JPH03244637A - Spherical composite particle, its production and dispersion thereof - Google Patents

Abstract

PURPOSE:To obtain the title particle having a reduced mean diameter, a narrow diame ter distribution, a specified shape, and improved dispersion properties by incorporating a polysiloxane and a vinyl polymer into the particles and specifying the mean diameter, standard deviation of diameter, and ratio of the major to minor diameter. CONSTITUTION:The title particle having a mean diameter of 0.05-30 mum, a standard deviation of the diameter of 1.0-2.5, and a ratio of the major to minor diameter of 1.0-1.2 and contg. 97-30 wt.% polysiloxane of formula V (wherein (n) is 0-3; and R is a (substd.) hydrocarbon group having a C atom directly attached to the Si atom and having no radical polymerizability) and 3-70 wt.% vinyl polymer is prepd. by dispersing a silanol compd. and a vinyl compd. in a wt. ratio of (99:1) to (33:67) in an aq. medium, hydrolyzing and polymerizing the silanol compd. and polymerizing the vinyl compd. in the presence of a radical polymn. catalyst. The silanol compd. contains a silanol group-forming silicon compds. of formula I [wherein R<1> is as de scribed above 3 is 1-4C alkoxy(-contg. alkoxyethyoxy), 2-4C acyloxy, 1-4C alkyo-contg. N, N-dialkylamino, OH, halogen, or H] and/or formula II and comprises a compd. shown by formula III or IV (wherein (p) is 0-3; (q) is 3-20; and R<2> and R<3> are each R<1>).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to spherical composite fine particles, a method for producing the same, and a dispersion thereof.

BACKGROUND OF THE INVENTION In order to modify coatings, cosmetics, rubber, plastics, paper, etc., fine particles are added during their manufacturing or processing steps. In recent years, such fine particles have become popular because their properties can be easily designed and controlled.
Spherical fine particles with a narrow particle size distribution are attracting attention.

The present invention relates to spherical fine particles having a narrow particle size distribution as described above, particularly spherical composite fine particles mainly formed from polysiloxane and a vinyl polymer, a method for producing the same, and a dispersion thereof.

<Conventional technology and its problems> Conventionally, as the above-mentioned fine particles, polystyrene, polyvinyl acetate, polyethylene, nylon, epoxy resin,
Various types of fine particles such as phenol resin and polysiloxane have been proposed. Among these, as polysiloxane-based fine particles, silica particles (J, Co11oid a
nd Interface Sci, Volume 26, 62~
69.1968), polymethylsilsesquioxane particles (Japanese Unexamined Patent Publication No. 63-77940), polyorgan/siloxane particles (Japanese Unexamined Patent Publication No. 63-312324), etc., and modifications using such polysiloxane-based fine particles have been proposed. Regarding the quality, when this is added to polyester film,
There are also reports that it can impart good lubricity (
Japanese Patent Publication No. 59-171623).

However, these conventional microparticles have the following problems: 1) They are easily broken by mechanical impact, 2) They are difficult to disperse in media and polymeric materials, and 3) They are difficult to disperse in media and polymeric materials.
Poor dispersion stability; 4) irregular particle shape and particle size distribution;
In reality, there is a problem that it is difficult to obtain the modification as designed.

<Problems to be Solved by the Invention, Means for Solving the Problems> The present invention provides new spherical composite fine particles, a method for producing the same, and a dispersion thereof, which solve the conventional problems as described above.

However, as a result of intensive research to obtain micron-order spherical particles with a narrow particle size distribution that solves the problems 1) to 4) above, the inventors of the present invention have found that both are integrally mixed together, and both are integrated. The present inventors have found that specific spherical composite fine particles mainly formed from a specific polysiloxane and a specific vinyl polymer that are not substantially covalently bonded are suitable, and have completed the present invention.

That is, the present invention provides the following polysiloxane (I) and the following polysiloxane (II), in which both are integrally mixed and both are not substantially covalently bonded.
), the polysiloxane/vinyl polymer has a ratio of 97/3 to 30/70 (volume ratio), and has an average particle size of 0.
．． 05~30gm, standard deviation value of particle size is 1.0~2
．． 5. The present invention also relates to spherical composite fine particles characterized in that the ratio of the major axis to the minor axis is 1.0 to 162, a method for producing the spherical composite fine particles, and a dispersion of the spherical composite fine particles.

(I): A polysiloxane consisting of one or more types of structural units represented by the general formula [Rn5iO(i-n)z21, and where n is 1 or less, at least 15
Polysiloxane containing mol% or more.

[However, n is an integer of 0 to 3, R is an unsubstituted or substituted hydrocarbon group X having a carbon atom directly bonded to a silicon atom, and a hydrocarbon group having no radical polymerizability.] (TI ): A vinyl polymer obtained by polymerizing one or more vinyl monomers that have no reactivity with silanol groups and silanol group-forming atomic groups.

In the present invention, the average particle size is 50
The major diameter of each selected particle (
The longest diameter passing through the center of the particle = Dt) and the shortest diameter (shortest diameter passing through the center of the particle - Ds) were measured and calculated (OL+
Ds)/2, and the ratio of the major axis to the minor axis is the average value of DL105 measured and calculated in the same manner. The standard deviation f〆1 of the particle size is the image obtained by centrifugal sedimentation type particle size phase separation measurement. The deviation value is in the range of 1.0 to 2.5, and the ratio of the major axis to the minor axis is in the range of 1.0 to 1.2, and the ratio of the major axis to the minor axis is 1.0 to 2.5. It is spherical because it is in the range of 1.2, but among these, for purposes of purpose, the average particle size is 0.1 to logm, and the standard deviation value of the particle size is 1.
It is in the range of 0 to 2.0, and the ratio of the major axis to the minor axis is 1.
Those in the range of 0 to 1.1 are preferred.

The polysiloxane, which is one of the main components of the spherical composite fine particles of the present invention, is a polysiloxane consisting of one or more constituent units represented by the general formula (I) above, and It is a polysiloxane containing at least 15 mol% or more of a structural unit in which n is 1 or less. Specifically, [5i02], [R5103/21. [
RzSiO] or [R35iO+721] A polysiloxane consisting of one or more types of structural units, and where n is 1 or less, that is, one of the structural units represented by [5i02] or [R91Ch/2] species or two
At least 15 mol% or more, preferably 20 mol% of seeds
This is a polysiloxane containing the above. If the content of the structural unit in which n is 1 or less is less than 15 mol %, it is not possible to obtain spherical composite fine particles having the characteristics related to the particle size as described above.

In the structural unit of polysiloxane as described above, R is an unsubstituted or W1-substituted hydrocarbon group having a carbon atom directly bonded to a silicon atom, but among such hydrocarbon groups, a hydrocarbon group that does not have radical polymerizability It is a hydrogen group. The fact that R is a hydrocarbon group that does not have radical polymerizability is because the polysiloxane and vinyl polymer, which mainly form the spherical composite fine particles of the present invention, coexist integrally without substantially covalently bonding. is an essential requirement.

Examples of R when it is an unsubstituted hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, an aralkyl group II/1 &, among others, a methyl group, an ethyl group, a butyl group, etc. Alkyl radicals having 1 to 4 carbon atoms or phenyl radicals are advantageously chosen. Further, when R is a substituted hydrocarbon group, examples thereof include substituted hydrocarbon groups having halogen, epoxy group, cyano group, ureido group, etc. as substituents, and among them, γ-glycidoxyprobyl group, β-(3,4-epoxy)cyclohexylethyl, γ-chloropropyl, trifluoropropyl and the like are advantageously selected. These unsubstituted hydrocarbon groups and substituted hydrocarbon groups can be in any ratio.

The vinyl polymer, which is another component that mainly forms the spherical composite fine particles of the present invention, is a vinyl monomer that does not have reactivity with silanol groups and silanol group-forming atomic groups, as described in (II) above. It is a vinyl polymer obtained by polymerizing one type or 21a or more of the following. The vinyl polymer is obtained by polymerizing a vinyl monomer that has no reactivity with silanol groups and silanol group-forming atomic groups.1. This is an essential requirement for the polymer to coexist integrally with the polymer without substantially covalent bonding.

Examples of the vinyl polymers mentioned above include aromatic vinyl polymers such as polystyrene and polyα-methylstyrene, polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyvinyl acetate, polyvinyl propionate, and polyacrylonitrile. Vinyl copolymers such as aliphatic vinyl polymers, styrene/α-methylstyrene copolymers, styrene/acrylonitrile copolymers, styrene/methyl methacrylate copolymers, and styrene/divinylbenzene copolymers, methyl methacrylate/
Examples include crosslinked vinyl copolymers such as trimethylolpropane trimethacrylate copolymers, among others, aromatic vinyl polymers obtained by polymerizing styrene, α-methylstyrene, etc., or alkyl methacrylic acid or acrylic acid. Aliphatic vinyl polymers obtained by polymerizing esters are advantageously chosen.

The vinyl polymer in the present invention is as exemplified above.
Vinyl polymers obtained by polymerizing water-insoluble vinyl monomers are preferred, but vinyl copolymers obtained by copolymerizing water-insoluble vinyl monomers and water-soluble vinyl monomers may also be used. In this case, the copolymerization ratio of water-soluble vinyl monomer is
It can be arbitrarily selected as long as the vinyl copolymer obtained does not dissolve or swell excessively in water, but it is usually preferably 10 mol% or less.

The spherical composite fine particles of the present invention are mainly formed from the polysiloxane (I) and the vinyl polymer (II), both of which are integrally mixed and which are not substantially covalently bonded. The polysiloxane/vinyl polymer is in the range of 97/3 to 30/70 (weight ratio). When the proportion of polysiloxane is higher than this range, the resulting spherical composite fine particles tend to break due to mechanical impact, and their dispersibility in the polymeric material deteriorates. On the other hand, if the ratio of the vinyl polymer is higher than this range, the low energy properties of the obtained spherical composite fine particles due to polysiloxane will decrease.

Next, the method for producing the spherical composite fine particles of the present invention will be explained.

The silanol group-forming silicon compound is hydrated in an aqueous medium in which the following silanol group-forming silicon compound (III)/the following (■) vinyl monomer coexists in a weight ratio of 99/1 to 33/67. It is produced by condensation polymerization while being decomposed to once produce spherical fine particles of polysiloxane in which the vinyl monomer is mixed, and then by polymerizing the vinyl monomer in the presence of a radical polymerization catalyst.

(III): A silanol group-forming silicon compound represented by the general formula (V) or (VI), and R,'-S
Contains a silanol group-forming silicon compound represented by iX3 and/or a silanol group-forming silicon compound represented by SiXa in an amount of at least 15 mol% in terms of silicon of the total silanol group-forming silicon compounds. Silanol group-forming silicon compound.

General formula (V); R'p-9iXa-p General formula (VI); 2 [However, p is an integer of 0 to 3, q is an integer of 3 to 20, 1
lllJ2J3 is an unsubstituted or substituted hydrocarbon group having a carbon atom directly bonded to a silicon atom.

A hydrocarbon group that does not have radical polymerizability; X is an alkoxy group having 1 to 4 carbon atoms; an alkoxyethoxy group having an alkoxy group having 1 to 4 carbon atoms; N,N-dialkylamino group having 1 to 4 alkyl groups, hydroxyl group, halogen atom or hydrogen atom,] (■): Vinyl monomer having no reactivity with silanol group and silanol group-forming atomic group IML or two or more types.

The silanol group-forming silicon compound (III) is
A raw material for polysiloxane, which is one of the main components of the spherical composite fine particles of the present invention, which has the general formula (V) or (V
A silanol group-forming silicon compound represented by I) and a silanol group-forming silicon compound represented by R1 to 5ih and/or a silanol group-forming silicon compound represented by SiX4. At least 15 in terms of silicon of all silanol group-forming silicon compounds
It is a silanol group-forming silicon compound containing more than mol%. Specifically, the silanol group-forming silicon compound represented by the general formula (V) includes SiXa, R1SiX3. R1
The silanol group-forming silicon compound represented by 2SiX2 or R13SiX is 1. The silanol group-forming silicon compound used in the present invention is the silanol group-forming silicon compound represented by RISih and/or the silanol group-forming silicon compound represented by SiX4. A silanol group-forming silicon compound containing the compound in an amount of 15 mol % or more, preferably 20 mol % or more in terms of silicon based on the total silanol group-forming silicon compound. If the amount is less than 15 mol %, it is impossible to obtain spherical composite fine particles having the characteristics related to the particle size as described above.

A silanol group-forming silicon compound as described above.
'Te, -a formula (V) Also c (VI) (7) R1, R2
, R3 is an unsubstituted or substituted hydrocarbon group having a carbon atom directly bonded to a silicon atom, and is a hydrocarbon group having no radical polymerizability. This is the same as what was described above in section H.

In addition, in the above-mentioned silanol group-forming silicon compound, the general formula (V) or an alkoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group, or an alkoxy group having 1 to 4 carbon atoms such as a methoxyethoxy group or a butoxyethoxy group. an alkoxyethoxy group having 4 alkoxy groups, an acyloxy group having 2 to 4 carbon atoms such as an acetoxy group and a propioxy group, and an N,N-dialkylamide having an alkyl group having 1 to 4 carbon atoms such as a dimethylamino group and a diethylamino group. 7 group, a hydroxyl group, a halogen atom such as a chlorine atom or a bromine atom, or a hydrogen atom.

Therefore, more specifically, examples of the silanol group-forming silicon compound represented by SiX4 include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and tetrachlorosilane. Also, the above R
Silanol group-forming silicon compounds represented by ISih include methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, phenyltrimethoxysilane, methyltris(dimethylamino)silane, methyltrichlorosilane, phenyltrichlorosilane, and methyldichloro. Examples include methoxysilane, methyldichlorohydrodienesilane, methylsilanetriol, methyldichlorosilanol, methylchlorosilanediol, and the like. Furthermore, examples of the silanol group-forming silicon compound represented by R'2SiX2 include dimethyldimethoxysilane, dimethyljethoxysilane, methylphenyldimethoxysilane, dimethyldiacetoxysilane, dimethylbis(dimethylamino)silane, and dimethyldichlorosilane. , diethyldichlorosilane, diphenyldichlorosilane, dimethylchloromethoxysilane, methylethyldichlorosilane, dimethylsilanediol, diethylsilanediol, and the like. And the above R'3Si
Examples of the silanol group-forming silicon compound represented by Can be mentioned. All of the exemplified compounds are silanol group-forming silicon compounds when R1 in general formula (V) is a non-21-substituted hydrocarbon group; Examples of silanol group-based silicon compounds include epoxy groups such as γ-glycidoxyprobyltrimethoxysilane, γ-glycidoxyprobyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Containing silane compound, γ-chloropropyltrimethoxysilane,
Examples include haloalkyl group-containing silane compounds such as trifluoropropyltrimethoxysilane, ureido group-containing silane compounds such as γ-ureidopropyltrimethoxysilane, and cyano group-containing silane compounds such as cyanopropyltrimethoxysilane. Examples of the silanol group-forming silicon compound represented by the general formula (VI) include octamethylcyclotetrasiloxane and tetramethyltetraphenylcyclotetrasiloxane.

The vinyl monomer (IV) is a raw material for the vinyl polymer, which is another component that mainly forms the spherical composite fine particles of the present invention, and is reactive with silanol groups and silanol group-forming atomic groups. One or more types of vinyl monomers having no. Regarding such vinyl monomers, see (!■) above.
The same applies to the vinyl polymer described above.

More specifically, such vinyl monomers include:

Methacrylic esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, inbutyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, styrene, α-methyl Aromatic vinyl monomers such as styrene, other monovalent monomers such as vinyl acetate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol acrylate, polyethylene glycol dimethacrylate, divinylbenzene, glycerin trimethacrylate,
Divalent or higher monomers such as trimethylolpropane trimethacrylate, bisphenol A dimethacrylate, and jetoxylated bisphenol A dimethacrylate can be mentioned.

All of the above examples are water-insoluble vinyl monomers, but in addition to these, a small amount of water-soluble vinyl monomers such as acrylic acid and methacrylic acid, usually 10 mol% or less, are also used. You can leave it there.

When producing the spherical composite fine particles of the present invention, the above (
III) silanol group-forming silicon compound/(r
V) vinyl monomer is 99/1 to 33/67 (weight ratio)
The reaction is carried out in a state in which the particles coexist within the range of 1. If the reaction is outside this range, the desired spherical composite fine particles cannot be obtained.

The method for producing spherical composite fine particles of the present invention is roughly divided into a first step of producing polysiloxane and a second step of producing vinyl polymer.

In the first step, a silanol group-forming silicon compound as described above, which is a raw material for polysiloxane, is hydrolyzed in an aqueous medium in the presence of a vinyl monomer as described above, which is a raw material for a vinyl polymer. Polycondensation occurs. The aqueous medium used here is water or a homogeneous solvent system containing 30% by weight or more, preferably 50% by weight or more of water. In this case, solvents that can be used in addition to water include methanol, ethanol,
Water-soluble solvents include impropatol, acetone, tetrahydrofuran, and ethyl acetate.

The catalyst used for condensation polymerization while hydrolyzing a silanol group-forming silicon compound may be any conventionally known catalyst, such as ammonia, trimethylamine, triethylamine, organic bases such as tetraethylammonium hydroxide, sodium hydroxide, etc. , potassium hydroxide,
Inorganic bases such as sodium carbonate, sodium hydrogen oxide, sodium methoxide, titanium compounds such as tetramethoxytitanium and tetrabutoxytitanium, tin compounds such as dibutyltin oxide and dibutyltin laurate, and even P-
There are organic acids such as 1-luenesulfonic acid and dodecylbenzenesulfonic acid. Among these, ammonia, trimethylamine, and triethylamine are preferred because they have little effect on coexisting vinyl monomers and are easy to remove from the product.

The reaction of polycondensation while hydrolyzing is carried out by adding the silanol group-forming silicon compound and the vinyl monomer to an aqueous medium in which the catalyst is dissolved and stirring.The method of adding is not particularly limited, but - From the viewpoint of performance and operability, it is preferable to mix both components in advance and then add them to the reaction system.

The temperature and time for condensation polymerization while hydrolyzing vary depending on the type and concentration of raw materials, the type of solvent, the type and concentration of catalyst, etc., but the temperature is usually in the range of 0 to 90°C, preferably 0 to 60°C. and the time is usually in the range of 30 minutes to 24 hours. Thus, the first stage reaction is carried out to produce polysiloxane and obtain spherical fine particles of the polysiloxane in which vinyl monomer is mixed.

In the second step, vinyl monomers mixed in the spherical fine particles of polysiloxane are polymerized in an aqueous medium in the presence of a radical polymerization catalyst. Various methods are possible for transitioning from the first stage to the second stage. For example, if the catalyst used in the first stage has no problem with the second stage reaction, it can be used directly in the second stage.
If there is a problem, the catalyst can be removed or deactivated before proceeding to the second stage.

The aqueous medium in the second stage is the same as the aqueous medium in the first stage, but here it is preferable to use water alone as a solvent.

The radical polymerization catalyst used in polymerizing vinyl monomers may be conventionally known catalysts, such as persulfates such as potassium persulfate and ammonium persulfate, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, etc. .

Hydroperoxides such as cumene hydroperoxide, di-t-butyl peroxide, t-butyl perbenzoate, dicumyl peroxide, t-butyl peracetate, L-butyl peroctanoate, t-
Organic peroxides such as butyl perphthalate lauroyl peroxide, cyclohexanone peroxide, methyl isobutyl ketone peroxide, 2,2°-azobisisobutyronitrile, 2,2'-7zobis-2,4-dimethylvaleronitrile, 2-Carbamoylazoisobutyronitrile, dimethyl-2,2°-7zobisisobutyrate, 1,1°-azobiscyclohexanecarbonitrile azo compound of 1, persulfate/sodium thiosulfate/copper sulfate, hydro There are redox catalysts such as peroxide, ferrous sulfate, sodium pyrophosphate, sodium phosphate, hydroperoxide, ferrous sulfate, glucose, and sodium pyrophosphate.

The reaction of polymerizing the vinyl monomer is carried out by introducing a radical polymerization catalyst into an aqueous medium in which spherical fine particles of polysiloxane containing the vinyl monomer are dispersed under an inert gas atmosphere and stirring the mixture. The temperature at this time varies depending on various conditions, as in the case of the first stage, but is usually between room temperature and
The boiling point of the vinyl monomer is preferably in the range of 50 to 80°C. In this way, the ff12 step reaction is carried out to produce a vinyl polymer, and the desired compound is formed mainly from a polysiloxane and a vinyl polymer in which both are integrally mixed and both are not substantially covalently bonded. Obtain spherical composite fine particles.

The average particle diameter, standard deviation value of particle diameter, and ratio of major axis to minor axis of the obtained spherical composite fine particles depend on the type and concentration of the raw materials used, the type of solvent, the type and concentration of the catalyst, and also the reaction temperature and reaction time. etc., and can be adjusted by appropriately selecting and adjusting these conditions. It can also be adjusted by the presence of an emulsifier, a dispersant, etc. in the reaction system, and it can also be adjusted by crushing, dispersing, and classifying the resulting spherical composite fine particles in a dry or wet process.

When the spherical composite fine particles of the present invention are added as a modifier to paints, cosmetics, rubber, plastics, paper, etc., they can be directly added as they are, but usually the spherical composite fine particles are kept in a liquid or liquid state at room temperature. Advantageously, it is added as a dispersion in a solid organic or aqueous medium at a concentration of 1 to 40% by weight, preferably 5 to 30% by weight. In this case, the type of medium in which the spherical composite fine particles are dispersed can be appropriately selected depending on the object to be modified.8 For example, the spherical composite fine particles can be dispersed in oil-based ink or oil-based paint.

When used as a modifier for magnetic paint, examples of the medium include fatty acid esters such as ethyl acetate, aromatic hydrocarbons such as toluene and xylene, and ketones such as methyl ethyl ketone. When used as a modifier for plastic resins or coating agents, vinyl monomers such as styrene, (meth)acrylic acid esters, and vinyl acetate may be used as the medium, and the spherical composite fine particles may be treated with lubricating oil or fibers. When used as a modifier for commercial oils, mineral oil, liquid paraffin, various synthetic esters, more specifically butyl stearate,
Examples include organic media such as 2-ethylhexyl palmitate, trimethylolpropane, trifatty acid esters, polyethers, and polydimethylsiloxane. When the spherical composite fine particles are used as a modifier for a mold release agent in mold molding of thermoplastic resin or thermosetting resin, the medium may be a room-temperature material such as hydrocarbon wax, sherry, natural or synthetic ester wax, etc. Solid organic media are mentioned below. When the spherical composite fine particles are used as a modifier for cosmetics or water-based paints or paper coating agents, the medium may be water, an aqueous medium prepared by mixing water and a water-soluble organic solvent, or more specifically water-based medium mixed with water and a water-soluble organic solvent. Examples include aqueous media mixed with ethanol, glycerin, etc.

The spherical composite fine particles of the present invention are particularly effective in smoothing the surface and preventing blocking of various molded products such as thermoplastic resin films and sheets. The spherical composite fine particles can be added to these materials by directly adding them to the molten polymer of the thermoplastic resin, or by adding them to the polymerization system when producing the thermoplastic resin, such as adding terephthalic acid or ester-forming particles. There is a method in which the terephthalic MU conductor and ethylene glycol are condensed and polymerized to produce polyethylene terephthalate. In the case of direct addition, it is advantageous to prepare a masterbatch of thermoplastic resin containing 5 to 40% by weight of spherical composite fine particles and use this masterbatch. In this case, the medium may be polypropylene, Examples include thermoplastic organic polymers such as polyethylene and polystyrene. Examples of the medium to be added to the polymerization system include diols such as ethylene glycol, propylene glycol, 1,4-butanediol, hexamethylene glycol, and polyalkylene gelylcol, among which Alkylene glycols are preferred.

Although there are no particular limitations on the method for preparing the dispersion containing the spherical composite fine particles of the present invention, in order for the dispersion to better exhibit the desired effect, the secondary agglomerated particles of the spherical composite fine particles are subjected to crushing treatment. In such a case, the dispersion may be prepared by dry crushing the spherical composite fine particles and then dispersing them in a medium, or by dispersing them in a medium and then wet crushing them. Good 1: Even if the spherical composite fine particles of the present invention are subjected to such crushing treatment, the secondary agglomerated particles are only crushed into the original primary particles, and the original primary particles themselves are not damaged. I almost never receive it.

In this way, a dispersion containing the spherical composite fine particles of the present invention is prepared, and in addition to the dispersant, a surfactant as a protective colloid, a polymeric substance, etc. can also be coexisting in the dispersion.

Examples are given below to make the structure of the present invention more specific, but the present invention is not limited to these Examples.

<Examples, etc.> Test Category 1 (Production Examples of Spherical Composite Fine Particles, etc.) Examples of producing spherical composite fine particles, etc. are listed below, and their contents and results are summarized in Table 1.

The contents and results in Table 1 were measured using the following method.

l) Average particle size and ratio of major axis to minor axis The spherical composite fine particles obtained in each case were photographed using a scanning electronic WJ microscope (SEM). Then, 50 fine particles are randomly selected from the photographed image, and the major axis (the longest diameter passing through the center of the particle = D5) and the short axis (the shortest diameter passing through the center of the particle = D5) of each selected fine particle. The average value of (OL + O3) / 2 calculated by measuring ) was taken as the average particle diameter, and the average value of 0L10S was taken as the ratio of the major axis to the minor axis.

2) Ultrasonic dispersion of spherical composite fine particles, etc., each with a standard deviation value of particle size (; The particle size was measured using a 9-meter particle size measuring device (CAP-700 model manufactured by Horiba Seisakusho Co., Ltd.).

3) Polysiloxane content (wt%) The spherical composite fine particles obtained individually were mixed with nitric acid/perchlorine vinegar (5% by weight).
/2) After decomposing organic matter by heating to dryness in a compound, molybdenum blue method (colorimetric method: Anal, Chem,
19, 873, 1947), and the value calculated from the Si02 content and the composition of the charged silicon compound was taken as the polysiloxane content.

・Example 1 658 μl of water and 8.3 liters of 28% ammonia water in a flask
6 g of ethyl orthosilicate (0,0
29 mol), octamethylcyclotetrasiloxane 23
g (0,078 mol) trimethoxymethylsilane 71 g
(0,52 mol) and 10 g of styrene (0,9s9g
) was added dropwise over a period of 1 hour, and as the reaction progressed, the product gradually settled to the lower layer, which became cloudy, but about 2 Over time, the two-calendar state disappeared and became a homogeneous system. After stirring a little more strongly under the same conditions for 3 hours, the white fine particles were filtered out.Then, the white fine particles were charged into another flask with 1000.1 of water, and the contents were reduced to 70.0 mm under nitrogen flow.
The temperature was raised to 0.degree. C., and a 1% potassium persulfate aqueous solution lOOen 1 was added dropwise over 1 hour. Subsequently, the mixture was aged for 3 hours under the same conditions to perform radical polymerization, and then the contents were cooled to room temperature and the white composite fine particles were filtered off. The white composite fine particles were washed and dried to obtain 61 gt of spherical composite fine particles.

The obtained spherical composite fine particles had an average particle diameter of 1.1 gm, a ratio of major axis to minor axis of 1.02, and a standard deviation value of 1.42. The polysiloxane content was 86.3% by weight.

・Example 2 Same as Example 1, 658 ml of water, 8.3 g of 1.28% ammonia water, 6 g of ethyl orthosilicate (0,029
mol), octamethylcyclotetrasiloxane 23g (
0,078 mol), trimethoxymethylsilane 71 g (
0.52 mol), 38 g (0.36 mol) of styrene, and 2 g (0.015 mol) of divinylbenzene were used to perform hydrolysis, polycondensation, and radical polymerization to obtain 93 g of spherical composite fine particles.

The obtained spherical composite fine particles had an average particle diameter of 1.0 gm and a ratio of major axis to minor axis of 1.03. The standard deviation value was 1.50, and the polysiloxane content was 64.7% by weight.

・Example 3 Same as Example 1, 658 ml of water, 1.28% aqueous ammonia 8.3 g, ethyl orthosilicate) 75 g (0.36 mol), trimethoxymethylsilane 75 g (0.55 mol) and styrene 5 g ( 0,048 mol), hydrolysis, 11i! Polymerization and radical polymerization were performed to obtain 55 g of spherical composite fine particles.

The obtained spherical composite fine particles had an average particle diameter of 1.2 μm and a ratio of major axis to minor axis of 1.04. The standard deviation value was 1.67, and the polysiloxane content was 92.9% by weight.

・Example 4 Same as Example 1, 658 μl of water, 16.6 g of 28% ammonia water, 6 g of ethyl orthosilicate (0,029
mol), octamethylcyclotetrasiloxane 23g (
0,078 mol), trimethoxymethyl silica 771 g (
0,52 mol) and methyl methacrylate) 10 g (0,
Hydrolysis, condensation polymerization and radical polymerization were carried out using 1 mol) of the spherical composite particles to obtain 59 g of spherical composite fine particles.

The obtained spherical composite fine particles had an average particle diameter of 0.5 μm, a ratio of major axis to minor axis of 1.01, a standard deviation value of 1.31, and a polysiloxane content of 87.1% by weight.

・Example 5 Same as Example 1, 329 ml of water. 329g methanol
, 16.6 g of 28% ammonia water, 6 g (0,029 mol) of ethyl orthosilicate, 23 g (0,078 mol) of octamethylcyclotetrasiloxane, 71 g (0,52 mol) of trimethoxymethylsilane, and 10 g of styrene.
(0,096 mol) was used to perform hydrolysis, condensation polymerization, and radical polymerization to obtain 60 g of spherical composite fine particles.

The obtained spherical composite fine particles have an average particle size of 0.4 p m
, the ratio of the major axis to the minor axis is 1.05, and the standard deviation value is 1.45.
．． The polysiloxane content was 87.9% by weight.

・Example 6 Same as Example 1, 658'ml of water, 8.3g of 28% ammonia water, 6g of ethyl orthosilicate (0,0
29 mol), octamethylcyclotetrasiloxane 23
g (0,078 mol), trimethoxymethylsilane 71
After hydrolysis and polycondensation using 64 g (0.61 mol) of styrene and 64 g (0.61 mol) of styrene, 9 g of 89% phosphoric acid was added to the reaction system without filtering out the white particles. The reaction system was neutralized, 330 ml of water was added, and radical polymerization was then carried out in the same manner as in Example 1 to obtain 110 g of spherical composite fine particles.

The obtained spherical composite fine particles had an average particle diameter of 0.8 pm, a ratio of major axis to minor axis of 1.04, a standard deviation value of 1.77, and a polysiloxane content of 5 to 20% by weight.

・Example 7 Same as Example 1, 858 ml of water, 1.28% ammonia water 8.3 g, 26 g (0.12 mol) of ethyl orne silica, 19 g (0.12 mol) of octamethylcyclotetrasiloxane
,064 mol), trimethoxymethylsilane 17g (0
, 12 moles) and 62 g (0.60 moles) of styrene were used to carry out hydrolysis, condensation polymerization, and radical polymerization to obtain 75 g of spherical composite fine particles.

The obtained spherical composite fine particles had an average particle size of 0.71 Lm,
The ratio of the major axis to the minor axis is 1.06. fi standard deviation value is 1.71
, the polysiloxane content was 39.3% by weight.

・Example 8 Same as Example 1, 658 ml of water, 1.28% ammonia water 8.3 g, ethyl orthosilicate) 40 g (0.19 mol), octamethylcyclotetrasiloxane 53 g (0.
, 18 mol), trimethoxymethylsilane 12 g (0,
Hydrolysis, polycondensation and radical polymerization were carried out using 0.088 mol) and 15 g (0.14 mol) of styrene to obtain 65 g of spherical composite fine particles.

The obtained spherical composite fine particles had an average particle diameter of 1.1 pm, a ratio of major axis to minor axis of 1.04, a standard deviation value of 1.56, and a polysiloxane content of 81.5% by weight.

・Example 9 Same as Example 1, 8.3 g of wood 658 1,28% ammonia water, 6 g (0,029 mol) of ethyl orthosilicate, 23 g of octamethylcyclotetrasiloxane (
0,078 mol), trimethoxymethylsilane 71 g (
0,52 mol), 12 g (0,12 mol) of styrene and 1 g (0,0025 mol) of polyethylene glycol (molecule M400) monomethacrylate,
By performing condensation polymerization and radical polymerization, spherical composite fine particles 60
I got g.

The obtained spherical composite fine particles had an average particle diameter of 1.0 pm, a ratio of major axis to minor axis of 1.03, a standard deviation value of 1.45, and a polysiloxane content of 85.8% by weight.

・Comparative example 1 Flask contains 658 wood 1 and 28% ammonia water 8.3
6 g of ethyl orthosilicate (0,0
29 mol), octamethylcyclotetrasiloxane 23
g (0,078 mol) and trimethoxymethylsilane 7
1 g (0.52 mol) of the mixture was added dropwise over 1 hour,
Polycondensation occurred while being hydrolyzed at the interface of the two-layered solution.

After stirring somewhat vigorously for 3 hours under the same conditions, the contents were neutralized and further wet-pulverized to obtain a white fine particle suspension.

The obtained white fine particle suspension had an average particle size of 1°3 gm,
The ratio of the major axis to the minor axis is 1.02. Standard deviation value is 1.1μm
Next, this white fine particle suspension was heated to 70°C under a nitrogen stream, 1 g of potassium persulfate was dissolved therein, and then 10 g (0,096 mol) of styrene was added dropwise over 1 hour. did. Subsequently, the mixture was aged for 3 hours under the same conditions to perform radical polymerization, and then the contents were cooled to room temperature and the white cake-like powder was filtered off. This white cake-like powder was washed and dried to obtain 60 g of white powder.

The shape of the obtained white powder was not spherical but irregular.

Comparative Example 2 Same as Example 1, 65 Bml of water, 8.3 g of 28% ammonia water, 6 g of ethyl orthosilicate (0,029
mol), octamethylcyclotetrasiloxane 92g (
0,31 mol), trimethoxymethylsilane 2g (0,
Hydrolysis and polycondensation were carried out using 0.015 mol) and 10 g (0.096 mol) of styrene. In the reaction system exhibiting a cloudy emulsion, there were no spherical fine particles, and a liquid upper layer 'MM was observed in some parts. 89% phosphoric acid was added to this reaction system to make it neutral, water 33 (1+1) and 1 g of potassium persulfate were added to the reaction system, and radical polymerization was subsequently performed in the same manner as in Example 1. The shape of the particles was not spherical but irregular.

Comparative Example 3 Same as Example 1, 658 g of water, 8.3 g of 1.28% ammonia water, 6 g (0,029 mol) of ethyl orthosilicate, 23 g of octamethylcyclotetrasiloxane (
0,078 mol) and 71 g of trimethoxymethylsilane
(0.52 mol) was used for hydrolysis and polycondensation to obtain spherical fine particles.

The obtained spherical fine particles had an average particle diameter of 1.2←m and a ratio of major axis to minor axis of 1.03. The standard deviation value was 2.1.

Comparative Example 4 In the same manner as in Example 1, using 658 ml of water, 8.3 g of 1.28% ammonia water, 75 g (0.36 mol) of ethyl orne silica, and 75 g (0.55 mol) of trimethoxymethylsilane, Hydrolysis and llii polymerization were performed to obtain one spherical fine particle.

The obtained spherical fine particles had an average particle diameter of 1.1 pm, a ratio of major axis to minor axis of 1.03, and a standard deviation value of 20.

・Comparative Example 5 Same as Example 1, 658 ml of water, 1.28% ammonia water 8.3 g, ethyl orne silica) 2 g (0,009
7 mol), octamethylcyclotetrasiloxane 7.7
g (0,028 mol), trimethoxymethylsilane 23
．． 7 g (0,17 mol) and 80 g (0,7 mol) of styrene
7 mol).

Separation of styrene was observed in some parts of the 0 reaction system in which hydrolysis and polycondensation were carried out. 89% phosphoric acid was added to this reaction system to make it neutral, water 33011 and potassium persulfate Ig were added to the reaction system, and radical polymerization was subsequently carried out in the same manner as in Example 1. A mixture of styrene homopolymer and styrene homopolymer was produced.

Note) In Table 1.

(I); Polysiloxane (II); Vinyl polymer n≦l: Among the structural units of polysiloxane, the above (I)
) in the general formula where n is 1 or less; ratio of major axis to minor axis (0110S) Test Category 2 (Example of manufacturing a dispersion of spherical composite fine particles, etc.) The following is a dispersion of spherical composite fine particles, etc. The contents and results are summarized in Table 2.

The results in Table 2 were evaluated using the following method.

l) Shape retention (For each dispersion, 50 fine particles were arbitrarily selected from the above-mentioned electron microscope photographed image.
The presence or absence of damage to each selected fine particle was observed and evaluated based on the following criteria.

○; 1 or less fine particles found to be damaged 0; 2 to 6 fine particles found to be damaged Δ; 7 to 24 fine particles found to be damaged ×; 25 or more fine particles found to be damaged 2
) The presence or absence of aggregated particles was observed by observing each dispersion obtained with a 1000x optical microscope,
The degree of aggregation of fine particles existing in the range of 20×20 gm was evaluated based on the following criteria.

O: Agglomerated particles are less than 1% of all particles Δ; Agglomerated particles are 1% or more and less than 10% of all particles ×; Agglomerated particles are 10% or more of all particles Place it in a molded glass container and leave it at room temperature with a hermetically sealed cap (however, in Example 20, leave it in a thermostat at 80°C), observe the state of separation of fine particles over time, and evaluate based on the primary criteria. did.

O: Separation of fine particles is not observed even after one month 0; Separation of fine particles is observed from 7 days to January Δ: Separation of fine particles is 2
x: Separation of fine particles was observed after 1 day - Examples 10 to 14 and Comparative Examples 6 to 10: j',
Weigh out 40 g of the spherical composite fine particles shown in Table 2 and an amount of ethylene glycol that will give a predetermined concentration of the spherical composite fine particles, etc., pre-disperse this with a homomixer, and then
．． Batch type sand grinder using 85mmφ glass beads (manufactured by Igarashi Kikai Co., Ltd., vessel capacity 400
cc) for 5 hours to obtain 1 dispersion.

The dispersions of Examples 10 to 14 are useful as modifiers that impart good lubricity to polyester molded articles. Example 15 40 g of spherical composite fine particles shown in Table 2 and 160 g of ethylene glycol were weighed This was dispersed for 30 minutes using a homomixer to obtain a dispersion.

・Example 16.17 40 g of spherical composite fine particles shown in Table 2, 16 g of ion-exchanged water
0 g, nonylphenol ethylene oxide 3 mole adduct 1.2 g and nonylphenol ethylene oxide 1
Weighed out 2.8 g of the 0 mole adduct and added it to Examples 10-1.
A dispersion treatment was carried out in the same manner as in 4 to obtain a dispersion.

These dispersions are useful as modifiers for water-based paints, cosmetics, paper coating agents, textile treatment oils, and the like.

・Example 18 40 g of spherical composite fine particles shown in Table 2 and 160 g of styrene
g was weighed out and subjected to a dispersion treatment in the same manner as in Examples 10 to 14 to obtain a dispersion.

This dispersion is useful as a quality agent for radically polymerizable resins and coating agents.

- Example 19 30 g of spherical composite fine particles shown in Table 2 and 170 g of trimethylolpropanetrioctanoate were weighed out and dispersed in the same manner as in Examples 10 to 14 to obtain one dispersion.

This dispersion is useful as a modifier for fiber processing oils and lubricants.

・Example 20 30 g of spherical composite fine particles shown in Table 2 and 170 g of stearyl stearate melted and liquefied at 80°C were weighed and mixed, and this was subjected to a dispersion treatment in the same manner as in Examples 10 to 14 to obtain a dispersion. Ta.

This dispersion is a thermoplastic resin or thermosetting resin gold N! Useful as a mold release agent in molding.

Table 2 Note) In Table 2, Example 14: The spherical composite fine particles used here were those obtained in Example 1 before drying (65% moisture). The average particle size listed in 1. Opm's spherical polymethylsilsesquioxane fine particles B; Spherical silica test category 3 (example of use of spherical composite fine particles) with an average particle diameter of 0.8 parts m described in JP-A No. 63-185439 (example of use) 1) A mixture of the spherical composite fine particles obtained in Example 1, polyethylene resin (Yukalon LF-540B, manufactured by Mitsubishi Yuka Co., Ltd.), and 41) antistatic agent (glycerin monostearate/N, N-bishydroxyethyl laurylamine 171) ) to 25
The mixture was kneaded using a Kamaro φ twin-screw extruder to prepare a masterbatch containing 3% by weight of spherical composite fine particles and 2% by weight of an antistatic agent.

Next, using a polyethylene resin (same as above) mixed with 10% by weight of the masterbatch, a 30+smφ inflation film II! A polyethylene film with a thickness of 30 gm was produced using im. The appearance of the produced film was good, and no blocking was observed even after one film roll was left in an atmosphere of 23° C. and 65% RH for two weeks.

On the other hand, a film prepared in the same manner as above without using the 1 spherical composite particles had no foreign matter and had a good appearance, but significant blocking was observed after leaving it in the same manner as above. .

Test Category 4 (Example of use of dispersion of spherical composite fine particles, etc.) Examples of use of dispersion of spherical composite fine particles, etc. are listed below, and their contents and results are summarized in Table 3.

The results in Table 3 were evaluated using the following method.

1) Presence or absence of aggregated particles Each of the produced films was photographed using the above-mentioned electron microscope, and a 70×50 gm area of the image was observed and evaluated based on the following criteria.

0: Absolutely no aggregated particles Δ; Slight presence of aggregated particles ×; Agglomerated particles present in 10% or more of all particles 2) Presence or absence of voids Observe the image in l) above to identify voids around the fine particles. We quantified the difference between the two.

3) Prepare 1311 pieces of tape-like sample 1 from each of the prepared films, and place this sample in a stainless steel fixed bottle (7 pieces φ
) with an entrance load of 30 g, and a speed of 30 at 2°5 m/min.
I ran it back and forth several times. After the reciprocating run, the surface condition of the sample was observed with the naked eye and evaluated based on the following criteria.

■: No change such as whitening or scratches 0; Slight whitening or scratches Δ; Clear whitening or scratches ×: Significant whitening or scratches - Usage Examples 2 to 8 Dimethyl terephthalate 100 Parts by weight, 70 parts by weight of ethylene glycol and 0.0'35 parts by weight of manganese acetate tetrahydrate
After adding 0.03 parts by weight of trimethyl phosphate to 0.03 parts by weight, the temperature was raised to 230°C according to a conventional method to perform a transesterification reaction. were added so that the concentration of spherical composite fine particles, etc. was 0.3% by weight based on the polymer, and the mixture was stirred. After adding 0.03 parts by weight of antimony trioxide, the temperature was started to increase, and a polycondensation reaction was carried out under high temperature and high vacuum according to a conventional method, and the intrinsic viscosity was 0.61 dl.
/g of polyethylene terephthalate was obtained. The polyethylene terephthalate obtained here was dried at 180°C, formed into a sheet using an extruder set at 290°C, and then heated to 90°C.
Stretched 3° in the longitudinal direction and 4.0 times in the transverse direction, and further stretched 2.
A film with a thickness of 15 pm was produced by heat setting at 10°C.

Table 3 Note) In Table 3, Usage Examples 6 to 8: Examples in which the spherical composite fine particles of the present invention are not used. Presence of void column: Meaning clearly recognized (effect of the invention) As explained above. Therefore, in the present invention, it is possible to obtain stable spherical composite fine particles and dispersions thereof, which have a small average particle size, a narrow particle size distribution, and a constant shape, and are free from agglomerated particles. In the end, the effect is that the modification can be carried out as designed.

Claims (1)

[Scope of Claims] 1. Mainly formed from the following polysiloxane (I) and the vinyl polymer (II) below, in which both are integrally mixed and both are not substantially covalently bonded. spherical composite fine particles having a polysiloxane/vinyl polymer ratio of 97/3 to 30/70 (weight ratio), an average particle size of 0.05 to 30 μm, and a standard deviation value of particle size of 1 .0～
2.5, and a spherical composite fine particle characterized in that the ratio of the major axis to the minor axis is 1.0 to 1.2. (I): General formula [RnSiO_(_4_−_n_)_
/_2] A polysiloxane consisting of one or more types of structural units, and containing at least 15 mol% or more of a structural unit in which n is 1 or less. [However, n is an integer from 0 to 3. R is an unsubstituted or substituted hydrocarbon group having a carbon atom directly bonded to a silicon atom, and is a hydrocarbon group having no radical polymerizability. ] (II): A vinyl polymer obtained by polymerizing one or more vinyl monomers that do not have reactivity with silanol groups and silanol group-forming atomic groups. 2. The average particle size is 0.1 to 10 μm, the standard deviation value of the particle size is 1.0 to 2.0, and the ratio of the major axis to the minor axis is 1.0 to
1.1. The spherical composite fine particles according to claim 1. 3. The spherical composite fine particles according to claim 1 or 2, wherein R in the general formula (I) is an alkyl group having 1 to 4 carbon atoms or a phenyl group. 4. The spherical composite fine particles according to claim 1, 2 or 3, wherein the vinyl monomer in (II) is a water-insoluble vinyl monomer. 5. The spherical composite fine particles according to claim 4, wherein the water-insoluble vinyl monomer is one or more selected from alkyl esters of acrylic acid or methacrylic acid and aromatic vinyl monomers. 6. When producing the spherical composite fine particles according to claim 1 or 2, the following silanol group-forming silicon compound (III)/the vinyl monomer (IV) below is mixed in a proportion of 99/1 to 33/67 (
The silanol group-forming silicon compound is hydrolyzed and polycondensed in an aqueous medium coexisting at a weight ratio of 10 to 30% by weight to form spherical fine particles of polysiloxane in which the vinyl monomer is mixed, and then a radical polymerization catalyst is added. A method for producing spherical composite fine particles, which comprises polymerizing the vinyl monomer in the presence of. (III): A silanol group-forming silicon compound represented by the general formula (V) or (VI), and a silanol group-forming silicon compound represented by R^1-SiX_3 and/or a silanol group-forming silicon compound represented by SiX_4. A silanol group-forming silicon compound containing at least 15 mol% or more of the silanol group-forming silicon compound, calculated as silicon based on the total silanol group-forming silicon compound. General formula (V); R^1_p-SiX_4_-_p General formula (VI); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, p is an integer from 0 to 3, and q is an integer from 3 to 20. R^
1, R^2, and R^3 are unsubstituted or substituted hydrocarbon groups having a carbon atom directly bonded to a silicon atom, and are non-radically polymerizable hydrocarbon groups. X has 1 to 4 carbon atoms
an alkoxy group having an alkoxy group having 1 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms,
N,N-dialkylamino group having an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom or a hydrogen atom. ](IV): One or more vinyl monomers that have no reactivity with silanol groups and silanol group-forming atomic groups. 7. R^1, R^2 in general formula (V) or (VI),
7. The method for producing spherical composite fine particles according to claim 6, wherein R^3 is an alkyl group having 1 to 4 carbon atoms or a phenyl group. 8. The method for producing spherical composite fine particles according to claim 6 or 7, wherein the vinyl monomer in (IV) is a water-insoluble vinyl monomer. 9. The method for producing spherical composite fine particles according to claim 8, wherein the water-insoluble vinyl monomer is one or more selected from alkyl esters of acrylic acid or methacrylic acid and aromatic vinyl monomers. 10. A dispersion of spherical composite fine particles comprising the spherical composite fine particles according to claim 1, 2, 3, 4 or 5 and an organic medium or an aqueous medium that is liquid or solid at room temperature. 11. The dispersion of spherical composite fine particles according to claim 10, wherein the organic medium is an alkylene glycol having 2 to 4 carbon atoms. 12. The dispersion of spherical composite fine particles according to claim 10, wherein the aqueous medium is water. 13. Claim 10, wherein the secondary agglomerated fine particles are subjected to crushing treatment.
A dispersion of spherical composite fine particles according to , 11 or 12.