JP4854474B2 - Emulsifier type skin external preparation - Google Patents

Description

  The present invention relates to a skin external preparation, and more particularly to an emulsifier type skin external preparation.

In cosmetics, increasing the softness of the skin due to its use is a favorable phenomenon and is counted as one of the beneficial effects of cosmetics. Even as a means of measuring the flexibility of such skin, known methods resides, and already using this method, commercially available equipment that Sons (e.g., Patent Document 1, Patent Document 2, Patent Document 3) . However, it is not known at all what kind of cosmetics are excellent in the action of softening the skin in this way, and the present condition is that they do not have the cause. That is, it can be said that development of a means for designing cosmetics having an action of softening the skin according to the purpose by clarifying at least a part of these factors has been desired. To improve the flexibility of the skin, different and to smooth the surface of the skin.

  As an ingredient that exerts such an effect, the action of oily components can be considered, but the stratum corneum is an organ that functions to inhibit the penetration of substances from outside to the living body and to protect the living body, It was difficult to transfer the oily component into the stratum corneum and improve the flexibility of the skin as an organ. The oily component was present on the surface and the friction coefficient was temporarily reduced at best.

On the other hand, an ester of N- acylamino acids such as diester of N- lauroyl glutamic acid is an oily component having a water-holding property, that is known to be excellent in moisture retention (see, for example, Patent Document 4, Patent Document 5). Hydroxyl phospholipids are compounds in which double bonds existing in the lipid portion of phospholipids such as lecithin and phosphatidylglycerol are oxidized to introduce two hydroxyl groups. cosmetic use in the Examples that are known (e.g., see Patent Document 6, Patent Document 7, Patent Document 8, Patent Document 9, Patent Document 10, Patent Document 11, Patent Document 12). However, no topical skin preparation containing 1) N-acylamino acid ester and 2) hydroxylated phospholipid is known at all, and the oily component can be transferred to the stratum corneum by such a combination. Is not known at all.

JP 20066541 A Japanese Patent Laid-Open No. 2005-348991 Japanese Patent Laid-Open No. 2005-220084 JP 2004-346045 A JP 09-235211 A JP-A-2005-008591 JP-A-2005-008590 JP 2003-146872 A JP 2002-161017 A Japanese Patent Application Laid-Open No. 08-026964 JP-A-06-116116 Special table 2003-533491 gazette

  The present invention has been made under such circumstances, and an object of the present invention is to provide a means for improving skin flexibility.

In view of such a situation, the present inventors have sought for means for improving skin flexibility and have made extensive research efforts. 1) From N-acylglutamic acid esters and N-acylglycine esters. at least one selected, 2) lecithin hydroxide, and Heading that (3) the skin external preparation containing a hydrogenated rapeseed oil is provided with such a property, and completed the invention. That is, the present invention is as follows.
(1) An emulsifier type comprising at least one selected from 1) an ester of N-acylglutamic acid and an ester of N-acylglycine , 2) hydroxylated lecithin, and 3) hydrogenated rapeseed oil Skin external preparation.
(2) The emulsifier-type skin external preparation according to (1), wherein the ester of N-acylglutamic acid is an ester of N-lauroyl -L-glutamic acid .
(3) The skin external preparation in the form of an emulsifier according to (1) or (2), wherein the ester of N-acylglycine is an ester of N-capryloylglycine.
(4) The emulsifier-type skin external preparation according to any one of (1) to (3) , wherein the content of the hydroxylated lecithin is 0.1 to 1% by mass .

  According to the present invention, a means for improving skin flexibility can be provided.

(1) N-acylamino acid ester which is an essential component of the skin external preparation of the present invention The skin external preparation of the present invention is an emulsifier type and contains an N-acylamino acid ester as an essential component. To do. As the acyl group constituting the ester of N-acylamino acid, an aliphatic acyl group which may have an unsaturated bond having 8 to 30 carbon atoms can be suitably exemplified, for example, capryloyl group, 2-ethyl More preferred examples include a hexanoyl group, a decanoyl group, a lauroyl group, a myristoyl group, a palmitoyl group, a stearoyl group, a behenoyl group, an isostearoyl group, and an oleoyl group. Particularly preferred is a lauroyl group. Examples of the amino acid to be acylated include acidic amino acids such as aspartic acid and glutamic acid, neutral amino acids such as glycine and alanine, and basic amino acids such as lysine and arginine. Among them, glutamic acid and glycine are preferable, and glycine is particularly preferable. Is preferred. Moreover, the hydrocarbon group which comprises ester can illustrate a cholesteryl group, a behenyl group, an octyldecyl group etc. suitably. Such N-acyl amino acid ester is preferably a diester if it is an acidic amino acid, and is preferably an ester of N, N′-diacylamino acid if it is a basic amino acid. Such an ester of N-acylamino acid can be obtained by reacting an amino acid with acyl chloride under alkaline conditions to derive N-acylamino acid, and then reacting the alkyl halide or alkenyl with a halide in the presence of alkali. . Specific examples of the compound include N-acylglycine esters such as N-capryloylglycine behenyl ester and N-caproylglycine octyldodecyl ester. If N-acylglutamic acid ester is used, N -Lauroyl-L-glutamate di (cholesteryl / behenyl / octyldodecyl), N-lauroyl-L-glutamate di (cholesteryl / octyldodecyl), N-lauroyl-L-glutamate di (phytosteryl / behenyl / octyldodecyl), N- Preferred examples include lauroyl-L-glutamate di (phytosteryl / octyldodecyl). Among these, N-capryloylglycine octyldodecyl ester and N-lauroyl-L-glutamate di (cholesteryl / octyldodecyl) can be particularly preferably exemplified. N-acylamino acid esters can be synthesized as described above, but some of them are already marketed as cosmetic raw materials, and such commercial products can be purchased and used. . Particularly preferred commercially available products are “El Deu PS203” (N-lauroyl-L-glutamate di (phytosteryl / octyldecyl)) and “El Deu CL-301” (N-lauroyl glutamate di (cholesteryl / Behenyl / octyldodecyl)), “Elduu CL-202” (N-lauroylglutamate di (cholesteryl / octyldodecyl)), “Elduu PS-304” (N-lauroylglutamate di (phytosteryl / behenyl / octyldodecyl)), etc. Among them, “El Dew PS203” is particularly preferable. Can be illustrated. These components can be contained alone or in combination of two or more. The preferred content is 0.005 to 5% by mass, more preferably 0.01 to 10% by mass, and more preferably 0.1 to 5% by mass, based on the total amount of the external preparation for skin. . Such components are excellent in the action of transferring oily components into the stratum corneum together with phospholipids described later.

(2) Hydroxylated phospholipid which is an essential component of the cosmetic of the present invention The external preparation for skin of the present invention is characterized by containing hydroxyphospholipid as an essential component. The hydroxylated phospholipid referred to in the present invention is obtained by oxidizing the unsaturated bond present in the acyl group of the phospholipid to form a dihydroxy body, and the phospholipid as a base is usually used in cosmetics and the like. For example, lecithin, phosphatidic acid, phosphatidylglycerol, phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine, or lysates thereof can be preferably exemplified. The double bond of the acyl group of such phospholipid is defined as an epoxide using an oxidizing agent such as benzoyl peroxide, and then water is added to lead to the dihydroxy form, which is defined as a hydroxylated phospholipid. Such hydroxylated phospholipids already exist in the market, and such commercial products can be purchased and used. Preferable examples of commercially available products include “NIKKOL Resinol SH50” (manufactured by Nippon Surfactant Kogyo Co., Ltd.), which is an equivalent mixture of hydroxylated lecithin and glycerin based on soybean. These hydroxylated phospholipids can contain only one species, or can contain two or more species in combination. In the emulsification system, this component works together with the other essential component, N-acylamino acid ester, to improve the transfer of the oily component into the skin. In order to exert such effects, the phospholipid is preferably contained in a total amount of 0.01 to 2% by mass, more preferably 0.05 to 1% by mass, based on the total amount of the cosmetic.

(3) External preparation for skin of the present invention The external preparation for skin of the present invention contains the above-mentioned components as essential components and is in an emulsifier form. As such an emulsifier form, an oil-in-water emulsifier form, a water-in-oil emulsifier form, a complexed multi-layer emulsifier form thereof and the like can be exemplified, and an oil-in-water emulsifier form is particularly preferred among these. This is because the effect of the present invention is particularly evident in the oil-in-water emulsifier form. Here, the external preparation for skin in the present invention is a composition for transdermal administration that keeps the skin healthy and excludes those for pharmaceutical use, and includes quasi drugs.

In the cosmetic of the present invention, in addition to the components described so far, optional components usually used in cosmetics can be contained within a range that does not impede the effects of the present invention. Examples of such optional components, e.g., macadamia nut oil, Abou transient oil, corn oil, olive oil, rape seed oil which has not been cured, sesame oil, castor oil, safflower oil, cottonseed oil, jojoba oil, coconut oil, palm oil, Liquid lanolin, hydrogenated coconut oil, hydrogenated oil, molasses, hydrogenated castor oil, beeswax, candelilla wax, carnauba wax, ibotarou, lanolin, reduced lanolin, hard lanolin, jojoba wax and other oils, waxes; liquid paraffin, squalane, pristane, ozokerite , Hydrocarbons such as paraffin, ceresin, petrolatum, 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 Higher alcohols such as isostearyl alcohol, behenyl alcohol, octyldodecanol, myristyl alcohol, cetostearyl alcohol; cetyl palmitate, cetyl stearate, cetyl isooctanoate, isopropyl myristate, hexyldecyl isostearate, diisopropyl adipate, sebacic acid di-2-ethylhexyl, cetyl lactate, diisostearyl malate, ethylene glycol di-2-ethylhexanoate, neopentyl glycol dicaprate, glyceryl di-2-heptylundecanoate, Application Benefits 2-ethylhexanoic acid trimethylol Synthetic ester oils such as propane and trimethylolpropane triisostearate; dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane Linear polysiloxanes such as octane; cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexanesiloxane; amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane Oils such as silicone oil such as modified polysiloxane such as fatty acid soap (sodium laurate, sodium palmitate, etc.), anionic surfactants such as potassium lauryl sulfate, alkylsulfuric triethanolamine ether; stearyltrimethylammonium chloride, Cationic surfactants such as benzalkonium chloride and laurylamine oxide; imidazoline-based amphoteric surfactants (2-cocoyl-2-imidazolinium hydroxide-1-carbon Ruboxyethyloxy disodium salt), betaine surfactants (alkyl betaine, amide betaine, sulfobetaine, etc.), amphoteric surfactants such as acylmethyl taurine; sorbitan fatty acid esters (sorbitan monostearate, sesquiolein) Sorbitan acid), 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) , Monostearic acid polyoxyethylene sorbitan, etc.), POE sorbite fatty acid esters (POE-sorbite monolaurate, etc.), POE glycerin fatty acid esters (POE-glycerin mono) Sotearate, etc.), POE fatty acid esters (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE2-octyldodecyl ether, etc.), POE alkyl phenyl ethers (POE nonyl phenyl ether, 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.), sucrose fatty acid esters, alkyl glucosides, etc. Nonionic surfactants: polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, maltitol, propylene glycol, dipropylene glycol , Diglycerin, isoprene glycol, 1,2-pentanediol, 2,4-hexanediol, 1,2-hexanediol, 1,2-octanediol and other polyhydric alcohols; sodium pyrrolidonecarboxylate, lactic acid, sodium lactate Moisturizing ingredients such as mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, anhydrous silicic acid (silica), aluminum oxide, barium sulfate and the like ; Inorganic pigments of bengara, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, bitumen, titanium oxide, zinc oxide, which may be treated; titanium mica, fish phosphorus foil, whose surface may be treated, 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, Yellow 203, Blue 1, Green 201, Purple 201, Red organic pigments such as No. 204, polyethylene powder, polymethyl methacrylate, nylon powder, organic powders such as organopolysiloxane elastomers; para-aminobenzoic acid UV absorbers; anthranilic acid UV absorbers; salicylic acid ultraviolet absorbers ; cinnamic acid-based ultraviolet absorbents; benzophenone ultraviolet absorbers; sugar-based ultraviolet absorbent; 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 4-methoxy-4'-t-butyl di UV absorbers such as benzoylmethane; lower alcohols such as ethanol and isopropanol; vitamin A or a derivative thereof; Vitamin Bs such as tamin B ₆ hydrochloride, vitamin B ₆ tripalmitate, vitamin B ₆ dioctanoate, vitamin B ₂ or derivatives thereof, vitamin B ₁₂ , vitamin B ₁₅ or derivatives thereof; α-tocopherol, β-tocopherol, γ -Vitamin E such as tocopherol and vitamin E acetate, vitamin D, vitamin H, pantothenic acid, panthetin, pyrroloquinoline quinone and the like; and antibacterial agents such as phenoxyethanol are preferred. Among these components, particularly preferred are those that are suitable for softening the skin, cause the loss of elasticity of collagen, suppress inflammation, and have an action of increasing the collagen production ability of fibroblasts. Specific ingredients such as glycyrrhetinic acid derivative, hypericum extract, royal jelly extract, cucumber extract, perennial extract, yarrow extract, mussel extract, mussel extract, pearl extract, soybean Extract, clove extract, bacmond extract, bumblebee extract, mulberry extract, birch extract, birch extract, rosemary extract, sage extract, ginseng extract, horse chestnut extract, oil-soluble licorice extract, vitamin E and Selected from its derivatives, arbutin, vitamin C and its derivatives and safflower extracts Than is. Preferred examples of the glycyrrhetinic acid derivative include esters of glycyrrhetinic acid such as stearyl glycyrrhetinic acid, and dipotassium glycyrrhizinate which is a salt of a glycoside of glycyrrhetinic acid. preferable. These can also be contained as an extract of licorice. It is preferable that the extract of hypericum contains at least 100 μM of farellol. Royal jelly extract 1) forms a single band in non-denaturing polyacrylamide gel electrophoresis of proteins in royal jelly 2) has a molecular weight measured by SDS-polyacrylamide gel electrophoresis under reducing conditions of about 57 It is preferable to contain 0.001 to 0.1% by mass of protein that is kilodalton (see, for example, Patent Document 6) and contains at least 9% by mass of the total protein. The kujin extract preferably contains at least 0.001% by mass of the sophoraflavanone G containing at least 100 μM. It is preferable that the Achillea millefact contains 0.01 to 1% by mass of at least 100 μM centauridine. As a soybean extract, what hydrolyzed soybean protein and soybean isoflavone are preferable, and the preferable content of this component is 0.01-0.2 mass% in total. The mussel extract is preferably extracted from mussel scallop or string glycogen, and the content thereof is preferably 0.001 to 0.2% by mass. The clove extract preferably contains 0.1 to 1% by mass of eugenol, and preferably contains 0.01 to 0.3% by mass of such extract. It is preferable that Bacmondow contains 0.01-0.2 mass% of what contains 0.01-0.1 mass% of ophiopogonanone B. The birch extract preferably contains 200 μM or more of betulin or betulinic acid, and preferably contains 0.01 to 0.1% by mass of such extract. The horse chestnut extract is preferably a fruit extract, and it is preferable to contain 0.01 to 1% by mass of escin. The oil-soluble licorice preferably contains 0.01 to 0.1% by mass of globradine 0.01 to 1% by mass. The safflower extract should just contain a Casamin, and it is preferable to contain 0.01-0.2 mass% in conversion of a Casamin content. The rosemary preferably contains 0.001 to 0.1% by mass of rosmarinic acid. Vitamin C is preferably contained in an amount of 1 to 5% by mass, and arbutin or a salt thereof is preferably contained in an amount of 1 to 10% by mass. Furthermore, it is preferable to contain 0.1 to 1% by mass of cetyl palmitate in order to improve the feeling after use of the cosmetic and to allow the user to recognize the improvement in skin flexibility.

  More preferable examples include hardened rapeseed oil. Here, the hardened rapeseed oil is obtained by hydrogenating rapeseed oil obtained by extraction or pressing from the seed of Nanohana, in the presence of a catalyst, and has an iodine value of 45 to 15, more preferably 40. ~ 20. This is because even if the iodine value is below or above the lower limit, the skin softening action due to the interaction with phospholipids described later is reduced, and the effect may not be sufficient. As such hardened rapeseed oil, those already on the market exist, and such commercially available products can be purchased and used. As a preferable commercial item, for example, “rapeseed oil HR-35” (manufactured by Yokoseki Yushi Kogyo Co., Ltd.) can be exemplified. Such an ingredient works together with phospholipids described later, and has an effect of improving the softness of the skin after use by using such a cosmetic in an emulsifier type cosmetic. The effect of improving the flexibility of the skin can be grasped as a measurement value by “Venustron” manufactured by AXIOM. This measuring device emits a certain frequency (Hz) from the probe, and evaluates the softness by the frequency difference Δf when it comes in contact with the object. Specifically, when a soft object is touched, the frequency decreases, so Δf becomes negative, and when a hard object touches, the frequency increases, so Δf becomes positive. That is, the value obtained by subtracting the measurement value before the treatment from the measurement value after the treatment is a negative value, and the larger the absolute value, the more the skin flexibility can be identified. As a threshold value of such an effect, −3 is preferable, and −3.5 is more preferable. In order to achieve such an effect, in the cosmetic of the present invention, the hardened rapeseed oil is preferably contained in an amount of 1 to 10% by mass, more preferably 2 to 8%, based on the total amount of the cosmetic. % By mass. This is because if the amount is too small, the above-described effect may not be achieved, and if the amount is too large, the effect reaches a peak and the degree of freedom of prescription may be impaired. By using such an ingredient together with the ester of the N-acylamino acid, it is possible to transfer the hardened rapeseed oil into the stratum corneum and to make an external preparation for skin that can maintain the flexibility-imparting effect.

  The external preparation for skin of the present invention can be produced by treating the above components according to a conventional method. The skin external preparation of the present invention thus obtained takes the form of an emulsifier excellent in salt resistance. Since it is excellent in salt tolerance, it is excellent in transdermal absorbability of the active ingredient after administration to the skin.

  Hereinafter, the present invention will be described in more detail with reference to examples, but it goes without saying that the present invention is not limited to such examples.

  According to the formulation shown below, emulsion 1 (oil-in-water emulsifier type cosmetic), which is an external preparation for skin of the present invention, was produced. That is, the components of A, B, C, D, E and F are heated to 80 ° C., and the dissolved A and B are mixed well, made uniform, cooled once, and then heated and dissolved again. I let you. This was diluted by adding c, and stirred uniformly, and this was added to d to prepare an oil phase. While the oil phase was kept at 80 ° C., the mixture was gradually added and emulsified while stirring, and the emulsion particles were adjusted with a homogenizer. This was stirred and cooled to obtain an emulsion 1 which is a cosmetic of the present invention. In the same manner, Comparative Example 1 in which “Resinol SH50” was replaced with ordinary soybean lecithin, Comparative Example 2 in which “Elduu PS203” and “Elduu PS306” were replaced with “Resinol SH50”, and “Resinol SH50” with “Elduo” A comparative example 3 in which “PS203” and “Ldew PS306” (mass ratio of 1: 1) were substituted was also produced in the same manner.

<Test Example 1>
The skin softening action was compared using the emulsion 1 and Comparative Examples 1 and 2. That is, 10 panelists per group, 30 people in total, were prepared, and after skin flexibility was measured with “Venustron” on Day 0, they were treated with each cosmetic twice a day in the morning and evening. After performing this operation continuously for 2 weeks, the skin softness was measured again with “Venustron”. (Difference 1) After measurement, the measurement site was wiped off with acetone, the oil on the surface was removed, and the skin softness was measured again. (Difference 2) A value (difference) obtained by subtracting a numerical value before processing from a numerical value after processing was obtained. The results are shown in Table 2. From this, it can be seen that the cosmetic of the present invention is excellent in sustaining flexibility maintenance.

  Similarly to the emulsion 1, the emulsions 2 to 4, which are the cosmetics of the present invention, were prepared according to the following formulation. Table 4 shows the results of evaluation according to the method of Test Example 1. This shows that these emulsions have the same effect as the emulsion 1. It can also be seen that N-acylamino acid esters are preferably N-acylglycine esters.

  The present invention can be applied to skin external preparations such as cosmetics.

Claims (4)

1) At least one selected from esters of N-acylglutamic acid and esters of N-acylglycine , 2) hydroxylated lecithin, and 3) hardened rapeseed oil. . The emulsifier-type skin external preparation according to claim 1, wherein the ester of N-acyl glutamic acid is an ester of N-lauroyl -L-glutamic acid . The emulsifier-type skin external preparation according to claim 1 or 2, wherein the N-acylglycine ester is an ester of N-capryloylglycine. The emulsifier-type skin external preparation according to any one of claims 1 to 3 , wherein the content of the hydroxylated lecithin is 0.1 to 1% by mass.