JP6013043B2 - External composition for skin containing 3-O-ethylascorbic acid - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composition for external use on skin, in which the viscosity of a preparation is markedly increased by blending alginic acid with an ascorbic acid derivative having an excellent whitening effect on the skin, and the use feeling and the preparation stability are excellent. is there.

Ascorbic acid and ascorbic acid derivatives inhibit tyrosinase, which is involved in the production of melanin, which causes skin spots, buckwheat and sunburn. Moreover, it has the effect | action which raises the collagen synthesis | combination which comprises the connective tissue in a body, prevents and improves a skin wrinkle and sagging, and is a chemical | medical agent useful as cosmetics.

Among these, 3-O-substituted ascorbic acid derivatives in which the hydroxyl group at the 3-position is substituted with an alkyl group such as a lower alkyl group or a lower alkylcarbonyl lower alkyl group are more stable than ascorbic acid and exhibit an antioxidative effect, and are therefore used in foods and cosmetics. In addition to being useful for preventing quality degradation, it is also useful as a pharmaceutical based on radical scavenging action. In addition, the usefulness as a medicine such as cancer metastasis preventing action is known. In particular, in the composition for external use of skin, among the 3-O-substituted ascorbic acid derivatives, 3-O-ethylascorbic acid is excellent in water solubility, high stability, and easy to synthesize (for example, Patent Document 1). It is widely used.

However, when 3-O-ethylascorbic acid is blended in a composition for external use on the skin, due to its characteristics, the thickening action of the polymer is reduced, the viscosity of the preparation is lowered, and the composition for external use on the skin is especially a cosmetic. As a result, it was extremely unfavorable in terms of use feeling and formulation stability, which are very important factors. However, it is known that alkyl methacrylate copolymers, xanthan gum, and the like impart some viscosity (Patent Document 2). However, in this degree of viscosity application, the viscosity decreased upon standing at a high temperature at 50 ° C. or over time, and a desirable situation was not obtained in terms of use feeling and formulation stability, and there was a problem.

Japanese Patent Laid-Open No. 8-134555 JP 2002-284623 A

An object of the present invention is to provide a composition for external use on skin, which is formulated with 3-O-ethylascorbic acid having an excellent whitening effect on the skin, has a high viscosity of the preparation, and is excellent in use feeling and preparation stability.

In view of such a situation, the present inventors have used a combination of polymers that can be used in the cosmetics field, and as a result of earnest research aimed at new skin compositions, the following skin external composition However, the present inventors have found that the formulation has a high viscosity and is excellent in use feeling and formulation stability, thereby completing the present invention. That is, the present invention is as follows.

(1) An external composition for skin comprising 1) 3-O-ethylascorbic acid, 2) alginic acid or a salt thereof, and 3) a polyvalent metal salt.
(2) The external composition for skin according to (1), wherein the polyvalent metal salt is calcium chloride.
(3) The external composition for skin according to (1) or (2), which contains polyoxybutylene polyglycerin monoalkyl (monoalkenyl) ether.
(4) The external composition for skin according to any one of (1) to (3), which is an emulsified composition.

ADVANTAGE OF THE INVENTION According to this invention, the viscosity of a formulation becomes remarkably high and can provide the new external composition for skin excellent in use feeling and formulation stability.

(1) 3-O-ethylascorbic acid which is an essential component of the present invention The 3-O-ethylascorbic acid used in the present invention generally has an antioxidant action, a carcinogenesis-inhibiting action, a cancer metastasis-inhibiting action, and whitening. The action is recognized. As 3-O-ethylascorbic acid, L-3-O-ethylascorbic acid is preferably used. It can also be synthesized by a known method described in JP-A-8-134055. Since there are commercially available products (“VC ethyl” manufactured by Nippon Seika Co., Ltd.), these can be obtained and used, which is preferable. In the external composition for skin of the present invention, including Yuryou of such 3-O-ethyl ascorbic acid, the skin external composition the total amount is 0.1 to 3 wt%, good Mashiku is 0 0.5 to 1.5% by mass.

(2) Alginic acid and / or its salt which is an essential component of the present invention Alginic acid and / or its salt is widely used as a water-soluble thickening component in the fields of skin external compositions such as cosmetics and foods. . There are several grades of these depending on the degree of thickening. Examples include ultra-low viscosity products, high-purity products, and high-viscosity products. As the salt, if it is usually known, it can be applied without particular limitation, for example, alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium and magnesium, ammonium, etc. Preferred examples include organic amine salts such as salts, triethanolamine salts and triethylamine salts, and basic amino acid salts such as lysine salts and arginine salts. Viscosity definitive to 1 mass% for such ultra-low viscosity products is about 100～200Cp, in the high purity product is about 300～700Cp, the high viscosity products are said to be about 900～1200Cp. Within this viscosity range, the composition for external use of the present invention can be used without any particular limitation. In the composition for external use of the present invention, it can be said that it is acceptable without particular limitation as long as the 1 mass% aqueous solution has a viscosity of 1 to 20 ° C. of 10 to 1500 cp. Preferred viscosities are between 200 and 1000 cp under these conditions. In the composition for external use of the skin of the present invention, such alginic acid and / or a salt thereof may contain only one species or may contain two or more species in combination. In the external composition for skin of the present invention, including Yuryou such alginic acid and / or its salt, in total, to the skin external composition the total amount is 0.03 to 3 wt%.

(3) The polyvalent metal salt essential for the present invention is an important component because the viscosity can be increased by crosslinking alginic acid or alginic acid salt. For example, alkaline earth metal salts such as calcium and magnesium, neutral metal salts such as zinc salts and aluminum salts, and transition metal salts such as manganese salts, iron salts and nickel salts can be preferably exemplified. Especially, the form which uses calcium as a counter ion, for example, calcium chloride, is more preferable. In the external composition for skin of the present invention, including Yuryou of such polyvalent metal salts, relative to the content of alginic acid or alginate, 2-20% by weight in total (the content of alginic acid or alginate 100 If the ratio of the polyvalent metal salt is 2-20), good Mashiku is, when 5 to 10 mass% (the content of alginic acid or alginate and 100, the ratio of the polyvalent metal salt is 5-10 ).

(4) Polyoxybutylene polyglycerin monoalkyl (monoalkenyl) ether essential for the present invention The skin external composition of the present invention comprises polyoxybutylene polyglycerin monoalkyl (monoalkenyl) ether as an essential component. And Polyoxybutylene polyglycerin monoalkyl (monoalkenyl) ether is a compound obtained by ring-opening polymerization of glycidol and tetrahydrofuran to monoalkyl (monoalkenyl) glyceryl ether, and the alkyl group or alkenyl group of such compound is carbon. Number 1
Among them, those having 0 to 24 are preferable, and among them, lauryl group, myrylyl group, palmityl group, stearyl group, oleyl group, behenyl group and the like can be suitably exemplified, and stearyl group and oleyl group are particularly preferable. Moreover, 10-20 are respectively preferable and, as for the addition mole number of polyglycerol and polyoxybutylene, 10-16 are more preferable. Although such a compound can be produced and used as described above, such a compound is already available on the market and can also be used. Among the commercially available products, “High Glyol S-26 (Nikko) in which the alkyl (alkenyl) group is a stearyl group, the number of added moles of polyglycerol is 13 on average, and the number of added moles of polyoxybutylene is 14 on average. Chemicals Corporation). Such polyoxybutylene polyglycerin monoalkyl (monoalkenyl) ether may contain only one species, or may contain two or more species in combination. The preferable content of such polyoxybutylene polyglycerin monoalkyl (monoalkenyl) ether is 0.05 to 5% by weight, more preferably 0.1 to 0.5% by weight.

(5) External composition for skin of the present invention The external composition for skin referred to in the present invention is not particularly limited as long as it is externally administered to the skin. For example, cosmetics including quasi drugs, A skin external goods etc. can be illustrated suitably. Of these, cosmetics are particularly preferred. In addition, the external composition for skin of the present invention can take any of the conventionally known lotion dosage forms, emulsion dosage forms, essence dosage forms, cream dosage forms, and powder-containing dosage forms. As the cosmetic, any of basic cosmetics, hair cosmetics, and makeup cosmetics can be applied, but it is particularly preferable to apply to basic cosmetics.

The composition for external use of the skin thus obtained can be a new composition for external use of the skin, which has a remarkably high viscosity of the preparation and is excellent in use feeling and preparation stability.

In the composition for external use of the skin of the present invention, in addition to the above-mentioned components, optional components usually used in cosmetics and external preparations for skin can be contained. Examples of such optional ingredients include macadamia nut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower oil, cottonseed oil, jojoba oil, coconut oil, palm oil, liquid lanolin, and hardened coconut oil. Oil, wax, liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum, oil, wax, liquid wax, liquid paraffin, squalane, bean wax, candelilla wax, carnauba wax, ibotarou, lanolin, reduced lanolin, hard lanolin , Hydrocarbons such as microcrystalline wax, higher fatty acids such as oleic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, cetyl alcohol, stearyl alcohol, isostearyl alcohol, Higher alcohols such as alcohol, octyldodecanol, myristyl alcohol, cetostearyl alcohol, cetyl isooctanoate, isopropyl myristate, hexyldecyl isostearate, diisopropyl adipate, di-2-ethylhexyl sebacate, cetyl lactate, diacid malate Isostearyl, ethylene glycol di-2-ethylhexanoate, neopentyl glycol dicaprate, glycerin di-2-heptylundecanoate, glycerin tri-2-ethylhexanoate, tri-2-ethylhexanoate trimethylolpropane, triisostearin Synthetic ester oils such as acid trimethylolpropane, tetra-2-ethylhexanoic acid pentane erythritol, dimethylpolysiloxane, methylphenylpolysiloxane, diphenyl Linear polysiloxanes such as polypolysiloxane, cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexanesiloxane, amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified Oil agents such as silicone oils such as modified polysiloxanes such as polysiloxane, fatty acid soap (sodium laurate, sodium palmitate, etc.), anionic surfactants such as potassium lauryl sulfate, alkyl sulfate triethanolamine ether, stearyl trimethyl chloride Cationic surfactants such as ammonium, benzalkonium chloride, laurylamine oxide, betaine surfactants (alkyl betaines, amide betaines, sulfobetaines, etc.) ), Imidazoline-based amphoteric surfactants (2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc.), amphoteric surfactants such as acylmethyltaurine, sorbitan fatty acid esters (sorbitan monoester) Stearate, sorbitan sesquioleate, etc.)
Glycerin fatty acids (such as glyceryl monostearate), propylene glycol fatty acid esters (such as propylene glycol monostearate), hydrogenated castor oil derivatives, glycerin alkyl ethers, POE sorbitan fatty acid esters (POE sorbitan monooleate, monostearic acid) Polyoxyethylene sorbitan, etc.), POE sorbite fatty acid esters (POE-sorbite monolaurate, etc.), POE glycerin fatty acid esters (POE-glycerin monoisostearate, etc.), POE fatty acid esters (polyethylene glycol monooleate, POE distearate). etc)
POE alkyl ethers (POE2-octyldodecyl ether, etc.), POE alkylphenyl ethers (POE nonylphenyl ether, etc.), Pluronic types, POE / POP alkyl ethers (POE / POP2-decyltetradecyl ether, etc.), Te Tronics, POE castor oil / hardened castor oil derivatives (POE castor oil, POE hardened castor oil, etc.), nonionic surfactants such as sucrose fatty acid ester, alkyl glucoside, polyethylene glycol, glycerin, 1,3-butylene glycol Erythritol, sorbitol, xylitol, maltitol, propylene glycol, dipropylene glycol, diglycerin, isoprene glycol, 1,2-pentanediol, 2,4-hexylene glycol, 1,2-he Polyhydric alcohols such as sundiol, 1,2-octanediol, moisturizing ingredients such as sodium pyrrolidonecarboxylate, lactic acid, sodium lactate, guar gum, quince seed, carrageenan, galactan, gum arabic, pectin, mannan, starch, xanthan gum , Curdlan, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, methylhydroxypropylcellulose, chondroitin sulfate, dermatan sulfate, glycogen, heparan sulfate, hyaluronic acid, sodium hyaluronate, tragacanth gum, keratan sulfate, chondroitin, mucoitin sulfate, hydroxyethyl guar gum, carboxy Methyl guar gum, dextran, keratosulfate, locust bean gum, succinoglucan, caronic acid, chitin, Thickeners such as tosan, carboxymethyl chitin, agar, polyvinyl alcohol, polyvinyl pyrrolidone, carboxy vinyl polymer, alkyl-modified carboxy vinyl polymer, sodium polyacrylate, polyethylene glycol, bentonite, surface may be treated, mica, Powders such as talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, silicic anhydride (silica), aluminum oxide, barium sulfate, surface may be treated, bengara, yellow iron oxide, black iron oxide, Cobalt oxide, ultramarine, bitumen, titanium oxide, zinc oxide inorganic pigments, surface may be treated, pearlescent agents such as titanium mica, fish phosphorus foil, bismuth oxychloride, red may be raked 202, Red 228, Red 226, Yellow 4, Blue 40 No. 4, Yellow No. 5, Red No. 505, Red No. 230, Red No. 223, Orange No. 201, Red No. 213, Yellow No. 204, Yellow No. 203, Blue No. 1, Green No. 201, Purple No. 201, Red No. 204 Organic dyes such as polyethylene powder, polymethyl methacrylate, nylon powder, organic powders such as organopolysiloxane elastomers, paraaminobenzoic acid UV absorbers, anthranilic acid UV absorbers, salicylic acid UV absorbers, cinnamon Acid UV absorber, benzophenone UV absorber, sugar UV absorber, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 4-methoxy-4′-t-butyldibenzoylmethane ultraviolet absorbing agents and the like, ethanol, lower alcohols such as isopropanol, vitamin a or a derivative thereof, vitamin B Hydrochloride, vitamin _{B 6} tripalmitate, vitamin _{B 6} dioctanoate, vitamin _{B 2} or derivatives thereof, vitamin _{B 12,} vitamin B such as vitamin _{B 15} or a derivative thereof, alpha-tocopherol, beta-tocopherol, .gamma.-tocopherol, Preferable examples include vitamin E such as vitamin E acetate, vitamin D, vitamin H, pantothenic acid, panthetin, pyrroloquinoline quinone and the like.

<Manufacture example 1> Manufacture of the composition for external use of skin of this invention According to the prescription shown below, the emulsion which is an emulsion composition of this invention was produced (Example 1). That is, the components (A) were mixed and dissolved by heating at 70 ° C. On the other hand, each component of (B) was mixed and dissolved and heated to 80 ° C. (B) was added to the mixture of (A) and stirred to emulsify. Thereafter, the mixture was stirred and cooled to 40 ° C., (C) was mixed, (D) was mixed, and finally (E) was mixed to obtain an external composition for skin. Among Examples 1, Examples 2 to 5 and Comparative Examples 1 and 2 in which the contents of both sodium alginate and calcium chloride were changed, Examples 6 and 7 and Comparative Example 3 in which the contents of calcium chloride were changed, 4, Examples 8 and 9 in which the content of 3-O-ethylascorbic acid was changed, Comparative Examples 5 and 6, and Examples 10 and 11 in which the content of High Glyol S-26 was changed were also adjusted. Further, in Example 1, Comparative Examples 7 and 8 in which sodium alginate was replaced with another polymer, and Comparative Example 9 in which High Glyol S-26 was replaced with another surfactant were also prepared. Shown in Tables 1 and 2.

<Test Example 1> Appearance, color, and odor evaluation of composition for external skin The composition for external skin prepared in Production Example 1 was stored at 20 ° C. for 1 day, and the appearance was evaluated. Then, it stored at 50 degreeC and evaluated the external appearance, the color, and the smell after one month. However, on the day before the evaluation, the external composition for skin stored at 50 ° C. was stored at 20 ° C. for 24 hours and evaluated. In terms of appearance, the absolute evaluation was evaluated by comparing the color and odor with those separately stored at 5 ° C. The criteria for each evaluation are shown below. The results are shown in Tables 1 and 2.

<Appearance evaluation>
0: Emulsified neatly.
1: Although emulsified, the emulsified particles are enlarged and the transparency is enhanced.
2: Emulsification failure is observed (less than 5% of the total).
3: Emulsification is broken and oil is separated.

<Color, smell evaluation>
0: Same as 5 ° C.
1: There is a slight difference compared to 5 ° C. It is a level that cannot be understood unless compared with 5 ° C.
2: A difference is seen compared with 5 degreeC. Even if it is not compared with 5 ° C., it can be easily understood.
3: Discoloration or odor change is remarkable. It is not suitable as a composition for external use on the skin.

<Test Example 2> Measurement of Viscosity of External Composition for Skin The external composition for skin prepared in Production Example 1 was stored at 20 ° C for 1 day, and the viscosity was measured. Then, it stored at 50 degreeC and the viscosity measurement was performed again after one month. However, on the day before the evaluation, the composition for external use stored at 50 ° C. stored at 20 ° C. for 24 hours was measured. In the viscosity measurement, the B-type viscometer No. 3 rotor was measured under the condition of 6 revolutions per minute (unit: mPa · s). The results are shown in Tables 1 and 2.

<Test Example 3> Evaluation of use feeling of the composition for external use on skin The questionnaire regarding the use feeling at the time of application of the test sample in which the viscosity was measured was conducted. The evaluation criteria are shown below. Tables 1 and 2 show the most frequent results for five people.
A: There is no stickiness and it is a very good feeling.
B: Although it feels a little sticky, it is a relatively good feeling.
C: A feeling of stickiness is felt and the feeling of use is bad.
D: A feeling of stickiness is considerably felt, and it is a very bad feeling of use. It is not suitable as a composition for external use on the skin.

From the results shown in Tables 1 and 2, it can be seen that according to the present invention, the viscosity of the preparation is remarkably increased, and a new composition for external use on the skin excellent in use feeling and preparation stability is provided.

INDUSTRIAL APPLICABILITY The present invention can be applied to a new skin external composition excellent in use feeling and formulation stability.

Claims (3)

1) 0.1 to 3% by mass of 3-O-ethylascorbic acid with respect to the total amount of the composition, 2) 0.03 to 3% by mass of alginic acid and / or a salt thereof with respect to the total amount of the composition, 3 2) 20 to 20% by mass of the polyvalent metal salt based on the alginic acid and / or salt thereof, and 4) 0.1 to 0.00 % of the polyoxybutylene polyglycerin monoalkyl (monoalkenyl) ether based on the total amount of the composition. An external composition for skin containing 5% by mass . The external composition for skin according to claim 1, wherein the polyvalent metal salt is calcium chloride. The external composition for skin according to claim 1 or 2, wherein the composition is an emulsified composition.