WO2008035669A1

WO2008035669A1 - Oxide fine particle-containing organic-inorganic hybrid polymer composition and method for producing the same

Info

Publication number: WO2008035669A1
Application number: PCT/JP2007/068079
Authority: WO
Inventors: Tarou Kanamori; Keisuke Yajima
Original assignee: Jsr Corporation
Priority date: 2006-09-19
Filing date: 2007-09-18
Publication date: 2008-03-27
Also published as: JPWO2008035669A1; CN101517003A; KR20090061659A

Abstract

Disclosed is an oxide fine particle-containing organic-inorganic hybrid polymer composition, which is obtained by mixing (A) a silicon oxide fine particle and/or a metal oxide fine particle with (B) an organic-inorganic hybrid polymer, which is obtained by a hydrolysis/condensation reaction of at least one silane compound (b1) selected from the group consisting of at least one organosilane represented by the formula (1) below, hydrolysis products of the organosilane and condensation products of the organosilane, and a polymer (b2) having a silyl group containing a silicon atom bonded with a hydrolyzable group and/or a hydroxyl group, in an organic solvent in the presence of a basic compound, an acidic compound or a metal chelate compound, thereby dispersing the oxide fine particle (A) into the organic solvent. R1nSi(OR2)4-n (1) (In the formula, R1 represents a monovalent organic group having 1-8 carbon atoms; R2 represents an alkyl group having 1-5 carbon atoms or an acyl group having 1-6 carbon atoms; and n represents an integer of 0-2.)

Description

Specification

Oxide fine particle-containing organic-inorganic hybrid polymer composition and method for producing the same

Technical field

TECHNICAL FIELD [0001] The present invention relates to an organic-inorganic hybrid polymer composition in which key oxide fine particles and / or metal oxide fine particles are highly dispersed in an organic solvent containing an organic-inorganic hybrid polymer, and a cured product thereof.

Background art

Conventionally, as a means for imparting various functions to a siloxane material having excellent durability, a binder having a siloxane skeleton (hereinafter, also referred to as “siloxane binder”! /, U), cation oxide fine particles, and various metals. Compounding with oxide fine particles (hereinafter collectively referred to as “oxide fine particles”) is being studied. At this time, the siloxane-based binder and oxide fine particles are often prepared in the form of a dispersion containing them. On the other hand, since siloxane-based binders are difficult to dissolve in water, it is necessary to use an organic solvent as a dispersion medium. On the other hand, oxide fine particles tend to aggregate in an organic solvent and are often dispersed in an aqueous medium. . Therefore, in order to finely disperse oxide fine particles in an organic solvent, phosphoric acid, sulfonic acid or carboxylic acid having an organic group having 6 or more carbon atoms (see Patent Document 1), an organic compound having an oxyalkylene group, It was necessary to use an ester such as phosphoric acid having an oxyalkylene group (see Patent Document 2) or a silane compound having an oxyalkylene group (see Patent Document 3).

[0003] However, when oxide fine particles and a siloxane-based binder are combined by a method of finely dispersing oxide fine particles in an organic solvent using these compounds, the dispersibility of the dispersion is good. However, the compatibility between the above compound and the siloxane-based binder is poor. For example, when a coating film is formed by removing the solvent, the coating film may be whitened. In addition, even if a transparent coating film is formed by controlling the film forming conditions, etc., phosphoric acid having an organic group having 6 or more carbon atoms or a compound having an oxyalkylene group remains in this coating film. For this reason, problems such as coloration of the coating and generation of cracks may occur under ultraviolet irradiation. [0004] On the other hand, the key oxide fine particles have an organic solvent dispersion that maintains dispersibility with its own surface charge. Although this dispersion has good dispersion stability, it is mixed with a siloxane binder. In this case, the silicon oxide fine particles may aggregate and whiten, or crack force S may occur.

[0005] In addition, when a dispersion containing a silane monomer and oxide fine particles is prepared in advance and this silane monomer is hydrolyzed and condensed to form a siloxane binder, the resulting dispersion has a low dispersibility. The transparency of the film is also low (see the comparative example in Patent Document 3).

[0006] Such a problem is that even when an organic-inorganic hybrid polymer is used as a siloxane-based binder and combined with oxide fine particles, it has a function with oxide fine particles, and a transparent coating film is obtained. I couldn't do it.

Patent Document 1: Japanese Patent Application Laid-Open No. 2004-283822

Patent Document 2: Japanese Patent Laid-Open No. 2005-185924

Patent Document 3: Japanese Patent Application Laid-Open No. 2004-99879

Disclosure of the invention

Problems to be solved by the invention

[0007] The present invention is intended to solve the problems associated with the prior art as described above, and has a polysiloxane-based cured body having various functions and excellent in transparency and outdoor weather resistance, and the present invention. It is an object of the present invention to provide an organic-inorganic hybrid polymer composition in which oxide fine particles are highly dispersed and a method for producing the same, from which such a cured product can be obtained.

Means for solving the problem

[0008] As a result of diligent research to solve the above problems, the present inventors have previously made a polymer having a silane group and a silyl group containing a hydrolyzable group and / or a silicon atom bonded to a hydroxyl group. Is then hydrolyzed and condensed to prepare an organic-inorganic hybrid polymer, and in the presence of a basic compound, acid compound or metal chelate compound in an organic solvent containing the organic-inorganic hybrid polymer, oxide fine particles Has been found to produce an organic-inorganic hybrid polymer composition in which fine oxide particles are highly dispersed in an organic solvent containing an organic-inorganic hybrid polymer. Further, the cured body strength obtained from this composition is transparent. Excellent in heat resistance and weather resistance, and more flexible and resistant to substrates As a result, the present invention has been completed.

[0009] That is, the organic fine particle-containing organic-inorganic hybrid polymer composition according to the present invention is present in an organic solvent in the presence of a basic compound, an acidic compound, or a metal chelate compound.

(A) silicon oxide fine particles and / or metal oxide fine particles, and

(B) Following formula (1)

R ¹ Si (OR ² ) ― (1)

(In the formula, R ^1, number of carbon atoms;!. Represents a monovalent organic group having 1-8, when present two may be different from one another the same R ² are each independently A C 1-5 alkyl group or a C 1-6 acyl group n is an integer of 0-2.)

At least one silane compound (bl) selected from the group consisting of at least one organosilane, a hydrolyzate of the organosilane, and a condensate of onoleganosilane, and a hydrolyzable group and / or Alternatively, the oxide fine particles (A) are mixed with an organic-inorganic hybrid polymer obtained by hydrolysis / condensation reaction with a polymer (b2) having a silyl group containing a silicon atom bonded to a hydroxyl group. It is obtained by dispersing in a solvent.

[0010] The oxide fine particles (A) and the organic-inorganic hybrid polymer (B) are preferably mixed in the presence of a basic compound.

[0011] The oxide fine particles (A) and the organic-inorganic hybrid polymer (B) are preferably mixed by a bead mill.

[0012] The organic-inorganic hybrid polymer (100 parts by weight of the oxide fine particles (A))

B) is preferably 1 to 1000 parts by weight in terms of complete hydrolysis condensate.

[0013] The silane compound (bl) and the polymer (b2) are combined into a completely hydrolyzed condensate content (Wbl) of the silane compound (bl) and a solid content content of the polymer (b2). Weight ratio with (Wb2)

(Wbl / Wb2) is in the range of 5/95 to 95/5, where Wbl + Wb2 = 100. ] Hydrolysis · Condensation power is preferred.

[0014] In the polymer (b2), the content of a silyl group containing a hydrolyzable group and / or a silicon atom bonded to a hydroxyl group is converted into the content of the silicon atom, 0.;! ~ 2 weight % Is preferred.

[0015] A cured product according to the present invention is obtained from the above-mentioned organic-inorganic hybrid polymer composition containing fine oxide particles.

[0016] A coating composition according to the present invention is characterized by comprising the above-mentioned organic fine particle-containing organic / inorganic hybrid polymer composition.

The laminate according to the present invention is characterized by having an organic base material and a coating film obtained from the coating composition provided on the organic base material.

The invention's effect

[0018] According to the present invention, oxide fine particles are highly developed in an organic solvent containing an organic-inorganic hybrid polymer without using a phosphoric acid having an organic group having 6 or more carbon atoms or a compound having an oxyalkylene group. A dispersed composition is obtained. This composition is excellent in dispersion stability and can form a transparent cured product containing fine oxide particles and the organic-inorganic hybrid polymer. Since this cured product does not substantially contain the above-mentioned compound, it does not easily turn yellow even if left in an environment such as outdoors where it is irradiated with ultraviolet rays. Also, it is flexible due to the action of the organic-inorganic hybrid polymer. And excellent trackability to the substrate. Furthermore, a cured product using zinc oxide fine particles, cerium oxide fine particles, or rutile-type titanium oxide fine particles as oxide fine particles is useful as an ultraviolet cut material. BEST MODE FOR CARRYING OUT THE INVENTION

[0019] The oxide fine particle-containing organic-inorganic hybrid polymer composition according to the present invention comprises an oxide fine particle (A) and an organic-inorganic hybrid polymer (B), phosphoric acid or the like having an organic group having 6 or more carbon atoms. The power S can be obtained by mixing and dispersing in an organic solvent in the presence of a basic compound, acidic compound or metal chelate compound without using a compound having a xyalkylene group.

[0020] [Oxide fine particles (A)]

The oxide fine particles (A) used in the present invention are silicon oxide fine particles and / or metal oxide fine particles. The metal oxide fine particles are not particularly limited as long as they are metal element oxide fine particles. For example, antimony oxide, zirconium oxide, anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, suboxide oxide Lead, tantalum oxide, indium oxide, hafnium oxide, tin oxide, niobium oxide, anorenium oxide, cerium oxide, scandium oxide, yttrium oxide, lanthanum oxide, prasedium oxide, neodymium oxide, samarium oxide, pium oxide, gadolinium oxide Terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, lithium oxide, ytterbium oxide, lutetium oxide, calcium oxide, gallium oxide, lithium oxide, strontium oxide, tungsten oxide, barium oxide, magnesium oxide, and these And metal oxide fine particles such as an oxide of a composite of two or more of the above metals such as an indium tin oxide composite oxide. Further, as the oxide fine particles (A), composite oxide fine particles of a key oxide and a metal oxide, or oxide fine particles in which the surface of a metal oxide fine particle is coated with a key oxide can be used.

In the present invention, the oxide fine particles may be used alone or in combination of two or more. The oxide fine particles (A) can be appropriately selected depending on the function to be imparted. For example, in the case of imparting a high refractive property, the TiO fine particles are preferable in the ultraviolet region.

2

ZrO fine particles are preferable in order to achieve both high properties and high refractive properties. In addition, UV cut function

2

In the case of applying, cerium oxide fine particles and zinc oxide fine particles are preferable. In addition, when imparting conductivity, antimony oxide-doped tin oxide fine particles and indium tin-based composite oxide fine particles are preferable.

[0022] The primary average particle size of the oxide fine particles (A) is preferably 0.1 to 100 nm, more preferably 0. !! to 70 nm, and particularly preferably 0.;! To 50 nm. When the primary average particle diameter of the oxide fine particles (A) is in the above range, a cured product having excellent light transmittance can be obtained.

[0023] Such oxide fine particles (A) are dispersed in a solvent! /, N! /, Even when added in a powder state, in a polar solvent such as isopropyl alcohol or a nonpolar solvent such as toluene. It may be added in the state of a dispersion dispersed therein. The oxide fine particles (A) before the addition may be aggregated to form secondary particles. In the present invention, it is preferable to use a powder because an appropriate organic solvent can be appropriately selected in consideration of the solubility of the organic-inorganic hybrid polymer (B). The production method of the present invention is particularly effective when added in the form of powder.

[0024] [Organic inorganic hybrid polymer (B)]

The organic-inorganic hybrid polymer (B) used in the present invention contains a specific silane compound (bl ) And a polymer (b2) containing a specific silyl group are prepared by hydrolysis / condensation reaction. More specifically, it is prepared by adding a catalyst for promoting hydrolysis / condensation reaction and water to a mixture containing the silane compound (bl) and the polymer (b2) containing a silyl group.

[0025] (Silane compound (bl))

The silane compound (b 1) used in the present invention has the following formula (1)

R ¹ Si (OR ² ) ― (1)

At least one selected from the group consisting of organosilane (1) hydrolysates and organosilane (1) condensates (hereinafter also referred to as “organosilane (1)”) Of these three silane compounds, any one silane compound may be used, or any two silane compounds may be used in combination, or all three silane compounds may be used. You may mix and use a compound. Further, when organosilane (1) is used as the silane compound (bl), organosilane (1) may be used alone or in combination of two or more. Further, the hydrolyzate and condensate of the organosilane (1) may be formed from one kind of organosilane (1), or may be formed by using two or more kinds of organosilane (1) in combination. Good.

[0026] The hydrolyzate of the organosilane (1) is sufficient if at least one of the ² OR 4 groups contained in the organosilane (1) is hydrolyzed. It may be a product obtained by hydrolyzing an OR ² group, a product obtained by hydrolyzing two or more OR ² groups, or a mixture thereof.

[0027] The condensate of organosilane (1) is formed by condensation of silanol groups in the hydrolyzate generated by hydrolysis of organosilane (1) to form a Si—O—Si bond. In the present invention, it is not necessary that all the silanol groups are condensed. The condensate may be a product obtained by condensing a small part of silanol groups, most (including all) of the silanol groups, These mixtures are also included. In the above formula (1), R ¹ is a monovalent organic group having 1 to 8 carbon atoms, specifically, a methylol group, an ethyl group, an n propyl group, an i propyl group, an n butyl group. Group, alkyl group such as i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group;

Isacyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group, force profile group;

Examples thereof include a bur group, an aryl group, a cyclohexyl group, a phenyl group, an epoxy group, a glycidyl group, a (meth) acryloxy group, a ureido group, an amide group, a fluoroacetamide group, and an isocyanate group.

Furthermore, examples of R ¹ include substituted derivatives of the above organic groups. Examples of the substituent of the substituted derivative of R ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexylene group, and (meth) An acryloxy group, a ureido group, an ammonium base, etc. are mentioned. However, the carbon number of R ¹ composed of these substituted derivatives is preferably 8 or less including the carbon atom in the substituent. When a plurality of R ¹ are present in the formula (1), they may be the same or different.

[0030] R ² which is an alkyl group having 1 to 5 carbon atoms includes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, and an n-pen. Examples of R ² which is an acyl group having 1 to 6 carbon atoms include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a force profile group. When a plurality of R ² are present in the formula (1), they may be the same or different.

[0031] Specific examples of the organosilane (1) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane (formula (1) N = 0); methyltrimethoxysilane, methinoretriethoxysilane, ethinoretrimethoxysilane, ethinoretriethoxysilane, n-propyl trimethoxysilane, n-propyltriethoxysilane, i-propyl trimethoxysilane, i Propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriet Noretreethoxysilane, Cyclohexenoretrimethoxysilane, Cyclohexenoretriethoxysilane, Phenyltrimethoxysilane, Phenyltriethoxysilane, 3-Clopropropyl Trimethoxysilane, 3-Clopropropyltriethoxysilane 3, 3, 3-trifurenoreo propylene trimethoxysilane, 3, 3, 3-trifluoropropyltriethoxysilane, 3-aminopropyl trimethoxysilane, 3 aminopropyltriethoxysilane, 2 hydroxyethyl Rimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyl trimethoxysilane, 2 hydroxypropyltriethoxysilane, 3 hydroxypropyl trimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyl G Limethoxysilane, 3—

—Isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 glycidoxypropinoletriethoxysilane, 2— (3,4 epoxy cyclohexylenolate) ethinoretrimethoxysilane, 2— (3 , 4 Epoxycyclohexenole) Ethinoretriexysila Oral pill triethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidoprobilt triethoxysilane, etc. Trialkoxysilanes (in formula (1), n = l );

Dimethylol Norre dimethoxysilane, dimethylcarbamoyl Honoré jet silane, Jefferies Chino registration silane, Jefferies Chino Leger butoxy silane, _di-n propyl Honoré dimethoxysilane, di n pro Pinot Leger butoxy silane, di-i prop Honoré dimethoxysilane, di i Puropinoreje Toxisilane, G-n-Butinoresimethoxysilane, G-n-Butinoresoxymethoxysilane, G-n-Pentinoresimethoxysilane, G-n-Pentino-Resioxysilane, G-n-Hexinoresimethoxysilane, Di-n-Hexino-Legetoxysilane , Gen n heptinoresin methoxysilane, gen _n heptyl noregetoxy silane, gen _n — talino chinenoresi methoxy silane, gen n octinolegetoxysilane, gen n cyclohexinoresin methoxy silane, gen n cyclohexino Regetoxysila n = 2) in the formula (1); Silane (n = 2 in formula (1)) and the like can be mentioned.

[0032] Of these, trifunctional silane compounds in which n = l in formula (1) are mainly used. This trifunctional silane compound is preferably used in combination with a bifunctional silane compound in which n = 2 in the formula (1) from the viewpoint of the stability of the organic-inorganic hybrid polymer composition according to the present invention. As the trifunctional silane compound, trialkoxysilanes are particularly preferable. As the bifunctional silane compound, dialkoxysilanes are preferable.

[0033] When a trifunctional silane compound and a bifunctional silane compound are used in combination, the trifunctional silane compound / bifunctional silane compound is preferably 95/5 to 10% by weight ratio in terms of the total hydrolysis condensate of each. / 90, more preferably 90/10 to 30/70, particularly preferably 85/15 to 40/60. However, the sum of the trifunctional silane compound and the bifunctional silane compound (in terms of a complete water-hydrolysis condensate) is 100. If the content of the trifunctional silane compound is too large, the dispersibility of the oxide fine particles may be inferior because it tends to aggregate. If the content of the trifunctional silane compound is too small, the functionality required for dispersing the oxide fine particles may be reduced. The dispersibility of the oxide fine particles may be inferior because the number of groups decreases. In the present specification, the completely hydrolyzed condensate means a product in which the —OR group of a silane compound is hydrolyzed to 100% to be a SiOH group and further completely condensed to a siloxane structure.

In the present invention, one type of organosilane (1) may be used alone as the silane compound (bl), but two or more types of organosilane (1) may be used in combination. When the two or more organosilanes (1) used as the silane compound (bl) are averaged and expressed by the above formula (1), the average value is n (hereinafter also referred to as “the average value of n”). ) Is preferably 0.5 to 1.9, more preferably 0 to 6 to 1.7, and particularly preferably 0.7 to 1.5. When the average value of n is less than the above lower limit, the storage stability of the organic-inorganic hybrid polymer composition may be inferior, and when the upper limit is exceeded, the curability of the cured body (coating film) may be inferior.

[0035] The average value of n can be adjusted to the above range by appropriately using a bifunctional to tetrafunctional silane compound and appropriately adjusting the blending ratio thereof.

[0036] This is the same when a hydrolyzate or a condensate is used as the silane compound (bl).

In the present invention, organosilane (1) may be used as it is as silane compound (bl). However, a hydrolyzate and / or condensate of organosilane (1) can be used. When the organosilane (1) is used as a hydrolyzate and / or a condensate, it may be prepared by hydrolyzing and condensing the organosilane (1) in advance. When preparing the hybrid polymer (B), water is added to hydrolyze and condense the organosilane (1) with water to prepare a hydrolyzate and / or condensate of the organosilane (1). I like it! / The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) measured by the above method is preferably <= 300 to 100,000, more preferably <500 to 50,000.

[0039] When a condensate of organosilane (1) is used as the silane compound (b1) in the present invention, it may be prepared from the above organosilane (1) or may be obtained by shrinking a commercially available organosilane. A compound may be used. Commercially available condensates of organosilane include Mitsubishi Chemical Corporation

) MKC silicate, Colcoat ethyl silicate, Toray Dow Coung Silicone Co., Ltd. silicone resin, GE Toshiba Silicone Co., Ltd. silicone resin, Shin-Etsu Chemical Co., Ltd. silicone resin And silicone oligomers, hydroxyl group-containing polydimethylsiloxane manufactured by Dow Co., Ltd., and silicone oligomers manufactured by Nippon Tunica. These commercially available condensates of organosilanes may be used as they are or after further condensation.

[0040] (Silyl group-containing polymer (b2))

The polymer (b2) containing a specific silyl group used in the present invention (hereinafter also referred to as “specific silyl group-containing polymer (b2)”) is bound to a hydrolyzable group and / or a hydroxyl group. It contains a silyl group having a carbon atom (hereinafter referred to as “specific silyl group”). The specific silyl group-containing polymer (b2) preferably has a specific silyl group at the terminal and / or side chain of the polymer molecular chain.

[0041] The hydrolyzable group and / or hydroxyl group in the specific silyl group is co-condensed with the silane compound (b 1) to form the organic-inorganic hybrid polymer (B). When polymer (B) and oxide fine particles (A) are mixed and dispersed in an organic solvent in the presence of a basic compound, acidic compound or metal chelate compound The oxide fine particles (A) are highly dispersed in the organic solvent. This is because the hydrolyzable group and / or hydroxyl group in the specific silyl group remaining in the organic-inorganic hybrid polymer (B) is condensed on the surface of the oxide fine particles (A) by the catalytic action of a basic compound or the like. This is presumably because the surface of the fine particles (A) becomes hydrophobic and the oxide fine particles (A) are easily finely dispersed in the organic solvent.

[0042] The content of the specific silyl group in the specific silyl group-containing polymer (b2) is usually 0.;! To 2 with respect to the polymer before the introduction of the specific silyl group, in terms of the amount of silicon atoms. % By weight, preferably 0.3-; 1.7% by weight. When the specific silyl group content in the specific silyl group-containing polymer (b2) is less than the above lower limit, the covalent bond site with the silane compound (bl) and the specific silyl group remaining in the organic-inorganic hybrid polymer (B) Therefore, the effect of the mixed dispersion process may not be obtained. On the other hand, if the above upper limit is exceeded, gelation may occur during storage of the composition.

[0043] The specific silyl group has the following formula (3):

[0044] [Chemical 1]

(In the formula, X represents a hydrolyzable group such as a halogen atom, an alkoxyl group, an acetoxy group, a phenoxy group, a thioalkoxyl group, an amino group, or a hydroxyl group, and R ⁵ is a hydrogen atom having 1 to 10 carbon atoms. Represents an alkyl group or an aralkyl group having 1 to 10 carbon atoms, and i is an integer of !! to 3).

It is preferred that the group represented by

[0046] Such a specific silyl group-containing polymer (b2) is obtained, for example, by the following methods (I) and (ii):

It is a power S to manufacture.

[0047] (I) A hydrosilane compound having a specific silyl group represented by the above formula (3) (hereinafter, simply referred to as “hydrosilane compound (I)”) is converted to a bulle having a carbon-carbon double bond. A method of causing an addition reaction to the carbon-carbon double bond in a polymer (hereinafter referred to as “unsaturated butyl polymer”). [0048] (Π) The following formula (4)

[0049] [Chemical 2]

[0050] (wherein, X, R ^5, i have the same meanings as X, R ^5, i in the formula (3), R ⁶ is an organic group having a polymerizable double bond)

A method of copolymerizing a silane compound represented by the formula (hereinafter referred to as “unsaturated silane compound (/)” and! /, U) with other bulle monomers.

[0051] Examples of the hydrosilane compound (I) used in the above method (I) include halogenated silanes such as methyldichlorosilane, trichlorosilane, and phenyldichlorosilane; methyldimethoxysilane, methinolegoxysilane. , Pheninoresimethoxysilane, trimethoxysilane, acetoxysilane, triacetoxysilane, and other acyloxysilanes; methyldiaminoxysilane, triaminoxysilane, dimethyl'aminoxysilane, and other aminoxysilanes . These hydrosilane compounds (I) can be used alone or in combination of two or more.

[0052] The unsaturated bulle polymer used in the method (I) is not particularly limited as long as it is a polymer having a hydroxyl group. For example, the following (I 1) and (I 2) It can be produced by a method or a combination thereof.

[0053] (I-1) After a (co) polymerization of a butyl monomer having a functional group (hereinafter referred to as “functional group (”), the functional group (α) in the (co) polymer is converted to By reacting a functional group capable of reacting with the functional group (α) (hereinafter referred to as “functional group (/ 3)”) with an unsaturated compound having a carbon-carbon double bond, A method for producing an unsaturated bur polymer having a carbon-carbon double bond in the side chain.

[0054] A radical polymerization initiator (for example, 4, 4'-azobis-4-cyanovaleric acid) having (1-2) functional group) is used, or both radical polymerization initiator and chain transfer agent are used. A compound having a functional group (α) (for example, 4, 4'-azobis 4-cyananovaleric acid and dithio) Glycolic acid etc.) (co) polymerization of bulle monomers, and the functional group (<<) derived from radical polymerization initiator or chain transfer agent at one or both ends of the polymer molecular chain After synthesizing the (co) polymer having the functional group in the (co) polymer, the polymer is reacted with an unsaturated compound having a functional group (β) and a carbon / carbon double bond. A method for producing an unsaturated bur polymer having a carbon-carbon double bond at one or both ends of a molecular chain.

[0055] Examples of the reaction between the functional group (α) and the functional group (/ 3) in the methods (1-1) and (I 2) include, for example, esterification reaction between a carboxyl group and a hydroxyl group, carboxylic acid anhydride, Ring-opening esterification reaction between a hydroxyl group and a hydroxyl group, ring-opening esterification reaction between a carboxyl group and an epoxy group, amidation reaction between a carboxyl group and an amino group, ring-opening between a carboxylic anhydride group and an amino group amide And urethanation reaction between an epoxy group and an amino group, a urethanation reaction between a hydroxyl group and an isocyanate group, and a combination of these reactions.

[0056] Examples of the bull monomers having a functional group (α) include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid; maleic anhydride, anhydrous Unsaturated carboxylic acid anhydrides such as itaconic acid; 2-hydroxyethyl (meth) acrylate

水 Hydroxyl group-containing butyl monomers such as methylol (meth) acrylamide and 2-hydroxyethyl butyl ether; 2-aminoethinole (meth) acrylate, 2-aminopropynole (meth) acrylate, 3 aminopropyl (meth) attaly 1, 2, 1-trimethylamine (meth) acrylimide, 1 -methyl-1-ethylamine (meth) acrylimide, 1, 1 dimethyl 1 (2-Hydroxypropyl) amine (meth) acrylimide, 1, 1-dimethyl 1- (2, 2-phenyl 2, -hydro-chichetil) amamine (meth) acrylimide, 1, 1 dimethyl 1 ( ₂ , hydroxy) ₂ ,

—Phenoxypropyl) amine (meth) acrylimide and other amine-containing butyl monomers; epoxy group-containing butyl monomers such as glycidyl (meth) acrylate and allylic glycidyl ether . These bule monomers having these functional groups (α) can be used alone or in admixture of two or more.

[0057] As other bull monomers that can be copolymerized with a bull monomer having a functional group (α), For example, styrene, α-methyl styrene, 4 methyl styrene, 2 methyl styrene, 3 methyl styrene, 4-methoxy styrene, 2 hydroxymethyl styrene, 4-ethyl styrene, 4-ethoxy styrene, 3, 4 dimethyl styrene, 3, Aromatic bullets such as 4 Jetylstyrene, 2 Chlorostyrene, 3-Chlorostyrene, 4 Chloro-3-Methylstyrene, 4 t-Butyl Styrene, 2, 4-Dichlorostyrene, 2,6-Dichlorostyrene, 1-Burnaphthalene Mer;

Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i butyl (meth) acrylate, amyl (meth) acrylate, i- amyl (meta) ) (Meth) acrylate compounds such as acrylate, hexyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, n octyl (meth) acrylate, cyclohexyl methacrylate;

Dibutenebenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylol Polyfunctional monomers such as propanetri (meth) acrylate and pentaerythritol tetra (meth) acrylate;

Acid amide compounds such as (meth) acrylamide, N methylol (meth) acrylamide, N methoxymethyl (meth) amide, diacetone acrylamide, maleic acid amide and maleimide; Bull compounds such as butyl chloride, vinylidene chloride and fatty acid butyl ester;

1,3 Butadiene, 2-Methyl-1,3 Butadiene, 2,3 Dimethyl-1,3 Butadiene, 2-Neopentyl-1,3-Butadiene, 2-Chloro-1,3-Butadiene, 2-Cyanol 1,3— Substituted conjugated pentagens substituted with a substituent such as butadiene, isoprene, alkyl group, halogen atom, cyano group, and aliphatic conjugated gens such as linear and side chain conjugated hexene;

Cyanide bur compounds such as acrylonitrile and methacrylonitrile; Fluorine atom-containing monomers such as trifluoroethyl (meth) acrylate and pentadecafluorooctyl (meth) acrylate;

2, 2, 6, 6 piperidine monomers such as pentamethylpiperidine;

2— (2′-Hydroxy 5′-methacryloxychetyl phenyl) 2H Benzotriazol Nore, 2— (2′-Hydroxy 3′—t Butyl-5′-methacryloxychetyl phenyl) -2 H benzotriazole, 2 UV-absorbing monomers such as hydroxy-4- (methacryloyloxyethoxy) benzophenone and 2-hydroxy-4 (ataryloxyethoxy) benzophenone;

Examples include dicaprolataton. These can be achieved by using S alone or in combination of two or more.

[0058] Examples of the unsaturated compound having a functional group (/ 3) and a carbon-carbon double bond include, for example, a bull monomer similar to a bull monomer having a functional group (α), An isocyanate group-containing unsaturated compound obtained by reacting the hydroxyl group-containing vinyl monomer and the diisocyanate compound in an equimolar amount can be exemplified.

[0059] Further, as the unsaturated silane compound (に) used in the method (Π),

CH = CHSi (CH) (OCH), CH = CHSi (OCH),

2 3 3 2 2 3 3

CH = CHSi (CH) C1, CH = CHSiCl,

2 3 2 2 3

CH = CHCOO (CH) Si (CH) (OCH),

2 2 2 3 3 2

CH = CHCOO (CH) Si (OCH),

2 2 2 3 3

CH = CHCOO (CH) Si (CH) (OCH),

2 2 3 3 3 2

CH = CHCOO (CH) Si (OCH),

2 2 3 3 3

CH = CHCOO (CH) Si (CH) C1,

2 2 2 3 2

CH = CHCOO (CH) SiCl,

2 2 2 3

CH = CHCOO (CH) Si (CH) C1,

2 2 3 3 2

CH = CHCOO (CH) SiCl,

2 2 3 3

CH = C (CH) COO (CH) Si (CH) (OCH),

[0061] The ability to raise S. These can be used alone or in combination of two or more.

[0062] Examples of other bulle monomers to be copolymerized with the unsaturated silane compound include, for example, a bulle type monomer having the functional group (α) exemplified in the method (I 1) above! And other vinyl monomers.

[0063] Examples of the method for producing the specific silyl group-containing polymer (b2) include, for example, a method in which each monomer is added at once and polymerized. Continuously Alternatively, there may be mentioned a method in which polymerization is carried out by intermittent addition, or a method in which a monomer is continuously added from the start of polymerization. These polymerization methods may be combined.

[0064] Preferable! / The polymerization method includes solution polymerization. The solvent used in the solution polymerization is not particularly limited as long as it can produce the specific silyl group-containing polymer (b2). For example, alcohols, aromatic hydrocarbons, ethers, ketones, esters The ability to list things. Examples of the alcohols include methanol, ethanol, n-propylenoleanolone, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol monole, tert-butylenorenolenole, and n-hexenoleanoreconole. , N-Otatinolenoreconole, Ethylene glycolate, Diethyleneglycolanol, Triethyleneglycolanol, Ethyleneglycolanol Monobutyl ether, Ethyleneglycolmonoethyletheracetate, Diethyleneglycolenomonoethylenoate, Propyleneglycolole Examples thereof include monomethylenoatenole, propylene monomethyl ether acetate, diacetone alcohol and the like. In addition, examples of aromatic hydrocarbons include benzene, toluene, xylene, etc., examples of ethers include tetrahydrofuran, dioxane, etc., and examples of ketones include acetonitrile, methyl ethyl ketone, and methyl isobutyl ketone. Examples of esters include ethyl acetate, propyl acetate, butyl acetate, propylene carbonate, methyl lactate, ethyl lactate, normal propyl lactate, isopropyl lactate, methyl 3-ethoxypropionate, 3 — Ethyl ethoxypropionate and the like. These organic solvents may be used alone or in combination of two or more.

[0065] In the above polymerization, known polymerization initiators, molecular weight regulators, chelating agents, and inorganic electrolytes can be used.

In the present invention, as the specific silyl group-containing polymer (b2), in addition to the specific silyl group-containing polymer polymerized as described above, the specific silyl group-containing epoxy resin, the specific silyl group-containing polyester resin Other specific silyl group-containing polymers such as can also be used. The specific silyl group-containing epoxy resin is, for example, in epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, aliphatic polydaricidyl ether, and aliphatic polyglycidyl ester. Amino silanes, bur silanes, carboxy silanes, darines having specific silyl groups on the epoxy group of It can be produced by reacting sidylsilanes. The above-mentioned specific silyl group-containing polyester resin is produced, for example, by reacting a carboxyl group or hydroxyl group contained in the polyester resin with aminosilanes, carboxysilanes, darisidylsilanes, etc. having a specific silyl group. can do.

[0067] The Mw in terms of polystyrene measured by the GPC method of the specific silyl group-containing polymer (b2) is preferably 2,000-100,000, more preferably 3,000-50,000.

[0068] In the present invention, the specific silyl group-containing polymer (b2) is determined by the power to use alone or in combination of two or more.

[0069] (Catalyst)

In the present invention, in order to promote hydrolysis / condensation reaction of the silane compound (bl) and the specific silyl group-containing polymer (b2), the silane compound (a) and the specific silyl group-containing polymer (b) It is preferred to add a catalyst to the mixture. By adding a catalyst, the degree of crosslinking of the organic-inorganic hybrid polymer (B) obtained can be increased, and the molecular weight of the polysiloxane produced by the polycondensation reaction of the organosilane (1) is increased. As a result, A cured product having excellent strength and long-term durability can be obtained, and the coating film can be thickened and applied easily. Furthermore, the addition of the catalyst promotes the reaction between the silane compound (bl) and the specific silyl group-containing polymer (b2), and sufficient reaction sites (alkoxy groups) are formed in the organic-inorganic hybrid polymer (B). . When this organic-inorganic hybrid polymer (B) and oxide fine particles (A) are mixed and dispersed in an organic solvent in the presence of a basic compound or the like, the oxide fine particles (A) are highly dissolved in the organic solvent. Distributed. This is because the organic / inorganic hybrid polymer (B) is condensed on the surface of the oxide fine particles (A), the surface of the oxide fine particles (A) becomes hydrophobic, and the oxide fine particles (A) are finely dispersed in the organic solvent. This is presumed to be easier.

[0070] Examples of the catalyst used for promoting the hydrolysis' condensation reaction include basic compounds, acidic compounds, salt compounds, and metal chelate compounds.

[0071] (Basic compound)

Examples of the basic compound include ammonia (including aqueous ammonia), organic amine compounds, alkali metals such as sodium hydroxide and potassium hydroxide, and hydroxides of alkaline earth metals. And alkali metal alkoxides such as sodium methoxide and sodium ethoxide. Of these, ammonia and organic amine compounds are preferred.

[0072] Examples of organic amines include anolequinoleamine, alkoxyamine, alkanolamine, and arylamine.

[0073] Examples of the alkylamine include methenoreamine, ethenoreamine, propylamine, butylamine, hexylamine, octylamine, N, N dimethylamine, N, N dimethylamine, N, N dipropylamine, N, N dibutylamine, trimethinoreamine, triethinoreamine, Examples thereof include alkylamines having an alkyl group having 1 to 4 carbon atoms such as tripropylamine and tributylamine.

[0074] Examples of alkoxyamines include methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethyl. Alkoxy groups having an alkoxy group having 1 to 4 carbon atoms, such as amines, propoxychetylamines, propoxypropylamines, propoxybutylamines, butoxymethylamines, butoxysethylamines, butoxypropylamines, butoxybutylamines. Min etc. are mentioned.

[0075] Examples of alkanolamines include methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine. Min, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine N methylbutanolamine, N ethylbutanolamine, N propylbutanolamine, N butylbutanolamine, N, N dimethylmethanolamine, N, N jetylmethanolamine, N, N dipropylmethanolamine N, N-dibutylmethanolamine, N, N Dimethylethanolamine, N, N Jetylethanolamine, N, N Dipropylethanolamine, N, N Dibutylethanolamine, N, N Dimethylpropanolamine, N, N Jetenopropanolamine N, N Dipropylpropanolamine, N, N-Dibutylpropanolamine, N, N Dimethylbutanolamine, N, N Jetylbutanolamine , N, N-dipropylbutanolamine, N, N-dibutylbutanolamine, N-methyldimethanolamine, N-ethyldimethanolamine, N-propyldimethanolamine, N-butinoresi Methanolanolamine, N-Methinoresidanolethanolamine, N-Ethinoregetanolone Noramine, N-Propyldiethanolamine, N-Butylethanolamine, N-Methylenolpropanolamine, N-Ethyldipropanol N-propyldipropanolamine, N-butyldipropanolamine, N-methyldibutanolamine, N-ethyldibutanolamine, N-propyldibutanolamine, N-butyldibutanolamine, N — (Aminomethyl) methanolamine, N— (Aminomethyl) ethanolamine, N— (Aminomethyl) pro Panolamine, N— (Aminomethyl) butanolamine, N— (Aminoethyl) methanolamine, N— (Aminoethyl) ethanolamine, N— (Aminoethyl) propanolamine, N— (Aminoethyl) butanolamine, N — (Aminopropino) methanolamine, N— (Aminopropyl) ethanolamine, N— (Aminopropyl) propanolamine, N— (Aminopropyl) butanolamine, N— (Aminobutyl) methanolamine, N— (Aminobutyl) Examples of such alcohols include ethanolamine, N- (aminobutyl) propanolamine, and N- (aminobutyl) butanolamine.

[0076] Examples of arylamine include aniline and N-methylaniline.

[0077] Further, as other organic amines, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide are used.

, Tetraalkylammonium hydride such as tetraptylammonium hydroxide; tetraalkylethylenediamine such as tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine, tetrabutylethylenediamine Methylaminomethylamine, methylaminoethylamine, methylaminopropylamine, methylaminobutyramine, ethylaminomethylamine, ethylaminoethylamine, ethylaminopropylamine, Tilaminobutylamine, propylaminomethylamine, propylaminoethylamine, propylaminopropylamine, propylaminobutylamine, butylaminoaminomethylamine, butylaminoethylamine, butylaminopropylamine, The Alkylaminoalkylamines such as til aminobutylamine; ethylenediamine, hexamethy Polyamines such as rangenamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-phenylenediamine, p-phenylenediamine; pyridine, pyrrolinole, piperazine, pyrrolidine, piperidine, picoline, morpholine, Examples also include methylmorpholine, diazabicycloocrane, diazabicyclononane, and diazabicycloundecene.

[0078] Such basic compounds may be used singly or in combination of two or more. Of these, triethylamine, tetramethylammonium hydroxide, and pyridine are particularly preferable.

[0079] (Acid compound)

Examples of the acidic compound include organic acids and inorganic acids. Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, maleic anhydride, and methylmalonic acid. Adipic acid, sebacic acid, gallic acid, butyric acid, meritic acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, P- Examples include aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochrome oral acetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, methanesulfonic acid, phthalic acid, fumaric acid, citrate, and tartaric acid. It is done. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0080] Such acidic compounds may be used singly or in combination of two or more.

Of these, maleic acid, maleic anhydride, methanesulfonic acid, and acetic acid are particularly preferred.

[0081] (Salt compound)

Examples of the salt compound include alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid.

[0082] (Metal chelate compound)

Examples of the metal chelate compounds include organometallic compounds and / or partial hydrolysates thereof (hereinafter, organometallic compounds and / or partial hydrolysates thereof are collectively referred to as “organic metal compounds”). It is done.

[0083] Examples of the organometallic compounds include, for example, the following formula (a):

M (OR ⁷ ) (R ⁸ COCHCOR ⁹ ) (a) (Wherein, M represents at least one metal atom selected from the group consisting of zirconium, titanium and aluminum, and R ⁷ and R ⁸ are each independently a methyl group, an ethyl group, or an n-propyl group. A monovalent hydrocarbon group having 1 to 6 carbon atoms such as a group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, and phenyl group. R ⁹ represents the carbon number;! To 6 monovalent hydrocarbon group, or methoxy group, ethoxy group, n propoxy group, i propoxy group, n butoxy group, sec-butoxy group, t butoxy group Represents an alkoxyl group having 1 to 16 carbon atoms such as lauryloxy group and stearyloxy group, and r and s are each independently an integer of 0 to 4, and (r + s) = (M atom Value))

(Hereinafter referred to as “organometallic compound (a)”),

An organic metal compound of tetravalent tin (hereinafter referred to as “organotin compound”) in which 1 to 2 alkyl groups having 1 to 10 carbon atoms are bonded to one tin atom, or

These partial hydrolysates are exemplified.

In addition, as organometallic compounds, tetraalkoxytitaniums such as tetramethoxytitanium, tetraethoxytitanium, tetraipropoxytitanium, tetranbutoxytitanium; mesopropyltriethoxysilane, nhexyltrimethoxysilane, cyclohexyltri Ethoxysilane, phenyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2 aminoethyl) aminopropyltrimethoxysilane, 3 — (2-Aminoethyl) monoaminopropyltriethoxysilane, 3- (2aminoethyl) -aminopropylmethyldimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanate Pills trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-Ureidopuropi Honoré trimethoxysilane thoria Roh record silanes such as; dimethylcarbamoyl Honoré jet silane, Jechinore diethoxy silane, _di-n propyl Honoré dimethoxysilane, di- i Titanium alcoholates such as propenolegetoxysilane, di-n-pentinoresimethoxy silane, di-n-year-old cutinolegetoxysilane, di-n- and the condensates thereof can be used. [0085] As the organometallic compound (a), for example, tetra-n-butoxyzirconium, tri-n-butoxy-ethylacetoacetate zirconium, di-n-butoxy'bis (ethylacetylacetate) zirconium, n-butoxy'tris (ethyl) Organic zirconium compounds such as acetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium;

Organic such as tetra-i-propoxytitanium, di-i-propoxy.bis (ethylacetoacetate) titanium, di-i-propoxy'bis (acetylacetate) titanium, dii-propoxy'bis (acetylacetone) titanium Titanium compounds;

Tree i Propoxy Aluminum, G i Propoxy Ethylacetoacetate Aluminum, Di i-Propoxy. Acetylacetonate Aluminum, i-Propoxy 'Bis (Ethylacetoacetate) Aluminum, i-Propoxy' Bis Organic aluminum such as (acetylacetate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetate) aluminum, monoacetylacetate.bis (ethylacetoacetate) aluminum Compounds.

[0086] As an organotin compound, for example,

[0087] [Chemical 4]

(c ₄ H ₃ ) ₂ Sn (OCOC ^ H ^) ₂ ,

(c ₄ H ₃ ) ₂ Sn (OCOCH = CHCOOCH ₃ ) ₂ ,

(c ₂ Sn (OCOCH-CHCOOC ₄ H ₉ ) ₂ ,

(c 2 Sn (OCOC ₈ H ₁₇ ) ₂ ,

(c 3- ^ 17 ^ ₂ S n (OCOC „H ₂₃ ) ₂ ,

(c 8- ^ 17 ' ₂ S n (OCOCH = CHCOOCH ₃ ) ₂ ,

(c 8 ^H 17) ₂ Sn (OCOCH = CHCOOC ₄ H ₉ ) ₂

(c ₂ S n (OCOCH-CHCOOC ₈ H ₁₇ )

(c ₃ S n (OCOCH = CHCOOC ₁₇ H ₃₅ )

(c sH-t ₇ ) ₂ Sn (OCOCH = CHCOOC ₁₈ H ₃₇ )

(C 8 ^ 17 ₂ Sn (OCOCH-CHCOOC ₂₀ H ₄₁ )

(c ₄ H ₉ ) ₂ S n OCOCH3 o

(C ₄ H ₉ ) ₂ SnOCOCH ₃ ,

(C ₄ H _& ) S n (OCOC ^ Haa) ₃ ,

(C ₄ H ₉ ) S n (OCONa) ₃

[0088] Carboxylic acid-type organotin compounds such as

[0089] [Chemical 5]

(C ₄ H ₉ ) ₂ Sn (SCH ₂ COO C ₈ H ₁₇ ) ₂ ,

(C, jH ₉ ) ₂ Sn (SCH ₂ CH ₂ COOC _g H ₁₇ ) ₂ , (C ₃ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COOC _s H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₁₂ H ₂₅ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COOC ₁₂ H ₂₅ ) ₂ , (C ₄ H ₉ ) Sn (SCOCH = CHCOOC ₈ H ₁₇ ) ₃ , (C ₈ H ₁₇ JS n (SCOCH = CHCOOC ₈ H ₁₇ ) ₃ (CH ₉ ) ₂ Sn (SCH ₂ COOC _a H ₁₇ )

!

o

i

_{_{_{(C 4 H &) 2 S}}} n (S CH 2 COOC 8 H 17)

[0090] Mercaptide-type organotin compounds such as

[0091] [Chemical 6]

(C ₄ H ₉ ) ₂ S n = S, (C _a H ₁₇ ) ₂ Sn = S,

(C ₄ H _q ) Sn = S

I

S

I

(C ₄ H ₉ ) Sn = S

[0092] Sulfide-type organotin compounds such as

[0093] [Chemical 7]

(C ₊ H ₉ ) S nC] ₃ , (C ₄ H ₉ ) ₂ S nC l ₂ , (C ₈ H ₁₇ ) ₂ S nC 1 ₂ ,

(CH ₉ ) ₂ SnC 1

(C ₄ H ₉ ) _E S nC 1 [0094] chloride-type organotin compounds such as;

Organic tin oxides such as (C H) SnO and (C H) SnO, and these organic tin oxides

4 9 2 8 17 2

Reaction products of side and ester compounds such as silicate, dimethyl maleate, jetyl maleate, dioctyl phthalate;

Etc.

[0095] Such metal chelate compounds may be used singly or in combination of two or more. Of these, tri-n-butoxy ethyl acetate acetate, di-propoxy bis (acetyl acetate) titanium, zi-propoxy ethyl acetate acetate, tris (ethyl acetate acetate) aluminum, or These partial hydrolysates are preferred.

[0096] The catalyst can also be used by mixing with a zinc compound or other reaction retarder.

[0097] When the catalyst is other than an organometallic compound, the amount of the catalyst used is 100 parts by weight of the silane compound (bl) (in terms of a completely hydrolyzed condensate of the organosilane (1)). Usually from 0.001 to 100 parts by weight, preferably from 0.0 to 80 parts by weight, more preferably from 0.1 to 50 parts by weight. When the catalyst is an organometallic compound, it is usually 100 parts by weight or less, preferably 0. 0 parts by weight based on 100 parts by weight of the silane compound (bl) (in terms of complete hydrolysis condensate of organosilane (1)). ! To 80 parts by weight, more preferably 0.5 to 50 parts by weight. If the amount of the catalyst used exceeds the upper limit, the storage stability of the composition may be lowered, or the degree of crosslinking of the organic-inorganic hybrid polymer (B) may be too high.

[0098] (Wed)

In the present invention, water is added to the mixture of the silane compound (bl) and the specific silyl group-containing polymer (b2) to co-condense the silane compound (bl) and the specific silyl group-containing polymer (b2). It is preferable to prepare the organic / inorganic hybrid polymer (B).

[0099] The amount of water added at this time is usually 0.1-1 to 1.0 monole, preferably (or 0.2-0 to 1 mol of all OR ² groups in the silane compound (bl)). 8 Monole, more preferably (between 0.25 and 0.6 mol. A composition in which gelation hardly occurs when the amount of water added is in the above range shows good storage stability. Fully cross-linked organic inorganic when the amount of water added is in the above range A hybrid polymer (B) is obtained, and a cured product having excellent mechanical strength can be obtained by using a composition containing such an organic-inorganic hybrid polymer (B).

[0100] (Organic solvent)

In the present invention, the silane compound (bl) and the specific silyl group-containing polymer (b2) may be hydrolyzed and condensed in an organic solvent. At this time, the organic solvent used in the preparation of the silyl group-containing polymer (b2) can be used as it is. Moreover, in order to adjust the solid content concentration at the time of preparing the organic-inorganic hybrid polymer (B), an organic solvent can be added if necessary. Further, the organic solvent used in the preparation of the silyl group-containing polymer (b2) may be removed and a new organic solvent may be added.

[0101] The organic solvent, concentration of solids during the preparation organic-inorganic hybrid polymer (B), preferred lay (or 10 to 60 wt ^_0/0, more preferably (or 15 to 50 weight ^_0/0, especially ί this Preferably (amount in the range of 20 to 40% by weight can be added. The organic solvent used in the preparation of the silyl group-containing polymer (b2) is used as it is, and the organic-inorganic hybrid polymer (B ) When the solid concentration at the time of preparation is in the above range, an organic solvent may be added or not.

[0102] The reactivity of the silane compound (bl) and the specific silyl group-containing polymer (b2) can be controlled by adjusting the solid content concentration during the preparation of the organic-inorganic hybrid polymer (B). If the solid content concentration during the preparation of the organic-inorganic hybrid polymer (B) is less than the above lower limit, the reactivity between the silane compound (bl) and the specific silyl group-containing polymer (b2) may be lowered. If the solid content concentration during the preparation of the organic-inorganic hybrid polymer (B) exceeds the upper limit, gelation may occur. The amount of solid content at the solid content concentration mentioned here is the amount used in terms of solid hydrolysis condensate of the silane compound (bl) (Wbl) and the amount used in terms of solid content of the specific silyl group-containing polymer (b 2). This is the total amount of (Wb2).

[0103] The organic solvent is not particularly limited as long as the above components can be mixed uniformly. The alcohols exemplified as the organic solvent used in the production of the specific silyl group-containing polymer (b2), The ability to list aromatic hydrocarbons, ethers, ketones, esters, etc. In addition, these organic solvents may be used alone or in combination of two or more. [0104] (Stability improver)

In the present invention, in order to improve the storage stability of the organic-inorganic hybrid polymer composition, particularly the organic-inorganic hybrid polymer (B), the organic-inorganic hybrid polymer (B) is prepared, and if necessary, the stability is increased. It is preferable to add an improver. The stability improver used in the present invention is represented by the following formula (6):

R ¹⁰ COCH COR ¹¹ (6)

2

(In the formula, R ^1Q is methyl group, ethyl group, n-propyl group, i-propyl group, n butyl group, sec butyl group, t butyl group, n pentyl group, n hexyl group, cyclohexyl group, Represents a monovalent hydrocarbon group having 6 to 6 carbon atoms, such as a phenyl group, and R ¹¹ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a methoxy group, an ethoxy group, n- (Represents an alkoxyl group having 1 to 16 carbon atoms such as propoxy group, i-poxy group, n-butoxy group, sec-butoxy group, t-butoxy group, lauryloxy group, and stearoxy group.)

It is at least one compound selected from the group consisting of β-diketones, β-ketoesters, carboxylic acid compounds, dihydroxy compounds, amine compounds and oxyaldehyde compounds represented by

[0105] When organometallic compounds are used as the catalyst, it is preferable to add a stability improver represented by the above formula (6). By using the stability improver, the stability improver coordinates to the metal atom of the organometallic compound, and this coordination is excessive between the silane compound (bl) and the specific silyl group-containing polymer (b2). It is considered that the storage stability of the obtained organic-inorganic hybrid polymer composition, particularly the organic-inorganic hybrid polymer (B), can be further improved by suppressing the co-condensation reaction.

[0106] Examples of such stability improvers include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, acetoacetate t. --Butyl, hexane 2,4-dione, heptane 2,4 dione, heptane 3,5 dione, octane 2,4 dione, nonane 1,2,4 dione, 5 methyl hexane 1,4 dione, malonic acid, Oxalic acid, phthalic acid, glycolic acid, salicylic acid, aminoacetic acid, iminoacetic acid, ethylenediamine tetraacetic acid, glycol, catechol, ethylenediamine, 2, 2-biviridine, 1, 10-phenanthate Examples include phosphorus, diethylenetriamine, 2-ethanolamine, dimethyl darling oxime, dithizone, methionine, and salicylaldehyde. Of these, acetylacetone and cetyl acetate are preferred.

[0107] Further, the stability improver may be used alone or in combination of two or more.

[0108] The amount of the stability improver used in the present invention is usually 2 moles or more, preferably 3 to 20 moles per mole of the organometallic compound of the organometallic compound. If the amount of the stability improver is less than the above lower limit, the effect of improving the storage stability of the resulting composition will be insufficient.

[0109] (Preparation method of organic-inorganic hybrid polymer (B))

The organic-inorganic hybrid polymer (B) used in the present invention can be prepared by co-condensing the silane compound (bl) and the specific silyl group-containing polymer (b2). Particularly preferably, it can be prepared by adding a hydrolysis / condensation reaction application catalyst and water to a mixture of the silane compound (bl) and the specific silyl group-containing polymer (b2) to perform cocondensation.

[0110] At this time, the weight 匕 (Wbl / Wb2) between the content (Wbl) of the silane compound (bl) and the content (Wb2) of the specific silyl group-containing polymer (b2) is Wbl + Wb2 = 100 5 / 95-95 / 5, preferably 15/85 to 85/15. Wbl is a value converted into a complete hydrolysis condensate of the silane compound (M), and Wb2 is a value converted into a solid content of the specific silyl group-containing polymer (b2). When the weight ratio (Wbl / Wb2) is in the above range, it is possible to obtain a cured product having excellent weather resistance if it is transparent. Further, in the case of Wbl / Wb2 force, preferably 5/95 to 50/50, more preferably 15/85 to 40/60, the organic substrate surface such as an acrylic plate is organic without being treated with a primer or the like. Good adhesion to the substrate.

[0111] Specifically, the organic-inorganic hybrid polymer (B) is preferably prepared by the following methods (1) to (3).

[0112] (1) Water in the above range is added to a mixture of the silane compound (bl), the specific silyl group-containing polymer (b2), and the hydrolysis / condensation reaction catalyst, and the temperature is 40-80. The organic-inorganic hybrid polymer (B) is prepared by co-condensing the silane compound (bl) and the specific silyl group-containing polymer (b2) within 12 hours at ° C and a reaction time of 0.5 to 12 hours. Then, if necessary, other additives such as stability improvers may be added! / ヽ. [0113] (2) Using organosilane (1) as the silane compound (bl), adding water in the above range to the temperature, temperature of 40-80 ° C, time of 0.5-; Carry out the hydrolysis-condensation reaction of (1). Next, the specific silyl group-containing polymer (b2) and a catalyst for hydrolysis / condensation reaction are added and mixed, and further, the condensation reaction is carried out at a temperature of 40 to 80 ° C., a reaction time of 0.5 to 12 hours, and organic inorganic A hybrid polymer (B) is prepared. Then, if necessary, add other additives such as stability improvers.

[0114] (3) Water in the above range is added to a mixture of the silane compound (bl), the specific silyl group-containing polymer (b2) and the hydrolysis' condensation reaction catalyst, and the temperature is 40-80. The organic-inorganic hybrid polymer (B) is prepared by hydrolyzing and condensing the silane compound (bl) and the specific silyl group-containing polymer (b2) in 12 hours. Then, if necessary, add other additives such as a stability improver.

[0115] From the viewpoint of ensuring the storage stability of the organic-inorganic hybrid polymer (B) obtained above and the subsequent dispersion stability of the metal oxide fine particles, it may be washed with water as a decatalyzing step after hydrolysis condensation. good. In particular, when a basic compound is used as the hydrolysis-condensation catalyst, it is more preferable to carry out water washing after neutralization with an acidic compound after the reaction.

[0116] As the acidic compound used for neutralization, the acidic compounds exemplified above can be used.

The amount of the acidic compound used is usually 0.5 to 2.0 monole, preferably 0.8 to 1.5 monole, more preferably 0.9 to 1. mol per 1 mol of the basic compound used for hydrolysis condensation. 3 mono. When an acidic compound is used by dissolving in water, it is usually 10 to 500 parts by weight, preferably 20 to 200 parts by weight with respect to 100 parts by weight in total of the silane compound (bl) and the specific silyl group-containing polymer (b2). Dissolve in 300 parts, more preferably 30-200 parts of water. After neutralization, the mixture is sufficiently stirred and allowed to stand, and after confirming phase separation between the aqueous phase and the organic solvent phase, the lower layer moisture is removed.

[0117] The water used for the water washing after neutralization is usually 10 to 500 parts by weight, preferably 20 to 300 parts per 100 parts by weight in total of the silane compound (bl) and the specific silyl group-containing polymer (b2). 30 to 200 parts, more preferably 30 to 200 parts.

[0118] Washing with water is performed by adding water, stirring sufficiently, and then allowing to stand, and after confirming phase separation between the aqueous phase and the organic solvent phase, removing the moisture in the lower layer. The number of washings is preferably 1 or more times, more preferably 2 or more times. [0119] On the other hand, when a metal chelate compound is used as the hydrolysis-condensation catalyst, it is preferable to add the stability improver after the reaction.

[0120] The weight-average molecular weight of the organic-inorganic hybrid polymer (B) obtained by the above method is usually 3,0 in terms of polystyrene measured by gel permeation chromatography.

00—200,000, preferred <is 4,000—150,000, more preferred <is 5,000—100,000.

[Oxide fine particle-containing organic-inorganic hybrid polymer composition]

The organic fine particle-containing organic / inorganic hybrid polymer composition according to the present invention comprises an oxide fine particle (A) and an organic / inorganic hybrid polymer (B), phosphoric acid having an organic group having 6 or more carbon atoms or an oxyalkylene group. It can be obtained by mixing with an organic solvent in the presence of a basic compound, an acidic compound or a metal chelate compound and subjecting it to a dispersion treatment, without using a compound having s.

[0122] (Organic solvent)

Examples of the organic solvent include the organic solvents exemplified in the organic-inorganic hybrid polymer (B). Among these organic solvents, organic solvents other than alcohols such as methyl ethyl ketone, methyl isobutyl ketone, diisoptyl ketone, and the like in that the dispersion stability of the organic inorganic hybrid polymer composition containing fine oxide particles is good. Toluene, xylene, ethyl acetate, butyl acetate, and mixtures thereof are preferred. These organic solvents are preferably used in a state where moisture has been removed by dehydration in advance.

[0123] The amount of the organic solvent used is not particularly limited as long as it is an amount that can uniformly disperse the oxide fine particles (A)! /, But the solid content of the obtained organic / inorganic hybrid polymer composition containing oxide fine particles is not limited. The concentration is preferably 5 to 80% by weight, more preferably 7 to 70% by weight, and particularly preferably 10 to 60% by weight.

[0124] (Basic compounds, acidic compounds and metal chelate compounds)

Examples of the basic compound, acidic compound, and metal chelate compound include the compounds exemplified in the organic-inorganic hybrid polymer (B). Of these basic compounds, acidic compounds and metal chelate compounds, basic compounds and acidification Triethylamine, tetramethylammonium hydroxide, and pyridine are particularly preferred, in which a basic compound in which a compound is preferred and an organic amine compound in which a compound is preferred is more preferred.

[0125] The basic compound, acidic compound or metal chelate compound is usually added to the oxide fine particle-containing organic-inorganic hybrid polymer composition of the present invention in an amount of 0.00 with respect to 100 parts by weight of the oxide fine particles (A). ! ~ 20 parts by weight, preferably 0.005 ~ 10 parts by weight, more preferably 0.0;! ~ 5 parts by weight, more preferably 0.01 ~; It is desirable to contain 5 parts by weight. When the basic compound, acidic compound or metal chelate compound is in the above range, the composition of the oxide fine particle-containing polysiloxane exhibits good dispersion stability.

[0126] (Method for Producing Oxide Fine Particle-Containing Organic-Inorganic Hybrid Polymer Composition)

The above-mentioned organic / inorganic hybrid polymer composition containing fine oxide particles is obtained by adding oxide fine particles (A), an organic / inorganic hybrid polymer (B), a basic compound, an acidic compound or a metal chelate compound to an organic solvent. The oxide fine particles (A) can be prepared by dispersing them sufficiently in an organic solvent. At this time, it is particularly preferable to use a known disperser such as a ball mill, a sand mill (bead mill, a high shear bead mill), a homogenizer, an ultrasonic homogenizer, a nanomizer, a propeller mixer, a high shear mixer, or a paint shaker. A dispersed fine particle dispersion ball mill and a sand mill (bead mill, high shear bead mill) are preferably used. As described above, when the oxide fine particles (A) are mixed with the organic / inorganic nano- or hybrid polymer (B) in the presence of a basic compound, acidic compound or metal chelate compound, the basic compound, acidic compound or metal chelate is mixed. The organic-inorganic hybrid polymer (B) condensation reaction proceeds on the surface of the oxide fine particles (A) by the catalytic action of the oxide compound, and the surface of the oxide fine particles (A) becomes hydrophobic and is finely dispersed in the organic solvent. It is assumed that it will be easy to do.

[0127] The organic / inorganic hybrid polymer composition containing fine oxide particles of the present invention is preferably an organic-inorganic hybrid polymer (B) based on 100 parts by weight of the fine oxide particles (A) in terms of complete hydrolysis condensate. 1 to 1000 parts by weight, more preferably 5 to 900 parts by weight, and particularly preferably 10 to 800 parts by weight.

[0128] Also, the above-mentioned organic / inorganic hybrid polymer composition containing fine oxide particles comprises fine oxide particles. The child (A) is a highly dispersed composition having a volume average dispersed particle size of 300 nm or less, preferably 200 nm or less, more preferably 150 nm or less.

[Curing body]

Coating the oxide fine particle dispersion of the present invention on a substrate or the like, and removing the solvent by drying to cure the polyfunctional polysiloxane, thereby forming a cured body (film) having excellent transparency. Power S can be. Since this cured product contains the organic-inorganic hybrid polymer (B), it is excellent in weather resistance, flexibility and followability to the substrate. Moreover, when the said base material is an organic base material, the adhesiveness of a base material and a hardening body improves further by processing the surface of an organic base material with a primer. In particular, the weight ratio (Wbl / Wb2) of the content (Wbl) of the silane compound (bl) and the content (Wb2) of the specific silyl group-containing polymer (b2) is preferably 50 / 50-95 / 5, More preferably, when the organic / inorganic hybrid polymer (B) of 60/40 to 85/15 is used, the effect of primer treatment is great. Examples of the primer include a solution containing the specific silyl group-containing polymer (b2).

[0130] [Example]

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the examples. In the examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight” unless otherwise specified. Further, various measurements in Examples and Comparative Examples were performed by the following methods.

[0131] [GPC measurement]

The weight average molecular weights of the specific silyl group-containing polymer and the organic-inorganic hybrid polymer are shown as polystyrene conversion values measured by gel permeation chromatography under the following conditions.

Equipment: HLC-8120C (manufactured by Tosohichi Corporation)

Column: TSK—gel MultiporeH —M (Toso Co., Ltd.)

XL

Eluent: THF, flow rate 0.5 mL / min, load 5.0%, 100 L

(Dispersibility 1)

The appearance of the obtained composition was visually observed. The volume average dispersed particle size of the composition in which no sedimentation of the fine particles was observed was measured using a microtrack ultrafine particle size distribution meter (manufactured by Nikkiso Co., Ltd. UPA150 ") and evaluated according to the following criteria.

A: No separation / sedimentation. Volume average dispersed particle size ≤200nm.

B: No separation / sedimentation. 200 nm <volume average dispersed particle size ≦ 300 nm.

C: No separation / sedimentation. 300 nm <volume average dispersed particle size.

D: There is separation and sedimentation.

[0132] [Dispersibility 2]

Dispersibility was also evaluated according to the following criteria. That is, the appearance of the obtained composition was visually observed. The volume average dispersed particle size of the composition in which no sedimentation of fine particles was observed was measured with a Microtrac ultrafine particle size distribution meter (“UPA150” manufactured by Nikkiso Co., Ltd.) and evaluated according to the following criteria.

AA: No separation / sedimentation. Volume average dispersed particle size ≤ 150nm.

A: No separation / sedimentation. 150 nm <volume average dispersed particle size ≦ 200 nm.

D: There is separation and sedimentation.

[0133] [Paint transparency]

After coating the obtained composition on a quartz glass plate so that the dry film thickness is 5 inches, 1

A cured product having a thickness of 5 m was produced on a quartz glass plate by drying and curing at 00 ° C. for 1 hour. The cured product was measured for spectral transmittance at a wavelength of 500 to 700 nm with an ultraviolet-visible spectrophotometer and evaluated according to the following criteria.

A: Light transmittance is over 90%.

B: Light transmittance is 70% or more and 90% or less.

C: Light transmittance is less than 70%.

[0134] [Yellowness]

The obtained composition was applied on a quartz glass plate so that the dry film thickness was 5 in, and then dried and cured at 100 ° C. for 1 hour to form a cured product having a thickness of 5 m on the quartz glass plate. Produced. The light transmittance of this cured product at a wavelength of 450 nm was measured with an ultraviolet-visible spectrophotometer and evaluated according to the following criteria. A: Light transmittance is over 90%.

8: Light transmittance is 70 to 90%.

C: Light transmittance is less than 70%.

[0135] [Weather resistance]

To 100 parts of the resulting composition, add 5 parts of i-butyl alcohol solution of dioctyltin dimaleate ester (solid content concentration of about 10%) and add a well-stirred solution to the surface as needed. After applying to the treated acrylic board (trade name: Atarilite # 001, manufactured by Engineering Test Service Co., Ltd.) so that the dry film thickness is 2 πι, it is dried at 80 ° C for 30 minutes and cured ( Cured film) was formed. In addition, the primer treatment was carried out using 100 parts by weight of the solution containing the specific silyl group-containing polymer (b2-1) obtained in Preparation Example 11 below, and i-butyl alcohol solution of dioctyltin dimaleate ester (solid content concentration: about 10%) A solution obtained by adding 10 parts of the mixture and stirring sufficiently was applied so that the dry coating film was 1, im.

[0136] About the obtained cured product, sunshine weather meter according to JIS K5400

An irradiation test for 2,000 hours was conducted with Suga Test Instruments Co., Ltd., and the appearance was visually observed and evaluated according to the following criteria. In addition, a tape peeling test was performed using cellophane tape (trade name: Cellotape (registered trademark) No. 405) manufactured by Nichiban Co., Ltd., and the adhesion was evaluated according to the following criteria.

(Appearance) A: No crack, no peeling of film No change before and after irradiation test

B: Film does not peel off, but some cracks

C: The film does not peel off, but there are cracks on the entire surface

D: Film peeling

(Adhesiveness) AA: No peeling of film on all parts where tape is applied

A: Less than 5% of the part where the tape is applied is peeled off

B: Of the part where the tape is applied, the part where the film is peeled is 5-50%

C: Over 50% of the part where the tape is affixed.

[Preparation of specific silyl group-containing polymer (b2)]

<Preparation Example 1 1> In a reactor equipped with a reflux condenser and a stirrer, _add 55 parts of methyl methacrylate, 5 parts of ₂ - _ethyl hexyl acrylate, 5 parts of cyclohexyl methacrylate, 10 parts of _{プロ -methacryloxypropyltrimethoxysilane} , Add 20 parts of glycidyl metatalylate, 4 parts of 4- (meth) atalyloyloxy 2, 2, 6, 6 5 parts of tetramethylpiperidine, 75 parts of i-butyl alcohol, 50 parts of methyl ethyl ketone and 25 parts of methanol, and stir. While heating to 80 ° C. A solution prepared by dissolving 3 parts of azobisisovaleronitryl in 8 parts of xylene was added dropwise to this mixture over 30 minutes, and then reacted at 80 ° C. for 5 hours. After cooling, 36 parts of methylethylketone was added, the solid content concentration was 35%, the Mw measured by GPC method was 12,000, and the content of carbyl in the solid content was 1.1% by weight. A solution containing the union (b2 1) was obtained.

Similar to Preparation Example 1-1, except that 20 parts of 2-hydroxyethyl methacrylate were used instead of 20 parts of glycidyl methacrylate, the solid content concentration was 35%, Mw was 13,000, solid A solution containing a specific silyl group-containing polymer (b2-2) having a carbon content of 1.1% by weight in the form was obtained.

A reactor equipped with a reflux condenser and a stirrer was charged with 30 parts of methyl methacrylate, 10 parts of n-propyl acrylate, 10 parts of γ-methacryloxypropyltrimethoxysilane, glycidyl methacrylate.

0 parts, 2— (2′-hydroxy-1 5′-methacryloxychetylphenyl) 2Η 20 parts of benzotriazole, 75 parts of i-butinoreanolanolone, 50 parts of methyl ethyl ketone and 25 parts of methanol After mixing, the mixture was heated to 80 ° C. with stirring. A solution prepared by dissolving 4 parts of azobisisovaleronitryl in 10 parts of xylene was added dropwise to this mixture over 30 minutes, and then reacted at 80 ° C. for 5 hours. After cooling, 83 parts of methylethylketone was added to contain a specific silyl group with a solid content of 30%, Mw measured by GPC method of 10,000, and the content of silicon in the solid content was 1.1% by weight. A solution containing the polymer (b2-3) was obtained.

In a reactor equipped with a reflux condenser and stirrer, add 75 parts of methyl metatalylate, 2 5 parts of _norhexyl acrylate, 5 parts of cyclohexyl methacrylate, 5 parts of _{クリ -methacryloxypropiperidine} , 75 parts of i- _butino - _{reanolanolone} , 50 parts of methyl ethyl ketone and 25 parts of methanol After mixing, the mixture was heated to 80 ° C with stirring. A solution prepared by dissolving 3 parts of azobis isovaleritol in 8 parts of xylene was added dropwise to this mixture over 30 minutes, followed by reaction at 80 ° C. for 5 hours. After cooling, 35 parts of methyl ethyl ketone was added, the solid content concentration was 35%, the Mw measured by GPC method was 8,000, and the content of carbene in the solid content was 1.1% by weight. A polymer (b2-4) solution was obtained.

[0141] [Preparation of organic-inorganic hybrid polymer (B)]

In a reactor equipped with a stirrer and a reflux condenser, 24 parts of methyltrimethoxysilane and 10 parts of dimethyldimethoxysilane as the silane compound (bl) and the above-mentioned specific silyl group-containing polymer (b2) as the specific silyl group-containing polymer (b2) — 118 parts of a solution containing 1), 10 parts of i-propyl alcohol as the organic solvent (e), and 2 parts of a di-propoxy-ethyl acetate acetate aluminum 75% dilute solution of di-propoxy-ethyl acetate acetate as the hydrolysis / condensation reaction catalyst. The mixture was mixed and heated to 50 ° C with stirring. 6 parts of water (corresponding to 0.48 mol per 1 mol of all OR ² groups in the silane compound (M)) was dropped into this over 30 minutes, and then reacted at 60 ° C for 4 hours. A solution containing an organic-inorganic hybrid polymer (B-1) having an Mw of 13,000 measured by the GPC method was obtained. Thereafter, 2 parts of acetylylacetone as a stability improver was added and stirred for 1 hour, then cooled to room temperature, and 29 parts of methylisobutyl ketone as a diluent solvent was added to adjust the solid content concentration to 20% by weight.

[0142] <Preparation Example 2-2 to 2-9>

A solution containing the organic-inorganic hybrid polymer (B-2) to (B-9) (both solid content concentration: 20% by weight) in the same manner as in Preparation Example 21 except that each component was changed to the components shown in Table 1. ) Was prepared. The results are shown in Table 1.

[0143] [Table 1]

[Example 1]

100 parts by weight of powdery rutile-type titanium oxide fine particles (primary average particle size: 30 nm) and 500 parts by weight of a solution containing the organic-inorganic hybrid polymer (B-1) (100 parts by weight in terms of solid content), 0.1 part by weight of triethylamine and 400 parts by weight of methyl isobutyl ketone are put in a container, and 2000 parts by weight of 0.1 mm diameter zircoyu beads are added to this mixture, followed by stirring at 1500 rpm for 1 hour using a beads mill. Disperse the fine particles, solid content concentration 20 weight % Oxide fine particle-containing organic-inorganic hybrid polymer composition (1) was obtained. The results of evaluating the properties of this composition are shown in Table 21.

[0145] [Example 2]

Powdered zinc oxide fine particles (primary average particle size:

20 nm) A metal oxide fine particle-containing organic-inorganic hybrid polymer composition (2) having a solid content concentration of 20% by weight was prepared in the same manner as in Example 1 except that 100 parts by weight were used. The results of the evaluation of the properties of this composition are shown in Table 21.

[Example 3]

A metal oxide having a solid content concentration of 20% by weight in the same manner as in Example 1 except that 100 parts by weight of powdery zirconium oxide fine particles (primary average particle size: 20 nm) were used instead of the rutile type titanium oxide fine particles. A fine particle-containing organic-inorganic hybrid polymer composition (3) was prepared. The results of evaluating the properties of this composition are shown in Table 21.

[Example 4]

Examples were used except that 0.1 part by weight of methanesulfonic acid was used instead of triethylamine.

In the same manner as in 2, a metal oxide fine particle-containing organic-inorganic hybrid polymer composition (4) having a solid content concentration of 20% by weight was prepared. The results of evaluating the properties of this composition are shown in Table 2-1.

[Example 5]

Similar to Example 2 except that 500 parts by weight of the solution containing the organic-inorganic hybrid polymer (B-2) (100 parts by weight in terms of solid content) was used instead of the solution containing the organic-inorganic hybrid polymer (B-1). Thus, an organic-inorganic hybrid polymer composition (5) containing metal oxide fine particles having a solid content concentration of 20% by weight was prepared. The results of evaluating the properties of this composition are shown in Table 21.

[Example 6]

Similar to Example 2 except that 500 parts by weight of the solution containing the organic-inorganic hybrid polymer (B-3) (100 parts by weight in terms of solid content) was used instead of the solution containing the organic-inorganic hybrid polymer (B-1). Thus, an organic-inorganic hybrid polymer composition (6) containing metal oxide fine particles having a solid content concentration of 20% by weight was prepared. The results of evaluating the properties of this composition are shown in Table 2. Shown in 1.

[0150] [Example 7]

The same as Example 2 except that 500 parts by weight of the solution containing the organic-inorganic hybrid polymer (B-4) (100 parts by weight in terms of solid content) was used instead of the solution containing the organic-inorganic hybrid polymer (B-1). Thus, an organic-inorganic hybrid polymer composition (7) containing metal oxide fine particles having a solid content concentration of 20% by weight was prepared. The results of evaluating the properties of this composition are shown in Table 21.

[0151] [Examples 8 to 12]

Other than using 500 parts by weight (100 parts by weight in terms of solid content) of a solution containing organic-inorganic hybrid polymers (B-5) to (B-9) in place of the solution containing organic-inorganic hybrid polymer (B-1) In the same manner as in Example 2, metal oxide fine particle-containing organic-inorganic hybrid polymer compositions (8) to (; 12) having a solid content concentration of 20% by weight were prepared. The results of evaluating the properties of this composition are shown in Table 21.

[0152] [Comparative Example 1]

100 parts by weight of powdery rutile-type titanium oxide fine particles (primary average particle size: 30 nm) and 500 parts by weight of a solution containing the organic-inorganic hybrid polymer (B-1) (100 parts by weight in terms of solid content), 9 parts by weight of polyoxyethylene alkyl phosphate ester (manufactured by Enomoto Kasei Co., Ltd., trade name: PL ADD EDI 51), 5 parts by weight of acetylylacetone, and 400 parts by weight of methyl isobutyl ketone are placed in a container. Add 2000 parts by weight of 0.1 mm diameter Zircoyu beads to the mixture, and stir at 1500 rpm for 1 hour using a bead mill to disperse the fine particles. Oxide fine particle-containing organic / inorganic hybrid polymer with a solid concentration of 20% by weight A composition (C1) was obtained. The results of evaluating the properties of this dispersion are shown in Table 2-2.

[Comparative Example 2]

Powdery rutile type titanium oxide fine particles were dispersed in methylisoptyl ketone in the same manner as in Example 1 except that triethylamine was not used, but the titanium oxide fine particles settled.

[Comparative Example 3]

Example 1 except that the solution containing the organic-inorganic hybrid polymer (B-1) was used. In the same manner as above, powdery rutile-type titanium oxide fine particles were dispersed in methylisobutyl ketone, but the titanium oxide fine particles settled.

[0155] [Comparative Example 4]

Titanium oxide fine particle water dispersion (Ishihara Sangyo Co., Ltd. “STS-01”, TiO concentration 30% by weight, titanium oxide fine particle volume level)

2

Uniformly dispersed particle size: 60 nm, organic dispersant: 0 wt%) 300 parts by weight is put in a container, and 500 parts by weight of the solution containing the above organic-inorganic hybrid polymer (B-1) is added (100% in terms of solid content). Part by weight) and 400 parts by weight of methylisobutyl ketone, and further 2000 parts by weight of 0.1 mm diameter zircoyu beads were added to this mixture, and the mixture was stirred at 1500 rpm for 1 hour using bead minole. The titanium oxide fine particles settled.

[0156] [Comparative Example 5]

Instead of the solution containing the organic-inorganic hybrid polymer (B-1), polysiloxane with Mw = 20,000 (GE Toshiba Silicone Co., Ltd., trade name: XR31—B2733U00 parts by weight and methinoisoisobutyl ketone 400 weights) A metal oxide fine particle-containing polysiloxane composition (C5) having a solid content concentration of 20% by weight was obtained in the same manner as in Example 1 except that the solution containing the components was used. Is shown in Table 2-2.

[0157] [Table 2-1]

[Table 2 1]

[Table 2-2]

Claims

The scope of the claims

[1] In the presence of a basic compound, acidic compound or metal chelate compound in an organic solvent,

(A) silicon oxide fine particles and / or metal oxide fine particles, and

(B) Following formula (1)

R ¹ Si (OR ² ) ― (1)

At least one silane compound (bl) selected from the group consisting of at least one organosilane, a hydrolyzate of the organosilane, and a condensate of onoleganosilane, and a hydrolyzable group and / or Alternatively, the oxide fine particles (A) are mixed with an organic-inorganic hybrid polymer obtained by hydrolysis / condensation reaction with a polymer (b2) having a silyl group containing a silicon atom bonded to a hydroxyl group. An organic-inorganic hybrid polymer composition containing oxide fine particles obtained by dispersing in a solvent.

2. The oxide fine particle-containing organic-inorganic hybrid polymer according to claim 1, wherein the oxide fine particles (A) and the organic-inorganic hybrid polymer (B) are mixed in the presence of a basic compound. Composition.

3. The oxide fine particle-containing organic-inorganic hybrid polymer composition according to claim 1 or 2, wherein the oxide fine particles (A) and the organic-inorganic hybrid polymer (B) are mixed by a bead mill. .

[4] The organic-inorganic hybrid polymer (B) is mixed in an amount of 1 to 1000 parts by weight in terms of complete hydrolysis condensate with respect to 100 parts by weight of the oxide fine particles (A). The organic-inorganic hybrid polymer composition containing oxide fine particles according to any one of.

[5] The silane compound (bl) and the polymer (b2) are combined into a completely hydrolyzed condensate content (Wbl) of the silane compound (bl) and a solid content content of the polymer (b2). The weight ratio (Wbl / Wb2) to (Wb2) is in the range of 5/95 to 95/5, where Wbl + Wb2 = 100. ] The oxide fine particle-containing organic-inorganic hybrid polymer composition according to any one of claims 1 to 4, wherein the composition is hydrolyzed / condensed.

[6] In the polymer (b2), the content of the silyl group containing a hydrolyzable group and / or a silicon atom bonded to a hydroxyl group is converted into the content of the silicon atom, The organic fine particle-containing organic-inorganic hybrid polymer composition according to any one of claims 5 to 6, wherein the content is from 0 to 2% by weight.

[7] A cured product obtained from the organic-inorganic hybrid polymer composition containing oxide fine particles according to any one of claims 6 to 6.

[8] A coating composition comprising the organic fine particle-containing organic-inorganic hybrid polymer composition according to any one of claims 6 to 6.

[9] A laminate having an organic substrate and a coating film obtained from the coating composition according to claim 8, provided on the organic substrate.

[10] Formula (1)

R ¹ Si (OR ² ) ― (1)

At least one silane compound (bl) selected from the group consisting of at least one organosilane, a hydrolyzate of the organosilane, and a condensate of onoleganosilane, and a hydrolyzable group and / or Alternatively, after preparing an organic-inorganic hybrid polymer (B) by hydrolyzing and condensing a polymer (b2) having a silyl group containing a silicon atom bonded to a hydroxyl group,

The organic-inorganic hybrid polymer (B) is mixed with the fine oxide particles and / or fine metal oxide particles (A) in an organic solvent in the presence of a basic compound, acidic compound or metal chelate compound. A method for producing an oxide fine particle-containing organic-inorganic hybrid polymer composition.

11. The oxide fine particle-containing organic-inorganic hybrid polymer according to claim 10, wherein the oxide fine particles (A) and the organic-inorganic hybrid polymer (B) are mixed in the presence of a basic compound. A method for producing the composition.

[12] The oxide fine particles (A) and the organic-inorganic hybrid polymer (B) are mixed with a bead mill. 12. The method for producing an organic inorganic hybrid polymer composition containing oxide fine particles according to claim 10 or 11, wherein the mixture is mixed.

[13] The organic-inorganic hybrid polymer (B) is mixed in an amount of 1 to 1000 parts by weight in terms of complete hydrolysis condensate with respect to 100 parts by weight of the oxide fine particles (A). A process for producing an organic-inorganic hybrid polymer composition containing oxide fine particles according to any one of 12;

[14] The content of the silane compound (bl) and the polymer (b2) in terms of the completely hydrolyzed condensate of the silane compound (bl) (Wbl) and the content of the polymer (b2) in terms of solid content The weight ratio (Wbl / Wb2) to (Wb2) is in the range of 5/95 to 95/5, where Wbl + Wb2 = 100. 14. The method for producing an oxide fine particle-containing organic-inorganic hybrid polymer composition according to any one of claims 10 to 13;

[15] In the polymer (b2), the content of the silyl group containing a hydrolyzable group and / or a silicon atom bonded to a hydroxyl group is converted into the content of the silicon atom, The method for producing an organic inorganic hybrid polymer composition containing oxide fine particles according to any one of claims 10 to 14, wherein the content is from! To 2% by weight.