WO2019030872A1 - Hair treatment method - Google Patents

Abstract

This hair treatment method uses a hair cosmetic which is configured from one or more compositions, and contains the following components (A)-(C) among the constituent compositions: (A) one or more types of compound selected from glyoxylic acid, glyoxylic acid hydrate, glyoxylate salt, and glyoxylamide; (B) a phenol compound having an electron-donating group in one or more meta positions, and having a hydrogen atom in one or more ortho and/or para positions (however, the meta-position electron-donating group or groups may, along with an adjacent carbon atom, form a benzene ring which may be substituted with a hydroxyl group); and (C) a reducing agent. The hair treatment method includes (i) a step for applying components (A) and (B) to hair, and (ii) a step for heating and shaping the hair to which the components (A) and (B) have been applied, wherein the component (C) is applied to the hair at any point in time during the steps of this hair treatment method.

Description

Hair treatment method

The present invention relates to a method of treating hair that can deform the shape of the hair semipermanently or permanently.

As a method for deforming the shape of the hair semipermanently or permanently, there is a method using a reducing agent such as permanent wave or a method using a strong alkaline treating agent having a pH of 12 to 14 represented by an alkaline relaxer. However, it is well known that these methods have a large load on the hair and damage to the hair is likely to remain. Also, in recent years, a method of correcting hair loss using a large amount of formaldehyde has been developed as a method of reducing the damage to the hair in order to deform the shape of the hair semipermanently or permanently. However, the method using formaldehyde with high toxicity must be handled carefully because of its high volatility, and it can not be said that it is a preferable hair treatment method.

Therefore, a safer treatment method for the human body without damaging the hair and without using formaldehyde is being sought. For example, Patent Document 1 discloses a technique of straightening strong crimped hair by applying an α-keto acid, particularly glyoxylic acid, to the hair and heat-treating it with a flat iron at 200 ° C. ± 50 ° C. Patent Document 2 discloses a method of permanently relaxing keratin fibers by applying a polyhydroxylated aromatic compound to hair and heating the hair to 110 ° C. or higher.

On the other hand, temporary hair deformation that can reset the hairstyle by rinsing with water can be realized by using a styling agent. For example, Patent Document 3 discloses a hair composition in which glyceraldehyde and resorcinol are heated and refluxed in the presence of boric acid or silicic acid to form an oligomer. It is described that this composition has improved set holding power and moisture resistance, can be restyled by wetting with water, and improves the mechanical strength of the hair.

In addition, in Patent Document 4, undesirable yellowing occurs with time in hair treated with the hair composition described in Patent Document 3, and this yellowing is caused by the above-mentioned composition for hair. It is described that it is suppressed by containing.

Further, according to Patent Document 5, the method of deforming the hair shape under acidic conditions using glyoxylic acid and resorcinol causes less damage to the hair, and the shape of the hair can be deformed semipermanently or permanently. It is disclosed that the style once made can be changed to another hair shape without using hair cosmetics such as a reducing agent, and further, coloring immediately after processing and with time is suppressed.

(Patent Document 1) European Patent Application Publication No. 2538916 (Patent Document 2) Japanese Patent Application Publication No. 2009-537619 (Patent Document 3) US Patent No. 4,278,659 (Patent Document 4) US Patent No. 4338295 (Patent Document 5) Japanese Patent Application Laid-Open No. 2016-108319

The present invention consists of single or multiple compositions, in the total composition the following components (A) to (C);
(A): one or more compounds selected from glyoxylic acid, glyoxylic acid hydrate, glyoxylate, and glyoxylamide (B): having an electron donating group at at least one position of the meta position, ortho Phenolic compounds in which at least one position of position and para position is a hydrogen atom (however, the electron donating group at meta position may form a benzene ring which a hydroxyl group may substitute with an adjacent carbon atom)
(C): A hair treatment method using a hair cosmetic containing a reducing agent, which comprises the following steps (i) and (ii):
(i) applying components (A) and (B) to the hair (ii) heating and shaping the hair to which the components (A) and (B) are applied, all of the hair treatment method It provides a hair treatment method in which component (C) is applied to the hair at any point in the process.

Detailed Description of the Invention

When the hair is treated with the hair treatment agent according to the method described in Patent Document 1 or 2, even though semipermanent straight hair can be obtained, the hair is given a semipermanent to permanent wave shape or a curled shape. I could not. Also, if it is desired to change the semipermanent or permanent straight shape once made into another semipermanent or permanent hair shape such as wave or curl again, the conventional treatment using a reducing agent is necessary again As a result, it takes a great deal of time and effort, and the hair is damaged.

On the other hand, the techniques described in Patent Documents 3 and 4 are characterized by the point that they can be washed away with water by using an oligomer as the treatment agent, so that the hair shape returns to the original hair shape by repeated hair washing. It is difficult to say that it is a semi-permanent or permanent hair shape deformation.

Further, the method described in Patent Document 5 can change the style once made to another hair shape by applying heat after the hair deformation treatment, and further suppress the coloring of the hair immediately after the treatment and over time Although it is a method that can be performed, the coloring suppression effect in the case of repeated heat treatment for re-deformation was not sufficient.

The present invention is safe for the human body, less damage to the hair, semi-permanently to permanent, can deform the hair, and also once made style, without damaging the hair, semi-permanent to permanent Can be changed to a different form of hair, and not only the coloring immediately after the hair treatment, the coloring of the treated hair with time, but also the coloring of the hair when the re-deformation treatment by heating is repeated It relates to a method of treating hair that can.

In the present invention, "semi-permanent to permanent hair deformation" means that the hair-resistance is extremely excellent and the shape of the hair does not change even after repeated shampooing. Specifically, when the deformed hair is washed with shampoo, thoroughly washed away with water, and naturally dried, it means that the shape of the hair is maintained before and after shampooing. It should be noted that maintaining the shape of the hair means that, for example, in the case of wave-shaped hair, the number of waves does not substantially change before and after shampooing, and in the case of straight-shaped hair, waves and crimped hair are substantially generated by shampoo. It says that it does not occur.
In the present invention, “hair deformation” refers to deformation that does not occur due to cleavage and recombination of S—S bond of protein in the hair, and it is possible to transform straight hair into curls and the like. It includes deforming the hair to which deformation such as curling has been applied, natural crimped hair and the like into a straight hair shape.

The hair cosmetic composition used in the present invention may be either one-component hair cosmetic composition composed of a single composition, or any form of multi-component hair cosmetic composition composed of a plurality of compositions such as a two-component composition. Is included. In addition, the multi-component hair cosmetic composition is a single application type in which the first agent and the second agent are mixed and applied to the hair, a sequential application type in which the first agent, the second agent and the like are sequentially applied to the hair. being classified.
In the present invention, "the total composition of the hair cosmetic" refers to the composition of a single composition constituting the one-component hair cosmetic in the case of a one-component hair cosmetic, and is a single application multi-component In the case of formula hair cosmetics, all the compositions constituting the multi-part hair cosmetics are mixed prior to application of hair in such an amount ratio that the ratio of each component is within the range intended by the present invention. The composition of the mixture Further, even in the case of a sequential application type multi-component hair cosmetic composition which is not actually mixed, all the compositions constituting the multi-component hair cosmetic composition and the ratio of the respective components are within the range intended by the present invention. The composition of the mixture when it is virtually mixed is referred to as "the total composition of the hair cosmetic" in such an amount ratio.

[Component (A): glyoxylic acid, glyoxylic acid hydrate, glyoxylate or glyoxylamide]
Component (A) includes, in addition to glyoxylic acid, hydrates of glyoxylic acid, salts of glyoxylic acid, and glyoxyamide. Glyoxylic acid hydrate includes glyoxylic acid monohydrate. Examples of glyoxylic acid salts include glyoxylic acid alkali metal salts and glyoxylic acid alkaline earth metal salts, and examples of the alkali metal salts include lithium salts, sodium salts, potassium salts and the like, and examples of the alkaline earth metal salts And magnesium salts, calcium salts and the like. Examples of glyoxyl amides include N-glyoxyloylcarbocysteine, N-glyoxyloylkeratin amino acid and the like.

The content of the component (A) in the hair cosmetic composition to be used in the present invention makes the change of the hair shape after hair treatment more remarkable, and makes the hair resistance of the hair shape more excellent. From the viewpoint of making the change of shape during semi-permanent re-deformation more remarkable and making the hair-resistance to hair shape after re-deformation even more excellent, based on the whole composition of the hair cosmetic, in glyoxylic acid conversion Preferably, it is 1.0% by mass or more, more preferably 1.5% by mass or more, still more preferably 2.0% by mass or more, still more preferably 2.5% by mass or more, still more preferably 3.0% by mass or more, still more preferably 3.5% by mass or more In addition to the above-mentioned viewpoints, from the viewpoint of suppressing skin irritation, it is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, still more preferably 15% by mass or less Preferred 10 mass%, more preferably not more than 7 wt%.

[Component (B): Phenolic Compound of Specific Structure]
Component (B) is a phenolic compound having an electron donating group at at least one position, preferably at two positions in the meta position, and at least one position in the ortho position and the para position with a hydrogen atom. The electron donating group at the meta position of the phenol compound may form a benzene ring together with the adjacent carbon atom, and the benzene ring may be further substituted with a hydroxyl group. From the viewpoint of improving the permeability into the hair, the molecular weight of the component (B) is preferably 100 or more, more preferably 105 or more, still more preferably 110 or more, and preferably 1000 or less, more preferably 700 or less, 500 or less Is more preferred. As a phenol compound of a component (B), the following components (B1), (B2), and (B3) are mentioned, for example.

(B1) Resorcinol (B2) Compound Represented by Formula (1) (B3) Compound Represented by Formula (2)

Component (B1) is a resorcin represented by the following formula.

The component (B2) is a compound represented by the following general formula (1).

[In the formula,
R ¹ represents a hydrogen atom or a methyl group,
A ¹ and A ^{2, which} may be the same or different, each represents a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, or an aralkyl having 7 to 12 carbon atoms which may have a substituent Group or arylalkenyl group, linear or branched alkoxy group or alkenyloxy group having 1 to 6 carbon atoms, halogen atom or -CO-R ² (R ² is linear or branched alkyl having 1 to 12 carbon atoms Group or alkenyl group, an aralkyl group having 7 to 12 carbon atoms which may have a substituent, an arylalkenyl group, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent;
B represents a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, an aralkyl or aryl alkenyl group having 7 to 12 carbon atoms which may have a substituent, -OR ³ or- COOR ³ (R ³ represents a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms),
D represents a hydrogen atom, a hydroxyl group, a methyl group or a linear or branched alkoxy group having 1 to 12 carbon atoms or an alkenyloxy group,
E represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms.
However, two or three of A ¹ , A ² , B and E are hydrogen atoms, and the remaining groups do not contain a sulfo group. When D is a hydrogen atom or a methyl group, A ¹ and B, or A ² and B, together with two adjacent carbon atoms form a benzene ring which may be substituted by a hydroxyl group. ]

In the general formula (1), when the aralkyl group, the aryl alkenyl group or the aromatic hydrocarbon group has a substituent, examples of the substituent include a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or an alkenyl group Groups, and alkoxy groups having 1 to 12 carbon atoms. Moreover, carbon number of an aralkyl group, an aryl alkenyl group, and an aromatic hydrocarbon group points out the total carbon number containing the number of carbon atoms of a substituent.

The linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms as R ³ and E is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- Examples include butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, 1-methylpentyl, n-hexyl, isohexyl, vinyl, allyl, butenyl and hexenyl groups.

Examples of the linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms as A ¹ , A ² and E include groups in which an oxygen atom is bonded to the above-mentioned alkyl or alkenyl group having 1 to 6 carbons. Be

Examples of the linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms as A ¹ , A ² , R ² and B include, in addition to the aforementioned alkyl and alkenyl groups having 1 to 6 carbons, n-heptyl Group, 2,4-dimethylpentyl group, 1-n-propylbutyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, 1-methylnonyl group, n-decyl group, 3, 7-dimethyl group Examples include octyl group, 2-isopropyl-5-methylhexyl group, n-undecyl group, n-dodecyl group, decenyl group and the like.

Examples of the linear or branched alkoxy group or alkenyloxy group having 1 to 12 carbon atoms in D include groups in which an oxygen atom is bonded to the above-mentioned alkyl or alkenyl group having 1 to 12 carbon atoms.

As the optionally substituted aralkyl or aryl alkenyl group having 7 to 12 carbon atoms for A ¹ , A ² , R ² or B, benzyl, hydroxybenzyl, dihydroxybenzyl, phenylethyl, phenyl Ethenyl group, hydroxyphenylethyl group, dihydroxyphenylethyl group, hydroxyphenylethenyl group, dihydroxyphenylethenyl group, phenylpropyl group, phenylpropenyl group, phenylbutyl group, phenylbutenyl group, phenylpentyl group, phenylpentenyl group , Phenylhexyl group, phenylhexenyl group and the like.

The aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent in R ² includes phenyl group, hydroxyphenyl group, dihydroxyphenyl group, trihydroxyphenyl group, naphthyl group, hydroxynaphthyl group, dihydroxynaphthyl group And the like.

The halogen atom of A ^1, A ^2, a fluorine atom, a chlorine atom, a bromine atom.

Specific examples of the compound represented by the general formula (1) include resorcine derivatives represented by the following general formula (1-1), benzophenone derivatives represented by the general formula (1-2), and Naphthol derivatives represented by 1-3-a) or (1-3-b) can be mentioned.

[Wherein, R ¹ , A ¹ , A ² , B and E have the same meaning as described above, and D ¹ represents a hydroxyl group or a methoxy group. ]

[Wherein, R ¹ represents the same meaning as described above, D ² represents a hydroxyl group or an alkoxy group having 1 to 12 carbon atoms, and G represents a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or an alkenyl group Group or an alkoxy group having 1 to 6 carbon atoms, n is an integer of 0 to 2; ]

[Wherein, R ¹ , A ² , E, D, G and n have the same meaning as described above. ]

[Wherein, R ¹ , A ¹ , E, D, G and n have the same meaning as described above. ]

As the compound represented by the general formula (1-1), the following compounds (1-1-1) to (1-1-3) are preferable.

(1-1-1) m-Dimethoxybenzene derivative represented by the following general formula (1-1-1)

[Wherein, A ¹ , A ² , B and E have the same meaning as described above. ]

As A ¹ and A ² , a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alkenyl group is preferable, and a hydrogen atom is more preferable.
B is preferably a hydrogen atom, an alkyl or alkenyl group having 1 to 4 carbon atoms, an arylalkenyl group having 7 to 10 carbon atoms which may have a substituent, a hydroxyl group, and a hydrogen atom or a substituent More preferable is an arylalkenyl group having 7 to 10 carbon atoms and a hydroxyl group.
As E, a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alkenyl group is preferable, and a hydrogen atom is more preferable.

Examples of the compound corresponding to (1-1-1) include 1,3-dimethoxybenzene, 3,5-dimethoxyphenol, 2,6-dimethoxyphenol, 5- (hydroxyphenylethenyl) -1,3- Dimethoxybenzene (common name: pterostilbene) etc. are mentioned.

(1-1-2) m-Methoxyphenol Derivative Represented by the Following General Formula (1-1-2)

[Wherein, A ¹ , A ² , B and E have the same meaning as described above. ]

As A ¹ and A ² , a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, and an aralkyl or aryl alkenyl group having 7 to 12 carbon atoms which may have a substituent are preferable. Preferably, a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or an arylalkenyl group having 7 to 10 carbon atoms which may have a substituent is preferable.
B represents a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, an aralkyl or aryl alkenyl group having 7 to 12 carbon atoms which may have a substituent, -OR ³ ( R ³ is preferably a hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, and may have a hydrogen atom, an alkyl or alkenyl group having 1 to 4 carbons, or a substituent Preferred is a C7-10 arylalkenyl group, a hydroxyl group is more preferable, and a hydrogen atom, a C7-10 arylalkenyl group which may have a substituent, and a hydroxyl group are more preferable.
E is preferably a hydrogen atom, a hydroxyl group, a linear or branched alkyl or alkenyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy or alkenyloxy group having 1 to 4 carbon atoms, and a hydrogen atom or a hydroxyl group Is preferred.

Examples of the compound corresponding to (1-1-2) include 3-methoxyphenol, 5-methoxyresorcinol, 3-methoxybenzene-1,2-diol, 4-butyl-3-methoxyphenol, 3-methoxy- 4- (1-phenylethyl) phenol, 5- (4-hydroxyphenylethenyl) -1-hydroxy-3-methoxybenzene (conventional name: Pinostilbene), etc. may be mentioned.

(1-1-3) Resorcinol derivative represented by the following general formula (1-1-3)

[Wherein, A ¹ , A ² , B and E have the same meaning as described above. ]

Examples of resorcin derivatives represented by the general formula (1-1-3) include those represented by the following general formula (i) or (ii).

[Wherein, A ¹ , A ² and B are as defined above, and E ¹ is a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms or alkenyl group, or a linear group having 1 to 6 carbon atoms] Or a branched alkoxy group or alkenyloxy group. ]

As A ¹ and A ² , a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms is preferable, and a hydrogen atom is more preferable.
As B, a hydrogen atom, an aralkyl group having 7 to 12 carbon atoms which may have a substituent, or an arylalkenyl group, -OR ³ (R ³ is a hydrogen atom or a linear or branched chain having 1 to 4 carbon atoms Preferred is an alkyl group or an alkenyl group).
As E ¹ , a hydroxyl group, a linear or branched alkyl or alkenyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy or alkenyloxy group having 1 to 4 carbon atoms is preferable.

As resorcin derivatives represented by the general formula (i), 2-alkylresorcins such as 2-methylresorcin, 2-ethylresorcin, 2-propylresorcin, etc .;
Pyrogallol;
2-alkoxyresorcins such as 2-methoxyresorcin;
Gallic acid esters such as gallic acid, methyl gallate, ethyl gallate, propyl gallate, butyl gallate and the like;
5- (phenylethenyl) 2-isopropylresorcin etc. may be mentioned.

[Wherein, A ¹ , A ² and B have the same meaning as described above. ]

As the resorcin derivative represented by the general formula (ii), a resorcin derivative further represented by the general formula (ii-1) or (ii-2) is preferable.

[Wherein, A ¹ and A ² have the same meaning as described above. ]

Examples of resorcin derivatives represented by the general formula (ii-1) include 4-methylresorcin, 4-ethylresorcin, 4-propylresorcin, 4-isopropylresorcin, 4-butylresorcin (conventional name: Rucinol), 4-isobutyl resorcinol, 4-sec-butyl resorcinol, 4-tert-butyl resorcinol, 4-pentyl resorcinol, 4-isopentyl resorcinol, 4-sec-pentyl resorcinol, 4-tert-pentyl resorcinol, 4-neopentyl resorcinol, 4-Hexyl resorcinol, 4-isohexyl resorcinol, 4-heptyl resorcinol, 4-octyl resorcinol, 4- (2-ethylhexyl) resorcinol, 4-nonyl resorcinol, 4-decyl resorcinol, 4-undecyl resorcinol, 4-dodecyl resorcinol Etc. 4-alkyl resorcins;
4-alkenyl resorcins such as 4-vinyl resorcinol, 4-allyl resorcinol, 4-butenyl resorcinol, 4-hexenyl resorcinol, 4-decenyl resorcinol;
4-benzyl resorcinol, 4- (1-phenylethyl) resorcinol (conventional name: Simwhite 377), 4-furanylethyl resorcinol, 4-tetrahydropyranyl resorcinol, 4- (2-phenylethyl) resorcinol , 4-aralkyl resorcins such as 4- (3-phenylpropyl) resorcin;
4-hydroxy such as 4- (4-hydroxybenzyl) resorcinol, 4- (2,4-dihydroxybenzyl) resorcinol, 4- (4-hydroxyphenylethyl) resorcinol, 4- (2,4-dihydroxyphenylethyl) resorcinol Aralkyl resorcinol;
4-arylalkenyl resorcins such as 4- (1-phenylethenyl) resorcin, 4- (3-phenylpropenyl) resorcin;
4-hydroxyarylalkenyl resorcins such as 4- (4-hydroxyphenylethenyl) resorcin, 4- (2,4-dihydroxyphenylethenyl) resorcin;
4- (1-methylnaphthyl) resorcinol;
4-Alkoxyresorcinol, 4-Ethoxyresorcinol, 4-Isopropoxyresorcinol, 4-Propoxyresorcinol, 4-Butoxyresorcinol, 4-Butoxyresorcinol, 4-sec-Butoxyresorcinol, 4-Tert-Butoxyresorcinol Resorcinol;
4-halogenated resorcins such as 4-chlororesorcin, 4-bromoresorcin;
4-Alkanoyl resorcin such as 4-acetyl resorcinol, 4-propanoyl resorcinol, 4-butanoyl resorcinol, 4-pentanoyl resorcinol, 4-hexanoyl resorcinol;
4-phenylethanoylresorcinol, 4-phenylpropanoylresorcinol, 4-phenylbutanoylresorcinol, 4-phenylpentanoylresorcinol, 4-phenylhexanoylresorcinol, 3- (hydroxyphenyl) -1- (2,4-dihydroxy) And 4-arylalkanoyl resorcins such as phenyl) propen-1-one (common name: Isoliquiritigenin).

Among these, the condensation product of the component (A) and the component (B) formed in the hair makes the change of the hair shape after the hair treatment of the present invention more remarkable, and the hair resistance of the hair shape is further enhanced. 4-alkylresorcinol, from the viewpoint of making it excellent, making the change in shape during semipermanent re-deformation of the hair shape due to heating more remarkable, and making the hair shape after the re-deformation even more excellent in hair-washing resistance, 1 type or 2 or more types selected from 4-aralkyl resorcin, 4-halogenated resorcin is preferable, 1 type or 2 selected from 4-hexyl resorcinol, rucinol, 4- (1-phenylethyl) resorcinol, 4-chloro resorcinol More than species are more preferred.

[Wherein, A ¹ and A ² are as defined above, and B ¹ is a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, or a substituent having 7 to 12 carbon atoms] And an aralkyl group or an arylalkenyl group, -OR ³ or -COOR ³ (R ³ is a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms). ]

As the resorcin derivative represented by the general formula (ii-2), a resorcin derivative further represented by the general formula (ii-2-a) or (ii-2-b) is preferable.

[Wherein, B ¹ represents the same meaning as described above. ]

Examples of resorcin derivatives represented by the general formula (ii-2-a) include 5-methylresorcin, 5-ethylresorcin, 5-propylresorcin, 5-isopropylresorcin, 5-butylresorcin, 5-isobutylresorcin, 5- sec-butyl resorcinol, 5-tert-butyl resorcinol, 5-pentyl-resorcinol (conventional name: Olivetol), 5-isopentyl resorcinol, 5-neopentyl resorcinol, 5-hexyl resorcinol, 5-isohexyl resorcinol, 5-heptyl resorcin, 5-octyl resorcinol, 5- (2-ethylhexyl) resorcinol, 5-nonyl resorcinol, 5-decyl resorcinol, 5-undecyl resorcinol, 5-alkyl resorcins such as 5-dodecyl resorcinol;
5-alkenyl resorcins such as 5-vinyl resorcinol, 5-allyl resorcinol, 5-butenyl resorcinol, 5-hexenyl resorcinol, 5-decenyl resorcinol;
Phloroglucinol;
5-alkoxybenzene-1,3-diols such as 5-ethoxybenzene-1,3-diol, 5-propoxybenzene-1,3-diol, 5-butoxybenzene-1,3-diol;
3,5-dihydroxybenzoic acid;
Methyl 3,5-dihydroxybenzoate, ethyl 3,5-dihydroxybenzoate, propyl 3,5-dihydroxybenzoate, butyl 3,5-dihydroxybenzoate, pentyl 3,5-dihydroxybenzoate, 3,5-dihydroxybenzoate 3,5-Dihydroxybenzoic acid esters such as hexyl benzoate;
5-aralkyl resorcins such as 5-benzyl resorcinol, 5- (1-phenylethyl) resorcinol, 5- (2-phenylethyl) resorcinol, 5- (phenylpropyl) resorcinol;
5- (4-hydroxybenzyl) resorcinol, 5- (2,4-dihydroxybenzyl) resorcinol 5- (hydroxyphenylethyl) resorcinol (conventional name: dihydro-resveratrol), 5- (2,4-dihydroxy) 5-hydroxyaralkyl resorcins such as phenylethyl) resorcin etc;
5- (phenylethenyl) resorcinol (conventional name: Pinosylvin) 5- (arylpropenyl) resorcin, such as 5-arylalkenyl resorcin;
5- (4-hydroxyphenylethenyl) resorcine (conventional name: Resveratrol), 5- (4-methoxyphenylethenyl) resorcin (conventional name: 4-methoxyresveratrol) 5- (2,4-Dihydroxyphenylethenyl) resorcinol (conventional name: Oxyresveratrol), 5- (2-methoxy-4-hydroxyphenylethenyl) resorcinol (conventional name: Gunez Kraistol) D (Gnetucleistol D)), 5- (3,4-Dimethoxyphenylethenyl) resorcinol (conventional name: Gnetucleistol E), 5- (3-hydroxy-4-methoxyphenylethenyl) resorcinol (Conventional name: Rapontigenin), 5- (4-hydroxy-3-methoxyphenylethenyl) resorcine (conventional name: Isorapontigenin), 5- (dihydroxyphenyl) And 5-hydroxyarylalkenyl resorcin such as ethenyl) resorcine (common name: Piceatannol).

[Wherein, A ¹ , A ² and B ¹ have the same meaning as described above. ]

As A ¹ and A ² , a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 4 carbon atoms, or an alkoxy or alkenyloxy group having 1 to 4 carbon atoms is preferable.

As resorcin derivatives represented by the general formula (ii-2-b), 2-methylbenzene-1,3,5-triol, 2-ethylbenzene-1,3,5-triol, 2-propylbenzene-1, 3,5-triol, 2-butylbenzene-1,3,5-triol, 2-hexylbenzene-1,3,5-triol, 2-octylbenzene-1,3,5-triol, 2-dodecylbenzene 2-alkylbenzene-1,3,5-triols such as 1,3,5-triol;
2-aralkyl such as 2-benzylbenzene-1,3,5-triol, 2- (phenylethyl) benzene-1,3,5-triol, 2- (phenylpropyl) benzene-1,3,5-triol 1,3,5-triol;
2-acetylbenzene-1,3,5-triol, 2-propanoylbenzene-1,3,5-triol, 2-butanoylbenzene-1,3,5-triol, 2-phenylethanoylbenzene-1, 3,5-triol, 2-hydroxyphenyl-1- (benzene-2,4,6-triol) ethane-1-one, 3-hydroxyphenyl-1- (benzene-2,4,6-triol) propane- 1-one (conventional name: Phloretin), 4-hydroxyphenyl-1- (benzene-2,4,6-triol) butan-1-one, 2-benzoylbenzene-1,3,5-triol, 2- (hydroxybenzoyl) benzene-1,3,5-triol, 2- (3,5-dihydroxybenzoyl) benzene-1,3,5-triol, 2- (2,4-dihydroxybenzoyl) benzene-1, 2,4,6-trihydroxyphenyl aralkyl ketones such as 3,5-triol;
3,5-dihydroxy-2-methylbenzoic acid, methyl 3,5-dihydroxy-2-methylbenzoate, 3,5-dihydroxy-2-ethylbenzoic acid, methyl 3,5-dihydroxy-2-ethylbenzoate, 3,5-Dihydroxy-2-propylbenzoic acid, methyl 3,5-dihydroxy-2-propylbenzoate 3,5-dihydroxy-2-butylbenzoic acid, methyl 3,5-dihydroxy-2-butylbenzoate, etc. Examples include 3,5-dihydroxybenzoic acid ester and the like.

Examples of benzophenone derivatives represented by the general formula (1-2) include 4-benzoylresorcin (conventional name: benzophenone-1 (benzophenone-1)), 4- (hydroxybenzoyl) resorcin, 4- (dihydroxybenzoyl) resorcin, 4- (2,4-Dihydroxybenzoyl) resorcinol (conventional name: benzophenone-2 (benzophenone-2)), 4- (methylbenzoyl) resorcinol, 4- (ethylbenzoyl) resorcinol, 4- (dimethylbenzoyl) resorcinol, 4 -(Diethylbenzoyl) resorcinol, 4-naphthoylresorcinol, 2-hydroxy-4-methoxybenzophenone (conventional name: benzophenone-3 (benzophenone-3), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (conventional use) Name: Benzophenone-6 (Benzophenone-6), 2,2'-Dihydroxy-4-methoxybenzophenone (conventional name: Benzophenone-8 (Benzophenone-8), 2-hydroxy 4-methoxy-4'-methylbenzophenone (common name: Benzophenone -10 (Benzophenone-10), 2- hydroxy-4-octyloxy benzophenone (common name: Benzophenone -12 (Benzophenone-12)), and the like.

As the naphthol derivative represented by the general formula (1-3-a) or (1-3-b), in the general formula (1-3-a) or (1-3-b), R ¹ is a hydrogen atom or It is preferably an alkyl group having 1 to 4 carbon atoms or alkenyl, more preferably a hydrogen atom.
Further, A ¹ and A ² is a hydrogen atom, a hydroxyl group, preferably has a straight-chain or branched alkyl or alkoxy group having 1 to 4 carbon atoms of 1 to 4 carbon atoms, those which are hydrogen atom or a hydroxyl group More preferable.
Further, it is preferable that D is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
Further, it is preferable that E is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

Such compounds include 1-naphthol, 2-naphthol, 3-methylnaphthalen-1-ol, naphthalene-1,4-diol, naphthalene-1,5-diol, naphthalene-1,8-diol and the like. Be

Among the compounds represented by the general formula (1), an m-dimethoxybenzene derivative represented by the general formula (1-1-1), a resorcin derivative represented by the general formula (1-1-3), and the general formula One or more selected from benzophenone derivatives represented by (1-2) and naphthol derivatives represented by general formula (1-3-a) or (1-3-b) are preferable. Furthermore, 2-methylresorcin, 4-chlororesorcin, 4-alkylresorcin, 4-aralkylresorcin, 4-acylated resorcin, 5-alkylresorcin, 5-aralkylresorcin, 5-hydroxyarylalkenylresorcin, 2,4,6 One or more selected from trihydroxyphenyl aralkyl ketone, gallic acid and gallic acid ester are preferable. Furthermore, 4-butyl resorcinol (conventional name: Rucinol), 4-hexyl resorcinol, 4- (1-phenylethyl) resorcinol (conventional name: Simwhite 377 (Symwhite 377)), 4-furanyl ethyl resorcinol, 4 -Tetrahydropyranyl resorcinol, 5- (hydroxyphenylethenyl) resorcinol (conventional name: resveratrol), 3-hydroxyphenyl-1- (benzene-2,4,6-triol) propan-1-one (Conventional name: Phloretin), 4- (2,4-Dihydroxybenzoyl) resorcinol (conventional name: benzophenone-2 (benzophenone-2)), 5- (hydroxyphenylethenyl) -1,3-dimethoxybenzene ( Common name: Pterostilbene, 1-naphthol is preferred, 2-methylresorcinol, 4-chlororesorcinol, 1-naphthol, 4-n-butylresorcinol, 4- (1-phenylether) Le) resorcinol, 5- (hydroxyphenylethenyl) resorcinol, 3-hydroxyphenyl-1- (benzene-2,4,6-triol) propan-1-one, 4- (2,4-dihydroxybenzoyl) resorcinol One or two or more selected are preferable.

Further, among the compounds represented by the general formula (1), the condensation product of the component (A) and the component (B) formed in the hair makes the change of the hair shape after hair treatment more remarkable, and From the viewpoint of improving damage repair of hair damaged by treatment, the m-dimethoxybenzene derivative represented by the general formula (1-1-1), the resorcinol derivative represented by the general formula (1-1-3) It is preferable to use one or more selected from benzophenone derivatives represented by the general formula (1-2) and naphthol derivatives represented by the general formula (1-3-a) or (1-3-b).
Furthermore, 2-alkylresorcin, 4-alkylresorcin, 4-aralkylresorcin, 4-halogenated resorcin, 5-hydroxyarylalkenyl resorcin, 2,4,6-trihydroxyphenylaralkyl ketone, benzophenone derivative, naphthol, 4-acyl It is preferable to use one or more selected from resorcinol, 5-alkylresorcin, 5-aralkylresorcinol, gallic acid and gallic acid ester.
Furthermore, 2-methyl resorcinol, 4-butyl resorcinol (conventional name: Rucinol), 4-hexyl resorcinol, 4- (1-phenylethyl) resorcin (conventional name: Simwhite 377 (Symwhite 377)), 4-chloro Resorcinol, 5- (hydroxyphenylethenyl) resorcinol (conventional name: resveratrol), 5- (hydroxyphenylethenyl) -1,3-dimethoxybenzene (conventional name: Pterostilbene), 3 -Hydroxyphenyl-1- (benzene-2,4,6-triol) propan-1-one (conventional name: Phloretin), 4- (2,4-dihydroxybenzoyl) resorcinol (conventional name: benzophenone-2 ( One or more selected from Benzophenone-2)) and 1-naphthol are preferable.

The molecular weight of the compound represented by the general formula (1) is preferably 120 or more, and from the viewpoint of improving the penetration into the hair, it is preferably 1000 or less, more preferably 500 or less, still more preferably 300 or less.

The component (B3) is a compound represented by the following general formula (2).

[In the formula,
R ⁴ represents a hydrogen atom or a methyl group,
X represents a hydrogen atom, a hydroxyl group or a methoxy group,
Y represents a hydrogen atom, an oxygen atom, a hydroxyl group or a methoxy group,
Z represents a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms,
R ^x is a hydrogen atom, an oxygen atom, a hydroxyl group, a methoxy group, or an aromatic hydrocarbon group which may be substituted by up to 3 hydroxyl groups or methoxy groups and may form a condensed ring with 1,3-dioxolane Show
R ^y is a hydrogen atom, a hydroxyl group, a methoxy group, or an aromatic hydrocarbon group which may be substituted by up to 3 hydroxyl groups or methoxy groups and may form a condensed ring with 1,3-dioxolane, or a hydroxyl group or Represents an arylcarbonyloxy group or an aralkylcarbonyloxy group which may be substituted by up to 3 methoxy groups,
The dashed line indicates that it may be a double bond.
However, the broken line and the solid line adjacent to the R ^x or Y, R ^x or Y represents only double bond when an oxygen atom, a single bond in other cases.
In addition, Z is a linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms only when R ^x or R ^y is an o, p-dihydroxy aromatic hydrocarbon group, In other cases it is a hydrogen atom. ]

The linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms as Z is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, A tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, 1-methylpentyl group, vinyl group, allyl group, butenyl group and the like can be mentioned.

As an aromatic hydrocarbon group in R ^x or R ^y , a phenyl group, a naphthyl group and the like can be mentioned. Examples of the aromatic hydrocarbon group in which a condensed ring with 1,3-dioxolane is formed include 1,3-benzodioxol-5-yl group.

Examples of the arylcarbonyloxy group in R ^y include benzoyloxy group and the like, and examples of the aralkylcarbonyloxy group include benzyl carbonyloxy group, phenylethyl carbonyloxy group, phenylpropyl carbonyloxy group, phenylbutyl carbonyloxy group and the like. Be

Specific examples of the compound represented by the general formula (2) include the following (2-1) to (2-5).

(2-1) Flavanols represented by the following general formula (2-1)

[In the formula,
R ⁴ and X have the same meaning as described above,
Y ¹ represents a hydrogen atom, a hydroxyl group or a methoxy group,
R ^x1 represents an aromatic hydrocarbon group which may be substituted by up to three hydroxyl groups or methoxy groups and may form a condensed ring with 1,3-dioxolane;
R ^y1 is a hydrogen atom, a hydroxyl group, a methoxy group, an aromatic hydrocarbon group which may be substituted by up to 3 hydroxyl groups or methoxy groups and may form a condensed ring with 1,3-dioxolane, or a hydroxyl group or This represents an arylcarbonyloxy group or an aralkylcarbonyloxy group which may be substituted by up to three methoxy groups. ]

(2-2) Flavanones or flavanonols represented by the following general formula (2-2)

[Wherein, R ⁴ , X, Z and R ^x1 have the same meaning as described above, and R ^y2 represents a hydrogen atom, a hydroxyl group or a methoxy group.
However, Z is a linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms only when R ^x1 is an o, p-dihydroxy aromatic hydrocarbon group, otherwise Are hydrogen atoms. ]

(2-3) Flavones or flavonols represented by the following general formula (2-3)

[Wherein, R ⁴ , X, Z, R ^x1 and R ^y2 have the same meaning as described above.
However, Z is a linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms only when R ^x1 is an o, p-dihydroxy aromatic hydrocarbon group, otherwise Are hydrogen atoms. ]

(2-4) Isoflavones or isoflavans represented by the following general formula (2-4)

[In the formula,
R ⁴ , X, Z and a broken line have the same meaning as described above,
Y ² represents a hydrogen atom or an oxygen atom,
R ^x2 represents a hydrogen atom, a hydroxyl group or a methoxy group,
R ^y3 represents an aromatic hydrocarbon group which may have up to three hydroxyl groups or methoxy groups or may form a condensed ring with 1,3-dioxolane.
However, the broken line and the solid line adjacent to Y ² is, Y ² represents only double bond when an oxygen atom, a single bond in other cases.
In addition, Z is a linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms only when R ^y3 is an o, p-dihydroxy aromatic hydrocarbon group, otherwise Are hydrogen atoms. ]

(2-5) Coumarins represented by the following general formula (2-5)

[Wherein, R ⁴ and X are as defined above]

As the compound of (2-1), the following (2-1-A) to (2-1-C) are preferable.

(2-1-A) Flavan-3-ols (Flavan-3-ol) represented by the following general formula (2-1-A)

[Wherein R ⁴ , X and R ^x1 have the same meaning as described above, and R ^y11 may be substituted with up to three hydroxyl groups, methoxy groups, or hydroxyl groups or methoxy groups, and condensation with 1,3-dioxolane This represents an aromatic hydrocarbon group which may form a ring, or an arylcarbonyloxy group or an aralkylcarbonyloxy group which may be substituted by up to three hydroxyl groups or methoxy groups. ]

As the flavan-3-ols represented by the general formula (2-1-A), R ⁴ and X in the formula have the same meaning as described above, and R ^x1 has up to 3 hydroxyl groups or methoxy groups A compound which represents an aromatic hydrocarbon group which may be substituted, and R ^y1 represents a hydrogen atom, a hydroxyl group, a methoxy group, or an arylcarbonyloxy group or an aralkylcarbonyloxy group which may be substituted by up to 3 hydroxyl groups or methoxy groups. .

Examples of compounds corresponding to (2-1-A) include catechin (Catechin), epicatechin (Epicatechin), epigallocatechin (Epigallocatechin), mesiadanol (Meciadanol), afzelechin (Afzelechin), epiafzelechin (Epiafzelechin), catechin gallate Catechin gallate), epicatechin gallate (Epicatechin gallate), epigallocatechin gallate (Epigallocatechin gallate), filoflavan (Phylloflavan), fisetinidol (Fisetinidol), guiburutinidol (Guibourtinidol), robinetinidol (Robinetinidol) and the like.

(2-1-B) Flavan-4-ol (Flavan-4-ol) represented by the following general formula (2-1-B)

[Wherein, R ⁴ , X and R ^x1 have the same meaning as described above, and Y ¹¹ represents a hydroxyl group or a methoxy group. ]

As the flavan-4-ols represented by the general formula (2-1-B), R ⁴ and X in the formula have the same meaning as described above, Y ¹¹ represents a hydroxyl group, and R ^x1 represents a hydroxyl group or methoxy Compounds are preferred which exhibit aromatic hydrocarbon radicals which may be substituted up to three.

Examples of the compound corresponding to (2-1-B) include apiphorol (Apiforol), luteoforol (Luteoforol) and the like.

(2-1-C) Flavan-3,4-diol (Flavan-3,4-diol) represented by the following general formula (2-1-C)

[Wherein, R ⁴ , X, Y ¹¹ , R ^x1 and R ^y11 have the same meaning as described above. ]

As flavan-3,4-diols represented by the general formula (2-1-C), R ⁴ and X in the formula have the same meaning as described above, Y ¹¹ represents a hydroxyl group or a methoxy group, and R Compounds in which ^x1 is an hydroxyl group or an aromatic hydrocarbon group which may have up to 3 methoxy groups substituted, and R ^y1 is a hydroxyl group or a methoxy group are preferable.

Examples of the compound corresponding to (2-1-C) include leucocyanidin (Lucococyanidin), leuco delphinidin (Leucodelphinidin), leucopelargonidin (Leucopelargonidin), leucopeonidin (Leucopeponidin), leucophysetinidin (Leucofisetinidin) and the like.

As the compound (2-2), the following (2-2-A) and (2-2-B) are preferable.

(2-2-A) Flavanones represented by the following general formula (2-2-A)

[Wherein, R ⁴ , X, Z and R ^x1 have the same meaning as described above.
However, Z is a linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms only when R ^x1 is an o, p-dihydroxy aromatic hydrocarbon group, otherwise Are hydrogen atoms. ]

As the flavanones represented by the general formula (2-2-A), R ⁴ and X in the formula are as defined above, Z is a hydrogen atom, and R ^x1 is a hydroxyl group or three methoxy groups. Compounds which exhibit an aromatic hydrocarbon group which may be substituted are preferred.

Examples of the compound corresponding to (2-2-A) include eriodictyol (Eriodictyol), naringenin (Naringenin), pinocembulin (Pinocembrin), hesperetin (Hesperetin), homoeriodiocthiol (Homoeriodictyol), isochrapnetin (Isosakuranetin), and stelvin. (Sterubin), sakura netin (Sakuranetin), alpinetine (Alpinetin), butin (Butin) and the like.

(2-2-B) Flavanonols represented by the following general formula (2-2-B)

[Wherein, R ⁴ , X, Z and R ^x1 have the same meaning as described above, and R ^y21 represents a hydroxyl group or a methoxy group.
However, Z is a linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms only when R ^x1 is an o, p-dihydroxy aromatic hydrocarbon group, otherwise Are hydrogen atoms. ]

As the flavanonols represented by the general formula (2-2-B), R ⁴ and X in the formula are as defined above, Z is a hydrogen atom, and R ^x1 is a hydroxyl group or three methoxy groups. The compound which shows the aromatic hydrocarbon group which may be substituted, and R ^y1 shows a hydroxyl group or a methoxy group is preferable.

Examples of the compound corresponding to (2-2-B) include aromadendrin (Aromadendrin), taxifolin (Taxifolin), dihydro kaempferide and the like.

As the compound (2-3), the following (2-3-A) and (2-3-B) are preferable.

(2-3-A) Flavones represented by the following general formula (2-3-A)

[Wherein, R ⁴ , X, Z and R ^x1 have the same meaning as described above.
However, Z is a linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms only when R ^x1 is an o, p-dihydroxy aromatic hydrocarbon group, otherwise Are hydrogen atoms. ]

As the flavones represented by the general formula (2-3-A), R ⁴ and X in the formula have the same meaning as described above, Z represents a hydrogen atom, and R ^x1 represents three hydroxyl groups or methoxy groups. Compounds which exhibit an aromatic hydrocarbon group which may be substituted are preferred.

Examples of compounds corresponding to (2-3-A) include luteolin (Luteolin), apigenin (Apigenin), chrysin (Chrysin), noraltocarpetin (Norartocarpetin), tricetin (Tricetin), diosmetin (diosmetin), and acetetine (Acacetin) , Chrysoeriol, Genkwanin, Techtochrysin, Tricin, 4 ', 7-Dihydroxyflavone (4', 7-Dihydroxyflavone), Pratol (Pratol) and the like.

(2-3-B) Flavonols represented by the following general formula (2-3-B)

[Wherein, R ⁴ , X, Z, R ^x1 and R ^{y 21} have the same meaning as described above.
However, Z is a linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms only when R ^x1 is an o, p-dihydroxy aromatic hydrocarbon group, otherwise Are hydrogen atoms. ]

In the flavonols represented by the general formula (2-3-B), R ⁴ and X in the formula are as defined above, Z is a hydrogen atom, and R ^x1 is up to 3 hydroxyl groups or methoxy groups. The compound which shows the aromatic hydrocarbon group which may be substituted, and R ^y1 shows a hydroxyl group or a methoxy group is preferable.

Examples of compounds corresponding to (2-3-B) include quercetin (Quercetin), myricetin (Myricetin), morin (Morin), kaempferol (Kaempferol), galangin (Galangin), kaemperide (Kaempferide), tamarixetin (Tamarixetin), and laricitrin. (Laricitrin), annulatin (Annulatin), isorhamnetin (Isorhamnetin), syringetin (Syringetin), rhamnetin (Rhamnetin), euperotin (Europetin), azaleatin (Azaleatin), 5-O-methyl myricetin (5-O-Methylmyricetin), letussin (Retusin), Pachypodol (Pachypodol), Rhamnadin (Rhamnazin), Ayanine (Ayanin), Ombuin (Ombuin), Fisetin (Fisetin) and the like.

As the compound (2-4), the following (2-4-A) to (2-4-C) are preferable.

(2-4-A) Isoflavones (Isoflavone) represented by the following general formula (2-4-A)

[Wherein, R ⁴ , X, Z and R ^y3 have the same meaning as described above.
However, Z is a linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms only when R ^y3 is an o, p-dihydroxy aromatic hydrocarbon group, and in the other cases Are hydrogen atoms. ]

As the isoflavones represented by the general formula (2-4-A), R ⁴ and X in the formula have the same meaning as described above, and Z is a hydrogen atom or a linear or branched chain having 1 to 5 carbon atoms. The compound which shows an aromatic hydrocarbon group which shows an alkyl group or an alkenyl group and which R ^<y3 may substitute with a hydroxyl group or a methoxy group to 3 or may form a condensed ring with 1, 3- dioxolane is preferable.

As compounds corresponding to (2-4-A), genistein (Danistein), daidzein (Daidzein), olobol (Orobol), biochanin A (Biochanin A), platensein (Pratensein), 5-O-methyl genistein (5) -O-Methylgenstein), Prunetin (Prunetin), Calycosin, Formononetin (Formononetin), 7-O-Methylrutheone (7-O-Methyluteone), Rutheone (Luteone), Pseudobaptigenin (Pseudobaptigenin), etc. Be

(2-4-B) Isoflavans (Isoflavanes) represented by the following general formula (2-4-B)

[Wherein, R ⁴ , X and R ^y3 represent the same meaning as described above. ]

As isoflavans represented by the general formula (2-4-B), R ⁴ and X in the formula have the same meaning as described above, and R ^y 3 may be substituted with up to 3 hydroxyl groups or methoxy groups 1 The compound which shows the aromatic hydrocarbon group which may form a condensed ring with 2, 3- dioxolane is preferable.

Examples of the compound corresponding to (2-4-B) include equol (Equol) and the like.

(2-4-C) Isoflavenes represented by the following general formula (2-4-C)

[Wherein, R ⁴ , R ^x2 and R ^y3 have the same meaning as described above. ]

In the isoflavenes represented by the general formula (2-4-C), R ⁴ and R ^x2 in the formula may have the same meaning as described above, and R ^y3 may be substituted with up to 3 hydroxyl groups or methoxy groups. Compounds which exhibit an aromatic hydrocarbon group which may form a condensed ring with 1,3-dioxolane are preferred.

Examples of the compound corresponding to (2-4-C) include Haginin D, Haginin E, 2-Methoxyjudaicin and the like.

As a compound applicable to (2-5), umbelliferone (Umbelliferone) etc. are mentioned.

Among these, as the compound represented by the general formula (2), the change of the hair shape after the hair treatment of the present invention can be obtained by the condensation product of the component (A) and the component (B) formed in the hair. Makes the hair shape more resistant to hair-washing, makes the shape change during semi-permanent re-deformation of the hair shape due to heating more remarkable, and has a much better hair-resistance after hair re-deformation From the point of view of the flavon-3-ol represented by the general formula (2-1-A), and the flavonol represented by the general formula (2-3-B) A flavanone represented by the general formula (2-2-A), a flavone represented by the general formula (2-3-A), a table represented by the general formula (2-4-A) 1 or 2 selected from isoflavones (Isoflavone), isoflavanes represented by the general formula (2-4-B), coumarins represented by the general formula (2-5) More than species Preferably, more specifically, catechin (Catechin), epicatechin (Epicatechin), epigallocatechin (Epigallocatechin), catechin gallate (Catechin gallate), epicatechin gallate (Epicatechin gallate), epigallocatechin gallate (Epigallocatechin gallate) One or more selected from quercetin (Quercetin), morin (Morin), hesperetin (Hesperetin), naringenin (Naringenin), chrysin (Chrysin), daidzein (Daidzein), equol (Equol), umbelliferone (Umbelliferone) Is preferred. Furthermore, one or more selected from catechin, epigallocatechin, epigallocatechin gallate, naringenin and equol are preferable. In addition, mixtures containing the above-mentioned compounds, such as green tea extract, can also be used.

Moreover, as for the molecular weight of the compound represented by General formula (2), molecular weight 150 or more is preferable. Further, from the viewpoint of improving the penetration into the hair, the molecular weight is preferably 1000 or less, more preferably 700 or less, and still more preferably 500 or less.

Among the component (B), the condensation product of the component (A) and the component (B) formed in the hair makes the change of the hair shape after hair treatment more remarkable, and the hair resistance to hair shape is further excellent The formula (ii-1) is used from the viewpoint of making the shape change during semipermanent re-deformation of the hair shape due to heating more remarkable, and making the hair shape after the re-deformation even more excellent in the hair-washing resistance. Resorcine derivatives represented by the formula, m-dimethoxybenzene derivatives represented by the general formula (1-1-1), resorcine derivatives represented by the general formula (1-1-3), Benzophenone derivatives represented by the formula, naphthol derivatives represented by the formula (1-3-a) or (1-3-b), flavan-3-ols represented by the formula (2-1-A) -3-ol), Flavonols represented by the general formula (2-3-B), flavanones represented by the general formula (2-2-A), and the general formula (2-3) Flavone represented by -A) (Flavone And isoflavones represented by the general formula (2-4-A), isoflavans represented by the general formula (2-4-B), and is represented by the general formula (2-5) 1 type, or 2 or more types selected from coumarins (Coumarin) are preferable, and preferable things classified into each component are as above-mentioned.

The component (B) can be used alone or in combination of two or more kinds, and two or more types of (B1) to (B3) can be used in combination. (B2) or (B3) is preferable in that the hair shape can be deformed more firmly by the constitution of the present invention.

The total content of the component (B) as a whole in the hair cosmetic composition to be used in the present invention makes the change of the hair shape after hair treatment more remarkable, and makes the hair resistance of the hair shape more excellent. From the viewpoint of making the change of shape during semi-permanent re-deformation of the hair shape more remarkable and making the hair-resistance of the hair shape after re-deformation even more excellent, it is preferable based on the whole composition of the hair cosmetic Is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, and in addition to the above viewpoints, preferably 30 It is not more than mass%, more preferably not more than 25 mass%, still more preferably not more than 23 mass%, still more preferably not more than 20 mass%.

When component (B1) is particularly used as component (B), the content of component (B1) in the hair cosmetic composition used in the present invention is the above-mentioned component based on the entire composition of the hair cosmetic composition from the same viewpoint. The content of (B) is more preferably 2% by mass or more, still more preferably 3% by mass or more, still more preferably 4% by mass or more, still more preferably 5% by mass or more. More preferably, the content is 19% by mass or less, more preferably 17% by mass or less, still more preferably 15% by mass or less, and still more preferably 14% by mass or less.

When the component (B2) is particularly used as the component (B), the content of the component (B2) in the hair cosmetic composition used in the present invention is the same as that of the component (B). The content is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, and from the viewpoint of formulation, more preferably 17% by mass or less, still more preferably 12% by mass or less More preferably, it is 8% by mass or less.

When the component (B3) is used as the component (B), the content of the component (B3) in the hair cosmetic composition used in the present invention is more preferably in the preferable content as the component (B) from the same viewpoint Is 2% by mass or more, more preferably 3% by mass or more, still more preferably 3.5% by mass or more, still more preferably 4.0% by mass or more, and from the viewpoint of formulation and compounding, more preferably 17% by mass or less Preferably it is 15 mass% or less, More preferably, it is 12 mass% or less, More preferably, it is 8 mass% or less.

The molar ratio (B) / (A) of the components (A) and (B) applied to the hair by the hair treatment method of the present invention is a condensate of the component (A) and the component (B) formed in the hair Changes the hair shape after hair treatment more significantly, makes the hair shape more resistant to hair-washing, makes the change in shape during semi-permanent re-deformation of the hair shape due to heating more remarkable, and re-deforms From the viewpoint of further improving the hair-resistance to hair shape, it is preferably 0.001 or more, more preferably 0.1 or more, still more preferably 0.2 or more, still more preferably 0.25 or more, more preferably 0.28 or more, more preferably 0.30 or more, preferably less than 2.5, more preferably 2.1 or less, further preferably 1.4 or less, still more preferably 1.2 or less, still more preferably 0.8 or less, more preferably 0.5 or less.

[Component (C): reducing agent]
As a reducing agent of component (C), thioglycolic acid or a salt thereof, sodium sulfite, ascorbic acid, butyrolactone thiol, L-, from the viewpoint of suppressing coloring of the hair even when reheating treatment is performed repeatedly by heating One or more reducing agents selected from the group consisting of cysteine (2-amino-3-sulfanyl propionic acid) and cysteamine are preferred.

The component (C) can be used alone or in combination of two or more types, and the content of the component (C) in the hair cosmetic composition used in the present invention is from the viewpoint of suppressing coloring of the hair even when heated repeatedly. 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, still more preferably 1.0% by mass or more, based on the total composition of the hair cosmetic. More preferably, it is 1.5% by mass or more, more preferably 1.5% by mass or more, and from the viewpoint of making the change of the hair shape after hair treatment more remarkable, in addition to the above viewpoints, preferably 20% by mass or less. The content is preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass or less, still more preferably 8% by mass or less, still more preferably 5% by mass or less, still more preferably 3% by mass or less .

The molar ratio (B) / (C) of the components (B) and (C) applied to hair by the hair treatment method of the present invention is preferably from the viewpoint of achieving both the effect of suppressing damage to hair and the shape-imparting effect. 0.05 or more, more preferably 0.1 or more, further preferably 0.2 or more, further preferably 0.4 or more, more preferably 0.6 or more, still more preferably 0.7 or more, preferably 10 or less, more preferably 7 or less, more preferably 5 The following is more preferably 4 or less, further preferably 2 or less, more preferably 1.5 or less.

The molar ratio [(A) + (B)] / (C) of the sum of the components (A) and (B) to the component (C) applied to the hair by the hair treatment method of the present invention From the viewpoint of achieving both the suppression effect and the shape-imparting effect, it is preferably 0.2 or more, more preferably 0.6 or more, still more preferably 1.2 or more, still more preferably 2.0 or more, still more preferably 3.0 or more. From the viewpoint of coexistence of the shaping effect, it is preferably 30 or less, more preferably 20 or less, still more preferably 15 or less, still more preferably 10 or less, still more preferably 6 or less.

[Component (D): Compound Represented by General Formula (3)]
The hair cosmetic composition used in the present invention is further represented by the following general formula (3) as a component (D) from the viewpoint of suppressing coloring immediately after hair treatment and temporal coloring of treated hair. It is preferred to contain a compound.

[Wherein, Q represents a polymethylene group having 2 to 5 carbon atoms which may be substituted by a carboxy group, or a carbonyl group, and T ¹ and T ² may be each independently substituted with a hydrogen atom or a hydroxyl group A linear or branched alkyl group of 1 to 5 carbon atoms is shown, or both are combined to form a polymethylene group of 2 to 5 carbon atoms to form a ring with -NH-Q-NH-. ]

Among Q, when the carboxy group substitutes a polymethylene group having 2 to 5 carbon atoms, the number of substitution is preferably 1, and the substitution position is preferably terminal.

Examples of such Q include a carbonyl group, an ethylene group, a propylene group, a butylene group, 1-carboxy-1,3-propanediyl, 1-carboxy-1,4-butanediyl, 1-carboxy-1,5-pentanediyl and the like. Among them, carbonyl group, ethylene group and 1-carboxy-1,5-pentanediyl group are preferable, and carbonyl group is more preferable.

As T ¹ and T ² , a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group, and an ethylene formed by combining the two. Examples thereof include a group, a propylene group and a butylene group, and a hydrogen atom, a 2-hydroxyethyl group and an ethylene group formed by combining the two are preferable.

Examples of the component (D) include urea, 2-hydroxyethyl urea, ethylene urea, lysine hydrochloride, ethylene diamine and the like. Among them, urea and 2- (2-hydroxyurea) having excellent shape imparting, feel and suppression of coloring relatively well. Hydroxyethyl urea is preferred, and urea is preferred.

Component (D) can be used alone or in combination of two or more. The content of the component (D) in the hair cosmetic composition to be used in the present invention is preferably 0.1% by mass or more, more preferably 0.3% by mass, based on the total composition of the hair cosmetic composition, from the viewpoint of coloration suppressing effect and feel improving effect. % By mass, more preferably 0.5% by mass or more, further preferably 1.0% by mass or more, further preferably 1.5% by mass or more, still more preferably 1.8% by mass or more, and the above-mentioned effect and the shape-imparting effect are both satisfied From the viewpoint, preferably 15% by mass or less, more preferably 12% by mass or less, further preferably 10% by mass or less, still more preferably 8% by mass or less, further preferably 5% by mass or less, more preferably 3% by mass or less is there.

The molar ratio of the components (A), (B) and (D) of the sum of the components (B) and (D) to the component (A) applied to the hair by the hair treatment method of the present invention [(B) + (D)] / (A) is preferably 0.01 or more, more preferably 0.5 or more, still more preferably 0.1 or more, still more preferably 0.2 or more, still more preferably 0.3 or more, from the viewpoint of the coloring suppression effect and the touch improving effect. More preferably, it is at least 0.7, and from the viewpoint of coexistence of the above-mentioned effects and the shape imparting effect, it is preferably 2.5 or less, more preferably 2.3 or less, still more preferably 2.1 or less, more preferably 1.9 or less, more preferably 1.7 or less More preferably, it is 1.5 or less.

〔water〕
The hair cosmetic composition used in the present invention uses water as a medium. In the case of the multi-agent system, both the first agent and the second agent use water as a medium.

[Formulation type]
The hair cosmetic composition to be used in the present invention may be any one-component type, two-component type or other multi-component type, but the permeability of the component (A) and the component (B) into the hair is good. From the viewpoint of enhancing the effect of the present invention, the component (A) and the component (B) are contained in separate agents, respectively, in a multiple agent system of the sequential application type, and further in a two agent system or a three agent system Is more preferred. In the case of the multi-component type of the sequential application type, the first agent initially applied to the hair contains the component (B) and water, and the second agent applied to the hair after the application of the first agent is the component (A) And water are preferred. At this time, the components (C) and (D) may be contained in the first agent or in the second agent, or may be contained in both the first agent and the second agent, and further separately A third agent may be incorporated and applied to the hair after the hair treatment with the components (A) and (B) or after the step of heating the hair. When component (D) is further contained, it is preferable to be contained in the hair cosmetic used before the step of heating the hair, that is, the first agent or the second agent.

[PH]
The pH of the hair cosmetic composition used in the present invention is preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.5 or less, in the case of one-component type, from the viewpoint of improving the permeability of the hair cosmetic into the hair. It is more preferably 2.0 or less, and preferably 1.0 or more, more preferably 1.2 or more, still more preferably 1.5 or more, and still more preferably 1.7 or more from the viewpoint of hair damage suppression and skin irritation suppression. In the case of the multi-drug type, it is preferable to set the agent containing the component (A), that is, the second agent in the above range. In the case of a multi-agent system, the pH of the agent containing the component (B), that is, the first agent is preferably 6.0 or less, more preferably 5.0 or less, still more preferably 4.5, from the viewpoint of preventing discoloration of the composition. Or less and preferably 2.5 or more, more preferably 3.0 or more, and still more preferably 3.5 or more. In the present invention, the pH of the hair cosmetic is obtained by directly measuring the pH of the hair cosmetic with a pH meter (manufactured by HORIBA / model number: F-52) at room temperature (25 ° C.) without diluting the hair cosmetic. Point to the

In order to adjust the pH of the hair cosmetic composition to the above range, a pH adjuster may be used as appropriate. As a pH adjuster, ammonia or a salt thereof as an alkaline agent; alkanolamine or a salt thereof such as monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol; 1,3-propanediamine etc. Alkanediamines or salts thereof; carbonates such as guanidine carbonate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate and potassium hydrogencarbonate; and hydroxides such as sodium hydroxide and potassium hydroxide. In addition, as an acid agent, inorganic acids such as hydrochloric acid and phosphoric acid, hydrochlorides such as monoethanolamine hydrochloride and the like; phosphates such as monopotassium dihydrogen phosphate and disodium dihydrogen phosphate monobasic, components such as lactic acid and malic acid Organic acids other than (A) can be used.

[Other ingredients]
The cosmetic for hair used in the present invention further includes cationic surfactants such as mono long-chain alkyl quaternary ammonium salts; silicones such as dimethylpolysiloxane and amino-modified silicone; other, ethanol, antioxidants, pH adjusters The ingredients which are usually blended in hair cosmetics can be suitably contained. However, it is preferable that the hair cosmetic used in the present invention does not substantially contain a precursor blended in an oxidative hair dye for dyeing the hair by an oxidation reaction of the precursor and the coupler. That is, the hair cosmetic composition used in the present invention has at least one amino group, another amino group or hydroxyl group at the ortho position or para position of one amino group, and has a closed shell quinoid structure when oxidized. It contains substantially no aromatic compound. The compound of component (B) is a compound similar in structure to resorcin representative of couplers used in oxidative hair dyes. However, the present invention is characterized in that by polymerizing the component (A) and the component (B) in the hair, it is possible to freely change the shape of the hair by the subsequent heating; The use of resorcin in an agent is a completely different technology.

〔hydrogen peroxide〕
The hair treatment method of the present invention is a technology that allows semi-permanent to permanent hair deformation by permeating components (A) and (B) into the hair and then heating to condense both compounds. However, if the hair cosmetic applied to the hair prior to the heating step (ii) contains hydrogen peroxide, the component (B) is consumed in the reaction with the hydrogen peroxide, so that The amount of active ingredient (B) used for the condensation will be reduced. For this reason, it is preferable that the hair cosmetic applied to the hair before the step (ii) does not contain hydrogen peroxide, and even when it is contained, the content of hydrogen peroxide is 1% by mass or less. The content is preferably 0.1% by mass or less, more preferably 0.01% by mass or less. In addition, since condensation of the component (A) and the component (B) in hair is completed if it is after process (ii), 0.1 mass of hair cosmetics applied to hair after that % Hydrogen peroxide may be included.

[Boric acid, silicic acid]
Further, the hair cosmetic composition used in the present invention is also substantially free of boric acid and silicic acid, unlike the technology of Patent Document 3 in which boric acid or silicic acid is used to form an oligomer of glyceraldehyde and resorcinol. Even if it is contained, the content of boric acid and silicic acid in the hair cosmetic is preferably less than 0.1% by mass, and less than 0.01% by mass, based on the total composition of the hair cosmetic. It is more preferable that the hair cosmetic composition does not contain boric acid and silicic acid.

The hair cosmetic composition used in the present invention can be suitably used particularly for human hair, because it is highly safe for the human body and causes less hair damage.

[Hair treatment method]
The hair treatment method of the present invention is carried out using the hair cosmetic described above, and the following steps (i) and (ii)
(i) applying components (A) and (B) to the hair (ii) heating and shaping the hair to which the components (A) and (B) are applied; At the point of time, it is a hair treatment method in which component (C) is applied to the hair.

By heating in a state where the components (A) and (B) are applied to the hair, the components (A) and (B) are polymerized to shape the hair. On the other hand, in the step of heating in a state where only one of the component (A) and the component (B) is applied to the hair, shaping by polymerization is not performed, and penetration of the component (A) or the component (B) into the hair Is promoted. The latter step is a step of heating the hair in a state where the components (A) and (B) do not coexist with the hair.

In the present invention, with the components (A) and (B) applied to the hair, the step of heating and shaping the hair is called "the step of heating and shaping the hair", and The step of heating the hair in a state where (B) and (B) do not coexist in the hair is referred to as the "heating and standing step" to distinguish the two steps.

The step of heating the hair in the state where neither of the components (A) and (B) is present in the hair is also referred to as the "step of heating and leaving". An example of this is the step of heating and shaping the hair, followed by, for example, the step of applying and heating component (C).

In the following description of the treatment method for hair, when simply referred to as "hair cosmetic", it refers to a composition that is actually applied to the hair, one-component hair cosmetic, multiple application of single application type Mixture of the first and second agents of the cosmetic hair cosmetic composition or the mixture of the first and second agents and the second agent, the first and second agents of the multi-component hair cosmetic of the sequential application type, and the presence In the case where it carries out, any of 3rd agent shall be said. In addition, the description of the treatment method shown below is only an illustration, and the hair treatment method of this invention is not limited to these.

In the case of a one-part hair cosmetic, in the case of a one-part hair cosmetic, the hair treatment method of the present invention comprises the following steps (i) and (ii). Since the one-component hair cosmetic composition contains the components (A), (B) and (C) in a single composition, the component (A) can be prepared by applying it to the hair in step (i). (B) and (C) are simultaneously applied to the hair.
(i) applying one-part hair cosmetic to the hair (ii) heating and shaping the hair to which the hair cosmetic has been applied

Single-application multi-component hair cosmetic In the case of a single-application multi-component hair cosmetic, the hair treatment method of the present invention includes the following steps (i) and (ii). In the single-application multi-component hair cosmetic composition, component (A) in the total composition of the first and second agents, and in the entire composition of the first to third agents when the third agent is further present. , (B) and (C), by mixing these agents in step (i) and applying to hair, as in the case of one-component type, components (A), (B) and (C) ) Is simultaneously applied to the hair. In addition, in the whole composition, it is as the above-mentioned definition, and in the case of a multi-component hair cosmetic, it is not the composition of the individual composition which constitutes this, but these compositions are a ratio of each component Is the composition of the mixture when it is mixed in such an amount ratio as to be within the intended range of the present invention.
(i) mixing the first and second agents of the multi-component hair cosmetic composition of the present invention and the third agent, if any, with the third agent, and applying them to the hair (ii) the above hair cosmetic composition Heating and shaping the applied hair

In the case of a multi-component hair cosmetic composition of a sequential application type In the case of a multi-component hair cosmetic composition of a sequential application type, the hair cosmetic composition used in step (i) comprises at least components (A) and (B) contains. Since the component (C) may be applied to the hair at any time of the whole process, it may be contained in the hair cosmetic composition used in the process (i), or a process separately performed after the process (ii) You may contain in the hair cosmetics applied to hair in iii).

In the former case, that is, when it is contained in the hair cosmetic used in step (i), the hair treatment method of the present invention comprises the following steps (i) and (ii). Components (A), (B) and (C) in the total composition of the first and second agents used in step (i), or in the total composition of the first to third agents when the third agent is present (A), (B) and (C) are applied to the hair by sequentially applying these agents to the hair in step (i).
(i) The first agent of the multi-component hair cosmetic composition is applied to the hair, and then the second agent of the multi-component hair cosmetic composition is overlapped and applied onto the first component application part of the hair, Step of applying the third agent on top of the first and second agent application parts of the hair when using the agent (ii) heating and shaping the hair on which the hair cosmetic has been applied

In the latter case, that is, when the component (C) is contained in the hair cosmetic applied to the hair in the step (iii) performed after the step (ii), the hair treatment method of the present invention comprises the following steps i), (ii) and (iii). Components (A) and (B) are contained in the total composition of the first and second agents used in step (i), and component (C) is contained in the third agent used in step (iii) Do.
(i) applying the first agent of the multi-component hair cosmetic composition to the hair, and then applying the second agent of the multi-component hair cosmetic composition on the first agent-applied portion of the hair in an overlapping manner (ii) The step of heating and shaping the hair on which the hair cosmetic has been applied (iii) the step of applying the third agent of the multi-component hair cosmetic to the first agent and the second agent application part of the hair

In the step (i), the hair cosmetic may be applied to dry hair or to wet hair, but in order to swell the hair and promote the penetration of the hair cosmetic into the hair, the process It is preferable to wet the hair with water prior to (i). The mass of the hair cosmetic applied to the hair in the step (i) is preferably 0.05 or more, more preferably 0.10 or more, still more preferably 0.25 by the bath ratio to the mass of the hair (mass of the hair cosmetic / mass of the hair). The above is more preferably 0.5 or more, preferably 5 or less, more preferably 3 or less, still more preferably 2.5 or less, and still more preferably 2 or less. Further, in the case of the multi-component hair cosmetic of the sequential application type, the above-mentioned bath ratio is preferable for each of the first agent, the second agent, and the third agent when present, from the viewpoint of application property. The hair to be treated may be all or part of the hair.

In the step (i), in the case of the multi-component hair cosmetic of the sequential application type, the hair is applied with the first agent from the viewpoint of promoting the penetration of the hair cosmetic and enhancing the effect, and then applying the hair cosmetic. May be left at 10 to 40.degree. C. for a fixed time, and then the second agent may be applied. During this standing, the mixture may be heated to 40 to 90 ° C. to accelerate the penetration of the first agent. Furthermore, when the third agent is used in step (i), after applying the second agent, the hair to which the hair cosmetic is applied is allowed to stand at 10 to 40 ° C. for a certain period of time, and then the third agent is applied. May be During this standing, the mixture may be heated to 40 to 90 ° C. to accelerate the penetration of the second agent. The standing time in these cases is preferably 1 minute or more, more preferably 3 minutes or more, still more preferably 5 minutes or more, in order to penetrate and diffuse the hair cosmetic into the hair, and preferably 1 hour or less. More preferably, it is 30 minutes or less, More preferably, it is 20 minutes or less.

In the step (i), in the case of a multi-component hair cosmetic of a sequential application type, after applying and leaving the first agent, before the second agent is applied, the first agent is washed away (hereinafter referred to as intermediate May be included). It is preferable not to include the intermediate rinse step from the viewpoint of shortening the treatment time. When the intermediate rinse step is not included, the molecular weight of the component (B) contained in the first agent is preferably 100 to 180, and more preferably 100 to 140, from the viewpoint of further enhancing the hair deforming effect. On the other hand, it is preferable to include an intermediate rinse step from the viewpoint of improving the feel after hair deformation treatment. When an intermediate rinse step is included, the molecular weight of the component (B) contained in the first agent is preferably 140 to 1000, from the viewpoint of further enhancing the hair deforming effect and improving the feel after deformation. It is more preferable that it is -1000.

In the case of using the component (D) further in the case of using the multi-component hair cosmetic of the sequential application type, the process is carried out from the viewpoint of suppressing coloring immediately after hair treatment and temporal coloring of treated hair. It is preferred that the hair cosmetic used before (ii), preferably the first or second agent, contain the component (D).

Between the step (i) and the step (ii), a step of leaving the hair cosmetic composition-applied hair at 10 to 40 ° C. for a fixed time may be inserted. The standing time in that case is preferably 1 minute or more, more preferably 3 minutes or more, still more preferably 5 minutes or more, in order to penetrate and diffuse the hair cosmetic into the hair, and preferably 1 hour or less. More preferably, it is 30 minutes or less, More preferably, it is 20 minutes or less.

Between step (i) and step (ii), the hair cosmetic applied hair may be rinsed or not rinsed, but the ingredients of the hair cosmetic are sufficiently retained in the hair, and the hair In order to impart a semi-permanent shape to the hair and to further strengthen the effect of deforming the hair shape semi-permanently by heat again, it is preferable not to have a rinse.

The heating temperature in the step (ii) is preferably 50 ° C. or more, more preferably 60 ° C. or more, in view of giving the hair a semipermanent shape and further deforming the style once made semipermanently by heat again. The temperature is more preferably 70 ° C. or more, further preferably 80 ° C. or more, and in order to suppress rapid evaporation of water during heating, preferably 250 ° C. or less, more preferably 240 ° C. or less, still more preferably 230 ° C. or less More preferably, it is 210 ° C. or less. As a heating method, a method using a hair iron, an electric heating rod, a hot curler or the like can be mentioned.

The heating time in the step (ii) is appropriately selected depending on the heating device and heating temperature used, but from the viewpoint of causing the hair cosmetic to penetrate and diffuse into the hair and causing sufficient polymerization, preferably 1 second or more, more preferably Is 5 seconds or more, more preferably 1 minute or more, still more preferably 5 minutes or more, still more preferably 15 minutes or more, still more preferably 30 minutes or more, and preferably 2 hours or less, more preferably for hair damage suppression. Preferably, it is 1.7 hours or less, more preferably 1.5 hours or less, further preferably 1.2 hours or less, further preferably 1 hour or less, further preferably 45 minutes or less.

The shaping in step (ii) includes both straight and curled shaping. Methods for shaping the hair into a straight shape include a method in which the hair is pulled with a tool such as a hand, a comb or a brush while blowing with a dryer, a method in which heating is performed using a hair iron, etc. From the above, the method of using a hair iron is preferable. To straighten the shape of the hair while heating it with a hair iron, hold the hair with a flat iron and then slide it from the root to the end of the hair with a tool such as a hand, a comb or a brush. According to the method etc. which both are pinched and held as it is with a flat iron while pulling, and the combination of the both. In addition, when the hair is shaped in a curled manner, a method of holding the hair by winding it around an electric heating rod, a hot curler or the like while heating, a method of holding the hair by winding it on a curl iron, etc. may be mentioned.

Step (ii) is preferably performed in an environment where rapid evaporation of water is suppressed. As a specific means for suppressing the evaporation of water, a method of covering the hair to which the hair cosmetic is applied is covered with a plastic film such as a wrap film for food, a cap or the like, water vapor such as superheated water vapor is continuously sprayed on the hair. Methods etc.

After the step (ii), the hair may be rinsed or not rinsed, but rinsing is preferred from the viewpoint of preventing a reduction in hair feel due to excess polymer.

A hair treatment method using a multi-component hair cosmetic composition of a sequential application type, wherein a step of applying a hair cosmetic containing component (C) to the hair as a step (iii) is carried out after the step (ii) In the case where the mass of the hair cosmetic applied to the hair in step (iii) is the bath ratio to the mass of the hair (the mass of the hair cosmetic / the mass of the hair), coloring immediately after hair treatment or aging of the treated hair 0.01 or more, more preferably 0.05 or more, still more preferably 0.10 or more, still more preferably 0.5 or more, and preferably 4 or less, more preferably 3 or less, still more preferably 2.5, from the viewpoint of suppressing such coloration. More preferably, it is 2 or less.

After the step (iii), a step of leaving the hair cosmetic applied hair for a certain period of time may be included. The standing time in that case is preferably 1 minute or more, more preferably 5 minutes or more, still more preferably 10 minutes or more, still more preferably 20 minutes or more, still more preferably, in order to penetrate and diffuse the hair cosmetic into the hair. It is 30 minutes or more, preferably 2 hours or less, more preferably 1.7 hours or less, further preferably 1.5 hours or less, further preferably 1.2 hours or less, further preferably 1 hour or less. In addition, in the step of leaving, the hair may be heated to 40 to 90 ° C. from the viewpoint of promoting the penetration of the hair cosmetic.

After the step (iii), the hair may be rinsed or not rinsed, but rinsing is preferred from the viewpoint of preventing the deterioration of the hair feel due to the excess polymer.

(Re-transformation processing method)
After the hair is deformed by a method comprising steps (i) and (ii), or steps (i) to (iii), heat is applied to repermanently reshape the hair into another shape; it can. The heat applied upon re-deformation is preferably 30 ° C. or more, more preferably 40 ° C. or more, still more preferably 50 ° C. or more, and preferably 230 ° C. or less, more preferably 220 ° C. or less, still more preferably 210 It is less than ° C. Further, when the re-deformation treatment is performed, it is preferable that neither the hair cosmetic composition of the present invention nor a hair treatment agent containing a reducing agent such as a so-called perming agent or a hair treatment agent such as an alkaline relaxer is applied. In the present invention, the component (A) and the component (B) are condensed in the hair and the treatment with the component (C) is carried out, thereby suppressing the coloring of the hair even when the re-deformation treatment by heating is repeated. can do.

Hereinafter, a specific procedure in the case of performing a process of applying heat to re-permanently reshape the hair into another shape will be described.

· When straightening the curled hair to reshape To reshape the curled hair into a straight shape, blow the hair with a drier while pulling the hair with a hand, a comb, a tool such as a brush. There is a method of making, a method of heating using a hair iron, etc., but from the viewpoint of ease of deformation, a method of using a hair iron is preferable. In order to form a straight shape while heating the hair using a hair iron, there is a method of sliding the hair from the root to the end of the hair with the hair iron sandwiched and then using a tool such as a hand, a comb or a brush. The method may be a method of holding the hair iron while holding it and holding it as it is, a combination of the both, or the like.

Regardless of the type of hair iron used, the material of the heating unit, the set temperature, and the operation method of the iron, the temperature reached at the time of heating the hair (the temperature of the hair) in this case is a viewpoint from which the hair shape is deformed permanently or permanently. It is preferably 120 ° C. or more, more preferably 150 ° C. or more, and still more preferably 170 ° C. or more, from the viewpoint of achieving both prevention of hair damage and semipermanent or permanent deformation of the hair shape. It is 230 degrees C or less, More preferably, it is 220 degrees C or less, More preferably, it is 210 degrees C or less. The heating temperature of hair can be measured, for example, using a radiation thermometer (model number ST653) manufactured by SENTRY.

· When re-shaping straight hair that has been straightened to curl To straighten hair that has been straightened, the hair may be wound around a rod, curler, etc. and held while heating, or the hair may be straightened. The method of winding and holding on an iron etc. is mentioned.

In this case, the temperature reached at the time of heating the hair (the temperature of the hair) is preferably 30 ° C. or more, more preferably 35 ° C. or more, still more preferably 40 ° C. or more, from the viewpoint of deforming the hair shape semipermanently to permanent. It is more preferably 45 ° C. or more, more preferably 50 ° C. or more, and from the viewpoint of achieving both prevention of hair damage and semi-permanent or permanent deformation of the hair shape, it is preferably 180 ° C. or less, more preferably 120 C. or less, more preferably 100 ° C. or less, still more preferably 80 ° C. or less, still more preferably 60 ° C. or less.

Even when re-shaping the hair, when heating, it may be a method of heating while the hair is dry, or a method of heating after it is wetted with water, but the shape of the hair is deformed semipermanently to permanently. From the point of view of heating, a method of heating after wetting with water is preferred.

The heating time of the hair when re-shaping the hair is appropriately selected depending on the heating tool and heating temperature used, but from the viewpoint of deforming the hair shape semi-permanently to permanently, preferably 1 second or more, more preferably 5 Seconds, preferably 1 minute or more, more preferably 5 minutes or more, further preferably 15 minutes or more, further preferably 30 minutes or more, and for hair damage suppression, preferably 2 hours or less, more preferably It is preferably 1.7 hours or less, more preferably 1.5 hours or less, further preferably 1.2 hours or less, further preferably 1 hour or less, further preferably 45 minutes or less.

Although the present invention is not particularly limited to the embodiment, preferable hair treatment methods for deforming the hair semipermanently to permanently include, for example, the following 5 patterns. However, these five patterns are only examples, and the hair treatment method of the present invention is not limited to these.

Pattern 1: For one-part hair cosmetic 1) Optionally wet the hair with water.
2) The hair cosmetic composition of the present invention containing the following components (A) to (C) is applied to the hair.
Component (A): one or more compounds selected from glyoxylic acid, glyoxylic acid hydrate, glyoxylate, and glyoxylamide Component (B): at least one electron-donating group at the meta position A phenol compound in which at least one of the ortho and para positions is a hydrogen atom (however, the electron donor group at the meta position may form a benzene ring which may be substituted by a hydroxyl group together with the adjacent carbon atom)
Component (C): Reducing Agent 3) Optionally, the hair cosmetic applied hair is left at 10 to 40 ° C. for 1 minute to 1 hour.
4) Shape the hair by heating at 50-250 ° C.
5) optionally rinse the hair.
6) Optionally heat at 40-230 ° C. to reshape the hair.
7) Optionally reshape the hair again by heating at 40-230 ° C.

Pattern 2: In the case of a single-application two-component hair cosmetic 1) Optionally wet the hair with water.
2) A second agent containing the following component (B), preferably containing the component (C), and the component (A), preferably containing the component (C) The hair cosmetic composition of the present invention containing the components (A) to (C) is applied to the hair in which (C) is mixed with at least one of the first agent and the second agent.
Component (A): one or more compounds selected from glyoxylic acid, glyoxylic acid hydrate, glyoxylate, and glyoxylamide Component (B): at least one electron-donating group at the meta position A phenol compound in which at least one of the ortho and para positions is a hydrogen atom (however, the electron donor group at the meta position may form a benzene ring which may be substituted by a hydroxyl group together with the adjacent carbon atom)
Component (C): Reducing Agent 3) Optionally, the hair cosmetic applied hair is left at 10 to 40 ° C. for 1 minute to 1 hour.
4) Shape the hair by heating at 50-250 ° C.
5) optionally rinse the hair.
6) Optionally heat at 40-230 ° C. to reshape the hair.
7) Optionally reshape the hair again by heating at 40-230 ° C.

Pattern 3: In the case of a two-component hair cosmetic composition applied one after another (Part 1)
1) Optionally wet the water.
2) A first agent containing the following component (B), preferably containing the component (C), is applied to the hair.
Component (B): Phenolic compound having an electron donating group at at least one position of meta position, and at least one of ortho position and para position is a hydrogen atom (however, electron donating group at meta position is adjacent carbon atom) And a hydroxyl group may form a benzene ring which may be substituted)
Component (C): Reducing Agent 3) Optionally, leave the hair at 10-40 ° C. for 1 minute or more and 1 hour or less. At this time, it may be optionally heated to 40 to 90.degree.
4) Optionally, wash away the first agent on the hair.
5) A second agent containing the following component (A), preferably containing the component (C), is applied over the site of the hair to which the first agent has been applied (provided that the first agent is When the component (C) is not contained, the second agent necessarily contains the component (C)).
Component (A): one or more compounds selected from glyoxylic acid, glyoxylic acid hydrate, glyoxylate, and glyoxylamide Component (C): reducing agent 6) optionally, 10 to 40 ° C. in the hair Leave for 1 minute or more and 1 hour or less.
7) Shape the hair by heating at 50-250 ° C.
8) Optionally rinse the hair.
9) Optionally reheat the hair by heating at 40-230 ° C.
10) Optionally reshape the hair again by heating at 40-230 ° C.

Pattern 4: In the case of a two-component hair cosmetic composition applied one after another (Part 2)
1) Optionally wet the water.
2) The first agent containing the following components (A) and (B) is applied to the hair.
Component (A): one or more compounds selected from glyoxylic acid, glyoxylic acid hydrate, glyoxylate, and glyoxylamide Component (B): at least one electron-donating group at the meta position A phenol compound in which at least one of the ortho and para positions is a hydrogen atom (however, the electron donor group at the meta position may form a benzene ring which may be substituted by a hydroxyl group together with the adjacent carbon atom)
3) Optionally, leave the hair at 10-40 ° C for 1 minute to 1 hour.
4) Shape the hair by heating at 50-250 ° C.
5) optionally rinse the hair.
6) A second agent containing the following component (C) is overlapped and applied onto the first agent application portion of the hair.
Component (C): Reducing Agent 7) Optionally, leave the hair at 10-40 ° C. for 1 minute to 1 hour. At this time, it may be optionally heated to 40 to 90.degree.
8) Optionally rinse the hair.
9) Optionally reheat the hair by heating at 40-230 ° C.
10) Optionally reshape the hair again by heating at 40-230 ° C.

Pattern 5: In the case of a three-component hair cosmetic composition applied one after another 1) Wet water optionally.
2) A first agent containing the following component (B), preferably containing the component (C), is applied to the hair.
Component (B): Phenolic compound having an electron donating group at at least one position of meta position, and at least one of ortho position and para position is a hydrogen atom (however, electron donating group at meta position is adjacent carbon atom) And a hydroxyl group may form a benzene ring which may be substituted)
Component (C): Reducing Agent 3) Optionally, the hair may be heated.
4) Optionally, wash away the first agent on the hair.
5) A second agent containing the following component (A), preferably containing the component (C), is applied in an overlapping manner on the first agent-coated portion of the hair.
Component (A): one or more compounds selected from glyoxylic acid, glyoxylic acid hydrate, glyoxylate, and glyoxylamide Component (C): reducing agent 6) optionally, 10 to 40 ° C. in the hair Leave for 1 minute or more and 1 hour or less.
7) Shape the hair by heating at 50-250 ° C.
8) Optionally rinse the hair.
9) A third agent containing the following component (C) is overlapped and applied onto the first and second agent application parts of the hair.
Component (C): Reducing Agent 10) Optionally, leave the hair at 10-40 ° C. for 1 minute to 1 hour. At this time, it may be optionally heated to 40 to 90.degree.
11) Optionally rinse the hair.
12) Optionally reheat the hair by heating at 40-230 ° C.
13) Optionally reshape the hair again by heating at 40-230 ° C.

In addition, although the said pattern 5 is an illustration in the case of three-part type hair cosmetics, it is also possible to add the change of mixing a part beforehand and applying to hair, and in that case, two-part type It will be the same as the case where the first agent may contain the component (C) in the pattern 4 of the hair cosmetic.

With regard to the embodiments described above, the preferred embodiments of the present invention will be further disclosed below.

<1>
The following components (A) to (C) consisting of one or more compositions, in the total composition;
(A): one or more compounds selected from glyoxylic acid, glyoxylic acid hydrate, glyoxylate, and glyoxylamide (B): having an electron donating group at at least one position of the meta position, ortho Phenolic compounds in which at least one position of position and para position is a hydrogen atom (however, the electron donating group at meta position may form a benzene ring which a hydroxyl group may substitute with an adjacent carbon atom)
(C): A hair treatment method using a hair cosmetic containing a reducing agent, which comprises the following steps (i) and (ii):
(i) applying components (A) and (B) to the hair (ii) heating and shaping the hair to which the components (A) and (B) are applied, all of the hair treatment method A hair treatment method wherein component (C) is applied to the hair at any point in the process.

The content of the component (A) in the total composition of the <2> hair cosmetic composition is preferably 1.0% by mass or more, more preferably 1.5% by mass or more, still more preferably 2.0% by mass or more, more preferably in terms of glyoxylic acid. Is 2.5% by mass or more, more preferably 3.0% by mass or more, still more preferably 3.5% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less The hair treatment method according to <1>, which is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 7% by mass or less.

<3>
The content of component (B) in the total composition of the hair cosmetic composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more The hair treatment method according to <1> or <2>, which is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 23% by mass or less, and further preferably 20% by mass or less.

<4>
The molar ratio (B) / (A) of the components (A) and (B) applied to the hair is preferably 0.001 or more, more preferably 0.1 or more, still more preferably 0.2 or more, still more preferably 0.25 or more, more preferably Is more preferably 0.28 or more, still more preferably 0.30 or more, preferably less than 2.5, more preferably 2.1 or less, still more preferably 1.4 or less, still more preferably 1.2 or less, still more preferably 0.8 or less, more preferably 0.5 or less. The hair treatment method according to any one of 1> to <3>.

<5>
Component (C) is one or two selected from the group consisting of thioglycolic acid or a salt thereof, sodium sulfite, ascorbic acid, butyrolactone thiol, L-cysteine (2-amino-3-sulfanyl propionic acid), and cysteamine The hair treatment method according to any one of <1> to <4>, which is the above.

<6>
The content of the component (C) in the total composition of the hair cosmetic composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, more preferably Is 1.0% by mass or more, more preferably 1.5% by mass or more, still more preferably 1.5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 12% by mass or less The hair treatment according to any one of <1> to <5>, which is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less, still more preferably 3% by mass or less Method.

<7>
The molar ratio (B) / (C) of the components (B) and (C) applied to the hair is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.2 or more, still more preferably 0.4 or more, more preferably Is preferably 0.6 or more, more preferably 0.7 or more, preferably 10 or less, more preferably 7 or less, still more preferably 5 or less, still more preferably 4 or less, more preferably 2 or less, more preferably 1.5 or less. The hair treatment method according to any one of 1> to <6>.

<8>
The molar ratio [(A) + (B)] / (C) of the total of components (A) and (B) to component (C) applied to hair is preferably 0.2 or more, more preferably 0.6 or more , More preferably 1.2 or more, still more preferably 2.0 or more, still more preferably 3.0 or more, preferably 30 or less, more preferably 20 or less, still more preferably 15 or less, still more preferably 10 or less, more preferably 6 The hair treatment method according to any one of <1> to <7>, which is the following.

<9>
The hair treatment method according to any one of <1> to <8>, wherein the component (B) is preferably the following component (B2).
(B2): a compound represented by the following general formula (1), preferably the following general formula (1-1), (1-2), (1-3-a) or (1-3-b) Or a compound represented by the following general formula (1-1-1), (1-1-2) or (1-1-3)

[In the formula,
R ¹ represents a hydrogen atom or a methyl group,
A ¹ and A ^{2, which} may be the same or different, are each independently a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, or an aralkyl which may have a substituent having 7 to 12 carbon atoms Group or arylalkenyl group, linear or branched alkoxy group or alkenyloxy group having 1 to 6 carbon atoms, halogen atom or -CO-R ² (R ² is linear or branched alkyl having 1 to 12 carbon atoms Group or alkenyl group, an aralkyl group or arylalkenyl group which may have a substituent of 7 to 12 carbon atoms, or an aromatic hydrocarbon group which may have a substituent of 6 to 12 carbon atoms,
B represents a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, an aralkyl or aryl alkenyl group which may have a substituent having 7 to 12 carbon atoms, -OR ³ or- COOR ³ (R ³ represents a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms),
D represents a hydrogen atom, a hydroxyl group, a methyl group or a linear or branched alkoxy group having 1 to 12 carbon atoms or an alkenyloxy group,
E represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms.
However, two or three of A ¹ , A ² , B and E are hydrogen atoms, and the remaining groups do not contain a sulfo group. When D is a hydrogen atom or a methyl group, A ¹ and B, or A ² and B, together with two adjacent carbon atoms form a benzene ring which may be substituted by a hydroxyl group. ]

[Wherein, R ¹ , A ¹ , A ² , B and E have the same meaning as described above, and D ¹ represents a hydroxyl group or a methoxy group. ]

[Wherein, R ¹ represents the same meaning as described above, D ² represents a hydroxyl group or an alkoxy group having 1 to 12 carbon atoms, and G represents a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or an alkenyl group Group or an alkoxy group having 1 to 6 carbon atoms, n is an integer of 0 to 2; ]

[Wherein, R ¹ , A ² , E, D, G and n have the same meaning as described above. ]

[Wherein, R ¹ , A ¹ , E, D, G and n have the same meaning as described above. ]

[Wherein, A ¹ , A ² , B and E have the same meaning as described above. ]

[Wherein, A ¹ , A ² , B and E have the same meaning as described above. ]

[Wherein, A ¹ , A ² , B and E have the same meaning as described above. ]

<10>
Component (B2) is preferably 2-alkylresorcin, 4-alkylresorcin, 4-aralkylresorcin, 4-halogenated resorcin, 5-hydroxyarylalkenylresorcin, 2,4,6-trihydroxyphenylaralkyl ketone, benzophenone derivative , Naphthol, 4-acylated resorcinol, 5-alkyl resorcinol, 5-aralkyl resorcinol, gallic acid, and gallic acid ester, or one or more selected from them, more preferably 2-methyl resorcinol, 4-butyl resorcinol Name: Rucinol (rucinol), 4-hexyl resorcinol, 4- (1-phenylethyl) resorcinol (common name: Simwhite 377 (Symwhite 377)), 4-chlororesorcinol, 5- (hydroxyphenylethenyl) resorcinol (conventional Name: resveratrol, 5- (hydroxyphenylethenyl) -1,3-dimethoxy Sibenzene (common name: Pterostilbene), 3-hydroxyphenyl-1- (benzene-2,4,6-triol) propan-1-one (common name: Phloretin), 4- (2,4 (2,4) -A method for treating hair according to <9>, which is one or more selected from dihydroxybenzoyl) resorcin (common name: benzophenone-2 (benzophenone-2)), and 1-naphthol.

<11>
The content of the component (B2) in the total composition of the hair cosmetic composition is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, and from the viewpoint of formulation The hair treatment method according to <9> or <10>, which is preferably 17% by mass or less, more preferably 12% by mass or less, further preferably 8% by mass or less.

<12>
The hair treatment method according to any one of <1> to <8>, wherein the component (B) is preferably the following (B3).
(B3): a compound represented by the following general formula (2), preferably a compound represented by the following (2-1) to (2-5)

[In the formula,
R ⁴ represents a hydrogen atom or a methyl group,
X represents a hydrogen atom, a hydroxyl group or a methoxy group,
Y represents a hydrogen atom, an oxygen atom, a hydroxyl group or a methoxy group,
Z represents a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms,
R ^x is a hydrogen atom, an oxygen atom, a hydroxyl group, a methoxy group, or an aromatic hydrocarbon group which may be substituted by up to 3 hydroxyl groups or methoxy groups and may form a condensed ring with 1,3-dioxolane Show
R ^y is a hydrogen atom, a hydroxyl group, a methoxy group, or an aromatic hydrocarbon group which may be substituted by up to 3 hydroxyl groups or methoxy groups and may form a condensed ring with 1,3-dioxolane, or a hydroxyl group or Represents an arylcarbonyloxy group or an aralkylcarbonyloxy group which may be substituted by up to 3 methoxy groups,
The dashed line indicates that it may be a double bond.
However, the broken line and the solid line adjacent to the R ^x or Y, R ^x or Y represents only double bond when an oxygen atom, a single bond in other cases.
In addition, Z is a linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms only when R ^x or R ^y is an o, p-dihydroxy aromatic hydrocarbon group, In other cases it is a hydrogen atom. ]

[In the formula,
R ⁴ and X have the same meaning as described above,
Y ¹ represents a hydrogen atom, a hydroxyl group or a methoxy group,
R ^x1 represents an aromatic hydrocarbon group which may be substituted by up to three hydroxyl groups or methoxy groups and may form a condensed ring with 1,3-dioxolane;
R ^y1 is a hydrogen atom, a hydroxyl group, a methoxy group, an aromatic hydrocarbon group which may be substituted by up to 3 hydroxyl groups or methoxy groups and may form a condensed ring with 1,3-dioxolane, or a hydroxyl group or This represents an arylcarbonyloxy group or an aralkylcarbonyloxy group which may be substituted by up to three methoxy groups. ]

[Wherein, R ⁴ , X, Z and R ^x1 have the same meaning as described above, and R ^y2 represents a hydrogen atom, a hydroxyl group or a methoxy group.
However, Z is a linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms only when R ^x1 is an o, p-dihydroxy aromatic hydrocarbon group, otherwise Are hydrogen atoms. ]

[Wherein, R ⁴ , X, Z, R ^x1 and R ^y2 have the same meaning as described above.
However, Z is a linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms only when R ^x1 is an o, p-dihydroxy aromatic hydrocarbon group, otherwise Are hydrogen atoms. ]

[In the formula,
R ⁴ , X, Z and a broken line have the same meaning as described above,
Y ² represents a hydrogen atom or an oxygen atom,
R ^x2 represents a hydrogen atom, a hydroxyl group or a methoxy group,
R ^y3 represents an aromatic hydrocarbon group which may have up to three hydroxyl groups or methoxy groups or may form a condensed ring with 1,3-dioxolane.
However, the broken line and the solid line adjacent to Y ² is, Y ² represents only double bond when an oxygen atom, a single bond in other cases.
In addition, Z is a linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms only when R ^y3 is an o, p-dihydroxy aromatic hydrocarbon group, otherwise Are hydrogen atoms. ]

[Wherein, R ⁴ and X are as defined above]

<13>
Component (B3) is preferably catechin (Catechin), epicatechin (Epicatechin), epigallocatechin (Epigallocatechin), catechin gallate (Catechin gallate), epicatechin gallate (Epicatechin gallate), epigallocatechin gallate (Epigallocatechin gallate), One or two selected from quercetin (Quercetin), morin (Morin), hesperetin (Hesperetin), naringenin (Naringenin), chrysin (Chrysin), daidzein (Daidzein), equol (Equol), and umbelliferone (Umbelliferone) The hair treatment method according to <12>, which is one or more selected from catechin, epigallocatechin, epigallocatechin gallate, naringenin, and equol.

<14>
The content of the component (B3) in the total composition of the hair cosmetic composition is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 3.5% by mass or more, still more preferably 4.0% by mass or more The hair treatment method according to <12> or <13>, which is preferably 17% by mass or less, more preferably 15% by mass or less, still more preferably 12% by mass or less, further preferably 8% by mass or less.

<15>
The hair treatment method according to any one of <1> to <8>, wherein the component (B) is preferably the following component (B1).
(B1): resorcinol

<16>
The content of the component (B1) in the total composition of the hair cosmetic composition is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, still more preferably 5% by mass or more The hair treatment method according to <15>, which is preferably 19% by mass or less, more preferably 17% by mass or less, still more preferably 15% by mass or less, and further preferably 14% by mass or less.

<17>
Preferably, the hair treatment method according to any one of <1> to <16>, further comprising the step of applying the following component (D) to the hair before the step (ii).
(D): One or more selected from compounds represented by the following general formula (3)

[Wherein, Q represents a polymethylene group having 2 to 5 carbon atoms which may be substituted by a carboxy group, or a carbonyl group, and T ¹ and T ² may be each independently substituted with a hydrogen atom or a hydroxyl group A linear or branched alkyl group of 1 to 5 carbon atoms is shown, or both are combined to form a polymethylene group of 2 to 5 carbon atoms to form a ring with -NH-Q-NH-. ]

<18>
The hair treatment method according to <17>, wherein the component (D) is preferably one or more selected from urea, 2-hydroxyethyl urea, ethylene urea, lysine hydrochloride and ethylene diamine.

<19>
The content of the component (D) in the total composition of the hair cosmetic composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, more preferably Is preferably 1.5% by mass or more, more preferably 1.8% by mass or more, preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass or less, still more preferably 8% by mass or less The hair treatment method as described in <17> or <18> which is preferably 5 mass% or less, more preferably 3 mass% or less.

<20>
Molar ratio [(B) + (D)] / (A) of components (A), (B) and (D) of the sum of components (B) and (D) to component (A) applied to hair Is preferably 0.01 or more, more preferably 0.5 or more, still more preferably 0.1 or more, still more preferably 0.2 or more, still more preferably 0.3 or more, still more preferably 0.7 or more, and preferably 2.5 or less, more preferably The hair treatment method according to any one of <17> to <19>, which is 2.3 or less, more preferably 2.1 or less, further preferably 1.9 or less, more preferably 1.7 or less, further preferably 1.5 or less.

<21>
The content of hydrogen peroxide in the hair cosmetic applied to the hair before the step (ii) is preferably 1% by mass or less, more preferably 0.1% by mass or less, still more preferably 0.01% by mass or less. The hair treatment method according to any one of <1> to <20>.

<22>
After the step (i), the hair to which the hair cosmetic is applied is preferably 1 minute or more, more preferably 3 minutes or more, still more preferably 5 minutes or more, preferably 1 hour or less, more preferably 30 minutes or less, The hair treatment method according to any one of <1> to <21>, further comprising the step of leaving for 20 minutes or less.

<23>
The hair treatment method according to any one of <1> to <22>, which preferably comprises the step of wetting the hair before step (i).

<24>
The heating temperature in step (ii) is preferably 50 ° C. or more, more preferably 60 ° C. or more, still more preferably 80 ° C. or more, and preferably 250 ° C. or less, more preferably 240 ° C. or less, more preferably 230 The hair treatment method according to any one of <1> to <23>, which is not higher than ° C.

<25>
Preferably, the hair treatment method according to any one of <1> to <24>, wherein the step (ii) is performed under an environment in which water evaporation is suppressed.

<26>
Preferably, after step (ii), the hair treatment method according to any one of <1> to <25>, wherein the hair is re-deformed into a different shape by heating.

<27>
Preferably, the step (i) is a step of applying to the hair a one-component hair cosmetic containing the components (A), (B) and (C) in a single composition, <1> The hair treatment method of any one of <26>.

<28>
The pH of the one-part hair cosmetic composition is preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.5 or less, still more preferably 2.0 or less, and preferably 1.0 or more, more preferably 1.2 or more, more preferably The hair treatment method as described in <27> which is 1.5 or more, More preferably, 1.7 or more.

<29>
The hair treatment method as described in <27> or <28> including preferably the following process.
1) Optionally wet the hair with water.
2) Apply one-part hair cosmetic to hair.
3) Optionally, the hair cosmetic applied hair is left at 10 to 40 ° C. for 1 minute or more and 1 hour or less.
4) Shape the hair by heating at 50-250 ° C.
5) optionally rinse the hair.
6) Optionally heat at 40-230 ° C. to reshape the hair.
7) Optionally reshape the hair again by heating at 40-230 ° C.

<30>
Preferably, step (i) comprises components (A), (B) and (C) in the total composition consisting of the first and second agents or in the total composition consisting of the first to third agents. A method of treating hair according to any one of <1> to <26>, which is a step of mixing each agent of the formulated hair cosmetic and applying it to the hair.

<31>
Preferably, step (i) comprises components (A), (B) and (C) in the total composition consisting of the first and second agents or in the total composition consisting of the first to third agents. When the first agent of cosmetic hair cosmetic composition is applied to the hair, and then the second agent of multi-component hair cosmetic composition is overlapped and applied onto the first agent application portion of the hair, and the third agent is used The hair treatment method according to any one of <1> to <26>, which is a step of applying a third agent on top of the first agent and second agent application parts of the hair.

<32>
Preferably, step (i) contains components (A) and (B) in the total composition of the first agent and the second agent, and the component (C) is contained in the third agent. Applying the first agent of the hair powder to the hair, and then applying the second agent of the multi-part hair cosmetic composition over the first agent applied portion of the hair, and after the step (ii) The hair treatment method according to any one of <1> to <26>, comprising the following step (iii):
(iii) applying the third agent of the multi-component hair cosmetic composition to the first and second agent application parts of the hair

<33>
Preferably, in the step (i), after the first agent is applied to the hair, before the second agent is applied over the first agent applied portion of the hair, the step of washing out the first agent is included. 31> or the hair treatment method as described in <32>.

<34>
In the step (i), after the first agent is applied to the hair, the hair is preferably 1 minute or more, more preferably 3 minutes or more, still more preferably 5 minutes or more, until the first agent is washed out. The hair treatment method according to <33>, which comprises a step of standing for preferably 1 hour or less, more preferably 30 minutes or less, still more preferably 20 minutes or less.

<35>
Preferably, the pH of the agent containing the component (A) is preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.5 or less, still more preferably 2.0 or less, and preferably 1.0 or more, more preferably The hair treatment method according to any one of <30> to <34>, which is 1.2 or more, more preferably 1.5 or more, and further preferably 1.7 or more.

<36>
The hair treatment method as described in <30> or <35> preferably including the following steps.
1) Optionally wet the hair with water.
2) A second agent containing the component (B), preferably containing the component (C), and the component (A), preferably containing the component (C) (but the component (C) The two-component hair cosmetic composition containing the components (A) to (C), which is mixed with at least one of the first agent and the second agent) is applied to the hair.
3) Optionally, the hair cosmetic applied hair is left at 10 to 40 ° C. for 1 minute or more and 1 hour or less.
4) Shape the hair by heating at 50-250 ° C.
5) optionally rinse the hair.
6) Optionally heat at 40-230 ° C. to reshape the hair.
7) Optionally reshape the hair again by heating at 40-230 ° C.

<37>
The hair treatment method according to any one of <31>, <33> to <35>, preferably including the following steps.
1) Optionally wet the water.
2) A first agent containing component (B), preferably containing component (C), is applied to the hair.
3) Optionally, leave the hair at 10-40 ° C for 1 minute to 1 hour. At this time, it may be optionally heated to 40 to 90.degree.
4) Optionally, wash away the first agent on the hair.
5) A second agent containing the component (A), preferably containing the component (C), is applied one on top of the first agent-coated portion of the hair and applied (however, the first agent contains the component (C) If not (the second agent always contains the component (C)).
6) Optionally, leave the hair at 10-40 ° C. for 1 minute to 1 hour.
7) Shape the hair by heating at 50-250 ° C.
8) Optionally rinse the hair.
9) Optionally reheat the hair by heating at 40-230 ° C.
10) Optionally reshape the hair again by heating at 40-230 ° C.

<38>
The hair treatment method according to any one of <32> to <35>, which preferably comprises the following steps:
1) Optionally wet the water.
2) The first agent containing the components (A) and (B) is applied to the hair.
3) Optionally, leave the hair at 10-40 ° C for 1 minute to 1 hour.
4) Shape the hair by heating at 50-250 ° C.
5) optionally rinse the hair.
6) The second agent containing the component (C) is overlapped and applied onto the first agent applied portion of the hair.
7) Optionally, leave the hair at 10-40 ° C. for 1 minute to 1 hour. At this time, it may be optionally heated to 40 to 90.degree.
8) Optionally rinse the hair.
9) Optionally reheat the hair by heating at 40-230 ° C.
10) Optionally reshape the hair again by heating at 40-230 ° C.

<39>
The hair treatment method according to any one of <32> to <35>, which preferably comprises the following steps:
1) Optionally wet the water.
2) A first agent containing component (B), preferably containing component (C), is applied to the hair.
3) Optionally, the hair may be heated.
4) Optionally, wash away the first agent on the hair.
5) A second agent containing the component (A), preferably containing the component (C), is overlapped and applied onto the first agent-coated portion of the hair.
6) Optionally, leave the hair at 10-40 ° C. for 1 minute to 1 hour.
7) Shape the hair by heating at 50-250 ° C.
8) Optionally rinse the hair.
9) The third agent containing the component (C) is overlapped and applied onto the first and second agent application parts of the hair.
10) Optionally, leave the hair at 10-40 ° C. for 1 minute to 1 hour. At this time, it may be optionally heated to 40 to 90.degree.
11) Optionally rinse the hair.
12) Optionally reheat the hair by heating at 40-230 ° C.
13) Optionally reshape the hair again by heating at 40-230 ° C.

<40>
A hair treatment method which deforms a hair shape semipermanently to permanently, comprising the following steps (i) to (vi).
(i) Step of applying a first agent containing the following component (B2) to the hair (B2) One or more selected from 4-hexylresorcinol, rucinol, shim white, and 4-chlororesorcinol 2 17 mass%
(ii) heating the hair at 40 to 90 ° C. and standing for 1 minute to 1 hour (iii) washing out the first agent on the hair (iv) containing the following components (A) and (C) Optionally applying to the hair a second agent containing component (D) (A) glyoxylic acid, glyoxylic acid hydrate, glyoxylate, and glyoxylamide; one or more selected from 2.5 or more 25 mass%
(C) One or more reducing agents selected from thioglycollic acid or its salt, sodium sulfite, ascorbic acid, butyrolactone thiol, L-cysteine (2-amino-3-sulfanyl propionic acid), and cysteamine 0.2 to 20 mass %
(D) One or more selected from urea, 2-hydroxyethyl urea, ethylene urea, lysine hydrochloride, and ethylene diamine 0.1 to 20% by mass
(v) heating the hair at 50 to 250 ° C. and leaving it for 1 minute to 1 hour to form (vi) washing away the second agent on the hair

<41>
A hair treatment method which deforms a hair shape semipermanently to permanently, comprising the following steps (i) to (vi).
(i) A step of applying a first agent containing the following component (B1) to the hair (B1) Resorcinol 5 to 40% by mass
(ii) heating the hair at 40 to 90 ° C. and standing for 1 minute to 1 hour (iii) washing out the first agent on the hair (iv) containing the following components (A) and (C) Optionally applying to the hair a second agent containing component (D) (A) glyoxylic acid, glyoxylic acid hydrate, glyoxylate, and glyoxylamide; one or more selected from 2.5 or more 25 mass%
(C) One or more reducing agents selected from thioglycollic acid or its salt, sodium sulfite, ascorbic acid, butyrolactone thiol, L-cysteine (2-amino-3-sulfanyl propionic acid), and cysteamine 0.2 to 20 mass %
(D) One or more selected from urea, 2-hydroxyethyl urea, ethylene urea, lysine hydrochloride, and ethylene diamine 0.1 to 20% by mass
(v) heating the hair at 50 to 250 ° C. and leaving it for 1 minute to 1 hour to form (vi) washing away the second agent on the hair

<42>
A hair treatment method which deforms a hair shape semipermanently to permanently, comprising the following steps (i) to (vi).
(i) A step of applying a first agent containing the following component (B3) to the hair (B3) catechin (Catechin), epicatechin (Epicatechin), epigallocatechin (Epigallocatechin), mesidadanol (Meciadanol), afzelequin (A) Afzelechin), Epiafzelechin (Epiafzelechin), Catechin gallate, Epicatechin gallate, Epigallocatechin gallate, Epigallocatechin gallate, Phylloflavan, Fisetinidol (Guibutilidolol) And one or more selected from Robinetinidol: 0.1 to 30% by mass
(ii) heating the hair at 40 to 90 ° C. and standing for 1 minute to 1 hour (iii) washing out the first agent on the hair (iv) containing the following components (A) and (C) Optionally applying to the hair a second agent containing component (D) (A) glyoxylic acid, glyoxylic acid hydrate, glyoxylate, and glyoxylamide; one or more selected from 2.5 or more 25 mass%
(C) One or more reducing agents selected from thioglycollic acid or its salt, sodium sulfite, ascorbic acid, butyrolactone thiol, L-cysteine (2-amino-3-sulfanyl propionic acid), and cysteamine 0.2 to 20 mass %
(D) One or more selected from urea, 2-hydroxyethyl urea, ethylene urea, lysine hydrochloride, and ethylene diamine 0.1 to 20% by mass
(v) heating the hair at 50 to 250 ° C. and leaving it for 1 minute to 1 hour to form (vi) washing away the second agent on the hair

<43>
A hair treatment method which deforms a hair shape semipermanently to permanently, comprising the following steps (i) to (vi).
(i) applying to the hair a first agent containing the following components (A) and (B2) and optionally containing the component (D) (A) glyoxylic acid, glyoxylic acid hydrate, glyoxylic acid Salt, and one or more selected from glyoxylamide 2.5 to 25% by mass
(B2) One or more selected from 4-hexyl resorcinol, rucinol, sim white, and 4-chloro resorcinol 2 to 17% by mass
(D) One or more selected from urea, 2-hydroxyethyl urea, ethylene urea, lysine hydrochloride, and ethylene diamine 0.1 to 20% by mass
(ii) heating the hair at 50 to 250 ° C. and leaving it to stand for 1 minute to 1 hour to form (iii) washing away the first agent on the hair (iv) containing the following component (C) The step of applying the second agent to the hair (C) Thioglycolic acid or its salt, sodium sulfite, ascorbic acid, butyrolactone thiol, L-cysteine (2-amino-3-sulfanyl propionic acid), and cysteamine 1 Or two or more reducing agents 0.2 to 20% by mass
(v) leaving the hair for 1 minute to 1 hour (vi) washing away the second agent on the hair

<44>
A hair treatment method which deforms a hair shape semipermanently to permanently, comprising the following steps (i) to (vi).
(i) applying to the hair a first agent containing the following components (A) and (B1) and optionally containing the component (D) (A) glyoxylic acid, glyoxylic acid hydrate, glyoxylic acid Salt, and one or more selected from glyoxylamide 2.5 to 25% by mass
(B1) 5 to 40% by mass of resorcin
(D) One or more selected from urea, 2-hydroxyethyl urea, ethylene urea, lysine hydrochloride, and ethylene diamine 0.1 to 20% by mass
(ii) heating the hair at 50 to 250 ° C. and leaving it to stand for 1 minute to 1 hour to form (iii) washing away the first agent on the hair (iv) containing the following component (C) The step of applying the second agent to the hair (C) Thioglycolic acid or its salt, sodium sulfite, ascorbic acid, butyrolactone thiol, L-cysteine (2-amino-3-sulfanyl propionic acid), and cysteamine 1 Or two or more reducing agents 0.2 to 20% by mass
(v) leaving the hair for 1 minute to 1 hour (vi) washing away the second agent on the hair

<45>
A hair treatment method which deforms a hair shape semipermanently to permanently, comprising the following steps (i) to (vi).
(i) applying to the hair a first agent containing the following components (A) and (B3) and optionally containing the component (D) (A) glyoxylic acid, glyoxylic acid hydrate, glyoxylic acid Salt, and one or more selected from glyoxylamide 2.5 to 25% by mass
(B3) Catechin (Catechin), epicatechin (Epicatechin), epigallocatechin (Epigallocatechin), mesidadanol (Meciadanol), afzelechin (Afzelechin), epiafzelechin (Epiafzelechin), catechin gallate (Catechin gallate), epicatechin gallate (Epatechinolate) And / or epigallocatechin gallate (Epigallocatechin gallate), phyloflavan (Phylloflavan), fisetinidol (Fisetinidol), guiburutinidol (Guibourtinidol), and one or more selected from robinetinidol (Robinetinidol) 0.1 to 30% by mass
(D) One or more selected from urea, 2-hydroxyethyl urea, ethylene urea, lysine hydrochloride, and ethylene diamine 0.1 to 20% by mass
(ii) heating the hair at 50 to 250 ° C. and leaving it to stand for 1 minute to 1 hour to form (iii) washing away the first agent on the hair (iv) containing the following component (C) The step of applying the second agent to the hair (C) Thioglycolic acid or its salt, sodium sulfite, ascorbic acid, butyrolactone thiol, L-cysteine (2-amino-3-sulfanyl propionic acid), and cysteamine 1 Or two or more reducing agents 0.2 to 20% by mass
(v) leaving the hair for 1 minute to 1 hour (vi) washing away the second agent on the hair

<46>
A hair treatment method which deforms a hair shape semipermanently to permanently, comprising the following steps (i) to (iii):
(i) A step of applying a one-component hair cosmetic composition containing the following components (A), (B2) and (C) and optionally containing the component (D) (A) Glyoxylic acid, glyoxyl Acid hydrate, glyoxylate, and one or more selected from glyoxylamide 2.5 to 25% by mass
(B2) One or more selected from 4-hexyl resorcinol, rucinol, sim white, and 4-chloro resorcinol 2 to 17% by mass
(C) One or more reducing agents selected from thioglycollic acid or its salt, sodium sulfite, ascorbic acid, butyrolactone thiol, L-cysteine (2-amino-3-sulfanyl propionic acid), and cysteamine 0.2 to 20 mass %
(D) One or more selected from urea, 2-hydroxyethyl urea, ethylene urea, lysine hydrochloride, and ethylene diamine 0.1 to 20% by mass
(ii) heating the hair at 50 to 250 ° C. and leaving it to stand for 1 minute to 1 hour for shaping (iii) washing away the hair cosmetic on the hair

<47>
A hair treatment method which deforms a hair shape semipermanently to permanently, comprising the following steps (i) to (iii):
(i) Step of applying a one-component hair cosmetic composition containing the following components (A), (B1) and (C) and optionally containing the component (D) (A) Glyoxylic acid, glyoxyl Acid hydrate, glyoxylate, and one or more selected from glyoxylamide 2.5 to 25% by mass
(B1) 5 to 40% by mass of resorcin
(C) One or more reducing agents selected from thioglycollic acid or its salt, sodium sulfite, ascorbic acid, butyrolactone thiol, L-cysteine (2-amino-3-sulfanyl propionic acid), and cysteamine 0.2 to 20 mass %
(D) One or more selected from urea, 2-hydroxyethyl urea, ethylene urea, lysine hydrochloride, and ethylene diamine 0.1 to 20% by mass
(ii) heating the hair at 50 to 250 ° C. and leaving it to stand for 1 minute to 1 hour for shaping (iii) washing away the hair cosmetic on the hair

<48>
A hair treatment method which deforms a hair shape semipermanently to permanently, comprising the following steps (i) to (iii):
(i) Step of applying a one-component hair cosmetic composition containing the following components (A), (B3) and (C) and optionally containing the component (D) (A) Glyoxylic acid, glyoxyl Acid hydrate, glyoxylate, and one or more selected from glyoxylamide 2.5 to 25% by mass
(B3) Catechin (Catechin), epicatechin (Epicatechin), epigallocatechin (Epigallocatechin), mesidadanol (Meciadanol), afzelechin (Afzelechin), epiafzelezin (Epiafzelechin), catechin gallate (Catechin gallate), epicatechin gallate (Epatechinolate) And / or epigallocatechin gallate (Epigallocatechin gallate), phyloflavan (Phylloflavan), fisetinidol (Fisetinidol), guiburutinidol (Guibourtinidol), and one or more selected from robinetinidol (Robinetinidol) 0.1 to 30% by mass
(C) One or more reducing agents selected from thioglycollic acid or its salt, sodium sulfite, ascorbic acid, butyrolactone thiol, L-cysteine (2-amino-3-sulfanyl propionic acid), and cysteamine 0.2 to 20 mass %
(D) One or more selected from urea, 2-hydroxyethyl urea, ethylene urea, lysine hydrochloride, and ethylene diamine 0.1 to 20% by mass
(ii) heating the hair at 50 to 250 ° C. and leaving it to stand for 1 minute to 1 hour for shaping (iii) washing away the hair cosmetic on the hair

Below, the hair treatment method and evaluation method which were used by the Example and the comparative example are shown.

PH measurement method After preparing each composition, it was measured with a pH meter (manufactured by HORIBA / model: F-52) at room temperature (25 ° C.) without dilution to obtain a value.

● Coloration evaluation The following processing was performed to goat hair, and coloration evaluation was performed.
<Processing method 1>
1. 1.0 g of goat hair (untreated) was placed on a wrap and impregnated with 0.9 g of water.
2. After application of 1.5 mL of the first agent or one-part hair cosmetic composition described in each of the Examples or Comparative Examples described later to the hydrated hair bundle, the mixture is well blended and covered with a wrap from above and the hair bundle The cover was fixed with mending tape, and the hair bundle was sealed in a bag-like space, which was heated in an oven set at 90 ° C. for 1 hour.
3. The wrapped tress was removed from the oven and allowed to return to room temperature (25 ° C.).
4. Remove the tress from the wrap, rinse for 30 seconds with 30 ° C running tap water, foam for 60 seconds with the evaluation shampoo, rinse for 30 seconds with 30 ° C running tap water, and then pass the comb through the hair tress. Dried for 6 minutes with cold air.

<Processing method 2>
1. The hair bundle treated with the first agent according to treatment method 1 was placed on a wrap and impregnated with 0.9 g of water.
2. The second agent is applied to the hydrated hair bundle in the bath ratio shown in each example or comparative example described later, and after good mixing, a wrap is also covered from above to cover the hair bundle and mending It was fixed with a tape, and the hair bundle was sealed in a bag-like space, which was heated in an oven set at 40 ° C. for 1 hour.
3. The wrap sealed hair tress was removed from the oven and allowed to return to room temperature.
4. Remove the tress from the wrap, rinse for 30 seconds with 30 ° C running tap water, foam for 60 seconds with the evaluation shampoo, rinse for 30 seconds with 30 ° C running tap water, and then pass the comb through the hair tress. Dried for 6 minutes with cold air.

<Processing method 3>
1. 1.0 g of goat hair (untreated) was placed on a wrap and impregnated with 0.9 g of water.
2. To the hydrated hair bundle, apply 1.5 mL of the first agent shown in each example or comparative example to be described later, and after allowing them to blend well, cover the hair bundle from above with a wrapping and cover it with a mending tape The hair bundle was fixed in a bag-like space and sealed, and heated in an oven set at 90 ° C. for 1 hour to allow the first agent to penetrate the hair.
3. The wrap sealed hair tress was removed from the oven and allowed to return to room temperature.
4. Remove the tress from the wrap, rinse for 30 seconds with 30 ° C running tap water, foam for 60 seconds with the evaluation shampoo, rinse for 30 seconds with 30 ° C running tap water, and then pass the comb through the hair tress. Dried for 6 minutes with cold air.
5. The hair tresses treated by the above method were placed on a wrap and impregnated with 0.9 g of water.
6. Apply 1.5 mL of the second agent to the moistened hair bundle, and after allowing it to blend well, cover the hair bundle from above with a wrap and secure it with mending tape, and the hair bundle in the bag-like space Sealed and heated in an oven set at 90 ° C. for 1 hour.
7. The wrap sealed hair tress was removed from the oven and allowed to return to room temperature.
8. Remove the tress from the wrap, rinse for 30 seconds with 30 ° C running tap water, foam for 60 seconds with the evaluation shampoo, rinse for 30 seconds with 30 ° C running tap water, and then pass the comb through the hair tress. Dried for 6 minutes with cold air.

<Processing method 4>
1. The goat hair tress treated by treatment method 3 was placed on a wrap and impregnated with 0.9 g of water.
2. Apply 0.5 mL of the third agent described in each of the examples or comparative examples described later to the hydrated hair bundle, and after good mixing, cover the hair bundle from above with a wrap to cover the mending tape The hair bundle was sealed in a bag-like space, which was heated in an oven set at 40 ° C. for 1 hour.
3. The wrap sealed hair tress was removed from the oven and allowed to return to room temperature.
4. Remove the tress from the wrap, rinse for 30 seconds with 30 ° C running tap water, foam for 60 seconds with the evaluation shampoo, rinse for 30 seconds with 30 ° C running tap water, and then pass the comb through the hair tress. Dried for 6 minutes with cold air.

<Coloring evaluation method 1> (coloring immediately after treatment and one month after)
1. About each of the front and back of the goat hair bundle, near the root, near the middle, near the end of the hair was measured with a colorimeter (colorimeter CR-400 made by Konica Minolta), and the average value of a total of 6 points was used as the color measurement value (L, a, b).
2. The degree of coloring was evaluated by ΔE * ab on the basis of untreated goat hair (absolute evaluation).
3. After leaving the hair bundle at room temperature for 1 month, the color was evaluated again in the same manner as described above, and the coloration over time was evaluated with ΔE * ab based on untreated goat hair. The smaller the ΔE * ab value is, the more the color is reduced.

<Coloring evaluation method 2> (coloring by repeated ironing)
The hair bundle immediately after the treatment was pressed for 20 seconds with a flat iron at an actual measurement temperature of 140 ° C. Hair washing was performed once every 15 times of the iron press, and the degree of coloring at the time of repeated ironing 90 times was evaluated by ΔE * ab in the same manner as the coloring evaluation method 1 with reference to untreated goat hair. The smaller the ΔE * ab value is, the more the color is reduced.

Shape evaluation, touch evaluation The following processing was performed on the Caucasian hair, and shape evaluation and touch evaluation were performed.
<Processing method 5>
1. A wet bundle of 0.5 cm long, 25 cm long, of caussian straight hair (untreated hair) was wet with tap water at 30 ° C. for 30 seconds, and then the wet hair bundle was wound around a plastic rod having a diameter of 14 mm and fixed with a clip.
2. 1 g of the first agent shown in each Example or Comparative Example described later was applied to the hair bundle wound around the rod, and the hair bundle was placed on a balance dish and sealed with another balance dish. Then, it was heated in an oven set at 90 ° C. for 1 hour.
3. The tress was removed from the oven and allowed to return to room temperature.
4. The tress was removed from the rod, rinsed in running tap water at 30 ° C. for 30 seconds, and frothed with the evaluation shampoo for 60 seconds. Further, it was rinsed for 30 seconds with 30 ° C. running tap water.
5.1-treated hair tresses were wet for 30 seconds with 30 ° C. tap water, and then the wet hair tresses were wound around a 14 mm diameter plastic rod and fixed with clips.
6. 1 g of a second agent shown in each Example or Comparative Example described later was applied to the hair bundle wound around the rod, and the hair bundle was placed on a balance dish and sealed with another balance dish. Then, it was heated in an oven set at 90 ° C. for 1 hour.
7. The tress was removed from the oven and allowed to return to room temperature.
8. The tufts were removed from the rod and rinsed in running tap water at 30 ° C. for 30 seconds.
9. The foam for evaluation was used for 60 seconds. Further, it was rinsed for 30 seconds with 30 ° C. running tap water.

<Cold Perm Processing Method>
1. 1 g of a first agent of a commercial hair cosmetic (Straight'n Shine R, manufactured by Kao Professional Salon Services) was applied to a hair bundle of 0.5 g length of a Caucasian straight hair (untreated hair) and a length of 25 cm.
First component: water, ammonium thioglycollate, cetearyl alcohol, ethanolamine, steareth-2, diammonium dithiodiglycolate, behentrimonium chloride, liquid paraffin, isopropyl alcohol, EDTA-4Na, ascorbic acid, trideceth -12, cetrimonium chloride, phenoxyethanol, flavor, acid yellow 3
2. Heated in a constant temperature bath at 40 ° C. for 30 minutes.
3. The hair tress was taken out of the thermostat, rinsed for 30 seconds with 30 ° C. running water of tap water, bubbled with evaluation shampoo for 60 seconds, and rinsed the hair tress for 30 seconds with 30 ° C. running water of tap water.
4. 1 g of the second agent of a commercially available hair cosmetic (Straight'n Shine R, manufactured by Kao Professional Salon Services) was applied to the hair bundle.
Second agent Indicated components: cetearyl alcohol, polyoxyethylene lauryl ether sulfate, lauryl sulfate, salicylic acid, perfume 5. Heated in a thermostat at 40 ° C for 30 minutes.
6. The hair tress was taken out of the thermostat, rinsed for 30 seconds with 30 ° C. running water of tap water, bubbled with evaluation shampoo for 60 seconds, and rinsed the hair tress for 30 seconds with 30 ° C. running water of tap water.

<Measurement of tensile modulus>
The tensile modulus in a state in which the hair was immersed in ion exchange water was measured and calculated. The measurement was conducted using a Diastron Automatic Hair Tensile Tester, and the stress at a tensile rate of 0 to 0.8% (average of 20 hairs) was taken as the tensile modulus.

<Curl strength evaluation method>
1. Rinse the tress in 30 ° C running water for 30 seconds in tap water, and immerse in 30 ° C tap water for 60 seconds at an infinite bath ratio, then gently pull it out of the water with the root of the tress, lightly shake to give water Cut.
2. The hair tress was hung in the laboratory for 2 hours, allowed to stand, dried and passed through a comb.
3. The length when hanging the tress vertically (the distance to the farthest point from the root) was measured.
(Evaluation criteria)
The tres length of the untreated hair was L ₀ , and the treated tres length was L, and the tress length reduction rate (I) determined according to the following equation was calculated as the curl strength.
I = {(L ₀ -L) / L ₀ } × 100
Furthermore, with regard to the apparent curling strength, Comparative Example 5 was evaluated as A, and Comparative Example 3 (untreated) as E, and evaluated in five steps visually.

<Feeling evaluation method>
The softness of the touch when touched with a hand was evaluated (relative evaluation) with reference to the hair bundle of the untreated Caucasian hair (Comparative Example 3).
(Evaluation criteria)
5: Very soft touch compared to untreated hair 4: Soft touch compared to untreated hair 3: Equivalent to untreated hair 2: Hard touch compared to untreated hair 1: Untreated It has a very hard feel compared to hair

Formulation of Evaluation Shampoo Ingredient (% by mass)
Sodium laureth sulfate 15.5
Lauramide DEA 1.5
Sodium benzoate 0.5
EDTA-2Na 0.3
Amount adjusted to pH 7 Ion exchange water Balance Total 100

Example 1, Comparative Example 1
The 1st agent and 2nd agent of the prescription shown in Table 1 were prepared, and Comparative Example 1 processed the goat hair tress in accordance with the method shown in <treatment method 1>. In Example 1, goat hair bundles were treated according to the method shown in <treatment method 2>. However, the bath ratio (the weight of the second agent / the weight of the hair) to the weight of the hair of the second agent in <treatment method 2> was 0.5. The treated amount (mL) of each agent to 1 g of goat hair, and the content (mass%) and molar ratio of each component in the total treated amount of each agent are shown in Table 2.
The coloration immediately after the treatment was evaluated according to the procedure of 1-2 shown in <Coloring evaluation method>. The results are shown in Table 2 together.

Example 2, Comparative Example 2
A one-part hair cosmetic composition as shown in Table 3 was prepared, and goat hair bundles were treated according to the method shown in <treatment method 1>. The treated amount (mL) of each agent to 1 g of goat hair, and the content (mass%) and molar ratio of each component in the total treated amount of each agent are shown in Table 4.
The coloration immediately after treatment and one month after was evaluated according to the procedure described in <Coloration evaluation method 1>. The results are shown in Table 4 together.

Examples 3 to 9 and Comparative Examples 3 to 5
(Comparative example 3)
Caucasian tuft (untreated tuft) 0.5 g length 25 cm long hair bundle was prepared.
(Comparative example 4)
The Caucasian hair was treated according to the method described in <Cold Perm Treatment Method>.
(Comparative Example 5, Examples 3 to 9)
The first agent and the second agent of the formulations shown in Table 5 were prepared, and goat hair was treated according to the method shown in <treatment method 3>, and Caucasian hair was treated according to the method shown in <treatment method 5>. The treated amount (mL) of each agent to 1 g of goat hair or 1 g of Caucasian hair bundle, and the content (mass%) and molar ratio of each component in the total treated amount of each agent are shown in Table 6.

In Examples 3 to 9 and Comparative Example 5, the coloring of goat hair immediately after the treatment was evaluated according to the procedure shown in 1 to 2 of <Coloring evaluation method 1>. Furthermore, for Examples 4, 7 and 9 and Comparative Example 5, the color after repeated ironing was evaluated according to the procedure shown in <Color evaluation method 2>.
The tensile elastic modulus of the treated and non-treated caucasian hair of Example 9 and Comparative Examples 3 to 5 in a state where the hair was immersed in ion exchange water was measured and calculated according to <Tensile elastic modulus measurement method>.
The curling strength was measured and calculated according to the procedure shown in <Curl strength evaluation method> for the treated or non-treated Caucasian hair of Examples 4 and 7 to 9 and Comparative Examples 3 and 5. Further, regarding the Caucasian hair after the treatments of Examples 3 to 9, the apparent curling strength based on Comparative Examples 3 and 5 was evaluated.
The treated or untreated treated Caucasian hair of Examples 3 to 9 and Comparative Examples 3 and 5 was evaluated according to the procedure described in <Feeling evaluation method>.
These results are shown together in Table 6.

Example 10, Comparative Example 2
The first and second agents of Example 10 shown in Table 7 are prepared, and the bath ratio to the weight of hair (the weight of the hair cosmetic / the weight of the hair) is set to 1.5 according to the method shown in <treatment method 2>, Goat hair bundles were processed. The treated amount (mL) of each agent to 1 g of goat hair, and the content (mass%) and molar ratio of each component in the total treated amount of each agent are shown in Table 8.
The coloration immediately after treatment and one month after was evaluated according to the procedure described in <Coloration evaluation method 1>.
Note that Comparative Example 2 is also shown.

Examples 11 to 20, Comparative Example 6
The first agent, the second agent and the third agent of the formulations shown in Table 9 were prepared, and goat hair bundles were treated according to the method shown in <treatment method 3> in Examples 11 and 16 and Comparative Example 6. In Examples 12 to 15 and 17 to 20, goat hair bundles were treated according to the method shown in <treatment method 4>. The treated amount (mL) of each agent to 1 g of goat hair, and the content (mass%) and molar ratio of each component in the total treated amount of each agent are shown in Table 10.
The coloration immediately after the treatment was evaluated according to the procedure 1 to 2 shown in <Coloring evaluation method 1>. The results are shown in Table 10 together.

Claims (21)

The following components (A) to (C) consisting of one or more compositions, in the total composition;
(A): one or more compounds selected from glyoxylic acid, glyoxylic acid hydrate, glyoxylate, and glyoxylamide (B): having an electron donating group at at least one position of the meta position, ortho Phenolic compounds in which at least one position of position and para position is a hydrogen atom (however, the electron donating group at meta position may form a benzene ring which a hydroxyl group may substitute with an adjacent carbon atom)
(C): A hair treatment method using a hair cosmetic containing a reducing agent, which comprises the following steps (i) and (ii):
(i) applying components (A) and (B) to the hair (ii) heating and shaping the hair to which the components (A) and (B) are applied, all of the hair treatment method A hair treatment method wherein component (C) is applied to the hair at any point in the process. The hair treatment method according to claim 1, wherein the component (B) is the following component (B2).
(B2): a compound represented by the general formula (1)

[In the formula,
R ¹ represents a hydrogen atom or a methyl group,
A ¹ and A ^{2, which} may be the same or different, are each independently a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, or an aralkyl which may have a substituent having 7 to 12 carbon atoms Group or arylalkenyl group, linear or branched alkoxy group or alkenyloxy group having 1 to 6 carbon atoms, halogen atom or -CO-R ² (R ² is linear or branched alkyl having 1 to 12 carbon atoms Group or alkenyl group, an aralkyl group or arylalkenyl group which may have a substituent of 7 to 12 carbon atoms, or an aromatic hydrocarbon group which may have a substituent of 6 to 12 carbon atoms,
B represents a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, an aralkyl or aryl alkenyl group which may have a substituent having 7 to 12 carbon atoms, -OR ³ or- COOR ³ (R ³ represents a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms),
D represents a hydrogen atom, a hydroxyl group, a methyl group or a linear or branched alkoxy group having 1 to 12 carbon atoms or an alkenyloxy group,
E represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms.
However, two or three of A ¹ , A ² , B and E are hydrogen atoms, and the remaining groups do not contain a sulfo group. When D is a hydrogen atom or a methyl group, A ¹ and B, or A ² and B, together with two adjacent carbon atoms form a benzene ring which may be substituted by a hydroxyl group. ] The hair treatment method according to claim 1, wherein the component (B) is the following (B3).
(B3): a compound represented by the general formula (2)

[In the formula,
R ⁴ represents a hydrogen atom or a methyl group,
X represents a hydrogen atom, a hydroxyl group or a methoxy group,
Y represents a hydrogen atom, an oxygen atom, a hydroxyl group or a methoxy group,
Z represents a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms,
R ^x is a hydrogen atom, an oxygen atom, a hydroxyl group, a methoxy group, or an aromatic hydrocarbon group which may be substituted by up to 3 hydroxyl groups or methoxy groups and may form a condensed ring with 1,3-dioxolane Show
R ^y is a hydrogen atom, a hydroxyl group, a methoxy group, or an aromatic hydrocarbon group which may be substituted by up to 3 hydroxyl groups or methoxy groups and may form a condensed ring with 1,3-dioxolane, or a hydroxyl group or Represents an arylcarbonyloxy group or an aralkylcarbonyloxy group which may be substituted by up to 3 methoxy groups,
The dashed line indicates that it may be a double bond.
However, the broken line and the solid line adjacent to the R ^x or Y, R ^x or Y represents only double bond when an oxygen atom, a single bond in other cases.
In addition, Z is a linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms only when R ^x or R ^y is an o, p-dihydroxy aromatic hydrocarbon group, In other cases it is a hydrogen atom. ] The hair treatment method according to claim 1, wherein the component (B) is the following component (B1).
(B1): resorcinol Component (C) is one or more selected from the group consisting of thioglycolic acid or a salt thereof, sodium sulfite, ascorbic acid, butyrolactone thiol, L-cysteine (2-amino-3-sulfanyl propionic acid), and cysteamine The hair treatment method according to any one of claims 1 to 4, which is a reducing agent. The hair treatment method according to any one of claims 1 to 5, further comprising the step of applying the following component (D) to the hair before the step (ii).
(D): One or more selected from compounds represented by the following general formula (3)

[Wherein, Q represents a polymethylene group having 2 to 5 carbon atoms which may be substituted by a carboxy group, or a carbonyl group, and T ¹ and T ² may be each independently substituted with a hydrogen atom or a hydroxyl group A linear or branched alkyl group of 1 to 5 carbon atoms is shown, or both are combined to form a polymethylene group of 2 to 5 carbon atoms to form a ring with -NH-Q-NH-. ] The hair treatment method according to claim 6, wherein the component (D) is one or more selected from urea, 2-hydroxyethyl urea, ethylene urea, lysine hydrochloride and ethylene diamine. The hair treatment method according to any one of claims 1 to 7, wherein the content of hydrogen peroxide in the hair cosmetic applied to the hair before the step (ii) is 0.1% by mass or less. 9. The method according to any one of claims 1 to 8, wherein step (i) is a step of applying to the hair a one-part hair cosmetic composition containing components (A), (B) and (C) in a single composition. A hair treatment method according to any one of the preceding claims. 10. The hair treatment method according to claim 9, wherein the pH of the one-component hair cosmetic composition is 4.0 or less. Multi-component hair in which step (i) contains components (A), (B) and (C) in the total composition consisting of the first and second agents or in the total composition consisting of the first to third agents. The hair treatment method according to any one of claims 1 to 8, which is a step of applying to the hair after mixing each agent of the cosmetic. Multi-component hair in which step (i) contains components (A), (B) and (C) in the total composition consisting of the first and second agents or in the total composition consisting of the first to third agents. The first agent of the cosmetic composition is applied to the hair, and then the second agent of the multi-component hair cosmetic composition is overlapped and applied onto the first agent application portion of the hair, and further, the third agent is used. The hair treatment method according to any one of claims 1 to 8, which is a step of applying three agents on the first agent and second agent application parts of the hair in an overlapping manner. The step (i) comprises the components (A) and (B) in the total composition of the first agent and the second agent, and further comprises the component (C) in the third agent. Applying one agent to the hair and thereafter applying the second agent of the multi-component hair cosmetic composition on top of the first agent application part of the hair, and after the step (ii): The hair treatment method according to any one of claims 1 to 8, comprising step (iii).
(iii) applying the third agent of the multi-component hair cosmetic composition to the first and second agent application parts of the hair The hair treatment method according to any one of claims 11 to 13, wherein the pH of the agent containing the component (A) is 4.0 or less. The method according to claim 12, further comprising the step of washing the first agent after applying the first agent to the hair in the step (i) and before applying the second agent over the first agent applied portion of the hair. The hair treatment method of any one of 14. The hair treatment method according to claim 15, further comprising a step of leaving the hair for 1 minute or more and 1 hour or less after the first agent is applied to the hair and before the first agent is washed out in the step (i). The hair treatment method according to any one of claims 1 to 16, comprising the step of leaving the hair to which the hair cosmetic has been applied for 1 minute to 1 hour after the step (i). A method of treating hair according to any one of the preceding claims comprising the step of wetting the hair prior to step (i). The hair treatment method according to any one of claims 1 to 18, wherein the heating temperature in step (ii) is 50 属 C or more and 250 属 C or less. The hair treatment method according to any one of claims 1 to 19, wherein the step (ii) is performed under an environment in which the evaporation of water is suppressed. The hair treatment method according to any one of claims 1 to 20, wherein after step (ii), the hair is re-deformed into a different shape by heating.