JP2018053206A - Composite particle, manufacturing method therefor and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a composite particle containing a polymer particle, high in hydrophilic property and excellent in uniform dispersibility in an aqueous mixture such as an aqueous coating agent, high in stability and having excellent tactile (elasticity); a manufacturing method therefor; and an application thereof.SOLUTION: A composite particle contains a polymer particle consisting of a crosslinkable oligomer having a plurality of radical polymerizable groups and a crosslinked (meth)acrylic acid ester resin derived from a (meth)acrylic acid ester-based mono-functional monomer, and a hydrophilic inorganic particle adhered to a surface of the polymer particle and having average primary particle diameter of 10 to 1000 nm, the crosslinkable oligomer is manufactured by reacting (a) polymer, (b) polyisocyanate, and (c) (meth)acrylic acid ester having a hydroxyl group, and hydrophobicity index of the composite particle is 0 to 10.SELECTED DRAWING: Figure 1

Description

  The present invention relates to composite particles and a method for producing the same. More specifically, the present invention relates to composite particles that can be suitably used for the purpose of forming an aqueous coating agent, a method for producing the same, and a use thereof (coating agent, coating film, and cosmetic).

  Polymer particles with an average particle size of micron order include, for example, additives for coating agents and inks (matting agents, etc.), fillers for external preparations such as cosmetics (fillers for improving slipperiness), films It is used in applications such as anti-blocking agents and light diffusing agents.

  As a coating agent, a urethane-based coating agent has been generally known for a long time, but when adding polymer particles as a matting agent to such a coating agent, it should be soft so as not to impair the soft texture of the urethane-based coating agent. There is a need for polymer particles that are highly scratchable.

  For example, in Japanese Patent No. 5297845 (Patent Document 1), by polymerizing a mixture containing two specific types of crosslinkable monomers having vinyl groups at both ends of a molecule and (meth) acrylic acid ester. Resin particles that can form a coating film having an excellent restoration rate and a soft feel excellent in scratch resistance are described.

Japanese Patent No. 5297845

  By the way, in recent years, water-based coating agents are becoming more water-soluble from the viewpoint of environmental protection, and water-based urethane-based coating agents are becoming common for urethane-based coatings. The resin particles described in Patent Document 1 have high hydrophobicity and are not well-suited to an aqueous coating agent, so that they are not uniformly dispersed in the aqueous coating agent due to aggregation or the like. As a result, an aqueous coating agent is used. Thus, when the coating film is formed, a coating film having the desired matte property cannot be obtained.

  If a hydrophilic inorganic pigment such as silica, which has been used as a matting agent for a long time, is dispersed alone in the aqueous coating agent, the familiarity of the polymer particles with the aqueous coating agent can be improved. However, the coating film formed using the aqueous coating agent in which the hydrophilic inorganic pigment is dispersed alone has a hard feel due to the hard and brittle nature of the hydrophilic inorganic pigment itself, and the scratch resistance decreases. The original performance of the coating is impaired.

  In this way, it is possible to impart matteness and scratch resistance to the aqueous coating agent, and it is highly hydrophilic and excellent in uniform dispersibility in the aqueous coating agent, and has high resilience and excellent tactile feeling (elasticity). There were no coalesced particles in the past.

  The present invention has been made in view of the above-described conventional problems, and is a composite particle including polymer particles, which is highly hydrophilic and excellent in uniform dispersibility in an aqueous mixed liquid such as an aqueous coating agent. An object of the present invention is to provide composite particles having high tactile properties and excellent tactile sensation (elasticity), a production method thereof, and a coating agent, a coating film, and a cosmetic using the composite particles.

  The composite particle of the present invention is a polymer particle comprising a crosslinkable oligomer having a plurality of radical polymerizable groups and a crosslinked (meth) acrylate ester-based resin derived from a (meth) acrylate monofunctional monomer; A composite particle comprising inorganic particles attached to the surface of the polymer particle, wherein the cross-linkable oligomer comprises (a) a polyol, (b) a polyisocyanate, and (c) a (meth) acryl having a hydroxy group. It is characterized by reacting with an acid ester, the inorganic particles are hydrophilic inorganic particles having an average primary particle diameter of 10 to 1000 nm, and the hydrophobicity index of the composite particles is 0 to 10.

  According to the said structure, the inorganic particle adhering to the surface of a polymer particle is a hydrophilic inorganic particle with an average primary particle diameter of 10-1000 nm, and a hydrophobicity index is 0-10, Therefore Hydrophilic property is high and aqueous. Composite particles having excellent uniform dispersibility in an aqueous mixed liquid such as a coating agent can be realized.

  Moreover, according to the said structure, the bridge | crosslinking (meth) acrylic-ester type resin which comprises the said polymer particle is (a) polyol, (b) polyisocyanate, (c) (meth) acryl which has a hydroxyl group. By deriving from a crosslinkable oligomer obtained by reacting with an acid ester and a (meth) acrylic acid ester monofunctional monomer, composite particles having high restorability and excellent touch (elasticity) can be realized. In the application documents, “(meth) acryl” means acryl and / or methacryl, and “(meth) acrylate” means acrylate and / or methacrylate.

  The method for producing composite particles of the present invention is a method for producing the composite particles of the present invention, wherein the hydrophilic inorganic particles include hydrophilic silica particles derived from colloidal silica and hydrophilic inorganic particles not derived from colloidal silica. The colloidal with the water-soluble cellulose adsorbed on a polymerizable mixture containing 20 to 80% by weight of the (meth) acrylic acid ester monofunctional monomer and 80 to 20% by weight of the crosslinkable oligomer Composite particles containing the polymer particles and the hydrophilic silica particles derived from the colloidal silica attached to the surface of the polymer particles by suspension polymerization in an aqueous medium in the presence of silica and a surfactant. And a step of adsorbing the composite particles with hydrophilic inorganic particles not derived from the colloidal silica when the composite particles are separated from the aqueous medium and dried. More is characterized in that it comprises a step of incorporating the colloidal silica is not derived from hydrophilic inorganic particles to the polymer particle surface.

  According to the above method, since suspension polymerization is carried out in the presence of a colloidal silica adsorbed on the surface of a water-soluble cellulose functioning as a dispersant and a surfactant, suspension polymerization can be performed stably. The composite particles of the present invention can be easily obtained.

  In addition, according to the above method, hydrophilic silica particles derived from colloidal silica are adhered before adsorbing hydrophilic inorganic particles not derived from colloidal silica to the composite particles. Cellulose can be stably attached to the surface of the polymer particles via colloidal silica adsorbed on the surface. Therefore, according to the above method, more hydrophilic inorganic particles can be adhered to the surface of the polymer particles more stably, so that the composite particles of the present invention having a hydrophobicity index of 0 to 10 can be easily obtained. Can be obtained.

  Furthermore, according to the method, since the polymerizable mixture contains 20 to 80% by weight of the (meth) acrylic acid ester monofunctional monomer and 80 to 20% by weight of the crosslinkable oligomer, it has a high resilience. Composite particles having the following can be obtained.

  The coating agent of the present invention is characterized by containing the composite particles of the present invention.

Since the coating agent of this invention contains the composite particle | grains of this invention with high restoring property, it can form the coating film which has high scratch resistance and soft touch. In addition, since the coating agent of the present invention includes the composite particles of the present invention that are excellent in uniform dispersibility in an aqueous mixed solution, the composite particles can be uniformly dispersed even in the case of an aqueous coating agent. A uniform coating film can be formed.

  The coating film of the present invention is characterized by being formed using the coating agent of the present invention.

  Since the coating film of this invention contains the composite particle | grains of this invention with high recoverability, it has high scratch resistance and soft touch. Further, since the coating film of the present invention is formed using the coating agent of the present invention containing the composite particles of the present invention having excellent uniform dispersibility in an aqueous mixed liquid, the coating agent to be used is an aqueous coating. Even in the case of an agent, it is uniform.

  The cosmetic of the present invention is characterized by including the composite particles of the present invention.

  Since the cosmetic of the present invention contains the composite particles of the present invention having a high restorability, it has a soft touch. Further, since the cosmetic of the present invention includes the composite particles of the present invention that are excellent in uniform dispersibility in an aqueous mixed solution, the composite particles can be uniformly dispersed even in the case of an aqueous cosmetic. .

  According to the present invention, composite particles containing polymer particles, which are highly hydrophilic and have excellent uniform dispersibility in an aqueous mixed solution such as an aqueous coating agent, have a high resilience and an excellent feel (elasticity). A composite particle, a production method thereof, and a coating agent, a coating film, and a cosmetic using the composite particle can be provided. Since the composite particles of the present invention are excellent in uniform dispersibility in an aqueous coating agent, they can be suitably used as a matting agent for an aqueous coating agent. Since the composite particles of the present invention have high restorability and excellent tactile sensation (elasticity), if this composite particle is used as a coating agent, the coating film formed using the coating agent has high scratch resistance and softness. Can provide a tactile feel.

2 is a scanning electron microscope (SEM) image showing the composite particles obtained in Example 1. FIG.

[Composite particles]
The composite particle of the present invention is a polymer particle comprising a crosslinkable oligomer having a plurality of radical polymerizable groups and a crosslinked (meth) acrylate ester-based resin derived from a (meth) acrylate monofunctional monomer; A composite particle comprising inorganic particles attached to the surface of the polymer particle, wherein the cross-linkable oligomer comprises (a) a polyol, (b) a polyisocyanate, and (c) a (meth) acryl having a hydroxy group. The inorganic particles are hydrophilic inorganic particles having an average primary particle diameter of 10 to 1000 nm, and the composite particles have a hydrophobicity index of 0 to 10.

  The hydrophobicity index of the composite particles of the present invention is 0-10. A hydrophobicity index greater than 10 is not preferable because the dispersion stability of the composite particles in an aqueous mixture (for example, an aqueous coating agent or an aqueous cosmetic) is lowered and the composite particles are likely to settle. For example, if the composite particles easily settle in the aqueous coating agent, it may not be possible to impart matte properties to the coating film formed using the aqueous coating agent. The hydrophobicity index of the composite particles of the present invention is preferably 7 or less, and more preferably 5 or less. In this application document, the hydrophobicity index of the composite particles shall be measured by the method described below.

(Measurement method of hydrophobicity index of composite particles)
In a glass beaker having an internal volume of 100 ml with a stirrer placed at the bottom, 50 ml of ion-exchanged water is poured and 0.2 g of composite particles are floated on the water surface, and then the stirrer is gently rotated. Then, at the center of the beaker, the tip of the burette is submerged to the middle of the water between the water surface and the bottom surface of the beaker. Gradually introduce into the water at a rate of minutes. 1 ml of methanol is introduced and stirred for 5 minutes each time 1 ml is introduced. Methanol is continuously introduced until the total amount of composite particles on the water surface sinks in water (until there are virtually no composite particles floating on the water surface), and the amount of methanol introduced until the total amount of composite particles sinks in water (ml) Measure.

Then, the hydrophobicity index is obtained from the amount of ion-exchanged water (= 50 (ml)) and the amount of methanol introduced (ml) based on the following formula.
Hydrophobicity index (%) = 100 × methanol introduction amount (ml)
/ (Amount of ion exchange water (ml) + amount of methanol introduced (ml))
In addition, when the composite particles floated on the water surface completely sink in the water before introducing methanol from the burette into the water, the hydrophobicity index is determined to be zero.

  The composite particles of the present invention preferably have a restoration rate of 20% or more. When the composite particles having a restoration rate of 20% or more are added to the coating agent, a coating agent capable of forming a highly restoring coating film can be realized. When composite particles having a restoration rate of less than 20% are added to a coating agent and a coating film is formed using the coating agent, a coating film having a high restoration property may not be obtained. The restoration rate of the composite particles is more preferably 25% or more, and further preferably 30% or more. In the present application document, the restoration rate of the composite particles shall be measured by the method described below.

(Measurement method of restoration rate of composite particles)
The restoration rate of the composite particles is measured by a load-unloading test using a micro compression tester “MCTM-200” manufactured by Shimadzu Corporation.

That is, first, composite particles are placed on a lower pressure plate (SKS flat plate), and one independent fine composite particle is selected with an optical microscope of “MCTM-200” (objective lens magnification: 50 times). The diameter of the selected composite particle is measured with a particle diameter measurement cursor of “MCTM-200”. The composite particles to be selected are determined according to the particle size to be measured. Next, by dropping the test indenter at the apex of the selected composite particle at the following load speed, the particle diameter A when the composite particle is loaded up to the maximum test force of 9.81 mN, and then the minimum test force 1. Measure particle diameter B when unloaded to 1.96 mN. From the amount of displacement (restoration amount) obtained from the particle diameter A and the particle diameter B and the diameter measured with the particle diameter measurement cursor, the following formula for calculating the restoration rate: Restoration rate (%) = Restoration amount (μm) / diameter (Μm) × 100
Thus, the restoration rate of individual composite particles is obtained. The restoration rate is measured for the six composite particles, the maximum value and the minimum value are excluded from the six restoration rates, and the average value of the remaining four data is taken as the restoration rate.

<Measurement conditions for restoration rate>
Test temperature: normal temperature (20 ° C), relative humidity 65%
Upper pressure indenter: Flat indenter with a diameter of 50 μm (material: diamond)
Lower pressure plate: SKS flat plate Test type: Load-unloading test Maximum test force: 9.81 mN
Minimum test force: 1.96 mN
Load speed: 0.732 mN / sec
Load holding time: 1 sec
Unloading retention time: 1 sec

  The composite particles of the present invention preferably have an angle of repose of 30 to 60 degrees. By setting the angle of repose to 30 degrees or more, the cohesiveness of the composite particles is moderate, and when a coating film is formed using a coating agent containing the composite particles, a coating film having a desired matte property can be obtained. By setting the angle of repose to 60 degrees or less, composite particles having good fluidity and good handling properties can be realized. The composite particles of the present invention have improved fluidity due to the hydrophilic inorganic particles adhering to the surface of the polymer particles, and the angle of repose is relatively low.

(Measurement method of repose angle of composite particles)
300 cm ³ (bulk volume) of the composite particles is put into a cylindrical frame body having a diameter of 80 mm and a height of 70 mm that is raised on a horizontal plane. Next, measure the angle between the two ridges of the mountain when viewed from the front, using a protractor, with respect to the mountain of conical composite particles formed when lifted. Let the average value be the average angle. An arithmetic average value of average angles obtained by repeating this five times is defined as an angle of repose.

  The volume average particle diameter of the composite particles of the present invention is not particularly limited, but is preferably 1 to 200 μm, and preferably 3 to 50 μm. When the composite particles having a volume average particle diameter within this range are added to the coating agent, the matte and finished appearance of the coating film formed using the coating agent can be further improved.

The composite particles of the present invention preferably have a volume-based particle diameter variation coefficient in the range of 20 to 40%. When the coefficient of variation of the volume-based particle diameter is within this range, it becomes difficult to form gaps between the composite particles. When a coating film is formed using a coating agent containing composite particles, a highly uniform matte is formed. A coating film having properties can be obtained.
In the present application document, the volume average particle diameter of the composite particles and the coefficient of variation of the volume-based particle diameter are measured by the method described below.

(Measurement method of volume average particle diameter of composite particles and coefficient of variation of volume-based particle diameter)
The volume average particle diameter of the composite particles is measured by Coulter Multisizer III (measurement device manufactured by Beckman Coulter, Inc.). Measurement shall be performed using an aperture calibrated according to the Multisizer ^™ 3 User's Manual issued by Beckman Coulter, Inc.

  Note that the aperture used for the measurement is appropriately selected according to the size of the composite particles. When an aperture having a size of 50 μm is selected, the current (aperture current) is set to −800 and the gain (gain) is set to 4.

  As a sample for measurement, 0.1 g of composite particles in 10 ml of a 0.1% by weight nonionic surfactant aqueous solution was mixed with a touch mixer (manufactured by Yamato Kagaku Co., Ltd., “TOUCMIXER MT-31”) and an ultrasonic cleaner (Co., Ltd.). Dispersed using "ULTRASONIC CLEANER VS-150" manufactured by Vervocrea, and used as a dispersion. During the measurement, the beaker is gently stirred to the extent that bubbles do not enter, and the measurement ends when the measurement of 100,000 composite particles is completed. The volume average particle diameter of the composite particles is an arithmetic average in the volume-based particle size distribution of 100,000 composite particles.

  The coefficient of variation (CV value) of the particle diameter of the composite particles is calculated by the following mathematical formula.

Coefficient of variation of particle diameter of composite particles = (standard deviation of particle size distribution of composite particles / volume average particle diameter of composite particles) × 100

[Crosslinked (meth) acrylic ester resin]
The polymer particles constituting the composite particles of the present invention include a crosslinkable oligomer having a plurality of radical polymerizable groups and a crosslinked (meth) acrylate ester resin derived from a (meth) acrylate monofunctional monomer. It has become.

  The content of the structural unit derived from the crosslinkable oligomer in the crosslinked (meth) acrylic acid ester resin is preferably in the range of 20 to 80% by weight, and in the range of 30 to 75% by weight. It is more preferable. Further, the content of the structural unit derived from the (meth) acrylate monofunctional monomer in the crosslinked (meth) acrylate ester resin is preferably in the range of 20 to 80% by weight. More preferably, it is within the range of 30 to 75% by weight. By having the content of the structural unit derived from the crosslinkable oligomer and the content of the structural unit derived from the (meth) acrylic acid ester monofunctional monomer within the above range, a composite having higher resilience Particles can be realized. In addition, the content of the structural unit derived from each monomer in the crosslinked (meth) acrylate resin is in the monomer mixture used to obtain the crosslinked (meth) acrylate resin. This corresponds to the content of each monomer in.

[(Meth) acrylic acid ester monofunctional monomer]
The (meth) acrylic acid ester monofunctional monomer is not particularly limited as long as it is a (meth) acrylic acid ester having one ethylenically unsaturated group, methyl acrylate, ethyl acrylate, Propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, 2-chloroethyl acrylate, phenyl acrylate, acrylic acid Acrylic acid esters such as 2- (dimethylamino) ethyl, 2- (diethylamino) ethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid n-butyl, me Isobutyl chlorate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, 2- (dimethylamino) ethyl methacrylate, 2- (diethylamino) ethyl methacrylate And methacrylic acid esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

  Of the (meth) acrylate monofunctional monomers, alkyl acrylates having 1 to 12 carbon atoms in the alkyl group are preferred, and alkyl acrylates having 1 to 8 carbon atoms in the alkyl group are more preferred. . By using such an alkyl acrylate, the restoration rate of the composite particles can be increased.

[Crosslinkable oligomer (urethane acrylate oligomer)]
The crosslinkable oligomer comprises a compound (urethane acrylate) having a plurality of radical polymerizable groups obtained by reacting (a) polyol, (b) polyisocyanate, and (c) (meth) acrylic acid ester having a hydroxy group. Oligomer).

  The urethane acrylate oligomer preferably has a glass transition temperature (Tg) of 0 to 30 ° C. measured from the viscoelasticity of a cured product obtained when cured alone. When the Tg is less than 0 ° C., the cross-linked (meth) acrylic ester resin may become sticky. When the Tg exceeds 30 ° C., composite particles with high recoverability may not be obtained. The Tg is more preferably 0 to 28 ° C, and further preferably 0 to 25 ° C.

  Moreover, although the said urethane acrylate oligomer is not specifically limited, It is preferable that the pencil hardness of the hardened | cured material obtained when it hardens independently is H-HB. When the urethane acrylate oligomer whose pencil hardness of the cured product obtained when cured alone is in the above range is used, composite particles having a higher restoration rate can be obtained.

  Examples of the commercially available urethane acrylate oligomer include “New Frontier (registered trademark) RST-402” and “New Frontier (registered trademark) RST-” of New Frontier (registered trademark) RST series manufactured by Daiichi Kogyo Seiyaku Co., Ltd. New Frontier (registered trademark) series urethane acrylate oligomer such as “201”, UF series “UF-A01P” manufactured by Kyoeisha Chemical Co., Ltd., and the like.

(A) Polyol Examples of the polyol include polyester polyols, polyether polyols, polycarbonate polyols, aliphatic hydrocarbon polyols, and alicyclic hydrocarbon polyols. These polyols may be used alone or in combination of two or more.

  The polyol preferably has a number average molecular weight of 200 to 3000 and 2 to 4 hydroxy groups. When the number average molecular weight is less than 200 or more than 3000, the cross-linked (meth) acrylic acid ester resin becomes too hard, and a composite with high recoverability may not be realized. When the polyol has more than 4 hydroxy groups, the crosslinkability is excessively increased, and composite particles having high restoration properties may not be realized.

(A-1) Polyester polyol Examples of the polyester polyol include a condensation polymer of a polyhydric alcohol and a polycarboxylic acid; a ring-opening polymer of a cyclic ester (lactone); or a polyhydric alcohol and a polycarboxylic acid. , And a cyclic ester three-component reaction product in which each raw material is selected so as to contain three or more hydroxy groups.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethyl. Methylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, methane Triol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol, cyclohexanediol (1,4-cyclohexanediol etc.), bisphenol (bisphenol A etc.), Alcohols (xylitol and sorbitol) and the like.

  Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; -Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, trimellitic acid, and the like.

  Examples of the cyclic ester (lactone) include γ-butyrolactone, δ-valerolactone, and ε-caprolactone.

(A-2) Polyether polyol Examples of the polyether polyol include polyether polyols containing three or more hydroxy groups at the molecular ends (side chains) obtained by dehydrating and condensing polyhydric alcohols as raw materials. It is done.

  Examples of the polyol include low molecular weight polyols such as methanetriol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol, and alkylene oxide adducts of these low molecular weight polyols. A trifunctional or higher functional polyol (having 3 or more hydroxy groups) such as polyoxyalkylene polyol can be used.

(A-3) Polycarbonate polyol The polycarbonate polyol is, for example, a reaction product of polyol and phosgene, wherein the polyol is selected so as to contain three or more hydroxy groups; cyclic carbonate (alkylene carbonate, etc.) Ring-opening polymerization products, and those containing three or more hydroxy groups.

Examples of the polyol include low molecular weight (preferably molecular weight 64 to 250) polyhydric alcohols such as methanetriol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, and pentaerythritol, and Examples thereof include tri- or higher functional polyols such as polyoxyalkylene polyols, which are adducts of alkylene oxides of these polyhydric alcohols.
The polycarbonate polyol may be a compound having a carbonate bond in the molecule and containing three or more hydroxyl groups at the terminal, and may have an ester bond together with the carbonate bond.

(A-4) Aliphatic hydrocarbon-based polyol Examples of the aliphatic hydrocarbon-based polyol include polyolefin polyol and hydrogenated polybutadiene polyol. The polyolefin polyol only needs to have a total of three or more hydroxy groups at the molecular ends (side chains) of the hydrocarbon skeleton having at least one branched structure. The hydrogenated polybutadiene polyol has a structure in which all of the ethylenically unsaturated groups contained in the structure of the polybutadiene polyol are hydrogenated, and has a total of three or more hydroxy groups at the molecular ends (side chains). If it is.

(B) Polyisocyanate Examples of the polyisocyanate include aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and araliphatic polyisocyanate. The polyisocyanate preferably has 2 to 4 isocyanate groups. When the number of isocyanate groups exceeds 4, the polyisocyanate may have too high crosslinkability, and composite particles having high recoverability may not be realized.

  Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane- Examples include 1,5-diisocyanate and 3-methylpentane-1,5-diisocyanate.

  Examples of the alicyclic polyisocyanate include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and the like. Is mentioned.

  Examples of the aromatic polyisocyanate include tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-dibenzyl diisocyanate, 1, Examples include 5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate.

Examples of the araliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and α, α, α, α-tetramethylxylylene diisocyanate. In addition, examples of the polyisocyanate include modified polyisocyanates such as dimers, trimers, and bullet-modified isocyanates.
These polyisocyanates may be used alone or in combination of two or more.

(C) (Meth) acrylic acid ester having a hydroxy group Examples of the (meth) acrylic acid ester having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy (Meth) acrylic acid ester of a C1-C8 alcohol having a hydroxy group such as propyl methacrylate, 4-hydroxybutyl acrylate, caprolactone-modified-2-hydroxyethyl acrylate; polyethylene glycol mono (meth) acrylic acid ester, polypropylene glycol Monoacrylic acid ester, polybutylene glycol mono (meth) acrylic acid ester, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalate, phenylglycidyl Examples include ether (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and caprolactone-modified dipentaerythritol penta (meth) acrylate. These (meth) acrylic acid esters having a hydroxy group may be used alone or in combination of two or more.

Among these (meth) acrylic acid esters having a hydroxy group, (meth) acrylic acid esters and pentaerythritol triacrylates of a C 1-8 alcohol having a hydroxy group are preferred. Here, examples of the alcohol having 1 to 8 carbon atoms include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol and the like. These alcohols include structural isomers.
The (meth) acrylic acid ester having a hydroxy group realizes a composite particle having a higher resilience, whereby a coating having a higher resilience is formed when a coating film is formed using a coating agent to which the composite particle is added. From the viewpoint of obtaining a film, it is preferably a (meth) acrylic acid ester of an alcohol having 1 to 8 carbon atoms, among which 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate are particularly preferable.

[Other vinyl monomers]
The cross-linked (meth) acrylic acid ester resin of the present invention may be derived only from the cross-linkable oligomer and the (meth) acrylic acid ester monofunctional monomer. ) In addition to the structural unit derived from the acrylate ester monofunctional monomer, it may contain a structural unit derived from another vinyl monomer as long as the effects of the present invention are not impaired.

  The other vinyl monomer is used. Examples of the other vinyl monomers include other monofunctional vinyl monomers (compounds having one ethylenically unsaturated group) other than the (meth) acrylic acid ester monofunctional monomers or the crosslinks. Other polyfunctional vinyl monomers (compounds having two or more ethylenically unsaturated groups) other than the functional oligomer can be used.

  Examples of the other monofunctional vinyl monomers include styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, and pn-butylstyrene. , P-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p- Styrene derivatives such as phenylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene; vinyl carboxylates such as vinyl acetate, vinyl propionate and vinyl butyrate; acrylic acid derivatives other than acrylic esters such as acrylonitrile and acrylamide ; Methacrylic acid esters such as methacrylonitrile, methacrylamide, etc. Other methacrylic acid derivatives; α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and fumaric acid; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl methyl ketone and vinyl hexyl Examples thereof include vinyl ketones such as ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalene.

  Examples of the other polyfunctional vinyl monomers include divinylbenzene; ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (2 to 10 repeat units), propylene glycol di (meth) acrylate, and polypropylene. Glycol di (meth) acrylate (2-10 repeat units), 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, alkoxylated neopentyl glycol di (meth) acrylate, propoxylation Bifunctional alkylene glycol di (meth) acrylates such as neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, dioxane glycol di (meth) acrylate; Chirenediol di (meth) acrylate, hexanediol di (meth) acrylate, alkoxylated hexanediol di (meth) acrylate, cyclohexanediol di (meth) acrylate, dodecanediol di (meth) acrylate, tricyclodecanediol di (meta) ) Bifunctional alkylenediol di (meth) acrylate such as acrylate; Bifunctional ethoxylated bisphenol A di (meth) acrylate such as ethoxylated (2 to 10 repeat units) bisphenol A di (meth) acrylate; Trimethylolpropane tri Trifunctional trimethylol such as (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryloyloxyethyl phosphate Propane tri (meth) acrylates; tetrafunctional tetra (meth) acrylates such as pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate; hexafunctional dipentaerythritol hexa such as dipentaerythritol hexa (meth) acrylate (Meth) acrylates; octafunctional pentaerythritol (meth) acrylates such as poly (pentaerythritol) acrylate; trifunctional nitrogen atom-containing cyclic (meth) acrylates such as ethoxylated isocyanuric acid tri (meth) acrylate Can be mentioned. These other vinyl monomers may be used alone or in combination of two or more.

[Hydrophilic inorganic particles]
The composite particles of the present invention include hydrophilic inorganic particles attached to the polymer particle surfaces. In the present application document, “hydrophilic inorganic particles” means inorganic particles that can be dispersed in water, and more specifically, inorganic particles that exhibit hydrophilic behavior when introduced into water and stirred, that is, By means of inorganic particles dispersed in water whose surface is completely wetted by water and thus has a contact angle of less than 90 ° to water. Whether inorganic particles adhering to the surface of the polymer particles in the composite particles are hydrophilic or not depends on whether the composite particles begin to settle immediately as a result of the hydrophilicity test of the composite particles (see Examples). It can also be confirmed indirectly by Moreover, the said hydrophilic inorganic particle is an inorganic particle which has the number of hydroxyl groups of the grade which shows hydrophilic property.

  The hydrophilic inorganic particles have an average primary particle size of 10 to 1000 nm. When the average primary particle diameter is larger than 1000 nm, the hydrophilic inorganic particles hardly adhere to the polymer particles and may be peeled off, which is not preferable. The average primary particle diameter of the hydrophilic inorganic particles is preferably in the range of 12 to 500 nm, and more preferably in the range of 15 to 300 nm. In this application document, the average primary particle diameter of the hydrophilic inorganic particles shall be measured by the method described below.

(Measurement method of average primary particle diameter of hydrophilic inorganic particles)
The average primary particle size of the hydrophilic inorganic particles (specifically, the Z average particle size calculated by the cumulant analysis method) is, for example, a particle size measuring device by a dynamic light scattering method (“Zetasizer Nano ZS” manufactured by Malvern). Measure with

  As a measurement sample, a dispersion liquid in which hydrophilic inorganic particles to be measured are dispersed in ion-exchanged water is used. When the assumed average primary particle diameter of the hydrophilic inorganic particles is less than 100 nm, the dispersion is prepared so that the concentration of the hydrophilic inorganic particles is 1% by weight, and the assumed average primary of the hydrophilic inorganic particles is When the particle diameter is 100 nm or more, the dispersion is prepared so that the concentration of the hydrophilic inorganic particles is 0.1% by weight. A polyethylene cell is set in the measurement part of the particle size measuring device (Malvern's “Zetasizer Nano ZS”) by the dynamic light scattering method, and the dispersion is dispensed into the polyethylene cell to make it hydrophilic. The Z average particle diameter of the inorganic particles is measured.

  The Z average particle diameter is a value obtained by analyzing measurement data of a dynamic light scattering method such as a particle dispersion using a cumulant analysis method.

  In the cumulant analysis method, an average value of the particle diameter and a polydispersity index (PDI) are obtained, and the average value of the particle diameter is defined as the Z average particle diameter. Strictly speaking, the work of fitting a polynomial to the logarithm of the G1 correlation function obtained by measurement is called cumulant analysis, and the constant b in the following equation is called a second-order cumulant or Z-average diffusion coefficient.

LN (G1) = A + bt + ct ² + dt ³ + et ⁴ +...
A value obtained by converting the constant b into a particle diameter using the viscosity of the dispersion and several apparatus constants is the Z average particle diameter.

  Moreover, it is preferable that content of the said hydrophilic inorganic particle in the composite particle of this invention exists in the range of 1-15 weight% with respect to 100 weight% of said composite particles. When the content of the hydrophilic inorganic particles is less than 1% by weight, the composite particles are bonded to each other, and handling properties may be deteriorated. When the content of the hydrophilic inorganic particles is more than 15% by weight, the hardness of the composite particles becomes high and the soft feel may be impaired. The content of the hydrophilic inorganic particles is more preferably in the range of 2 to 10% by weight, and further preferably in the range of 3 to 8% by weight.

  The shape of the hydrophilic inorganic particles is not limited to a true sphere (spherical shape), and may be a non-spherical shape such as a scale shape or a plate shape. Examples of the hydrophilic inorganic particles include hydrophilic metal oxide particles such as hydrophilic silica particles, alumina particles, and titanium oxide particles.

Examples of the commercially available hydrophilic silica particles include hydrophilic fumed silica “AEROSIL (registered trademark)” series manufactured by Nippon Aerosil Co., Ltd., for example, a hydrophilic general-purpose type that is a spherical particle having an average primary particle diameter of 5 to 40 nm. ("AEROSIL (registered trademark) 50", "AEROSIL (registered trademark) 90G", "AEROSIL (registered trademark) 130", "A
"EROSIL (registered trademark) 200", "AEROSIL (registered trademark) 200CF", "AEROSIL (registered trademark) 200V", "AEROSIL (registered trademark) 200FAD", "AEROSIL (registered trademark) 300", "AEROSIL (registered trademark) 380" , “AEROSIL (registered trademark) OX 50” and the like.

  Examples of commercially available alumina particles include a spherical alumina series manufactured by Denka Corporation, such as “ASFP-20” with an average primary particle diameter of 200 nm, “DAW-01” with an average primary particle diameter of 1000 nm; Synthetic plate-like alumina “Seraph (registered trademark)” series, for example, “YFA00310” having an average primary particle diameter of 300 nm, “YFA00610” having an average primary particle diameter of 600 nm, and the like can be mentioned.

  Examples of commercially available titanium oxide particles include ultra-fine particle titanium oxide TTO series manufactured by Ishihara Sangyo Co., Ltd., for example, “TTO-51 (A)”, “TTO-51 (C)” and “TTO-51 (C)” having an average primary particle size of 100 nm to 500 nm. TTO-55 (A) "etc. can be mentioned.

[Hydrophilic silica particles derived from colloidal silica]
The hydrophilic inorganic particles attached to the surface of the polymer particles preferably include colloidal silica-derived hydrophilic silica particles. Colloidal silica-derived hydrophilic silica particles and colloidal silica-derived hydrophilic inorganic particles (previous stage) It is more preferable to include hydrophilic inorganic particles as exemplified above.

  Examples of the colloidal silica include powdered colloidal silica such as precipitated silica powder and gas phase method silica powder; colloidal silica sol stably dispersed to a primary particle level in a medium. Among these, colloidal silica sols stably dispersed to the primary particle level in a medium are more suitable for use in the production method of the present invention.

  As the colloidal silica sol, an aqueous silica sol, an organosilica sol, or the like can be preferably used. In particular, in the production method of the present invention, since the vinyl monomer is polymerized in an aqueous medium, it is most preferable to use aqueous colloidal silica from the viewpoint of dispersion stability of the colloidal silica sol. The silica concentration (solid content concentration) in the sol of colloidal silica is preferably 5 to 50% by weight because it is generally commercially available and can be easily obtained.

  Examples of commercially available colloidal silica include Snowtex (registered trademark) series manufactured by Nissan Chemical Industries, Ltd., for example, general-purpose type Snowtex (registered trademark) (alkaline, which is spherical particles having an average primary particle diameter of 10 to 100 nm. : "ST-30", "ST-50", "ST-30L", "ST-ZL", acidity: "STO", "ST-O-40", "ST-OL", "ST-OZL35" ), Large-sized SNOWTEX (registered trademark) (alkaline: “ST-MP-2040”, “ST-MP-4540M”), which are spherical particles having an average primary particle size of 70 to 480 nm, and an average primary particle size of 40 A chain type Snowtex (registered trademark) having an elongated shape of ˜100 nm (alkaline: “ST-UP”, acidic: “ST-OUP”), an average primary particle size is Pearl necklace type Snowtex (registered trademark) connected with spherical particles of 0 to 25 nm (alkalinity: “ST-PS-S”, “ST-PS-M”, acidic: “ST-PS-SO”, “ ST-PS-MO ") and the like.

The average primary particle diameter of the colloidal silica (the average primary particle diameter of the hydrophilic silica particles derived from the colloidal silica) is not particularly limited as long as it is in the range of 10 to 1000 nm, but may be in the range of 12 to 200 nm. preferable. If the average primary particle diameter of the colloidal silica is larger than 200 nm, the dispersion stability during the production of composite particles is lowered, which is not preferable. The average primary particle diameter of the colloidal silica is preferably as small as possible,
It is more preferably in the range of 15 to 150 nm, and further preferably in the range of 20 to 100 nm.

  The content of the hydrophilic silica particles derived from the colloidal silica in the composite particles of the present invention is preferably in the range of 0.1 to 10% by weight with respect to 100% by weight of the composite particles. When the content of the hydrophilic silica particles derived from the colloidal silica is less than 0.1% by weight, the dispersion stability at the time of polymerization is lowered, and composite particles may not be obtained. When the content of the hydrophilic silica particles derived from the colloidal silica is more than 10% by weight, the hydrophilic inorganic particles are difficult to adhere to the polymer particle surface, and the desired composite particles may not be obtained. The content of the hydrophilic silica particles derived from the colloidal silica is more preferably in the range of 0.2 to 8% by weight, and still more preferably in the range of 0.3 to 5% by weight.

[Water-soluble celluloses]
The composite particles of the present invention preferably further contain water-soluble celluloses, more preferably contain water-soluble celluloses, and more preferably contain hydrophilic silica particles derived from colloidal silica as the hydrophilic inorganic particles. More preferably, the hydrophilic inorganic particles further include hydrophilic silica particles derived from colloidal silica and hydrophilic inorganic particles not derived from colloidal silica. Thereby, the hydrophilic inorganic particle which is not derived from colloidal silica can be stably attached to the polymer particle surface via the water-soluble celluloses and colloidal silica. Therefore, more hydrophilic inorganic particles can be adhered to the surface of the polymer particles more stably, so that the composite particles of the present invention having a hydrophobicity index of 0 to 10 can be easily obtained.

  In the composite particles further including water-soluble celluloses and hydrophilic silica particles derived from colloidal silica as the hydrophilic inorganic particles, the hydrophilic silica particles are disposed on the surface of the polymer particles via the water-soluble celluloses. It may be attached or may be attached directly to the surface of the polymer particles. In other words, the water-soluble celluloses may adhere to both the hydrophilic silica particles and the polymer particles, or may adhere to only one of the hydrophilic silica particles and the polymer particles. Good.

  The water-soluble cellulose is not particularly limited, and examples thereof include alkyl celluloses such as methyl cellulose; hydroxyalkyl celluloses such as hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose; hydroxyalkylalkyl such as hydroxyethyl methyl cellulose and hydroxypropyl methyl cellulose. Compounds such as celluloses are listed. Among these compounds, hydroxyalkylcelluloses and hydroxyalkylalkylcelluloses are preferable, and hydroxypropylcellulose (HPC) and hydroxypropylmethylcellulose (HPMC) are more preferable. These compounds may be used alone or in combination of two or more.

  Hydroxypropyl cellulose (HPC) is generally known to have a lower critical solution temperature (LCST) of 45 ° C., and commercially available products include, for example, NISSO (registered trademark) manufactured by Nippon Soda Co., Ltd. The HPC series (“SSL”, “SL”, “L”, “M”, “H”, etc.) can be mentioned.

Moreover, as a commercial item of hydroxypropyl methylcellulose (HPMC), Shin-Etsu Chemical Co., Ltd.'s Metroles (registered trademark) series, more specifically, Metrows (registered trademark) 60SH series having a cloud point of 60 ° C. (“ SH60-50 "," 60SH-4000 "," 60SH-10000 "), and Metrows (registered trademark) 65SH series (" 65SH-50 "," 65SH-400 "," 65SH-1500 ") having a cloud point of 65 ° C. , "65SH-4000"), Metroles (registered trademark) 90SH series having a cloud point of 90 ° C ("90SH-100", "90SH-400", "90SH-4000", "90SH-15000"), etc. be able to.

[Production method of composite particles]
The method for producing composite particles of the present invention is a method for producing the composite particles of the present invention, wherein the hydrophilic inorganic particles include hydrophilic silica particles derived from colloidal silica and hydrophilic inorganic particles not derived from colloidal silica. The colloidal with the water-soluble cellulose adsorbed on a polymerizable mixture containing 20 to 80% by weight of the (meth) acrylic acid ester monofunctional monomer and 80 to 20% by weight of the crosslinkable oligomer Composite particles containing the polymer particles and the hydrophilic silica particles derived from the colloidal silica attached to the surface of the polymer particles by suspension polymerization in an aqueous medium in the presence of silica and a surfactant. And a step of adsorbing the composite particles with hydrophilic inorganic particles not derived from the colloidal silica when the composite particles are separated from the aqueous medium and dried. More, and a step of containing the colloidal silica is not derived from hydrophilic inorganic particles to the polymer particle surface.

(Colloidal silica with water-soluble cellulose adsorbed on the surface)
The amount of the water-soluble cellulose adsorbed on the colloidal silica is not particularly limited and can be appropriately set according to the specific surface area of the colloidal silica, but is 0.05 g to 0.5 g per 1 g of the colloidal silica. Is preferred.

  The amount of water-soluble celluloses adsorbed on colloidal silica can be determined by, for example, Japan Journal of Polymer Science and Technology Vol. 40, No.10, pp. It can be measured using the method described in 697-702 (Oct, 1983).

  The production method of the present invention includes an adsorption step of treating the colloidal silica with the water-soluble celluloses and adsorbing the water-soluble celluloses on the surface of the colloidal silica before the suspension polymerization step. Is preferred.

  A treatment method of the colloidal silica with the water-soluble celluloses for adsorbing the water-soluble celluloses on the surface of the colloidal silica is not particularly limited, and a known method can be applied, for example, an aqueous system A method in which colloidal silica and water-soluble cellulose coexist in a medium and water-soluble cellulose is physically adsorbed on the surface of colloidal silica (specific examples include Rheological and Interfacial Properties of Silicon Oil Prepared by Polymer Pre-solder Polymer onto Silica Particles, Colloids Surfaces A: Physicochem. Eng. 28,2008,114-122 method described in. The literature) are preferred. The water-soluble celluloses adsorbed on the colloidal silica by this treatment method are in a stable state with almost no desorption from the colloidal silica in the polymerization step.

  Moreover, more than (T-15) degreeC (T means the lower critical solution temperature (degreeC) or cloud point (degreeC) of the said water-soluble cellulose) more than the said water-soluble cellulose temperature conditions. Preferably, by making the colloidal silica and the water-soluble cellulose coexist under a temperature condition of (T−15) ° C. or more and (T + 20) ° C. or less, the surface of the colloidal silica is more effectively dissolved in water. Cellulose can be physically adsorbed. In addition, the said water-soluble cellulose has only one of a lower critical solution temperature or a cloud point by the characteristic.

  In the adsorption step, water-soluble celluloses that have not been adsorbed on the colloidal silica may be removed by centrifugation or the like before the suspension polymerization step, or after the suspension polymerization step. You may remove by washing | cleaning in the refinement | purification process which refine | purifies the composite particle obtained by turbid polymerization.

(Surfactant)
Examples of the surfactant include (non-reactive) anionic surfactants, reactive anionic surfactants, (non-reactive) nonionic surfactants, reactive nonionic surfactants, Non-reactive) cationic surfactants, (non-reactive) zwitterionic surfactants, and the like.

  Examples of the anionic surfactant include sodium oleate; fatty acid soap such as castor oil potash soap; alkyl sulfate ester salt such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylbenzene sulfonate such as sodium dodecylbenzenesulfonate; alkyl Naphthalenesulfonate; alkanesulfonate; dialkylsulfosuccinate such as sodium dioctylsulfosuccinate; alkyl phosphate ester salt; naphthalenesulfonate formalin condensate; polyoxyethylene alkylphenyl ether sulfate ester; polyoxyethylene alkyl sulfate ester Examples include salts.

  As the reactive anionic surfactant, for example, Adeka Soap (registered trademark) ER-10 (100% by weight) manufactured by ADEKA Corporation, Adeka Soap (registered trademark) ER-20 (pure component) 75% by weight), Adekalia Soap (registered trademark) ER-30 (65% by weight pure, Adekalia Soap (registered trademark) ER-40 (60% by weight pure), Adekalia Soap (registered trademark) NE-10 (100% by weight pure), Adekaria soap (registered trademark) NE-20 (80% by weight pure), Adekaria soap (registered trademark) NE-30 (80% by weight pure), and Adekaria soap (registered) (Trademark) NE-40 (pure content 40 weight%) etc. are mentioned.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, Examples thereof include oxyethylene-oxypropylene block polymers.

  Examples of the reactive nonionic surfactant include AQUALON (registered trademark) RN-20 (100% by weight pure) which is polyoxyethylene nonylpropenyl phenyl ether manufactured by Daiichi Kogyo Seiyaku Co., Ltd., AQUALON (registered trademark). RN-2025 (pure content 25% by weight), Aqualon (registered trademark) RN-30 (pure content 100% by weight), and Aqualon (registered trademark) RN-50 (pure content 65% by weight); Laterum (R) PD-420 (100% by weight pure), Latem (R) PD-430 (100% by weight), and Latem (R) PD-450 (pure content) which are oxyalkylene alkenyl ethers 100% by weight) and the like.

  Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate; quaternary ammonium salts such as lauryltrimethylammonium chloride.

  Examples of the zwitterionic surfactants include lauryl dimethylamine oxide, phosphate ester surfactants, and phosphite surfactants. These surfactants may be used alone or in combination of two or more.

  The surfactant is appropriately selected in consideration of the diameter of the resulting composite particles and the dispersion stability of the monomer mixture during polymerization, and the amount used is appropriately adjusted. The amount of the surfactant used is preferably in the range of 0.01 to 5 parts by weight and in the range of 0.1 to 2.0 parts by weight with respect to 100 parts by weight of the monomer mixture. More preferably. When the usage-amount of the said surfactant is less than the said range, there exists a possibility that polymerization stability may become low. Moreover, when the usage-amount of the said surfactant is more than the said range, the cost for the said surfactant will deteriorate.

(Aqueous medium)
Examples of the aqueous medium used in the production method of the present invention include water or a mixed medium of water and a water-soluble medium (for example, alcohol such as methanol and ethanol). The amount of the aqueous medium used is preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the monomer mixture in order to stabilize the composite particles.

(Polymerization initiator)
In the production method of the present invention, the suspension polymerization of the monomer mixture in the aqueous medium is preferably performed in the presence of a polymerization initiator.

  As the polymerization initiator, oil-soluble peroxide-based polymerization initiators or azo-based polymerization initiators that are generally used for polymerization in an aqueous medium can be suitably used.

  Examples of the peroxide-based polymerization initiator include benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide. , Cyclohexanone peroxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide and the like.

  Examples of the azo polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,3- Dimethylbutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,3,3-trimethylbutyronitrile), 2,2′-azobis (2-isopropyl) Butyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), (2-carbamoylazo) isobutyronitrile 4,4′-azobis (4-cyanovaleric acid), dimethyl-2,2′-azobisisobutyrate and the like.

  Among these polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, from the viewpoint of decomposition rate and the like. Are preferred as polymerization initiators that can be used in the production method of the present invention.

  The amount of the polymerization initiator used is preferably 0.01 to 10 parts by weight, and preferably 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the vinyl monomer used. Is more preferable. When the amount of the polymerization initiator used is less than 0.01 parts by weight with respect to 100 parts by weight of the vinyl monomer used, it is difficult to sufficiently perform the polymerization initiation function, and 10 parts by weight. Exceeding this is not preferable because an effect commensurate with the amount of use cannot be obtained and the cost is uneconomical.

  The polymerization initiator may be mixed with the monomer mixture, and then the resulting mixture may be dispersed in an aqueous medium, or both the polymerization initiator and the monomer mixture may be separately added to the aqueous medium. You may mix what was disperse | distributed.

(Polymerization inhibitor)
In the production method of the present invention, the suspension polymerization of the monomer mixture in the aqueous medium is prohibited from water-soluble polymerization in order to suppress the generation of emulsion particles (polymer particles having a particle size too small) in an aqueous system. You may carry out in presence of an agent.

  Examples of the water-soluble polymerization inhibitor include nitrites, sulfites, hydroquinones, ascorbic acids, water-soluble vitamin Bs, citric acid, and polyphenols. The addition amount of the polymerization inhibitor is preferably in the range of 0.02 to 0.2 parts by weight with respect to 100 parts by weight of the monomer mixture.

(Other additives)
In the production method of the present invention, the suspension polymerization of the monomer mixture in the aqueous medium does not interfere with the effects of the present invention, and other additives such as pigments, dyes, antioxidants, UV absorption It may be performed in the presence of an agent or the like.

  Examples of the pigment include inorganic pigments such as lead white, red lead, yellow lead, carbon black, ultramarine, zinc oxide, cobalt oxide, titanium dioxide, iron oxide, titanium yellow, and titanium black; Navels Yellow, Naphthol Yellow S , Yellow pigments such as Hansa Yellow 10G, Benzidine Yellow G, Benzidine Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG, Tartrazine Lake; Orange Pigments such as Molybdenum Orange, Permanent Orange RK, Benzidine Orange G, Indanthrene Brilliant Orange GK Permanent red 4R, risor red, pyrazolone, red 4R, watching red calcium salt, lake red D, brilliant carmine 6B, eosin lake, rhodamine lake B, alizarin lake, brilia Red pigments such as Tocarmine B; Purple pigments such as Fast Violet B, Methyl Violet Lake, Dioxane Violet; Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Metal-free Phthalocyanine Blue, Phthalocyanine Blue Partial Chloride; Fast Sky Blue, Indance Blue pigments such as Ren Blue BC; Green pigments such as Pigment Green B, Malachite Green Lake, and Fanal Yellow Green G; Isoindolinone pigments, quinacridone pigments, perinone pigments, perylene pigments, insoluble azo pigments, soluble azo pigments, dye lakes Organic pigments such as pigments can be mentioned.

  Examples of the dye include a nitroso dye, a nitro dye, an azo dye, a stilbene azo dye, a diphenylmethane dye, a triphenylmethane dye, a xanthene dye, an acridine dye, a quinoline dye, a methine dye, a polymethine dye, a thiazole dye, an indamine dye, and an Indian dye. A phenol dye, an azine dye, an oxazine dye, a thiazine dye, a sulfur dye, etc. can be mentioned.

Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol (BHT), n-octadecyl-3 ′-(3 ′, 5′-di-t-butyl-4′-hydroxyphenyl). ) Propionate, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4- Hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and other phenolic compounds Antioxidant; distearyl pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, tetrakis (
2,4-di-tert-butylphenyl) 4,4′-biphenylenediphosphonite, bis (2-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,4,8,10-tetra Phosphorus series such as -t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine Antioxidants; amine-based antioxidants such as phenyl-1-naphthylamine, octylated diphenylamine, 4,4-bis (α, α-dimethylbenzyl) diphenylamine, N, N′-di-2-naphthyl-p-phenylenediamine An agent etc. can be mentioned.

  Examples of the ultraviolet absorbers include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers (for example, “ADEKA STAB (registered trademark) LA-31” manufactured by ADEKA Corporation), hydroxyphenyltriazine ultraviolet absorbers, and the like. .

(Suspension polymerization method)
In the polymerization step of the production method of the present invention, the monomer mixture is subjected to suspension polymerization in an aqueous medium in the presence of colloidal silica adsorbed on the surface of the water-soluble cellulose and a surfactant. For example, in the polymerization step, the monomer mixture is mixed with a polymerization initiator and / or a polymerization inhibitor and / or other additives as necessary, and then the monomer mixture is mixed with water-soluble celluloses. Suspension polymerization is carried out by dispersing in an aqueous medium containing colloidal silica adsorbed on the surface and a surfactant (if necessary, further containing other suspension stabilizers).

  As a method for dispersing the monomer mixture in the aqueous medium, for example, a method in which the monomer mixture is directly added to the aqueous medium and dispersed as monomer droplets by a stirring force of a propeller blade or the like; A method in which a monomer mixture is directly added and the monomer mixture is dispersed in an aqueous medium using a homomixer which is a disperser using a high shear force composed of a rotor and a stator; A method in which a monomer mixture is directly added and the monomer mixture is dispersed in an aqueous medium using an ultrasonic disperser; a monomer mixture is directly added in an aqueous medium, and a high-pressure type such as a microfluidizer or nanomizer A method of dispersing a monomer mixture as droplets in an aqueous medium by using collision of droplets of the monomer mixture and collision of droplets of the monomer mixture against the inner wall of the reaction vessel using a disperser MPG method for press-fitting the monomer mixture through (microporous glass) membrane in an aqueous medium, and the like. Among these methods, the method using a high-pressure disperser such as the above-mentioned microfluidizer or nanomizer, or the method passing through the above-mentioned MPG (microporous glass) porous membrane can be more uniform in particle size. It can be preferably used as a method of dispersing the monomer mixture in an aqueous medium.

  Next, suspension polymerization is started by heating the aqueous medium (aqueous suspension) in which the monomer mixture is dispersed. It is preferable to stir the aqueous suspension during the polymerization reaction. The stirring may be performed to such an extent that the monomer mixture can be prevented from floating as droplets and the composite particles generated by polymerization can be prevented from settling.

  In suspension polymerization, the polymerization temperature is preferably in the range of 30 to 120 ° C, and more preferably in the range of 40 to 80 ° C. The time for maintaining this polymerization temperature is preferably in the range of 0.1 to 20 hours.

(Method of adsorbing hydrophilic inorganic particles not derived from colloidal silica to composite particles)
Examples of a method for adsorbing the hydrophilic inorganic particles not derived from colloidal silica to the composite particles when the composite particles are separated from the aqueous medium and dried include, for example, suction filtration, centrifugal dehydration, centrifugal separation, and pressure dehydration. The composite particles can be separated from the aqueous medium by washing with water or the like if necessary, and then hydrophilic inorganic particles not derived from colloidal silica are added, followed by drying. As a drying method, for example, vacuum drying can be used.

[Coating agent and coating film]
The composite particles of the present invention can be contained in a coating agent as a coating film (coating) softening agent, a matting agent for paint, a light diffusing agent, or the like. The coating agent of the present invention contains the composite particles of the present invention. Since the composite particles of the present invention are excellent in uniform dispersibility in an aqueous mixed liquid, when the coating agent of the present invention is an aqueous coating agent (a coating agent containing an aqueous medium), an aqueous solution excellent in uniform dispersibility. A coating agent can be realized, and a uniform coating film can be formed using an aqueous coating agent.

  The coating agent usually contains a binder resin. As the binder resin, a resin soluble in an organic solvent or water, or an emulsion-type aqueous resin that can be dispersed in water can be used, and any known binder resin can be used. Examples of the binder resin include trade names “Dianar (registered trademark) LR-102” and “Dianar (registered trademark) BR-106” manufactured by Mitsubishi Rayon Co., Ltd., or manufactured by Dainichi Seika Kogyo Co., Ltd. Acrylic resin such as “Medium VM”; alkyd resin; polyester resin; model number “UVTKA-520” (ultraviolet curable aqueous polyurethane coating agent) manufactured by Tokushiki Co., Ltd., trade name manufactured by Daido Kasei Kogyo Co., Ltd. Polyurethane resins such as “E-5221P”; chlorinated polyolefin resins; amorphous polyolefin resins; silicone resins and the like. As the binder resin, the crosslinkable oligomer (for example, “New Frontier (registered trademark) RST-402” (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)) is used as a photopolymerization initiator (for example, 2-hydroxy-2-methylpropiophenone). ). These binder resins may be appropriately selected depending on the adhesion of the coating agent to the substrate to be coated (substrate to be coated), the environment in which it is used, and the like.

  The compounding amount of the composite particles in the coating agent is appropriately determined depending on the thickness of the coating film formed using the coating agent, the average particle diameter of the composite particles, the coating method of the coating agent, the use of the coating agent, and the like. Although adjusted, it is preferably in the range of 1 to 300 parts by weight and more preferably in the range of 5 to 100 parts by weight with respect to 100 parts by weight of the binder resin. When the compounding amount of the composite particles in the coating agent is less than 1 part by weight with respect to 100 parts by weight of the binder resin, the matte effect may not be sufficiently obtained. In addition, when the compounding amount of the composite particles in the coating agent exceeds 300 parts by weight with respect to 100 parts by weight of the binder resin, the viscosity of the coating agent becomes excessively high, resulting in poor dispersion of the composite particles. As a result, the appearance of the coating film surface may be poor, such as micro cracks occurring on the coating film surface formed using the coating agent, or roughness of the resulting coating film surface. There is.

  The coating agent contains a medium as necessary. As the medium, it is preferable to use a solvent (solvent) capable of dissolving the binder resin or a dispersion medium capable of dispersing the binder resin. As the dispersion medium or solvent, both an aqueous medium and an oily medium can be used. Examples of the oily medium include hydrocarbon solvents such as toluene, xylene and cyclohexane; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; dioxane, ethylene glycol diethyl ether and ethylene glycol mono And ether solvents such as butyl ether. Examples of the aqueous medium include water and alcohols (for example, isopropanol). These media may use only 1 type and may mix and use 2 or more types. The content of the medium in the coating agent is usually in the range of 20 to 60% by weight with respect to the total amount of the coating agent.

Further, the coating agent includes a curing agent, a colorant (external pigment, color pigment, metal pigment, mica powder pigment, dye, etc.), an antistatic agent, a leveling agent, a fluidity modifier, an ultraviolet absorber, and a light stabilizer. Other additives such as may be included.

  The coating film of the present invention is formed using the coating agent, and can be formed by applying the coating agent to a substrate to be coated and then curing it by drying or ultraviolet irradiation. . Since the composite particles of the present invention have high resilience, the coating film formed using the coating agent containing the composite particles of the present invention has high scratch resistance and soft touch.

It does not specifically limit as said to-be-coated base material, The base material according to a use can be used.
For example, in optical applications, a transparent substrate such as a glass substrate or a transparent resin substrate is used as the substrate to be coated. Light diffusion is achieved by using a transparent substrate as the substrate to be coated and applying a coating agent (coating agent for light diffusion) containing no colorant on the transparent substrate to form a transparent coating film. An optical film such as a film or an antiglare film can be produced. In this case, the composite particles function as a light diffusing agent.

  Further, matte paper is manufactured by using paper as the substrate to be coated and coating the paper with a coating agent (paper coating agent) that does not contain a colorant to form a transparent coating film. be able to.

  The coating method of the coating agent is not particularly limited, and any known method can be used. Examples of the coating method include a comma direct method, a spin coating method, a spray coating method, a roll coating method, a dipping method, a knife coating method, a curtain flow method, and a laminating method. The coating agent may be diluted by adding a diluent in order to adjust the viscosity as necessary. Diluents include hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as dioxane and ethylene glycol diethyl ether; water An alcohol solvent or the like. These diluents may be used alone or in combination of two or more. When manufacturing the said optical film, it is preferable to use the method that the unevenness | corrugation derived from a composite particle is formed in the coating-film surface as a coating method.

[Cosmetics]
The cosmetic of the present invention contains the composite particles of the present invention. Since the composite particles of the present invention are excellent in uniform dispersibility in an aqueous mixed liquid, when the cosmetic of the present invention is an aqueous cosmetic (cosmetics containing an aqueous medium), an aqueous solution excellent in uniform dispersibility. Cosmetics can be realized. Since the composite particles of the present invention have a high resilience, the cosmetic containing the composite particles of the present invention has a very soft touch and a light feeling of use.

  The cosmetic preferably contains the composite particles in a range of 1 to 40% by mass. If the content of the composite particles is less than 1% by mass, the composite particles may be too small and the effect of adding the composite particles may not be clearly recognized. In addition, when the content of the composite particles exceeds 40% by mass, even if the addition amount of the composite particles is further increased, the remarkable effect corresponding to the increase in the addition amount may not be recognized.

  Examples of the cosmetics include soaps, body shampoos, facial cleansing creams, scrub facial cleansing cosmetics, skin lotions, creams, emulsions, packs, funny products, foundations, lipsticks, lip balms, blushers, eyebrow cosmetics, nail polish cosmetics. , Hair wash cosmetics, hair dyes, hair styling, aromatic cosmetics, toothpaste, bath preparations, antiperspirants, sunscreen products, suntan products, body powder, baby powder and other body cosmetics, shaving cream, pre-shave lotion And lotions such as after-shave lotion and body lotion.

  Moreover, the component generally used for cosmetics can be mix | blended according to the objective in the range which does not impair the effect of this invention. Examples of such components include water, lower alcohols, fats and waxes, hydrocarbons, higher fatty acids, higher alcohols, sterols, fatty acid esters, metal soaps, moisturizers, surfactants, polymer compounds, coloring material raw materials, Perfumes, antiseptics / bactericides, antioxidants, UV absorbers, and special ingredients.

  The fats and waxes include avocado oil, almond oil, olive oil, cacao butter, beef tallow, sesame butter, wheat germ oil, safflower oil, shea butter, turtle oil, persimmon oil, persic oil, castor oil, grape oil, macadamia nut oil , Mink oil, egg yolk oil, owl, palm oil, rosehip oil, hydrogenated oil, silicone oil, orange luffy oil, carnauba wax, candelilla wax, whale wax, jojoba oil, montan wax, beeswax, lanolin and the like.

  Examples of the hydrocarbon include liquid paraffin, petrolatum, paraffin, ceresin, microcrystalline wax, squalane and the like. Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, undecylenic acid, oxystearic acid, linoleic acid, lanolin fatty acid, and synthetic fatty acid.

  Examples of the higher alcohol include lauryl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyl decanol, octyl decanol, isostearyl alcohol, jojoba alcohol, decyltetra A decanol etc. are mentioned.

Examples of the sterol include cholesterol, dihydrocholesterol, phytocholesterol and the like.
Examples of the fatty acid ester include ethyl linoleate, isopropyl myristate, lanolin fatty acid isopropyl, hexyl laurate, myristyl myristate, cetyl myristate, octadodecyl myristate, decyl oleate, octadodecyl oleate, hexadecyl dimethyloctanoate, isooctane Cetyl acid, decyl palmitate, glyceryl trimyristate, glycerin tri (capryl / capric acid), propylene glycol dioleate, glyceryl triisostearate, glycerin triisooctanoate, cetyl lactate, myristyl lactate, diisostearyl malate and isostearic acid Examples thereof include cyclic alcohol fatty acid esters such as cholesteryl and cholesteryl 12-hydroxystearate.

Examples of the metal soap include zinc laurate, zinc myristate, magnesium myristate, zinc palmitate, zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, and zinc undecylenate.
Examples of the humectant include glycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol, sodium dl-pyrrolidonecarboxylate, sodium lactate, sorbitol, sodium hyaluronate, polyglycerin, xylit, maltitol and the like.

  Examples of the surfactant include anionic surfactants such as higher fatty acid soap, higher alcohol sulfate, N-acyl glutamate, and phosphate ester salts, and cationic surfactants such as amine salts and quaternary ammonium salts, Amphoteric surfactants such as betaine type, amino acid type, imidazoline type and lecithin, nonionic surfactants such as fatty acid monoglyceride, propylene glycol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, ethylene oxide condensate Is mentioned.

  Examples of the polymer compound include gum arabic, tragacanth gum, guar gum, locust bean gum, karaya gum, iris moss, quince seed, gelatin, shellac, rosin, casein and other natural polymer compounds, sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose , Semi-synthetic polymer compounds such as sodium alginate, ester gum, nitrocellulose, hydroxypropylcellulose, crystalline cellulose, polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyvinyl methyl ether, polyamide resin, silicone oil, nylon Particles, polymethyl methacrylate particles, crosslinked polystyrene particles, silicone particles, urethane particles, polyester Ren particles, synthetic polymer compounds such as resin particles of the silica particles and the like.

  Examples of the color material raw materials include iron oxide, ultramarine, conger, chromium oxide, chromium hydroxide, carbon black, manganese violet, titanium oxide, zinc oxide, talc, kaolin, mica, calcium carbonate, magnesium carbonate, mica, and aluminum silicate. , Barium silicate, calcium silicate, magnesium silicate, silica, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, hydroxyapatite, ceramic powder and other inorganic pigments, azo, nitro, nitroso, xanthene And tar dyes such as quinoline, quinoline, anthraquinoline, indigo, triphenylmethane, phthalocyanine, and pyrene.

  Here, the powder material such as the polymer compound or the color material material may be subjected to surface treatment in advance. A conventionally known surface treatment technique can be used as the surface treatment method. For example, oil treatment with hydrocarbon oil, ester oil, lanolin, etc., silicone treatment with dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, perfluoroalkyl group-containing ester, perfluoroalkylsilane, perfluoropolyether , Fluorine compound treatment with a polymer having a perfluoroalkyl group, silane coupling agent treatment with 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, isopropyltriisostearoyl titanate, isopropyltris ( Dioctylpyrophosphate) Titanium coupling agent treatment with titanate, metal soap treatment, amino acid treatment with acylglutamic acid, etc., lecithin with hydrogenated egg yolk lecithin, etc. Treatment, collagen treatment, polyethylene process, moisture retention treatment, an inorganic compound treatment, and processing methods such as mechanochemical treatment.

Examples of the fragrances include natural fragrances such as lavender oil, peppermint oil, and lime oil, and synthetic fragrances such as ethyl phenyl acetate, geraniol, and p-tert-butylcyclohexyl acetate.
Examples of the antiseptic / bactericidal agent include methyl paraben, ethyl paraben, propyl paraben, benzalkonium, benzethonium and the like.

Examples of the antioxidant include dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, tocopherol and the like.
Examples of the ultraviolet absorber include inorganic absorbents such as fine particle titanium oxide, fine particle zinc oxide, fine particle cerium oxide, fine particle iron oxide, fine particle zirconium oxide, benzoic acid-based, paraaminobenzoic acid-based, anthranilic acid-based, salicylic acid And organic absorbents such as cinnamate, cinnamic acid, benzophenone, and dibenzoylmethane.

Examples of the special ingredients include hormones such as estradiol, estrone, ethinylestradiol, cortisone, hydrocortisone, prednisone, vitamins such as vitamin A, vitamin B, vitamin C, vitamin E, citric acid, tartaric acid, lactic acid, aluminum chloride, Skin astringents such as aluminum sulfate / potassium sulfate, allantochlorohydroxyaluminum, zinc paraphenolsulfonate, zinc sulfate, cantalis tincture, pepper tincture, ginger tincture, assembly extract, garlic extract, hinokitiol, carpronium chloride, pentadecanoic acid glyceride, Examples thereof include hair growth promoters such as vitamin E, estrogen, and photosensitizer, and whitening agents such as magnesium phosphate-L-ascorbate and kojic acid.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited by these Examples. First, a method for measuring the content of inorganic particles in the composite particles of Examples and Comparative Examples will be described.

[Method for measuring content of inorganic particles in composite particles]
For the composite particles obtained in Examples and Comparative Examples described later, the ignition residue is almost equal to the content (% by weight) of inorganic particles such as hydrophilic inorganic particles. The ignition residue measured by the measurement method was defined as the content (% by weight) of inorganic particles.

(Measurement method of ignition residue)
After weighing 1.0 g of the composite particles, the weighed composite particles were burned out in an electric furnace at 550 ° C. for 30 minutes, and the weight (g) of the remaining residue was measured. And the weight (g) of the measured residue was remove | divided by the weight (1.0g) of the particle | grains before a measurement, and it converted into percentage, and obtained the ignition residue (weight%).

[Example 1]
In a 5 L internal vessel having a stirrer, 300 parts by weight of ion exchange water as an aqueous medium and “Snowtex (registered trademark) O-40” (average primary particle size 25 nm, solid content 40 weight as colloidal silica) %, Manufactured by Nissan Chemical Industries, Ltd.) 15 parts by weight (6 parts by weight of pure SiO ₂ ) and “Metroze (registered trademark) 65SH-50 (cloud point 65 ° C., manufactured by Shin-Etsu Chemical Co., Ltd.) as water-soluble celluloses ) 1.2 parts by weight, and mixed for 12 hours at a temperature of 60 ° C. to adsorb water-soluble celluloses on colloidal silica to obtain a dispersant. The aqueous phase was adjusted by mixing 0.25 parts by weight of sodium dodecyl sulfate.

  Next, 50 parts by weight of n-butyl acrylate as a (meth) acrylic acid ester monofunctional monomer and “New Frontier (registered trademark) RST-402” (No. 1) as a crosslinkable oligomer (urethane acrylate oligomer) Manufactured by Ichiko Pharmaceutical Co., Ltd .; 50 parts by weight of a glass transition temperature (Tg) measured from the viscoelasticity of a cured product obtained by curing alone and having a pencil hardness of F, and a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) (trade name “ABN-V”, manufactured by Nippon Finechem Co., Ltd.) and 0.2 part by weight of benzoyl peroxide The oil phase was adjusted.

  Next, the oil phase is dispersed in the aqueous phase using an emulsifier / disperser (trade name “Homomixer MARK II 2.5”, manufactured by Primics Co., Ltd.) for 10 minutes at a rotational speed of 8000 rpm. A suspension having a droplet size of 10 μm was obtained. Thereafter, the suspension is put into a polymerization vessel equipped with a stirrer and a thermometer, the internal temperature of the polymerization vessel is raised to 50 ° C., and the suspension is stirred for 5 hours to perform a suspension polymerization reaction. Completed.

After the suspension is cooled, the suspension is dehydrated by filtration to separate the solid content, washed with 10 L of water, and adhered to the polymer particles and the polymer particle surface (water-soluble cellulose). Composite particles containing colloidal silica-derived hydrophilic silica particles (which were adsorbed on the surface) were obtained. 3 parts by weight of hydrophilic fumed silica “AEROSIL (registered trademark) 200” (manufactured by Nippon Aerosil Co., Ltd., average primary particle size: about 12 nm) as hydrophilic inorganic particles not derived from colloidal silica are added to the composite particles. And adsorbed onto the composite particles, and dried under reduced pressure at 60 ° C. for 24 hours to obtain unclassified composite particles. Thereafter, the unclassified composite particles were classified by passing through a mesh having an opening of 45 μm to remove particles having a particle diameter larger than the upper limit (45 μm), thereby obtaining composite particles.

  When the obtained composite particles were imaged by SEM, as shown in FIG. 1, the composite particles were polymer particles (circular gray portions in FIG. 1) and hydrophilic inorganic particles (see FIG. 1) attached to the polymer particles. 1) (white part in 1).

  The obtained composite particles had a volume average particle diameter of 9.91 μm, and the content of hydrophilic inorganic particles in the composite particles (the total content of hydrophilic silica particles derived from colloidal silica and hydrophilic fumed silica) was 4. .26% by weight. The composite particles had a restoration rate of 22.4%, a hydrophobicity index of 2.0, and an angle of repose of 52 degrees.

[Example 2]
The amount of n-butyl acrylate used as a (meth) acrylate monofunctional monomer is 65 parts by weight, and the amount of “New Frontier (registered trademark) RST-402” used as a crosslinkable oligomer is 35%. In the same manner as in Example 1, except that the rotation speed of the emulsifier / disperser when obtaining the suspension was changed to 5000 rpm, and the mesh used for classification after drying was changed to a mesh having a mesh size of 53 μm. Composite particles were prepared.

  The volume average particle diameter of the obtained composite particles was 18.38 μm, and the content of hydrophilic inorganic particles in the composite particles was 3.60% by weight. The composite particles had a restoration rate of 37.8%, a hydrophobicity index of 3.8, and an angle of repose of 40 degrees.

Example 3
Composite particles were produced in the same manner as in Example 1 except that ethyl acrylate was used in place of n-butyl acrylate as the (meth) acrylate monofunctional monomer.

  The obtained composite particles had a volume average particle diameter of 7.92 μm, and the content of hydrophilic inorganic particles in the composite particles was 4.82% by weight. The composite particles had a restoration rate of 22.0%, a hydrophobicity index of 2.0, and an angle of repose of 41 degrees.

Example 4
As hydrophilic inorganic particles not derived from colloidal silica added before drying under reduced pressure, instead of 3 parts by weight of “AEROSIL (registered trademark) 200”, spherical alumina fine particles “ASFP-20” (average primary particle size 200 nm, Denka Corporation) Product) Composite particles were produced in the same manner as in Example 1 except that 5 parts by weight were used.

  The obtained composite particles have a volume average particle size of 9.16 μm, and the content of the hydrophilic inorganic particles in the composite particles (the total content of the hydrophilic silica particles derived from colloidal silica and the spherical alumina fine particles) is 4.86. % By weight. The composite particles had a restoration rate of 24.7%, a hydrophobicity index of 3.8, and an angle of repose of 41 degrees.

Example 5
The amount of n-butyl acrylate used as a (meth) acrylate monofunctional monomer is 30 parts by weight, and the amount of “New Frontier (registered trademark) RST-402” used as a crosslinkable oligomer is 70%. Composite particles were produced in the same manner as in Example 1 except that each part was changed.

  The volume average particle diameter of the obtained composite particles was 30.03 μm, and the content of hydrophilic inorganic particles in the composite particles was 1.78% by weight. The composite particles had a restoration rate of 43.9%, a hydrophobicity index of 2.0, and an angle of repose of 38 degrees.

Example 6
As a crosslinkable oligomer, instead of “New Frontier (registered trademark) RST-402”, “New Frontier (registered trademark) RST-201” (Daiichi Kogyo Seiyaku Co., Ltd .; pencil hardness when cured alone is F A composite particle was produced in the same manner as in Example 1 except that the cured product was obtained.

  The volume average particle diameter of the obtained composite particles was 11.73 μm, and the content of hydrophilic inorganic particles in the composite particles was 4.23 wt%. Further, this composite particle had a restoration rate of 21.6%, a hydrophobicity index of 2.0, and an angle of repose of 47 degrees.

[Comparative Example 1]
Instead of hydrophilic fumed silica as hydrophilic inorganic particles not derived from colloidal silica, “AEROSIL (registered trademark) R974” (hydrophobic silica particles manufactured by Nippon Aerosil Co., Ltd.), which is hydrophobic inorganic particles, was used. Except for the above, composite particles were produced in the same manner as in Example 1.

  The volume average particle diameter of the obtained composite particles was 10.69 μm, and the content of hydrophilic inorganic particles in the composite particles was 4.29% by weight. Further, this composite particle had a restoration rate of 22.2%, a hydrophobicity index of 12.3, and an angle of repose of 42 degrees.

[Comparative Example 2]
Mixing 300 parts by weight of ion-exchanged water as an aqueous medium, 7.5 parts by weight of magnesium pyrophosphate which is one of inorganic phosphates as a dispersant, and 0.25 parts by weight of sodium dodecyl sulfate as a surfactant Then, composite particles were produced in the same manner as in Example 1 except that the aqueous phase was adjusted.

  The volume average particle diameter of the obtained composite particles was 13.03 μm, and the content of hydrophilic inorganic particles in the composite particles was 3.84% by weight. Further, this composite particle had a restoration rate of 23.4%, a hydrophobicity index of 20.6, and an angle of repose of 41 degrees.

[Comparative Example 3]
Composite particles were produced in the same manner as in Example 1 except that 1,6-hexanediol diacrylate was used instead of “New Frontier (registered trademark) RST-402” as a crosslinkable oligomer.

  The volume average particle diameter of the obtained composite particles was 8.01 μm, and the content of hydrophilic inorganic particles in the composite particles was 4.92% by weight. The composite particles had a restoration rate of 15.6%, a hydrophobicity index of 28.5, and an angle of repose of 50 degrees.

  Table 1 summarizes the types and amounts of the composite particle raw materials and the measurement results of the characteristics of the composite particles in the above Examples and Comparative Examples.

As described above, in Examples 1 to 8, a polymerizable mixture containing 20 to 80% by weight of a (meth) acrylic acid ester monofunctional monomer and 80 to 20% by weight of a urethane acrylate oligomer is used as a water-soluble cellulose. After suspension polymerization in an aqueous medium in the presence of colloidal silica having an average primary particle size of 10 to 1000 nm adsorbed on the surface and a surfactant, the resulting composite particles are separated from the aqueous medium and dried Sometimes derived from the (meth) acrylate monofunctional monomer and the urethane acrylate oligomer by a production method in which hydrophilic inorganic particles having an average primary particle size of 10 to 1000 nm not derived from colloidal silica are adsorbed to the composite particles. Polymer particles made of a crosslinked (meth) acrylic acid ester-based resin, and the average primary particle size attached to the surface of the polymer particles is Composite particles comprising hydrophilic silica particles derived from 0 to 1000 nm colloidal silica and hydrophilic inorganic particles not derived from colloidal silica, having a hydrophobicity index of 0 to 10 and a restoration rate of 20% or more Could get.

  In contrast, the production method of Comparative Example 1 using hydrophobic inorganic particles instead of hydrophilic inorganic particles as inorganic particles not derived from colloidal silica, and inorganic phosphorus instead of colloidal silica having water-soluble cellulose adsorbed on the surface as a dispersant. In the production method of Comparative Example 2 using an acid salt, composite particles having a hydrophobicity index of 0 to 10 could not be obtained. Further, in the production method of Comparative Example 3 using alkylene glycol diacrylate instead of urethane acrylate oligomer as the crosslinking agent, composite particles having a hydrophobicity index of 0 to 10 cannot be obtained, and the restoration rate is 20%. The above composite particles could not be obtained.

[Example 7] (Example of production of aqueous coating agent)
By compounding 0.8 g of the composite particles obtained in Example 1 with 10 g of an ultraviolet curable aqueous polyurethane coating agent (manufactured by Tokushi Co., Ltd., model number “UVTKA-520”) as a binder resin, A coating agent was obtained. The obtained aqueous coating agent was one in which the composite particles did not aggregate and were uniformly dispersed.

  The aqueous coating agent is applied on an ABS (acrylonitrile-butadiene-styrene copolymer) plate using an applicator having a slit width of 40 μm, dried, and then cured by irradiation with ultraviolet rays to obtain a coating film. It was. The obtained coating film was uniform with no unevenness.

[Comparative Example 4] (Comparative production example of aqueous coating agent)
An aqueous coating agent was obtained in the same manner as in Example 7 except that the composite particles obtained in Comparative Example 1 were used instead of the composite particles obtained in Example 1. The obtained aqueous coating agent was non-uniform due to aggregation of composite particles. A coating film was obtained in the same manner as in Example 7 except that the obtained aqueous coating agent was used in place of the aqueous coating agent obtained in Example 7. The obtained coating film was an uneven and uneven coating film.

  As described above, polymer particles comprising a crosslinked (meth) acrylate ester resin derived from a (meth) acrylate monofunctional monomer and a urethane acrylate oligomer, and a colloid attached to the surface of the polymer particle In the aqueous coating agent using composite particles containing inorganic particles not derived from silica, the inorganic particles not derived from colloidal silica adhering to the surface of the polymer particles are not hydrophilic inorganic particles but hydrophobic inorganic particles. In the case of Comparative Example 4 having a sex index exceeding 10, the composite particles were not uniformly dispersed and a uniform coating film could not be formed, whereas it was not derived from colloidal silica adhering to the surface of the polymer particles. In Example 7 where the inorganic particles are hydrophilic inorganic particles and the hydrophobicity index of the composite particles is 0 to 10, the composite particles are uniformly dispersed. , It could be formed a uniform coating film.

[Example 8] (Production example of scratch-resistant coating agent)
4 g of “New Frontier (registered trademark) RST-402” (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as the binder resin and 0.8 g of the composite particles obtained in Example 1 as the photopolymerization initiator. By blending 0.15 g of hydroxy-2-methylpropiophenone (trade name “Darocur (registered trademark) 1173” manufactured by BASF Corporation) and 6 g of butyl acetate as an oily medium (solvent), a scratch-resistant coating agent Got. The obtained scratch-resistant coating agent was applied on an ABS plate using an applicator having a slit width of 40 μm, dried, and then cured by irradiation with ultraviolet rays to obtain a coating film.

  About the obtained coating film, using a Gakushin type friction fastness tester (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd., model number “RT-200”), a brass brush 100 times at a test load of 300 g and a reciprocating speed of 60 times / min. A repeated abrasion test was conducted. As a result, it was confirmed that almost no streaks remained and a highly scratch-resistant coating film was obtained.

[Comparative Example 5] (Comparative production example of scratch-resistant coating agent)
A coating film was produced in the same manner as in Example 8, except that the composite particles obtained in Comparative Example 3 were used instead of the composite particles obtained in Example 1. The obtained coating film was subjected to the same repeated scratch test as in Example 8. As a result, white streaks remained and the obtained coating film had low scratch resistance.

  As described above, polymer particles composed of a (meth) acrylic acid ester monofunctional monomer and a crosslinked (meth) acrylic acid ester resin derived from a crosslinking agent, and hydrophilicity attached to the surface of the polymer particles The coating film using the composite particles containing inorganic particles has low scratch resistance in the case of Comparative Example 5 in which the crosslinking agent is alkylene glycol diacrylate instead of the urethane acrylate oligomer, whereas the crosslinking agent is a urethane acrylate oligomer. In Example 8, it was confirmed that the scratch resistance was high.

Claims (10)

Polymer particles comprising a cross-linkable oligomer having a plurality of radical polymerizable groups and a cross-linked (meth) acrylic acid ester resin derived from a (meth) acrylic acid ester monofunctional monomer, and on the surface of the polymer particles A composite particle comprising adhering inorganic particles,
The crosslinkable oligomer is obtained by reacting (a) a polyol, (b) a polyisocyanate, and (c) a (meth) acrylic acid ester having a hydroxy group,
The inorganic particles are hydrophilic inorganic particles having an average primary particle size of 10 to 1000 nm,
A composite particle, wherein the composite particle has a hydrophobicity index of 0 to 10.   The composite particle according to claim 1, which has a restoration rate of 20% or more.   The composite particles according to claim 1 or 2, wherein the glass transition temperature measured from the viscoelasticity of a cured product obtained when the crosslinkable oligomer is cured alone is 0 to 30 ° C. The composite particles further include water-soluble celluloses,
The composite particle according to any one of claims 1 to 3, wherein the hydrophilic inorganic particles include colloidal silica-derived hydrophilic silica particles.   Content of the said hydrophilic inorganic particle in the said composite particle exists in the range of 1 to 15 weight%, The composite particle of any one of Claims 1-4 characterized by the above-mentioned.   The repose angle is 30 to 60 degrees, and the composite particles according to any one of claims 1 to 5. The method for producing composite particles according to any one of claims 1 to 6, wherein the hydrophilic inorganic particles include hydrophilic silica particles derived from colloidal silica and hydrophilic inorganic particles not derived from colloidal silica,
The colloidal silica in which the water-soluble celluloses are adsorbed on the surface of a polymerizable mixture containing 20 to 80% by weight of the (meth) acrylate monofunctional monomer and 80 to 20% by weight of the crosslinkable oligomer And composite particles containing the polymer particles and the hydrophilic silica particles derived from the colloidal silica adhering to the surface of the polymer particles are obtained by suspension polymerization in an aqueous medium in the presence of a surfactant and a surfactant. Process,
When the composite particles are separated from the aqueous medium and dried, the hydrophilic inorganic particles not derived from the colloidal silica are adsorbed on the composite particles, so that the hydrophilic inorganic particles not derived from the colloidal silica are contained on the surface of the polymer particles. A process for producing composite particles, comprising the step of:   A coating agent comprising the composite particles according to claim 1.   A coating film formed using the coating agent according to claim 8.   Cosmetics comprising the composite particles according to any one of claims 1 to 6.