JP3526355B2 - Cosmetics - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic composition which enhances the water-retaining function of the stratum corneum and is excellent in improving rough skin.

[0002]

2. Description of the Related Art Conventionally, it has been known that moisture in the stratum corneum is important for moisturizing and softening the skin.
The retention of the water is said to be due to the water-soluble components contained in the stratum corneum, that is, free amino acids, organic acids, urea or inorganic ions.

From these viewpoints, it is attempted to improve or prevent rough skin by blending these substances alone or in combination with a medicated external preparation for skin or cosmetics. In addition to the above substances, many moisturizing substances having high affinity with water have been developed and used for the purpose of improving rough skin.

However, when these moisturizing substances are applied to the skin, the effect is to supply water to the stratum corneum on the skin stratum corneum, and the effect is temporary, and basically the stratum corneum Improve its water retention capacity,
It could not be said that it essentially prevents or treats rough skin.

Therefore, the present applicant has previously proposed that a skin external preparation containing an amide derivative represented by the following formula (6) as a skin external preparation having an effect of fundamentally improving the water-retaining ability of the stratum corneum. Japanese Examined Patent Publication (Kokoku) No. 1-42934 (Japanese Patent Laid-Open No. Sho 6-62
2-228048)]].

[0006]

[Chemical 6]

(Wherein R ^1b is a linear or branched, saturated or unsaturated hydrocarbon group having 10 to 26 carbon atoms, R ^2b
Represents a linear or branched saturated or unsaturated hydrocarbon group having 9 to 25 carbon atoms. )

Furthermore, the applicant of the present invention has disclosed a skin external preparation containing an amide derivative having the same effect in JP-A-63-216.
812, JP-A-63-218609, JP-A-63-222107, and JP-A-63-22751.
No. 3, JP 64-29347 A, and JP 6
It was proposed in Japanese Patent Publication No. 4-31752 and the like.

Further, the present applicant has found that a hair cosmetic composition containing an amide derivative represented by the following formula (7) penetrates hair to enhance its protective effect, and also prevents scalp whitening, and It was found that the feel can be improved, and it was proposed in JP-A-64-9913.

[0010]

[Chemical 7]

[0011]

However, although these amide derivatives bring about the above-mentioned excellent effects, they have properties such as high melting point, high crystallinity, and low solubility in the base material, and therefore, they are not suitable for the skin. When compounded in cosmetics such as external preparations and hair cosmetics, problems still remain in terms of penetration into the skin and hair.

Therefore, the object of the present invention is to have the effect of fundamentally improving (maintaining / reinforcing) the water retention capacity of the stratum corneum,
In addition, when compounded in cosmetics such as skin external preparations and hair cosmetics, amides having improved penetration into the skin and hair due to improvements such as lowering of melting point, lower crystallization or improvement of solubility in the base. By forming a lamellar liquid crystal in the presence of a derivative and an organic acid or its salt, and applying this to the skin, the water retention capacity of the stratum corneum is improved, and rough skin and inflammation are prevented.
To provide a skin external preparation that can be treated and further prevent skin aging, and a cosmetic such as a hair cosmetic that has excellent hair and scalp protection and maintenance performance and can improve the feel of the hair To do.

[0013]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a cosmetic containing a novel amide derivative represented by the following general formula (1) and an organic acid or a salt thereof has the above object. The inventors have found that they can achieve this, and have completed the present invention.

That is, the present invention provides the following components (A) and (B): (A) The following general formula (1)

[0015]

[Chemical 8]

(In the formula, R ¹ and R ² are the same or different and each represents an optionally hydroxylated hydrocarbon group having 1 to 40 carbon atoms, and R ³ is a straight chain or branched chain having 1 to 6 carbon atoms. Represents an alkylene group or a single bond, R ⁴ is a hydrogen atom,
A linear or branched alkoxy group having 1 to 12 carbon atoms or a 2,3-dihydroxypropyloxy group is shown. However, when R ³ is a single bond, R ⁴ is a hydrogen atom. )

[0017]

[0018]

[0019]

[0020]

[0021]

1 selected from amide derivatives represented by
Or two or more, (B) glycolic acid, lactic acid, citric acid, 2-hydroxyoctanoic acid, succinic acid, fumaric acid, maleic acid, malonic acid, 1,3-propanedicarboxylic acid, stearic acid, palmitic acid, myristin The present invention provides a cosmetic comprising an organic acid selected from acids, isostearic acid, linoleic acid, linolenic acid, arachidonic acid, glutamic acid and aspartic acid, or a salt thereof.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION In the amide derivative (1) represented by the general formula (1) of the component (A) of the present invention, R ¹
And R ² are the same or different and represent a linear or branched, saturated or unsaturated, optionally hydroxylated hydrocarbon group having 1 to 40 carbon atoms. R ¹ and R ² are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, heneicosyl, docosyl, Nonacosyl, triacontyl, isostearyl, isoheptadecyl, 2-
Ethylhexyl, 1-ethylheptyl, 8-heptadecyl, 8-heptadecenyl, 8,11-heptadecadienyl, 2-heptylundecyl, 9-octadecenyl, 1
-Hydroxynonyl, 1-hydroxypentadecyl, 2
-Hydroxypentadecyl, 15-hydroxypentadecyl, 11-hydroxyheptadecyl, 11-hydroxy-8-heptadecenyl and the like can be mentioned.

R ¹ is preferably a linear or branched alkyl or alkenyl group having 8 to 26 carbon atoms, for example, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, docosyl, triacontyl, isostearyl, 2-ethylhexyl, 2-heptyl undecyl, 9-octadecenyl and the like can be mentioned. A particularly preferable hydrocarbon group as R ¹ is a linear or branched alkyl group having 12 to 22 carbon atoms, and examples thereof include dodecyl, tetradecyl, hexadecyl, octadecyl, docosyl and methyl-branched isostearyl groups.

R ² is preferably a linear or branched alkyl or alkenyl group having 9 to 25 carbon atoms, for example, nonyl, undecyl, tridecyl, tetradecyl, pentadecyl, heptadecyl, heneicosyl, nonacosyl, isoheptadecyl, 1-ethylheptyl, 8-heptadecyl, 8-heptadecenyl, 8,11-heptadecadienyl, 1-hydroxynonyl, 1-hydroxypentadecyl, 2-hydroxypentadecyl, 15-hydroxypentadecyl, 11-hydroxyheptadecyl and 11-hydroxy- 8-heptadecenyl and the like can be mentioned. Particularly preferred hydrocarbon groups as R ² have 11 to 11 carbon atoms.
21 straight-chain and branched-chain alkyl groups such as undecyl, tridecyl, tetradecyl, pentadecyl, heptadecyl, heneicosyl and methyl-branched isoheptadecyl groups.

R ³ represents a linear or branched alkylene group having 1 to 6 carbon atoms or a single bond, and examples of the alkylene group include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene and 1-methylethylene. , 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-ethylethylene,
1-methyl tetramethylene, 2-ethyl trimethylene, etc. are mentioned. As R ³ , a linear alkylene group having 1 to 6 carbon atoms is preferable, and among these, methylene, ethylene and trimethylene are particularly preferable.

R^FourIs a hydrogen atom, a straight chain having 1 to 12 carbon atoms or
Is a branched chain alkoxy group or 2,3-dihydroxyproton
A pyroxy group is shown, and an alkoxy group is, for example, meth
Xy, ethoxy, propoxy, butoxy, hexyloxy
Ci, octyloxy, decyloxy, 1-methylethoki
And 2-ethylhexyloxy and the like. R ^Four
Is a hydrogen atom, an alkoxy group having 1 to 8 carbon atoms and
2,3-dihydroxypropyloxy group is preferred,
Hydrogen atom, methoxy, ethoxy, propoxy,
Toxy, 1-methylethoxy, 2-ethylhexyloxy
Ci and 2,3-dihydroxypropyloxy groups are particularly preferred.
Good

The amide derivative (1) of the component (A) of the present invention
In the case of blending with the above-mentioned external preparation for skin and hair cosmetics, a particularly preferable compound is a compound in which R ¹ , R ² , R ³ and R ⁴ in the general formula are groups in the above particularly preferable ranges respectively. Is.

[0029]

[0030]

[0031]

The amide derivative (1) of the component (A) of the present invention
Can be obtained, for example, by the following production method.

[0033]

[Chemical 12]

[0034]

[Chemical 13]

(In the formula, R ¹ , R ² and R ³ have the same meanings as described above, and R ^4f represents a hydrogen atom or a linear or branched alkoxy group having 1 to 12 carbon atoms. ³
When is a single bond, R ^4f is a hydrogen atom. R ⁶ , R ⁸ ,
R ¹⁰ and R ¹¹ represent a linear or branched saturated or unsaturated hydrocarbon group having 1 to 8 carbon atoms, preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and particularly preferably Is a methyl group. R ⁹ represents a hydrogen atom, an alkali metal atom or a COR ⁸ group, and R ⁷ and R ¹² represent a leaving group such as a halogen atom, a mesylate group and a tosylate group. R ⁷ is preferably a chlorine atom or a bromine atom, particularly a chlorine atom, from the viewpoint of easy availability, and R ¹² is preferably a mesylate group or a tosylate group from the viewpoint of easy availability. )

The reaction conditions in each step of the above production method are as follows.

Step 1) Glycidyl ether (7) and amine (8F) without solvent, or with water or methanol,
Room temperature to 150 ° C. in lower alcohols such as ethanol and isopropanol, ether solvents such as tetrahydrofuran, dioxane and ethylene glycol dimethyl ether, hydrocarbon solvents such as hexane, benzene, toluene and xylene, or a mixed solvent thereof.
The amino alcohol derivative (2
F) can be produced.

Step 2) Amino alcohol derivative (2F)
In addition, fatty acid ester (9), preferably fatty acid lower alkyl ester such as fatty acid methyl ester and fatty acid ethyl ester, alkali metal hydroxide such as potassium hydroxide and sodium hydroxide, alkaline earth metal hydroxide such as calcium hydroxide. Substances, alkali metal carbonates such as potassium carbonate,
Alkaline earth metal carbonates such as calcium carbonate, sodium methoxide, sodium ethoxide, potassium-te
By reacting at room temperature to 150 ° C. in the presence of a basic catalyst such as an alkali metal alcoholate such as rt-butoxide at a normal pressure to a pressure of 0.01 mmHg, the amide derivative (3
F) can be produced. At this time, the amount of the basic catalyst used is 0.0 with respect to the amino alcohol derivative (2F).
1 to 0.2 equivalents are preferable, and it is preferable to carry out the reaction while removing alcohol produced by the reaction from the system, because the reaction proceeds rapidly.

Step 3) The amide derivative (3F) is also converted into the amino alcohol derivative (2F) by fatty acid chloride (1).
0) without solvent or with a halogenated hydrocarbon solvent such as chloroform, methylene chloride or 1,2-dichloroethane, an ether solvent such as tetrahydrofuran, dioxane or ethylene glycol dimethyl ether, a carbonization of hexane, benzene, toluene, xylene, etc. A amide-ester derivative (11F) is obtained by reacting in a hydrogen-based solvent or an arbitrary mixed solvent thereof in the presence or absence of a base such as pyridine and a tertiary amine such as triethylamine at room temperature to 100 ° C. After conversion,

Step 4) The ester group is converted to an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an alkaline earth metal hydroxide such as calcium hydroxide, an alkali metal carbonate such as potassium carbonate or calcium carbonate. Alkaline earth metal carbonates such as, sodium methoxide, sodium ethoxide, potassium-tert-butoxide and the like, under alkaline conditions such as alkali metal alcoholates, etc., can also be produced by selective hydrolysis. .

Step 5) 1-20 for the amide derivative (3F)
An equivalent amount of epoxide (12), preferably epichlorohydrin, is used without solvent or with water or tetrahydrofuran,
1 to 10 equivalents of an alkali such as potassium hydroxide or sodium hydroxide in an ether solvent such as dioxane or ethylene glycol dimethyl ether, a hydrocarbon solvent such as hexane, benzene, toluene, xylene, or an arbitrary mixed solvent thereof. By reacting at room temperature to 150 ° C. in the presence of a metal hydroxide, an alkaline earth metal hydroxide such as calcium hydroxide, an alkali metal carbonate such as potassium carbonate, an alkaline earth metal carbonate such as calcium carbonate. The amide derivative (4F) can be produced. At this time, quaternary ammonium salts such as tetrabutylammonium bromide, tetrabutylammonium chloride, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, stearyltrimethylammonium chloride, bistetraoxyethylenestearylmethylammonium chloride and lauryldimethylcarboxyammonium The reaction is preferably performed in the presence of a phase transfer catalyst such as betaine such as betaine in terms of yield and the like.

Step 6) The amide derivative (4F) is treated with an alkali metal hydroxide such as potassium hydroxide and sodium hydroxide, an alkaline earth metal hydroxide such as calcium hydroxide,
Alkali metal carbonates such as potassium carbonate, alkaline earth metal carbonates such as calcium carbonate, etc. under basic conditions or mineral acids such as sulfuric acid and hydrochloric acid, Lewis acids such as boron trifluoride and tin tetrachloride, acetic acid, tetradecane Acid, carboxylic acid such as hexadecanoic acid, sulfonic acid such as p-toluene sulfonic acid, or the like under acidic conditions or base-acid mixed conditions at room temperature to 3
The amide derivative (1F) can be produced by hydrating at 00 ° C.

Step 7) The amide derivative (1F) is also a carboxylic acid derivative (13), preferably a lower fatty acid such as acetic acid, a lower fatty acid alkali metal salt such as sodium acetate, or a lower carboxylic acid derivative such as acetic anhydride. The fatty acid anhydrides, alone or in combination, are reacted in the presence or absence of a basic catalyst such as a tertiary amine such as triethylamine to convert the ester-amide derivative (14F),

Step 8) The ester group is converted to an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an alkaline earth metal hydroxide such as calcium hydroxide, an alkali metal carbonate such as potassium carbonate or calcium carbonate. Alkaline earth metal carbonates such as, sodium methoxide, sodium ethoxide, potassium-tert-butoxide and the like, under alkaline conditions such as alkali metal alcoholates, etc., can also be produced by selective hydrolysis. .

Step 9) The amide derivative (1F) may also be obtained by adding to the amide derivative (4F) a carbonyl compound (15), preferably a lower aliphatic ketone such as acetone or methyl ethyl ketone, a mineral acid such as sulfuric acid, hydrochloric acid or phosphoric acid. After conversion to a 1,3-dioxolane-amide derivative (16F) by reacting in the presence of an acid catalyst such as a carboxylic acid such as acetic acid, a boron trifluoride, a tin tetrachloride or the like Lewis acid,

Step 10) Mineral acids such as sulfuric acid, hydrochloric acid and phosphoric acid,
It can also be produced by deketalization under acidic conditions such as carboxylic acid such as acetic acid and sulfonic acid such as p-toluenesulfonic acid.

Step 11) The 1,3-dioxolane-amide derivative (16F) may also be prepared by adding the amide derivative (3F) with the glycerol derivative (17), an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, or a hydroxide. In the presence of a base such as an alkaline earth metal hydroxide such as calcium, an alkali metal carbonate such as potassium carbonate, an alkaline earth metal carbonate such as calcium carbonate, an alkali metal hydride such as sodium hydride, and no solvent. Or an aprotic polar solvent such as N, N-dimethylformamide or dimethylsulfoxide, an ether solvent such as tetrahydrofuran, dioxane or ethylene glycol dimethyl ether, a hydrocarbon solvent such as hexane, benzene, toluene or xylene, or any of these. By reacting in a mixed solvent of And it can also be produced.

The amide derivative (1) of the component (A) of the present invention thus obtained can be purified by a known method. When the amide derivative (1) is blended in a skin external preparation and a hair cosmetic composition, even a purified product purified to 100% has a purity of 70 to 100% containing an intermediate or a reaction by-product without any particular purification. Even if it is a mixture, it is excellent in effect and performance and has no problem in safety. Further, the compound of the component (A) of the present invention also includes a solvate represented by a hydrate.

Examples of the amide derivative represented by the general formula (1) of the component (A) of the present invention obtained by the above production method include the following.

[0050]

[Chemical 14]

[0051]

[Chemical 15]

The organic acid or salt thereof as the component (B) of the present invention is not particularly limited, but as the organic acid, glycolic acid, lactic acid, citric acid, 2-hydroxyoctanoic acid or the like oxycarboxylic acid having 2 to 28 carbon atoms. C2-C12 dicarboxylic acids such as acids, succinic acid, fumaric acid, maleic acid, malonic acid, and 1,3-propanedicarboxylic acid; stearic acid, palmitic acid, myristic acid, isostearic acid,
10 carbon atoms such as linoleic acid, linolenic acid and arachidonic acid
To 24 amino acids such as monocarboxylic acid, aspartic acid, asparagine, glycine, glutamic acid, glutamine, γ-aminobutyric acid, arginine, cysteine and alanine; dicarboxylic acid monoesters such as octyl succinate and methyl maleate and the general formula (5 )

[0053]

[Chemical 16]

The sterin derivative represented by

The sterin derivative is preferably one having 1 to 2 in the general formula (5), R ^Y is hexadecenyl and octadecenyl, and R ^Z is cholesteryl and sitosteryl. As the organic acid as the component (B),
Particularly preferred are glycolic acid, lactic acid, citric acid, succinic acid, and sterin derivatives.

Further, as the salt of the organic acid as the component (B),
Although not particularly limited, examples thereof include salts of lactic acid, citric acid, and succinic acid. When the organic acid has a basic group, examples thereof include acid addition salts of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like.

Further, it is preferable to use a polyol in combination with the cosmetic of the present invention. As such a polyol,
Examples thereof include glycerin, 1,3-butylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, 1,3-propanediol, sorbit, and polyoxyalkylene alkyl glucoside, of which glycerin and 1,3-propanediol are preferable.

In the cosmetic of the present invention, the amide derivative as the component (A) can be used alone or in combination of two or more kinds, and the compounding amount is not particularly limited, but the total composition is not limited. In the above, 0.001 to 50% by weight (hereinafter, simply referred to as “%”) is preferable, and the range of 0.1 to 20% is particularly preferable in order to enhance the water retention function of the stratum corneum and improve rough skin. preferable.

In the cosmetic of the present invention, the organic acid or salt thereof as the component (B) can be used alone or in combination of two or more kinds, and the compounding amount thereof is not particularly limited. However, in the total composition, 0.00001 to 30% is preferable, and a range of 0.001 to 20% is particularly preferable from the viewpoint of enhancing the water retaining function of the stratum corneum and improving rough skin.

Further, in the cosmetics of the present invention, one type of polyol may be used alone or two or more types may be used in combination, and the compounding amount thereof is not particularly limited, but 0.001 to 10% of the total composition is used. 50% is preferable, especially 0.1-2
The range of 0% is more preferable.

The cosmetics of the present invention include external preparations for skin, skin cosmetics and hair cosmetics. When used as a skin external preparation or a skin cosmetic, a surfactant can be used in combination, if necessary. As the surfactant, any of nonionic surfactant, anionic surfactant and amphoteric surfactant can be used. As the nonionic surfactant, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, polyoxyethylene hydrogenated castor oil, poly Examples thereof include oxyethylene castor oil, foliglycerin fatty acid ester, sucrose fatty acid ester, and glyceryl ether.
Among them, the following general formula (8):

[0062]

[Chemical 17]

[0063] (. Wherein, R ¹³ is showing an alkyl group having 8 to 24 carbon atoms) glyceryl ether represented by, among R ¹³ have the following formula (9):

[0064]

[Chemical 18]

(Where p is an integer of 4 to 10 and q is 5 to 1)
The distribution has an integer of 1 and has p + q = 11 to 17 and q = 8 as vertices. Those represented by) are particularly preferable.

As the anionic surfactant, a linear or branched alkylbenzene sulfonate, a linear or branched alkyl or alkenyl ether sulfate, an alkyl or alkenyl sulfate having an alkyl group or an alkenyl group, an olefin Sulfonate, alkane sulfonate, unsaturated fatty acid salt, alkyl or alkenyl ether carboxylate, α-sulfo fatty acid salt or ester having an alkyl group or alkenyl group, N-acyl having an acyl group and a free carboxylic acid residue Examples thereof include amino acid type surfactants and phosphoric acid mono- or diester type surfactants having an alkyl group or an alkenyl group. As the zwitterionic surfactant, an imidazoline-based amphoteric surfactant having an alkyl group, an alkenyl group, or an acyl group, carbobetaine-based, amidobetaine-based, sulfobetaine-based, hydroxysulfobetaine-based or amidosulfobetaine-based amphoteric surfactant Etc.

In the external preparation for skin or skin cosmetic of the present invention, the amount of the surfactant to be added is 0.01 to 20 of the total composition.
%, Particularly 0.1-5% is preferable.

Examples of the external preparation for skin include various ointments containing medicinal components. The ointment may be either an oil-based base, an oil / water, or a water / oil-type emulsion base. The oily base is not particularly limited, and examples thereof include vegetable oil, animal oil, synthetic oil, fatty acid, and natural or synthetic glyceride. In addition, the medicinal component is not particularly limited, and for example, an analgesic / anti-inflammatory agent, an antipruritic agent, a bactericidal disinfectant, an astringent agent, an emollient agent, a hormone agent and the like can be appropriately used as necessary.

When used as a cosmetic, in addition to the essential components, oils, moisturizers, UV absorbers, alcohols, chelating agents, preservatives, thickeners, and pigments that are commonly used as cosmetic ingredients. , And fragrances can be combined in any combination.

As the cosmetics, various forms such as water /
Skin cosmetics such as oils, oil / water emulsion cosmetics, creams, lotions, lotions, oily cosmetics, lipsticks, foundations, and skin cleansers can be used.

In the hair cosmetic composition of the present invention, the blending amounts of the components (A) and (B) are not particularly limited, but in the case of shampoo etc., 0.001 to 5%, rinse, treatment It is preferable to add 0.1 to 20% for conditioners and 0.01 to 5% for hair liquids and hair tonics.

In the hair cosmetic composition of the present invention, when it is a shampoo, a hair rinse, a hair conditioner, a hair treatment, etc., the surface active agent may be an anionic surface active agent, a zwitterionic surface active agent or a nonionic surface active agent. Activators and cationic surfactants are mentioned.
Examples of the anionic surfactant and the zwitterionic surfactant are the same as those blended with the above-mentioned external preparation for skin. Nonionic surfactants include polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkylphenyl ethers, polyoxypropylene alkyl or alkenyl ethers, polyoxybutylene alkyl or alkenyl ethers, ethylene oxide and propylene oxide or ethylene oxide and butylene oxide. Examples of the nonionic surfactant added with alkanolamide, higher fatty acid alkanolamide or alkylene oxide adduct thereof, sucrose fatty acid ester, fatty acid glycerin monoester, alkylamine oxide and the like.
Examples of cationic surfactants include mono- or di-long chain alkyl quaternary ammonium salts.

As counter ions of the anionic residues of these surfactants, alkali metal ions such as sodium and potassium, alkaline earth metal ions such as calcium and magnesium, ammonium ion, and alkanol groups having 2 or 3 carbon atoms can be used. Examples thereof include alkanolamines having 1 to 3 (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.). Examples of the counter ion of the cationic residue include halogen ions such as chlorine, bromine and iodine, and methosulfate and saccharinate ions.

In the shampoo and the like, among these surfactants, anionic surfactants such as alkyl ether sulfates, alkyl sulfates and olefin sulfonates are preferable as the main surfactant. Preferred examples include polyoxyethylene lauryl ether sodium sulfate (ethylene oxide average 2-3 mol addition), lauryl sulfate triethanolamine, sodium α-olefin sulfonate (average carbon number 12-14) and the like.

In a shampoo or the like, these surfactants are contained in the composition in a total amount of 5 to 30%, preferably 1%.
In the range of 0 to 20%, and in the hair rinse, hair treatment, hair conditioner, etc., a nonionic or cationic surfactant is added in the composition in an amount of 0.1 to 20%.
It is compounded in the range of 50%, preferably 0.5 to 20%.

When the hair cosmetic composition is a hair rinse, a hair treatment, and a hair conditioner, a long-chain alkyl quaternary ammonium salt and oils and fats may be blended in order to impart a good feel to the hair. Examples of long-chain alkyl quaternary ammonium salts include the following general formula (10):

[0077]

[Chemical 19]

(In the formula, one or two of R ^{14 to} R ¹⁷ is a linear or branched long-chain alkyl group having 8 to 24 carbon atoms, and the rest is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a benzyl group. And X represents a halogen atom or an alkylsulfuric acid group having 1 or 2 carbon atoms.), And a long-chain alkyl quaternary ammonium salt represented by the formula (1) or two or more is used. Among the long-chain alkyl quaternary ammonium salts represented by the above formula (10), those in which the long-chain alkyl group is a branched chain are synthesized by a known method using a branched higher fatty acid or a branched higher alcohol as a raw material.
These raw materials may be natural products or synthetic products. As natural raw materials, lanolin fatty acids such as isoacid and anteisoic acid, terpene alcohols such as farnesol, and the like, and as raw materials for synthesis, oxo alcohols obtained by oxo method using olefins as raw materials. Alternatively, there may be mentioned Guerbet alcohols and 2-alkylalkanols obtained by Guerbet condensation or aldol condensation using alcohols and aldehydes as raw materials. For example, in the case of oxo alcohol, the raw material is α-
In the case of an olefin, the branching ratio of the produced higher alcohol is small, in the case of an internal olefin, the branching ratio is large, and in the case of a branched olefin, the branching ratio is 100%.
Becomes

Among these branched long-chain alkyl quaternary ammonium salts, the branched alkyl group has the following general formula (1
1):

[0080]

[Chemical 20]

(In the formula, R ¹⁸ represents a straight-chain alkyl group having 5 to 13 carbon atoms.) A 2-methylalkyl group is preferable, and preferable specific examples thereof include 2-methyloctyl and 2-methyldecyl. , 2-methylundecyl,
Examples thereof include 2-methyldodecyl, 2-methyltridecyl, 2-methyltetradecyl and 2-methylheptadecyl groups. These 2-methylalkyl groups are usually derived from oxo alcohols, which are generally obtained as a mixture with straight chain alcohols.

Examples of the branched long-chain alkyl quaternary ammonium salt having a branched alkyl group include alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, alkyldimethylbenzylammonium chloride, alkyltrimethylammonium bromide, alkyltrimethylammonium methosulfate and dialkylmethyl. Examples thereof include hydroxymethyl chloride. Among them, particularly preferable are those having a 2-methylalkyl group represented by the formula (11),
For example, a branched mono-long chain alkyl quaternary ammonium salt such as 2-methyldecyltrimethylammonium chloride, 2-methyldodecyltrimethylammonium chloride, 2-methyltetradecylammonium chloride; 2-methyldecylundecyldimethylammonium chloride,
A branched di-long chain alkyl quaternary ammonium salt in which one long chain alkyl group such as 2-methyldodecyltridecyldimethylammonium chloride and 2-methyltetradecylpentadecyldimethylammonium chloride is branched;
And di (2-methyldecyl) dimethylammonium chloride, di (2-methyldodecyl) dimethylammonium chloride, di- (2-methyltetradecyl) dimethylammonium chloride, etc. -Long-chain alkylammonium salts.

Examples of long-chain alkyl groups having a straight chain include decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl and eicosanyl groups.

As the oils and fats, those generally used can be used, and examples thereof include liquid paraffin, glycerides, higher alcohols, lanolin derivatives, esters, and higher fatty acids. As the glyceride, a monoglyceride derived from a saturated or unsaturated linear or branched fatty acid having 12 to 24 carbon atoms is used. Among these oils and fats, higher alcohols having a linear or branched alkyl group or alkenyl group having 12 to 26 carbon atoms are particularly preferable, and specific preferable examples thereof include cetyl alcohol, stearyl alcohol, araquin alcohol, and behenyl alcohol. , Caranavir alcohol, ceryl alcohol and the like.

The preferable blending amount of each of these long-chain alkyl quaternary ammonium salts and fats and oils is 0.01 to 20.
% And 0.1 to 30%.

When the hair cosmetic composition is hair liquid, hair tonic, etc., a nonionic surfactant may be used in combination. Examples of the nonionic surfactant include those similar to those blended with the external preparation for skin.

The above-mentioned nonionic surfactant is contained in the following composition:
It is preferable to add 0.01 to 20%, particularly 0.1 to 5%.

The hair cosmetic composition of the present invention in which the component (A) and the component (B) or a polyol is further blended has a dosage form such as an aqueous solution, an ethanol solution, an emulsion, a suspension, a gel, a solid type, an aerosol and a powder. There is no particular limitation. Further, if necessary, in addition to the above-mentioned components, the same components as those to be incorporated into the skin cosmetics can be blended as cosmetic components.

[0089]

The external preparation for skin of the present invention has an excellent ability to retain water. It also prevents and treats rough skin and inflammation, and prevents skin aging. Further, the hair cosmetic composition of the present invention has excellent hair / scalp protection / maintenance performance and improves the feel of hair.

[0090]

EXAMPLES Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples. The evaluation method for the rough skin improving effect in this example is shown below.

(Test Method) Ten females aged 20 to 50, who have rough skin on the cheeks in winter, were used as test subjects, and different skin external preparations were applied to the left and right cheeks for 2 weeks. The following items were tested on the day after the application for two weeks was completed.

(1) Skin conductance After washing the face with warm water of 37 ° C. and resting in a room at a temperature of 20 ° C. and a humidity of 40% for 20 minutes, the water content of the stratum corneum was measured by a skin conductance meter (manufactured by IBS). Measured. The smaller the conductance value is, the rougher the skin is, and when the conductance value is 5 or less, the skin is severely rough. On the other hand, this value is 20
If it is above, almost no rough skin is observed.

(2) Rough skin score Rough skin was visually observed and judged according to the following criteria. The score is shown as an average value.

[0094] 0: No rough skin 1: Admit slight skin roughness 2: recognize rough skin 3: Appreciate slightly rough skin 4: Admits severe skin roughness

Example 1 O / W type creams having the following compositions were prepared, and the effect of improving rough skin by continuous application was evaluated for each of them.
Tables 1 to 4 show the structure of the amide derivative used, the organic acid or its salt and the polyol, and the blending amounts, and Table 6 shows the evaluation results of the rough skin improving effect.

[0096]

[Table 1]

[0097]

[Table 2]

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

(Table 5) (Composition) (%) (1) Amide derivative (Tables 1 to 4) Tables 1 to 4 (2) Organic acids and salts (Tables 1 to 4) Tables 1 to 4 (3) Polyol (Tables 1 to 4) 4) Tables 1 to 4 (4) Polyoxyethylene (10) hydrogenated castor oil 1.0 (5) sorbitan monostearate 0.5 (6) sodium stearoylmethyl taurine 0.5 (7) polyoxyethylene lauryl ether phosphorus Sodium acid salt 0.5 (8) Cholesterol 1.3 (9) Cetostearyl alcohol 2.0 (10) Cholesteryl isostearate 1.0 (11) Squalane 2.0 (12) Neopentyl glycol dicaprate 8.0 ( 13) Methyl polysiloxane ^{* 1} 4.0 (14) Cyclic silicone ^{* 2} 4.0 (15) Preservative Suitable amount (16) Purified water Remaining amount (17) Ethanol 3.0 (18) Perfume Suitable amount 100 * 1: Silicone KF96A (6cs), manufactured by Shin-Etsu Chemical Co., Ltd. * 2: Silicone SH-244, SH-245 or a 3: 2 (weight ratio) mixture of SH-244 and SH-245, manufactured by Toray Dow Corning Silicone Co., Ltd.

(Production method) Oil phase component [(1), (4),
(5), (7) to (14) and (2) may be an aqueous phase depending on the compound]
Aqueous phase components heated to ℃ [(3), (6), (15),
(16)] was added and emulsified, and the mixture was stirred and cooled to 50 ° C., then [(17) and (18)] were added, and the mixture was further cooled to room temperature with stirring to prepare an O / W cream.

[0102]

[Table 3]

Example 2 A W / O cream having the following composition was prepared. This improved the water retention capacity of the stratum corneum and was excellent in the effect of preventing and healing rough skin.

[0104]

Table 7 (Composition) (%) (1) Amide derivative (Invention product 1 in Tables 1 to 4) 3.5 (2) Citric acid 0.5 (3) Glycerin 1.0 (4) Cholesterol 5 (5) Cholesteryl isostearate 0.5 (6) Polyether-modified silicone ^{* 4} 2.0 (7) Cyclic silicone ^{* 5} 20.0 (8) Methylphenylpolysiloxane ^{* 6} 5.0 (9) Magnesium sulfate 0.5 (10) Purified water Remaining amount (11) Preservative Suitable amount (12) Perfume Suitable amount 100 * 4: Silicone KF-6015, manufactured by Shin-Etsu Chemical Co., Ltd. * 5: Silicone SH-244 and SH-245 3: 2. (Weight ratio) Mixture, manufactured by Toray Dow Corning Silicone * 6: Silicone SF-557, manufactured by Toray Dow Corning Silicone

(Production method) Oil phase component [(1), (4)-
(6), (8)] heated and dissolved at 80 ° C., and an aqueous phase component [(2), (3)
(9) to (11)] were added and emulsified, and the mixture was stirred and cooled to 50 ° C., (7) and (12) were added, and the mixture was further cooled to room temperature with stirring to prepare a W / O cream.

Example 3 A hair tonic having the following composition was prepared. It improved the water retention capacity of the stratum corneum, protected the hair and scalp, and had a good feel on the hair.

[0107]

(Table 8) (Composition) (%) (1) Amide derivative (Invention product 1 in Tables 1 to 4) 1.0 (2) Sterin derivative ^{* 7} 1.0 (3) 1,3-butylene glycol 3. 0 (4) Pyrrolidonecarboxylic acid-aluminum salt 0.5 (5) Ethanol 55.0 (6) Water Remaining amount (7) Perfume Suitable amount 100 * 7: In the general formula (5), l = 2, R ^z = cholesteryl

(Production method) (6) with stirring, (1), (2)
Uniformly dispersed, and then (3), (4), (5),
(7) was added and mixed well to prepare a hair tonic.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takeshi Morita 2-1-3 Fumika, Sumida-ku, Tokyo Kao Co., Ltd. Research Institute (56) Reference JP-A-64-31752 (JP, A) JP-A-6 -157276 (JP, A) JP-A 64-9913 (JP, A) JP-A 5-211838 (JP, A) JP-A 5-320188 (JP, A) JP-A 5-294989 (JP, A) ) Fragrance Journal, 1983, No. 62, p. 41-45 Fragrance Journal, 1983, No. 62, p. 46-49 (58) Fields surveyed (Int.Cl. ⁷ , DB name) A61K ^7/ 00-7/50 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. The following components (A) and (B): (A) The following general formula (1): (In the formula, R ¹ and R ² are the same or different and have 1 to 40 carbon atoms.
Represents an optionally hydroxylated hydrocarbon group of
R ³ represents a linear or branched alkylene group having 1 to 6 carbon atoms or a single bond, R ⁴ represents a hydrogen atom, 1 to 12 carbon atoms
Is a linear or branched alkoxy group or a 2,3-dihydroxypropyloxy group. However, when R ³ is a single bond, R ⁴ is a hydrogen atom. (B) Glycolic acid, lactic acid, citric acid, 2-hydroxyoctanoic acid, succinic acid, fumaric acid, maleic acid, malonic acid, 1,3-propane A cosmetic comprising an organic acid selected from dicarboxylic acid, stearic acid, palmitic acid, myristic acid, isostearic acid, linoleic acid, linolenic acid, arachidonic acid, glutamic acid and aspartic acid or a salt thereof. 2. The component (A) is 0.001 to 50% by weight,
The cosmetic according to claim 1, which contains 0.00001 to 30% by weight of the component (B). 3. The cosmetic according to claim 1, which is a skin cosmetic. 4. The cosmetic composition according to claim 1, which is a hair cosmetic composition.