JP2006008709A - Composition for external use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stable bleaching agent composition for external use, which gives a good sense of use, and does not cause the lowering of viscosity and the separation of the composition, even when stored for a long period. <P>SOLUTION: Compositions for external uses, containing ascorbic acid derivatives, have problems that the compositions are affected by the ascorbic acid derivatives to lower the viscosity and easily separate. This composition for external use comprises ascorbic acid glucoside, an alkylated water-soluble polymer, a pH-adjusting agent, and water, and does not cause the lowering of viscosity and the separation of the composition, even when stored for a long period. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an external composition that maintains stable properties. More specifically, the present invention relates to a whitening gel composition for external use that is excellent in feeling of use and does not cause deterioration such as viscosity reduction or separation even when stored for a long time.

  In recent years, the effects of excessive UV exposure have attracted attention as a cause of accelerated skin aging and skin cancer. When exposed to UV light, melanocyte-stimulating hormone is secreted from the pituitary midlobe, promoting the synthesis of melanin pigments in the melanocytes present in the skin, and causing skin tanning. At the same time, cytokines released from keratinocytes also promote melanin synthesis. On the other hand, it is known that melanin is synthesized by aging, disorder of hormone secretion, various skin diseases, and may cause stains, sparrow spots, abnormal skin tone, and the like. As a method for preventing and coping with these pigmentation and color abnormalities, conventionally known methods include taking tyrosinase inhibitors and vitamin C, or blending kojic acid and hydroquinone derivatives into creams and ointments and applying them to the skin. It was done.

  Among the whitening agents currently in use, ascorbic acid derivatives are generally well known and are blended in various whitening external preparations. However, when an ascorbic acid derivative is blended with an external preparation such as a gel or cream, the viscosity of the gel or cream may be affected.

  When making external preparations such as those mentioned above, thickeners such as carboxyvinyl polymers and emulsion stabilizers are used as compounding agents, but they are easily affected by salts such as ascorbic acid, and these gel emulsions Is physicochemically unstable, and the viscosity may be significantly reduced or separated by long-term storage. In addition, when a non-ionic polymer such as hydroxyethyl cellulose is blended to make a gel cream, a large amount of a polymer component must be blended in order to ensure a suitable hardness as an external preparation, There are problems with the feeling of use, such as poor stretch when applied to the skin and strong stickiness. Therefore, development of a stable whitening agent that is excellent in use feeling on the skin and that does not change properties such as viscosity and spreadability even after long-term storage has been awaited.

  As a result of intensive studies in view of these circumstances, the present inventors have found that the above problems can be solved by unexpectedly blending an ascorbic acid derivative with an alkylated water-soluble polymer, and completed the present invention.

  That is, the present invention is an external composition comprising an ascorbic acid derivative, an alkylated water-soluble polymer, a pH adjuster and water. Moreover, this invention is the said external composition further containing an oil component and / or an emulsifier.

  According to the present invention, a gel-like composition of an ascorbic acid derivative having excellent usability can be produced without changing properties such as appearance, pH, and spreadability even after long-term storage.

  Examples of the alkylated water-soluble polymer in the present invention include alkylated carboxyvinyl polymer, alginate, propylene glycol alginate, xanthan gum, hydroxypropylcellulose, hydroxypropylmethylcellulose, ceratin, gellan gum, carrageenan, agar, pectin, locust bean gum , Guar gum, tragacanth gum, crystalline cellulose, polyvinylpyrrolidone, and representative examples include alkyl-modified carboxyvinyl polymer. The alkyl-modified carboxyvinyl polymer (hereinafter sometimes abbreviated as A-CP) in the present invention is also referred to as acrylic acid / alkyl methacrylate copolymer, which is a linear or branched chain having 10 to 30 carbon atoms and acrylic acid. It is an O / W type polymer emulsifier having a large hydrophilic group and a small lipophilic group, which is a copolymer of a branched alkyl group ester and an alkyl group ester similar to methacrylic acid. A-CP is commercially available under the trade name PEMULEN TR-1 (Nikko Chemicals Co., Ltd.) and is readily available.

  In the present invention, the compounding amount of the alkyl-modified carboxyvinyl polymer is not particularly limited, but is usually 0.05 to 2%, preferably 0.3 to 1%, more preferably based on the total weight of the composition for external use according to the present invention. Is 0.4 to 0.8%.

In the present invention, the pH adjuster is not particularly limited, but hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, etc. Organic acids such as alkanolamine, citric acid, malic acid, tartaric acid, lactic acid, fumaric acid, succinic acid, maleic acid, acetic acid and their salts, hydrochloric acid, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, phosphorus Examples thereof include inorganic acids such as acids, trisodium phosphate, sodium hydrogen phosphate, dipotassium phosphate, potassium dihydrogen phosphate, and salts thereof. Of these, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine are particularly preferable. What is necessary is just to adjust pH to the range of about 5-8 with these pH adjusters.

  Oil components in the present invention are not particularly limited, but vegetable oils such as olive oil, rice bran oil, soybean oil, sunflower oil, macadamia nut oil, avocado oil, animal oils such as squalane, fish oil, horse oil, carnauba wax, candelilla wax , Waxes such as rice bran, lanolin, jojoba oil, hydrocarbons such as liquid paraffin, paraffin, petrolatum, polybutene, synthetic squalane, higher alcohols such as cetanol, cetostearyl alcohol, stearyl alcohol, cholesterol, phytosterol, octyldodecanol, and behenyl alcohol , Isopropyl myristate, isopropyl palmitate, cetyl palmitate, octyl stearate, cetyl octanoate, medium chain fatty acid triglyceride, glyceryl trioctanoate, cetyl lactate, triethyl citrate , Mention may be made of diisopropyl adipate, diisopropyl sebacate, ester oil of diethyl sebacate, methyl polysiloxane, silicone resin, cyclic dimethyl silicone, silicone oil and the like perfluoro polyether. Preferably, hydrocarbons such as liquid paraffin, paraffin, petrolatum, polybutene, synthetic squalane, isopropyl myristate, isopropyl palmitate, cetyl palmitate, octyl stearate, cetyl octanoate, medium chain fatty acid triglyceride, glyceryl trioctanoate, cetyl lactate And ester oils such as triethyl citrate, diisopropyl adipate, diisopropyl sebacate and diethyl sebacate, and fat-soluble vitamins such as vitamins A, vitamins D and vitamins E.

The emulsifier that can be used in the present invention is not limited. For example, polyoxyethylene alkyl ether, polyoxyethylene hydrogenated castor oil, polyoxyethylene polyoxypropylene alkyl ether, polyglycerin fatty acid ester, polyoxyethylene alkyl sodium sulfate, polyoxyethylene sorbitan Nonionic surfactants such as fatty acid esters, polyethylene glycol fatty acid esters, sucrose fatty acid esters, glycerin fatty acid esters, propylene glycol fatty acid esters, sorbitan fatty acid esters, methyl glucoside fatty acid esters, fatty acid soaps (sodium stearate, sodium oleate, Ionic surfactants such as sodium lauroyl sarcosine), sodium lauryl sulfate, sodium stearoyl sulfate Lecithins (soybean lecithin, egg yolk phospholipids, hydrogenated lecithins, such as hydroxylated lecithin), saponins (soybean saponin, licorice saponin, such as enzyme treatment saponin), naturally occurring surfactants such as gum arabic and the like. Preferred are nonionic surfactants such as polyglyceric acid fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl ether, and the like.

  In addition to the ascorbic acid derivative, a medicinal component can be added to the external composition according to the present invention. Specifically, glycyrrhizic acid and derivatives thereof and salts thereof, glycyrrhetinic acid and derivatives thereof, ε-aminocaproic acid, lysozyme chloride, guaiazulene, allantoin and other anti-inflammatory agents, retinol, retinoic acid, vitamin A oil, retinol palmitate, Carotenes, ascorbic acid, ascorbic acid derivatives (such as ascorbic acid glucoside, magnesium L-ascorbyl phosphate, ascorbyl dipalmitate, L-ascorbyl tetra-2-hexyldecanoate), tocopherol acetate, d-α-tocopherol acetate, tocopherol acetate, D-α-tocopherol succinate, vitamin E linoleate, d-α-tocopherol, d-β-tocopherol, d-γ-tocopherol, d-δ-tocopherol, natural vitamin E, pyridoxine hydrochloride, dicaprylic acid pi Vitamins such as doxin, pyridoxine dipalmitate, riboflavin, sodium riboflavin phosphate, riboflavin butyrate, nicotinamide, pantothenyl alcohol, pantothenyl ethyl ether, calcium pantothenate, cholecalciferol, arbutin, ellagic acid, kojic acid, Magnesium ascorbate phosphate, dipalmitate ascorbate, hydroquinone derivatives, oil-soluble licorice extract and other whitening agents, anti-epileptics such as crotamiton and diphenhydramine, hair growth and hair restoration agents such as hinokitiol, cephalanthin and tocopherol nicotinate, γ-oryzanol, ferulic acid Etc.

  The external gel composition of the present invention may contain various commonly used additives. Such additives are not particularly limited. For example, suspending agents, preservatives, stabilizers, coloring agents, cooling agents, flavoring agents, adsorbents, absorption enhancers, thickeners, wetting agents, An oxidizing agent etc. can be mentioned.

  Examples of the suspending agent include methyl cellulose, polysorbate 80, hydroxypropyl cellulose, gum arabic, tragacanth powder, carmellose, polyoxyethylene sorbitan monolaurate, polyoxyethylene polypropylene glycol and the like.

  Examples of the preservative include sodium benzoate, potassium sorbate, sodium dehydroacetate, phenoxyethanol, hinokitiol and the like.

  Stabilizers include fatty acids such as stearic acid, myristic acid, oleic acid, higher alcohols such as cetanol, cetostearyl alcohol, stearyl alcohol, cholesterol, phytosterol, octyldodecanol, and behenyl alcohol, carboxyvinyl polymers, alginates, propylene alginate Glycol, xanthan gum, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, gelatin, gellan gum, carrageenan, agar, pectin, locust bean gum, guar gum, tragacanth gum, crystalline cellulose, polyvinylpyrrolidone and other water-soluble polymers, edetic acid, glucone Chelating agents such as acids, citric acid, malic acid, natural vitamin E, d-α-tocopherol, δ-tocopher , Β-tocopherol, γ-tocopherol, ascorbic acid, erythorbic acid and their salts or derivatives, dibutylhydroxytoluene, butylhydroxyanisole, sodium gallate, phytic acid, sodium sulfite, catechins, polyphenols and other antioxidants Glyceryl monoalkyl ether, dextrin palmitate and the like.

  Examples of the colorant include titanium oxide, yellow ferric oxide, talc, safflower dye, gardenia dye, paprika dye, β-carotene, caramel, copper chlorophyllin sodium, silk powder, and the like.

  Examples of the refreshing agent include d-camphor, mint oil, l-menthol, d-borneol and the like.

  As flavoring agents, in addition to fragrances generally used in cosmetics and external preparations, fennel powder, orange oil, chamomile oil, spearmint oil, pine oil, mint oil, bergamot oil, l-menthol, lemon oil, etc. Examples include essential oils.

  Examples of the adsorbent include carmellose calcium, magnesium silicate, aluminum oxide, dextrin and the like.

  Absorption accelerators include lower alcohols such as ethanol and isopropyl alcohol, higher alcohols such as oleyl alcohol and isostearyl alcohol, fatty acids such as oleic acid, ricinoleic acid and isostearic acid, surfactants such as lecithins, higher alcohols and Examples include fatty acids such as chain fatty acids and isopropyl palmitate, lactic acid and salts thereof, and l-menthol.

  As thickeners, carboxyvinyl polymer, alginate, propylene glycol alginate, xanthan gum, hydroxypropyl cellulose, hydroxypropyl methylcellulose, hydroxyethyl cellulose, gelatin, gellan gum, agar, agar, pectin, locust bean gum, guar gum, tragacanth gum, crystals Examples thereof include cellulose and polyvinylpyrrolidone.

Wetting agents include sorbitol, xylitol, reduced maltose starch syrup, maltitol, erythritol, sucrose, trehalose, glucose and other sugars or sugar alcohols, sodium hyaluronate, collagen, elastin, sericin, deoxyribonucleic acid or salts thereof, hydrolyzed collagen , Polyglutamic acid, polyalginic acid, wheat peptide, chondroitin sulfate sodium, chitin, chitosan and other polymer wetting agents, glycerin, propylene glycol, dipropylene glycol, butylene glycol, polyethylene glycol, polyglycerin and other polyhydric alcohols, aloe extract, Plant extracts such as peach leaf extract, loquat extract, fermented rice extract, rice bran extract, cowberry extract, walnut extract, licorice extract, pyrrolidone carboxylate sodium , Glycine, arginine, glutamic acid, serine, proline, hydroxyproline, diglycerol, amino acids such as betaine, sphingolipids, ceramides, lecithin, oil wetting agents, such as cholesterol, lactic acid, sodium lactate and the like.

  In the present invention, antioxidants include sodium nitrite, erythorbic acid, butylhydroxyanisole, ascorbic acid, L-ascorbic acid stearate, ascorbyl palmitate, tocopherol acetate, natural vitamin E, d-δ-tocopherol, etc. Means.

The composition for external use concerning this invention can be manufactured with the formulation method currently performed normally. Add water phase with water-soluble wetting agent and stabilizer to oil component (which may contain emulsifier) that has been heated and melted, emulsify at around 80 ° C, cool to about 55 ° C and emulsify Obtain a liquid. On the other hand, an alkyl-modified carboxyvinyl polymer is dispersed in purified water at about 55 ° C., and an ascorbic acid derivative such as ascorbic acid glucoside is added to obtain an aqueous polymer solution. Add the polymer aqueous solution at about the same temperature to the emulsion cooled to about 55 ° C, stir until uniform while maintaining the temperature, then cool with stirring and adjust the pH when it reaches about 35 ° C An aqueous solution containing an agent can be added, gelled, and stirred uniformly to obtain the desired composition.

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

(Example 1)
D-α-tocopherol acetate 0.3g, liquid paraffin 1.3g, stearic acid 0.4g, cetostearyl alcohol 0.3g, lipophilic glyceryl monostearate 0.3g and decaglyceryl monostearate 1.5g An oil phase was obtained. Next, 2.5 g of dipropylene glycol, 2.0 g of powdered reduced maltose starch syrup, 1.5 g of polyethylene glycol, 0.2 g of methylparapene and 0.38 g of L-arginine were placed in 12.5 g of purified water and dissolved by heating to obtain a uniform aqueous phase. The aqueous phase was added to the oil phase, and the mixture was emulsified by stirring with a simple stirrer at about 80 ° C. for 5 minutes, and then cooled to about 55 ° C. On the other hand, 0.45 g of A-CP was dispersed in 63.97 g of purified water and stirred at about 55 ° C. to obtain a polymer solution. This polymer solution was added to the above emulsion and stirred for 15 minutes. To this solution, a neutralizer solution in which 0.4 g of sodium hydroxide was dissolved in 10 g of purified water was added to cause gelation, and the mixture was cooled while continuing to stir. Furthermore, 2.0 g of ascorbic acid glucoside was added at around 35 ° C. and stirred until uniform to obtain 100 g of a gel emulsion composition.

(Example 2)
D-α-tocopherol acetate 0.3g, liquid paraffin 1.3g, stearic acid 0.4g, cetostearyl alcohol 0.3g, lipophilic glyceryl monostearate 0.3g and decaglyceryl monostearate 1.5g An oil phase was obtained. Next, 2.5 g of dipropylene glycol, 2.0 g of powdered reduced maltose starch syrup, 1.5 g of polyethylene glycol, and 0.2 g of methylparapene were placed in 12.5 g of purified water and dissolved by heating to obtain a uniform aqueous phase. The aqueous phase was added to the oil phase, and the mixture was emulsified by stirring with a simple stirrer at about 80 ° C. for 5 minutes, and then cooled to about 55 ° C. 0.5 g of A-CP and 2.0 g of ascorbic acid glucoside were dispersed in 71.7 g of purified water and stirred at about 55 ° C. to obtain a polymer solution. This polymer solution was added to the above emulsion and stirred for 15 minutes. Further, while cooling to about 30 ° C., 0.5 g of sodium hydroxide dissolved in 2.5 g of purified water was added and stirred for 10 minutes to obtain 100 g of a gel emulsion composition.

Example 3
In the same manner as in Example 1, the oil phase and the aqueous phase were mixed to obtain an emulsion. 0.7 g of A-CP and 2.0 g of ascorbic acid glucoside were dispersed in 63.82 g of purified water and stirred at about 55 ° C. to obtain a polymer solution. This polymer solution was added to the above emulsion and stirred for 15 minutes. Further, while cooling to about 30 ° C., 0.3 g of sodium hydroxide dissolved in 10 g of purified water was added and stirred for 10 minutes to obtain 100 g of a gel emulsion composition.

Example 4
100 g of a gel emulsion composition was obtained in the same manner as in Example 1 except that 1 g of AC-P and 0.56 g of sodium hydroxide were used.

(Example 5)
100 g of an external composition was obtained in the same manner as in Example 3 except that a polymer solution was prepared with purified water of A-CP 0.65 g and 63.87 g.

(Example 6)
100 g of an external composition was obtained in the same manner as in Example 3 except that a polymer solution was prepared with 0.6 g of A-CP and 56.42 g of purified water.

(Comparative Example 1)
D-α-tocopherol acetate 0.3g, liquid paraffin 1.3g, stearic acid 0.4g, cetostearyl alcohol 0.3g, lipophilic glyceryl monostearate 0.3g and decaglyceryl monostearate 1.5g An oil phase was obtained. Next, 2.5 g of dipropylene glycol, 2.0 g of powdered reduced maltose starch syrup, 1.5 g of polyethylene glycol, 0.2 g of methylparapene and 0.38 g of L-arginine were placed in 12.5 g of purified water and dissolved by heating to obtain a uniform aqueous phase. The aqueous phase was added to the oil phase, and the mixture was emulsified by stirring with a simple stirrer at about 80 ° C. for 5 minutes, and then cooled to about 55 ° C. Carboxyvinyl polymer (trade name: UltreZ10, manufactured by Bfgoodrich) (0.35 g) was dispersed in 74.57 g of purified water and stirred at about 55 ° C. to obtain a polymer solution. This polymer solution was added to the above emulsion and stirred for 15 minutes. Ascorbic acid glucoside (2.0 g) was added at around 35 ° C. and stirred until uniform to obtain 100 g of a gel emulsion composition.

(Comparative Example 2)
100 g of a gel emulsion composition was obtained in the same manner as in Example 2 except that 0.5 g of carboxyvinyl polymer was used instead of A-CP.

(Comparative Example 3)
A gel emulsion composition 100 g was obtained in substantially the same manner as in Example 1 except that 1 g of L-arginine was used instead of sodium hydroxide.

(Test Example 1)
The properties of the compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were visually inspected, and an appropriate amount was applied to the back of the hand to compare the feeling of use.
As a result, the compositions of Examples 1 to 3 were white gel-like creams, which could be uniformly applied to the back of the hand and the usability was good. Although the composition of Example 4 was a white gel-like cream, it was not glossy as compared with the compositions of Examples 1 to 3, and felt slightly sticky when applied to the hand. The compositions of Comparative Examples 1 and 2 did not gel and remained in a liquid state and could not be creamed. The composition of Comparative Example 3 did not gel and became a liquid agent with separated components. Therefore, in the compositions of Comparative Examples 1 to 3, the usability could not be confirmed.

  From the above results, it was revealed that when A-CP was used instead of carboxyvinyl polymer, a good gel composition of ascorbic acid glucoside was obtained.

(Test Example 2)
The gel compositions prepared by the methods of Examples 1, 3, 5 and 6 were stored at 45 and 50 ° C. for 1 month. The properties of each sample were visually inspected one month before the start of storage, and a 10% aqueous solution of each sample was prepared to measure the pH. Moreover, the spreadability was measured using a spread meter to evaluate the gel hardness. For the spreadability, the diameter of the composition 60 seconds after the start of measurement was calculated from the average value of the vertical axis and the horizontal axis orthogonal to each other.

The property of each formulation example was a white gel-like cream, and no change was observed even when stored for 1 month under the above conditions. Further, as shown in Tables 2 and 3, no change was observed in the spreadability and pH.

Claims (8)

An external composition comprising ascorbic acid glucoside, an alkyl-modified carboxyvinyl polymer, a pH adjuster and water. The composition for external use according to claim 1, wherein the pH adjuster is an alkali metal hydroxide and / or an alkanolamine. The composition for external use according to claim 1 or 2, comprising 0.3 to 1% of an alkyl-modified carboxyvinyl polymer. The external composition according to any one of claims 1 to 3, wherein the external composition is a gel. The composition for external use in any one of Claims 1 thru | or 4 containing an oil component and / or an emulsifier. The composition for external use according to claim 5, wherein the oil component is at least one selected from the group consisting of hydrocarbons, higher alcohols, ester oils and fat-soluble vitamins. The composition for external use according to claim 5, wherein the emulsifier is a nonionic surfactant. The nonionic surfactant is at least one selected from the group consisting of polyglycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene polyoxypropylene alkyl ether, and polyoxyethylene alkyl ether. Composition for external use.