JP4786535B2 - Hair cosmetics - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a hair cosmetic, and more particularly to a hair cosmetic that provides good fingering properties during rinsing and conditioning effects such as smoothness and smoothness after drying.

Background Art Various efforts have been made to improve the conditioning effect of hair cosmetics such as shampoos, and representative examples include those containing cationized cellulose or cationized guar gum, or those containing a silicone compound. For example, a shampoo composition using a fine particle size silicone and a cationized cellulose ether derivative (JP-A-7-277931), or a shampoo combining a high viscosity silicone emulsion of a specific particle size and a cationic derivative of guar gum. Composition (JP-A-4-234309), cosmetic composition comprising fine particles of siloxane gum or amino group-containing silicone and a cationic derivative of guar rubber or cellulose ether (JP-A-5-194142), a specific charge density A shampoo composition containing a cationic derivative of guar rubber and a water-insoluble and non-volatile silicone (JP-A-4-364111), and a guar rubber cationic derivative and an insoluble and non-volatile silicone having a specific average particle size Shampoo composition (JP-A-4-36226) Broadcast), and the like. However, the conditioning effect is not sufficient, especially for consumers whose hair has been damaged by coloring. The reason for this is that silicone as a conditioning component is difficult to adsorb on hair during shampooing, and this tendency is particularly noticeable in hair damaged by coloring or the like.

DISCLOSURE OF THE INVENTION The present invention aims to solve the above-mentioned problems, and is a hair cosmetic excellent in conditioning effect, in particular, it is easy to follow the finger when rinsing with rich foaming, and the hair feel after drying. It is to provide a hair cosmetic material excellent in hair quality. In women's hair washing behavior, conditioners (or rinses and treatments) are often used to improve the condition of the hair, such as reducing hairiness, after the hair has been cleaned with shampoo. If you do not want to take the time to bathe with your child, you may use only shampoo. In particular, the present invention provides a hair cosmetic having a conditioning effect that can sufficiently improve the condition of hair even when only a shampoo is used.

  As a result of intensive studies in view of the above-mentioned problems, the present inventors are conditioning components in hair cosmetics by blending (a) component with (b) component resin and (c) component surfactant. The present inventors have found that it is possible to provide a hair cosmetic that is excellent in the amount of adsorption of silicone and mild to the scalp. Specifically, it was achieved by the following means.

（式中、Ｒ¹は水素原子またはメチル基を表し、Ｒ²は水素原子または炭素原子数１〜４のアルキル基若しくはヒドロキシアルキル基を表す。ａは１〜４の整数を表す）
式（２）

（式中、Ｒ³は水素原子またはメチル基を表し、Ｒ⁴及びＲ⁵はそれぞれ独立して炭素原子数１〜２４のアルキル基、アリール基またはアラルキル基を表し、Ｒ⁶は水素原子、炭素原子数１〜２４のアルキル基、アリール基若しくはアラルキル基またはＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−Ｎ⁺Ｒ⁷Ｒ⁸Ｒ⁹・Ｙ^-を表し、Ｒ⁷〜Ｒ⁹はそれぞれ独立して炭素原子数１〜２４のアルキル基、アリール基またはアラルキル基を表す。Ｘ^-及びＹ^-は、それぞれ独立して陰イオンを表す。ｂは０または１を表す。ｃは１〜１０の整数を表す。）
（３）更にシリコーン化合物（ｄ）０．１〜５．０質量％を含む（１）または（２）に記載の毛髪化粧料。
（４）更にカチオン性界面活性剤（ｅ）０．０１〜５．０質量％、及び／または式（１２）で表される芳香族カルボン酸またはその塩（ｆ）０．０１〜１０質量％を含有する（１）乃至（３）のいずれかに記載の毛髪化粧料

（式中、Ｒ¹⁰、Ｒ¹¹及びＲ¹²はそれぞれ炭素数１〜３のアルキル基、水酸基または水素原子を示し、Ａ¹はカルボキシル基またはその塩を示す）
（５）毛髪化粧料のｐＨが３．０〜６．５の範囲である（１）乃至（４）のいずれかに記載の毛髪化粧料。
（６）カラーリングを施した傷んだ髪に使用することを特徴とする、（１）乃至（５）のいずれかに記載の毛髪化粧料。
（７）式（１２）で表される芳香族カルボン酸またはその塩（ｆ）が、安息香酸またはサリチル酸及びこれらのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩またはアルカノールアミン塩からなる群の少なくとも一種である（１）乃至（６）のいずれかに記載の毛髪化粧料。 (1) Anionic surfactant (a) 0.1 to 40% by mass, a vinyl monomer (A) having a hydroxyl group and an amide bond, and a vinyl monomer (B) having a cationic group Water-soluble resin (b) having a structure corresponding to a copolymer of a monomer mixture containing 0.01 to 5.0% by mass, and nonionic and / or amphoteric surfactant (c) 0.1 to 10 Hair cosmetics comprising:
(2) The vinyl monomer (A) having a hydroxyl group and an amide bond is represented by the formula (1), and the vinyl monomer (B) having a cationic group is represented by the formula (2). Hair cosmetics as described in (1).
Formula (1)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group. A represents an integer of 1 to 4)
Formula (2)

(Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 24 carbon atoms, an aryl group or an aralkyl group, and R ⁶ represents a hydrogen atom, carbon Represents an alkyl group having 1 to 24 atoms, an aryl group or an aralkyl group, or CH ₂ —CH (OH) —CH ₂ —N ⁺ R ⁷ R ⁸ R ⁹ • Y ⁻ , wherein R ^{7 to} R ⁹ are each independently an alkyl group having a carbon number of 1 to 24, .X represents an aryl group or an aralkyl group ^- and Y ^- is, each .c .b independently represent a anions represents 0 or 1 is an integer of from 1 to 10 To express.)
(3) The hair cosmetic composition according to (1) or (2), further comprising 0.1 to 5.0% by mass of a silicone compound (d).
(4) Cationic surfactant (e) 0.01 to 5.0% by mass and / or aromatic carboxylic acid represented by formula (12) or a salt thereof (f) 0.01 to 10% by mass The hair cosmetic composition according to any one of (1) to (3),

(Wherein R ¹⁰ , R ¹¹ and R ¹² each represent an alkyl group having 1 to 3 carbon atoms, a hydroxyl group or a hydrogen atom, and A ¹ represents a carboxyl group or a salt thereof)
(5) The hair cosmetic according to any one of (1) to (4), wherein the pH of the hair cosmetic is in the range of 3.0 to 6.5.
(6) The hair cosmetic composition according to any one of (1) to (5), which is used for damaged hair that has been colored.
(7) The aromatic carboxylic acid represented by the formula (12) or a salt thereof (f) is selected from the group consisting of benzoic acid or salicylic acid and alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts thereof. The hair cosmetic composition according to any one of (1) to (6), which is at least one kind.

DETAILED DESCRIPTION OF THE INVENTION The contents of the present invention are described in detail below. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. Further, the concentrations in the present invention are those at 25 ° C. unless otherwise specified.
In the present invention, the damaged hair that has been colored means, for example, hair that has been dyed in a color such as brown or black using a hair color bleaching agent.
Furthermore, the hair cosmetic composition of the present invention, for example, shampoo, conditioner, hair wax, liquid or foam hair styling agent, and the like.

(A) Anionic surfactant (a) The component is preferably α-olefin sulfonate, polyoxyethylene alkenyl ether sulfate, or polyoxyethylene alkyl ether sulfate.
As the alkyl group of the polyoxyethylene alkyl ether sulfate, an octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like are preferable.
As the alkenyl group of the polyoxyethylene alkenyl ether sulfate, an octenyl group, nonenyl group, decenyl group, dodecenyl group, undecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group and the like are preferable. 1-5 are preferable and, as for the average addition mole number of the ethylene oxide of polyoxyethylene alkyl ether sulfate and polyoxyethylene alkenyl ether sulfate, 2-3 are more preferable.
The α-olefin sulfonate is preferably one having 10 to 18 carbon atoms, more preferably 12 to 16 carbon atoms, and still more preferably tetradecene sulfonate having 14 carbon atoms.
These counter ions include alkali metal salts (eg, sodium, potassium), alkaline earth metal salts (eg, magnesium), ammonium salts, alkanolamine salts (eg, triethanolamine, diethanolamine, monoethanolamine, triethanolamine). Isopropanolamine) and the like.
These anionic surfactants are blended in an amount of 0.1 to 40% by weight, more preferably 0.3 to 30% by weight, in the total composition of the hair cosmetic (eg, hair conditioner, treatment, hair wax). . If it is less than 0.1% by mass, the effect is poor, and if it exceeds 40% by mass, handling becomes difficult due to an increase in viscosity.
In particular, when a hair cosmetic is used as a shampoo composition, it is preferably added in an amount of 5 to 40% by mass, more preferably 10 to 30% by mass in the entire composition from the viewpoint of detergency and foaming power.
Moreover, when using hair cosmetics as compositions other than shampoos, such as a hair conditioner, a treatment, and hair wax, from the point of an effect, Preferably it is 0.1-2 mass% in a whole composition, More preferably, it is 0.3. -0.8 mass% is mix | blended.
Two or more anionic surfactants may be used in combination, and in this case, the above content means the total amount of these.

Water-soluble resin (b)
The component (b) has a structure corresponding to a copolymer of a monomer mixture containing a vinyl monomer (A) having a hydroxyl group and an amide bond and a vinyl monomer (B) having a cationic group. Have The vinyl monomer (A) having a hydroxyl group and an amide bond is a hydroxyalkyl (meth) acrylamide type represented by the formula (1) (where “(meth) acryl” represents acrylic and methacrylic). It is preferable to use a monomer.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group. A represents an integer of 1 to 4)
Here, R ¹ is preferably a hydrogen atom. R ² is preferably a hydrogen atom. a is preferably 2.
Examples of the vinyl monomer (A) having a hydroxyl group and an amide bond represented by the formula (1) include N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N, N-dihydroxyethyl ( N-hydroxyalkyl (meth) acrylamides, such as (meth) acrylamide, are mentioned. Of these, N-hydroxyethyl (meth) acrylamide is preferred because the solubility of the monomer in water and the solubility of the resulting polymer in water are high.

  The structural unit corresponding to the vinyl monomer (A) having a hydroxyl group and an amide bond is preferably contained in the copolymer in an amount of 20 to 90% by mass. More preferably, it is 30-80 mass%, Most preferably, it is 40-70 mass%. It is considered that the constitutional unit corresponding to the vinyl monomer (A) having a hydroxyl group and an amide bond increases the effect of adsorbing to hair by the action of hydrogen bonds derived from the amide bond portion.

  In general, a hair cosmetic uses an anionic surfactant to form a complex of the anionic surfactant and a water-soluble resin. After applying the hair cosmetic to the hair, or after washing the hair It is considered that this complex precipitates and adheres to the hair during rinsing. However, in the water-soluble resin (b) employed in the present invention, the structural unit corresponding to the vinyl monomer (B) having a cationic group in the copolymer, and the anionic surfactant used in combination, Even after forming the complex, the water solubility of the copolymer is maintained by the hydrophilicity of the structural unit corresponding to the vinyl monomer (A) having a hydroxyl group and an amide bond.

  By making the structural unit corresponding to the vinyl monomer (A) having a hydroxyl group and an amide bond 20% by mass or more in the copolymer, it is possible to more effectively maintain the adsorptive power to hair, In addition, the smoothness and smoothness after drying are further improved. Moreover, by setting it as 90 mass% or less, the content of the structural unit corresponding to the vinyl-type monomer (B) which has a cationic group is more fully maintained, and an anionic surfactant and more sufficient composite are made. It can be formed, the amount of adsorption to hair is improved, and it is more effective due to smoothness during rinsing.

  Examples of vinyl monomers (B) having a cationic group include diallyl quaternary ammonium salts such as N, N-dimethyl-N, N-diallylammonium chloride, and N-methacryloyloxyethyl-N, N, N. -(Meth) acrylic ester quaternary ammonium salts such as trimethylammonium chloride, (meth) acrylamide quaternary ammonium salts such as N-methacryloylaminopropyl-N, N, N-trimethylammonium chloride, L-arginine and glycidyl Amino acid cationic species such as methacrylate reactants can be exemplified, and among these, (meth) acrylic quaternary ammonium salt monomers are more preferable. In particular, a (meth) acrylic quaternary ammonium salt monomer represented by the formula (2) is preferable.

(Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 24 carbon atoms, an aryl group or an aralkyl group, and R ⁶ represents a hydrogen atom, carbon Represents an alkyl group having 1 to 24 atoms, an aryl group or an aralkyl group, or CH ₂ —CH (OH) —CH ₂ —N ⁺ R ⁷ R ⁸ R ⁹ • Y ⁻ , wherein R ^{7 to} R ⁹ are each independently an alkyl group having a carbon number of 1 to 24, .X represents an aryl group or an aralkyl group ^- and Y ^- is, each .c .b independently represent a anions represents 0 or 1 is an integer of from 1 to 10 To express.)
R ³ is preferably a methyl group, and R ⁴ and R ⁵ are each independently preferably a methyl group. R ⁶ is preferably an alkyl group or alkenyl group having 1 to 24 carbon atoms, and more preferably a methyl group. R ^{7 to} R ⁹ are preferably each independently a methyl group. X ^- and Y ^- as an anion represented by each independently, a chlorine ion, bromine ion preferably, chloride ion is more preferable. b is preferably 1, and c is preferably 2.

  Examples of some vinyl monomers having a cationic group represented by formula (2) include N- (meth) acryloyloxyethyl-N, N, N-trimethylammonium chloride, N- (meth) acryloyl. Oxyethyl-N-ethyl-N, N-dimethylammonium = monoethyl sulfate, N- (meth) acryloyloxyethyl-N, N, N-triethylammonium = monoethyl sulfate, N- [3- {N ′-( (Meth) acryloyloxyethyl-N ', N'-dimethylammonium} -2-hydroxypropyl] -N, N, N-trimethylammonium chloride, N- [3- {N'-(meth) acryloyloxyethyl-N ' , N′-diethylammonium} -2-hydroxypropyl] -N, N, N-triethylammonium chloride (Meth) acrylic acid esters having a cationic group such as: N- (meth) acryloylaminopropyl-N, N, N-trimethylammonium chloride, N- (meth) acryloylaminopropyl-N-ethyl-N, N -Dimethylammonium monoethyl sulfate, N- (meth) acryloylaminopropyl-N, N-diethyl-N-methylammonium chloride, N- (meth) acryloylaminopropyl-N, N-diethyl-N-methylammonium = monomethyl Sulfate, N- [3- {N ′-(meth) acryloylaminopropyl-N ′, N′-dimethylammonium} -2-hydroxypropyl] -N, N, N-trimethylammonium chloride, N- [3- {N ′-(meth) acryloylaminopropyl-N ′, N′-die Le ammonium} -2-hydroxypropyl] -N, N, N- trimethyl ammonium chloride having a cationic group of the ride, etc. (meth) acrylamides, and the like.

Of these, N- (meth) acryloyloxyethyl-N, N, N-trimethylammonium chloride and N- (meth) acryloylaminopropyl-N, N, N-trimethylammonium chloride are preferably used. ) Acryloylaminopropyl-N, N, N-trimethylammonium chloride is preferred.
The structure corresponding to the copolymer of the vinyl monomer (B) having a cationic group is, for example, a copolymer of a precursor of a vinyl monomer having a cationic group represented by the formula (3). After polymerization, it can be obtained by converting to a structure having a corresponding cationic group with a cationizing agent.

(In formula, R < ³ > -R < ⁵ >, b, c are synonymous with those in Formula (2), and a preferable range is also synonymous.)
Examples of the cationic vinyl monomer precursor include tertiary amines such as N- (meth) acryloyloxyethyl-N, N-dimethylamine and N- (meth) acryloyloxyethyl-N, N-diethylamine. (Meth) acrylic acid esters; (meth) acrylamides having tertiary amines such as N- (meth) acryloylaminopropyl-N, N-dimethylamine and N- (meth) acryloylaminopropyl-N, N-diethylamine Etc.

Examples of the cationizing agent include alkyl halides such as methyl chloride and cation group-containing cationizing agents such as 3-chloro-2-hydroxypropyl-N, N, N-trimethylammonium chloride. The cationization reaction can be carried out, for example, by adding a cationizing agent to a polymer solution under the conditions of 20 to 100 ° C. and 1 to 20 hours.
In addition, a cationic vinyl monomer or its precursor may be used individually by 1 type, or may use 2 or more types together.

  The content of the structural unit corresponding to the vinyl monomer (B) having a cationic group in the copolymer is preferably 10 to 80% by mass. More preferably, it is 20-70 mass%, Most preferably, it is 30-60 mass%. When the anionic surfactant is used in combination with the composition of the present invention, the structural unit corresponding to the vinyl monomer (B) having the cationic group forms a complex with the copolymer, Facilitates adhesion to hair. By setting the structural unit corresponding to the vinyl monomer (B) having a cationic group to 10% by mass or more, a more sufficient complex can be formed with the anionic surfactant. For example, during rinsing during hair washing Smoothness can be maintained more effectively. By adjusting the amount to 40% by mass or less, the adsorptive power to hair and the like can be more sufficiently maintained, so that the smoothness and smoothness after drying can be more effectively maintained.

  The copolymer may further contain a structural unit derived from another vinyl monomer. However, since the presence of an anionic functional group in the copolymer may hinder the formation of a complex with the anionic surfactant described above, those having a small number of anionic functional groups are preferable (for example, all 10% or less of the functional group), and it is more preferable if it does not substantially contain this. Here, being substantially free means 1% or less. Other vinyl 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 , Monoesters of 1,3-propylene glycol and the like with (meth) acrylic acid, further esters in which the hydroxyl groups of the monoester are etherified with methanol, ethanol, etc., nonionic monomers such as (meth) acryloylmorpholine And semipolar monomers such as amphoteric monomers such as betaine group-containing (meth) acrylic esters, betaine group-containing (meth) acrylamides, amine oxide group-containing (meth) acrylic esters, amine oxide group-containing (meth) acrylamides Body, etc.

The content of structural units derived from other vinyl monomers can be determined as appropriate within the scope of the present invention. For example, it can be appropriately determined in consideration of the solubility of the water-soluble resin, the conditioning effect, and the like. Therefore, 30 mass% or less in a copolymer is preferable.
Structural unit corresponding to vinyl monomer (A) having a hydroxyl group and an amide bond in the copolymer, structural unit corresponding to vinyl monomer (B) having a cationic group, and other vinyl monomers The content of structural units derived from the body is measured by IR absorption of hydroxyl groups and amide bond sites, ¹ H-NMR of methyl groups adjacent to hydroxyl groups, amide bond sites, and cation groups, or ¹³ C-NMR thereof. I can do it.

The water-soluble resin employed in the present invention can form an aqueous solution having a concentration of 5% by mass or more at room temperature, that is, 25 ° C., that is, the transmittance (550 nm) of an aqueous solution having a concentration of 5% by mass or more is 80%. As described above, the aqueous solution is preferably uniform and stable. More preferably, an aqueous solution having a concentration of 10% by mass or more can be formed.
For example, the water-soluble resin according to the present invention is mixed with a monomer that gives each structural unit or a precursor thereof, and copolymerized by a method such as solution polymerization, suspension polymerization, emulsion polymerization, or the like. And can be produced by performing a cationization reaction.

  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. It is preferable to use an alcohol solvent or water.

  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 ′ -Azo compounds such as azobis (2-methyl-N- (2-hydroxyethyl) -pripionamide), 2,2'-azobis (2-amidinopropane) dihydrochloride, benzoyl peroxide, dicumyl peroxide, A peroxide such as di-t-butyl peroxide and lauroyl peroxide, a persulfate, or a redox system thereof 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. 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 for production of the composition according to the present invention as it is or after further purification. Purification can be performed by combining appropriate means such as reprecipitation, solvent washing, and membrane separation as required.

  The water-soluble resin employed in the present invention preferably has a weight average molecular weight of 5,000 to 5,000,000. More preferably, it is 10,000-2,000,000, More preferably, it is 20,000-1,000,000. When the weight average molecular weight is 5,000 or more, the feel during rinsing is deteriorated, and the conditioning effect can be more effectively maintained. By setting it to 5,000,000 or less, the viscosity can be kept moderate, and the handling becomes easier in production. The weight average molecular weight of the copolymer can be measured by gel permeation chromatography (for example, using water / methanol / acetic acid / sodium acetate as a developing solvent).

  Examples of the water-soluble polymer (b-1) other than the water-soluble resin (b) of the present invention include methyl cellulose and hydroxymethyl cellulose. Examples of the cationic polymer include a cation-modified cellulose ether derivative, polydimethyldiallylammonium halide, a copolymer of dimethyldiallylammonium halide and acrylamide. Further, as anionic polymers, acrylic acid derivatives (polyacrylic acid and salts thereof, acrylic acid / acrylamide / ethyl acrylate copolymer and salts thereof), methacrylic acid derivatives, crotonic acid derivatives, etc. are nonionic polymers. As acrylic acid derivatives (hydroxyethyl acrylate / methoxyethyl acrylate copolymer, polyacrylamide, etc.), vinyl pyrrolidone derivatives (polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymer, etc.), and amphoteric polymers, chloride And dimethyldiallylammonium derivatives (acrylamide / acrylic acid / dimethyldiallylammonium chloride copolymer, acrylic acid / dimethyldiallylammonium chloride copolymer, etc.). These are contained in the hair cosmetic composition in an amount of 0.01 to 0.1% by mass.

(C) Nonionic and / or amphoteric surfactants (c) The nonionic or amphoteric surfactants of the component are preferably those represented by the following formulas (4) to (9).

（式中、Ｒ⁴¹ 、Ｒ⁵¹、Ｒ⁶¹、Ｒ⁷¹、Ｒ⁸¹およびＲ⁹¹は、それぞれ独立に炭素数８〜２２のアルキル基またはアルケニル基を示し、Ｒ⁶²、Ｒ⁶³、Ｒ⁷²、Ｒ⁷³、Ｒ⁸²およびＲ⁸³は、それぞれ独立に炭素数１〜３のアルキル基またはアルケニル基および水素原子を示す。またＺは水酸基または水素原子を表し、ｐは平均付加モル数として３〜２０の数を表す。ｍおよびｎは、それぞれ独立して０〜４の整数を表し、０＜ｍ＋ｎ＜６である。）

(In the formula, R ⁴¹ , R ⁵¹ , R ⁶¹ , R ⁷¹ , R ⁸¹ and R ⁹¹ each independently represents an alkyl group or alkenyl group having 8 to 22 carbon atoms, and R ⁶² , R ⁶³ , R ⁷² , R ⁷³ , R ⁸² and R ⁸³ each independently represents an alkyl group or alkenyl group having 1 to 3 carbon atoms and a hydrogen atom, Z represents a hydroxyl group or a hydrogen atom, and p represents an average added mole number of 3 to 20 M and n each independently represents an integer of 0 to 4, and 0 <m + n <6.)

 These nonionic or amphoteric surfactants have a function of mildening the action on the skin, making it hard to cause rough skin, and enhancing foaming. Use one or a combination of two or more. 0.1 to 10% by mass, preferably 1 to 5% by mass, in the hair cosmetic composition of the present invention. If it is less than 0.1% by mass, a sufficient effect may not be obtained, and if it exceeds 10% by mass, the viscosity of the composition may remarkably increase or the solution stability may deteriorate.

(D) Silicone compound The type of the silicone compound as the component (d) is not particularly limited, and those normally used in hair cosmetics can be used. For example, dimethylpolysiloxane (including highly polymerized dimethylpolysiloxane and silicone rubber), methylphenylpolysiloxane, polyether modified silicone, polyamino modified silicone, betaine modified silicone, alcohol modified silicone, fluorine modified silicone, epoxy modified silicone, mercapto Examples thereof include modified silicone, carboxy-modified silicone, fatty acid-modified silicone, silicone graft polymer, cyclic silicone, alkyl-modified silicone, trimethylsilyl group-terminated dimethylpolysiloxane, silanol group-terminated dimethylpolysiloxane, and the like. Two or more species can be used in appropriate combination. Among these, dimethylpolysiloxane, polyether-modified silicone, and polyamino-modified silicone are particularly preferably used.
Moreover, 0.1-5.0 mass% of silicone compounds are mix | blended in the whole composition, Preferably, 0.3-3.0 mass% is mix | blended. If it is less than 0.1% by mass, the effect may be poor, and if it exceeds 5.0% by mass, it may be difficult to stabilize the dispersion of silicone in the product.
These silicone compounds are not particularly limited in viscosity, but the viscosity at a temperature of 25 ° C. is preferably 0.0001 to 2,000 m ² / S, more preferably 0.003 to 1, 000 m ² / S. Further, for example, in also a preferred method the viscosity is easier to handle as a mixture with the silicone compound of low viscosity 0.0001~0.2m ² / S greater silicone compound having a molecular weight of 200~1,200m ² / S is there.
Further, as the silicone compound, an emulsion obtained by emulsifying the silicone compound with a surfactant can be used. In addition, there is no restriction | limiting in particular in an emulsifier and the emulsification method, and such an emulsion can be used variously.
The viscosity of the silicone compound can be measured by using a Brookfield viscometer which is a general test method based on cosmetic raw materials.

Other oils may include higher alcohol, olive oil, jojoba oil, liquid paraffin, fatty acid alkyl ester oil, and the like.
In addition, fatty acid ethylene glycol or the like may be included as the pearlizing agent, and polystyrene emulsion or the like may be included as the suspending agent.

(E) Cationic surfactant The cationic surfactant as the component (e) is not particularly defined as long as it does not depart from the spirit of the present invention, but is a quaternary tetraalkylammonium salt represented by the following formula (10): Preferred are guanidine derivatives or salts thereof, amino acid cationic surfactants and amidoamine type surfactants, and more preferred are quaternary tetraalkylammonium salts.
A quaternary tetraalkylammonium salt can be preferably used as a cationic surfactant. Specific examples include stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, cetostearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dibehenyl dimethyl ammonium chloride and the like. Among these, those having a linear alkyl group of 16 to 22 are preferred, specifically, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride are more preferred, stearyltrimethylammonium chloride, More preferred is behenyltrimethylammonium chloride. The cationic surfactant is preferably in the form of hydrochloride or bromate.

（式中、Ｒ¹⁰¹は炭素数１〜２１の直鎖状もしくは分岐鎖状のアルキル基またはアルケニル基、Ａは炭素数１〜１０の直鎖状もしくは分岐鎖状のアルキレン基またはアルケニレン基であり、ｔは１〜５の整数であって、ｔが２以上の場合、各ブロック中のＡは互いに異なってもよい。） Moreover, the guanidine derivative represented by following formula (10) or its salt can also be used preferably as a cationic surfactant.

Wherein R ¹⁰¹ is a linear or branched alkyl group or alkenyl group having 1 to 21 carbon atoms, and A is a linear or branched alkylene group or alkenylene group having 1 to 10 carbon atoms. , T is an integer of 1 to 5, and when t is 2 or more, A in each block may be different from each other.)

R ¹⁰¹ in the general formula (10) is preferably a linear or branched alkyl group or alkenyl group of _{11 to 19} , for example, C ₁₁ H ₂₃ —, C ₁₂ H ₂₅ —, C _{13. H 27 -, C 14 H 29} -, C 15 H 31 -, C 16 H 33 -, C 17 H 35 -, (C 8 H 17) 2 CH-, 4-C 2 H 5 C 15 H 30 - , etc. These groups are preferred examples.
The substituent A is preferably a 2-6 linear or branched alkylene group or alkenylene group, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an isopropylene group. , 2-pentenyl group, 2-ethylbutylene group and the like.
The guanidine derivative represented by the above formula (10) is preferably blended in the form of a salt, specifically, inorganic salts such as hydrochloride, bromate, sulfate, phosphate, glycolate, acetic acid It can be used as an organic acid salt such as a salt, lactate, succinate, tartrate, citrate, acidic amino acid salt, higher fatty acid salt, pyroglutamate, and p-toluenesulfonate. Of these, the hydrochloride, bromate, acetate, glycolate, citric acid and acidic amino acid salt forms are preferred.

Furthermore, amino acid-based cationic surfactants can also be preferably used as the cationic surfactant. Examples of amino acid-based cationic surfactants include mono-N-long chain acyl basic amino acid lower alkyl ester salts. Examples of basic amino acids constituting this compound include natural amino acids such as ornithine, lysine and arginine. It is also possible to use synthetic amino acids such as α, γ-diaminobutyric acid. These may be optically active or racemic.
The acyl group is preferably a saturated or unsaturated higher fatty acid residue having 8 to 22 carbon atoms. These may be natural or synthesized. For example, single higher fatty acid residues such as lauroyl group, myristoyl group, palmitoyl group and stearoyl group, and natural mixed higher fatty acid residues such as coconut oil fatty acid residue and beef tallow higher fatty acid residue can be employed.
As the lower alkyl ester component, methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester and octyl ester are preferable. The lower alkyl ester component is preferably in the form of a salt, specifically, inorganic salts such as hydrochloride, bromate, sulfate, phosphate, glycolate, acetate, lactate, succinate, tartrate Citrate, acidic amino acid salt, higher fatty acid salt, L- or DL-pyrrolidone carboxylate, pyroglutamate, p-toluenesulfonate, and other organic acid salts. Of these, the hydrochloride, L- or DL-pyrrolidone carboxylate and acidic amino acid salt forms are preferred.

（式中、Ｒ¹¹¹は炭素数７〜２３の脂肪酸残基を表し、Ｒ¹¹²は炭素数１〜４のアルキル基を表し、ｐは２〜４の整数を表す。）
Ｒ¹¹¹は、好ましくは９〜２２の脂肪酸残基、さらに好ましくは１３〜２２の脂肪酸残基であり、Ｒ¹¹²は、好ましくはメチル基またはエチル基である。 Furthermore, an amidoamine type surfactant can also be suitably used as a cationic surfactant. As the amidoamine type surfactant, a compound represented by the following formula (11) can be used.

(In the formula, R ¹¹¹ represents a fatty acid residue having 7 to 23 carbon atoms, R ¹¹² represents an alkyl group having 1 to 4 carbon atoms, and p represents an integer of 2 to 4).
R ¹¹¹ is preferably a fatty acid residue of 9 to 22, more preferably 13 to 22, and R ¹¹² is preferably a methyl group or an ethyl group.

As the amidoamine type surfactant represented by the above formula (11), stearic acid diethylaminoethylamide, stearic acid dimethylaminoethylamide, palmitic acid diethylaminoethylamide, coconut oil fatty acid diethylaminopropylamide, palmitic acid dimethylaminoethylamide, Myristic acid diethylaminoethylamide, myristic acid dimethylaminoethylamide, behenic acid diethylaminoethylamide, behenic acid dimethylaminoethylamide, stearic acid diethylaminopropylamide, stearic acid dimethylaminopropylamide, palmitic acid diethylaminopropylamide, palmitic acid dimethylaminopropyl Amides, diethyl myristamide of myristic acid, dimethylaminopropylamidyl myristate , Behenic acid diethylaminopropylamide, behenic acid dimethylaminopropylamide preferred examples include. These are preferably formulated in the form of salts, specifically inorganic salts such as hydrochloride, bromate, sulfate, phosphate, glycolate, acetate, lactate, succinate, tartrate Citrate, acidic amino acid salt, higher fatty acid salt, pyroglutamate, p-toluenesulfonate, and other organic acid salts. Of these, acidic amino acid salts, citrates, and hydrochlorides are more preferable. In addition, the salt used for neutralization may use together 1 type, or 2 or more types. Among these, stearic acid dimethylaminopropylamide, stearic acid diethylaminoethylamide, and coconut oil fatty acid diethylaminopropylamide are preferably used.
In the present invention, one or more of these amidoamine surfactants can be used.

 These cationic surfactants are blended in order to assist the conditioning effect of the resin of component (b), preferably 0.01 to 5.0% by mass, more preferably 0.1 to 2.0% by mass. Blended. The conditioning effect is more effective when the content is 0.01% by mass or more, and more uniform with the base of the anionic surfactant of component (a) by being 5.0% by mass or less. Easier to dissolve.

（式中、Ｒ¹⁰、Ｒ¹¹及びＲ¹²はそれぞれ炭素数１〜３のアルキル基、水酸基または水素原子を示し、Ａ¹はカルボキシル基またはその塩を示す）
安息香酸、サリチル酸及びこれらの塩がより好ましい。塩としては、アルカリ金属塩（例えば、ナトリウム塩、カリウム塩）、アルカリ土類金属塩（例えば、マグネシウム塩、カルシウム塩、アルミニウム塩）、アンモニウム塩（例えば、アンモニウム）、アルカノールアミン塩（例えば、トリエタノールアミン、ジエタノールアミン、モノエタノールアミン、トリイソプロパノールアミン）が好ましい。
（ｆ）成分は、全組成中に好ましくは０．０１〜１０質量％、より好ましくは０．１〜３質量％配合される。０．０１質量％以上とすることにより、コンディショニング効果がより向上し、１０質量％以下とすることにより分散安定性が悪くなるのをより効果的に抑止できる。 (F) Aromatic carboxylic acid or salt thereof (f) Aromatic carboxylic acid or salt thereof as component (f) has an effect of assisting the conditioning effect of component (b). When used in combination with component (e), the conditioning effect is further improved. Can be increased.
The aromatic carboxylic acid or salt thereof as the component (f) is preferably an aromatic carboxylic acid represented by the following formula (12) or a salt thereof.

(Wherein R ¹⁰ , R ¹¹ and R ¹² each represent an alkyl group having 1 to 3 carbon atoms, a hydroxyl group or a hydrogen atom, and A ¹ represents a carboxyl group or a salt thereof)
Benzoic acid, salicylic acid and their salts are more preferred. Examples of the salt include alkali metal salts (for example, sodium salts, potassium salts), alkaline earth metal salts (for example, magnesium salts, calcium salts, aluminum salts), ammonium salts (for example, ammonium), alkanolamine salts (for example, trivalent salts). Ethanolamine, diethanolamine, monoethanolamine, triisopropanolamine) are preferred.
The component (f) is preferably blended in the total composition in an amount of 0.01 to 10% by mass, more preferably 0.1 to 3% by mass. By setting it as 0.01 mass% or more, a conditioning effect improves more, and it can suppress more effectively that dispersion stability worsens by setting it as 10 mass% or less.

  Further, when used as a shampoo composition, adding a milky whitening agent to give a rich liquid appearance provides a preferred hair cosmetic for consumers. There is no particular limitation as long as it can be dispersed in the form of a crystal or a solid in hair cosmetics and can give a pearly luster or milky white color. For example, those derived from natural products such as fish scales and mica pieces are also used. However, those chemically synthesized are preferred from the standpoints of quality stability, economic efficiency, ease of handling during production, and the like. Furthermore, when points, such as dispersion stability and foaming property, are considered, especially the compound represented by Formula (13) and / or Formula (14), and glycerol mono fatty acid (C16-C24) ester are preferable.

（式中、Ｒ¹³は炭素数１５〜２３のアルキル基またはアルケニル基を表し、Ａ¹³は炭素数１６〜２４の脂肪酸残基を示し、ｎは１〜３の数を示す）
これらの乳白化剤は１種または２種以上を組合わせて用いることができ、毛髪化粧料中に、好ましくは１〜１０質量％、より好ましくは１〜５質量％配合される。１質量％以上とすることにより、より美しい真珠様光沢が得られ、１０質量％以下とすることにより、分散安定性をより効果的に保つことができる。

(In the formula, R ¹³ represents an alkyl group or alkenyl group having 15 to 23 carbon atoms, A ¹³ represents a fatty acid residue having 16 to 24 carbon atoms, and n represents a number of 1 to 3)
These opacifiers can be used alone or in combination of two or more, and are preferably incorporated in the hair cosmetic composition in an amount of 1 to 10% by mass, more preferably 1 to 5% by mass. By setting the content to 1% by mass or more, a more beautiful pearly luster is obtained. By setting the content to 10% by mass or less, the dispersion stability can be more effectively maintained.

  In addition to the above-mentioned components, the hair cosmetic of the present invention includes components used in normal hair cosmetics, such as ethanol, isopropanol and other lower alcohols, as long as the effects of the present invention are not impaired. Polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, sorbitol, and polyethylene glycol; thickeners such as carboxymethyl cellulose and hydroxyethyl cellulose; citric acid, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid ( NTA) and other chelating agents, fragrances, pigments, antiseptic / antifungal agents, pH adjusting agents, and the like can be appropriately blended as necessary.

The fragrance and fragrance composition used in the hair cosmetic composition of the present invention include the fragrance ingredients described in JP-A-2003-300121 [0021] to [0035], and the fragrance described in [0050] of the same publication. For example.
The amount of the perfume solvent used is preferably 0.1 to 99% by mass, more preferably 1 to 50% by mass in the perfume composition.
Examples of the fragrance stabilizer include dibutylhydroxytoluene, butylhydroxyanisole, vitamin E and its derivatives, catechin compounds, flavonoid compounds, polyphenol compounds and the like, and preferably 0.0001 to 10 in the fragrance composition. It is blended by mass%, more preferably 0.001 to 5 mass%. Among these, a preferable stabilizer is dibutylhydroxytoluene.
The fragrance composition is a mixture composed of the above fragrance components, a solvent, a fragrance stabilizer and the like.
In the hair cosmetic composition of the present invention, the perfume composition is preferably added in an amount of 0.005 to 40 mass%, more preferably 0.01 to 10 mass%, based on the total amount of the hair cosmetic composition.

  The hair cosmetic composition of the present invention can be produced by mixing and stirring each component according to a known method. In this case, the component (a) is preferably an aqueous anionic surfactant solution having a concentration of 20 to 70% by mass previously diluted with purified water or ethanol from the viewpoint of ease of production. The component (b) is preferably dissolved in water or the like, or dispersed in a solvent such as propylene glycol and added. As the components (c) and (e), it is convenient to use those previously diluted in purified water, ethanol, or the like. However, if the components are solid, the components are heated to a temperature higher than the dissolution temperature and fluidized. ) While stirring the liquid in the middle of production in which the components and purified water are mixed, the fluidized product is added little by little, so that it can be easily dissolved in a short time. As the component (f), a water-soluble component may be added as it is or as an aqueous solution, and an oil-soluble component may be dissolved in a fragrance or the like.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
<Example 1-1>
(Production of copolymer (1))
In a reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas introduction pipe and a stirring device, 300 parts by weight of distilled water, 100 parts by weight of monomer of Table 1 (copolymer (1)) and distilled water The monomer mixture was charged into a dropping funnel, and the reactor was purged with nitrogen, and then heated to 70 ° C. After adding 0.5 part by weight of 2,2′-azobis (2-amidinopropane) dihydrochloride to the reactor, the monomer mixture was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction was performed for 4 hours, followed by heating to 80 ° C. and further reaction for 2 hours.

The resulting copolymer was gel permeation chromatography (apparatus: manufactured by Tosoh Corporation, SC8010, SD8022, RI8020, CO8011, PS8010, column: Wako Pure Chemical Industries, Ltd. Wakopak (Wakobeads G-50), developing solvent: The weight average molecular weight was measured using water / methanol / acetic acid / sodium acetate = 6/4 / 0.3 / 0.41), and the results are shown in Table 1.
Further, the water solubility of the obtained copolymer was measured according to the following criteria by preparing a 5% by mass aqueous solution at 25 ° C., measuring its transmittance (550 nm, 10 mm glass cell). The results are shown in Table 1.
○: 80% or more Δ: 50% or more to less than 80% ×: less than 50%

DMC: N-methacryloyloxyethyl-N, N, N-trimethylammonium chloride DMAPAAC: N-acryloylaminopropyl-N, N, N-trimethylammonium chloride DMAPMAC: N-methacryloylaminopropyl-N, N, N-trimethyl Ammonium chloride DADMAC: N, N-dimethyl-N, N-diallylammonium chloride GMAArg: Reaction product of L-arginine and glycidyl methacrylate HEAA: N-hydroxyethylacrylamide NMAA: N-methylolacrylamide DMAPMAO: N-methacryloylaminopropyl -N, N-dimethylamine oxide HEA: hydroxyethyl acrylate

(Preparation of hair cosmetics)
A shampoo having this composition was prepared using the copolymer (1) as the resin described in Table 2. Preparation was performed by first mixing other than silicone oil and then blending the mixture with silicone oil. Using the prepared shampoo, foaming, smoothness at the time of rinsing, smoothness after drying, flexibility after drying, and silicone oil adsorption amount were evaluated by the methods described below.

(Evaluation of hair cosmetics)
The hair cosmetic obtained by the above method was evaluated by the method described below. The evaluation results when using untreated hair as the hair bundle are shown in Table 4, and the evaluation results when using damaged hair are shown in Table 5.

<Examples 1-2 to 1-9>
(Production of copolymers (2) to (9))
Copolymer (2) to copolymer in the same manner as the production of copolymer (1) except that the monomer composition described in Table 1 (copolymers (2) to (9)) was used. (9) was produced. The weight average molecular weight of the obtained copolymer is shown in Table 1.
(Preparation and evaluation of hair cosmetics)
Hair cosmetics were prepared and evaluated in the same manner as described in Example 1-1. The evaluation results are shown in Tables 3 and 4.

<Example 1-10>
(Production of copolymer (10))
Using the monomer composition described in Table 1 (copolymer (10)), the amount of distilled water initially placed in the reactor was changed to 500 parts by weight, and this was the same as the production of copolymer (1). A copolymer (10) was produced.
The weight average molecular weight of the obtained copolymer is shown in Table 1.
(Preparation and evaluation of hair cosmetics)
Hair cosmetics were prepared and evaluated in the same manner as described in Example 1-1. The evaluation results are shown in Tables 3 and 4.

<Comparative Example 1-1>
(Production of copolymer (11))
A copolymer (11) was produced in the same manner as in the production of the copolymer (1) except that the monomer composition described in Table 1 (copolymer (11)) was used. The weight average molecular weight of the obtained copolymer is shown in Table 1.
(Preparation and evaluation of hair cosmetics)
Hair cosmetics were prepared and evaluated in the same manner as described in Example 1-1. The evaluation results are shown in Tables 3 and 4.

<Comparative Example 1-2>
(Production of copolymer (12))
Except for using the monomer composition described in Table 1 (copolymer (12)), using ethanol as the solvent, and using dimethyl-2,2′-azobisisobutyrate as the polymerization initiator. The copolymer (12) was produced in the same manner as in the production of the copolymer (1). The obtained copolymer was made into an aqueous solution by adding distilled water and distilling off ethanol. The weight average molecular weight of the obtained copolymer is shown in Table 1.
(Preparation and evaluation of hair cosmetics)
Hair cosmetics were prepared and evaluated in the same manner as described in Example 1-1. The evaluation results are shown in Tables 3 and 4.

<Comparative Example 1-3>
(Preparation and evaluation of hair cosmetics)
Hair cosmetics were prepared and evaluated in the same manner as described in Example 1-1 except that cationized hydroxyethyl cellulose (Calgon: JR400) was used as the resin described in Table 2. The evaluation results are shown in Tables 3 and 4.

<Comparative Example 1-4> (Standard)
(Preparation and evaluation of hair cosmetics)
Hair cosmetics were prepared and evaluated in the same manner as described in Example 1-1 except that the resins listed in Table 2 were not blended. The evaluation results are shown in Tables 3 and 4.

<Evaluation method>
Each hair cosmetic was applied to the prepared hair bundle, and the following items were evaluated. The hair bundle used was “human hair black hair (100%), root alignment (untreated hair 10 g × 30 cm); Viewlux, Inc.” as “untreated hair”. Further, “untreated hair” obtained by the following bleaching treatment was used as “damage hair”. The bleaching treatment was performed by mixing a blend of Progatis Brave Oxytan 6.0 (hydrogen peroxide 6% cream) manufactured by Milbon Co., Ltd .; 12 g, and 6 g of Powder Bleach MR2 manufactured by Melos Chemical Co., Ltd. as a bleaching agent. It was applied to a book, allowed to stand for 30 minutes, then washed with water, and further applied with polyoxyethylene (3) sodium lauryl ether sulfate and washed.

(1) Foaming After adding 10 g of hair bundles with running water at 40 ° C., excess water is removed, and 1 g of shampoo is applied and foamed. The speed of foaming at this time and the degree of fineness of the generated foam were evaluated in 4 stages and scored.
+2: Excellent foaming speed and fineness of the generated foam compared to the standard sample (resin-free product) +1: Excellent foaming speed and fineness of the generated foam compared to the standard sample 0 : Same as standard sample-1: Inferior to standard sample

(2) Smoothness at the time of rinsing After the foaming evaluation, the smoothness of the finger when the hair bundle was rinsed in running water at 40 ° C. and the duration of the smoothness were evaluated in four stages.
+2: Excellent smoothness compared to the standard sample, and smoothness lasts for more than 1 minute +1: Either smoothness or sustainability is superior compared to the standard sample 0: Same as the standard sample -1: Standard sample Inferior

(3) Smooth feeling after drying The hair bundle after the smoothness evaluation at the time of rinsing was dried overnight in a thermostatic chamber at 23 ° C. and 60% RH, and then the smooth feeling of the hair bundle was evaluated in four stages.
+2: The smoothness is remarkably superior to the standard sample +1: The smoothness is superior to the standard sample 0: Same as the standard sample -1: Inferior to the standard sample

(4) Softness after drying The softness after drying was evaluated in four stages using a hair bundle evaluated for smoothness.
+2: Little sensation compared to the standard sample +1: Little sensation compared to the standard sample but slightly felt 0: Same as the standard sample -1: Inferior to the standard sample

(5) Amount of silicone oil adsorbed After wetting 10 g of hair bundle with running water at 40 ° C. for 30 seconds, drain the water until no water drops fall, apply 1 g of shampoo, and foam with a comb for 100 minutes for 1 minute. This is rinsed in running water at 40 ° C. for 30 seconds and then dried overnight. After repeating this treatment twice, the silicone oil adsorbed on the hair was extracted, and the amount of adsorption was evaluated by NMR measurement of the extract (1H-NMR determined H of Si—CH ₃ ).
For extraction, the hair bundle was immersed in a solvent of chloroform / methanol = 4/1 and subjected to ultrasonic treatment, the solvent was dried under reduced pressure, dissolved in deuterated chloroform, and dimethyl terephthalate was added as an internal standard to obtain the concentration. .

<Evaluation of results>
1) Since Comparative Example 1-1 uses N-methacryloylaminopropyl-N, N-dimethylamine oxide for the production of a water-soluble resin, the structural unit of the water-soluble resin does not have a hydroxyl group. Therefore, the amount of silicone oil adsorbed by damaged hair is low, and the smoothness after drying is inferior.
2) Since Comparative Example 1-2 uses hydroxyethyl acrylate for the production of the water-soluble resin, it does not have an amide bond in the structural unit of the water-soluble resin. For this reason, both untreated hair and damaged hair are foamed, smooth when rinsed, smooth after drying, softness after drying, and poor silicone oil adsorption.
3) Since Comparative Example 1-3 uses cationized hydroxyethyl cellulose having no amide bond as the water-soluble resin, both untreated hair and damaged hair are inferior in flexibility after drying.
4) Since Comparative Example 1-4 (standard sample) does not contain a resin, both untreated hair and damaged hair are foamed compared to the hair cosmetic containing the water-soluble resin of the present invention, smoothness during rinsing, and drying Later smoothness, flexibility after drying, silicone oil adsorption amount is inferior.

<Examples 2-1 to 2-4, Comparative Examples 2-1 to 2-3>
The hair cosmetics shown in Table 5 below were prepared and evaluated as follows. In addition, the unit in Table 5 is mass%.
(Evaluation methods)
Ten women aged 20 to 50 used hair cosmetics for 7 days and evaluated the feeling of use. Specifically, the evaluation was made in three stages: good, neither, bad, and the final evaluation was made according to the following criteria.

◎: Reply if 8-10 out of 10 are good ○: Reply if 5-7 out of 10 are good △: Reply if 3-4 out of 10 are good ×: 0-2 out of 10 are good Answer

  As shown in the above table, the shampoos of Examples 2-1 to 2-4 were excellent in evaluation by women.

<Example 2-5>
Moreover, after filling the hair cosmetics obtained in Example 2-1 into the following container and storing it in a thermostat controlled at 40 ° C. and −5 ° C. for one month, the environment at 22 to 27 ° C. For 3 days, and the appearance of the hair cosmetic was evaluated. The whole content of the stored liquid was transferred into a container such as a petri dish and the appearance was observed. As a result, no layer separation, significant discoloration, or generation of foreign matter such as crystals was observed at any temperature and storage container.

<Bottle container>
(1) Bottle part: Material PP Cap: Material PP
(2) Bottle: Material HDPE Cap: Material PP
(3) Bottle part: Material PET Cap: Material PP
(4) Bottle part: Material PP / HDPE Cap: Material PP
<Pump container>
(5) Bottle part: Material PP Dispenser part: Used material PP, PE and SUS304
(6) Bottle part: HDPE Dispenser part: Materials PP, PE and SUS304 used
(7) Bottle part: PET Dispenser part: Materials PP, PE and SUS304 used
(8) Bottle part: PP / HDPE Dispenser part: Materials PP, PE and SUS304 used
<Pouch container>
(9) Material: Aluminum-deposited polyethylene pouch

  Here, PE represents polyethylene, PP represents polypropylene, PET represents polyethylene terephthalate, and HDPE represents high-density polyethylene.

<Example 3>
Hair conditioner composition The hair conditioner composition shown in Table 6 below was produced. Furthermore, after using the shampoo shown below, the hair conditioner composition shown in Table 6 was used and rinsed off with hot water. After towel drying, the conditioner was evaluated for use feeling by drying with a dryer. The usability was evaluated in the same manner as in Example 1.

Shampoo composition used in the evaluation of Example 3 (the amount is pure (mass%))
POE alkyl ether sodium sulfate: 10% by mass
Sodium tetradecenesulfonate: 1% by mass
Lauric acid amidopropyl betaine: 4% by mass
POE (2) lauric acid monoethanolamide: 2% by mass
Dimethyldiallylammonium chloride / acrylamide copolymer
: 0.5% by mass
Citric acid: appropriate amount (adjusted to pH = 5.2)
Sodium benzoate: 1.1% by mass
Fragrance A: 1.0% by mass
Purified water: residue

<Example 4> Hair wax Hair waxes shown in Table 8 below were produced.
After using the shampoo and hair conditioner shown below, the hair wax was used to evaluate the feeling of use on the hair dried with a dryer. The usability was evaluated in the same manner as in Example 1.

Shampoo composition used in the evaluation of Example 4
POE alkyl ether sodium sulfate: 10% by mass
Sodium tetradecenesulfonate: 1% by mass
Lauric acid amidopropyl betaine: 4% by mass
POE (2) lauric acid monoethanolamide: 2% by mass
Dimethyldiallylammonium chloride / acrylamide copolymer
: 0.5% by mass
Citric acid: appropriate amount (adjusted to pH = 5.2)
Sodium benzoate: 1.1% by mass
Fragrance A: 1.0% by mass
Purified water: residue

Hair conditioner composition used in the evaluation of Example 4 (mixing amount is described in pure)
4-Guanidinobutyllaurylamide: 0.8% by mass
Stearyltrimethylammonium chloride: 0.2% by mass
Dimethyl silicone (viscosity 100 m ² / S): 1.0% by mass
Dimethyl silicone (viscosity 10 m ² / S): 1.0% by mass
Dimethyl silicone (viscosity 0.005 m ² / S): 1.0% by mass
Cetanol: 1.5% by mass
Behenyl alcohol: 0.2% by mass
Arginine: 0.3% by mass
Sodium benzoate: 0.2% by mass
Phosphoric acid: appropriate amount (adjusted to pH = 3.5)
Fragrance A: 1.0% by mass
Purified water: residue

The following raw materials were used.
Ingredient (a)
(Polyoxyethylene (POE) sodium alkyl ether sulfate)
A TAIPAPOL NE1230E (manufactured by TAICA) was employed. This raw material is a polyoxyethylene alkyl (12-14) ether sulfate sodium sulfate solution (3E.O.) in accordance with the formulation standard for cosmetic varieties (hereinafter abbreviated as makeup regulation), and is an aqueous solution having a pure content of about 28%. .
(Sodium tetradecenesulfonate)
Sodium tetradecene sulfonate (manufactured by Lion Corporation) was employed. This raw material is an aqueous solution of sodium tetradecene sulfonate according to the makeup regulations and containing sodium hydroxyalkane sulfonate with a pure content of about 35%.
(N-coconut oil fatty acid-L-glutamic acid TEA)
Amisoft CT-12 (manufactured by Ajinomoto Co., Inc.) conforming to the makeup regulations was used. This raw material is a 30% mass product.

Ingredient (b)
(Copolymer (2))
N-methacryloyloxyethyl-N, N, N-trimethylammonium chloride (DMC) / N-hydroxyethylacrylamide (HEAA) copolymer (manufactured by Mitsubishi Chemical Corporation) was employed. DMA: HEAA = 40: 60 and the weight average molecular weight is about 420,000.
(Copolymer (3))
N-methacryloyloxyethyl-N, N, N-trimethylammonium chloride (DMC) / N-hydroxyethylacrylamide (HEAA) copolymer (manufactured by Mitsubishi Chemical Corporation) was employed. DMA: HEAA = 60: 40 and the weight average molecular weight is about 360,000.
(Copolymer (4))
N-acryloylaminopropyl-N, N, N-trimethylammonium chloride (DMAPAAC) / N-hydroxyethylacrylamide (HEAA) copolymer (manufactured by Mitsubishi Chemical Corporation) was employed. DMAPAAC: HEAA = 40: 60 and the molecular weight was about 400,000.

Ingredient (c)
(Amidopropyl betaine laurate)
LPB-30 (manufactured by Yushi Co., Ltd.) was employed. This raw material is an aqueous solution having a pure content of about 30% by mass in accordance with the makeup regulations.
(POE (10) cetyl ether)
EMALEX110 (manufactured by Nippon Emulsion Co., Ltd.) was employed. This raw material complies with the makeup regulations, is in the form of white wax, and is HLB11.
(Coconut oil fatty acid monoethanolamide)
It is Comparan KM (manufactured by Henkel), and this raw material complies with cosmetic raw material standards (hereinafter abbreviated as makeup base).
(POE (2) lauric acid monoethanolamide)
Amidette 2L-Y (manufactured by Kawaken Fine Chemical Co., Ltd.) was employed. This raw material complies with the makeup regulations. The average number of EO addition moles is about 2.
(POE (20) hydrogenated castor oil)
CW-20-90 (Aoki Yushi Kogyo Co., Ltd.) was employed. This raw material conforms to the makeup primaries, and is a polyoxyethylene hydrogenated castor oil, which is an aqueous solution having a pure content of about 90%.
(Sorbitan monolaurate)
Soybon S-20 (manufactured by Toho Chemical Industry Co., Ltd.) was employed. Conforms to Jingyuan
(Polyoxyethylene octyl tesil ether)
Emalex OD-5 (manufactured by Nippon Emulsion Co., Ltd.) was employed. Conforms to Jingyuan

Ingredient (d)
(Highly polymerized dimethyl silicone)
Highly polymerized dimethyl silicone (manufactured by Lion) was employed. This raw material complies with the makeup regulations, (1) highly polymerized methylpolysiloxane having a viscosity of 400 m ² / S (KF-9029: manufactured by Shin-Etsu Chemical Co., Ltd.), and (2) 1000 m ² / S highly polymerized methyl. Polysiloxane (KF-9030: manufactured by Shin-Etsu Chemical Co., Ltd.) and (3) methylpolysiloxane (KF-96: manufactured by Shin-Etsu Chemical Co., Ltd.) having a viscosity of 0.1 m ² / S based on the makeup base (1) : (2) :( 3) = 15: 15: 70 mixed, and emulsified and dispersed in water by mechanical force using POE (15) cetyl ether (NPO-97: manufactured by Lion Chemical Co., Ltd.) according to the makeup base as an emulsifier It is an emulsion. The silicone ((1) + (2) + (3)) concentration of the emulsion was about 60% by mass. The viscosity of the emulsion liquid was about 1.5 Pa · s (25 ° C .: General Method 2 of Cosmetic Basic Standard, used rotor No. 3, rotation speed 30 rpm), and the average particle size of dimethyl silicone was about 0.9 μm. The pH was adjusted to 3 with hydroxyethanediphosphonic acid (Feliox 115: manufactured by Lion Corporation), and 0.2% by mass of benzoic acid was added as a preservative.
(Amojimethicone)
SM8704C (manufactured by Toray Dow Corning) was employed. This raw material was an aqueous dispersion of amodimethicone in accordance with the makeup regulations, and the concentration of amino-modified silicone was about 40% by mass. The average particle size of the amino-modified silicone in the aqueous dispersion was about 0.1 μm.
(Dimethyl silicone (viscosity 100m ² /S~0.005m ² / S)
KF-96 dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd.) was employed. Conforms to Jingyuan
(Methylsiloxane / polyoxyethylene copolymer)
SH3775M (manufactured by Toray Dow Corning Silicone) was employed. Conforms to Jingyuan

Ingredient (e)
(Stearyltrimethylammonium chloride)
ARCARD T833 (manufactured by Lion Corporation) was adopted. This raw material is stearyltrimethylammonium chloride based on the makeup base, and is an aqueous solution having a pure content of about 33% (remaining 29% makeup base anhydrous ethanol, 38% makeup base purification water).
(Cetyltrimethylammonium chloride)
ARCARD 16-50 (manufactured by Lion Corporation) was employed. This raw material is a 50% pure product, and isopropyl alcohol and water are solvents. This raw material complies with the makeup base.
(4-Guanidinobutyllaurylamide)
An lauric acid amide butyl guanidine solution (manufactured by Lion Corporation) was employed. It is about 32% pure and contains water and ethanol as solvents.

Ingredient (f)
(Sodium benzoate)
Sodium benzoate (BFGoodrich Kalama Inc.) was employed. This raw material complies with the makeup base.
(benzoic acid)
Benzoic acid (manufactured by BFGoodrich Kalama Inc.) was employed. Conforms to Jingyuan
(Salicylic acid)
Adopted by Yoshitomi Pharmaceutical Co., Ltd.

Other components (Polyoxyethylene (acrylates / lauryl acrylate / stearyl acrylate / ethylamine oxide methacrylate) copolymer)
A diamond former Z-631 (manufactured by Mitsubishi Chemical Corporation) was employed. (Acrylates / lauryl acrylate / stearyl acrylate / methacrylic acid ethylamine oxide) The ethanol / water solution of the copolymer had a pure content of about 30% by mass.
(Propylene glycol)
A product made by Asahi Glass Co., Ltd. was adopted. This raw material complies with the makeup base.
(Bentonite)
Kunipia G (Kunimine Kogyo Co., Ltd.) was used. This raw material complies with the makeup base.
(Hydroxypropylmethylcellulose)
Metroze 60SH-4000 (manufactured by Shin-Etsu Chemical Co., Ltd.) was employed. This raw material complies with the makeup base.
(Diglucosyl gallic acid)
DGA (Iwaki Pharmaceutical Co., Ltd.) was employed. The essence of this raw material is a powder containing 90% by mass or more of gallic acid-3,5-diglucoside. The remainder is mainly water, but in addition, 3 mass% or less of mono-isomers as impurities and gallic acid as unreacted material is 0.15 mass% or less. The pH of the 1% by mass aqueous solution of this raw material is 2.0 to 4.0.
(Hydrolyzed wheat protein)
Gladin WLM (manufactured by Cognis Japan) was employed. This is an aqueous solution having an active ingredient amount of about 23% by mass in accordance with the cosmetic regulations. As preservatives, sodium benzoate 0.6% by mass, phenoxyethanol 0.5% by mass, methylparaben 0.25% by mass, and propylparaben 0.05% by mass are contained.
(Raffinose)
Oligo GGF (manufactured by Asahi Kasei Corporation) was employed. It is an oligosaccharide composed of D-galactose, D-glucose and D-fructose. It is obtained by crystallizing from molasses.
(Hydroxyethanediphosphonic acid)
Ferriox 115 (manufactured by Lion) conforming to the makeup regulations was adopted. This raw material is an aqueous solution of about 60% by mass.

(Plant extract)
Falco Rex BX-46 (manufactured by Ichimaru Falcos) was employed. This raw material is a mixture of cedar extract, hop extract, pine extract, lemon extract, and rosemary extract, which is a makeup ruler, and is a solution of 1,3-butylene glycol (1,3-BG) and purified water.
(Piroctone olamine)
Octopirox (Clariant) was used.
(Dipotassium glycyrrhizinate)
Glycyrrhizin K2 (manufactured by Maruzen Pharmaceutical Co., Ltd.) was employed. This raw material complies with the makeup base.
(ethanol)
A 99% content product was used.
(Dimethyldiallylammonium chloride / acrylamide copolymer)
Kayaacryl resin MN-50 (manufactured by Nippon Kayaku Co., Ltd.) was employed. This raw material is a dimethyldiallylammonium chloride-acrylamide copolymer solution in accordance with the makeup regulations and an aqueous solution of about 5.5% by mass.
The charge ratio of dimethyldiallylammonium chloride, which is a monomer, and acrylamide is about 1: 1.
(citric acid)
Citric acid (manufactured by Fuso Chemical Industry Co., Ltd.) based on the makeup base was used. The raw material source of this raw material is a vegetable raw material such as millet.
(Yellow 203)
Quinoline yellow WS-G (manufactured by Chuo Gosei Chemical Co., Ltd.) was employed.
(Green No. 3)
A product made by Kasei Chemical Co., Ltd. was adopted.
(Red 106)
A product made by Kasei Chemical Co., Ltd. was adopted.
(glycine)
Aminoacetic acid (manufactured by Hamari Pharmaceutical Co., Ltd.) was employed. Conforms to Jingyuan
(Cetanol)
NAA-44 (manufactured by NOF Corporation) was employed. Conforms to Jingyuan
(Behenyl alcohol)
Lanette 22 (manufactured by Cognis Japan) was employed. Conforms to Jingyuan
(Oleyl alcohol)
HD-oithanol (manufactured by Cognis Japan) was employed. Conforms to Jingyuan
(oleic acid)
NAA-180 (manufactured by NOF Corporation) was employed. Conforms to Jingyuan
(Isostearic acid)
Isostearic acid EX (manufactured by Higher Alcohol Industry) was employed. Conforms to Jingyuan
(Vaseline)
White petrolatum (Penreco) was used. Complies with the Japanese Pharmacopoeia.
(Squalane)
Squalane (manufactured by Kishimoto Special Liver Oil Industry) was used. Conforms to Jingyuan
(Candelilla Row)
Refined candelilla wax (manufactured by Yokoseki Yushi Kogyo Co., Ltd.) was employed. Conforms to Jingyuan
(Arginine)
L-arginine (manufactured by Ajinomoto Co., Inc.) was employed. Conforms to Jingyuan
(Cysteine)
L-cysteine (manufactured by Kyowa Hakko Kogyo Co., Ltd.) was employed. Conforms to Jingyuan
(Polyoxypropylene glyceryl ether)
Uniol TG-700 (manufactured by NOF Corporation) was employed. Conforms to the makeup regulations.
(phosphoric acid)
Phosphoric acid (manufactured by Junsei Kagaku) was used. Conforms to Jingyuan
(Dihydroxybenzophenone)
Yubinar 400 (manufactured by BASF Japan) was adopted. Conforms to the makeup regulations.
(Propylparapen)
Propylparapen (manufactured by Midori Kagaku) was employed. Conforms to Jingyuan
(Methylparapen)
Methyl parapen (manufactured by Midori Kagaku) was adopted. Conforms to Jingyuan
(Phenoxyethanol)
Phenoxyethanol-S (manufactured by Yokkaichi Gosei Co., Ltd.) was employed. Conforms to Jingyuan
(Tetrasodium edetate)
Kyrest 2D (manufactured by Kyrest) was adopted. Conforms to Jingyuan
(Triethanolamine)
Triethanolamine (Mitsui Toatsu Chemical Co., Ltd.) was employed. Conforms to Jingyuan
(Carboxyvinyl polymer)
Carpopol 941 (manufactured by BFGoodrich Kalama Inc.) was employed. Conforms to Jingyuan
(Xanthan gum)
Aquagel VS-500 (manufactured by Nitta Gelatin Co.) was employed. Conforms to the makeup regulations.
(Fragrance)
The fragrance | flavors A, C, D, and E employ | adopted the fragrance | flavors A, C, D, and E of Tables 5-10 of Unexamined-Japanese-Patent No. 2003-89620, respectively.

Industrial Applicability When the hair cosmetic composition of the present invention is used, for example, as a shampoo composition, hair makeup in which cationized cellulose or cationized guar gum, which is a resin component conventionally incorporated in shampoos, is combined with silicone. Since the effect of adsorbing silicone on the hair is higher than that of the preparation, even when only the shampoo is used, the finger of the hair at the time of rinsing is good and the hair feel after drying is excellent.
Further, by adding a cationic surfactant as the component (e) or an aromatic carboxylic acid or a salt thereof as the component (f) to the hair cosmetic, a product having an enhanced conditioning effect can be obtained.

Claims (6)

Anionic surfactant (a) 0.1 to 40% by mass, a vinyl monomer (A) having a hydroxyl group and an amide bond represented by formula (1), and a cationic property represented by formula (2) Water-soluble resin (b) having a structure corresponding to a copolymer of a monomer mixture containing a vinyl monomer (B) having a group, 0.01 to 5.0% by mass, nonionic and / or Or hair cosmetics containing amphoteric surfactant (c) 0.1-10 mass%.
Formula (1)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group. A represents an integer of 1 to 4)
Formula (2)

(Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 24 carbon atoms, an aryl group or an aralkyl group, and R ⁶ represents a hydrogen atom, carbon Represents an alkyl group having 1 to 24 atoms, an aryl group or an aralkyl group, or CH ₂ —CH (OH) —CH ₂ —N ⁺ R ⁷ R ⁸ R ⁹ • Y ⁻ , wherein R ^{7 to} R ⁹ are each independently an alkyl group having a carbon number of 1 to 24, .X represents an aryl group or an aralkyl group ^- and Y ^- is, each .c .b independently represent a anions represents 0 or 1 is an integer of from 1 to 10 To express.) A silicone compound (d) 0.1 to 5.0 The hair cosmetic according to claim 1 comprising by weight%. Furthermore, it contains 0.01 to 5.0% by mass of a cationic surfactant (e) and / or an aromatic carboxylic acid represented by the formula (12) or a salt thereof (f) of 0.01 to 10% by mass. The hair cosmetic composition according to claim 1 or 2.

(Wherein R ¹⁰ , R ¹¹ and R ¹² each represent an alkyl group having 1 to 3 carbon atoms, a hydroxyl group or a hydrogen atom, and A ¹ represents a carboxyl group or a salt thereof) The hair cosmetic according to any one of claims 1 to 3 , wherein the pH of the hair cosmetic is in the range of 3.0 to 6.5. The hair cosmetic composition according to any one of claims 1 to 4 , which is used for damaged hair that has been colored. The aromatic carboxylic acid represented by the formula (12) or a salt thereof (f) is at least one member selected from the group consisting of benzoic acid or salicylic acid and alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts thereof. The hair cosmetic according to any one of claims 3 to 5 .