JPH11158037A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cosmetic with improves resistance to water and oil and good makeup sustainability. SOLUTION: This cosmetic contains 0.01-50 wt.% of a water-soluble copolymer with a number-average molecular weight of 2,000-200,000 in terms of polyethylene glycol determined by GPC, which dissolves at >=1 wt.% in water at 30 deg.C and pH 3-12, as a copolymer composed of a fluoroalkyl (meth)acrylate component and a water-soluble vinyl compound component bearing functional group selected from carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, phenolic group or salt thereof, quaternary ammonium salt group, amino group or salt thereof, amido group, formyl group and polyether chain-contg. group, or a hydrolyzable group-beating vinyl compound component, in the weight ratio of (10:90) to (90:10).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cosmetic containing a specific water-soluble copolymer and an aqueous emulsion polymer and having excellent water resistance, water repellency and oil resistance.

[0002]

2. Description of the Related Art Conventionally, cosmetics include aqueous, non-aqueous, emulsified, and powdery cosmetics. In any of these systems, the cosmetic effect is sustained by moisture such as sweat or oil such as sebum. It was difficult. In order to maintain the functions and effects of the cosmetic, attempts have been made to improve the water resistance, water repellency, and oil resistance of the cosmetic film applied to the skin. The mainstream of this technique is a cosmetic using perfluoropolyether as a compounding oil.

[0003]

However, cosmetics using perfluoropolyether as an oil agent are more difficult to stabilize when other components are blended than conventional oil agents, so that the cosmetic effect lasts longer. If the compounding amount is increased in anticipation of, it is difficult to further secure the stability. In addition, when used in an emulsifying system, there are few emulsifiers for emulsifying perfluoropolyether, and there are restrictions on usability. Furthermore, cosmetics using perfluoropolyether have a limited feeling on use of cosmetics because the feel of the oil agent remains on the skin due to the feeling of use. The present invention is water-based, non-aqueous, emulsified, and powdered, regardless of the system, without any restrictions on usability, easy to secure stability, and excellent in water resistance, water repellency, and oil resistance. The purpose is to provide cosmetics.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, by including a specific water-soluble copolymer, the water-resistant, water-repellent, and oil-resistant properties have been improved. It has been found that such a cosmetic can be obtained, and the present invention has been completed. That is, the present invention provides a fluoroalkyl (meth)
Acrylate component, carboxyl group or salt thereof, sulfone group or salt thereof, phosphoric acid group or salt thereof, phenol group or salt thereof, quaternary ammonium base, amino group or salt thereof, amide group, formyl group, and polyether chain containing A water-soluble vinyl compound component having a functional group selected from the group or a vinyl compound component having a hydrolyzable group:
A copolymer having a weight ratio of 90 to 90:10, a number average molecular weight in terms of polyethylene glycol determined by GPC of 2,000 to 200,000, and a pH of 3
It is a cosmetic characterized by containing a water-soluble copolymer which dissolves in water at 30 ° C. of 1% by weight or more.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The water-soluble copolymer used in the present invention is a copolymer of a fluoroalkyl (meth) acrylate and the above-described water-soluble vinyl compound or a vinyl compound having a hydrolyzable group, or a fluoroalkyl (meth) acrylate, A copolymer of the above-mentioned water-soluble vinyl compound or vinyl compound having a hydrolyzable group with another copolymerizable monomer. The ratio of the fluoroalkyl (meth) acrylate component to the water-soluble vinyl compound component or the vinyl compound component having a hydrolyzable group in the copolymer is from 10:90 to 90:10 by weight. When another copolymerizable monomer component is used, its proportion is less than 50% by weight of the copolymer (hereinafter, "% by weight" is simply indicated by "%").

The fluoroalkyl (meth) acrylate which is a copolymer component of the water-soluble copolymer used in the present invention is:
An ester of acrylic acid or methacrylic acid with a fluoroalkyl group. Preferred are vinyl compounds represented by the following general formula (1). CH ₂ ＣC (R) · COOC _m H _2m C _n F _{2n + 1} (1) (wherein, R is hydrogen or a methyl group, m is an integer of 1 or 2, n is 5 to 10) Represents an integer.)

For example, the following compounds can be mentioned. CH ₂ ＣC (CH ₃ ) ・ COOCH ₂ (CF ₂ ) ₄ CF ₃ CH ₂ ＣＨCH ・ COO (CH ₂ ) ₂ (CF ₂ ) ₅ CF ₃ CH ₂ ＣＨCH ・ COO (CH ₂ ) ₂ (CF ₂ ) ₅ CF (C
F ₃ ) ₂ CH ₂ ＣＨCH ・ COOCH ₂ (CF ₂ ) ₉ CF ₃

A particularly preferred fluoroalkyl (meth) acrylate is a compound represented by the following general formula (2). CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ (CF ₂ ) _p CF ₃ (2) (wherein R ¹ is CH ₃ or H, and p is an integer of 4 to 9) .)

The water-soluble vinyl compound which is a copolymer component of the water-soluble copolymer used in the present invention or a water-soluble vinyl compound is a carboxyl group or a salt thereof, a sulfone group or a salt thereof. , A water-soluble vinyl compound having a functional group selected from a phosphoric acid group or a salt thereof, a phenol group or a salt thereof, a quaternary ammonium base, an amino group or a salt thereof, an amide group, a formyl group and a polyether chain-containing group, or hydrolyzable It is a vinyl compound having a group.

Specifically, (meth) acrylic acid or a salt thereof (Na, K, ammonium, etc.) styrenesulfonic acid or a salt thereof, p-vinylbenzylphosphonium sulfonate, 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof Salt, diacetone (meth) acrylamide, N
-Isopropylacrylamide, N-methylol (meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, 4-vinylpyridine, 4-vinylbenzoic acid, methacryloyloxyethyltrimethylammonium chloride, N-vinylformamide, glucose and fructose, etc. Esters of sugar and acrylic acid, compounds having a polyether chain, for example, polyethers shown in the following group that do not have a hydrocarbon group in the middle or at the end of the polyether chain, and the like.

CH ₂ ＣＨCH ・ COO (CH ₂ CH ₂ O) _k H CH ₂ ＣC (CH ₃ ) COO (CH ₂ CH ₂ O) _k H CH ₂ ＣC (CH ₃ ) COO (CH ₂ CH ₂ O) _k COC (C
_{H 3) = CH 2 CH 2} = CH · COOCH (CH 3) (CH in ₂ O) _k H (the above equation, k is an integer of 4-20.)

Among them, (meth) acrylic acid or its salt, styrenesulfonic acid or its salt,
2-acrylamido-2-methylpropanesulfonic acid or a salt thereof, methacryloyloxyethyltrimethylammonium chloride, N-vinylformamide, an ester of sugar and acrylic acid, having a hydrocarbon group at the middle or terminal represented by the following general formula group Compounds having unreacted polyether chains are preferred. CH ₂ ＣＨCHCOO (CH ₂ CH ₂ O) ₁ H CH ₂ ＣC (CH ₃ ) COO (CH ₂ CH ₂ O _{) 1} H CH ₂ ＣＨCHCOO (CH (CH ₃ ) CH ₂ O) ₁ H (the above formula In the formula, l represents an integer of 5 to 10.)

A vinyl compound having a hydrolytic capacity is hardly soluble in water itself. However, when it is hydrolyzed at 30 ° C. using an acidic aqueous solution of pH 2.0 or an alkaline aqueous solution of pH 13.0, it takes 8 hours. Within 75% or more, a water-soluble vinyl compound that hydrolyzes, specifically, compounds such as benzyl (meth) acrylate, vinyl acetate, and maleic anhydride. Under the above conditions, the fluoroalkyl (meth) acrylate is not substantially hydrolyzed, and the water-repellent copolymer is provided with water repellency. Preferably, vinyl acetate is particularly high in water solubility after hydrolysis and the degree of hydrolysis is relatively easy to control.

The water-soluble copolymer of the component (a) used in the present invention can be obtained by copolymerizing a fluoroalkyl (meth) acrylate with a water-soluble vinyl compound or a vinyl compound having a hydrolyzable group. . The ratio of both in the copolymer is from 10:90 to 90:10 by weight. And, if necessary, further copolymerizable compounds such as styrene, alkyl (meth) acrylate,
Polyester (meth) acrylate, urethane (meth)
Acrylate or the like may be copolymerized at a ratio of less than 50%. The polymerization method is carried out by a known method such as radical polymerization, cationic polymerization, anionic polymerization and the like, and radical polymerization is preferred in view of easy control of the polymerization reaction. In the case of radical polymerization, in the presence of various known radical polymerization initiators such as benzoyl peroxide and azobisisobutyronitrile at a temperature of 60 to 90 ° C. and a temperature of 4 to 7 ° C.
Copolymerize for hours.

The ratio of the fluoroalkyl (meth) acrylate to the water-soluble vinyl compound or the vinyl compound having hydrolytic ability is copolymerized in a weight ratio of 10:90 to 90:10. When the ratio exceeds 90, a copolymer having poor water solubility is obtained. On the contrary, when the ratio of the water-soluble radically polymerizable compound exceeds 90, sufficient water repellency is imparted to the final coating film. It becomes difficult to do. However, when the water solubility must be particularly emphasized, the ratio of the water-soluble radically polymerizable compound is preferably 70 or more. When the water repellency is particularly important, the ratio of the fluoroalkyl (meth) acrylate is Should be set to 70 or more.

In the copolymer of the present invention, a fluoroalkyl (meth) acrylate that contributes to water repellency and a vinyl compound that contributes to water solubility are used in combination to increase the pH.
A water-soluble copolymer which is soluble in 3 to 12% of water at 30 ° C. by 1% or more is obtained. The molecular weight of this water-soluble copolymer was determined by a GPC (gel permeation chromatography) measurement using a mixture of 10% or 40% methyl alcohol added to an acetate buffer at pH 4 under the following conditions. The number average molecular weight in terms of glycol is from 2,000 to 200,000, preferably 50,000
00 to 80,000.

(Conditions) Equipment: system 80 manufactured by TOSOH (Tosoh)
10 column: TSKgel G manufactured by TOSOH (Tosoh)
One MPW + one GP2500PW Temperature: 40 ° C Flow rate: 1 ml / min Injection volume: 100 μl Concentration: Injection concentration 0.1% by weight Detector: RI (refractometer)

If the molecular weight of the water-soluble copolymer is less than 2,000, the advantage of increasing the molecular weight is lost, the copolymer easily bleeds out from the final film, and long-term water repellency is imparted. Can not do. On the other hand, when the molecular weight of the water-soluble copolymer is more than 200,000, the water solubility is inferior and is not preferred. The amount of the water-soluble copolymer blended into the cosmetics is effective, in terms of product viscosity and usability,
It is preferably 0.01 to 50% in terms of solid content, and more preferably 0.1 to 50%.
-40% is more preferable.

The cosmetic of the present invention may contain, in addition to the above essential components, components used in ordinary cosmetics, for example, oily components such as hydrocarbons, higher fatty acid esters, animal and vegetable oils and fats, silicone oils, fluorine oils, etc. The present invention includes powders such as organic pigments and inorganic pigments, aqueous components such as water-soluble polymers, alcohols, and water, surfactants, ultraviolet absorbers, humectants, antioxidants, cosmetic ingredients, preservatives, and fragrances. Can be appropriately compounded as long as the effect of the above is not impaired.

The oily component includes hydrocarbons, oils and fats regardless of the origin of animal oils, vegetable oils, synthetic oils and the like generally used in cosmetics, and solid oils, semi-solid oils, liquid oils, volatile oils and the like. , Waxes, hardened oils, ester oils, fatty acids, higher alcohols, silicone oils, fluorinated oils, lanolin derivatives, oily gelling agents, lipophilic surfactants, and the like. Specifically, liquid paraffin,
Squalane, petrolatum, polyisobutylene, polybutene, paraffin wax, ceresin wax, microcrystalline wax, mokurou, montan wax,
Hydrocarbons such as fishtrophs wax, oils and fats such as olive oil, castor oil, jojoba oil, mink oil, macadamian nut oil, beeswax, carnauba wax, candelilla wax, waxes such as gay wax, cetyl isooctanoate Isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, polyglyceryl diisostearate, diglyceryl triisostearate, glyceryl tribehenate, pentaerythritol rosinate, neopentyl glycol dioctanoate, cholesterol fatty acid ester , Esters such as N-lauroyl-L-glutamate di (cholesteryl behenyl octyldodecyl), stearic acid, lauric acid, myristic acid,
Fatty acids such as behenic acid, isostearic acid, oleic acid, rosin acid, and 12-hydroxystearic acid; higher alcohols such as stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, and behenyl alcohol; Siloxane, high polymerization degree dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, polyether-modified polysiloxane, cross-linked organopolysiloxane, silicones such as fluorine-modified silicone, perfluoropolyether , Fluorinated oils such as perfluorodecane and perfluorooctane, lanolin, lanolin acetate, isopropyl lanolin fatty acid, and lanolin alcohol. Phosphorus derivatives, dextrin fatty acid esters, sucrose fatty acid esters, starch fatty acid esters, 12-hydroxystearic acid aluminum, oily gelling agents such as calcium stearate, etc., and can be used alone or in combination.

As the powder component, any powder used as a powder generally used in cosmetics, such as spherical, plate-like, needle-like, fume-like, fine particle, pigment grade, etc. There is no particular limitation on the particle structure such as porous or nonporous, and examples thereof include inorganic powders, glitter powders, organic powders, dye powders, and composite powders. Specifically, titanium oxide, konjo, ultramarine, red iron oxide, yellow iron oxide, black iron oxide, titanium oxide, zinc oxide, aluminum oxide, silicon dioxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, chromium oxide, water Inorganic such as chromium oxide, carbon black, aluminum silicate, magnesium silicate, aluminum magnesium silicate, mica, synthetic mica, synthetic sericite, sericite, talc, kaolin, silicon carbide, barium sulfate, bentonite, smectite, boron nitride, etc. Powders, bismuth oxychloride, titanium mica, iron oxide coated mica, iron oxide mica titanium, organic pigment treated mica titanium, glittering powders such as aluminum powder, nylon powder, polymethyl methacrylate, acrylonitrile-methacrylic acid copolymer Body powder, vinylidene chloride-methacrylic acid copolymer powder, polystyrene, polyethylene powder, polystyrene powder, organopolysiloxane elastomer powder, polymethylsilsesquioxane powder, polytetrafluoroethylene powder, wool powder, silk powder, crystalline cellulose, Organic powders such as magnesium stearate, zinc stearate, and N-acyl lysine; dye powders such as organic tar pigments and lake pigments of organic dyes; fine titanium oxide-coated mica titanium, fine zinc oxide-coated mica titanium, and sulfuric acid Composite powders such as barium-coated mica titanium, titanium oxide-containing silicon dioxide, and zinc oxide-containing silicon dioxide, and the like, and one or more of these can be used. These powders may be used alone or in combination of two or more.
Surface treatment may be performed by a known method using a fluorine compound other than the essential components, a silicone oil agent, a metal soap, a wax, a surfactant, an oil or a hydrocarbon, or the like.

The aqueous component may be any one of water and water-soluble components. In addition to water, for example, glycols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol and polyethylene glycol And glycerols such as glycerin, diglycerin and polyglycerin, and plant extracts such as aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender and rose. As the water-soluble polymer, guar gum, sodium chondroitin sulfate, hyaluronic acid, gum arabic, sodium alginate, carrageenan and other natural polymers, methyl cellulose, hydroxyethyl cellulose, semi-synthetic materials such as carboxymethyl cellulose, carboxyvinyl polymer, alkyl Synthetic ones such as addition carboxyvinyl polymer, polyvinyl alcohol, polyvinylpyrrolidone, and sodium polyacrylate can be mentioned.

The surfactant may be any surfactant generally used in cosmetics, and examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Examples of the nonionic surfactant include glycerin fatty acid ester and its alkylene glycol adduct, polyglycerin fatty acid ester and its alkylene glycol adduct, propylene glycol fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkylene glycol addition Sorbitol fatty acid ester and its alkylene glycol adduct, polyalkylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyalkylene alkyl ether, glycerin alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene hydrogenated castor oil, lanolin alkylene Glycol adducts, polyoxyalkylene-modified silicones, polyether-modified silicones and the like. That.

Examples of the anionic surfactant include fatty acids such as stearic acid and lauric acid and inorganic and organic salts thereof, alkylbenzene sulfate, alkyl sulfonate, α-olefin sulfonate, dialkyl sulfosuccinate, α-sulfonated fatty acid salt, acylmethyltaurine salt, N-methyl-N-alkyltaurine salt,
Polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate,
Polyoxyethylene alkyl phenyl ether phosphate,
N-acyl amino acid salts, N-acyl-N-alkyl amino acid salts, o-alkyl-substituted malates, alkyl sulfosuccinates, and the like.

As the amphoteric surfactant, there are carboxylic acid type, sulfate type, sulfonic acid type and phosphate type of amino acid type and betaine type, and those which are safe for human body can be used. For example, N, N-
Dimethyl-N-alkyl-N-carboxylmethylammonium betaine, N, N-dialkylaminoalkylenecarboxylic acid, N, N, N-trialkyl-N-sulfoalkyleneammonium betaine, N, N-dialkyl-N, N- Bis (polyoxyethylene sulfate) ammonium betaine, 2-alkyl-1-hydroxyethyl-
1-carboxymethylimidazolinium betaine and the like.

Examples of the ultraviolet absorber include, for example, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and 2-hydroxy-4-methoxybenzophenone-5 as benzophenones. Sodium sulfonate, 2,2 '
-Dihydroxy-4,4'-dimethoxybenzophenone, sodium 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sulfonate, 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetra Hydroxybenzophenone and the like, and PABAs such as para-aminobenzoic acid, ethyl para-aminobenzoate, glyceryl para-aminobenzoate, amyl para-dimethyl amino benzoate, and para-dimethyl amino benzoic acid-2
-Ethylhexyl, ethyl paradihydroxypropyl benzoate, etc., and as the cinnamic acid type, p-methoxycinnamic acid-2-ethylhexyl, 4-methoxycinnamic acid-2-ethoxyethyl, etc., and salicylic acid type Examples thereof include 2-ethylhexyl salicylate, phenyl salicylate, homomenthyl salicylate, and the like, and 2- (2-hydroxy-5-methylphenyl) benzotriazole, 4-tert-butyl-4′-methoxydibenzoylmethane, Oxybenzone and the like.

The humectant includes, for example, protein, mucopolysaccharide, collagen, elastin, keratin and the like. As antioxidants, for example, α-tocopherol,
Ascorbic acid and the like. Examples of the beauty component include vitamins, anti-inflammatory agents, crude drugs, and the like. Examples of the preservative include alkyl paraoxybenzoate, phenoxyethanol and the like.

When the copolymer is blended with the cosmetic blended with the powder, the powder used in advance can be used after being treated with the water-soluble copolymer of the present invention. The water repellency of the powder is improved, and the dispersibility of the powder is improved.

The cosmetics of the present invention include, for example, basic cosmetics such as creams, emulsions, gels, liquid creams, emulsions, packs, lotions, detergents, and hairs such as shampoos, rinses, set lotions, creams, etc. Cosmetics, makeup cosmetics such as foundation, white powder, makeup base, blusher, eyeshadow, lipstick, eyeliner, mascara, eyebrow and the like can be mentioned. Examples of the dosage form include powder, solid powder, oil-in-water emulsion, water-in-oil emulsion, lotion, oily solid, oily liquid, paste, and multilayer.

[0030]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Production Example 1 (Water-soluble copolymer 1) 1H, 1H, 2H, 2H heptadecafluorodecyl acrylate ("Biscoat 17" manufactured by Osaka Organic Chemical Industry Co., Ltd.)
F ") 4 g and polyethylene glycol monomethacrylate (" Blemmer PME400 "manufactured by NOF Corporation)
12 g was dissolved in 48 g of methyl isobutyl ketone,
0 mg of azobisisobutyronitrile was added as a radical polymerization initiator, and the temperature was increased to 70 ° C. with stirring, and at the same temperature,
After polymerizing for 7 hours, it was reprecipitated in hexane to obtain a copolymer.

Production Example 2 (Water-soluble copolymer 2) 1H, 1H, 2H, 2H 4 g of heptadecafluorodecyl acrylate and 8 g of N-vinylformamide were dissolved in 48 g of N-methylpyrrolidone, and 80 mg of azobisisobutylnitrile was added. It was added as a radical polymerization initiator, polymerized at 70 ° C. for 7 hours under stirring, and then reprecipitated in diethyl ether to obtain a copolymer.

Production Example 3 (Water-soluble copolymer 3) 1H, 1H, 2H, 2H Heptadecafluorodecyl acrylate 4g, acrylic acid 8g and polyester acrylate (PLACCEL F manufactured by Daicel Chemical Industries, Ltd.)
A-1) 0.2 g was dissolved in 48 g of dioxane, 20 mg of azobisisobutyronitrile was added as a radical polymerization initiator, polymerized at 70 ° C. for 7 hours with stirring, and reprecipitated in hexane to obtain a copolymer. A polymer was obtained.

Production Example 4 (Water-soluble copolymer 4) 1H, 1H, 2H, 2H Heptadecafluorodecyl acrylate 4g, acrylic acid 8g and polyester acrylate (PLACCEL F manufactured by Daicel Chemical Industries, Ltd.)
A-1) 0.2 g was dissolved in 48 g of dioxane, 20 mg of azobisisobutyronitrile was added as a radical polymerization initiator, and the mixture was polymerized at 70 ° C. for 7 hours with stirring.
3.6 g of 8% aqueous ammonia is added to precipitate (copolymer)
I got

Production Example 5 (Water-soluble copolymer 5) 4 g of 1H, 1H, 2H, 2H heptadecafluorodecyl acrylate and 16 g of benzyl methacrylate were added to 1,
Dissolved in 60 g of 4-dioxane, 80 mg of azobisisobutyronitrile was added as a radical polymerization initiator,
After polymerization at 70 ° C. for 7 hours with stirring, 45 g of a 0.5 M aqueous sodium hydroxide solution was added, and a precipitate (hydrolyzed copolymer) was immediately obtained.

Production Example 6 (Water-soluble copolymer 6) 4 g of 1H, 1H, 2H, 2H-9-trifluoromethyl-hexadecafluoroundecyl methacrylate and N
-8 g of vinylformamide is added to N-methylpyrrolidone 48
g of azobisisobutyronitrile as a radical polymerization initiator, and 60 g of terpinolene as a chain transfer agent. The mixture was polymerized at 70 ° C. for 7 hours under stirring, and then reprecipitated in diethyl ether. A copolymer was obtained.

Comparative Production Example 1 (Water-soluble copolymer 7) 12 g of 1H, 1H, 2H, 2H heptadecafluorodecyl acrylate and 1 g of N-vinylformamide were dissolved in 48 g of N-methylpyrrolidone to give azobisisobutyronitrile. 80 mg is added as a radical polymerization initiator,
After polymerizing at 70 ° C. for 7 hours with stirring, it was reprecipitated in diethyl ether to obtain a copolymer.

Production Comparative Example 2 (Water-soluble copolymer 8) 0.1 g of 1H, 1H, 2H, 2H heptadecafluorodecyl acrylate and 15 g of acrylic acid were dissolved in 60 g of 1,4-dioxane. Isobutyronitrile 1
00 mg as a radical polymerization initiator,
After polymerizing at 0 ° C. for 7 hours, it was reprecipitated in hexane to obtain a copolymer.

The molecular weight, water repellency (contact angle) and solubility of the water-soluble copolymers of Production Examples 1 to 5 and Comparative Examples 1 and 2 were measured by the following methods.

(Measurement method) Solubility The solubility of each fluorine-based water-soluble copolymer in 100 parts by weight of purified water was visually determined. 2. Contact angle 10 parts by weight of each fluorine-based water-soluble copolymer was mixed with 100 parts by weight of an acrylic emulsion polymer, applied to a polycarbonate substrate with a # 80 bar coater, and dried.
A film having a thickness of 40 microns was formed, and the contact angle with water was measured. 3. Molecular Weight For each fluorine-based water-soluble copolymer, the number average molecular weight in terms of polyethylene glycol was measured by GPC (gel permeation chromatography) using a mixed solvent obtained by adding 40% of methanol to an acetate buffer at pH 4 as an eluent.

[0040]

[Table 1]

Examples 1 to 4 and Comparative Example 1 Hand creams having the compositions shown in Table 2 were prepared and evaluated for water resistance, oil resistance, cosmetic durability, stability, and feeling of use by the following methods. The results are also shown in Table 2.

[0042]

[Table 2]

(Production method) Heat and dissolve components 1 to 5 and mix uniformly. B. Components 6 to 13 are uniformly mixed by heating. C. A is gradually added to B, emulsified, and filled into a container to obtain a product.

(Evaluation Method and Criteria) (Evaluation Items) a. Water resistance b. Oil resistance c. Makeup d. Stability e. Usability Evaluation items a to c and e are as follows. The sensory evaluation was performed. A stability test was performed.

1. Sensory evaluation For each sample, a use test was conducted by 20 specialized panels to evaluate the continuity of the cosmetic effect, and a judgment was made according to the following criteria based on the average score of the five-grade evaluation. (Evaluation criteria) 5 points: Very good 4 points: Good 3 points: Normal 2 points: Somewhat poor 1 point: Poor (Judgment criteria) A: 4.0 or more 5.0 points O: 3.0 or more 4 points Less than 2.0 points Δ: 2.0 points or more and less than 3.0 points ×: 1.0 points or more and less than 2.0 points

2. Stability test Each sample was set in a constant temperature bath at 40 ° C. for one month, and evaluated in the following four stages. A: No separation or discoloration. ：: Almost no separation or discoloration. Δ: There is some separation or discoloration. ×: There is separation or discoloration.

As is evident from the above results, the hand creams of Examples 1 to 4 according to the present invention have all of the water resistance, oil resistance, cosmetic durability, stability and feeling of use as compared with Comparative Example 1. It was an excellent cosmetic in that respect.

Examples 5 to 7 and Comparative Examples 2 to 3 Set lotions having the compositions shown in Table 3 were prepared.
Examples of oil resistance, makeup durability, stability and usability
Each evaluation was performed in the same manner as in Example 4. The results are also shown in Table 3.

[0049]

[Table 3]

(Production method) Components 1 to 11 are uniformly mixed and filled into a container to obtain a product. As is apparent from the above results, Example 5 according to the present invention
The set lotions of ~ 7 are compared with Comparative Examples 2-3,
The cosmetic was excellent in all respects of water resistance, oil resistance, long-lasting makeup, stability and feeling of use.

Examples 8 to 10 and Comparative Examples 4 to 5 Mascaras having the compositions shown in Table 4 were prepared.
Each evaluation was carried out in the same manner as in Examples 1 to 4 for the durability of the makeup, stability, and feeling of use. The results are also shown in Table 4.

[0052]

[Table 4]

(Note) In Comparative Example 5, the water-soluble copolymer 7 was aggregated in the mascara. (Production method) A. Heat and dissolve components 1 to 5 and mix uniformly. B. Components 6 to 14 are uniformly mixed by heating. C. B is gradually added to A, emulsified, and filled into a container to obtain a product. As is clear from the above results, Example 8 according to the present invention.
The mascaras of Nos. To 10 were excellent cosmetics in all respects of water resistance, oil resistance, makeup durability, stability and feeling of use as compared with Comparative Examples 4 and 5.

Example 11 and Comparative Example 6 A liquid foundation having the composition shown in Table 5 was prepared.
Each evaluation was performed in the same manner as in Examples 1 to 4 for water resistance, oil resistance, makeup durability, stability, and feeling of use. The results are also shown in Table 5.

[0055]

[Table 5]

(Production method) Components 1 to 4 are heated and dissolved, and mixed uniformly. B. The components 5 to 10 are uniformly heated and mixed. C. B is gradually added to A, emulsified, and filled into a container to obtain a product. As is clear from the above results, Example 1 according to the present invention
The liquid foundation No. 1 was a cosmetic excellent in all points of water resistance, oil resistance, makeup durability, stability and usability as compared with Comparative Example 6.

Example 12 and Comparative Example 7 Lipsticks having the compositions shown in Table 6 were prepared and evaluated for water resistance, oil resistance, cosmetic durability, stability, and feeling of use in the same manner as in Examples 1 to 4. Was. Table 6 also shows the results.

[0058]

[Table 6]

(Production method) A. Mix components 1 to 7 uniformly. B. Mix components 8 to 10 uniformly. C. B is gradually added to A, emulsified, and filled into a container to obtain a product. As is clear from the above results, Example 1 according to the present invention
The lipstick No. 2 was a cosmetic excellent in all respects in water resistance, oil resistance, cosmetic durability, stability, and feeling of use as compared with Comparative Example 7.

Example 13 and Comparative Example 8 A pressed foundation having the composition shown in Table 7 was prepared.
Regarding water resistance, oil resistance, makeup durability, press moldability, feeling of use, and lack of color unevenness (decorative coating film), water resistance, oil resistance, makeup durability, feeling of use, and lack of color unevenness are described in Examples 1 to 4. Each evaluation was performed in the same manner as described above, and press moldability was evaluated by the following method. Table 7 also shows the results.

[0061]

[Table 7]

(Production method) A. Component 1 is dissolved in purified water, components 2 to 5 are added, and purified water is distilled off while heating and mixing to process the powder. B. Add components 6 to 8 to A and mix uniformly with a mixer. C. B is pulverized and press-molded in a metal plate to obtain a product.

(Evaluation Method and Judgment Criteria) Press moldability The press moldability of each sample was visually evaluated in the following four stages. A: No cracks or cracks. ：: Almost no crack or crack. Δ: Some cracks or cracks were found. ×: There are cracks or cracks.

As is apparent from the above results, the press-type foundation of Example 13 according to the present invention was compared with Comparative Example 8 in terms of water resistance, oil resistance, cosmetic durability, press moldability, usability, and color unevenness. It was an excellent cosmetic in all aspects of its absence.

[0065]

The cosmetic of the present invention contains a specific water-soluble copolymer to improve water resistance and oil resistance,
The cosmetics lasted unsatisfactory without deteriorating stability and usability.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takayo Kinoshita 1-10-1, Yurakucho, Chiyoda-ku, Tokyo Mitsubishi Chemical Co., Ltd., Tokyo branch office (72) Inventor Jiro Nakabayashi 48-18 Sakaemachi, Kita-ku, Tokyo No. Within Kose Research Institute, Inc. (72) Inventor Atsushi Matsushita 48-18 Sakaemachi, Kita-ku, Tokyo Inside Kose Research Laboratory, Inc. (72) Inventor Yukako Ishihara 48-18 Sakaemachi, Kita-ku, Tokyo Kose Research Inside

Claims (3)

[Claims] 1. A fluoroalkyl (meth) acrylate component, a carboxyl group or a salt thereof, a sulfone group or a salt thereof, a phosphoric acid group or a salt thereof, a phenol group or a salt thereof, a quaternary ammonium base, an amino group or a salt thereof, and an amide. Water-soluble vinyl compound component having a functional group selected from the group consisting of a vinyl group, a formyl group, and a polyether chain-containing group or a vinyl compound component having a hydrolyzable group in a ratio of 10:90 to 90:10.
And a number average molecular weight in terms of polyethylene glycol by GPC measurement of 2,000.
A cosmetic comprising 0 to 200,000 and containing a water-soluble copolymer soluble in water of 1% by weight or more in 30 ° C. water having a pH of 3 to 12. 2. The method according to claim 1, wherein the fluoroalkyl (meth) acrylate has the following general formula (1).
The cosmetic described. CH ₂ ＣC (R) · COOC _m H _2m C _n F _{2n + 1} (1) (wherein, R is hydrogen or a methyl group, m is an integer of 1 or 2, n is 5 to 10) Represents an integer.) 3. The compounding amount of the water-soluble copolymer is 0.01 to 50.
The cosmetic according to claim 1, wherein the cosmetic is a weight%.