JP4147180B2 - Gel-like skin external preparation - Google Patents

Description

The present invention relates to a gel cleansing material .

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 gel-like external preparation for 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 and the like in a very small amount, but in the gel structure formed by the salt of the carboxyvinyl polymer, the gel structure 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, alkyl starch, such as technology used in combination alkyl methacrylate-acrylic acid copolymer and the like that have been known (e.g., see Patent Document 1). However, such a system has a hard gel structure and tends to be 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 cosmetics specification as essential components two types of water-soluble polymers, sodium alginate is disclosed in kind, that Sons those salts other carboxyvinyl polymers are disclosed ( for example, Patent Document 2, see Patent Document 3), do not have it at all known to blend actually combined, by such a configuration, it is completely unknown also high gel composition of salt tolerance is achieved. Further, also contain a water-absorbing polymer to the gel dosage form that already known (e.g., refer to Patent Document 4, Patent Document 5, Patent Document 6). However, there is no known technique for combining this with alginic acid and / or a salt thereof to be contained in a gel preparation. Further, (see e.g., Patent Document 7) carboxyvinyl polymer salt and polyoxyethylene fatty acid glyceryl and technique for obtaining gel-cleansing agent in combination is that that already known, a carboxyvinyl polymer and / or its salt 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

The present invention has been made under such circumstances, and an object of the present invention is to provide a cleansing material having a gel structure excellent in salt resistance.

In view of such circumstances, the present inventors seek cleansing agent having a gel structure which is excellent in salt tolerance, the results of extensive research efforts, 1) and alkaline earth metal salts of alginic acid, 2)
The present inventors have found that a gel-type cleansing material containing a water-absorbing polymer has such characteristics, and completed the invention. That is, the present invention relates to the following technique. (1) 1) carboxyvinyl polymer and / or salt thereof, 2) alkaline earth metal salt of alginic acid, and 3) cross-linked polyacrylic acid and / or salt thereof, or polyacrylic acid / starch graft polymer and / or A gel-type cleansing material comprising a water-absorbing polymer selected from salts thereof.
(2) The gel cleansing material according to (1), wherein the alkaline earth metal salt is a calcium salt .

According to the present invention, it is possible to provide a cleansing material having a gel structure excellent in salt resistance.

(1) cleansing agent of the water-absorbing polymer present invention is an essential component of the cleansing agent of the present invention is characterized by containing a water-absorbing polymer. The water-absorbing polymer that can be used in the present invention includes an acrylic acid structure as the main component of the polymer and can contain water at least twice its own weight. Cross-linked polyacrylic acid and / or a salt thereof, polyacrylic acid / starch graft Examples thereof include a 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 cleansing material of the present invention is preferably 0.01 to 5% by weight, more preferably 0.05 to 1% by weight. In this content range, these not only improve the stabilizing action of the carboxyvinyl polymers on the salt, but can also significantly improve the slimy feeling of the carboxyvinyl polymers.

(2) cleansing agent of cleansing agent an essential component is an alkaline earth metal salt present invention alginate of the present invention contains an alkaline earth metal salt of alginic acid as an essential component. Since alginic acid is a general-purpose raw material for cosmetics, alginic acid for cosmetics can be purchased and used. In the present invention, the alkaline earth metal salt of alginic acid has the action of strengthening the gel structure formed by the carboxyvinyl polymer and increasing the salt resistance. In order to achieve such an object, the alkaline earth metal salt of alginic acid is contained together with the carboxyvinyl polymer in the form of free alginic acid, and then a part or all of the alkaline earth metal salt is converted into a salt by neutralization. It is preferable to make it contain in the form made. This is because the structure of the carboxyvinyl polymer and their salts may destroy the structure of the carboxyvinyl polymer due to the counter ion of the salt when included in the form of an alkaline earth metal salt of alginic acid. Because. For the purpose of strengthening the gel structure, a calcium salt can be particularly preferably exemplified as the alkaline earth metal salt of alginic acid. 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 cleansing agent of the present invention, alkaline earth metal salts of alginic acid to achieve such a effect is as free of alginic acid, with respect to cleansing agent the total amount, to contain 0.01 to 0.2 wt% Preferably, 0.02 to 0.15% by mass is contained. Furthermore, the content is preferably 50 to 150% by mass with respect to the water-absorbing polymer converted to free.

(3) cleansing agent of the cleansing agent present invention the invention features in that it contains a carboxyvinyl polymer and / or its salt described later and the essential components a gel form. Because of its excellent cleansing agent is resistant salt of the present invention, the structure is not destroyed by the salt on the skin, until the end smoothly moderate friction and flow, cleansing form with suppressed sag done, to improve the cleansing effect come out. In the cleansing composition of the present invention, in addition to the essential components, optional components usually used in a skin external preparation 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 (eg, glyceryl monostearate), propylene glycol fatty acid esters (eg, propylene glycol monostearate), 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, carolinic acid, chitin, chitosan, carboxymethylchitin, agar, polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate, polyethylene glycol, bentonite Thickeners such as mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, silicic anhydride (silica), aluminum oxide, barium sulfate, etc. May be treated, bengara, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, bitumen, titanium oxide, zinc oxide inorganic pigments, surface may be treated, titanium mica, fish phosphorus foil, Pearl agents such as bismuth oxychloride, raked Red 202, Red 228, Red 226, Yellow 4, Blue 404, Yellow 5, Red 505, Red 230, Red 223, Orange 201, Red 213, Yellow 204 No., yellow 203, blue 1, green 201, purple 201, red 204, organic dyes such as polyethylene powder, polymethyl methacrylate, nylon powder, organopolysiloxane elastomer, and other organic powders, paraamino Benzoic acid UV absorbers, anthranilic acid UV absorbers, salicylic acid UV absorbers, cinnamic acid UV absorbers, benzophenone UV absorbers, sugar UV absorbers, 2- (2'-hydroxy-5'- UV absorbers such as t-octylphenyl) benzotriazole, 4-methoxy-4′-t-butyldibenzoylmethane, ethanol, Lower alcohols such as propanol, vitamin A or its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 or its derivatives, vitamin B such as vitamin B12, vitamin B15 or its derivatives, α- Tocopherol, β-tocopherol, γ-tocopherol, vitamin E such as vitamin E acetate, vitamin D, vitamin H, pantothenic acid, panthetin,
Preferred examples include vitamins such as pyrroloquinoline quinone.
As described above, the present invention contains a carboxyvinyl polymer and / or a salt thereof that exhibits excellent gel properties in the absence of a salt. 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 cleansing material of the present invention, such carboxyvinyl polymer has the effect of imparting structure to the system. To form such a structure, one or the two or more kinds selected from carboxyvinyl polymers, in total, relative to the cleansing agent the total amount, preferably contains 0.05 to 1 wt%, More preferably, it is 0.1-0.8 mass part. 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 cleansing material of the present invention can be produced by treating the essential components and optional components according to 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>
A gel cleansing material 1 of the present invention was prepared according to the formulation shown below. 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 example, alginic acid was replaced with sodium acrylate / starch graft polymer ("Sunfresh ST100"), and the same operation was carried out in the same manner, and "Sunfresh ST100" was replaced with alginic acid and treated in the same manner for comparison. 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 cleansing material 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 parts by mass polyoxyethylene (20) glyceryl monoisostearate
7.3 parts by mass of polyoxyethylene (20) glyceryl triisostearate
5.4 parts by mass of water 45 parts by mass c 10% aqueous potassium hydroxide 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. This gel was prepared by applying a solution of 0.1% by weight sodium chloride and 0.01% by weight sodium lauryl sulfate in water to a slide glass at a thickness of 0.5 mil with a doctor blade and drying. When 0.1 g of the cleansing material 2 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% aqueous potassium hydroxide 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. Alginate of this compound in place of the sodium starch graft polymers of acrylic acid ( "Sun Fresh ST100"), the same manipulation to specific Comparative Examples 3, instead of the "Sun Fresh ST100" alginate, similarly treated with It has created a ratio Comparative Examples 4. When similarly evaluated using the slide glass of Example 1, the gel cleansing material 3 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% potassium hydroxide aqueous 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 material 1 and Comparative Examples 1 and 2, 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 of 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) was 0.33 in the site treated with the gel cleansing material 1 of the present invention, 0.85 in the site treated in Comparative Example 1, and the site treated in Comparative Example 2 The part was 0.76. From this, it can be seen that the gel cleansing material 1 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

The present invention can be applied to a cleansing fee that can be administered to a site to be accurately administered.

Claims (2)

1) carboxyvinyl polymer and / or salt thereof, 2) alkaline earth metal salt of alginic acid, and 3) cross-linked polyacrylic acid and / or salt thereof, or polyacrylic acid / starch graft polymer and / or salt thereof A gel-type cleansing material comprising a water-absorbing polymer selected. The gel cleansing material according to claim 1, wherein the alkaline earth metal salt is a calcium salt.