JP2002284627A - Composition for external use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for external use that excellently retains its active ingredient in the hair and skin. SOLUTION: This composition for external use includes (A) a cationic polymer which is a copolymer of a) a polymerizable monomer containing a quaternary cation group and b) a polymerizable monomer containing polyoxyetylene chain, of which N content is 0.5-6 mass% of the total mass of the polymer, and (B) an active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for external use applied to hair, skin and the like, and more particularly, to the retention of various active ingredients such as medicinal ingredients on hair and skin when applied to hair and skin. And a composition for external use for hair and skin which is excellent.

[0002]

2. Description of the Related Art Hitherto, in a composition containing a compound having a medicinal effect to be used for hair or skin, a device for maximizing the medicinal effect of the compound has been devised.
For example, in cleaning compositions such as shampoos and body soaps, a polymer compound having a film-forming property on hair and skin after rinsing is used as a prescription for enhancing the retention of medicinal components on hair and skin when washed away. Incorporation into compositions has been performed. In addition, in the case of facial cleansing agents for the purpose of imparting a medicinal effect such as acne, various measures have been devised such that the amount of a detergent that reduces persistence on the skin is reduced to the necessary minimum amount.

However, when a polymer compound having a film forming property is used for the purpose of improving the retention of the active ingredient on hair and skin, the retention on the hair and skin is improved, but the active ingredient is coated. Since the stagnation in the state is a hindrance in transdermal absorption into hair and skin, there is a problem that the efficacy of the medicinal component is not good for the compounding amount of the medicinal component, and the expensive medicinal component Has to be incorporated more economically. In addition, when the amount of the detergent that reduces persistence on the skin is suppressed to the minimum necessary amount, it has been a factor that reduces the degree of freedom regarding performance other than medicinal properties in formulating a prescription.

Further, JP-A-58-27800, JP-A-3-184907 and JP-A-3-184908 disclose a shampoo composition containing a 1-hydroxy-2-pyridone compound and capable of exhibiting a hair conditioning property. A shampoo composition having both a washing effect and a finishing effect, a shampoo composition having an excellent Kayumi-preventing effect, and having a good blending stability at low temperatures have been proposed. Scalp and hair cosmetics containing an agent have been proposed, but in each of these proposals, there is room for improvement in terms of efficacy.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and has an excellent retention property of an active ingredient on hair or skin when applied to hair or skin. It is an object of the present invention to provide a composition for external use which is suitably used for skin and the like.

[0006]

Means for Solving the Problems and Embodiments of the Invention As a result of intensive studies to achieve the above object, the present inventor has found that a specific cationic polymer has a medicinal effect like a 1-hydroxy-2-pyridone compound. It has been found that when compounded with a compound having an active ingredient (medicinal ingredient) as an active ingredient, the retention of the medicinal ingredient on the hair or skin when the composition is externally applied to skin, hair, etc. is significantly improved. As a result of further intensive studies, it has been found that, when such an externally applied composition is further blended with an anionic surfactant, the retention of the medicinal component on hair and skin is further improved, and the present invention has been achieved. Reached.

That is, the present invention relates to a cationic polymer which is a copolymer of (A) a) a polymerizable monomer containing a quaternary cationic group and b) a polymerizable monomer containing a polyoxyethylene chain. A polymer having a nitrogen content of 0.5 to 6% by mass relative to the total mass of the polymer, and (B) an active ingredient;
More preferably, the present invention further provides an external composition containing an anionic surfactant. Here, (A) a) the polymerizable monomer containing a quaternary cation group is represented by the following general formula (1) or (2), and b) the polyoxyethylene chain-containing polymerizable monomer is The compound represented by the general formula (3) is more preferable, and the compound (B) is more effective when the active ingredient is a 1-hydroxy-2-pyridone compound.

[0008]

Embedded image (However, in the above formulas (1), (2) and (3), R ¹ is
A hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^{2 to} R ⁶ are
Each independently represents an alkyl group having 1 to 4 carbon atoms, X, X ¹ and X ² each represent an alkylene group having 2 to 4 carbon atoms, M represents an anion, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , R ⁸ are a hydrogen atom, an alkyl group or an aryl group having 1 to 6 carbon atoms, and n is 2 to 50. )

Hereinafter, the present invention will be described in more detail. The composition for external use of the present invention comprises (A) a) a polymerizable monomer containing a quaternary cationic group, and b) a polyoxyethylene chain-containing polymerizable monomer. A cationic polymer which is a copolymer, comprising: a cationic polymer having a nitrogen content of 0.5 to 6% by mass based on the total mass of the polymer; and (B) an active ingredient. It is.

Here, as the component (A) of the present invention, a) a polymerizable monomer containing a quaternary cation group, such as a vinyl monomer containing at least one, preferably one quaternary cation group in the molecule, etc. Among them, among these,
As the polymerizable monomer a) having a quaternary cation group of the present invention, a monomer represented by the following general formula (1) or (2) is more preferable.

[0011]

Embedded image (However, in the above formulas (1) and (2), R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^{2 to} R ⁶ are each independently an alkyl group having 1 to 4 carbon atoms, X , X ¹ and X ² are each an alkylene group having 2 to 4 carbon atoms, and M is an anion.)

Here, in the general formulas (1) and (2), the alkyl group may have a substituent such as a hydroxyl group or a halogen group. R ¹ is preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and R ^{2 to} R ⁶ are each independently 1 or 2 carbon atoms.
Is preferred. Note that the above equation (2)
The two R ^{1 's} may be the same or different. M
Is an anionic counter ion such as a halogen ion, a sulfate ion, and a methyl sulfate ion.

Further, as the cationic monomer represented by the above formula (1), R ¹ is particularly preferably a hydrogen atom or a methyl group, X is an alkylene group having 2 or 3 carbon atoms, R ² to R ⁴ is an alkyl group having 1 to 3 carbon atoms, especially methyl and ethyl are preferred. M is preferably a halogen ion, more preferably a chloride ion, a bromide ion or the like.

Specific examples of the cationic monomer represented by the general formula (1) include, for example, ethyltrimethylammonium (meth) acrylate, propyltrimethylammonium (meth) acrylate, and butyltrimethylammonium (meth) acrylate. , Triethylammonium (meth) acrylate, propyltriethylammonium (meth) acrylate, butyltriethylammonium (meth) acrylate and the like are used, and especially ethyltrimethylammonium (meth) acrylate and propyltrimethylammonium (meth) acrylate And the like are more preferable.

The cationic polymer of the component (A) according to the present invention is preferably a copolymer obtained by the above-mentioned a).
Any copolymer may be used as long as it is a copolymer of a polymerizable monomer containing a quaternary cationic group and b) a polymerizable monomer containing a polyoxyethylene chain. Not only a copolymer obtained by copolymerizing a polyoxyethylene chain-containing polymerizable monomer but also the above a)
Instead of a polymerizable monomer containing a quaternary cationic group,
After copolymerizing with the above b) polyoxyethylene chain-containing polymerizable monomer using a vinyl monomer having at least one, and preferably one tertiary amino group in the molecule, the tertiary amino nitrogen in the monomer unit May be reacted with a cationizing agent to quaternize it.

The vinyl monomer having a tertiary amino group in the molecule includes -N ⁺ in the above general formula (1).
R ² R ³ R ⁴ groups may be -NR ² R ³ groups. More specifically, for example, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, diethylaminobutyl (meth) Acrylate, dipropylaminoethyl (meth) acrylate, dipropylaminopropyl (meth) acrylate, dipropylaminobutyl (meth) acrylate and the like are preferable, and among these, dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) Acrylate, diethylaminoethyl (meth) acrylate and the like are more preferred.

The quaternizing agent used when the tertiary amino nitrogen in the monomer unit is reacted with a cationizing agent to quaternize, for example, an alkyl halide (C _n H _{2n + 1)}
^{X 3; n = 1~3, X} 3 = Br, Cl or I) and, cationic agents such as dialkyl sulfates are preferred. As those cationizing agents, more specifically, for example, methyl bromide, methyl chloride, methyl iodide, ethyl bromide, ethyl chloride, ethyl iodide, propyl bromide, propyl chloride, propyl iodide, dimethyl sulfate, diethyl Sulfuric acid, dipropyl sulfate and the like can be used, and among these, ethyl bromide, methyl chloride, dimethyl sulfate, diethyl sulfate and the like are more preferable.

After using the vinyl monomer having a tertiary amino group and copolymerizing it with the above b) polyoxyethylene chain-containing polymerizable monomer, the tertiary amino nitrogen in the monomer unit is reacted with a cationizing agent. When the cationic polymer (A) of the present invention is quaternized, it is desirable that 50 mol% or more of the nitrogen content in the polymer is quaternized, more preferably 70 mol% or more. .

The a) polymerizable monomer having a quaternary cation group of the present invention represented by the above general formula (2) includes, in the above formula (2), X ¹ and X ² each having 2 carbon atoms. Or an alkylene group of 3 is preferred, more preferably an ethylene group, and R ⁵ and R ⁶ are more preferably an alkyl group having 1 to 3 carbon atoms, particularly a methyl group and an ethyl group. M is
It is an anionic counter ion such as a halogen ion, a sulfate ion, and a methyl sulfate ion. Among them, a halogen ion is preferable, and a chloride ion and a bromide ion are more preferable.

More specifically, examples of the polymerizable monomer represented by the general formula (2) include dimethyldiallylammonium halide, diethyldiallylammonium halide, dipropyldiallylammonium halide, and dibutyldiallylammonium halide.
Of these, dimethyldiallylammonium halide is particularly preferred.

Next, as the (A) b) a polyoxyethylene chain-containing polymerizable monomer used in the present invention, a vinyl monomer containing at least one polyoxyethylene chain in a molecule and the like can be mentioned. Here, the polyoxyethylene chain has an addition mole number of ethylene oxide of 2 to 50.
And more preferably 2 to 30.
Among them, as the b) polyoxyethylene chain-containing polymerizable monomer of the present invention, a monomer represented by the following general formula (3) is more preferable.

[0022]

Embedded image (However, in the above formula (3), R ⁷ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁸ is an alkyl group or an aryl group having 1 to 6 carbon atoms, and n is 2 to 50. .)here,
In the general formula (3), the alkyl group may have a substituent such as a hydroxyl group or a halogen group. R ⁷ is preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and more preferably a hydrogen atom or a methyl group.
R ⁸ is preferably an alkyl group having 1 or 2 carbon atoms or a phenyl group, more preferably a hydrogen atom, a methyl group,
Examples include an ethyl group, a propyl group, and a benzyl group. Also,
In the above general formula (3), the number of oxyethylene groups n
Represents 2 to 50. n is preferably 2 to 30.

More specifically, examples of the monomer represented by the general formula (3) include polyoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, and phenoxypolyethylene glycol. (Meth) acrylate and the like, and among these, methoxypolyethylene glycol (meth) acrylate and the like are more preferable.

The (A) cationic polymer of the present invention has a nitrogen content in the polymer of 0.5 to the total mass of the polymer.
To 6% by mass (hereinafter abbreviated as%), preferably 2 to
It is obtained by copolymerizing a) the polymerizable monomer containing a quaternary cation group and b) the polymerizable monomer containing a polyoxyethylene chain so that the content becomes 5%. If the nitrogen content in the polymer is too low, the retention of the active ingredient will decrease, and if it is too high, the stability of the formulation will decrease.

Here, the cationic polymer (A) of the present invention can be used as long as the nitrogen content in the polymer is within the above range.
The monomers other than the polymerizable monomers of the above a) and b) are further added to, for example, 15% or less, preferably 10% of the total monomers.
% Or less. Examples of such a monomer include anionic, amphoteric and other nonionic ester-based monomers. Here, when a monomer having an anion group is used, it is desirable that the ratio (molar ratio) of the cation group / anion group be not larger than 7/3, and particularly not larger than 8/2. Then, it is more preferable.

Although the molecular weight of the cationic polymer (A) of the present invention is not particularly limited, it is preferable that the weight-average molecular weight is from 1,000 to 1,000,000, more preferably from 5,000 to 100,000, More preferably, it is 10,000 to 500,000. If the molecular weight is too small, the retention of the active ingredient may decrease, and if it is too large, the stability of the preparation may decrease.

The cationic polymer (A) of the present invention can be copolymerized by various known methods, and the copolymerization method is not particularly limited, but it is preferable to carry out solution polymerization or emulsion polymerization. The copolymerization may be random or block.

Further, as a polymerization solvent at the time of copolymerization,
It is preferable to use a single solvent or a mixed solvent such as a lower alcohol such as methanol, ethanol and 2-propanol, a lower ketone such as acetone, or a mixed solvent thereof with water. Here, when using a mixed soot containing water,
The amount of water in the solvent is preferably from 10 to 50%, more preferably from 20 to 35%.

The polymerization initiator is not particularly limited as long as it is soluble in a solvent before use. For example, 2,2-azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile) 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (2-amidinopropane) dihydrochloride, 2,2-azobis (N, N-dimethyleneisobutylamidine), potassium persulfate , Ammonium persulfate, aqueous hydrogen peroxide, and the like, and the amount thereof is preferably 0.02 to 5% based on the total amount of the monomers. The polymerization temperature varies depending on the polymerization solvent used, but is preferably 40 to 90 ° C., and the polymerization time is preferably 3 to 8 hours.

As the component (A) of the present invention, the above-mentioned cationic polymers can be used alone or in combination of two or more. In the composition for external use of the present invention, the amount of the cationic polymer (A) to be blended is not particularly limited, but may be in the range of 0.
It is suitable that it is 001 to 30%, more preferably 0.05 to 20%, and still more preferably 0.05 to 10%. When used in this range, the effects of the cationic polymer of the present invention can be particularly favorably exhibited.

The active ingredient (B), which is the second essential component of the present invention, is usually used in cosmetic compositions, pharmaceutical compositions, quasi-drug compositions and the like, and has a medicinal effect on hair and skin. Any compound can be used as long as it imparts utility. For example, 1-hydroxy-2-pyridone compounds, salicylic acid and salts thereof, zinc pyrithione, trichlorocarbanilide, benzalkonium chloride, hydrochloric acid Alkyl diaminoethyl glycine, methyl chloroisothiazoline / methyl isothiazoline bactericides, bactericidal compounds such as sulfur, anti-inflammatory agents often contained in licorice such as dipotassium glycyrrhizinate and glutylretinic acid, blood circulation promoters such as tocopherol acetate, Ellag Whitening agents such as acid, kojic acid, arbutin and the like, and these may be used alone or in combination of two or more. It can be used in combination as appropriate.

In the case of the present invention, when the 1-hydroxy-2-pyridone compound represented by the following general formula (4) is combined with the above-mentioned cationic polymer (A), the retentivity to hair and skin is obtained. In this regard, it is particularly effective.

[0033]

Embedded image [However, in the above formula, R ⁹ is an alkyl group having 1 to 17 carbon atoms, an alkenyl group having 2 to 17 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, 7 to A bicycloalkyl group having 9 carbon atoms,
A cycloalkyl group having 5 to 8 carbon atoms and a cycloalkyl-alkyl group having 1 to 4 carbon atoms (provided that a part of the hydrogen atoms An alkyl group having 4 carbon atoms), an aryl group having 6 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. An aralkyl group having 4 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an alkenyl group having 2 to 4 carbon atoms, an arylalkenyl group having 6 to 14 carbon atoms, and an aryl group having 6 to 14 carbon atoms. An aryloxyalkyl group or an arylmercaptoalkyl group, a benzhydryl group, or an alkyl group having 1 to 4 carbon atoms each having 1 to 4 carbon atoms Phenylsulfonyl group having children, furyl group or an alkenyl group a furyl alkenyl group having 2 to 4 carbon atoms. However, in the above-mentioned aryl group, a part of the hydrogen atoms is substituted by an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyano group or a halogen atom. May be. R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, a halogen atom, a phenyl group or a benzyl group. Represents a group. Y represents an organic base, an alkali metal ion, an ammonium ion or a divalent to tetravalent cation. ]

Specific examples of the compound represented by the general formula (4) include the following compounds and salts thereof.

1-hydroxy-2-pyridone, 1-hydroxy-4-methyl-2-pyridone, 1-hydroxy-
6-methyl-2-pyridone, 1-hydroxy-4,6-
Dimethyl-2-pyridone, 1-hydroxy-4-methyl-6-heptyl-2-pyridone, 1-hydroxy-4-
Methyl-6- (1-ethylpentyl) -2-pyridone,
1-hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2-pyridone, 1-hydroxy-4
-Methyl-6-undecyl-2-pyridone, 1-hydroxy-4-methyl-6-propenyl-2-pyridone, 1
-Hydroxy-4-methyl-6-octenyl-2-pyridone, 1-hydroxy-4-methyl-6- (2,2-dibutyl-vinyl) -2-pyridone, 1-hydroxy-4
-Methyl-6- (cyclohexenylidene-methyl) -2
-Pyridone, 1-hydroxy-4-methyl-6-cyclohexyl-2-pyridone, 1-hydroxy-4-methyl-6- (methyl-cyclohexyl) -2-pyridone,
-Hydroxy-4-methyl-6- (2-bicyclo [2,
2,1] heptyl) -2-pyridone, 1-hydroxy-
4-methyl-6- [2- (dimethylcyclohexyl)-
Propyl] -2-pyridone, 1-hydroxy-4-methyl-6- (4-methyl-phenyl) -2-pyridone,
-Hydroxy-4-methyl-6- (3-methyl-phenyl) -2-pyridone, 1-hydroxy-4-methyl-6
-(4-tert-butyl-phenyl) -2-pyridone, 1-
Hydroxy-4-methyl-6- (3-methyl-4-chloro-phenyl) -2-pyridone, 1-hydroxy-4-
Methyl-6- (3,5-dichloro-phenyl) -2-pyridone, 1-hydroxy-4-methyl-6- (3-bromo-4-chloro-phenyl) -2-pyridone, 1-hydroxy-4- Methyl-6- (4-methoxystyryl)-
2-pyridone, 1-hydroxy-4-methyl-6- [1
-(4-nitrophenoxy) -butyl] -2-pyridone, 1-hydroxy-4-methyl-6- (4-cyanophenoxymethyl) -2-pyridone, 1-hydroxy-4
-Methyl-6- (phenylsulfonylmethyl) -2-pyridone, 1-hydroxy-4-methyl-6- [1- (4
-Chlorophenylsulfonyl) -butyl] -2-pyridone, 1-hydroxy-4-methyl-6-benzyl-2-
Pyridone, 1-hydroxy-4-methyl-6- (2,4
-Dimethylbenzyl) -2-pyridone, 1-hydroxy-4-methyl-6- (tert-butyl-benzyl) -2-pyridone, 1-hydroxy-4-methyl-6- (2-chloro-benzyl) -2 -Pyridone, 1-hydroxy-4-
Methyl-6- (4-chlorobenzyl) -2-pyridone,
1-hydroxy-4-methyl-6- (2,5-dichloro-benzyl) -2-pyridone, 1-hydroxy-4-methyl-6- (4-bromo-benzyl) -2-pyridone,
1-hydroxy-4-methyl-6- (phenoxymethyl) -2-pyridone, 1-hydroxy-4-methyl-6
-(3-methylphenoxy-methyl) -2-pyridone,
1-hydroxy-4-methyl-6- (4-secondary-butylphenoxy-methyl) -2-pyridone, 1-hydroxy-
4-methyl-6- (2,4,5-trichlorophenoxy-methyl) -2-pyridone, 1-hydroxy-4-methyl-6- (4-bromophenoxy-methyl) -2-pyridone, 1-hydroxy- 4-methyl-6- (4-chlorophenylmercapto-methyl) -2-pyridone, 1-hydroxy-4-methyl-6- (4-methylphenylmercapto-methyl) -2-pyridone, 1-hydroxy-4
-Methyl-6- (2-naphthyl) -2-pyridone, 1-
Hydroxy-4-methyl-6-benzhydryl-2-pyridone, 1-hydroxy-4-methyl-6-furyl-2
-Pyridone, 1-hydroxy-4-methyl-6- (furylvinyl) -2-pyridone, 1-hydroxy-4-methyl-6-styryl-2-pyridone, 1-hydroxy-4
-Methyl-6- (phenylbutadienyl) -2-pyridone, 1-hydroxy-4-phenyl-6-methyl-2-
Pyridone, 1-hydroxy-4,6-diphenyl-2-
Pyridone and the like can be mentioned.

The above compounds are used as salts, and can be suitably used, for example, as salts with organic amines.
Specifically, for example, ethanolamine, diethanolamine, N-ethylethanolamine, N-methyl-diethanolamine, triethanolamine, diethylamino-ethanol, 2-amino-2-methyl-n-propanol, dimethylaminopropanol, 2-amino -2
-Methyl-propanediol, tri-isopropanolamine, ethylenediamine, hexamethylenediamine,
Morpholine, piperidine, cyclohexylamine, tributylamine, dodecylamine, N, N-dimethyl-dodecylamine, stearylamine, oleylamine, benzylamine, dibenzylamine, N-ethylbenzylamine, dimethylstearylamine, N-methyl-morpholine, N-methylpiperazine, 4-methylcyclohexylamine, N-hydroxyethyl-morpholine and the like can be mentioned.

The 1-hydroxy-2-pyridone compound used as the component (B) in the present invention may be a salt with an inorganic ion, for example, an alkali metal salt such as a sodium salt or a potassium salt, or ammonium salt. Salts and alkaline earth metal salts such as magnesium salts and calcium salts can be used. Further, salts with divalent to tetravalent cations such as zinc salts, aluminum salts and zirconium salts can also be used.

The amount of the component (B) in the composition for external use of the present invention is not particularly limited, but when one of the above compounds is used alone or in combination of two or more, the composition is usually used. 0.01-3% of the whole, especially 0.05-2%
It is preferable that If the amount is too small, sufficient medicinal effect may not be obtained, and if the amount is too large, for example, the dissolution may be insufficient and the stability may be poor such as precipitation upon storage at a low temperature.

When the composition for external use of the present invention further contains an anionic surfactant in addition to the above components (A) and (B), the retention of the component (B) at the application site is further improved. , Is more effective. Here, as the anionic surfactant, for example, various substances such as polyoxyethylene alkyl ether sulfate and alkyl sulfate can be used, and the type thereof is not particularly limited. In these cases, among these,
It is particularly effective to use one of the above formulas alone or in an appropriate combination of two or more.

A sulfonic acid represented by the following general formula (5) or a salt thereof R ¹¹ SO ₃ M ¹ (5) wherein R ¹¹ is an alkyl group or alkenyl group having 8 to 22 carbon atoms or hydroxyalkyl And the alkenyl group includes α-olefin type, vinylidene type and inner olefin type alkenyl groups.
M ¹ represents a hydrogen atom or a cation derived from a base used for neutralization of sulfonic acid. This cation includes an alkali metal ion or an alkaline earth metal ion, an alkyl-substituted ammonium ion or a hydroxyalkyl-substituted ion. Cations formed by amines such as ammonium ions and basic amino acids are included. ]

As the sulfonic acid of the general formula (5) or a salt thereof, more specifically, various α-olefin sulfonates (AOS salts), paraffin sulfonates and the like can be mentioned.

The following general formula (6) ether sulfate or a salt thereof represented by ^{R 12 - (R 13 -O)} p -SO 3 M 2 (6) [where, in the formula, R ¹² is from 8 to 22 carbon atoms And an alkylphenyl group having an alkyl group having 5 to 15 carbon atoms, and R ¹³ represents an alkylene group having 2 to 3 carbon atoms. M ² represents a hydrogen atom or a cation derived from a base used for neutralizing ether sulfate, and this cation includes an alkali metal ion or an alkaline earth metal ion, an alkyl-substituted ammonium ion or a hydroxyalkyl-substituted ion. Cations formed by amines such as ammonium ions and basic amino acids are included. p is an integer of 0-6. ]

As the ether sulfates represented by the general formula (6), more specifically, polyoxyethylene (p =
3) Lauryl ether sulfate, aliphatic alcohol oxyethylene ether sulfate having 12 to 13 carbon atoms, and the like, and these are preferably sodium salts, potassium salts, or alkanolamine salts. Among them, sodium polyoxyethylene (p = 3) lauryl ether sulfate is particularly preferred. Here, p is the average number of moles added.

N-acylglutamic acid represented by the following general formula (7) or a salt thereof:

[0045]

Embedded image Wherein R ¹⁴ represents an alkyl group or an alkenyl group having 9 to 17 carbon atoms or a hydroxyalkyl group, and M ³ and M ⁴ may be the same or different; Represents a cation derived from an atom or a base used for neutralization of N-acylglutamic acid, which includes alkali metal ions and alkaline earth metal ions, as well as alkyl-substituted ammonium ions and hydroxyalkyl-substituted ammonium ions. Cations formed by amines such as substituted ammonium ions and basic amino acids are included. ]

As the N-acylglutamic acid represented by the above general formula (7) or a salt thereof, more specifically, N-acylglutamic acid such as N-lauroylglutamic acid, N-myristoylglutamic acid, N-palmitoylglutamic acid or a mixture thereof Or a monoethanolamine salt, diethanolamine salt, triethanolamine salt, sodium salt, potassium salt and the like of the N-acylglutamic acid. N-acyl-N-alkyl amino acids or N-acyl amino acids represented by the following general formula (8) and salts thereof

[0047]

Embedded image [Wherein, in the above formula, R ¹⁵ represents an alkyl group or alkenyl group having 9 to 17 carbon atoms or a hydroxyalkyl group, and R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. M ⁵ is a hydrogen atom or the above general formula (8)
Represents a cation derived from a base used for neutralization of the compound represented by
In addition to alkaline earth metal ions and ammonium ions,
Cations formed by amines such as alkyl-substituted ammonium ions and hydroxyalkyl-substituted ammonium ions and basic amino acids are included. q is 1 or 2. ]

More specifically, the compounds represented by the general formula (8) include N-lauroyl-N-ethylglycine, N-lauroyl-N-isopropylglycine,
-Lauroyl sarcosine, N-palmitoyl sarcosine, N-lauroyl-N-methyl-β-alanine, N-
Lauroyl-N-ethyl-β-alanine, N-myristoyl-β-alanine, N-palmitoyl-β-alanine; a mixture of the compounds; monoethanolamine salt, diethanolamine salt, triethanolamine salt, sodium salt of the compound; And potassium salts.

Acylmethyltaurine represented by the following general formula (9) or a salt thereof

[0050]

Embedded image Wherein R ¹⁷ represents an alkyl group or an alkenyl group having 9 to ¹⁷ carbon atoms or a hydroxyalkyl group; M ⁶ represents a hydrogen atom or a cation derived from a base used for neutralizing taurine; The cations include alkali metal ions, alkaline earth metal ions and ammonium ions, as well as cations formed by amines and basic amino acids such as alkyl-substituted ammonium ions and hydroxyalkyl-substituted ammonium ions. ]

As the acylmethyltaurine represented by the general formula (9) or a salt thereof, more specifically, sodium N-cocoylmethyltaurine and the like can be mentioned.

A sulfosuccinic acid type compound represented by the following general formula (10)

[0053]

Embedded image [However, in the above formula, R ¹⁸ represents a substituent represented by the following formula a or b, and M ⁷ and M ⁸ may be the same or different, but they are hydrogen atom or the above general formula (10) Represents a cation derived from a base used for neutralization of the compound represented by the formula. The cation includes an alkali metal ion, an alkaline earth metal ion, an ammonium ion, an alkyl-substituted ammonium ion, a hydroxyalkyl-substituted ammonium ion, and the like. And cations formed by basic amino acids and basic amino acids. ]

[0054]

Embedded image Wherein R ¹⁹ represents an alkyl group or alkenyl group or a hydroxyalkyl group having 8 to 22 carbon atoms, R ²⁰ represents a hydrogen atom or a methyl group, and u represents 1
It is an integer of 0 to 20. ]

[0055]

Embedded image Wherein R ²¹ represents an alkyl group or an alkenyl group having 9 to 17 carbon atoms or a hydroxyalkyl group; R ²² represents a hydrogen atom or a methyl group;
Is an integer of up to 20. ]

As the sulfosuccinic acid type compound represented by the general formula (10), more specifically, for example, polyoxyethylene lauryl sulfosuccinate-2-sodium and the like can be mentioned.

A sulfosuccinic acid type compound represented by the following general formula (11)

[0058]

Embedded image [However, in the above formula, R ¹⁸ , M ⁷ and M ⁸ represent the same meaning as in the above formula (10). ]

[0059] As sulfosuccinic acid-type compound represented by the above formula (11), more specifically, except that substitution sites of SO ₃ M ⁷ are different, the same structure as the compound represented by the above formula (10) Compounds.

Alkyloylalkyltaurine type compound represented by the following general formula (12)

[0061]

Embedded image [However, in the above formulas, R ²³ represents an alkyl group having 7 to 19 carbon atoms, alkenyl or hydroxyalkyl group, R ²⁴ is a lower alkyl group having 1 to 3 carbon atoms, M ⁹ is an alkali metal, alkaline earth metal or Each represents an organic amine. ]

As the alkylloylalkyltaurine type compound represented by the general formula (12), more specifically,
N-lauroyl-N-methyltaurine sodium and the like.

An ether carboxylic acid type compound represented by the following general formula (13): R ²⁵ O (CH ₂ CH ₂ O) _m COOM ¹⁰ (13) wherein, in the above formula, R ²⁵ is an alkyl having 10 to 22 carbon atoms. or alkenyl group, m represents an integer of 2 to 15, M ¹⁰ represents an alkali metal, alkaline earth metal, ammonium or organic ammonium, respectively. ]

As the ether carboxylic acid type compound represented by the general formula (13), more specifically, sodium polyoxyethylene (p = 3) lauryl ether acetate can be mentioned.

When the above-mentioned anionic surfactant is blended with the composition for external use of the present invention, its blending amount (total blending amount when two or more kinds are used in combination) is not particularly limited. 0.5-50% of the whole is suitable, more preferably 1-30%. If the amount of the anionic surfactant is too large, there may be a disadvantage to the retention of the active ingredient on the hair or scalp.If the amount is too small, the effect of the anionic surfactant may not be sufficiently obtained. is there.

In the composition for external use of the present invention, a high-molecular compound other than the above-mentioned component (A) may be used in combination with the above-mentioned component (B), particularly for the purpose of enhancing the retention of the active ingredient on the hair or skin. it can. The composition for external use of the present invention, as long as it does not hinder the effects of the present invention, depends on its type and usage mode, etc.
If necessary, in addition to the above-mentioned components as optional components, a composition for hair, an amphoteric surfactant or a semipolar surfactant, a cationic surfactant, a nonionic surfactant, or the like, which is a common component of a composition for external use on the skin, may be added. And various polymer compounds such as a cationic polymer compound, an anionic polymer compound, an amphoteric polymer compound other than the component (A), a nonionic polymer compound, a solid or liquid oil, silicones, and higher alcohols. , Ester oils, polyhydric alcohols, preservatives, hydrotropes, inorganic salts, thickeners, fragrances, extracts of animals and plants, antidandruff agents, emulsifiers, pearling agents, ultraviolet absorbers, ultraviolet scattering agents, Can contain tonics, pH adjusters, dyes, antioxidants, lower alcohols, vitamins, volatile oils, hydrophobic solvents, diluent solvents, etc. Is not particularly limited, it may be made formulated according to the purpose.

Specific examples of the fragrance include hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons and aromatic hydrocarbons, alcohols such as aliphatic alcohols, terpene alcohols and aromatic alcohols, and aliphatic ethers. , Aromatic ethers and other ethers, aliphatic oxides, terpenes and other oxides, aliphatic aldehydes, terpene aldehydes, aliphatic cyclic aldehydes, thioaldehydes, aromatic aldehydes and other aldehydes, aliphatic ketones, Ketones such as terpene ketone, aliphatic cyclic ketone, non-benzene aromatic ketone, aromatic ketone, acetal, ketal, phenol, phenol ether, fatty acid, terpene carboxylic acid, aliphatic cyclic carboxylic acid, aromatic Acids such as aromatic carboxylic acids, acid amides,
Lactones such as aliphatic lactone, macrocyclic lactone, terpene lactone, aliphatic cyclic lactone, aromatic lactone, aliphatic ester, furan carboxylic acid ester, aliphatic cyclic carboxylic acid ester, cyclohexyl carboxylic acid ester, terpene carboxylic acid Esters such as acid esters and aromatic carboxylic acid esters, nitromusks, nitriles, amines, pyridines, quinolines, pyrroles,
One or two or more kinds of synthetic fragrances such as nitrogen-containing compounds such as indole and natural fragrances from animals and plants, and compounded fragrances containing natural fragrances and / or synthetic fragrances can be used.

For example, as synthetic fragrances, “Synthetic fragrance chemistry and product knowledge” by Motoichi Indo, published by Kagaku Kogyo Nippo, 1996, MONTCLAIR, N.K. J. Published by Stefan Arctander
ANDER), "Perfume and Flavor C
chemicals) "and the like. As the natural fragrance, fragrances described in “Scent Encyclopedia” (edited by Japan Fragrance Association) can be used.

Specific examples of main flavors include aldehyde C ₆ -C ₁₂ , anisaldehyde, acetal R, acetophenone, acetylsedren, adoxal, allyl amyl glycolate, allyl cyclohexane propionate, α-damascon, β-damascon, δ-damascon, ambroxane, amylcinamic aldehyde,
Amylcinnamic aldehyde dimethyl acetal, amyl valerinate, amyl salicylate, isoamyl acetate, isoamyl salicylate, ouranciol, acetyl eugenol, bacdanol, benzyl acetate, benzyl alcohol, benzyl salicylate, bergamyl acetate, bornyl acetate, butyl butyrate, p -T-butylcyclohexanol,
pt-butylcyclohexyl acetate, ot-butylcyclohexanol, ot-butylcyclohexyl acetate, benzaldehyde, benzylformate, caryophyllene, cashmeren, carvone, sedroambar, cetyl acetate, cedrol, celestrid, cinamic Alcohol, cinnamic aldehyde, cis jasmon, citral, citral dimethyl acetal, citrasal, citronellal, citronellol, citronellyl acetate, citronellyl formate, citronellyl nitrile, cyclaset, cyclamenaldehyde, cyclaprop, caron, coumarin, cinnamyl acetate , Δ-C ₆ -C ₁₃ lactone,
Dimethylbenzylcarbinol, dihydrojasmon,
Dihydro linalool, dihydromyrcenol, Jimetoru, Jimirusetoru, diphenyl oxide, Echiruwanirin, eugenol, Furuiteto, Fen chill alcohol, phenylethyl phenylacetate, Garakusorido, γ-C ₆ ~C ₁₃ lactone, alpha-pinene, beta-pinene, limonene , Myrcene, β-caryophyllene, geraniol, geranyl acetate, geranyl formate,
Granyl nitrile, hedion, helional, heliotropin, cis-3-hexenol, cis-3-hexenyl acetate, cis-3-hexenyl salicylate, hexylcinnamic aldehyde, hexyl salicylate, hyacinthium dimethyl acetal, hydrotropic alcohol, Hydroxycitronellal,
Indole, ionone, isobornyl acetate, isocyclocitral, iso-E super, isoeugenol, isononyl acetate, isobutylquinoline, jasmar, jasmolactone, jasmophylan, coabon, rigstral, lilial, lime oxide, linalool, linalool oxide , Linalyl acetate, lilal, manzanate, mayol, menthanyl acetate, menthone, methyl anthranilate, methyl eugenol, menthol, α-methyl ionone, β-methyl ionone, γ-methyl ionone, methyl iso eugenol, methyl lavender ketone, methyl salicylate, muguet Aldehyde, mugol, musk TM-II, musk 781, musk C14, muscone, cibetone, cyclopen Decanone, cyclohexadecen cyclohexenone, cyclopentadecanolide, Anne bread Lido,
Cyclohexadecanolide, 10-oxahexadecanolide, 11-oxahexadecanolide, 12-oxahexadecanolide, ethylene brassate, ethylene dodecandioate, oxahexadecen-2-one, 14-
Methyl-hexadecenolide, 14-methyl-hexadecanolide, musk ketone, musktibetain, nopyr alcohol, nopyr acetate, neryl acetate, nerol, methyl phenyl acetate, mirac aldehyde,
Neobergamate, Oak Moss No. 1, oribbon, oxyphenylone, p-cresol methyl ether, pentalid, phenylethyl alcohol, phenylethyl acetate, rubafuran, damacenone, raspberry ketone, dimethylbenzyl carvinyl acetate, jasmacyclene, methyl naphthyl ketone, rosephenone,
Rose oxide, Sandalore, Sandella, Santarex, Stillyl acetate, Stillyl propionate, Terpineol, Tervinyl acetate, Tetrahydrolinalool, Tetrahydrolinalyl acetate, Tetrahydrogeraniol, Tetrahydrogeranyl acetate, Tonalid, Traseolide, Tripral, Thymol, Thymol Crocodile, berdox, yarayara, anise oil, bay oil, boad rose oil, cananga oil, cardamom oil, cassia oil, cedar wood oil, orange oil, mandarin oil, tangerine oil, basil oil, nutmeg oil, citronella oil, clove oil, coriander Oil, elemi oil,
Eucalyptus oil, fennel oil, galvanum oil, geranium oil, hiba oil, cypress oil, jasmine oil, lavandin oil, lavender oil, lemon oil, lemongrass oil, lime oil, neroli oil, oak moss oil, okotia oil, patchouli oil, peppermint oil Oil, perilla oil, petitgren oil, pine oil, rose oil, rosemary oil, camphor oil, fragrant oil, clary sage oil, sandalwood oil, spearmint oil, spike lavender oil, star anise oil, thyme oil, tonka bean tincture, turpentine Oil, crocodile bean tincture, vetiver oil, ylang-ylang oil, grapefruit oil, citron oil, benzoin,
Peruvian sam, true balsam, tuberose oil, absolute oak moss, fabal sam, musk tincture, castorium tincture, civet tincture, ambergris tincture and the like.

Further, diethyl phthalate, dipropylene glycol, benzyl benzoate, isopropyl myristate, hercoline, isopentane, orange terpene and the like can be used as a solvent or a retaining agent for the fragrance.

The external use composition of the present invention is not particularly limited in its use. For example, a body wash composition such as a hair cleanser such as a shampoo, a face cleanser, a skin cleanser such as a body shampoo, etc. Various medicinal ingredients such as hair rinses, hair tonics, hair creams, hair tonics, hair dyes, hair compositions such as hair gels, skin lotions, skin creams, emulsions and other cosmetics, and skin external compositions. It can be suitably used as an external composition containing an active ingredient. The dosage form, preparation method, and the like are not particularly limited, and can be prepared according to a conventional dosage form suitable for each application.

[0072]

The composition for external use of the present invention is excellent in retention of the active ingredient contained in the composition on hair and skin.

[0073]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples,% is based on mass.

[Examples 1 to 17 and Comparative Examples 1 to 3] In accordance with the compositions shown in Tables 1, 2 and 3 and 4, external compositions (hair composition and skin composition) were prepared in accordance with conventional methods. After preparation, the external compositions of Examples and Comparative Examples were obtained. 1-hydroxy-2- as an active ingredient contained in each composition
With respect to pyridone compounds and the like (medicinal ingredients), their persistence on hair or skin and storage stability after filling in containers were evaluated according to the following evaluation methods. The results are shown in Tables 1 and 2 and Tables 3 and 4.

<Retentivity of Compound Having a Pharmaceutical Effect on Hair or Skin> For each of the formulated compositions, a solvent which dissolves the medicinal component adsorbed on the hair or skin after use on the hair or skin, and dissolves the respective medicinal component well. , And the retention amount was determined by liquid chromatography by the quantitative method of each medicinal component, and the retention amount was compared with the time of use of Comparative Example 1 and evaluated by the retention ratio.

Evaluation criteria ◎: Retention rate is clearly improved as compared with Comparative Example 1 (retention rate of 121% or more). 〇: Retention rate is improved as compared with Comparative Example 1 (retention rate 111 to 11). 120%) Δ: Retention rate is equivalent to that when Comparative Example 1 is used (retention rate: 91 to 110%) ×: Retention rate is lower than when Comparative Example 1 is used (retention rate is 90% or less)

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

[Table 4]

According to the results shown in Tables 1 to 4, it was confirmed that all of the compositions for external use of the present invention had excellent medicinal ingredients retention properties on hair or skin.

Here, (A) a cationic polymer, (B) a medicinal ingredient and other ingredients used in Examples and Comparative Examples of the present invention are shown below.

(A) Cationic polymer A 1 L four-neck separable flask equipped with a stirrer, a reflux condenser and a nitrogen inlet tube was charged with a total of 100 g of each monomer having the composition shown in Table 5 (the numerical value of each monomer in the table). Is the molar ratio) and 100 g of ethanol are added and uniformly dissolved.
While stirring, nitrogen gas was introduced from a nitrogen introduction tube. 20
After a minute, an air blowing agent solution obtained by dissolving 0.8 g of 2,2-azobis (2-methyl-butyronitrile) in 100 g of ethanol was added thereto.
Polymerized for hours. Remove the solvent from the contents of the flask,
Unreacted monomers and odorous residues were removed by dialysis with distilled water, and further concentrated and freeze-dried to obtain the intended cationic polymers (A-1 to A-10). Each of the freeze-dried cationic polymers is dissolved in a solvent of water / methanol = 4/1 (vo1 / vo1) containing 50 mM lithium chloride, and polyacrylic acid of known molecular weight is standardized by aqueous GPC using the same solvent as an eluent. The weight average molecular weight of each cationic polymer was determined. Table 5 also shows the weight average molecular weight and nitrogen (N) content (% by mass) of each cationic polymer.

[0084]

[Table 5]

[0085]

Embedded image

[0086]

Embedded image

B-3 Isothiazolone liquid (“Caisson C”
G ": Rohm & Haas, methyl chloroisothiazoline / methylisothiazoline fungicide)

D-1 Cationized cellulose (manufactured by Union Carbide, polymer JR-400) D-2 Cationized guar gum (manufactured by Rhodia, Jaguar C-14S) D-3 Cationized guar gum (manufactured by Rhodia, Jaguar C-C) 162) D-4 Dimethyldiallylammonium chloride / acrylamide copolymer (manufactured by Calgon, Marcoat 550) D-5 N-methacryloylethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine polymer (weight average) D-6 Potato starch-derived cationized polymer (Narco, Sensormer CI-50) D-7 Potato starch-derived polymer (Narco, Sensormer NI) D-8 Polyquaternium 47 (Nalco, Marcoat 2001) D-9 vinyl pyrrolide -Methylvinylimidazole copolymer (BASF, Rubicut Care) D-10 Acrylic acid / aminoacrylate copolymer (Nippon NSC, Structure Plus) D-11 Sodium polystyrene sulfonate (Nippon NSC) , Flexan 130) D-12 Acrylic acid / acrylamidomethylpropanesulfonic acid sodium salt copolymer (manufactured by Narco, CG4
500) D-13 Polyquaternium 5 (Narco Corporation, Marcoat 5)

C-1 Sodium polyoxyethylene lauryl ether sulfate (2.EO) C-2 Sodium polyoxyethylene lauryl ether sulfate (3.EO) C-3 Sodium lauryl sulfate C-5 Coconut fatty acid acyl Methyl sulfonate C-6 Coconut oil fatty acid acylmethyl taurine salt C-7 Polyoxyethylene coconut oil fatty acid amide ether sodium sulfate (5.EO) C-8 Sodium polyoxyethylene lauryl ether acetate (3.EO) ) C-9 N-lauroylglutamic acid triethanolamine salt C-10 lauroylsarcosinate triethanolamine salt

Activator other than anionic and other components E-1 Trimethylsilyl-terminated dimethylpolysiloxane (100,000 cst) (manufactured by Dow Corning Toray Co., Ltd., “BY22-029”, average particle size 500 nm, silicone content about 50%, E-2 Amino-modified methyl polysiloxane (1000c
st) Oil ("XF42-19" manufactured by Toshiba Silicone Co., Ltd.)
89 ") E-3 Betaine lauryldimethylaminoacetate E-4 Polyoxyethylene stearyl ether (Emarex 605) E-5 Polyoxyethylene hydrogenated castor oil (20.E.
O) E-6 Methyl glucond of polyoxyethylene dioleate (120.EO) E-7 Dodecyl polyglucoside E-8 Decaglycerin monolaurate E-9 Isopropyl palmitate E-10 Carnauba wax

The composition of the fragrance A in Tables 1 to 4 is as follows. Lemon oil 5% Sweet orange oil 10% Geranium oil 3% Lavender oil 6% Sandalwood oil 1% Liliar 5% Nopyr acetate 1% Linalool 2% Benzyl benzoate 2% Benzyl salicylate 3% β-ionone 2% Methyl ionone 3% 2% Hedion 8% Iso-E Super 3% cis-3-hexenol 0.3% Ligantral 0.3% Tripral 0.4% Cyclamenaldehyde 1.5% Hexylcinnamic aldehyde 6% Beltofix 3% Galaxolide 5% Tonalid 6 % Pentalid 1% Bakdanol 0.5% Kashmeran 2% Musk T 1% Fruit base 3% Rose base 3% Jasmine base 1% Mugue base 3% Amber base 1% Nanaru 10% dipropylene glycol solution 2% decanal 10% dipropylene glycol solution 1% 10% methyl nonyl aldehyde dipropylene glycol solution 2% dipropylene glycol balance Total 100%

Example 18 Composition Component Amount (%) A-1 0.25 A-3 1.0 B-1 0.5 B-3 0.03 Polyoxyethylene (3 mol) alkyl ether sulfate Sodium 15.0 Sodium α-olefin sulfonate 5.0 Amidopropyl betaine laurate 7.0 Alkyl dimethylamine oxide 2.0 Coconut oil fatty acid diethanolamide 3.0 Polyoxyethylene dioleate methyl glucoside 0.8 Lauryl pyrrolidone 3 0.0 Coleus extract 0.2 Cationized cellulose 0.6 Dimethyldiallylammonium chloride / acrylamide copolymer 0.5 Polyoxyethylene hydrogenated castor oil (HLB9) 1.5 Polyoxyethylene (15 mol) alkyl ether 0.9 Sodium sulfate 2.0 Sodium benzoate 1. Ethylene glycol distearate 2.0 Glycerin fatty acid ester 0.2 Dipotassium glycyrrhizinate 0.2 Glycine 0.5 1,3-butylene glycol 1.0 Dibutylhydroxytoluene 0.005 Oxybenzone 0.5 Yellow No. 203 0.001 Orange 205 issue 0.002 perfume 0.7 citric acid 0.5 purified water balance total 100.0

According to the above composition, a shampoo composition was prepared according to a conventional method to obtain a shampoo composition of Example 18. This shampoo composition provides B-1 for hair and skin.
The retention of the compound, the B-3 compound and dipotassium glycyrrhizinate was excellent.

Example 19 Composition Ingredients Compounding Amount (%) A-2 2.0 B-2 0.2 Sodium α-olefin sulfonate 2.0 Sodium alkane sulfonate 5.0 Amidopropyl betaine laurate 3 0.0 alkyl carboxyethyl hydroxyethyl imidazolinium betaine 5.0 sodium polyoxyethylene lauroyl sulfosuccinate 0.5 alkyl dimethylamine oxide 1.5 polyoxyethylene (20) lauryl ether 2.0 cationized cellulose 0.3 cationization Guar gum 0.7 Wax 0.5 Sodium chloride 0.2 Trimethylglycine 0.2 Calophyllis extract 0.5 Isopropyl methylphenol 1.0 Disodium edetate 2.0 Alkyl dimethyl ammonium chloride / acrylic acid / acrylic Amide terpolymer 0.6 Glycerin 0.1 2-Ethylhexyl methoxycinnamate 0.5 Dye 0.1 Fragrance 0.3 Citric acid 3.0 Glycolic acid 3.0 Purified water Remaining total 100.0

According to the above composition, a shampoo composition was prepared according to a conventional method to obtain a shampoo composition of Example 19. This shampoo composition had good retention of the B-2 compound on hair and scalp.

Example 20 Composition Ingredients Amount (%) A-1 0.5 B-1 0.5 B-2 0.2 Polyoxyethylene (3 mol) alkyl ether sulfate 7.0 Myristic acid Potassium 15.0 Palmitic acid 8.0 Stearic acid 8.0 Oleyl alcohol 1.0 Glycerin 10.0 Polyethylene glycol 5.0 Coconut oil fatty acid monoethanolamide 0.1 Cationized guar gum 1.2 Both dimethyldiallylammonium chloride and acrylamide Polymer 0.8 Propylene glycol 1.0 Vegetable squalane 0.5 Sodium edetate tetrahydrate 0.2 Polyoxyethylene hydrogenated castor oil (HLB9) 1.5 Glycerin fatty acid ester 0.2 Benclay 0.8 Isoprene glycol 1.0 blue No. 403 0.001 perfume 0.2 purified Balance Total 100.0

According to the above composition, a face wash composition was prepared according to a conventional method to obtain a face wash composition of Example 20. This facial cleansing composition has a good feeling of use as a composition, and B
The retention of compounds -1 and B-2 on the skin was excellent.

Example 21 Composition Ingredients Amount (%) A-2 2.0 B-1 0.7 Zinc pyrithione 1.0 Sodium acylmethyltaurine 5.5 Alkyl betaine 3.0 Polyoxyethylene alkyl ether 6.5 Alkyl glyceroglucoside 1.0 Dimethyldiallylammonium chloride / acrylic acid copolymer 0.7 Polyoxyethylene dioleic acid methylglucoside 1.0 Coconut oil fatty acid diethanolamide 3.0 Coconut oil fatty acid monoethanolamide 1.0 Ethylene glycol distearate 2.0 Hydroxyethyl cellulose 0.6 Dimethyldiallylammonium chloride / acrylamide / acrylic acid terpolymer 0.6 Laurylpyrrolidone 5.0 Cetyl isooctanoate 1.0 Dibutylhydroxytoluene 0.002 Gly Rurechin acid 0.5 Zegna OY extract 0.5 highly polymerized dimethylpolysiloxane 3.0 cetostearyl alcohol 0.1 Tocopherol acetate 0.5 Dye 0.002 Perfume 0.2 Purified water balance Total 100.0

According to the above composition, a shampoo composition was prepared according to a conventional method to obtain a shampoo composition of Example 21. This shampoo composition had good retention of the B-1 compound, zinc pyrithione, glycyrrhetinic acid, and tocopherol acetate on hair and skin.

Example 22 Composition Ingredients Compounding Amount (%) A-1 2.0 B-1 1.5 Acylmethyl-β-alaninetriethanolamine 10.0 Triethanolamine acylglutamate 5.0 Ether carboxylic acid Sodium 1.0 Alkylaminopropionic acid 0.05 Lauryldimethylamine oxide 0.8 Stearyltrimethylammonium chloride 1.0 Palm kernel oil fatty acid diethanolamide 2.0 Polyoxyethylene hydrogenated castor oil (HLB9) 3.0 Propylene glycol 0.0 2 Ethanol 3.0 Dipotassium glycyrrhizinate 0.3 Liquid paraffin 0.2 Glycerin fatty acid ester 0.8 Sodium benzoate 0.7 Hydrolyzed protein 0.5 Magnesium sulfate 1.5 Cationized cellulose 0.2 Alkyl dimethyl chloride Ammonium acrylate copolymer 0.4 dibutylhydroxytoluene 0.2 perfume 0.3 Citric acid 0.1 edetate 1.0 Purified water balance Total 100.0

According to the above composition, a shampoo composition was prepared according to a conventional method to obtain a shampoo composition of Example 22. The shampoo composition comprises a B-1 compound for scalp,
The retention of dipotassium glycyrrhizinate was excellent.

[0102] Example 23 Composition Ingredient amount (%) A-1 1.2 B -1 2.5 polyoxyethylene (2 mol) alkyl ether sulfate 7.0 Potassium myristate 15.0 lauroylmethyl -Β-alanine potassium salt 2.0 lauroyl glutamic acid monopotassium salt 2.0 lauryl dimethylamine oxide 1.0 oleyl alcohol 1.0 polyethylene glycol 5.0 coconut oil fatty acid diethanolamide 3.0 propylene glycol 6.0 hydroxypropyl methylcellulose ^{* 1} 0.5 Vegetable squalane 0.5 Sodium edetate tetrahydrate 0.2 Polyoxyethylene hydrogenated castor oil (HLB9) 1.5 Benclay 0.8 Potassium hydroxide Trace Blue 403 0.001 Fragrance 0. 2 purified water balance total 100.0 * 1 "meth Over the scan 65SH-1500 ", manufactured by Shin-Etsu Chemical Co., Ltd.

According to the above composition, a skin cleansing composition was prepared according to a conventional method to obtain a skin cleansing composition of Example 23. This skin cleansing composition was excellent in the retention of the B-1 compound on the skin.

Example 24 Composition Ingredients Compounding Amount (%) A-1 0.5 A-2 2.0 B-2 0.8 Salicylic Acid 0.2 Sulfur Pharmacopoeia 5.0 Potassium Myristate 16.0 Palmitic acid 5.0 Stearic acid 5.0 Oleyl alcohol 1.0 Glycerin 15.0 Polyethylene glycol 4000 5.0 Coconut oil fatty acid diethanolamide 1.1 Propylene glycol 1.0 Calofilis extract 0.5 Sodium edetate 4 water Salt 0.2 Benclay 0.8 Perfume 0.3 Purified water Remainder total 100.0

According to the above composition, a face wash composition was prepared according to a conventional method to obtain a face wash composition of Example 24. This facial cleansing composition was excellent in the retention of the B-2 compound, salicylic acid and sulfur in the skin on the skin.

Example 25 Composition Ingredients Amount (%) A-1 0.4 B-1 0.3 Behenyltrimethylammonium chloride 1.0 4-Guanidinobutyllauramide 0.8 N- [3-alkyl (12,14) oxy-2-hydroxypropyl] -L-arginine 0.5 polyethylene glycol (average molecular weight 5,000,000) 0.2 diethylaminoethylamide bevenate 0.2 dimethyl silicone (viscosity 1,000,000 cst) 0 diglycerin isopalmitate sebacic acid condensate 1.0 glycine 0.7 cetanol 1.5 behenyl alcohol 0.2 oleyl alcohol 0.3 oleic acid 0.2 isostearic acid 0.2 trimethylglycine 0.2 arginine 0.3 Cysteine 0.3 Glyceryl monostearate 0.1 M Sorbitan nolaurate 0.1 Phosphoric acid Appropriate amount Methyl parahydroxybenzoate Appropriate amount Propyl paraoxybenzoate Appropriate amount Perfume Appropriate amount Purified water Remainder total

According to the above composition, a rinse composition was prepared according to a conventional method to obtain a rinse composition of Example 25. This rinse composition had excellent retention of the B-1 compound on hair and skin, and had good storage stability in a container.

Example 26 Composition Ingredients Amount (%) A-1 1.0 B-1 0.5 Bentonite 1.0 Hexaglyceryl monostearate 1.0 Diglyceryl monostearate 0.5 Glyceryl mono Stearate 1.5 Liquid paraffin 10.0 Solid paraffin 1.5 Dimethyl silicone 3.0 Cetyl palmitate 2.0 Cetostearyl alcohol 4.0 Glycerin 5.0 1,3-butylene glycol 2.0 Trimethylglycine 0.2 Carboxyvinyl polymer (molecular weight 1,000,000 to 1.5 million) 0.08 Xanthan gum 0.1 Methyl parahydroxybenzoate Appropriate amount Propyl parahydroxybenzoate Appropriate amount Water extract of Callophyllis japonica Water sodium 5.0 Trace amount of perfume Appropriate purified water Parts Total 100.0

According to the above composition, a cream composition was prepared according to a conventional method to obtain a cream composition of Example 26.
This cream composition was excellent in the retention of B-1 on the skin.

Example 27 Composition Ingredients Amount (%) A-2 0.1 B-1 0.1 Glycerin 5.0 1,3-butylene glycol 5.0 Carboxyvinyl polymer 0.5 Potassium hydroxide Traces of tocopherol acetate 0.2 Coleus extract 0.3 Decaglyceryl monoisostearate 1.0 Decaglycerin triisostearate 0.5 Ethanol 1.0 Polyoxyethylene (40 mol) hydrogenated castor oil 0.5 Callophyllis firma Water extract 0.5 Trimethylglycine 3.0 Benclay 0.2 Perfume Micro- purified water Remainder total 100.0

According to the above composition, a lotion composition was prepared according to a conventional method to obtain a lotion composition of Example 27. This lotion composition was excellent in retention of the B-1 compound and tocopherol acetate on the skin.

Example 28 Composition Ingredients Compounding Amount (%) A-1 0.1 B-1 0.1 Monopentadecanoic Acid Glyceride 3.0 Tocopherol Acetate 0.1 Coconut Oil Fatty Acid Sorbitan 1.0 Sucrose Myristin Acid ester 0.5 Biotin 0.002 Succinic acid 0.3 Assembly extract 1.0 Hinokitiol 0.1 l-menthol 0.3 Perfume Appropriate amount Ethanol Remainder total 100.0

According to the above composition, a hair restorer composition was prepared according to a conventional method to obtain a hair restorer composition of Example 28. This hair restorer composition was excellent in retention of the B-1 compound and tocopherol acetate on hair and skin.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A61K 7/075 A61K 7/075 7/08 7/08 7/50 7/50 C08F 220/28 C08F 220 / 28 220/34 220/34 226/02 226/02 290/06 290/06 C08K 5/00 C08K 5/00 5/3415 5/3415 C08L 33/04 C08L 33/04 33/14 33/14 39/00 39/00 55/00 55/00 // C11D 3/28 C11D 3/28 3/37 3/37 F term (reference) 4C083 AA122 AB032 AB102 AB112 AB352 AB442 AC012 AC022 AC072 AC102 AC112 AC122 AC182 AC242 AC302 AC312 AC342 AC352 AC392 AC422 AC432 AC472 AC482 AC532 AC542 AC552 AC562 AC582 AC642 AC662 AC692 AC712 AC742 AC782 AC792 AC851 AC852 AC862 AD042 AD072 AD092 AD132 AD152 AD162 AD192 AD222 AD242 AD282 AD352 AD412 AD532 AD552 AD662 BB05 BB34 BB60 CC01 CC31 CC31 CC31 CC01 EE12 EE22 4H003 AB05 AB09 AB10 AB11 AB15 AB23 AB27 AB31 AB34 AB46 AC03 AC05 AC08 AC12 AC13 AC15 AD02 AD04 AE05 DA02 EA12 EB04 EB07 EB08 EB09 EB13 EB20 EB28 EB30 EB37 EB40 EB41 EB42 EB43 B02 EB46 EB46 EB46 FAW EU036 EV257 EV326 FD206 FD317 GB00 HA06 4J027 AC03 AC06 AJ02 BA13 BA17 CA27 CC02 CD07 4J100 AL08P AL08Q AN13P BA03Q BA08Q BA32P CA04 DA01 EA01 FA03 JA61

Claims (4)

[Claims] 1. A cationic polymer which is a copolymer of (A) a) a polymerizable monomer containing a quaternary cationic group and b) a polymerizable monomer containing a polyoxyethylene chain, wherein nitrogen in the polymer is used. A cationic polymer having a content of 0.5 to 6% by mass relative to the total mass of the polymer,
(B) An external composition comprising an active ingredient. 2. The (A) a) a polymerizable monomer containing a quaternary cationic group is represented by the following general formula (1) or (2), and b) a polyoxyethylene chain-containing polymerizable monomer is The composition for external use according to claim 1, which is represented by the following general formula (3). Embedded image (However, the above formula (1) and (2) and (3), R ¹ is,
A hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^{2 to} R ⁶ are
Each independently represents an alkyl group having 1 to 4 carbon atoms, X, X ¹ and X ² each represent an alkylene group having 2 to 4 carbon atoms, M represents an anion, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , R ⁸ are a hydrogen atom, an alkyl group or an aryl group having 1 to 6 carbon atoms, and n is 2 to 50. ) 3. The method according to claim 1, wherein the active ingredient (B) is 1-hydroxy-
3. The composition for external use according to claim 1, which is a 2-pyridone compound. 4. The external composition according to claim 1, further comprising an anionic surfactant.