JP2012097030A - Oil in water emulsion type cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil in water emulsion type cosmetic comprising 3-O-alkylascorbic acid, and having good emulsion stability at about pH 4.SOLUTION: There is provided an oil in water emulsion type cosmetic comprising (A) an ascorbic acid derivative represented by the general formula (wherein, R is 1-4C alkyl), (B) a carboxyvinyl polymer and/or an alkyl-modified carboxyvinyl polymer and (C) a water-soluble polysaccharide derivative having a hydrophilic group and a hydrophobic group.

Description

  The present invention relates to an oil-in-water emulsified cosmetic that stably contains 3-O-alkylascorbic acid.

  Vitamin C has many functions as a cosmetic raw material such as a whitening action, a collagen synthesis promoting action, and a lipid peroxide inhibiting action, but it is difficult to blend into a skin external preparation as it is because of its poor oxidative stability and easy coloration. Various derivatives have been developed in the past. Representative examples of water-soluble vitamin C derivatives include L-ascorbyl glucoside (see Patent Document 1), L-ascorbic acid phosphate ester salt (see Patent Document 2), and 3-O-alkylascorbic acid (see Patent Document 3). Etc., and is blended in many external preparations for skin.

JP-A-5-112594 JP-A-6-24931 JP 58-27373 A

  Among these vitamin C derivatives, 3-O-alkylascorbic acid undergoes oxidation under neutral to alkaline conditions, causing discoloration and off-flavor, so the pH of the preparation must be set to about 4. . However, when an electrolyte is added to set the pH to about 4, there is a problem that the emulsion stability of the oil-in-water emulsified cosmetic deteriorates and gelation and separation occur. Therefore, an object of the present invention is to provide an oil-in-water emulsion type cosmetic containing 3-O-alkylascorbic acid and having good emulsification stability even at a pH of about 4.

（式中Ｒは、炭素数１〜４のアルキル基である。）で表されるアスコルビン酸誘導体と、（Ｂ）カルボキシビニルポリマー及び／又はアクリル酸・メタクリル酸アルキル共重合体と、（Ｃ）疎水基と親水基とを有する水溶性多糖誘導体を含有する水中油乳化型化粧料に関する。 The present invention comprises (A) a general formula

(Wherein R is an alkyl group having 1 to 4 carbon atoms), (B) a carboxyvinyl polymer and / or an acrylic acid / alkyl methacrylate copolymer, and (C) The present invention relates to an oil-in-water emulsion cosmetic containing a water-soluble polysaccharide derivative having a hydrophobic group and a hydrophilic group.

  The oil-in-water emulsified cosmetic of the present invention has good emulsification stability even at a pH of about 4, and can stably incorporate 3-O-alkylascorbic acid.

  The oil-in-water emulsified cosmetic of the present invention will be described in detail.

（式中Ｒは、炭素数１〜４のアルキル基である。）で表されるアスコルビン酸誘導体は、３−Ｏ−アルキルアスコルビン酸であり、Ｒ（アルキル）は、直鎖若しくは分岐アルキル基を意味し、例えば、エチル基、メチル基、ｎ−ブチル基、ｉｓｏ−ブチル基、ｔ−ブチル基などがあげられる。本発明においては、水相への配合のし易さから、３−Ｏ−エチルアスコルビン酸が最も好ましい。 General formula of component (A) used in the present invention

(Wherein R is an alkyl group having 1 to 4 carbon atoms), the ascorbic acid derivative is 3-O-alkylascorbic acid, and R (alkyl) is a linear or branched alkyl group. Meaning, for example, ethyl group, methyl group, n-butyl group, iso-butyl group, t-butyl group and the like. In the present invention, 3-O-ethylascorbic acid is most preferable from the viewpoint of easy incorporation into the aqueous phase.

  The blending amount of 3-O-alkyl ascorbic acid in the oil-in-water emulsion type cosmetic is preferably 0.01 to 20% by mass, more preferably 0.1 to 10.0% by mass in the total amount of the cosmetic. If it is less than 0.01% by mass, it is difficult to obtain the effect of the ascorbic acid derivative.

  The component (B) carboxyvinyl polymer and / or alkyl-modified carboxyvinyl polymer used in the present invention is a polyacrylic acid polymer whose viscosity increases by neutralization. The carboxyvinyl polymer preferably has an average molecular weight of 100,000 to 5,000,000. Examples of commercially available products include Carbo Pole 940, Carbo Pole 941, Carbo Pole 980, Carbo Pole 981, Carbo Pole ETD2050 (manufactured by BF Goodrich), Singtalen K, Singtalen L (manufactured by 3V Sigma), etc. Is mentioned. The alkyl-modified carboxyvinyl polymer preferably has an average molecular weight of 100,000 to 5,000,000. Examples of commercially available products include Pemulen TR-1, Pemulen TR-2, and Carbopol ULTREZ-21 (manufactured by BF Goodrich). The carboxyvinyl polymer and / or the alkyl-modified carboxyvinyl polymer can be used singly or in combination of two or more.

  The component (B) carboxyvinyl polymer and / or alkyl-modified carboxyvinyl polymer is blended in the total composition in an amount of 0.01 to 10% by mass, particularly 0.02 to 5% by mass, and further 0.05 to 3% by mass. However, it is preferable because a sufficient viscosity is obtained and the feeling in use is good.

  As the water-soluble polysaccharide derivative having a hydrophobic group and a hydrophilic group of the component (C) used in the present invention, those having a hydrocarbon group having 8 or more carbon atoms are preferable, for example, a hydrogen atom of a hydroxyl group of a polysaccharide or a derivative thereof. A part or all of (a) a substituent having a hydrophobic part selected from an alkyl group having 8 to 40 carbon atoms, an alkenyl group, an arylalkyl group and an alkylaryl group, and (b) a hydroxyl group is substituted. A water-soluble polysaccharide which is substituted with a substituent having a good ionic or nonionic hydrophilic part, and the ratio of the degree of substitution between the substituent (a) and the substituent (b) is 1: 1000 to 100: 1 Derivatives and the like.

  Here, examples of the substituent (a) include an alkyl group having 8 to 40 carbon atoms, an alkenyl group, an arylalkyl group, an alkylaryl group, an alkyl ether group, an alkenyl ether group, and an arylalkyl ether group. A substituted glyceryl ether group having an alkyl group or an alkenyl group having 10 to 40 carbon atoms is preferred. Specifically, 2-hydroxy-3-alkoxypropyl group, 2-alkoxy-1- (hydroxymethyl) ethyl group, 2-hydroxy-3-alkenyloxypropyl group, 2-alkenyloxy-1- (hydroxymethyl) An ethyl group is mentioned.

  Examples of the substituent (b) include a methyl group, a hydroxyethyl group, a hydroxypropyl group, a polyoxyethylene group, a polyglycerin group, and a sulfoalkyl group. Among these, a sulfoalkyl group having 1 to 5 carbon atoms which may be substituted with a hydroxyl group or a salt thereof is preferable, and specifically, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfo-2-hydroxy Propyl group, 2-sulfo-1- (hydroxymethyl) ethyl group and the like, and all or part of the sulfo group is an organic cation group such as alkali metal, alkaline earth metal, amines, ammonium ion, etc. It may be salt.

  The degree of substitution of the substituent (a) is preferably 0.001 to 1, particularly 0.002 to 0.5, more preferably 0.003 to 0.1 per constituent monosaccharide residue, and the substituent (b) The substitution degree is preferably 0.01 to 2.5, particularly 0.02 to 2, and more preferably 0.1 to 1.5 per constituent monosaccharide residue. The ratio of the degree of substitution between the substituent (a) and the substituent (b) is 1: 1000 to 100: 1, particularly 1: 500 to 10: 1, and more preferably 1: 300 to 10: 1.

  The basic skeleton of the polysaccharide derivative of component (C) is selected from known polysaccharides, and cellulose, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, and hydroxypropyl cellulose are particularly preferable. The weight average molecular weight of these polysaccharides or derivatives thereof is preferably 10,000 to 10,000,000, particularly 100,000 to 5,000,000, and more preferably 300,000 to 2,000,000.

  Such a water-soluble polysaccharide derivative having a hydrophobic group and a hydrophilic group can be obtained, for example, by the method described in JP-A No. 11-12119, by applying a hydrophobic substituent (a) and a hydrophilic substituent ( It is produced by introducing b) sequentially or simultaneously.

  Examples of water-soluble polysaccharide derivatives having a hydrophobic group and a hydrophilic group as component (C) include modified cellulose ethers described in Examples 1 to 3 of JP-A-3-12401, and U.S. Pat. No. 4,228,277. Nonionic long-chain alkylated cellulose ethers, modified hydroxyethyl celluloses, hydrophobized modified sulfonated polysaccharide derivatives and the like described in the above can be suitably used, and as commercially available products, Poise 310 (manufactured by Kao Corporation), Natrosol Plus (NATROSOL) An alkyl such as PLUS) 330 or Natrosol PLUS D-67 (manufactured by Aqualon Company) can be suitably used.

  One or more of the water-soluble polysaccharide derivatives having a hydrophobic group and a hydrophilic group as the component (C) can be used, and 0.01 to 10% by mass, particularly 0.02 to 5% by mass in the total composition, It is preferable to add 0.05 to 3% by mass because sufficient viscosity is obtained and the feeling in use is good.

  The water-soluble polymer of component (B) and component (C) can be used by dissolving in an aqueous phase component before emulsification, or by adding a water-soluble polymer aqueous solution to an emulsion prepared in advance. .

  The oil-in-water emulsified cosmetic of the present invention includes, in addition to the above-described components (A), (B), and (C), an aqueous phase component, an oil phase component, and an emulsifier that form the oil-in-water emulsified cosmetic. contains.

  The water phase component is not particularly limited as long as it is a water-soluble component that can be blended in cosmetics such as water, a lower alcohol, a polyhydric alcohol, a water-soluble polymer other than component (B) and component (C), and the like.

  Examples of such lower alcohols include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol and the like.

  Examples of such polyhydric alcohols include dihydric alcohols (for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2,3-butylene glycol. , Pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, octylene glycol, etc.); trivalent alcohol (eg, glycerin, trimethylolpropane, etc.); tetravalent alcohol (eg, 1,2, Pentaerythritol such as 6-hexanetriol); pentavalent alcohol (such as xylitol); hexavalent alcohol (such as sorbitol and mannitol); polyhydric alcohol polymer (such as diethylene glycol and dipropylene glycol) Triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, etc.); divalent alcohol alkyl ethers (for example, 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, ethylene Glycol jib Dihydric alcohol alkyl ethers (for example, 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, dipropylene Glycol butyl ether, etc.); dihydric alcohol ether esters (for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazinate, ethylene glycol disuccinate) 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 ether (For example, xyl alcohol, ceralkyl alcohol, batyl alcohol, etc.); sugar alcohol (for example, sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, xylitol, starch decomposition) Iso-reduced alcohol, etc.); glycolide; tetrahydrofurfuryl alcohol; POE-tetrahydrofurfuryl alcohol, POP-butyl ether; POP / POE-butyl ether; tripolyoxypropylene glycerin ether; POP-glycerin ether; POP-glycerin ether phosphate POP · POE-pentane erythritol ether, polyglycerin and the like.

  The oil phase component is not particularly limited as long as it is an oil phase component that can be usually blended in cosmetics. For example, liquid oils and fats, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, silicone oils, oil solubility Examples include drugs.

  Examples of liquid 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, flaxseed oil, Examples include safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, jojoba oil, germ oil, and triglycerin.

  Examples of the solid fat include cacao butter, palm oil, horse fat, hydrogenated palm oil, palm oil, beef tallow, sheep fat, hydrogenated beef tallow, palm kernel oil, pork fat, beef bone fat, owl kernel oil, hydrogenated oil, cattle Leg fats, moles, hydrogenated 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, sugarcane wax, lanolin fatty acid isopropyl, hexyl laurate, and 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.

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

  Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, toluic acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid ( DHA) and the like.

  Examples of the higher alcohol include linear alcohols (eg, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol); branched chain alcohols (eg, monostearyl glycerin ether (batyl alcohol)) 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyl decanol, isostearyl alcohol, octyldodecanol, etc.).

  Synthetic ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate Lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, apple Acid diisostearyl, di-2-heptylundecanoic acid glycerin, tri-2-ethylhexanoic acid trimethylolpropane, Trimethylolpropane phosphate, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, glycerin trioctanoate, glyceryl triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleyl oleate, 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-hexyldemyristate Le, palmitic acid 2-hexyl decyl, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, and triethyl citrate.

  Examples of the silicone oil include linear polysiloxanes (for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.); cyclic polysiloxanes (for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexyl). Silicone resins, silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.), acrylic silicone And the like.

The emulsifier is not particularly limited as long as it is used in oil-in-water emulsion cosmetics. For example, anionic surfactants such as alkyl sulfates, acylamino acid salts, fatty acid salts, polyoxyalkylene alkyl ethers, polyoxyalkylenes Nonionic surfactants such as fatty acid esters, polyoxyalkylene polyhydric alcohol fatty acid esters, polyhydric alcohol fatty acid esters, and sucrose fatty acid esters, cationic surfactants such as tetraalkylammonium salts, betaine type, sulfobetaine type, sulfoamino acid type , Amphoteric surfactants such as imidazolinium type, lecithin and lysolecithin.

  In the oil-in-water emulsified cosmetic of the present invention, in addition to the essential components described above, an aqueous component, an oily component, a moisturizer, a pigment, and an emulsifier are usually blended in the oil-in-water emulsified cosmetic as necessary. , Solubilizers, ultraviolet absorbers, thickeners, drugs, fragrances, resins, antibacterial and antifungal agents, alcohols, and the like can be appropriately blended.

  Further, the features of the present invention will be described in detail by way of examples.

  Oil-in-water emulsified cosmetics were prepared by the usual method with the formulation shown in Table 1, and the stability was evaluated. In Table 1, as the hydrophobized modified sulfonated polysaccharide derivative, sodium hydroxyethylcellulose hydroxypropyl stearyl ether hydroxypropyl sulfonate was used.

  Emulsification stability was evaluated using Examples 1 and 2 and Comparative Examples 1 to 3. Evaluation of emulsification stability evaluated the emulsified state visually after leaving the adjusted oil-in-water emulsion type cosmetics to stand at room temperature and 50 degreeC for one month.

  As a result, as shown in Table 1, Comparative Example 1 in which the water-soluble polysaccharide derivative having a hydrophobic group and a hydrophilic group of component (C) was replaced with hydroxyethyl cellulose having no hydrophobic group was a room temperature storage product, 50 Gelation was observed in the products stored at 0 ° C., and the emulsion stability was not good. In Comparative Example 2 in which the water-soluble polysaccharide derivative having a hydrophobic group and a hydrophilic group of component (C) was replaced with gellan gum which is a water-soluble polymer having no hydrophobic group, separation was observed in a 50 ° C. stored product. The emulsion stability was not good. In Comparative Example 3 in which the water-soluble polysaccharide derivative having a hydrophobic group and a hydrophilic group of component (C) was blended and the carboxyvinyl polymer of component (B) was not blended, gelation and separation were performed at 50 ° C. Was observed, and the storage stability was not good. On the other hand, in Examples 1 and 2 of the present invention, gelation and separation were not observed in the room temperature storage product and the 50 ° C. storage product, indicating that the emulsion stability was good.

Claims (1)

(A) General formula

(Wherein R is an alkyl group having 1 to 4 carbon atoms), (B) a carboxyvinyl polymer and / or an alkyl-modified carboxyvinyl polymer, (C) a hydrophobic group and a hydrophilic group An oil-in-water emulsified cosmetic containing a water-soluble polysaccharide derivative having a group.