JP2013035758A - Method for producing composite particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing, regardless of the kind of inorganic powders, a composite particle in which a silicone elastomer is adhered uniformly onto the surface of an inorganic powder.SOLUTION: In the method for producing a composite particle, a compound selected from an alkoxy silane, a silanol group-containing silane, and a partial condensate of them is added into a mixed solution obtained by blending at least a mixed aqueous disperse solution in which an inorganic powder and a silicone elastomer are dispersed, a cationic water-soluble polymer, and an alkaline substance, whereby carrying out a hydrolysis-condensation reaction to produce a composite particle formed of the inorganic powder whose surface is adhered with the silicone elastomer by using a silicone resin as a binder.

Description

  The present invention relates to a method for producing composite particles, specifically, composite particles obtained by attaching a silicone elastomer to the surface of an inorganic powder.

  Make-up cosmetics such as foundations are intended to hide skin troubles such as wrinkles, pores, texture roughness, and color troubles such as skin spots and freckles, and to make the skin look smooth and beautiful. However, emphasis is placed on a natural finish that is not artificial (feeling of the skin). In addition, the natural finish of cosmetics is evaluated when there is no unnatural luster, excellent uniformity of the makeup film, and high transparency.

Conventionally, many new materials and new technologies have been proposed in order to obtain a natural finish feeling while following the effects of the makeup cosmetics.
In particular, the present inventor has proposed composite particles obtained by adhering a silicone elastomer having light diffusibility to the surface of an arbitrary core powder using a silicone resin as a binder (see Patent Document 1). Cosmetics can visually improve skin shape troubles, and have a soft and moist feeling as a smoothness unique to silicone elastomers. A correction effect can be imparted.

  This composite particle is obtained by adding an acidic substance or an alkaline substance and a compound selected from an alkoxysilane, a silanol group-containing silane and a partial condensate thereof to a mixed water dispersion in which a core powder and a silicone elastomer are dispersed, This compound can be produced by hydrolysis / condensation reaction. However, when the core powder is an inorganic powder, there are problems that the silicone elastomer particles do not adhere or the adhesion becomes uneven depending on the type.

JP 2011-1332 A

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing composite particles capable of uniformly attaching a silicone elastomer to the surface of an inorganic powder regardless of the kind of the inorganic powder. .

  In order to solve the above problems, the present invention is a method for producing composite particles, comprising at least a mixed water dispersion in which an inorganic powder and a silicone elastomer are dispersed, a cationic water-soluble polymer, and an alkaline substance. By adding a compound selected from alkoxysilane, silanol group-containing silane, and a partial condensate thereof to the blended liquid mixture and subjecting it to hydrolysis / condensation reaction, the surface of the inorganic powder is used as a silicone resin as a binder. Provided is a method for producing composite particles, characterized by producing composite particles formed by adhering a silicone elastomer.

  If such a production method is used, composite particles in which the silicone elastomer is uniformly adhered to the surface of the inorganic powder can be produced regardless of the kind of the inorganic powder.

The cationic water-soluble polymer is a synthetic system in which the polymer skeleton is synthesized by any one of vinyl polymerization, addition polymerization, and condensation, and does not contain an anionic group or an amphoteric group. It is preferable to use it.
If such a cationic water-soluble polymer is used, the polymer helps the silicone elastomer to be adsorbed to the inorganic powder, so that the silicone elastomer can be uniformly applied to the surface of the inorganic powder without aggregation. Can adhere.

Moreover, it is preferable to use what was synthesize | combined without using the monomer which has a nonionic group as said cationic water-soluble polymer.
The cationic water-soluble polymer synthesized without using a monomer having a nonionic group can make the silicone elastomer attached to the surface of the inorganic powder more uniform.

Moreover, it is preferable to use a polymer of dimethyldiallylammonium chloride as the cationic water-soluble polymer.
The dimethyldiallylammonium chloride polymer can make the silicone elastomer adhered to the surface of the inorganic powder more uniform.

Moreover, it is preferable that the compounding quantity of the cationic water-soluble polymer with respect to the said mixed water dispersion shall be 0.0001-1 mass part with respect to 100 mass parts of water in the said mixed water dispersion.
With such a blending amount, the silicone elastomer adhering to the surface of the inorganic powder can be made more uniform, and the adhesion state becomes better.

  As described above, according to the present invention, it is possible to obtain composite particles obtained by uniformly adhering a silicone elastomer to the surface of an inorganic powder regardless of the type of inorganic powder. By blending in cosmetics, it is expected that good spreading, softness, adhesion, mixing, and excellent skin shape correction effect can be imparted.

2 is an electron micrograph of composite particles obtained in Example 1. FIG. 2 is an electron micrograph of composite particles obtained in Comparative Example 1.

Hereinafter, the present invention will be described in more detail.
As described above, in the conventional method for producing composite particles, when the core powder is an inorganic powder, there are problems that the silicone elastomer particles do not adhere or the adhesion becomes uneven depending on the type.

  As a result of diligent investigations to solve the above problems, the present inventors have found that mixed water dispersions in which inorganic powder and silicone elastomer are dispersed include alkaline substances, alkoxysilanes, silanol group-containing silanes, and partial condensates thereof. In the method of producing composite particles by adding a selected compound and subjecting the compound to hydrolysis / condensation reaction, by adding a cationic water-soluble polymer to the mixed water dispersion, Regardless of the type, the present inventors have found that composite particles obtained by uniformly adhering a silicone elastomer to the surface of an inorganic powder using a silicone resin as a binder can be obtained.

  That is, the method for producing composite particles according to the present invention comprises at least an alkoxysilane in a mixed solution in which an inorganic powder and a silicone elastomer are dispersed, a cationic water-soluble polymer, and an alkaline substance. , A silanol group-containing silane, and a compound obtained by adding the compound selected from these partial condensates and causing hydrolysis / condensation reaction to attach the silicone elastomer to the surface of the inorganic powder using a silicone resin as a binder It is characterized by producing particles.

  As the inorganic powder used in the present invention, powders that can be substantially used in cosmetics and those having a particle size in the entire range can be applied. Further, as long as the geometrical form is usually used for cosmetics, it may be any shape such as spherical, polyhedral, spindle, needle or plate, and any of nonporous and porous But you can.

  The average particle size is preferably in the range of 0.5 to 50 μm, more preferably 1 to 30 μm. When the particle size is smaller than 0.5 μm, the feeling of use such as smooth feeling and smoothness and the effect of imparting extensibility may be lowered. When the particle size is larger than 50 μm, the feeling of roughness may appear. The average particle size is measured by appropriately selecting from a microscope method, a light scattering method, a laser diffraction method, a liquid phase precipitation method, an electric resistance method, etc. according to each shape.

  Inorganic powders include titanium oxide, mica titanium, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, cleaved talc, mica, kaolin, and sericite. Muscovite, synthetic mica, phlogopite, saucite, biotite, lithia mica, silicic acid, silicon dioxide, hydrous silicon dioxide, aluminum silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium silicate, Strontium silicate, metal tungstate, hydroxyapatite, vermiculite, hydrite, bentonite, montmorillonite, hectorite, zeolite, ceramics, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride , Nitride boron, include particles of glass.

  Furthermore, inorganic pigments can be mentioned. Specific examples include inorganic red pigments such as iron oxide, iron hydroxide and iron titanate, inorganic brown pigments such as γ-iron oxide; yellow iron oxide, ocher and the like. Inorganic yellow pigments; inorganic black pigments such as black iron oxide and carbon black; inorganic purple pigments such as manganese violet and cobalt violet; inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate; Inorganic blue pigments such as bitumen and ultramarine blue; colored pigments such as raked tar dyes and raked natural dyes; titanium oxide coated mica, titanium oxide coated mica, bismuth oxychloride, titanium oxide coated oxychloride Pearl pigments such as bismuth, titanium oxide coated talc, fish scale foil, titanium oxide coated colored mica; aluminum powder, copper powder, stainless powder And metal powder pigments and the like.

  The inorganic powder may be surface-treated with metal soap, silane, silicone, silicone resin, fluorine compound, amino acid, iron oxide, titanium oxide, iron oxide titanium oxide, or aluminum hydroxide.

  The silicone elastomer used in the present invention is produced by, for example, a method of emulsifying a curable liquid silicone composition to be described later, and therefore the shape is often spherical. Depending on the reaction conditions, even if it is substantially spherical or partially agglomerated particles, the effect is not greatly impaired. Further, the particle size is preferably smaller than the above-mentioned inorganic powder to which the silicone elastomer is attached in order to effectively express the feeling of use of the silicone elastomer. If it is larger than the inorganic powder, characteristics such as a feeling of use such as smoothness and smoothness, extensibility and adhesion may not be exhibited. The smaller particle size is not particularly limited, and for example, when it is produced by a method of emulsifying curable liquid silicone, the minimum particle size obtained by the method is the lower limit.

The silicone elastomer has the following formula (1)
-(R ¹ ₂ SiO _2/2 ) _n- (1)
It is a rubber elastic body which has the linear organosiloxane block shown by these.
R ¹ in the formula is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, and n is a positive number of 5 to 5,000.

Examples of R ¹ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group. Group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, henicosyl group, docosyl group, tricosyl group, tetrasyl group, triacotyl group and the like alkyl group; cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and the like cycloalkyl group Aryl groups such as phenyl, tolyl and naphthyl groups; aralkyl groups such as benzyl, phenethyl and β-phenylpropyl groups; alkenyl groups such as vinyl and allyl groups; and carbon atoms of these groups Some or all of the hydrogen atoms are Atoms, chlorine atoms, bromine atoms, iodine atoms) and / or hydrocarbon groups substituted with substituents such as acryloyloxy groups, methacryloyloxy groups, epoxy groups, glycidoxy groups, amino groups, mercapto groups, carboxyl groups, etc. Is mentioned.

  The rubber hardness of the silicone elastomer is preferably 10 or more as measured by a type E durometer as defined in JIS K 6253, and preferably 90 or less as measured by a type A durometer. More preferably, it is 20 or more in the type E durometer and 80 or less in the type A durometer. If the type E durometer is less than 10, the cohesiveness is increased, and the feeling of use such as a smooth feeling and smoothness and the extensibility may be poor. Moreover, when it exceeds 90 with a type A durometer, a soft touch may be poor.

  The silicone elastomer may be sticky so long as the feeling of use such as smoothness and smoothness and the extensibility are not significantly reduced. The silicone elastomer may contain cosmetically acceptable components such as silicone oil, organosilane, silicone resin, inorganic particles, organic particles, and hydrocarbon liquid oil.

The silicone elastomer is obtained from a curable liquid silicone composition.
The curing reaction includes a condensation reaction between a methoxysilyl group (≡SiOCH ₃ ) and a hydroxysilyl group (≡SiOH), a hydrosilyl group (≡SiH) and a hydroxysilyl group (≡SiOH), a mercaptopropylsilyl group (≡Si— Examples include radical reaction between C ₃ H ₆ SH) and vinylsilyl group (≡SiCH═CH ₂ ) and addition reaction between vinylsilyl group (≡SiCH═CH ₂ ) and hydrosilyl group (≡SiH). From the viewpoint of reactivity, it is preferable to use a condensation reaction or an addition reaction.

For example, when a silicone elastomer is obtained by curing by addition reaction, the following average composition formula (2)
R ² _a R ³ _b SiO _{(4-ab) / 2} (2)
An organopolysiloxane having at least two monovalent olefinically unsaturated groups in one molecule represented by the following average composition formula (3)
R ⁴ _c H _d SiO _{(4-cd) / 2} (3)
The organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atoms in one molecule represented by the formula is such that 0.5 to 2 hydrosilyl groups per one monovalent olefinically unsaturated group What is necessary is just to carry out addition polymerization of the curable liquid silicone composition mix | blended by the ratio in presence of a platinum-type catalyst.

Here, in the average composition formula (2), R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, excluding an aliphatic unsaturated group, and R ³ has 2 to 6 carbon atoms. These are monovalent olefinically unsaturated groups. a and b are positive numbers represented by 0 ≦ a <3, 0 <b ≦ 3, and 0.1 ≦ a + b ≦ 3, and preferably 0 ≦ a ≦ 2.295, 0.005 ≦ b ≦ 2. 3, 0.5 ≦ a + b ≦ 2.3.

In the average composition formula (3), R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms excluding an aliphatic unsaturated group. c and d are positive numbers represented by 0 ≦ c <3, 0 <d ≦ 3, 0.1 ≦ c + d ≦ 3, preferably 0 ≦ c ≦ 2.295, 0.005 ≦ d ≦ 2.3. 0.5 ≦ c + d ≦ 2.3.

Examples of R ² include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group. Group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, henicosyl group, docosyl group, tricosyl group, tetrasyl group, triacotyl group and the like alkyl group; cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and the like cycloalkyl group Aryl groups such as phenyl group, tolyl group and naphthyl group; aralkyl groups such as benzyl group, phenethyl group and β-phenylpropyl group; and some or all of hydrogen atoms bonded to carbon atoms of these groups are halogen atoms (Fluorine atom, chlorine atom, bromine atom, iodine source ) Atoms and / or acryloyloxy groups such as, methacryloyloxy group, an epoxy group, glycidoxy group, etc. hydrocarbon group substituted with a substituent such as a carboxyl group. R ² is preferably 80 mol% or more, preferably 90 mol% or more, and is a non-reactive group such as an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group.

Examples of R ³ include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and the like, but industrially a vinyl group is preferable. Examples of R ⁴ are the same as R ² .

Since the kinematic viscosity at 25 ° C. of the organopolysiloxane and organohydrogenpolysiloxane having an olefinically unsaturated group can be obtained efficiently in the following production, 1,000,000 mm ² / S or less is preferable, More preferably, it is 500,000 mm < ² > / s or less.
This kinematic viscosity is a value measured with a capillary viscometer.

  In addition, the structure of the organopolysiloxane having an olefinically unsaturated group and the organohydrogenpolysiloxane may be linear, cyclic, or branched.

Examples of the platinum-based catalyst include platinum group metals such as platinum (including platinum black), rhodium, and palladium; H ₂ PtCl ₄ · kH ₂ O, H ₂ PtCl ₆ · kH ₂ O, NaHPtCl ₆ · kH ₂ O, KHPtCl ₆ · kH ₂ O, Na ₂ PtCl ₆ · kH ₂ O, K ₂ PtCl ₄ · kH ₂ O, PtCl ₄ · kH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ · kH ₂ O (where, k Is an integer from 0 to 6, preferably 0 or 6), such as platinum chloride, chloroplatinic acid and chloroplatinate; alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972) A complex of chloroplatinic acid and an olefin (see US Pat. Nos. 3,159,601, 3,159,662, and 3,775,452); A platinum group metal such as palladium supported on alumina, silica, carbon or the like; rhodium-olefin complex; chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst); platinum chloride, chloroplatinic acid or chloroplatinate And a vinyl group-containing siloxane, in particular, a vinyl group-containing siloxane complex.

  For example, when a silicone elastomer is obtained by curing by a condensation reaction, an organopolysiloxane having at least two hydroxyl groups bonded to silicon atoms in one molecule and at least three hydrogen atoms bonded to silicon atoms in one molecule. What is necessary is just to carry out condensation polymerization of the liquid silicone composition consisting of the organohydrogenpolysiloxane having in the presence of a condensation catalyst.

In the present invention, it is preferable to use a silicone elastomer as a dispersion.
The method for preparing the silicone elastomer dispersion is not particularly limited, and a known method for preparing a silicone elastomer dispersion is used. For example, it can be produced by emulsifying a curable liquid silicone composition in water using a surfactant and then causing a curing reaction. For example, when a silicone elastomer is obtained by curing by an addition reaction, a surfactant and water are added to a curable liquid silicone composition comprising an organopolysiloxane having an olefinically unsaturated group and an organohydrogenpolysiloxane. There is a method of emulsifying and making an emulsion and then adding a platinum-based catalyst to carry out addition polymerization.

Moreover, the method of using the curable liquid silicone composition manufactured by emulsion polymerization as another method is mentioned. For example, when a silicone elastomer is obtained by curing by a condensation reaction, the general formula [R ⁵ ₂ SiO] _m (R ⁵ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, m is a number of 3 to 7). ) Is added to the cyclopolysiloxane to emulsify, and then acid is added to cause the polymerization reaction, followed by neutralization by addition of alkali, An emulsion of organopolysiloxane containing a hydroxyl group bonded to a silicon atom at the end is prepared. A method in which an organotrialkoxysilane and a condensation catalyst are added to this and subjected to condensation polymerization can be mentioned.

  The surfactant used for emulsification of the curable liquid silicone composition is not particularly limited. For example, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol fatty acid ester, Sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene Castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid ester Polyoxyethylene phytostanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, polyoxyethylene alkylamine, alkyl alkanolamide, sucrose fatty acid ester, methyl glucoside fatty acid ester, alkyl polyglycoside, Linear or branched polyoxyethylene-modified organopolysiloxane, linear or branched polyoxyethylene polyoxypropylene-modified organopolysiloxane, polyoxyethylene / alkyl co-modified organopolysiloxane, linear or branched polyoxyethylene polyoxy Propylene / alkyl co-modified organopolysiloxane, linear or branched polyglycerin-modified organopolysiloxane, linear or Nonionic surfactants such as branched polyglycerin / alkyl co-modified organopolysiloxanes; alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, fatty acid alkylolamide sulfuric acid Ester salt, alkylbenzene sulfonate, polyoxyethylene alkyl phenyl ether sulfonate, α-olefin sulfonate, α-sulfo fatty acid ester salt, alkyl naphthalene sulfonic acid, alkyl diphenyl ether disulfonate, alkane sulfonate, N- Acyl taurate, dialkyl sulfosuccinate, monoalkyl sulfosuccinate, polyoxyethylene alkyl ether sulfosuccinate, fatty acid salt, polyoxyethylene alkyl ether Anionic surfactants such as alkyl carboxylate, N-acyl amino acid salt, monoalkyl phosphate salt, dialkyl phosphate salt, polyoxyethylene alkyl ether phosphate salt; alkyltrimethylammonium salt, dialkyldimethylammonium salt, Polyoxyethylene alkyldimethylammonium salt, dipolyoxyethylenealkylmethylammonium salt, tripolyoxyethylenealkylammonium salt, alkylbenzyldimethylammonium salt, alkylpyridium salt, monoalkylamine salt, dialkylamine salt, trialkylamine salt, mono Cationic surfactants such as alkylamidoamine salts; alkyldimethylamine oxide, alkyldimethylcarboxybetaine, alkylamidopropyl dimethylcal Examples thereof include amphoteric surfactants such as boxybetaine, alkylhydroxysulfobetaine, and alkylcarboxymethylhydroxyethylimidazolinium betaine.

  These surfactants can be used individually by 1 type or in combination of 2 or more types as appropriate. Preferably, it is selected from nonionic surfactants. The amount of the surfactant used is preferably in the range of 0.1 to 50 parts by mass with respect to 100 parts by mass of the curable liquid silicone composition.

  When emulsifying, a general emulsifying disperser may be used. Examples thereof include a high-speed rotary centrifugal type agitator such as a homodisper; a high-speed rotary shear type agitator such as a homomixer; and a high-pressure jet type such as a homogenizer. Emulsifying and dispersing machine; colloid mill; ultrasonic emulsifying machine and the like.

The obtained dispersion of the silicone elastomer is preferably used as it is without being subjected to solid-liquid separation.
The mixed water dispersion in which the inorganic powder and the silicone elastomer are dispersed can be obtained, for example, by mixing inorganic powder, a dispersion of the silicone elastomer, and water as necessary.

  3-150 mass parts is preferable with respect to 100 mass parts of water mix | blended, and, as for inorganic powder, 5-50 mass parts is more preferable. If it is less than 3 parts by mass, the production efficiency may be deteriorated, and if it exceeds 150 parts by mass, the kinematic viscosity of the mixed water dispersion becomes high, so that it may be difficult to attach the silicone elastomer to the inorganic powder. As the inorganic powder, one prepared in advance as a dispersion may be used.

  The amount of the silicone elastomer is not particularly limited in the case where the effect of addition to cosmetics is manifested, but is more favorable, such as a more pronounced soft focus effect, smooth feeling, smoothness, extensibility, moist feeling, softness, etc. When a feeling of use is desired, the amount is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass or more with respect to 100 parts by mass of the inorganic powder. When the amount of silicone elastomer increases, the cohesiveness increases, and the feeling of use such as smoothness and smoothness and the extensibility may be poor. Therefore, the amount is preferably 100 parts by mass or less with respect to 100 parts by mass of the inorganic powder. Preferably it is 70 mass parts or less, More preferably, it is 50 mass parts or less.

In the present invention, a cationic water-soluble polymer is blended in a mixed water dispersion in which inorganic powder and silicone elastomer are dispersed.
Here, the cationic water-soluble polymer is a water-soluble polymer having a cationic group in the molecule, and the cationic group is specifically a quaternary ammonium salt or an amino group. The cationic water-soluble polymer used in the present invention is not particularly limited, but a synthetic system in which the polymer skeleton is synthesized by vinyl polymerization, addition polymerization, condensation or the like is preferable. Moreover, what does not contain an anionic group and an amphoteric group is preferable. The average molecular weight is 5,000 to 10,000,000, preferably 10,000 to 1,000,000.

  Examples of cationic water-soluble polymers include dimethyldiallylammonium chloride / polymer, dimethyldiallylammonium chloride / acrylamide copolymer, dimethyldiallylammonium chloride / vinylimidazoline / vinylpyrrolidone copolymer, and vinylimidazoline polymer. , Methyl vinyl imidazolium chloride polymer, methyl vinyl imidazolium chloride / vinyl pyrrolidone copolymer, methyl vinyl imidazolium methyl sulfate / vinyl pyrrolidone / vinyl caprolactam copolymer, methyl vinyl imidazolium chloride / vinyl imidazoline / vinyl Pyrrolidone / methacrylic acid amide copolymer, ethyl trimethylammonium acrylate polymer, ethyl acrylate trimethyl Ammonium chloride / vinyl pyrrolidone copolymer, ethyltrimethylammonium acrylate chloride / acrylamide copolymer, ethyltrimethylammonium methacrylate polymer, ethyltrimethylammonium methacrylate methylsulfate / acrylamide copolymer, ethyl methacrylate Copolymer of trimethylammonium chloride / methyl methacrylate, ethyltrimethylammonium methacrylate / dimethylacrylamide / polyethylene glycol dimethacrylate, ethyltrimethylammonium methacrylate / acrylamidopropyltrimethylammonium chloride / dimethylacrylamide Coalescence, ethyl trimethylammonium methacrylate Copolymer of rhoride / acrylamidopropyltrimethylammonium chloride / dimethylacrylamide / hydroxyethyl methacrylate, polymer of acrylamidepropyltrimethylammonium chloride, copolymer of acrylamidepropyltrimethylammonium chloride / acrylamide, acrylamidepropyltrimethylammonium chloride / dimethylacrylamide / Copolymer of hydroxyethyl methacrylate, polymer of methacrylamide propyl trimethyl ammonium chloride, copolymer of methacrylamide propyl trimethyl ammonium chloride / vinyl pyrrolidone, ethylene imine polymer, quaternized product of ethylene imine polymer, allylamine Examples include hydrochloride polymers and polylysine. These can be used individually by 1 type or in combination of 2 or more types.

Among these, those that do not use a monomer having a nonionic group are preferable. For example, a polymer of dimethyldiallylammonium chloride, a polymer of vinylimidazoline, a polymer of methylvinylimidazolium chloride, an ethyltrimethylammonium acrylate chloride, and the like. Polymer, ethyltrimethylammonium methacrylate polymer, acrylamidepropyltrimethylammonium chloride polymer, methacrylamidopropyltrimethylammonium chloride polymer, ethyleneimine polymer, quaternized ethyleneimine polymer, allylamine hydrochloride It is selected from a salt polymer, polylysine and the like.
Particularly preferred is a polymer of dimethyldiallylammonium chloride.

  The cationic water-soluble polymer may be blended as it is in the mixed water dispersion in which the inorganic powder and the silicone elastomer are dispersed, or may be blended as an aqueous solution. Further, the blending order is not particularly limited, and the inorganic water and the silicone elastomer mixed water dispersion may be added after the cationic water-soluble polymer is blended and dissolved in water first.

  The amount of the cationic water-soluble polymer to be blended is preferably 0.0001 to 1 part by mass with respect to 100 parts by mass of water in the mixed water dispersion. When the blending amount is 0.0001 parts by mass to 1 part by mass, the silicone elastomer adhering to the surface of the inorganic powder can be made more uniform, and the adhesion state is also improved. More preferably, it is the range of 0.001-0.1 mass part.

In the method for producing composite particles of the present invention, an alkaline substance is further used.
The alkaline substance is a catalyst for hydrolysis / condensation reaction of alkoxysilane, silanol group-containing silane, and partial condensates thereof.

  The alkaline substance is preferably added to water in which the inorganic powder and the silicone elastomer are dispersed and the cationic water-soluble polymer is dissolved. However, the blending order is not particularly limited, and the alkaline substance is first dissolved in water. After that, other components may be blended, or after adding a part of the other components, an alkaline substance may be added, and the remaining components may be added sequentially.

  The blending amount of the alkaline substance is preferably such that the pH of the mixed liquid of at least the alkaline substance and the mixed aqueous dispersion in which the inorganic powder and the silicone elastomer are dispersed is 10.0 to 13.0, more preferably 10. The amount is in the range of 5 to 12.5. When an alkaline substance in an amount such that the pH is 10.0 to 13.0 is added, the hydrolysis / condensation reaction of a compound selected from the alkoxysilanes, silanol group-containing silanes described below, and partial condensates thereof is sufficient. Become.

  The alkaline substance is not particularly limited, and examples thereof include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; potassium carbonate and carbonate Alkali metal carbonates such as sodium; ammonia; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; or monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, dimethylamine, diethylamine Further, amines such as trimethylamine, triethanolamine and ethylenediamine can be used.

  Among them, ammonia is most suitable because it can be easily removed from the resulting silicone fine particle powder by volatilization. As ammonia, a commercially available aqueous ammonia solution can be used.

In the present invention, an alkoxysilane, a silanol group-containing silane, and a portion thereof are further added to a mixed solution in which an inorganic powder and a silicone elastomer are dispersed, a mixture of a cationic water-soluble polymer, and an alkaline substance. A compound selected from condensates is added.
Alkoxysilanes, silanol group-containing silanes, and partial condensates thereof are hydrolyzed and condensed by the catalytic action of the above-mentioned alkaline substance to form resinous silicone.

The alkoxysilane used in the present invention is represented by the general formulas R ⁶ Si (OR ⁷ ) ₃ , R ⁶ ₂ Si (OR ⁷ ) ₂ , R ⁶ ₃ SiOR ⁷ and Si (OR ⁷ ) ₄ . R ⁶ in the formula is each independently a monovalent organic group having 1 to 20 carbon atoms. Examples of R ⁶ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and the like alkyl groups; cyclobutyl group, cyclopentyl group Cycloalkyl group such as cyclohexyl group and cycloheptyl group; aryl group such as phenyl group, tolyl group and naphthyl group; aralkyl group such as benzyl group, phenethyl group and β-phenylpropyl group; alkenyl such as vinyl group and allyl group A part or all of the hydrogen atoms bonded to the carbon atoms of these groups; Carbon atoms substituted with a substituent such as an atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) and / or an acryloyloxy group, a methacryloyloxy group, an epoxy group, a glycidoxy group, an amino group, a mercapto group, a carboxyl group, etc. A hydrogen group etc. are mentioned. By the method described later, a resinous silicone is produced by hydrolysis / condensation reaction of a compound selected from alkoxysilane, silanol group-containing silane, and partial condensates thereof. From the viewpoint of the condensation reactivity, R ⁶ is 50. It is preferable that mol% or more is a methyl group, and more preferably 70 mol% or more. R ⁷ is an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and examples of R ⁷ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. From this point, a methyl group is preferable.

Alkoxysilane R ⁶ Si (OR ⁷ ) ₃ , R ⁶ ₂ Si (OR ⁷ ) ₂ , R ⁶ ₃ SiOR ⁷ , and Si (OR ⁷ ) ₄ are each a structural unit of resin-like silicone [R ⁶ SiO _3/2. ], [R ⁶ ₂ SiO _2/2 ], [R ⁶ ₃ SiO _1/2 ], [SiO _4/2 ]. A silicone resin is produced by a hydrolysis / condensation reaction. However, since silanol groups remain without partial condensation reaction, it is precisely a copolymer including those selected from the following structural units containing silanol groups. is there.

_{Unless it} is a structure containing [R ⁶ SiO _3/2 ] or [SiO _4/2 ] units, it cannot be a resinous solid. If it contains at least [R ⁶ SiO _3/2 ] or [SiO _4/2 ] units, is a resin-like solid at room temperature, and is insoluble in oils used in cosmetics as described below, the structure The unit ratio, the degree of polymerization, and the hardness are not particularly limited. However, when the melting point is low, the composite particles are fused with each other during storage in a high-temperature atmosphere or in the drying step. Therefore, the melting point is preferably 50 ° C. or higher, more preferably 80 ° C. or higher.

Since there is a decrease in slipperiness when there are many [SiO _4/2 ] units, the unit is selected from [R ⁶ SiO _3/2 ], [R ⁶ ₂ SiO _2/2 ] and [R ⁶ ₃ SiO _1/2 ] units. , ^[R 6 _{SiO 3/2]} one comprising units or of two or more structural units polymer are preferable, structure preferably further 50 mol% or more ^[R 6 _{SiO 3/2]} units, more Preferably it is 70 mol% or more.

Therefore, the blending ratio of R ⁶ Si (OR ⁷ ) ₃ , R ⁶ ₂ Si (OR ⁷ ) ₂ , R ⁶ ₃ SiOR ⁷ , Si (OR ⁷ ) ₄ is set to a desired resinous silicone structure. Just decide. That is, in a molar ratio, the desired structural unit [R ⁶ SiO _3/2 ]: [R ⁶ ₂ SiO _2/2 ]: [R ⁶ ₃ SiO _1/2 ]: [SiO _4/2 ]
= R ⁶ Si (OR ⁷ ) ₃ : R ⁶ ₂ Si (OR ⁷ ) ₂ : R ⁶ ₃ SiOR ⁷ : Si (OR ⁷ ) ₄
And it is sufficient.

A silanol group-containing silane is a compound in which R ^{7 in} the general formula of the alkoxysilane is hydrogen. What is necessary is just to select suitably from an alkoxysilane, silanol group containing silane, and these condensates so that it may become a desired structural unit.

  While stirring the mixed water containing inorganic powder, silicone elastomer, cationic water-soluble polymer, and alkaline substance, a compound selected from alkoxysilane, silanol group-containing silane, and partial condensates thereof is added to the hydrolysis / Allow condensation reaction. Compounds selected from alkoxysilanes, silanol group-containing silanes and partial condensates thereof may be gradually added dropwise, or may be added in a form dissolved in water or dispersed in water, You may add what mix | blended water-soluble organic solvents, such as alcohol.

  Stirring may cause aggregation of inorganic particles when strong stirring is performed, so it is preferable to use paddle blades, propeller blades, swept blades, saddle blades, etc., but it is preferable to use inorganic powder, alkoxysilane, silanol group The stirring intensity | strength in which the compound chosen from containing silane and these partial condensates is disperse | distributed in a liquid mixture is required.

  The temperature at which a compound selected from alkoxysilane, silanol group-containing silane and partial condensates thereof is added to the mixed solution is preferably 0 to 60 ° C, more preferably 0 to 39 ° C. If this temperature is lower than 0 ° C, the mixed solution may be solidified. If the temperature is higher than 60 ° C, the obtained particles may be aggregated.

  Resin-like silicone is formed on the surface of the inorganic powder and / or the surface of the silicone elastomer by the hydrolysis / condensation reaction. At the same time, the inorganic powder and the silicone elastomer adhere to each other. Composite particles to which a silicone elastomer is adhered are formed using a silicone-like binder.

  The amount of the compound selected from alkoxysilanes, silanol group-containing silanes and partial condensates thereof is not particularly limited. However, in order to uniformly attach the silicone elastomer to the surface of the inorganic powder, From the viewpoint of enhancing the sticking property, the amount is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 30 parts by mass or more with respect to 100 parts by mass of the silicone elastomer. Further, since the soft feel of the silicone elastomer may not be exhibited when the silicone resin is increased, the amount is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and still more preferably 100 parts by mass of the silicone elastomer. It is 200 parts by mass or less.

  For the purpose of uniformly adhering the silicone elastomer to the surface of the inorganic powder, a water-soluble organic solvent such as alcohol may be added to the mixed solution. When the particles are surface-treated with a silylating agent, the finished composite particles may be treated, but a compound selected from the above alkoxysilanes, silanol group-containing silanes and partial condensates thereof is added to the mixture. Then, a silylating agent may be added and treated. Examples of the silylating agent include dimethyldichlorosilane, trimethylchlorosilane, trimethylmethoxysilane, trimethylsilanol group-containing silane, hexamethyldisilazane, and the like.

  It is preferable to continue stirring for a while after completion of the addition of a compound selected from alkoxysilane, silanol group-containing silane and partial condensates thereof until the hydrolysis / condensation reaction is completed. In order to accelerate the reaction, heating may be performed at 40 to 100 ° C., or an alkaline substance may be added. Thereafter, if necessary, an acidic substance may be added for neutralization.

  After the hydrolysis / condensation reaction, water is removed. The removal of water can be performed, for example, by heating the mixed solution after the reaction under normal pressure or reduced pressure, and specifically, a method of removing water by leaving the mixed solution standing under heating, mixing Examples thereof include a method of removing moisture while stirring and flowing the liquid under heating, a method of spraying and dispersing the mixed liquid in a hot air stream like a spray dryer, and a method of using a fluidized heat medium. In addition, as a pretreatment of this operation, the mixed solution may be concentrated by a method such as filtration separation such as heat dehydration and pressure filtration, centrifugation, decantation, etc. You may wash.

When the powder obtained by removing moisture from the mixed solution after the reaction is agglomerated, it may be crushed or classified by a pulverizer such as a jet mill, a ball mill, or a hammer mill.
The silicone resin may be partially or entirely attached to the inorganic powder surface and / or the silicone elastomer surface.

The composite particles obtained by the present invention are particles formed by attaching a silicone elastomer to the surface of an inorganic powder using a silicone resin as a binder. For the purpose of imparting and improving water repellency and improving dispersibility in oils. In addition, the particle surface may be treated with a silylating agent, silicone oil, waxes, paraffins, organic fluorine compounds, surfactants and the like.
The state in which the silicone elastomer is adhered to the surface of the inorganic powder can be confirmed with an electron microscope.

EXAMPLES Hereinafter, although a manufacture example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the examples, the kinematic viscosity is a value measured using a capillary viscometer at 25 ° C., and “%” indicating the concentration and the content indicates “mass%”.
[Production example]
(Manufacture of aqueous dispersion of silicone elastomer)
400 g of methyl vinyl polysiloxane having a kinematic viscosity of 4,900 mm ² / s represented by the following formula (4) and 7 g of methyl hydrogen polysiloxane having a kinematic viscosity of 30 mm ² / s represented by the following formula (5) The amount of 1.1 hydrosilyl groups per vinyl group) was charged into a 1 liter glass beaker and mixed and dissolved using a homomixer. Thereafter, 33 g of polyoxyethylene lauryl ether (trade name: Emulgen 109P, manufactured by Kao Corporation) and 35 g of water were added, and the mixture was further stirred using a homomixer. The thickened material was kneaded for 15 minutes using a homodisper. Next, when 523 g of water was added and mixed using a homomixer, a uniform white emulsion was obtained. This emulsion was transferred to a glass flask having a capacity of 1 liter equipped with a stirrer with a vertical stirring blade, adjusted to a temperature of 15 to 20 ° C., and then stirred with a toluene solution of a chloroplatinic acid-olefin complex (with a platinum content of 0.1%). 5%) 0.6 g, 1.2 g of polyoxyethylene lauryl ether (trade name: Emulgen 109P, manufactured by Kao Corporation) was added and stirred for 24 hours at the same temperature, and an aqueous dispersion of silicone elastomer Got.

It was 280 nm when the volume average particle diameter of the obtained silicone elastomer was measured using "Laser diffraction / scattering type particle size distribution analyzer LA-920" (manufactured by Horiba, Ltd.). The formula (4), the kinematic viscosity is represented by methyl vinyl polysiloxane 4,900mm ² / s, the equation (5), a kinematic viscosity of 30 mm ² / s methylhydrogenpolysiloxane, and platinum chloride A toluene solution of acid-olefin complex (platinum content: 0.5%) is mixed at the above-mentioned mixing ratio, poured into an aluminum petri dish so that the thickness becomes 10 mm, left at 25 ° C. for 6 hours, and then a thermostatic bath at 50 ° C. For 1 hour. The obtained cured product was a rubber elastic body without stickiness, and its hardness was 20 as measured by a durometer A hardness meter.

[Example 1]
In a glass flask having a capacity of 3 liters equipped with a stirrer with a vertical stirring blade, 120 g of talc particles (trade name: JA-69R, manufactured by Asada Flour Milling Co., Ltd., shape = plate shape, average particle size = 10 μm) and the above 40% dimethyldiallyl was added to a mixed aqueous dispersion obtained by mixing 41 g of the silicone elastomer aqueous dispersion obtained in the production example (an amount of 14 parts by mass of the silicone elastomer with respect to 100 parts by mass of the talc particles) and 1,280 g of water. Ammonium chloride polymer aqueous solution (trade name: ME polymer H40W, manufactured by Toho Chemical Industry Co., Ltd., average molecular weight = 240,000) 0.33 g (amount to be 0.01 parts by mass with respect to 100 parts by mass of water), and 28 30% aqueous ammonia was charged. The pH of the liquid at this time was 11.5. After adjusting the temperature to 5 to 10 ° C., 29 g of methyltrimethoxysilane (an amount in which the silicone resin after hydrolysis and condensation reaction becomes 85 parts by mass with respect to 100 parts by mass of the silicone elastomer) is dropped over 20 minutes. The liquid temperature was kept at 5 to 10 ° C. and further stirred for 1 hour. Subsequently, it heated to 55-60 degreeC, it stirred for 1 hour, maintaining the temperature, and the hydrolysis and condensation reaction of methyltrimethoxysilane was completed. The obtained suspension was dehydrated using a pressure filter. The dehydrated product was transferred to a 3 liter glass flask equipped with a stirrer with a vertical stirring blade, added with 1,000 g of water, stirred for 30 minutes, and then dehydrated using a pressure filter. Again, the dehydrated product was transferred to a glass flask, and the flask was immersed in an oil bath at 110 ° C. and dried with stirring to obtain fluid particles.

  When the obtained particles were observed with an electron microscope, spherical particles of about 300 nm were uniformly attached to the surface of the plate-like particles, and it was a composite particle formed by attaching a silicone elastomer to the surface of the talc particles. It was confirmed (FIG. 1). Moreover, it turned out that resin-like silicone becomes a binder and the silicone elastomer is made to adhere to a talc particle. That is, if there is no binder for attaching the silicone elastomer to the surface of the talc particles, even if the silicone elastomer is attached to the surface of the talc particles, it is considered that the silicone elastomer is detached from the surface of the talc particles by the water washing and drying operation. . When the silicone elastomer falls off, the silicone elastomer has high cohesiveness, and thus it is considered that the particles are aggregated. However, particles having such a shape were not observed with an electron microscope.

  Furthermore, after weighing 20 g of sodium bromide, polyoxyethylene lauryl ether (trade name: Emulgen 109P, Kao (manufactured)) 0.5 g, water 80 g and composite particles 5 g in a 100 mL glass bottle and shaking for 30 minutes, When the silicone elastomer dropped off from the surface of the talc particles, the silicone elastomer floated because the specific gravity was smaller than that of sodium bromide water, but the whole amount had settled. This suggests that the silicone resin becomes a binder and the silicone elastomer is adhered to the talc particles.

[Example 2]
40% dimethyldiallylammonium chloride polymer aqueous solution of Example 1 (trade name: ME polymer H40W, manufactured by Toho Chemical Co., Ltd., average molecular weight = 240,000) 0.33 g (0.01 mass relative to 100 mass parts of water) Part) was 42% dimethyldiallylammonium chloride polymer aqueous solution (trade name: Marquat 100, manufactured by Nalco Japan, average molecular weight = 150,000), 0.32 g (0.01 parts by mass with respect to 100 parts by mass of water). A fluid particle was obtained in the same manner as in Example 1 except that the amount was 1).

  When the obtained particles were observed with an electron microscope, spherical particles of about 300 nm were uniformly attached to the surface of the plate-like particles, and it was a composite particle formed by attaching a silicone elastomer to the surface of the talc particles. confirmed. Moreover, it turned out that resin-like silicone becomes a binder and the silicone elastomer is made to adhere to a talc particle.

  Furthermore, after weighing 20 g of sodium bromide, polyoxyethylene lauryl ether (trade name: Emulgen 109P, Kao (manufactured)) 0.5 g, water 80 g and composite particles 5 g in a 100 mL glass bottle and shaking for 30 minutes, When the silicone elastomer dropped off from the surface of the talc particles, the silicone elastomer floated because the specific gravity was smaller than that of sodium bromide water, but the whole amount had settled. This suggests that the silicone resin becomes a binder and the silicone elastomer is adhered to the talc particles.

[Example 3]
In a glass flask having a capacity of 3 liters equipped with a stirrer with a vertical stirring blade, 120 g of mica particles (trade name: Y-2300X, manufactured by Yamaguchi Mica Co., Ltd., shape = plate shape, average particle size = 19 μm) and the above 40% dimethyldiallyl was added to a mixed aqueous dispersion obtained by mixing 39 g of the silicone elastomer aqueous dispersion obtained in the production example (13 parts by mass of silicone elastomer with respect to 100 parts by mass of mica particles) and 1,284 g of water. Ammonium chloride polymer aqueous solution (trade name: ME polymer H40W, manufactured by Toho Chemical Industry Co., Ltd., average molecular weight = 240,000) 0.33 g (amount to be 0.01 parts by mass with respect to 100 parts by mass of water), and 28 30% aqueous ammonia was charged. The pH of the liquid at this time was 11.4. After adjusting the temperature to 5 to 10 ° C., 27 g of methyltrimethoxysilane (an amount in which the silicone resin after hydrolysis / condensation reaction becomes 85 parts by mass with respect to 100 parts by mass of the silicone elastomer) is dropped over 20 minutes. The liquid temperature was kept at 5 to 10 ° C. and further stirred for 1 hour. Subsequently, it heated to 55-60 degreeC, it stirred for 1 hour, maintaining the temperature, and the hydrolysis and condensation reaction of methyltrimethoxysilane was completed. The obtained suspension was dehydrated using a pressure filter. The dehydrated product was transferred to a 3 liter glass flask equipped with a stirrer with a vertical stirring blade, added with 1,000 g of water, stirred for 30 minutes, and then dehydrated using a pressure filter. Again, the dehydrated product was transferred to a glass flask, and the flask was immersed in an oil bath at 110 ° C. and dried with stirring to obtain fluid particles.

  Observation of the obtained particles with an electron microscope reveals that spherical particles of about 300 nm are uniformly attached to the surface of the plate-like particles, and that the composite particles are formed by attaching a silicone elastomer to the surface of the mica particles. confirmed. Moreover, it turned out that a silicone resin becomes a binder and makes the silicone elastomer adhere to the mica particle.

  Furthermore, after weighing 20 g of sodium bromide, polyoxyethylene lauryl ether (trade name: Emulgen 109P, Kao (manufactured)) 0.5 g, water 80 g and composite particles 5 g in a 100 mL glass bottle and shaking for 30 minutes, When the silicone elastomer dropped off from the surface of the mica particles, the silicone elastomer floated because the specific gravity was smaller than that of sodium bromide water, but the whole amount had settled. This suggests that the silicone resin becomes a binder and the silicone elastomer is adhered to the mica particles.

[Example 4]
In a glass flask with a capacity of 3 liters equipped with a stirrer with a vertical stirring blade, 120 g of sericite particles (trade name: Sanshin Mica FSE, manufactured by Sanshin Mining Co., Ltd., shape = plate, average particle size = 10 μm) 40% of a mixed aqueous dispersion obtained by mixing 41 g of the silicone elastomer aqueous dispersion obtained in the above production example (14 parts by mass of the silicone elastomer with respect to 100 parts by mass of sericite) and 1,281 g of water. Dimethyldiallylammonium chloride polymer aqueous solution (trade name: ME polymer H40W, manufactured by Toho Chemical Industry Co., Ltd., average molecular weight = 240,000) 0.33 g (amount to be 0.01 parts by mass with respect to 100 parts by mass of water), And 30 g of 28% aqueous ammonia were charged. The pH of the liquid at this time was 11.4. After adjusting the temperature to 5 to 10 ° C., 28 g of methyltrimethoxysilane (an amount in which the silicone resin after hydrolysis and condensation reaction is 85 parts by mass with respect to 100 parts by mass of the silicone elastomer) is dropped over 20 minutes. The liquid temperature was kept at 5 to 10 ° C. and further stirred for 1 hour. Subsequently, it heated to 55-60 degreeC, it stirred for 1 hour, maintaining the temperature, and the hydrolysis and condensation reaction of methyltrimethoxysilane was completed. The obtained suspension was dehydrated using a pressure filter. The dehydrated product was transferred to a 3 liter glass flask equipped with a stirrer with a vertical stirring blade, added with 1,000 g of water, stirred for 30 minutes, and then dehydrated using a pressure filter. Again, the dehydrated product was transferred to a glass flask, and the flask was immersed in an oil bath at 110 ° C. and dried with stirring to obtain fluid particles.

  When the obtained particles were observed with an electron microscope, it was confirmed that spherical particles of about 200 nm were attached to the surface of the plate-like particles, and the composite particles were formed by attaching a silicone elastomer to the sericite surface. It was. Moreover, it turned out that a silicone resin becomes a binder and the silicone elastomer is made to adhere to a sericite.

  Furthermore, after weighing 20 g of sodium bromide, polyoxyethylene lauryl ether (trade name: Emulgen 109P, Kao (manufactured)) 0.5 g, water 80 g and composite particles 5 g in a 100 mL glass bottle and shaking for 30 minutes, When the silicone elastomer dropped off from the surface of the sericite particles, the silicone elastomer floated because the specific gravity was smaller than that of sodium bromide water, but the whole amount had settled. Therefore, it is suggested that the silicone resin becomes a binder and the silicone elastomer is adhered to the sericite particles.

[Comparative Example 1]
40% dimethyldiallylammonium chloride polymer aqueous solution of Example 1 (trade name: ME polymer H40W, manufactured by Toho Chemical Co., Ltd., average molecular weight = 240,000) 0.33 g (0.01 mass relative to 100 mass parts of water) A fluid particle was obtained in the same manner as in Example 1 except that the amount to be a part) was not added.
When the obtained particles were observed with an electron microscope, there were few spherical particles adhering to the surface of the plate-like particles, but aggregates of spherical particles were observed, and the desired adhesion state was not achieved (FIG. 2). ).

[Comparative Example 2]
40% dimethyldiallylammonium chloride polymer aqueous solution of Example 1 (trade name: ME polymer H40W, manufactured by Toho Chemical Co., Ltd., average molecular weight = 240,000) 0.33 g (0.01 mass relative to 100 mass parts of water) In the same manner as in Example 1 except that sodium acrylate (anionic water-soluble polymer, trade name: Aquaric IH, manufactured by Nippon Shokubai Co., Ltd.) 0.13 g was used. Some particles were obtained.
When the obtained particles were observed with an electron microscope, there was little adhesion of spherical particles to the surface of the plate-like particles, but aggregates of spherical particles were observed, and the desired adhesion state was not achieved.

[Comparative Example 3]
40% dimethyldiallylammonium chloride polymer aqueous solution of Example 1 (trade name: ME polymer H40W, manufactured by Toho Chemical Co., Ltd., average molecular weight = 240,000) 0.33 g (0.01 mass relative to 100 mass parts of water) The amount was 30% dodecyltrimethylammonium chloride aqueous solution (trade name: Cation BB, manufactured by Nippon Oil & Fats Co., Ltd.) 0.44 g (amount to be 0.01 parts by mass with respect to 100 parts by mass of water). In the same manner as in Example 1, fluid particles were obtained.
When the obtained particles were observed with an electron microscope, as in Comparative Example 1, there was little adhesion of spherical particles to the surface of the plate-like particles, but aggregates of spherical particles were observed, and the desired adhesion state was It wasn't.

[Comparative Example 4]
40% dimethyldiallylammonium chloride polymer aqueous solution of Example 1 (trade name: ME polymer H40W, manufactured by Toho Chemical Co., Ltd., average molecular weight = 240,000) 0.33 g (0.01 mass relative to 100 mass parts of water) Except that the amount of 30 parts dodecyltrimethylammonium chloride aqueous solution (trade name: Cation BB, manufactured by Nippon Oil & Fats Co., Ltd.) is 4.4 g (amount to be 0.1 parts by mass with respect to 100 parts by mass of water). In the same manner as in Example 1, fluid particles were obtained.
When the obtained particles were observed with an electron microscope, spherical particles adhered to the surface of the plate-like particles, but about half of the particles adhered in an aggregated state, and the desired adhesion state was not achieved. It was.

[Comparative Example 5]
40% dimethyldiallylammonium chloride polymer aqueous solution of Example 1 (trade name: ME polymer H40W, manufactured by Toho Chemical Co., Ltd., average molecular weight = 240,000) 0.33 g (0.01 mass relative to 100 mass parts of water) Example 1 except that sodium lauryl sulfate (trade name: Nikkor SLS, manufactured by Nikko Chemicals Co., Ltd.) 0.13 g (amount to be 0.01 parts by mass with respect to 100 parts by mass of water) was used. In the same manner as above, fluid particles were obtained.
When the obtained particles were observed with an electron microscope, as in Comparative Example 1, there was little adhesion of spherical particles to the surface of the plate-like particles, but aggregates of spherical particles were observed, and the desired adhesion state was It wasn't.

[Comparative Example 6]
40% dimethyldiallylammonium chloride polymer aqueous solution of Example 1 (trade name: ME polymer H40W, manufactured by Toho Chemical Co., Ltd., average molecular weight = 240,000) 0.33 g (0.01 mass relative to 100 mass parts of water) Example 1 except that sodium lauryl sulfate (trade name: Nikkor SLS, manufactured by Nikko Chemicals Co., Ltd.) 1.3 g (amount to be 0.1 parts by mass with respect to 100 parts by mass of water) was used. In the same manner as above, fluid particles were obtained.
When the obtained particles were observed with an electron microscope, aggregates of spherical particles were observed, and adhesion of spherical particles to the plate-like particle surface was not observed at all.

[Comparative Example 7]
0.33 g (0.01 mass with respect to 100 mass parts of water) of 40% dimethyldiallylammonium chloride polymer aqueous solution of Example 3 (trade name: ME polymer H40W, manufactured by Toho Chemical Industry Co., Ltd., average molecular weight = 240,000) A fluid particle was obtained in the same manner as in Example 3 except that the amount of the component was not added.
When the obtained particles were observed with an electron microscope, there was little adhesion of spherical particles to the surface of the plate-like particles, but aggregates of spherical particles were observed, and the desired adhesion state was not achieved.

[Comparative Example 8]
40% dimethyldiallylammonium chloride polymer aqueous solution of Example 4 (trade name: ME polymer H40W, manufactured by Toho Chemical Industry Co., Ltd., average molecular weight = 240,000) 0.33 g (0.01 mass relative to 100 mass parts of water) A fluid particle was obtained in the same manner as in Example 4 except that the amount to be a part) was not added.
When the obtained particles were observed with an electron microscope, spherical particles adhered to the surface of the plate-like particles, but there were particles with much adhesion and particles with little adhesion, and the adhesion was uneven and the desired adhesion state was achieved. It was not.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

Inorganic powders include titanium oxide, mica titanium, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, cleaved talc, mica, kaolin, and sericite. Muscovite, synthetic mica, phlogopite, saucite, biotite, lithia mica, silicic acid, silicon dioxide, hydrous silicon dioxide, aluminum silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium silicate, Strontium silicate, metal tungstate, hydroxyapatite, vermiculite, hydrite, bentonite, montmorillonite, hectorite, zeolite, ceramics, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride Include particles such as glass.

Furthermore, inorganic pigments can be mentioned. Specific examples include inorganic red pigments such as iron oxide, iron hydroxide and iron titanate, inorganic brown pigments such as γ-iron oxide; yellow iron oxide, ocher and the like. Inorganic yellow pigments; inorganic black pigments such as black iron oxide and carbon black; inorganic purple pigments such as manganese violet and cobalt violet; inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate; that laked tar-based dyes, colored pigments such as those of natural pigments and lake; iron blue, an inorganic blue pigment ultramarine blue titanium oxide-coated mica, o alkoxy bismuth chloride, titanium oxide-coated bismuth oxychloride, titanium oxide Pearl pigments such as coated talc, fish scale foil, and titanium oxide coated colored mica; metal powder pigments such as aluminum powder, copper powder, and stainless steel powder It is.

Claims (5)

  A method for producing composite particles, wherein at least a mixed water dispersion in which inorganic powder and silicone elastomer are dispersed, a cationic water-soluble polymer, and an alkaline substance are mixed with an alkoxysilane and a silanol group. Manufactures composite particles made by adding the silicone elastomer to the surface of the inorganic powder using a silicone resin as a binder by adding a compound selected from the silane and the partial condensate to cause hydrolysis / condensation reaction. A method for producing composite particles, comprising:   As the cationic water-soluble polymer, a polymer having a polymer skeleton synthesized by any one of vinyl polymerization, addition polymerization and condensation and containing no anionic group or amphoteric group is used. The method for producing composite particles according to claim 1.   The method for producing composite particles according to claim 2, wherein the cationic water-soluble polymer is synthesized without using a monomer having a nonionic group.   The method for producing composite particles according to claim 3, wherein a polymer of dimethyldiallylammonium chloride is used as the cationic water-soluble polymer.   The blending amount of the cationic water-soluble polymer with respect to the mixed water dispersion is 0.0001 to 1 part by mass with respect to 100 parts by mass of water in the mixed water dispersion. The manufacturing method of the composite particle of any one of these.

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