JP2010090049A - Hair cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair cosmetic imparting smoothness to the hair, also having excellent dandruff prevention and itchiness inhibition effects, and inhibiting a base agent smell. <P>SOLUTION: The hair cosmetic includes (A) a 0.2 to 2.0 mass% acrylic acid-based polymer, (B) a 0.1 to 1.0 mass% 1-hydroxy-2-pyridone-based compound and (C) a 0.2 to 5.0 mass% cationic surfactant, and having 0.30 to 1.60 (A)/(C) (mass ratio). The acrylic acid-based polymer (A) includes (recurring units of) formula (1) [wherein, R<SP>1</SP>is H or methyl; R<SP>2</SP>is H or -CH<SB>2</SB>OH; and A is O or -NH-] and formula (2) [wherein, R<SP>3</SP>is H or methyl; and M is H, an alkali metal, ammonium or an amine]. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hair cosmetic composition that imparts smoothness to hair, has excellent dandruff improvement and itching suppression effects, and suppresses a base odor.

  In recent years, there has been an increasing need for hair cosmetics intended for damage care, and many of these products are sold in the market. These hair cosmetics for the purpose of damage care exhibit effects by adsorbing various surfactants, silicones, oils, higher alcohols, polymer compounds and the like to the hair. However, these components remain in not only the hair but also the scalp, which may cause irritation and itching of the scalp and cause symptoms such as inflammation. As a result, the remaining cosmetic ingredients on the scalp, dandruff, itchiness, and roughness due to dry skin have become the mainstream of skin problems rather than dandruff itself, which has been the main cause of bacterial growth.

  Conventionally, for improving dandruff and itching, for example, hair cosmetics containing medicinal ingredients such as dandruff improvement and itch suppression such as 1-hydroxy-2-pyridone, sulfur and zinc pyrithione have been used. A certain effect has been obtained by using these hair cosmetics, but with the change in the above situation, an effect sufficient to satisfy the scalp trouble which has recently become a problem has not been obtained. In order to obtain a higher scalp care effect, if these ingredients are blended at a high concentration, the cost of medicinal ingredients is high, the quality stability of the preparation containing medicinal ingredients, the smell of medicinal ingredients, etc. There was a problem that it was difficult to ensure a good feeling of use. In addition, the following is mentioned as a prior art document relevant to this invention.

JP 2006-176446 A JP 2001-261529 A JP 2007-137830 A JP 2007-161986

  The present invention has been made in view of the above circumstances, and provides a hair cosmetic that imparts smoothness to hair, has excellent dandruff improvement and stagnation suppression effects, and suppresses base odor such as component (B). The purpose is to provide.

  As a result of intensive studies to achieve the above object, the inventors of the present invention contain (A) a specific acrylic acid polymer, (B) a 1-hydroxy-2-pyridone compound, and (C) a cationic surfactant. Hair cosmetics, the content of the component (A) in the hair cosmetics is 0.2 to 2.0 mass%, the content of the component (B) is 0.1 to 1.0 mass%, ( The content of the component (C) is 0.2 to 5.0% by mass, and the mass ratio of the component (A) and the component (C) represented by (A) / (C) is 0.30 to 1.60. In addition to imparting smoothness to the hair, it exhibits excellent anti-dandruff and itching suppression effects, and in particular, it has been found that the base odor of component (B) and component (A) is suppressed. This has led to the invention.

Therefore, the present invention
[1]. A hair cosmetic containing the following components (A), (B) and (C), wherein the content of the component (A) in the hair cosmetic is 0.2 to 2.0% by mass, and the component (B) Content of 0.1 to 1.0 mass%, content of component (C) is 0.2 to 5.0 mass%, and component (A) represented by (A) / (C) (C) Hair cosmetics characterized by having a mass ratio of 0.30 to 1.60 with the component,
(A) 70-95 mol% of monomer units represented by the following general formula (1) and 5-30 mol% of monomer units represented by the following general formula (2) are included as structural units. Acrylic acid polymer (B) 1-hydroxy-2-pyridone compound (C) cationic surfactant represented by the following general formula (3)
[2]. (B) The hair cosmetic composition according to [1], wherein the component is piroctone olamine.

  ADVANTAGE OF THE INVENTION According to this invention, while giving smoothness to hair, it has the outstanding dandruff improvement and the stagnation suppression effect, and can provide the hair cosmetics by which the base odor was suppressed.

  The present invention relates to hair containing (A) the acrylic acid polymer of the present invention, (B) a 1-hydroxy-2-pyridone compound represented by the general formula (3), and (C) a cationic surfactant. Cosmetics, wherein the content of the component (A) in the hair cosmetic is 0.2 to 2.0% by mass, the content of the component (B) is 0.1 to 1.0% by mass, (C) The content of the component is 0.2 to 5.0% by mass, and the mass ratio of the component (A) and the component (C) represented by (A) / (C) is 0.30 to 1.60. It is a hair cosmetic characterized by being.

(A) Acrylic acid-based polymer 70 to 95 mol% of a monomer unit represented by the following general formula (1) and 5 to 30 mol% of a monomer unit represented by the following general formula (2), It is an acrylic acid polymer comprising a copolymer contained as a structural unit, and can be used alone or in combination of two or more.

（式中、Ｒ¹は水素原子又はメチル基を示し、Ｒ²は水素原子又は−ＣＨ₂ＯＨ基を示し、Ａは酸素原子又は−ＮＨ−を示す。）

（式中、Ｒ³は水素原子又はメチル基を示し、Ｍは水素原子、アルカリ金属原子、アンモニウム又はアミンを示す。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or a —CH ₂ OH group, and A represents an oxygen atom or —NH—).

(In the formula, R ³ represents a hydrogen atom or a methyl group, and M represents a hydrogen atom, an alkali metal atom, ammonium or an amine.)

  Examples of the alkali metal atom include sodium atom, potassium atom, and amine include monoethanolamine, diethanolamine, triethanolamine and the like. When M is an alkali metal atom, ammonium or amine, -COOM forms a salt. To do.

As the monomer unit represented by the general formula (1), those in which R ¹ is a hydrogen atom, R ² is a hydrogen atom, and A is —NH— are preferable, and the monomer unit represented by the following general formula (2) is preferable. As the monomer unit, R ³ is preferably a hydrogen atom, and M is preferably a hydrogen atom and / or a sodium atom.

  The ratio of the monomer unit represented by the general formula (1) is 70 to 95 mol% in the acrylic acid polymer (in 100 mol% of all monomer units), preferably 75 to 90 mol%, The ratio of the monomer unit represented by the formula (2) is 5 to 30 mol% in the acrylic acid polymer (in 100 mol% of all monomer units), and preferably 10 to 25 mol%. When the ratio of the monomer unit represented by the general formula (1) exceeds 95 mol%, the fingering becomes worse and the smoothness decreases, and when it is less than 70 mol%, the softness decreases and the texture is increased. .

  As long as the effects of the present invention are not impaired, the acrylic acid-based polymer can contain monomer units other than the monomer unit represented by the general formula (1) or (2). Examples of other monomer units include nonionic monomers, amphoteric monomers, semipolar monomers, and cationic monomers other than the monomer units represented by the general formula (1) or (2). And monomer units corresponding to monomers and polysiloxane group-containing monomers. As for the ratio of monomer units other than the monomer unit represented by General formula (1) or (2), 0-25 mol% in an acrylic acid polymer is preferable. The acrylic acid polymer of the present invention may be a random copolymer or a block copolymer, and the acrylic acid polymer of the present invention comprises monomer units represented by the general formulas (1) and (2). An acrylic acid polymer comprising a copolymer as a unit is preferred.

  Examples of nonionic monomers include esters of alcohols having 1 to 22 carbon atoms and (meth) acrylic acid, amides of alkylamines having 1 to 22 carbon atoms and (meth) acrylic acid, ethylene glycol, 1 , 3-propylene glycol, etc. and (meth) acrylic acid monoesters, esters in which the monoester's hydroxyl group is etherified with methanol, ethanol, etc., (meth) acryloylmorpholine, etc. Examples of the body include betaine group-containing (meth) acrylic esters, betaine group-containing (meth) acrylamides, etc., and examples of semipolar monomers include amine oxide group-containing (meth) acrylic esters and amine oxide groups (Meth) acrylamide and the like, and examples of the cationic monomer include quaternary ammonia. Um group-containing (meth) acrylic esters, quaternary ammonium group-containing (meth) acrylamide and the like.

  The polysiloxane group-containing monomer is a compound having a polysiloxane structure and a structure capable of being covalently linked to an acrylic acid polymer. Such a structural unit has a high affinity with the silicone oil usually used together in the cosmetic composition, and serves to bind the silicone oil with other structural units in the acrylic acid-based polymer. In particular, it is considered that there is a function to increase the adsorption power of silicone oil to damaged hair and the like.

In addition, the ratio of each monomer unit in the acrylic acid polymer is the carbonyl group, amide bond, IR absorption of polysiloxane structure and various functional groups, and the methyl group or amide bond site of polydimethylsiloxane and adjacent to them. It can be measured by ¹ H-NMR such as methyl group and methylene group, or ¹³ C-NMR thereof.

  The weight average molecular weight of the acrylic acid polymer is preferably 3,000 to 100,000. If it is less than 3,000, the conditioning effect may be weakened, and if it exceeds 100,000, a feeling of adhesion may occur. In order to increase the smoothness after drying without causing a feeling of adhesion, it is more preferably 10,000 to 30,000, further preferably 10,000 to 20,000, and particularly preferably 12,000 to 17,000. preferable.

  The weight average molecular weight can be measured by gel permeation chromatography. Specifically, apparatus: manufactured by Tosoh Corporation, SC8010, SD8022, RI8020, CO8011, PS8010, column: Wako Pure Chemical Industries, Ltd. Wakopak (Wakobeads) G-50), developing solvent: water / methanol / acetic acid / sodium acetate = 6/4 / 0.3 / 0.41 (volume ratio)) can be determined using polyethylene glycol as a standard substance.

  The molecular weight of the acrylic acid polymer can be adjusted, for example, by controlling the degree of polymerization of the polymer. The molecular weight and viscosity can also be controlled by increasing or decreasing the addition amount of a crosslinking agent such as a polyfunctional acrylate. However, if a crosslinking agent is added as much as possible, the molecular weight and the viscosity are rapidly increased, and thus there are aspects that are difficult to control in industrial production. For this reason, it is preferable not to contain a crosslinking agent.

  The acrylic acid polymer can be obtained in accordance with the method described in Japanese Patent Application Laid-Open No. 2007-161986. For example, it can be obtained by mixing monomers that give respective structural units or precursors thereof and copolymerizing them by a method such as solution polymerization, suspension polymerization, emulsion polymerization or the like. In addition, the counter ion in the general formula (2) can be subjected to polymerization by substituting a part or all of it for other than hydrogen ion by a neutralization reaction before polymerization, and neutralized after polymerization or other reaction. A part or all of the reaction can be replaced with other than hydrogen ions. These can be appropriately selected depending on the ease of synthesis. The polymerization reaction is preferably carried out in a hydrophilic solvent such as ethanol, and a known polymerization initiator such as dimethyl 2,2'-azobis (2-methylpropionate) can be used as the polymerization initiator. In addition, each monomer is mix | blended so that each monomer may become specific mole with respect to the total amount (100 mol%) of all the monomers. The proportion of the structural unit composed of each monomer in the copolymer of the present invention is the same as the blending amount of each monomer at the time of copolymerization.

  The polymerization reaction is preferably performed in a hydrophilic solvent. Examples of the hydrophilic solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, alcohol solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, and sec-butanol, water, and the like. Is mentioned. These may be used alone or in combination of two or more. Among these, it is preferable to use an alcohol solvent.

  As polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethyl) Valeronitrile), dimethyl-2,2′-azobisisobutyrate, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (1-cyclohexanecarbonitrile), 2,2 ′ -Azobis (2-methyl-N- (2-hydroxyethyl) -propionamide), 2,2'-azobis (2-amidinopropane) dihydrochloride, dimethyl 2,2'-azobis (2-methylpropionate) ), Benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, etc., persulfate, or redox thereof. Scan system and the like, can be used without particular limitation. The polymerization initiator is preferably used in the range of 0.01 to 5% by mass with respect to all monomers.

  The polymerization reaction can be performed, for example, under an inert gas atmosphere such as nitrogen or argon, preferably at 30 to 120 ° C., more preferably at 40 to 100 ° C., usually for 1 to 30 hours. After completion of the polymerization, the produced copolymer may be isolated from the reaction solution by an appropriate means such as solvent distillation or addition of a poor solvent. This copolymer can be used as it is or after further purification, for example, in the production of cosmetics. Purification can be carried out by combining appropriate means such as reprecipitation, solvent washing, membrane separation and the like as necessary.

  Content of (A) component in hair cosmetics is 0.2-2.0 mass%, and 0.4-1.0 mass% is preferable. If the amount is less than 0.2% by mass, the effect of the present invention is insufficient. If the amount exceeds 2.0% by mass, stickiness occurs, and the base odor of the component (A) becomes strong.

（式中、Ｒ⁴は、１〜１７個の炭素原子を有するアルキル基、２〜１７個の炭素原子を有するアルケニル基、５〜８個の炭素原子を有するシクロアルキル基、７〜９個の炭素原子を有するビシクロアルキル基、シクロアルキル基が５〜８個の炭素原子を有し、かつアルキル基が１〜４個の炭素原子を有するシクロアルキル−アルキル基（但し、シクロアルキル基は、その水素原子の一部が１〜４個の炭素原子を有するアルキル基によって置換されていてもよい）、６〜１４個の炭素原子を有するアリール基、アリール基が６〜１４個の炭素原子を有し、かつアルキル基が１〜４個の炭素原子を有するアラルキル基、アリール基が６〜１４個の炭素原子を有し、かつアルケニル基が２〜４個の炭素原子を有するアリールアルケニル基、アリール基が６〜１４個の炭素原子を有し、かつアルキル基がそれぞれ１〜４個の炭素原子を有するアリールオキシアルキル基もしくはアリールメルカプトアルキル基、ベンズヒドリル基、アルキル基が１〜４個の炭素原子を有するフェニルスルフォニルアルキル基、フリル基又はアルケニル基が２〜４個の炭素原子を有するフリルアルケニル基を示す。但し、上述のアリール基は、その水素原子の一部が１〜４個の炭素原子を有するアルキル基、１〜４個の炭素原子を有するアルコキシ基、ニトロ基、シアノ基又はハロゲン原子によって置換されていてもよい。Ｒ⁵は、水素原子、１〜４個の炭素原子を有するアルキル基、２〜４個の炭素原子を有するアルケニル基、２〜４個の炭素原子を有するアルキニル基、ハロゲン原子、フェニル基又はベンジル基を示す。Ｘ⁺は、有機塩基、アルカリ金属イオン、アンモニウムイオン又は２〜４価の陽イオンを示す。） (B) 1-hydroxy-2-pyridone compound A 1-hydroxy-2-pyridone compound represented by the following general formula (3), which can be used alone or in combination of two or more. .

Wherein R ⁴ 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 9 A bicycloalkyl group having a carbon atom, a cycloalkyl group having 5 to 8 carbon atoms and an alkyl group having 1 to 4 carbon atoms (provided that the cycloalkyl group is Some hydrogen atoms may be substituted by alkyl groups having 1 to 4 carbon atoms), aryl groups having 6 to 14 carbon atoms, aryl groups having 6 to 14 carbon atoms. An aryl group having 1 to 4 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an alkenyl group having 2 to 4 carbon atoms, aryl An aryloxyalkyl group or an arylmercaptoalkyl group, a benzhydryl group, an alkyl group having 1 to 4 carbon atoms and an alkyl group having 1 to 4 carbon atoms. A phenylsulfonylalkyl group, a furyl group or an alkenyl group having a furylalkenyl group having 2 to 4 carbon atoms, provided that the above aryl group has a part of hydrogen atoms of 1 to 4 carbon atoms. An alkyl group having, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyano group or a halogen atom, R ⁵ may be 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 benzine .X ⁺ is showing a group, an organic base, an alkali metal ion, an ammonium ion or a divalent to tetravalent cations.)

Specific examples of the compound represented by the general formula (3) 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- (cyclohexe Ridene-methyl) -2-pyridone, 1-hydroxy-4-methyl-6-cyclohexyl-2-pyridone, 1-hydroxy-4-methyl-6- (methyl-cyclohexyl) -2-pyridone, 1-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, 1-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-dimethylben Dil) -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 phenphenoxy-methyl) -2-pyridone, 1-hydroxy-4-methyl-6- (2,4,4) 5-to Chlorophenoxy-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 Down, 1-hydroxy-4-phenyl-6-methyl-2-pyridone, mention may be made of 1-hydroxy-4,6-diphenyl-2-pyridone and the like.

  The said compound is used as a salt, for example, can be used conveniently as a salt with an organic amine. 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, di Benzylamine, N-ethylbenzylamine, dimethylstearylamine, N-methyl-morpholine, N-methylpiperazine, 4-methylcyclohexylamine, N- Dorokishiechiru - morpholine, and the like.

  Further, the hydroxypyridone compound used in the present invention may be a salt with an inorganic ion, for example, an alkali metal salt such as sodium salt or potassium salt, an ammonium salt, an aluminum salt, a zirconium salt or the like. A salt with a cation can also be used.

  As the 1-hydroxy-2-pyridone compound of the above formula (3), cyclopirox olamine, piroctone olamine represented by the following formula (4) is preferable, and piroctone olamine is more preferable.

  Content of (B) component in hair cosmetics is 0.1-1.0 mass%, and 0.2-0.8 mass% is preferable. When the amount is less than 0.1% by mass, the effect of the present invention becomes insufficient. When the amount exceeds 1.0% by mass, the base odor of the component (B) becomes strong.

(C) Cationic surfactants Cationic surfactants include aliphatic amines, quaternary ammonium salts, fatty acid amide amine salts, alkyltrialkylene glycol ammonium salts, acylguanidine derivatives, mono-N-long chain acyl bases. Amino acid-based cationic surfactants such as functional amino acid lower alkyl ester salts, alkylbenzalkonium salts, alkylpyridinium salts, imidazolinium salts, and the like. These may be used alone or in combination of two or more. it can. Among these, quaternary ammonium salts of aliphatic amines are preferable, quaternary ammonium salts having 18 to 22 carbon atoms are more preferable, and behenyltrimethylammonium chloride, stearyltrimethylammonium chloride, and the like are more preferable.

  Content of (C) component in hair cosmetics is 0.2-5.0 mass%, and 0.5-3.0 mass% is preferable. If it is less than 0.2% by mass, the smoothness of the hair is poor, and if it exceeds 5.0% by mass, the stability of the preparation is adversely affected.

  In the present invention, the content of the component (A) is 0.2 to 2.0 mass%, the content of the component (B) is 0.1 to 1.0 mass%, and the content of the component (C) is 0. The mass ratio of the component (A) and the component (C) represented by (A) / (C) is in the range of 0.30 to 1.60. 50-1.25 is preferable. By setting (A) / (C) in the above range, the hair can be given smoothness and can have excellent dandruff improvement and stagnation suppression effects. Moreover, since the adsorption amount of (B) component to the scalp increases in the said mass ratio, adsorption | suction to the scalp of (B) component is accelerated | stimulated, and it is thought that a dandruff improvement and a stagnation suppression effect improve. This ratio is a value obtained by rounding off the third decimal place.

  The present invention relates to a hair cosmetic containing the above components (A), (B) and (C), wherein the content of the component (A) in the hair cosmetic is 0.2 to 2.0% by mass, (B (A) component represented by (A) / (C), with the content of component 0.1-1.0% by mass and the content of component (C) 0.2-5.0% by mass. And the mass ratio of the component (C) to 0.30 to 1.60, a method for promoting the scalp adsorption of the component (B) can be provided, and suitable components, contents, and the like are the same as those for the hair cosmetic composition described above. It is.

  In the hair cosmetic composition of the present invention, various additive components used in general hair cosmetic compositions can be blended as desired within a range that does not impair the effects of the present invention. These additive components can be used singly or in appropriate combination of two or more, and can be blended at an appropriate stage when preparing a hair cosmetic.

  Examples of the additive component include silicone polymers such as dimethylpolysiloxane and amino-modified silicone, dimethyldiallylammonium chloride / acrylamide copolymer, methacryloylethylbetaine / methacrylic acid ester copolymer, and O- [2-hydroxy-3 chloride]. -(Trimethylammonio) propyl] cationized guar gum, polymer compounds such as hydroxyethyl cellulose, hydroxypropyl cellulose, anionic surfactants such as alkyl sulfate ester salt, sodium polyoxyethylene alkyl ether sulfate, palm oil fatty acid amidopropyl betaine , Amphoteric surfactants such as betaines such as lauryldimethylaminoacetic acid betaine, hydrogenated soybean phospholipid, alkyldiaminoethylglycine hydrochloride, sodium laurylaminopropionate, Nonionic surfactants such as sucrose fatty acid ester, sorbitan fatty acid ester, sorbitol fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene alkyl ether, rice germ oil, rice bran oil, camellia oil, almond oil, water Fats and waxes such as added jojoba oil, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, pantothenic acid, gallic acid-3,5-diglucoside, gallic acid-3,4-diglucoside, methyl gallate- Organic acids such as 3,5-diglucoside, edetic acid, hyaluronic acid, amino acids, pyrrolidone carboxylic acid and glycolic acid and salts thereof, polyvalent alcohols such as ethylene glycol, propylene glycol, glycerin and 1,3-butylene glycol Glucose, sucrose, xyl Sugar alcohols such as salt, erythritol, sorbitol, other hydrocarbons, ester oils, higher alcohols, crude drugs, various protein hydrolysates, vitamins, bactericides, UV absorbers, antioxidants, colorants, fragrances, A solvent (water, ethanol, etc.), fine particle powder, etc. are mentioned.

  As for pH of the hair cosmetics of this invention, 3-6 are preferable. This pH is close to the pH of the hair and is difficult to damage the hair. Examples of the pH adjusting agent include inorganic acid salts such as sodium pyrophosphate, and organic acids such as glycolic acid and citric acid. In the present invention, the pH is measured with a pH meter of HM-30G manufactured by Toa DKK Corporation, and the value 2 minutes after the electrode is immersed in the preparation at 25 ° C. is taken as the reading value.

  The hair cosmetic composition of the present invention can be widely used in many dosage forms such as liquids, creams, foams, sprays, gels, etc., and is a conditioner, treatment, hair color, non-washing type treatment, hair serum. Suitable for hair packs and the like. The hair cosmetic composition of the present invention can be prepared based on a conventional method of dosage form, and can be appropriately filled in a container.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, unless otherwise specified, “%” in the composition indicates mass%, the ratio indicates the mass ratio, and the amount of each component in the table is an amount converted into a pure component.

[Preparation Example 1]
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device was charged with 100 parts by mass of ethanol, and 88.6 parts by mass of 2-hydroxyethylacrylamide and 11.4 parts by mass of acrylic acid were added to the dropping funnel. A monomer mixed solution consisting of 80 parts by mass of ethanol and 80 parts by mass of ethanol was charged, the reactor was purged with nitrogen, and then heated to 80 ° C. Into the reactor, 1 part by mass of dimethyl 2,2′-azobis (2-methylpropionate) (V-601; manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the monomer mixture was added over 2 hours. It was dripped. After the completion of the dropwise addition, the mixture was reacted for 6 hours, cooled, and neutralized with sodium hydroxide to obtain an acrylic acid polymer (1). 2-hydroxyethylacrylamide / sodium acrylate = 83 mol% / 17 mol%

[Preparation Example 2]
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirrer was charged with 100 parts by mass of ethanol, and 82.5 parts by mass of 2,3-dihydroxypropylacrylamide, and acrylic acid 17. A monomer mixture consisting of 5 parts by mass and 80 parts by mass of ethanol was charged, and the reactor was purged with nitrogen, and then heated to 80 ° C. Into the reactor, 1 part by mass of dimethyl 2,2′-azobis (2-methylpropionate) (V-601; manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the monomer mixture was added over 2 hours. It was dripped. After reacting for 6 hours after the completion of the dropwise addition, the mixture was cooled and neutralized with sodium hydroxide corresponding to half of the molar ratio of acrylic acid to obtain an acrylic acid polymer (2). 2,3-dihydroxypropyl acrylic acid amide / acrylic acid (sodium) = 70 mol% / 30 mol%

[Preparation Example 3]
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device was charged with 100 parts by mass of ethanol, and 97.5 parts by mass of 2,3-dihydroxypropylacrylamide was added to the dropping funnel. A monomer mixture consisting of 5 parts by mass and 80 parts by mass of ethanol was charged, and the reactor was purged with nitrogen, and then heated to 80 ° C. Into the reactor, 1 part by mass of dimethyl 2,2′-azobis (2-methylpropionate) (V-601; manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the monomer mixture was added over 2 hours. It was dripped. After reacting for 6 hours after completion of the dropwise addition, the mixture was cooled and neutralized with sodium hydroxide corresponding to half of the molar ratio of acrylic acid to obtain an acrylic acid polymer (3). 2,3-dihydroxypropylacrylamide / acrylic acid (sodium) = 95 mol% / 5 mol%

[Preparation Example 4]
An acrylic acid polymer (4) was obtained in the same manner as in Preparation Example 1 except that the blending amount was adjusted so as to be the structural unit shown in Table 1 below.

[Preparation Example 5]
An acrylic acid polymer (5) was obtained in the same manner as in Preparation Example 1 except that the blending amount was adjusted so as to be the structural unit shown in Table 1 below.

[Comparative Preparation Example 6]
An acrylic acid polymer (6) was obtained in the same manner as in Preparation Example 1 except that the blending amount was adjusted so as to be the structural unit shown in Table 1 below.

  The functional groups of the general formula (1) or (2) of the acrylic acid polymers (1) to (6), the ratio (molar ratio) of the monomer units of the general formula (1) or (2), and the weight average molecular weight are shown. It is shown in 1. The weight average molecular weight is as follows: apparatus: manufactured by Tosoh Corporation, SC8010, SD8022, RI8020, CO8011, PS8010, column: Wako Pure Chemical Industries, Ltd. Wakopak (Wakobeads G-50), developing solvent: water / methanol / acetic acid / acetic acid Sodium = 6/4 / 0.3 / 0.41 (volume ratio)) was used to obtain polyethylene glycol as a standard substance.

What was used by (B) component (1-hydroxy-2- pyridone type compound) is shown below.

[Examples 1 to 20, Comparative Examples 1 to 13]
Hair conditioners having the compositions shown in Tables 3 to 6 were prepared by the following method. About the obtained hair conditioner, the transparent glass bottle was filled with the hair conditioner and measured with a pH meter (HM-30G / manufactured by Toa DKK Co., Ltd.). The measurement was performed at 25 ° C., and the value two minutes after the electrode was immersed in the preparation was taken as the reading value. Moreover, the following evaluation was performed. The results are also shown in the table.

[Preparation method]
In a hot water bath at 80 ° C., (C) a cationic surfactant and stearyl alcohol were mixed and dissolved, methylpolysiloxane and amino-modified silicone were added and stirred, and sorbitol and purified water were added for phase inversion emulsification. (A) Acrylic acid polymer and glycolic acid were added and stirred. After cooling to 40 ° C., (B) 1-hydroxy-2-pyridone previously dissolved in perfume and propylene glycol After adding the system compound, the mixture was further cooled to room temperature with stirring.

[Evaluation methods]
Panelists were 20 women in their 20s and 40s who felt dandruff and itching on their scalp. The hair conditioner obtained in the above example was continuously used for 14 days at a daily use amount of about 6 g once a day by a normal usage method, and sensory evaluation was performed on the following items. As the shampoo, “Plant Story Herb Blend Refreshing Smooth Type (manufactured by Lion Corporation)” was used. A result is shown based on the following reference | standard.

(1) Smoothness of hair After the hair was dried with a dryer after use, sensory evaluation was performed on the smoothness of the hair, and the results were tabulated to make a determination based on the following evaluation criteria.
◎: 15 or more people who answered good ○: 10 or more people 14 or less who answered that it was good Δ: 5 or more people 9 or less who answered that it was good ×: Good Less than 5 people

(2) Absence of base odor Sensory evaluation was performed on the absence of base odor during and after use, and the results were tabulated to determine based on the following evaluation criteria.
◎: 15 or more people who answered good ○: 10 or more people 14 or less who answered that it was good Δ: 5 or more people 9 or less who answered that it was good ×: Good Less than 5 people

(3) Dandruff Improvement Effect A sensory evaluation was performed on “dandruff improvement effect” before and after the start of the test, and a determination was made based on the following evaluation criteria from the tabulated results.
◎: 15 or more people who said that dandruff was improved ○: 10 or more people who answered that dandruff was improved 14 or less △: 5 or more people who said that dandruff was improved ×: Less than 5 people answered that dandruff has improved

(4) Suppression effect of itchiness Sensory evaluation was performed on “itchiness felt on the scalp” before and after the start of the test, and the totaled results were determined based on the following evaluation criteria.
◎: More than 15 people who answered that the grudge was gone or less ○: More than 10 people who answered that the grudge was gone or less △: People who answered that the grudge was gone or less 5 or more and 9 or less ×: Less than 5 people answered that the grudge was gone or decreased

(B) Component (Piroctone Olamine) Scalp Adsorption Measurement Method The adsorption amount of piroctone olamine on the scalp when the hair cosmetic obtained in the examples was used by the following method was measured.
The hair near the top of the head was shaved with a razor to create a 3 cm × 3 cm square test site. 1 mL of hair cosmetic was applied to this test site, rubbed for 30 seconds, left for 1 minute, rinsed with running water at 40 ° C., and dried with a dryer. A stratum corneum stripping tape (D-SQUAME (trademark) Skin Sampling Discs 22mm / CuDerm) was firmly attached to the treated test site, and one stratum corneum was peeled off together with the tape. This was immersed in methanol and subjected to ultrasonic treatment for 10 minutes with an ultrasonic cleaner (US-3 / manufactured by SND). The tape was rinsed and removed with methanol, and methanol was removed under a nitrogen stream, and 1 mL each of the following internal standard solution and mobile phase was added to make a total volume of 2 mL, and a sample solution passed through a 0.45 μm filter is shown in Table 7 below. Measurement was performed by high performance liquid chromatography under conditions. From the obtained results, the amount of piroctone olamine was calculated from the following formula. From this piroctone olamine, the absorption ratio (%) of piroctone olamine scalp when Comparative Example 1 is 100% is shown in Table 8 and FIG.
(Preparation of internal standard solution)
Dissolve n-butyl salicylate in methanol (0.1g → 1000mL)
(Preparation of standard solution)
Standard piroctone olamine was dissolved in methanol (0.1 g → 1000 mL), and this solution and the internal standard solution prepared at 1: 1 (volume ratio) were used.
Adsorption amount of piroctone olamine (μg / cm ² ) = W _S / Q _S × Q _T × 2 / S × 1000
W _S : piroctone olamine concentration (mg / mL) in standard solution
Q _S : Peak area ratio of piroctone olamine in the standard solution to the internal standard (Piroctone olamine / internal standard)
Q _T : Peak area ratio of piroctone olamine and internal standard of sample solution (Piroctone olamine / internal standard)
S: Tape area (cm ² )

（Ａ）／（Ｃ）＝０．６０
評価結果
髪のなめらかさ：◎
基剤臭のなさ ：◎
フケ改善効果 ：◎
痒みの抑制効果：◎ [Example 21]
A hair treatment having the following composition was prepared according to a conventional method.

(A) / (C) = 0.60
Evaluation results Smoothness of hair: ◎
No base odor: ◎
Dandruff improvement effect: ◎
Itching suppression effect: ◎

（Ａ）／（Ｃ）＝１．００
評価結果
髪のなめらかさ：◎
基剤臭のなさ ：◎
フケ改善効果 ：◎
痒みの抑制効果：◎ [Example 22]
A hair serum having the following composition was prepared according to a conventional method.

(A) / (C) = 1.00
Evaluation results Smoothness of hair: ◎
No base odor: ◎
Dandruff improvement effect: ◎
Itching suppression effect: ◎

The raw material used in the above example is shown.

It is a graph which shows a piroctone olamine scalp adsorption ratio (%).

Claims (2)

A hair cosmetic containing the following components (A), (B) and (C), wherein the content of the component (A) in the hair cosmetic is 0.2 to 2.0% by mass, and the component (B) Content of 0.1 to 1.0 mass%, content of component (C) is 0.2 to 5.0 mass%, and component (A) represented by (A) / (C) (C) Hair cosmetics characterized by mass ratio with a component being 0.30-1.60.
(A) 70-95 mol% of monomer units represented by the following general formula (1) and 5-30 mol% of monomer units represented by the following general formula (2) are included as structural units. Acrylic acid polymer

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or a —CH ₂ OH group, and A represents an oxygen atom or —NH—).

(In the formula, R ³ represents a hydrogen atom or a methyl group, and M represents a hydrogen atom, an alkali metal atom, ammonium or an amine.)
(B) 1-hydroxy-2-pyridone compound represented by the following general formula (3)

Wherein R ⁴ 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 9 A bicycloalkyl group having a carbon atom, a cycloalkyl group having 5 to 8 carbon atoms and an alkyl group having 1 to 4 carbon atoms (provided that the cycloalkyl group is Some hydrogen atoms may be substituted by alkyl groups having 1 to 4 carbon atoms), aryl groups having 6 to 14 carbon atoms, aryl groups having 6 to 14 carbon atoms. An aryl group having 1 to 4 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an alkenyl group having 2 to 4 carbon atoms, aryl An aryloxyalkyl group or an arylmercaptoalkyl group, a benzhydryl group, an alkyl group having 1 to 4 carbon atoms and an alkyl group having 1 to 4 carbon atoms. A phenylsulfonylalkyl group, a furyl group or an alkenyl group having a furylalkenyl group having 2 to 4 carbon atoms, provided that the above aryl group has a part of hydrogen atoms of 1 to 4 carbon atoms. An alkyl group having, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyano group or a halogen atom, R ⁵ may be 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 benzine .X ⁺ is showing a group, an organic base, an alkali metal ion, an ammonium ion or a divalent to tetravalent cations.)
(C) Cationic surfactant   The hair cosmetic composition according to claim 1, wherein the component (B) is piroctone olamine.

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