JPH1095706A - Emulsifying agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an emulsifying agent composition substantially not containing a surfactant, excellent in long-term stability of emulsification, having a feeling in use free from greasiness, by using a specific compound as an emulsifying agent in a system comprising a water-soluble polyhydric alcohol, water and an oily component. SOLUTION: This emulsifying agent composition comprises L-ascorbic acid and/or its derivative as an emulsifying agent. L-Ascorbyl palmitate, L-ascorbyl isopalmitate, etc., are used as L-ascorbic acid and Lascorbyl dipalmitate is especially preferable. The amount of the emulsifying agent blended is preferably about 0.001-2.0wt. A polyethylene glycol, propylene glycol, etc., may be used a watersoluble polyhydric alcohol containing two or more hydroxyl groups in the molecule and the amount of the alcohol is about 0.1-50.0wt.%. A linseed oil, coconut oil, cetyl octanoate, liquid paraffin, dimethylpolysiloxane, etc., are used as the oily component. The oil-in-water type emulsifying agent composition is also excellent in humectant effect and antioxidizing effect.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an emulsifier composition and an emulsifier composition using the emulsifier composition, and particularly has a refreshing feeling without using a surfactant.
The present invention relates to a cosmetic oil-in-water emulsion composition having excellent long-term stability.

[0002]

2. Description of the Related Art Conventionally, creams and emulsions emulsifying various oily and aqueous materials have been widely used as emulsifying compositions for cosmetics. In the production of such an emulsion composition, not only the raw materials are processed under various conditions strictly set, but also a surfactant may be used in order to guarantee the stability over time of the emulsion composition. Was required. However, in recent years, even higher safety is expected for cosmetics, and from this viewpoint, the presence of a surfactant may be a problem. Therefore, there is a method of obtaining a cosmetic emulsion composition by using an alkyl-modified water-soluble polymer without using a surfactant, but these emulsion compositions have large emulsified particles and long-term stability of emulsification. The properties were not always satisfactory, and there was a slimy feeling peculiar to the polymer.

[0003]

Means for Solving the Problems As a result of repeated studies to solve the above problems, the present inventors have found that the use of L-ascorbic acid and / or a derivative thereof as an emulsifier can improve the long-term stability of emulsification. It has been found that an emulsified composition having an excellent, non-sticky feeling in use can be obtained, and the present invention has been completed.

That is, the present invention relates to L-ascorbic acid and / or a derivative thereof, a water-soluble polyhydric alcohol having two or more hydroxyl groups in a molecule, and water of the same weight or less as the water-soluble polyhydric alcohol. And an oily component. This emulsifier composition is a polyhydric alcohol-in-oil type emulsifier composition and has excellent long-term stability.

Further, according to the present invention, L-ascorbic acid and / or a derivative thereof, a water-soluble polyhydric alcohol having two or more hydroxyl groups in the molecule, And an oil-in-water emulsified composition obtained by further mixing an emulsifier composition comprising an oil component and water. This oil-in-water emulsion composition is preferably used as an oil-in-water emulsion composition for cosmetics. The oil-in-water emulsion composition of the present invention is excellent in long-term stability and has high safety because it does not require the use of a surfactant.

The L-ascorbic acid and / or its derivative used in the present invention includes L-ascorbic acid,
Examples thereof include L-ascorbic acid alkyl ester, L-ascorbic acid phosphate ester, L-ascorbic acid sulfate ester, and the like. Specific examples thereof include L-ascorbyl palmitate, L-ascorbyl isopalmitate, and L-ascorbyl dipalmitate. L-ascorbyl stearate, L-ascorbyl isostearate, L-ascorbyl distearate, L-ascorbyl diisostearate, L-ascorbyl myristate, L-ascorbyl isomyristate, L-ascorbyl dimyristate, L-isomyristate L-ascorbic acid alkyl ethers such as ascorbyl, L-ascorbyl 2-ethylhexanoate, L-ascorbyl di-2-ethylhexanoate, L-ascorbyl oleate and L-ascorbyl dioleate; L Ascorbic acid-2-phosphate, L- ascorbic acid 3-phosphate ester, DL-
L-ascorbic acid phosphate such as α-tocopherol-2-L-ascorbic acid diester;
L-ascorbic acid sulfates such as ascorbic acid-2-sulfate and L-ascorbic acid-3-sulfate are exemplified. In the present invention, these salts can also be used, and alkali metal salts such as sodium salt and potassium salt, and alkaline earth metal salts such as calcium salt and magnesium salt are preferably used. These L-
Particularly preferred among ascorbic acid and / or derivatives thereof is L-ascorbyl dipalmitate.

[0007] The above-mentioned L-ascorbic acid or a derivative thereof can be obtained mainly by a known synthetic method, but it is also possible to use those obtained by other methods. Derivatives can be used. The amount of L-ascorbic acid and / or a derivative thereof as an emulsifier is determined in the total emulsified composition,
0.001 to 2.0% by weight, preferably 0.01 to 0.
6% by weight.

The water-soluble polyhydric alcohol having two or more hydroxyl groups in the molecule used in the present invention includes polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, hexylene glycol, glycerin, Examples include glycerin, xylitol, maltitol, maltose, sorbitol, polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside, and D-mannitol. The compounding amount of the water-soluble polyhydric alcohol is 0.1% in the whole emulsified composition.
It is 1 to 50.0% by weight, preferably 1.0 to 35.0% by weight.

As the oil component used in the present invention, various oil components commonly used in cosmetics as described below can be used.

As liquid oils and fats, linseed oil, camellia oil,
Macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, kyonin oil, cinnamon oil, jojoba oil, grape oil, sunflower oil, almond oil, rapeseed oil, sesame oil, wheat germ oil Rice germ oil, rice bran oil, cottonseed oil, soybean oil, peanut oil, teaseed oil, evening primrose oil, egg yolk oil, beef tallow, liver oil, triglycerin, trioctanoic acid glycerin, triisopalmitic acid glycerin and the like.

[0011] Examples of solid fats and oils include cocoa butter, coconut oil, palm oil, palm kernel oil, tallow, sheep fat, lard, horse fat, hardened oil, hardened castor oil, mocro, shea butter, and the like.

[0012] The waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, botaro wax, whale wax, montan wax, bran wax, lanolin,
There are reduced lanolin, hard lanolin, kapok wax, sugar cane wax, jojoba wax, shellac wax and the like.

Examples of ester oils include octanoic acid esters such as cetyl octanoate, lauric acid esters such as hexyl laurate, myristic acid esters such as isopropyl myristate and octyldodecyl myristate, palmitic acid esters such as octyl palmitate, and stearic acid. Stearic acid esters such as isocetyl acid, isostearic acid esters such as isopropyl isostearate, isopalmitic acid esters such as octyl isopalmitate,
Oleic acid esters such as isodecyl oleate, dioleyl oxalate, dimethyl malonate, diethyl malonate,
Dibutyl malonate, di-2-ethylhexyl malonate,
Di-2-ethyldecyl malonate, dihexyl succinate,
Diesters such as diisopropyl succinate, dihexyl succinate, dioleyl succinate, dioctyl succinate, dipropyl adipate, isopropyl adipate, diisobutyl adipate, di-2-heptylundecyl adipate, glyceryl trioctanoate, tetra-2-ethylhexyl Acid pentaerythritol.

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

Examples of the silicone include chain silicones such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. There are silicone resin, silicone rubber, and the like forming a three-dimensional network structure.

In the emulsified composition used in the present invention, various raw materials usually used for cosmetics can be used as other components.

The lower alcohol includes methanol, ethanol, propanol, isopropanol and the like.

Sterols include cholesterol, sitosterol, phytosterol, lanosterol and the like.

Examples of the humectant include water syrup, glucose, fructose, lactose, chondroitin sulfate, sodium hyaluronate, sodium adenosine phosphate, sodium lactate, bile salts, pyrrolidone carboxylic acid, in addition to the above-mentioned water-soluble polyhydric alcohols. Acid salts, glucosamine, cyclodextrin and the like.

As the water-soluble polymer, gum arabic, tragacanth, galactan, carob gum, guar gum,
Plant-based macromolecules such as karaya gum, carrageenan, pectin, agar, quince seed (quince), starch (rice, corn, potato, wheat), and alge colloid (brown algae extract); Molecules, collagen, casein, albumin, animal polymers such as gelatin, carboxymethyl starch, starch polymers such as methylhydroxypropyl starch, methylcellulose, nitrocellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, Hydroxypropyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose,
Cellulose polymers such as cellulose powder, alginic acid polymers such as sodium alginate and propylene glycol alginate, polyvinyl methyl ether, carboxyvinyl polymer (Carbopol (trade name) etc.)
Such as vinyl polymers, polyoxyethylene polymers, polyoxyethylene polyoxypropylene copolymer polymers, sodium polyacrylate, polyethyl acrylate, polyacrylamide and other acrylic polymers, polyethylene imine, cationic polymers, There are inorganic water-soluble polymers such as bentonite, aluminum magnesium silicate, laponite, hectorite, and silicic anhydride.

Examples of the ultraviolet absorber include benzoic acid-based ultraviolet absorbers such as para-aminobenzoic acid; anthranilic acid-based ultraviolet absorbers such as methyl anthranilate; salicylic acid-based ultraviolet absorbers such as octyl salicylate, phenyl salicylate and homomethyl salicylate; Isopropyl methoxycinnamate, octyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate, glyceryl mono-2-ethylhexanoate diparamethoxycinnamate, [4-bis (trimethylsiloxy) methylsilyl-3-methylbutyl Cinnamate-based ultraviolet absorbers such as 3,4,5, -trimethoxycinnamate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-
5-sulfonic acid, benzophenone-based ultraviolet absorbers such as sodium 2-hydroxy-4-ethoxybenzophenone-5-sulfonate, urocanic acid, ethyl urocanate,
2-phenyl-5-methylbenzoxazole, 2-
(2'-Hydroxy-5'-methylphenyl) benzotriazole, 4-tert-butyl-4'-methoxybenzoylmethane and the like.

Examples of the sequestering agent include alanine, sodium edetate, sodium polyphosphate, sodium metaphosphate, phosphoric acid and the like.

Examples of the neutralizing agent include 2-amino-2-methyl-1-propanol and 2-amino-2-methyl-1,3.
-Propanediol, potassium hydroxide, sodium hydroxide, triethanolamine, sodium carbonate and the like.

Examples of the pH adjuster include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dL-malic acid, potassium carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate and the like.

Examples of the antioxidant include α-tocopherol, dibutylhydroxytoluene, butylhydroxyanisole and the like.

Antibacterial agents include benzoic acid, salicylic acid,
Examples include phenolic acid, sorbic acid, paraoxybenzoate, parachloromethcresol, hexachlorophen, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, photosensitizer, phenoxyethanol and the like.

The drugs include vitamin A oil, retinol, retinol palmitate, inosit, pyridoxine hydrochloride, benzyl nicotinate, nicotinamide, DL-α-tocopherol nicotinate, magnesium ascorbate phosphate, vitamin D ₂ (ergocash Ferrol), dL-α-tocopherol, dL-α-tocopherol acetate, pantothenic acid, vitamins such as biotin,
Hormones such as estradiol and ethinyl estradiol, amino acids such as arginine, aspartic acid, cystine, cysteine, methionine, serine, leucine and tryptophan, allantoin, glycyrrhetinic acid, anti-inflammatory agents such as azulene, whitening agents such as arbutin, zinc oxide,
Astringents such as tannic acid; cooling agents such as L-menthol and camphor; sulfur, lysozyme chloride, pyridoxine hydrochloride, and γ-oryzanol.

As various kinds of extracts, dokudami extract,
Oak extract, melilot extract, bonito extract, liquorice extract, peonies extract, bonsai extract, loofah extract, kina extract, saxifrage extract,
Clara extract, Kouhone extract, Fennel extract, Primrose extract, Rose extract, Jiao extract, Lemon extract, Sikon extract, Aloe extract, Shobu root extract, Eucalyptus extract, Japanese cedar extract, Sage extract, Thyme extract, Tea extract, Seaweed extract, Cucumber extract, Clove Extract, raspberry extract, melissa extract, carrot extract, carrot extract, marronie extract, peach extract, peach leaf extract, mulberry extract, cornflower extract, hamamelis extract, placenta extract, chest wire extract, silk extract and the like.

The above-mentioned drugs can be used in a free state, those capable of forming a salt can be used in the form of an acid or base salt, and those having a carboxylic acid group can be used in the form of an ester thereof. . Further, if necessary, an appropriate fragrance, a colorant, and the like can be added to the emulsion composition of the present invention as long as the emulsion stability is not impaired. In addition, monoglyceride, sorbitan fatty acid ester, polyglycerin fatty acid ester,
The stability is further improved by adding a small amount of a surfactant such as polyoxyethylene hydrogenated castor oil and polyoxyethylene fatty acid ether.

[0030]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to this. All amounts are by weight.

Example 1, Comparative Example 1 An emulsified composition for cosmetics was produced according to the composition shown in Table 1 by the following method.

[Preparation method] (2), (1% by weight)
(3) and (4) are dissolved, and homomixer treatment is performed while gradually adding (6) to obtain an emulsifier composition. This is the rest of (1) (7),
(8) was added to the dissolved parts to obtain an emulsified composition. In addition, about the comparative example, it obtained by the same manufacturing method as the above except having replaced said (4) with (5).

Next, the stability of the obtained emulsified composition left at 50 ° C. for one month and the usability (stickiness) were evaluated according to the following criteria. Table 1 also shows the results. Stability evaluation criteria ：: No oil separation was observed. Δ: Oil separation was slightly observed. X: Oil separation is clearly recognized. Usability evaluation criteria ：: Not sticky. Δ: Somewhat sticky. ×: Sticky.

[0034]

Table 1 Component Ingredient Example 1 Comparative Example 1 ─────────────────────────── (1) Ion-exchanged water Residual Residual (2) Glycerin 10.0 10.0 (3) Methyl parahydroxybenzoate 0.1 0.1 (4) L-ascorbyl dipalmitate 0.05-(5) Polyoxyethylene (60) hydrogenated castor oil-0.2 (6) Liquid paraffin 5.0 5.0 (7) CARBOPOL 941 0.2 0.2 (8) Triethanolamine 0.4 0.4 ───安定 Stability ○ ○ Usability (sticky) ○ △ ────────────────────────

From these results, it is found that the use of L-ascorbyl dipalmitate has excellent long-term stability of emulsification,
It was found that an emulsified composition having a non-sticky feeling was obtained.

Example 2 Emulsion A. Oil phase Squalane 10.0% by weight Isopropyl palmitate 5.0 Vaseline 3.0 Dimethylpolysiloxane 2.0 Hexyldecanol 3.0 α-Tocopherol 0.3 B. Aqueous phase Triethanolamine 0.25 Polyethylene glycol 8.0 1,3-butylene glycol 5.0 Methyl parahydroxybenzoate 0.1 Sodium metaphosphate 0.1 CARBOPOL 1342 0.3 Hydroxypropyl methylcellulose 0.1 Dipalmitic acid L -Ascorbyl 0.2 Potassium hydroxide 0.2 Ion exchange water Residue [Production method] The oil phase of A was added to the water phase of B and emulsified by an emulsifier to obtain an emulsion.

Example 3 Makeup Removal A. Oil phase Liquid paraffin 40.0% by weight Glyceryl trioctanoate 15.0 Methylpolysiloxane 10.0 Ethyl parahydroxybenzoate 0.1 B. Water phase Ion-exchanged water 4.4 Glycerin 30.0 L-ascorbyl diisostearate 0.5 [Production method] The oil phase of A is gradually added to the aqueous phase of B while stirring, and after addition, the mixture is emulsified by an emulsifier. Make-up was obtained.

Example 4 Sunscreen Emulsion A. Oil phase pentaerythritol tetra-2-ethylhexanoate 1.0% by weight cetanol 1.0 diethyl sebacate 4.0 2-ethylhexyl paramethoxycinnamate 3.0 4-tert-butyl-4′-methoxybenzoylmethane 2. 0 Dibutylhydroxytoluene 0.1 2-Hydroxy-4-methoxybenzophenone 0.5 Mono-2-ethyl diparamethoxycinnamate Glyceryl hexanoate 1.0 [4-Bis (trimethylsiloxy) methylsilyl 3-methylbutyl] -3 1,4,5-Trimethoxycinnamic acid 1.0 Perfume Appropriate amount B. Glycerin 10.0 Ethanol 5.0 Ion-exchanged water 5.0 L-ascorbyl diisostearate 0.3 Methyl parahydroxybenzoate 0.1 C.I. Ion-exchanged water residue carboxyvinyl polymer 0.2 caustic potassium 0.05 sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate 0.1 trisodium edetate 0.1 citric acid 0.1 sodium citrate 0.01 [ Production method] The oil phase of A is gradually added to B while stirring, and after the addition,
After emulsification by an emulsifier, it was added to C and stirred to obtain a sunscreen emulsion.

Example 5 Cream A. Oil phase Cetostearyl alcohol 4.0% by weight Vaseline 3.0 Hardened oil 3.0 Squalane 8.0 Cetyl octanoate 5.0 Methyl polysiloxane 1.0 Liquid paraffin 5.0 Ethyl parahydroxybenzoate 0.1 Paraoxybenzoic acid Butyl 0.1 fragrance appropriate amount B. Glycerin 10.0 1,3-butylene glycol 5.0 Deionized water 10.0 L-ascorbyl di-2-ethylhexanoate 0.1 C.I. Ion-exchanged water Residue Carboxyvinyl polymer 0.4 Caustic potash 0.1 2-Hydroxy-4-methoxybenzophenone-5-sulfonate 0.05 Citric acid 0.1 Sodium citrate 0.01 [Production method] The oil phase of A is gradually added, and after the addition,
After emulsification with an emulsifier, the mixture was added to C and stirred to obtain a cream.

Example 6 Cleansing Emulsion A. Oil phase Liquid paraffin 15.0% by weight Glyceryl trioctanoate 5.0 Diisobutyl adipate 10.0 Ethyl parahydroxybenzoate 0.1 B. Glycerin 10.0 Dipropylene glycol 5.0 Ethanol 2.0 Deionized water 5.0 L-Ascorbyl oleate 0.5 C.I. Ion-exchanged water Residue Carboxyvinyl polymer 2.0 Caustic potassium 0.05 [Preparation method] The oil phase of A is gradually added to B while stirring, and after addition,
After emulsification with an emulsifier, the mixture was added to C and stirred to obtain a cream.

[0041]

As described above, according to the present invention,
Provided is an emulsifier composition which is excellent in long-term stability of emulsification without using a surfactant and can obtain an emulsified composition having a non-sticky feeling. Further, the oil-in-water emulsion composition of the present invention has excellent moisturizing effects and antioxidant effects.

Claims (5)

[Claims] 1. An L-ascorbic acid and / or a derivative thereof, a water-soluble polyhydric alcohol having two or more hydroxyl groups in a molecule, water of not more than the same weight% as the water-soluble polyhydric alcohol, and an oil component. An emulsifier composition comprising: 2. The method according to claim 1, wherein the composition is substantially free of a surfactant.
The emulsifier composition according to any one of the preceding claims. 3. An oil-in-water emulsion composition obtained by further mixing the emulsifier composition according to claim 1 or 2 with water. 4. The oil-in-water emulsion composition according to claim 3, which is an emulsion composition for cosmetics. 5. The method of claim 3, wherein the composition is substantially free of a surfactant.
Or the oil-in-water emulsion composition according to 4.