JP2002265620A - Wet material of (meth)acrylic acid ester-based resin particle, method for producing the same and external preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin having excellent dispersibility, capable of providing an external preparation with an excellent feeling such as soft feeling, spreadability, softness, etc. SOLUTION: This wet material of (meth)acrylic acid ester-based resin particle is obtained by adding 5-100 pts.wt. of an aqueous solution of an organic solvent to 100 pts.wt. of a crosslinked (meth)acrylic acid ester-based resin particle having 0.01-0.6 kgf/mm<2> compression strength at 10% deformation. This external preparation comprises the wet material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a (meth) acrylate-based resin particle wet product, a method for producing the same, and an external preparation containing the wet product. More specifically, it is easily and satisfactorily dispersed in a liquid such as water or an organic solvent, or an inorganic or organic powder (meta).
The present invention relates to a wet product of acrylic acid ester-based resin particles, a method for producing the same, and an external preparation having a smooth feeling in use blended with the wet product.

[0002]

BACKGROUND OF THE INVENTION Cosmetics containing cosmetic powders include makeup cosmetics such as foundation, white powder, blusher, eye shadow, body cosmetics such as body powder and baby powder, and pre-shave. Lotions such as lotions, aftershave lotions and body lotions are widely used.

[0003] Nylon particles, polymethyl methacrylate particles, and the like are used in these cosmetics for the purpose of improving elongation and feel on the skin and imparting functions such as a wrinkle concealing effect.
Cross-linked polystyrene particles, silicon particles, urethane particles,
Resin particles such as polyethylene particles and inorganic particles such as silica particles are blended as cosmetic powder.

[0004] However, polymethyl methacrylate particles, cross-linked polystyrene particles and silica particles are satisfactory in that they impart excellent elongation to cosmetics, but have a soft touch and a smooth touch. It was insufficient in terms of providing. In addition, nylon particles and silicon particles can give a smooth feel, but are insufficient in that they give a soft feel, and polyethylene particles can give a soft feel but give a smooth feel. Insufficiently, and urethane particles can give a soft touch, but there is a problem that it is unsuitable for industrial use because the production method is special and expensive.

[0005] In order to solve such a problem, soft particles made of a (meth) acrylate-based resin which gives an excellent soft feeling to cosmetics and can be obtained at a relatively low cost by a general suspension polymerization method have been proposed. However, as the soft particles themselves become softer, the adhesiveness of the particle surface becomes stronger and the particles coalesce, so that it was difficult to incorporate them into cosmetics and the like.

In addition, soft particles which are made of inorganic particles and / or organic particles adhered to the surface of soft particles made of a (meth) acrylate resin having a specific compressive strength to prevent coalescence of the particles are blended. Cosmetics have also been proposed (JP-A-2000-186017 and JP-A-20
00-302624). However, such cosmetics have good elongation and feel, but are not yet satisfactory, and there is still a need for cosmetics that have even better elongation, smoothness, and softness. .

[0007] The present invention provides better dispersibility, elongation, smoothness, softness, and other tactile sensations by blending particles having no inorganic particles and / or organic particles on the surface with cosmetics and the like. It is an object to provide such particles that can be applied to cosmetics.

[0008]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a crosslinked (meth) acrylate resin particle having a specific compressive strength was added to a specific amount of an organic solvent. It has been found that when a wet product containing an aqueous solution is mixed with a liquid, powder, or the like, it is easily and satisfactorily dispersed. Further, it has been found that, by blending the wet product with an external preparation such as a cream, an ointment or an emulsion, the external preparation is stretched and imparted with an excellent tactile sensation such as softness and smoothness, thereby completing the present invention. Reached.

Thus, according to the present invention, crosslinked (meth) acrylate resin particles having a compressive strength at the time of 10% deformation of 0.01 to 0.6 kgf / mm ² (hereinafter referred to as “resin particles”) (Meth) acrylate-based resin particle wet material (hereinafter, referred to as "wet material") comprising 100 parts by weight of an organic solvent aqueous solution in an amount of 5 to 100 parts by weight.
"Wet resin particles" is provided.

Further, according to the present invention, crosslinked (meth) acrylate resin particles having a compressive strength at the time of 10% deformation of 0.01 to 0.6 kgf / mm ² are formed in an aqueous medium, A method for producing a wet resin particle is provided, wherein a water-soluble organic solvent or an aqueous solution thereof is added to the resin particle during and / or after the solid-liquid separation step to be performed. Further, according to the present invention, there is provided an external preparation prepared by blending the above-mentioned wet resin particles.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The wet resin particles of the present invention are resin particles having a specific compressive strength and containing a specific amount of an aqueous solution of an organic solvent. In addition, here (meta)
Acrylic acid is a concept that includes both acrylic acid and methacrylic acid. The wet resin particle refers to a resin particle containing at least an organic solvent aqueous solution in the resin particles, and the organic solvent aqueous solution may adhere to the surface of the particles.

The crosslinked (meth) acrylate resin particles have a compressive strength at the time of 10% deformation of 0.01 to 0.6 kg.
f / mm ² , preferably 0.1 to 0.4 kgf /
mm ² . If compression strength is below 0.01 kgf / mm ^2, when the resin particles wet obtained were formulated into external preparation, since the feel of the resin particles is not felt, the feel of external preparation (e.g., soft feeling and elongation) It cannot be improved and is not preferred. Also, the compressive strength is 0.60 kgf /
If it exceeds mm ² , on the contrary, the feel of the resin particles becomes hard like the conventional resin particles, and a sufficient soft feeling cannot be imparted to the external preparation, which is not preferable.

The compressive strength is a value measured using a micro compression tester HCTM200 manufactured by Shimadzu Corporation. Specifically, when one resin particle is subjected to a compression test at a constant load speed to a load of 1 gf, the load when the particle diameter is deformed by 10% and the particle diameter before compression are included in the following equation. It is the value obtained by Compressive strength (kgf / mm ² ) = 2.8 × Load (kgf)
/ {Π × particle diameter (mm) × particle diameter (mm)}

The average particle size of the resin particles in the present invention is as follows:
It is preferably about 0.5 to 800 μm. When it is less than 0.5 μm or more than 800 μm, when the obtained resin particle wet product is blended in, for example, an external preparation,
It is not preferable because it is difficult to improve the feel of the external preparation.

The resin particles of the present invention can be obtained by polymerizing a (meth) acrylate monomer in an aqueous medium in the presence of a crosslinkable monomer.

The (meth) acrylic acid ester monomer is preferably an oil-soluble monomer, and a (meth) acrylic acid ester having 1 to 12 carbon atoms in a substituent forming an ester bond with (meth) acrylic acid. A system monomer is preferred. Specifically, for example, methyl acrylate, ethyl acrylate,
Acrylic esters such as n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid Examples include methacrylates such as 2-ethylhexyl and lauryl methacrylate. Among them, acrylates having 1 to 8 carbon atoms are preferable. These (meth) acrylate monomers may be used in combination of two or more. When two or more (meth) acrylic ester monomers are used in combination, it is preferable that the acrylic acid ester having 1 to 8 carbon atoms be contained in the monomer at a ratio of 50 to 99.5% by weight. .

As long as the performance of the obtained wet resin particles does not deteriorate, a monomer copolymerizable with the (meth) acrylate monomer, for example, styrene, p-methylstyrene, α-methylstyrene One or more other monomers having a vinyl group such as vinyl acetate may be used in combination.

The crosslinking monomer is not particularly limited as long as it has a plurality of vinyl groups. Examples thereof include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. , Decaethylene glycol di (meth) acrylate, pentadecaethylene glycol di (meth) acrylate, pentacontaector ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, allyl methacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acryl (Meth) acrylates such as diethylene glycol di (meth) acrylate, phthalate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified hydroxypivalate neopentyl glycol diacrylate, polyester acrylate, urethane acrylate, etc. And aromatic divinyl monomers which are divinylbenzene, divinylnaphthalene and derivatives thereof. Among them, ethylene glycol di (meth)
Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate,
(Meth) acrylate-based cross-linking agents such as 1,6-hexanediol di (meth) acrylate and caprolactone-modified dipentaerythritol hexaacrylate,
Caprolactone-modified hydroxypivalic acid ester neopentyl glycol diacrylate, polyester acrylate and the like are particularly preferred in that they have low skin irritation and are suitable for cosmetic use. These crosslinkable monomers are
Each can be used alone or in combination of two or more.

The proportion of the crosslinkable monomer used is as follows:
It is preferably from 0.5 to 50% by weight. These crosslinkable monomers are used for imparting a desired compressive strength to the obtained resin particles, and for imparting a preferable feel (soft feeling, elongation) to the external preparation when blended with the external preparation. (Meta) so that the compression strength of the finally obtained resin particles is 0.01 to 0.6 kgf / mm ^2.
The composition and the mixing ratio of the acrylate monomer and the crosslinkable monomer are determined.

The polymerization of the (meth) acrylic acid ester monomer may be any of suspension polymerization, emulsion polymerization, seed polymerization and dispersion polymerization. Among them, suspension polymerization is preferred in that the effects of the present invention are remarkable. Polymerization is preferred. At the time of polymerization of the (meth) acrylate monomer, a color pigment may be added to the reaction mixture and dispersed. Thereby, it is possible to prevent aggregation of the color pigment which occurs when the obtained resin particles and the color pigment are simply mixed, and color unevenness caused by a drastic change in color from dry powder to wet powder.

As the coloring pigment, it is preferable to use a coloring pigment which is hardly soluble in the solvent used for the polymerization reaction of the (meth) acrylate monomer and the monomer composition. Examples of such color pigments include titanium oxide, zinc oxide, zirconium oxide, magnesium oxide, iron oxide, iron hydroxide,
Chromium oxide, chromium hydroxide, ultramarine, navy blue, manganese violet, ultramarine purple, titanium black, carbon black, aluminum powder, mica titanium, bismuth oxychloride, iron oxide treated mica titanium, navy blue treated mica titanium, carmine treated mica titanium, silica , Calcium carbonate, magnesium carbonate, barium sulfate, barium silicate, calcium silicate, magnesium silicate, calcium phosphate, hydroxyapatite, zeolite, alumina, talc,
Inorganic pigments such as mica, bentonite, kaolin and sericite, aluminum lakes such as tartrazine, sunset yellow FCF, brilliant blue FCF, zirconium lake, barium lake, herringdon pink CN,
Organic pigments such as Lisor Rubin BCA, Lake Red CBA, Phthalocyanine Blue, and Permanent Orange are exemplified. These coloring pigments can be used alone or in combination of two or more.

The proportion of the color pigment used is preferably from 1 to 70% by weight based on the total weight of the resin particles. When the use ratio of the color pigment is less than 1% by weight, the effect of blending the color pigment is extremely low, which is not preferable. On the other hand, if the use ratio of the coloring pigment is more than 70% by weight, the viscosity of the dispersion becomes high at the stage of preparing the dispersion before polymerization, and it is not preferable because the production of the resin particles becomes difficult.

The coloring pigment may be added to the polymerization system after the surface is hydrophobized with a surface treating agent. Examples of the surface treatment agent include carboxylic acid, sulfonic acid, sulfate ester, phosphate ester, phosphonic acid and salts thereof,
Coupling agents such as silane, titanate and aluminate are exemplified. The use ratio of the surface treatment agent is preferably about 0.1 to 30% by weight based on the color pigment.

The apparatus used for dispersing the color pigment is not particularly limited as long as it can give sufficient dispersion energy to the dispersion system, and examples thereof include a ball mill, a sand mill, an ultrasonic disperser, and a homogenizer. In the polymerization of the (meth) acrylate-based monomer, a polymerization initiator, a dispersant, a surfactant and the like may be added as required.

Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, orthochlorobenzoic peroxide, methyl ethyl ketone peroxide, diisopropylperoxydicarbonate, cumene hydroperoxide and t-butyl hydroperoxide. Examples thereof include oil-soluble peroxides, oil-soluble azo compounds such as 2,2'-azobisisobutyronitrile, and 2,2'-azobis (2,4-dimethylvaleronitrile).

Examples of the dispersant include poorly water-soluble inorganic salts such as calcium phosphate and magnesium pyrophosphate, and water-soluble polymers such as polyvinyl alcohol, methylcellulose and polyvinylpyrrolidone.

Examples of the surfactant include anionic surfactants such as sodium oleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, alkyl naphthalene sulfonate, alkyl phosphate ester salt, polyoxyethylene alkyl ether, and polyoxyethylene alkyl ether. Nonionic surfactants such as oxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, and amphoteric surfactants such as lauryl dimethylamine oxide And the like.

These polymerization initiators, dispersants and surfactants can be used alone or in combination of two or more. The ratio of the polymerization initiator used is 0.01 to 1 with respect to the (meth) acrylate monomer.
% By weight, and the dispersing agent is used in a ratio of 0.1 to the monomer.
Preferably, the surfactant is used in an amount of about 0.005 to 0.2% by weight with respect to water.

The polymerization reaction is carried out in a monomer phase (for example, a monomer,
After mixing a polymerization initiator (eg, a polymerization initiator) and a dispersion medium phase (eg, water, a dispersant, a surfactant), the mixture can be started by elevating the temperature while stirring. The dispersing medium phase is a monomer phase 10
It is used in an amount of 100 to 1000 parts by weight with respect to 0 parts by weight.
The polymerization initiation temperature is preferably from 40 to 90 ° C. It is generally preferable to polymerize for about 1 to 10 hours while maintaining the temperature.

The average particle size of the resin particles can be appropriately adjusted by adjusting the mixing conditions of the monomer and the dispersion medium and the stirring conditions. In order to disperse the monomer phase as fine droplets in the dispersion medium phase, for example, use a stirring force of a propeller blade or the like, use a homogenizer, or use a high shear applied to the gap between the rotating blades and the vessel wall or the rotating blades. By using a suitable emulsifying disperser, dispersing using an ultrasonic disperser, or the like, or by appropriately pressing a method such as passing a monomer aqueous solution through a ceramic microporous membrane by pressurizing and pressing into a dispersion medium. It can be carried out.

After the completion of the polymerization reaction of the (meth) acrylate monomer, the dispersant may be decomposed with an acid or the like, if necessary. During and / or after the step of solid-liquid separation of the obtained resin particles, an aqueous solution of an organic solvent is added to the resin particles, whereby a wet resin particle, which is the object of the present invention, can be produced. At this time, when the resin particles contain water, only an organic solvent may be added. Specifically, by adding an organic solvent or an aqueous solution thereof after the step of washing or filtering the resin particles or after each step, and adding an aqueous solution of the organic solvent after the step of drying. By doing so, a wet resin particle can be produced. Of these, it is particularly preferable to add an organic solvent or an aqueous solution thereof after the washing step and / or the filtration step without performing the drying step, because the obtained resin particle wet product has more excellent dispersibility.

The water-soluble organic solvent is not particularly limited. For example, the water-soluble organic solvent has 1 carbon atom such as ethanol, n-propanol, isopropanol, butanol, isobutanol and the like.
And lower alcohols, polyhydric alcohols such as glycerin, propylene glycol and 1,3-butylene glycol, esters such as methyl acetate and ethyl acetate, and ketones such as acetone. Among these water-soluble organic solvents, lower alcohols such as ethanol, n-propanol and isopropanol are preferable because they have excellent dispersibility when mixed, are widely used widely in cosmetics and the like, and are easy to handle. When the wet resin particles are mixed with an external preparation, for example, those which are non-toxic to the body are preferable, and if the same organic solvent as the component mixed with the external preparation is selected, the composition of the external preparation is reduced. Is more preferable because the influence of the above can be avoided.

The proportion of the aqueous solution of the organic solvent is as follows.
It is at least 5 parts by weight, preferably 5 to 100 parts by weight, based on 00 parts by weight. When the use ratio of the organic solvent aqueous solution is less than 5 parts by weight, the resin particle wet of the present invention is not easily and uniformly dispersed when mixed with a liquid or powder, so that long and strong mechanical stirring is required. And the like, which is not preferable because there is a possibility that the particles may be crushed. Further, when the use ratio of the organic solvent aqueous solution exceeds 100 parts by weight, the dispersibility is favorably exhibited, but not only the effect due to the increase in the amount is not seen but also the drying after blending the wet resin particles. It is not preferable because the required time and energy increase.

The organic solvent aqueous solution has an organic solvent concentration of 1 to 3.
It is preferably about 50% by weight. If the concentration of the organic solvent is less than 1% by weight, the effect of reducing the stickiness between the particles is not sufficient, and the mixture is not easily dispersed when mixed with a liquid or powder, and is mixed for a long time with strong mechanical stirring. Processing is required, and there is a possibility that the particles may be crushed, which is not preferable. When the concentration of the organic solvent is higher than 50% by weight,
The swelling of the wet resin particles becomes remarkable, the viscosity of the surface of the wet resin particles increases, and the wet resin particles adhere to each other. Not preferred.

The content ratio of the organic solvent aqueous solution of the present invention is preferably determined in the filtration step using a suction or pressure filtration device or a centrifugal filter. It can be adjusted as appropriate by changing the amount of resin to be provided. The resin particle wet product of the present invention is used as a compounding component in an external preparation such as an external medicine or a cosmetic. Further, since it has excellent dispersibility, it is also used as an additive to paints and resin compositions for molding.

The topical drug is not particularly limited as long as it is applied to the skin, and examples thereof include creams, ointments, and emulsions. Examples of cosmetics include washing cosmetics such as soaps, body shampoos, facial cleansers, and scrubs, lotions, creams, milky lotions, packs, whiteners, foundations, lipsticks, lip balms, blushes, eyebrows cosmetics, and nail polish cosmetics. , Shampoo cosmetics, hair dyes, hair styling, aromatic cosmetics, toothpastes, bath preparations, antiperspirants, sunscreen products, suntan products, body powders, baby powders, and other body cosmetics, shaving creams, massage creams And lotions such as pre-shave lotion, after-shave lotion, body lotion and the like, but there is no limitation as long as the effects of the present invention are recognized.

The compounding amount of the resin particle wet material in the external preparation is 1
~ 50% by weight is desirable. Resin particle wet content is 1
When the amount is less than 50% by weight, the compounding effect is not clearly recognized. When the compounding amount of the wet resin particles is more than 50% by weight, the effect is not enhanced even if the compounding amount is further increased, which is not preferable. .

Since the wet resin particles of the present invention are uniformly dispersed in a liquid or a powder, they can impart not only an excellent softness to the external preparation but also a smoother feeling in use. From the point that such an effect appears remarkably,
The wet resin particles of the present invention are particularly suitably used for cosmetics.

When the wet resin particles of the present invention are blended with a powdery cosmetic, the wet resin particles and the powder are sufficiently stirred with a mixer or the like, and then water and an organic solvent are removed by heating or the like. . Components commonly used in cosmetics can be appropriately added to the wet resin particles of the present invention according to the purpose within the range not impairing the effects of the present invention. Such components include, for example, water, lower alcohols, fats and waxes, hydrocarbons, higher fatty acids, higher alcohols, sterols, fatty acid esters, metal soaps, humectants,
Examples include surfactants, polymer compounds, coloring material raw materials, fragrances, preservatives / bactericides, antioxidants, ultraviolet absorbers, and special compounding components.

The lower alcohol includes, for example, ethanol, propanol and the like. As fats and waxes, for example, avocado oil, almond oil, olive oil, cocoa butter, beef tallow, sesame fat, wheat germ oil, safflower oil, shea butter, turtle oil, camellia oil, persic oil, castor oil, grape oil, macadamia nut Examples include oil, mink oil, egg yolk oil, mokuro, coconut oil, rosehip oil, hardened oil, silicone oil, orange roughy oil, carnauba wax, candelilla wax, whale wax, jojoba oil, montan wax, beeswax, lanolin and the like.

Examples of the hydrocarbon include liquid paraffin, vaseline, paraffin, ceresin, microcrystalline wax, squalane and the like. Examples of the higher fatty acids 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 acids.

As higher alcohols, for example, lauryl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyldecanol, octyldecanol, isostearyl alcohol, jojoba alcohol ,
Decyltetradecanol and the like. Sterols include, for example, cholesterol, dihydrocholesterol, phytocholesterol and the like.

Examples of the fatty acid ester include ethyl linoleate, isopropyl myristate, isopropyl lanolin fatty acid, hexyl laurate, myristyl myristate, cetyl myristate, octyldodecyl myristate, decyl oleate, octyldodecyl oleate, dimethyloctane. Hexyldecyl acid, cetyl octanoate, cetyl isooctanoate, decyl palmitate,
Glycerin trimyristate, glyceryl tricaprylate, glycerin tricaprate, propylene glycol dioleate, glycerin triisostearate, glyceryl triisooctanoate, cetyl lactate, myristyl lactate, diisostearyl malate and cholesteryl isostearate, cholesteryl 12-hydroxystearate And the like, and cyclic alcohol fatty acid esters.

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 humectants include glycerin, propylene glycol,
Examples thereof include 1,3-butylene glycol, polyethylene glycol, sodium dl-pyrrolidonecarboxylate, sodium lactate, sorbitol, sodium hyaluronate, polyglycerin, xylitol, and maltitol.

Examples of the surfactant include anionic surfactants such as higher fatty acid soaps, higher alcohol sulfates, N-acyl glutamates, phosphates and alkyl sulfates, amine salts and quaternary ammonium salts. Cationic surfactants such as, betaine type, amino acid type, imidazoline type, amphoteric surfactants such as lecithin, fatty acid monoglyceride, propylene glycol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, alkyl alkanolamide, Nonionic surfactants such as ethylene oxide condensate and the like can be mentioned.

Examples of high molecular compounds include natural high molecular compounds such as gum arabic, gum tragacanth, guar gum, locust bean gum, karaya gum, iris moth, quince seed, gelatin, shellac, rosin, casein, sodium carboxymethyl cellulose, hydroxyethyl cellulose, and the like. Methyl cellulose, ethyl cellulose, sodium alginate, ester gum, nitrocellulose, hydroxypropyl cellulose, semi-synthetic polymer compounds such as crystalline cellulose, polyvinyl alcohol,
Polyvinyl pyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyvinyl methyl ether,
Synthetic polymer compounds such as polyamide resin, silicone oil, nylon particles, polymethyl methacrylate particles, crosslinked polystyrene particles, silicon particles, urethane particles, and resin particles such as polyethylene particles.

As a coloring material, 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,
Inorganic pigments such as ceramic powder, azo type, nitro type,
Examples include tar dyes such as nitroso, xanthene, quinoline, anthraquinoline, indigo, triphenylmethane, phthalocyanine, and pyrene.

Powder materials such as these polymer compounds and color material materials may have been subjected to a surface treatment in advance. As the surface treatment method, conventionally known surface treatment techniques can be used. For example, oil treatment with hydrocarbon oil, ester oil, lanolin, etc., silicone treatment with dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, etc. Fluoro compound treatment with fluoroalkyl group-containing ester, perfluoroalkylsilane, perfluoropolyether and polymer having perfluoroalkyl group, etc., with γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc. Silane coupling agent treatment, titanium coupling agent treatment with isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, etc., metal soap treatment, acyl gluta Amino acid treatment with minic acid, etc., lecithin treatment with hydrogenated egg yolk lecithin, collagen treatment,
Treatment methods such as polyethylene treatment, moisture retention treatment, inorganic compound treatment, mechanochemical treatment, and the like can be given.

Examples of the flavor include natural flavors such as lavender oil, peppermint oil and lime oil, and synthetic flavors such as ethylphenyl acetate, geraniol, p-tert-butylcyclohexyl acetate, and the like. Examples of the antiseptic / bactericide 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. As the ultraviolet absorber, for example, inorganic absorbers such as fine-particle titanium oxide, fine-particle zinc oxide, fine-particle cerium oxide, fine-particle iron oxide, fine-particle zirconium oxide, benzoic acid, para-aminobenzoic acid, anthranilic acid, salicylic acid, Organic absorbents such as cinnamic acid, benzophenone, and dibenzoylmethane are exemplified.

Examples of the special components include hormones such as estradiol, estrone, ethinyl estradiol, cortisone, hydrocortisone, and prednisolone; vitamins such as vitamin A, vitamin B, vitamin C, and vitamin E; citric acid, tartaric acid, lactic acid, Skin astringents such as aluminum chloride, aluminum / potassium sulfate, allantoinchlorohydroxyaluminum, zinc paraphenolsulfonate, and zinc sulfate, cantharistinus, capsicum tincture, ginger tincture, assembly extract, garlic extract, hinokitiol, carpronium chloride, pentadecane Hair growth-promoting agents such as acid glyceride, vitamin E, estrogen, and photosensitizer; and whitening agents such as magnesium phosphate-L-ascorbate and kojic acid.

[0052]

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

[Evaluation Method] The dispersibility of the wet resin particles of the present invention was evaluated by the following methods when mixed with a liquid and a powder.

(Evaluation of dispersibility in liquid) Diameter 175 m
m, a cylindrical stainless steel container having a height of 215 mm and a mixing container having a three-bladed propeller-shaped agitating blade having a diameter of 88 mm and having a vertical axis at a height of 3 cm from a circular bottom, and a resin particle. A total of 3 kg of the wet resin particles containing 500 g and deionized water was added thereto, and the number of rotations was 1
Stir and mix at 95 rpm. A magnification of 100
By visually observing with a double-magnification projector, the time required for the particles to be unraveled and dispersed uniformly was measured, and judged according to the following criteria. ◎: uniformly dispersed within 1 minute ○: more than 1 minute but uniformly dispersed within 2 minutes △: more than 2 minutes but uniformly dispersed within 10 minutes ×: even if it exceeds 10 minutes Does not spread

(Evaluation of dispersibility in powder) Henschel mixer (manufactured by FM Corporation, trade name: Robocoup,
160 g of talc and a wet resin particle containing 40 g of resin particles were placed in an inner volume of 2 liters and a stirring blade diameter of 165 mm), and mixed by stirring at a rotation speed of 1500 rpm. By visually observing the collected sample with a magnifying projector having a magnification of 100, the time required for the particles to be disintegrated and dispersed uniformly was measured, and judged according to the following criteria. ◎: uniformly dispersed within 1 minute ○: more than 1 minute but uniformly dispersed within 2 minutes △: more than 2 minutes but uniformly dispersed within 10 minutes ×: dispersed even after 10 minutes do not do

(Evaluation of Powder Foundation) The produced powder foundation was evaluated by a sensory test by 10 panelists. As the evaluation items in this test, four items were selected: soft feeling, elongation, smoothness, and adhesiveness to the skin.
The average value of the 0 evaluation points was taken. 1: Bad 2: Somewhat bad 3: Normal 4: Somewhat good 5: Good

Example 1 (Oil phase) Ethyl acrylate 90 parts by weight 1,6-hexanediol dimethacrylate 10 parts by weight Benzoyl peroxide 0.5 parts by weight (aqueous phase) Deionized water 400 parts by weight Polyvinyl alcohol (degree of saponification) 85%) 8 parts by weight Sodium lauryl sulfate 0.04 parts by weight

After dispersing the above oil phase in the aqueous phase using a tabletop type TK homomixer (6000 rpm) manufactured by Tokushu Kika, this dispersion was placed in a polymerization reactor equipped with a stirrer and a thermometer. Then, stirring was continued at 60 ° C. for 6 hours to complete the suspension polymerization. After cooling, the suspension was sieved to remove coarse particles, 1/10 of the suspension was weighed out, and after deliquoring by suction filtration, washing was repeated by repeating water addition and filtration several times. Was replaced with a 20% by weight aqueous ethanol solution, and filtration was repeated several times. After the final filtration, suction was continued for 30 minutes. In this way, a wet cake of ethyl acrylate resin particles containing an aqueous ethanol solution was obtained. The compressive strength of the crosslinked ethyl acrylate resin particles contained in the wet resin particles is 0.15 kgf / m.
m ² , and the average particle size was 8.3 μm. Also,
The content of the aqueous ethanol solution of the wet resin particles was calculated to be 13.4% by weight from the weight difference before and after drying when the wet resin particles were dried in an oven at 105 ° C for 2 hours. The ethanol concentration in the aqueous ethanol solution was 19.3 based on the results of gas chromatography measurement of the wet resin particles.
Weight percent was calculated.

The wet cake-like resin particles obtained in this example show excellent dispersibility when the cake is easily disintegrated and quickly dispersed in both liquid and powder mixing. Was. Table 1 summarizes the specifications of the wet resin particles and the evaluation results of the dispersibility.

Example 2 A cake containing an aqueous ethanol solution was prepared in the same manner as in Example 1 except that 1/20 of the suspension after the polymerization reaction was weighed, and suction was performed for 60 minutes after the final filtration. Of ethyl acrylate resin particles was obtained. This wet resin particle has an ethanol aqueous solution content of 5.6% by weight,
The ethanol concentration was 18.7% by weight. Table 1 shows the specifications of the wet resin particles and the evaluation results of the dispersibility.

Example 3 A cake containing an aqueous ethanol solution was prepared in the same manner as in Example 1 except that 1/5 of the suspension after the polymerization reaction was weighed out and suctioned for 15 minutes after the final filtration. Of ethyl acrylate resin particles was obtained. This resin particle wet product is
The content of the aqueous ethanol solution was 33.1% by weight, and the ethanol concentration was 18.5% by weight. Table 1 shows the specifications of the wet resin particles and the evaluation results of the dispersibility.

Example 4 A wet product of ethyl acrylate resin particles was obtained in the same manner as in Example 1, except that the 20% by weight aqueous ethanol solution was changed to a 45% by weight aqueous ethanol solution. This wet product had an ethanol aqueous solution content of 14.2% by weight and an ethanol concentration of 44.3% by weight. Table 1 summarizes the specifications of the wet resin particles and the evaluation results of the dispersibility.

Example 5 A wet product of ethyl acrylate resin particles was obtained in the same manner as in Example 1 except that the 20% by weight aqueous ethanol solution was changed to a 3% by weight aqueous ethanol solution. This wet product had an ethanol aqueous solution content of 15.6% by weight and an ethanol concentration of 2.7% by weight. Table 1 shows the specifications of the wet resin particles and the evaluation results of the dispersibility.

Example 6 A wet product of ethyl acrylate resin particles was obtained in the same manner as in Example 1 except that the aqueous solution of 20% by weight of ethanol was replaced with the aqueous solution of 10% by weight of 1,3-butylene glycol. This wet product had a 1,3-butylene glycol aqueous solution content of 14.7% by weight and a 1,3-butylene glycol concentration of 9.1% by weight. Table 1 shows the specifications of the wet resin particles and the evaluation results of the dispersibility.

Example 7 (Oil phase) Ethyl acrylate 90 parts by weight 1,6-hexanediol dimethacrylate 10 parts by weight 0.5 parts by weight of benzoyl peroxide (aqueous phase) 400 parts by weight of deionized water Polyvinyl alcohol (degree of saponification) 85%) 1 part by weight Sodium lauryl sulfate 0.01 part by weight

After the above oil phase was dispersed in the aqueous phase, this dispersion was put into a polymerization reactor equipped with a stirrer and a thermometer, and stirred at 60 ° C. for 6 hours to complete the suspension polymerization. .
After cooling, classification and washing were performed, 1/10 of the suspension was weighed out, followed by drainage by suction filtration, washing by repeating water addition and filtration several times, and washing water was added at 20% by weight immediately before the end of washing. The operation of filtration in place of the acetone aqueous solution was repeated several times, and suction was continued for 30 minutes after the final filtration. In this way, a wet cake of ethyl acrylate resin particles containing an aqueous acetone solution was obtained. The compressive strength of the crosslinked ethyl acrylate resin particles contained in the wet resin particles is 0.1.
It was 7 kgf / mm ² and the average particle size was 86 μm. The wet resin particles had an aqueous solution of acetone of 12.9% by weight and an acetone concentration of 19.5% by weight. Table 1 shows the specifications of the wet resin particles and the evaluation results of the dispersibility.

Example 8 (Oil phase) Ethyl acrylate 60 parts by weight 30 parts by weight of butyl methacrylate 10 parts by weight of tetraethylene glycol dimethacrylate 0.5 parts by weight of benzoyl peroxide (aqueous phase) 400 parts by weight of deionized water Third Calcium phosphate 10 parts by weight Sodium lauryl sulfate 0.08 parts by weight

After dispersing the above oil phase in the aqueous phase using a tabletop type TK homomixer (13000 rpm) manufactured by Tokushu Kika, this dispersion was placed in a polymerization reactor equipped with a stirrer and a thermometer. Then, stirring was continued at 60 ° C. for 6 hours to complete the suspension polymerization. After cooling, hydrochloric acid was added to this suspension to decompose the dispersant, followed by classification and washing, and 1/1 of the suspension was removed.
0, rinsing is performed by repeating dehydration by suction filtration, followed by addition of water and filtration several times. Immediately before the completion of the washing, the operation of replacing the washing water with a 20% by weight aqueous isopropyl alcohol solution and repeating the filtration is repeated several times. After performing, suction was continued for 30 minutes. In this way, a wet cake (ethyl acrylate-butyl methacrylate) resin particles containing an aqueous isopropyl alcohol solution was obtained. The compressive strength of the resin particles contained in the wet resin particles is 0.51 kgf / m.
m ² and the average particle size was 2.5 μm. Also,
The wet resin particles had an isopropyl alcohol aqueous solution content of 14.8% by weight and an isopropyl alcohol concentration of 19.7% by weight. Table 1 summarizes the specifications of the wet resin particles and the evaluation results of the dispersibility.

Example 9 (Oil phase) Ethyl acrylate 95 parts by weight 1,6-hexanediol dimethacrylate 5 parts by weight 2,2′-azobis (2,4-dimethylvaleronitrile) 0.5 parts by weight (aqueous phase) ) Deionized water 400 parts by weight Double decomposition method magnesium pyrophosphate 10 parts by weight Sodium lauryl sulfate 0.08 parts by weight

After dispersing the above oil phase in the aqueous phase using a table-top TK homomixer (8000 rpm) manufactured by Tokushu Kika, this dispersion was placed in a polymerization reactor equipped with a stirrer and a thermometer. Then, stirring was continued at 60 ° C. for 6 hours to complete the suspension polymerization. After cooling, hydrochloric acid was added to the suspension to decompose the dispersant, followed by classification and washing.
, Rinsing was performed by repeating water removal and filtration several times, followed by dewatering by suction filtration.
The operation of filtration was repeated several times in place of the 0 wt% ethanol aqueous solution, and suction was continued for 30 minutes after the final filtration was performed. In this way, a wet cake of ethyl acrylate resin particles containing an aqueous ethanol solution was obtained. The compressive strength of the resin particles contained in the wet resin particles is 0.06 kgf /
mm ² and the average particle size was 8.1 μm. In addition, the wet resin particles have an ethanol aqueous solution content of 1%.
4.1% by weight and ethanol concentration of 19.4% by weight
Met. Table 1 shows the specifications of the wet resin particles and the evaluation results of the dispersibility.

Comparative Example 1 After the filtration step was completed, the wet product of ethyl acrylate resin particles was prepared in the same manner as in Example 1 except that the reaction product was dried until the content of the aqueous ethanol solution became 0.8% by weight. I got Table 1 summarizes the specifications of the wet product and the evaluation results of the dispersibility.

Comparative Example 2 A wet product of ethyl acrylate resin particles was obtained in the same manner as in Example 1, except that the 20% by weight aqueous ethanol solution was replaced with water. This wet product had a water content of 14.4% by weight. Table 1 shows the specifications of the wet resin particles and the evaluation results of the dispersibility.

[0073]

[Table 1]

As shown in Table 1, it was found that the wet resin particles of the present invention (Examples 1 to 9) were extremely easily and well dispersed when mixed with liquids or powders. . On the other hand, the resin particle wet product obtained in Comparative Example 1 has an organic solvent aqueous solution content outside the range of the present invention, and the resin particle wet product obtained in Comparative Example 2 does not contain an organic solvent. Both have poor dispersibility.

[Production of cosmetics] (Production of powder foundation)

Example 10 Resin Particle Wet (Example 1) 15 parts by weight Talc 47 parts by weight Sericite 17 parts by weight Titanium oxide 10 parts by weight Red iron oxide 0.6 parts by weight Yellow iron oxide 1 part by weight Black iron oxide 0 .1 part by weight Liquid paraffin 2 parts by weight Octyldecyl myristate 3.5 parts by weight Sorbitan isostearate 0.5 part by weight 2-octyldodecanol 3.0 parts by weight Preservatives appropriate amount perfume appropriate amount

The wet ethyl acrylate resin particles obtained in Example 1, talc, sericite, titanium oxide, red iron oxide, yellow iron oxide and black iron oxide were mixed with a Henschel mixer, and then heated to give an aqueous ethanol solution. Was removed. Next, a solution obtained by mixing and dissolving liquid paraffin, octyldecyl myristate, sorbitan isostearate, 2-octyldodecanol and a preservative was added and uniformly mixed. Furthermore, after adding and mixing a fragrance, it was pulverized and passed through a sieve to obtain a powder. This powder was compression-molded on a metal plate to produce a powder foundation. Table 2 shows the evaluation results of the powder foundation.

Comparative Example 3 A powder foundation was prepared in the same manner as in Example 10 except that the wet ethyl acrylate resin particles (Example 1) were replaced with the dry ethyl acrylate resin particles obtained in Comparative Example 1. Obtained. Table 2 shows the evaluation results of the powder foundation.

Comparative Example 4 The procedure of Example 10 was repeated, except that the wet resin particles (Example 1) were replaced with commercially available methyl methacrylate resin particles (average particle diameter 8.1 μm) containing no organic solvent aqueous solution. I got a powder foundation. Table 2 shows the evaluation results of the powder foundation. (Production of emulsion)

Example 11 (Oil phase) Squalane 5 parts by weight Vaseline 2 parts by weight Beeswax 0.5 parts by weight Sorbitan sesquioleate 0.8 parts by weight Polyoxyethylene oleyl ether (20EO) 1.2 parts by weight (aqueous phase) 54.9 parts by weight of purified water Wet resin particles (Example 1) 15 parts by weight Ethanol 5 parts by weight Propylene glycol 5 parts by weight Titanium oxide 10 parts by weight (Others) Carboxyvinyl polymer (1% aqueous solution) 10 parts by weight Hydroxide Potassium 0.05 part by weight Preservative / antioxidant appropriate amount Fragrance 0.5 part by weight

The above oil phase and aqueous phase were each dissolved by heating to 70 ° C., and the oil phase was gradually added to the aqueous phase while stirring, followed by pre-emulsification. Mixed. After neutralization by adding potassium hydroxide, the mixture was uniformly emulsified by a homomixer. Thereafter, a preservative, an antioxidant and a fragrance were added, mixed uniformly, and cooled to 30 ° C. to obtain an emulsion. Table 2 shows the evaluation results of the emulsion.

[0082]

[Table 2]

As shown in Table 2, cosmetics produced using the resin particle wet product of the present invention (Examples 10 and 1)
1) was found to be excellent in elongation, smoothness and skin adhesion during use due to the extremely good dispersion of the wet resin particles in addition to the soft feeling due to the flexibility of the wet resin particles. . On the other hand, the powder foundation obtained in Comparative Example 4 contains a wet resin particle containing an organic solvent aqueous solution in an amount outside the specified range of the present invention,
The powder foundation obtained in Comparative Example 4 was
Since the resin particles containing no organic solvent aqueous solution were contained, unfavorable results were obtained.

(Production of paint) Example 12 A paint was produced by mixing 20 parts by weight of the wet resin particles obtained in Example 1, 20 parts by weight of acrylic resin and water.
When this coating material was applied to a plastic plate and dried at 100 ° C., a coating film having a soft feeling and a smooth surface was obtained.

[0085]

According to the present invention, a wet (meth) acrylate resin particle of the present invention comprising a crosslinked (meth) acrylate resin particle having a specific compressive strength and a specific amount of an aqueous organic solvent solution, It disperses very easily and well when mixed with liquids such as water or inorganic or organic powders. Further, the external preparation prepared by mixing the (meth) acrylate-based resin particle wet material of the present invention has a soft touch and excellent touch feeling such as elongation and smoothness due to excellent dispersibility.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 33/04 C08L 33/04 F term (Reference) 4C083 AA082 AB032 AB232 AB242 AB432 AC012 AC022 AC092 AC102 AC122 AC182 AC352 AC442 AD091 AD092 CC05 CC12 DD21 DD31 EE06 EE07 FF01 4F070 AA32 AC36 AC39 AC43 AE28 DA50 DC16 4J002 BG041 BG051 BG061 EC036 EC046 EC056 EE036 EH036 FD090 FD200 FD310

Claims (5)

[Claims] The compression strength at the time of 10% deformation is 0.01 to 1.
To 100 parts by weight of the crosslinked (meth) acrylate-based resin particles of 0.6 kgf / mm ² ,
A (meth) acrylic acid ester-based resin particle wet material comprising 100 parts by weight. 2. The method according to claim 1, wherein the concentration of the organic solvent in the organic solvent aqueous solution is 1 or more.
The (meth) acrylic acid ester-based resin particle wet material according to claim 1, wherein the amount is from 50 to 50% by weight. 3. The wet (meth) acrylate resin particle according to claim 1, wherein the organic solvent is selected from monohydric or polyhydric alcohols, esters and ketones. 4. The compressive strength at the time of 10% deformation is 0.01 to
A crosslinked (meth) acrylate-based resin particle of 0.6 kgf / mm ² is produced in an aqueous medium, and during and / or after the solid-liquid separation step to be performed, a water-soluble organic solvent or The method for producing a wet (meth) acrylate resin particle according to any one of claims 1 to 3, wherein the aqueous solution is added. 5. An external preparation comprising the wetted (meth) acrylate resin particle according to any one of claims 1 to 3.