JPH09255543A - W/o-type anti-suntan cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a W/O-type anti-suntan cosmetic free from ultraviolet absorber, having excellent ultraviolet protecting effect and high safety to the skin, giving excellent feeling to the skin and effective for preventing the secondary sticking of the powder contained in the base material. SOLUTION: This anti-suntan cosmetic contains 20-60wt.% of a volatile component (e.g. light liquid paraffin), 0.1-1.5wt.% of an organic-modified clay mineral (e.g. dodecyltrimethylammonium chloride), 0.5-20wt.% of spherical resin powder (e.g. nylon powder) and 0.1-30wt.% of a film-forming agent (e.g. polyvinyl pyrrolidone). The cosmetic is preferably further incorporated with 1-20wt.% of an ultraviolet scattering agent (e.g. titanium oxide). It may further be compounded with various components ordinarily used in cosmetics, pharmaceuticals, etc. The cosmetic exhibits excellent ultraviolet protecting effect without using an ultraviolet absorber and is smoothly spreadable on the skin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a water-in-oil type sunscreen cosmetic, and more specifically, to provide a UV absorber which is excellent in UV protection effect, highly safe to the skin, and excellent in feeling of use. It relates to a water-in-oil type sunscreen cosmetic which does not contain.

[0002]

2. Description of the Related Art It is known that a water-in-oil type (W / O type) emulsified preparation has excellent water resistance and sweat resistance as compared with an oil-in-water type (O / W type) emulsified preparation. There is. This W /
Among O-type emulsified products, sun care products such as sunscreen cosmetics that block UV rays and prevent skin reactions caused by UV rays are protected against UV rays in any use situation in combination with diversification of leisure in recent years. High SPF (= Sun Protection Fac
The development of products with a tor) value is being actively conducted.

As a method for obtaining such a high SPF value,
A high content of an ultraviolet absorber is generally used. However,
A high SPF value can be obtained with a high content of an ultraviolet absorber, but on the other hand, there may be concerns about safety to the skin, such as some ultraviolet absorbers that may cause skin disorders. . Furthermore, in the base compounded with powder, there have been problems such as the powder being dropped by physical rubbing and being adhered to clothes (secondary adhesion).

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and is highly safe to the skin and has an excellent UV protection effect, and prevents secondary adhesion of powder contained in the base. It is an object of the present invention to provide a water-in-oil type sunscreen cosmetic that can be used.

[0005]

Means for Solving the Problems As a result of intensive research to solve the above problems, the present inventors have found that by adding an organically modified clay mineral, a volatile component, a spherical resin powder and a film forming agent, It is non-chemical, has an excellent UV protection effect without the addition of an UV absorber, has high safety to the skin, and has an excellent feeling of use. Furthermore, the powder contained in the base is difficult to fall off. It was found that a sunscreen cosmetic capable of preventing adhesion can be obtained, and based on this, the present invention was completed.

[0006] That is, according to the present invention, there is provided a water-in-oil type sunscreen cosmetic containing no ultraviolet absorber, which comprises an organically modified clay mineral, a volatile component, a spherical resin powder and a film forming agent. To be done.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The volatile components used in the present invention include:
Low boiling hydrocarbons or silicone oils are preferably used. Examples of the low boiling point hydrocarbon include linear, branched, or cyclic hydrocarbons having 6 to 15 carbon atoms and having a boiling point of 260 ° C. or lower under atmospheric pressure. Specifically, light liquid paraffin. Etc. are exemplified, and they are commercially available under trade names such as “ISOPAR G” and “ISOPAR H”. Examples of the low boiling point silicone oil include those having a boiling point of 260 ° C. or lower (at atmospheric pressure), and specific examples thereof include dimethylpolysiloxane and cyclodimethylpolysiloxane.
These volatile components may be used alone or in combination of two or more.

The content of the volatile component is preferably 20 to 60% by weight, more preferably 30 to 50% by weight, based on the total amount of the cosmetic composition of the present invention. If it is less than 20% by weight, "spreading" on the skin is heavy, while if it exceeds 60% by weight, "oiliness" is exhibited and the usability is poor.

The organically modified clay mineral used in the present invention is
Generally, it can be arbitrarily used without limitation as long as it can be used as an organically modified clay mineral in cosmetics, etc., but among them, a water-swellable clay mineral is treated with a quaternary ammonium salt type cationic surfactant. Cation-modified clay minerals are preferably used.

Examples of the water-swellable clay mineral include layered silicate minerals belonging to the genus Smectite, and specific examples thereof include montmorillonite, beidellite, nontrolite, saponite, and herculite. These may be natural or synthetic products, and commercially available products such as Kunipia, Smecton (all manufactured by Kunimine Industry Co., Ltd.), and Veegum (Vanderbild Co., Ltd.).
), Dimonite, Fluorotetrasilicon mica (all manufactured by Topy Industries, Ltd.), Laponite (manufactured by Laporte)
Etc., and these can be preferably used. These water-swellable clay minerals may be used alone or in any combination of two or more.

The above quaternary ammonium salt type cationic surfactant has the following general formula (I):

[0013]

Embedded image (In the formula, R ¹ represents an alkyl group having 10 to 22 carbon atoms or a benzyl group; R ² is a methyl group or 10 to 2 carbon atoms.
2 represents an alkyl group; R ³ and R ⁴ are each independently
Represents an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group; X represents a halogen atom or a methylsulfate residue). Specifically, for example, dodecyltrimethylammonium chloride, myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, alkyltrimethylammonium chloride, behenyltrimethylammonium chloride, myristyldimethylethylammonium chloride, cetyldimethylethylammonium chloride, stearyldimethyl. Ethylammonium chloride, alkyldimethylethylammonium chloride, behenyldimethylethylammonium chloride, myristyldiethylmethylammonium chloride, cetyldiethylmethylammonium chloride, stearyldiethylmethylammonium chloride,
Alkyldiethylmethylammonium chloride, behenyldiethylmethylammonium chloride, benzyldimethylmyristylammonium chloride, benzyldimethylcetylammonium chloride, benzyldimethylstearylammonium chloride, benzyldimethylbehenylammonium chloride, benzylmethylethylcetylammonium chloride, benzylmethylethylstearylammonium chloride, Examples thereof include distearyldimethylammonium chloride, dibehenyldihydroxyethylammonium chloride, bromide compounds in place of the chlorides of the above compounds, and dipalmitylpropylethylammonium methylsulfate. These quaternary ammonium salt-type cationic surfactants may be used alone or in combination of two or more.

The cation-modified clay mineral is commercially available, and is commercially available, for example, as "Benton 38" (Reox Co.), "Vegum Ultra" (Vanderbild Co.) and the like. Can be used. It is also possible to mix a water-swelling clay mineral and a quaternary ammonium salt type cationic surfactant and to carry out organic modification in the formulation, and the product thus obtained can also be suitably used.

The amount of the organically modified clay mineral compounded is preferably 0.1 to 1.5% by weight, more preferably 0.1 to 1% by weight, based on the total amount of the cosmetic composition of the present invention. If it is less than 0.1% by weight, the stability of the cosmetic is poor and the effect of addition cannot be obtained. On the other hand, if it exceeds 1.5% by weight, the viscosity of the base increases and the "spread" becomes heavy, resulting in a feeling in use Inferior. In the present invention, one kind or two or more kinds can be arbitrarily selected and used from these organically modified clay minerals.

The spherical resin powder used in the present invention is not particularly limited as long as it can be generally used as a spherical resin powder in cosmetics and the like, but may be any polyamide resin powder (nylon powder). , Polyethylene powder, polymethylmethacrylate powder, polystyrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, trimethylsilsesquioxane powder and the like are preferable. It is illustrated.

The shape and the like of these spherical resin powders are not particularly limited, but those having a particle size of about 1 to 50 μm are preferably used. Further, these resin powders may be hydrophobized. The hydrophobic treatment method may be any method as long as it can impart water repellency, and the method is not limited. For example, a normal surface treatment method such as a gas phase method, a liquid phase method, an autoclave method, a mechanochemical method, etc. can be used. Can be used.

For example, when a hydrophobizing agent is added to the raw material powder for treatment, it may be added after diluting it with an appropriate solvent (dichloromethane, chloroform, hexane, ethanol, xylene, volatile silicone, etc.), or You may add directly. For mixing and stirring the powder and the treating agent, a ball mill, a Hogersight ball mill, a vibrating ball mill, an attritor, a pot mill, a rod mill, a pan mill, a homomixer, a homodisper, a Henschel mixer, a Nauter mixer, and the like can also be used. In addition to this, a method of utilizing the activity of the powder surface to polymerize a cyclic organosiloxane on the powder surface at a low temperature of 100 ° C. or lower by a gas phase reaction (Japanese Patent Publication No. 1-54380), or the method described above. A method in which a pendant group such as glycerol monoallyl ether is later added to the Si-H portion of the silicone polymer on the surface (Japanese Patent Publication No. 1-54381) can also be used.

The hydrophobizing agent is not particularly limited, but fatty acid dextrin-treated powder, trimethylsiloxysilicic acid-treated powder, fluorine-modified trimethylsiloxysilicic acid-treated powder, methylphenylsiloxysilicic acid-treated powder, fluorine-modified methylphenylsiloxy. Silicic acid treated powder,
Dimethyl polysiloxane, diphenyl polysiloxane,
Low-viscosity oily polysiloxane-treated powder such as methylphenylpolysiloxane, gum-like polysiloxane-treated powder, methylhydrogenpolysiloxane-treated powder, fluorine-modified methylhydrogenpolysiloxane-treated powder, methyltrichlorosilane, methyltrialkoxysilane Powder treated with an organic silyl compound such as hexamethyldisilane, dimethyldichlorosilane, dimethyldialkoxysilane, trimethylchlorosilane, trimethylalkoxysilane or a fluorine-substituted product thereof, ethyltrichlorosilane, ethyltrialkoxysilane, propyltrichlorosilane, Propyl trialkoxysilane, hexyl trichlorosilane, hexyl trialkoxysilane, long-chain alkyltrichlorosilane, long-chain alkyltriethoxysilane Organic modified silane or treated powder according to their fluorine substitution products, amino-modified polysiloxane treatment powder, fluorine-modified polysiloxane treatment powder,
Fluorinated alkyl phosphoric acid treated powder and the like can be mentioned.

The amount of the spherical resin powder blended is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight, based on the total amount of the cosmetic of the present invention. If it is less than 0.5% by weight, the free-flowing feel of the spherical resin powder cannot be obtained,
On the other hand, if the amount exceeds 20% by weight, the spherical resin powder is too much, resulting in a rough feeling in use, which is not preferable. In the present invention,
One or more of these spherical resin powders can be arbitrarily selected and used.

The film-forming agent used in the present invention is not particularly limited as long as it can be generally used as a film-forming agent in cosmetics and the like. Among them, polyvinylpyrrolidone (PVP), PVP / Dimethylaminoethyl methacrylic acid copolymer, PVP / eicosene copolymer, PVP / ethyl methacrylate / methacrylic acid copolymer, PVP / hexadecene copolymer, PVP
/ VA copolymers, PVP / vinyl acetate / itaconic acid copolymers, styrene / PVP copolymers and other PVP-based coating agents; ethyl acrylate / acrylic acid amide / acrylic acid copolymers, ethyl acrylate / acrylic acid Butyl copolymer, ethyl acrylate / ethyl methacrylate copolymer, ethyl acrylate / methacrylic acid copolymer, ethyl acrylate / methyl methacrylate copolymer, octyl acrylate / vinyl acetate copolymer, octyl acrylate /
Styrene copolymer, butyl acrylate / vinyl acetate copolymer, butyl acrylate / ethyl hydroxymethacrylate copolymer, butyl acrylate / methyl methacrylate copolymer, methoxyethyl acrylate / hydroxyethyl acrylate / acrylic acid Butyl copolymer, lauryl acrylate / vinyl acetate copolymer, polyethyl acrylate,
Acrylic acid type coating agents such as polybutyl acrylate and polystyrene acrylic acid resin; Vinyl acetate type coating agents such as polyvinyl acetate; Polymethyl methacrylate, methyl methacrylate / butyl acrylate / octyl acrylate / diethyl vinylpyrrolidone sulfate Methacrylic acid type coating agents such as / N, N'-dimethylaminomethacrylic acid copolymers; vinyl methyl ether type skin coatings such as vinyl methyl ether / ethyl maleate copolymers and vinyl methyl ether / butyl maleate copolymers Agent; styrene / methylstyrene /
Styrene-based coating agents such as indene copolymers; alkyd resin-based coating agents such as cyclohexane-based alkyd resins; silicone resin-based coating agents such as trimethylsiloxysilicic acid are suitable examples. In the present invention, one kind or two or more kinds can be arbitrarily selected and used from these film forming agents.

The content of such a film-forming agent is preferably 0.1 to 30% by weight, and more preferably 0.5 to 20% by weight, based on the total amount of the cosmetic composition of the present invention. If the amount is less than 0.1% by weight, the effect of the film forming agent, that is, the effect of preventing the powder from rubbing off and the effect of preventing secondary adhesion cannot be sufficiently obtained. On the other hand, if the amount exceeds 30% by weight, the filming feeling of the film forming agent becomes strong. It is inferior in feeling and is not preferable.

In the present invention, in addition to the above-mentioned components, it is preferable to add an ultraviolet scattering agent in order to further enhance the ultraviolet protection effect on the skin. Examples of the ultraviolet scattering agent include titanium oxide, zinc oxide, cerium oxide, iron oxide, mica and the like. There is no particular limitation on the particle size and the like as long as they have an ultraviolet protection effect. Further, there is no particular problem even if a composite treatment such as alumina treatment, various surface treatments such as hydrophobization treatment with silicon or fatty acid, or coated mica obtained by coating mica or the like with titanium oxide or the like is performed. The blending amount of this ultraviolet scattering agent is preferably 1 to 20% by weight, more preferably 5 to 1 based on the total amount of the cosmetic of the present invention in order to more effectively exert the ultraviolet protective effect on the skin.
0% by weight.

A nonionic surfactant is preferably used as an emulsifier used to prepare a W / O type emulsion preparation in the present invention. Among them, an HLB value of 2 to 1 is preferred.
6, especially 3 to 12, are preferable. Examples of such agents include ethylene oxide addition type surfactants and polyhydric alcohol fatty acid ester type surfactants.

Specific examples of the ethylene oxide addition type surfactant include polyoxyethylene in an amount of 2 to 30 moles [hereinafter abbreviated as "POE (2 to 30)" and the like] oleyl ether, POE (2 to 35) stearyl ether. , PO
E (2-20) lauryl ether, POE (1-20)
Alkyl phenyl ether, POE (6-18) behenyl ether, POE (5-25) 2-decyl pentadecyl ether, POE (3-30) 2-decyl tetradecyl ether, POE (8-16) 2-octyl decyl ether Ether type surfactants such as POE (4-60)
Hydrogenated castor oil, POE (3-14) fatty acid monoester, POE (6-30) fatty acid diester, POE (5
To 20) ester type surfactants such as sorbitan fatty acid ester; POE (2 to 30) glyceryl monoisostearate, POE (10 to 60) glyceryl triisostearate, POE (7 to 50) hydrogenated castor oil monoisostear Examples thereof include ether ester type surfactants such as rate, POE (12 to 60) hydrogenated castor oil triisostearate, and the like.

Specific examples of the polyhydric alcohol fatty acid ester type surfactant include polyglycerin fatty acid esters such as decaglyceryl tetraoleate, hexaglyceryl triisostearate, tetraglyceryl diisostearate and diglyceryl isostearate. , Glyceryl monostearate, glyceryl monoisostearate, glyceryl fatty acid ester such as glyceryl monooleate, and the like.

In the present invention, among these, polyglycerin fatty acid esters of diglycerin or more such as decaglyceryl tetraoleate, hexaglyceryl triisostearate, tetraglyceryl diisostearate, diglyceryl isostearate; POE (2-12) ) Oleyl ether, POE (3-12) stearyl ether, PO
E (2-10) lauryl ether, POE (2-10)
Nonyl phenyl ether, POE (6-15) behenyl ether, POE (5-20) 2-decyl pentadecyl ether, POE (5-17) 2-decyl tetradecyl ether, POE (8-16) 2-octyl decyl ether POE-added ether type surfactants such as POE (1
0-20) hydrogenated castor oil, POE (5-14) oleic acid monoester, POE (6-20) oleic acid diester, POE (5-10) sorbitan oleic acid ester and other POE addition ester type surfactants; POE (3 ~
15) Glyceryl monoisostearate, POE (10
~ 40) Nonionic surfactants such as POE-added ether ester type surfactants such as glyceryl triisostearate are particularly preferably used. Further, polyoxyalkylene-modified oreganopolysiloxane or the like may be used. These emulsifiers may be used alone or in combination of two or more.

The water-in-oil type sunscreen cosmetics of the present invention include
Various components generally used in cosmetics, pharmaceuticals and the like can be added within a range that does not impair the effects of the present invention. Examples of such components include vitamins, fats and oils, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, silicones, humectants, anionic surfactants,
Cationic surfactant, amphoteric surfactant, lipophilic nonionic surfactant, hydrophilic nonionic surfactant, preservative, antiphlogistic, whitening agent, plant extract, activator, blood circulation promoter, antiseborrheic agent , Natural water-soluble polymer, semi-synthetic water-soluble polymer, synthetic water-soluble polymer, inorganic water-soluble polymer, thickener, powder component,
Examples include sequestering agents for metal ions.

The vitamins include vitamin A such as vitamin oil, retinol and retinol acetate; vitamin B ₂ such as riboflavin, riboflavin butyrate and flavin adenine nucleotide; vitamin B ₆ such as pyridoxine hydrochloride and pyridoxine dioctanoate. Kinds; L-ascorbic acid, L-ascorbic acid dipalmitate,
L-ascorbic acid-2-sodium sulfate, L-ascorbic acid phosphoric acid ester, DL-α-tocopherol-
Vitamin Cs such as dipotassium L-ascorbic acid diester phosphate; pantothenic acids such as calcium pantothenate, D-pantothenyl alcohol, pantothenyl ethyl ether and acetyl pantothenyl ethyl ether; vitamin D such as ergocalciferol and cholecalciferol Nicotinic acids such as nicotinic acid, nicotinamide, benzyl nicotinate; α-tocopherol, tocopherol acetate, DL-α-tocopherol nicotinate;
Vitamin Es such as DL-α-tocopherol succinate;
Vitamin P; biotin and the like are exemplified.

Examples of fats and oils include avocado oil, camellia oil, evening primrose oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern oil, castor oil. , Linseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnamon oil, Japanese tallow oil, jojoba oil, germ oil, triglycerin,
Liquid fats and oils such as glycerin trioctanoate and glycerin triisopalmitate; cocoa butter, coconut oil, horse fat, hardened coconut oil, palm oil, beef tallow, sheep fat, hardened beef tallow, palm kernel oil,
Examples include solid fats such as lard, beef bone fat, molle kernel oil, hydrogenated oil, beef leg fat, molle, and hydrogenated castor oil.

Examples of the waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ivota wax, whale wax, montan wax, nuka wax, lanolin, capock wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, and reduction. Lanolin, jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether, PO
E Lanolin Alcohol Acetate, POE Cholesterol Ether, Lanolin Fatty Acid Polyethylene Glycol,
Examples include POE hydrogenated lanolin alcohol ethers.

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

As the higher fatty acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, 12-hydroxystearic acid,
Undecylenic acid, tall acid, isostearic acid, linoleic acid, linoleic acid, eicosapentaenoic acid (EP
A) and docosahexaenoic acid (DHA).

The higher alcohols include straight chain alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol and cetostearyl alcohol; monostearyl glycerin ether (batyl alcohol), 2-decyltetradecinol, Examples thereof include branched chain alcohols such as lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, and octyldodecanol.

As synthetic ester oils, isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate,
Decyl oleate, hexyl decyl dimethyl octoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate,
Cholesteryl 2-hydroxystearylate, ethylene glycol di-2-ethylhexylate, fatty acid ester of dipentaerythritol, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate Trimethylolpropane tri-2-ethylhexylate, trimethylolpropane triisostearate, pentaneerythritol tetra-2-ethylhexylate, glycerin tri-2-ethylhexylate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2 -Ethylhexyl palmitate, glyceryl trimmyristate, tri-2-
Heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleic acid oil, cetostearyl alcohol, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester,
Di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, succinic acid 2 -Ethylhexyl, ethyl acetate,
Examples include butyl acetate, amyl acetate, triethyl citrate and the like.

As the silicone, a chain polysiloxane such as dimethylpolysiloxane, methylphenylpolysiloxane and methylhydrogenpolysiloxane; a cyclic polysiloxane such as decamethylpolysiloxane, dodecamethylpolysiloxane and tetramethyltetrahydrogenpolysiloxane. Examples thereof include silicone resin and silicone rubber which form a three-dimensional network structure.

Examples of moisturizers include polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, hexylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-. 12-hydroxystearate, sodium lactate, bile salt, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, Issai rose extract, Astragalus membranaceus extract, Merrilot extract, etc. It is illustrated.

As the anionic surfactant, a base material for soap, fatty acid soap such as sodium laurate, sodium palmitate and the like; higher alkyl sulfate ester salt such as sodium lauryl sulfate and potassium lauryl sulfate; PO
Alkyl ether sulfates such as E-lauryl sulfate triethanolamine and POE sodium lauryl sulfate;
N-acyl sarcosine acids such as sodium lauroyl sarcosine; higher fatty acid amide sulfonates such as N-myristoyl-N-methyl taurine sodium, coconut oil fatty acid methyl tauride sodium, sodium lauryl methyl tauride; POE sodium oleyl ether phosphate; Phosphoric acid ester salts such as POE stearyl ether phosphoric acid; sulfosuccinates such as sodium di-2-ethylhexylsulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate; linear dodecylbenzenesulfonic acid Alkyl benzene sulfo such as sodium, linear dodecyl benzene sulfonic acid triethanolamine, linear dodecyl benzene sulfonic acid, etc. Acid salts; N-acyl glutamates such as monosodium N-lauroylglutamate, disodium N-stearoylglutamate and monosodium N-myristoyl-L-glutamate; higher fatty acid ester sulfates such as hydrogenated coconut oil fatty acid sodium glycerin sulfate; In addition to sulfated oils such as funnel oil, POE 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 monoethanolamide succinate, N-palmitoyl aspartate ditriethanolamine, sodium caseinate, sodium dodecane-1,2-diol acetate ether, maltitol And hydroxyalkyl (C ₁₂ , C ₁₄ ) ethers.

Examples of the cationic surfactant include alkyl trimethyl ammonium salts such as stearyl trimethyl ammonium chloride and lauryl trimethyl ammonium chloride;
Distearyl dimethyl ammonium chloride dialkyl dimethyl ammonium chloride, poly (N, N'-dimethyl-chloride)
3,5-methylenepiperidinium), alkylpyridinium salts such as cetylpyridinium chloride, alkyl quaternary ammonium salts, alkyldimethylbenzylammonium salts, alkylisoquinolinium salts, dialkylmorphonium salts, POE alkylamines, Examples thereof include an alkylamine salt, a polyamine fatty acid derivative, an amyl alcohol fatty acid derivative, benzalkonium chloride, and benzethonium chloride.

As the amphoteric surfactant, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) is used.
Imidazoline amphoteric surfactants such as 2-imidazoline sodium and 2-cocoyl-2-imitazolinium hydroxide-1-carboxyethyloxy disodium salt; 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazo Examples include betaine surfactants such as rhinium betaine, lauryl dimethylaminoacetic acid betaine, alkyl betaine, amido betaine and sulfobetaine.

As the lipophilic nonionic surfactant, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, penta-. Two
Sorbitan fatty acid esters such as diglycerol sorbitan ethylhexylate and diglycerol sorbitan tetra-2-ethylhexylate; glycerin mono-cottonseed oil fatty acid, glyceryl monoerucate, glycerin sesquioleate, glyceryl monostearate, α, α'-pyrooleate Glycerin polyglycerin fatty acids such as glyceryl glutamate and glyceryl monostearate; propylene glycol fatty acid esters such as propylene glycol monostearate; hydrogenated castor oil derivatives, glycerin alkyl ether, and polyoxyethylene methylpolysiloxane Coalescence is exemplified.

As the hydrophilic nonionic surfactant, PO is used.
E sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, PO
POE sorbitan fatty acid esters such as E-sorbitan tetraoleate; POE sorbit fatty acid esters such as POE-sorbit monolaurate, POE-sorbit monooleate, POE-sorbit pentaoleate, POE-sorbit monostearate; PO
POE glycerin fatty acid esters such as E-glycerin monostearate, POE-glycerin monoisostearate, POE-glycerin triisostearate;
POE fatty acid esters such as OE monooleate, POE distearate, POE monodioleate, ethylene glycol cysteate; POE lauryl ether;
POE oleyl ether, POE stearyl ether,
POE alkyl ethers such as POE behenyl ether, POE2-octyldodecyl ether, POE cholestanol ether; POE octylphenyl ether;
POE alkylphenyl ethers such as POE nonyl phenyl ether and POE dinonyl phenyl ether; Pluronic types such as Bourronic; POE / POP cetyl ether, POE / POP 2-decyl tetradecyl ether, POE / POP monobutyl ether, POE
-POE hydrogenated lanolin, POE-POP alkyl ethers such as POE-POP glycerin ether; tetra-POE-tetra-POP ethylenediamine condensates such as tetronic; POE castor oil, POE hardened castor oil, PO
E-hardened castor oil monoisostearate, POE-hardened castor oil triisostearate, POE-hardened castor oil monopyroglutamic acid monoisostearate diester, PO
POE castor oil hardened castor oil derivatives such as E-hardened castor oil maleic acid; POE beeswax lanolin derivatives such as POE sorbitol beeswax; alkanolamides such as coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, and fatty acid isopropanolamide;
Propylene glycol fatty acid ester, POE alkylamine, POE fatty acid amide, sucrose fatty acid ester,
Examples include POE nonylphenylformaldehyde condensate, alkylethoxydimethylamine oxide, and trioleyl phosphoric acid.

Examples of preservatives include ethylparaben and butylparaben.

Examples of anti-inflammatory agents include glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, and allantoin.

Examples of the whitening agent include placenta extract, glutathione, and Yukinoshita extract.

Examples of the plant extract include psyllium, laurel, cycon, peony, assembly, birch, sage,
Loquats, carrots, aloe, mallow, iris, grapes, yochinin, loofah, lily, saffron, senkyu, shokukyu, hypericum, ononis, rosemary, garlic, capsicum, chimpi, touki, seaweed,
An extract such as tea is exemplified.

Examples of the activator include royal jelly, photosensitizer, cholesterol derivative, calf blood extract and the like.

Examples of the blood circulation promoter include nonyl acid warenylamide, nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, zingerone, cantharitin tincture, ictamol, caffeine, tannic acid, α-borneol, nicotinic acid tocopherol, Inositol hexanicotinate, cyclanderate, cinnarizine, tolazoline, acetylcholine, verapamil, cepharanthin, γ-oryzanol and the like are exemplified.

Examples of antiseborrheic agents include sulfur and thiantol.

Examples of natural water-soluble polymers include araavia gum, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), arge colloid (cassius extract), starch (rice, corn,
Plant-based water-soluble polymers such as potato, wheat) and glycyrrhizic acid; Microbial water-soluble polymers such as xanthan gum, dextran, succinoglucan, and burlan; Animal-based water-soluble polymers such as collagen, casein, albumin, and gelatin Is exemplified.

Examples of the semi-synthetic water-soluble polymer include starch-based water-soluble polymers such as carboxymethyl starch and methyl hydroxypropyl starch; methyl cellulose, nitrocellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl. cellulose,
Cellulose-based water-soluble polymers such as sodium carboxymethylcellulose (CMC), crystalline cellulose and cellulose powder; alginic acid-based water-soluble polymers such as sodium alginate and propylene glycol alginate;

As the synthetic water-soluble polymer, polyvinyl water-soluble polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone and carboxyvinyl polymer (Carbopol); polyethylene glycol 2
50,000, 4,000,000, 600,000
Polyoxyethylene-based water-soluble polymers such as; polyoxyethylene-polyoxypropylene copolymers and other copolymer-based water-soluble polymers; sodium polyacrylate, polyethyl acrylate, polyacrylamide and other acrylic water-soluble polymers Other examples include polyethyleneimine and cationic polymers.

Examples of the inorganic water-soluble polymer include bentonite, AlMg silicate (veegum), laponite, hectorite, and silicic acid anhydride.

As the thickener, gum arabic, carrageenan, karaya gum, tragacanth gum, carob gum,
Quince seed (quince), casein, dextrin, gelatin, sodium pectate, sodium alginate, methylcellulose, ethylcellulose, CM
C, hydroxyethyl cellulose, hydroxypropyl cellulose, PVA, PVM, PVP, sodium polyacrylate, carboxyvinyl polymer, locust bean gum, guar gum, tamarind gum, dialkyldimethylammonium cellulose sulfate, xanthan gum,
Examples thereof include aluminum magnesium silicate, bentonite, and hectorite.

As powder components, talc, carion, mica, sericite, muscovite, phlogopite, synthetic mica, phlogopite, biotite, lithia mica, permiculite,
Magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate metal salt, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (calculated gypsum), calcium phosphate, Fluorapatite, hydroxyapatite, ceramic powder, metallic soap (zinc myristate, calcium palmitate, aluminum stearate), inorganic powder such as boron nitride; polyamide resin powder (nylon powder), polyethylene powder, polymethylmethacrylate powder, polystyrene Powder, styrene-acrylic acid copolymer resin powder, benzoguanamine resin powder, polytetrafluoroethylene powder, organic powder such as cellulose powder; inorganic white such as titanium dioxide and zinc oxide Fee; iron oxide (red iron oxide),
Inorganic red pigments such as iron titanate; Inorganic brown pigments such as γ-iron oxide; Inorganic yellow pigments such as yellow iron oxide and ocher; Inorganic black pigments such as black iron oxide, carbon black and low order titanium oxide. Inorganic purple pigments such as mango violet and cobalt violet; inorganic green pigments such as chromium oxide, chromium hydroxide and cobalt titanate; inorganic blue pigments such as ultramarine blue and navy blue; titanium oxide coated mica, titanium oxide coated oxychloride Pearl pigments such as bismuth, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil; aluminum powder,
Metal powder pigments such as copper powder; Red 201, Red 202, Red 204, Red 205, Red 220
No. Red 226, Red 228, Red 405, Orange 203, Orange 204, Yellow 205, Yellow 401
No. 3, blue 404 and the like; red No. 3, red 104
No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3, Blue No. 1, etc. Organic pigments lacquered with zirconium, barium or aluminum; and natural pigments such as chlorophyll and β-caroline.

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

In addition to fragrance, water and alcohol, coloring agents such as titanium yellow, carsamine, safflower red and the like can be appropriately blended if necessary.

[0058]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention. In addition, unless otherwise specified, the evaluation method adopted in each example will be described prior to the example shown in% by weight.

[Evaluation of sunburn prevention effect] Special panel 20
According to the name, the samples were used on sunny days in June and July when the ultraviolet rays were strong, and the sunburn preventing effect was evaluated. (Evaluation) ◎: 16 or more out of 20 answered as good ○: 12 or more out of 20 answered as good △: 6 or more out of 20 answered as good ×: Less than 6 out of 20 answered good Answer [Expansion] (Expanded) Each example was given to a specialized panel (50 people)
The cosmetics (sample) of the comparative example were used, and sensory evaluation (comprehensive evaluation) was performed. (Evaluation) ◎: Very good spread ○: Good spread Δ: Not so good ×: Poor spread

[Secondary Adhesiveness] The cosmetics (samples) of Examples and Comparative Examples were applied to the upper arm, and after 5 minutes, a glass plate was pressed to observe the adhered state of the powder in the sample. Adhesion was evaluated. (Evaluation) ⊚: No sample adhered to the glass plate ◯: Almost no sample adhered to the glass plate Δ: Sample slightly adhered to the glass plate ×: Sample considerably adhered to the glass plate <Example> Example 1 (W / O cream) (Ingredient) (wt%) (1) Decamethylcyclopentasiloxane 30 (2) Silicone resin 0.1 (3) Cetyl isooctanoate 2 (4) Polyoxyethylene / methyl polysiloxane copolymer 2 (5) Vitamin E acetate 0.05 (6) Parabens in proper amount (7) Perfume in proper amount (8) Organically modified clay mineral (Benton 38) 1 (9) Hydrophobization Treated titanium oxide 20 (10) Nylon powder 12 (11) Hydrophobized talc 8 (12) Dipropylene glycol 5 (13) EDTA.3Na.2H ₂ O 0.1 (14) Purified water Residual production method (1) to ( 8) is heated to 70 ° C. and dissolved, and (9) to (1
1) was added and dispersed and mixed with a disper. (12)-(1
4) were mixed, heated to 70 ° C., gradually added to the oil phase while stirring with a disper, and mixed and stirred sufficiently uniformly and cooled.

Evaluation Sun protection effect: ⊚, feeling of use (spreading): ⊚, secondary adhesion: Δ.

Example 2 (W / O emulsion) (Compounding ingredients) (wt%) (1) Octamethylcyclotetrasiloxane 50 (2) Liquid paraffin 3 (3) Polyoxyethylene-methylpolysiloxane copolymer 3 ( 4) Silicone resin 10 (5) Distearyldimethylammonium chloride 0.15 (6) Vitamin E acetate 0.02 (7) Paraben proper amount (8) Perfume proper amount (9) Spherical polyethylene powder 2 (10) Hydrophobized talc 5 (11) Hydrophobized zinc oxide 10 (12) Glycerin 4 (13) Water-swelling clay mineral (trade name: Smecton) 0.35 (14) Sodium hexametaphosphate 0.03 (15) Purified water Residual production method (1) ~ (8) is dissolved by heating to 70 ° C,
1) was added and dispersed and mixed with a disper. (12) to (1
Wet 3), mix (14) and (15), 70 ° C
The mixture was heated to 0, gradually added to the oil phase while stirring with a disper, and mixed and stirred sufficiently uniformly and cooled.

Evaluation Sun protection effect: ⊚, feeling of use (spreading): ⊚, secondary adhesion: ⊚.

Example 3 (W / O cream) (Ingredient) (% by weight) (1) Light isoparaffin 2 (2) Decamethylcyclopentasiloxane 18 (3) Glyceryl monooleate 1.5 (4) Diglyceryl di Isostearate 2.1 (5) Distearyldimethylammonium chloride 0.05 (6) Squalane 5 (7) Polymer dimethylpolysiloxane (20000cs) 0 (8) Paraben proper amount (9) Perfume proper amount (10) Trimethylsilsesqui Oxane powder 10 (trade name: Tospearl 145) (11) Hydrophobized titanium oxide 2 (12) 1,3-butylene glycol 7 (13) Montmorillonite (trade name: Kunipia G-4) 0.05 (14) Glycyrrhizin Dipotassium acid 0.05 (15) EDTA / 3Na / 2H ₂ O 0.05 ( 16) Purified water The residual production methods (1) to (9) are heated and dissolved at 70 ° C., and (10) and (1)
1) was added and dispersed and mixed with a disper. (12) to (1
3) Wet, mix with (14)-(16), 70 ° C
The mixture was heated to 0, gradually added to the oil phase while stirring with a disper, and mixed and stirred sufficiently uniformly and cooled.

Evaluation Sun protection effect: △, feeling of use (spreading): ○, secondary adhesion: ○.

Example 4 (W / O emulsion) (blending component) (% by weight) (1) Decamethylcyclopentasiloxane 20 (2) Octamethylcyclotetrasiloxane 22 (3) Methylpolysiloxane 4 (4) POE glycerol Triisostearate 1.5 (5) Organically modified clay mineral (Bendon 38) 1.5 (6) Silicone resin 5 (7) Vitamin E acetate 0.05 (8) Paraben appropriate amount (9) Perfume appropriate amount ( 10) Hydrophobicized zinc oxide 5 (11) Polymethylmethacrylate powder 1 (12) Glycerin 5 (13) Polyethylene glycol (molecular weight 6000) 0.2 (14) Purified water Residual production method (1) to (9) 70 It was melted by heating at ℃ and dispersed and mixed by a disper. (10) to (11) were added and the mixture was dispersed and mixed again using a disper. (12) to (13) are dissolved, and (1
4) was added and the mixture was heated to 70 ° C., gradually added to the oil phase while stirring with a disper, and mixed and stirred sufficiently uniformly and cooled.

Evaluation Sun protection effect: ◯, feeling of use (spreading): ◯, secondary adhesion: ◯.

Example 5 (W / O cream) (Ingredient) (% by weight) (1) Decamethylcyclopentasiloxane 60 (2) Cetylisooctanoate 8 (3) Vaseline 2 (4) Solid paraffin 5 (5) Distearyldimethylammonium chloride 0.5 (6) Polyoxyethylene / methylpolysiloxane copolymer 3 (7) Polyvinylpyrrolidone-eicosene derivative 20 (8) Paraben proper amount (9) Perfume proper amount (10) Hydrophobization Treated zinc oxide 2.0 (11) Spherical polyethylene powder 0.5 (12) 1,3-butylene glycol 8.0 (13) Water-swelling clay mineral (trade name: Smecton) 0.8 (14) Purified water residue The remaining production methods (1) to (9) are heated and dissolved at 70 ° C., and (10) to (1
1) was added and dispersed and mixed with a disper. (12) to (1
3) Wet, mix with (14), heat to 70 ° C.,
The mixture was gradually added to the oil phase while stirring with a disper, and the mixture was stirred and cooled sufficiently uniformly.

Evaluation Sun protection effect: △, feeling of use (spreading): ○, secondary adhesion: ◎.

Example 6 (W / O cream) (Ingredient) (% by weight) (1) Decamethylcyclopentasiloxane 25 (2) Cetylisooctanoate 5 (3) Polyoxyethylene / methylpolysiloxane copolymer Combined 1 (4) Silicone Resin 20 (5) Vitamin E Acetate 0.01 (6) Paraben Suitable amount (7) Perfume Suitable amount (8) Organically modified clay mineral (Benton 38) 2 (9) Nylon powder 8 (10 ) Hydrophobized talc 2 (11) Dipropylene glycol 5 (12) EDTA.3Na.2H ₂ O 0.5 (13) Purified water Residual production methods (1) to (8) were dissolved by heating at 70 ° C., (9) ), (1
0) was added and dispersed and mixed by a disper. (11)-(1)
3) was mixed, heated to 70 ° C., gradually added to the oil phase while stirring with a disper, and mixed and stirred sufficiently uniformly and cooled.

Evaluation Sun protection effect: Δ, feeling of use (spreading): Δ, secondary adhesion: ⊚.

Comparative Example 1 (W / O emulsion) (blending component) (% by weight) (1) Octamethylcyclotetrasiloxane 35 (2) Liquid paraffin 3 (3) Polyoxyethylene-methylpolysiloxane copolymer 3 ( 4) Distearyldimethylammonium chloride 0.4 (5) Vitamin E acetate 0.05 (6) Paraben proper amount (7) Perfume proper amount (8) Spherical polyethylene powder 3 (9) Hydrophobized zinc oxide 1 (10) Glycerin 3 (11) Water-swelling clay mineral (trade name: smecton) 0.4 (12) Sodium hexametaphosphate 0.05 (13) Purified water Residual production method : (1) to (7) are heated and dissolved at 70 ° C., ( 8) and (9) were added and dispersed and mixed by a disper. Wet (11) with (10), mix (12) and (13), and
The mixture was heated to 0 ° C., gradually added to the oil phase while stirring with a disper, and mixed and stirred sufficiently uniformly and cooled.

Evaluation Sun protection effect: Δ, feeling of use (spreading): ×, secondary adhesion: ×.

[0074]

As described above in detail, according to the present invention, an ultraviolet protective agent is not added and the ultraviolet protective effect is excellent, the safety to the skin is high, and the "spread" when applied on the skin. It has the effect of providing a sunscreen cosmetic which is light in weight, has excellent feeling in use, and has an excellent effect of preventing secondary adhesion of powder components contained in the base.

Claims (3)

[Claims] 1. A water-in-oil type sunscreen cosmetic containing no ultraviolet absorber, which comprises a volatile component, an organically modified clay mineral, a spherical resin powder and a film forming agent. 2. A volatile component of 20 to 60 in the total amount of cosmetics.
% By weight, 0.1 to 1.5% by weight of organically modified clay mineral, 0.5 to 20% by weight of spherical resin powder and 0.1% by weight of film-forming agent.
The water-in-oil type sunscreen cosmetic containing no ultraviolet absorber according to claim 1, which is contained in an amount of -30% by weight. 3. A water-in-oil type sunscreen cosmetic containing no ultraviolet absorber according to claim 1, which further comprises an ultraviolet scattering agent.