JP2854670B2 - Method for producing spherical composite fine particles, spherical composite fine particles and dispersion thereof - Google Patents

Description

The present invention relates to a method for producing spherical composite fine particles, spherical composite fine particles, and a dispersion thereof.

BACKGROUND ART In order to modify paints, cosmetics, rubber, plastics, paper, and the like, fine particles have been added in the manufacturing or processing steps thereof. In recent years, as such fine particles, spherical fine particles having a narrow particle size distribution have been attracting attention because their characteristics are easy to design and control.

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

<Prior art and its problems> Conventionally, various fine particles such as polystyrene, polyvinyl acetate, polyethylene, nylon, epoxy resin, phenol resin, and polysiloxane have been proposed as the fine particles described above. Among these, silica particles (J. Colloid and Interf.)
ace Sci. 26, 62-69, 1968), polymethylsilsesquioxane particles (JP-A-63-77940), polyorganosiloxane particles (JP-A-63-312324), and the like.
In addition, there is a report that such a modification with polysiloxane-based fine particles can impart good lubricity when added to a polyester film (JP-A-59-171623).

However, these conventional fine particles are 1) easily broken by mechanical impact, 2) hardly dispersed in a medium or a polymer material,
3) Poor dispersion stability; 4) Irregularities in particle shape, particle size distribution, etc., and in fact, ultimately, it is difficult to obtain the desired modification.

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

The inventors of the present invention have conducted intensive studies to obtain micron-order spherical composite fine particles having a narrow particle size distribution to solve the above-mentioned problems 1) to 4). A group-forming silicon compound and a water-insoluble vinyl monomer are used at a predetermined ratio, and the silanol group-forming silicon compound is first subjected to polycondensation to form a polysiloxane under conditions where both are present, and then the water-insoluble The present inventors have found that it is preferable to graft a vinyl monomer while polymerizing the same, and have completed the present invention.

That is, the present invention relates to the following (A) a silanol group-forming silicon compound and the following (B) water-insoluble vinyl monomer: (A) a silanol group-forming silicon compound / (B) a water-insoluble vinyl monomer. The monomer is used at a ratio of 99/1 to 22/78 (weight ratio). First, a polycondensation is performed by hydrolyzing the silanol group-forming silicon compound (A) in an aqueous medium in which both are present (B) )) To produce polysiloxane spherical fine particles mixed with a water-insoluble vinyl monomer, and then, in an aqueous medium in which the spherical fine particles are dispersed, in the presence of a radical polymerization catalyst (B).
The present invention relates to a method for producing spherical composite fine particles, which comprises grafting while polymerizing the water-insoluble vinyl monomer.

(A): one or more of the silanol group-forming silicon compounds represented by the general formula (1) or (2) is 99.0 to 0 mol% and a silanol group represented by the general formula (3) or (4) A silanol group-forming silicon compound in which at least one kind of the silicon compound is 0.1 to 100 mol%, and p is 1 or less and / or a silanol group whose r + s is 1 A silanol group-forming silicon compound containing a total of 15 mol% or more of a forming silicon compound.

General formula (1); R ⁴ _p -SiX _(4-p) General formula (2); General formula (3); R ⁷ _r R ⁸ _s SiX _(4-rs) General formula (4); [However, p is an integer of 0-3. r is an integer of 0 to 2, s is 1
An integer satisfying 1 ≦ r + s ≦ 3;
q and t are integers from 3 to 20. R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different unsubstituted or substituted non-radical polymerizable hydrocarbon groups having a carbon atom directly bonded to a silicon atom. R ⁸ and R ⁹ are --CH
= CH _2, One or more selected from (where y is an integer of 2 or 3). R ¹⁰ is the same hydrocarbon group as R ⁴ , R ⁵ , R ⁶ and R ⁷ or the same organic group as R ⁸ and R ⁹ . X is an alkoxy group having 1 to 4 carbon atoms, an alkoxyethoxy 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 4 alkyl groups, hydroxyl group, halogen atom or hydrogen atom. (B): One or more water-insoluble vinyl monomers containing a radically polymerizable ethylenically unsaturated group.

The silanol group-forming silicon compound (A) is a raw material of a polysiloxane block which is a block of the copolymer forming the spherical composite fine particles of the present invention, and is represented by the general formulas (1), (2) and (3). ) Or the silanol group-forming silicon compound represented by (4), and the total of the silanol group-forming silicon compounds represented by R ⁴ SiX ₃ , SiX ₄ and / or R ⁸ SiX ₃ is defined as the total silanol group. It is a silanol group-forming silicon compound containing at least 15 mol% of the silicon-forming compound in terms of silicon. Specifically, silanol group-forming silicon compounds represented by the general formula (1) include SiX ₄ , R ⁴ Si
X _3, R ⁴ ₂ SiX ₂ or R ⁴ ₃ silanol-forming silicon compound represented by SiX, also silanol-forming silicon compound represented by the general formula (3) _{^{is, R 8 SiX 3, R 8}} 2 SiX ₂ , R ⁷ R
_{^{8 SiX 2, R 8 3 SiX}} , R 7 R 3 2 SiX or R ⁷ ₂ R ⁸ is a silanol-forming silicon compound represented by SiX, silanol-forming silicon compound used in the present invention, R ⁴ SiX ₃ , a silanol group-forming compound containing the total of silanol group-forming silicon compounds represented by SiX ₄ and / or R ⁸ SiX ₃ in a proportion of at least 15 mol%, preferably at least 20 mol%, in terms of silicon of the silanol group-forming silicon compound It is a silicon compound. If it is less than 15 mol%, spherical composite fine particles having the characteristic values described below cannot be obtained.

In the silanol group-forming silicon compound as described above, R ⁴ , R ⁵ and R ⁶ in the general formula (1) or (2) are unsubstituted or substituted hydrocarbon groups having a carbon atom directly bonded to a silicon atom. And has no radical polymerizability.

Examples of R ⁴ , R ⁵ , R ⁶ in the case of an unsubstituted hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, and an aralkyl group.
An alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group and a butyl group or a phenyl group is advantageously selected. When R ⁴ , R ⁵ , and R ⁶ are a substituted hydrocarbon group, examples of the substituent include a substituted hydrocarbon group having a halogen atom, an epoxy group, a cyano group, a ureido group, and the like. Glycidoxypropyl, 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.

R ^{7 in the} general formula (3) is the same as R ⁴ , R ⁵ and R ⁶ described above, and R ⁸ and R ^{9 in} the general formula (3) or (4) are an ethylenically unsaturated group or a mercapto group; For example, a vinyl group, an allyl group, an acryloxypropyl group, a methacryloxypropyl group or a mercaptopropyl group, wherein R ^{10 in the} general formula (4) is the same as the above R ⁴ , R ⁵ , R ⁶ or R ⁸ , R ⁹ The same is true.

In the silanol group-forming silicon compound as described above, X in the general formulas (1) and (3) represents an alkoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group, a methoxyethoxy group or a butoxyethoxy group. Alkoxyethoxy groups having an alkoxy group having 1 to 4 carbon atoms, acyloxy groups having 2 to 4 carbon atoms such as acetoxy group and propoxy group, N having an alkyl group having 1 to 4 carbon atoms such as dimethylamino group and diethylamino group, It is an N-dialkylamino group, a hydroxyl group, a halogen atom such as a chlorine atom or a bromine atom, or a hydrogen atom.

Therefore, more specifically, the silanol group-forming silicon compound represented by SiX ₄ includes tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetrachlorosilane and the like. R ⁴ SiX ₃
As the silanol group-forming silicon compound represented by
Methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, phenyltrimethoxysilane, methyltris (dimethylamino) silane, methyltrichlorosilane, phenyltrichlorosilane, methyldichloromethoxysilane, methyldichlorohydrogensilane, methylsilane Triol, methyldichlorosilanol, methylchlorosilanediol and the like can be mentioned. The aforementioned R ⁴ silanol group forming silicon compound represented by the ₂ SiX _2, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl phenyl dimethoxy silane, dimethyl diacetoxy silane, dimethyl bis (dimethylamino) silane, dimethyldichlorosilane , Diethyldichlorosilane, diphenyldichlorosilane, dimethylchloromethoxysilane, methylethyldichlorosilane, dimethylsilanediol, diethylsilanediol and the like. The silanol-forming silicon compound represented by the above R ⁴ ₃ SiX, trimethyl methoxy silane, trimethyl ethoxy silane, dimethyl ethyl silane, acetoxytrimethylsilane, trimethyl (dimethylamino) silane, trimethylchlorosilane,
Triphenylchlorosilane, trimethylsilanol and the like. Each of the above examples is a silanol group-forming silicon compound when R ^{4 in the} general formula (1) is an unsubstituted hydrocarbon group, and a silanol group when R ⁴ is a substituted hydrocarbon group. As the forming silicon compound, γ-glycidoxypropyltrimethoxysilane, γ
Glycidoxypropyltriethoxysilane, β- (3,
Epoxy group-containing silane compounds such as 4-epoxycyclohexyl) ethyltrimethoxysilane; haloalkyl group-containing silane compounds such as γ-chloropropyltrimethoxysilane and trifluoropropyltrimethoxysilane;
Examples include ureido group-containing silane compounds such as ureidopropyltrimethoxysilane, and cyano group-containing silane compounds such as cyanopropyltrimethoxysilane. Examples of the silanol group-forming silicon compound represented by the general formula (2) include octamethylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, and the like.

R ⁸ serving as a connecting hand for cross-linking the polysiloxane block and the vinyl polymer block to each other or
More specifically, the silanol group-forming silicon compound represented by the general formula (3) or (4) having R ⁹
Examples of the silanol group-forming silicon compound represented by R ⁸ SiX ₃ include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, allyltrimethoxysilane, methacryloxypropyltrimethoxysilane,
And mercaptopropyltrimethoxysilane. The silanol-forming silicon compound represented by the R ⁸ ₂ SiX _2, divinyl dimethoxysilane, divinyl dichlorosilane, and the like. Examples of the silanol group-forming silicon compound represented by R ⁷ R ⁸ SiX ₂ include vinylmethyldimethoxysilane, vinylmethyldichlorosilane, methacryloxypropylmethyldimethoxysilane,
Mercaptopropylmethyldimethoxysilane, mercaptopropylmethyldichlorosilane and the like can be mentioned. The silanol-forming silicon compound represented by the above R ⁸ ₃ SiX, trivinyl silane, trivinyl chlorosilane, and the like. The silanol-forming silicon compound represented by the above R ⁷ R ⁸ ₂ SiX, divinyl methyl silane, divinyl methylchlorosilanes and the like. Examples of the silanol group-forming silicon compound represented by R ⁷ ₂ R ⁸ SiX include vinyldimethylmethoxysilane, vinyldimethylchlorosilane, methacryloxypropyldimethylmethoxysilane, methacryloxypropyldimethylchlorosilane, and mercaptopropyldimethylmethoxysilane. Is mentioned. Specific examples of the silanol group-forming silicon compound represented by the general formula (4) include tetramethyltetravinylcyclotetrasiloxane.

The water-insoluble vinyl monomer (B) is a raw material of a vinyl polymer block which is another block of the copolymer forming the spherical composite fine particles of the present invention, and is a radical polymerizable ethylenically unsaturated monomer. One or more water-insoluble vinyl monomers containing a group.

Examples of such water-insoluble vinyl monomers include methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, and cyclohexyl methacrylate; and acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate. , Aromatic vinyl monomers such as styrene and α-methylstyrene, other monovalent monomers such as vinyl acetate, ethylene glycol dimethacrylate, divinylbenzene, glycerin trimethacrylate, trimethylolpropane trimethacrylate, bisphenol A Examples thereof include divalent or higher-valent monomers such as dimethacrylate and diethoxylated bisphenol A dimethacrylate.

In producing the spherical composite fine particles of the present invention, the silanol group-forming silicon compound (A) / (B)
Are reacted in the range of 99/1 to 22/78 (weight ratio). If it is out of this range, the desired spherical composite fine particles cannot be obtained.

According to the method for producing the spherical composite fine particles of the present invention, the following two reactions can partially proceed at the same time depending on the method, but they are roughly classified into a reaction for producing a polysiloxane and a reaction for producing a vinyl polymer. Is done.

In the reaction for producing the polysiloxane, the silanol group-forming silicon compound as a raw material of the polysiloxane is mixed with an aqueous medium in the presence of the water-insoluble vinyl monomer as a raw material of the vinyl polymer. Polycondensates while hydrolyzing in the polymer. The aqueous medium used here is water or water.
It is a homogeneous solvent system containing at least 30% by weight, preferably at least 50% by weight. In this case, examples of the solvent that can be used other than water include water-soluble solvents such as methanol, ethanol, isopropanol, acetone, tetrahydrofuran, and ethyl acetate.

The catalyst used for condensation polymerization while hydrolyzing the silanol group-forming silicon compound may be a conventionally known catalyst. This includes, for example, organic bases such as ammonia, trimethylamine, triethylamine, and tetraethylammonium hydroxide; inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, and sodium methoxide; tetramethoxytitanium; Titanium compounds such as butoxytitanium; tin compounds such as dibutyltin oxide and dibutyltin laurate;
-Organic acids such as toluenesulfonic acid and dodecylbenzenesulfonic acid. Of these, ammonia, trimethylamine and triethylamine are preferred. This is because it has little effect on the water-insoluble vinyl monomer and is easily removed from the product.

The polycondensation reaction while hydrolyzing is carried out by charging a silanol group-forming silicon compound and a water-insoluble vinyl monomer into an aqueous medium in which a catalyst is dissolved and stirring the mixture. The temperature and time for polycondensation while hydrolyzing vary depending on the type and concentration of the raw materials, the type of solvent, the type and concentration of the catalyst, and the like, but the temperature is usually 0 to 90 ° C, preferably 0 to 60 ° C. And the time is usually in the range of 30 minutes to 24 hours. Thus, polysiloxane is formed, and spherical fine particles of the polysiloxane are obtained.

In the reaction for forming a vinyl polymer, grafting is performed while polymerizing a water-insoluble vinyl monomer in an aqueous medium in which spherical fine particles of polysiloxane are dispersed in the presence of a radical polymerization catalyst. Various methods are possible for the transition from the reaction for producing the polysiloxane to the reaction for producing the vinyl polymer. For example, if the catalyst used in the reaction for producing the polysiloxane has no problem in the reaction for producing the vinyl polymer, it can be transferred as it is, and if there is a problem, the catalyst is removed or inactivated. Migrate from The aqueous medium in the reaction for producing the vinyl polymer is the same as the aqueous medium in the reaction for producing the polysiloxane, but here, it is preferable to use a solvent consisting of water alone.

A conventionally known radical polymerization catalyst may be used for grafting while polymerizing a water-insoluble vinyl monomer. This includes, for example, persulfates such as potassium persulfate and ammonium persulfate, hydroperoxides such as t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and di-t-butylperoxide. Oxide, t-butyl per-benzoate, dicumyl peroxide, t-butyl per-
Organic peroxides such as acetate, t-butyl per-octanoate, t-butyl per-phthalate, lauroyl peroxide, cyclohexanone peroxide, methyl isobutyl ketone peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobisisobutyronitrile, 2'-azobis-2,4-dimethylvaleronitrile, 2-carbamoylazoisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, 1,1 '
Azo compounds such as azobiscyclohexanecarbonitrile, persulfates, sodium thiosulfate, copper sulfate, hydroperoxides, ferrous sulfate, sodium pyrophosphate,
There are redox catalysts such as sodium phosphate, hydroperoxide / ferrous sulfate, and glucose / sodium pyrophosphate.

In the reaction of grafting while polymerizing a water-insoluble vinyl monomer, an aqueous medium in which the water-insoluble vinyl monomer and polysiloxane spherical fine particles are dispersed is placed in an inert gas atmosphere in the presence of a radical polymerization catalyst. It is performed by stirring with. The temperature at this time varies depending on various conditions as in the case of the reaction for producing polysiloxane, but is usually from room temperature to room temperature.
The boiling point of the water-insoluble vinyl monomer is preferably in the range of 50 to 80 ° C. Thus, a vinyl polymer is formed, that is, the vinyl polymer is grafted while being polymerized, and desired spherical composite fine particles formed of a copolymer in which a polysiloxane block and a vinyl polymer block are cross-linked to each other are obtained. obtain.

The spherical composite fine particles obtained by the production method of the present invention have a polysiloxane block selected by polycondensation of the silanol group-forming silicon compound and a vinyl polymer block obtained by graft polymerization of a water-insoluble vinyl monomer. And the polysiloxane block and the vinyl polymer block are formed from a copolymer cross-linked to each other.

In the above-described production method, the ratio of the silanol group-forming silicon compound to the water-insoluble vinyl monomer to be used is 99%.
Assuming that the weight ratio is 1/1 to 22/78, in the obtained spherical composite fine particles, the ratio of polysiloxane block to vinyl polymer block is polysiloxane block / vinyl polymer block = 97/3 to 20/80 ( (Weight ratio). If the ratio of the polysiloxane block is higher than this range, the resulting spherical composite fine particles are liable to be broken by mechanical impact, and the dispersibility in the polymer material is deteriorated. Conversely, if the ratio of the vinyl polymer is higher than this range, the low energy properties of the resulting spherical composite fine particles due to the polysiloxane are reduced.

According to the production method of the present invention, the average particle diameter is 0.1 ~ 10μ
m and the standard deviation of the particle size distribution are 1.0 to 2.0, and the ratio of the major axis to the minor axis is in the range of 1.0 to 1.1. Here, the standard deviation value of the particle size distribution means a standard deviation value of the particle size distribution obtained by an ultracentrifugal sedimentation method as described later in detail. The spherical composite fine particles of the present invention having such characteristic values are useful as modifiers for paints, cosmetics, rubber, plastics, paper, and the like.

When the spherical composite fine particles of the present invention are added as a modifier for paints, cosmetics, rubber, plastics, paper, etc., they can be added directly as they are, but usually, the spherical composite fine particles are liquid or liquid at room temperature. It is advantageous to add it as a dispersion dispersed 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 the medium in which the spherical composite fine particles are dispersed can be appropriately selected depending on the object to be modified. For example, when the spherical composite fine particles are used as a modifier for oil-based inks, oil-based paints, and magnetic paints, as a medium, fatty acid esters such as ethyl acetate, aromatic hydrocarbons such as toluene and xylene, and ketones such as methyl ethyl ketone. In the case where the spherical composite fine particles are used as a modifier for a radical-curable resin or a coating agent, examples of the medium include vinyl monomers such as styrene, (meth) acrylate, and vinyl acetate. Further, when the spherical composite fine particles are used as a modifier for a lubricating oil or an oil agent for treating fibers, as a medium, mineral oil, liquid paraffin, various synthetic esters, more specifically, butyl stearate, Ethylhexyl palmitate, trimethylolpropane trifatty acid ester, polyethers, polydimethylsiloxane, etc. Media, and the like. When the spherical composite fine particles are used as a modifier for a release agent in molding a thermoplastic resin or a thermosetting resin, a medium such as a hydrocarbon wax, a jelly, a natural or synthetic ester wax, or the like may be used. Below are mentioned solid organic media. When the spherical composite fine particles are used as a modifier for cosmetics, water-based paints, and paper coating agents, the medium is water, an aqueous medium in which water and a water-soluble organic solvent are mixed, and more specifically, water. An aqueous medium in which ethanol, glycerin, or the like is mixed is exemplified.

The spherical composite fine particles of the present invention are particularly effective for surface lubrication and prevention of blocking of various molded products such as thermoplastic resin films and sheets. As a method of adding the spherical composite fine particles to these, there are a method of directly adding to the molten polymer of the thermoplastic resin and a method of adding to the polymerization system in producing the thermoplastic resin, for example, terephthalic acid or ester-forming There is a method in which a terephthalic acid derivative and ethylene glycol are polycondensed to be added to a polycondensation system in producing polyethylene terephthalate. In the case of direct addition, it is advantageous to prepare a thermoplastic resin masterbatch containing 5 to 40% by weight of the spherical composite fine particles, and use the masterbatch. 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 glycol. Among them, alkylene having 2 to 4 carbon atoms is preferred. Glycols are preferred.

There is no particular limitation on the method for preparing the dispersion containing the spherical composite fine particles of the present invention, but in order to better exhibit the intended effect of the dispersion, the secondary aggregated particles of the spherical composite fine particles are crushed. Is preferred. In such a case, the dispersion may be prepared by disintegrating the spherical composite fine particles in a dry method and then dispersing them in a medium, or may be dispersed in the medium and disintegrating them in a wet method. Even if the spherical composite fine particles of the present invention are subjected to such a disintegration treatment, only the secondary aggregated particles are disintegrated into the original primary particles, and the original primary particles themselves are damaged. Is almost nonexistent.

In this way, a dispersion containing the spherical composite fine particles of the present invention is prepared. In addition to the dispersant, a surfactant as a protective colloid, a polymer substance, and the like may be present in the dispersion.

Hereinafter, examples and the like will be described in order to make the configuration of the present invention more specific, but the present invention is not limited to the examples.

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

The contents and results in Table 1 were measured by the following methods.

1) Average particle diameter and ratio of major axis to minor axis The spherical composite fine particles and the like obtained in each example were photographed with a scanning electron microscope (SEM). The shortest diameter passing through the center of the photographing image arbitrarily selected 50 particles from the (longest diameter = D _L passing through the center of the particle) Selection was longer diameter of the individual particles and the minor axis (particles = D _S ) was measured and calculated (D _L
The average value of + D _S ) / 2 was defined as the average particle size, and the average value of D _L / D _S was defined as the ratio of the major axis to the minor axis.

2) Standard deviation value of particle size distribution The spherical composite fine particles and the like obtained in each example are ultrasonically dispersed in water containing 1% by weight of a 10 mol adduct of nonylphenol ethylene oxide, and an ultracentrifugal automatic dispersion is performed using the dispersion. The average particle size and the particle size distribution were measured using a particle size distribution analyzer (CAPA-700 manufactured by Horiba, Ltd.). The value obtained by dividing the sum of the standard deviation of the particle size distribution and the average particle size by the average particle size was defined as the standard deviation value of the particle size distribution.

3) Polysiloxane content (% by weight) After the spherical composite fine particles obtained in each example were heated and dried in a nitric acid / perchloric acid (5/2) mixture to decompose organic substances,
Molybdenum blue method (colorimetric method; Anal. Chem., 19, 873, 194)
Seeking SiO ₂ content of 7 years) was a value calculated from the composition ratio of the SiO ₂ content and the charged silicon compound and a polysiloxane content.

Example 1 A flask was charged with 658 ml of water and 8.3 g of 28% ammonia water, and slowly stirred at room temperature to maintain the contents in a two-layer state, while 6 g (0.029 mol) of ethyl orthosilicate and octamethylcyclotetrasiloxane were added. 23 g (0.078 mol),
A mixture of 69 g (0.51 mol) of trimethoxyethylsilane, 2 g (0.0081 mol) of γ-methacryloxypropyltrimethoxysilane and 10 g (0.096 mol) of styrene was added dropwise over 1 hour, and hydrolyzed at the solution interface in a two-layer state. Polycondensation occurred during the polymerization. As the reaction proceeded, the product gradually settled to the lower layer, and the lower layer became cloudy, but after about 2 hours, the two-layer state disappeared and became a homogeneous system. Subsequently, the mixture was stirred at room temperature for 2 hours, further at 60 ° C. for 3 hours, cooled to room temperature, and the generated white fine particles were separated by filtration. Next, the white fine particles were charged into another flask together with 965 g of ion-exchanged water, dispersed in a homomixer, and then heated to 70 ° C. under a nitrogen stream,
50 g of a 3% aqueous potassium persulfate solution was added dropwise over 1 hour. After aging at 70 ° C. for 3 hours to carry out 8-radical polymerization, the content was cooled to room temperature, and white composite fine particles were separated by filtration. Then, the white composite fine particles were washed and dried to obtain 60.12 g of spherical composite fine particles.

The resulting spherical composite fine particles have an average particle size of 1.0 μm, a ratio between the major axis and the minor axis of 1.04, and a standard change value of the particle size distribution of 1.49.
The polysiloxane content was 86.8% by weight.

・ Example 2 As in Example 1, 658 ml of water, 8.3% of 28% aqueous ammonia
g, ethyl orthosilicate 6 g (0.029 mol), octamethylcyclotetrasiloxane 23 g (0.078 mol), trimethoxymethylsilane 69 g (0.51 mol), vinyltrimethoxysilane 2 g (0.0135 mol), styrene 38 g (0.36 mol) and divinyl Using 2 g (0.015 mol) of benzene,
Hydrolysis, condensation polymerization and radical polymerization were performed to obtain 90.0 g of spherical composite fine particles.

The resulting spherical composite fine particles have an average particle size of 0.9 μm, a ratio between the major axis and the minor axis of 1.04, and the standard deviation of the particle size distribution is 1.48,
The polysiloxane content was 63.9% by weight.

Example 3 As in Example 1, 658 ml of water, 8.3 of 28% aqueous ammonia were used.
g, ethyl orthosilicate 75 g (0.36 mol), trimethoxymethylsilane 54.5 g (0.40 mol), vinyltrimethoxysilane 22.2 g (0.15 mol) and styrene 46.8 g (0.45 mol)
), Hydrolysis, condensation polymerization and radical polymerization were carried out to obtain 92.1 g of spherical composite fine particles.

The resulting spherical composite fine particles have an average particle size of 1.2 μm, a ratio between the major axis and the minor axis of 1.02, and the standard deviation of the particle size distribution is 1.58,
The polysiloxane content was 57.5% by weight.

Example 4 As in Example 1, 658 ml of water, 16.6% of 28% aqueous ammonia
g, ethyl orthosilicate 6 g (0.029 mol), octamethylcyclotetrasiloxane 23 g (0.078 mol), trimethoxymethylsilane 69 g (0.51 mol), γ-methacryloxypropyltrimethoxysilane 2 g (0.0081 mol) and methyl methacrylate 10 g ( 0.1 mol) to carry out hydrolysis, condensation polymerization and radical polymerization to obtain spherical composite fine particles.
62.5 g were obtained.

The resulting spherical composite fine particles have an average particle size of 0.4 μm, a ratio between the major axis and the minor axis of 1.02, and the standard deviation of the particle size distribution is 1.43,
The polysiloxane content was 88.0% by weight.

Example 5 As in Example 1, 658 ml of water, 8.3 of 28% ammonia water
g, ethyl orthosilicate 6 g (0.029 mol), octamethylcyclotetrasiloxane 23 g (0.078 mol), trimethoxymethylsilane 69 g (0.51 mol), vinyltrimethoxysilane 2 g (0.0135 mol) and styrene 64 g (0.61 mol) After performing hydrolysis and polycondensation, 9 g of 89% phosphoric acid was added to the reaction system without filtering white fine particles to make the reaction system neutral, and 330 ml of water was further added. Radical polymerization is performed in the same manner as in
106 g were obtained.

The resulting spherical composite fine particles have an average particle size of 1.0 μm, a ratio between the major axis and the minor axis of 1.07, and the standard deviation of the particle size distribution is 1.75,
The polysiloxane content was 49.5% by weight.

Example 6 As in Example 1, 658 ml of water, 8.3 of 28% aqueous ammonia were used.
g, ethyl orthosilicate 6 g (0.029 mol), octamethylcyclotetrasiloxane 23 g (0.078 mol), trimethoxymethylsilane 69 g (0.51 mol), mercaptopropylmethyldimethoxysilane 2 g (0.012 mol) and styrene 10 g (0.096 mol) The resultant mixture was subjected to hydrolysis, condensation polymerization and radical polymerization to obtain 62.0 g of spherical composite fine particles.

The resulting spherical composite fine particles have an average particle diameter of 0.9 μm, a ratio between the major axis and the minor axis of 1.03, and the standard deviation of the particle diameter distribution is 1.50,
The polysiloxane content was 85.5% by weight.

Comparative Example 1 A flask was charged with 658 ml of water and 8.3 g of 28% aqueous ammonia, and slowly stirred at room temperature to keep the contents in a two-layer state, while ethyl orthosilicate 6 g (0.029 mol) and octamethylcyclotetrasiloxane were added. A mixture of 23 g (0.078 mol) and 71 g (0.52 mol) of trimethoxymethylsilane was added dropwise over 1 hour, and polycondensation was carried out while hydrolyzing at the solution interface in a two-layer state. Followed by stirring at room temperature for 2 hours,
After further stirring at 60 ° C. for 3 hours, the content was neutralized and wet-pulverized to obtain a white fine particle suspension.

The resulting white fine particle suspension has an average particle size of 1.3 μm,
The ratio of the major axis to the minor axis is 1.02, and the standard deviation of the particle size distribution is 1.1.
Met. Next, the suspension of the white fine particles was heated to 70 ° C. under a nitrogen stream, and 1 g of potassium persulfate was dissolved therein. Then, 10 g (0.096 mol) of styrene was further added dropwise over 1 hour. After aging at 70 ° C. for 3 hours for radical polymerization, the content was cooled to room temperature, and the white cake-like powder was separated by filtration. Then, the white cake-like powder was washed and dried to obtain 60 g of a white powder.

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

Comparative Example 2 As in Example 1, 658 ml of water, 8.3% of 28% aqueous ammonia
g, ethyl orthosilicate 6 g (0.029 mol), octamethylcyclotetrasiloxane 92 g (0.31 mol), trimethoxymethylsilane 2 g (0.015 mol) and styrene 10 g
(0.096 mol) for hydrolysis and polycondensation. There were no spherical fine particles in the reaction system that exhibited a cloudy emulsion, and release of the liquid monomer was partially observed. 89% phosphoric acid was added to the reaction to make the reaction system neutral, and 330 m
l and 1 g of potassium persulfate were added, followed by radical polymerization in the same manner as in Example 1. The shape of the particles generated in the reaction system was not spherical but amorphous.

Comparative Example 3 As in Example 1, 658 ml of water, 8.3 of 28% ammonia water
g, ethyl orthosilicate 6 g (0.029 mol), octamethylcyclotetrasiloxane 23 g (0.078 mol) and trimethoxymethylsilane 71 g (0.52 mol) were subjected to hydrolysis and polycondensation to obtain spherical fine particles.

The resulting spherical fine particles had an average particle size of 1.2 μm, a ratio between the major axis and the minor axis of 1.03, and a standard deviation value of the particle size distribution of 2.1.

Comparative Example 4 As in Example 1, 658 ml of water, 8.3 of 28% aqueous ammonia were used.
g, 75 g (0.36 mol) of ethyl orthosilicate and 75 g (0.55 mol) of trimethoxymethylsilane were subjected to hydrolysis and polycondensation to obtain spherical fine particles.

The resulting spherical fine particles had an average particle size of 1.1 μm, a ratio between the major axis and the minor axis of 1.03, and a standard deviation value of the particle size distribution of 2.0.

Comparative Example 5 As in Example 1, 658 ml of water, 8.3 of 28% aqueous ammonia were used.
g, ethyl orthosilicate 2 g (0.0097 mol), octamethylcyclotetrasiloxane 7.7 g (0.026 mol), trimethoxysilane 23.7 g (0.17 mol) and styrene 80 g
(0.77 mol) for hydrolysis and polycondensation. In the reaction system, styrene was partially separated. 89% phosphoric acid was added to this reaction to make the reaction system neutral,
Example 1 was continued by adding 330 ml and 1 g of potassium persulfate.
Radical polymerization was performed in the same manner as described above. In the reaction system, a mixture of spherical fine particles and styrene homopolymer was produced.

Comparative Example 6 A flask was charged with 658 ml of water and 8.3 g of 28% aqueous ammonia, and 0.39 g (0.0019 mol) of ethyl orthosilicate and octamethylcyclotetraethyl were added at room temperature while slowly stirring to keep the contents in a two-layer state. 60.16 g of siloxane (0.
204 mol), 4.46 g (0.033 mol) of trimethoxymethylsilane and 2 g (0.0081 mol) of γ-methacryloxypropyltrimethoxysilane were added dropwise over 50 minutes.
Polycondensation occurred while hydrolyzing at the solution interface in the layer state.
As the reaction proceeded, the product gradually settled into the lower layer, and the lower layer became cloudy, but after about 1.5 hours, the two-layer state disappeared and became a homogeneous system. Subsequently, the mixture was stirred at room temperature for 2 hours, further at 60 ° C. for 3 hours, cooled to room temperature, and the generated white fine particles were separated by filtration. Next, the white fine particles were charged into another flask together with 10 g (0.096 mol) of styrene and 965 g of ion-exchanged water, and dispersed by a homomixer.
The temperature was raised to 70 ° C., and 50 g of a 3% aqueous potassium persulfate solution was added dropwise over 1 hour. After aging at 70 ° C. for 3 hours to carry out radical polymerization, the content was cooled to room temperature, and white composite fine particles were separated by filtration. The white composite fine particles were washed and dried to obtain 59.6 g of spherical composite fine particles.

The resulting spherical fine particles had an average particle size of 1.0 μm, a ratio between the major axis and the minor axis of 1.30, a standard deviation of the particle size distribution of 2.8, and a polysiloxane content of 86.8% by weight.

Comparative Example 7 In the same manner as in Comparative Example 6, 658 ml of water and 8.3 g of 28% aqueous ammonia were charged into a flask, and 6 g of ethyl orthosilicate was slowly stirred at room temperature so as to keep the contents in a two-layer state.
(0.029 mol), octamethylcyclotetrasiloxane 2
3 g (0.078 mol), 69 g of trimethoxymethylsilane (0.51
Mol) and 2 g (0.0081 mol) of γ-methacryloxypropyltrimethoxysilane were added dropwise over a period of 50 minutes to react, and the white fine particles produced were filtered off. Next, 900 g of styrene (8.654
Mol) and ion-exchanged water (10,000 g), radical polymerization was carried out in the same manner as in Comparative Example 6, and the same treatment as in Comparative Example 6 was carried out to obtain 907 g of spherical composite fine particles.

The resulting spherical fine particles had an average particle size of 15.2 μm, a ratio of major axis to minor axis of 1.09, a standard deviation of the particle size distribution of 2.9, and a polysiloxane content of 10.0% by weight.

Test Category 2 (Production Example of Dispersion of Spherical Composite Fine Particles and the Like) Production examples of dispersions of spherical composite fine particles and the like are listed below, and their contents and results are summarized in Table 2.

The results in Table 2 were evaluated by the following methods.

1) Shape Retention For each of the obtained dispersions, 50 fine particles were arbitrarily selected from the image taken by the electron microscope described above, and the presence or absence of breakage of each selected fine particle was observed. Was evaluated.

◎: 1 or less broken particles observed ○: 2 to 6 broken particles observed △: 7 to 24 broken particles observed ×: 25 or more broken particles observed 2) Aggregated particles The presence or absence of each obtained dispersion was observed with an optical microscope of 1000 times, and
The degree of aggregation of the fine particles present in the range of × 20 μm was evaluated according to the following criteria.

○: Aggregated particles are less than 1% of all particles △: Aggregated particles are 1% or more and less than 10% of all particles ×: Aggregated particles are 10% or more of all particles 3) Dispersion stability Each obtained dispersion is conical. Place in a glass container and leave it tightly closed at room temperature (however, in Example 20, leave it tightly closed in a thermostat at 80 ° C), observe the separation state of fine particles daily, and evaluate according to the following criteria. did.

◎: No separation of fine particles was observed even after one month ○: Separation of fine particles was observed from 7 days to January △: Separation of fine particles was observed from 2 days to 6 days ×: Separation of fine particles was 1 Examples 7 to 10 and Comparative Examples 8 to 14 40 g of the spherical composite fine particles and the like shown in Table 2 and ethylene glycol in such an amount that the spherical composite fine particles and the like had a predetermined concentration were weighed and homogenized. After pre-dispersing with a mixer, 0.60 ~ 0.85
The dispersion was obtained by treating with a batch type sand grinder using glass beads of mmφ (manufactured by Igarashi Kikai Co., Ltd., vessel capacity: 400 cc) for 5 hours.

The dispersions of Examples 7 to 10 are useful as modifiers for imparting good lubricity to polyester molded articles.

Example 11 40 g of the spherical composite fine particles and 160 g of ethylene glycol shown in Table 2 were weighed and dispersed with a homomixer for 30 minutes to obtain a dispersion.

Example 12 40 g of spherical composite fine particles shown in Table 2 and 160 ion-exchanged water
g, nonylphenol ethylene oxide 3 mol adduct
1.2 g and 2.8 g of a nonylphenol ethylene oxide 10-mol adduct were weighed and subjected to dispersion treatment in the same manner as in Examples 7 to 10, to obtain a dispersion.

These dispersions are useful as modifiers for aqueous paints, cosmetics, paper coatings, oils for fiber treatment, and the like.

Example 13 40 g of the spherical composite fine particles and 160 g of styrene shown in Table 2 were weighed and subjected to dispersion treatment in the same manner as in Examples 14 to 19 to obtain a dispersion.

This dispersion is useful as a modifier for a radical polymer resin or a coating agent.

Test category (Example of use of spherical composite fine particles)-Usage example 1 The spherical composite fine particles obtained in Example 1, polyethylene resin (Yukaron LF-540B, manufactured by Mitsubishi Yuka Co., Ltd.) and antistatic agent (glycerin monostearate / N, N-bishydroxyethyllaurylamine (mixture of 1/1)) was kneaded with a 25 mmφ twin screw extruder to obtain 3% by weight of spherical composite fine particles and an antistatic agent 2
A masterbatch containing% by weight was prepared.

Next, using a polyethylene resin (same as above) mixed with 10% by weight of the master batch, a polyethylene film having a thickness of 30 μm was produced with a 30 mmφ inflation film forming machine. The appearance of the produced film was good, and no blocking was observed even after the wound film roll was allowed to stand in an atmosphere of 23 ° C. × 65% RH for 2 weeks.

On the other hand, the film prepared and prepared in the same manner as above except that the spherical composite fine particles were not used was free of foreign matter and had a good appearance, but remarkable blocking was observed after standing as described above. .

Test Category 4 (Examples of Use of Dispersion such as Spherical Composite Fine Particles) Examples of use of dispersions such as spherical composite fine particles are shown below, and their contents and results are summarized in Table 3.

The results in Table 3 were evaluated by the following methods.

1) Presence or Absence of Agglomerated Particles Each of the produced films was photographed by an electron microscope as described above, and the image was observed in a range of 70 × 50 μm and evaluated according to the following criteria.

○: no aggregated particles existed △: aggregated particles existed slightly ×: aggregated particles existed in 10% or more of all particles 2) Presence / absence of voids Observation of the image of 1) above shows voids around fine particles Was determined.

3) Abrasion resistance A 13 mm wide tape-shaped sample was prepared from each of the prepared films, and this sample was brought into contact with a stainless steel fixing pin (7 mmφ) with an incoming load of 30 g, and reciprocated 30 times at 2.5 m / min. I let it. Then, the surface state of the sample after the reciprocation was visually observed and evaluated according to the following criteria.

◎: No change such as whitening or scratches is observed. ；: Slight whitening or scratches are observed. Δ: Clear whitening or scratches are observed. X: Remarkable whitening or scratches are detected. Use Examples 2 to 10 Dimethyl terephthalate 100 Using 100 parts by weight of ethylene glycol and 70 parts by weight of ethylene glycol and 0.035 part by weight of manganese acetate tetrahydrate, the ester exchange reaction was carried out by raising the temperature to 230 ° C. in a conventional manner. Next, after adding 0.03 parts by weight of trimethyl phosphate, an ethylene glycol dispersion such as spherical composite fine particles shown in Table 3 was added so that the concentration of the spherical composite fine particles and the like became 0.3% by weight with respect to the polymer, followed by stirring.
After 0.03 parts by weight of antimony trioxide was added, the temperature was raised, and a polycondensation reaction was performed under a high temperature and a high vacuum according to a conventional method to obtain polyethylene terephthalate having an intrinsic viscosity of 0.61 dl / g. The polyethylene terephthalate obtained here was dried at 180 ° C, formed into a sheet with an extruder set at 290 ° C, stretched 3.5 parts vertically and 4.0 times horizontally at 90 ° C, and further heat-set at 210 ° C. Thus, a film having a thickness of 15 μm was produced.

<Effects of the Invention> As described above, the present invention has a small average particle size, a small standard deviation value of the particle size distribution, a constant shape, and a stable shape without aggregated particles. In this case, it is possible to obtain fine spherical composite fine particles and a dispersion thereof, and eventually has the effect of being able to carry out the modification as designed.

Claims (6)

(57) [Claims] (1) a silanol group-forming silicon compound of the following (A) and a water-insoluble vinyl monomer of the following (B): The monomer is used at a ratio of 99/1 to 22/78 (weight ratio). First, a polycondensation is performed by hydrolyzing the silanol group-forming silicon compound (A) in an aqueous medium in which both are present (B) )) To form spherical fine particles of a polysiloxane mixed with a water-insoluble vinyl monomer, and then subjecting the water-insoluble vinyl monomer of (B) to an aqueous medium in which the spherical fine particles are dispersed in the presence of a radical polymerization catalyst. A method for producing spherical composite fine particles, comprising grafting a polymer while polymerizing the same. (A): one or more of the silanol group-forming silicon compounds represented by the general formula (1) or (2) is 99.0 to 0 mol% and a silanol group represented by the general formula (3) or (4) A silanol group-forming silicon compound in which at least one kind of the silicon compound is 0.1 to 100 mol%, and p is 1 or less and / or a silanol group whose r + s is 1 A silanol group-forming silicon compound containing a total of 15 mol% or more of a forming silicon compound. General formula (1); R ⁴ _p -SiX _(4-p) General formula (2); General formula (3); R ⁷ _r R ⁸ _s SiX _(4-rs) General formula (4); [However, p is an integer of 0-3. r is an integer of 0 to 2, s is 1
An integer satisfying 1 ≦ r + s ≦ 3;
q and t are integers from 3 to 20. R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different unsubstituted or substituted non-radical polymerizable hydrocarbon groups having a carbon atom directly bonded to a silicon atom. R ⁸ and R ⁹ are --CH
= CH _2, One or more selected from (where y is an integer of 2 or 3). R ¹⁰ is the same hydrocarbon group as R ⁴ , R ⁵ , R ⁶ and R ⁷ or the same organic group as R ⁸ and R ⁹ . X is an alkoxy group having 1 to 4 carbon atoms, an alkoxyethoxy 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 4 alkyl groups, hydroxyl group, halogen atom or hydrogen atom. (B): One or more water-insoluble vinyl monomers containing a radically polymerizable ethylenically unsaturated group. 2. A spherical composite fine particle obtained by the production method according to claim 1, having an average particle size of 0.1 to 10 μm, a standard deviation value of the particle size distribution of 1.0 to 2.0, and a difference between a major axis and a minor axis. Spherical composite fine particles having a ratio of 1.0 to 1.1. 3. A dispersion of spherical composite fine particles containing the spherical composite fine particles according to claim 2 and a liquid or solid organic or aqueous medium at room temperature. 4. The dispersion of spherical composite fine particles according to claim 3, wherein the organic medium is an alkylene glycol having 2 to 4 carbon atoms. 5. The dispersion of spherical composite fine particles according to claim 3, wherein the aqueous medium is water. 6. The dispersion of spherical composite fine particles according to claim 3, wherein the secondary aggregated fine particles are subjected to a crushing treatment.