the fine particles of the present invention, and examples thereof include processed papers such as internally added papers, coated papers, impregnated papers and film laminated papers. The internally added paper is obtained by adding and mixing the fine particles at an arbitrary time in the process from beating of pulp to papermaking. The fine particles are dispersed and contained inside and / or outside the paper. Means paper. The method of adding and mixing the fine particles is not particularly limited, and usually the fine particles of the present invention can be used as a powder or in the state of a dispersion liquid dispersed in water or the like. Further, the steps of papermaking and drying may be carried out according to a conventionally known papermaking method. As the raw material used, conventionally known materials can be used as they are. For example, a pulp slurry is prepared by beating pulp with a pulper or the like. After the aqueous dispersion of fine particles of the present invention is added to and mixed with the slurry, a paper-making step and a drying step can be performed to obtain a paper in which fine particles are dispersed and contained. At this time, if necessary, a sizing agent, a sulfuric acid band, a paper strengthening agent and the like may be added at any stage.

The coated paper is a paper on which a film containing the fine particles is formed by applying a coating material containing the fine particles on a paper base material and drying it. The impregnated paper is formed by impregnating the paper base material in an aqueous or organic solvent dispersion liquid or the like containing or not containing a binder in which the fine particles are dispersed, and drying the fine particles to fix the inner and outer surfaces of the paper. Means These, coated paper, the production method of the impregnated paper is not particularly limited, except that the fine particles of the present invention is used, the paper obtained by a conventionally known general production method as a base material, a conventionally known coating method, The impregnation method can be applied as it is.

For the coating composition containing the fine particles to be used, the composition of the dispersion liquid, the solvent to be used, the kind of the binder, and the preparation method thereof, conventionally known raw materials can be used as they are, and they can be prepared according to the conventionally known preparation method. Good. The content of the fine particles in the coating composition and the dispersion is not particularly limited as long as it is in the range of 0.1 to 100% by weight in the solid content, and is appropriately selected depending on the purpose of use and the like. The solid content here means the total amount of the fine particles of the present invention and the binder contained in the coating composition and the dispersion liquid. Examples of the coating composition used for making coated paper include those containing a solvent among the coating compositions of the present invention described above. Examples of the dispersion medium of the dispersion liquid used for making the coated paper include the solvents that can be used in the coating composition of the present invention described above. Additives other than these, such as pigments, waterproofing agents, lubricants, defoamers, flow modifiers, and water retention agents may be mixed in the coating composition depending on the purpose of use.

The film-laminated paper means a paper obtained by sticking a polymer film containing the fine particles dispersed therein obtained according to the above-mentioned method on a paper base material. As the polymer film, the resin molded product of the present invention described above can be used. The paper obtained by blending the fine particles of the present invention obtained by the above production method is useful as a paper excellent in appearance.
The use of the obtained paper is arbitrary, and it can be used in various uses such as art paper and wallpaper. All the particles of the present invention have a similar shape,
Number average particle size 0.1 to 10 μm, particle size variation coefficient 30
%, The surface flatness is unprecedented,
Moreover, it is possible to obtain a paper having improved printability.

[4] Cosmetic of the Present Invention The cosmetic of the present invention comprises at least one selected from the group consisting of the zinc oxide based fine particles of the present invention and the zinc oxide based fine particles obtained by the production method of the present invention. Contains 1% by weight or more. The amount of the zinc oxide-based fine particles is usually 0.1 to 50% by weight based on the total weight of the solid content of the cosmetic. Depending on the purpose other than the above essential components, liquid oil, solid oil, waxes, oils such as hydrocarbons, polyethylene glycol, at least one selected from the group consisting of polyhydric alcohols such as propylene glycol, Surfactants, thickeners, fragrances, drugs, antioxidants, chelating agents, dyes, water,
Ingredients usually used in cosmetics, such as at least one selected from the group consisting of preservatives and antifungal agents, are blended within a range that does not impair the effects of the present invention. Further, at least one selected from the group consisting of extender pigments such as kaolin, talc and mica, inorganic coloring pigments such as iron oxide and TiO2, and organic coloring pigments such as red 202 and yellow 4, and /
Alternatively, at least one selected from the group consisting of benzoic acid-based, cinnamic acid-based, salicylic acid-based, and benzophenone-based organic UV absorbers can be used in combination with the fine particles of the present invention.

The cosmetic of the present invention is a cosmetic capable of shielding ultraviolet rays and heat rays. That is, the purpose of blending the fine particles in the cosmetic of the present invention is mainly to impart sunscreen and aesthetics. The use of the cosmetics of the present invention is not particularly limited, powdery, creamy or oily foundation,
It can be used as facial cosmetics such as lotion, milky lotion, cosmetic oil and cream, makeup cosmetics such as lipstick and eye shadow. The composition of the cosmetic is not particularly limited as long as it contains the fine particles, and a conventionally known cosmetic composition depending on the application (type) of the cosmetic contains the fine particles. . Therefore, the raw materials generally used in cosmetics can be used as they are.

Therefore, the method for producing the cosmetic of the present invention is not particularly limited, and the fine particles may be added at any time to produce a conventionally known cosmetic composition according to the application (type) of the cosmetic.
The necessary amount may be added, mixed, and dispersed. The fine particles of the present invention are hard to aggregate and can be easily dispersed in a general cosmetic composition. Therefore, as a method for dispersing the fine particles, the mixing and dispersing method generally used for cosmetic powder can be applied as it is, and according to the method, a cosmetic in which the fine particles are highly dispersed can be obtained. When the fine particles are added and mixed, the fine particles may be added and mixed as they are, but if necessary, for example, anionic, cationic, nonionic and amphoteric surfactants, metal soaps,
A surface treatment method using silicone or the like, which is generally used for cosmetic powders, for the purpose of making it lipophilic or hydrophilic may be performed. The surface treatment may be performed prior to the addition and mixing, or may be performed in the addition and mixing process.

The cosmetic of the present invention has at least (1) ultraviolet ray cutting ability and (2) infrared ray cutting ability (near infrared ray = heat ray and far infrared ray). Transparency (= transparency)
The fine particles having a multi-layered structure such as a hollow body are excellent in light diffusion.

The zinc oxide type fine particles of the present invention are
Since O is the main component, it has excellent antibacterial properties, and the cosmetics obtained also have antibacterial properties. When the fine particles of the present invention have pores in the crystal gaps and / or are hollow, the cosmetics of the present invention can have moisturizing properties and moisturizing sensation, and perfume and the like can be used as fine particles. By holding it, it is possible to provide a sustained release function of perfume and the like. The solvent dispersion of zinc oxide type fine particles and the plasticizer dispersion of zinc oxide type fine particles of the present invention have already been described above.

However, the use of the fine particles of the present invention and the fine particles obtained by the production method of the present invention is not limited to those described above.

[0165]

[Function] Zinc oxide has a high ultraviolet ray shielding ability, but does not have a heat ray shielding ability. On the other hand, oxides of IIIB group metal elements and IVB group metal elements also have no heat ray shielding ability. But III
When zinc oxide is formed into a crystalline coprecipitate by adding a group B metal element or a group IVB metal element, the heat ray shielding ability comes out by the synergistic action of both metal elements. Here, the ultraviolet ray shielding ability refers to the absorptivity of ultraviolet rays having an absorption edge at a wavelength of 360 nm or more, and the heat ray shielding ability is defined as the heat ray region in the heat ray region.
It refers to the shielding property having a cutoff wavelength of 2.0 μm or less.

In this case, it is important that the zinc oxide type fine particles are a crystalline coprecipitate. If it is non-crystalline, even if it is a coprecipitate, it does not have a heat-ray shielding ability, and the zinc oxide-based fine particles crystallized by firing the non-crystalline co-precipitate are crystalline but have a heat-ray shielding ability. do not do. It is possible to impart conductivity to zinc oxide by adding a Group IIIB metal element or a Group IVB metal element to zinc oxide.

[0167]

EXAMPLES The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. Regarding the obtained zinc oxide-based fine particle dispersion, the crystallinity, particle shape, primary particle diameter, dispersion
Physical properties such as agglomeration state, fine particle concentration, composition, etc. were analyzed and evaluated by the following methods. When it is necessary to pulverize the powder prior to analysis and evaluation, the powder obtained was pulverized according to the following method, unless otherwise specified, and the obtained powder was used as a measurement sample. In addition, the powdered product was directly subjected to all analyzes.

(Preparation Method of Powder Sample) After the fine particles in the obtained dispersion were separated by a centrifugation operation, they were vacuum dried at 80 ° C. to completely remove volatile components to obtain fine particle powder. Was used as the powder sample. (Crystallinity) It was evaluated by powder X-ray diffraction measurement. (Particle shape) It was judged by a scanning electron microscope or a transmission electron microscope with a magnification of 10,000.

(Average particle diameter) The particle diameter of 100 arbitrary particles in a scanning electron microscope image or a transmission electron microscope image of 10,000 times was measured and determined from the following formula. In the case of a scanning electron microscope image, the precious metal alloy is vapor-deposited prior to the measurement, but the value of the obtained particle size is larger than that of the transmission electron microscope image due to the thickness of the vapor-deposition layer. It was shown by the value after.

[0170]

[Equation 1]

[0171]

[Equation 2]

[0172]

[Equation 3]

(Fine Particle Concentration in Dispersion)
It is possible to completely remove volatile components such as solvents at 100 ° C.
Dry powder is obtained by vacuum drying with
Residue after heating at 500 ℃ for 1 hour
As a result, the weight fraction of the dispersion of metal oxide is calculated.
Therefore, this value is used as the concentration of fine particles in the dispersion (concentration in terms of metal oxide).
Degree). (Particle composition) Fluorescent X-ray analysis, atomic absorption of powder sample
It was determined by analysis and weight analysis. (Heat ray cutting performance of fine particles) Fine particles obtained by reaction
By concentrating the dispersion to a fine particle concentration of 10% by weight,
A concentrated dispersion is obtained, and the concentrated dispersion is used with a bar coater.
Coating on a glass plate with a thickness of 2 mm and drying (nitrogen atmosphere
(80 ° C. under air) to obtain a dry film. Apply amount
1 to 10 g / m in terms of fine particles² Change variously within the range of
Write down the spectral characteristics of the dry film (wavelength 2200 to 200 nm)
Measured with a spectrophotometer (UV-3100, Shimadzu Corporation)
To do. From the obtained spectral curve, the coating amount was 3 in terms of fine particles.
g / m ² For the film in the case of, compared with the following criteria,
Evaluate each performance.

Standard Evaluation (UV Cutting Ability) Transmittance at a wavelength of 350 nm: ≦ 1% ◎ 1 to 10% ○> 10% × (heat ray cutting ability) Cut amount at a wavelength of 2 μm:> 40% ○ 20 to 40% △ <20% × * Amount of heat ray cut: [Light transmittance (%) at wavelength 2 μm in base material]-[Light transmittance (%) at wavelength 2 μm in coated product] (Visible light transmittance ) Transmittance at a wavelength of 600 nm: ≧ 80% +++ 70 to 80% ++ 60 to 70% + <60% -Reference) Transmittance of the glass substrate used 350 nm 600 nm 2 μm Transmittance (%) 86 91 91 91 (Coating) Optical characteristics of products, etc.) Regarding the spectral characteristics, the transmittance for each wavelength light at the irradiation wavelength of 2200 to 200 nm was measured and evaluated by a self-recording spectrophotometer (UV-3100, Shimadzu Corporation).

From the measured spectral characteristics, the heat ray cutting performance, the ultraviolet ray cutting performance and the like were evaluated based on the following criteria. Heat ray cut amount: light transmittance (%) of the substrate itself at a wavelength of 2 μm-light transmittance (%) of a coated product at a wavelength of 2 μm
[100 for molded articles with or without fine particles
(%)-Light transmittance (%) of the molded product at a wavelength of 2 μm] Ultraviolet ray cutting ability: Light transmittance at a wavelength of 350 nm was evaluated according to the above criteria.

Total light transmittance and haze: Turbidimeter (NDH-
1001 DP Nippon Denshoku Industries Co., Ltd. measurement and evaluation. (Conductivity of Fine Particles) Pyrex (registered trademark) obtained by previously depositing a gold comb-shaped electrode on 0.1 ml of the powder sample described above.
It is sandwiched between glass (1.5 cm square) and Pyrex glass (1.5 cm square) on which nothing is vapor-deposited, a constant pressure is applied, and the temperature is 20 ° C. and the relative humidity is 60%. After standing for 1 hour, a current value (dark current) was measured under the same conditions using an electrometer type 617 manufactured by Kessley Co., and converted into a resistance value (Ω) for evaluation.

Commercially available zinc oxide (made by Sakai Chemical Co., Ltd., Zinc Hua No. 1 special product) was used as a standard sample, and the conductivity was evaluated by the relative value of the resistance value of this and the resistance value of the powder sample. That is, the resistance value of the standard sample / the resistance value of the sample of the example or the comparative example = r
Then, the range of r is conductivity 1 × 10 ⁻¹ ≦ r <1 × 10 ¹ × 1 × 10 ¹ ≦ r <1 × 10 ² + 1 × 10 ² ≦ r <1 × 10 ³ +++ 1 × 10 ³ ≦ r +++ [Production of fine particle dispersion] Example I-1 In a 10 L glass reactor equipped with a stirrer, a dropping port, a thermometer, and a reflux condenser, a mixed solvent of 1.6 kg of acetic acid and 1.6 kg of ion-exchanged water. Then, 0.3 kg of zinc oxide powder and 36.3 g of indium acetate dihydrate were added and mixed, and then heated to 100 ° C. with stirring to obtain a zinc-containing solution (A1) as a uniform solution.

Next, a stirrer capable of heating the heat medium from the outside,
A 20 L glass reactor equipped with a dropping port, a thermometer, and a distillate gas outlet was charged with 14 kg of 2-butoxyethanol, and the internal temperature was raised to 153 ° C. and maintained. to this,
The total amount of the zinc-containing solution (A1) kept at 100 ° C. was added dropwise by a metering pump over 30 minutes. The bottom temperature varied from 153 ° C to 131 ° C. After the dropping was completed, when the internal temperature was raised to 168 ° C., 36.9 g of lauric acid was added.
400 g of a 2-butoxyethanol solution in which was dissolved was added over 1 minute, and the mixture was further heated and held at this temperature for 5 hours to obtain 7.89 kg of a blue-gray dispersion (DI-1). Dispersion (DI-1) was a dispersion of flaky fine particles having an average particle diameter of 5 nm at a concentration of 3.5% by weight. The fine particles in the dispersion are crystalline zinc oxide in terms of X-ray diffraction, and the composition has a metal oxide content of 94.5 wt% and an In content of 3.0% with respect to the total metal atoms. It was a fine particle.

Table 3 shows the physical properties of the resulting dispersion and fine particles. Example I-2 Example I-2 except that the kind and amount of the raw materials in the zinc-containing solution (A1) in Example I-1 were changed as shown in Table 1.
A zinc-containing solution (A2) was obtained in the same manner as in -1, and
A dispersion (DI-2) was obtained in the same manner as in Example I-1, except that the amount of 2-butoxyethanol charged in Example I-1 was 12 kg and lauric acid was not added.
Table 3 shows the physical properties of the resulting dispersion and fine particles.

The dispersion obtained in Example I-2 (DI-
2) Octadecyltriethoxysilane 1 in 227 parts by weight
After adding 1 part by weight and stirring, the solvent was removed by heating under reduced pressure in an evaporator at a bath temperature of 130 ° C., and further 1
Fine powder (PI
2-1) 12 parts by weight were obtained. Example I-3 In a 10 L glass reactor equipped with a stirrer, a dropping port, a thermometer, and a reflux condenser similar to Example I-1, acetic acid.2.
After 0.809 kg of zinc acetate dihydrate was added and mixed to a mixed solvent of 2 kg and 2.2 kg of ion-exchanged water, the temperature was raised to 100 ° C. with stirring to obtain a zinc-containing solution (A3) as a uniform solution. It was

Next, a stirrer capable of heating the heat medium from the outside,
A 20 L glass reactor equipped with a dropping port, a thermometer, and a distillate gas outlet was charged with 8 kg of 2-butoxyethanol and 5 kg of ethylene glycol acetate-n-butyl ether,
The internal temperature was raised to 162 ° C. and maintained. To this
The total amount of the zinc-containing solution (A3) kept at 0 ° C. was added dropwise by a metering pump over 30 minutes. After the dropping was completed, when the internal temperature was raised to 168 ° C., aluminum tris (se
A solution of 90.8 g of c-butoxide) uniformly dissolved in 400 g of 2-butoxyethanol was added all at once, and further 1
By heating and holding at 70 ° C for 5 hours, the dispersion (DI
-3) was obtained.

Table 3 shows the physical properties of the resulting dispersion and fine particles. Example I-4 Acetic acid in a 10 L glass reactor equipped with a stirrer, a dropping port, a thermometer, and a reflux condenser as in Example I-1.
To a mixed solvent of 2 kg and 2.2 kg of ion-exchanged water, 0.809 kg of zinc acetate dihydrate and alumina sol-200 (manufactured by Nissan Kagaku Co., AS-200, Al2 O3) were sequentially added and mixed, and then stirred at 100 ° C. By heating up to, a zinc-containing solution (A4) as a uniform solution was obtained. Next, 14 kg of 2-butoxyethanol was charged into a 20 L glass reactor equipped with a stirrer, a dropping port, a thermometer, and a distillate gas outlet that can heat a heat medium from the outside, and the internal temperature was raised to 150 ° C. It was kept warm. The total amount of the zinc-containing solution (A4) kept at 100 ° C. was added dropwise thereto by a metering pump over 30 minutes. After the dropping, when the internal temperature was raised to 168 ° C, polyethylene glycol (average molecular weight 600
0) A solution of 30.0 g uniformly dissolved in 100 g of 2-butoxyethanol was added within a few seconds, and the solution was further added at 170 ° C. for 5 minutes.
The dispersion (DI-4) was obtained by heating and holding for a time.

Table 3 shows the physical properties of the resulting dispersion and fine particles. Example I-5 In a 10 L glass reactor equipped with a stirrer, a dropping port, a thermometer and a reflux condenser similar to Example I-1, acetic acid 1.
0.30 kg of zinc oxide was added to and mixed with a mixed solvent of 5 kg and ion-exchanged water 1.5 kg, and then stirred at 80 ° C.
By raising the temperature to, the zinc-containing solution (A
5) was obtained. Next, a stirrer that can heat the heat medium from the outside,
In a 20 L glass reactor equipped with a dropping port, a thermometer, and a distillation gas outlet, 14 kg of 2-butoxyethanol and ethyl acetoacetate aluminum diisopropylate 6 were added.
0.6 g was charged, the internal temperature was raised to 150 ° C. and the temperature was maintained. To this, a zinc-containing solution (A
5) The whole amount was dropped by a metering pump over 30 minutes.
After the dropping is completed, the internal temperature is raised to 170 ° C.
The dispersion (DI-5) was obtained by heating and holding for a time.

Table 3 shows the physical properties of the resulting dispersion and fine particles. Further, the fine particles contained in the dispersion (DI-5) are separated from the dispersion medium by a centrifugation operation, and the separated fine particles are washed with methanol and then at 50 ° C. for 2 hours.
Fine particle powder (PI-5) was obtained by vacuum drying (10 Torr) for 4 hours. Fine particle powder obtained (PI
-5) has a thickness average diameter of 0.025 μm, a long diameter average particle diameter of 0.08 μm, a length / shortness of 2, and a flatness of 3.2.
The metal oxide content is 87.3% by weight and the composition of Al is 5.5% in terms of the number of atoms with respect to the total amount of metal atoms. The particles were fine particles in which 2 to 5 layers of crystals were laminated.

Comparative Example I-1 In Example I-1, no indium acetate was used and 2
-A fine particle dispersion (DI-) was prepared in the same manner as in Example I-1, except that the amount of butoxyethanol charged was 12.0 kg.
R1) was obtained. Table 3 shows the physical properties of the resulting dispersion and fine particles. Example I-6 In a 10 L glass reactor equipped with a stirrer, a dropping port, a thermometer, and a reflux condenser, 0.3 kg of zinc oxide powder was added to a mixed solvent of 1.6 kg of acetic acid and 1.6 kg of ion-exchanged water, After adding and mixing 36.3 g of indium acetate dihydrate, the temperature was raised to 100 ° C. with stirring to obtain a zinc-containing solution (A6) as a uniform solution.

Next, a stirrer capable of heating the heat medium from the outside,
Into a 20 L glass reactor equipped with a dropping port, a thermometer, and a distillation gas outlet, 12 kg of 2-butoxyethanol was charged, and the internal temperature was raised to 158 ° C. and maintained. to this,
The total amount of the zinc-containing solution (A6) kept at 100 ° C. was added dropwise by a metering pump over 60 minutes. After the dropping was completed, when the internal temperature was raised to 168 ° C., acrylic polymer: methyl methacrylate-hydroxyethyl methacrylate-maleic acid copolymer (weight ratio 8: 1: 1, weight average molecular weight 4,500). 500 g of a 2-butoxyethanol solution containing 300.0 g was added over 1 minute, and the mixture was further heated and held at 168 ° C. for 5 hours to obtain 9.80 kg of a blue-gray dispersion (DI-6).

The dispersion (DI-6) had an average particle size of 20.
nm fine particles were dispersed at a concentration of 3.1% by weight. The fine particles in the dispersion are crystalline zinc oxide in terms of X-ray diffraction, and have a composition of a metal oxide content of 55% by weight and an In content of 3.0% with respect to the total amount of metal atoms. Met. Furthermore, it was confirmed by observation with a transmission electron microscope that the fine particles were coated with an acrylic polymer to which the surface of the metal oxide was added. Next, the fine particles contained in the dispersion (DI-6) are separated from the dispersion medium by a centrifugation operation, the separated fine particles are washed with isopropyl alcohol, and then vacuum dried at 50 ° C. for 24 hours (10 Torr). By doing so, a fine particle powder (PI-6) was obtained.

It was confirmed that the fine particles in the obtained fine particle powder (PI-6) were substantially the same as those in the dispersion. Furthermore, fine particle powder (PI-
6) is alcohols such as methanol, isopropanol, n-butanol, benzyl alcohol, 2-ethoxyethanol, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, butyl acetate,
It was excellent in dispersibility in organic solvents such as esters such as ethyl acetate, aromatic compounds such as benzene and toluene, and was easily redispersed in the form of single particles.

Example I-7 In a 10 L glass reactor equipped with a stirrer, a dropping port, a thermometer, and a reflux condenser, zinc oxide powder 0 was added to a mixed solvent of 1.6 kg of acetic acid and 1.6 kg of ion-exchanged water. After adding and mixing 0.3 kg and 36.3 g of indium acetate dihydrate, the temperature was raised to 100 ° C. with stirring to obtain a zinc-containing solution (A7) as a uniform solution. Next, into a 20 L glass reactor equipped with a stirrer, a dropping port, a thermometer, and a distillate gas outlet capable of heating a heat medium from the outside, 12 kg of 2-butoxyethanol was charged, and the internal temperature was raised to 158 ° C. It was kept warm. To this, a zinc-containing solution (A
7) The whole amount was dropped by a metering pump over 30 minutes.
After the dropping was completed, when the internal temperature was raised to 168 ° C., a methyl methacrylate-acrylic acid copolymer (9: weight ratio:
1, weight average molecular weight 7,200) 400 g of 2-butoxyethanol solution containing 50.0 g was added in a few seconds, and the mixture was further heated and held at 168 ° C. for 5 hours,
11.79 kg of a blue-grey dispersion (DI-7) was obtained. The dispersion (DI-6) has a hollow body structure in which fine crystals of about 20 to 30 nm form an outer shell layer having a thickness of 0.2 μm, an average particle diameter of 0.5 μm, and a metal oxide content of 86 in the fine particles. .0
The dispersion was obtained by dispersing spherical fine particles in an amount of 3.1% by weight at a concentration of 3.1% by weight.

Further, the fine particles contained in the dispersion (DI-7) were separated from the dispersion medium by a centrifugal separation operation, the separated fine particles were washed with isopropyl alcohol, and then vacuum dried at 50 ° C. for 24 hours ( Fine particle powder (PI-7) was obtained by performing 10 Torr). The obtained fine particle powder (PI-7) has an average particle diameter of 0.5 μm,
The composition was a spherical fine particle having a metal oxide content of 86.0% by weight and an In content of 3.0% in terms of the number of atoms with respect to the total amount of metal atoms, and showing an X-ray diffraction pattern of crystalline zinc oxide. Furthermore, it was confirmed that the internal structure of the fine particles was hollow metal fine particles in which the metal oxide fine particles having a particle size of about 25 nm and the methyl methacrylate-acrylic acid copolymer were localized in the outer shell. The diameter of the hollow portion was 0.1 μm on average. Further, it was confirmed by scanning electron microscope observation that the surface of the fine particles was rich in irregularities.

Further, the fine particle powder (PI-7) includes methanol, isopropanol, n-butanol, benzyl alcohol, alcohols such as 2-ethoxyethanol, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, butyl acetate, It was excellent in dispersibility in organic solvents such as esters such as ethyl acetate and aromatic compounds such as benzene and toluene. Example I-8 In Example I-7, indium acetate dihydrate 36.
Propylene in which 72.5 g of indium acetate dihydrate was replaced with 3 g, and 30 g of polymethyl methacrylate (PMMA, weight average molecular weight: 60,000) was dissolved in place of the 2-butoxyethanol solution of a methyl methacrylate-acrylic acid copolymer. Glycol methyl ether acetate solution 8
Example I-6, except using 00g,
By carrying out the reaction, a blue-gray dispersion (DI-8) 1
0.0 kg was obtained.

Further, the fine particles contained in the dispersion (DI-8) are separated from the dispersion medium by a centrifugal separation operation,
The separated fine particles were washed with isopropyl alcohol and then vacuum dried (10 Torr) at 50 ° C. for 24 hours to obtain fine particle powder (PI-8). The resulting fine particle powder (PI-8) had an average particle size of 3.0 μm, a metal oxide content of 90.1% by weight, and an In content of 5.8% based on the total number of metal atoms. The spherical fine particles showed an X-ray diffraction pattern of crystalline zinc oxide. Furthermore, it was confirmed that the internal structure of the fine particles was such that particulate metal oxide fine particles of about 20 nm were uniformly dispersed in PMMA.

Example I-9 In Example I-7, indium acetate dihydrate 36.
Except for using indium acetate dihydrate 6.05 g instead of 3 g and 2-butoxyethanol solution 200 g in which lactic acid 7 g was dissolved instead of 2-butoxyethanol solution of methyl methacrylate-acrylic acid copolymer. By performing a reaction in the same manner as in Example I-7, a blue-gray dispersion (DI-9) was obtained. Further dispersion (DI-9)
The fine particles contained therein are separated from the dispersion medium by a centrifugation operation, the separated fine particles are washed with methanol, and then vacuum dried (10 Torr) at 50 ° C. for 24 hours to obtain a fine particle powder (PI-9). Got

The obtained fine particle powder (PI-9) had an average particle diameter of 1.2 μm, a metal oxide content of 96.0% by weight,
The spherical particles were composed of In in a proportion of 0.5% with respect to the total amount of metal atoms and had an X-ray diffraction pattern of crystalline zinc oxide. Further, the internal structure of the fine particles was a dense stack of flaky metal oxide fine particles having a major axis of 0.3 μm and a flatness of 18, and were hollow particles having a hollow diameter of 0.6 μm. Furthermore, the fine particle powder (PI-9) is
Water, methanol, isopropanol, n-butanol,
It was a fine particle powder having excellent dispersibility in polar solvents such as benzyl alcohol, alcohols such as 2-ethoxyethanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and esters such as butyl acetate and ethyl acetate.

Example I-10 A zinc-containing solution (in the same manner as in Example I-1 except that the kind and amount of raw materials in the zinc-containing solution (A1) in Example I-1 were changed as shown in Table 2) A10) was obtained, and the amount of 2-butoxyethanol charged in Example I-1 was 12 kg, and 30.0 g of monoethanolamine was added instead of lauric acid.
A dispersion (DI-10) was obtained in the same manner as. Table 3 shows the physical properties of the resulting dispersion and fine particles. Example I-
1, the dispersion obtained in Comparative Example I-1 (DI-
1) and (DI-R1) were concentrated in an evaporator under reduced pressure at a bath temperature of 130 ° C. to a fine particle concentration of 10% by weight, and concentrated dispersion (DI-1C),
(DI-RC) was obtained. Acrylic resin solution: Aroset 5210 (solid content 45% by weight, manufactured by Nippon Shokubai Co., Ltd.) 1.11 parts by weight was added to 100 parts by weight of each concentrated dispersion and mixed, and then stirred for 2 hours to prepare a coating solution. did.

A coating film was formed on a Pyrex glass on which a gold comb-shaped electrode had been vapor-deposited in advance by using a spin coater with each coating solution, dried at room temperature, and dried by heating at 50 ° C. to obtain a dry film (DI). -1M) and (DI-RM) were obtained.
Each of the obtained films was a uniform film having a thickness of 1.0 μm. After each dried film was left in a light-shielded state for 1 hour in an atmosphere at a temperature of 20 ° C. and a relative humidity of 60%, the surface resistance value was measured under the same conditions using an electrometer 617 manufactured by Kessley Co. , Was as follows. DI-1M 2.7 × 10 ¹¹ Ω / □ DI-RM 3.9 × 10 ¹⁴ Ω / □ Further, with respect to DI-1M, a light-shielding state when left for 1 hour in a relative humidity atmosphere at a temperature of 20 ° C. The results of measuring the surface resistance value in the are shown below.

Relative humidity Surface resistance value (Ω / □) 20% 1.9 × 10 ¹¹ 60% 2.7 × 10 ¹¹ 85% 2.8 × 10 ^{11 In} Examples I-2 to I-5, respectively. For the obtained dispersions (DI-2) to (DI-5)), a coating solution was prepared in the same manner, and a film having a thickness of 1 μm was formed. As a result of measuring the resistance value,
The surface resistance value (unit: Ω / □) of each film was 10 ¹¹ order or 10 ¹² order, and moreover, Example I
It was confirmed that the surface resistance value was constant irrespective of humidity as in the case of -1.

From the above results, the fine particles in each of the dispersions obtained in Examples I-1 to I-5 are conductive fine particles which are made conductive as compared with conventional zinc oxide, and It was confirmed that there was substantially no humidity dependence.
Therefore, it can be said that the fine particles (dispersion) obtained in the present invention are suitable raw materials for, for example, an antistatic film. From the dispersion (DI-2) and the dispersion (DI-R1) obtained in Example I-2 and Comparative Example I-1, a powder sample was obtained according to the method described above, and the result of X-ray diffraction measurement was performed. (X-ray diffraction pattern of each powder) is shown in FIG. In FIG. 2, the horizontal axis represents the diffraction angle (2θ) [unit: °], and the vertical axis represents the intensity [cps]. As seen in FIG. 2, DI-2 and DI-R1 are
It can be seen that all show sharp diffraction peaks attributed to ZnO.

Comparative Example I-2 35.0 g of ammonium bicarbonate was added to 500 g of deionized water.
A solution was obtained by dissolving in A. Aluminum sulfate hydrate _{(Al 2 (SO 4) 3} · nH 2 O, n = 14~18) 6.1778
g was dissolved in ion-exchanged water to give 50 g, and a solution B was obtained. A slurry C was obtained by adding 100 g of zinc oxide (French method No. 1 special order, manufactured by Sakai Chemical Industry Co., Ltd.) to 180 g of ion-exchanged water and mixing.
Silica fine powder (Aerosil 200, Nippon Aerosil Co., Ltd.)
Dispersion D was obtained by adding and mixing 1.00 g to 50 g of ion-exchanged water and stirring.

Liquid B was added to liquid A while stirring liquid A at room temperature to obtain a mixture. The mixture is
After mixing, the emulsion immediately became cloudy. The obtained emulsion was directly stirred for 10 minutes. Next, 1 L equipped with a stirrer, a dropping port, a thermometer, and a reflux condenser capable of heating the heat medium from the outside.
Into the glass reactor of No. 3, slurry C was charged, and while stirring at room temperature, the emulsion obtained above was added and mixed from the dropping port, and the heating medium temperature was set to 80 ° C. to start heating. did. After about 30 minutes, when the internal temperature reached 61 ° C., the dispersion D was added and mixed, and stirring was continued under heating for 1 hour. After 1 hour, when the internal temperature was 76.6 ° C., heating was stopped and the mixture was allowed to cool while continuing stirring. When the internal temperature reached room temperature, the entire amount of the obtained slurry was filtered under reduced pressure to separate fine particles, and further washed sufficiently with ion-exchanged water, then at 12 ° C at 12 ° C.
After vacuum drying for an hour, and further vacuum drying at 100 ° C. for 4 hours, a white powder was obtained.

As a result of X-ray diffraction measurement, the obtained white powder had basic zinc carbonate in addition to the diffraction peaks attributed to ZnO.
This shows a diffraction pattern in which impurity peaks considered to be Zn ₄ CO ₃ (OH) ₆ .H ₂ O are mixed, and it was confirmed that the crystallinity of ZnO is low. The X-ray diffraction pattern of the powder is shown in FIG. Comparative Example I-3 of zinc chloride (ZnCl2) 8.3753g, aluminum chloride _{(AlCl 3 · 6H 2 O)} 0.3167g of deionized water 50g
A homogeneous solution was obtained by dissolving in. Next, 14 wt% ammonia water was added dropwise while stirring the solution at room temperature, and the addition was stopped when the pH reached 8.21. 14
The amount of the wt% aqueous ammonia added was 20.0 g.

After completion of dropping, after stirring for 10 minutes, the whole amount was filtered and further thoroughly washed with water, and then fine particles were taken out by a centrifugal separation operation and vacuum dried at 50 ° C. for 12 hours and further at 100 ° C. for 4 hours. A white powder was obtained by performing. The obtained white powder was Zn
It was confirmed that it did not show a diffraction peak attributed to O. The X-ray diffraction pattern of the powder is shown in FIG. Comparative Example I-4 A white powder was obtained in exactly the same manner as Comparative Example I-2, and then the white powder was heated from room temperature to 640 ° C. under a nitrogen atmosphere in a heating and firing furnace at 640 ° C. After holding for 1 hour, it was cooled to room temperature to obtain an off-white powder.

The obtained powder was analyzed by X-ray diffraction and found to have Z
It was confirmed to be nO crystal. The X-ray diffraction pattern of the powder is shown in FIG. In addition, using the obtained powder,
A paint having the following composition was prepared and formed into a film on a glass substrate to obtain a coated product (II-R4C) having a film having a thickness of 3.1 μm. The obtained coated product (II-R4C) has a haze value of 78.
%, Which is highly opaque, has low transparency to visible light, and has a shielding property against ultraviolet rays (UV),
It did not show heat ray shielding properties. Painted product (II-R4
The spectral transmittance curve of C) is shown in FIG.

(Paint composition) Powder 10 parts by weight 2-butoxyethanol 90 parts by weight Acrylic resin solution * 50 parts by weight * Aroset 5247 (manufactured by Nippon Shokubai, solid content 45% by weight) with toluene to a solid content concentration of 20% by weight The diluted powder (coating method) was added to 2-butoxyethanol, mixed and dispersed for 20 minutes with an ultrasonic homogenizer, then an acrylic resin solution was added and stirred for 2 hours. Furthermore, a coating material was obtained by performing a dispersion treatment for 20 minutes with an ultrasonic homogenizer.

Comparative Example I-5 A white powder was obtained in exactly the same manner as Comparative Example I-3. The white powder was heated at room temperature under a nitrogen atmosphere in a heating and firing furnace for 6 minutes.
The temperature was raised to 40 ° C., the temperature was kept at 640 ° C. for 1 hour, and then the mixture was cooled to room temperature to obtain a slightly greenish ashy powder.
As a result of X-ray diffraction measurement, it was confirmed that the obtained powder was a ZnO crystal. The X-ray diffraction pattern of the powder is shown in FIG.
Shown in. In FIG. 3, the horizontal axis represents the diffraction angle (2θ) [unit: °], and the vertical axis represents the intensity [cps].

Also, using the obtained powder, Comparative Example I
In the same manner as in the case of No. -4, a paint is prepared, a film is formed on a glass substrate, and a coated product (II with a thickness of 3.2 μm) is formed.
-R5C) was obtained. The resulting coated product (II-R5C) is
The haze value was as high as 83%, which was cloudy and had low transparency to visible light and showed UV shielding properties, but did not exhibit heat ray shielding properties. The spectral transmittance curve of the coated product (II-R5C) is shown in FIG. [Production Example of Paint and Coated Product] Example II-1 The dispersion (DI-1) obtained in Example I-1 was dried in an evaporator under reduced pressure at a bath temperature of 130 ° C. and a fine particle concentration of The mixture was concentrated to 10% by weight to obtain a concentrated dispersion (DI-1C).

Next, an acrylic resin solution (Allocet 5
210; a coating material was prepared by using Nippon Shokubai Co., Ltd., solid content 45% by weight) as a binder component. That is, 1 part of the concentrated dispersion (DI-1C) was added to 50 parts by weight of a resin solution prepared by diluting the acrylic resin solution with toluene to a resin concentration of 20% by weight.
After adding and mixing 100 parts by weight, 150 parts by weight of the coating material (II-1) was obtained by stirring. Example II-2 The dispersion (DI-2) obtained in Example I-2 was concentrated in an evaporator under reduced pressure at a bath temperature of 130 ° C. to a fine particle concentration of 10% by weight. , Concentrated dispersion (DI-2C) was obtained.

Next, the obtained concentrated dispersion (DI-2C)
Is separated into a fine particle precipitate and a solvent component (supernatant) by a centrifugal separation operation, and the fine particle precipitate is added to ion-exchanged water and dispersed by a sand mill to finely disperse the fine particles at 10% by weight in water. Body (DI-2
W) was obtained. Vinyl resin (POVAL R2105,
To 100 parts by weight of an aqueous solution containing 10% by weight of Kuraray Co., Ltd., 100 parts by weight of an aqueous dispersion (DI-2W) was added, and the mixture was stirred to contain fine particles and a binder containing 5% by weight each (II -2) was obtained.

Example II-3 The dispersion (DI-1) obtained in Example I-1 was placed in an evaporator under reduced pressure at a bath temperature of 130 ° C. so that the fine particle concentration became 10% by weight. To give a concentrated dispersion (DI-1C). On the other hand, 24 parts by weight of isopropyl alcohol, 16 parts by weight of water, and 0.005 parts by weight of 35% hydrochloric acid were sequentially charged into a four-necked flask equipped with a reflux condenser, a stirrer, and a thermometer, and methyltrimethoxysilane 10 was added while stirring. After adding 30 parts by weight of tetraethoxysilane, the temperature was raised to 80 ° C. and the mixture was reacted at 80 ° C. for 2 hours and then cooled. The resulting mixture (x) has a nonvolatile content of 1
It was a 7.0% by weight homogeneous solution.

Next, while stirring 80 parts by weight of the concentrated dispersion (DI-1C), 12 parts by weight of the mixture (x) were added and mixed to obtain a paint (II-3). Example II-4 An aqueous dispersion (DI) in which fine particles were finely dispersed at 10% by weight from the dispersion (DI-2) obtained in Example I-2 in the same manner as in Example II-2. -2W) was obtained. To 20 parts by weight of an aqueous solution containing 10% by weight of a vinyl resin (Poval 205, manufactured by Kuraray Co., Ltd.), 100 parts by weight of an aqueous dispersion (DI-2W) was added, and further 1.23 of copper acetate monohydrate was added. A coating solution (II-4) was obtained by adding 20 parts by weight of an aqueous solution containing 1 part by weight, stirring, and subjecting to ultrasonic irradiation.

The coating materials (II-1) to (II-4) obtained in Examples II-1 to 4 were applied to various substrates by a bar coater and dried to obtain coated articles. (II-1C1), (II-1C2), (II-2C), (II
-3C), (II-4C) were produced. Table 4 shows the film forming conditions, the film thickness of the obtained coated product, and the optical properties. All of the coated products obtained were homogeneous and were films that shielded ultraviolet rays and heat rays while having excellent transparency to visible light.
As a result of measuring the solar radiation transmittance and the visible light transmittance of the coated products (II-1C1) and (II-1C2), it was confirmed that the film was transparent but had a heat blocking property.

The coated product (II-3C) had a pencil hardness of 6H and a surface resistance of 1 × 10 ^9.
It was confirmed to be of Ω / □ and antistatic level. Comparative Example II-1 Instead of using the dispersion (DI-1) in Example II-1, the dispersion (DI-R) obtained in Comparative Example I-1 was used.
A coating material (II-R1) was prepared in the same manner as in Example II-1 except that 1) was used. A film thickness of 6.3 μm was obtained by applying the coating composition (II-R1) on the same glass substrate as used in the coated products II-1 and II and applying the coating material in the same manner as in the coated products II-1 and II, followed by drying. A coated article (II-R1C) having a film containing ZnO fine particles was obtained. Obtained coated product (II
-R1C) effectively shielded ultraviolet rays but did not show a shielding effect on heat rays.

The coated products (II-1) obtained in each of the examples.
FIG. 1 shows the spectral transmittance curves of C1), (II-1C2) and the coated article (II-R1C) obtained in Comparative Example (II-1). FIG. 1 also shows the spectral transmittance curve of the glass substrate used. In FIG. 1, the horizontal axis represents the wavelength (nm) of incident light and the vertical axis represents the transmittance (%). Example II-5 In the same manner as in Example II-2, an aqueous dispersion (DI) in which fine particles were finely dispersed at 10% by weight from the dispersion (DI-2) obtained in Example I-2. -2W) was obtained. 100 parts by weight of the water dispersion, an acrylic emulsion as a binder resin (Akuriset RES-28 manufactured by Nippon Shokubai Co., Ltd.)
A coating material (II-5) was prepared by mixing 20 parts by weight of 5E, solid content 50% by weight). 3. A polyester fiber is dipped in the coating material and dried to give a fine particle areal weight of 4.
0 g / m @ 2 polyester fiber was obtained. The obtained fiber was excellent in transparency that cuts ultraviolet rays and heat rays.

Comparative Example II-5 In the same manner as in Example II-2, 10% by weight of fine particles were obtained from the dispersion (DI-R1) obtained in Comparative Example I-1.
A finely dispersed aqueous dispersion was obtained. A coating material (II-R5) was prepared by mixing 100 parts by weight of the water dispersion and 20 parts by weight of an acrylic emulsion (Akuriset RES-285E manufactured by Nippon Shokubai Co., Ltd., solid content 50% by weight) as a binder resin. The polyester fiber is dipped in the coating material and dried to give a fine particle areal weight of 4.2 g /
m2 polyester fiber was obtained. The obtained fiber was excellent in transparency that cuts off ultraviolet rays, but did not have a heat ray shielding effect.

Example II-6 An aqueous dispersion in which 10% by weight of fine particles were finely dispersed from the dispersion (DI-2) obtained in Example I-2 in the same manner as in Example II-2. A body (DI-2W) was obtained. 100 parts by weight of the water dispersion, an acrylic emulsion as a binder resin (Akuriset RES-28 manufactured by Nippon Shokubai Co., Ltd.)
A coating material (II-5) was prepared by mixing 30 parts by weight of 5E and a solid content of 50% by weight. By soaking the cotton fiber in the paint and drying it, the fine particle areal weight of 3.0 g / m 2
To obtain a polyester fiber. The obtained fiber was excellent in transparency that cuts ultraviolet rays and heat rays.

Example II-7 Fine particle powder (PI-2-1) 1 obtained in Example I-2
By melting and kneading 0 part by weight of 90 parts by weight of PP (polypropylene) pellets, fine powder (PI-2-
PP pellets (A) containing 10% by weight of 1) were obtained.
Next, a two-layer PP film was obtained using an extruder equipped with a multilayer feed block die. That is, the PP pellets (B) containing no fine particle component are supplied to the main extruder,
Melting at 220 ° C., supplying PP pellets (A) to the sub-extruder, melting at 180 ° C., and adjusting the discharge amount of each extruder, the PP (A) layer (containing fine particle powder) and the PP layer ( A laminated sheet comprising B) is obtained, and the obtained sheet is stretched to obtain PP (A) having a thickness of 8 μm.
An OPP film (biaxially oriented polypropylene film) in which a layer and a PP layer (B) having a thickness of 20 μm were laminated was obtained.

The film was a multilayer film having a thin film layer (A) in which fine particles were uniformly and highly dispersed, and was excellent in visible light transmittance, and also in ultraviolet ray shielding property and heat ray shielding property. Example II-8 50 parts by weight of the fine particle powder (PI-6) obtained in Example I-6 and 50 parts by weight of PET pellets were melt-kneaded to contain 50% by weight of the fine particle powder (PI-6). P
ET pellets (A) were obtained. Next, a two-layer PET film was produced using the same extruder and stretcher as those used in Example II-7. That is, PET pellets (B) containing no fine particle component are supplied to the main extruder, melted at 310 ° C., and PET pellets (A) are supplied to the auxiliary extruder 280.
By melting at ℃, by adjusting the discharge rate of each extruder,
A laminated sheet comprising a PET (A) layer (containing fine particle powder) and a PET layer (B) was obtained, and the resulting sheet was stretched to obtain a PET (A) layer having a thickness of 2 μm and a PET (A) layer having a thickness of 20 μm ( A laminated PET film of layer B) was obtained.

The film was a multi-layer film containing a thin film layer (A) in which fine particles were uniformly and highly dispersed, and was excellent in visible light transmittance, ultraviolet ray shielding property and heat ray shielding property. [Production Example of Molded Article Containing Fine Particles] Example III-1 By mixing 5 parts by weight of the fine particle powder (PI-6) obtained in Example I-6 and 995 parts by weight of polycarbonate resin pellets and melt-kneading the mixture. Then, a melt having 0.5% by weight of fine particles uniformly dispersed therein was obtained, and subsequently extrusion-molded to obtain a polycarbonate plate having a thickness of 2.0 mm. The obtained polycarbonate plate was highly dispersed with fine particles and had a total light transmittance of 85% or more, which was excellent in visible light transmittance,
It showed an ultraviolet ray shielding property and a heat ray shielding property.

Example III-2 By mixing 25 parts by weight of the fine particle powder (PI-7) obtained in Example I-7 and 475 parts by weight of methacrylic resin pellets and melt-kneading, 5% by weight of fine particles were obtained. A uniformly dispersed melt was obtained and then extrusion-molded to obtain a methacrylic resin sheet having a thickness of 2 mm. The obtained sheet had fine particles highly dispersed and a total light transmittance of 83.
%, The haze was 86%, and it had a high visible light transmittance and an excellent light diffusion transmittance, and was also excellent in the ultraviolet ray preventing effect and the heat ray shielding effect. Comparative Example III-1 In Example III-1, instead of the powder (PI-6), zinc oxide fine particles (Zinc white 1
No .: Sakai Chemical Industry Co., Ltd.) Example III-
A polycarbonate plate having a thickness of 2 mm and containing 0.5% by weight of fine particles was obtained in the same manner as in 1. The obtained polycarbonate plate was contained in a non-uniform state in which fine particles were secondarily aggregated, was not transparent and was cloudy as compared with the one obtained in Example III-1, and had an ultraviolet shielding property. Not only was it low, but it did not have the ability to shield against heat rays.

Example III-3 2 parts by weight of the fine particle powder (PI-6) obtained in Example I-6 and 98 parts by weight of polyester resin pellets were mixed and melt-kneaded to obtain 2 parts by weight of zinc oxide fine particles. %, A polyester composition uniformly dispersed was obtained, molded into a sheet by extrusion molding, and further stretched to obtain a polyester film having a thickness of 40 μm. The film was a film in which fine particles were uniformly and highly dispersed, and was excellent in visible light transmittance, ultraviolet ray shielding property, and heat ray shielding property. Comparative Example III-2 In Example III-3, instead of the powder (PI-6), zinc oxide fine particles (Zinc white 1
No .: manufactured by Sakai Chemical Industry Co., Ltd.) except that 2 parts by weight is used.
In the same manner as in 3, containing 2% by weight of fine particles, thickness 40
A μm polyester film was obtained. The obtained film contained fine particles in a state of secondary agglomeration, and therefore had a low ultraviolet ray-preventing effect and had no transparency and became cloudy. In addition, it did not have the ability to shield against heat rays.

The cross sections of the films obtained in Example III-3 and Comparative Example III-2 were observed by a transmission electron microscope. As a result, in the film obtained in Example III-3, fine particles were highly dispersed. The film obtained in Comparative Example III-2 is not uniform in surface characteristics such as the presence of coarse protrusions on the film surface because the particles are aggregated. Since there is a gap between a certain PET, the abrasion resistance and scratch resistance were insufficient. Example III-4 In the same manner as in Example III-3, the fine particles (PI-6) contained 2
After obtaining the polyester composition containing the composition in a weight percentage, the polyester fiber was obtained by melt spinning. The fiber was a fiber in which fine particles were uniformly and highly dispersed, had a transparent feeling, and was excellent in ultraviolet ray shielding property and heat ray shielding property.

Comparative Example III-3 Instead of the fine particle powder (PI-6) used in Example III-4, zinc oxide fine particles (Zinc white 1
No .: manufactured by Sakai Chemical Industry Co., Ltd.) was used, and a polyester fiber containing the zinc oxide fine particles was obtained in the same manner as in Example III-4. The fiber thus obtained contained fine particles in a state of secondary aggregation, and therefore had a low ultraviolet ray-preventing effect and was cloudy with no transparency. In addition, it did not have the ability to shield against heat rays. [Production Example of Cosmetics] Example IV-1 Fine particles of 10% by weight were finely dispersed from the dispersion (DI-1) obtained in Example I-1 in the same manner as in Example II-2. The obtained water dispersion (DI-1W) was obtained. A cosmetic (O / W type cream) having the following composition containing the aqueous dispersion was produced.

<Composition> (Aqueous phase part) (a) Aqueous dispersion of fine particles 50 parts by weight (b) Propylene glycol 5 parts by weight (c) Glycerin 10 parts by weight (d) Potassium hydroxide 0.2 parts by weight (oil Phase part) (e) Cetanol 5 parts by weight (f) Liquid paraffin 5 parts by weight (g) Stearic acid 3 parts by weight (h) Isostearyl myristate 2 parts by weight (i) Glycerin monostearate 2 parts by weight Component (a) (D) were mixed by stirring and maintained at 80 ° C. to prepare an aqueous phase part. On the other hand, the oil phase part was prepared by uniformly mixing the components (e) to (i) and maintaining the temperature at 80 ° C. After adding the oil phase part to the water phase part and stirring and emulsifying with a homomixer,
The cream was prepared by cooling to room temperature. The obtained cream was excellent in transparency, but also in ultraviolet ray prevention effect and heat ray shielding effect.

Comparative Example IV-1 In Example IV-1, 5 weight parts of zinc oxide fine particle powder (Zinc Hua No. 1; manufactured by Sakai Chemical Industry Co., Ltd.) obtained by the French method in place of the hydrous acid form (DI-1W) A cream was produced in the same manner as in Example IV-1, except that 50 parts by weight of a hydrous acid body containing 10 parts by weight of 10 parts by weight was used. The obtained cream was insufficient in the dispersibility of the fine particles, and thus had an insufficient effect of preventing ultraviolet rays. Moreover, the cream had a high whiteness, and thus lacked transparency. Moreover, it did not have a shielding property against heat rays. [Production Example of Paper] Example V-1 In the same manner as in Example II-2, fine particles were finely dispersed at 10% by weight from the dispersion (DI-2) obtained in Example I-2. A water dispersion (DI-2W) was obtained.

Next, a quantitative filter paper (manufactured by Toyo Paper Co., Ltd .: product number 5C) was beaten with a Niagara beater to prepare 400 ml Canadian Standard Freeness pulp, and an aqueous dispersion was added to the pulp to give a fine particle weight to the pulp. The mixture was added and mixed so that the ratio was 1% by weight. Next, the obtained pulp slurry was diluted to a solid content concentration of 0.1% by weight, dehydrated by a tapping sheet machine, and pressed to make a basis weight of 75 g / m @ 2. Subsequently, it was dried at 100 ° C. in a rotary dryer to obtain a paper containing 1% by weight of fine particles. The obtained paper had a fine particle dispersion state, and therefore had excellent ultraviolet ray shielding properties, a heat ray shielding effect, and excellent surface flatness. Furthermore, it was difficult for dust to adhere.

Comparative Example V-1 Instead of the hydrous acid form (DI-2W) in Example V-1, 10 parts of zinc oxide fine particle powder (Zinc Hua No. 1: manufactured by Sakai Chemical Industry Co., Ltd.) obtained by the French method were used. A paper was produced in the same manner as in Example V-1 except that the water acid body containing the dispersion by weight was used. The obtained paper contains fine particles in a secondary agglomerated state, and therefore has a low UV protection effect, and has poor surface properties such as the presence of coarse projections due to agglomerated particles on the surface. there were. In addition, it does not have a heat ray shielding property and is easily attached with dust and the like.

[0227]

[Table 1]

[0228]

[Table 2]

[0229]

[Table 3]

[0230]

[Table 4]

Example I-11 Example I-11 except that the kind and amount of the raw materials in the zinc-containing solution (A1) in Example I-1 were changed as shown in Table 5.
A zinc-containing solution (A11) was obtained in the same manner as in -1, and the amount of 2-butoxyethanol charged in Example I-1 was 20 kg, and instead of adding lauric acid, the compounds shown in Tables 5 and 7 were used. A dispersion (DI-11) was obtained in the same manner as in Example I-1, except that the amount shown in Table 5 was added. Table 9 shows the physical properties of the resulting dispersion and fine particles. Example I-12 The reaction was carried out in the same manner as in Example I-1 except that the starting materials for the reaction were changed as shown in Table 5, to obtain a dispersion in which fine particles were dispersed (DI
-12pre), after adding the compounds shown in Tables 5 and 7 in the amounts shown in Table 5, the dispersion was charged into a pressure vessel (autoclave) made of stainless steel capable of heating a heating medium, and the system was replaced with nitrogen. After purging and filling with nitrogen so that the nitrogen pressure at room temperature was 20 kgf / cm 2, the liquid temperature was adjusted to 2 with stirring.
The temperature was raised to 20 ° C., the temperature was maintained for 5 hours, and the mixture was allowed to cool to obtain a dispersion (DI-12).

Table 9 shows the physical properties of the resulting dispersion and fine particles.
Shown in. Example I-13 The reaction was performed in the same manner as in Example I-1 except that the starting materials for the reaction were changed as shown in Table 5, to obtain a dispersion (DI) in which fine particles were dispersed.
-13pre) was obtained, and the mixture was stirred at room temperature with stirring in Tables 5 and 7.
After adding the compound shown in Table 1 in the amount shown in Table 5, stirring was carried out for 3 hours to obtain a dispersion (DI-13). Table 9 shows the physical properties of the resulting dispersion and fine particles. Examples I-14 to I-19 Example I-except that the reaction raw materials were changed as shown in Tables 5 and 6.
The reaction was performed in the same manner as in 1 to obtain dispersions (DI-14pre to DI-19pre) in which fine particles were dispersed, and the compounds added after the heat treatment were changed to those shown in Tables 5 to 8 A dispersion (DI-14 was prepared in the same manner as in Example I-13 except that the treatment conditions were changed to those shown in Tables 5 and 6.
~ DI-19) was obtained.

Table 9 shows the physical properties of the resulting dispersion and fine particles.
Shown in. Example I-20 The reaction was carried out in the same manner as in Example I-1 except that the starting materials for the reaction were changed as shown in Table 6, to obtain a dispersion (DI) in which fine particles were dispersed.
-20) was obtained. Table 9 shows the physical properties of the resulting dispersion and fine particles.

[0234]

[Table 5]

[0235]

[Table 6]

[0236]

[Table 7]

[0237]

[Table 8]

[0238]

[Table 9]

<Synthesis of Various Solvent Dispersions> Example I-11 (2) After the dispersion (DI-11) obtained in Example I-11 was centrifuged, the precipitate was added to toluene and mixed, followed by stirring. By doing so, a toluene dispersion (DI-11-T) having a metal oxide conversion concentration of 20 wt% was obtained. Toluene dispersion (DI
-11-T) has a dispersed average particle diameter of 0.03 μm,
The sedimentation stability was excellent (evaluation ○). The dispersed average particle size measured one month after synthesis was 0.0
It was also confirmed that there was no change of 3 μm.

The dispersed particle size of the dispersion is measured by a centrifugal sedimentation type particle size distribution analyzer using the dispersion as a main solvent (toluene in the case of DI-11-T) as a measurement solvent. Sedimentation stability is 30 ° C for 1 month
The settling state when left to stand under constant temperature was evaluated according to the following criteria. Sedimentation stability O: No sedimentation and no sedimentation. Δ: A small amount of sedimentation deposit was generated. X: A large amount of sedimentation deposit is generated. Table 10 shows the physical properties of the obtained dispersion.

Example I-2 (2) On the other hand, after the dispersion (DI-2) obtained in Example I-2 was centrifuged, the precipitate was added to toluene and mixed, and the mixture was stirred.
Toluene dispersion with a metal oxide concentration of 20 wt% (DI
-2-T) was obtained. Toluene dispersion (DI-2-T)
Had a dispersed average particle size of 1.51 μm and had poor sedimentation stability (evaluation x). Therefore, Example I-11
It is apparent that the fine particles in the dispersion (DI-11) and the toluene dispersion (DI-11-T) obtained in 1. were surface-modified with the compound S1.

Physical properties of the resulting dispersion are shown in Table 10. Example I-11 (3) The dispersion (DI-11) obtained in Example I-11 was heated under reduced pressure with an evaporator to evaporate the solvent until a paste was formed, and then mixed with ethyl acetate and stirred. By doing so, an ethyl acetate dispersion (DI-11-EA) having a fine particle (metal oxide equivalent) concentration of 20 wt% was obtained. Table 10 shows the physical properties of the obtained dispersion. Examples I-12 (2) to I-19 (2) The dispersions (DI-1) obtained in Examples I-12 to I-19.
2 to DI-19), the above (DI-11-E)
After the paste-like material was obtained in the same manner as in A), the solvents shown in Table 10 were mixed to obtain various solvent dispersions.

Physical properties of the resulting dispersion are shown in Table 10. Example I-20 (2) From the dispersion (DI-20), the above (DI-11-EA)
After obtaining a paste-like product in the same manner as above, by mixing with n-butanol, an n-butanol dispersion (DI-
20-BuOH) was obtained. Table 10 shows the physical properties of the obtained dispersion.

[0244]

[Table 10]

<Plasticizer Dispersion> Example I-21 As the raw material A, the dispersion obtained in Example I-20 (DI-
20) 500 parts by weight of phthalic acid di-2-2 as raw material B
After 400 parts by weight of ethylhexyl were added and mixed, the obtained dispersion was heated to 150 ° C. under reduced pressure, the solvent in the dispersion was distilled off at the same temperature, and then filtered with a stainless wire mesh, Fine particle concentration (metal oxide equivalent) 20.
1% by weight di-2-ethylhexyl phthalate dispersion (D
I-20-PL) was obtained.

It was confirmed by gas chromatography that the solvent component in the dispersion was <1% by weight or less. Further, the obtained dispersion had a bluish, transparent feeling and was excellent in sedimentation stability. Table 12 shows the physical properties of the dispersion. Examples I-22 to I-25 Various dispersions were prepared in the same manner as in Example 1-21 except that the types of raw materials A and B and the mixing ratio in Example I-21 were changed as shown in Table 11. Got In the dispersions obtained in each example, it was confirmed that the total content of the solvent components contained in the raw materials A and B was 1% by weight or less.

Table 12 shows the physical properties of each dispersion.

[0248]

[Table 11]

[0249]

[Table 12]

<Paint and Coated Product> Example II-9 From the n-butanol dispersion (DI-20-BuOH) obtained in Example I-20, an acrylic resin solution (Aroset 5858: Nippon Shokubai) was used. A coating material was prepared by using (manufacturing, solid content 60% by weight) as a binder component. That is, 17 parts by weight of the acrylic resin solution, the dispersion (DI-20-Bu
50 parts by weight of OH) and 13 parts by weight of n-butanol were mixed and stirred, and then dispersed by an ultrasonic homogenizer to obtain 80 parts by weight of the paint (II-9).

Example II-10 In the same manner as in Example II-2, 10% by weight of fine particles were obtained from the n-butanol dispersion (DI-20-BuOH) obtained in Example I-20. Finely dispersed water dispersion (DI
-20 W) was obtained. Vinyl resin (Poval 205,
After adding 100 parts by weight of an aqueous dispersion (DI-20W) to 100 parts by weight of an aqueous solution containing 10% by weight of Kuraray Co., Ltd., the mixture was stirred and dispersed by an ultrasonic homogenizer to obtain a coating (II-10). ) Got. Example II-11 Mixture (x) (synthesized in Example II-3) 150 while stirring 100 parts by weight of the n-butanol dispersion (DI-20-BuOH) obtained in Example I-20. After adding and mixing parts by weight, the mixture was stirred and dispersed with an ultrasonic homogenizer to obtain a coating material (II-11).

The coating compositions (9C) and (1
0C) and (11C) were produced. Table 13 shows the physical properties of the obtained coated product.

[0253]

[Table 13]

Examples II-12 to II-24 Solvent-based paints were synthesized using the various dispersions and various binders obtained in Examples I-11 to I-20 shown in Tables 14 and 15. Then, each coated product was obtained by applying to the base material shown in Tables 16 to 18. Table 1 shows the physical properties of each coated product.
6 and 17. Coated products 11C, 16C, 18C and 20 obtained in Examples II-11, 16, 18 and 20, respectively.
The pencil hardness of C is 11C: HB, 16C:> 9H, 18
It was C: 7H, 20C: 3H, and was also excellent in abrasion resistance and scratch resistance.

The coated products 13C and 14C obtained in Examples II-13 and 14, respectively, were excellent in oxygen and water vapor barrier properties. In addition, Example II-
The coated product 24C obtained in No. 24 was a film whose coated surface showed excellent adhesion to glass, polycarbonate and the like.

[0256]

[Table 14]

[0257]

[Table 15]

[0258]

[Table 16]

[0259]

[Table 17]

[0260]

[Table 18]

<Resin Composition, Molded Product> Example III-5 50 parts by weight of di-2-ethylhexyl phthalate dispersion (DI-20-PL) obtained in Example I-21, polyvinyl chloride resin 100 parts by weight of (PVC) was melt-mixed at 160 ° C. to produce a PVC compound. Using the compound, extrusion molding was performed to obtain a vinyl chloride film having a thickness of 50 μm and containing fine particles dispersed therein.
The obtained film was excellent in transparency to visible light and effectively shielded from ultraviolet rays and heat rays.

Table 19 shows the physical properties of the obtained film. Examples III-6 to III-9 Using the dispersions obtained in Examples I-22 to I-25 as fine particle raw materials, various resin films containing fine particles dispersed therein were produced. That is, the dispersion raw material, the resin raw material, and optionally di-n-octyl phthalate shown in Table 19 were heated and mixed at a ratio shown in Table 19 to obtain various resin compounds, and then each Various films were obtained by molding the compound. All of the obtained films were excellent in transparency to visible light and also effectively shielded from ultraviolet rays and heat rays. Table 19 shows the physical properties of the obtained films.

The film obtained in Example III-7 was also excellent in flame retardancy. Comparative Example III-4 In Example III-5, the fine particle dispersion was not used,
A PVC compound and a film were produced in the same manner as in Example III-5, except that di-n-octyl phthalate and a polyvinyl chloride resin were used in the proportions shown in Table 19. The obtained film was excellent in transparency to visible light, but did not block ultraviolet rays and heat rays. Table 19 shows the physical properties of the obtained film.

[0264]

[Table 19]

[0265]

The zinc oxide type fine particles of the present invention contain at least one additive element selected from the group consisting of IIIB group metal elements and IVB group metal elements and zinc as a metal component,
The content of zinc is 80 to 99.9% in terms of the ratio of the number of zinc atoms to the total number of atoms of the metal component, and a metal oxide exhibiting zinc oxide (Zn0) crystallinity as seen from X-ray diffraction. Since the coprecipitate is used as at least a main component, it has an infrared ray shielding property such as a heat ray and a conductivity in addition to the ultraviolet ray shielding property inherent to zinc oxide. Moreover, since fine particles having these properties can be produced even at a low temperature (for example, 200 ° C. or lower), they can be used as fine particles having excellent secondary dispersibility and excellent secondary dispersibility.

The zinc oxide type fine particles of the present invention are excellent in heat ray shielding property and conductivity when containing indium and / or aluminum as an additive element constituting the metal oxide coprecipitate, and particularly when indium is contained, heat ray shielding property. And it becomes more excellent in conductivity. The zinc oxide-based fine particles according to the present invention are excellent in transparency when they are composed of only single particles of the metal oxide coprecipitate. In this case, the size of a single particle is 0.001 to 0.001 as the average particle size when viewed in the shortest part.
The range is preferably 0.1 μm, and 0.001 to
The range of 0.05 μm is more preferable. Single particles having an average particle diameter in the above range are ultrafine particles and are particularly excellent in transparency, and therefore can be used as raw material particles for transparent ultraviolet / heat ray shielding films, conductive films, and antistatic films. In this application, it is preferable to use a single particle as a dispersion prepared by dispersing the above-mentioned dispersion medium.

The zinc oxide type fine particles according to the present invention are suitable for applications requiring light diffusivity when the single particles are primary particles and the primary particles are secondary particles which are aggregated. is there. In particular, when the secondary particles are hollow particles having only the outer shell portion, the light diffusion and transmission properties are more excellent. In this case, regarding the relationship between the size of the single particle and the size of the zinc oxide-based fine particles as an aggregate thereof, it is preferable that the ratio of the particle diameter of the shortest part of the single particle to the particle diameter of the shortest particle of the particle is 1/10 or less. . The average particle diameter of the zinc oxide based fine particles is preferably in the range of 0.001 to 10 μm.
The zinc oxide-based fine particles according to the present invention further have the advantage of being particularly excellent in affinity and dispersibility with respect to the resin when the single particles are combined with a polymer. When the composite particles of the single particles and the polymer are hollow, the light diffusion and transmission properties are excellent, as in the second case. In this case, the content of the polymer is not particularly limited, but is in the range of 1 to 90% by weight based on the total amount of the single particles and the polymer. The average particle diameter of the zinc oxide based fine particles is preferably in the range of 0.001 to 10 μm.

The aggregate is suitable for use where light diffusivity is required, and for use where transparency is required, a single particle is composed of a polymer and the single particle is localized in fine particles. Fine particles that are present in a homogeneously dispersed state without being solidified are preferred. The fine particles have excellent affinity and dispersibility for organic solvents and resins. For example, it is easy to disperse it in a resin molding, disperse it in a paint, or mix it in a cosmetic. The method for producing zinc oxide-based fine particles according to the present invention, a zinc source and a monocarboxylic acid, in a medium consisting of at least alcohol, and
Since fine particles are generated by holding at a temperature of 100 ° C. or higher in the coexistence of a compound containing at least one additive element selected from the group consisting of Group IIIB metal elements and Group IVB metal elements, The zinc oxide based fine particles of the invention can be obtained with high productivity.

The process for producing zinc oxide type microparticles according to the present invention comprises adding a mixture of a zinc source and a monocarboxylic acid to water to a medium heated to 100 ° C. or higher and containing at least an alcohol, and mixing the mixture. , Said water and /
Alternatively, it is preferable to include a step of removing at least a part of the monocarboxylic acid by evaporation. The zinc source and the monocarboxylic acid are preferably used by dissolving them in water, but they prevent the crystallinity of the fine particles from being impaired, and
This is because it is preferable to remove water or monocarboxylic acid out of the system as much as possible in order to prevent the subsequent aggregation and obtain the uniformity of the size and shape of the fine particles. Although fine particles may be produced during the addition of the mixture to the heating medium, the fine particles are usually produced by keeping the reaction system at a temperature of 100 ° C. or higher after that. During this period, water and monocarboxylic acid are usually removed by evaporation.

In the method for producing zinc oxide type fine particles of the present invention, when indium and / or aluminum is contained as an additive element constituting the metal oxide coprecipitate, the heat ray shielding property and the conductivity are excellent, and particularly when indium is contained, the heat ray is absorbed. It is possible to obtain zinc oxide-based fine particles that are more excellent in shielding properties and conductivity. In the method for producing zinc oxide-based fine particles of the present invention, when the zinc source is at least one selected from the group consisting of zinc oxide, zinc hydroxide and zinc acetate, it inhibits the reaction of forming zinc oxide crystals in the heating process. It does not substantially contain such impurities, and it is easy to control the size and shape of crystals and fine particles. In the method for producing zinc oxide-based fine particles of the present invention, when the monocarboxylic acid is a saturated fatty acid having a boiling point of 200 ° C. or less under normal pressure, it is easy to control the amount of the monocarboxylic acid in the reaction system, and the zinc oxide crystallinity is improved. It is easy to strictly control the precipitation reaction of the metal oxide co-precipitate showing.

In the method for producing zinc oxide type fine particles of the present invention, the zinc source and the monocarboxylic acid are selected from the group consisting of Group IIIB metal elements and Group IVB metal elements in a medium containing at least alcohol. When maintaining at a temperature of 100 ° C. or higher in the presence of a compound containing at least one additional element, a polymer is allowed to coexist in this system, or a carboxyl group, an amino group, a quaternary ammonio group, an amide group is present in the molecule. , Imide bond, alcoholic and / or phenolic hydroxyl group, carboxylic acid ester bond, urethane group,
One or two at least one atomic group selected from the group consisting of urethane bond, ureido group, ureylene bond, isocyanate group, epoxy group, phosphoric acid group, metal hydroxyl group, metal alkoxy group and sulfonic acid group. Have more than
Coexistence of additive compounds with a molecular weight of less than 1000,
Carbon dioxide and / or a carbonic acid source may coexist, or a lactic acid source may coexist.

When the system is maintained at a temperature of 100 ° C. or higher,
When a polymer is allowed to coexist, fine particles of zinc oxide based on the single particles combined with the polymer are obtained. System at 100 ℃
When the above-mentioned compound having a specific functional group is allowed to coexist when the temperature is maintained, the surface treatment of the fine particles becomes possible and the particle diameter can be controlled. When the system is maintained at a temperature of 100 ° C. or higher, when carbon dioxide and / or a carbonic acid source is allowed to coexist, it is excellent in water dispersibility and fine (0.05 μm or less).
Easy to obtain fine particles. When the system is kept at a temperature of 100 ° C. or higher, when a lactic acid source is allowed to coexist, single particles composed of a metal oxide coprecipitate are used as primary particles, and these primary particles are aggregated to form secondary particles. It is easy to obtain zinc oxide type fine particles in the form of.

The coating composition of the present invention comprises the above-mentioned zinc oxide type fine particles of the present invention and a binder component capable of forming a film which binds the zinc oxide type fine particles, based on the total weight of the solid content of both of them. The zinc oxide fine particles 0.1 to 99
Since the binder component is contained in an amount of 1% by weight to 19.9% by weight, it has an ultraviolet ray shielding ability and an infrared ray shielding ability including a heat ray, and can form a coated article with controlled conductivity. it can. In this case, it is preferable that the total solid content of the zinc oxide type fine particles and the binder component is 1 to 80% by weight, and the balance is solvent. The coated article of the present invention comprises one substrate selected from the group consisting of a resin molded article, glass and paper, and a coating film formed on the surface of the substrate. The zinc oxide fine particles and the binder component that binds the zinc oxide fine particles are added to the zinc oxide fine particles 0.1 to 9 based on the total weight of the two.
Since it is contained in an amount of 9% by weight and 1 to 99.9% by weight of the binder component, it has an ultraviolet ray shielding ability and an infrared ray shielding ability including heat rays, and has a controlled conductivity. In this case, the resin molded product is, for example, at least one selected from the group consisting of plates, sheets, films and fibers.

The resin composition of the present invention comprises the zinc oxide type fine particles of the present invention and a resin capable of forming a continuous phase in which the zinc oxide type fine particles are dispersed, relative to the total weight of the solid content of both. , 0.19 to 99% by weight of the above zinc oxide type fine particles and 1 to 99.9% by weight of the above resin, so that they have an ultraviolet ray shielding ability and an infrared ray shielding ability including heat rays, and are conductive. A controlled resin molded product can be formed. The resin molded article of the present invention is a resin composition of the present invention, which is formed into a shape selected from the group consisting of a plate, a sheet, a film and a fiber, and therefore has an ultraviolet shielding ability, It has the ability to shield infrared rays including heat rays and has a controlled conductivity.

The paper of the present invention comprises a pulp made into paper and the zinc oxide type fine particles of the present invention dispersed in the pulp, and the amount of the zinc oxide type fine particles is 0.01 to the pulp. Since it is up to 50% by weight, it is useful as a paper excellent in appearance. Since the cosmetic of the present invention contains 0.1% by weight or more of the zinc oxide-based fine particles of the present invention, it has an ultraviolet shielding ability and an infrared shielding ability including heat rays.

[Brief description of drawings]

FIG. 1 is a diagram showing a spectral transmittance curve of a coated product.

FIG. 2 is a diagram showing an X-ray diffraction pattern of powder.

FIG. 3 is a diagram showing an X-ray diffraction pattern of powder.

FIG. 4 is a diagram showing a spectral transmittance curve of a coated product.

[Procedure amendment]

[Submission date] August 30, 2002 (2002.8.3)
0)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

[0013]

SUMMARY OF THE INVENTION Therefore, the present invention is based on zinc oxide, which is excellent in ultraviolet ray shielding property, and is provided with heat ray shielding property and conductivity, and it is easy to obtain transparency. The first object is to provide zinc-based fine particles .

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

Further, by containing the zinc oxide type fine particles of the present invention, a coating having excellent transparency, capable of blocking infrared rays such as ultraviolet rays and heat rays, and having controlled conductivity such as antistatic property. The second object is to provide a composition, a coated product, a resin composition, and a resin molded product .

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0015

[Correction method] Change

[Correction content]

[0015]

The zinc oxide type fine particles of the present invention have at least one additive element selected from the group consisting of IIIB group metal elements and IVB group metal elements and zinc as a metal component, The content of zinc is 80 to 99.9% in terms of the ratio of the number of zinc atoms to the total number of atoms of the metal component, and a metal oxide exhibiting zinc oxide (Zn0) crystallinity as seen from X-ray diffraction. Coprecipitate is at least the main constituent ,
Infrared shielding property as defined below are Der Ru zinc oxide type fine particles more than 20%. [Definition of infrared shielding property of fine particles] From the fine particles on the substrate
Forming a dry film (coating amount: 3 g / m ^{2 in} terms of fine particles)
And get a coated product. The light transmission of the dry film at a wavelength of 2 μm
Excess ratio (%), that is, light for a wavelength of 2 μm of the base material
Light transmission from the transmittance (%) to a wavelength of 2 μm of the coated product
The value obtained by subtracting the rate (%) is defined as the infrared ray shielding property of the fine particles.
To do. Infrared shielding property of fine particles (%) = [pair of wavelength of base material 2 μm
Transmittance (%)]-[Wavelength of coating product 2 μm
Light transmittance (%) ] Here , the crystal form of zinc oxide is not particularly limited.
Hexagonal crystals (wurtzite structure), cubic crystals (salt type structure), cubic face-centered structures, and the like are known, and any one showing an X-ray diffraction pattern may be used. In the zinc oxide-based fine particles of the present invention, the zinc content of the metal oxide coprecipitate is 80 to 99.9%, preferably 90 to 99.5, expressed as the ratio of the number of zinc atoms to the total number of metal components. %. If it is less than the above range, it becomes difficult to form fine particles having a controlled uniformity of particle shape, particle diameter, higher order structure, etc., and if it exceeds the above range, the function as a coprecipitate, that is, the infrared ray shielding property including heat rays becomes insufficient.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

From the viewpoint of versatility, preferred solvents are alcohols, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons, aromatic and aliphatic compounds having a boiling point of 40 to 250 ° C. under normal pressure. It is one or more mixed solvents selected from carboxylic acid esters, ketones, (cyclic) ethers, ether esters, and water. Furthermore, main Tano <br/> Lumpur, ethanol, n- propanol, isopropyl alcohol, n- butanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, di ethylene glycol < br /> monoethyl ether, diethylene glycol monobutyl ether, e Chi glycol methyl ether acetate, ethylene glycol ethyl ether acetate,
Ethylene glycol butyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methyl-3-methoxybutanol, 3 - methyl-3-methoxybutyl acetate, toluene, xylene, benzene, cyclohexane, n- hexane, ethyl acetate, propyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, one selected from water or Ranaru group Alternatively, solvent dispersions containing at least two or more mixed solvents can be used in various coating systems. Particularly preferred.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0030

[Correction method] Change

[Correction content]

The zinc oxide fine particles according to the present invention will be described below.
A method of manufacturing the will be described. As a method for producing the zinc oxide-based fine particles according to the present invention, a zinc source and a monocarboxylic acid in a medium containing at least alcohol, and
A method of forming fine particles by holding at a temperature of 100 ° C. or higher in the coexistence of a compound containing at least one additive element selected from the group consisting of Group IIIB metal elements and Group IVB metal elements is mentioned. is Ru. In this case, for example, the group IIIB metal element is exemplified as described above, and indium and / or aluminum is preferable among these additive elements.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

The above-mentioned method for producing zinc oxide-based fine particles is specifically, for example, the first step of preparing a first mixture containing a zinc source and a monocarboxylic acid, and the first mixture containing at least an alcohol. And a third step of maintaining the second mixture at a temperature of 100 ° C. or higher, and the first and second steps.
And in any one of the third step, the first and / or
Alternatively, a compound containing at least one additional element selected from the group consisting of IIIB group metal elements and IVB group metal elements is added to and mixed with the second mixture. At this time, the compound containing the additional element may be added alone, or may be dissolved in a medium containing at least alcohol and added. In the first step, it is preferable that the zinc source is dissolved in a mixed solvent in which monocarboxylic acid is dissolved in water.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

In the above-mentioned method for producing zinc oxide type fine particles,
A mixture of a zinc source and a monocarboxylic acid in water,
It is preferable to include a step of evaporating and removing at least a part of the water and / or the monocarboxylic acid by adding and mixing to a medium which is heated to 100 ° C. or higher and which is composed of at least alcohol. The zinc source and the monocarboxylic acid are preferably dissolved in water before use, but the crystallinity of the fine particles is prevented from being impaired and secondary agglomeration is prevented to ensure uniformity of the size and shape of the fine particles. To get
This is because it is good to remove water and monocarboxylic acid out of the system as much as possible. Although fine particles may be produced during the addition of the mixture to the heating medium, the fine particles are usually produced by keeping the reaction system at a temperature of 100 ° C. or higher after that. During this period, water and monocarboxylic acid are usually removed by evaporation.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction content]

In the above method for producing zinc oxide type fine particles, the zinc source is at least one selected from the group consisting of zinc oxide, zinc hydroxide and zinc acetate. In the method for producing the zinc oxide based fine particles, it is preferable that the monocarboxylic acid is a saturated fatty acid having a boiling point of 200 ° C. or less under normal pressure. In the above method for producing zinc oxide type fine particles, the zinc source and the monocarboxylic acid are added in a medium containing at least alcohol and at least one selected from the group consisting of Group IIIB metal elements and Group IVB metal elements. When maintaining a temperature of 100 ° C or higher in the coexistence of a compound containing an additional element,
A polymer is allowed to coexist in this system, or a carboxyl group, amino group, quaternary ammonio group, amide group,
Imido bond, alcoholic and / or phenolic hydroxyl group, carboxylic acid ester bond, urethane group, urethane bond, ureido group, ureylene bond, isocyanate group, epoxy group, phosphoric acid group, metal hydroxyl group, metal alkoxy group and sulfonic acid group Lactic acid containing at least one atomic group selected from the group consisting of 1 or 2 or more and having an additive compound having a molecular weight of less than 1000 coexisting with carbon dioxide and / or a carbonic acid source. Sources may coexist.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0082

[Correction method] Change

[Correction content]

Hereinafter, the zinc oxide type fine particles of the present invention will be manufactured.
That way will be described in detail. The zinc oxide-based fine particles of the present invention
From The way of manufacturing, for example, at least dissolved in the vehicle comprised of alcohol or dispersed comprising a mixture (m) is a zinc source and a monocarboxylic acid of the a III B Group metal elements and Group IVB metal elements A compound containing at least one additive element (hereinafter sometimes referred to as "metal (M)") selected from the group (this compound is a concept including a metal such as a simple metal or an alloy) In the following,
1 in the coexistence of "metal (M) compound"
By holding at a temperature of 00 ° C. or higher, a crystal of a metal oxide containing 80 to 99.9% zinc and 0.1 to 20% metal (M) in terms of the number of atoms to the total number of metal elements. A method for precipitating zinc oxide-based fine particles composed of a co-precipitate has been proposed.
Gerare Ru.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0087

[Correction method] Change

[Correction content]

The monocarboxylic acid also includes a monocarboxylic acid salt of zinc such as zinc acetate, and when the zinc salt is used, it is not always necessary to separately add the monocarboxylic acid as a raw material. The amount of the monocarboxylic acid used (or charged) in the above production method is, for example, 0.5 to 50, preferably 2.2 to 10, in terms of molar ratio with respect to the amount of Zn atoms in the zinc source. Within the above range, it is preferable in terms of economical efficiency, easiness of forming fine particles, and ease of obtaining fine particles which are hard to aggregate and have excellent dispersibility. Below the above range, Z
There is a possibility that it may be difficult to obtain zinc oxide type fine particles having good nO crystallinity and fine particles having high uniformity in shape and particle diameter.
If it exceeds the above value, not only economical efficiency is deteriorated, but also fine particles having good dispersibility may not be easily obtained.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0090

[Correction method] Change

[Correction content]

Examples of the metal (M) compound used in the above-mentioned production method include, for example, metal (M) such as metal simple substance and alloy; oxide; hydroxide; (basic) carbonate, nitrate, Inorganic salts such as halides such as sulfates, chlorides and fluorides; carboxylates such as acetates, propionates, butyrates and laurates; metal alkoxides; β-diketones, hydroxycarboxylic acids, ketoesters, All compounds containing a trivalent or tetravalent metal (A) such as a metal chelate compound with keto alcohol, amino alcohol, glycol, quinoline and the like; a metal capable of having a plurality of valences such as In and Tl In the case of an element, at least one compound selected from the group consisting of compounds containing a low-valent metal that can finally change to trivalent or tetravalent in the process of forming fine particles (this compound Object is a concept including a metal such as an elemental metal or an alloy) is used.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0098

[Correction method] Change

[Correction content]

In the above-mentioned manufacturing method, it is preferable that step I is a step of preparing the mixture (n) further containing water.
By this step, the mixture (n) in the form of solution is easily obtained. The zinc source, the monocarboxylic acid and water may be added in any order. For example, the mixture (n) is prepared by dissolving the zinc source in the mixed solvent of the monocarboxylic acid and water. In the above-mentioned production method, it is preferable that step II and step III are constituted by a step of adding the mixture (n) to a medium made of at least alcohol and held at a temperature of 100 ° C. or higher and mixing. By this step, the mixture (m) is easily made. Mixture (n) consisting of the zinc source and a monocarboxylic acid, or a mixture of these with a metal (M) compound
When added to a medium consisting of at least alcohol,
It is preferred that mixture (n) is a solution. When the mixture (n) is a solution, the zinc source and the monocarboxylic acid, or these and the metal (M) compound are compatible with each other, or are dissolved in a solvent having a high compatibility with them. Is desirable. As a solvent used for that purpose, a zinc source and a monocarboxylic acid, or these and a metal (M) compound can be easily dissolved at a temperature of from room temperature to about 100 ° C., and the solvent also forms a phase with the medium. From the viewpoint of high solubility, water, alcohols, ketones and esters are preferable. The alcohols mentioned here include all of the above-mentioned alcohols.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0114

[Correction method] Change

[Correction content]

The polymer used in the above production method is the same as that described for the polymer contained in the zinc oxide type fine particles of the present invention. The amount of the polymer used is not particularly limited, but is a weight ratio of the amount of zinc atoms in the zinc source (that is, in the second mixture) to the amount converted to zinc oxide, for example, in the range of 0.01 to 2.0. Done.
If it is less than the above range, it is difficult to obtain composite particles, and if it is more than the above range, the precipitation reaction of zinc oxide crystals may be difficult to occur, so that it is difficult to obtain the intended zinc oxide-based fine particles. In order to obtain zinc oxide type fine particles having the above-mentioned multi-layered structure among the composite particles and having a uniform particle shape and particle size and good dispersibility, it depends on the type of polymer and other reaction conditions. The amount is based on the above zinc oxide equivalent amount.
A weight ratio of 0.05 to 0.5 is preferred.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0115

[Correction method] Change

[Correction content]

In the above production method, the polymer is added in any one of the above steps or in two or more steps. The addition of the polymer is performed at any time before the zinc oxide based fine particles are deposited. For example, a method of adding and mixing to the mixture (n) or adding and mixing to the mixture (m) is exemplified. In the above production method, the polymer may be added in any of the above steps as long as it is a stage before the zinc oxide based fine particles are formed. The polymer is pre-dissolved in the alcohol used in the medium because it can spread rapidly into the reaction system,
Alternatively, it is preferably dissolved in any solvent and added to the reaction system. The solvent used for dissolving the polymer is not particularly limited as long as it is a liquid capable of dissolving the polymer, and examples thereof include alcohols (described above), aliphatic and aromatic carboxylic acids, aliphatic and aromatic carboxylic acid esters. , Ketones, ethers, ether esters, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons and other organic solvents; water; mineral oils; vegetable oils; wax oils; at least one selected from the group consisting of silicone oils Is one.

[Procedure Amendment 16]

[Document name to be amended] Statement

[Correction target item name] 0117

[Correction method] Change

[Correction content]

[0117] Of the above-mentioned production methods, a metal oxide coprecipitate and a polymer are contained by heat treatment at a temperature of 100 ° C or higher in the coexistence of the above-mentioned polymer.
Zinc oxide fine particles having a number average particle diameter of 1 to 10 μm and a coefficient of variation of particle diameter of 30% or less are dispersedly contained in the range of 1 to 80% by weight, and alcohol and / or the ester compound and / or organic solvent are contained. A dispersion having the solvent as a solvent is obtained. Furthermore, for the purpose of controlling the particle size, particle shape, dispersion state or higher-order structure of single particles of the finally obtained zinc oxide-based fine particles, and / or the polarity or composition of the fine particle surface, a specific additive is added. It is also possible to coexist in the heating process. The addition timing of the additive is not particularly limited, and it may be either a step of preparing the mixture (m) or the mixture (n) or a step of heat treatment, and is appropriately selected depending on the purpose and the kind of the additive. For example, when added immediately before or after the zinc oxide crystals are precipitated, the effect of the additive can be sufficiently exhibited, which is often preferable.

[Procedure Amendment 17]

[Document name to be amended] Statement

[Correction target item name] 0130

[Correction method] Change

[Correction content]

[0130] Of the above process, according to the particular above-described production conditions, the average particle diameter in the range of 0.001～0.1Myuemu, particle shape, surface condition, is controlled in such dispersed and aggregation state, oxidation When the zinc concentration is in the range of 1 to 80% by weight, a dispersion of fine particles of zinc oxide based on alcohol and / or the ester compound and / or organic solvent can be obtained. The dispersion of zinc oxide-based fine particles obtained as described above can be used as it is, but if necessary, zinc oxide-based fine particle powder, a paint containing zinc oxide-based fine particles, and solvent replacement may be used. It can be easily converted into a dispersion or the like in which zinc oxide type fine particles are dispersed in the solvent.

[Procedure 18]

[Document name to be amended] Statement

[Name of item to be corrected] 0131

[Correction method] Change

[Correction content]

As a method for obtaining the powder of zinc oxide type fine particles obtained above , the fine particles are separated by subjecting the dispersion to a commonly used method such as filtration, centrifugation, solvent evaporation, and then dried. Alternatively, a method of firing may be adopted as needed. Among them, the powderization method by the solvent evaporation method using the vacuum flash evaporation device after performing the concentration operation of the dispersion as needed is a method in which the secondary agglomeration of the fine particles, which tends to occur in the drying process, is suppressed. Therefore, it is preferable as a method for pulverizing zinc oxide based fine particles having excellent dispersibility. As a method for obtaining a dispersion in which zinc oxide fine particles are dispersed in a solvent different from the dispersion containing the zinc oxide fine particles obtained in the present invention, the powder obtained after pulverization according to the method described above is used. After mixing with a solvent such as water to be replaced, a known method of dispersing by mechanical energy such as a ball mill, a sand mill, an ultrasonic homogenizer or a dispersion is heated and a part or all of the solvent in the dispersion is evaporated and distilled off. While
A so-called heating solvent substitution method in which a solvent to be replaced is mixed can be adopted. The solvent component constituting the dispersion is not particularly limited, and alcohols, aliphatic and aromatic carboxylic acid esters, ketones, ethers, ether esters, aliphatic and aromatic hydrocarbons, halogenated carbonized Examples include organic solvents such as hydrogen, water, mineral oil, vegetable oil, wax oil, silicone oil and the like, which may be appropriately selected according to the purpose of use. Preferred solvent components are as described above.

[Procedure Amendment 19]

[Document name to be amended] Statement

[Correction target item name] 0132

[Correction method] Change

[Correction content]

As for the method for obtaining the plasticizer dispersion containing the zinc oxide type fine particles obtained above , the finely powdered fine particles are treated with a plasticizer or a plasticizer as in the case of the above-mentioned solvent dispersion. After adding and mixing to a solution containing, etc., a method of dispersing by mechanical energy, or a method of mixing a dispersion of fine particles and a plasticizer or a solution containing a plasticizer and heating the solvent component to evaporate and distill off Can be adopted. Further, when the plasticizer dispersion is produced, the resin component is mixed with the dispersion of fine particles or the plasticizer in advance,
By coexisting, a compound with fine particles, a plasticizer and a resin can be produced.

[Procedure amendment 20]

[Document name to be amended] Statement

[Name of item to be corrected] 0133

[Correction method] Change

[Correction content]

[0133] zinc oxide-based fine particles of the present invention is, for example,
The composition containing at least one of these may be used in various industrial applications or applications. A resin composition for forming a film, a sheet, a fiber, a resin plate, glass, a paper, a cosmetic, etc. for increasing the added value of a film, a sheet, a fiber, a resin plate, etc .; a film, a fiber, a resin plate, a glass, a paper the coating composition is coated at equal; paper; zinc oxide-based fine particles of the present invention in a cosmetic or the like is added. [1] of the present invention, coating compositions and painted coating composition of the present invention, a zinc oxide-based fine particles of the present invention,
And a binder component capable of forming a film that binds the zinc oxide-based fine particles. The amounts of the zinc oxide-based fine particles and the binder component are 0.1 to 99% by weight of the fine particles and 1 to 99.9% by weight of the binder component with respect to the total solid content of both of them.

[Procedure correction 21]

[Document name to be amended] Statement

[Correction target item name] 0134

[Correction method] Change

[Correction content]

The coated article of the present invention comprises one substrate selected from the group consisting of resin molded articles, glass and paper, and a coating film formed on the surface (for example, one side or both sides) of the substrate. ing. The coating film is the zinc oxide-based fine particles of the present invention.
And a binder component that binds the zinc oxide-based fine particles. The amount of the zinc oxide-based fine particles and the binder component is 0.1 to 99, based on the total solid content of both.
% By weight, and 1-99.9% by weight of binder component. The form of the resin molded product is, for example, at least one selected from the group consisting of plates, sheets, films and fibers. The base material may be a transparent base material or a semitransparent base material.

[Procedure correction 22]

[Document name to be amended] Statement

[Correction target item name] 0140

[Correction method] Change

[Correction content]

Polyvinylidene chloride type, vinylidene chloride-
When a vinyl chloride copolymer is used as the binder component,
When polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylidene chloride, etc., which have excellent water vapor barrier properties, are used as binder components, they have excellent barrier properties against gases such as oxygen and carbon dioxide (coating). Product) is obtained. These coated products, particularly coated films, are extremely useful in food packaging and the like as a film having a high gas barrier ability while having the ultraviolet ray and infrared ray shielding ability originally possessed by the zinc oxide based fine particles of the present invention. Is. The method for producing the coating composition of the present invention is not particularly limited. For example, a powder of fine particles of the present invention, a method of dispersing by adding and mixing a solvent containing a binder component, a method of mixing a solvent containing a dispersion and a binder component in which fine particles are dispersed in a solvent, the fine particles in a solvent A method of adding a binder component to the dispersed dispersion and mixing them may be employed.
The dispersion method is not particularly limited, and a conventionally known method using, for example, a stirrer, a ball mill, a sand mill, an ultrasonic homogenizer, or the like can be adopted.

[Procedure amendment 23]

[Document name to be amended] Statement

[Correction target item name] 0144

[Correction method] Change

[Correction content]

The zinc oxide type fine particles of the present invention are
Since O is a main component, the antibacterial property is excellent, and the coated product obtained also has the antibacterial property. All particles of the fine particles of the present invention have the same shape and have a number average particle diameter of 0.1 to 0.1.
When the particle diameter variation coefficient is 30% or less at 10 μm,
A coating film formed from the coating composition of the present invention and a coated article of the present invention have at least the above-mentioned properties (1) to (3), and have a slip property and an anti-blocking property without impairing the surface flatness. Will have. [2] of the present invention, a resin composition and a resin molded product resin composition of the present invention, a zinc oxide-based fine particles of the present invention,
And a resin capable of forming a continuous phase in which zinc oxide-based fine particles are dispersed. The amount of the zinc oxide based fine particles and the resin is 0.1 to 99% by weight of the fine particles and 1 to 99.9% by weight of the resin, preferably 0.1 of the fine particles, based on the total weight of the solid content of both of them.
˜50% by weight and resin 50 to 99.9% by weight.

[Procedure correction 24]

[Document name to be amended] Statement

[Correction target item name] 0154

[Correction method] Change

[Correction content]

On the other hand, in order to obtain a polyester film, a polyester polymer in which fine particles are dispersed and contained in a polyester is similarly obtained, and then extruded into a sheet by extrusion molding, and if necessary, uniaxially or biaxially. A method of performing stretching treatment in the axial direction can be adopted. [3] paper using zinc oxide-based particles of the paper present invention has a papermaking pulp, and a zinc oxide-based <br/> fine particles of the present invention which are dispersed in the pulp. The amount of zinc oxide type fine particles is 0.01 to 50% by weight, preferably 0.1 to 20% by weight based on the pulp.
% By weight. Below the range, there is a problem that the effect of adding fine particles is insufficient, and above the range, there is a problem that the mechanical properties of the paper are deteriorated.

[Procedure correction 25]

[Document name to be amended] Statement

[Name of item to be corrected] 0159

[Correction method] Change

[Correction content]

[0159] [4] of粧料cosmetic using zinc oxide-based particles of the present invention, a zinc oxide-based fine particles of the present invention contains more than 0.1 wt%. The amount of the zinc oxide-based fine particles is usually 0.1 to 50% by weight based on the total weight of the solid content of the cosmetic. In addition to the above essential components, depending on the purpose, liquid oils, solid oils, waxes, oils such as hydrocarbons,
At least one selected from the group consisting of polyhydric alcohols such as polyethylene glycol and propylene glycol, a surfactant, a thickener, a fragrance, a drug, an antioxidant, a chelating agent, a pigment, water, antiseptic / antifungal. Ingredients usually used in cosmetics, such as at least one selected from the group consisting of agents, are blended within a range that does not impair the effects of the present invention. Further, at least one selected from the group consisting of extender pigments such as kaolin, talc and mica, inorganic coloring pigments such as iron oxide and TiO2, and organic coloring pigments such as red 202 and yellow 4, and / or At least one selected from the group consisting of organic UV absorbers such as benzoic acid-based, cinnamic acid-based, salicylic acid-based, and benzophenone-based can be used in combination with the fine particles of the present invention.

[Procedure Amendment 26]

[Document name to be amended] Statement

[Name of item to be corrected] 0160

[Correction method] Change

[Correction content]

The above cosmetics are cosmetics capable of shielding ultraviolet rays and heat rays. That is, the purpose of blending the fine particles in the above cosmetics is mainly to impart sunscreen and aesthetics. The use of the above cosmetics is not particularly limited, powdery,
Facial cosmetics such as creamy or oily foundation, lotion, emulsion, cosmetic oil, cream, lipstick,
It can be used as makeup cosmetics such as eye shadow. The composition of the cosmetic is not particularly limited as long as it contains the fine particles, and a conventionally known cosmetic composition depending on the application (type) of the cosmetic contains the fine particles. . Therefore, the raw materials generally used in cosmetics can be used as they are.

[Procedure Amendment 27]

[Document name to be amended] Statement

[Correction target item name] 0161

[Correction method] Change

[Correction content]

Therefore, the method for producing the above-mentioned cosmetics is not particularly limited, and the fine particles may be added in a required amount at any time to produce a conventionally known cosmetic composition according to the use (type) of the cosmetic. It may be added, mixed and dispersed. The fine particles of the present invention are hard to aggregate and can be easily dispersed in a general cosmetic composition. Therefore, as a method for dispersing the fine particles, the mixing and dispersing method generally used for cosmetic powder can be applied as it is, and according to the method, a cosmetic in which the fine particles are highly dispersed can be obtained. When the fine particles are added and mixed, the fine particles may be added and mixed as they are, but if necessary, for example, anionic, cationic, nonionic and amphoteric surfactants, metal soaps,
A surface treatment method using silicone or the like, which is generally used for cosmetic powders, for the purpose of making it lipophilic or hydrophilic may be performed. The surface treatment may be performed prior to the addition and mixing, or may be performed in the addition and mixing process.

[Procedure correction 28]

[Document name to be amended] Statement

[Correction target item name] 0162

[Correction method] Change

[Correction content]

The above cosmetics have (1) ultraviolet ray cutting ability and (2) infrared ray cutting ability (near infrared ray = heat ray and far infrared ray).
And at least, and further, if ultrafine particles are transparent to visible light (= transparency)
The fine particles having a multi-layered structure such as a hollow body are excellent in light diffusivity.

[Procedure correction 29]

[Document name to be amended] Statement

[Name of correction target item] 0164

[Correction method] Change

[Correction content]

[0164] However, the use of fine particles of the present invention is not limited to those described above.

[Procedure amendment 30]

[Document name to be amended] Statement

[Correction target item name] 0269

[Correction method] Change

[Correction content]

The zinc oxide-based fine particles according to the present invention are produced .
As a method for mixing, a mixture of a zinc source and a monocarboxylic acid is mixed with water, and the mixture is added to a medium heated to 100 ° C. or higher and made of at least alcohol to mix at least the water and / or the monocarboxylic acid. It is preferable to include a step of removing a part by evaporation. It is good to use the zinc source and the monocarboxylic acid dissolved in water, but to prevent the crystallinity of the fine particles from being impaired,
In addition, in order to prevent the secondary aggregation and obtain the uniformity of the size and shape of the fine particles, it is preferable to remove water or monocarboxylic acid from the system as much as possible. Although fine particles may be produced during the addition of the mixture to the heating medium, the fine particles are usually produced by keeping the reaction system at a temperature of 100 ° C. or higher after that. During this period, water and monocarboxylic acid are usually removed by evaporation.

[Procedure correction 31]

[Document name to be amended] Statement

[Correction target item name] 0270

[Correction method] Change

[Correction content]

In the above method for producing fine particles of zinc oxide, when indium and / or aluminum is contained as an additional element constituting the metal oxide coprecipitate, the heat ray shielding property and the conductivity are excellent, and particularly when indium is contained, the heat ray shielding property is excellent. It is possible to obtain zinc oxide-based fine particles having excellent properties and conductivity.
In the above method for producing zinc oxide-based fine particles, when the zinc source is at least one selected from the group consisting of zinc oxide, zinc hydroxide and zinc acetate, it inhibits the reaction of forming zinc oxide crystals in the heating process. Such impurities are not substantially contained, and the sizes and shapes of the crystals and the fine particles can be easily controlled. In the above method for producing zinc oxide-based fine particles, when the monocarboxylic acid is a saturated fatty acid having a boiling point of 200 ° C. or less under normal pressure, it is easy to control the amount of monocarboxylic acid in the reaction system, and zinc oxide crystallinity is improved. It is easy to strictly control the precipitation reaction of the metal oxide coprecipitate shown.

[Procedure correction 32]

[Document name to be amended] Statement

[Name of item to be corrected] 0271

[Correction method] Change

[Correction content]

In the above method for producing zinc oxide type fine particles, the zinc source and the monocarboxylic acid are at least selected from the group consisting of Group IIIB metal elements and Group IVB metal elements in a medium containing at least alcohol. When a temperature of 100 ° C. or higher is maintained in the presence of a compound containing one kind of additional element, a polymer is allowed to coexist in this system, or a carboxyl group, an amino group, a quaternary ammonio group, an amide group in the molecule, Imido bond, alcoholic and / or phenolic hydroxyl group, carboxylic acid ester bond, urethane group, urethane bond, ureido group, ureylene bond, isocyanate group, epoxy group, phosphoric acid group, metal hydroxyl group, metal alkoxy group and sulfonic acid group An additive having at least one atomic group selected from the group consisting of 1 or 2 or more and having a molecular weight of less than 1000. The compound or coexist, or the coexistence of carbon dioxide and / or carbonate source, which may or coexist lactic acid source.

[Procedure amendment 33]

[Document name to be amended] Statement

[Name of item to be corrected] 0275

[Correction method] Delete

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI Theme Coat (Reference) C09C 1/04 C09C 1/04 3/06 3/06 3/10 3/10 C09D 7/12 C09D 7 / 12 201/00 201/00 C09K 3/16 101 C09K 3/16 101A D01F 1/09 D01F 1/09

Claims (9)

[Claims] 1. A metal component comprising at least one additive element selected from the group consisting of Group IIIB metal elements and Group IVB metal elements and zinc, the content of zinc being relative to the total number of atoms of the metal component. 80-99.9 expressed as the ratio of the number of zinc atoms
%, And zinc oxide fine particles containing at least a metal oxide coprecipitate that exhibits zinc oxide crystallinity in X-ray diffraction diffraction as a main constituent. 2. The zinc oxide type fine particles according to claim 1, wherein the additive element is indium and / or aluminum. 3. The zinc oxide-based fine particles according to claim 1, which consist of only a single particle of the metal oxide coprecipitate. 4. Zinc oxide-based fine particles, which are secondary particles formed by arranging the single particles constituting the zinc oxide-based fine particles according to claim 3 as primary particles, and collecting these primary particles. 5. Zinc oxide-based fine particles obtained by combining the single particles constituting the zinc oxide-based fine particles according to claim 3 with a polymer. 6. The zinc oxide-based fine particles according to any one of claims 1 to 5 and a binder component capable of forming a coating film that binds the zinc oxide-based fine particles, relative to the total weight of the solid content of both of them. And the above zinc oxide fine particles 0.1 to 9
A coating composition containing 9% by weight and 1 to 99.9% by weight of the binder component. 7. A base material selected from the group consisting of a resin molded product, glass and paper, the zinc oxide type fine particles according to any one of claims 1 to 5, and the zinc oxide type fine particles. A binder component that binds to the surface of the base material, in the proportions of 0.1 to 99% by weight of the zinc oxide based fine particles and 1 to 99.9% by weight of the binder component, based on the total weight of the two. And a coating film formed on. 8. The zinc oxide-based fine particles according to any one of claims 1 to 5 and a resin capable of forming a continuous phase in which the zinc oxide-based fine particles are dispersed, in the total solid content of both of them. On the other hand, a resin composition containing 0.1 to 99% by weight of the zinc oxide based fine particles and 1 to 99.9% by weight of the resin. 9. A resin molded product obtained by molding the resin composition according to claim 8 into any shape selected from the group consisting of plates, sheets, films and fibers.