JP2005179317A - Gel-like skin care preparation for external use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a skin care preparation for external use having a gel structure excellent in salt resistance. <P>SOLUTION: This gel-like skin care preparation contains (1) alginic acid and/or its salt and (2) a starch-grafted acrylic acid and/or its salt. Calcium alginate is preferable as the alginic acid salt. Preferably, the preparation further contains a carboxyvinyl polymer and/or its salt. A preferable example of application of such a gel-like cosmetic is a cleansing gel cosmetic. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an external preparation for skin, and more particularly to an external preparation for gel.

  Gel-like external preparations for skin are applied to various external preparations for skin and cosmetics because of their good feeling of use. In such an external preparation for gelled skin, a carboxyvinyl polymer and / or a salt thereof is used as a gelling agent. This is because the salt of the carboxyvinyl polymer is excellent in the action of gelling the aqueous carrier and stabilizing the emulsification in a very small amount. However, in the gel structure formed by the salt of the carboxyvinyl polymer, the gel structure is formed by the presence of the salt. The biggest drawback is that it is easily broken. Due to such drawbacks, in gel compositions that depend only on the gel structure of the salt of the carboxyvinyl polymer, the gel structure is immediately affected by the salt contained in the sweat when administered to the skin. It is known that there may be cases where it collapses and impairs usability. In order to suppress such a phenomenon, for example, a technique using an alkylated starch, an alkyl methacrylate / acrylic acid copolymer, or the like is known. (For example, see Patent Document 1) However, in such a system, the gel structure tends to be hard and brittle, and its use is limited.

  On the other hand, alginic acid and / or a salt thereof and carboxyvinyl polymer and / or a salt thereof are often classified into the same water-soluble polymer. In particular, in the description of cosmetics comprising two types of water-soluble polymers as essential constituents, there is one in which sodium alginate is disclosed in one type and a salt of carboxyvinyl polymer is disclosed in the other. For example, see Patent Document 2 and Patent Document 3), it is not known at all to actually combine and blend, and it is not known at all that a gel composition having high salt resistance can be obtained by such a configuration. It is already known to include a water-absorbing polymer in a gel dosage form. (For example, refer to Patent Document 4, Patent Document 5, and Patent Document 6) However, there is no known technique for combining this material with alginic acid and / or a salt thereof to be contained in a gel preparation. Furthermore, although a technique for obtaining a gel cleansing material by combining a salt of carboxyvinyl polymer and a polyoxyethylene fatty acid glyceryl is already known (see, for example, Patent Document 7), carboxyvinyl polymer and / or its salt Also, there is no known technique for combining alginic acid and / or a salt thereof with polyoxyethylene fatty acid glyceryl.

JP 2000-327516 A JP 2000-239147 A JP 2000-119166 A JP 2000-327516 A JP 2000-143547 A Japanese translation of PCT publication No. 2003-503316 JP 11-199438 A

  This invention is made | formed under such a condition, and makes it a subject to provide the skin external preparation which has a gel structure excellent in salt tolerance.

In view of such circumstances, the present inventors have sought for an external preparation for skin having a gel structure excellent in salt resistance, and as a result of intensive research efforts, 1) alginic acid and / or a salt thereof and 2) water absorption. The inventors have found that a gel-like external preparation for skin containing a polymer has such characteristics, and have completed the invention. That is, the present invention relates to the following technique.
(1) A gel-like external preparation for skin comprising 1) alginic acid and / or a salt thereof and 2) acrylic acid grafted with starch and / or a salt thereof.
(2) The external preparation for skin according to (1), comprising calcium alginate as a salt of alginic acid.
(3) Further. The skin external preparation according to (1) or (2), comprising a carboxyvinyl polymer and / or a salt thereof.
(4) The skin external preparation according to any one of (1) to (3), which is a cleansing gel cosmetic.

  ADVANTAGE OF THE INVENTION According to this invention, the skin external preparation which has a gel structure excellent in salt tolerance can be provided.

(1) Water-absorbing polymer which is an essential component of the skin external preparation of the present invention The skin external preparation of the present invention is characterized by containing a water-absorbing polymer. The water-absorbing polymer that can be used in the present invention is not particularly limited as long as it can contain water having an acrylic acid structure as the main component of the polymer, and can contain water at least twice its own weight. Specific examples include, for example, cross-linked polyacrylic acid and / or a salt thereof, polyacrylic acid / starch graft polymer and / or a salt thereof, and these are already commercially available. Among such commercially available products, preferred are sunfresh ST500DC, ST500MPS, polyacrylic acid / starch graft polymer and / or salt, which are cross-linked polyacrylic acid and / or salt, sunfresh ST100, ST100MPS, An example is ST100SP. These are all commercially available from Sanyo Chemical Industries. These can be used as a salt at the time of use, or as a free form by an acid or the like. At this time, as long as it is physiologically acceptable as a salt, it can be applied without any particular limitation. For example, an alkali metal salt such as sodium or potassium, or an alkaline earth such as magnesium. Preferred examples include metal salts, ammonium salts, organic amine salts, basic amino acid salts and the like. Further, it is possible to contain only one species, or it is possible to contain two or more species in combination. The total content of these water-absorbing polymers in the external composition for skin of the present invention is preferably 0.01 to 5% by weight, more preferably 0.05 to 1% by weight. In these containing halves, not only the stabilizing action of the carboxyvinyl polymers on the salt is improved, but also the slimy feeling of the carboxyvinyl polymers can be remarkably improved.

(2) Alginic acid which is an essential component of the external preparation for skin of the present invention The external preparation for skin of the present invention contains alginic acid and / or a salt thereof as an essential component. Since the alginic acid and / or salt thereof is a general-purpose raw material for cosmetics, alginic acid or a salt thereof for cosmetics can be purchased and used. In the present invention, alginic acid and / or a salt thereof has an action of strengthening the gel structure formed by the carboxyvinyl polymer and increasing the salt resistance. In order to achieve such an object, the alginic acid and / or salt thereof is contained in the form of free alginic acid together with the carboxyvinyl polymer, and then a part or all of the alginic acid and / or salt thereof is converted into a salt by neutralization. It is preferable to make it contain with a form. This is because the structure of the carboxyvinyl polymer may be destroyed by the counter ion of the salt when it is contained in the form of an alginate while the carboxyvinyl polymer and the salt thereof are forming a structure. For the purpose of strengthening such a gel structure, the alginic acid salt preferably includes an alkaline earth metal salt, and a calcium salt is particularly preferable. The content of the alkaline earth metal is preferably 0.0005 to 0.1% by mass, and preferably 0.001 to 0.05% by mass in terms of hydroxide. The base source containing such an alkaline earth metal is preferably calcium hydroxide. In the external preparation for skin of the present invention, in order for alginic acid and / or a salt thereof to exert such effects, 0.01 to 0.2% by mass is contained as free alginic acid with respect to the total amount of external preparation for skin. It is preferable to contain 0.02-0.15 mass%. Furthermore, the content is preferably 50 to 150% by mass with respect to the water-absorbing polymer converted to free.

(3) External preparation for skin of the present invention The external preparation for skin of the present invention has a gel-like shape and contains the essential components. The external preparation for skin of the present invention can be applied without particular limitation as long as it is administered externally to the skin, and suitable examples include, for example, external preparations for skin and cosmetics. Particularly preferred are gel cleansing cosmetics. This is because the external preparation for skin of the present invention has excellent salt-tolerance, so that the structure is not destroyed by salt on the skin, and it can be cleansed in a form that is moderately smooth with friction and flow to the end, with drooping suppressed, and has a cleansing effect It is because it can improve. In the cosmetic of the present invention, in addition to the essential components, optional components usually used in cosmetics can be contained. Such optional ingredients include, for example, 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, hydrogenated coconut oil Oils such as hardened oil, mole, hardened castor oil, beeswax, candelilla wax, carnauba wax, ibotarou, lanolin, reduced lanolin, hard lanolin, jojoba wax, waxes, liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum , Hydrocarbons such as microcrystalline wax, higher fatty acids such as oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, cetyl alcohol, stearyl alcohol, isostearyl Alcohol, behenyl alcohol, octyldodecanol, higher alcohol such as myristyl alcohol, cetostearyl alcohol, cetyl isooctanoate, isopropyl myristate, hexyldecyl isostearate, diisopropyl adipate, di-2-ethylhexyl sebacate, cetyl lactate, malic acid Diisostearyl, di-2-ethylhexanoic acid ethylene glycol, dicaprate neopentyl glycol, di-2-heptylundecanoic acid glycerin, tri-2-ethylhexanoic acid glycerin, tri-2-ethylhexanoic acid trimethylolpropane, tri Synthetic ester oils such as trimethylolpropane isostearate and pentane erythritol tetra-2-ethylhexanoate, dimethylpolysiloxane, methylphenylpoly Loxane, linear polysiloxane such as diphenylpolysiloxane, cyclic polysiloxane such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexanesiloxane, amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, Oil agents such as silicone oil such as modified polysiloxane such as fluorine-modified polysiloxane, anionic surfactants such as fatty acid soap (sodium laurate, sodium palmitate, etc.), potassium lauryl sulfate, triethanolamine ether of alkyl sulfate, chloride Cationic surfactants such as stearyltrimethylammonium, benzalkonium chloride, laurylamine oxide, imidazoline-based amphoteric surfactants (2-cocoyl-2-imida Zolinium hydroxide-1-carboxyethyloxy disodium salt, etc.), betaine surfactants (alkyl betaine, amide betaine, sulfobetaine, etc.), amphoteric surfactants such as acylmethyltaurine, sorbitan fatty acid esters (sorbitan) Monostearate, sorbitan sesquioleate, etc.), glycerin fatty acids (glyceryl monostearate, etc.), propylene glycol fatty acid esters (propylene glycol monostearate, etc.), hardened castor oil derivatives, glycerin alkyl ethers, POE sorbitan fatty acid esters (POE sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc.), POE sorbite fatty acid esters (POE-sorbitol monolaurate, etc.), POE glycerin fatty acid ester Tells (POE-glycerol monoisostearate, etc.), POE fatty acid esters (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE2-octyldodecyl ether, etc.), POE alkyl phenyl ethers (POE nonylphenyl) Ethers, etc.), Pluronic types, POE / POP alkyl ethers (POE / POP2-decyltetradecyl ether, etc.), Tetronics, POE castor oil / hardened castor oil derivatives (POE castor oil, POE hardened castor oil, etc.), Nonionic surfactants such as sucrose fatty acid ester and alkyl glucoside, polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, maltitol, propylene Polyols such as recall, dipropylene glycol, diglycerin, isoprene glycol, 1,2-pentanediol, 2,4-hexylene glycol, 1,2-hexanediol, 1,2-octanediol, pyrrolidone carboxylic acid Moisturizing ingredients such as sodium, 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, hyaluronan Droxyethyl guar gum, carboxymethyl guar gum, dextran, keratosulfuric acid, locust bean gum, succinoglucan, caronic acid, chitin, chitosan, carboxymethylchitin, agar, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, sodium polyacrylate, Thickeners such as polyethylene glycol and bentonite, surface may be treated, powder such as mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, silicic anhydride (silica), aluminum oxide, barium sulfate The surface may be treated, bengara, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, bitumen, titanium oxide, zinc oxide inorganic pigments, the surface may be treated, mica titanium, Fish phosphorus foil, bismuth oxychloride Pearl agents, which may be raked Red 202, Red 228, Red 226, Yellow 4, Blue 404, Yellow 5, Red 505, Red 230, Red 223, Orange 201 No., Red No. 213, Yellow No. 204, Yellow No. 203, Blue No. 1, Green No. 201, Purple No. 201, Red No. 204, and the like, polyethylene powder, polymethyl methacrylate, nylon powder, organopolysiloxane elastomer Organic powders such as paraaminobenzoic acid UV absorbers, anthranilic acid UV absorbers, salicylic acid UV absorbers, cinnamic acid UV absorbers, benzophenone UV absorbers, sugar UV absorbers, 2- ( UV of 2'-hydroxy-5'-t-octylphenyl) benzotriazole, 4-methoxy-4'-t-butyldibenzoylmethane, etc. Absorbents, lower alcohols such as ethanol and isopropanol, vitamin A or derivatives thereof, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 or derivatives thereof, vitamin B12, vitamin B15 or derivatives thereof, etc. Vitamin E such as vitamin B, α-tocopherol, β-tocopherol, γ-tocopherol and vitamin E acetate, vitamin D such as vitamin D, vitamin H, pantothenic acid, panthetin, pyrroloquinoline quinone and the like can be preferably exemplified. Among such components, particularly preferred are carboxyvinyl polymers and / or their salts that exhibit excellent gel properties in the absence of salts. Carboxyvinyl polymer or a salt thereof is a general-purpose raw material for cosmetics, and is used as a thickening / gelling agent in the form of a salt. In cosmetic raw materials, in addition to this, those obtained by substituting acryloyl groups of carboxyvinyl polymers with methacryloyl groups, or copolymers in which some of these carboxyl groups are esterified with alkyl groups having 10 to 30 carbon atoms, etc. In some cases, such copolymers are also classified as carboxyvinyl polymers in a broad sense. In the present invention, the term carboxyvinyl polymer has a meaning as a broad term including such copolymers. These may be used alone or in combination. Further, neutralization is performed to form a salt to form a structure, and such neutralization can be limited to a part of the carboxyl group. In the external preparation for skin of the present invention, such carboxyvinyl polymer has an action of imparting structure to the system. In order to form such a structure, it is preferable that 0.05 to 1% by mass of one or more selected from carboxyvinyl polymers is contained in a total amount with respect to the total amount of the external preparation for skin. More preferably, it is 0.1 to 0.8 part by mass. Furthermore, these carboxyvinyl polymers are neutralized to form salts, and as base residues (carboxyvinyl polymer salts) for forming a structure, for example, alkali metal salts such as sodium salts and potassium salts, Preferred examples include alkaline earth metal salts such as calcium and magnesium. It is preferable to adjust the content of the base residue, in other words, the alkali metal ion in the cation root to 2 equivalents or less, more preferably 1.5 equivalents or less with respect to the carboxyvinyl polymer. This is because a gel with high salt resistance is formed by taking such a form. The skin external preparation of this invention can be manufactured by processing the said essential component and arbitrary component in accordance with a conventional method.

  Hereinafter, the present invention will be described in more detail with reference to examples, but it is needless to say that the present invention is not limited to such examples.

<Example 1>
According to the formulation shown below, gel cleansing material 1 which is an external preparation for skin of the present invention was prepared. In other words, the components (a), (b), and (c) are heated to 80 ° C., and (a) is uniformly dispersed, and then added to (b) to make them compatible with each other. A gel structure was prepared and stirred and cooled to obtain a gel cleansing material 1. In this case, alginic acid was replaced with sodium acrylate / starch graft polymer ("Sunfresh ST100"), and the same operation was carried out in the same manner as in Comparative Example 1, except that "Sunfresh ST100" was replaced with alginic acid. Example 2 was created. A solution prepared by dissolving 0.1% by mass of sodium chloride and 0.01% by mass of sodium lauryl sulfate in water on a slide glass at a thickness of 0.5 mil with a doctor blade was dried. When 0.1 g of the gel cleansing material 1 and Comparative Examples 1 and 2 were discharged onto this slide glass and the height was measured after 5 minutes, the gel cleansing material 1 was 0.7 mm, and Comparative Example 1 was 0. 0.1 mm and Comparative Example 2 was 0.3 mm. From this, it can be seen that the gel structure has salt resistance in the cosmetic of the present invention. The potassium ion content is 0.9 equivalent.
I Polyethylene glycol 4000 0.5 parts by mass Dipropylene glycol 25 parts by mass Carboxyvinyl polymer 0.6 parts by mass Alginic acid 0.1 parts by mass “Sunfresh ST100” 0.1 part by mass Polyoxyethylene (20) glyceryl monoisostearate 7 .3 parts by mass polyoxyethylene (20) glyceryl triisostearate 5.4 parts by mass water 45 parts by mass C 10% potassium hydroxide aqueous solution 2.4 parts by mass water 13.59 parts by mass calcium hydroxide 0.01 parts by mass

<Example 2>
“Sunfresh ST100” in Example 1 was replaced with “Sunfresh DC500”, which is a crosslinked polyacrylate, to prepare a gel cleansing material 2 in the same manner as in Example 1. The slide glass was coated with a solution of 0.1% by weight sodium chloride and 0.01% by weight sodium lauryl sulfate in water at a thickness of 0.5 mil with a doctor blade and dried. When 0.1 g of the material was discharged, the height after 5 minutes was 0.65 mm. Cross-linked polyacrylic acid and / or its salt was found to have the same effect as the acrylate starch graft polymer.
I Polyethylene glycol 4000 0.5 parts by mass Dipropylene glycol 25 parts by mass Carboxyvinyl polymer 0.6 parts by mass Alginic acid 0.1 parts by mass “Sunfresh DC500” 0.1 part by mass Polyoxyethylene (20) glyceryl monoisostearate 7 .3 parts by mass polyoxyethylene (20) glyceryl triisostearate 5.4 parts by mass water 45 parts by mass C 10% potassium hydroxide aqueous solution 2.4 parts by mass water 13.59 parts by mass calcium hydroxide 0.01 parts by mass

<Example 3>
The carboxyvinyl polymer of Example 1 was replaced with acrylic acid / alkyl acrylate (C10-30) (“Carbopol 1382” manufactured by Goodrich), and the same operation was performed to obtain gel cleansing material 3. The alginic acid was replaced with sodium acrylate / starch graft polymer ("Sunfresh ST100"), and the same operation was carried out in the same manner as in Comparative Example 3, except that "Sunfresh ST100" was replaced with alginic acid. Example 4 was made. When similarly evaluated using the slide glass of Example 1, the gel cleansing material 1 was 0.6 mm, the comparative example 3 was 0.1 mm, and the comparative example 4 was 0.2 mm.
Polyethylene glycol 4000 0.5 parts by mass Dipropylene glycol 25 parts by mass “Carbopol 1382” 0.6 parts by mass Alginic acid 0.1 parts by mass “Sunfresh ST100” 0.1 parts by mass polyoxyethylene (20) monoisostearic acid Glyceryl 7.3 parts by mass Polyoxyethylene (20) Glyceryl triisostearate 5.4 parts by mass Water 45 parts by mass C 10% aqueous potassium hydroxide solution 2.4 parts by mass Water 13.59 parts by mass Calcium hydroxide 0.01 Parts by mass

<Test Example 1>
Using the gel cleansing cosmetic 1 and Comparative Example 1, the cleansing action was compared. That is, 0.05 g of the lip color for evaluation shown below was applied to a 2 cm × 4 cm portion on the inner side of the upper arm, 0.05 g of cleansing material was administered to this, and after rubbing well, wiped with cut cotton, Then, the color difference between the administration site and the non-treatment site was measured with a color difference meter. (Number of Examples 1) The color difference (ΔE) is 0.33 in the site treated with the gel cleansing cosmetic 1 of the present invention, and 0.85 in the site treated in Comparative Example 1, and the processed in Comparative Example 2 The portion thus obtained was 0.76. From this, it can be seen that the gel cleansing cosmetic 1 as an external preparation for skin of the present invention has an excellent cleansing action. This is presumably because the gel structure has a salt resistance, and therefore has a property of accurately staying in a place with oily soil.
(Lip color)
Polyethylene 5 parts by weight microcrystalline wax 5 parts by weight silicone elastomer 5 parts by weight carnauba wax 20 parts by weight hydrogenated coconut oil 15 parts by weight diisostearyl malate 10 parts by weight squalane 10 parts by weight castor oil 10 parts by weight Bengala 15 parts by weight red 202 No. 1 part by weight titanium mica 4 parts by weight

<Example 4>
According to the formulation shown below, the skin external preparation 1 which is the skin external preparation of the present invention was prepared. In other words, the components (a), (b), and (c) are heated to 80 ° C., and (a) is uniformly dispersed, and then added to (b) to make them compatible with each other. A gel structure was prepared and stirred and cooled to obtain a skin external medicine 1.
I Polyethylene glycol 4000 0.5 parts by mass Dipropylene glycol 25 parts by mass Carboxyvinyl polymer 0.6 parts by mass Alginic acid 0.1 parts by mass “Sunfresh ST100” 0.1 part by mass Polyoxyethylene (20) glyceryl monoisostearate 7 .3 parts by mass polyoxyethylene (20) glyceryl triisostearate 5.4 parts by mass norethisterone 2 parts by mass water 45 parts by mass C 10% potassium hydroxide aqueous solution 2.4 parts by mass water 11.59 parts by mass calcium hydroxide 0 .01 parts by mass

  The present invention can be applied to an external preparation for skin that can be administered to a site to be accurately administered.

Claims (4)

A gel external preparation for skin comprising 1) alginic acid and / or a salt thereof and 2) a water-absorbing polymer. The external preparation for skin according to claim 1, comprising calcium alginate as a salt of alginic acid. Furthermore. The skin external preparation according to claim 1 or 2, comprising a carboxyvinyl polymer and / or a salt thereof. It is a cleansing gel cosmetic, The skin external preparation of any one of Claims 1-3 characterized by the above-mentioned.