JPH111420A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cosmetic excellent in durability of makeup, capable of continuing inhibitory effects on ultraviolet rays, having improved touch. SOLUTION: This cosmetic comprises a polysiloxane-based copolymer containing a benzophenone group or a benzotriazole group having 2,000-2,000,000 number-average molecular weight obtained by copolymerizing a polysiloxane- containing vinyl-based monomer (A) of formula I: CH2 =CR<1> -X-(Si(R<2> )2 O)n -Si(R<3> )2 (in the formula, R<1> is a hydrogen atom or a methyl group; R<2> and R<3> are each a 1-3C alkyl or a phenyl group and may be the same or different; (n) is an integer of 6-100; X is a phenylene group of a carbonyl oxyalkylene group of the formula COOCm H2m ((m) is an integer of 1-5), etc.) with an ultraviolet ray absorbing group-containing vinyl-based monomer (B) of formula II: CH2 CR<1> -Y (in the formula, R<1> is a hydrogen atom or a methyl group; Y is a benzophenone group or a benzotriazole group) in the ratio of the components A to B in the range of 10:90 to 90:10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cosmetic containing a durable ultraviolet absorber. More specifically, water resistance,
The present invention relates to a cosmetic comprising a copolymer having both oil resistance and excellent ultraviolet absorbing ability.

[0002]

2. Description of the Related Art In the field of plastic additives, ultraviolet absorbers having a benzotriazole skeleton or a benzophenone skeleton are used in the field of plastic additives in order to prevent deterioration due to ultraviolet rays. Studies have been made to improve the properties and to achieve stable film forming properties.

[0003] In addition, ultraviolet rays cause an acute skin reaction such as erythema and blackening on human skin and cause skin aging and cancer in the long term. The development of sunscreen cosmetics containing an ultraviolet absorber has been actively conducted, and many ultraviolet absorbers suitable for cosmetics have been developed.

[0004] On the other hand, in order to improve the durability of the makeup and the durability of the effect of preventing ultraviolet rays, a silicone resin resistant to sweat and sebum is used as a film agent in cosmetics.

[0005]

However, depending on the compounding amount of the silicone resin, the compounding amount is limited due to the poor solubility of the ultraviolet absorber in the solvent of the resin and the resin. Despite the need for skilled technology, the UV protection effect of the product as a whole may be reduced as a result, or the durability of the UV protection effect may not always be sufficient.

[0006] Therefore, by forming a film having water resistance and oil resistance, it is possible to simultaneously provide a long lasting ultraviolet ray preventing effect which is excellent in cosmetic durability, and to develop an ultraviolet absorbing film agent which is excellent in the feeling of use. The development of blended cosmetics was expected.

The inventors of the present invention have conducted intensive studies in view of the above points, and have found that a specific siloxane-containing vinyl monomer and a specific vinyl monomer having an ultraviolet absorbing group are copolymerized at a specific ratio. The obtained copolymer has water resistance and oil resistance and has an ultraviolet ray preventing effect, and is a film agent excellent in use feeling, and a cosmetic compounded with this is excellent in cosmetic durability and has a sufficient ultraviolet ray preventing effect. At the same time, they found that the effect of preventing ultraviolet rays was maintained, and completed the present invention.

SUMMARY OF THE INVENTION An object of the present invention is to provide a cosmetic composition which has a long lasting effect and a sufficient ultraviolet light-preventing effect, and has a good feel upon use.

[0009]

That is, the present invention comprises a polysiloxane-containing vinyl monomer (A) represented by the following general formula (I) and an ultraviolet absorbing group represented by the following general formula (II). The vinyl monomer (B) was obtained by copolymerizing (A) and (B) in a weight ratio of 10:90 to 90:10,
It is intended to provide a cosmetic comprising a polysiloxane copolymer having a benzophenone group or a benzotriazole group having a number average molecular weight of 2,000 to 2,000,000.

Embedded image ^{_{CH 2 = CR 1 -X- (Si}} (R 2) 2 O) n -Si (R 3) 3 (I) ( In the formula, R ¹ and .R ² represents a hydrogen atom or a methyl group R ³ is an alkyl group or phenyl group having 1 to 3 carbon atoms, may .n be different or the same groups represents an integer of 6 to 100 .X is a phenylene group or _{-COOC m H 2m - (m =} 1 A carbonyloxyalkylene group represented by -COOC _m H _2m -OC _m H
_2m represents a carbonyloxyalkyleneoxyalkylene group represented by (m = 1 to 5). )

Embedded image CH ₂ CRCR ¹ -Y (II) (wherein, R ¹ represents a hydrogen atom or a methyl group, and Y represents a substituent having a group selected from a benzophenone group and a benzotriazole group. .)

[0010] The present invention also relates to the present invention, wherein the copolymer further comprises, in addition to the polysiloxane-containing vinyl monomer (A) and the vinyl monomer having an ultraviolet absorbing group (B), other copolymers. The present invention provides the above-mentioned cosmetic, which is obtained by copolymerizing a system monomer.

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of the present invention will be described below in detail.

The copolymer used in the present invention is obtained by copolymerizing the following (I) a polysiloxane-containing vinyl monomer (A) and (II) a vinyl monomer (B) having an ultraviolet absorbing group. It is a thing. (I) Polysiloxane-containing vinyl monomer (A): CH ₂ = CR ¹ -X- (Si (R ² ) ₂ O) _n -Si (R ³ ) ₃ (wherein R ¹ is a hydrogen atom or R ² and R ³ are an alkyl group having 1 to ³ carbon atoms or a phenyl group, which may be the same or different, and n represents an integer of 6 to 100. X represents a phenylene group or-. _{COOC m H 2m - (m =} 1~5 integer) carbonyl oxyalkylene group represented by or, -COOC _m H _2m -O-
Shows the (m = 1 to 5 integer) carbonyloxy alkylene oxyalkylene group represented by - C _m H _2m. Among the compounds of the above general formula (I), preferred polysiloxane-containing vinyl monomers include CH ₂ = CR ¹ COO-C _m H _2m- (Si
Compounds represented by (CH ₃ ) ₂ O) _n -Si (CH ₃ ) ₃ can be mentioned, and particularly preferred polysiloxane-containing vinyl monomers include CH ₂ = C (CH ₃ ) COO-C ₃ A compound represented by H _6- (Si (CH ₃ ) ₂ O) _n -Si (CH ₃ ) ₃ is mentioned. The synthesis method of these polysiloxane-containing vinyl monomers is, for example, Adv.Polym.Sc
i. Vol. 86, pp. 1-86 (1988).

(II) Vinyl monomers having an ultraviolet absorbing group
(B): CH ₂ = CR ¹ -Y (wherein, R ¹ represents a hydrogen atom or a methyl group, and Y represents a substituent having a group selected from a benzophenone group and a benzotriazole group.) The group Y may be any substituent having a benzophenone group or a benzotriazole group as a characteristic group,
There is no particular limitation. Specific examples of Y include the following substituents.

Embedded image

Embedded image The vinyl-based monomer having a benzophenone group and the vinyl-based monomer having a benzotriazole group may be copolymerized alone or in combination. The method for producing the vinyl monomer of the general formula (II) having these substituents Y is described in, for example, J. Appl.Polym.Sci.
Volume 663-672 (1966), USP 3072585 and the like.

In the present invention, the method for producing a polysiloxane-based copolymer having a benzophenone group or a benzotriazole group comprises the steps of:
(A) and a vinyl monomer having an ultraviolet absorbing group (B) can be carried out by a known method such as radical polymerization, cationic polymerization, anionic polymerization, etc. It is preferred in that respect. In the case of radical polymerization, various known radical polymerization initiators can be used.

In order to improve the solubility and affinity of the copolymer in cosmetic oils and solvents, the copolymer used in the present invention may further contain another copolymerizable compound, for example, , Styrene, alkyl (meth) acrylate having 1 to 23 carbon atoms, urethane (meth) acrylate or the like may be added to the copolymerization reaction system and copolymerized.

The radical copolymerization method of these polysiloxane-containing vinyl monomers (A) and general vinyl monomers (B) is described in, for example, Adv. Polym. Sci. Vol. 86, pp. 1-86. (198
8 years). In the copolymerization reaction, for example, the polysiloxane-containing vinyl monomer (A) and the vinyl monomer having an ultraviolet absorbing group (B) are dissolved in a solvent such as methyl isobutyl ketone and 1,4-dioxane. After that, the reaction can be carried out in the presence of a radical polymerization initiator such as benzoyl peroxide and azobisisobutyronitrile at a temperature of 60 to 110 ° C. for 4 to 8 hours.

The structural unit comprising the polysiloxane-containing vinyl monomer (A) in the polysiloxane copolymer having a benzophenone group or a benzotriazole group of the present invention and a vinyl monomer having an ultraviolet absorbing group ( The ratio of the constituent units consisting of B) ranges from 10:90 to 90:10 by weight,
Preferably it is 70:30 to 30:70. This copolymer composition ratio is appropriately adjusted by the charge ratio of the monomer at the time of copolymerization, but is usually 10:90 to 90:10, or 70:30 to 30:
Obtained by charging in the range of 70. When the ratio of the constituent unit composed of the polysiloxane-containing vinyl monomer (A) is less than 10, water resistance and oil resistance are difficult to develop, and thus it is not preferable, and the vinyl monomer having an ultraviolet absorbing group is not preferable.
When the ratio of the structural unit comprising (B) is less than 10, the ultraviolet absorbing ability of the copolymer becomes small, and it becomes difficult to exhibit the ultraviolet protective effect.

The amount of the copolymer in the cosmetic of the present invention can be appropriately adjusted according to the kind of the cosmetic to be treated, and is not particularly limited.
Weight%, and if you want to show the UV protection effect,
It is preferably at least 1.0% by weight, more preferably at least 5.0% by weight.

The dosage form of the cosmetic of the present invention is arbitrary, and for example, it can be adjusted to cream, paste, stick, lotion, spray, gel, emulsion, powder, pack, etc. it can.

The cosmetic of the present invention comprises, besides the above-mentioned copolymer of the essential constituents, other components usually used in cosmetics, such as powder components, liquid fats and oils, solid fats and oils, waxes, hydrocarbons,
Higher fatty acids, higher alcohols, esters, silicones, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, humectants, water-soluble polymer compounds, thickeners, coating agents, ultraviolet absorption Agents, ultraviolet scattering agents, anti-inflammatory agents, sequestering agents, lower alcohols, polyhydric alcohols, sugars, amino acids, organic amines, synthetic resin emulsions, pH adjusters, skin nutritional agents, vitamins, antioxidants, oxidation It can be produced by a conventional method according to the desired cosmetic formulation by appropriately blending a preventive aid, fragrance, water and the like as needed. Specific examples of the above components are shown below. The cosmetic of the present invention is produced by arbitrarily combining a copolymer of essential components and one or more of the following components.

Examples of the powder component include talc, kaolin, mica, sericite (sericite), muscovite, phlogopite,
Synthetic mica, mica, biotite, lithia mica, permiculite, magnesium carbonate, calcium carbonate, zirconium silicate, aluminum silicate, barium silicate, calcium silicate, zinc silicate, magnesium silicate, strontium silicate, tungstic acid Metal salts, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate, (calcined gypsum), calcium phosphate, fluoroapatite, hydroxyapatite, ceramic powder,
Metallic soaps (zinc myristate, calcium palmitate, aluminum stearate), inorganic powders such as boron nitride, polyamide resin powders (nylon powders), polyethylene powders, polymethyl methacrylate powders, polystyrene powders, styrene and acrylic acid Organic powders such as coalesced resin powder, benzoguanamine resin powder, polytetrafluoroethylene powder and cellulose powder; inorganic white pigments such as titanium dioxide and zinc oxide; inorganic red pigments such as iron oxide (iron oxide) and iron titanate; -Inorganic brown pigments such as iron oxide; inorganic yellow pigments such as yellow iron oxide and loess; inorganic black pigments such as black iron oxide, carbon black and low titanium oxide; and inorganic purple pigments such as mango violet and cobalt violet. Green pigments such as chromium oxide, chromium hydroxide, cobalt titanate, ultramarine, navy blue Blue pigments, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil and other pearl pigments, aluminum powder, copper powder and other metal powders Pigment, Red 201, Red 202, Red 2
04, Red 205, Red 220, Red 226,
Red No. 228, Red No. 405, Orange No. 203, Orange No. 20
Organic pigments such as No. 4, Yellow 205, Yellow 401 and Blue 404, Red No. 3, Red No. 104, Red No. 106
No. Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 2
Organic pigments such as zirconium, barium or aluminum lake such as No. 02, Yellow No. 203, Green No. 3 and Blue No. 1, natural pigments such as chlorophyll and β-caroline. These powders can be blended as they are,
Even if a hydrophobic treatment powder obtained by hydrophobizing a silicone treatment such as methyl hydrogen polysiloxane or a silane coupling agent, a metal soap treatment, or a fluorine treatment such as a perfluoroalkylphosphate diethanolamine salt or a perfluoroalkylsilane is mixed. Good.

Examples of liquid fats and oils include avocado oil,
Camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanqua oil, castor oil, linseed oil, safflower oil, cottonseed oil, eno oil, Soybean oil, peanut oil, teaseed oil, kaya oil, rice bran oil, sinagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin,
Glycerin trioctanoate, glycerin triisopalmitate and the like can be mentioned.

Examples of solid fats and oils include cocoa butter, coconut oil, horse fat, hardened coconut oil, palm oil, tallow, sheep fat, hardened tallow, palm kernel oil, lard, beef bone fat, mokuro kernel oil, and hardened kernel oil. Oil, beef tallow, mocro, hardened castor oil and the like.

Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin,
Sugar cane wax, isopropyl lanolin fatty acid, hexyl laurate, 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 and the like. Can be

Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalene, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax and the like.

Examples of higher fatty acids include, for example, lauric acid, myristic acid, palmitic acid, stearic acid, behenic (behenic) acid, oleic acid, 12-hydroxystearic acid, undecylenic acid, tallic acid, isostearic acid, linoleic acid, and linoleic acid. Acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA) and the like.

As the higher alcohol, for example, linear alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, monostearyl glycerin ether (bacyl alcohol), and 2-decyltetradecyl And branched chain alcohols such as knol, lanolin alcohol, cholesterol, phytosterol, hexyldecanol, isostearyl alcohol, octyldodecanol and the like.

Examples of synthetic ester oils include isopropyl myristate, cetyl octoate, octyl dodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyl octanoate, Cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexylate, fatty acid ester of dipentaerythritol, N-alkyl glycol monoisostearate, neodicaprate Pentyl glycol, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylol tri-2-ethylhexylate Bread, trimethylolpropane triisostearate, pentaneerythritol tetra-2-ethylhexylate, glycerin triethyl 2-ethylhexylate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glycerin trimyristate Glyceride, tri-2-heptylundecanoic acid methyl ester, castor oil fatty acid methyl ester, oleic oil, cetostearyl alcohol, acetoglyceride, palmitic acid 2-
Heptylundecyl, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate and the like.

Examples of the silicone include linear polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane and methylhydrogenpolysiloxane, and cyclic polysiloxanes such as decamethylpolysiloxane, dodecamethylpolysiloxane and tetramethyltetrahydrogenpolysiloxane. Examples include polysiloxane, silicon resin and silicon rubber forming a three-dimensional network structure.

Examples of the anionic surfactant include soap base, fatty acid soaps such as sodium laurate and sodium palmitate, higher alkyl sulfates such as sodium lauryl sulfate and potassium lauryl sulfate, POE lauryl sulfate triethanolamine, PO
E Alkyl ether sulfates such as sodium lauryl sulfate; N-acyl sarcosine acids such as sodium lauroyl sarcosine; sodium N-myristoyl-N-methyltaurine; higher fatty acids such as sodium coconut fatty acid methyl tauride and sodium lauryl methyl tauride. Amidosulfonic acid salts, phosphate salts such as POE sodium oleyl ether phosphate, POE stearyl ether phosphoric acid, sodium di-2-ethylhexylsulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sulfosuccinate, lauryl polypropylene glycol sulfosuccinate Sulfosuccinates such as sodium, sodium linear dodecylbenzenesulfonate, triethanolamine linear dodecylbenzenesulfonate Alkylbenzenesulfonates such as linear dodecylbenzenesulfonic acid, monosodium N-lauroylglutamate, disodium N-stearoylglutamate, N-acylglutamate such as monosodium N-myristoyl-L-glutamate, and hydrogenated coconut oil fatty acid sodium glycerin sulfate Sulphate oils such as funnel oils, sulfated oils such as funnel oils, PO
E alkyl ether carboxylic acid, POE alkyl allyl ether carboxylate, α-olefin sulfonate,
Higher fatty acid ester sulfonate, secondary alcohol sulfate, higher fatty acid alkylolamide sulfate, sodium lauroyl monoethanolamidosuccinate, N-palmitoyl aspartate ditriethanolamine, sodium caseinate and the like.

Examples of the cationic surfactant include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride and lauryltrimethylammonium chloride, distearyldimethylammonium dialkyldimethylammonium chloride, and poly (N, N′-dimethyl-3, Alkylpyridinium salts such as 5-methylenepiperidinium) and cetylpyridinium chloride, alkyl quaternary ammonium salts, alkyldimethylbenzylammonium salts, alkylisoquinolinium salts, dialkylmorphonium salts, POE alkylamines, alkylamine salts, Examples thereof include polyamine fatty acid derivatives, amyl alcohol fatty acid derivatives, benzalkonium chloride, benzethonium chloride and the like.

Examples of the amphoteric surfactant include 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium and 2-cocoyl-2-imitazolinium hydroxide-1-carboxy. Betaines such as imidazoline amphoteric surfactants such as ethyloxy disodium salt, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryl dimethylaminoacetic acid betaine, alkyl betaine, amido betaine and sulfobetaine. Surfactants and the like.

Examples of the lipophilic nonionic surfactant include sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, Sorbitan fatty acid esters such as penta-2-ethylhexyl diglycerol sorbitan, tetra-2-ethylhexyl diglycerol sorbitan, mono-cottonseed oil fatty acid glycerin, glycerin monoerucate, glycerin sesquioleate, glyceryl monostearate, α,
Glycerin polyglycerin fatty acids such as glycerin α'-oleate pyroglutamate and glyceryl monostearate; propylene glycol fatty acid esters such as propylene glycol monostearate; hydrogenated castor oil derivatives; glycerin alkyl ether;

Examples of the hydrophilic nonionic surfactant include POE sorbitan fatty acid esters such as POE sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate, and POE-sorbitan. Sorbit Monolaurate, POE-Sorbit Monooleate, POE
POE sorbitol fatty acid esters such as sorbit pentaoleate, POE-sorbit monostearate, POE glycerin fatty acid esters such as POE-glycerin monostearate, POE-glycerin monoisostearate, POE-glycerin triisostearate; POE monooleate, POE distearate, POE monodioleate, POE fatty acid esters such as ethylene glycol cysteate, POE lauryl ether, POE oleyl ether, POE stearyl ether, POE behenyl ether, POE 2-octyldodecyl ether, POE such as POE cholestanol ether Alkyl ethers, POE octyl phenyl ether, POE nonyl phenyl ether, POE dinonyl phenyl ether Phenyl ethers such as POE, pluronic type such as bruronic, PO
E-POP cetyl ether, POE-POP2-decyltetradecyl ether, POE-POP monobutyl ether, POE-POP hydrogenated lanolin, POE-POP
POE / POP alkyl ethers such as glycerin ether, tetra POE / tetra POP ethylenediamine condensates such as tetronic, POE castor oil, POE hardened castor oil, POE hardened castor oil monoisostearate,
POE-cured castor oil triisostearate, POE-cured castor oil monopyroglutamic acid monoisostearate diester, POE-casted oil-cured castor oil derivatives such as POE-cured castor oil maleic acid, POE beeswax lanolin derivatives such as POE sorbitol beeswax, coconut oil Fatty acid diethanolamide, lauric acid monoethanolamide,
Alkanolamides such as fatty acid isopropanolamide, POE propylene glycol fatty acid ester, PO
E alkylamine, POE fatty acid amide, sucrose fatty acid ester, POE nonylphenylformaldehyde condensate, alkylethoxydimethylamine oxide, trioleyl phosphoric acid and the like.

Examples of the humectant include polyethylene glycol, propylene glycol, glycerin, 1,3
-Butylene glycol, xylitol, sorbitol,
Maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salts, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO Examples include an adduct, an extract of Perilla, an extract of St. John's wort, and an extract of melilot.

Examples of natural water-soluble polymers include, for example, arabia gum, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), alge colloid (cassow extract), starch (rice, corn, Potato, wheat), plant polymers such as glycyrrhizic acid, microbial polymers such as xanthan gum, dextran, succinoglucan, burlan, collagen,
Animal-based polymers such as casein, albumin, and gelatin are exemplified.

As the semi-synthetic water-soluble polymer, for example,
Starch-based polymers such as carboxymethyl starch and methylhydroxypropyl starch, methylcellulose, nitrocellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, cellulose sodium sulfate, hydroxypropylcellulose, sodium carboxymethylcellulose (CM
C), cellulosic polymers such as crystalline cellulose and cellulose powder, and alginic acid polymers such as sodium alginate and propylene glycol alginate.

Examples of the synthetic water-soluble polymer include vinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone and carboxyvinyl polymer (Carbopol), polyethylene glycol 20,000, 4,000,000, and the like. Polyoxyethylene polymer such as 600,000, polyoxyethylene polyoxypropylene copolymer copolymer polymer, acrylic polymer such as sodium polyacrylate, polyethyl acrylate, polyacrylamide, polyethyleneimine, cationic polymer And the like.

Examples of the inorganic water-soluble polymer include bentonite, silicic acid A1Mg (beegum), laponite, hectorite, silicic anhydride and the like.

As the thickener, for example, gum arabic,
Carrageenan, karaya gum, tragacanth gum, carob gum, quince seed (quince), casein, dextrin, gelatin, sodium pectate, sodium alginate, methylcellulose, ethylcellulose,
CMC, hydroxyethylcellulose, hydroxypropylcellulose, PVA, PVM, PVP, sodium polyacrylate, carboxyvinyl polymer, locust bean gum, guar gum, tamarind gum, dialkyldimethylammonium cellulose sulfate, xanthan gum, aluminum magnesium silicate, bentonite,
Hectorite and the like.

Examples of the ultraviolet absorber include para-aminobenzoic acid (hereinafter abbreviated as “PABA”), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N- Dimethyl PABA ethyl ester, N,
Benzoic acid-based ultraviolet absorbers such as N-dimethyl PABA butyl ester and N, N-dimethyl PABA tyl ester;
Anthranilic acid ultraviolet absorbers such as homomenthyl-N-acetylanthranilate, salicylic acid ultraviolet absorbers such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, and octyl Cinnamate, ethyl-4-isopropyl cinnamate, 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, glycerylmono-2-ethylhexanoyl-diparamethoxycinnamate, 4-methyl-3-
[Methylbis (trimethylsiloxy) silyl] butyl 3,4,5-trimethoxycinnamate and other cinnamic acid ultraviolet absorbers; 2,4-dihydroxybenzophenone;
2'-dihydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methyl Benzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4′-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n
Benzophenone-based ultraviolet absorbers such as -octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, 3- (4'-methylbenzylidene) -d, 1-camphor, 3-benzylidene-d, 1-camphor, urocanic acid, Urocanic acid ethyl ester, 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-butyldi Benzoylmethane, 5- (3,3-dimethyl-2-norbornylidene) -3-pentan-2-one, etc. By using one or more of these ultraviolet absorbers in the cosmetic of the present invention. It can be expected that the UV effect will be further enhanced.

As the ultraviolet scattering agent, for example, inorganic compounds such as titanium dioxide, zinc oxide, iron oxide, cerium oxide, zirconium oxide, titanium silicate, zinc silicate and cerium silicate, and those inorganic compounds such as mica and Examples thereof include those coated with an inorganic powder such as talc and composited with an organic resin powder such as PMMA or nylon powder. By using one or more of these ultraviolet scattering agents in the cosmetic of the present invention, it can be expected that the effect of preventing ultraviolet rays will be synergistically enhanced.

Examples of the anti-inflammatory agent include glycyrrhetic acid and its derivatives such as dipotassium glycyrrhetic acid and monoammonium glycyrrhetic acid, glycyrrhetic acid and its derivatives such as stearyl glycyrrhetic acid, allantoin, tranexamic acid, indomethacin and the like.
Salicylic acid derivatives, zinc white, hinokitiol, azulene and the like can be mentioned. By using one or more of these anti-inflammatory agents in the cosmetic of the present invention,
It can be expected to suppress "hot flashes" on the skin due to sunlight.

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

As the lower alcohol, for example, methanol, ethanol, propanol, isopropanol,
Isobutyl alcohol, t-butyl alcohol and the like.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, and 2,3-butylene glycol.
Butylene glycol, pentamethylene glycol, 2-
Dihydric alcohols such as butene-1,4-diol, hexylene glycol and octylene glycol; trihydric alcohols such as glycerin, trimethylolpropane and 1,2,6-hexanetriol; and tetrahydric alcohols such as pentaerythritol Pentahydric alcohols such as xylitol, sorbitol, hexahydric alcohols such as mannitol,
Polyhydric alcohol polymers such as diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, 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, d Dihydric alcohol alkyl ethers such as lenglycol dibutyl ether, diethylene glycol monomethyl ether, diethylene 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 monoethyl 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 Dihydric alcohol alkyl ethers such as dipropylene glycol butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diadibate, ethylene glycol disuccinate Dihydric alcohol ethers such as 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 ethers such as ter, xyl alcohol, serachyl alcohol, and batyl alcohol, sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, starch-degrading sugar, maltose, xylitolose,
Sugar alcohols such as starch-decomposed sugar-reducing alcohol, glysolid, tetrahydrofurfuryl alcohol, PO
E Tetrahydrofurfuryl alcohol, POP butyl ether, POP / POE butyl ether, tripolyoxypropylene glycerin ether, POP glycerin ether, POP glycerin ether phosphoric acid, POP
POE pentane erythritol ether and the like.

Examples of the monosaccharide include tricarbonates such as D-glyceryl aldehyde and dihydroxyacetone, tetracarbons such as D-erythrose, D-erythrulose, D-threose and erythritol, L-arabinose, D-xylose, and the like. Pentoses such as L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, D-glucose, D-talose, D-
Bucose, D-galactose, D-fructose, L
-Hexoses such as galactose, L-mannose, D-tagatose, heptose such as aldoheptose and heppulose;
Octanose such as octulose, 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-
Deoxy sugars such as L-mannose, D-glucosamine, D
-Amino sugars such as galactosamine, sialic acid, aminouronic acid and muramic acid, and uronic acids such as D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D-galacturonic acid and L-iduronic acid.

Examples of the oligosaccharide include sucrose, guntianose, umbelliferose, lactose, planteose, isoliqunoses, α, α-trehalose,
Raffinose, liqunoses, umbilicin, stachyose bell bath courses and the like.

Examples of polysaccharides include cellulose, quince seed, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate, hyaluronic acid, tragacanth gum, keratan sulfate, chondroitin, xanthan gum, mucoitin sulfate, guar gum, dextran Keratosulfuric acid, locust bingham, succinoglucan, caronic acid and the like.

Examples of the amino acid include neutral amino acids such as glycine, alanine, valine, leucine, isoleucine, serine, threonine, tryptophan, cystine, cysteine, methionine, proline and hydroxyproline, aspartic acid, glutamic acid, asparagine and glutamine. Examples include acidic amino acids and basic amino acids such as arginine, histidine, lysine, hydroxylysine and the like. Examples of amino acid derivatives include acyl sarcosine sodium (sodium lauroyl sarcosine), acyl glutamate, sodium acyl β-alanine, glutathione, and pyrrolidone carboxylic acid.

Examples of the organic amine include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol and 2-amino-2-methyl-1. -Propanol and the like.

As the synthetic resin emulsion, for example,
An acrylic resin emulsion, a polyethyl acrylate emulsion, an acrylic resin liquid, a polyacryl alkyl ester emulsion, a polyvinyl acetate resin emulsion, and the like are included.

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

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

Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic esters and the like.

As the antioxidant aid, for example, phosphoric acid,
Examples thereof include citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, kephalin, hexametaphosphate, phytic acid, and ethylenediaminetetraacetic acid.

The cosmetic of the present invention can produce cosmetics having various objective effects by combining the copolymer having an ultraviolet absorbing group with the above-mentioned optional components, and can be used as a basic cosmetic or a makeup cosmetic. It is used, and the application site to the body is not limited. For example, it can be used as a skin cosmetic or a hair cosmetic.

[0058]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[Production Example 1: Copolymer (CI)] Methacrylate containing polysiloxane (“X-22-17” manufactured by Shin-Etsu Chemical Co., Ltd.)
4DX ”) 3.51 g, 2-hydroxy-4-methacryloyloxyethyl benzophenone 2.50 g, stearyl methacrylate 2.50 g are dissolved in 25 g of toluene, and 90 mg of azobisisobutyronitrile is added as a radical polymerization initiator. After the temperature was raised to ° C., polymerization was carried out at the same temperature for 7 hours, followed by reprecipitation in 450 ml of ethanol to obtain a desired copolymer (CI) having a benzophenone group. The number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) of this copolymer (CI) using tetrahydrofuran as an eluent was 22,100. Structural formula of "X-22-174DX" manufactured by Shin-Etsu Chemical Co., Ltd .:

Embedded image CH ₂ = CR ¹ -X- (Si (R ² ) ₂ O) _n -Si (R ³ ) ₃ (where R ¹ = R ² = R ³ = -CH ₃ , X = -COOC ₃ H ₆ −, the average value of n = 60.1.)

[Production Example 2: Copolymer (CII)] Polysiloxane-containing methacrylate (“Siler Plain FM-0711” manufactured by Chisso Corp.) 11.5 g, 2-hydroxy-4-methacryloyloxyethyl benzophenone 15.0 g, butyl Dissolve 3.2 g of methacrylate in 89 g of methyl isobutyl ketone, 900
mg of t-butyl peroxyisopropyl carbonate was added as a radical polymerization agent, and the mixture was heated to 110 ° C. with stirring, polymerized at the same temperature for 7 hours, reprecipitated in 450 ml of methanol, and subjected to a desired benzophenone group. A copolymer (CII) having the following formula was obtained. The number average molecular weight in terms of polystyrene of the copolymer (CII) measured by GPC (gel permeation chromatography) using tetrahydrofuran as an eluent was 29,000. Structural formula of Chisso Co., Ltd. “Siler Plane FM-0711”:

Embedded image CH ₂ = CR ¹ -X- (Si (R ² ) ₂ O) _n -Si (R ³ ) ₃ (wherein, R ¹ = R ² = R ³ = -CH ₃ , X = -COOC ₃ H ₆ -, is the average value = 9.8 for n).

[Production Example 3: Copolymer (CIII)] Polysiloxane-containing methacrylate ("X-22-" manufactured by Shin-Etsu Chemical Co., Ltd.)
174DX ") 11.0 g, 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole 8.0 g,
1.0 g of butyl methacrylate in methyl isobutyl ketone 58
g), 630 mg of t-butyl peroxyisopropyl carbonate is added as a radical polymerization agent, 470 mg of terpinolene as a chain transfer agent, and while stirring, the temperature is raised to 110 ° C., and the mixture is polymerized at the same temperature for 7 hours. The precipitate was reprecipitated in 450 ml of methanol to obtain a desired copolymer (CIII) having a benzotriazole group. The number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) of this copolymer (CIII) using tetrahydrofuran as an eluent was 9,100.

The cosmetic prepared according to the present invention was prepared by blending the copolymer prepared as described above. The compounding amount is% by weight.

The UV protection effect, water resistance, oil resistance (sweat resistance), makeup durability and usability of the cosmetic of the present invention were evaluated by the following tests.

[Evaluation test (for general cosmetics)] a) UV protection effect test According to “J. Soc. Cosmet. Chem. Japan, 23 (3), 207 (1989)” (Suetsui et al., Shiseido Co., Ltd.) The color developed by the transmitted light of each sample was measured using an ultraviolet sensor. The color development of each sample (Example) was evaluated based on the following criteria, with the color development of ethanol alone being 100 and the color development of an ethanol solution corresponding to the ultraviolet absorber in the sample being 0. (Evaluation criteria) ・ ・ ・: less than 25 ・ ・ ・: 25 or more and less than 50 ・ ・ ・: 50 or more and less than 75 ×… 75 or more b) UV protection effect persistence test Apply a fixed amount, 30
After a minute, the coating was washed with water, and then the application site was extracted with a solvent.
Using this extracted sample, a test was conducted using an ultraviolet sensor in the same manner as described above. Evaluation criteria are the same as above. c) Water resistance test Each sample was applied to 20 specialized panels for evaluation, washed with water 30 minutes later, and evaluated for water resistance. (Evaluation Criteria) ◎ ・ ・ ・ 15-20 people judged good water resistance ○ ・ ・ ・ 10-14 people judged good water resistance △ ・ ・ ・ 5-9 people judged good water resistance × ・ ・ ・0 to 4 persons judged that the water resistance was good. D) Oil resistance test Each sample was applied to 20 evaluation specialist panels, and after lightly exercising for 1 hour, the oil resistance was evaluated. (Evaluation Criteria) ◎ ・ ・ ・ 15-20 people judged good oil resistance ○ ・ ・ ・ 10-14 people judged good oil resistance △ ・ ・ ・ 5-9 people judged good oil resistance × ・ ・ ・0 to 4 persons judged that the oil resistance was good. E) Makeup durability Each sample was applied to 20 evaluation specialty panels, and a sensory test was conducted on the makeup durability. (Evaluation criteria) ・ ・ ・: 15 to 20 persons are judged to have good makeup holding ・ ・ ・: 10 to 14 persons are judged to have good makeup holding △: 5 to 9 persons are judged to have good makeup holding × ・ ・ ・D) Usability Each sample was applied to 20 panelists specialized in evaluation, and a sensory test was conducted for usability. (Evaluation Criteria) ◎ ・ ・ ・ 15-20 persons judged good usability ○ ・ ・ ・ 10-14 persons judged good usability △ ・ ・ ・ 5-9 persons judged good usability × ・ ・ ・5 to 9 people judged good usability

Example 1 Sunscreen cosmetics (oil type) (1) Decamethylcyclopentasiloxane 48.0% (2) Dimethylpolysiloxane (10 CS / 25 ° C.) 20.0 (3) Methylphenylpolysiloxane (20 CS / 25 ° C.) 20.0 (4) Copolymer (CI) 12.0 (Production method) After mixing (1) to (4) and sufficiently dissolving,
Filtration gave a sunscreen cosmetic.

[Comparative Example 1a] In the formulation of Example 1, (4)
The product was prepared in the same manner as in Example 1 except that the copolymer (CI) was replaced with 2.5% of an ultraviolet absorber of 3,5-dimethoxy-2-hydroxybenzophenone and 9.5% of decamethylcyclopentasiloxane. I got

"Comparative Example 1b" In the formulation of Example 1, (1)
Decamethylcyclopentasiloxane and (4) copolymer
(CI) 60% in total, 2.5% of 3,5-dimethoxy-2-hydroxybenzophenone as an ultraviolet absorber, and a silicone resin trimethylsiloxysilicate-decamethylcyclopentasiloxane solution (50%) as a coating agent, 19.0. % And decamethylcyclopentasiloxane were replaced by 38.5% to obtain a product in the same manner as in Example 1.

The results of evaluation of this sunscreen cosmetic are shown in Table 1. As is clear from "Table 1," the sunscreen cosmetic of Example 1 is excellent in all items of UV protection effect, UV protection effect persistence, water resistance, oil resistance, makeup durability and usability. There was found.

[0069]

[Table 1] ---------------------------------------------- ----------------------- Example 1 Comparative Example 1a Comparative Example 1b ------------------ -------------------------------------------------- -UV protection effect ◎ ○ ◎ UV protection effect persistence ◎ × △ Water resistance ◎ ○ ◎ Oil resistance ◎ ○ ◎ Makeup ◎ △ ◎ Usability ◎ ○ ○ --------------- -------------------------------------------------- ----

Example 2 Sunscreen Cosmetic (W / O Cream) (1) Octamethylcyclotetrasiloxane 28.0% (2) Dimethylpolysiloxane (100 CS / 25 ° C.) 5.0 (3) Dimethylpoly Siloxane (2,500,000 CS / 25 ° C.) 3.0 (4) Liquid paraffin 5.0 (5) Copolymer (CII) 3.5 (6) Polyether-modified silicone (400 CS / 25 ° C.) 6.0 (Polyoxyethylene group content 20% by weight) (7) Purified water 41.1 (8) Sodium L-glutamate 3.0 (9) 1,3-butylene glycol 5.0 (10) Preservative 0.2 (11) ) Fragrance 0.2 (Production method) (1) to (6) and (11) are mixed, dissolved by heating, and kept at 70 ° C to obtain an oil phase. Separately (7)-(10)
Is heated and dissolved at 70 ° C. to obtain an aqueous phase. The aqueous phase is added to the oil phase and sufficiently emulsified by an emulsifier. After emulsification, the mixture was cooled with stirring, poured into a container at 35 ° C. or lower, allowed to cool, and solidified to obtain a sunscreen cosmetic.

"Comparative Example 2a" In the formulation of Example 2, (5)
A product was obtained in the same manner as in Example 2 except that the copolymer (CII) was replaced with 0.3% of 3,5-dimethoxy-2-hydroxybenzophenone as an ultraviolet absorber and 3.2% of purified water.

[Comparative Example 2b] In the formulation of Example 2, (1)
Octamethylcyclotetrasiloxane and (5) copolymer (CII) total 31.5%, UV absorber 3,5-dimethoxy-2-hydroxybenzophenone 0.3%, Silicone resin trimethylsiloxysilicic acid as coating agent -A product was obtained in the same manner as in Example 2 except that 6.4% of octamethylcyclotetrasiloxane solution (50%) and 24.8% of octamethylcyclotetrasiloxane were substituted.

The results of evaluation of this sunscreen cosmetic were as follows:
The results are shown in Table 2. As is clear from "Table 2," the sunscreen cosmetic of Example 1 is excellent in all items of ultraviolet protection effect, durability of ultraviolet protection effect, water resistance, oil resistance, cosmetic durability and usability. There was found.

[0074]

[Table 2] ---------------------------------------------- ----------------------- Example 2 Comparative Example 2a Comparative Example 2b ------------------ -------------------------------------------------- -UV protection effect ◎ ◎ ◎ UV protection effect persistence ◎ × △ Water resistance ◎ ◎ ◎ Oil resistance ◎ ○ ◎ Makeup ◎ △ ◎ Usability ◎ ◎ ○ --------------- -------------------------------------------------- ----

"Example 3" Sunscreen cosmetics (O / W cream) (1) Decamethylcyclopentasiloxane 9.0% (2) Liquid paraffin 3.0 (3) Isopropyl myristate 2.0 (4) Vaseline 5.0 (5) Cetanol 5.0 (6) Stearic acid 3.0 (7) Glycerin monoisostearate 3.0 (8) Copolymer (CIII) 0.1 (9) Preservative 0.2 (10) Fragrance 0.2 (11) Glycerin 10.0 (12) Propylene glycol 5.0 (13) Hyaluronic acid 0.01 (14) Potassium hydroxide 0.2 (15) Purified water 54.29 (Production method) (1) to (10) are heated and stirred at 70 ° C. to make an oil phase. (11) to (15) are heated and dissolved at 70 ° C. to obtain an aqueous phase. The oil phase is added to the water phase and emulsified by an emulsifier. The emulsion was cooled to 30 ° C. with a heat exchanger and then filled to obtain a sunscreen cosmetic. This sunscreen cosmetic was evaluated as ◎ in all of the evaluation items in “Table 1”.

Example 4 Sunscreen lotion (1) Dimethylpolysiloxane (5CS / 25 ° C.) 10.0% (2) Methylphenylpolysiloxane 7.0 (3) Stearic acid 1.0 (4) Co-weight Combined (CI) 20.0 (5) Preservative 0.2 (6) Fragrance 0.2 (7) Glycerin 5.0 (8) Montmorillonite 0.5 (9) Potassium hydroxide 0.2 (10) Purified water 55.9 (Preparation) (1) to (6) are heated and stirred at 70 ° C. to obtain an oil phase. (7) to (10) are heated and dissolved at 70 ° C. to obtain an aqueous phase. The oil phase is added to the aqueous phase and emulsified by an emulsifier. The emulsion was cooled to 30 ° C. with a heat exchanger and filled to obtain a sunscreen lotion. This sunscreen lotion was evaluated as ◎ in all of the evaluation items in “Table 1”.

“Example 5” Dual-use foundation (1) Silicon-treated titanium oxide 9.5% (2) Silicon-treated mica 40.0 (3) Silicon-treated talc 20.45 (4) Silicon-treated iron oxide 7.5 ( 5) Spherical nylon powder 10.0 (6) Trimethylolpropane triisostearate 5.0 (7) Squalane 3.0 (8) Beeswax 2.0 (9) Copolymer (CII) 0.5 (10 ) Sorbitan triolate 1.0 (11) Preservative 0.5 (12) Vitamin E 0.05 (13) Fragrance 0.5 (Production method) (1) to (5) were mixed with a Henschel mixer, A mixture of 6) to (13) heated and mixed was added, mixed and pulverized, and molded into a middle plate to obtain a sunscreen dual-use foundation. The obtained dual-use foundation had a light finish and a natural finish, and all of the evaluation items in Table 1 were evaluated as ◎.

Example 6 Stick Cosmetic (1) Titanium oxide 10.0% (2) Zinc oxide 7.0 (3) Mica 16.0 (4) Red iron oxide 1.5 (5) Yellow iron oxide 1.5 (6) Black iron oxide 1.0 (7) Dimethylpolysiloxane (20 CS / 25 ° C.) 29.4 (8) Trimethylolpropane tri-2-ethylhexanoate 10.0 (9) Liquid paraffin 8 0.0 (10) Microcrystalline wax 2.0 (11) Celesin 1.0 (12) Solid paraffin 6.0 (13) Copolymer (CIII) 5.0 (14) Fragrance 0.5 (15) Antioxidant Agent 0.1 (16) Sorbitan sesquiolate 1.0 (Preparation method) (1) to (6) were mixed with a Henschel mixer, and (7) to (9), (13), (15) and (16) were mixed. In addition to what was heated and stirred, To focus. Next (10)
What melt | dissolved-(12) and (14) was added to the said mixture, and after mixing well, it shape | molded in the stick form and obtained the sunscreen stick cosmetic. This sunscreen stick cosmetic was evaluated as ◎ in all of the evaluation items in “Table 1”.

Example 7 Makeup Base (1) Dimethylpolysiloxane (2CS / 25 ° C.) 19.0% (2) Glyceryl triisostearate 10.0 (3) Isopar® G 5.0 ( 4) Sorbitan sesquiolate 1.0 (5) Polyoxyethylene-modified organopolysiloxane 3.0 (6) Purified water 46.0 (7) 1,3-butylene glycol 5.0 (8) Fine particle titanium oxide 10.0 (9) Copolymer (CI) 1.0 (10) Preservative appropriate amount (11) Antioxidant appropriate amount (12) Flavor appropriate amount (Production method) (1) to (5), (9), (11), ( 12)
Was stirred and dissolved at 70 ° C., and (6) to (8) and (10), which were previously heated to 70 ° C., were added thereto, emulsified and dispersed, and then cooled to obtain a desired sunscreen cosmetic base. The obtained makeup base was evaluated as ◎ in all of the evaluation items in “Table 1”.

Example 8 Stick Cosmetic (1) Titanium oxide 10.0% (2) Zinc oxide 7.0 (3) Mica 16.0 (4) Red iron oxide 1.5 (5) Yellow iron oxide 1.5 (6) Black iron oxide 1.0 (7) Dimethylpolysiloxane (20 CS / 25 ° C.) 26.4 (8) Trimethylolpropane tri-2-ethylhexanoate 8.0 (9) Liquid paraffin 8 2.0 (10) Microcrystalline wax 2.0 (11) Celesin 1.0 (12) Solid paraffin 6.0 (13) Copolymer (CII) 10.0 (14) Fragrance 0.5 (15) Antioxidant Agent 0.1 (16) Sorbitan sesquiolate 1.0 (Preparation method) (1) to (6) were mixed with a Henschel mixer, and (7) to (9), (13), (15) and (16) were mixed. Heat and stir in addition to Combine. Next (10)
What melt | dissolved-(12) and (14) was added to the said mixture, and after mixing well, it shape | molded in the stick form and obtained the sunscreen stick cosmetic. The obtained stick cosmetic had a high ultraviolet ray preventing effect, was also excellent in persistence of the ultraviolet ray preventing effect, and was also excellent in makeup durability. All the evaluation items in Table 1 were evaluated as ◎.

Example 9 Powdery Foundation (1) Talc 27.7% (2) Mica 30.0 (3) Kaolin 5.0 (4) Titanium dioxide 10.0 (5) Titanium mica 3.0 (6) ) Zinc stearate 1.0 (7) Iron oxide red 1.0 (8) Iron oxide yellow 3.0 (9) Iron oxide black 0.2 (10) Polymethylsilsesquioxane powder 5.0 (11) Squalane 6.0 (12) Copolymer (CIII) 5.0 (13) Octyldodecyl myristate 2.0 (14) Sorbitan monooleate 0.5 (15) Fragrance 0.5 (16) Antioxidant 0 .1 (Preparation method) (1) to (10) were mixed with a Henschel mixer, and a mixture obtained by dissolving and mixing (11) to (16) with heat was added and mixed, followed by pulverization. Got a foundation. The obtained powdery foundation was evaluated as ◎ in all items of “Table 1”.

Example 10 Ultraviolet ray preventing essence (1) 3.0% of stearic acid (2) cetanol 1.0 (3) lanolin derivative 3.0 (4) squalane 5.0 (5) 2-ethylhexyl stearate 3.0 (6) 1,3-butylene glycol 6.0 (7) POE cetyl alcohol ether 2.0 (8) triethanolamine 1.0 (9) 2-hydroxy-4-methoxybenzophenone 4.0 (10 ) Copolymer (CI) 3.0 (11) Preservative appropriate amount (12) Flavor appropriate amount (13) Antioxidant appropriate amount (14) Purified water residue (Production method) Dissolve (6) and (8) in (14) And heat 7
Keep at 0 ° C to make aqueous phase. (1) to (5) at 70 to 80 ° C
After heating and dissolving in (7), (7) and (9) to (13) are sequentially dissolved and kept at 70 ° C. to obtain an oil phase. While stirring the aqueous phase, the oil phase is added to emulsify. After uniformly adjusting the emulsified particles with a homomixer, deaeration and cooling were performed to obtain an ultraviolet protection essence.

Example 11 Whitening Essence (1) Dipropylene glycol 5.0% (2) PEG 400 5.0 (3) Ethanol 10.0 (4) Carboxyvinyl polymer 0.3 (5) Sodium alginate 3 (6) Potassium hydroxide 0.15 (7) POE sorbitan monostearate 1.0 (8) Sorbitan monooleate 0.5 (9) Copolymer (CII) 0.5 (10) Placenta extract 0.5 (11) Arbutin 1.0 (12) Kojic acid 1.0 (13) Vitamin E acetate 0.1 (14) Allantoin 0.5 (15) Perfume proper amount (16) Preservative proper amount (17) Antioxidant (16) Purified water residue (Preparation method) After dissolving (4) and (5) in (18) and heating, (1), (2), (10) to (12), (14) And sequentially dissolved aqueous phase. (3) to (7) to (9), (1)
3) Dissolve (15)-(17) and add to the aqueous phase.
A solution obtained by dissolving (6) in a part of (18) was further added, followed by stirring, deaeration and filtration to obtain a whitening essence.

Example 12 Emulsion (1) Stearic acid 2.0% (2) Cetyl alcohol 1.5 (3) Vaseline 4.0 (4) Squalane 5.0 (5) Copolymer (CIII) 1 2.0 (6) Glycerin tri-2-ethylhexanoate 2.0 (7) Sorbitan monooleate 2.0 (8) Dipropylene glycol 5.0 (9) PEG 1500 3.0 (10) Triethanolamine 1 0.0 (11) Stearyl glycyrrhetinate 0.1 (12) Preservative appropriate amount (13) Perfume appropriate amount (14) Purified water residue (Production method) Add (8) to (10) to (14), heat to 70 ° C, Water phase. (1)-(7), (11)-(1
3) is heated and dissolved to form an oil phase. Add oil phase to water phase and emulsify. The emulsified particles were adjusted using a homogenizer, deaerated and cooled to obtain an emulsion.

Example 13 Hair Foam (Stock solution formulation) (1) Polyoxyethylene hydrogenated castor oil (POE60) 1.0% (2) Copolymer (CI) 5.0 (3) Glycerin 3.0 ( 4) Appropriate amount of perfume (5) Preservative appropriate amount (6) Purified water residue (7) Ethyl alcohol 15.0 (filling formulation) (8) Stock solution 90.0 (9) Liquefied petroleum gas 10.0 (Production method) (2) Is added to the melts of (3) and (1) and stirred. (6) and (7) are added, and the mixture is uniformly emulsified with a homogenizer. Other components are added and stirred to obtain a stock solution. For filling, a stock solution was filled in a can, and after mounting a valve, gas was filled to obtain a hair foam.

Example 14 Sunscreen Hair Gel (1) Carbopol 940 0.6% (2) Purified Water 68.0 (3) Triethanolamine 0.1 (4) Ethanol 14.0 (5) 2 -Hydroxy-methoxybenzophenone-5 sulfonic acid 5.0 (6) Copolymer (CII) 6.0 (7) Polyethylene glycol 1.0 (8) Dimethicone copolymer 4.0 (9) Methyl paraben 0.25 ( 10) Propylparaben 0.05 (11) Appropriate amount of flavor (Preparation method) (1) was dissolved in (2) with stirring, and (3) was added thereto, followed by dispersion with a dispersing machine. (4) ~
(11) was added and stirred to obtain a desired sunscreen hair gel. This sunscreen hair gel had an excellent UV protection effect, and was excellent in water resistance, oil resistance and usability.

“Example 15” Cosmetic oil (1) Olive oil 49.8% (2) Liquid paraffin 30.0 (3) Copolymer (CIII) 20.0 (4) Vitamin E acetate 0.2 (5) Appropriate amount of antioxidant (6) Appropriate amount of fragrance (Preparation method) Each component of (1) to (6) was added and stirred and dissolved to obtain cosmetic oil.

Example 16 Lipstick (1) Titanium dioxide 5.0% (2) Red 201 No. 0.6 (3) Red 202 No. 1.0 (4) Red No. 223 0.2 (5) Candelilla Wax 9.0 (6) Solid paraffin 8.0 (7) Beeswax 5.0 (8) Carnauba wax 5.0 (9) Lanolin 11.0 (10) Castor oil 25.2 (11) Copolymer (CI) 20.0 (12) Isopropyl myristate 10.0 (13) Antioxidant appropriate amount (14) Fragrance appropriate amount (Production method) (1) to (3) are added to a part of (10) and treated with a roller (pigment) Department). (4) is dissolved in a part of (10) (dye part). After mixing and melting the other ingredients,
A pigment part and a dye part are added and uniformly dispersed with a homomixer.
After dispersion, the mixture was poured into a mold and rapidly cooled to obtain a lipstick as a stick. This lipstick was excellent for long-lasting makeup.

Example 17 Lipstick (1) Titanium dioxide 4.5% (2) Red No. 201 0.5 (3) Red 202 No. 2.0 (4) Red No. 223 0.05 (5) Celesin 4 0.0 (6) Candelilla wax 8.0 (7) Carnauba wax 2.0 (8) Castor oil 30.0 (9) Copolymer (CII) 10.0 (10) Diglyceride isostearate 29.95 (11) Polyoxyethylene (25) polyoxypropylene (20) 2-tetradecylethyl 1.0 (12) ion-exchanged water 5.0 (13) glycerin 2.0 (14) propylene glycol 1.0 (15) UV protection Agent proper amount (16) Antioxidant proper amount (17) Fragrance proper amount (Production method) Add (1) to (3) to a part of (8) and treat with a roller (pigment part). (4) is dissolved in (8) (dye part). (12) to (14) are uniformly dissolved at 80 ° C (aqueous phase). After the other components are mixed and melted by heating, the pigment part and the dye part are added, and the mixture is uniformly dispersed with a homomixer. Thereafter, the aqueous phase was added, and the mixture was emulsified and dispersed by a homomixer, poured into a mold and rapidly cooled to obtain a stick-like lipstick. This lipstick was excellent for long-lasting makeup.

Example 18 Cream-type skin protective agent (1) Cetostearyl alcohol 2.0% (2) Squalane 2.0 (3) Beeswax 1.0 (4) Reduced lanolin 1.0 ( 5) Ethylparaben 0.3 (6) Polyoxyethylene (20 mol) sorbitan monopalmitate 2.0 (7) Monoglyceride stearate 2.0 (8) Sodium N-stearoylglutamate 0.5 (9) Octamethyl Cyclotetrasiloxane 15.0 (10) Decamethylcyclopentasiloxane 10.0 (11) Copolymer (CIII) 15.0 (12) Polyethylene powder 10.0 (13) Vitamin E acetate 0.1 (14) ) Stearyl glycyrrhetinate 0.1 (15) Ergocalciferol solution (2 million units) 0.1 (16) 1,3-butyric acid Lenglycol 2.0 (17) Polyethylene glycol 1500 2.0 (18) Purified water residue (Preparation method) (1) to (15) were dissolved by heating and heated to 70 ° C. (16) to (18) ) With stirring. After homogenizer treatment to make the emulsified particles fine, the mixture was rapidly cooled while stirring to obtain a cream-based skin protective agent.

Example 19 Nail Enamel (1) Nitrocellulose 12.5% (2) Alkyd resin 11.0 (3) Copolymer (CI) 10.0 (4) Ethyl acetate 20.0 (5) Butyl acetate 15.0 (6) Ethanol 5.0 (7) Toluene 25.0 (8) Pigment 1.0 Herringdon pink CN: Titanium dioxide = 4: 1 (9) Antioxidant 0.5 (10) Fragrance An appropriate amount (production method) (1) to (10) were mixed to prepare a nail enamel. The following evaluation tests were performed on the obtained nail enamel and the nail enamel of Comparative Example 3.

Comparative Example 3 Nail Enamel A product was obtained in the same manner as in Example 19 except that (3) nitrocellulose was used as the copolymer (CI).

[Evaluation test (for nail enamel)] a) Anti-fading test An anti-fading test was carried out using Herringdon Pink CN: titanium dioxide = 4: 1 as a pigment. After applying each nail enamel on white paper and exposing it to sunlight for 3 days, the degree of fading (fading, dullness) was visually assessed by a panel of 10 professionals as follows, and the average score was obtained. Was used as the evaluation point of the sample. Fading and dulling were remarkably observed: 0 points Fading and dulling were slightly observed: 1 point Fading and dulling were not observed at all: 2 points b) Observation of coating film condition The sample was divided into three groups of 10 persons, and the sample was applied to nails. The formed film was visually observed. The judgment was made based on the following criteria. Peeling and turning are noticeable: 0 points Peeling and turning are slightly observed: 1 point Smooth peeling and no turning are observed: 2 points

As a result of the above test, in the fading prevention effect test, 1.7 points were obtained in Example 19 and 0.3 points in Comparative Example 3, and 1.5 points were obtained in Example 19 in the state of the coating film. In Example 3, the score was 1.1, and the nail enamel of Example 19 was found to have a superior anti-fading effect and a longer film durability than the comparative example.

Example 20 Basecoat (1) Ethanol 80.0% (2) Alkyd resin 9.0 (3) Copolymer (CII) 1.0 (4) Ethyl acetate 5.0 (5) Purified water 5.0 (Production method) (1) to (5) were mixed to prepare a base coat.

Example 21 Hand Lotion (1) Dimethylsiloxane 1.5 cs (n = 2) 93.0% (2) Copolymer (CIII) 2.0 (3) Methylphenylpolysiloxane 5.0 ( Production method) (1) to (3) were stirred and dissolved at 70 to 80 ° C,
Upon cooling, a hand lotion was obtained. The obtained hand lotion was non-greasy, had a good feeling of use, had good water repellency, and had an effect of protecting the skin for a long time.

Example 22 Hand cream (1) Octamethylcyclotetrasiloxane 15.0% (2) Copolymer (CI) 65.0 (3) Microcrystalline wax 5.0 (4) Liquid paraffin 0 (Production method) (1) to (4) were stirred and dissolved at 70 to 80 ° C.
Upon cooling, a hand cream was obtained. The obtained hand cream was non-greasy, had a refreshing feeling, and had an effect of protecting the skin for a long time.

Example 23 Hand Moisture Lotion (1) Decamethylcyclopentasiloxane 30.0% (2) Copolymer (CII) 40.0 (3) Sorbitan monooleate 5.0 (4) Water 22. 0 (5) Dipropylene glycol 3.0 (Production method) (1) to (3) were stirred and mixed at 70 to 80 ° C,
The solution obtained by dissolving (5) in (4) is added thereto,
The mixture was emulsified to obtain a hand moisture lotion. The obtained hand moisture lotion has a good feeling of use,
It had the effect of protecting the skin for a long time.

[0099]

According to the present invention, it is possible to provide a cosmetic composition which is excellent in long-lasting makeup, has a long-lasting effect on ultraviolet rays, and has good usability.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI A61K 7/043 A61K 7/043 7/06 7/06 (72) Inventor Kazuhisa Ohno 1050 Nippa-cho, Kohoku-ku, Yokohama-shi, Kanagawa In Shiseido Daiichi Research Center (72) Inventor Masato Aoyama 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Corporation Yokohama Research Laboratory (72) Inventor Toshiyuki Tanaka 1000-Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Mitsubishi Chemical Corporation Yokohama Research Laboratory (72) Inventor Hiroaki Yamaoka 1-10-1 Yurakucho, Chiyoda-ku, Tokyo Mitsubishi Chemical Corporation Tokyo branch office

Claims (2)

[Claims] 1. A polysiloxane-containing vinyl monomer (A) represented by the following general formula (I) and a vinyl monomer (B) having an ultraviolet absorbing group represented by the following general formula (II): , (A)
And a polysiloxane copolymer having a benzophenone group or a benzotriazole group having a number average molecular weight of 2,000 to 2,000,000, obtained by copolymerizing the weight ratio of (B) to 10:90 to 90:10. A cosmetic comprising a coalescence. ## STR1 ## ^{_{CH 2 = CR 1 -X- (Si}} (R 2) 2 O) n -Si (R 3) 3 (I) ( In the formula, R ¹ and .R ² represents a hydrogen atom or a methyl group R ³ is an alkyl group or phenyl group having 1 to 3 carbon atoms, may .n be different or the same groups represents an integer of 6 to 100 .X is a phenylene group or _{-COOC m H 2m - (m =} 1 A carbonyloxyalkylene group represented by -COOC _m H _2m -OC _m H
_2m represents a carbonyloxyalkyleneoxyalkylene group represented by (m = 1 to 5). Embedded image CH ₂ CRCR ¹ -Y (II) (wherein, R ¹ represents a hydrogen atom or a methyl group, and Y represents a substituent having a group selected from a benzophenone group and a benzotriazole group. Shown.) 2. The copolymer according to claim 1, wherein the copolymer is a vinyl monomer having a polysiloxane-containing monomer (A) and a vinyl monomer having an ultraviolet absorbing group (B). 2. The copolymer of claim 1, wherein
The cosmetic described.