KR101104659B1 - Hair cosmetic material - Google Patents

Abstract

Provided are hair cosmetics having a good conditioning effect, in particular hair cosmetics which are effective in providing good bubbling, imparting good finger passability when rinsing, and allowing the hair to have a good feel after drying. Corresponds to the copolymer of a monomer mixture containing 0.1 to 40% by mass of anionic surfactant (a), a vinyl monomer (A) having a hydroxyl group and an amido bond, and a vinyl monomer (B) having a cationic group Hair cosmetics containing 0.01-5.0 mass% of water-soluble resin (b) which has a structure to make, and 0.1-10 mass% of nonionic and / or zwitterionic surfactant (c).

Description

Hair cosmetics {HAIR COSMETIC MATERIAL}

TECHNICAL FIELD This invention relates to the hair cosmetics, and relates to the hair cosmetics which provide favorable conditioning effects, such as the favorable finger passing property at the time of rinsing, the smoothness after drying, and the flicker after drying.

Various attempts have been made to increase the conditioning effect of hair cosmetics such as shampoos. Typically, methods of adding cationized cellulose or cationized guar gum to hair cosmetics, and methods of adding silicone compounds thereto, are known. Shampoo compositions (JP-A 7-277931) containing, for example, fine particulate silicone and cationized cellulose ether derivatives; Shampoo compositions (JP-A 4-234309) comprising a combination of a high-viscosity silicone emulsion having a specific particle size and a cationic derivative of guar gum; Cosmetic compositions comprising siloxane gums or amino group-containing silicones and cationic derivatives or cellulose ethers of guar gum (JP-A 5-194142); Shampoo compositions containing a cationic derivative of guar gum having a specific charge density, and water insoluble nonvolatile silicone (JP-A 4-364111); And shampoo compositions (JP-A 4-36226) containing cationic derivatives of guar gum and insoluble and nonvolatile silicones having a specific average particle size. However, their conditioning effects are not sufficient and are particularly unsatisfactory for consumers whose hair is damaged by dyeing. One reason for this is that during the shampoo cleaning the hair hardly absorbs the conditioning component, silicone, in particular it is said that it stands out for hair damaged by dyeing.

Summary of the Invention

The present invention has been made to solve the above-mentioned problems, to impart good finger passability of hair cosmetics, in particular, good bubbling and rinsing hair with excellent conditioning effect, and shampoo washed hair has a good feel after drying To provide a hair cosmetic to have. When a woman washes the hair with a shampoo, the conditioner (or rinse or treatment) is often used for the purpose of preventing the shampoo washed hair from becoming too dry or matted after shampoo cleaning to remove dirt from the hair. do. However, only shampoo can be used if the shampoo cleaning time is limited or if you want to shorten the time because you bathe the child. The present invention is to provide a hair cosmetic having a conditioning effect that can improve the hair condition even when only shampoo is used.

The inventors have continually studied in view of the above-mentioned problems, and as a result, when the resin (b) of the component and the surfactant (c) of the component are added to the component (a), the conditioning component silicone has good absorption to the hair. It has been found to be capable and provide mild hair cosmetics to the scalp. Specifically, the present invention is achieved by the following method.

(1) air of a monomer mixture containing 0.1 to 40% by mass of anionic surfactant (a), a vinyl monomer (A) having a hydroxyl group and an amido bond, and a vinyl monomer (B) having a cationic group A hair cosmetic comprising 0.01 to 5.0 mass% of a water-soluble resin (b) having a structure corresponding to the coalescence, and 0.1 to 10 mass% of a nonionic and / or zwitterionic surfactant (c).

(2) The vinyl monomer (A) having a hydroxyl group and an amido bond is represented by the following general formula (1), and the vinyl monomer (B) having a cationic group is represented by the following general formula (2) (1), hair cosmetics:

(Wherein R ¹ represents a hydrogen atom or a methyl group; R ² represents a hydrogen atom or an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms; a represents an integer of 1 to 4),

Wherein R ³ represents a hydrogen atom or a methyl group; R ⁴ and R ⁵ each independently represent an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms; R ⁶ represents a hydrogen atom, of 1 to 24 alkyl having a carbon atom, an aryl or an aralkyl group, or a _{CH 2 -CH (OH) -CH 2} -N + R 7 R 8 R 9 · Y - represents; of R ⁷ to R ⁹ are each independently from 1 to 24 An alkyl, aryl or aralkyl group having a carbon atom; X ^- and Y ^- each independently represent an anion; b represents 0 or 1; c represents an integer from 1 to 10).

(3) The hair cosmetic according to the above (1) or (2), which further contains 0.1 to 5.0% by mass of the silicone compound (d).

(4) Said (1) which further contains 0.01-5.0 mass% of cationic surfactant (e) and / or 0.01-10 mass% of aromatic carboxylic acid or its salt (f) of following General formula (12) Hair cosmetic according to any one of (3):

(Wherein R ¹⁰ , R ¹¹ and R ¹² each represent an alkyl group, a hydroxyl group, or a hydrogen atom having 1 to 3 carbon atoms; 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 is 3.0 to 6.5.

(6) The hair cosmetic according to any one of the above (1) to (5), which is used for dyed hair and damaged hair.

(7) The above (4) to (4), wherein the aromatic carboxylic acid of formula (12) or a salt (f) thereof is at least one selected from the group consisting of benzoic acid or salicylic acid and their alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts; 6) hair cosmetic in any one.

The invention will be described in detail below. In the present specification, a number range represented by the term "number to another number" means a range corresponding between a front number indicating a minimum of a range and a rear number indicating a maximum of a range. Unless indicated otherwise specifically, the concentrations mentioned herein are concentrations at 25 ° C.

Dyed hair and damaged hair of the present invention means hair dyed brown or black using, for example, a hair dye or a bleaching agent.

Hair cosmetics of the present invention include, for example, shampoos, conditioners, hair waxes, and liquid or foam hair-styling agents.

(a) Anionic Surfactants:

Component (a) is preferably α-olefinsulfonate, polyoxyethylene alkenyl ether sulfate, or polyoxyethylene alkyl ether sulfate.

The alkyl group in the polyoxyethylene alkyl ether sulfate is preferably octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group or octadecyl It is a practical skill.

Alkenyl groups in the polyoxyethylene alkenyl ether sulfate are preferably octenyl, nonenyl, decenyl, dodecenyl, undecenyl, tridecenyl, tetradecenyl, pentadecenyl, and hexade A senyl group, a heptadecenyl group, or an octadecenyl group. The average number of added ethylene oxide moles in polyoxyethylene alkyl ether sulfuric acid and polyoxyethylene alkenyl ether sulfate is preferably 1 to 5, more preferably 2 to 3.

Also preferably, the α-olefinsulfonate has 10 to 18 carbon atoms, more preferably 12 to 16 carbon atoms. Even more preferably, tetradecenesulfonate having 14 carbon atoms is used.

Counter ions among them include alkali metal salts (e.g. sodium salts, potassium salts), alkaline earth metal salts (e.g. magnesium salts), ammonium salts, alkanolamine salts (e.g. triethanolamines, diethanolamines, monoethanolamines, triisopropanolamines) This includes.

The anionic surfactant is in the amount of 0.1-40 mass%, more preferably 0.3-30 mass% of the total composition of the material in the hair cosmetic (eg hair conditioner, hair treatment, hair wax). If less than 0.1% by mass, the effect is insufficient; If it is more than 40% by mass, the viscosity of the material may increase greatly, making it difficult to operate.

In particular, when the hair cosmetic is used as a shampoo, the content of the anionic surfactant therein is preferably 5 to 40% by mass, more preferably 10 to 30, of the total composition of the material in view of washing ability and foaming ability. Mass%.

When the hair cosmetic is used as a composition for a hair conditioner, hair treatment or hair wax, but not a shampoo, the content of the anionic surfactant therein is preferably 0.1 to 2% by mass of the total composition of the material in view of its effect. More preferably, it is 0.3-0.8 mass%.

Two or more different types of anionic surfactants can be combined for use herein, in which case the above-mentioned content means the total amount of the anionic surfactant combined.

Water Soluble Resin (b):

Component (b) has a structure corresponding to a copolymer of a monomer mixture containing a vinyl monomer (A) having a hydroxyl group and an amido bond and a vinyl monomer (B) having a cationic group. The vinyl monomer (A) having a hydroxyl group and an amido bond is preferably a hydroxyalkyl (meth) acrylamide-type monomer of the following general formula (1). "(Meth) acryl" as referred to herein means acryl and methacryl.

(Wherein R ¹ represents a hydrogen atom or a methyl group; R ² represents a hydrogen atom or an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms; a represents an integer of 1 to 4).

R ¹ is preferably a hydrogen atom. R ² is preferably a hydrogen atom. a is preferably 2.

Vinyl monomers (A) of the general formula (1) having a hydroxyl group and an amido bond include N-hydroxyalkyl (meth) acrylamides, for example N-hydroxyethyl (meth) acrylamide, N-hydroxy Oxypropyl (meth) acrylamide, N, N-dihydroxyethyl (meth) acrylamide. Among them, the solubility in water is high, and the solubility in water of the polymer obtained therefrom is also high, so that N-hydroxyethyl (meth) acrylamide is preferable.

Preferably, the content of the structural unit corresponding to the vinyl monomer (A) having a hydroxyl group and an amido bond in the copolymer is 20 to 90 mass%, more preferably 30 to 80 mass%, even more preferably Is 40 to 70 mass%. It is believed that the structural units corresponding to vinyl-based monomers (A) having hydroxyl groups and amido bonds can increase their ability to be absorbed by the hair due to the action of hydrogen bonds derived from their amido bond moieties.

In general, when the anionic surfactant is in the hair cosmetic, the anionic surfactant and the water-soluble resin in the material may form a complex, and when the hair cosmetic is applied to the hair or while the hair is shampooed or rinsed with it, It is believed that the complex can precipitate or adsorb to the hair. However, in the hair cosmetic of the present invention, the structural unit corresponding to the vinyl monomer (B) having a cationic group in the copolymer to the water-soluble resin (b) forms a complex with the anionic surfactant present in the material. It is believed that the copolymer can still maintain its solubility in water due to the hydrophilic nature of the structural unit corresponding to the vinyl monomer (A) having hydroxyl groups and amido bonds in the resin.

When the content of the structural unit corresponding to the vinyl monomer (A) having a hydroxyl group and an amido bond in the copolymer is 20% by mass or more, the ability of the hair cosmetic absorbed by the hair can be maintained better, In addition, its ability to maintain the smoothness and crackling after drying is further improved. If it is 90 mass% or less, the content of the structural unit corresponding to the vinylic monomer having a cationic group will be sufficient, so that the resin can form a good complex with anionic surfactant, and the ability to absorb and rinse the hair cosmetic against hair It may be more effective to improve the smoothness of the hair during.

Examples of vinyl monomers having cationic groups (B) include diallyl-type quaternary ammonium salts, for example N, N-dimethyl-N, N-diallylammonium chloride; (Meth) acrylic ester-type quaternary ammonium salts such as N-methacryloyloxyethyl-N, N, N-trimethylammonium chloride; (Meth) acrylamide-type quaternary ammonium salts such as N-methacryloylaminopropyl-N, N, N-trimethylammonium chloride; And amino acid-type cationic species such as L-arginine and glycidyl methacrylate. Among these, more preferable are (meth) acrylic quaternary ammonium salt monomers. In particular, more preferred are (meth) acrylic quaternary ammonium salt monomers of the formula (2):

Wherein R ³ represents a hydrogen atom or a methyl group; R ⁴ and R ⁵ each independently represent an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms; R ⁶ represents a hydrogen atom, of 1 to 24 alkyl having a carbon atom, an aryl or an aralkyl group, or a _{CH 2 -CH (OH) -CH 2} -N + R 7 R 8 R 9 · Y - represents; of R ⁷ to R ⁹ are each independently from 1 to 24 An alkyl, aryl or aralkyl group having a carbon atom; X ^- and Y ^- each independently represent an anion; b represents 0 or 1; c represents an integer from 1 to 10).

Preferably, R ³ is a methyl group. Preferably, R ⁴ and R ⁵ are independently methyl groups. Preferably, R ⁶ is an alkyl or aralkyl group having 1 to 24 carbon atoms, more preferably a methyl group. Preferably, R ⁷ to R ⁹ are independently a methyl group. Preferably, the anions for X ^- and Y ^- are independently chloride ions or bromide ions, more preferably chloride ions. Preferably, b is 1; Preferably c is 2.

Some examples of vinyl monomers having a cationic group of the above formula (2) are mentioned. These are (meth) acrylic esters having a cationic group, for example N- (meth) acryloyloxyethyl-N, N, N-trimethylammonium chloride, N- (meth) acryloyloxyethyl-N-ethyl- N, N-dimethylammonium = monoethyl sulfate salt, N- (meth) acryloyloxyethyl-N, N, N-triethylammonium = monoethyl sulfate salt, N- [3- {N '-( Meth) acryloyloxyethyl-N ', N'-dimethylammonium} -2-hydroxypropyl] -N, N, N-trimethylammonium chloride, N- [3- {N'-(meth) acryloyl Oxyethyl-N ', N'-diethylammonium} -2-hydroxypropyl] -N, N, N-triethylammonium chloride; And (meth) acrylamides having cationic groups, for example N- (meth) acryloylaminopropyl-N, N, N-trimethylammonium chloride, N- (meth) acryloylaminopropyl-N-ethyl- N, N-dimethylammonium = monoethyl sulfate salt, N- (meth) acryloylaminopropyl-N, N-diethyl-N-methylammonium chloride, N- (meth) acryloylaminopropyl-N, N-dimethyl-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'-diethylammonium} -2-hydroxypropyl] -N, N, N -Trimethylammonium chloride.

Among these, preferred are N- (meth) acryloyloxyethyl-N, N, N-trimethylammonium chloride, N- (meth) acryloylaminopropyl-N, N, N-trimethylammonium chloride; More preferred is N- (meth) acryloylaminopropyl-N, N, N-trimethylammonium chloride.

The structure corresponding to the copolymer of the vinyl monomer (B) having a cationic group is, for example, copolymerized with a vinyl monomer precursor having a cationic group of the following general formula (3) and then reacted with the cationic agent. By making the structure have a corresponding cationic group.

(Wherein R ³ to R ⁵ , b and c have the same meaning as in the above formula (2), and the preferred range thereof is the same as mentioned above).

Cationic vinyl monomer precursors include, for example, (meth) acrylates with tertiary amines, for example N- (meth) acryloyloxyethyl-N, N-dimethylamine, N- (meth) acryloyl Oxyethyl-N, N-diethylamine; And (meth) acrylamides with tertiary amines such as N- (meth) acryloylaminopropyl-N, N-dimethylamine, N- (meth) acryloylaminopropyl-N, N-diethyl Amines are included.

Cationic agents include alkyl halides such as methyl chloride; And cationic agents having cationic groups such as 3-chloro-2-hydroxypropyl-N, N, N-trimethylammonium chloride. Cationization can be achieved, for example, by adding a cationic agent to a solution of the polymer and reacting them at 20-100 ° C. for 1-20 hours.

One or more different types of cationic vinyl monomers or precursors thereof may be used herein alone or in combination.

Preferably, the content of the structural unit corresponding to the vinyl monomer (B) having a cationic group in the copolymer is 10 to 80 mass%, more preferably 20 to 70 mass%, even more preferably 30 to 60 mass % to be. The structural unit corresponding to the vinyl monomer (B) having a cationic group can form a complex with the anionic surfactant in the composition of the present invention, making the copolymer more adsorbed to the hair. When the content of the structural unit corresponding to the vinyl monomer having a cationic group (B) is 10% by mass or more, a satisfactory complex with the anionic surfactant may be formed, for example, the hair cosmetic may be shampoo washed during rinsing. It may be more effective to keep the hair smooth. When the content is 40 mass% or less, the ability of the hair cosmetic to be absorbed by the hair can be maintained better, and furthermore, its ability to maintain the smoothness and the luster of the dried hair is further improved.

The copolymer may further contain structural units derived from any other vinylic monomers. However, when the copolymer has an anionic functional group, it may interfere with the formation of the above-mentioned complex with an anionic surfactant. Therefore, it is desirable that the content of such anionic functional groups in the copolymer be as small as possible (eg, 10% or less of all functional groups in the copolymer). More preferably, the copolymer is substantially free of groups. The term "substantially free of groups" as referred to herein may mean less than 1% of the content of groups. Optional other vinylic monomers include esters of (meth) acrylic acid and alcohols having 1 to 22 carbon atoms; Amides of (meth) acrylic acid and alkylamines having 1 to 22 carbon atoms; Monoesters of ethylene glycol or 1,3-propylene glycol with (meth) acrylic acid; Esters derived from monoesters by esterification of their hydroxyl groups with methanol or ethanol; Nonionic monomers such as (meth) acryloylmorpholine; Zwitterionic monomers such as (meth) acrylic esters having betaine groups, (meth) acrylamides having betaine groups; Semi-polar monomers such as (meth) acrylic esters with amine oxide groups, (meth) acrylamides with amine oxide groups.

The content of the structural unit derived from other vinylic monomers may be suitably defined as a range within the scope and spirit of the present invention. For example, it can be suitably defined in consideration of the solubility of the water-soluble resin and the conditioning effect of the hair cosmetic. Preferably, the content of other vinyl copolymer is 30 mass% or less.

The content of the structural unit corresponding to the vinyl monomer (A) having a hydroxyl group and an amido bond in the copolymer, the content of the structural unit corresponding to the vinyl monomer (B) having a cationic group and the additional vinyl monomer The content of the corresponding structural unit is determined via IR absorption at the hydroxyl or amido binding site, or ¹ H-NMR of the methyl group adjacent to the hydroxyl or amido binding site or cationic group, or ¹³ C-NMR thereof. It can be measured.

Preferably, the water-soluble resin for use in the present invention may form an aqueous solution having a concentration of at least 5 mass% at room temperature or at a temperature of 25 ° C., and transmittance (550 nm) of an aqueous solution having a concentration of 5 mass%. Is 80% or more, and the aqueous solution is uniform and stable. More preferably, the resin can form an aqueous solution having a concentration of at least 10 mass%.

Water-soluble resins for use in the present invention are, for example, by mixing monomers or precursors capable of providing the corresponding structural units, copolymerizing them in the manner of solution polymerization, suspension polymerization or emulsion polymerization and optionally resulting copolymers. Can be prepared by cationization.

Preferably, the polymerization is accomplished in a hydrophilic solvent. Hydrophilic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; Alcohol solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol; And water. One or more of the above may be used herein alone or in combination. Preferred are alcohol solvents or water.

Polymerization initiators usable herein include azo compounds, such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azo Bis (1-cyclohexanecarbonitrile), 2,2'-azobis (2-methyl-N- (2-hydroxyethyl) -propionamide), 2,2'-azobis (2-amidinopropane) Dihydrochloride; Peroxides such as benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide; Persulfate; And their redox-type agents, without being particularly limited. Preferably, the amount of polymerization initiator used is from 0.01 to 5% by mass of all monomers.

The polymerization can be achieved in an inert gas atmosphere, for example nitrogen or argon, preferably at 30 to 120 ° C., more preferably at 40 to 100 ° C. for 1 to 30 hours. After polymerization, the copolymer formed can be isolated from the reaction solution in any way, preferably through solvent evaporation or addition of poor solvents. Copolymers can be used in the preparation of the compositions of the invention, either directly or after further purification. Purification can be accomplished by any method of reprecipitation, solvent washing or membrane separation, or a combination of methods.

The weight-average molecular weight of the water-soluble resin for use in the present invention is preferably 5,000 to 5,000,000, more preferably 10,000 to 2,000,000, even more preferably 20,000 to 1,000,000. When the weight-average molecular weight is 5,000 or more, the feeling at rinsing is not bad, and the conditioning effect of the composition can be maintained better. If it is 5,000,000 or less, the composition has a suitable viscosity and its handling capability at the time of manufacture may be better. The weight-average molecular weight of the copolymer can be measured via gel permeation chromatography (eg, using water / methanol / acetic acid / sodium acetate as the developing solvent).

Except for the water-soluble resin (b), the water-soluble polymer (b-1) usable herein includes methyl cellulose and hydroxymethyl cellulose. Cationic polymers including cationic modified cellulose ether derivatives, polydimethyldiallylammonium halides, dimethyldiallylammonium halide / acrylamide copolymers; Anionic polymers including acrylic acid derivatives (polyacrylic acid and salts thereof, acrylic acid / acrylamide / ethyl acrylate copolymers and salts thereof), methacrylic acid derivatives and crotonic acid derivatives; B, including acrylic acid derivatives (hydroxyethyl acrylate / methoxyethyl acrylate copolymer, polyacrylamide), vinylpyrrolidone derivatives (e.g., polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer) Soluble polymers; And zwitterionic polymers including dimethyldiallylammonium chloride derivatives (eg, acrylamide / acrylic acid / dimethyldiallylammonium chloride copolymers, acrylic acid / dimethyldiallylammonium chloride copolymers) are also usable herein. Their content in the hair cosmetic can be 0.01 to 0.1 mass%.

(c) nonionic and / or zwitterionic surfactants:

Preferably, the nonionic and / or zwitterionic surfactants of component (c) are represented by any of the following formulas (4) to (9):

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

Nonionic or zwitterionic surfactants act to mitigate the action of the composition on the skin, preventing the skin from being roughened by the composition, and enhance the bubbling ability of the composition. One or more such surfactants may be alone or in combination in the composition. The content of the surfactant in the hair cosmetic of the present invention is 0.1 to 10% by mass, preferably 1 to 5% by mass. If the content is less than 0.1% by mass, the surfactant may be insufficient in effect; If it is more than 10% by mass, the viscosity of the composition may increase greatly or its solution stability may deteriorate.

(d) silicone compounds:

The silicone compound for component (d) is not particularly limited in terms of its type, and any of those generally used in conventional hair cosmetics can be used herein. For example, this includes dimethylpolysiloxanes (including high-polymer dimethylpolysiloxanes, silicone rubbers), methylphenylpolysiloxanes, polyether-modified silicones, polyamino-modified silicones, betaine-modified silicones, alcohol-modified Silicone, fluorine-modified silicone, epoxy-modified silicone, mercapto-modified silicone, carboxy-modified silicone, fatty acid-modified silicone, silicone graft polymer, cyclic silicone, alkyl-modified silicone, trimethylsilyl Group-terminated dimethylpolysiloxanes, silanol group-terminated dimethylpolysiloxanes. One or more of the above may be used herein alone or in combination. Of these, particularly preferred are dimethylpolysiloxanes, polyether-modified silicones, polyamino-modified silicones.

The content of silicone compound in the composition may be 0.1 to 5.0 mass%, preferably 0.3 to 3.0 mass% of all the components of the composition. If less than 0.1% by mass, the compound may not be effective; If it is more than 5.0 mass%, the silicon may be difficult to disperse and stabilize in the product.

Although not specifically limited, the viscosity of the silicone compound at 25 ° C is preferably 0.0001 to 2,000 m ² / S, more preferably 0.003 to 1,000 m ² / S. For example, a silicone compound having a viscosity of 200 to 1,200 m ² / S and having a large molecular weight can be combined with a low-viscosity silicone compound having a viscosity of 0.0001 to 0.2 m ² / S to prepare a manageable mixture. This is preferred in the present invention.

If desired, the silicone compound can be emulsified with the surfactant and the resulting emulsion can also be used herein. Regarding the emulsion, the emulsifier and the emulsification method are not particularly limited, and various methods can be used herein.

The viscosity of the silicone compound can be measured using a Brookfield viscometer for the general test method against Japanese cosmetic raw material standards.

The composition may contain any other oil, such as higher alcohols, olive oil, jojoba oil, liquid paraffin, fatty acid alkyl ester oils, and the like.

The composition may further contain fatty acid ethylene glycol as the pulping agent and polystyrene emulsion as the suspending agent.

(e) Cationic Surfactants:

The cationic surfactant for component (e) is not particularly limited, without departing from the scope and spirit of the invention. Preferably, it is a quaternary tetraalkylammonium salt, a surfactant of the guanidine derivative of formula (10) or a salt thereof, an amino acid-type cationic surfactant, or an amideamine-type surfactant. More preferably it is a quaternary tetraalkylammonium salt.

Quaternary tetraalkylammonium salts are preferably used as cationic surfactants. Specifically, this includes stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, behenyltrimethylammonium chlorine, cetostearyltrimethylammonium chloride, distearyldimethylammonium chloride, dibehenyldimethylammonium chloride. Among the above, preferred are those having a linear alkyl group having 16 to 22 carbon atoms. Specifically, more preferred are cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chlorine, and distearyldimethylammonium chloride; Even more preferred are stearyltrimethylammonium chloride, and behenyltrimethylammonium chlorine. Preferably, the cationic surfactant is in the form of its hydrochloride or bromate.

Guanidine derivatives of formula (10) below or salts thereof are also preferably used as cationic surfactants.

(Wherein R ¹⁰¹ represents a straight or branched chain alkyl or alkenyl group having 1 to 21 carbon atoms; A represents a straight or branched chain alkylene or alkenylene group having 1 to 10 carbon atoms; t is Represents an integer of 1 to 5; when t is 2 or more, A 'in each block may be the same or different.

In the formula (10), R ¹⁰¹ is preferably a straight or branched chain alkyl or alkenyl group having 11 to 19 carbon atoms. For example, preferred examples thereof include 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- .

Substituent A is preferably a straight or branched chain alkylene or alkenylene group having 2 to 6 carbon atoms. For example, this includes methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, isopropylene group, 2-pentenylene group, and 2-ethylbutylene group.

Preferably, the guanidine derivative of formula (10) is added to the composition in the form of a salt thereof, and salts include inorganic salts such as hydrochloride, bromate, sulfate, phosphate; Organic acid salts such as glycolate, acetate, lactate, succinate, tartrate, citrate, acidic amino acid salts, higher fatty acid salts, pyroglutamic acid salts, p-toluenesulfonate. Among these, preferred forms are hydrochloride, bromate, acetate, glycolate, citrate and acidic amino acid salts.

In addition, amino acid-type cationic surfactants are also preferably used herein as cationic surfactants. Amino acid-type cationic surfactants include salts of lower alkyl ester salts of mono-N-long chain acyl-basic amino acids. The basic amino acids that make up the compound can be, for example, natural amino acids such as ornithine, lysine or arginine. In addition, synthetic amino acids may also be used, for example α, γ-diaminobutyric acid. These may optionally be active compounds or racemic compounds.

Acyl groups are preferably residues of saturated or unsaturated higher fatty acids having 8 to 22 carbon atoms. It can be a natural or synthetic moiety. For example, useable herein includes sole higher fatty acid residues such as lauroyl groups, myristoyl groups, palmitoyl groups and stearoyl groups; And natural, mixed higher fatty acid residues such as coconut oil fatty acid residues or tallow higher fatty acid residues.

Lower alkyl ester components are preferably methyl esters, ethyl esters, propyl esters, butyl esters, pentyl esters, hexyl esters, heptyl esters, and octyl esters. More preferably, the lower alkyl ester component is in the form of a salt thereof. Specifically, salts of lower alkyl esters include inorganic salts such as hydrochloride, bromate, sulfate, phosphate; And organic acid salts such as glycolate, acetate, lactate, succinate, tartrate, citrate, acidic amino acid salts, higher fatty acid salts, L- or DL-pyrrolidonecarboxylate, pyroglutamate, p-toluene Sulfonates are included. Among these, preferred forms are hydrochloride, L- or DL-pyrrolidonecarboxylate, and acidic amino acid salts.

In addition, amideamine-type surfactants are also preferably used as cationic surfactants. Amideamine-type surfactants usable herein may be compounds of formula (11)

(Wherein 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; p represents an integer of 2 to 4).

Preferably, R ¹¹¹ represents a fatty acid residue having 9 to 22 carbon atoms, more preferably a fatty acid residue having 13 to 22 carbon atoms. Preferably, R ¹¹² is a methyl group or an ethyl group.

Preferred examples of the amideamine-type surfactant of the formula (11) are stearoyldiethylaminoethylamide, stearoyldimethylaminoethylamide, stearoylpalmitodiethylaminoethylamide, cocodiethylaminopropylamide, palmi Toyldimethylaminoethylamide, myristoyldiethylaminoethylamide, myristoyldimethylaminoethylamide, behenoyldiethylaminoethylamide, behenoyldimethylaminoethylamide, stearoyldiethylaminopropylamide, stearoyldimethylamino Propylamide, palmitoyldiethylaminopropylamido, palmitoyldimethylaminopropylamide, myristoyldiethylaminopropylamide, myristoyldimethylaminopropylamide, behenoyldiethylaminopropylamide, behenoyldimethylaminopropylamide . Preferably, they are added to the composition in the form of their salts. Specifically, salts include inorganic salts such as hydrochloride, bromate, sulfate, phosphate; And organic acid salts such as glycolate, acetate, lactate, succinate, tartrate, citrate, acidic amino acid salts, higher fatty acid salts, pyroglutamate, p-toluenesulfonate. Among these, more preferred forms are acidic amino acid salts, citrate and hydrochloride. One or more types of different salts may be used for neutralization, alone or in combination. Among them, preferred are stearoyldimethylaminopropylamide, stearoyldiethylaminoethyl amido and cocodiethylaminopropylamide.

In the present invention, one or more selected from the above amideamine-type surfactants can be used.

The cationic surfactant is added to the composition for the purpose of assisting the conditioning effect of the component (b) resin, and the amount thereof is preferably 0.01 to 5.0 mass%, more preferably 0.1 to 2.0 mass%. If its amount is 0.01% by mass or more, the surfactant is more effective to improve the conditioning effect; If it is 5.0 mass% or less, the surfactant can be more easily and uniformly dissolved in the anionic surfactant substrate of component (a).

(f) aromatic carboxylic acids or salts thereof:

Aromatic carboxylic acids or salts thereof of component (f) are effective at helping the conditioning effect of component (b) and, when combined with component (e), are more effective to enhance the conditioning effect.

The aromatic carboxylic acid or salt thereof of component (f) is preferably an aromatic carboxylic acid or salt thereof of formula (12):

(Wherein R ¹⁰ , R ¹¹ and R ¹² each represent an alkyl group, a hydroxyl group, or a hydrogen atom having 1 to 3 carbon atoms; A ¹ represents a carboxyl group or a salt thereof).

More preferably, it is benzoic acid, salicylic acid and salts thereof. The salts are preferably alkali metal salts (eg sodium salts, potassium salts), alkaline earth metal salts (eg magnesium salts, calcium salts, aluminum salts), ammonium salts (eg ammonium), alkanolamine salts (eg triethanolamine, di Ethanolamine, monoethanolamine, triisopropanolamine).

Preferably, the content of component (f) in all components of the composition is from 0.01 to 10 mass%, more preferably from 0.1 to 3 mass%. If the content is 0.01% by mass or more, the component is more effective to improve the conditioning effect; When it is 10 mass% or less, it can prevent more effectively that the dispersion stability of a composition deteriorates.

When used as a shampoo composition, an opaque agent can be added to the hair cosmetic. Containing such an opaque agent can have a liquid appearance rich in the composition and can be a hair cosmetic that is favorable to the defender. Although not particularly limited, the opaque agent may be any that is capable of being dispersed as a crystal or a solid in the hair cosmetic and that is capable of causing the resulting composition to have a pearly, glossy or opaque white appearance (eg, natural- Derived substances, for example fish scales, mica flakes). However, in view of qualitative stability, economic advantages and handling ability in the manufacture, chemical synthesis products are preferred. In addition, when considering dispersion stability and bubbling ability, not only the compounds of the following formulas (13) and / or (14), but also glycerin monofatty acid esters (carbons 16-24) are particularly preferred.

(Wherein R ¹³ represents an alkyl or alkenyl group having 15 to 23 carbon atoms; A ¹³ represents a fatty acid residue having 16 to 24 carbon atoms; n represents a number from 1 to 3).

One or more such opaque agents may be used herein alone or in combination. Preferably, the opaque agent content of the hair cosmetic is 1 to 10% by mass, more preferably 1 to 5% by mass. When the content is at least 1% by mass, the hair cosmetic can have a beautiful pearly luster; If it is 10 mass% or less, the hair cosmetic is more effective to ensure its dispersion stability.

In addition to the components mentioned above, the hair cosmetic of the present invention may further contain any conventional ingredients that may be present in the general hair cosmetic. For example, the hair cosmetic may optionally contain lower alcohols, such as ethanol, isopropanol, or polyalcohols such as ethylene glycol, propylene glycol, glycerin, sorbitol, polyethylene glycol, which perform as solubilizers. If necessary, hair cosmetics can be formulated as viscosity modifiers, such as carboxymethyl cellulose, hydroxyethyl cellulose, chelating agents, for example citric acid, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), fragrances, anticorrosion agents , And pH-adjusting agents.

With respect to the fragrances and fragrance compositions which can be used in the hair cosmetics of the present invention, mention is made of the fragrance components described in JP-A 2003-300811, paragraphs [0021] to [0035], and the same document, paragraphs [0050] It is a solvent for fragrances.

Preferably, the amount of perfume solvent that may be in the perfume composition is 0.1 to 99 mass%, more preferably 1 to 50 mass%.

Preferred examples of perfume stabilizers are dibutylhydroxytoluene, butylhydroxyanisole, vitamin E and its derivatives, catechin compounds, flavonoid compounds and polyphenol compounds. The content of the perfume stabilizer in the perfume composition is preferably 0.0001 to 10% by mass, more preferably 0.001 to 5% by mass. Among them, dibutylhydroxytoluene is preferred for the stabilizer.

The perfume composition is a mixture comprising a perfume component, a solvent and a perfume stabilizer.

Preferably, the hair cosmetic of the present invention contains the fragrance composition in an amount of 0.005 to 40 mass%, more preferably 0.01 to 10 mass% of all the components of the hair cosmetic.

The hair cosmetic of the present invention can be prepared by mixing and stirring the components according to known methods. In this case, from the viewpoint of its ease of preparation, component (a) is preferably used in the form of an aqueous solution of anionic surfactant previously diluted in pure water or ethanol, and the concentration is preferably 20 to 70 mass%. Also preferably, component (b) is previously dissolved in water or dispersed in a solvent such as propylene glycol and added to other components. It is also preferable that the components (c) and (e) are diluted with pure water or ethanol because they can be operated by a simple method. However, if they are solids, they can be heated and fluidized to temperatures above their melting point, and the resulting fluids can be slowly added to component (a) during preparation or with stirring to the liquid mixed with pure water. In this way, the solid component can be easily dissolved in a short time. If component (f) is soluble in water, it can be added directly to the system or after its aqueous solution is formed; If soluble in oil, it can be dissolved in perfume.

The invention is specifically described by reference in connection with the following examples. Without departing from the scope and spirit thereof, the present invention is not limited to the following examples.

<Example 1-1>

(Preparation of Copolymer (1))

Using a reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas-introducing tube and a stirrer, 300 parts by weight of distilled water, and a monomer mixture of the monomers shown in Table 1 (copolymer (1)) and 100 parts by weight of distilled water were Inject into the dropping funnel. The air in the reactor was replaced with nitrogen. The reactor was heated to 70 ° C. 0.5 parts by weight of 2,2'-azobis (2-amidinopropane) dihydrochloride was added to the reactor and the monomer mixture was added dropwise therein over 1 hour. It was added dropwise into the reactor and reacted for 4 hours, then heated to 80 ° C and further reacted for 2 hours.

The copolymer so obtained was subjected to gel permeation chromatography (device, Tosoh's SC8010, SD8022, RI8020, CO8011, PS8010; column, Wako Jun-yaku's Wakopak (Wakobeads G-50); developing solvent, water / methanol / acetic acid / sodium acetate = 6/4 / 0.3 / 0.41) to determine its weight-average molecular weight. The results are shown in Table 1.

The water solubility of the obtained copolymer was confirmed as follows: A 5 wt% aqueous solution of the copolymer was prepared at 25 ° C., and its transmittance (550 nm, 10 mm glass cell) was measured. The next criterion indicates the water solubility of the copolymer. The results are shown in Table 1.

0: 80% or more.

A: 50% to less than 80%.

x: less than 50%.

(Production of the hair cosmetic)

Copolymer (1) was used as the resin in Table 2. Shampoos containing the compositions in Table 2 were prepared. Specifically, other components except silicone oil were mixed and silicone oil was added to the resulting mixture. The shampoos thus prepared were tested for bubbling, smoothness after rinsing, flickering after drying, flexibility after drying, and silicone oil adsorption amounts according to the methods mentioned below.

Formulation % By weight as solid Suzy 0.3 Anionic Surfactants * 1 10 Lauroyl Amidopropyl Betaine 5 Silicone oil * 2 2 Marcoat550 * 3 0.5 Stearyltrimethylammonium Chloride * 4 One Distilled water Rest (total 100)

* 1 sodium polyoxyethylene (3) -lauryl ether sulfate, LES-Na (Lion)

* 2 Silicone oil emulsion BY22029 (Toray Dow Corning, concentration 50%)

* 3 Dimethyldiallylammonium halide / acrylamide copolymer (Merck)

* 4 stearyltrimethylammonium chloride, Arcard T-28 (Lion Chemical)

(Evaluation of hair cosmetics)

The hair cosmetic obtained in the above-mentioned method was evaluated according to the method mentioned below. Test results with untreated (untouched) tress are shown in Table 4; Experiments with damaged tresses are shown in Table 5.

<Examples 1-2 to 1-9>

(Preparation of Copolymers (2) to (9))

The copolymers (2) to (9) were produced in the same manner as the preparation of the copolymer (1), except that the monomer compositions (copolymers (2) to (9)) shown in Table 1 were used. Table 1 shows the weight average molecular weight of the obtained copolymer.

(Manufacture and Evaluation of Hair Cosmetics)

Hair cosmetics were prepared and evaluated in the same manner as in Example 1-1. The evaluation results are shown in Table 3 and Table 4.

<Example 1-10>

(Preparation of Copolymer (10))

Using the monomer composition (copolymer (10)) shown in Table 1, except that the amount of distilled water introduced into the reactor in the initial stage was changed to 500 parts by weight, the copolymer ( 10) was prepared.

Table 1 shows the weight average molecular weight of the obtained copolymer.

(Manufacture and Evaluation of Hair Cosmetics)

Hair cosmetics were prepared and evaluated in the same manner as in Example 1-1. The evaluation results are shown in Table 3 and Table 4.

<Comparative Example 1-1>

(Preparation of Copolymer 11)

Except having used the monomer composition (copolymer (11)) of Table 1, the copolymer (11) was manufactured in the same manner as the manufacture of the copolymer (1). Table 1 shows the weight average molecular weight of the obtained copolymer.

(Manufacture and Evaluation of Hair Cosmetics)

Hair cosmetics were prepared and evaluated in the same manner as in Example 1-1. The evaluation results are shown in Table 3 and Table 4.

<Comparative Example 1-2>

(Preparation of Copolymer 12)

Preparation of copolymer (1) except using the monomer composition (copolymer (12)) of Table 1, using ethanol as a solvent, and using dimethyl-2,2'- azobisisobutyrate as a polymerization initiator. Copolymer 12 was prepared in the same manner as. Distilled water was added to the obtained copolymer, and ethanol was distilled off. Thus, the copolymer was in the form of its aqueous solution. Table 1 shows the weight average molecular weight of the copolymer.

(Manufacture and Evaluation of Hair Cosmetics)

Hair cosmetics were prepared and evaluated in the same manner as in Example 1-1. The evaluation results are shown in Table 3 and Table 4.

<Comparative Example 1-3>

(Manufacture and Evaluation of Hair Cosmetics)

A hair cosmetic was prepared and evaluated in the same manner as in Example 1-1 except that cationic hydroxyethyl cellulose (JR400 manufactured by Calgon) was used as the resin of Table 2. The evaluation results are shown in Table 3 and Table 4.

<Comparative Example 1-4> (Reference)

(Manufacture and Evaluation of Hair Cosmetics)

Except not adding the resin of Table 2, the hair cosmetics were manufactured and evaluated in the same manner as in Example 1-1.

<Test method>

Each hair cosmetic was applied to the tresses prepared herein and tested for the items mentioned below. For the "untreated tress" "root-trimmed human hair black hair (100%) (untreated hair 10 g x 30 cm); Viewlax" was used. The "damaged hair" was prepared by decolorizing the "untreated hair". Decolorization was as follows: 12 g of Milbon's Promatis Brave Oxitan 6.0 (6% hydrogen peroxide cream) and 6 g of Melos Chemical's Powder Bleach MR2 were mixed and the resulting mixture was applied to one tress. After standing for 30 minutes, the tress was rinsed with water. Then sodium polyoxyethylene (3) -lauroyl ether sodium sulfate was applied and rinsed further.

(1) Bubbling:

After 10 g of tress contained water in 40 ° C. flowing water, excess water was removed. 1 g of shampoo was applied to the tress. Foamed shampoo of tress. In this process, the rate of bubbling and the degree of fineness of the resulting bubbles were evaluated according to the following four steps, and the samples were scored.

+2: The sample is excellent in both the speed of bubbling and the degree of fineness of bubbles generated compared to the reference sample (no resin added).

+1: The sample is superior to either the rate of bubbling or the degree of fineness of the bubbles produced compared to the reference sample.

0: The sample is about the same as a reference sample.

-1: The sample is inferior to the reference sample.

(2) smoothness when rinsing:

After the bubbling test, the smoothness at the time of rinsing and the smoothness of the finger when passing the tress when rinsing the tress in 40 ° C. running water were tested. Samples were evaluated according to the following four steps.

+2: The sample is smoother than the reference sample, and the smoothness lasts for at least 1 minute.

+1: The sample is superior in either smoothness or smoothness sustainability as compared to the reference sample.

0: The sample is about the same as a reference sample.

-1: The sample is inferior to the reference sample.

(3) flicker after drying:

After the rinse smoothness test, the tress was dried overnight in a constant temperature room at 23 ° C. and 60% RH (relative humidity). The sample was evaluated for glazing according to the following four steps.

+2: The sample is noticeably better than the reference sample.

+1: The sample has a better luster than the reference sample.

0: The sample is about the same as a reference sample.

-1: The sample is inferior to the reference sample.

(4) flexibility after drying:

The tresses tested for fluff were further tested for flexibility after drying and evaluated according to the following four steps.

+2: The sample hardly felt stiff compared to the reference sample.

+1: The sample is less stiff than the reference sample but feels slightly.

0: The sample is about the same as a reference sample.

-1: The sample is inferior to the reference sample.

(5) Silicone oil adsorption amount:

10 g of tresses were soaked with running water at 40 ° C. for 30 seconds, and then water was removed until there was no dripping. 1 g of the shampoo to be tested was applied to the wet tress. It was then combed 100 times for 1 minute to foam. It was rinsed for 30 seconds in 40 ° C. running water and then dried overnight. After the treatment was repeated twice, the silicone oil adsorbed on the hair was extracted. The oil adsorption amount was measured by NMR (quantifying H of Si-CH ₃ by ¹ H-NMR) of the extract.

The oil extraction is as follows: the tress was sonicated by dipping in a solvent of chloroform / methanol = 4/1. The solvent was removed by drying under reduced pressure. This was dissolved in heavy chloroform, and dimethyl terephthalate was added as an internal standard to measure the concentration.

Evaluation of test results

1) In Comparative Example 1-1, N-methacryloylaminopropyl-N, N-dimethylamine oxide is used for manufacture of water-soluble resin, and does not have a hydroxyl group in the structural unit of water-soluble resin. Therefore, the amount of silicone oil adsorption to the damaged hair is low, and the dried hair does not have a flicker.

2) In Comparative Example 1-2, hydroxyethyl acrylate is used for production of the water-soluble resin, and the structural unit of the water-soluble resin does not have an amido bond. Therefore, both untreated hair and damaged hair are not good in bubbling, rinsing feel, feeling after drying, flexibility after drying, and silicon oil adsorption amount.

3) In Comparative Example 1-3, cationized hydroxyethyl cellulose having no amido bond was used as the water-soluble resin. Therefore, both untreated hair and damaged hair do not have good flexibility after drying.

4) In Comparative Example 1-4 (reference), no resin is added to the composition. Therefore, compared to the hair cosmetic of the present invention containing a water-soluble resin, both untreated hair and damaged hair are not good in bubbling, rinsing feel, feeling after drying, flexibility after drying, and silicone oil adsorption amount.

<Examples 2-1 to 2-4, and Comparative Examples 2-1 to 2-3>

The hair cosmetics set forth in Table 5 were prepared and tested according to the methods mentioned below. In Table 5, the unit is weight percent.

(Test Methods)

A panel of 10 females, 20 to 50 years old, tried the hair cosmetic for 7 days and evaluated its feel during use. Specifically, the samples were evaluated in three grades, good, average and bad. The final evaluation of the sample is as follows:

00: 8 to 10 of the 10 panels said they were good.

O: Five to seven of the ten panels said they were good.

A: Three or four out of ten panels said they were good.

x: 0 to 2 of 10 panels said they were good.

As in the table above, female panels said that the shampoos of Examples 2-1 to 2-4 were all good.

<Example 2-5>

The hair cosmetic of Example 2-1 was filled in the following container, stored in a temperature-controlled tank for 1 month at 40 ° C and -5 ° C, and then left in the air at 22-27 ° C for 3 days. The appearance of the hair cosmetic thus stored was evaluated. Specifically, the stored sample was transferred to an experimental dish and its appearance was checked. As a result, in all samples stored in different containers at different temperatures, no layer separation, noticeable fading and changes in impurities such as crystals were observed.

<Bottle container>

(1) bottle body material PP; Lid material PP

(2) bottle body material HDPE; Lid material PP

(3) bottle body material PET; Lid material PP

(4) bottle body material PP / HDPE; Lid material PP

<Pump type container>

(5) bottle body material PP; Dispenser material PP, PE and SUS304

(6) bottle body material HDPE; Dispenser material PP, PE and SUS304

(7) bottle body material PET; Dispenser material PP, PE and SUS304

(8) bottle body material PP / HDPE; Dispenser material PP, PE and SUS304

<Pouch container>

(9) Material, aluminum-deposited polyethylene pouch

PE is polyethylene; PP is polypropylene; PET is polyethylene terephthalate; HDPE is a high density polyethylene.

<Example 3>

Hair Conditioner Composition:

The hair conditioner composition of Table 6 was prepared. After shampoo cleaning with the shampoo composition shown below, the hair was treated with the hair conditioner composition of Table 6 and then rinsed with warm water. It was dried with a towel and then further dried with a dryer to check the texture of the hair treated with the conditioner. The texture evaluation is the same as in Example 1.

ingredient Volume (mass%) 4-guanidinobutylaluramide 0.8 Stearyltrimethylammonium Chloride 0.1 Dimethylsilicone (viscosity 100 m ² / S) 1.0 Dimethylsilicone (viscosity 10 m ² / S) 1.0 Dimethylsilicone (viscosity 0.005 m ² / S) 1.0 Copolymer (2) 0.3 Glycine 0.7 Setanol 1.5 Behenyl alcohol 0.2 Oleyl alcohol 0.3 Oleic acid 0.2 Isostearic acid 0.2 Arginine 0.3 Cysteine 0.3 Sorbitan monolaurate 0.1 POE-Sodium Alkyl Ether Sulfate 0.3 Lauryl Amidopropylbetaine 0.2 Benzoic acid 0.2 Phosphoric Acid Arbitrarily (pH = 3.4) Spice A 0.9 Pure water Remainder

* The amount of each ingredient is based on the pure content.

Shampoo compositions were used to evaluate in Example 3 (amounts relative to pure content (mass%)):

10% by mass of POE-sodium alkyl ether sulfate

Sodium tetradecenesulfonate 1% by mass

4% by weight of lauryl amidopropyl betaine

2% by mass of POE (2) -lauryl monoethanolamide

Dimethyldiallylammonium chloride / acrylamide copolymer 0.5 mass%

Citric acid arbitrarily (pH = 5.2)

Sodium benzoate 1.1 mass%

Perfume A 1.0 mass%

Pure water rest

Items tested for the hair conditioner of Example 3 Test result Smoothness after drying 00 Smoothness without brittleness after drying 00 Solid texture after drying 00 Tingling after drying 00

Example 4 Hair Wax:

To prepare a hair wax of Table 8 below.

After shampoo cleaning and treatment of the shampoo composition and hair conditioner shown below, the hair was dried with a dryer, the hair wax prepared herein was applied and the texture thereof was tested. The texture evaluation is the same as in Example 1.

ingredient Volume (mass%) Stearyltrimethylammonium Chloride 0.1 Copolymer (1) 0.3 Carboxyvinyl Polymer 0.5 Xanthan gum 0.3 Methylsiloxane / Polyoxyethylene Copolymer 2.0 vaseline 3.0 Squalene 2.0 Candelina wax 1.0 Polyoxyethylene octyl dodecyl ether 0.3 Polyoxypropylene Glyceryl Ether 4.0 Dihydroxybenzophenone 0.1 Propylparaben 0.1 Methyl paraben 0.3 Phenoxyethanol 0.5 POE-Sodium Alkyl Ether Sulfate 0.2 Lauryl Amidopropylbetaine 0.2 Sodium benzoate 0.2 Tetrasodium Edetate 0.05 Triethanolamine 0.5 Spice A 0.2 Citric acid Arbitrarily (pH = 5.5) Pure water Remainder

* The amount of each ingredient is based on the pure content.

Shampoo compositions were used to evaluate in Example 4 (amounts relative to pure content):

10% by mass of POE-sodium alkyl ether sulfate

Sodium tetradecenesulfonate 1% by mass

4% by weight of lauryl amidopropyl betaine

2% by mass of POE (2) -lauryl monoethanolamide

Dimethyldiallylammonium chloride / acrylamide copolymer 0.5 mass%

Citric acid arbitrarily (pH = 5.2)

Sodium benzoate 1.1 mass%

Perfume A 1.0 mass%

Pure water rest

The hair conditioner composition was used to evaluate in Example 4 (the amount is relative to the pure content):

4-guanidinobutyl laurylamide 0.8% by mass

0.2% by mass of stearyltrimethylammonium chloride

Dimethylsilicone (viscosity 100 m ² / S) 1.0 mass%

Dimethylsilicone (viscosity 10 m ² / S) 1.0 mass%

Dimethylsilicon (viscosity 0.005 m ² / S) 1.0 mass%

Cetanol 1.5 mass%

Behenyl alcohol 0.2% by mass

Arginine 0.3 mass%

0.2% by mass of sodium benzoate

Phosphoric Acid Randomly (pH = 3.5)

Perfume A 1.0 mass%

Pure water rest

Items tested for hair wax of Example 4 Test result Smoothness after drying 00 Smoothness without brittleness after drying 00 Solid texture after drying 00 Tingling after drying 00

The materials used herein are mentioned below.

Ingredient (a):

(Polyoxyethylene (POE) -Sodium Alkyl Ether Sulfate)

This is Teikapole NE1230E (Teika). This is a polyoxyethylene sodium alkyl (12-14) ether sulfate solution (3 E. O.) that satisfies the Japanese cosmetic ingredient standard (hereinafter abbreviated as "JCIC"), and is an aqueous solution having a pure content of about 28%.

(Sodium Tetradecenesulfonate)

Sodium tetradecenesulfonate (Lion) is used. This is a sodium tetradecenesulfonate solution that satisfies JCIC and is an aqueous solution of sodium hydroxyalkanesulfonate having a pure content of about 35%.

(N-cocoyl-L-glutamic acid TEA)

This is Amosoft CT-12 (Ajinomoto) which meets JCIC. This is a 30 mass% product.

Component (b):

(Copolymer (2))

N-methacryloyloxyethyl-N, N, N-trimethylammonium chloride (DMC) -N-hydroxyethylacrylamide (HEAA) copolymer (Mitsubishi Chemical) is used. DMA / HEAA = 40/60. Its weight-average molecular weight is about 420,000.

(Copolymer (3))

N-methacryloyloxyethyl-N, N, N-trimethylammonium chloride (DMC) -N-hydroxyethylacrylamide (HEAA) copolymer (Mitsubishi Chemical) is used. DMA / HEAA = 60/40. Its weight-average molecular weight is about 360,000.

(Copolymer (4))

N-acryloylaminopropyl-N, N, N-trimethylammonium chloride (DMAPAAC) .N-hydroxyethylacrylamide (HEAA) copolymer (Mitsubishi Chemical) is used. DMAPAAC: HEAA = 40: 60. Its weight-average molecular weight is about 400,000.

Component (c):

(Lauryl amidopropylbetaine)

LPB-30 (Ippohsha Yushi Kogyo) is used. This is an aqueous solution which satisfies JCIC and has a pure content of about 30% by mass.

(POE (10) cetyl ether)

Use EMALEX 110 (Nippon Emulsion). This satisfies JCIC and is white waxy. Its HLB is 11.

(Cocoyl Monoethanolamide)

This is Conpalan KM (Henkel). This satisfies the Japanese cosmetic ingredient standard (hereinafter abbreviated as "JSCI").

(POE (2) lauryl monoethanolamide)

Amizet 2L-Y (Kawaken Fine Chemical) is used. This satisfies JCIC. The average mole number of EO added to this is about 2.

(POE (20) hardened castor oil)

CW-20-90 (Aoki Yushi Kogyo) is used. This satisfies JSCI. This is an aqueous solution of polyoxyethylene hardened castor oil with a pure content of about 90%.

(Sorbitan monolaurate)

Soybon S-20 (Toho Chemical Industry) is used. This satisfies JSCI.

(Polyoxyethylene Octyl Dodecyl Ether)

Emalex OD-5 (Nippon Emulsion) is used. This satisfies JSCI.

Component (d):

(High-polymer dimethylsilicone)

High-polymer dimethylsilicone (Lion) is used. Which satisfies JCIC, which is (1) high-polymer methylpolysiloxane with a viscosity of 400 m ² / S (KF-9029 Shin-etsu Chemical Industry), (2) high-polymer methylpolysiloxane with a viscosity of 1000 m ² / S ( KF-9039 Shin-etsu Chemical Industry), and (3) methylpolysiloxane (KF-96, Shin-etsu Chemical Industry) which satisfies JSCI and has a viscosity of 0.1 m ² / S, (1) :( 2) :( 3) = An emulsion prepared by mixing in a ratio of 15:15:70 and mechanically emulsifying in water with an emulsifier of POE (15) cetyl ether (NPO-97, Lion Chemical) satisfying JSCI. The silicon concentration ((1) + (2) + (3)) in the emulsion is about 60 mass%. The viscosity of the emulsion is about 1.5 Pa.s (at 25 ° C., method 2 of the General Test Method according to JSCI, using rotor number 3 at 30 rpm); The average particle size of dimethylsilicone is about 0.9 μm. With hydroxyethanediphosphonic acid (Feriox 115, Lion) added here, it adjusts to pH 3 and adds 0.2 mass% benzoic acid as a preservative.

(Amodimethicone)

Use SM8704C (Toray Dow Corning). This is an aqueous dispersion of amodimethicone that satisfies JCIC, with an amino-modified silicone concentration of about 40% by mass. The average particle size of the amino-modified silicone in the aqueous dispersion is about 0.1 μm.

(Dimethylsilicon (viscosity 100 m ² / S to 0.005 m ² / S))

KF-96 dimethylsilicone (Shin-etsu Chemical Industry) is used. This satisfies JSCI.

(Methylsiloxane / Polyoxyethylene Copolymer)

Use SH3775M (Toray Dow Corning Silicone). This satisfies JSCI.

Ingredient (e):

(Stearyltrimethylammonium chloride)

Use ArcardT833 (Lion). This is an aqueous solution of stearyltrimethylammonium chloride which satisfies JSCI and whose pure content is about 33% (the rest is 29% anhydrous ethanol satisfying JSCI, and 38% pure water satisfying JSCI).

(Cetyltrimethylammonium chloride)

Use Arcard 16-50 (Lion). It has a pure content of 50% in a mixed solvent of isopropyl alcohol and water. This satisfies JSCI.

(4-guanidinobutyl laurylamide)

Acetyl / laurylamidobutylguanidine solution (Lion) is used. It has a pure content of about 32% and contains water and ethanol as solvents.

Ingredient (f):

(Sodium benzoate)

Sodium benzoate (BF Goodrich Kalama Inc.) is used. This satisfies JSCI.

(Benzoic acid)

Benzoic acid (BF Goodrich Kalama Inc.) is used. This satisfies JSCI.

(Salicylic acid)

This is a product of Yoshitomi Pharmaceutical.

Other Ingredients:

(Polyoxyethylene (acrylate / lauryl acrylate / stearyl acrylate / ethyl methacrylate amine oxide) copolymer)

Diafoamer Z-631 (Mitsubishi Chemical) is used. This is an ethanol / water solution of (acrylate / lauryl acrylate / stearyl acrylate / ethyl methacrylate amine oxide) copolymer and has a pure content of about 30% by mass.

(Propylene glycol)

This is a product of Asahi Glass. This satisfies JSCI.

(Bentonite)

Use Kunipia G (Kunimine Kogyo). This satisfies JSCI.

(Hydroxypropylmethyl cellulose)

Metolose 60SH-4000 (Shin-etsu Chemical Industry) is used. This satisfies JSCI.

(Diglucosyl gallic acid)

DGA (Iwaki Pharmaceutical) is used. The material is essentially a powder containing at least 90% by mass of 3,5-diglucosyl gallic acid, the remainder of which is essentially water. As impurities, it contains up to 3 mass% monoesters and up to 0.15 mass% unreacted gallic acid. A 1 mass% aqueous solution of the material has a pH of 2.0 to 4.0.

(Hydrated Wheat Protein Solution)

Gluadin WLM (Cognis Japan) is used. This is an aqueous solution with a content of about 23 mass% of the active ingredient satisfying JCIC. As a preservative, it contains 0.6 mass% sodium benzoate, 0.5 mass% phenoxyethanol, 0.25 mass% methylparaben, and 0.05 mass% propylparaben.

(Rapinose)

Oligo GGF (Asahi Chemical) is used. This is an oligosaccharide comprising D-galactose, D-glucose and D-fructose. It is obtained from molasses through crystallization.

(Hydroxyethane diphosphonic acid)

Use Feriox 115 (Lion), which meets JCIC. This is an aqueous solution with a concentration of about 60 mass%.

(Plant extract solution)

Falcolex BX-46 (Ichimaru Falcos) is used. This is a mixture of horsetail extract, hop extract, pine extract, lemon extract and rosemary extract, and a solution of a mixture of 1,3-butylene glycol (1,3-BG) and pure water.

(Pyroxtone olamine)

Octopyrox (Clariant) is used.

(Dipotassium glycyrizinate)

Glycyrrhizin K2 (Maruzen Pharmaceutical) is used. This satisfies JSCI.

(ethanol)

Use 99% product.

(Dimethyldiallyl ammonium chloride acrylamide copolymer)

Kayacryl Resin MN-50 (Nippon Kayaku) is used. This is an aqueous solution of about 5.5% by mass of dimethyldiallylammonium chloride acrylamide copolymer satisfying JCIC.

The monomer blend ratio of dimethyldiallylammonium chloride to acrylamide is about 1: 1.

(Citric acid)

Citric acid (Fuso Chemical Industry) is used to satisfy JSCI. Its source is of vegetable material, such as cereals.

(Yellow 203)

Quinoline Yellow WS-G (Chuo Synthetic Chemical) is used.

(Green 3)

This is a product of Kishi Kasei.

(Red 106)

This is a product of Kishi Kasei.

(Glycine)

This is aminoacetic acid (Hamari Yakuhin Kogyo). This satisfies JSCI.

(Setanol)

NAA-44 (Nippon Yushi) is used. This satisfies JSCI.

(Behenyl alcohol)

Ranette 22 (Cognis Japan) is used. This satisfies JSCI.

(Oleyl alcohol)

HD-Oitanol (Cognis Japan) is used. This satisfies JSCI.

(Oleic acid)

NAA-180 (Nippon Yushi) is used. This satisfies JSCI.

(Isostearic acid)

Isostearic acid EX (Kokyu Alcohol Kogyo) is used. This satisfies JSCI.

(vaseline)

White Vaseline (Penreco) is used. This meets Japanese drug standards.

(Squalene)

Squalene (Kishimoto Tokushu Kan-yu Kogyo) is used. This satisfies JSCI.

(Candella wax)

Pure candelina wax (Yokozeki Yushi Kogyo) is used. This satisfies JSCI.

(Arginine)

L-arginine (Ajinomoto) is used. This satisfies JSCI.

(L-cysteine)

This is Kyowa Hakko's product. This satisfies JSCI.

(Polyoxypropylene glyceryl ether)

Uniol TG-700 (Nippon Yushi) is used. This satisfies JCIC.

(Phosphate)

Phosphoric acid (Junsei Kagaku) is used. This satisfies JSCI.

(Dihydroxybenzophenone)

Ubinal 400 (by BASF Japan) is used. This satisfies JCIC.

(Propyl paraben)

Propylparaben (Midori Kagaku) is used. This satisfies JSCI.

(Methyl paraben)

Methyl paraben (Midori Kagaku) is used. This satisfies JSCI.

(Phenoxyethanol)

Phenoxyethanol-S (Yokkaichi Gosei) is used. This satisfies JSCI.

(Tetra sodium edetate)

Chelest 2D (Chelest) is used. This satisfies JSCI.

(Triethanolamine)

Triethanolamine (Mitsui Toatsu Chemical) is used. This satisfies JSCI.

(Carboxyvinyl polymer)

Carbopol 941 (BF Goodrich Kalama Inc.) is used. This satisfies JSCI.

(Xanthan Gum)

Aquagel VS-500 (Nitta Gelatin) is used. This satisfies JCIC.

(Spices)

Fragrances A, C, D and E are fragrances A, C, D and E described in Tables 5 to 10 of JP-A 2003-89620, respectively.

When hair cosmetics are used as shampoo compositions, they can improve the ability to be absorbed compared to known hair compositions containing resins as cellulose or cationized guar gum and silicone, and impart good finger passability when rinsing and Even when only shampoo is used, it is effective to make the hair have a good feel after drying. In addition, the conditioning effect is improved by adding a cationic surfactant (e) or an aromatic carboxylic acid or its salt (f) to the hair cosmetic.

Claims (8)

0.1-40 mass% of anionic surfactant (a), a vinyl monomer (A) having a hydroxyl group and an amido bond, and a vinyl monomer (B) having a cationic group represented by the following general formula (2): At least one selected from the group consisting of 0.01 to 5.0 mass% of water-soluble resin (b) having a structure corresponding to the copolymer of the monomer mixture containing, and 0.1 to 10 mass% of nonionic surfactants and zwitterionic surfactants. Hair cosmetics comprising surfactant (c):

Wherein R ³ represents a hydrogen atom or a methyl group; R ⁴ and R ⁵ each independently represent an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms; R ⁶ represents a hydrogen atom, of 1 to 24 alkyl having a carbon atom, an aryl or an aralkyl group, or a _{CH 2 -CH (OH) -CH 2} -N + R 7 R 8 R 9 · Y - represents; of R ⁷ to R ⁹ are each independently from 1 to 24 An alkyl, aryl or aralkyl group having a carbon atom; X ^- and Y ^- each independently represent an anion; b represents 0 or 1; c represents an integer from 1 to 10). The hair cosmetic according to claim 1, wherein the vinyl monomer (A) having a hydroxyl group and an amido bond is represented by the following general formula (1):

(Wherein R ¹ represents a hydrogen atom or a methyl group; R ² represents a hydrogen atom or an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms; a represents an integer of 1 to 4). The hair cosmetic of Claim 1 which further contains 0.1-5.0 mass% of a silicone compound (d). The hair cosmetic according to claim 1, wherein the vinyl monomer (A) having a hydroxyl group and an amido bond is represented by the following general formula (1) and further contains 0.1 to 5.0 mass% of a silicone compound (d). :

(Wherein R ¹ represents a hydrogen atom or a methyl group; R ² represents a hydrogen atom or an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms; a represents an integer of 1 to 4). The method according to any one of claims 1 to 4, wherein 0.01 to 5.0 mass% of cationic surfactant (e), 0.01 to 10 mass% of aromatic carboxylic acid or salt thereof (f) Or hair cosmetics further comprising:

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