JP2002088102A - Method for producing spherical resin particle, spherical resin particle and external agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing spherical resin particles having a high function and adoptable for various uses. SOLUTION: This method for producing spherical resin particles is characterized by dissolving 100 pts.wt. polymerizable vinyl monomer with 3-40 pt.wt. hydrophobic fluorine-based liquid organic compound without having copolymerizing property with the above polymerizable vinyl monomer and having 0.1-<3 cSt viscosity at 25 deg.C, and performing an aqueous suspension polymerization in the absence of a cross-linking agent to obtain spherical resin particles having a bowl-shaped recess on the surface of the particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymerized toner, LC
Electronics industry such as D spacer, surface modifier for silver salt film, film modifier for magnetic tape, thermal paper running stabilizer, etc., ink and adhesives, medical field such as particles for antigen-antibody reaction test, slip agent・ Cosmetic field such as extender, low shrinkage agent ・ Paper ・ Dental material ・ Anti-blocking agent ・ Light diffusing agent ・
The present invention relates to a spherical resin particle having a bowl-like depression suitable for use in general industrial fields such as a resin modifier, a method for producing the same, and an external preparation containing the spherical resin particle.

[0002]

2. Description of the Related Art To improve the mechanical properties of plastics, to improve the cleaning properties without changing the chargeability of a developer,
BACKGROUND ART Various resin particles are used for various purposes, such as improving matting and hiding properties of paints, and improving slipperiness of cosmetics. Since such resin particles are produced by a pulverization method, an emulsion polymerization method, a suspension polymerization method, a seed polymerization method, a dispersion polymerization method, etc., usually only amorphous resin particles or spherical resin particles are obtained, It has not been sufficiently satisfactory for applications in which higher functionality is required.

[0003] Therefore, porous resin particles, resin particles having a distorted depression on the particle surface, composite resin particles having a bowl-shaped depression, and a composite having a bowl-shaped depression containing a large amount of additives in the particles. Although resin particles and the like have been proposed,
The particles are porous (Japanese Patent Application Laid-Open No. 10-7704), or the shape of the dent is distorted (Japanese Patent Application Laid-Open No. 11-140).
No. 139), since the resin particles are a composite (Japanese Patent Application Laid-Open No. 5-88409), its use is limited, and its function is not sufficiently satisfactory.

On the other hand, the present inventor has disclosed in Japanese Patent Application
In -170747, a resin particle having a bowl-shaped depression on the surface was proposed. Such resin particles are highly functional and satisfy various purposes. Further, according to the patent application, a method for producing resin particles having a bowl-shaped depression on the surface by mixing and dissolving a hydrophobic liquid compound in a polymerizable vinyl monomer and performing aqueous suspension polymerization is also proposed. . However, in this method, since a hydrophobic liquid compound having a relatively high viscosity is used, the workability of handling the liquid compound, the solubility of the liquid compound in the polymerizable vinyl monomer, and the workability of cleaning the polymerization equipment and the like still remain. There was room for improvement.

The main object of the present invention is to provide a method for easily producing spherical resin particles having a bowl-shaped depression on the surface and having high performance and meeting various purposes of use. It is an object of the present invention to provide spherical resin particles obtained by a leverage manufacturing method and an external preparation prepared by blending the spherical resin particles.

[0006]

Means for Solving the Problems The present inventor has conducted intensive studies to solve the above-mentioned problems, and as a result, in the absence of a crosslinking agent, a fluorine-based liquid organic compound having specific properties,
The present inventors have found that spherical resin particles having a bowl-shaped depression on the particle surface can be easily obtained by mixing and dissolving in a polymerizable vinyl monomer at a specific ratio and performing aqueous suspension polymerization, and completed the present invention.

According to the present invention, in the absence of a crosslinking agent, 100 parts by weight of a polymerizable vinyl monomer have no copolymerizability with the polymerizable vinyl monomer and have a viscosity at 25 ° C. of 0.1 to 0.1%. Hydrophobic liquid organic compound having a hydrophobicity of less than 3 cSt (hereinafter referred to as "fluorine compound")
By mixing and dissolving parts by weight, and performing aqueous suspension polymerization,
In a front view having a bowl-shaped depression on the surface of the particle and defining the boundary line at the opening of the depression as the horizontal direction, the particle diameter in the horizontal direction is D (μm), and the height of the particle in the vertical direction is d ( μm)
Wherein a spherical resin particle satisfying the formula: 0.8 <d / D <1.0 (I) 0.1 μm ≦ D ≦ 500 μm (II) is obtained. Is done. According to the present invention,
A spherical resin particle obtained by the above-mentioned production method and an external preparation prepared by blending the spherical resin particle are provided.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The process of the present invention provides a polymerizable vinyl monomer which is not copolymerizable with the polymerizable vinyl monomer and has a viscosity at 25.degree. It is carried out by mixing and dissolving a hydrophobic fluorine compound having a viscosity of less than ３3 cSt, followed by aqueous suspension polymerization.

The polymerizable vinyl monomer used in the method of the present invention dissolves a hydrophobic fluorine-containing compound as described below uniformly, but does not undergo a polymerization reaction or a crosslinking reaction with this compound. Such polymerizable vinyl monomers include, for example, styrene, p-methylstyrene, p-methylstyrene,
Styrene monomers such as -tert-butylstyrene; acrylate monomers such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and lauryl acrylate; methacrylic acid Methyl, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid
Methacrylate monomers such as -butyl, t-butyl methacrylate, benzyl methacrylate, phenyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, glycidyl methacrylate, hydrofurfuryl methacrylate, lauryl methacrylate; polyethylene glycol Alkyl vinyl ethers such as mono (meth) acrylate and methyl vinyl ether; vinyl ester monomers such as vinyl acetate, vinyl butyrate, vinyl pivalate, vinyl benzoate and vinyl neodecanoate; N-methyl acrylamide, N-ethyl acrylamide and the like N-alkyl-substituted acrylamides; monofunctional hydrophobic vinyl monomers having one vinyl group in the molecule, such as nitrile monomers such as acrylonitrile and (meth) acrylonitrile; These halogen (fluorine, bromine, chlorine) substituted products thereof.

[0010] These polymerizable vinyl monomers are appropriately selected according to the purpose, and can be used alone or in combination of two or more. The hydrophobic fluorine-based compound used in the method of the present invention has no copolymerizability with the polymerizable vinyl monomer, and has a viscosity of 0.1 to 0.1 at 25 ° C.
It has a viscosity of less than 3 cSt. Further, it is preferable that the resin does not undergo a crosslinking reaction with a functional group present in the polymerizable vinyl monomer during suspension polymerization, does not react with water as a medium, or does not dissolve or deteriorate the obtained resin particles.

Examples of such fluorine compounds include organic compounds in which part or all of the hydrogen atoms have been replaced by fluorine (for example, hydrocarbons, halogenated hydrocarbons, nitro hydrocarbons, amines, alcohols, Ethers, ketones, esters, acids, etc.). Further, the boiling point is 25 to 200 ° C. under one atmosphere, and 50 to 15 ° C.
A hydrophobic fluorine-based compound having a temperature of 0 ° C. is preferable because resin particles can be produced without using a high-pressure polymerization facility or the like, the fluorine-based compound is easily removed, and the residue in the resin particles can be suppressed as much as possible. .

Among the above organic compounds, saturated hydrocarbons and ethers in which part or all of the hydrogen atoms have been replaced by fluorine are preferred in that, for a wide variety of resin types, the spherical resin particles of the present invention can be easily obtained. In addition, the fluorine content is 30 to 90% by weight, furthermore 40 to 80% by weight
Is particularly preferred. Examples of such a hydrophobic fluorine compound include perfluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorobutyl methyl ether, perfluorobutyl ethyl ether, perfluorobutyl propyl ether, perfluorobutyl Butyl ether and the like.

The hydrophobic fluorine-containing compound is a common organic solvent which is insoluble in water and non-reactive with the polymerizable vinyl monomer and the fluorine-containing compound, as long as the object of the present invention is not hindered. It may be used in combination with a hydrocarbon solvent such as pentane, hexane, heptane and the like, or an ether solvent such as diethyl ether, methyl ethyl ether and dibutyl ether.

The amount of the hydrophobic fluorine compound to be used is 3 to 40 parts by weight, preferably 5 to 35 parts by weight, based on 100 parts by weight of the polymerizable vinyl monomer. Since these hydrophobic fluorine-based compounds have a low viscosity, they can be easily handled and mixed and dissolved in a polymerizable vinyl monomer, and the polymerization reaction equipment can be easily washed after the production of the resin particles. preferable. In the method of the present invention, a fluorine-based compound is mixed with the above polymerizable vinyl monomer and uniformly dissolved in the absence of a crosslinking agent.

A polymerization initiator may be added to a polymerizable vinyl monomer in which a fluorine compound is dissolved (hereinafter, referred to as “monomer composition”). As the polymerization initiator, use should be made of an oil-soluble peroxide-based or azo-based initiator used for suspension polymerization, which can be dissolved in a mixture of a polymerizable vinyl monomer and a fluorine-based compound. Can be. Such polymerization initiators include, for example, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide Oxide, t
-Peroxide initiator such as butyl hydroperoxide, diisopropylbenzene hydroperoxide,
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-isopropylbutyronitrile), 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 can be mentioned. Among them, benzoyl peroxide, lauroyl peroxide, 2,2′-azobisisobutyronitrile, and 2,2′-azobis (2,4-dimethylvaleronitrile) are suitable for suspension polymerization in the method of the present invention. It is preferred because it has a half-life.

The amount of the polymerization initiator used is, for example, 0.05 to 10.0 with respect to 100 parts by weight of the polymerizable vinyl monomer.
% By weight, preferably about 0.1 to 5.0% by weight. The above monomer composition is easily dispersed in a dispersion medium as described below in the form of droplets having a desired particle size, and enables the spherical resin particles of the present invention to be easily produced, and furthermore, the shape of the resin particles Can be easily controlled. The method of the present invention is carried out by subjecting the above monomer composition to aqueous suspension polymerization. In the aqueous suspension polymerization, it is preferable to use 100 to 1000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer composition in order to stabilize the suspended particles.

The dispersion medium may contain a dispersion stabilizer. The dispersion stabilizer is not particularly limited as long as the desired resin particles can be obtained, for example, calcium phosphate, magnesium phosphate, aluminum phosphate, phosphates such as zinc phosphate, calcium pyrophosphate, Pyrophosphates such as magnesium pyrophosphate, aluminum pyrophosphate, and zinc pyrophosphate; difficulties such as calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, and colloidal silica And water-soluble inorganic compounds. Among them, tricalcium phosphate, magnesium pyrophosphate, calcium pyrophosphate, and colloidal silica produced by a double decomposition method are preferable because the target resin particles can be stably obtained.

The dispersion medium includes an anionic surfactant, a cationic surfactant, a zwitterionic surfactant,
A surfactant such as a nonionic surfactant may be added. Examples of the anionic surfactant include fatty acid oils such as sodium oleate and castor oil, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, and alkyl naphthalene sulfonates. Alkane sulfonate, dialkyl sulfosuccinate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl sulfate, and the like.

Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride. Examples of the amphoteric ionic surfactant include lauryl dimethylamine oxide. 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, oxyethylene- Oxypropylene block polymers and the like can be mentioned.

The above-mentioned dispersion stabilizers and surfactants may be used alone or in combination of two or more. The type and amount used depend on the particle size of the obtained resin particles and the polymerization time. It is appropriately selected and adjusted in consideration of dispersion stability. For example, the addition amount of the dispersion stabilizer is usually about 0.5 to 15% by weight based on 100 parts by weight of the monomer composition, and the addition amount of the surfactant is based on 100 parts by weight of the dispersion medium. Usually, it is about 0.001 to 0.1% by weight.

In the method of the present invention, for example, an aqueous suspension polymerization may be carried out by adding the monomer composition to the dispersion medium thus prepared. The monomer composition is dispersed in a dispersion medium as monomer droplets by a stirring force of a propeller blade or the like, or a general homomixer or ultrasonic disperser which is a disperser using a high shear force composed of a rotor and a stator. Can be dispersed in the dispersion medium. At this time, the monomer composition is pressed into the dispersion medium through a high-pressure disperser using a collision force between droplets of a microfluidizer, a nanomizer, or the like, a collision force on the machine wall, or a MPG (microporous glass) porous film. It is preferable to disperse the resin particles by the method described above because the particle diameters of the obtained resin particles can be made more uniform.

As described above, suspension polymerization is started by, for example, heating the dispersion medium in which the monomer composition is dispersed as spherical droplets. It is preferable to stir the dispersion medium during the polymerization reaction, and the stirring may be performed slowly enough to prevent, for example, floating of monomer droplets and sedimentation of resin particles after polymerization. The polymerization temperature is usually about 30 to 100 ° C,
The temperature is preferably about 40 to 80 ° C. The polymerization time is usually about 0.1 to 20 hours. When the boiling point of the hydrophobic fluorine compound or the polymerizable vinyl monomer is around the polymerization temperature or lower than the polymerization temperature, the fluorine compound or the polymerizable vinyl monomer is volatilized using a pressure-resistant polymerization equipment such as an autoclave. It is preferable to carry out the polymerization in a sealed or pressurized state so as not to prevent the polymerization.

The fluorine-based compound mixed in the spherical resin particles obtained as described above can be subjected to a simple operation such as normal pressure distillation, reduced pressure distillation, steam distillation, gas bubbling treatment, reduced pressure treatment, heat treatment and the like. It can be easily separated and removed from spherical resin particles. Specifically, for example, a method of directly distilling the slurry after polymerization under normal pressure or reduced pressure or a method of distilling with steam, or a method of separating resin particles from a dispersion medium and drying the resin particles at normal pressure or reduced pressure, Fluorine compounds can be removed.

The spherical resin particles obtained by the method of the present invention have a depression on a bowl on the particle surface, and in a front view when the boundary line at the opening of the depression is set to the horizontal direction, the particle size in the horizontal direction is reduced. D (μm), the height of the particles in the vertical direction is d (μm)
m), the following formula is satisfied. 0.8 <d / D <1.0 (I) 0.1 μm ≦ D ≦ 500 μm (II)

Among them, spherical resin particles having one bowl-shaped depression on the particle surface and satisfying the following formula are preferable in terms of light reflectivity, light condensing property, and light scattering property in a specific direction. . 0.1 μm ≦ D ≦ 20 μm (III) From the viewpoint of light scattering, surface reactivity, and the ability to carry a functional substance, the particle has a plurality of bowl-shaped depressions on the particle surface and satisfies the following formula: Spherical resin particles are preferred. 20 μm <D ≦ 500 μm (IV)

As shown in FIGS. 1 and 2, the particle diameter D is the maximum width in the horizontal direction in the front view when the boundary line at the opening of the depression is set to the horizontal direction. The height d of the particle is the maximum height in the vertical direction in the front view. When there are a plurality of bowl-shaped depressions, D and d are determined with the boundary line at the opening of the largest depression as the horizontal direction. The number of dents can be calculated by observing one surface of n particles by an optical microscope or an electron microscope or an observation technique similar thereto, and when m dents are observed in total, the formula: (m / n) × 2.

Then, 1.0 ≦ (m / n) × 2 <2.0
, The number of depressions is one, and 2.0 ≦ (m /
When n) × 2, the number of depressions is plural. The average value of the particle diameter D means a number average value. The shape of the resin particles obtained by the method of the present invention depends on the type and specific gravity of the polymerizable vinyl monomer and the fluorine-based compound, the polymerization rate, the particle diameter D (μm) of the resin particles, and the like. Depends greatly on That is, as the particle diameter D is smaller, for example, the particle diameter D is represented by the formula
When 0.1 μm ≦ D ≦ 20 μm is satisfied, it is easy to obtain resin particles having one bowl-shaped depression on the particle surface, and the larger the particle diameter D is, for example, the particle diameter D is represented by the formula: 20 μm <
When D ≦ 500 μm is satisfied, resin particles having a plurality of bowl-shaped depressions on the particle surface are easily obtained.

The particle diameter D of the resin particles can be adjusted by controlling the mixing conditions of the monomer composition and water, the amount of the dispersion stabilizer and the like, the stirring conditions and the dispersion conditions, and the like. The particle diameter D of the resin particles is appropriately determined according to the application, and according to the production method of the present invention, the particle diameter D is 0.1.
The particle diameter can be adjusted within a range of 1 to 500 μm.

The spherical resin particles obtained by the method of the present invention include:
Because it has a bowl-shaped depression on the surface, conventional porous particles with fine pores on the surface, spherical resin particles with distorted depressions, a large amount of addition to composites and particles of resin and resin Unique optical properties not found in the composite resin particles having depressions containing the agent, such as optical properties such as light reflectivity, light condensing, light scattering in a specific direction, and excellent slipperiness It has friction characteristics. In addition, the spherical resin particles obtained by the method of the present invention have a large specific surface area, and thus have increased surface reactivity and ability to carry functional materials and the like. Therefore, in addition to having unique optical characteristics that could not be expected with conventional amorphous particles or spherical particles, improvement in chemical characteristics by surface modification or the like and improvement in physical characteristics such as fluidity can be expected.

Therefore, the spherical resin particles obtained by the method of the present invention are suitably used not only in the fields of electronics, adhesives, medicine, cosmetics and general industry but also in other wide fields. Specifically, the spherical resin particles obtained by the method of the present invention are suitably used as a compounding component such as an external preparation. Examples of such external preparations include, for example, external preparations and cosmetics, and the external preparations are not particularly limited as long as they are applied to the skin.
Specific examples include creams, ointments, emulsions, and the like.
As cosmetics, for example, washing cosmetics such as soap, body shampoo, facial cleansing cream, scrub face wash, toothpaste; makeup cosmetics such as whitening, foundation, lipstick, lip balm, blush, eyebrows cosmetics, nail polish; Lotions such as lotions and body lotions; external preparations for the body such as body powders and baby powders; lotions, creams, emulsions, packs, cosmetics for hair washing, hair dyes, hair styling, aromatic cosmetics, bath preparations, antiperspirants Agents, sunscreen products, suntan products,
And shaving creams.

The mixing ratio of the spherical resin particles in the external preparation is not particularly limited, and is appropriately adjusted depending on the type of the external preparation.
Usually, about 0.5 to 80% by weight is preferable, and about 2 to 30% by weight is more preferable. When the blending ratio of the spherical resin particles is less than 0.5% by weight, the effect is not clearly recognized. Conversely, when the blending ratio is more than 80% by weight, even if the blending amount is further increased, it is commensurate with it. It is not preferable because the effect is not enhanced. The spherical resin particles may be treated in advance with a surface treatment agent such as an oil agent, a silicone compound and a fluorine compound, an organic powder, an inorganic powder, and the like.

As the oil agent, any oil agent that is usually used in external preparations may be used. For example, hydrocarbon oils such as liquid paraffin, squalane, petrolatum, paraffin wax, lauric acid, myristic acid, palmitic acid,
Esters such as stearic acid, oleic acid, behenic acid, undecylenic acid, higher fatty acids such as oxystearic acid, linoleic acid, lanolin fatty acid and synthetic fatty acid, glyceryl trioctanoate, propylene glycol dicaprate, cetyl ethyl ethylhexanoate and isocetyl stearate Waxes such as oil, beeswax, whale wax, lanolin, carnauba wax, candelilla wax, linseed oil, cottonseed oil, castor oil, egg yolk oil, oils such as coconut oil, metal soaps such as zinc stearate and zinc laurate, cetyl Higher alcohols such as alcohol stearyl alcohol and oleyl alcohol are exemplified.

The method of treating the spherical resin particles with an oil agent is not particularly limited. For example, a dry method of coating the oil agent by adding the above oil agent to the spherical resin particles and stirring with a mixer or the like, Utilizing a wet method of coating oils by heating and dissolving in a suitable solvent such as ethanol, propanol, ethyl acetate, hexane, etc., adding particles to the mixture, mixing and stirring, and then removing the solvent under reduced pressure or heating. Can be.

As the silicone compound, any compounds can be used as long as they are usually used in external preparations. For example, dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, acryl-silicone graft polymer, organic silicone resin Partially crosslinked organopolysiloxane polymers and the like can be mentioned. The method of treating the particles with the silicone compound is not particularly limited, and for example, the above-mentioned dry method and wet method can be used. If necessary, a baking treatment may be performed, or a reaction catalyst or the like may be appropriately added in the case of a reactive silicone compound.

The fluorine compound may be any compound as long as it is usually compounded in an external preparation, and examples thereof include perfluoroalkyl group-containing esters, perfluoroalkylsilanes, perfluoropolyethers, and polymers having a perfluoro group. Can be The method of treating the particles with a fluorine compound is not particularly limited, either. For example, the above-mentioned dry method or wet method can be used. If necessary, a baking treatment may be performed, or a reaction catalyst or the like may be appropriately added in the case of a reactive silicone compound.

As the organic powder, for example, gum arabic,
Tragacanth gum, guar gum, locust bean gum,
Natural polymer compounds such as karaya gum, iris moth, quince seed, gelatin, shellac, rosin, casein, sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, sodium alginate, ester gum, nitrocellulose, hydroxypropyl cellulose, crystalline cellulose, etc. Semi-synthetic polymer compound, polyvinyl alcohol,
Polyvinyl pyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyvinyl methyl ether,
Resin particles such as polyamide resin, silicone oil, nylon particles, polymethyl methacrylate particles, cross-linked polystyrene particles, silicon particles, urethane particles, polyethylene particles, and fluorine particles.

As the inorganic powder, for example, iron oxide, ultramarine,
Konjo, chromium oxide, chromium hydroxide, carbon black, manganese violet, titanium oxide, zinc oxide,
Talc, kaolin, mica, calcium carbonate, magnesium carbonate, mica, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, silica,
Zeolite, barium sulfate, calcined calcium sulfate (baked gypsum), calcium phosphate, hydroxyapatite,
Ceramic powder and the like can be mentioned.

These organic powders and inorganic powders may have been subjected to a surface treatment in advance. As the surface treatment method, known surface treatment techniques as described above can be used.
In addition, as long as the effects of the present invention are not impaired, ordinary additives generally used in external preparations may be appropriately blended according to the purpose. Such components include, for example, water, lower alcohols, fats and waxes, hydrocarbons, higher fatty acids, higher alcohols, sterols, fatty acid esters, metal soaps, humectants, surfactants, polymer compounds, coloring materials Raw materials, fragrances, preservatives / bactericides, antioxidants, ultraviolet absorbers, and other special compounding ingredients are included.

As fats and waxes, avocado oil,
Almond oil, olive oil, cocoa butter, beef tallow, sesame butter,
Wheat germ oil, safflower oil, shea butter, turtle oil,
Camellia oil, persic oil, castor oil, grape oil, macadamia nut oil, mink oil, egg yolk oil, mokuro, palm oil, rose hip oil, hydrogenated oil, silicone oil, orange roughy oil, carnauba wax, candelilla wax, whale wax, jojoba oil , Montan wax, beeswax, lanolin and the like.

Examples of the hydrocarbons include liquid paraffin, vaseline, paraffin, ceresin, microcrystalline wax, squalane and the like. Higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, undecylenic acid,
Examples include oxystearic acid, linoleic acid, lanolin fatty acids, and synthetic fatty acids. As higher alcohols, lauryl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyldecanol, octyldecanol, isostearyl alcohol, jojoba alcohol, decyltetradeca Knol and the like.

Sterols include cholesterol, dihydrocholesterol, phytocholesterol and the like. Fatty acid esters include ethyl linoleate, isopropyl myristate, isopropyl lanolin fatty acid, hexyl laurate, myristyl myristate, cetyl myristate, octyldodecyl myristate, decyl oleate, octyldodecyl oleate, hexyldecyl dimethyloctanoate, isooctane Cetyl acid,
Decyl palmitate, glyceryl trimyristate, glycerin tri (caprylate / caprate), propylene glycol dioleate, glyceryl triisostearate, glyceryl triisooctanoate, cetyl lactate, myristyl lactate, diisostearyl malate, cholesteryl isostearate, 12 And cyclic alcohol fatty acid esters such as cholesteryl hydroxystearate.

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

Examples of the surfactant include anionic surfactants such as higher fatty acid soaps, higher alcohol sulfates, N-acyl glutamates and phosphates, and cationic surfactants such as amine salts and quaternary ammonium salts. Agents, betaine type, amino acid type, imidazoline type, amphoteric surfactant such as lecithin, fatty acid monoglyceride, propylene glycol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, nonionic interface such as ethylene oxide condensate Activators.

As the high molecular compound, gum arabic, tragacanth gum, guar gum, locust bean gum, karaya gum, irismos, quince seed, gelatin,
Shellac, rosin, natural polymer compounds such as casein, sodium carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, ethylcellulose,
Semi-synthetic polymer compounds such as sodium alginate, ester gum, nitrocellulose, hydroxypropyl cellulose, crystalline cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyvinyl methyl ether, polyamide resin, silicone oil, nylon particles And synthetic polymer compounds such as resin particles such as polymethyl methacrylate particles, crosslinked polystyrene particles, silicon particles, urethane particles, polyethylene particles and silica particles.

As the coloring material raw materials, iron oxide, ultramarine, konjo, chromium oxide, chromium hydroxide, carbon black,
Manganese violet, titanium oxide, zinc oxide, talc, kaolin, mica, calcium carbonate, magnesium carbonate, mica, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, silica, zeolite, barium sulfate, calcined calcium sulfate ( Inorganic pigments such as calcined gypsum, calcium phosphate, hydroxyapatite, and ceramic powder; azo, nitro, nitroso, xanthene, quinoline, anthraquinoline, indigo, triphenylmethane, phthalocyanine, pyrene, etc. And tar dyes. In addition, as a powder raw material such as a powder raw material or a coloring material raw material of these polymer compounds, those that have been subjected to a surface treatment in advance can be used.

As the surface treatment method, known surface treatment techniques can be used. For example, oil treatment with hydrocarbon oil, ester oil, lanolin, etc., dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, etc. Silicone treatment, perfluoroalkyl group-containing ester, perfluoroalkylsilane,
Fluorine compound treatment with perfluoropolyether and polymer having a perfluoroalkyl group, etc., silane coupling agent treatment with 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc., isopropyl triisostearoyl titanate Titanium coupling agent treatment with isopropyltris (dioctyl pyrophosphate) titanate, etc., metal soap treatment, amino acid treatment with acylglutamic acid, etc., lecithin treatment with hydrogenated egg yolk lecithin, etc., collagen treatment, polyethylene treatment, moisturizing treatment, inorganic compound treatment And a treatment method such as mechanochemical treatment.

As the fragrance, for example, anisaldehyde,
Benzyl acetate, geraniol and the like can be mentioned. Examples of the antiseptic / bactericide include methyl parapen, ethyl parapen, propyl parapen, benzalkonium, benzethonium and the like. Examples of the antioxidant include dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, and tocopherol.

Examples of the ultraviolet absorber include inorganic absorbers such as fine titanium oxide, fine zinc oxide, fine cerium oxide, fine iron oxide, fine zirconium oxide, benzoic acid, para-aminobenzoic acid, anthranilic acid, and the like.
Organic absorbents such as salicylic acid, cinnamic acid, benzophenone, and dibenzoylmethane may be used.

The special compounding components include, for example, hormones such as estradiol, estrone, ethinyl estradiol, cortisone, hydrocortisone, prednisone, vitamin A, vitamin B, vitamin C, vitamin E
Skin astringents such as vitamins such as citric acid, tartaric acid, lactic acid, aluminum chloride, potassium aluminum sulfate, allantoinchlorohydroxyalumnium, zinc paraphenolsulfonate, and zinc sulfate, cantaritis tincture, capsicum tincture, and ginger Tincture, assembly extract, garlic extract, hinokitiol, carpronium chloride, glyceride pentadecanoate, vitamin E, estrogen, hair growth promoters such as photosensitizers, and whitening agents such as magnesium phosphate-L-ascorbate and kojic acid. .

[0050]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 500 g of a dispersion medium in which 20 g of magnesium pyrophosphate as a dispersion stabilizer was formed by a double decomposition method with respect to 200 g of water was used.
Then, 0.25 g of sodium lauryl sulfate as a surfactant was added and dissolved under stirring in a ml separable flask. Separately, 80 g of styrene as a polymerizable vinyl monomer, perfluorobutyl ethyl ether [C ₄ F ₉ OC ₂ H _5] as a hydrophobic fluorine compound, viscosity 0.4 cSt (25 ° C.), surface tension 13. 6 dynes / cm
(25 ° C.), density 1.43 g / ml (25 ° C.), boiling point 7
At 8 ° C., a fluorine content of 64.8%], a monomer composition obtained by uniformly mixing and dissolving 20 g of 4.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator is dispersed in the above-described manner. Added to the medium. This mixture was mixed with a homomixer (ULTRA TURRAX T-2 manufactured by IKA).
Finely dispersed at 8000 rpm for about 10 seconds using 5).
The flask was equipped with a stirring blade, a thermometer, and a reflux condenser, and was placed in a 60 ° C water bath. After sufficiently replacing the inside of the flask with nitrogen gas, heating was continued at a stirring speed of 200 rpm for 20 hours to carry out a polymerization reaction.

After confirming that the polymerization reaction was completed, the reaction solution was cooled, and hydrochloric acid was added until the pH of the slurry became about 2 to decompose the dispersant. The particles were suction-filtered with a Buchner funnel using filter paper, and washed with 1.2 liters of ion-exchanged water to remove the dispersant. 5 pieces of dehydrated cake after washing
The resin particles were dried in an oven at 0 ° C. at normal pressure for 10 hours to obtain target resin particles, and their shapes were observed with an electron microscope and photographed.

The resin particles were taken with an electron microscope photograph (FIG. 3).
As shown in the above, spherical resin particles having a plurality of smooth bowl-shaped depressions. Arbitrary particles 10 in the photo
Zero was selected, the diameter of the particles was measured, and the number average center particle diameter was calculated. Furthermore, the number of depressions (calculated value), the particle diameter D and d / D were measured for 40 particles belonging to a range of 30% above and below the central particle diameter, and the average value was calculated. Obtained. Number of depressions: 7.2 D = 22.5 μm d / D = 0.83 In this example, the fluorine-based compound could be easily removed by drying in the oven described above.

Example 2 Resin particles were obtained in the same manner as in Example 1 except that the rotation speed of the homomixer was changed to 25,000 rpm. This resin particle has one smooth bowl-shaped depression,
The number of the depressions (calculated value), the average value of the particle diameter D and the average value of d / D were respectively as follows. Number of depressions: 1.6 D = 2.3 μm d / D = 0.81

Example 3 Resin particles were obtained in the same manner as in Example 1 except that the monomer composition was added to the dispersion medium without using the homomixer, and the rotation speed of the stirring blade was changed to 50 rpm. The resin particles have a plurality of smooth bowl-shaped depressions,
The number of the depressions (calculated value), the average value of the particle diameter D and the average value of d / D were respectively as follows. Number of depressions: 150 D = 350 μm d / D = 0.99

Example 4 Same as Example 1 except that styrene was changed to 95 g and perfluorobutyl ethyl ether to 5 g, and instead of heating and drying, the fluorine-based compound was removed by distillation from the slurry after polymerization. To obtain resin particles. The resin particles have a plurality of smooth bowl-shaped depressions,
The number of the depressions (calculated value), the average value of the particle diameter D and the average value of d / D were respectively as follows. Number of depressions: 4.4 D = 17.8 μm d / D = 0.90 In this example, the fluorine-based compound could be easily removed by the above-mentioned distillation operation.

Example 5 Resin particles were obtained in the same manner as in Example 1 except that the composition of the dispersion medium was changed to 100 g of water and 10 g of tribasic calcium phosphate as a dispersion stabilizer. The resin particles had a plurality of smooth bowl-shaped depressions, and the number of the depressions (calculated value) and the average values of the particle diameter D and d / D were as follows. Number of depressions: 6.3 D = 28.8 μm d / D = 0.85

Example 6 Styrene was used as trifluoroethyl methacrylate, and perfluorobutylethyl ether was used as perfluorooctane [C ₈ F ₁₈ , viscosity 0.7 cSt (25 ° C.), surface tension 15 dynes / cm (25 ° C.), density 1 .76 g / ml (25
C), a boiling point of 102 ° C, and a fluorine content of 78%], and the polymerization initiator was changed to 0.24 g to obtain resin particles in the same manner as in Example 1. As shown in the electron micrograph (FIG. 4), the resin particles are spherical having one smooth bowl-shaped depression, and the number of the depressions (calculated value), the average of the particle diameter D and the d / D are obtained. The values were as follows. Number of depressions: 1.8 D = 15.1 μm d / D = 0.88

Example 7 Resin particles were obtained in the same manner as in Example 6, except that the rotation speed of the homomixer was changed to 12000 rpm. This resin particle has one smooth bowl-shaped depression,
The number of the depressions (calculated value), the average value of the particle diameter D and the average value of d / D were respectively as follows. Number of depressions: 1.8 D = 7.3 μm d / D = 0.81

Comparative Example 1 Resin particles were obtained in the same manner as in Example 1 except that 99.9 g of styrene and 0.1 g of perfluorobutyl ether were used. These resin particles have an average particle size of 7.0 μm.
Was a spherical particle having no depression.

Comparative Example 2 Resin particles were obtained in the same manner as in Example 1, except that perfluorobutyl ether was changed to n-hexane having a viscosity of 0.65 cSt at 25 ° C. The resin particles were porous spherical particles having an average particle diameter of 28.1 μm.

Comparative Example 3 Resin particles were obtained in the same manner as in Example 1, except that 80 g of styrene was changed to 60 g of methyl methacrylate and 20 g of ethylene glycol dimethacrylate. The resin particles were particles having an average particle diameter of 15.8 μm and having a distorted shape.

Comparative Example 4 200 g of water was mixed with magnesium pyrophosphate 2 by the metathesis method.
The dispersion medium in which 0 g was generated was placed in a 500 ml separable flask, and 0.25 g of sodium lauryl sulfate was dissolved therein. Separately, methyl methacrylate (MM
A) 98 g, dimethylpolysiloxane [viscosity 0.65c]
St (25 ° C.)] 2 g and 2,2′-azobis (2,
A monomer composition obtained by uniformly mixing and dissolving 0.3 g of 4-dimethylvaleronitrile) was added to the above dispersion medium.
This mixture is mixed with a homomixer (ULTRA manufactured by IKA).
TURRAX T-25) at approx.
Finely dispersed for 0 seconds. The flask was equipped with a stirrer, a thermometer, and a cooler, and placed in a 60 ° C. water bath. After sufficiently replacing the inside of the flask with nitrogen gas, the stirring speed is 200 rpm.
m for 10 hours to carry out a polymerization reaction.

After confirming that the polymerization reaction was completed, the reaction solution was cooled, and hydrochloric acid was added until the pH of the slurry became about 2 to decompose the dispersant. The particles were suction-filtered with a Buchner funnel using filter paper, and washed with 1.2 liters of ion-exchanged water to remove the dispersant. After the dehydrated cake after suction filtration was dried, it was dispersed in cyclohexane and suction filtration was repeated several times to obtain desired resin particles, and the shape was observed with an electron microscope and photographed. The resin particles had an average particle diameter of 7.2 μm, had no dents, and were spherical.

Example 8 Production of Body Lotion Resin Particles (Example 7) 3 parts by weight Ethanol 50 parts by weight Glycyrrhizic acid 0.1 parts by weight Fragrance 0.5 parts by weight Purified water 46.4 parts by weight Resin particles, ethanol , Glycyrrhizic acid, perfume and purified water were sufficiently mixed with a mixer to obtain a body lotion.

Example 9 [Production of powder foundation] (Powder part) Resin particles (Example 7) 10 parts by weight Silicon-treated mica 22 parts by weight Silicon-treated talc 40 parts by weight Silicon-treated titanium oxide 10 parts by weight Red iron oxide 0 0.6 parts by weight Yellow iron oxide 1 part by weight Black iron oxide 0.1 part by weight (oil part) Cetyl 2-ethylhexanoate 15 parts by weight Sorbitan sesquioleate 1 part by weight Preservative 0.2 parts by weight Fragrance 0.1 part by weight Department

The powder was mixed with a Henschel mixer and then ground with a hammer mill. The resulting mixture was mixed with a Henschel mixer while gradually adding a mixture obtained by dissolving the oil portion, and pulverized with a hammer mill. After passing this through a sieve, it was compression-molded on a metal plate to obtain a powder foundation.

The cosmetics thus produced were subjected to a sensory test by five panelists. As evaluation items in this test, elongation at the time of application, smoothness, and feeling of creaking were selected, and sensory evaluation was performed for each item according to the following criteria.・ ・ ・: 4 or more panelists answered that it was good (“nothing” for squeakiness) △: 2-3 panelists answered that it was good ×: 1 or less panelists answered that it was good Table 1 shows the results of the sensory test.

[0069]

[Table 1]

As described above, the external preparations of Examples 8 and 9 containing the resin particles of the present invention have elongation, smoothness,
It can be seen that the feeling without squeaky feeling is excellent.

[0071]

According to the method of the present invention, by using a hydrophobic fluorine-based liquid organic compound, the workability of the fluorine-based compound during the production of the resin particles, the solubility in the polymerizable vinyl monomer, and the polymerization are improved. The cleaning workability of the equipment is improved. In addition, the resin particles and the fluorine-based compound can be separated by a simple method such as distillation or drying without using a complicated means such as solvent washing, and the resin-based resin is hardly residual in the resin particles. Particle quality is also improved. Further, the spherical resin particles obtained by this method can be applied to a wide range of fields such as the fields of electronics, adhesives, medicine, cosmetics and general industry, and excellent effects are expected.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a spherical resin particle (one depression) of the present invention.

FIG. 2 is a schematic view showing a spherical resin particle (a plurality of depressions) of the present invention.

FIG. 3 is an electron micrograph of the spherical resin particles obtained in Example 1.

FIG. 4 is an electron micrograph of the spherical resin particles obtained in Example 6.

Claims (9)

[Claims] 1. In the absence of a cross-linking agent, 100 parts by weight of a polymerizable vinyl monomer have no copolymerizability with the polymerizable vinyl monomer and have a viscosity at 25 ° C. of 0.1 to 3 c.
Hydrophobic fluorinated liquid organic compounds less than St 3-4
By mixing and dissolving 0 parts by weight and performing aqueous suspension polymerization,
In a front view having a bowl-shaped depression on the surface of the particle and defining the boundary line at the opening of the depression as the horizontal direction, the particle diameter in the horizontal direction is D (μm), and the height of the particle in the vertical direction is d ( μm)
Wherein a spherical resin particle satisfying the formula: 0.8 <d / D <1.0 (I) 0.1 μm ≦ D ≦ 500 μm (II) is obtained. 2. The method according to claim 1, wherein the spherical resin particles have one bowl-shaped depression on the surface thereof and satisfy the following formula: 0.1 μm ≦ D ≦ 20 μm (III). 3. The method according to claim 1, wherein the spherical resin particles have a plurality of bowl-shaped depressions on the surface thereof and satisfy the following expression: 20 μm <D ≦ 500 μm (IV). 4. The method according to claim 1, wherein the hydrophobic fluorine-containing liquid organic compound is 1
The method according to any one of claims 1 to 3, having a boiling point of 25 to 200C under atmospheric pressure. 5. The method according to claim 1, wherein the hydrophobic fluorine-containing liquid organic compound is a saturated hydrocarbon or ether in which part or all of the hydrogen atoms have been replaced with fluorine, and has a fluorine content of 30 to 90% by weight. The production method according to any one of claims 1 to 4, wherein 6. The method according to claim 1, wherein the hydrophobic fluorine-containing liquid organic compound is removed by distillation or drying after the aqueous suspension polymerization. 7. The production method according to claim 1, wherein in the aqueous suspension polymerization, a poorly water-soluble inorganic compound is used as a dispersion stabilizer. 8. Spherical resin particles obtained by the production method according to any one of claims 1 to 7. 9. An external preparation comprising the spherical resin particles according to claim 8.