JP5025163B2 - New hair treatment agent - Google Patents

Description

The present invention relates to a hair treatment agent that can be applied as a permanent pretreatment agent or a hair dyeing pretreatment agent with reduced damage to hair.

  Permanent waving agents (perm liquid) are those that reduce and oxidize the hair, impart waves to the hair, correct curly hair, comb hair, etc., and make straight hair. However, during this process, the hair is exposed to severe conditions such as reduction and oxidation, so that the hair strength and feel decreases, and when it progresses, the cuticle is peeled off, the split ends, and the hair are damaged. Arise. In curly hair straightening in particular, excessive physical force may be applied to curly hair, and the degree increases.

  Similarly, bleaching agents decolorize hair melanin pigments mainly by the oxidizing action of oxidizing agents such as hydrogen peroxide, and hair dyes (also known as oxidative hair dyes) also penetrated into the hair. Color develops when the dye precursor is oxidized and polymerized. Moreover, although the effect | action of hair dye (alias: acid hair dye) is mild compared with these, the fixed damage to the hair surface was unavoidable.

  Damaged hair such as these has been problematic because it is stiff and lacks a unity of the hairstyle, or the hair strength is reduced and the hair tends to be broken or split. In addition, there is no more method than using a large amount of a drug in order to obtain a permanent effect sufficiently or to achieve uniform hair dyeing, which also causes hair damage.

In order to solve these problems, for example, methods for improving the use of a damage prevention component such as a protein hydrolyzate or using an intermediate treatment agent have been disclosed (see Patent Documents 1 to 8). Their effects were not always satisfactory.
JP-A-8-40852 JP-A-8-268848 Japanese Patent Application Laid-Open No. 11-139941 JP 2000-319143 A JP 2002-154939 A JP 2002-255757 A JP 2003-252734 A JP 2003-55169 A

An object of the present invention is to provide a hair treatment agent that reduces damage to hair when used as a permanent pretreatment agent or a hair dyeing pretreatment agent .

  As a result of intensive studies to solve the above problems, the present inventor has developed a specific compound, that is, a compound having two or more hydrophobic groups and hydrophilic groups in the molecule (multi-chain polyhydrophilic group type compound). Attention was focused on, and it was found that the hair treatment agent was formulated by blending this into a hair treatment agent with reduced damage to the hair, and the present invention was completed.

That is, the present invention is as follows.
1. A perm or hair dyeing pretreatment agent of a non-washing type characterized by containing 0.01 to 5% by mass of one or more kinds of multi-chain polyhydrophilic group compounds represented by the following general formula .
(In the above general formula, R ¹ CO represents an acyl group derived from a saturated or unsaturated fatty acid having 12 to 18 carbon atoms, and X is independently H, Na or K.)

When used as a permanent pretreatment agent or a hair dyeing pretreatment agent , damage to the hair during use thereof is reduced, the effect of the permanent is promoted, and hair dyeing is performed evenly.

  Hereinafter, the present invention will be specifically described focusing on its preferred form. The hair treatment agent of the present invention comprises one or more multi-chain polyhydrophilic group type compounds each having two or more hydrophobic groups and hydrophilic groups in the molecule.

  The two or more hydrophobic groups possessed by the multi-chain polyhydrophilic group-type compound may be each independently a hydrophobic group having 2 to 20 carbon atoms, a saturated or unsaturated linear, branched or cyclic chain. preferable. Further, the two or more hydrophilic groups possessed by the multi-chain polyhydrophilic group type compound are each independently a carboxyl group, a sulfonic acid group, a sulfuric acid residue, a phosphoric acid residue or a salt thereof, or an oxyalkylene group, polyethylene A glycol group or the like, or an amino group, a quaternary ammonium group, a pyridinium group, a sulfonium group or a salt thereof is preferable.

  The number of hydrophobic groups or hydrophilic groups contained in the multi-chain polyhydrophilic group-type compound is preferably 2 or more and 60 or less, and more preferably 2 or more and 40 or less. Further, it is particularly preferably 2 or more and 20 or less.

  Preferred examples of the hydrophobic group of the polychain polyhydrophilic group compound include n-acetyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl. , N-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, and their branches Examples of the chain isomers and unsaturated residues having an unsaturated moiety at one, two or three positions corresponding to these are given.

  Further, the hydrophobic group of the multi-chain polyhydrophilic group type compound is more preferably an acyl group derived from a saturated or unsaturated fatty acid having 2 to 20 carbon atoms. That is, the multi-chain polyhydrophilic group-type compound is preferably an acyl compound having two or more acyl groups. Two or more acyl groups may be independently different or the same. The acyl group is preferably derived from a saturated or unsaturated fatty acid having 2 to 20 carbon atoms, and may be linear, branched or cyclic. However, the carboxyl group is not included.

  Examples of the acyl group include acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, Linear fatty acids such as margaric acid, stearic acid, nonadecanoic acid, arachidic acid;

  2-butyl-5-methylpentanoic acid, 2-isobutyl-5-methylpentanoic acid, dimethyloctanoic acid, dimethylnonanoic acid, 2-butyl-5-methylhexanoic acid, methylundecanoic acid, dimethyldecanoic acid, 2-ethyl- 3-methylnonanoic acid, 2,2-dimethyl-4-ethyloctanoic acid, methyldocosanoic acid, 2-propyl-3-methylnonanoic acid, methyltridecanoic acid, dimethyldodecanoic acid, 2-butyl-3-methylnonanoic acid, methyltetradecanoic acid , Ethyltridecanoic acid, propyldodecanoic acid, butylundecanoic acid, pentyldecanoic acid, hexylnonanoic acid, 2- (3-methylbutyl) -3-methylnonanoic acid, 2- (2-methylbutyl) -3-methylnonanoic acid, butylethylnonane Acid, methylpentadecanoic acid, ethyltetradecanoic acid, propyltri Canic acid, butyldodecanoic acid, pentylundecanoic acid, hexyldecanoic acid, heptylnonanoic acid, dimethyltetradecanoic acid, butylpentylheptanoic acid, trimethyltridecanoic acid, methylhexadecanoic acid, ethylpentadecanoic acid, propyltetradecanoic acid, butyltridecanoic acid, pentyldodecane Acid, hexylundecanoic acid, heptyldecanoic acid, methylheptylnonanoic acid, dipentylheptanoic acid, methylheptadecanoic acid, ethylhexadecanoic acid, ethylhexadecanoic acid, propylpentadecanoic acid, butyltetradecanoic acid, pentyltridecanoic acid, hexyldodecanoic acid, heptyl Undecanoic acid, octyldecanoic acid, dimethylhexadecanoic acid, methyloctylnonanoic acid, methyloctadecanoic acid, ethylheptadecanoic acid, dimethylheptadecanoic acid, Octyl decanoic acid, Mechirunonadekan acid, Mechirunonadekan acid, dimethyl octadecanoic acid, branched fatty acids such as butyl heptyl nonanoic acid;

  Octenoic acid, nonenoic acid, decenoic acid, caproleic acid, undecylenic acid, Lindelic acid, touric acid, lauroleic acid, tridecenoic acid, tuzuic acid, myristoleic acid, pentadecenoic acid, hexedenoic acid, palmitoleic acid, heptadecenoic acid, octadecenoic acid, Linear monoenoic acids such as oleic acid, nonadecenoic acid, gondoic acid;

  Such as methylheptenoic acid, methylnonenoic acid, methylundecenoic acid, dimethyldecenoic acid, methyldodecenoic acid, methyltridecenoic acid, dimethyldodecenoic acid, dimethyltridecenoic acid, methyloctadecenoic acid, dimethylheptadecenoic acid, ethyloctadecenoic acid Branched monoenoic acid;

  Di- or trienoic acids such as linoleic acid, linoleic acid, eleostearic acid, linolenic acid, linolenic elaidic acid, pseudoeleostearic acid, parinaric acid, arachidonic acid;

  Acetylene acids such as octinoic acid, nonic acid, decinic acid, undecinic acid, dodecinic acid, tridecinic acid, tetradecinic acid, pentadecinic acid, heptadesinic acid, octadecinic acid, nonadesinic acid, dimethyloctadesinic acid;

Of methyleneoctadecenoic acid, methyleneoctadecanoic acid, aleprolic acid, alepresinic acid, allepuric acid, alepuric acid, hydnocarpic acid, shoulmuccinic acid, gorulic acid, α-cyclopentylic acid, α-cyclohexylic acid, α-cyclopentylethylic acid Cyclic acids such as;
And those derived from fatty acids such as

  The acyl group may be a fatty acid-derived acyl group obtained from natural fats and oils, and is preferably a mixed fatty acid-derived acyl group containing 80% or more of the above saturated or unsaturated fatty acid having 2 to 20 carbon atoms. For example, acyl groups derived from coconut oil fatty acid, palm oil fatty acid, linseed oil fatty acid, sunflower oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, castor oil fatty acid, olive oil fatty acid, camellia oil fatty acid, rapeseed oil fatty acid, palm kernel oil fatty acid, etc. Etc. Two or more of these acyl compounds having an acyl group may be used in combination. The acyl group is preferably derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms.

  When a polychain polyhydrophilic group type compound is used as a salt, examples thereof include alkali metal salts, alkaline earth metal salts, ammonium salts, organic amine salts, basic amino acid salts, and the like. Specifically, sodium, potassium Alkaline metals such as lithium, alkaline earth metals such as calcium and magnesium, metals such as aluminum and zinc, organic amines such as ammonia, monoethanolamine, diethanolamine, triethanolamine and triisopropanolamine, bases such as arginine and lysine Or a salt with one or more selected from amino acids and the like. Among these, sodium salts, potassium salts, organic amine salts, and basic amino acid salts are particularly preferable.

Furthermore, it is preferable that at least one of the multi-chain polyhydrophilic group type compounds is an acyl compound represented by the following general formula (1) and the following general formula (2) .
(In the above general formula (1), X is a linear, branched, cyclic or aromatic hydrocarbon chain having a molecular weight of 1,000,000 or less, which may have m functional groups and other substituents. The n (m ≧ n) Qs bonded to X are substituents represented by the following general formula (2), which may be the same as or different from each other. In formula (2), Z is a bond derived from a functional group of X, R ¹ CO represents an acyl group derived from a saturated or unsaturated fatty acid having 2 to 20 carbon atoms, and R ² represents Represents a lower alkyl group having 1 to 3 carbon atoms which is hydrogen, or may be substituted by a hydroxyl group or a carboxyl group, and Y represents a carboxyl group, a sulfonic acid group, a sulfate group, a phosphate group or The salt inside of J and k are each independently 0, 1, or 2 and j and k are not 0 at the same time, n is an integer of 2 to 20, and m is m ≧ n. Indicates an integer.)
As used herein, the term “acyl compound” refers to a compound having at least one acyl group and a hydrophilic group in the molecule, as shown in general formula (1) and general formula (2). The structure is connected by a spacer.

In the general formula (2), the acyl groups represented by R ¹ CO may be independently, that is, may be different or the same, and are derived from a saturated or unsaturated fatty acid having 2 to 20 carbon atoms as described above. Those are preferred, and may be linear, branched or cyclic.

In general formula (2), R ² is hydrogen, or the number of carbon atoms that may be substituted by a hydroxyl group, a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, or a salt thereof. 1 to 3 lower alkyl groups, and examples of the lower alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxy (iso) propyl group, and a dihydroxy (iso) propyl group. Group, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group and the like.

  In the general formula (1), n substituents Q (formula (2)) bonded to X may be different from each other or the same. Moreover, Formula (2) shows what is called an acidic amino acid N-acylated, and it does not ask | require whether they are optical isomers, for example, D-form, L-form, and a racemate.

  The acidic amino acid is a monoaminodicarboxylic acid having 2 and 1 carboxyl groups and 1 amino group, respectively, in the molecule, and the amino group may be an N-methyl group or an N-ethyl group. It does not matter whether it is an optical isomer, for example, a D-form, an L-form, or a racemate. Examples of acidic amino acids include glutamic acid, aspartic acid, lanthionine, β-methyllanthionine, cystathionine, diencholic acid, ferrinin, aminomalonic acid, β-oxyaspartic acid, α-amino-α-methylsuccinic acid, β-oxyglutamic acid. , Γ-oxyglutamic acid, γ-methylglutamic acid, γ-methyleneglutamic acid, γ-methyl-γ-oxyglutamic acid, α-aminoadipic acid, α-amino-γ-oxyadipic acid, α-aminopimelic acid, α-amino- Examples thereof include γ-oxypimelic acid, β-aminopimelic acid, α-aminosuberic acid, α-aminosebacic acid, pantothenic acid and the like.

  The n substituents (formula (2)) attached to X are preferable because the acidic amino acid is an L-acidic amino acid molecule because it is excellent in biodegradability.

In the general formula (2), Z is a bonding part (—O) derived from m functional groups (hydroxyl group, amino group, thiol group) substituted with X (m ≧ n and an integer of 2 to 20). -, -NR < ³ >-, -S-). Here, R ³ is hydrogen or an alkyl group, alkenyl group, aryl group or alkylaryl group having 1 to 10 carbon atoms.

  In general formula (1), X is a linear or branched or cyclic chain having a molecular weight of 1 million or less and having m functional groups consisting of one or more selected from a hydroxyl group, an amino group and a thiol group. It is a spacer which is an aromatic hydrocarbon chain, and X may have a substituent other than a hydroxyl group, an amino group and a thiol group.

  In the general formula (1), X is preferably a residue of an m-valent compound having a molecular weight of 1 million or less and having m functional groups of one kind or two or more kinds selected from a hydroxyl group, an amino group and a thiol group. , A compound residue that may have a substituent other than a hydroxyl group, an amino group, or a thiol group. Here, the m-valent compound means that a bond derived from m functional groups can be formed. It does not matter whether they are optical isomers such as D-form, L-form, and racemate.

  Examples of such m-valent compounds include amino acids such as serine, threonine, cysteine, cystine, cystine disulfoxide, cystathionine, methionine, arginine, lysine, tyrosine, histidine, tryptophan, and oxyproline;

  Aminoethanol, aminopropanol, aminobutanol, aminopentanol, aminohexanol, aminopropanediol, aminoethylethanolamine, aminoethylaminoethanol, aminocresol, aminonaphthol, aminonaphtholsulfonic acid, aminohydroxybenzoic acid, aminohydroxybutanoic acid Compounds having an amino group and a hydroxyl group in the molecule such as aminophenol, aminophenethyl alcohol, glucosamine;

Compounds having a thiol group and a hydroxyl group in the molecule such as mercaptoethanol, mercaptophenol, mercaptopropanediol, glucothiose;
Compounds having a thiol group and an amino group in the molecule such as aminothiophenol and aminotriazole thiol;
Is mentioned. Further, proteins, peptides, etc., or those obtained by hydrolyzing them may be used.

  In the general formula (1), X is preferably an m-valent (m ≧ n) polyhydroxyl compound residue having a molecular weight of 1,000,000 or less, which may have a substituent other than a hydroxyl group. Here, the m-valent polyhydroxyl compound means that m ester bonds can be formed. It does not matter whether they are optical isomers such as D-form, L-form, and racemate.

  Examples of such m-valent polyhydroxyl compounds include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. , Pentanediol, 1,6-hexanediol, cyclohexanediol, dimethylolcyclohexane, neopentyl glycol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, isoprene glycol, 3-methyl -1,5-pentanediol, sorbite, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, dimer diol, dimethylolpropionic acid, dimethylolbutanoic acid, tartaric acid, dihydro Shi tartaric, mevalonate, 3,4-dihydroxy cinnamic acid, 3,4-dihydroxy-hydro cinnamic acid, hydroxy benzoic acid, dihydroxy stearic acid, dihydroxyphenylalanine, and the like, and divalent hydroxyl compounds such as isomers thereof;

  Glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl- Trivalent poly, such as 2,3,4-pentanetriol, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane, trimethylolpropane, diethanolamine, triethanolamine, trihydroxystearic acid Hydroxyl compounds;

Pentaerythritol, erythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexane Tetravalent polyhydroxyl compounds such as tetrol, diglycerin and sorbitan;
Pentavalent polyhydroxyl compounds such as adonitol, arabitol, xylitol, triglycerin;
Hexavalent polyhydroxyl compounds such as dipentaerythritol, sorbitol, mannitol, iditol, inositol, dulcitol, talose, allose;
Or these dehydration condensates, polyglycerol, etc. are mentioned.

  Sugars such as tetroses such as erythrose, sreose, erythrulose;

  Pentose such as ribose, arabinose, xylose, lyxose, xylulose, ribulose; monosaccharides such as hexose such as allose, altrose, glucose, mannose, guylose, idose, galactose, talose, fructose, sorbose, psicose, tagatose;

  Examples thereof include oligosaccharides such as maltose, isomaltose, cellobiose, gentiobiose, melibiose, lactose, turanose, trehalose, saccharose, mannitolose, cellotriose, gentianose, raffinose, meletitose, cellotetorose, stachyose and the like.

  In addition, other saccharides such as heptose, deoxy sugar, amino sugar, thio sugar, seleno sugar, aldone sugar, uronic acid, sugar acid, ketoaldonic acid, anhydro sugar, unsaturated sugar, sugar ester, sugar ether, glycoside, etc. It may be a group, and may be a polysaccharide such as starch, glycogen, cellulose, chitin, chitosan or the like, or a hydrolyzed product thereof.

  In general formula (1), X is preferably an m-valent polyamino compound residue having a molecular weight of 1,000,000 or less, which may have a substituent other than an amino group. Here, the m-valent polyamino compound means that m acid amide bonds can be formed. It does not matter whether they are optical isomers such as D-form, L-form, and racemate.

  Examples of such m-valent polyamino compounds include N, N′-dimethylhydrazine, ethylenediamine, N, N′-dimethylethylenediamine, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, diaminononane, Aliphatic diamines such as diaminodecane, diaminododecane, diaminoadipic acid, diaminopropanoic acid, diaminobutanoic acid and their isomers;

  Diethylenetriamine, triaminohexane, triaminododecane, 1,8-diamino-4-aminomethyl-octane, 2,6-diaminocapric acid-2-aminoethyl ester, 1,3,6-triaminohexane, 1,6 , 11-triaminoundecane, aliphatic triamines such as di (aminoethyl) amine and isomers thereof;

Alicyclic polyamines such as diaminocyclobutane, diaminocyclohexane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, triaminocyclohexane;
Aromatic polyamines such as diaminobenzene, diaminotoluene, diaminobenzoic acid, diaminoanthraquinone, diaminobenzenesulfonic acid, diaminobenzoic acid, and their respective isomers;
Araliphatic polyamines such as diaminoxylene, di (aminomethyl) benzene, di (aminomethyl) pyridine, di (aminomethyl) naphthalene, and their isomers;
And polyamines substituted with hydroxyl groups such as diaminohydroxypropane and isomers thereof.

  In the general formula (1), X is preferably an m-valent polythiol compound residue having a molecular weight of 1,000,000 or less, which may have a substituent other than a thiol group. Here, the m-valent polythiol compound means that m thioester bonds can be formed. It does not matter whether they are optical isomers such as D-form, L-form, and racemate.

  Examples of such m-valent polythiol compounds include dithiol compounds such as dithioethylene glycol, dithioerythritol, and dithiothreitol.

  X is preferably a group having 1 to 40 carbon atoms among the residues of the compounds listed above, and more preferably X has 1 to 20 carbon atoms. X is preferably a naturally occurring type from the viewpoint of excellent biodegradability.

  In general formula (2), the carboxyl group, sulfonic acid group, sulfate ester group, phosphate ester group represented by Y and the carboxyl group, sulfonate group, sulfate ester group, phosphate ester group, etc. that can be contained in X are: Salts can be formed with various basic substances.

Examples of such salts include alkali metal salts, alkaline earth metal salts, ammonium salts, organic amine salts, basic amino acid salts, polyvalent metal salts, and the like, specifically, alkalis such as sodium, potassium, and lithium. Metals, alkaline earth metals such as calcium and magnesium, metals such as aluminum, zinc, iron, cobalt, titanium and zirconium, organic amines such as ammonia, monoethanolamine, diethanolamine, triethanolamine and triisopropanolamine, arginine and lysine Or a salt with one or more kinds selected arbitrarily from basic amino acids and the like.
The method for producing the acyl compound represented by the general formula (1) is selected from an N-acyl acidic amino acid anhydride represented by the following general formula (3) and a hydroxyl group, an amino group, and a thiol group in the molecule. By reacting a compound having one or more kinds of m functional groups with water and / or a mixed solvent of water and an organic solvent, or tetrahydrofuran, benzene, toluene, xylene, carbon tetrachloride, It can be obtained by reacting using an inert solvent such as chloroform or acetone, or by mixing at -5 ° C to 200 ° C at a temperature equal to or higher than any melting point without solvent.

  Alternatively, the acyl compound represented by the general formula (1) includes an N-acyl acidic amino acid mono-lower ester (for example, methyl ester, ethyl ester) and a polyhydroxyl compound, a polyamino compound, or a polythiol compound, or a hydroxyl group or an amino group in the molecule. , A compound having any two or three of the thiol groups is dissolved in a suitable solvent such as dimethylformamide, a catalyst such as potassium carbonate is added, and the reaction is performed at −5 ° C. to 250 ° C. under reduced pressure. Thereafter, it can be obtained by removing the reaction solvent. Alternatively, the acyl compound can be obtained by melting with heating without a solvent, adding a catalyst such as sodium hydroxide, and performing a transesterification reaction at room temperature to 250 ° C.

  There is no restriction | limiting in particular in the compounding quantity to the hair treatment agent of a polychain polyhydrophilic group type compound, Although it can adjust according to the objective, It is preferable to set it as 0.001-50 mass%. When the content of the multi-chain polyhydrophilic group-type compound is 50% by mass or less, the effect of preventing damage to the hair is likely to be sufficient, and imparting to the hair such effects as strain, cohesion, and smoothness is likely to be obtained. Further, when the content is 0.001% by mass or more, stickiness or the like is less likely to occur. More preferably, it is 0.001-30 mass%. More preferably, it is 0.01 to 20% by mass in the case where the hair treatment agent is washed away at the time of use, and 0.01 to 5% by mass in the case where the hair treatment agent is not washed away.

  Further, the hair treatment agent can be used by adjusting its pH appropriately with a neutralizing agent. For example, it can be used in a wide pH range of pH 3-12. It is preferable to use at pH 4.5-11. More preferably, the pH is 5-8.

  The hair treatment agent can be produced by appropriately selecting the material components to be used, putting these material components into a normal stirrer, mixer, disperser or the like at a predetermined ratio and mixing them uniformly.

  In addition, for hair treatment agents, as long as the object of the present invention is not impaired, a permanent solution, a bleaching agent, a hair dye, a hair dye, a permanent pre-treatment agent, a permanent post-treatment agent, a pre-dye treatment, and a post-hair dyeing Various base materials can be added according to the use and purpose of the treatment agent.

  For example, alkane sulfonates, alpha-olefin sulfonates (AOS), alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfonates (SAS), sulfonates of higher fatty acid esters, alpha-sulfonated fatty acid salts, Higher fatty acid amide sulfonate, N-acyl-N-alkyltaurine salt, dialkylsulfosuccinate, sulfated oil, alkyl sulfate ester (AS), alkyl ether sulfate, sulfate of higher fatty acid ester, higher fatty acid alkyl Rollamide sulfate, polyoxyalkylene alkyl ether sulfate (AES), polyoxyalkylene styrenated phenyl ether sulfate, alkyl phosphate, alkyl ether phosphate, polyoxyethylene alkyl ether phosphate, Polyoxyethylene alkyl phenyl ether phosphates, naphthalenesulfonic acid salt formalin condensates, alkyl ether carboxylates, anionic surfactants such as ether carboxylic acid salts;

  In particular, N-acyl amino acid type anionic surfactants are effective, and the acyl group includes those having 8 to 20 carbon atoms as described above, and the constituent amino acids include those such as glutamic acid and aspartic acid. Acidic amino acids or glycine, alanine, valine, leucine, isoleucine, proline, methionine, cysteine, tryptophan, tyrosine, phenylalanine, asparagine, glutamine, serine, threonine, oxyproline, β-aminopropionic acid, γ-aminobutyric acid, And amino acids such as anthranilic acid, m-aminobenzoic acid, and p-aminobenzoic acid.

  Other than anionic surfactants, polyhydric alcohol esters such as alkyl polyglucosides, (poly) glycerin fatty acid esters, propylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid esters such as sho, polyoxyethylene alkyl ether (AE), polyoxy Alkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene fatty acid alkanolamide, polyoxyalkylene alkyl glucoside, polyoxyalkylene hydrogenated castor oil, polyoxyalkylene alkylamine, polyoxyalkylene alkyl phenyl ether, polyoxyethylene polystyryl phenyl ether , Polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene Glycol, ethylene oxide condensation type etc., fatty acid alkanolamides, sugar Amin'ashiru products, triethanolamine fatty acid partial esters, alkyl amine oxides, nonionic surfactants and the like;

  Alkylbetaines, alkylamidobetaines, alkylsulfobetaines, imidazolinium betaines, lecithins, and the like, specifically, amphoteric surfactants such as lauric acid amidopropylbetaine;

  Primary to tertiary fatty amine salts, alkylammonium chloride salts, tetraalkylammonium salts, trialkylbenzylammonium salts, alkylpyridinium salts, alkylhydroxyethylimidazolinium salts, dialkylmorpholinium salts, alkylisoquinolium salts, Cationic surfactants such as benzethonium salts and benzalkonium salts;

  Cationized cellulose derivative, cationic starch, cationized guar gum derivative, diallyl quaternary ammonium salt / acrylamide copolymer, quaternized polyvinylpyrrolidone derivative, quaternized vinylpyrrolidone / vinylimidazole polymer, polyglycol / amine condensate, Cationic compounds such as quaternized collagen polypeptides, polyethyleneimine, cationic silicone polymers, adipic acid / dimethylaminohydroxypropyldiethylenetriamine copolymers, polyaminopolyamides, cationic chitin derivatives, quaternized polymers and other cationic polymers;

  Natural rubbers such as gum arabic and tragacanth, glucosides such as saponin, cellulose derivatives such as methylcellulose, carboxycellulose, and hydroxymethylcellulose, natural polymers such as lignin sulfonate and shellac, polyacrylate, and styrene-acrylic acid Polymer salts, vinyl naphthalene-maleic acid copolymer salts, sodium salts of β-naphthalene sulfonic acid formalin condensates, anionic polymers such as phosphates, and nonions such as polyvinyl alcohol, polyvinyl pyrrolidone and polyethylene glycol Dispersing agents such as functional polymers;

Polymeric surfactants such as sodium alginate, starch derivatives, tragacanth gum;
Natural surfactants such as lecithin, lanolin, cholesterol, saponin;
Avocado oil, almond oil, olive oil, cacao oil, sesame oil, safflower oil, soybean oil, camellia oil, persic oil, castor oil, mink oil, cottonseed oil, owl, palm oil, egg yolk oil, palm oil, palm kernel oil, synthetic triglyceride, Fats and oils such as jojoba oil;
Hydrocarbons such as liquid paraffin, petrolatum, ceresin, microcrystalline wax, isoparaffin;
Waxes such as beeswax, whale wax, lanolin, carnauba wax, candelilla wax and derivatives thereof;
Higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, behenic acid, undecylenic acid, lanolin fatty acid, hard lanolin fatty acid, soft lanolin fatty acid;

  Higher alcohols such as lauryl alcohol, cetanol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyldecanol, octyldodecanol;

Other ester oils such as isopropyl myristate and butyl stearate;
Metal soap, dimethylpolysiloxane, polyether-modified silicone, alcohol-modified silicone, methylphenylpolysiloxane, epoxy-modified silicone, fluorine-modified silicone, alkyl-modified silicone, alkoxy-modified silicone, amino-modified silicone, volatile silicone and other silicones Volatile and non-volatile oils;
Moisturizers such as trimethylglycine, sorbitol, raffinose, pyrrolidone carboxylates, lactates, hyaluronates, ceramides;

  Hydroxyethylcellulose, carboxymethylcellulose, hydroxyethylcellulose hydroxypropyltrimethylammonium chloride ether, methylcellulose, ethylcellulose, hydroxypropylcellulose, methylhydroxypropylcellulose, soluble starch, carboxymethylstarch, methylstarch,

  Propylene glycol alginate, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer, polyacrylate, guar gum, locust bin gum, quince seed, carrageenan, galactan,

  Gum arabic, pectin, mannan, starch, xanthan gum, dextran, succinoglucan, curdlan, hyaluronic acid, gelatin, casein, albumin, collagen, methoxyethylene maleic anhydride copolymer, amphoteric methacrylate copolymer, polychlorinated Water-soluble and oil-soluble polymers such as dimethylmethylene piperidinium, polyacrylate copolymer, polyvinyl acetate, nitrocellulose, silicone resin;

Thickening and foam increasing components such as polyethylene glycol fatty acid ester, polyoxyethylene fatty acid ester methyl glycoside, tetradecene sulfonate;
Sequestering agents such as ethylenediaminetetraacetic acid and its salts, hydroxyethylenediaminetriacetic acid and its salts, phosphoric acid, ascorbic acid, succinic acid, gluconic acid, polyphosphates, metaphosphates, hinokitiles;
Preservatives such as paraoxybenzoates, benzoic acid and its salts, phenoxyethanol, hinokitile;
PH adjusters such as citric acid, malic acid, adipic acid, glutamic acid, aspartic acid;
Other anti-dandruff and itching agents such as trichlorocarbanilide, salicylic acid, zinc pyrithione, isopropylmethylphenol;
Benzophenone derivatives, paraaminobenzoic acid derivatives, paramethoxycinnamic acid derivatives, salicylic acid derivatives and other UV absorbers;
Whitening agents such as arbutin, kojic acid, ascorbic acid, hinokitile and its derivatives;

Blood circulation promoters such as assembly extract, cephalanthin, vitamin E and its derivatives, gamma oryzanol;
Local stimulants such as pepper tincture, ginger tincture, cantharis tincture, nicotinic acid benzyl ester;
Nutrients such as various vitamins and amino acids;
Female hormone agent;
Hair root activator;
Anti-inflammatory agents such as glycyrrhetinic acid, glycyrrhizic acid derivatives, allantoin, azulene, aminocaproic acid, hydrocortisone;
Astringents such as zinc oxide, zinc sulfate, allantoin hydroxyaluminum, aluminum chloride, zinc sulfocolate, tannic acid;
Refreshing agents such as menthol and camphor;
Antihistamines;
Antioxidants such as silicone-based materials such as polymer silicone and cyclic silicone, tocopherols, BHA, BHT, gallic acid, NDGA;
Sebum inhibitors such as estradiol, estrone, ethinyl estradiol;
Exfoliating / dissolving agents such as sulfur, salicylic acid, resorcin;

  Organic synthetic pigments (dyes, lakes, organic pigments), natural pigments, inorganic pigments (external pigments, colored pigments, white pigments), pearlescent pigments, polymer powders, functional pigments It can be used without being limited to the shape of needles, etc., the particle size of fumes, fine particles, pigment grades, etc., and the structure of particles such as porous and nonporous. For example, talc, kaolin, sericite, calcium carbonate, zinc oxide, aluminum oxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, barium sulfate, chromium oxide, chromium hydroxide, tar dyes, mica, (synthetic) seric Site, silicon carbide, boron nitride, titanium dioxide, black titanium oxide, conger, red iron oxide, black iron oxide, yellow iron oxide, ultramarine, titanium coated mica, bismuth oxychloride, bengara, caking pigment, gunjo pink, gun Zou violet, chromium hydroxide, mica titanium, chromium oxide, aluminum cobalt oxide, carbon black, silicic anhydride, magnesium silicate, bentonite, (synthetic) mica, zirconium oxide, magnesium (meth) silicate aluminate, aluminum silicate Calcium oxide, Liethylene powder, nylon powder, polymethyl methacrylate, polyethylene terephthalate-polymethyl methacrylate laminated powder, acrylonitrile-methacrylic acid copolymer powder, vinylidene chloride-methacrylic acid copolymer powder, wool powder, silk powder, crystalline cellulose, N-acyl lysine, poly Methyl silsesquioxane powder, plant nuts and powdered powder, bismuth oxychloride, mica titanium, iron oxide coated mica, iron oxide mica titanium, organic pigment treated mica titanium, aluminum powder, fine particle titanium oxide, Fine zinc oxide, fine titanium oxide coated mica titanium, fine zinc oxide coated mica titanium, barium sulfate coated mica titanium, carmine, β-carotene, chlorophyll, sunset yellow FCF, Ponceau SX, eosin YS, TE Trabromofluorescein, rhodamine B, quinoline yellow SS, quinoline yellow WS, alizanin cyanine green, quinizarin green, resolbin BCA, resolbin BCA, permaton red, herringdon pink CN, phthalocyanine blue, β-apo-8-carotenal , Capsanthin, lylopine, bixin, crocin, canthaxanthin, shisonin, raphanin, ninocyanin, calsamine, safrole yellow, rutin, quercetin, cacao dye, lipoflavin, lacaic acid, carminic acid, kermesic acid, alizanin, shikonin, alkanine, niquinochrome, blood dye , Curcumin, betanin and other cosmetic colorants;

  Purified water, others, oyster extract, N-methyl-L-serine, whey, nicotinamide, diisopropylamine dichloroacetic acid, mevalonic acid, γ-aminobutyric acid (including γ-amino-β-hydroxybutyric acid), altea extract, Aloe extract, apricot kernel extract, turmeric extract, oolong tea extract, dried seawater, hydrolyzed wheat powder, hydrolyzed silk, carrot extract, cucumber extract, gentian extract, yeast extract, rice germ oil, comfrey extract, savonso extract, Giant extract, lion extract, birch extract, Atlantic mint extract, assembly extract, bisabolol, propolis, loofah extract, bodaiju extract, hop extract, marronnier extract, muroji extract, melissa extract, eucalyptus extract, yukinoshita extract, rosemary Kiss, Roman chamomile extract, royal jelly extract, seaweed, rice bran, licorice, citrus unshiu peel, angelica, pulverized Momonoha, sphingolipids, guaiazulene, vitamin C; can be included, and the like.

  The use of the hair treatment agent is not particularly limited as long as it is a hair treatment, but a permanent solution, a bleaching agent, a hair dye, a hair dye, a permanent pre-treatment agent, a permanent post-treatment agent, a hair dye pre-treatment agent, It is preferable to use a hair dyeing post-treatment agent because it has a significant meaning of manifesting a low damage characteristic.

  Hereinafter, the present invention will be described more specifically with reference to examples and the like.

The evaluation means used in the examples of the present invention are as follows.
(Hair damage evaluation test)

  50 hairs were sampled from each of the hair bundles treated with a conventional method according to the use of each composition such as a hair treatment agent, and the initial chuck distance 40 mm, 20 mm using a rheometer manufactured by Sun Science Co., Ltd. A tensile break test was performed at a rate of 1 minute. The maximum load obtained was defined as the hair strength after treatment.

Separately, the hair strength of untreated healthy hair bundles (hair strength before treatment) was measured in the same manner, and the ratio of the average value of the hair strength after treatment to the average value of these was retained. It was. The evaluation criteria for the retention rate were as follows.
When the retention rate is 100% to 95% or more
When retention rate is less than 95% to 85% or more
When the retention rate is less than 85%
(Evaluation of how to apply perm)

Visual evaluation was performed by five hairdressers with more than 3 years of experience. The evaluation criteria were as follows.
Five beauticians who evaluated that they had enough perm ...
1 to 4 beauticians evaluated as having sufficient perm
0 hairdressers who evaluated that they had enough perm ...
(Evaluation of uneven hair dyeing)

Visual evaluation was performed by five hairdressers with more than 3 years of experience. The evaluation criteria were as follows.
Five hairdressers who evaluated that there was no unevenness ...
1 to 4 hairdressers who evaluated that there is no unevenness
0 hairdressers who evaluated that there was no unevenness
(Production Example 1 of acyl compound)

  9.1 g (0.05 mol) of L-lysine hydrochloride was mixed with 57 g of water. While this solution was adjusted to a pH range of 10 to 11 with a 25% aqueous sodium hydroxide solution and the reaction temperature was maintained at 5 ° C., 31.1 g of N-lauroyl-L-glutamic anhydride (0. 1 mol) was added over 2 hours to carry out the reaction. After stirring for another 30 minutes, tertiary butanol was added to a concentration of 20% by mass in the liquid, 75% sulfuric acid was added dropwise to bring the pH value of the liquid to 2, and the liquid temperature to 65 ° C. It was adjusted. After completion of the dropwise addition, stirring was stopped and the mixture was allowed to stand at 65 ° C. for 20 minutes, so that the organic layer and the aqueous layer were separated, and the organic layer was separated therefrom. Tertiary butanol and water were added to the separated organic layer, the temperature was raised to 65 ° C., and the mixture was stirred for 20 minutes. When the mixture was allowed to stand after stirring was stopped, the organic layer and the aqueous layer were separated. After repeating the same water washing operation for the obtained organic layer, the solvent was removed from the obtained organic layer and neutralized with sodium hydroxide to an aqueous solution having a solid content of 30% by mass and a pH of 6.5 (25 ° C.). After the preparation, this was dried to obtain a composition containing an acyl compound represented by the following formula (4).

(In Formula 4, each X is independently H or Na)
(Production Example 2 of Acyl Compound)

The composition containing an acyl compound was carried out under the same conditions as in Production Example 1 except that 31.1 g of N-lauroyl-L-glutamic anhydride was changed to N-cocoyl-L-glutamic anhydride in Production Example 1. I got a thing.
(Acyl Compound Production Example 3)

In the manufacture example 1, it implemented on the same conditions as the method of the manufacture example 1 except having implemented the neutralization process with potassium hydroxide, and obtained the composition containing an acyl compound.
(Preparation of permanent wave agent)

In accordance with a conventional method, the 1st agent for permanent waves (compositions 1-8) of the composition of Table 1 and the 2nd agent for permanent waves (compositions 9-16) of the composition of Table 2, 3 were prepared, respectively. In addition, in each column of each composition in Tables 1 to 3, the numerical value indicates the blending ratio of the composition in mass%, and the notation “−” indicates that the composition is not blended.
[ Reference Examples 1-8 , Comparative Examples 1-2]

A hair damage evaluation test was performed using the first and second agents for permanent wave in the combinations shown in Table 4. The results are shown in Table 4.
[ Reference Example 9 ]

A hair dye having the following composition was prepared by a conventional method, and was tested on a healthy female paneler to conduct a hair damage evaluation test. The result was ○.
First agent (Mixed amount by mass)
Composition of Production Example 1 5
Paraphenylenediamine 3
Resorcin 0.5
Oleic acid 20
POE (10) oleyl ether 15
Isopropanol 10
Ammonia water (28%) 10
Purified water residue 2nd agent (blending amount% by mass)
Composition of Production Example 2 5
Hydrogen peroxide solution (30%) 20
Purified water residue [Comparative Example 3]

A hair dye having the following composition was prepared by a conventional method, and was tested on a healthy female paneler to conduct a hair damage evaluation test. The result was x.
First agent (Mixed amount by mass)
Paraphenylenediamine 3
Resorcin 0.5
Oleic acid 20
POE (10) oleyl ether 15
Isopropanol 10
Ammonia water (28%) 10
Purified water residue 2nd agent (blending amount% by mass)
Hydrogen peroxide solution (30%) 20
Purified water residue [ Reference Example 10 ]

A bleaching agent having the following composition was prepared by a conventional method, and a hair damage evaluation test was performed on a healthy female panelist. The result was ○.
First agent (Mixed amount by mass)
Composition of Production Example 3 10
POE (100) lauryl ether 20
POE (150) distearate 10
Palmitic acid 4
Ammonia water 9
Purified water residue 2nd agent (blending amount% by mass)
Composition of Production Example 1 5
POE (4) lauryl ether 5
POE (9) lauryl ether 5
Cetyl alcohol 52
Hydrogen peroxide solution (35%) 17
Purified water residue [Comparative Example 4]

A bleaching agent having the following composition was prepared by a conventional method, and a hair damage evaluation test was performed on a healthy female panelist. The result was x.
First agent (Mixed amount by mass)
POE (100) lauryl ether 20
POE (150) distearate 10
Palmitic acid 4
Ammonia water 9
Purified water residue 2nd agent (blending amount% by mass)
POE (4) lauryl ether 5
POE (9) lauryl ether 5
Cetyl alcohol 52
Hydrogen peroxide solution (35%) 17
Purified water residue [ Reference Example 11 ]

A bleaching agent having the following composition was prepared by a conventional method, and a hair damage evaluation test was performed on a healthy female panelist. The result was ○.
(Mixing amount by mass)
Composition of Production Example 2 0.05
Hydroxyethyl cellulose 1.6
Carboxyvinyl polymer 0.2
Benzyl alcohol 2.0
Glycolic acid 3.0
Red No. 104 (1) 0.3
Purified water residue [Comparative Example 5]

A bleaching agent having the following composition was prepared by a conventional method, and a hair damage evaluation test was performed on a healthy female panelist. The result was Δ.
(Mixing amount by mass)
Hydroxyethyl cellulose 1.6
Carboxyvinyl polymer 0.2
Benzyl alcohol 2.0
Glycolic acid 3.0
Red No. 104 (1) 0.3
Purified water residue [Example 12]

A perm treatment assistant with the following composition was prepared by a conventional method, and a beautician with 3 years experience on healthy female panelists before or after applying the first and second permanent wave agents shown in Comparative Example 1. The perm was applied and hair damage was evaluated. When this agent was used before the perm treatment, and when this agent was used after the perm treatment, the method of applying the perm was ○, and the degree of damage to the hair was ○.
(Mixing amount by mass)
Composition of Production Example 1 0.5
1,3-butylene glycol 2.0
Glycerin 1.0
Methylphenylpolysiloxane 1.0
Collagen hydrolyzate 1.0
(Product name: Seiwa Kasei Co., Ltd.
Promois W-42M)
Ethanol 50.0
Purified water residue [Comparative Example 6]

A perm treatment assistant with the following composition was prepared by a conventional method, and a beautician with 3 years experience on healthy female panelists before or after applying the first and second permanent wave agents shown in Comparative Example 1. The perm was applied and hair damage was evaluated. When this agent was used before the perm treatment, and when this agent was used after the perm treatment, the method of applying the perm was Δ, and the degree of hair damage was x.
(Mixing amount by mass)
1,3-butylene glycol 2.0
Glycerin 1.0
Methylphenylpolysiloxane 1.0
Collagen hydrolyzate 1.0
(Same as in Example 12)
Ethanol 50.0
Purified water residue [Example 13]

A hair dyeing assistant having the following composition was prepared by a conventional method, and after applying the hair dye shown in Comparative Example 3, it was applied to a healthy female panelist by a beautician with more than 3 years of experience to make hair unevenness. And hair damage was evaluated. When this agent was used before the hair dyeing treatment, in any case where this agent was used after the hair dyeing treatment, the unevenness of the hair dye was ○, and the degree of damage to the hair was ○.
(Mixing amount by mass)
Composition of Production Example 3 1.0
1,3-butylene glycol 1.0
Glycerin 2.0
Collagen hydrolyzate 1.0
(Same as in Example 12)
Ethanol 50.0
Purified water residue [Comparative Example 7]

A hair dyeing assistant having the following composition was prepared by a conventional method, and after applying the hair dye shown in Comparative Example 3, it was applied to a healthy female panelist by a beautician with more than 3 years of experience to make hair unevenness. And hair damage was evaluated. When this agent was used before the hair dyeing treatment, and when this agent was used after the hair dyeing treatment, the unevenness of the hair dye was x, and the degree of damage to the hair was x.
(Mixing amount by mass)
1,3-butylene glycol 1.0
Glycerin 2.0
Collagen hydrolyzate 1.0
(Same as in Example 12)
Ethanol 50.0
Purified water residue

Claims (1)

A perm or hair dyeing pretreatment agent of a non-washing type characterized by containing 0.01 to 5% by mass of one or more kinds of multi-chain polyhydrophilic group compounds represented by the following general formula .
(In the above general formula, R ¹ CO represents an acyl group derived from a saturated or unsaturated fatty acid having 12 to 18 carbon atoms, and X is independently H, Na or K.)