WO2005074868A1

WO2005074868A1 - Hair cosmetic material

Info

Publication number: WO2005074868A1
Application number: PCT/JP2005/002380
Authority: WO
Inventors: Shoya Yoda; Tomoaki Hiwatashi; Yuko Yoda; Eiji Nishimura; Yuichi Nishida; Masako Miyamae
Original assignee: Mitsubishi Chemical Corporation; Lion Corporation
Priority date: 2004-02-09
Filing date: 2005-02-09
Publication date: 2005-08-18
Also published as: JP2007522092A; JP4786535B2; WO2005074868A8; MY146611A; KR20060125893A; KR101104659B1

Abstract

Provided is a hair cosmetic material having a good conditioning effect, especially a hair cosmetic material which lathers well and gives a good touch in finger-combing in rinsing and which is effective for making hair have a good feel after dried. A hair cosmetic material comprising from 0.1 to 40% by mass of an anionic surfactant (a), from 0.01 to 5.0% by mass of a water soluble resin (b) having a structure corresponding to a copolymer of a monomer mixture that contains a vinylic monomer (A) having a hydroxyl group and an amido bond and a vinylic monomer (B) having a cationic group, and from 0.1 to 10% by mass of a nonionic and/or amphoteric surfactant (c).

Description

DESCRIPTION .HAIR COSMETIC MATERIAL

TECHNICAL FIELD The present invention relates to a hair cosmeticmaterial, and to a hair cosmetic material which gives a good conditioning effect such as a good touch of hair in finger-combing in rinsing and a smooth and silky feel of hair after dried.

BACKGROUND ART Various trials have been executed for increasing the conditioning effect of hair cosmetic materials such as shampoo. Typically, there are known a method of adding a cationated cellulose or a cationated guar gum to hair cosmetic materials, and a method of adding a silicone compound to them. For example, there are mentioned a shampoo composition containing a fine particulate silicone and a cationated cellulose ether derivative (JP-A 7-277931) ; a shampoo composition comprising a combination of a high-viscosity silicone emulsion having a specific particle size and a cation derivative of guar gum (JP-A 4-234309) ; a cosmetic composition comprising siloxane gum or an amino group-containing silicone, and a cation derivative of gar gum or cellulose ether (JP-A 5-194142) / a shampoo composition containing a cation derivative of guar gum having a specific charge density, and a water-insoluble nonvolatile silicone (JP-A 4-364111) ; and a shampoo composition containing a cation derivative of gar gum and an insoluble and nonvolatile silicone having a specific mean particle size (JP-A 4-36226) . However, their conditioning effect is not sufficient, and is especially unsatisfactory for consumers whose hair has been damagedbycoloring. For it, one reason is that, while shampooed, hair could hardly adsorb the conditioning component, silicone, and in particular, this is said to be remarkable for hair damaged by coloring.

DISCLOSURE OF THE INVENTION The invention is to solve the problems mentioned above, and is to provide a hair cosmetic material having an excellent conditioning effect, in particular, a hair cosmetic material which lathers well and gives a good touch of hair in finger-combing in rinsing and makes the shampooed hair have a good feel after dried. When women shampoo their hair, they often use a conditioner (or rinse or treatment) after having shampooed to remove the dirt from their hair, for the purpose of preventing their shampooed hair from being too much dried or disheveled. However, when the shampooing time is limited or is desired to be shortened owing to bathing with children, they may use only shampoo. The invention is to provide a hair cosmetic material having a conditioning effect, which can well improve the hair condition even when only shampoo is used. We, the present inventors have assiduously studied in consideration of the above-mentioned problems and, as a result, have found that when a resin of a component (b) and a surfactant of a component (c) are added to a component (a) , then it provides a hair cosmetic material in which the conditioning component silicone has good adsorbability to hair and which is mild to the skin of head. Concretely, the invention is attained by the following methods. (1) A hair cosmetic material comprising from 0.1 to 40% by mass of an anionic surfactant (a), from 0.01 to 5.0% by mass of a water soluble resin (b) having a structure corresponding to a copolymer of a monomer mixture that contains a vinylic monomer (A) having a hydroxyl group and an amido bond and a vinylic monomer (B) having a cationic group, and from 0.1 to 10% by mass of a nonionic and/or amphoteric surfactant (c) . (2) The hair cosmeticmaterial of (1) , wherein the vinylic monomer (A) having a hydroxyl group and an amido bond is represented by a formula (1) and the vinylic monomer (B) having a cationic group is represented by a formula (2) : CH₂=C(R¹)-CO-NR²-(CH )_a-OH (1) wherein R¹ represents a hydrogen atom or a methyl group; R² represents a hydrogen atom, or an alkyl or hydroxyalkyl group having from 1 to 4 carbon atoms; a indicates an integer of from 1 to 4,

CH₂=C (R³) -CO (0) - (NH) ι__b- (CH₂) _C-N⁺R⁴R⁵R⁶-X^~ (2) wherein R³ represents a hydrogen atom or a methyl group; R⁴ and R⁵ each independently represent an alkyl, aryl or aralkyl group having from 1 to 24 carbon atoms; R⁶ represents a hydrogen atom, an alkyl, aryl or aralkyl group having from 1 to 24 carbon atoms, or CH₂-CH(OH) -CH₂-N⁺R⁷R⁸R⁹-Y^"; R⁷ to R⁹ each independently represent an alkyl, aryl or aralkyl group having from 1 to 24 carbon atoms; X^" and Y^" each independently represent an anion; b indicates 0 or 1; and c indicates an integer of from 1 to 10. (3) The hair cosmetic aterial of (1) or (2) , which further contains from 0.1 to 5.0% by mass of a silicone compound (d) . (4) The hair cosmetic material of any of (1) to (3), which further contains from 0.01 to 5.0% by mass of a cationic surfactant (e) and/or from 0.01 to 10% by mass of an aromatic carboxylic acid or its salt (f) of a formula (12) :

wherein R 10, nRil a - , ^nd -R_D 12 each represent an alkyl group having from 1 to 3 carbon atoms, a hydroxyl group, or a hydrogen atom; A¹ represents a carboxyl group or its salt. (5) The hair cosmetic material of any of (1) to (4), which has a pH of from 3.0 to 6.5. (6) The hair cosmetic material of any of (1) to (5), which is used for colored and damaged hair. (7) The hair cosmeticmaterial of any of (4) to (6) , wherein the aromatic carboxylic acid or its salt (f) of formula (12) is at least one selected from a group consisting of benzole acid or salicylic acid and their alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts.

DETAILED DESCRIPTION OF THE INVENTION The invention is described in detail hereinunder. In this description, the numerical range expressed by the wording "a number to another number" means the range that falls between the former number indicating the lowermost limit of the range and the latter number indicating the uppermost limit thereof. Unless otherwise specifically indicated, the concentration as referred to herein is at 25°C. The colored and damaged hair of the invention means, for example, hair that has been dyed in brown or black by the use of a hair coloring or bleaching agent. The hair cosmetic material of the invention includes, for example, shampoo, conditioner, hair wax, and liquid or foam hair-styling agent, (a) Anionic Surfactant: The component (a) is preferably an α-olefinsulfonic acid salt, a polyoxyethylene alkenyl ether sulfate, or a polyoxyethylene alkyl ether sulfate. The alkyl group in the polyoxyethylene alkyl ether sulfate is preferably an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, atetradecyl group, apentadecyl group, ahexadecyl group, aheptadecyl group, or an octadecyl group. The alkenyl group in the polyoxyethylene alkenyl ether sulfate is preferably an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, an undecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, or an octadecenyl group. The mean number of added ethylene oxide moles in the polyoxyethylene alkyl ether sulfuric acid and the polyoxyethylene alkenyl ether sulfate is preferably from 1 to 5, more preferably from 2 to 3. Also preferably, the α-olefinsulfonic acid salt has from 10 to 18 carbon atoms, more preferably from 12 to 16 carbon atoms. Even more preferably, it is a tetradecenesulfonic acid salt having 14 carbon atoms. The counter ion in these includes an alkali metal salt (e.g., sodium salt, potassium salt), an alkaline earth metal salt (e.g., magnesium salt) , an ammonium salt, an alkanolamine salt (e.g., triethanolamine, diethanola ine, monoethanola ine, triisopropanolamine) . The anionic surfactant is in the hair cosmetic material (e.g., hair conditioner, hair treatment, hair wax) in an amount of from 0.1 to 40% by mass, more preferably from 0.3 to 30% by mass of the total composition of the material. If it is lower than 0.1% by mass, then its effect is poor; but if higher than 40% by mass, then the material may be difficult to handle as its viscosity may increase too much. In particular, when the hair cosmetic material is used as shampoo, then the content of the anionic surfactant therein is preferably from 5 to 40% by mass, more preferably from 10 to 30% by mass of the total composition of the material from the viewpoint of the washing power and the foaming power thereof. When the hair cosmetic material is used as a composition for hair conditioner, hair treatment or hair wax, not as shampoo, then the content of the anionic surfactant therein is preferably from 0.1 to 2% by mass, more preferably from 0.3 to 0.8% by mass of the total composition of the material from the viewpoint of its effect. Two or more different types of anionic surfactants may be combined for use herein, and in this case, the above-mentioned content means the total amount of the combined anionic surfactants . Water-Soluble Resin (b) : The component (b) has a structure corresponding to a copolymer of a monomer mixture that contains a vinylic monomer (A) having a hydroxyl group and an amido bond and a vinylic monomer (B) having a cationic group. The vinylic monomer (A) having a hydroxyl group and an amido bond is preferably a hydroxyalkyl (meth) acrylamide-type monomer of a formula (1). " (Meth) acryl" as referred to herein means acryl and methacryl. CH₂=C (R¹) -CO-NR²- (CH₂) _a-0H (1) wherein R¹ represents a hydrogen atom or a methyl group; R² represents a hydrogen atom, or an alkyl or hydroxyalkyl group having from 1 to 4 carbon atoms; a indicates an integer of from 1 to 4. R¹ is preferably a hydrogen atom. R² is preferably a hydrogen atom, a is preferably 2. The vinylic monomer (A) of formula (1) having a hydroxyl group and an amido bond includes N-hydroxyalkyl (meth) acrylamides such as

N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide,

N,N-dihydroxyethyl (meth) acrylamide. Of those, preferred is N-hydroxyethyl (meth) acrylamide, as its solubility in water is high and the solubility in water of the polymer obtained from it is also high. Preferably, the content of the structural unit corresponding to the vinylic monomer (A) having a hydroxyl group and an amido bond in the copolymer is from 20 to 90% by mass, more preferably from 30 to 80% by mass, even more preferably from 40 to 70% by mass. It is believed that the structural unit corresponding to the vinylic monomer (A) having a hydroxyl group and an amido bond may increase the ability thereof to be adsorbed by hair owing to the action of the hydrogen bond derived from the amido bond moiety thereof. Generally, it is believedthat, when an anionic surfactant is in a hair cosmetic material, then the anionic surfactant and a water-soluble resin in the material may form a complex, and when the hair cosmetic material is applied to hair or while the hair is shampooed or rinsed with it, then the complex may deposit and adhere to the hair. In the hair cosmetic material of the invention, however, after the structural unit corresponding to the vinylic monomer (B) having a cationic group in the copolymer for the water-soluble resin (b) has formed a complex with the anionic surfactant existing in the material, the copolymer may still keep its solubility in water owing to the hydrophilic property of the structural unit corresponding to the vinylic monomer (A) having a hydroxyl group and an amido bond in the resin. When the content of the structural unit corresponding to the vinylic monomer (A) having a hydroxyl group and an amido bond in the copolymer is at least 20% by mass, then the ability of the hair cosmetic material to be adsorbed by hair could be kept better, and, in addition, the ability thereof to keep a smooth and silky feel of dried hair is further improved. When it is at most 90% by mass, then the content of the structural unit corresponding to the vinylic monomer having a cationic group could be enough, and therefore the resin may form a good complex with the anionic surfactant and may be more effective for improving the adsorbability of the hair cosmetic material to hair and the smooth feel of hair during rinsing. Examples of the vinylic monomer (B) having a cationic group are diallyl-type quaternary ammonium salts such as N,N-dimethyl-N,N-diallylammonium chloride; (meth) acryl esterr-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 cation species such as reaction product of L—arginine and glycidyl methacrylate. Of those, more preferred are (meth) acrylic quaternary ammonium salt monomers . Especially, more preferred are (meth) acrylic quaternary ammonium salt monomers of formula (2): CH₂=C (R³) -CO (0)b- (NH) !-- (CH₂) _C-N⁺R⁴R⁵R⁶-X- (2) wherein R³ represents a hydrogen atom or a methyl group; R⁴ and R⁵ each independently represent an alkyl, aryl or aralkyl group having from 1 to 24 carbon atoms; R⁶ represents a hydrogen atom, an alkyl, aryl or aralkyl group having from 1 to 24 carbon atoms, or CH₂-CH(OH)-CH₂-N⁺R⁷R⁸R⁹-Y^"; R⁷ to R⁹ each independently represent an alkyl, aryl or aralkyl group having from 1 to 24 carbon atoms; X^" and Y^~ each independently represent an anion; b indicates 0 or 1; and c indicates an integer of from 1 to 10. Preferably, R³ is a methyl group. Preferably, R⁴ and R⁵ are independently a methyl group. Preferably, R⁶ is an alkyl or aralkyl group having froml to 24 carbon atoms, more preferably a methyl group. Preferably, R⁷ to R⁹ are independently a methyl group. Preferably, the anion for X^" and Y^" is independently a chloride ion or a bromide ion, more preferably a chloride ion. Preferably, b is 1; and preferably c is 2. Some examples of the vinylic monomer having a cationic group of formula (2) are mentioned. They are cationic group-having (meth) acrylic esters such as N- (meth) acryloyloxyethyl-N,N,N-trimethylammonium chloride, N- (meth) acryloyloxyethyl-N-ethyl-N,N-dimethylammonium=mono ethyl sulfate salt,

N- (meth) acryloyloxyethyl-N,N,N-triethylammonium=monoethyl sulfate salt,

N- [3-{N' - (meth) acryloyloxyethyl-N ' ,N' -dimethylammonium}-2- hydoxypropyl] -N,N,N-trimethylammonium chloride,

N- [3-{N" - (meth) acryloyloxyethyl-N' ,N' -diethylammonium}-2-h ydroxypropyl] -N,N,N-triethylammonium chloride; and cationic group-having (meth) acrylamides such as N- (meth) acryloylaminopropyl-N, N, N-trimethylammonium chloride, N- (meth) acryloylaminopropyl-N-ethyl-N,N-dimethylammonium=m onoethyl 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' -dimethylammonium} -2-hydroxypropyl] -N,N,N-trimethylammonium chloride, N- [3-{N ' - (meth) acryloylaminopropyl-N' , N'-diethylammonium}- 2-hydroxypropyl] -N,N,N-trimethylammonium chloride. Of those, preferred are

N- (meth) acryloyloxyethyl-N, N,N-trimethylammonium chloride, N- (meth) acryloylaminopropyl-N,N,N-trimethylammonium chloride; and more preferred is N- (meth) acryloylaminopropyl-N, ,N-trimethylammonium chloride. The structure corresponding to the copolymer of the cationic group-having vinylic monomer (B) may be prepared, for example, by copolymerizing with vinylic monomer precursor having a cationic group of a formula (3) followed by reacting the resulting copolymer with a cationating agent to thereby make its structure have the corresponding cationic group. CH₂=C (R³) -CO (0)b- (NH) i-b- (CH₂) _C-NR⁴R⁵ (3) wherein R³ to R⁵, b and c have the same meanings as iri formula (2) , and their preferred ranges are the same as those mentioned hereinabove. The cationic vinyl monomer precursor includes, for example, (meth) acrylates having tertiary amine such as N- (meth) acryloyloxyethyl-N, N-dimethylamine, N- (meth) acryloyloxyethyl-N, -diethylamine; and

(meth) acrylamides having tertiary amine such as N- (meth) acryloylaminopropyl-N, -dimethylamine, N- (meth) acryloylaminopropyl-N, -diethylamine . The cationating agent includes alkyl halides such as methyl chloride; and cationating agents having cationic group such as 3-chloro-2-hydroxypropyl-N,N,N-trimethylammonium chloride. The cationation may be attained, for example, by adding the cationating agent to a solution of the polymer and reacting them at 20 to 100°C for 1 to 20 hours. One or more different types of cationic vinyl monomers or their precursors may be used herein either singly or as combined. Preferably, the content of the structural unit corresponding to the vinyl monomer (B) having cationic group in the copolymer is from 10 to 80% by mass, more preferably from 20 to 70% by mass, even more preferably from 30 to 60% by mass. The structural unit corresponding to the vinylic monomer (B) having cationic group may form a complex with the anionic surfactant in the composition of the invention, thereby making the copolymer more adhere to hair . When the content of the structural unit corresponding to the vinylic monomer (B) having cationic group is at least 10% by mass, then it may form a satisfactory complex with the anionic surfactant, for example, the hair cosmetic material may be more effective for keeping the shampooed hair smooth during rinsing. When the content is at most 40% by mass, then the ability of the hair cosmetic material to be adsorbed by hair could be kept better, and, in addition, the ability thereof to keep a smooth and silky feel of dried hair is further improved. The copolymer may further contain a structural unit derived from any other vinylic monomer. However, if the copolymer has an anionic functional group, then it may interfere with the formation of the above-mentioned complex with the anionic surfactant. Therefore, it is desirable that the content of such an anionic functional group in the copolymer is as small as possible (for example, at most 10% of all the functional groups in the copolymer) . More preferably, the copolymer does not substantially contain the group. The wording "does not substantially contain" as referred to herein may mean that the content of the group is at most 1%. Any other vinylic monomer includes esters of (meth) acrylic acid with an alcohol having froml to 22 carbon atoms; amides of (meth) acrylic acid with an alkylamine having from 1 to 22 carbon atoms; monoesters of ethylene glycol or 1, 3-propylene glycol with (meth) acrylic acid; esters derived from the monoesters by etherifying the hydroxyl group therein withmethanol orethanol; nonionic onomers such as (meth) acryloylmorpholine; amphoteric monomers such as betaine group-having (meth) acryl esters, betaine group-having (meth) acrylamides; semi-polar monomers such as amine oxide group-having (meth) acryl esters, amine oxide group-having (meth) acrylamides . The content of the structural unit derived from the other vinylic monomer may be suitably defined within a range within the scope which does not overstep the scope and the sprit of the invention. For example, it may be suitably defined in consideration of the solubility of the water-soluble resin and the conditioning effect of the hair cosmetic material. Preferably, the content of the other vinylic copolymer is at most 30% by mass . The content of the structural unit corresponding to the vinylic monomer (A) having a hydroxyl group and an amido bond, that of the structural unit corresponding to the vinylicmonomer (B) having cationic group and that of the structural unit corresponding to the additional vinylicmonomer in the copolymer may be determined through IR absorption at the hydroxyl group or the amido bond site, or ¹H-NMR of the methyl group adjacent to the hydroxyl group or the amido bond site or to the cationic group, or ¹³C-NMR thereof. Preferably, the water-soluble resin for use in the invention may form an aqueous solution having a concentration of at least 5% by mass at room temperature, or that is, at 25°C, and the transmittance (550 nm) of the aqueous solution having a concentration of 5% by mass is at least 80%, and the aqueous solution is uniform and stable. More preferably, the resin may from an aqueous solution having a concentration of at least 10% by mass. The water-soluble resin for use in the invention may be prepared, for example, by mixing the monomers or precursors capable of giving the corresponding structural units, then copolymerizing them in a mode of solution polymerization, suspension polymerization or emulsion polymerization, and optionally cationating the resulting copolymer. Preferably, the polymerization is effected in a hydrophilic solvent. The hydrophilic solvent includes 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; andwater. One or more of these may be used herein either singly or as combined. Preferred are alcohol solvents or water. The polymerization initiator usable herein is not specifically defined, including azo compounds such as 2,2' -azobisisobutyronitrile, 2,2' -azobis (2, 4-dimethylvaleronitrile) , 2, 2 ' -azobis (4-methoxy-2, -dimethylvaleronitrile) , dimethyl-2, 2 ' -azobisisobutyrate, 2,2' -azobis (2-methylbutyronitrile) , 1,1' -azobis (1-cyclohexanecarbonitrile) ,

2,2' -azobis (2-methyl-N- (2-hydroxyethyl) -propionamide) ,

2, 2 ' -azobis (2-amidinopropane) dihydrochloride; peroxides such as benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide; persulfates; and their redox-type agent.

Preferably, the amount of the polymerization initiator to be used is from 0.01 to 5% by mass of all the monomers. The polymerization may be effected in 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 the polymerization, the copolymer formed may be isolated from the reaction solution in any method, preferably through solvent evaporation or addition of poor solvent. The copolymer may be used in producing the composition of the invention, directly or after further purified. The purification may be effected in any method of reprecipitation, solvent washing or membrane separation, or by combining the methods. The weight-average molecular weight of the water-soluble resin for use in the invention is preferably from 5,000 to 5, 000,000, more preferably from 10, 000 to 2, 000, 000, even more preferably 20,000 to 1,000,000. When the weight-average molecular weight is at least 5,000, then the feel in rinsing is not worse and the conditioning effect of the composition may be kept better. When it is at most 5,000,000, then the composition may have a suitable viscosity and its handlablity in production may be better. The weight-average molecular weight of the copolymer may be determined through gel permeation chromatography (for example, using water/methanol/acetic acid/sodium acetate as the developer solvent) . A water-soluble polymer (b-1) usable herein except the water-soluble resin (b) includes methyl cellulose and hydroxymethyl cellulose. A cationic polymer including cationic modified cellulose ether derivatives, polydimethyldiallylammonium halides, dimethyldiallylammonium halide/acrylamide copolymers; an anionic polymer including acrylic acid derivatives (polyacrylic acid and its salts, acrylic acid/acrylamide/ethyl acrylate copolymer and its salts) , methacrylic acid derivatives and crotonic acid derivatives; a nonionic polymer including acrylic acid derivatives (hydroxyethyl acrylate/methoxyethyl acrylate copolymer, polyacrylamide) , vinylpyrrolidone derivatives (e.g., polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymer) ; and an amphoteric polymer including dimethyldiallylammonium chloride derivatives (e.g., acrylamide/acrylic acid/dimethyldiallylammonium chloride copolymer, acrylic acid/dimethyldiallylammonium chloride copolymer) are also usable herein. Their content in the hair cosmetic material may be from 0.01 to 0.1% by mass, (c) Nonionic and/or Amphoteric Surfactant: Preferably, the nonionic and/or amphoteric surfactant of the component (c) is represented by any of the following formulae (4) to (9) :

R⁶¹ — HCH₂S0₃- (6)

_R82 I R^βi — C - NHCH₂CH₂CH₂ - N⁺ - CH₂COO^" ( 8 ) ⁰ ₈₃

In these formulae, R⁴¹, R⁵¹, R⁶¹, R⁷¹, R⁸¹ and R⁹¹ each independently represent an alkyl or alkenyl group having from 8 to22 carbonato s; R⁶², R⁶³, R⁷², R⁷³, R⁸² and R⁸³ each independently represent an alkyl or alkenyl group having from 1 to 3 carbon atoms, or a hydrogen atom. Z represents a hydroxyl group or a hydrogen atom; p indicates a mean number of addedmols, falling between 3 and 20. mandneach independently indicates an integer of from 0 to 4, and 0 < m 4- n < 6. The nonionic or amphoteric surfactant moderates the action of the composition on the skin, acting so as to prevent the skin from being roughened by the composition, and enhances the lathering power of the composition. One or more of such surfactants may be in the composition either singly or as combined. The content of the surfactant to be in the hair cosmetic material of the invention is from 0.1 to 10% by mass, preferably from 1 to 5% by mass. If its content is smaller than 0.1% by mass, then the surfactant may be poorly effective; but if larger than 10% by mass, then the viscosity of the composition may greatly increase or the solution stability thereof may worsen, (d) Silicone Compound: The silicone compound for the component (d) is not specifically defined in point of its type, and any one generally used in ordinary hair cosmetic materials may be used herein. For example, it includes di ethylpolysiloxane (including high-polymer dimethylpolysiloxane, silicone rubber) , methylphenylpolysiloxane, polyether-modified silicone, polyamino-modified silicone,. betaine-modified silicone, alcohol-modified silicone, fluorine-modified silicone, epoxy-modified silicone, mercapto- odified silicone, carboxy-modified silicone, fatty acid-modified silicone, silicone graft polymer, cyclic silicone, alkyl-modified silicone, trimethylsilyl group-terminated dimethylpolysiloxane, silanol group-terminated dimethylpolysiloxane. One or more of these may be used herein either singly or as combined. Of those, especially preferred are dimethylpolysiloxane, polyether-modified silicone, polyamino-modified silicone. The content of the silicone compound in the composition may be from 0.1 to 5.0% by mass, preferably from 0.3 to 3.0% by mass of all the constitutive components of the composition. If it is smaller than 0.1% by mass, then the compound may be ineffective; but if larger than 5.0% by mass, then the silicone may be difficult to disperse and stabilize in the product. Though not specifically defined, the viscosity of the silicone compound at 25°C is preferably from 0.0001 to 2,000 m²/S, more preferably from 0.003 to 1,000 m²/S. For example, a silicone compound having a viscosity of from 200 to 1,200 m²/S and having a large molecular weight may be combined with a low-viscosity silicone compound having a viscosity of from 0.0001 to 0.2 m²/S to prepare a mixture easy to handle. This is preferred in the invention. If desired, the silicone compound may be emulsified with a surfactant, and the resulting emulsionmay also be usedherein. For the emulsion, the emulsifier and the emulsifying method are not specifically defined, and various ones may be used herein. The viscosity of the silicone compound may be determined by the use of a Brookfield viscometer for general test methods for The Japanese Standards of Cosmetic Ingredients. The composition may contain any other oil such as higher alcohol, olive oil, jojoba oil, liquid paraffin, fatty acid alkyl ester oil, etc. The composition may further contain fatty acid ethylene glycol as a pearly agent, and polystyrene emulsion as a suspending agent, (e) Cationic Surfactant: Not overstepping the scope and the sprit of the invention, the cationic surfactant forthe component (e) is not specifically defined. Preferably, it is a quaternary tetraalkylammonium salt, a surfactant of a guanidine derivative of the following formula (10) or its salt, anamino acid-type cationic surfactant, or an amidamine-type surfactant. More preferably, it is a quaternary tetraalkylammonium salt. A quaternary tetraalkylammonium salt is preferably used as the cationic surfactant. Concretely, it includes stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, behenyltrimethylammoniu chlorine, setostearyltrimethylammonium chloride, distearyldimethylammonium chloride, dibehenyldimethylammonium chloride. Above all, preferred are those having a straight alkyl group having from 16 to 22 carbon atoms . Concretely, more preferred are cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chlorine, and distearyldimethylammonium chloride; and even more preferred are stearyltrimethylammonium chloride, and behenyltrimethylammonium chlorine. Preferably, the cationic surfactant is in the formof a hydrochloride or abromate thereof. A guanidine derivative of the following formula (10) or its salt is also preferably used as the cationic surfactant.

(10)

wherein R¹⁰¹ represents a straight-chain or branched-chain alkyl or alkenyl group having from 1 to 21 carbon atoms; A represents a straight-chain or branched-chain alkylene or alkenylene group having from 1 to 10 carbon atoms; t indicates an integer of from 1 to 5; and when t is 2 or more, then A's in each block may be the same or different. In formula (10) , R¹⁰¹ is preferably a straight-chain or branched-chain alkyl or alkenyl group having from 11 to 19 carbon atoms. For example, its preferred examples are CuH₂₃-, C₁₂H₂₅-, Cι₃H₂₇-, C14H2₉-, Ci₅H₃ι~, Ci6H₃₃-, Cχ H₃₅-, (C8Hι )₂CH-, 4-C₂H₅Ci₅H₃o- . The substituent A is preferably a straight-chain or branched chain alkylene or alkenylene group having from 2 to 6 carbon atoms. For example, it includes a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an isopropylene group, a 2-pentenylene group, 2-ethylbutylene group. Preferably, the guanidine derivative of formula (10) is added into the composition in the form of its salt, and the salt includes inorganic salts such as hydrochlorides, bromates, suifates, phosphates; organic acid salts such as glycolates, acetates, lactates, succinates, tartrates, citrates, acidic amino acid salts, higher fatty acid salts, pyroglutamic acid salts, p-toluenesulfonates. Of those, preferred forms are hydrochlorides, bromates, acetates, glycolates, citrates and acidic amino acid salts. In addition, an amino acid-type cationic surfactant is also preferably used as the cationic surfactant herein. The amino acid-type cationic surfactant includes salts of lower alkyl ester salts of mono-N-long chain acyl-basic amino acids. The basic amino acid that constitutes the compound may be, for example, a natural amino acid such as ornithine, lysine or arginine. In addition, synthetic amino acids may also be used, such as α,γ-diaminobutyric acid. Thesemaybe optically-active compounds or racemic compounds. The acyl group is preferably a residue of a saturated or unsaturated higher fatty acid having f om 8 to 22 carbon atoms. It may be a natural or synthetic one. For example, herein employable are single higher fatty acid residues such as a lauroyl group, a myristoyl group, a palmitoyl group and a stearoyl group; and natural, mixed higher atty acid residues such as a coconut oil fatty acid residue or a beef tallow higher fatty acid residue. The lower alkyl ester component is preferablymethyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester, and octyl ester. More preferably, the lower alkyl ester component is in the form of a salt thereof. Concretely, the salt of the lower alkyl ester includes inorganic salts such as hydrochlorides, bromates, suifates, phosphates; and organic acid salts such as glycolates, acetates, lactates, succinates, tartrates, citrates, acidic amino acid salts, higher fatty acid salts, L- or DL-pyrrolidonecarboxylates, pyroglutamates, p-toluenesulfonates . Of those, preferred forms are hydrochlorides, L- or DL-pyrrolidonecarboxylates, and acidic amino acid salts. Further, an amidamine-type surfactant is also preferably used as the cationic surfactant . The amidamine-type surfactant usable herein may be a compound of the following formula (11) :

wherein R¹¹¹ represents a fatty acid residue having from 7 to 23 carbon atoms; R¹¹² represents an alkyl group having from 1 to 4 carbon atoms; and p indicates an integer of from 2 to 4. Preferably, R¹¹¹ is a fatty acid residue having from 9 to 22 carbon atoms, more preferably a fatty acid residue having from 13 to 22 carbon atoms. Preferably, R¹¹² is a methyl group or an ethyl group. Preferred examples of the amidamine-type surfactant of formula (11) are stearoyldiethylaminoethyla ide, stearoyldimethylaminoethylamide, stearoylpalmitodiethylaminoethylamide, cocodiethylaminopropylamide, palmitoyldimethyla inoethylamide, myristoyldiethylaminoethylamide, msyristoyldimethylaminoethylamide, behenoyldiethylaminoethyla ide, behenoyldimethylaminoethylamide, stearoyldiethylaminopropylamide, stearoyldimethyla inopropylamide, pal itoyldiethylaminopropylamido, pal itoyldimethylaminopropylamide, myristoyldiethylaminopropylamide, myristoyldimethylaminopropylamide, behenoyldiethylaminopropylamide, behenoyldimethylaminopropylamide. Preferably, these are added to the composition in the form of their salt . Concretely, the salt includes inorganic salts such as hydrochlorides, bromates, suifates, phosphates; and organic acid salts such as glycolates, acetates, lactates, succinates, tartrates, citrates, acidic amino acid salts, higher fatty acid salts, pyroglutamates, p-toluenesulfonates . Of those, more preferred forms are acidic amino acid salts, citrates and hydrochlorides. One or more different types of salts may be used for neutralization, either singly or as combined. Among the above, preferred are stearoyldimethylaminopropylamide, stearoyldiethylaminoethylamido, cocodiethylaminopropylamide . In the invention, one or more selected rom these amidamine-type surfactants may be used. The cationic surfactant is added to the composition for the purpose of assisting the conditioning effect of the resin of the component (b) , and its amount is preferably from 0.01 to 5.0% by mass, more preferably from 0.1 to 2.0% by mass . When its amount is at least 0.01% by mass, then the surfactant is more effective for enhancing the conditioning effect; and when it is at most 5.0% by mass, then the surfactant may more readily and uniformly dissolve in the base of the anionic surfactant of the component (a) . (f) Aromatic Carboxylic Acid or Its Salt: The aromatic carboxylic acid or its salt of the component (f) is effective for assisting the conditioning effect of the component (b) , and when it is combined with the component (e) , then it is more effective for enhancing the conditioning effect . The aromatic carboxylic acid or its salt of the component (f) is preferably an aromatic carboxylic acid or its salt of the following formula (12) :

wherein R¹⁰, R¹¹ and R¹² each represent an alkyl group having from 1 to 3 carbon atoms, a hydroxyl group, or a hydrogen atom; A¹ represents a carboxyl group or its salt. More preferably, it is benzoic acid, salicylic acid and their salts. The salt is preferably an alkali metal salt (e.g., sodiumsalt, potassiumsalt) , an alkaline earthmetal salt (e.g. , magnesium salt, calcium salt, aluminium salt) , an ammonium salt (e.g., ammonium) , an alkanolamine salt (e.g., triethanolamine, diethanolamine, monoethanolamine, triisopropanola ine) . Preferably, the content of the component (f) in all the components of the composition is from 0.01 to 10% by mass, more preferably from 0.1 to 3% by mass. When its content is at least 0.01% by mass, the component is more effective for improving the conditioning effect; and when at most 10% by mass, then the dispersion stability of the composition may be more effectively prevented from being worsened. When used as a shampoo composition, an opacifier may be added to the hair cosmetic material. Containing such an opacifier, the composition could have a rich liquid appearance and could be a hair cosmetic material favored by consumers. Not specifically defined, the opacifier may be any one capable of being dispersed in the hair cosmetic material as crystal or solid and capable of making the resulting composition have a pearly gloss or a opaque white appearance. For example, natural-derived substances such as fish scales, mica flakes. However, in view of the quality stability, the economical advantage and the handlability in production, chemically syntheticproducts are preferred. Further, when the dispersion stability and the lathering property are taken into consideration, then compounds of formula (13) and/or formula (14) , as well as glycerin monofatty acid esters (Carbon 16-24) are especially preferred. R¹³—C-(-OCH₂CH₂^r-A¹³ (13) O

wherein R¹³ represents an alkyl or alkenyl group having from 15 to 23 carbon atoms; A¹³ represents a f tty acid residue having from 16 to 24 carbon atoms; n indicates a number of from 1 to 3. One or more such opacifiers may be used herein either singly or as combined. Preferably, the opacifier content of the hair cosmetic material is from 1 to 10% by mass, more preferably from 1 to 5% by mass. When the content is at least 1% by mass, then the hair cosmetic material may have a beautiful pearly gloss; and when it is at most 10% by mass, then the hair cosmetic material is more effective for ensuring the dispersion stability thereof. In addition to the above-mentioned components, the hair cosmetic material of the invention may further contain any ordinary component that could be in general hair cosmetic materials. For example, the hair cosmetic material may optionally contain a lower alcohol such as ethanol, isopropanol , or a polyalcohol such as ethylene glycol, propylene glycol, glycerin, sorbitol, polyethylene glycol, serving as a solubilizer. If necessary, the hair cosmetic material may contain a viscosity improver such as carboxymethyl cellulose, hydroxyethyl cellulose, a chelating agent such as citric acid, ethylenediaminetetraacetic acid (EDTA) , nitrilotriacetic acid (NTA) , a fragrance, a colorant, an antiseptic preservative, and a pH-controlling agent. For the fragrance and the fragrance composition usable in the hair cosmetic material of the invention, referred to are the fragrance components described in JP-A 2003-300811, paragraphs [0021] to [0035], and the solvents for fragrance described in the same publication, paragraph [0050] . Preferably, the amount of the fragrance solvent that may be in the fragrance composition is from 0.1 to 99% by mass, more preferably from 1 to 50% by mass. Preferred examples of the fragrance stabilizer are dibutylhydroxytoluene, butylhydroxyanisole, vitamin E and its derivatives, catechin compounds, flavonoid compounds and polyphenol compounds. The content of the fragrance stabilizer in the fragrance composition is preferably from 0.0001 to 10% bymass, more preferably from 0.001 to 5% by mass . Of the above , dibutylhydroxytoluene is preferred for the stabilizer. The fragrance composition is a mixture comprising the fragrance component, the solvent and the fragrance stabilizer . Preferably, the hair cosmetic material of the invention contains the fragrance composition in an amount of from 0.005 to 40% by mass, more preferably from 0.01 to 10% by mass of all the constitutive components of the hair cosmetic material. The hair cosmeticmaterial of the inventionmaybe produced bymixing and stirring the components according to a knownmethod. In this case, it is desirable that the component (a) is used in the form of an aqueous solution of an anionic surfactant previously diluted with pure water or ethanol and having a concentration of from 20 to 70% by mass, in view of the easiness in producing it. Also preferably, the component (b) is previously dissolved in water or dispersed in a solvent such as propylene glycol, and is added to the other components. It is also desirable that the components (c) and (e) are diluted with pure water or ethanol, as theymaybe handled in a simplified manner. However, if they are solid, they may be heated up to a temperature higher than their melting point and fluidized, and the resulting fluid may be added little by little with stirring to the component (a) or to the liquid mixed with pure water during production. In such amanner, the solid components may be readily dissolved within a short period of time. The component (f) , if soluble in water, may be directly added to the system or after it is formed into its aqueous solution; and if soluble in oil, it may be dissolved in fragrance. The invention is describedmore concretely with reference to the following Examples. Not overstepping the scope and the sprit thereof, the invention should not be limited to the following Examples. <Example 1-1> (Production of Copolymer (1) ) Using a reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas-introducing duct and a stirrer, 300 parts by weight of distilled water, and a monomer mixture of the monomer shown in Table 1 (copolymer (1) ) and 100 parts by weight of distilled water were fed into the dropping funnel. The air in the reactor was replaced with nitroge . The reactor was heated up to 70°C. 0.5 parts by weight of 2, 2 ' -azobis (2-amidinopropane) dihydrochloride was put into the reactor, and the monomer mixture was added dropwise into it , taking 1 hour. This was reacted for 4 hours after the addition of dropwise into the reactor, and then heated up to

80°C and further reacted for 2 hours. The copolymer thus obtained was analyzed through gel permeation chromatography (apparatus, Tosoh' s SC8010, SD8022, RI8020, CO8011, PS8010; column, Wako Jun-yaku's Wakopak (Wakobeads G-50) ; developer solvent, water/methanol/acetic acid/sodium acetate = 6/4/0.3/0.41) to determine its weight-average molecular weight. The result is shown in Table 1. The water solubility of the obtained copolymer was confirmed as follows: An aqueous 5 wt.% solution of the copolymer at 25°C is prepared, and its transmittance (550 nm, 10 mm glass cell) is determined. The following standards indicate the water solubility of the copolymer. The result is shown in Table 1. 0: 80% or more. Δ: From 50% to less than 80%. X: Less than 50%.

Table 1

en

DMC: N-methacryloyloxyethyl-N,N,N-trimethylaιπmoniuιtι chloride DMAPAAC: N-acryloylaminopropl-N,N,N-t'rimethylaιnmonium chloride DMAPMAC: N-methacryloylaminopropyl-N,N,N-trimethylammonium chloride DADMAC: N,N-dimethyl-N_/N-diallylammonium chloride G AArg: 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 Cosmetic Material) The copolymer (1) was used as the resin in Table 2. A shampoo containing the composition of Table 2 was prepared. Concretely, the other ingredients than silicone oil were mixed, and silicone oil was added to the resulting mixture. Thus prepared, the shampoo was tested for lathering, smooth feel in rinsing, silky feel after dried, softness after dried, and silicon oil adsorption, according to the methods mentioned below. Table 2

*1 Sodium polyoxyethylene (3) -lauryl ether sulfate, LES-Na (by Lion) *2 Silicone oil emulsion BY22029 (by Toray Dow Corning, concentration 50%) *3 Dimethyldiallylammonium halide/acrylamlde copolymer (by Merck) *4 Stearyltrimethylammonium chloride, ArcardT-28 (byLion Chemical)

(Evaluation of Hair Cosmetic Material) The hair cosmetic material obtained in the above-mentioned method was evaluated according to the methods mentioned below. The test results with non-processed (virgin) hair bundles are shown in Table 4; and those with damaged hair bundles are in Table 5. <Examples 1-2 to l-9> (Production of Copolymers (2) to (9)) Copolymers (2) to (9) were produced in the same manner as that for the copolymer (1) , for which, however, the monomer compositions shown in Table 1 (copolymers (2) to (9)) were used. The weight-average molecular weight of the copolymers thus obtained is shown in Table 1. (Preparation and Evaluation of Hair Cosmetic Materials) Hair cosmetic materials were prepared and evaluated accordingto the samemethods as inExample 1-1. The test results are given in Table 3 and Table . <Example 1-10> (Production of Copolymer (10) ) A copolymer (10) was produced in the same manner as that for the copolymer (1) , for which, however, the monomer composition shown in Table 1 (copolymer (10)) was used, and 500 parts by weight of distilled water was put into the reactor in the initial stage. The weight-average molecular weight of the copolymer thus obtained is shown in Table 1. (Preparation and Evaluation of Hair Cosmetic Material) A hair cosmetic material was prepared and evaluated accordingto the samemethods as inExample 1-1. The test results are given in Table 3 and Table 4. <Comparative Example 1-1> (Production of Copolymer (11) ) A copolymer (11) was produced in the same manner as that for the copolymer (1), for which, however, the monomer composition shown in Table 1 (copolymer (11) ) was used. The weight-average molecular weight of the copolymer thus obtained is shown in Table 1. (Preparation and Evaluation of Hair Cosmetic Material) A hair cosmetic material was prepared and evaluated accordingto the samemethods as inExample 1-1. The test results are given in Table 3 and Table 4. <Comparative Example l-2> (Production of Copolymer (12) ) A copolymer (12) was produced in the same manner as that for the copolymer (1) , for which, however, the monomer composition shown in Table 1 (copolymer (12)) was used, ethanol was used as the solvent, and dimethyl-2, 2 ' -azobisisobutyrate was used as the polymerization initiator. Distilled water was addedto the thus-obtained copolymer, and ethanol was evaporated away from it. Thus, the copolymer was in the form of an aqueous solution thereof. The weight-average molecular weight of the copolymer is shown in Table 1. (Preparation and Evaluation of Hair Cosmetic Material) A hair cosmetic material was prepared and evaluated according to the samemethods as inExample 1-1. The test results are given in Table 3 and Table 4. <Comparative Example l-3> (Preparation and Evaluation of Hair Cosmetic Material) A hair cosmetic material was prepared and evaluated according to the same methods as in Example 1-1, for which, however, cationated hydroxyethyl cellulose (Calgon's JR400) was used as the resin in Table 2. The test results are given in Table 3 and Table . <Comparative Example l-4> (Standard) (Preparation and Evaluation of Hair Cosmetic Material) A hair cosmetic material was prepared and evaluated according to the samemethods as inExample 1-1, towhich, however, the resin in Table 2 was not added. <Test Methods> Each hair cosmetic material was applied to hair bundles prepared herein, and tested for the matters mentioned below. For the "non-processed hair bundles", used was "root-trimmed human black hair (100%) (non-processed hair 10 g x 30 cm) , by Viewlax)". The "damaged hair" was prepared by bleaching the "non-processed hair". The bleaching is as follows: 12 g of Milbon ' s Promatis Brave Oxytan 6.0 (hydrogen peroxide 6% cream) and 6 g of Melos Chemical's Powder Bleach MR2 are mixed, and the resulting mixture is applied to one hair bundle. After left for 30 minutes, the hair bundle is rinsed with water. Then, sodium polyoxyethylene (3) -lauryl ether sulfate was applied to it and this was further rinsed. (1) Lathering: 10 g of a hair bundle is watered with running water at 40°C, and then excess water is removed. 1 g of a shampoo was applied to the hair bundle. The shampoo in the hair bundle was foamed. In this process, the lathering speed andthe texture of the lather are evaluated according to the following four ranks, and the test point is given to the sample. +2 : The sample is better than the standard (with no resin) in point of both the lathering speed and the texture of the later. +1: The sample is better than the standard in point of either the lathering speed or the texture of the later. 0: The sample is on the same level as the standard. -1: The sample is inferior to the standard. (2) Smooth feel in rinsing: After the test for lathering, the hair bundle is rinsed in running water at 40°C, whereupon it is tested in point of the smooth feel in finger-combing in rinsing and the smooth feel durability. The samples are evaluated according to the following four ranks. +2: The sample is better than the standard in point of the smooth feel, and its smooth feel lasts for 1 minute or more. +1: The sample is better than the standard in point of either the smooth feel or the smooth feel durability. 0: The sample is on the same level as the standard. -1: The sample is inferior to the standard. (3) Silky feel after dried: After the test for the smooth feel in rinsing, the hair bundle is dried overnight in a constant-temperature room at 23°C and 60% RH (relative humidity) . The samples are evaluated for the silky feel, according to the following four ranks. +2: The same is much better than the standard in point of the silky feel. +1: The sample is better than the standard in point of the silky feel. 0: The sample is on the same level as the standard. -1: The sample is inferior to the standard.

(4) Softness after dried: The hair bundle tested for the silky feel was further tested for the softness after dried, and it is evaluated according to the following four ranks. +2: As compared with the standard, the sample does not almost have a rough feel. +1: The sample has a rough feel in some degree, though better than the standard. 0: The sample is on the same level as the standard. -1: The sample is inferior to the standard. (5) Silicone Oil Adsorption: 10 g of a hair bundle is wetted with running water at

40°C for 30 seconds, and dewatered until it gives no water drop. 1 g of a shampoo to be tested is applied to the wetted hair bundle. Then, this is combed 100 times for 1 minutes and is thereby lathered. This is rinsed in running water at 40°C for 30 seconds and then dried overnight . This treatment is repeated twice, and the silicone oil adsorbed by the hair is extracted out. The oil adsorption is determinedthroughNMR of the extract (H of Si-CH₃ is quantified in ^-NMR) . The oil extraction is as follows: The hair bundle is dipped in a solvent of chloroform/methanol = 4/1 and ultrasonicated. The solvent is removed by evaporation under reduced pressure. This is dissolved in heavy chloroform, and its concentration is determined, based on an internal standard, dimethyl terephthalate added thereto.

Table 3 - Test Results with Non-Processed Hair

JR400: cationated hydroxyethyl cellulose In the^" Table, " (no) " means that no resin was added to the composition.

Table 4 - Test Results with Damaged Hair

^.

<Evaluation of Test Results> 1) In Comparative Example 1-1, N-methacryloylaminopropyl-N,N-dimethylamine oxide is used in producing the water-soluble resin, and the structural units of the water-soluble resin do not have a hydroxyl group. Accordingly, the silicone oil adsorption to the damaged hair is low, and the dried hair does not have a silky feel. 2) In Comparative Example 1-2, hydroxyethyl acrylate is used in producing the water-soluble resin, and the structural units of the water-soluble resin do not have an amido bond. Accordingly, this is not good both for the non-processed hair and the damaged hair in point of the lathering, the feel in rinsing, the feel after dried, the softness after dried, and the silicon oil adsorption. 3) In Comparative Example 1-3, cationated hydroxyethyl cellulose not having an amido bond is used as the water-soluble resin. Accordingly, this is not goodboth for the non-processed hair and the damaged hair in point of the softness after dried. 4) In Comparative Example 4 (standard) , no resin is added to the composition. Therefore, as compared with the hair cosmetic material of the invention containing a water-soluble resin, this is not good both for the non-processed hair and the damaged hair in point of the lathering, the feel in rinsing, the feel after dried, the softness after dried, and the silicon oil adsorption. <Examples 2-1 to 2-4, and Comparative Examples 2-1 to 2-3> Hair cosmetic materials shown in Table 5 were prepared, and tested according to the method mentioned below. In Table 5, the unit is % by weight. (Test Method) 10 women panelists of from 20 to 50 years old tried the hair cosmetic material for 7 days, and evaluated it in point of the feel thereof while used. Concretely, they evaluated the samples in three ranks, good, average and bad. The final evaluation of the samples is as follows: 00: From 8 to 10 of the 10 panelists said good. 0: From 5 to 7 of the 10 panelists said good. Δ: 3 or 4 of the 10 panelists said good. x: From 0 to 2 of the 10 panelists said good.

Table 5

* The amount of each component is in terms of the pure content thereof, As in the above Table, the women panelists said that the shampoos of Examples 2-1 to 2-4 are all good. <Example 2-5> The hair cosmetic material of Example 2-1 was filled in the following containers, and stored in temperature-controlled tanks at 40°C and -5°C for 1 month and then left in an atmosphere at 22 to 27°C for 3 days . Thus stored, the hair cosmetic material was evaluated in point of its outward appearance. Concretely, the stored sample was transferred into a laboratory dish, and checked for its appearance. As a result, no change was found in every sample stored in different containers at different temperatures, in point of any layer separation, noticeable discoloration and impurities such as crystals. <Bottle Containers> (1) Bottle body material PP; cap material PP (2) Bottle body material HDPE; cap material PP (3) Bottle body material PET; cap material PP (4) Bottle body material PP/HDPE; cap material PP <Pump Containers> (5) Bottle body material PP; dispenser materials PP, PE and SUS304 (6) Bottle body material HDPE; dispenser materials PP, PE and SUS304 (7) Bottle body material PET; dispenser materials PP, PE and SUS304 (8) Bottle body material PP/HDPE; dispenser materials PP, PE and SUS304

<Pouch Container> (9) Material, aluminium-deposited polyethylene pouch PE is polyethylene; PP is polypropylene; PET is polyethylene terephthalate; HDPE is high-densitypolyethylene .

Hair Conditioner Composition: A hair conditioner composition of the following Table 6 was prepared. After shampooed with a shampoo composition shown below, the hair was treated with the hair conditioner composition of Table 6, and then rinsed with warm water. This was dried with a towel and then further dried with a drier, and the hair treated with the conditioner was checked for its feel. The feel evaluation is in the same manner as in Example 1.

Table 6

* The amount of each component is in terms of the pure content thereof.

Shampoo composition used for evaluation in Example 3 (the amount is in terms of the pure content (% by mass) : POE-sodium alkyl ether sulfate 10 mas.% Sodium tetradecenesulfonate 1 mas.% Laurylamidopropylbetaine 4 mas.% POE (2) -laurylmonoethanolamide 2 mas.% Dimethyldiallylammonium chloride/acrylamide copolymer 0.5 mas.% Citric acid ad lib (for pH = 5.2) Sodium benzoate 1.1 mas . % Fragrance A 1.0 mas . % Pure water balance Table 7

<Example 4> Hair Wax: A hair wax of the following Table 8 was prepared. After shampooed and treated with a shampoo composition and a hair conditioner shown below, the hair was dried with a drier, and the hair wax prepared herein was applied to it and tested for its feel. The feel evaluation is in the same manner as in Example 1.

Table 8

* The amount of each component is in terras of the pure content thereof.

Shampoo composition used for evaluation in Example 4 (the amount is in terms of the pure content) : POE-sodium alkyl ether sulfate 10 mas.% Sodium tetradecenesulfonate 1 mas.% Laurylamidopropylbetaine 4 mas.% POE (2) -laurylmonoethanolamide 2 mas.% Dimethyldiallylammonium chloride/acrylamide copolymer 0.5 mas . % Citric acid ad lib (for pH = 5.2) Sodium benzoate 1.1 mas . % Fragrance A 1.0 mas . % Pure water balance

Hair conditioner composition used for evaluation in Example 4 (the amount is in terms of the pure content) : 4-Guanidinobutylaurylamide 0.8 mas.% Stearyltrimethylammonium chloride 0.2 mas.% Dimethylsilicone (viscosity 100 m²/S) 1.0 mas.% Dimethylsilicone (viscosity 10 m²/S) 1.0 mas.% Dimethylsilicone (viscosity 0.005 m²/S) 1.0 mas.% Cetanol 1.5 mas.% Behenyl alcohol 0.2 mas.% Arginine 0.3 mas.% Sodium benzoate 0.2 mas.% Phosphoric acid ad lib (for pH = 3.5) Fragrance A 1.0 mas% Pure water balance

Table 9

The materials used herein are mentioned below. Component (a) : (polyoxyethylene (POE) -sodium alkyl ether sulfate) This is Teikapole NE1230E (by Teika) . This is a polyoxyethylene sodium alkyl (12-14) ether sulfate solution (3 E.O. ) that satisfies the Japanese Cosmetic Ingredients Codex (hereinafter abbreviated to "JCIC") , and is an aqueous solution having a pure content of about 28%. (Sodium tetradecenesulfonate) Sodium tetradecenesulfonate (by Lion) is used. This is a sodium tetradecenesulfonate solution satisfying 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 (by Ajinomoto) satisfying JCIC. This is a 30 mas.% product. Component (b) : (Copolymer (2) ) N-methacryloyloxyethyl-N,N,N-trimethylammonium chloride (DMC) -N-hydroxyethylacrylamide (HEAA) copolymer (by 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 (by 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 (by Mitsubishi Chemical) is used. DMAPAAC: HEAA = 40 : 60. Its weight-average molecular weight is about 400,000. Component (c) : (Laurylamidopropylbetaine) LPB-30 (by Ippohsha Yushi Kogyo) is used. This is an aqueous solution satisfying JCIC and having a pure content of about 30% by mass. (POE (10) cetyl ether) EMALEX 110 (by Nippon Emulsion) is used. This satisfies JCIC, and is white waxy. Its HLB is 11. (Cocoyl monoethanolamide) This is Conpalan KM (by Henkel) . This satisfies the Japanese Standards of Cosmetic Ingredients (hereinafter abbreviated to "JSCI") . (POE (2) laurylmonoethanolamide) Amizet 2L-Y (by Kawaken Fine Chemical) is used. This satisfies JCIC. The mean number of mols of EO added to it is about 2.

(POE (20) hardened castor oil) CW-20-90 (by Aoki Yushi Kogyo) is used. This satisfies JSCI. This is an aqueous solution of polyoxyethylene hardened castor oil having a pure content of about 90%. (Sorbitan monolaurate) Soybon S-20 (by Toho Chemical Industry) is used. This satisfies JSCI. (Polyoxyethylene octyl dodecyl ether) Emalex OD-5 (by Nippon Emulsion) is used. This satisfies SCI.

Component (d) : (High-polymer dimethylsilicone) High-polymer dimethylsilicone (by Lion) is used. Satisfying JCIC, this is an emulsion prepared by mixing (1) high-polymer methylpolysiloxane having a viscosity of 400 m²/S (KF-9029 by Shin-etsu Chemical Industry), (2) high-polymer methylpolysiloxane having a viscosity of 1000 m²/S (KF-9039 by Shin-etsu Chemical Industry) , and (3) methylpolysiloxane satisfying JSCI and having a viscosity of 0.1 m²/S (KF-96, by Shin-etsu Chemical Industry), in a ratio of (1) : (2) : (3) = 15:15:70, and mechanically emulsifying it in water with an emulsifier of POE (15) cetyl ether (NPO-97, by Lion Chemical) that satisfies JSCI. The silicone concentration ((1) + (2) + (3)) in the emulsion is about 60% by mass. The viscosity of the emulsion is about 1.5 Pa-s (at 25°C, by Method 2 of general test methods according to JSCI, using rotor No. 3 at 30 rpm) ; and the mean particle size of dimethylsilicone is about 0.9 μm. With hydroxyethanediphosphonic acid (Feriox 115, by Lion) added thereto, this is controlled to have a pH of 3, and 0.2% by mass of benzoic acid is added thereto as a preservative. (Amodimethycone) SM8704C (by Toray Dow Corning) isused. This is an aqueous dispersion of amodimethycone satisfying JCIC, and the amino-modified silicon concentration in this is about 40% by mass. The mean particle size of the amino-modified silicone in the aqueous dispersion is about 0.1 μm. (Dimethylsilicone (viscosity 100 m²/S to 0.005 m²/S) ) KF-96 dimethylsilicone (by Shin-etsu Chemical Industry) is used. This satisfies JSCI. (Methylsiloxane/polyoxyethylene copolymer) SH3775M (by Toray Dow Corning Silicone) is used. This satisfies JSCI. Component (e) : (Stearyltrimethylammonium chloride) ArcardT833 (byLion) isused. This is an aqueous solution of stearyltrimethylammonium chloride satisfying JSCI, and its pure content is about 33% (the balance is 29% of anhydrous ethanol satisfying JSCI and 38% of pure water satisfying JSCI) . (Cetyltrimethylammonium chloride) Arcard 16-50 (by Lion) is used. This has a pure content of 50% in a mixed solvent of isopropyl alcohol and water. This satisfies JSCI. (4-Guanidinobutylalurylamide) Acetyl/laurylamidobutylguanidine solution (by Lion) is used. This has a pure content of about 32%, and contains water and ethanol as the solvent. Component (f) : (Sodium benzoate) Sodium benzoate (by BF Goodrich Kalama Inc.) is used. This satisfies JSCI. (Benzoic acid) Benzoic acid (by BF Goodrich Kalama Inc. ) is used. This satisfies JSCI. (Salicylic acid) This is a product of Yoshitomi Pharmaceutical. Other components:

(Polyoxyethylene (acrylates/lauryl acrylate/stearyl acrylate/ethyl methacrylate amine oxide) copolymer) Diafoamer Z-631 (by Mitsubishi Chemical) is used. This is an ethanol/water solution of (acrylates/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) Kunipia G (by Kunimine Kogyo) is used. This satisfies JSCI. (Hydroxypropylmethyl cellulose) Metolose 60SH-4000 (by Shin-etsu Chemical Industry) is used. This satisfies JSCI. (Diglucosyl gallic acid) DGA (by Iwaki Pharmaceutical) is used. This material is essentially a powder that contains at least 90% by mass of 3, 5-diglucosyl gallic acid, and its balance is essentiallywater . As impurities, it contains at most 3% by mass of monoester, and at most 0.15% by mass of unreacted gallic acid. An aqueous 1 mas.% solution of the material has a pH of from 2.0 to 4.0. (Hydrolyzed wheat protein solution) Gluadin WLM (by Cognis Japan) isused. This is an aqueous solution in which the content of the effective ingredient that satisfies JCIC is about 23% by mass. As a preservative, this contains 0.6% by mass of sodium benzoate, 0.5% by mass of phenoxyethanol, 0.25% by mass of methylparaben, and 0.05% by mass of propylparaben. (Raffinose) Oligo GGF (by Asahi Chemical) is used. This is an oligosaccharide comprising D-galactose, D-glucose and D-fructose. This is obtained from molasses through crystallization . (Hydroxyethanediphosphonic acid) Feriox 115 satisfying JCIC (by Lion) is used. This is an aqueous solution having a concentration of about 60% by mass . (Vegetable extract solution) Falcolex BX-46 (by Ichimaru Falcos) is employed. This is a mixture of field horsetail extract, hop extract, pine extract, lemon extract and rose marry extract, and is a solution of themixture with 1, 3-butylene glycol (1,3-BG) andpure water. (Piroctone olamine) Octopyrox (by Clariant) is used. (Dipotassium glycyrrhizinate) Glycyrrhizin K2 (by Maruzen Pharmaceutical) is used. This satisfies JSCI. (Ethanol) A 99% product is used. (Dimethyldiallylammonium chloride-acrylamide copolymer) Kayacryl Resin MN-50 (by Nippon Kayaku) is used. This is an aqueous solution of about 5.5% by mass of dimethyldiallylammonium chloride-acrylamide copolymer that satisfies JCIC. The monomer blend ratio of dimethyldiallylammonium chloride to acrylamide is about 1:1. (Citric acid) Citric acid (by Fuso Chemical Industry) satisfying JSCI is used. Its source is a phytogenic material such as cereals. (Yellow 203) Quinoline Yellow WS-G (by Chuo Synthetic Chemical) is used. (Green 3) This is a product by Kishi Kasei. (Red 106) This is a product by Kishi Kasei. (Glycine) This is an aminoacetic acid (by Hamari Yakuhin Kogyo) . This satisfies JSCI. (Cetanol) NAA-44 (by Nippon Yushi) is used. This satisfies JSCI. (Behenyl alcohol) Ranette 22 (by Cognis Japan) is used. This satisfies JSCI. (Oleyl alcohol) HD-Oitanol (by Cognis Japan) is used. This satisfies SCI. (Oleic acid) NAA-180 (by Nippon Yushi) isused. This satisfies JSCI . (Isostearic acid) Isostearic acidEX (by KokyuAlcohol Kogyo) isused. This satisfies JSCI. (Vaseline) White vaseline (by Penreco) is used. This satisfies the Japanese pharmacopoeia standards. (Squalane) Squalane (by Kishimoto Tokushu Kan-yu Kogyo) is used. This satisfies JSCI. (Candelilla wax) Pure candelilla wax (by Yokozeki Yushi Kogyo) is used. This satisfies JSCI. (Arginine) L-arginine (by Ajinomoto) isused. This satisfies JSCI. L-cysteine This is a product by Kyowa Hakko. This satisfies JSCI. (Polyoxypropylene glyceryl ether) UniolTG-700 (NipponYushi) isused. This satisfies JCIC. (Phosphoric acid) Phosphoric acid (by Junsei Kagaku) is used. This satisfies JSCI. (Dihydroxybenzophenone) Ubinal 400 (by BASF Japan) isused. This satisfies JCIC. (Propylparaben) Propylparaben (byMidori Kagaku) isused. This satisfies JSCI. (Methylparaben) Methylparaben (byMidori Kagaku) isused. This satisfies JSCI. (Phenoxyethanol) Phenoxyethanol-S (by Yokkaichi Gosei) is used. This satisfies JSCI. (Tetrasodium edetate) Chelest 2D (by Chelest) is used. This satisfies JSCI. (Triethanolamine) Triethanolamine (by Mitsui Toatsu Chemical) is used. This satisfies JSCI. (Carboxyvinyl polymer) Carbopol 941 (by BF Goodrich Kalama Inc.) is used. This satisfies JSCI. (Xanthane gum) AquagelVS-500 (byNittaGelatin) isused. This satisfies JCIC. (Fragrance) Fragrances A, C, D and E are fragrances A, C, D and E, respectively, described in Tables 5 to 10 in JP-A 2003-89620.

Industrial Applicability When the hair cosmetic material is used as shampoo composition, it may increase the ability thereof to be adsorbed compared with the known hair composition containing resin as cellulose or a cationated guar gum and silicone, and gives a good touch in finger-combing in rinsing and is effective for making hair have a good feel after dried, even when only shampoo is used. Furthermore, the conditioning effect is enhanced by adding cationic surfactant (e) or aromatic carboxylic acid or its salt (f) to the hair cosmetic material.

Claims

CLAIMS 1. A hair cosmetic material comprising from 0.1 to 40% by mass of an anionic surfactant (a) , from 0.01 to 5.0% by mass of a water soluble resin (b) having a structure corresponding to a copolymer of a monomer mixture that contains a vinylic monomer (A) having a hydroxyl group and an amido bond and a vinylic monomer (B) having a cationic group, and from 0.1 to 10% by mass of a nonionic and/or amphoteric surfactant (c) . 2. The hair cosmetic material of Claim 1, wherein the vinylic monomer (A) having a hydroxyl group and an amido bond is represented by a formula (1) and the vinylic monomer (B) having a cationic group is represented by a formula (2) : CH₂=C (R¹) -CO-NR²- (CH₂) _a-OH (1) wherein R¹ represents a hydrogen atom or a methyl group; R² represents a hydrogen atom, or an alkyl or hydroxyalkyl group having from 1 to 4 carbon atoms; a indicates an integer of from 1 to 4, CH₂=C (R³) -CO (0) _b- (NH) i-b- (CH₂) _C-N⁺RR⁵R⁶-X^" (2) wherein R³ represents a hydrogen atom or a methyl group; R⁴ and R⁵ each independently represent an alkyl, aryl or aralkyl group having from 1 to 24 carbon atoms; R⁶ represents a hydrogen atom, an alkyl, aryl or aralkyl group having from 1 to 24 carbon atoms, or CH₂-CH(OH)-CH₂-N⁺R⁷R⁸R⁹-Y^"; R⁷ to R⁹ each independently represent an alkyl, aryl or aralkyl group having from 1 to 24 carbon atoms; X^~ and Y^" each independently represent an anion; b indicates 0 or 1; and c indicates an integer of from 1 to 10. 3. The hair cosmetic material of Claims 1 or 2, which further contains from 0.1 to 5.0% by mass of a silicone compound (d) . 4. The hair cosmetic material of any of Claims 1 to 3, which further contains from 0.01 to 5.0% by mass of a cationic surfactant (e) and/or from 0.01 to 10% by mass of an aromatic carboxylic acid or its salt (f) of a formula (12) :

wherein R¹⁰, R¹¹ and R¹² each represent an alkyl group having from 1 to 3 carbon atoms, a hydroxyl group, or a hydrogen atom; A¹ represents a carboxyl group or its salt. 5. The hair cosmetic material of any of Claims 1 to 4,, which has a pH of from 3.0 to 6.5. 6. The hair cosmetic material of any of Claims 1 to 5, which is used for colored and damaged hair. 7. The hair cosmetic material of any of Claims 4 to 6, wherein the aromatic carboxylic acid or its salt (f) of formula (12) is at least one selected from a group consisting of benzoic acid or salicylic acid and their alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts.