JP4566010B2 - Composition for external use - Google Patents

Description

The present invention relates to a vesicle-based external composition, and more particularly, to a vesicle-based external composition suitable for cosmetics.

Ceramide is an important component constituting the skin, and is said to have a skin barrier function as its function. For this reason, many attempts have been made to blend into cosmetics, etc., but since there is not much compatibility with water and oily components, the blending is a lot difficult from a pharmaceutical standpoint. Accompanied by. For example, such that resides when forming a long-term insolubles storage can be exemplified. Based on such a problem by using a polyhydric alcohol, higher alcohol, and the like acylated polyglycerin, to create a liquid crystal structure, that has been devised a technique for stably contains a ceramide in liquid crystal form (for example, patent Reference 1 and Patent Reference 2) . However, in such a system, the range in which precipitation of ceramide can be suppressed and stabilized is narrow, and development of a technique for stably blending ceramide has been desired regardless of this means. As will be described later, there is a technique of blending ceramide into a vesicle / dispersion system using a cationic surfactant or the like, but it is difficult to say that the dispersion stability of the vesicle in such a system is good. Here, the vesicle system means that when a water-insoluble component is added to an aqueous carrier, the water-insoluble component forms small particles in the aqueous carrier, and the particles are uniformly dispersed. A vesicle / dispersion system refers to a system in which particles and components that do not form particles are mixed and dispersed.

1) phospholipids and 2) described later cleanser containing a cationic surfactant represented by the general formula (1) are known, further, that have skin cleanser that combines fatty acid soap is known (e.g., However, such cleaning agents are not vesicles or vesicles / dispersions, but are presumed to be systems in which fatty acid soap and dimethyldialkylammonium paired ion complexes are solubilized. The

On the other hand, an external composition containing 1) ceramide, 2) phospholipid, and 3) a cationic surfactant represented by the following general formula (1) is not known at all, and such a composition is not ceramide. It is not known at all that it is excellent in the action of stably containing as a vesicle system or vesicle / dispersion system.

JP 2004-331595 A JP 2004-331594 A Japanese National Patent Publication No. 11-507323 JP-T 09-511248

The present invention has been made under such circumstances, and provides a technique for forming a stable vesicle system in an external composition.

In view of such a situation, the present inventors have sought for a technique for forming a stable vesicle system in a composition for external use. As a result, 1) ceramide, 2) phospholipid, 3) The inventors have found that an external composition containing a cationic surfactant represented by the following general formula (1) has such characteristics, and has completed the invention. That is, the present invention is as follows.
(1) 1) Ceramide 0.01 to 5% by mass ; 2) One or two selected from lecithin or phosphatidylcholine, phosphatidylserine, phosphatidylethanolamine, phosphatidylinositol, phosphatidylglycerol, phosphatidylic acid and their lysates more phospholipid 0.01 to 5 mass%, 3) characterized by containing a 0.1 to 5 wt% cationic surfactant in the following general formula (1), external of the vesicle system Composition.

一般式（１）
（但し、式中Ｒ ₁ 、Ｒ ₂ はそれぞれ独立に炭素数１〜４のアルキル基を表し、Ｒ ₃ 、Ｒ ₄ はそれぞれ独立に炭素数１０〜２４のアルキル基又はアルケニル基を表し、Ｘ^-aは鉱酸根を表し、aは１〜３の整数を表す。）

General formula (1)
(In the formula, R ₁ and R ₂ each independently represents an alkyl group having 1 to 4 carbon atoms, R ₃ and R ₄ each independently represents an alkyl group or alkenyl group having 10 to 24 carbon atoms, and X ^{− a} represents ^a mineral acid radical, and a represents an integer of 1 to 3.)

(2 ) The composition for external use according to (1) , which is a cosmetic.

According to the present invention, it is possible to provide a technique for forming a stable vesicle system in an external composition .

(1) Ceramide as an essential component of the external composition of the present invention The external composition of the present invention is characterized by containing ceramide as an essential component. As ceramide, it is known that there are usually seven types of type 1 to type 7, and any of them can be used. Among them, type 2 is particularly preferable, and N-stearoyl dihydroxysphingosine is particularly preferable. Such ceramides have commercial products, and such commercial products can be purchased and used. Among such commercially available products, “Ceramide I” (manufactured by Cosmo Farm), type 2 which is composed of N- (27-octadecanoyloxy-heptacosanoyl-)-phytosphingosine, which is type 1, is preferable. "Ceramide TIC-001" (manufactured by Takasago Fragrance Co., Ltd.) having N-stearoyl dihydroxysphingosine as a component, "Ceramide III" (manufactured by Cosmo Farm) having N-stearoyl phytosphingosine as a component, type 3, "Ceramide IIIA" (made by Cosmo Farm) with N-linoleoyl phytosphingosine as a component, "Ceramide IIIB" (made by Cosmo Farm) with N-oleoyl phytosphingosine as a component "Ceramide VI", which contains N-2-hydroxystearoylphytosphingosine, which is type 6 (Cosmo Farm Co., Ltd.) etc. can be preferably exemplified. These can contain only the seed | species, and can also be made to contain in combination of 2 or more type. Such ceramides, in free Yuryou the external composition of the present invention in a total amount, with respect to the external preparation composition is 0.01 to 5 mass%, more preferably 0.1 to 2 wt% is there. This is because if the amount is too small, the desirable effect of ceramide may not be exhibited, and if it is too large, the vesicle system cannot be maintained and the vesicle / dispersion system may be transferred.

セラミドタイプ１
（Ｒ ₁ はアルキル基乃至はアルケニル基を表し、Ｒ ₂ はリノレオイルオキシアルキル基を表す。）
セラミドタイプ２
（Ｒ ₁ 、Ｒ ₂ はそれぞれ独立に、アルキル基乃至はアルケニル基を表す。）

Ceramide type 1
(R ₁ represents an alkyl group or an alkenyl group, and R ₂ represents a linoleoyloxyalkyl group.)
Ceramide type 2
(R ₁ and R ₂ each independently represents an alkyl group or an alkenyl group.)

セラミドタイプ３
（Ｒ ₁ 、Ｒ ₂ はそれぞれ独立に、アルキル基を表す。）

Ceramide type 3
(R ₁ and R ₂ each independently represents an alkyl group.)

セラミドタイプ４
（Ｒ ₁ はアルキル基を表し、Ｒ ₂ はリノレオイルオキシアルキル基を表す。）

Ceramide type 4
(R ₁ represents an alkyl group, and R ₂ represents a linoleoyloxyalkyl group.)

セラミドタイプ５
（Ｒ ₁ 、Ｒ ₂ はそれぞれ独立にアルキル基を表す。）

Ceramide type 5
(R ₁ and R ₂ each independently represents an alkyl group.)

セラミドタイプ６
（Ｒ ₁ 、Ｒ ₂ はそれぞれ独立にアルキル基を表し、Ｒ ₃ は水素原子乃至はアルキル基を表す。）

Ceramide type 6
(R ₁ and R ₂ each independently represents an alkyl group, and R ₃ represents a hydrogen atom or an alkyl group.)

セラミドタイプ７
（Ｒ ₁ 、Ｒ ₂ はそれぞれ独立にアルキル基を表す。）

Ceramide type 7
(R ₁ and R ₂ each independently represents an alkyl group.)

(2) Phospholipid which is an essential component of the external composition of the present invention The external composition of the present invention contains phospholipid as an essential component. In the composition for external use of the present invention, phospholipids usually used for cosmetics and the like can be used without particular limitation. Preferred examples of such phospholipids include those selected from lecithin, phosphatidylglycerol, phosphatidylserine, phosphatidylinositol, phosphatidylethanolamine, phosphatidylic acid, and lyso forms thereof. Here, lecithin is a common name for phospholipids containing phosphatidylcholine as a main component, and phosphatidylcholine which is a main component can be used instead of lecithin. As the base source, soybean, egg yolk and the like can be preferably exemplified, and soybean can be particularly preferably exemplified. In the composition for external use of the present invention, such a phospholipid may contain only one species or may contain two or more species in combination. In the external composition of the present invention, including Yuryou of such phospholipids in total, relative to the external composition the total amount is 0.01 to 5 mass%, more preferably 0.1 to 2 wt% It is. This is because if the amount is too small, a stable vesicle system cannot be obtained, and if the amount is too large, there may be cases where the system moves to a system other than the vesicle system such as a solubilizing system. In such a non-vesicle system, the cationic substance may not exist stably.

(3) Cationic surfactant represented by general formula (1), which is an essential component of the composition for external use of the present invention The composition for external use of the present invention is a cationic surfactant represented by general formula (1) Is contained as an essential component. In the formula, R ₁ and R ₂ each independently represents an alkyl group having 1 to 4 carbon atoms, R ₃ and R ₄ each independently represents an alkyl group or alkenyl group having 10 to 24 carbon atoms, and X ^-a represents ^a mineral. Represents an acid radical, and a represents an integer of 1 to 3. Examples of the alkyl group having 1 to 4 carbon atoms in R ₁ and R ₂ include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, an n-butyl group, an isobutyl group, and a t-butyl group. The group is particularly preferred. Further, examples of the alkyl group or alkenyl group having 10 to 24 carbon atoms in R ₃ and R ₄ include lauryl group, cetyl group, stearyl group, behenyl group, isostearyl group, oleyl group and the like. Preferable examples include a group having 18 carbon atoms, and examples include a stearyl group, an isostearyl group, and an oleyl group. Among them, a stearyl group is particularly preferable. Furthermore, a takes any integer of 1 to 3, and X represents a mineral acid radical having no valence, but as the mineral acid radical, hydrochloric acid radical (chlorine ion), nitrate radical, sulfate radical, phosphate radical, etc. Can be suitably exemplified. Particularly preferred is the hydrochloric acid radical (a = 1). Specific preferred compounds represented by the general formula (1) include, for example, dimethyldilauryl ammonium chloride, dimethyl distearyl ammonium chloride, dimethyl dicetyl ammonium chloride, dimethyl cetyl stearyl ammonium chloride, dimethyl dioleyl ammonium chloride, Examples thereof include dimethyl oleyl stearyl ammonium chloride. In the composition for external use of the present invention, such a cationic surfactant may be contained alone or in combination of two or more. In the external composition of the present invention, including Yuryou of such cationic surfactants are, in total, with respect to external total amount of the composition is 0.1 to 5 mass%, more preferably 0.5 4% by mass. This is because there are cases where the vesicle system cannot be maintained even if the amount is too small or too large.

(4) External composition of this invention The external composition of this invention contains the said essential component, and is applied to a biological body by external use. Examples of such an external composition include cosmetics (including quasi-drugs) and skin external medicines, with cosmetics being particularly preferred. As cosmetics, it can be used for external use on the skin to improve or maintain the condition of the skin, and it can also be used for the moisturizing and damage protecting effects of cationic surfactants and ceramides. It can also be applied to hair cleaning materials such as. Particularly preferred is a cosmetic for hair, and it is particularly preferred to apply to a hair cleanser. In the composition for external use of the present invention, in addition to the above-mentioned components, any component 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 not classified as essential components such as stearyltrimethylammonium chloride, benzalkonium chloride, laurylamine oxide, imidazoline-based amphoteric surfactants (2 -Amphoteric surfactants such as cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt), betaine surfactants (alkyl betaine, amide betaine, sulfobetaine, etc.), acylmethyl taurine, Sorbitan fatty acid esters (such as sorbitan monostearate and sorbitan sesquioleate), glycerin fatty acids (such as glyceryl monostearate), propylene glycol fatty acid esters (such as propylene glycol monostearate), hydrogenated castor oil derivatives, glycerin alkyl ether , POE sorbitan fatty acid esters (POE sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc.), POE sorbite fatty acid esters (POE-sorbite monolaurate, etc.), P E glycerol fatty acid esters (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 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.), nonionic surfactants such as sucrose fatty acid ester, alkyl glucoside, polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, ma Polyhydric alcohols such as tititol, propylene glycol, dipropylene glycol, diglycerin, isoprene glycol, 1,2-pentanediol, 2,4-hexylene glycol, 1,2-hexanediol, 1,2-octanediol, Moisturizing ingredients such as sodium pyrrolidone carboxylate, 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, chondroit , Mucoitin sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, dextran, keratosulfate, locust bean gum, succinoglucan, carolinic acid, chitin, chitosan, carboxymethyl chitin, agar, polyvinyl alcohol, polyvinyl pyrrolidone, carboxyvinyl polymer, poly Thickeners such as sodium acrylate, polyethylene glycol, bentonite, surface may be treated, mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, anhydrous silicic acid (silica), aluminum oxide, barium sulfate Such as powders, 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 , Titanium mica, fish phosphorus Pearls such as bismuth oxychloride, lake 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, blue 201, purple 201, red 204, organic dyes such as polyethylene powder, polymethyl methacrylate, nylon powder Organic powders such as organopolysiloxane elastomers, paraaminobenzoic acid UV absorbers, anthranilic acid UV absorbers, salicylic acid UV absorbers, cinnamic acid UV absorbers, benzophenone UV absorbers, sugar UV absorbers Agent, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 4-methoxy-4′-t-butyldibe UV absorbers such as zoylmethane, lower alcohols such as ethanol and isopropanol, vitamin A or its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 or its derivatives, vitamin B12, vitamin B15 or Vitamin B such as its derivatives, vitamin E such as α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate, vitamin D, vitamin H, vitamins such as pantothenic acid, panthetin, pyrroloquinoline quinone, etc. Preferred examples can be given. The composition for external use of this invention can be manufactured by processing this component according to a conventional method. In particular, as a production method, it is preferable to add all the components and heat to 85 to 95 ° C., and then perform a mixing treatment with significant mechanical force such as microfluidizer treatment, ultrahomogenizer treatment, sonicator treatment, and the like. it can. By such a process, a vesicle system in which particles having an average particle diameter of 100 to 400 nm are dispersed is formed.

  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.

According to the formulation shown below, the vesicle-based external composition of the present invention was obtained. That is, the prescription ingredients were heated to 90 ° C., strongly dispersed with a microfluidizer, stirred and cooled to obtain a vesicle-based slightly turbid solution-like cosmetic 1 having an average particle diameter of 215 nm. Cosmetics 1 of dimethyldiallylammonium chloride distearyl ammonium Comparative Example was replaced with stearyl trimethyl ammonium chloride 1, Comparative Example 2 in which the ceramide 2 was replaced by water, but the soy lecithin was attempted prepared similarly Comparative Example 3 was replaced with water No vesicle system was formed.

(Prescription)
Dimethyl distearyl ammonium chloride ("Arcade 2HP" manufactured by Lion Akzo Co., Ltd.) 2 % by mass
Stigmasterol β-glucoside 1% by mass
"Ceramide TIC-001" 0.2% by mass
Soybean lecithin 1% by mass
Glycerin 10% by mass
85.8% by weight of water

<Test Example 1>
Cosmetic 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3 were centrifuged at 4 ° C. and 10 × g for 10 minutes using a centrifuge. In cosmetic 1, no sedimentation was observed, but in Comparative Examples 1, 2 and 3, sedimentation was observed. It was proved that the composition for external use of the present invention is a vesicle system having excellent stability.

<Test Example 2>
For cosmetic 1, comparative example 1, comparative example 2, and comparative example 3, the effect of suppressing the amount of transdermally dissipated water when administered to the skin was examined. That is, transcutaneous water dispersion loss (TEWL) was measured before and after sample application using Skicon II (manufactured by EB Corporation), (TEWL before administration-TEWL after administration) / TEWL x 100 before administration Thus, the suppression value of the amount of dissipated water was calculated. As a result, the cosmetic 1 was 37%, the comparative example 1 was 15%, the comparative example 2 was 18%, and the comparative example 3 was 17%. From this, it can be seen that the composition for external use of the present invention has an excellent skin care effect.

<Test Example 3>
In order to test the usability of the cosmetic 1 as a rinse, a use test was conducted using 10 panelists. The evaluation was made by assigning absolute scores on a scale from very good (score 5) to very bad (score 1) by questionnaire. As a result, 4 people were given 5 points, 5 people were given 4 points, and 3 people were given 3 points.

In the same manner as in Example 1, the composition for external use of the present invention was produced according to the formulation shown below. This was a vesicle system having an average particle diameter of 211 nm, and no sedimentation was observed even by centrifugation at 4 ° C. and 10 × g for 10 minutes. In addition, the use as skin care cosmetics and rinses was confirmed by one expert panelist.

(Prescription)
Dimethyl distearyl ammonium chloride ("Arcade 2HP" manufactured by Lion Akzo Co., Ltd.) 2 % by mass
Sitosterol β-glucoside 1% by mass
"Ceramide TIC-001" 0.2% by mass
Glycerin 10% by mass
Phosphatidylglycerol 1% by mass
85.8% by weight of water

In the same manner as in Example 1, the composition for external use of the present invention was produced according to the formulation shown below. This was a vesicle system having an average particle diameter of 228 nm, and no sedimentation was observed even after centrifugation at 4 ° C. and 10 × g for 10 minutes. In addition, the use as skin care cosmetics and rinses was confirmed by one expert panelist.

(Prescription)
Dimethyl distearyl ammonium chloride ("Arcade 2HP" manufactured by Lion Akzo Co., Ltd.) 2 % by mass
Sitosterol β-glucoside 1% by mass
"Ceramide TIC-001" 0.2% by mass
Glycerin 10% by mass
Phosphatidylethanolamine 1% by mass
85.8% by weight of water

In the same manner as in Example 1, the composition for external use of the present invention was produced according to the formulation shown below. This was a vesicle system having an average particle size of 201 nm, and no sedimentation was observed even after centrifugation at 4 ° C. and 10 × g for 10 minutes. In addition, the expert panelists one person, skin care cosmetics, has been confirmed use for the property as a rinse.

(Prescription)
Dimethyl distearyl ammonium chloride ("Arcade 2HP" manufactured by Lion Akzo Co., Ltd.) 2 % by mass
Sitosterol β-glucoside 1% by mass
"Ceramide TIC-001" 0.2% by mass
Glycerin 10% by mass
Phosphatidylethanolamine 1% by mass
85.8% by weight of water

In the same manner as in Example 1, the composition for external use of the present invention was produced according to the formulation shown below. This was a vesicle system having an average particle size of 222 nm, and no sedimentation was observed even after centrifugation at 4 ° C. and 10 × g for 10 minutes. In addition, the use as skin care cosmetics and rinses was confirmed by one expert panelist.

(Prescription)
Dimethyl distearyl ammonium chloride ("Arcade 2HP" manufactured by Lion Akzo Co., Ltd.) 2 % by mass
Sitosterol β-glucoside 1% by mass
"Ceramide I" 0.2% by mass
Glycerin 10% by mass
Phosphatidylglycerol 1% by mass
85.8% by weight of water

  The present invention can be applied to cosmetics.

Claims (2)

1) and 0.01 to 5 mass% ceramides, 2) lecithin or phosphatidylcholine, phosphatidylserine, phosphatidylethanolamine, phosphatidylinositol, phosphatidylglycerol, one or more phosphorus is selected from phosphatidic acid and their lyso-form lipids and 0.01 to 5 wt%, 3) characterized by containing a 0.1 to 5 wt% cationic surfactant in the following general formula (1), the external composition of the vesicle system.

General formula (1)
(In the formula, R ₁ and R ₂ each independently represents an alkyl group having 1 to 4 carbon atoms, R ₃ and R ₄ each independently represents an alkyl group or alkenyl group having 10 to 24 carbon atoms, and X ^{− a} represents ^a mineral acid radical, and a represents an integer of 1 to 3.) The composition for external use according to claim 1, wherein the composition is a cosmetic .