JPH08259424A - Water-in-oil type emulsion preparation - Google Patents

Abstract

PURPOSE: To obtain the water-in-oil type emulsion preparation containing an UV light absorber and a liquid fatty acid, and excellent in stability without deteriorating safety required for a skin external preparation. CONSTITUTION: The preparation contains an UV light absorber in an amount of >=0.5wt.% based on the whole amount of the emulsion preparation and a liquid fatty acid (e.g. palmitoleic acid) in an amount of 0.1-5wt.% as active ingredients. The preparation is further suitably compounded with an oiling agent, a humectant, a surfactant, a medicine-coloring agent, a powdery material, a perfume, etc., which are generally used for cosmetics, and subsequently prepared into a cosmetic, etc. The further addition of the liquid fatty acid to the W/O emulsion preparation containing the UV light absorber improves the stability of the base agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-in-oil emulsion preparation, and more particularly to a water-in-oil emulsion preparation having excellent stability without impairing the safety as an external preparation for skin.

[0002]

2. Description of the Related Art Water-in-oil (W / O) emulsion preparations are superior in water resistance and sweat resistance to oil-in-water (O / W) emulsion preparations. In the external preparation for the skin, which is a sun care product such as corn, a W / O emulsion formulation is generally advantageously used.

However, when a W / O emulsified preparation is used as a skin external preparation, it is more difficult to stabilize the base as compared with the O / W emulsified preparation, and in particular, when an oil-soluble component such as an ultraviolet absorber is added, There was a problem that stability deteriorated extremely. Therefore, it was difficult to expand the application to products.

From these circumstances, it has been strongly desired to develop a highly stable W / O emulsion formulation containing a UV absorber without impairing the safety as an external preparation for skin. It was

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a W / O emulsion formulation containing an ultraviolet absorber, which is excellent in stability and does not impair safety as an external preparation for skin. An object of the present invention is to provide a W / O emulsion preparation having properties.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned conventional problems, the present inventors further added a liquid fatty acid to a W / O emulsion containing an ultraviolet absorber. As a result, they have found that the above object can be achieved, and have completed the present invention based on this finding.

That is, according to the present invention, there is provided a W / O emulsified preparation characterized by containing an ultraviolet absorber and a liquid fatty acid.

The W / O emulsion preparation of the present invention will be described in detail below.

The liquid fatty acid used in the present invention can be used without particular limitation as long as it is a liquid fatty acid at room temperature, and examples thereof include fatty acids having 8 to 18 carbon atoms, but are not limited thereto. Not something. Specific examples include 2-ethylhexanoic acid, undecylenic acid, palmitooleic acid, isostearic acid, ricinoleic acid, linoleic acid, and oleic acid. Among them, palmitooleic acid, isostearic acid, linoleic acid, Oleic acid and the like are preferably used. These may use 1 type, or may use 2 or more types.

The liquid fatty acid content is preferably 0.1 to 5.0% by weight, more preferably 0.5 to 3.0% by weight, based on the total weight of the emulsion preparation. When the amount of the liquid fatty acid is less than 0.1% by weight, it is difficult to stabilize the W / O emulsion formulation which is destabilized by the addition of the ultraviolet absorber. On the other hand, even if the amount of the liquid fatty acid compounded exceeds 5.0% by weight, no further effect on the stabilization of the W / O emulsion can be expected.

The ultraviolet absorber used in the present invention is not particularly limited as long as it can be generally used in cosmetics. Specifically, para-aminobenzoic acid (hereinafter referred to as “P
Abbreviated as "ABA"), PABA monoglycerin ester,
N, N-dipropoxy PABA ethyl ester, N, N
-Diethoxy PABA ethyl ester, N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA
Benzoic acid-based UV absorbers such as butyl ester and N, N-dimethyl PABA methyl ester; homomenthyl-N-
Anthranilic acid type UV absorbers such as acetylanthranilate; amyl salicylate, menthyl salicylate,
Salicylic acid ultraviolet absorbers such as homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate; octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, 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-
Cinnamic acid-based UV absorbers such as α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, and glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate; [3 -Bis (trimethylsiloxy) methylsilyl-1-methylpropyl] -3,4,5-trimethoxycinnamate, [3
-Bis (trimethylsiloxy) methylsilyl-3-methylpropyl] -3,4,5-trimethoxycinnamate
[3-bis (trimethylsiloxy) methylsilylpropyl] -3,4,5-trimethoxycinnamate,
[3-bis (trimethylsiloxy) methylsilylbutyl] -3,4,5-trimethoxycinnamate, [3-
Tris (trimethylsiloxy) silylbutyl] -3,
4,5-trimethoxycinnamate, [3-tris (trimethylsiloxy) silyl-1-methylpropyl]-
Silicone-based cinnamic acid UV absorbers such as 3,4-dimethoxycinnamate; 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4, 4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxy Benzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-
4-n-octoxybenzophenone, 4-hydroxy-
Benzophenone-based UV absorbers such as 3-carboxybenzophenone; 3- (4′-methylbenzylidene) -d,
l-camphor, 3-benzylidene-d, l-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-butyldibenzoylmethane, 5- (3,3'-dimethyl-2-
Examples thereof include, but are not limited to, norbornylidene) -3-pentan-2-one; silicone-modified UV absorbers; and fluorine-modified UV absorbers.

The blending amount of these UV absorbers depends on the desired UV protection effect, but in the sense of containing the UV absorber in the present invention, it is 0.5% by weight or more in the total amount of the emulsion preparation. .

In the W / O emulsion preparation of the present invention, an oil agent generally used in cosmetics within a quantitative and qualitative range that does not impair the quality such as appearance stability and viscosity and does not impair the effects of the present invention, Moisturizer, surfactant, drug, colorant, powder,
Fragrances and the like can be added.

Examples of the oil agent 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, southern oil, castor oil, linseed oil. Natural vegetable oils such as oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, teaseed oil, kaya oil, rice bran oil, cinnamon oil, Japanese tung oil, jojoba oil, germ oil, etc .; triglycerin, glyceryl trioctanoate. , Liquid oils and fats such as glycerin triisopalmitate; cocoa butter, coconut oil, horse fat, hardened coconut oil, palm oil, beef tallow, sheep fat, hardened beef tallow, palm kernel oil, lard, beef butter, mokuro kernel oil, Animal and vegetable liquid oils and fats such as hydrogenated oil, beef tallow, mokuro, hydrogenated castor oil; beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ivota Cormorant, whale wax, montan wax, wax wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, reduced lanolin, jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate , Waxes such as POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether; hydrocarbon oils such as liquid paraffin, ozokerite, squalene, pristane, paraffin, ceresin, vaseline, microcrystalline wax; isopropyl myristate, octane Acid cetyl, octyldodecyl myristate, isopropyl palmitate, butyl stearate, lauric acid hex Le,
Myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearylate, ethylene glycol di-2-ethylhexylate, dipentaerythritol. Fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, diisostearyl malate,
Glycerin di-2-heptyl undecanoate, tri-2-
Trimethylol propane ethylhexylate, trimethylol propane triisostearate, pentane erythritol tetra-2-ethylhexylate, glyceryl tri-2-ethylhexylate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate,
2-ethylhexyl palmitate, glycerin trimyristate, 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, myristic acid Synthetic ester oils such as 2-hexyldecyl, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate; dimethylpolysiloxane. , Methylphenyl polysiloxane, methyl hydrogen polysiloxane decamethyl polysiloxane,
Examples thereof include silicone oils such as dodecamethylpolysiloxane and tetramethyltetrahydrogenpolysiloxane.

Examples of moisturizing ingredients 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 salt, dl-pyrrolidone carboxylate, short chain soluble collagen, diglycerin (EO) PO Examples thereof include adducts, Issai rose extract, Astragalus sinensis extract, Merrilot extract and the like.

Examples of the surfactant include amphoteric surfactants, lipophilic nonionic surfactants, hydrophilic nonionic surfactants, etc., but are not particularly limited as long as W / O emulsification is possible. Not a thing.

Of these, lipophilic nonionic surfactants include, for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate,
Sorbitan fatty acid esters such as sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, penta-2-ethylhexylate diglycerol sorbitan, tetra-2-ethylhexylate diglycerol sorbitan; monocotton oil fatty acid glycerin, Glycerin monoerucate,
Glycerin glycerin sesquioleate, glyceryl monostearate, glycerin α, α'-oleate pyroglutamate, glyceryl monostearate Malic acid and other glycerin glycerin fatty acids; Propylene glycol fatty acid esters such as propylene glycol monostearate; Oil derivatives; glycerin alkyl ether and the like.

Examples of the hydrophilic nonionic surfactant include POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan monooleate and P
POE sorbitan fatty acid esters such as OE sorbitan tetraoleate; POE sorbit monolaurate,
POE sorbit monooleate, POE sorbit pentaoleate, POE sorbit monostearate, and other POE sorbit fatty acid esters; PE glycerin monostearate, POE glycerin monoisostearate, POE glycerin triisostearate, and other Ps
OE glycerin fatty acid esters; POE monooleate, POE distearate, POE monodiolate,
POE fatty acid esters such as ethylene glycol distearate; POE lauryl ether, POE oleyl ether, POE stearyl ether, POE behenyl ether, POE 2-octyldodecyl ether, POE
POE alkyl ethers such as cholestanol ether; POE alkyl phenyl ethers such as POE octyl phenyl ether, POE nonyl phenyl ether, POE dinonyl phenyl ether; Pluronic types such as Bourronic; POE / POP cetyl ether,
POE / POP2-decyl tetradecyl ether, PO
POE such as E ・ POP monobutyl ether, POE ・ POP hydrogenated lanolin, POE ・ POP glycerin ether
・ POP alkyl ethers; Tetronic such as Tetra POE / Tetra POP ethylenediamine condensates; PO
E castor oil, POE hydrogenated castor oil, POE hydrogenated castor oil monoisostearate, POE hydrogenated castor oil triisostearate, POE hydrogenated castor oil monopyroglutamic acid monoisostearate diester, POE hydrogenated castor oil POE castor oil such as maleic acid Hydrogenated castor oil derivative; P
POE beeswax lanolin derivatives such as OE sorbit beeswax; alkanol amides such as coconut oil fatty acid diethanolamide, lauric acid monoethanolamide and fatty acid isopropanolamide; POE propylene glycol fatty acid ester; POE alkylamine; POE fatty acid amide; sucrose fatty acid ester; Examples include POE nonylphenylformaldehyde condensate; alkylethoxydimethylamine oxide; trioleylphosphoric acid and the like.

The powder used in the present invention is not particularly limited as long as it can be used in general cosmetics. Specifically, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc. In addition to the organic powder, the silicon powder such as trimethylsilsesquioxane powder, various inorganic powders and metal powders are exemplified. Examples of these powder components include talc, kaolin, 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, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (calculated gypsum), calcium phosphate, fluoroapatite, hydroxyapatite, ceramic powder, metal soap (zinc myristate, calcium palmitate, stearic acid) Aluminum, etc.), inorganic powders such as boron nitride; inorganic white pigments such as titanium dioxide and zinc oxide; inorganic red pigments such as iron oxide (red iron oxide) and iron titanate; inorganic brown pigments such as γ-iron oxide; yellow. Inorganic yellow pigments such as iron oxide and loess; inorganic black pigments such as black iron oxide, carbon black, and lower titanium oxide; mango violet,
Inorganic purple pigments such as baltic violet; chromium oxide,
Inorganic green pigments such as chromium hydroxide and cobalt titanate;
Inorganic blue pigments such as ultramarine blue and dark blue; pearl pigments such as titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride and fish scale foil;
Metal powder pigments such as aluminum powder and copper powder; Red No. 201, Red No. 202, Red No. 204,
Red 205, Red 220, Red 226, Red 22
No. 8, Red No. 405, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401, Blue No. 404 and other organic pigments; Red No. 3, Red No. 104, Red No. 106, Red No. 22
Zirconium such as No. 7, 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, and Blue No. 1,
Organic pigments such as barium or aluminum lake; natural pigments such as chlorophyll and β-carotene. In the present invention, any of these powder components that have been hydrophobized or untreated may be used. The hydrophobic treatment method may be any method as long as it can impart water repellency, and the method is not limited, and examples thereof include a gas phase method, a liquid phase method,
Usual surface treatment methods such as autoclave method and mechanochemical method can be used.

One kind of these hydrophobic powders may be used,
Alternatively, two or more kinds may be used. Further, the powder is not limited to the above components as long as it is a powder applicable to general cosmetics.

[0021]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

Samples having the compositions shown in the following Examples 1 to 6 and Comparative Example 1 were manufactured. The stability of each of these samples was evaluated according to the following evaluation criteria.

[Stability] Each sample was filled in a sample container, and after one month, the W / O emulsion formulation containing an ultraviolet absorber was visually observed to evaluate the degree of appearance stability.

Example 1 (Ingredients) (% by weight) Squalane 25.0 Cetylisooctanoate 5.0 Vaseline 2.0 Isostearic acid 1.0 Octylmethoxycinnamate 7.0 2-Hydroxy-4-methoxybenzophenone 2.0 4-tert-butyl-4′-methoxydibenzoylmethane 1.0 Dioctamethoxycinnamate monooctylglycerin 2.0 Vitamin E acetate 0.05 Fragrance Suitable amount Organically modified clay mineral (trade name: “Benton 38]) 0.2 POE glycerol triisostearate 1.5 glycerin 5.0 dipropylene glycol 3.0 polyethylene glycol (PEG6000) 1.0 EDTA-3Na · 2H ₂ O 0.1 methylparaben 0.1 ion-exchanged water Remnant

[0025] Except for not blended in Comparative Example 1 isostearic acid in the same composition component as in Example 1 to produce a sample of Comparative Example 1.

<Appearance Stability of Base, (1 month elapsed)> (45 ° C.) (35 ° C.) (RT) Example 1 ○ Good ○ Good ○ Good Comparative Example 1 × Separation △ Separation ○ Good

The appearance stability of each of the samples of Example 1 and Comparative Example 1 was evaluated according to the above evaluation criteria. As a result, in the sample of Example 1, it was found that the base material did not aggregate at all and the stability was good. On the other hand, in the sample of Comparative Example 1, the agglomeration of the base material did not occur at room temperature, but the base material was separated at a temperature condition exceeding room temperature and the stability was poor. That is, it was confirmed from Example 1 and Comparative Example 1 that the addition of isostearic acid (liquid fatty acid) contributed to the stability of the W / O emulsion formulation containing the ultraviolet absorber.

Example 2 (Ingredients) (wt%) Decamethylpentacyclosiloxane 25.0 Dimethylpolysiloxane (6CS) 10.0 Oleic acid 0.5 Isopropyl paramethoxycinnamate 5.0 Octylmethoxycinnamate 5 .0 Silicone resin 3.0 Polyoxyethylene / methylpolysiloxane copolymer 3.0 Stearyl glycyrrhetinate 0.1 Perfume Appropriate amount Nylon powder (Nylon SP-500) 5.0 Methylhydrogenpolysiloxane treatment Titanium oxide 7.0 1,3-butylene glycol 5.0 Phenoxyethanol 0.3 Ion-exchanged water Residual

Using the sample of Example 2, stability was evaluated according to the above evaluation criteria. As a result, it was found that the base did not aggregate at all and the stability was good.

Example 3 (Ingredients) (wt%) Solid paraffin 2.0 Microcrystalline wax 6.0 Liquid paraffin 19.3 Isopropyl palmitate 6.0 Isostearic acid 3.0 Octyl methoxycinnamate 0.5 2- Hydroxy-4-methoxybenzophenone 0.2 POE (10) glyceryl triisostearate 2.5 POE (5) hydrogenated castor oil 2.2 diglycerin trioleate 1.2 propylparaben 0.2 dibutylhydroxytoluene (BHT) 0. 05 Glycerin 8.0 Hyaluronic acid 0.05 Sorbit solution (70%) 5.0 Polyethylene glycol (PEG6000) 2.5 Purified water Residual

Using the sample of Example 3, stability was evaluated according to the above evaluation criteria. As a result, it was found that the base did not aggregate at all and the stability was good.

Example 4 (Ingredients) (wt%) Glyceryl monooleate 1.5 Diglyceryl diisostearate 2.1 Linoleic acid 2.0 3,4,5-Trimethoxycinnamic acid 4- [bis ( Trimethy 5.0 Lucyloxy) methylsilyl] -3-methylbutyl 4-tert-butyl-4′-methoxydibenzoylmethane 2.0 Organically modified clay mineral (trade name: “Benton 38”) 2.2 Solid paraffin 3.0 Vaseline 5.0 Isopropyl myristate 2.0 Liquid paraffin 8.0 Polydimethylpolysiloxane (20CS) 5.0 Vitamin E acetate 0.2 Butylparaben 0.2 Dibutylhydroxytoluene (BHT) 0.02 Glycerin 9.0 Propylene glycol 4.0 Purified water Residual

Using the sample of Example 4, stability was evaluated according to the above evaluation criteria. As a result, it was found that the base did not aggregate at all and the stability was good.

Example 5 (Ingredient) (wt%) Decamethylpentacyclosiloxane 25.0 Dimethylpolysiloxane (6CS) 5.0 Palmitooleic acid 5.0 Isopropyl paramethoxycinnamate 5.0 Octylmethoxycinna Mate 12.0 Silicone resin 5.0 Polyoxyethylene / methylpolysiloxane copolymer 4.0 Glyceryl glycyrrhetinate 0.05 Fragrance Suitable amount Trimethylsilsesquioxane powder 5.0 (trade name: "Tospearl 145") Hydrophobic Chemical treatment Titanium oxide (stearic acid treatment) 5.0 1,3-butylene glycol 5.0 Ethanol 3.0 Phenoxyethanol 0.2 Ion-exchanged water Residual

Using the sample of Example 5, stability was evaluated according to the above evaluation criteria. As a result, it was found that the base did not aggregate at all and the stability was good.

Example 6 (Ingredients) (wt%) Decamethylpentacyclosiloxane 29.9 Dimethylpolysiloxane (6CS) 5.0 Isostearic acid 0.1 Isopropyl paramethoxycinnamate 5.0 Octylmethoxycinnamate 12 0.0 Silicone resin 5.0 Polyoxyethylene / methylpolysiloxane copolymer 4.0 Glyceryl glycyrrhetinate 0.05 Perfume Appropriate amount Trimethylsilsesquioxane powder 5.0 (Brand name: "Tospearl 145") Hydrophobizing treatment Titanium oxide (stearic acid treatment) 5.0 1,3-butylene glycol 5.0 Ethanol 3.0 Phenoxyethanol 0.2 Ion-exchanged water Residual

Using the sample of Example 6, stability was evaluated according to the above evaluation criteria. As a result, it was found that the base did not aggregate at all and the stability was good.

[0038]

As described in detail above, according to the present invention, the stability of the base is improved by adding a liquid fatty acid to a W / O emulsion formulation containing an ultraviolet absorber. .

Claims (3)

[Claims] 1. A water-in-oil type emulsion preparation, which comprises an ultraviolet absorber and a liquid fatty acid. 2. The water-in-oil emulsion preparation according to claim 1, wherein the liquid fatty acid is at least one selected from palmitooleic acid, isostearic acid, linoleic acid, and oleic acid. 3. A liquid fatty acid is added in an amount of 0.1 in the total amount of the emulsion.
The water-in-oil emulsion preparation according to claim 1 or 2, wherein the water-in-oil emulsion preparation is contained in an amount of ˜5.0% by weight.