KR102563845B1 - Underwater cosmetics - Google Patents

Abstract

The present invention provides (A) emulsified particles comprising the following (a1) and (a2), (a1) oil phase (a2) emulsifier (B) an aqueous phase in which the following (b1) is dispersed, and (b1) hydrophobic gel fine particles It relates to an oil-in-water emulsion composition comprising a core-corona type microgel in which a hydrophilic group is partially formed on the surface.

Description

Underwater cosmetics

The present invention relates to improving stability and imparting water resistance to oil-in-water cosmetics.

Polar oils such as ester oils are also widely used as oil-based components of cosmetics, and organic ultraviolet absorbers are also used in large quantities in sunscreen agents in particular (see Patent Document 1). The large amount of use of these polar oils tends to impair the stability of the oil-in-water emulsion composition, and the use of a large amount of a polymeric substance as an emulsion stabilizer is also a cause of remarkably deteriorating the usability such as stickiness.

Japanese Unexamined Patent Publication No. 2016-104712

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an oil-in-water cosmetic having excellent feeling of use while maintaining moistness and excellent water resistance.

As a result of intensive studies to solve the above problems, the inventors of the present invention dispersed the core-corona type microgel as a stabilizer in an aqueous phase containing emulsified particles, thereby providing an in-water cosmetic with excellent feeling of use and excellent water resistance while maintaining moistness. It was found that it could be provided, and it came to complete this invention.

In particular, in the case of using a large amount of ester oil such as an organic ultraviolet absorber in sunscreen or foundation, an excellent feeling of use can be imparted.

That is, the water-in-water cosmetic according to the present invention

(A) emulsified particles comprising the following (a1) and (a2);

(a1) Paid

(a2) emulsifier

(B) an aqueous phase in which the following (b1) is dispersed;

(b1) It is characterized by comprising a core-corona type microgel in which hydrophilic groups are partially formed on the surface of hydrophobic gel microparticles.

In the water-in-water cosmetic, it is preferable to include (C) a thickener.

In the water-in-water cosmetic, (a1) it is preferable to include a UV absorber in the oil phase.

The cosmetic according to the present invention is characterized in that it consists of the oil-in-water emulsion composition.

According to the present invention, by dispersing the core-corona type microgel as a stabilizer for the emulsified particles in the aqueous phase containing the emulsified particles, an in-water type cosmetic that maintains moisture while maintaining a feeling of use and has excellent water resistance is obtained.

Hereinafter, the present invention will be described in detail.

The water-in-water cosmetic according to the present invention includes (A) emulsified particles and (B) an aqueous phase. First, the components of the emulsified particles of the present invention will be described.

(A) Emulsion particles consist of (a1) oil phase and (a2) emulsifier.

(a1) The oil component is not particularly limited, and hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, oil-soluble ultraviolet absorbers, silicone oils, liquid oils, solid oils, waxes, fragrances, Powder etc. are mentioned.

Examples of the hydrocarbon oil include isododecane, isohexadecane, isoparaffin, liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, vaseline, and microcrystalline wax.

Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, tolic acid, isostearic acid, linoleic acid, linoleic acid, eicosapentaenoic acid (EPA) , docosahexaenoic acid (DHA), and the like.

Examples of the higher alcohol include straight-chain alcohols (eg, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, etc.), branched-chain alcohols (eg, lauryl alcohol, cetyl alcohol, stearyl alcohol, etc.) Examples thereof include monostearyl glycerin ether (batyl alcohol)-2-decyl tetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, octyldodecanol, etc.).

Examples of synthetic ester oils include octyl octanoate, nonanoic acid nonyl, cetyl octanoate, isopropyl myristate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, and myristate. Myristyl acid, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, di-2-ethylhexane Ethylene glycol acid, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, tripropylene glycol pivalate, diisostearyl malate, di-2-heptylundecanoate glycerin, diiso Glycerin stearate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, glycerin trioctanoate, triisopal Glycerin mitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate-2-ethylhexyl palmitate, glycerin trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleic acid Oleyl, acetglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl Laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristic acid, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, citric acid Triethyl etc. are mentioned.

Examples of the oil-soluble UV absorber include paraaminobenzoic acid (PABA), PABA monoglycerin ester, N,N-dipropoxy PABA ethyl ester, N,N-diethoxy PABA ethyl ester, N,N-dimethyl PABA ethyl ester benzoic acid-based ultraviolet absorbers such as N,N-dimethyl PABA butyl ester; anthranilic acid-based ultraviolet absorbers such as homomenthyl-N-acetylantranilate; salicylic acid-based ultraviolet absorbers such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropanolphenyl salicylate; Octylcinnamate, Ethyl-4-isopropylcinnamate, Methyl-2,5-diisopropylcinnamate, Ethyl-2,4-diisopropylcinnamate, Methyl-2,4-diisopropylcinnamate, Propyl -p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate, 2-ethylhexyl-p-methoxycinnamate, 2 -Ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate , glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, 3,4,5-trimethoxycinnamic acid 3-methyl-4-[methylbis(trimethylsiloxy)silyl]butyl cinnamic acid-based ultraviolet absorbers, etc. ; 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2-(2 '-Hydroxy-5'-methylphenylbenzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5-(3,3-dimethyl-2-norbor nylidene) -3-pentan-2-one, octocrylene, and the like.

Silicone oils include, for example, chain polysiloxanes (eg, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.), cyclic polysiloxanes (eg, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethyl Cyclohexasiloxane, etc.), silicone resins forming a three-dimensional network structure, silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.), acrylic silicones, etc. there is.

Liquid oils include, for example, avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, apricot oil, wheat germ oil, sandalwood oil, castor oil, flax human oil, safflower oil, cottonseed oil, perilla oil, soybean oil, peanut oil, tea oil, milkweed, rice bran oil, Chinese tung oil, Japanese tung oil, jojoba oil, germ oil, triglycerin and the like.

Examples of solid fats and oils include cacao butter, palm oil, marzipan, hydrogenated palm oil, palm oil, beef tallow, brisket, hydrogenated beef tallow, palm kernel oil, pork fat, beef bone fat, wax kernel oil, hydrogenated oil, beef tallow, Japan wax, hydrogenated castor oil, and the like. can

Waxes include, for example, beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, pewter wax, spermaceti wax, montan wax, rice bran wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, Lanolin fatty acid isopropyl, laurate hexyl, reduced lanolin, jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, etc. can

In the water-in-water cosmetic according to the present invention, (a1) it is preferable to blend a hydrophobic powder in the oil phase. According to the present invention, since the stability can be improved even without gelation by a large amount of surfactant or thickening by a polymer substance, it is possible to sufficiently exhibit the water resistance of the hydrophobic powder.

Since each of the core corona and the hydrophobic powder can improve water resistance, it is possible to further improve the water resistance by blending the core corona and the hydrophobic powder together.

The hydrophobic powder is not particularly limited as long as the surface of the powder has hydrophobicity. For example, silicone resin powder, fluororesin powder, etc., the powder itself has hydrophobicity, and the surface of the inorganic powder particle is made of methylhydrogenpolysiloxane, Silicones such as dimethylpolysiloxane, dextrin fatty acid esters, higher fatty acids, higher alcohols, fatty acid esters, metal soaps, alkyl phosphate ethers, fluorine compounds, or hydrocarbons such as squalane and paraffin Wet method using solvents, gas phase method, mecha What was hydrophobized by the no-chemical method etc. is mentioned. In addition, the average particle size of the hydrophobic powder needs to be smaller than the emulsified particles of the oil phase of the present invention. In particular, when the powder is used as an ultraviolet scattering agent, it is preferable that the average particle size after crushing with a wet disperser is 100 nm or less. Examples of inorganic powder particles subjected to hydrophobic treatment include titanium oxide, zinc oxide, talc, mica, sericite, kaolin, mica titanium, black iron oxide, iron sulfate, bengala, ultramarine blue, Prussian blue, chromium oxide, and chromium hydroxide. can

(a1) It is preferable that the compounding quantity of oil phase is 5-80 mass % in water-type cosmetics. More preferably, it is more preferable that it is 10-75 mass %.

(a2) The emulsifier is characterized by containing one or two or more of an amphoteric surfactant, a cationic surfactant, an anionic surfactant, a hydrophilic nonionic surfactant, a hydrophilic nonionic surfactant, and a polymeric surfactant.

The amphoteric surfactant has at least one cationic functional group and at least one anionic functional group, and becomes cationic when the solution is acidic and anionic when alkaline, and has properties close to nonionic surfactants near the isoelectric point.

Amphoteric surfactants are classified into carboxylic acid type, sulfuric acid ester type, sulfonic acid type, and phosphoric acid ester type according to the type of anionic group. Preferred in the present invention are carboxylic acid type, sulfuric acid ester type and sulfonic acid type. The carboxylic acid type is again classified into an amino acid type and a betaine type. Particularly preferred is a betaine type.

Specifically, for example, an imidazoline amphoteric surfactant (e.g., 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium, 2-cocoyl -2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc.); Betaine-based surfactants (e.g., 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkyl betaine, amide betaine, sulfobetaine etc.) and the like.

Examples of the cationic surfactant include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, behenyldimethylhydroxyethylammonium chloride, stearyldimethylbenzylammonium chloride, and cetyltriethylammoniummethylsulfate. Quaternary ammonium salts, such as these, are mentioned. In addition, diethylaminoethyl stearate, dimethylaminoethyl stearate, diethylaminoethyl palmitate, dimethylaminoethyl palmitate, diethylaminoethyl myristic acid, dimethylaminoethyl myristic acid, diethyl behenate Ethylaminoethylamide, dimethylaminoethylamide behenate, diethylaminopropyl stearate, dimethylaminopropyl stearate, diethylaminopropylamide palmitate, dimethylaminopropyl palmitate, diethylaminopropylamide myristic acid, Amide amine compounds, such as myristic acid dimethylaminopropylamide, behenic acid diethylaminopropylamide, and behenic acid dimethylaminopropylamide, etc. are mentioned.

Examples of anionic surfactants include fatty acid soaps, carboxylate types such as N-acylglutamates and alkyl ether acetic acids, sulfonic acid types such as α-olefin sulfonates, alkane sulfonates, and alkylbenzene sulfonic acids, and higher alcohol sulfate ester salts. It is classified into a sulfate ester salt type, a phosphoric acid ester salt type, and the like. Carboxylate type, sulfonic acid type, and sulfuric acid ester salt type are preferred, and sulfuric acid ester salt type is particularly preferred.

Specifically, for example, fatty acid soaps (eg, sodium laurate, sodium palmitate, etc.), higher alkyl sulfate ester salts (eg, sodium lauryl sulfate, potassium lauryl sulfate, etc.), alkyl ether sulfuric acid Ester salts (eg, POE-triethanolamine lauryl sulfate, POE-sodium lauryl sulfate, etc.), N-acylsarcosinic acids (eg, sodium lauroylsarcosine, etc.), higher fatty acid amide sulfonates (eg, For example, sodium N-myristoyl-N-methyl taurate, sodium coconut oil fatty acid methyl tauride, sodium lauryl methyl tauride, etc.), phosphate ester salts (POE-sodium oleyl ether phosphate, POE-stearyl ether phosphoric acid, etc.) , sulfosuccinates (e.g., sodium di-2-ethylhexyl sulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.), alkylbenzene Sulfonic acid salts (eg, linear sodium dodecylbenzenesulfonate, linear dodecylbenzenesulfonic acid triethanolamine, linear dodecylbenzenesulfonic acid, etc.), higher fatty acid ester sulfate ester salts (eg, hardened coconut oil fatty acid glycerin sodium sulfate, etc.) ), N-acylglutamate (for example, monosodium N-lauroylglutamate, disodium N-stearoylglutamate, monosodium N-myristoyl-L-glutamate, etc.), sulfurized oil (for example, , rod oil, etc.), POE-alkyl ether carboxylic acid, POE-alkyl allyl ether carboxylate, α-olefin sulfonate, higher fatty acid ester sulfonate, secondary alcohol sulfuric acid ester salt, higher fatty acid alkylolamide sulfuric acid ester salt , lauroyl monoethanolamide sodium succinate, N-palmitoyl aspartic acid ditriethanolamine, caseinate sodium, and the like.

Nonionic surfactants are surfactants that ionize in an aqueous solution and do not have an electric charge. As the hydrophobic group, a type using alkyl and a type using dimethyl silicone are known. Specific examples of the former include glycerin fatty acid esters, ethylene oxide derivatives of glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, ethylene oxide derivatives of propylene glycol fatty acid esters, polyethylene glycol fatty acid esters, and polyethylene glycol alkyl ethers. , polyethylene glycol alkyl phenyl ether, polyethylene glycol castor oil derivatives, polyethylene glycol hydrogenated castor oil derivatives, and the like. Examples of the latter include polyether-modified silicone and polyglycerin-modified silicone. Preferably, it is a type using alkyl as a hydrophobic group.

Specifically, examples of the lipophilic nonionic surfactant include sorbitan fatty acid esters (eg, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, Sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, penta-2-ethylhexylate diglycerol sorbitan, tetra-2-ethylhexylate diglycerol sorbitan, etc.), glycerin polyglycerin fatty acids (eg For example, mono-cottonseed oil fatty acid glycerin, monoerucic acid glycerin, sesquioleic acid glycerin, monostearate glycerin, α,α'-oleate pyroglutamic acid glycerin, monostearate glycerin malic acid, etc.), propylene glycol fatty acid esters (eg For example, propylene glycol monostearate, etc.), hydrogenated castor oil derivatives, glycerin alkyl ether, etc. are mentioned.

Examples of the hydrophilic nonionic surfactant include POE-sorbitan fatty acid esters (e.g., POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorb bitane tetraoleate, etc.), POE-sorbitic fatty acid esters (e.g., POE-sorbit monolaurate, POE-sorbit monooleate, POE-sorbit penta oleate, POE-sorbit monostearate etc.), POE-glycerin fatty acid esters (for example, POE-glycerin monostearate, POE-glycerin monoisostearate, POE-monooleate such as POE-glycerin triisostearate, etc.), POE-fatty acid esters (for example, POE-distearate, POE-monodioleate, ethylene glycol distearate, etc.), POE-alkyl ethers (for example, POE-lauryl ether, POE-oleyl ether, POE- stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-cholestanol ether, etc.), pluronic types (eg, pluronic, etc.), POE/POP-alkyl ethers (For example, POE POP-cetyl ether, POE POP-2-decyltetradecyl ether, POE POP-monobutyl ether, POE POP-hydrogenated lanolin, POE POP-glycerine ether, etc.), tetra POE Tetra POP-ethylenediamine condensates (e.g. Tetronic, etc.), POE-castor oil hydrogenated castor oil derivatives (e.g. POE-castor oil, POE-hydrogenated castor oil, POE-hydrogenated castor oil monoisostearate , POE-hydrogenated castor oil triisostearate, POE-hydrogenated castor oil monopyroglutamic acid monoisostearic acid diester, POE-hydrogenated castor oil maleic acid, etc.), POE-beeswax/lanolin derivatives (e.g., POE-sorbitol) beeswax, etc.), alkanolamides (eg, coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc.), POE-propylene glycol fatty acid esters, POE-alkylamines, POE-fatty acid amides, sucrose fatty acids esters, alkylethoxydimethylamine oxide-trioleylphosphoric acid, and the like.

Hydrophobic modified alkyl cellulose, (acrylate/alkyl acrylate (C10-30)) crosspolymer, etc. are mentioned as a macromolecular surfactant.

Among these, as an emulsifier in the present invention, (acrylate/alkyl acrylate (C10-30)) crosspolymer, sucrose stearate, sorbitan stearate, polysorbate 60 and the like can be preferably used.

A commercial item can be used as an emulsifier. For example, Pemulen TR-2 Polymeric Emulsifier (manufactured by Lubrizol Advanced Materials, Inc.), DK Ester S-160N (manufactured by Daiichi High School Pharmaceutical Co., Ltd.), Nicol TS-10V (manufactured by Nippon Surfactant Industry Co., Ltd.), etc. there is.

(a2) It is preferable that the compounding quantity of an emulsifier is 0.01-10 mass % in water-type cosmetics. More preferably, it is more preferable that it is 0.03-5 mass %.

(B) In the aqueous phase, (b1) a core-corona type microgel in which hydrophilic groups are partially formed is dispersed on the surface of the hydrophobic gel microparticles.

The core-corona type microgel according to the present invention can be obtained by radical polymerization of monomers represented by the following formulas (1) to (3) or (1), (2), and (4) under specific conditions.

R ₁ is an alkyl group having 1 to 3 carbon atoms, and n is a number of 8 to 200. X is H or CH ₃ .

It is preferable that the polyethylene oxide macromonomer represented by said formula (1) is an acrylic acid derivative or a methacrylic acid derivative. For example, a commercial product sold by Aldrich or a commercial product such as Bremmer (registered trademark) sold by Nichiyu Co., Ltd. can be used. As an example, PME-400, PME-1000, and PME-4000, which are methoxy polyethylene glycol monomethacrylates (n values in formula (1) are respectively n = 9, n = 23, and n = 90, all Nichiyu Corporation ) may be used.

R ₂ is an alkyl group having 1 to 3 carbon atoms.

R ₃ is an alkyl group of 1 to 12 carbon atoms, more preferably an alkyl group of 1 to 8 carbon atoms.

The hydrophobic monomer represented by the formula (2) is preferably an acrylic acid derivative or a methacrylic acid derivative, and examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, Decyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, methacrylic acid Decyl, dodecyl methacrylate, and the like can be used. Among these, methyl methacrylate (alias: methyl methacrylate), butyl methacrylate (alias: butyl methacrylate), and octyl methacrylate are particularly preferred.

The hydrophobic monomer is a general-purpose raw material and can be easily obtained as a general industrial raw material. For example, you may use the commercial item marketed by Aldrich Co., Ltd. or Tokyo Kasei Co., Ltd.

The crosslinkable monomer represented by Formula (3) can be obtained as a commercial item or an industrial raw material. It is preferable that this crosslinkable monomer is hydrophobic.

It is preferable that the value of m is 0-2. Specifically, it is preferable to use ethylene glycol dimethacrylate (hereinafter sometimes abbreviated as EGDMA) sold by Aldrich, Bremmer (registered trademark) PDE-50 sold by Nichiyu, etc.

R ₄ and R ₅ each independently represent an alkyl group having 1 to 3 carbon atoms, and m is a number of 0 to 2.

R ₆ represents H or an alkyl group having 1 to 3 carbon atoms, and R ₇ and R ₈ represent H or a substituent containing an alkyl group having 1 to 12 carbon atoms.

It is preferable that the hydrophobic monomer represented by said Formula (4) is an acrylamide derivative or a methacrylamide derivative. For example, t-butylacrylamide, N,N-dimethylacrylamide, N-[3-(dimethylamino)propyl]acrylamide, t-butylmethacrylamide, octylacrylamide, octylmethacrylamide, octadecyl Acrylamide etc. can be used preferably. Among these, t-butylacrylamide, N,N-dimethylacrylamide, and N-[3-(dimethylamino)propyl]acrylamide are particularly preferred.

The hydrophobic monomer is commercially available or available as an industrial raw material.

The core-corona type microgel represented by formulas (1) to (3) according to the present invention is obtained by radical polymerization of the above monomers under the following conditions (A) to (E).

(A) The molar ratio represented by the injection molar amount of the polyethylene oxide macromonomer/the injection molar amount of the hydrophobic monomer is 1:10 to 1:250.

(B) The injection amount of the crosslinkable monomer is 0.1 to 1.5% by mass relative to the injection amount of the hydrophobic monomer.

(C) The hydrophobic monomer represented by Formula (2) is a monomer composition in which one type or two or more types of methacrylic acid derivatives having an alkyl group having 1 to 8 carbon atoms are mixed.

(D) The polymerization solvent is a mixed solvent of water and organic solvent, and when a polyol is used as the organic solvent, it is one or two or more selected from dipropylene glycol, 1,3-butylene glycol, and isoprene glycol.

(E) The solvent composition of the mixed solvent of water and organic solvent is water: organic solvent = 90 to 10: 10 to 90 at a mass ratio of 20 ° C.

In the present invention, "the amount of the crosslinkable monomer injected relative to the amount of the hydrophobic monomer injected" is defined as the crosslinking density (% by mass). The crosslinking density of the core-corona type microgel used in the present invention must be 0.1 to 1.5% by mass of the injected amount of the crosslinkable monomer relative to the injected amount of the hydrophobic monomer under the condition (B).

(Condition (A))

The injection molar amount of the polyethylene oxide macromonomer and the hydrophobic monomer can be polymerized within the range of polyethylene oxide macromonomer:hydrophobic monomer = 1:10 to 1:250 (molar ratio). The injection molar amount is preferably 1:10 to 1:200, and more preferably 1:25 to 1:100.

When the molar amount of the hydrophobic monomer is 10 times or less relative to the molar amount of the polyethylene oxide macromonomer, the polymer to be polymerized becomes water-soluble, and a core-corona type polymer microgel is not formed. In addition, when the molar amount of the hydrophobic monomer is 250 times or more relative to the molar amount of the polyethylene oxide macromonomer, dispersion stabilization by the polyethylene oxide macromonomer becomes incomplete, and the hydrophobic polymer by the insoluble hydrophobic monomer aggregates and precipitates.

(Condition (B))

By copolymerizing the crosslinkable monomer, the hydrophobic polymer of the core portion can polymerize the crosslinked microgel.

When the injected amount of the crosslinkable monomer is less than 0.1% by mass of the injected amount of the hydrophobic monomer, the crosslinking density is low and the microgel collapses upon swelling. In addition, when the injected amount exceeds 1.5% by mass, microgel particles agglomerate with each other, making it impossible to polymerize desirable microgel particles with a narrow particle size distribution. The injection amount of the crosslinkable monomer is preferably 0.2 to 1.0, more preferably 0.2 to 0.8, and most preferably 0.2 to 0.5% by mass.

(Condition (C))

The hydrophobic monomer represented by Formula (2) needs to be a monomer composition obtained by mixing one type or two or more types of methacrylic acid derivatives having an alkyl group having 1 to 8 carbon atoms. When the number of carbon atoms is 0 (a monomer having no terminal ester bond), the monomer is too hydrophilic and emulsion polymerization may not be performed well. On the other hand, when the number of carbon atoms is 9 or more, steric hindrance occurs during polymerization, and a cross-linked structure may not be well established.

(Condition (D))

The polymerization solvent is required to be a mixed solvent of water-organic solvent. Although ethanol, propanol, butanol, polyol, etc. can be used as an organic solvent, when using a polyol, it is preferable to dissolve the hydrophobic monomer represented by Formula (2) and the crosslinkable monomer represented by Formula (3). As the polyol used in the present invention, dipropylene glycol, 1,3-butylene glycol, and isoprene glycol are required.

Considering that it can be produced industrially, that is, using the polymer solution as it is as a raw material without requiring a purification process such as dialysis, the solvent to be mixed with water is irritating when applied to the skin such as ethanol, propanol, or butanol It is not an organic solvent to be concerned about, but it is preferable that it is a polyol that can be blended in cosmetics for general purposes.

(Condition (E))

The solvent composition of the mixed solvent of water and organic solvent, which is the polymerization solvent, needs to be water:organic solvent = 90 to 10:10 to 90 at a mass ratio of 20°C. The solvent composition of the mixed solvent of water and organic solvent is preferably water: organic solvent = 90 to 10: 10 to 90 (volume ratio at 20 ° C.), water: organic solvent = 80 to 20: 20 to 80 (at 20 ° C. volume ratio) is more preferable.

As the polymerization solvent, it is necessary to add an organic solvent to uniformly dissolve the hydrophobic monomer. The mixing ratio of the organic solvent is 10 to 90 volume ratio. When the mixing ratio of the organic solvent is lower than 10 volume ratio, the solubility of the hydrophobic monomer is very low, and polymerization proceeds in the form of monomer droplets to form huge lumps and no microgel is formed. In addition, when the mixing ratio of the organic solvent exceeds 90 volume ratio, an emulsion of hydrophobic monomers due to hydrophobic interaction is not formed, emulsion polymerization does not proceed, and microgel is not obtained.

The core-corona type microgel represented by formulas (1), (2) and (4) according to the present invention is obtained by radical polymerization of the above monomers under the following conditions (A)' to (E)'.

(A) A molar ratio of 1:10 to 1:250, expressed as the molar amount of the polyethylene oxide macromonomer injected/molar amount injected (the acrylate derivative monomer and/or the acrylamide derivative monomer).

(B) 'The macromonomer represented by the following formula (1) is an acrylic acid derivative or a methacrylic acid derivative having a polyethylene glycol group having 8 to 200 repeating units,

The acrylate derivative monomer represented by the following formula (2) is an acrylic acid derivative or a methacrylic acid derivative having a substituent containing an alkyl group having 1 to 12 carbon atoms,

The acrylamide derivative monomer represented by the following formula (3) is an acrylamide derivative or methacrylamide derivative having a substituent containing an alkyl group having 1 to 12 carbon atoms;

(C) 'The polymerization solvent is a water-alcohol mixed solvent, and the alcohol is one or two or more selected from dipropylene glycol, 1,3-butylene glycol, and isoprene glycol;

(D) A water-alcohol mixed solvent having a solvent composition of water:alcohol=90 to 10:10 to 90 at a mass ratio of 20°C.

Below, each condition is further explained in detail.

(Condition (A)')

The injected molar amount of the polyethylene oxide macromonomer and the hydrophobic monomer (ie, the total sum of the acrylate derivative monomer and/or the acrylamide derivative monomer) is polyethylene oxide macromonomer:hydrophobic monomer = 1:10 to 1:250 (molar ratio) Polymerization is possible within the range. The injection molar amount is preferably 1:10 to 1:200, and more preferably 1:25 to 1:100.

When the molar amount of the hydrophobic monomer relative to the molar amount of the polyethylene oxide macromonomer is less than 10 times, the polymer to be polymerized becomes water-soluble and core-corona type particles are not formed. In addition, when the molar amount of the hydrophobic monomer relative to the molar amount of the polyethylene oxide macromonomer is 250 times or more, dispersion stabilization by the polyethylene oxide macromonomer becomes incomplete, and the hydrophobic polymer by the insoluble hydrophobic monomer aggregates and precipitates.

(Condition (B)')

Condition (B)' consists of the following three conditions (B-1)' to (B-3)'.

(B-1)'

The macromonomer represented by formula (1) is an acrylic acid derivative or a methacrylic acid derivative having a polyethylene glycol group having 8 to 200 repeating units. If the number of repeating units is 7 or less, particles stably dispersed in a solvent may not be obtained, and if the number exceeds 200, the particles may be refined and may become unstable when blended into cosmetics.

(B-2)'

The acrylate derivative monomer represented by the formula (2) is an acrylic acid derivative or a methacrylic acid derivative having a substituent containing an alkyl group having 1 to 12 carbon atoms. When the number of carbon atoms is 0 (a monomer having no terminal ester bond), the monomer is too hydrophilic and emulsion polymerization may not be performed well. On the other hand, when the number of carbon atoms is 13 or more, a desirable feeling during use may not be obtained.

(B-3)'

The acrylamide derivative monomer represented by the formula (3) is an acrylamide derivative or methacrylamide derivative having a substituent containing an alkyl group having 1 to 18 carbon atoms.

The hydrophobic monomer according to the present invention needs to be a monomer composition comprising one or a mixture of two or more selected from the acrylate derivative monomer represented by the above formula (2) and the acrylamide derivative monomer represented by the formula (3).

In the present invention, as a hydrophobic monomer, two types of methyl methacrylate and butyl methacrylate, or methyl methacrylate, t-butyl acrylamide, N, N-dimethylacrylamide and N-[3-(dimethylamino)propyl] It is particularly preferable to use four types of acrylamide. In the combination of the above hydrophobic monomers, it is preferable to further use methoxypolyethylene glycol monomethacrylate as a macromonomer.

Although not limited thereto, as the most preferred combination of macromonomer and hydrophobic monomer in the present invention,

Methoxy polyethylene glycol monomethacrylate, methyl methacrylate and butyl methacrylate having 8 to 90 repeating units of polyethylene glycol group, most preferably 15;

Methoxy polyethylene glycol monomethacrylate, methyl methacrylate, butyl methacrylate, t-butyl acrylamide, N,N-dimethyl acrylamide having a repeating unit of polyethylene glycol group of 8 to 200, most preferably 90 and N-[3-(dimethylamino)propyl]acrylamide, t-butylmethacrylamide, octylacrylamide, octylmethacrylamide, and octadecylacrylamide.

(Condition (C))'

The polymerization solvent is required to be a water-alcohol mixed solvent. As the alcohol, those capable of dissolving the hydrophobic monomers represented by formulas (2) and (3) are preferable. Therefore, one or two or more selected from dipropylene glycol, 1,3-butylene glycol, and isoprene glycol are preferred.

(Condition (D))'

The solvent composition of the water-alcohol mixed solvent as the polymerization solvent is preferably water: alcohol = 90 to 10: 10 to 90, more preferably water: alcohol = 80 to 20: 20 to 80 at a mass ratio of 20 ° C. When the mixing ratio of alcohol is lower than 10 volume ratio, the solubility of the hydrophobic monomer is very low, and microparticles may not be formed. In addition, when the mixing ratio of the alcohol exceeds 90 volume ratio, an emulsion of the hydrophobic monomer due to the hydrophobic interaction is not generated, and emulsion polymerization does not proceed, so that microparticles may not be obtained.

The core-corona type microgel according to the present invention obtained using polyol is a water-polyol mixed solvent as a polymerization solvent, does not contain ethanol, and can easily obtain cosmetics without skin irritation even for users with sensitive skin.

As the polymerization initiator used in the polymerization system, a commercially available polymerization initiator used in conventional water-soluble thermal radical polymerization may be used. In this polymerization system, it is possible to obtain a very narrow particle size distribution of the microgel particles to be polymerized even if the polymerization is performed without particularly strictly controlling the agitation conditions.

In addition, all conventional microgels made of synthetic polymers are polymer electrolytes, such as polyacrylic acid, which have no acid resistance or salt resistance in terms of dispersibility in water. However, when considering application as a compounding component of pharmaceuticals or cosmetics, acid resistance or salt resistance is a very important performance for adaptation under physiological conditions. The core-corona type microgel according to the present invention is a microgel stabilized with a polyethylene oxide chain, which is a nonionic polymer, and its dispersion stability in water can be expected to have acid resistance or salt resistance.

In the microgel used in the present invention, the hydrophilic macromonomer and the hydrophobic monomer are ordered in a solvent, the particle diameter is almost constant, and the core-corona type polymer microgel is considered to be produced with a crosslinked core portion.

The blending amount of the core-corona type microgel of the present invention in the oil-in-water cosmetic is preferably 0.01 to 9% by mass in the oil-in-water emulsion cosmetic. If the blending amount of the core-corona type microgel is less than 0.01% by mass, water resistance may not be obtained. When the compounding amount exceeds 9% by mass, there are cases where it is not preferable as a composition from the viewpoint of stability in long-term storage under high temperature conditions, and the feeling of use is poor.

In addition, as other aqueous phase components, water, water-soluble alcohol, thickener, etc., which are usually used in cosmetics and quasi-drugs, can be blended, and furthermore, a moisturizer, a chelating agent, a preservative, a colorant, etc. can be appropriately blended as desired.

The water contained in the oil-in-water emulsified cosmetic of the present invention is not particularly limited, and examples thereof include purified water, ion-exchanged water, and tap water.

Examples of water-soluble alcohols include lower alcohols, polyhydric alcohols, polyhydric alcohol polymers, dihydric alcohol alkyl ethers, dihydric alcohol alkyl ethers, dihydric alcohol ether esters, glycerin monoalkyl ethers, sugar alcohols, monosaccharides, oligosaccharides, polysaccharides and derivatives thereof; and the like.

As lower alcohol, ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol etc. are mentioned, for example.

Examples of the polyhydric alcohol include dihydric alcohols (eg, dipropylene glycol, 1,3-butylene glycol, ethylene glycol, trimethylene glycol, 1,2-butylene glycol, tetramethylene glycol, 2,3 -Butylene glycol, pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, octylene glycol, etc.), trihydric alcohol (eg glycerin, trimethylolpropane, etc.), tetrahydric alcohol (eg For example, diglycerin, pentaerythritol such as 1,2,6-hexanetriol, etc.), pentahydric alcohols (eg xylitol, triglycerin, etc.), hexahydric alcohols (eg sorbitol, mannitol, etc.) ), polyhydric alcohol polymers (eg, diethylene glycol, dipropylene glycol-triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin-triglycerin, tetraglycerin, polyglycerin, etc.), dihydric alcohol alkyl ethers (For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-methylhexyl ether, ethylene glycol isoamyl ether , ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, etc.), dihydric alcohol alkyl ethers (for example, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol mono Ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, etc.), dihydric alcohol Ether esters (e.g., ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diadipate, ethylene glycol disuccinate, diethylene glycol Monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc.), glycerin monoalkyl ether (eg For example, chimyl alcohol, cerachyl alcohol, batyl alcohol, etc.), sugar alcohols (for example, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, starch decomposed sugar, maltose, starch decomposed sugar reduced alcohol, etc. ); Glysolid; tetrahydrofurfuryl alcohol; POE-tetrahydrofurfuryl alcohol; POP-butyl ether; POP·POE-butyl ether tripolyoxypropylene glycerin ether; POP-glycerine ether; POP-glycerine ether phosphoric acid; POP·POE-pentane erythritol ether, polyglycerol, etc. are mentioned.

Monosaccharides include, for example, tricarbon sugars (eg, D-glycerylaldehyde, dihydroxyacetone, etc.), satanic sugars (eg, D-erythrose, D-erythrulose, D-threose). , erythritol, etc.), pentose (e.g., L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose , L-xylulose, etc.), hexose (e.g., D-glucose, D-talose, D-psicose, D-galactose, D-fructose, L-galactose, L-mannose, D- tagatose, etc.), heptose (eg, aldoheptose, heptulose, etc.), octane sugar (eg, octulose, etc.), deoxysugar (eg, 2-deoxy-D -ribose, 6-deoxy-L-galactose, 6-deoxy-L-mannose, etc.), amino sugars (eg, D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc.) ), uronic acids (eg, D-glucuronic acid, D-mannuronic acid, L-gluronic acid, D-galacturonic acid, L-iduronic acid, etc.), and the like.

Examples of the oligosaccharide include sucrose, gentianose, umbelliferose, lactose, planteose, isolychnose, α,α-trehalose, raffinose, lychnose, and Bilicin, stachyose, verbascoose, etc. are mentioned.

Examples of polysaccharides include cellulose, quince seed, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate-tragacanth gum, keratan sulfate, chondroitin, xanthan gum, guar gum, dextran, and keratosulfuric acid, locust bean gum, and succinoglucan.

Examples of other polyols include polyoxyethylene methyl glucoside (Glucam E-10) and polyoxypropylene methyl glucoside (Glucam P-10).

Natural water-soluble polymers include, for example, plant-based polymers (eg, gum arabic, gum tragacanth, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), algae colloid (brown algae extract), starch (rice, corn, potato, wheat), glycyrrhizic acid); microbial polymers (eg, xanthan gum, dextran, succinoglucan, pullulan, etc.); animal-based polymers (eg, collagen, casein, albumin, gelatin, etc.); and the like.

Semi-synthetic water-soluble polymers include, for example, starch-based polymers (eg, carboxymethyl starch, methylhydroxypropyl starch, etc.), cellulose-based polymers (methyl cellulose, ethyl cellulose, methylhydroxypropyl cellulose, hydroxyethyl cellulose, etc.) , cellulose sodium sulfate, hydroxypropyl cellulose, carboxymethyl cellulose, carboxymethyl cellulose sodium, crystalline cellulose, cellulose powder, etc.), alginic acid-based polymers (eg, sodium alginate, alginate propylene glycol ester, etc.), and the like.

Examples of synthetic water-soluble polymers include vinyl polymers (eg, polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, carboxyvinyl polymer, etc.); polyoxyethylene-based polymers (eg, polyethylene glycol 20,000, 40,000, 60,000, etc.); acrylic polymers (eg, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.); A polyethyleneimine, a cationic polymer, etc. are mentioned.

Moisturizers include, for example, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, cholanic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salts, DL-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, rose roxburgi extract, yarrow extract, merlot extract, and the like.

Examples of the sequestering agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, and edeate. tetrasodium citrate, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyltriacetate, and the like.

As an amino acid, neutral amino acids (for example, threonine, cysteine, etc.), basic amino acids (for example, hydroxylizine etc.) etc. are mentioned. Moreover, as an amino acid derivative, acyl sarcosine sodium (lauroyl sarcosine sodium), acyl glutamate, acyl β-alanine sodium, glutathione etc. are mentioned, for example.

Examples of the pH adjusting agent include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.

Examples of thickeners include xanthan gum, gum arabic, carrageenan, gum karaya, gum tragacanth, carob gum, quince seed (quince), casein, dextrin, gelatin, sodium pectate, sodium alginate, methylcellulose, ethyl Cellulose, CMC, hydroxyethyl cellulose, hydroxypropyl cellulose, PVA, PVM, PVP, sodium polyacrylate, carboxyvinyl polymer, locust bean gum, guar gum, tamarind gum, dialkyldimethylammonium cellulose sulfate, magnesium aluminum silicate, bentonite , hectorite, silicic acid AlMg (vee gum), laponite, silicic anhydride, and the like.

Considering stability in the present invention, it is preferable to blend 0.01 to 5% by mass of a thickener.

Examples of the spice include natural spice obtained from animals or plants, synthetic spice produced by chemical synthesis, and combined spice that is a mixture thereof, and is not particularly limited. By blending the fragrance, it is possible to obtain a cosmetic composition with excellent persistence of fragrance.

Specific examples of the fragrance include acetibenol, anisaldehyde, anethol, amyl acetate, amyl salicylate, allyl amyl glycolate, allyl caproate, aldehyde C6-20, ambretolide, ambroxane, ionone, ISO E SUPER, Eugenol, Ouranthiol, Galaxolide, Calone, Coumarin, Geraniol, Geranyl Acetate, Sandalore, Santalol, Sandela, Cyclamenaldehyde, Cis-3-Hex Cenyl Acetate, Cis-3-Hexenol, Citral, Citronellyl Acetate, Citronellol, Cineol, Dihydromyrcenol, Jasmolactone, Cinnamic Alcohol, Cinnamic Aldehyde, Styrallyl Acetate, Cedryl Acetate, Cedrol, Damascon, Damasenone, Decalactone, Terpinyl Acetate, Terpineol, Tonalide, Tripural, Nerol, Bacdanol, Vanillin, Hydroxycitronellal, Phenylethyl Acetate, Phenylethyl Alcohol, Hexylsal Resylate, Betiberyl Acetate, Hedione, Heliotropin, Helional, Bertopix, Benzyl Acetate, Benzyl Salicylate, Benzyl Benzoate, Pentalide, Bornylacetate, Myol, Musk Ketone, Methyl Anthranilate, Methyldihydrojasmonate, Yara Yara, Lime Oxide, Linalyl Acetate, Linalool, Limonene, Lyral, Lilyal, Rose Oxide, Rhodinol, Angelica Oil, Anise Oil, Mugwort Oil, Basil Oil, Laurel Oil, Bergamot oil, calamus oil, camphor oil, ylang ylang oil, cardamom oil, cassia oil, cedarwood oil, celery oil, chamomile oil, cinnamon oil, clove oil, coriander oil, cumin oil, dill oil, elemi oil, tarragon oil , Eucalyptus Oil, Fennel Oil, Fenugreek Oil, Galbanum Oil, Geranium Oil, Ginger Oil, Grapefruit Oil, Gaiac Wood Oil, Heba Oil, Cypress Oil, Juniper Berry Oil, Lavandin Oil, Lavender Oil, Lemon Oil, Lime Oil, Mandarin Oil, Giram Oil, Mimosa Oil, Peppermint Oil, Spearmint Oil, Myrrh Oil, Matel Oil, Nutmeg Oil, Oakmoss Oil, Olibanum Oil, Opoponax Oil, Orange Oil, Parsley Oil, Patchouli Oil, Pepper oil, perilla oil, petitgrain oil, neroli oil, orange blossom oil, allspice oil, allspice oil, pine oil, rose oil, rosemary oil, clary sage oil, sage oil, sandalwood oil, styrax oil, tazet oil, Thyme Oil, Tuberose Oil, Valerian Oil, Vetiver Oil, Violet Leaf Oil, Wintergreen Oil, Wormwood Oil, Ylang Ylang Oil, Citron Oil, Sweet Acacia Absolute, Broom Absolute, Hyacinth Absolute, Immortel Absolute, Jasmine Absolute, Zongquil Absolute, Narcissus Absolute, Rose Absolute, Violet Leaf Absolute, Benzoin Absolute, and the like.

[Other Ingredients]

In the composition according to the present invention, other ingredients commonly used in cosmetics or quasi-drugs, for example, ultraviolet absorbers, powders, organic amines, polymer emulsions, vitamins, antioxidants, etc. are appropriately added within the range that does not impair the effects of the present invention. can be combined.

Examples of the water-soluble ultraviolet absorber include 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxy. Toxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2 -Hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n- Benzophenone-based UV absorbers such as octoxybenzophenone and 4-hydroxy-3-carboxybenzophenone, phenylbenzimidazole-5-sulfonic acid and its salts, phenylene-bis-benzoimidazole-tetrasulfonic acid and its benzoimidazole-based UV absorbers such as salts, 3-(4'-methylbenzylidene)-d,l-camphor, 3-benzylidene-d,l-camphor, urocanic acid, urocanic acid ethyl ester, and the like. .

As the powder component, for example, inorganic powder (e.g., talc, kaolin, mica, sericite (sericite), muscovite mica, phlogopite, synthetic mica, red mite, biotite, vermiculite, magnesium carbonate, calcium carbonate, aluminum silicate, Barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, fluorine apatite, hydroxyapatite, ceramic powder, metal soap ( For example, zinc myristate, calcium palmitate, aluminum stearate), boron nitride, etc.), organic powders (for example, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, Polystyrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.), inorganic white pigment (eg titanium dioxide, zinc oxide, etc.), inorganic red pigment (eg For example, iron oxide (Bengala), iron titanate, etc.), inorganic brown pigments (eg, γ-iron oxide, etc.), inorganic yellow pigments (eg, iron sulfate, ocher, etc.), inorganic black pigments (eg, γ-iron oxide, etc.) for example, black iron oxide, low-order titanium oxide, etc.), inorganic purple pigments (eg, manganese violet, cobalt violet, etc.); Inorganic green pigments (eg, chromium oxide, chromium hydroxide, cobalt titanate, etc.), inorganic blue pigments (eg, ultramarine blue, Prussian blue, etc.), pearl pigments (eg, titanium oxide-coated mica, titanium oxide-coated Bismuth oxychloride, titanium oxide-coated talc, colored titanium oxide-coated mica, bismuth oxychloride, fish meal, etc.), metal powder pigments (eg aluminum powder, copper powder, etc.), organic pigments such as zirconium, barium or aluminum lake (e.g. Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 228, Red No. 405, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow Organic pigments such as No. 401, and Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5 No., Yellow No. 202, Yellow No. 203, Green No. 3 and Blue No. 1, etc.), natural pigments (eg, chlorophyll, β-carotene, etc.), and the like.

Organic amines include, for example, monoethanolamine, diethanolamine, triethanolamine, morpholine, tetrakis(2-hydroxypropyl)ethylenediamine, triisopropanolamine, 2-amino-2-methyl-1,3- Propanediol, 2-amino-2-methyl-1-propanol, etc. are mentioned.

Examples of the polymer emulsion include an acrylic resin emulsion, an ethyl polyacrylate emulsion, an acrylic resin liquid, a polyacrylalkyl ester emulsion, a polyvinyl acetate resin emulsion, and natural rubber latex.

Examples of vitamins include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, and biotin.

Other components that can be blended include, for example, preservatives (methylparaben, ethylparaben, butylparaben, phenoxyethanol, etc.), anti-inflammatory agents (eg, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, Zinc oxide, allantoin, etc.), whitening agent (eg, placenta extract, rock extract, arbutin, etc.), various extracts (eg, yellow white, yellow lotus, purple root, peony, bitter grass, birch, sage, loquat tree, carrot, Aloe, mallow, iris, grape, adlay, loofah, lily, saffron, cnidium, ginger, red pepper herb, ononis, garlic, red pepper, dermis, angelica, seaweed, etc.), activator (e.g., royal jelly, photoreceptor) , cholesterol derivatives, etc.), blood circulation promoters (eg, nonylic acid vanylamide, nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, gingerone, cantharistink, ichtamol, tannic acid, α-borneol, nicotinic acid Tocopherol, inositol hexanicotinate, cyclandelate, cinnarizine, tolazoline, acetylcholine, verapamil, cepharantin, γ-oryzanol, etc.), anti-seborrhea drugs (eg, sulfur, thianthol, etc.), anti-inflammatory drugs ( For example, tranexamic acid, thiotaurine, hypotaurine, etc.), etc. are mentioned.

Examples of antioxidants include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, and gallic acid esters.

Examples of the antioxidant adjuvant include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, keparin, hexametaphosphate, phytic acid, ethylenediaminetetraacetic acid and the like.

The water-in-water cosmetics according to the present invention, depending on the ingredients to be mixed, can be used as lotion, beauty essence, pack, cleansing, facial cleansing foam, hand cream, shampoo, rinse, conditioner, treatment, hair mask, hair wax, hair cream, hair mist, hair It can be in the form of any product, such as oil, hair mousse, or sunscreen.

Since it has high water resistance, it can be especially preferably commercialized as skin cosmetics such as point makeup cosmetics, foundation, and sunscreen cosmetics.

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited by these at all. The blending amount is expressed in mass% with respect to the system in which the component is blended unless otherwise specified. In addition, unless otherwise indicated, the concentration of an aqueous solution is shown.

First, the evaluation method and evaluation criteria used in the following tests are explained.

<feeling of use>

The use feeling (moisture during application) when the water-in-water cosmetic was applied to the skin was evaluated by 10 expert panelists according to the following criteria.

◎: More than 8 out of 10 people answered that the feeling of use was good.

○: 6 or more and less than 8 out of 10 answered that the feeling of use was good

△: More than 3 out of 10 people and less than 6 people answered that the feeling of use was good.

×: Less than 3 out of 10 people answered that the feeling of use was good

<water resistance>

Water resistance test method in Tables 1 to 4

2 mg/cm 2 of the sample was applied to a resin plate, and the UV spectrum of 290 to 400 nm was measured. The plate was attached to the wall of a container of about 20 L with double-sided tape and exposed to running water at 500 rpm for 30 minutes, and the same spectrum was measured again. The percentage of the integral of the spectrum before and after bathing in water is taken as water resistance, and when it is 100%, it shows that the protective effect does not decrease at all even if bathed in water.

○: 80% or more

x: less than 80%

<water resistance>

Water resistance test method in Tables 5 and 6

Water-type cosmetics were evaluated according to the following criteria using the tapping test method.

◎: More than 8 out of 10 people answered that the feeling of use was good.

○: 6 or more and less than 8 out of 10 answered that the feeling of use was good

△: More than 3 out of 10 people and less than 6 people answered that the feeling of use was good.

×: Less than 3 out of 10 people answered that the feeling of use was good

<stability>

The obtained water-in-water cosmetics were subjected to a lapse of time at 50°C for one month.

○: no problem

△: Slightly oily

×: Separation

First, the present inventors examined whether water resistance could not be imparted to water-in-water cosmetics. The present inventors prepared oil-in-water cosmetics by the following manufacturing method for each sample shown in Table 1 below, and evaluated them based on the above evaluation criteria. The results are shown in Table 1.

(Manufacturing method)

First, water phase components such as water, moisturizer, alcohol, neutralizer, preservative and emulsifier are mixed.

Mix oil-based ingredients with UV protection.

The obtained oil phase is added to the aqueous phase and emulsified with an emulsifier in the aqueous phase to prepare emulsified particles in the aqueous phase.

Further, by adding (b1) core-corona type microgel to the aqueous phase, emulsified particles according to the present invention were obtained.

*1 PEMULEN TR-2

* 2 Anon BL-SF

* 3 Esseran 200

* 4 Silicone KF-96L-1.5CS

*5 PPG-1000

*6 OTQ-MT-100Si

*7 OTS-FZO-50

* 8 Aerosil R972

* 9 Octyl Methoxycinnamate

* 10 Uvinul T150

* 11 Tinosorb S

* 12 Uvinul A Plus

* 13 Carbopol 980

As can be seen from Test Examples 1-1 to 1-5, water-in-water cosmetics with excellent stability and feeling of use were not obtained using only the emulsifier. It was found that when the core-corona type microgel was blended, an oil-in-water cosmetic with excellent usability and stability, and also excellent water resistance was obtained.

Next, the present inventors examined types of emulsifiers. The present inventors prepared oil-in-water cosmetics for each sample shown in Table 2 by the above production method, and evaluated them based on the above evaluation criteria. The results are shown in Table 2.

* 14 Sangelos

*15 Nicole HCO60

* 16 Methylpolysiloxane 20CS

* 17 Silicon KF-96A-6T

* 18 SUGEL

* 19 Leo Pearl KL

As can be seen from Test Examples 2-1 to 2-3, even in a system using an emulsifier other than (acrylate/alkyl acrylate (C10-30)) crosspolymer, excellent water resistance is exhibited when the core-corona type microgel is blended. could know that

In addition, in order to further improve the feeling of use, the present inventors confirmed that the water resistance is improved when the core-corona type microgel is formulated even in a system to which a thickener is added. The present inventors prepared oil-in-water cosmetics by the above manufacturing method for each sample shown in Table 3 below, and evaluated them based on the above evaluation criteria. The results are shown in Table 3.

As can be seen from Experimental Examples 3-1 to 3-4, it was found that the water resistance was improved by blending the core-corona type microgel even in a system to which a thickener was added.

Next, powder was added to the oil phase (a1) of the emulsified particles (A), and in order to further improve the feeling of use, it was confirmed that the water resistance was improved by blending the core-corona type microgel even in a system to which a thickener was added. The present inventors prepared oil-in-water cosmetics for each sample shown in Table 4 by the above production method, and evaluated them according to the above evaluation criteria. The results are shown in Table 4.

As can be seen from Test Examples 4-1 to 4-5, even in a system in which powder is added to emulsified particles and a thickener is added, when core-corona type microgel is blended, water-in-water cosmetics with excellent water resistance and feeling of use can be obtained. Could know.

Next, the present inventors used the present invention in a cosmetic for lips. The present inventors prepared oil-in-water cosmetics for each sample shown in Table 5 by the above production method, and evaluated them based on the above evaluation criteria. The results are shown in Table 5.

By blending all of the core-corona type microgels, a cosmetic for lips with excellent water resistance and comfortable feeling was obtained.

Next, the present inventors used the present invention in a cosmetic for eyelashes. The present inventors prepared oil-in-water cosmetics for each sample shown in Table 6 by the above production method, and evaluated them based on the above evaluation criteria. The results are shown in Table 6.

By blending all of the core-corona type microgels, a cosmetic for eyebrows excellent in water resistance and feeling in use was obtained.

Next, we used the present invention for treatment.

Cetyl 2-ethylhexanoate 1.0

Dimethylpolysiloxane 6CS 2.0

Stearyltrimethylammonium chloride 0.25

(Acrylates/methoxy methacrylate PEG-90) Crosspolymer 1.0

Ethanol 5.0

Cetanol 0.5

Behenyl Alcohol 3.0

BG 3.0

Citric acid 0.05

Sodium lactate solution 0.01

Ethylhexyl methoxycinnamate 0.1

Hydroxyethylcellulose 0.1

EDTA-2Na 2H2O 0.1

Appropriate amount of paraoxybenzoic acid ester

Purified water remaining

proper amount of spices

Next, we applied the present invention to hair wax.

water residue

Ethanol 10.0

Dipropylene glycol 5.0

Ceteth-25 1.5

Glyceryl Stearate (SE) 0.5

Behenyl Alcohol 3.5

Carnauba Wax 5.0

Candelilla Wax 5.0

Microcrystalline Wax 2.5

Vaseline 10.0

Tetraethylhexanoate Pentaerythrityl 2.0

Dimethylpolysiloxane 6CS 2.0

(Acrylates/methoxy methacrylate PEG-90) Crosspolymer 1.0

(VP/VA) copolymer 1.5

Ethylhexyl methoxycinnamate 0.1

Lactic acid Na 0.05

Lactic acid 0.1

Carbomer 0.1

Phenoxyethanol 0.5

EDTA-2Na 2H2O 0.02

proper amount of spices

All of these were excellent in usability and water resistance.

Claims (5)

(A) emulsified particles comprising the following (a1) and (a2);
(a1) oil phase containing hydrophobic powder
(a2) 0.2 to 1.2 mass of one or two or more selected from acrylate or alkyl alkyl (C10-30) crosspolymer, lauryl betaine, stearoxyhydroxypropylmethylcellulose, and PEG-60 hydrogenated castor oil Emulsifier containing %
(B) (b1) An oil-in-water emulsion composition comprising an aqueous phase in which core-corona type microgels having partially hydrophilic groups formed on the surface of hydrophobic gel microparticles are dispersed. According to claim 1,
(C) An oil-in-water emulsion composition containing a thickener. According to claim 1,
(a1) An oil-in-water emulsion composition containing a UV absorber in an oil phase. According to claim 2,
(a1) An oil-in-water emulsion composition containing a UV absorber in an oil phase. A cosmetic comprising the oil-in-water emulsion composition according to any one of claims 1 to 4.