JP2005206516A - Skin care preparation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a skin care preparation of gel form comprising dibenzylidene sorbitol and an alcohol, causing no change with time and keeping its stable condition well. <P>SOLUTION: The skin care preparation comprises dibenzylidene sorbitol, an alcohol, 4-n-butylresorcinol and/or a salt thereof. <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 skin suitable for stick-shaped cosmetics.

  Conventionally, it is known that cosmetics include cosmetics having a rod-like (so-called stick-like) dosage form.

This stick-shaped cosmetic has the advantage that it can be administered to a relatively narrow disease site and an active ingredient can be accurately administered, for example, as used as an antiperspirant stick or a whitening stick. . Moreover, there is little risk of spreading to other parts, and it can be said that it is excellent in usability in this sense. However, the disadvantage of this stick-like cosmetic is the poor feeling of use such as “stickiness” and “greasy” caused by the formulation characteristics of oil gel. Therefore, in order to improve the bad feeling of use, the development of non-oil gel type of stick-like cosmetic is being studied, and dibenzylidene sorbitol, cosmetics using a gel made of ethanol or polyhydric alcohol have been developed (For example, see Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, and Patent Document 5). However, it has been found that these cosmetics have a problem that dibenzylidene sorbitol, which is a gelling agent, is hydrolyzed due to the influence of water present in the cosmetics, thereby generating off-flavors. Therefore, in a non-oil gel type cosmetic containing dibenzylidene sorbitol and alcohol, there has been a demand for provision of a cosmetic that can maintain a stable state without change over time.

On the other hand, 4-n-butylresorcinol and a salt thereof are materials suitable for whitening cosmetics having excellent safety and excellent melanin production inhibitory activity (see, for example, Patent Document 6). Further, this substance is a known substance, and its production method is already known (for example, see Non-Patent Document 1). However, it is not known that 4-n-butylresorcinol and / or a salt thereof is contained in the gel dosage form cosmetic comprising dibenzylidene sorbitol and alcohol, and 4-n-butylresorcinol and / or It is not known at all that the stability of dibenzylidene sorbitol is improved by including the salt.
JP 2002-80324 A JP 2002-68950 A Japanese National Patent Publication No. 08-501795 Japanese National Patent Publication No. 11-501037 JP 2000-505470 A Japanese Patent Laid-Open No. 02-49715 Lille, J .; Bitter, LA; Peiner, V. Trudy-Nauchono-Issledovatel 'skii Institut Slantsev (1969), No. 18, 127-34

  The present invention has been made under the circumstances as described above, and in a gel external preparation containing dibenzylidene sorbitol and alcohol, there is no change over time, and a stable state is kept good. It is an object of the present invention to provide an external preparation for skin.

In order to solve the above problems, the present inventors have made extensive research efforts on a gel external preparation containing dibenzylidene sorbitol and alcohol, and as a result, 4-n-butylresorcinol and / or its It was found that a skin external preparation having desired characteristics can be obtained by containing a salt, and the present invention has been completed.

That is, the present invention is as follows.
(1) An external preparation for skin, comprising dibenzylidene sorbitol, alcohol, and 4-n-butylresorcinol and / or a salt thereof.
(2) The alcohol is one or more selected from ethanol, 1,3-butanediol, isoprene glycol, 1,2-pentanediol, 1,2-hexanediol and dipropylene glycol. The external preparation for skin according to (1), characterized in.
(3) The skin external preparation according to (1) or (2), wherein the content of the 4-n-butylresorcinol and / or a salt thereof is 0.05 to 5% by mass.
(4) The skin external preparation according to any one of (1) to (3), further comprising water.
(5) The external preparation for skin according to any one of (1) to (4), which is a stick-shaped cosmetic.

  ADVANTAGE OF THE INVENTION According to this invention, the external preparation for skin which can maintain a stable state favorably without a change with time in the gel external preparation for skin containing dibenzylidene sorbitol and alcohol can be provided. .

<1> About dibenzylidene sorbitol which is an essential component of the external preparation for skin of the present invention

The skin external preparation of the present invention contains dibenzylidene sorbitol.
Dibenzylidene sorbitol is a component used in solid fragrance compositions and the like as a gelling agent such as ethanol, and is well known as a raw material for skin external preparations such as cosmetics. In the skin external preparation of the present invention, dibenzylidene sorbitol marketed as a general-purpose raw material of the skin external preparation can be used. Preferred examples of such commercially available dibenzylidene sorbitol include “Gelol D” (trade name) manufactured by Shin Nippon Rika Co., Ltd.

  The preferable content of dibenzylidene sorbitol in the external preparation for skin of the present invention is 0.5 to 10% by mass, and more preferably 1 to 5% by mass with respect to the total amount of external preparation for skin. This is because if it is too much, it may become too hard and impair the usability, and if it is too little, it may not solidify.

<2> About alcohol 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 alcohol. In the present invention, alcohol is a generic term for aliphatic hydrocarbons having a hydroxyl group that are liquid (having fluidity) under the conditions of 1 atm and 25 ° C.

  Specifically, C1-C4 monohydric alcohols, such as ethanol and 2-propanol, and a polyhydric alcohol can be illustrated preferably. The polyhydric alcohol can be used without particular limitation as long as it is used in a skin external preparation such as cosmetics. For example, glycerin, diglycerin, polyethylene glycol, polyglycerin, 1,3-butane. Preferred examples include diol, isoprene glycol, 1,2-pentanediol, 1,2-hexanediol, dipropylene glycol, and hexylene glycol.

In the external preparation for skin of the present invention, these alcohols may contain only one species or in combination of two or more.

  In particular, in the present invention, among the above alcohols, one or more selected from ethanol, 1,3-butanediol, isoprene glycol, 1,2-pentanediol, 1,2-hexanediol and dipropylene glycol. The alcohol is preferably used.

The preferable content of these alcohols in the external preparation for skin of the present invention is 40 to 93% by mass, more preferably 50 to 90% by mass, based on the total amount of external preparation for skin. This is because if it is too much, it may not become solid, and if it is too little, there may be cases where the good feeling of use that is characteristic of the external preparation for skin is not realized.
Moreover, the skin external preparation of this invention WHEREIN: The said dibenzylidene sorbitol is good to make it contain in the ratio of 1-10 mass% with respect to the said alcohol, Preferably it is 1.2-5 mass%.

<3> About 4-n-butylresorcinol and / or its salt which is an essential component of the skin external preparation of this invention The skin external preparation of this invention is 4-n-butylresorcinol and / or its salt (following, 4- n-butylresorcinol and the like).

  4-n-butylresorcinol used for the external preparation for skin of the present invention can be produced according to a conventional method, for example, according to the method described in Non-Patent Document 1. That is, examples include a method of condensing resorcin and butanoic acid in the presence of zinc chloride and reducing with zinc amalgam / hydrochloric acid, and a method of condensing resorcin and n-butyl alcohol at a high temperature of 200 to 400 ° C.

  4-n-butylresorcinol can be converted into a salt by reacting with various basic compounds. Such a salt is not particularly limited as long as it is physiologically acceptable, and examples thereof include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt and magnesium salt, Preferred examples include organic amine salts such as ammonium salt, triethanolamine salt and triethylamine salt, and basic amino acid salts such as lysine salt and arginine salt. Among these salts, alkali metal salts are particularly preferable, and sodium salts are particularly preferable.

  In the external preparation for skin of the present invention, 4-n-butylresorcinol and the like may be contained singly or in combination of two or more. In the external preparation for skin of the present invention, these 4-n-butylresorcinol and the like exhibit an effect of improving the stability of dibenzylidene sorbitol, which is a gelling agent for the alcohol.

  The content of 4-n-butylresorcinol and the like in the external preparation for skin of the present invention is preferably 0.05 to 5% by mass, and 0.2 to 0. 5 mass% is still more preferable. This is because 4-n-butylresorcinol or the like acts effectively in this range and is stably contained in the external preparation for skin.

<4> Water which is a preferred component of the skin external preparation of the present invention The skin external preparation of the present invention contains water in addition to the essential components as a preferred embodiment. In the external preparation for skin of the present invention, water functions as a solubilizing medium for polar components or as an agent that exhibits a volatilization preventing effect on the alcohols. Furthermore, there is also a contribution to refreshing feeling in use.

As described above, in the preparation of gel dosage form containing dibenzylidene sorbitol and alcohol, when water is present in the preparation, dibenzylidene sorbitol is hydrolyzed, thereby causing problems such as off-flavor. . However, when 4-n-butylresorcinol or the like is added to a gel-form preparation containing dibenzylidene sorbitol and alcohol as in the present invention, the preparation is stable even if water is present in the preparation. Can keep the state.

  The preferable content of water in the skin external preparation of the present invention is 1 to 20% by mass, more preferably 5 to 15% by mass, based on the total amount of the skin external preparation. This is because when the amount is too large, the stability of the preparation is deteriorated, and when the amount is too small, the effect of the present invention may not be achieved.

<5> About the skin external preparation of this invention The skin external preparation of this invention contains the said essential component. Or the said essential component and the water which is a preferable component are contained.

  In addition to these components, the external preparation for skin of the present invention can contain optional components usually used in external preparations for skin.

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, myristyl alcohol, higher alcohols such as cetostearyl alcohol, alkyl (alkenyl) glyceryl ethers such as batyl alcohol and ceralkyl alcohol, cetyl isooctanoate, isopropyl myristate, hexyldecyl isostearate, adipine Diisopropyl acid, di-2-ethylhexyl sebacate, cetyl lactate, diisostearyl malate, ethylene glycol di-2-ethylhexanoate, neopentyl glycol dicaprate, glycerin di-2-heptylundecanoate, tri-2-ethyl Hexanoic acid glycerin, tri-2-ethylhexanoic acid trimethylolpropane, triisostearic acid trimethylolpropane, tetra-2-ethylhexanoic acid Synthetic ester oils such as tantalum erythrite, chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, and cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexanesiloxane Oil agents such as silicone oils such as amino-modified polysiloxanes, polyether-modified polysiloxanes, alkyl-modified polysiloxanes, and modified polysiloxanes such as fluorine-modified polysiloxanes,
Fatty acid soap (sodium laurate, sodium palmitate, etc.), anionic surfactants such as potassium lauryl sulfate, alkyl sulfate triethanolamine ether, cationic surfactants such as stearyltrimethylammonium chloride, benzalkonium chloride, laurylamine oxide , Imidazoline-based amphoteric surfactants (such as 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt), betaine surfactants (such as alkylbetaines, amidebetaines, sulfobetaines), acyls Amphoteric surfactants such as methyl taurine, sorbitan fatty acid esters (such as sorbitan monostearate, sorbitan sesquioleate), glycerin fatty acids (such as glyceryl monostearate), propylene glycol Fatty acid esters (propylene glycol monostearate, etc.), hardened castor oil derivatives, glycerin alkyl ethers, polyoxyethylene (PO
E) Sorbitan fatty acid esters (POE sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc.), POE sorbite fatty acid esters (POE-sorbitol monolaurate, etc.), POE glycerin fatty acid esters (POE-glycerin monoisostea) 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, nonionic surfactants such as alkyl glucosides,
Moisturizing ingredients such as sodium pyrrolidonecarboxylate, lactic acid, sodium lactate,
Gua gum, quince seed, carrageenan, galactan, arabic gum, pectin, mannan, starch, xanthan gum, curdlan, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, methylhydroxypropylcellulose, chondroitin sulfate, dermatan sulfate, glycogen, heparan sulfate , Hyaluronic acid, sodium hyaluronate, gum tragacanth, keratan sulfate, chondroitin, mucoitin sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, dextran, kerato sulfate, locust bean gum, succinoglucan, caronic acid, chitin, chitosan, carboxymethyl chitin, Agar, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl Rimmer, sodium polyacrylate, polyethylene glycol, a thickener such as bentonite,
Powders such as mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, anhydrous silicic acid (silica), aluminum oxide, barium sulfate, etc. whose surface may be treated,
Bengala, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, bituminous, titanium oxide, zinc oxide inorganic pigments whose surface may be treated,
Pearl agents such as titanium mica, fish phosphorus foil, bismuth oxychloride, etc. whose surface may be treated,
Red 202, Red 228, Red 226, Yellow 4, Blue 404, Yellow 5, Red 505, Red 230, Red 223, Orange 201, Red 213 which may be raked Organic pigments such as yellow 204, yellow 203, blue 1, green 201, purple 201, red 204,
Organic powders such as polyethylene powder, polymethyl methacrylate, nylon powder, organopolysiloxane elastomer, paraaminobenzoic acid UV absorber, anthranilic acid UV absorber, salicylic acid UV absorber, cinnamic acid UV absorber, UV absorbers such as benzophenone UV absorbers, sugar UV absorbers, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 4-methoxy-4′-t-butyldibenzoylmethane ,
Vitamin A or derivatives thereof, vitamin B ₆ hydrochloride, vitamin B ₆ tripalmitate, vitamin B ₆ dioctanoate, vitamin B ₂ or derivatives thereof, vitamin B ₁₂ such as vitamin B ₁₂ , vitamin B ₁₅ or derivatives thereof, vitamin C, Preferred examples include vitamin E such as α-tocopherol, β-tocopherol, γ-tocopherol, and vitamin E acetate, vitamin D, vitamin H, pantothenic acid, panthetin, and pyrroloquinoline quinone.

  The skin external preparation of this invention can be manufactured by processing an arbitrary component and the above-mentioned essential component (or the above-mentioned essential component and a preferable component) according to a conventional method. The skin external preparation of the present invention can be applied without particular limitation as long as it is a composition that is administered to the skin for external use. For example, cosmetics, skin external medicines, and the like can be suitably exemplified. Of these, cosmetics (including quasi drugs) are particularly preferable.

  The dosage form of the external preparation for skin of the present invention is not particularly limited, and examples thereof include lotion, essence, milky lotion, cream, gel, and stick (stick). Among these, a stick shape is preferable.

The external preparation for skin of the present invention is more preferably applied to a stick-like cosmetic containing an active ingredient, which can effectively administer the active ingredient locally. For example, by processing whitening cosmetics or the like into a stick shape, it can be locally administered with extremely limited area of the stain.
Examples of the active ingredient include paraaminobenzoic acid ultraviolet absorbers, anthranilic acid ultraviolet absorbers, salicylic acid ultraviolet absorbers, cinnamic acid ultraviolet absorbers, benzophenone ultraviolet absorbers, sugar ultraviolet absorbers, 2- UV absorbers such as (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 4-methoxy-4′-t-butyldibenzoylmethane, anti-inflammatory agents such as dipotassium glycyrrhizinate and indomethacin, butenafine, etc. An antibacterial agent etc. can be illustrated suitably.

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

<Example 1>
According to the formulation shown below, a stick-shaped cosmetic material, which is an external preparation for skin of the present invention, was prepared. That is, the formulation components were thoroughly mixed and defoamed and then poured into a mold to obtain a bar-shaped cosmetic 1 of Example 1. At the same time, Comparative Example 1 in which 4-n-butylresorcinol was replaced with sodium ascorbate as an antioxidant, Comparative Example 2 in which was replaced with disodium hydroxyethanediphosphonate as a chelating agent, and Comparative Example 1 in which ethanol was replaced. Was also produced in the same manner. These were stored at 5 ° C. and 40 ° C. for 1 month, respectively, and measured for color. Colorimetry was measured as a color difference (ΔE) between a product stored at 5 ° C. and a product stored at 40 ° C. The results are shown in Table 1.
From this, it can be seen that the stick-shaped cosmetic, which is the external preparation for skin of the present invention, is excellent in stability.
Further, for these samples, the perfume was judged by the perfumer. The determination was made according to the following criteria.

Score 0: No strange odor Score 1: Feeling a slightly strange odor Score 2: Feeling a slight odor Score 3: Clearly smelling odor Score 4: Slightly odor Score 5: Smelling

  The results are also shown in Table 1. It can be seen that the occurrence of off-flavor and coloring are well correlated.

1.5 parts by weight of dibenzylidene sorbitol (trade name “Gelall D”; manufactured by Shin Nippon Rika Co., Ltd.)
4-n-butylresorcinol 0.3 parts by weight Hydroxypropylcellulose 1 part by weight 1,2-hexanediol 9.7 parts by weight Ethanol 77.5 parts by weight Water 10 parts by weight

<Example 2>
In the same manner as in Example 1, according to the following formulation, a stick-shaped cosmetic 2 that is an external preparation for skin of the present invention was produced. This product was stored at 40 ° C. for 1 month, and the foul odor score was score 1.

1.5 parts by weight of dibenzylidene sorbitol (trade name “Gelall D”; manufactured by Shin Nippon Rika Co., Ltd.)
4-n-butylresorcinol 0.3 parts by weight Hydroxypropylcellulose 1 part by weight 1,2-hexanediol 4.7 parts by weight Isooctyl cinnamate 5 parts by weight Ethanol 77.5 parts by weight Water 10 parts by weight

<Example 3>
In the same manner as in Example 1, according to the following formulation, a stick-shaped cosmetic 3 that is an external preparation for skin of the present invention was produced. This product was stored at 40 ° C. for 1 month, and the odor change score was score 0.

Dibenzylidenesorbitol 1.5 parts by mass (trade name “Gelall D”; manufactured by Shin Nippon Rika Co., Ltd.)
4-n-butylresorcinol 0.3 parts by weight Hydroxypropylcellulose 1 part by weight 1,2-hexanediol 9.65 parts by weight Dipotassium glycyrrhizinate 0.05 part by weight Ethanol 77.5 parts by weight Water 10 parts by weight

<Example 4>
In the same manner as in Example 1, according to the following formulation, a rod-shaped skin external medicine 1 which is the skin external preparation of the present invention was prepared. This product was stored at 40 ° C. for 1 month, and the odor change score was score 0.

1.5 parts by weight of dibenzylidene sorbitol (trade name “Gelall D”; manufactured by Shin Nippon Rika Co., Ltd.)
4-n-butylresorcinol 0.3 parts by weight Hydroxypropylcellulose 1 part by weight 1,2-hexanediol 7.7 parts by weight Indomethacin 2 parts by weight Ethanol 77.5 parts by weight Water 10 parts by weight

<Example 5>
In the same manner as in Example 1, according to the following formulation, a rod-shaped skin external medicine 2 that is an external preparation for skin of the present invention was prepared. This product was stored at 40 ° C. for 1 month, and the odor change score was score 0.

1.5 parts by weight of dibenzylidene sorbitol (trade name “Gelall D”; manufactured by Shin Nippon Rika Co., Ltd.)
4-n-butylresorcinol 0.3 parts by weight Hydroxypropylcellulose 1 part by weight 1,2-hexanediol 7.7 parts by weight Butenafine 2 parts by weight Ethanol 77.5 parts by weight Water 10 parts by weight

The present invention can be applied to a skin external preparation excellent in usability and local administration.

Claims (5)

An external preparation for skin comprising dibenzylidenesorbitol, alcohol, and 4-n-butylresorcinol and / or a salt thereof. The alcohol is one or more selected from ethanol, 1,3-butanediol, isoprene glycol, 1,2-pentanediol, 1,2-hexanediol and dipropylene glycol. The external preparation for skin according to claim 1. Content of the said 4-n-butyl resorcinol and / or its salt is 0.05-5 mass%, The skin external preparation of Claim 1 or 2 characterized by the above-mentioned. Furthermore, water is contained, The skin external preparation in any one of Claims 1-3 characterized by the above-mentioned. The external preparation for skin according to any one of claims 1 to 4, which is a stick-shaped cosmetic.