HK1238133A1 - Hair deformation treatment agent - Google Patents

Description

Hair deforming agent

Technical Field

The present invention relates to a hair deformation treatment agent capable of deforming the shape of hair semi-permanently or permanently.

Background

As a method for deforming the hair shape semi-permanently or permanently, there are a method using a reducing agent such as permanent waving, and a method using a strongly alkaline treatment agent having a pH value of 12 to 14, typified by an alkaline softening agent (alkaline relaxer). However, these methods are known to place a heavy burden on the hair and easily damage the hair. In recent years, as a method for making hair shape deformed semi-permanently or permanently and causing less damage to hair, a hair curling correction method using formaldehyde in a large amount has been developed. However, the method using formaldehyde, which is highly toxic, requires careful handling because of its high volatility, and cannot be said to be a preferred hair treatment method.

Therefore, a treatment method which is safe to the human body without damaging the hair and without using formaldehyde has been sought. For example, patent document 1 discloses a technique of straightening intractable curls by applying an α -keto acid, particularly glyoxylic acid, to hair and performing a heat treatment at 200 ℃ ± 50 ℃ using a hair straightener (Flat iron). Patent document 2 discloses a method of applying a polyhydroxylated aromatic compound to hair and heating the hair to 110 ℃ or higher to permanently relax keratin fibers.

On the other hand, disposable hair deformation, such as by rinsing with water to enable re-styling, can be achieved by using styling agents. 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 also disclosed that the composition improves the style retention or moisture resistance, enables the re-formation of a style by wetting with water, and improves the mechanical strength of the hair.

(patent document 1) description of European patent application publication No. 2538916

(patent document 2) Japanese patent document No. 2009-537619

(patent document 3) specification of U.S. Pat. No. 4278659

Disclosure of Invention

The invention provides a hair deformation treatment agent, which contains the following components (A), (B) and (C), wherein the molar ratio (B)/(A) of the content of the component (B) to the content of the component (A) is more than 0.2 and less than 5,

(A) glyoxylic acid or a hydrate or salt thereof,

(B) the resorcinol is a mixture of resorcinol and a water-soluble organic solvent,

(C) and (3) water.

Further, the present invention provides a hair treatment method for deforming the shape of hair semi-permanently or permanently, comprising the following steps (i) and (ii):

(i) a step of applying the hair deformation treatment agent to the hair and allowing the agent to penetrate into the hair,

(ii) and a step of shaping the hair impregnated with the hair deformation treatment agent by heating.

Detailed Description

When hair is treated with the hair treatment agent according to the method described in patent document 1 or 2, although semipermanent straightening can be achieved, it is not possible to impart a semipermanent or permanent wavy or curly shape to hair. In addition, when the shape of the straight hair, which has been made semi-permanent or permanent, is to be changed into another semi-permanent or permanent shape such as a wave or curl, the hair must be treated with the reducing agent again, which has been done before.

On the other hand, the technique described in patent document 3 is characterized in that the treatment agent is removed by washing with water because an oligomer is used in the treatment agent. Therefore, repeated shampooing can return the hair to its original shape, which is hard to say a semi-permanent or permanent deformation of the hair shape.

Accordingly, the present invention relates to a hair deformation treatment agent and a hair treatment method which are safe to the human body and less harmful to the hair, and which can give a straight hair shape and a wavy or curly hair shape semi-permanently or permanently, and further can change the hair style so far to another semi-permanent or permanent hair shape simply and without damaging the hair without using a hair deformation treatment agent such as a reducing agent.

The present inventors have found that: the hair treatment agent containing glyoxylic acid and resorcinol can not only semipermanently impart a straight hair shape or a curly or wavy hair shape to hair, but also can be transformed into a completely different arbitrary hair style only by using a heating device such as a hair iron or a hair curler (curler) without using a hair treatment agent such as a reducing agent after the hair is treated with the hair treatment agent once, and the invention has been completed.

The hair deformation treatment agent of the present invention is highly safe to the human body, causes little damage to the hair, can deform the hair shape semi-permanently or permanently, and does not deform the hair even when shampooed. Further, if the treatment is performed once, the hair can be repeatedly deformed semipermanently or permanently by heating without penetrating the hair treatment agent into the hair again. Furthermore, the hair that is arbitrarily repeatedly deformed by heat has high washing fastness of the hair shape, and the hair does not lose its shape by shampoo, water, or the like.

In the present invention, the term "semipermanent or permanent hair deformation" means that the hair shape is not changed even if the hair is washed with a shampoo repeatedly and the hair is extremely excellent in the hair washing resistance. Specifically, the hair shape can be maintained before and after shampooing when the deformed hair is washed with a shampoo and then rinsed with water sufficiently and then allowed to dry naturally. The phrase "the hair shape is maintained" means that, for example, if the hair is a wavy hair, the number of waves does not substantially change before and after shampooing, and if the hair is a straight hair, the hair is not substantially wavy or curly due to shampooing.

In the present invention, "hair deformation" does not mean deformation caused by cleavage and recombination of S — S bonds of proteins in hair, and includes deformation of straight hair into curly hair, and also deformation of wavy, curly, or other deformed hair, natural curly hair, or the like into straight hair.

[ component (A): glyoxylic acid or a hydrate or salt thereof ]

The component (A) includes, in addition to glyoxylic acid, hydrates of glyoxylic acid and glyoxylates. As the hydrate of glyoxylic acid, glyoxylic acid monohydrate can be mentioned. As the salt of glyoxylic acid, there can be mentioned: alkali metal salts of glyoxylic acid and alkaline earth metal salts of glyoxylic acid, examples of the alkali metal salts include: lithium salt, sodium salt, potassium salt, and the like, and examples of the alkaline earth metal salt include: magnesium salts, calcium salts, and the like.

The content of the component (A) in the hair deformation treatment agent of the present invention is considered from the viewpoint of more significantly changing the hair shape after the treatment with the hair deformation treatment agent of the present invention, more excellent hair washing resistance of the hair shape, more significantly changing the shape when the hair shape is semipermanently deformed again by heating, and more excellent hair washing resistance of the hair shape after the re-deformation, preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 2.5% by mass or more, further preferably 3% by mass or more, in addition to the above, from the viewpoint of suppressing irritation to the skin, it is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, further preferably 15% by mass or less, and further preferably 12% by mass or less.

[ component (B): resorcinol ]

The content of the component (B) in the hair deformation treatment agent of the present invention is preferably 1 mass% or more, more preferably 2 mass% or more, even more preferably 3 mass% or more, even more preferably 4 mass% or more, even more preferably 5 mass% or more, from the viewpoint of more significantly changing the shape of hair after treatment with the hair deformation treatment agent of the present invention, and more preferably washing fastness of the shape of hair after re-deformation, and in addition to the above-described viewpoint, from the viewpoint of suppressing irritation to the skin, preferably 30 mass% or less, even more preferably 25 mass% or less, even more preferably 20 mass% or less, and even more preferably 17 mass% or less.

The molar ratio (B)/(a) of the content of the component (B) in the hair deformation treatment agent of the present invention to the content of the component (a) is 0.2 or more, preferably 0.3 or more, more preferably 0.4 or more, further preferably 0.5 or more, further preferably 0.7 or more, and further preferably 5 or less, preferably 2.5 or less, further preferably 2 or less, further preferably 1.5 or less, from the viewpoints of more remarkably changing the shape of the hair after the treatment with the hair deformation treatment agent of the present invention by a condensate of the component (a) and the component (B) formed in the hair, more excellent hair washing resistance of the hair shape, more remarkably changing the shape when the hair shape is semipermanently deformed again by heating, and more excellent hair washing resistance of the hair shape after the re-deformation, more preferably 1.2 or less.

[ component (C): water ]

The hair deformation treatment agent of the present invention uses water as a medium. In addition to water, a lower alcohol having 1 to 3 carbon atoms such as methanol or ethanol may be used in combination as necessary. In this case, the content of the lower alcohol having 1 to 3 carbon atoms in the hair deformation treatment agent of the present invention is preferably 60% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, yet more preferably 20% by mass or less, yet more preferably 15% by mass or less, yet more preferably 10% by mass or less, and further preferably 0.1% by mass or more.

[ component (D): compound represented by the general formula (1) ]

Further, in order to more easily impart a shape change to hair, the hair deformation treatment agent of the present invention preferably contains a compound represented by the following general formula (1) as the component (D).

[ in the formula,

R¹represents a hydrogen atom or a methyl group,

A¹and A²The same or different, represents a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, an aralkyl or arylalkenyl group having 7 to 12 carbon atoms, which may have a substituent, a linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms, a halogen atom, or-CO-R²Wherein R is²Is a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, an aralkyl or arylalkenyl group having 7 to 12 carbon atoms and optionally having a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms and optionally having a substituent,

b represents a hydrogen atom, a linear OR branched alkyl OR alkenyl group having 1 to 12 carbon atoms, an aralkyl OR arylalkenyl group having 7 to 12 carbon atoms and optionally having a substituent, -OR³or-COOR³Wherein R is³Is 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 or alkenyloxy group having 1 to 12 carbon atoms,

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.

Wherein A is¹、A²2 or 3 of B and E are hydrogen atoms, and the remaining groups are not sulfo-containing groups. When D is a hydrogen atom or a methyl group, A¹And B, or A²And B, together with the 2 carbon atoms to which they are adjacent, form a benzene ring which is unsubstituted or substituted with a hydroxyl group.

In the general formula (1), when the aralkyl group, the arylalkenyl group or the aromatic hydrocarbon group has a substituent, examples of the substituent include: a hydroxyl group, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. The number of carbon atoms of the aralkyl group, arylalkenyl group, or aromatic hydrocarbon group means the total number of carbon atoms including the number of carbon atoms of the substituent.

As R³The straight-chain or branched alkyl or alkenyl group having 1 to 6 carbon atoms in (b) includes, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, 1-methylpentyl, n-hexyl, isohexyl, vinyl, allyl, butenyl, hexenyl and the like.

As A¹、A²Examples of the linear or branched alkoxy group or alkenyloxy group having 1 to 6 carbon atoms in E include groups in which an oxygen atom is bonded to the alkyl group or alkenyl group having 1 to 6 carbon atoms.

As A¹、A²、R²The C1-12 linear or branched alkyl or alkenyl group in B includes, for example, in addition to the C1-6 alkyl or alkenyl group: n-heptyl, 2, 4-dimethylpentyl, 1-n-propylbutyl, n-octyl, 2-ethylhexyl, n-nonyl, 1-methylnonyl, n-decyl, 3, 7-dimethyloctyl, 2-isopropyl-5-methylhexyl, n-undecyl, n-dodecyl, decenyl, 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 alkyl group or alkenyl group having 1 to 12 carbon atoms.

As A¹、A²、R²C atom with or without substituent in BAralkyl or aralkenyl having 7 to 12 subgroups, as exemplified by: benzyl, hydroxybenzyl, dihydroxybenzyl, phenylethyl, phenylvinyl, hydroxyphenylethyl, dihydroxyphenylethyl, hydroxyphenylvinyl, dihydroxyphenylvinyl, phenylpropyl, phenylpropenyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-dihydroindenyl, and the like.

As R²The aromatic hydrocarbon group having 6 to 12 carbon atoms, which may be substituted or unsubstituted, includes: phenyl, hydroxyphenyl, dihydroxyphenyl, trihydroxyphenyl, naphthyl, hydroxynaphthyl, dihydroxynaphthyl, and the like.

As A¹、A²Examples of the halogen atom in (1) include: fluorine atom, chlorine atom, bromine atom.

Specific examples of the compound represented by the general formula (1) include: a compound represented by the general formula (1-1), a benzophenone derivative represented by the general formula (1-2), and a naphthol derivative represented by the general formula (1-3-a) or (1-3-b).

[ in the formula, R¹、A¹、A²B and E are as defined above, and D¹Represents a hydroxyl group or a methoxy group.]

[ in the formula, R¹Denotes the same meaning as above, D²Represents a hydroxyl group or an alkoxy group having 1 to 12 carbon atoms, G represents a hydroxyl group, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 2.]

[ in the formula, R¹、A¹E, D, G and n are as defined above.]

The compound represented by the general formula (1-1) is preferably a compound represented by the following (1-1-1) to (1-1-3).

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

[ in the formula, A¹、A²B and E are as defined above.]

As A¹And A²The alkyl group is preferably a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.

The B is preferably a hydrogen atom, an alkyl group or alkenyl group having 1 to 4 carbon atoms, an arylalkenyl group having 7 to 10 carbon atoms with or without a substituent, or a hydroxyl group, and more preferably a hydrogen atom, an arylalkenyl group having 7 to 10 carbon atoms with or without a substituent, or a hydroxyl group.

E is preferably a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.

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

(1-1-2) M-methoxyphenol derivative represented by the following general formula (1-1-2)

[ in the formula, A¹、A²B and E are as defined above.]

As A¹And A²The alkyl group is preferably a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 12 carbon atoms, or an aralkyl group or arylalkenyl group having 7 to 12 carbon atoms, with or without a substituent, and more 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, with or without a substituent.

B is preferably a hydrogen atom, a linear OR branched alkyl OR alkenyl group having 1 to 12 carbon atoms, an aralkyl OR arylalkenyl group having 7 to 12 carbon atoms, which may have a substituent, -OR³(R³A hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms), more preferably a hydrogen atom, an alkyl or alkenyl group having 1 to 4 carbon atoms, an arylalkenyl group having 7 to 10 carbon atoms with or without a substituent, or a hydroxyl group, and still more preferably a hydrogen atom, an arylalkenyl group having 7 to 10 carbon atoms with or without a substituent, or a hydroxyl group.

E is preferably a hydrogen atom, a hydroxyl group, a linear or branched alkyl or alkenyl group having 1 to 4 carbon atoms, a linear or branched alkoxy or alkenyloxy group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a hydroxyl group.

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-hydroxyphenylvinyl) -1-hydroxy-3-methoxybenzene (common name: Pinostilbene), and the like.

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

[ in the formula, A¹、A²B and E are as defined above.]

Examples of the resorcinol derivative include those represented by the following general formula (i) or (ii).

[ in the formula, A¹、A²And B represents the same meaning as above, E¹Represents a hydroxyl group, a linear or branched alkyl group or alkenyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy group or alkenyloxy group having 1 to 6 carbon atoms.]

As A¹And A²The alkyl group is preferably a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 12 carbon atoms, and more preferably a hydrogen atom.

B is preferably a hydrogen atom, an aralkyl OR aralkenyl group having 7 to 12 carbon atoms, which may have a substituent, -OR³(R³A hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 4 carbon atoms).

As E¹Preferably, the compound is 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.

Examples of the resorcinol derivative represented by the general formula (i) include: 2-alkylresorcinols such as 2-methylresorcinol, 2-ethylresorcinol and 2-propylresorcinol;

pyrogallol;

2-alkoxyresorcinols such as 2-methoxyresorcinol;

gallic acid esters such as gallic acid, methyl gallate, ethyl gallate, propyl gallate, and butyl gallate;

5- (phenylvinyl) 2-isopropylresorcinol, and the like.

[ in the formula, A¹、A²B and E are as defined above.]

The resorcinol derivative represented by the general formula (ii) is more preferably a resorcinol derivative represented by the general formula (ii-1) or (ii-2).

[ in the formula, A¹And A²The same meanings as described above are indicated.]

Examples of the resorcinol derivative represented by the general formula (ii-1) include: 4-methylresorcinol, 4-ethylresorcinol, 4-propylresorcinol, 4-isopropylresorcinol, 4-butylresorcinol (common name: Rucinol), 4-isobutylresorcinol, 4-sec-butylresorcinol, 4-tert-butylresorcinol, 4-pentylresorcinol, 4-isopentylresorcinol, 4-sec-pentylresorcinol, 4-tert-pentylresorcinol, 4-neopentyl resorcinol, 4-hexylresorcinol, 4-isohexylresorcinol, 4-heptylresorcinol, 4-octylresorcinol, 4- (2-ethylhexyl) resorcinol, 4-nonylresorcinol, 4-decyldcinol, 4-undecylresorcinol, 4-alkylresorcinols such as 4-dodecylresorcinol;

4-alkenylresorcinol such as 4-vinylresorcinol, 4-allylresorcinol, 4-butenylresorcinol, 4-hexenylresorcinol, and 4-decenylresorcinol;

4-aralkyl resorcinols such as 4-benzyl resorcinol, 4- (1-phenylethyl) resorcinol (common name: skin whitening 377(Symwhite377)), 4- (2-phenylethyl) resorcinol, and 4- (3-phenylpropyl) resorcinol;

4-hydroxyalkylalkyl resorcinols such as 4- (4-hydroxybenzyl) resorcin, 4- (2, 4-dihydroxybenzyl) resorcin, 4- (4-hydroxyphenylethyl) resorcin, and 4- (2, 4-dihydroxyphenylethyl) resorcin;

4-arylalkenylresorcinols such as 4- (1-phenylvinyl) resorcin and 4- (3-phenylpropenyl) resorcin;

4-hydroxyarylalkenylresorcinol such as 4- (4-hydroxyphenylvinyl) resorcinol and 4- (2, 4-dihydroxyphenylvinyl) resorcinol;

4- (1-methylnaphthyl) resorcinol;

4-alkoxyresorcinols such as 4-methoxyresorcinol, 4-ethoxyresorcinol, 4-isopropoxyresorcinol, 4-propoxresorcinol, 4-butoxyresorcinol, 4-sec-butoxyresorcinol, 4-tert-butoxyresorcinol, and 4-pentoxyresorcinol;

halogenated resorcinols such as 4-chlororesorcin and 4-bromoresorcin;

4-alkanoyl resorcinols such as 4-acetyl resorcinol, 4-propionyl resorcinol, 4-butyryl resorcinol, 4-valeryl resorcinol and 4-hexanoyl resorcinol;

4-arylalkanoyl resorcinols such as 4-phenylacetyl resorcin, 4-phenylpropionyl resorcin, 4-phenylbutyryl resorcin, 4-phenylpentanoyl resorcin, 4-phenylhexanoyl resorcin, and 3- (hydroxyphenyl) -1- (2, 4-dihydroxyphenyl) propen-1-one (common name: Isoliquiritigenin).

[ in the formula, A¹And A²Represents the same meaning as described above, B¹Represents a linear OR branched alkyl OR alkenyl group having 1 to 12 carbon atoms, an aralkyl OR arylalkenyl group having 7 to 12 carbon atoms and optionally having a substituent, -OR³or-COOR³(R³A hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms).]

The resorcinol derivative represented by the general formula (ii-2) is more preferably a resorcinol derivative represented by the general formula (ii-2-a) or (ii-2-b).

[ in the formula, B¹The same meanings as described above are indicated.]

Examples of the resorcinol derivative represented by the general formula (ii-2-a) include: 5-methylresorcinol, 5-ethylresorcinol, 5-propylresorcinol, 5-isopropylresorcinol, 5-butylresorcinol, 5-isobutylresorcinol, 5-sec-butylresorcinol, 5-tert-butylresorcinol, 5-pentyl-resorcinol (common name: Olivetol), 5-isopentylresorcinol, 5-alkylresorcinols such as 5-neopentyl resorcinol, 5-hexyl resorcinol, 5-isohexylresorcinol, 5-heptyl resorcinol, 5-octyl resorcinol, 5- (2-ethylhexyl) resorcinol, 5-nonyl resorcinol, 5-decyl resorcinol, 5-undecyl resorcinol, and 5-dodecyl resorcinol;

5-alkenylresorcinol such as 5-vinylresorcinol, 5-allylresorcinol, 5-butenylresorcinol, 5-hexenylresorcinol, and 5-decenylresorcinol;

phloroglucinol;

5-alkoxybenzene-1, 3-diol such as 5-ethoxybenzene-1, 3-diol, 5-propoxybenzene-1, 3-diol and 5-butoxybenzene-1, 3-diol;

3, 5-dihydroxybenzoic acid;

3, 5-dihydroxybenzoic acid esters such as methyl 3, 5-dihydroxybenzoate, ethyl 3, 5-dihydroxybenzoate, propyl 3, 5-dihydroxybenzoate, butyl 3, 5-dihydroxybenzoate, pentyl 3, 5-dihydroxybenzoate, and hexyl 3, 5-dihydroxybenzoate;

5-aralkyl resorcinols such as 5-benzyl resorcin, 5- (1-phenylethyl) resorcin, 5- (2-phenylethyl) resorcin, and 5- (phenylpropyl) resorcin;

5-hydroxyaralkyl resorcinols such as 5- (4-hydroxybenzyl) resorcin, 5- (2, 4-dihydroxybenzyl) resorcin, 5- (hydroxyphenylethyl) resorcin (common name: dihydroresveratrol), 5- (2, 4-dihydroxyphenylethyl) resorcin, etc.;

5-arylalkenylresorcinol such as 5- (phenylvinyl) resorcinol (common name: Pinosylvin), 5- (phenylpropenyl) resorcinol;

5- (4-Hydroxyphenylvinyl) resorcinol (common name: Resveratrol (Resveratrol)), 5- (4-methoxyphenylvinyl) resorcinol (common name: 4-MethoxyResveratrol (4-MethoxyResveratrole)), 5- (2, 4-dihydroxyphenylvinyl) resorcinol (common name: Oxyresveratrol (Oxyresveratrole)), 5- (2-methoxy-4-hydroxyphenylvinyl) resorcinol (common name: 2-methoxyoxyresveratrol (Gnetucitol D)), 5- (3, 4-dimethoxyphenylvinyl) resorcinol (common name: 3-methoxyisorhapontigenin (Gnetucitol E)), 5- (3-hydroxy-4-methoxyphenylvinyl) resorcinol (common name: Rhapontigenin (Rhapogenin)), (common name: Rhaponticin (Rhapogenin))), 5-hydroxyarylalkenylresorcinol such as 5- (4-hydroxy-3-methoxyphenylvinyl) resorcinol (a common name: Isorhapontigenin) and 5- (dihydroxyphenylvinyl) resorcinol (a common name: Piceatannol).

[ in the formula, A¹、A²And B¹The same meanings as described above are indicated.]

As A¹And A²Preferably, the alkyl group is a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms, or an alkoxy group or alkenyloxy group having 1 to 4 carbon atoms.

Examples of the resorcinol derivative represented by the general formula (ii-2-b) include: 2-alkylbenzene-1, 3, 5-trisphenols such as 2-methylbenzene-1, 3, 5-trisphenol, 2-ethylbenzene-1, 3, 5-trisphenol, 2-propylbenzene-1, 3, 5-trisphenol, 2-butylbenzene-1, 3, 5-trisphenol, 2-hexylbenzene-1, 3, 5-trisphenol, 2-octylbenzene-1, 3, 5-trisphenol, and 2-dodecylbenzene-1, 3, 5-trisphenol;

2-aralkyl-1, 3, 5-triphenol such as 2-benzylbenzene-1, 3, 5-triphenol, 2- (phenylethyl) benzene-1, 3, 5-triphenol and 2- (phenylpropyl) benzene-1, 3, 5-triphenol, 2-acetylbenzene-1, 3, 5-triphenol, 2-propionylbenzene-1, 3, 5-triphenol, 2-butyrylbenzene-1, 3, 5-triphenol, 2-phenylacetylbenzene-1, 3, 5-triphenol, 2-hydroxyphenyl-1- (benzene-2, 4, 6-triphenol) ethane-1-one, 3-hydroxyphenyl-1- (benzene-2, 4, 6-triphenol) propane-1-one (common name: Phloretin (Phloretin)), phloroglucinol carboxylate (Phloroglucinic acid ester) such as 4-hydroxyphenyl-1- (benzene-2, 4, 6-trisphenol) butan-1-one, 2-benzoylbenzene-1, 3, 5-trisphenol, 2- (hydroxybenzoyl) benzene-1, 3, 5-trisphenol, 2- (3, 5-dihydroxybenzoyl) benzene-1, 3, 5-trisphenol, 2- (2, 4-dihydroxybenzoyl) benzene-1, 3, 5-trisphenol, etc.;

3, 5-dihydroxybenzoic acid esters such as 3, 5-dihydroxy-2-methylbenzoic acid, methyl 3, 5-dihydroxy-2-methylbenzoate, 3, 5-dihydroxy-2-ethylbenzoic acid, methyl 3, 5-dihydroxy-2-ethylbenzoate, methyl 3, 5-dihydroxy-2-propylbenzoate, 3, 5-dihydroxy-2-butylbenzoate, and methyl 3, 5-dihydroxy-2-butylbenzoate.

Examples of the benzophenone derivative represented by the general formula (1-2) include: 4-benzoylresorcinol (conventional name: Benzophenone-1 (Benzophenone-1)), 4- (hydroxybenzoyl) resorcinol, 4- (dihydroxybenzoyl) resorcinol, 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 '-dihydroxy-4, 4' -dimethoxybenzophenone (conventional name: Benzophenone-6 (Benzophenone-6); and, 2, 2 '-dihydroxy-4-methoxybenzophenone (common name: Benzophenone-8 (Benzophenone-8)), 2-hydroxy-4-methoxy-4' -methylbenzophenone (common name: Benzophenone-10 (Benzophenone-10), 2-hydroxy-4-octyloxybenzophenone (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), R in the general formula (1-3-a) or (1-3-b) is preferable¹A hydrogen atom or an alkyl or alkenyl group having 1 to 4 carbon atoms, more preferably R¹A substance that is a hydrogen atom.

In addition, A is preferred¹And A²A 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, more preferably A¹And A²A hydrogen atom or a hydroxyl group.

D is preferably 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, E is preferably 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.

Examples of such compounds include: 1-naphthol, 2-naphthol, 3-methylnaphthalene-1-ol, 1, 4-naphthalenediol, 1, 5-naphthalenediol, 1, 8-naphthalenediol and the like.

Among the compounds represented by the general formula (1), m-dimethoxybenzene derivatives represented by the general formula (1-1-1), resorcinol derivatives represented by the general formula (1-1-3), benzophenone derivatives represented by the general formula (1-2), and naphthol derivatives represented by the general formula (1-3-a) or (1-3-b) are preferable. More preferred are 2-methylresorcinol, 4-chlororesorcinol, 4-alkylresorcinol, 4-aralkylresorcinol, 4-acylated resorcinol, 5-alkylresorcinol, 5-aralkylresorcinol, 5-hydroxyarenylresorcinol, phloroglucinol carboxylate, gallic acid and gallic acid ester. More preferably 4-butylresorcinol (customary name: Rucinol), 4- (1-phenylethyl) resorcinol (customary name: xinfu-bai 377(Symwhite377)), 5- (hydroxyphenylvinyl) resorcinol (customary name: resveratrol (resveratrol)), 3-hydroxyphenyl-1- (benzene-2, 4, 6-trisphenol) propan-1-one (customary name: Phloretin (Phloretin), 4- (2, 4-dihydroxybenzoyl) resorcinol (customary name: Benzophenone-2 (benphenone-2)), 5- (hydroxyphenylvinyl) -1, 3-dimethoxybenzene (customary name: Pterostilbene (Pterostilbene)), 1-naphthol, more preferably 4-butylresorcinol, 4- (1-phenylethyl) resorcinol, 1-naphthol, and, 4-n-hexylresorcinol.

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

The component (D) may be used alone or in combination of 2 or more, and more preferably 2 or more.

When the component (D) is contained in the hair deformation treatment agent of the present invention, the total content of the component (B) and the component (D) is preferably 5 mass% or more, more preferably 10 mass% or more, further preferably 15 mass% or more, further preferably 30 mass% or less, more preferably 27 mass% or less, further preferably 25 mass% or less, further preferably 23 mass% or less, from the viewpoints of making the change in hair shape after the treatment with the hair deformation treatment agent of the present invention more remarkable, making the hair shape more excellent in hair washing resistance, making the change in shape more remarkable when the hair shape is again semipermanently deformed by heating, and making the hair shape after the re-deformation more excellent in hair washing resistance.

The mass ratio (D)/(B) of the content of the component (D) to the content of the component (B) is preferably 0.1 or more, more preferably 0.15 or more, and further preferably 0.2 or more from the viewpoint of remarkable effects, and is preferably 3 or less, more preferably 2 or less, further preferably 1 or less, and further preferably 0.4 or less from the viewpoint of preventing insufficient penetration into the internal tissues due to precipitation of the component (D) having a low solubility after penetrating into the hair.

The molar ratio [ (B) + (D) ]/(a) of the total content of the components (B) and (D) to the content of the component (a) in the hair deformation treatment agent of the present invention is preferably 0.2 or more, more preferably 0.3 or more, further preferably 0.4 or more, further preferably 0.5 or more, further preferably 0.7 or more, further preferably 5 or less, more preferably 2.5 or less, further preferably 1.5 or less, further preferably 1.2 or less, from the viewpoint of further improving the effect of semipermanently or permanently deforming hair and the effect of repeatedly semipermanently or permanently deforming hair only by heating.

The hair deformation treatment agent of the present invention may be in any form of a multi-dose type such as a single-dose type or a two-dose type, and from the viewpoint of improving the penetration of the component (a) and the component (B) into the hair and improving the effect of the present invention, a multi-dose type containing the component (a) and the component (B) in separate preparations is more preferable, and a two-dose type is further preferable. In the case of the multi-dose form, in the present invention, the preparation containing the component (a) is referred to as a first dose, and the preparation containing the component (B) is referred to as a second dose.

In the case of the multi-dose formulation, the content of the component (a) in the first dose is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 2.5% by mass or more, further preferably 3% by mass or more, and further preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, further preferably 15% by mass or less, further preferably 12% by mass or less in terms of glyoxylic acid.

In the case of the multi-dose formula, the content of the component (B) in the second dose is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, further preferably 4% by mass or more, further preferably 5% by mass or more, and further preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, further preferably 17% by mass or less.

In the case of a multi-dose type, when the first dose and the second dose are used in combination, the mixing ratio is not particularly limited, and it is preferable that a composition obtained by mixing a plurality of the preparations is used as the hair styling agent of the present invention. Therefore, in the case of the multi-dose formulation, the content of each component is the content in the composition obtained by mixing a plurality of formulations unless otherwise specified. In addition, in the case of a multi-dose formula, the component (C) may be contained in the form of a solvent for each preparation, and in the case of a two-dose formula, the component (C) is preferably added to both of the preparation containing the component (a) and the preparation containing the component (B). When component (D) is further contained, component (B) and component (D) are preferably contained in the same preparation, and a multi-dose formula (including a first dose containing component (a) and a second dose containing component (B) and component (D)) is preferable, and a two-dose formula is more preferable.

When the component (D) is contained, the mass ratio (D)/(B) of the content of the component (D) to the content of the component (B) in the second agent is preferably 0.1 or more, more preferably 0.15 or more, further preferably 0.2 or more, and further preferably 3 or less, more preferably 2 or less, further preferably 1 or less, further preferably 0.4 or less.

The pH of the hair deformation treatment agent of the present invention is preferably 4 or less, more preferably 3 or less, further preferably 2.5 or less, and further preferably 2 or less from the viewpoint of the penetration of the component (a) into the hair, and is preferably 1 or more, more preferably 1.2 or more, and further preferably 1.5 or more from the viewpoint of the inhibition of hair damage and the inhibition of skin irritation. In the case of a multi-dose formulation, the pH of the preparation containing the component (a), i.e., the first dose, is preferably in the above range, and more preferably the pH after mixing all the preparations is in the above range. In the present invention, the "pH value of the hair treatment agent" refers to a value measured at room temperature (25 ℃) by a pH meter without diluting the hair deformation treatment agent.

In order to adjust the pH of the hair styling agent to the above range, a pH adjuster may be used as appropriate. As the pH adjuster, as the alkaline agent, there can be used: ammonia or a salt thereof; alkanolamines such as monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, and 2-aminobutanol, and salts thereof; alkyldiamines such as 1, 3-propanediamine, and salts thereof; carbonates such as guanidine carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate; hydroxides such as sodium hydroxide and potassium hydroxide. Further, as the acid agent, there can be used: inorganic acids such as hydrochloric acid and phosphoric acid; hydrochloride salts such as monoethanolamine hydrochloride; phosphates such as potassium dihydrogen phosphate and disodium hydrogen phosphate; organic acids other than the component (A) such as lactic acid and malic acid.

The hair deformation treatment agent of the present invention preferably contains a cationic surfactant from the viewpoint of improving the feel of hair after hair treatment and further improving the effect of the present invention. As the cationic surfactant, a mono-long alkyl quaternary ammonium salt having an alkyl group having 1 to 24 carbon atoms and an alkyl group having 3 to 4 carbon atoms is preferable.

Preferably, at least 1 mono-long alkyl quaternary ammonium surfactant is selected from the group consisting of compounds represented by the following general formula.

[ in the formula, R⁴Represents a saturated or unsaturated linear or branched alkyl group having 8 to 22 carbon atoms, R⁸-CO-NH-(CH₂)_m-or R⁸-CO-O-(CH₂)_m-(R⁸Represents a saturated or unsaturated straight chain or branched alkyl chain having 7 to 21 carbon atoms, m represents an integer of 1 to 4), R⁵、R⁶And R⁷Independently represent an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, X^-Represents chloride, bromide, methylsulfate or ethylsulfate.]

Preferred cationic surfactants include, for example: long-chain quaternary ammonium compounds such as cetyltrimethylammonium chloride, myristyltrimethylammonium chloride, behenyltrimethylammonium chloride, cetyltrimethylammonium bromide, stearamidopropyltrimethylammonium chloride, and the like, which may be used alone or in a mixture thereof.

The content of the cationic surfactant in the hair styling agent of the present invention is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and further preferably 10% by mass or less, more preferably 5% by mass or less. When the hair-setting treatment agent is a multi-agent type, the cationic surfactant may be contained in the first agent, may be contained in the second agent, or may be contained in both the first agent and the second agent.

In addition, the hair deformation treatment agent of the present invention preferably contains a silicone from the viewpoint of improving the feel of hair after hair treatment and improving the uniformity. The polysiloxane is preferably dimethyl polysiloxane or amino-modified polysiloxane.

As the dimethylpolysiloxane, any cyclic or acyclic dimethylpolysiloxane polymer can be used, and examples thereof include: SH200 series, BY22-019, BY22-020, BY11-026, B22-029, BY22-034, BY22-050A, BY22-055, BY22-060, BY22-083, FZ-4188 (all Dow Coming Toray Co., Ltd.), KF-9088, KM-900 series and MK-15H, MK-88 (all Xinyue chemical industry Co., Ltd.).

As the amino-modified polysiloxane, all polysiloxanes having an amino group or an ammonium group can be used, and as examples thereof, there can be mentioned: amino-modified polysiloxane oil in which all or a part of terminal hydroxyl groups are blocked with methyl groups or the like, and unblocked aminodimethylpolysiloxane (amodimithicone). As a preferred amino-modified polysiloxane, for example, a compound represented by the following formula can be used.

[ wherein R' represents a hydrogen atom, a hydroxyl group or R^X，R^XRepresents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, J represents R^X、R″-(NHCH₂CH₂)_aNH₂、OR^XOr a hydroxyl group, R' represents a divalent hydrocarbon group having 1 to 8 carbon atoms, a represents a number of 0 to 3, and b and c represent numbers such that the sum of them becomes 10 or more and less than 20000, preferably 20 or more and less than 3000, more preferably 30 or more and less than 1000, and further preferably 40 or more and less than 800 on average.]

Specific examples of the preferable commercially available products of the amino-modified polysiloxane include: amino-modified silicone oils such as SF8452C, SS3551 (both Dow Coming Toray Co., Ltd.), KF-8004, KF-867S, KF-8015 (both Wt., Ltd.) and the like; amidodimethylpolysiloxane (amodimithicone) emulsions such as SM8704C, SM8904, BY22-079, FZ-4671 and FZ4672 (all of Dow Corning Toray Co., Ltd.).

The content of the silicone in the hair styling agent of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.5% by mass or more, and further preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less. When the hair-setting treatment agent is a multi-dose type, the silicone may be contained in the first agent, may be contained in the second agent, or may be contained in both the first agent and the second agent.

The hair deformation treatment agent of the present invention preferably contains a cationic polymer from the viewpoint of improving the feel of hair after hair treatment.

The cationic polymer refers to a polymer having a cationic group or a group ionizable into a cationic group, and includes an amphoteric polymer which is cationic as a whole. That is, the aqueous solution containing an amino group or an ammonium group or a diallyl quaternary ammonium salt as a constituent unit in a side chain of a polymer chain includes, for example: cationized cellulose derivatives, cationic starches, cationized guar gum derivatives, polymers or copolymers of diallyl quaternary ammonium salts, quaternized polyvinylpyrrolidone derivatives, and the like. Among them, from the viewpoints of softness to the touch, smoothness and combability when washed or shampooed, ease of manageability and moisture retention when dried, and stability of the preparation, a polymer containing a diallyl quaternary ammonium salt as a constituent unit, a quaternized polyvinylpyrrolidone derivative, a cationized cellulose derivative are preferable, and a polymer or copolymer of a diallyl quaternary ammonium salt, and a cationized cellulose derivative are more preferable.

Specific examples of the preferred polymers or copolymers of diallyl quaternary ammonium salts include: dimethyldiallylammonium chloride polymers (Polyquaternium-6, such as Merquat 100; Lubrizol Advanced Materials), dimethyldiallylammonium chloride/acrylic acid copolymers (Polyquaternium-22, such as Merquat 280, Merquat 295; Lubrizol Advanced Materials), dimethyldiallylammonium chloride/acrylamide copolymers (Polyquaternium-7, such as Merquat 550; Lubrizol Advanced Materials), and the like.

Specific examples of preferred quaternized polyvinylpyrrolidone derivatives include polymers obtained by polymerizing a vinylpyrrolidone copolymer and dimethylaminoethyl methacrylate (polyquaternium 11 (polyquaternium-11), such as Gafquat 734, Gafquat 755, and Gafquat 755N (described above by Ashland corporation)).

Specific examples of preferred cationized cellulose include: polymers obtained by adding glycidyltrimethylammonium chloride to hydroxycellulose (Polyquaternium 10(Polyquaternium-10), such as Leogard G, LeogardGP (see above for LION), Polymer JR-125, Polymer JR-400, Polymer JR-30M, Polymer LR-400, Polymer LR-30M (see above for Amerchol)), or hydroxyethylcellulose dimethyldiallylammonium chloride (Polyquaternium-4, such as Cellcoat H-100, Cellcoat L-200 (see above for Akzo Nobel)).

The content of the cationic polymer in the hair styling agent of the present invention is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, and further preferably 20% by mass or less, more preferably 10% by mass or less. When the hair-setting treatment agent is a multi-agent type, the cationic polymer may be contained in the first agent, may be contained in the second agent, or may be contained in both the first agent and the second agent.

Further, the hair styling agent of the present invention may contain an antioxidant in an amount corresponding to that normally contained. The antioxidant may be any one commonly used in the field of hair cosmetics, and examples thereof include ascorbic acid.

The hair styling agent of the present invention may contain, in addition to the above components, components usually blended in hair cosmetics. However, the hair deformation treatment agent of the present invention preferably does not substantially contain a precursor formulated in an oxidation hair dye for dyeing hair by an oxidation reaction between a precursor (precursor) and a coupling agent (coupler). That is, the hair styling agent of the present invention does not substantially contain an aromatic compound having at least one amino group, another amino group or hydroxyl group in the ortho-position or para-position of the amino group, and having a closed-shell quinone form (a closed-shell quinone form) structure when oxidized. The component (B), resorcinol, is a representative compound used as a coupling agent in an oxidative hair dye, but the present invention is characterized in that the component (a) and the component (B) are polymerized in hair and thereafter heated to be able to freely deform the hair shape, and this technique is completely different from the use of resorcinol in an oxidative hair dye.

Further, unlike the technique of patent document 3 in which an oligomer of glyceraldehyde and resorcinol is formed using boric acid or silicic acid, the hair deformation treatment agent of the present invention preferably does not substantially contain boric acid or silicic acid.

Further, the hair deformation treatment agent of the present invention preferably contains substantially no hair reducing agent. The present invention is characterized in that the hair can be deformed without breaking the S — S bond of the protein in the hair, and this technique is completely different from a permanent wave agent that deforms hair by cutting the S — S bond of the protein in the hair using a reducing agent. As hair reducing agents, there may be mentioned: thiols such as thioglycolic acid, dithioglycolic acid, cysteine, acetylcysteine, and butyrolactone thiol, bisulfite, and salts thereof.

In the present invention, "substantially not contained" means that the content of the target compound in the hair deformation treatment agent is preferably less than 0.1% by mass, more preferably less than 0.01% by mass, and even more preferably that the target compound is not contained in the hair deformation treatment agent.

The hair deformation treatment agent of the present invention is highly safe to the human body and less harmful to the hair, and therefore can be suitably used for human hair.

[ Hair deformation treatment method ]

The hair treatment for deforming the hair shape semi-permanently or permanently by using the hair deformation treatment agent of the present invention can be carried out by a hair treatment method comprising the following steps (i) and (ii).

(i) The hair deformation treatment agent of the present invention is applied to the hair and allowed to penetrate into the hair.

(ii) And a step of shaping the hair impregnated with the hair deformation treatment agent by heating.

In step (i), the hair deformation treatment agent may be applied to dry hair or wet hair, and it is preferable to wet the hair with water before step (i) in order to swell the hair and promote penetration of the hair treatment agent into the hair. The mass of the hair deformation treatment agent applied to the hair in step (i) is preferably 0.05 or more, more preferably 0.1 or more, further preferably 0.25 or more, further preferably 0.5 or more, and further preferably 5 or less, more preferably 3 or less, and further preferably 2 or less in terms of a bath ratio (mass of hair deformation treatment agent/mass of hair) to the mass of the hair. The hair to be treated may be all or a part of the hair.

In step (i), the hair deformation treatment agent may be applied to the hair by any method. In the case where the hair-setting treatment agent is a multi-dose type, the first dose containing the component (a) and the second dose containing the component (B) may be mixed and applied to the hair, or one of the first dose and the second dose may be applied to the hair and then the other dose may be applied to the application portion in a superimposed manner. In the case of the double application, from the viewpoint of promoting penetration of the hair deformation treatment agent and improving the effect, it is possible to apply one preparation, then leave the hair applied with the hair treatment agent, and thereafter apply another preparation in a superposed manner. The standing time in this case is preferably 1 minute or more, more preferably 3 minutes or more, further preferably 5 minutes or more, and further preferably 1 hour or less, more preferably 30 minutes or less, and further preferably 20 minutes or less, in order to allow the hair deformation treatment agent to penetrate and diffuse into the hair. In this case, heating may be performed from the viewpoint of promoting penetration of the hair deformation treatment agent. In the case of heating, the temperature is preferably 40 to 90 ℃. In the case of the double application, the application order may be arbitrary, but from the viewpoint of promoting penetration of the hair deformation treatment agent and improving the effect, it is more preferable to apply the second agent to the hair and then apply the first agent to the hair.

In the case of the double application, the application amounts of the first and second agents are not particularly limited. The second preparation applied to the hair is applied so that the molar ratio (B)/(a) of the amount of the component (B) in the second preparation applied to the hair to the amount of the component (a) in the first preparation applied to the hair is preferably 0.3 or more, more preferably 0.4 or more, further preferably 0.5 or more, further preferably 5 or less, more preferably 2.5 or less, further preferably 2 or less, and further preferably 1.5 or less. Specifically, for example, the ratio of the amount of the component (a) applied to the hair calculated from the content of the component (a) in the first dose and the amount of the first dose applied to the hair to the amount of the component (B) applied to the hair calculated from the content of the component (B) in the second dose and the amount of the second dose applied to the hair may be in the above range in terms of a molar ratio.

When the second preparation further contains the component (D), the molar ratio [ (B) + (D) ]/(a) of the total content of the components (B) and (D) in the second preparation applied to the hair to the amount of the component (a) in the first preparation is preferably 0.2 or more, preferably 0.3 or more, more preferably 0.4 or more, further preferably 0.5 or more, further preferably 0.7 or more, and further preferably 5 or less, preferably 2.5 or less, more preferably 2 or less, further preferably 1.5 or less, and further preferably 1.2 or less.

Between step (i) and step (ii), a step of placing the hair applied with the hair treatment agent may be interposed. The standing time in this case is preferably 1 minute or more, more preferably 3 minutes or more, further preferably 5 minutes or more, and further preferably 2 hours or less, more preferably 1 hour or less, further preferably 30 minutes or less, and further preferably 20 minutes or less, in order to allow the hair deformation treatment agent to penetrate and diffuse into the hair.

In the setting step, the hair may be heated from the viewpoint of promoting penetration of the hair deformation treatment agent. In the case of heating, the temperature is preferably 40 to 90 ℃. This heating is preferable because the oligomer having low degree of polymerization can be polymerized in the hair before step (ii) and thus step (ii) can be performed more favorably.

Although the hair may or may not be rinsed between the steps (i) and (ii), it is preferable not to rinse from the viewpoint of sufficiently retaining the hair treatment agent component in the hair, further enhancing the effect of imparting a semi-permanent shape to the hair, and further deforming the hair shape semi-permanently again by heat.

The heating temperature in step (ii) is preferably 50 ℃ or higher, more preferably 60 ℃ or higher, and still more preferably 80 ℃ or higher, in order to enhance the interaction between the components (a) and (B) in the hair and the protein in the hair, and to promote the condensation reaction between the components (a) and (B) in the hair to obtain the effect of the present invention, and is preferably 250 ℃ or lower, more preferably 240 ℃ or lower, and still more preferably 230 ℃ or lower, in order to suppress rapid evaporation of water during heating. Examples of the heating method include a method using a hair iron, an electric rod, a heating curler (hot curler), and the like.

The heating time in step (ii) may be appropriately selected depending on the heating device and the heating temperature to be used, but is preferably 5 seconds or longer, more preferably 1 minute or longer, even more preferably 5 minutes or longer, even more preferably 15 minutes or longer, even more preferably 30 minutes or longer, and is preferably 2 hours or shorter, even more preferably 1 hour or shorter, even more preferably 45 minutes or shorter, from the viewpoint of allowing the hair deformation treatment agent to penetrate and diffuse into the hair and causing sufficient polymerization.

The shaping in step (ii) includes any of straight-hair shaping and curl shaping. As a method of shaping hair into a straight hair shape, there are a method of blowing hair with a hair dryer while stretching the hair with a hand or with a tool such as a comb or a brush, and a method of heating hair with a hair iron, and the method using a hair iron is preferable from the viewpoint of easy deformation. When the hair is shaped into a straight hair shape while being heated by using a hair iron, a method of holding the hair between the hair irons and sliding the hair from the root to the tail while holding the hair therebetween, a method of holding the hair between the hair irons while stretching the hair by hand or with a tool such as a comb or a brush, or the like, or a combination of these two methods, or the like can be used. When the hair is shaped into a curly shape, the following are listed: a method of winding hair around an electrically heated curling iron, a heated curler, or the like while heating it, a method of winding hair around a curler (curl iron) and holding it, and the like.

Step (ii) is preferably carried out in an environment in which rapid evaporation of water is suppressed. Specific methods for suppressing the evaporation of water include: a method of coating hair coated with a hair treatment agent with a plastic film such as a wrap film for food, a cap, or the like, a method of continuously spraying steam such as superheated steam on hair, or the like.

After the step (ii), the hair may be rinsed or may not be rinsed, and rinsing is preferably performed from the viewpoint of preventing the hair feel from being lowered by the remaining polymer.

The inventors considered that, by these treatments, the components (a) and (B) penetrated into the hair and interacted with the proteins in the hair. In addition, a thermoplastic condensate of the component (a) and the component (B) is generated in the hair. Therefore, the hair can be easily deformed in shape by heating the hair, and if the hair is treated once, the hair can be freely and repeatedly deformed semi-permanently or permanently by heating only without applying the hair treatment agent again. Further, the hair deformation imparted by the method of the present invention is not deformed even after shampooing, and can be maintained for a long period of time.

(method of reshaping)

The step of deforming the hair into another shape semi-permanently by heating after the hair is deformed by the method including the step (i) or the step (ii) may be performed. In the case of the re-deformation, the temperature is preferably 30 ℃ or higher, more preferably 40 ℃ or higher, and 230 ℃ or lower, more preferably 220 ℃ or lower, and still more preferably 210 ℃ or lower. In addition, it is preferable that the hair deformation treatment agent of the present invention, a hair treatment agent containing a reducing agent such as a so-called permanent wave agent, or a known hair deformation treatment agent such as an alkaline softening agent is not applied at the time of the re-deformation treatment.

Hereinafter, a specific procedure in the case of the step of heating to semipermanently reform the hair into another shape will be described.

The case of re-deforming the hair deformed into a curled shape into a straight hair shape

When the hair which has been deformed into a curved shape is to be deformed into a straight shape again, there are a method of blowing the hair with a hair dryer while stretching the hair with a hand or with a tool such as a comb or a brush, and a method of heating the hair with a hair iron, and the method using a hair iron is preferred from the viewpoint of easy deformation. When the hair is shaped into a straight hair while being heated by using a hair iron, a method of holding the hair between the hair roots and the hair tails and sliding the hair from the hair roots to the hair tails while holding the hair between the hair irons while stretching the hair by hand or with a tool such as a comb or a brush, or the like, or a combination of these two methods, or the like can be used.

In this case, the temperature reached when the hair is heated (hair temperature) is preferably 120 ℃ or higher, more preferably 150 ℃ or higher, from the viewpoint of semipermanent or permanent deformation of the hair shape, and is preferably 230 ℃ or lower, more preferably 220 ℃ or lower, and even more preferably 210 ℃ or lower, from the viewpoint of achieving both prevention of hair damage and semipermanent or permanent deformation of the hair shape, regardless of the type of hair iron used, the material of the heating portion, the set temperature, and the method of operating the hair iron. The heating temperature of the hair can be measured using, for example, a radiation thermometer (model ST653) manufactured by SENTRY corporation.

The hair treated in the straight state is reformed into a curly state

When the hair treated to be straight is reformed into a curly shape, there are included: a method of winding hair around a hair curling bar, a hair curler, or the like while heating and holding the hair, a method of winding hair around a hair curler and holding the hair, and the like.

In this case, the temperature reached by the hair when heated (hair temperature) is preferably 30 ℃ or higher, more preferably 40 ℃ or higher, from the viewpoint of semipermanent or permanent deformation of the hair shape, and is preferably 180 ℃ or lower, more preferably 120 ℃ or lower, further preferably 100 ℃ or lower, further preferably 80 ℃ or lower, and further preferably 60 ℃ or lower, from the viewpoint of preventing both hair damage and semipermanent or permanent deformation of the hair shape.

When the hair is to be reshaped, a method of heating the hair in a dry state or a method of heating the hair after being wetted with water may be employed in the heating, and a method of heating the hair after being wetted with water is preferred from the viewpoint of causing the hair to be deformed semi-permanently or permanently.

The heating time of the hair in the case of re-deforming the hair is appropriately selected depending on the heating temperature, and from the viewpoint of semi-permanently or permanently deforming the hair shape, is preferably 1 second or more, preferably 5 seconds or more, more preferably 1 minute or more, further preferably 5 minutes or more, further preferably 15 minutes or more, further preferably 30 minutes or more, and for suppressing hair damage, is preferably 2 hours or less, more preferably 1 hour or less, and further preferably 45 minutes or less.

The hair treatment method of the present invention is a technique capable of freely deforming hair by a completely different principle from permanent wave treatment using a reducing agent or soft hair treatment using a strongly basic hair treatment agent having a pH of 12 to 14, and therefore does not include a step of applying a hair treatment agent containing a reducing agent or a strongly basic hair treatment agent having a pH of 12 to 14 to hair. Therefore, the hair treatment method of the present invention is advantageous over the known hair deformation methods described above in that it can deform hair without damaging the hair.

Preferred hair treatment methods for deforming hair semi-permanently or permanently include the following 3 types.

Mode 1: the hair treatment agent is in the form of a single agent

1) The hair was optionally wetted with water.

2) The hair treatment agent of the present invention, which contains the following components (a), (B) and (C) and further optionally contains the component (D), and the molar ratio of the content of the component (B) to the content of the component (a) is 0.01 to 5, is applied to hair and allowed to penetrate into the hair.

Component (A): glyoxylic acid or hydrates or salts thereof

Component (B): resorcinol

Component (C): water (W)

Component (D): the resorcinol derivative represented by the general formula (1-1-3) is preferably 4-alkylresorcinol

3) The hair coated with the hair treatment agent is left for 1 minute or more and 1 hour or less. In this case, the temperature may be arbitrarily increased to 40 to 90 ℃.

4) Heating the hair at 50-250 deg.C for shaping.

5) The hair was rinsed ad libitum.

6) Optionally heating at 40-230 deg.C to re-deform the hair.

Mode 2: the hair treatment agent is in the form of a two-pack

1) The hair was optionally wetted with water.

2) A hair treatment agent of the present invention, which is obtained by mixing a first agent containing the following components (A) and (C) and a second agent containing the components (B) and (C) and optionally further containing the component (D) so that the molar ratio of the content of the component (B) to the content of the component (A) is 0.01 to 5, is applied to hair and allowed to penetrate into the hair,

component (A): glyoxylic acid or a hydrate or salt thereof,

component (B): the resorcinol is a mixture of resorcinol and a water-soluble organic solvent,

component (C): the amount of water is controlled by the amount of water,

component (D): the resorcinol derivative represented by the general formula (1-1-3) is preferably 4-alkylresorcinol.

3) The hair coated with the hair treatment agent is left for 1 minute or more and 1 hour or less. In this case, the temperature may be arbitrarily increased to 40 to 90 ℃.

4) Heating the hair at 50-250 deg.C for shaping.

5) The hair was rinsed ad libitum.

6) Optionally heating at 40-230 deg.C to re-deform the hair.

Mode 3: the hair treatment agent is in the form of a two-pack

1) The hair was optionally wetted with water.

2) Applying a first agent comprising the following components (A) and (C) to hair and allowing the agent to penetrate into the hair,

component (A): glyoxylic acid or a hydrate or salt thereof,

component (C): and (3) water.

3) The hair was left as desired for 1 minute or more and 1 hour or less. In this case, the temperature may be arbitrarily increased to 40 to 90 ℃.

4) A second preparation containing the following components (B) and (C) and optionally further containing a component (D) is applied to the first preparation application part of the hair in a superposed manner so that the ratio of the number of moles of the component (B) to the number of moles of the component (A) is 0.01 to 5, and allowed to penetrate into the hair,

component (B): the resorcinol is a mixture of resorcinol and a water-soluble organic solvent,

component (C): the amount of water is controlled by the amount of water,

component (D): the resorcinol derivative represented by the general formula (1-1-3) is preferably 4-alkylresorcinol.

5) The hair is left for 1 minute or more and 1 hour or less while being optionally heated to 40 to 90 ℃.

6) Heating the hair at 50-250 deg.C for shaping.

7) The hair was rinsed ad libitum.

8) Optionally heating at 40-230 deg.C to re-deform the hair.

Mode 4: the hair treatment agent is in the form of a two-pack

1) The hair was optionally wetted with water.

2) Applying a second agent comprising the following components (B) and (C) and optionally further comprising component (D) to the hair and allowing the second agent to penetrate into the hair,

component (B): the resorcinol is a mixture of resorcinol and a water-soluble organic solvent,

component (C): the amount of water is controlled by the amount of water,

component (D): the resorcinol derivative represented by the general formula (1-1-3) is preferably 4-alkylresorcinol.

3) The hair is left for 1 minute or more and 1 hour or less in any manner. In this case, the temperature may be arbitrarily increased to 40 to 90 ℃.

4) A first preparation containing the following components (A) and (C) is applied on the second preparation applying part of the hair in a superposed manner in such a way that the ratio of the mole number of the component (B) to the mole number of the component (A) is 0.01-5, and the first preparation is made to penetrate into the hair,

component (A): glyoxylic acid or a hydrate or salt thereof,

component (C): and (3) water.

5) The hair is left for 1 minute or more and 1 hour or less while being optionally heated to 40 to 90 ℃.

6) Heating the hair at 50-250 deg.C for shaping.

7) The hair was rinsed ad libitum.

8) Optionally heating at 40-230 deg.C to re-deform the hair.

Preferred embodiments of the present invention are further disclosed below with respect to the above-described embodiments.

<1>

A hair styling agent comprising the following components (A), (B) and (C), wherein the molar ratio (B)/(A) of the content of the component (B) to the content of the component (A) is 0.2 to 5,

(A) glyoxylic acid or a hydrate or salt thereof,

(B) the resorcinol is a mixture of resorcinol and a water-soluble organic solvent,

(C) and (3) water.

<2>

The hair deformation treatment agent according to <1>, wherein the molar ratio (B)/(A) of the content of the component (B) to the content of the component (A) is preferably 0.3 or more, more preferably 0.4 or more, further preferably 0.5 or more, further preferably 0.7 or more, and further preferably 2.5 or less, more preferably 2 or less, further preferably 1.5 or less, further preferably 1.2 or less.

<3>

The hair deformation treatment agent according to <1> or <2>, wherein the content of the component (A) as an acid is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 2.5% by mass or more, further preferably 3% by mass or more, and further preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, further preferably 15% by mass or less, further preferably 12% by mass or less.

<4>

The hair deformation treatment agent according to any one of <1> to <3>, wherein the content of the component (B) is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, further preferably 4% by mass or more, further preferably 5% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, further preferably 17% by mass or less.

<5>

The hair deformation treatment agent according to any one of <1> to <4>, which preferably further comprises a compound represented by the following general formula (1) as the component (D),

in the formula (I), the compound is shown in the specification,

R¹represents a hydrogen atom or a methyl group,

A¹and A²The same or different, represents a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, an aralkyl or arylalkenyl group having 7 to 12 carbon atoms, which may have a substituent, a linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms, a halogen atom or-CO-R²(R²Is a straight chain or branched chain having 1 to 12 carbon atomsAn alkyl group or alkenyl group, an aralkyl group or arylalkenyl group having 7 to 12 carbon atoms and optionally having a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms and optionally having a substituent),

b represents a hydrogen atom, a linear OR branched alkyl OR alkenyl group having 1 to 12 carbon atoms, an aralkyl OR arylalkenyl group having 7 to 12 carbon atoms and optionally having a substituent, -OR³or-COOR³(R³A 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 or alkenyloxy group having 1 to 12 carbon atoms,

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,

wherein A is¹、A²2 or 3 of B and E are hydrogen atoms, and the remaining groups are not sulfo-containing groups. When D is a hydrogen atom or a methyl group, A¹And B, or A²And B, together with the 2 carbon atoms to which they are adjacent, form a benzene ring which is unsubstituted or substituted with a hydroxyl group.

<6>

The hair deformation treatment agent according to <5>, wherein the molar ratio (D)/(B) of the content of the component (D) to the content of the component (B) is preferably 0.1 or more, more preferably 0.15 or more, further preferably 0.2 or more, and further preferably 3 or less, more preferably 2 or less, further preferably 1 or less, further preferably 0.4 or less.

<7>

The hair deformation treatment agent according to <5> or <6>, wherein the molar ratio [ (B) + (D) ]/(A) of the total content of the components (B) and (D) to the content of the component (A) is preferably 0.2 or more, more preferably 0.3 or more, further preferably 0.4 or more, further preferably 0.5 or more, further preferably 0.7 or more, and further preferably 5 or less, more preferably 2.5 or less, further preferably 2 or less, further preferably 1.2 or less.

<8>

The hair deformation treatment agent according to any one of <5> to <7>, wherein the total content of the component (B) and the component (D) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and further preferably 30% by mass or less, more preferably 27% by mass or less, further preferably 25% by mass or less, further preferably 23% by mass or less.

<9>

The hair deformation treatment agent according to any one of <5> to <8>, wherein the component (D) is preferably 1 or 2 or more selected from compounds represented by the following general formula (1-1), (1-2), (1-3-a) or (1-3-b).

[ in the formula, R¹、A¹、A²B and E are as defined above, and D¹Represents a hydroxyl group or a methoxy group.]

[ in the formula, R¹Denotes the same meaning as above, D²Represents a hydroxyl group or an alkoxy group having 1 to 12 carbon atoms, G represents a hydroxyl group, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 2.]

[ in the formula, R¹、A¹E, D, G and n are as defined above.]

<10>

The hair styling agent according to <9>, wherein the compound represented by the general formula (1-1) is preferably a m-dimethoxybenzene derivative represented by the following general formula (1-1-1).

[ in the formula, A¹、A²B and E are as defined above.]

<11>

Such as<10>The hair deformation treating agent according to (1), wherein A¹And A²Preferably a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.

<12>

Such as<10>Or<11>The hair-deforming agent according to the above, wherein B is preferably a hydrogen atom, a linear OR branched alkyl OR alkenyl group having 1 to 12 carbon atoms, an aralkyl OR arylalkenyl group having 7 to 12 carbon atoms which may have a substituent, OR-OR³(R³A hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms), more preferably a hydrogen atom, an alkyl or alkenyl group having 1 to 4 carbon atoms, an arylalkenyl group having 7 to 10 carbon atoms with or without a substituent, or a hydroxyl group, and still more preferably a hydrogen atom, an arylalkenyl group having 7 to 10 carbon atoms with or without a substituent, or a hydroxyl group.

<13>

The hair deformation treatment agent according to any one of <10> to <12>, wherein E is preferably a hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.

<14>

The hair styling agent according to <9>, wherein the compound represented by the general formula (1-1) is preferably a m-methoxyphenol derivative represented by the following general formula (1-1-2).

[ in the formula, A¹、A²B and E are as defined above.]

<15>

Such as<14>The hair deformation treating agent according to (1), wherein A¹And A²The alkyl group is preferably a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 12 carbon atoms, or an aralkyl group or arylalkenyl group having 7 to 12 carbon atoms with or without a substituent, and more 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 with or without a substituent.

<16>

Such as<14>Or<15>The hair-deforming agent according to the above, wherein B is preferably a hydrogen atom, a linear OR branched alkyl OR alkenyl group having 1 to 12 carbon atoms, an aralkyl OR arylalkenyl group having 7 to 12 carbon atoms which may have a substituent, OR-OR³(R³A hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms), more preferably a hydrogen atom, an alkyl or alkenyl group having 1 to 4 carbon atoms, an arylalkenyl group having 7 to 10 carbon atoms with or without a substituent, or a hydroxyl group, and still more preferably a hydrogen atom, an arylalkenyl group having 7 to 10 carbon atoms with or without a substituent, or a hydroxyl group.

<17>

The hair deformation treatment agent according to any one of <14> to <16>, wherein 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 more preferably a hydrogen atom or a hydroxyl group.

<18>

The hair deformation treatment agent according to <9>, wherein the compound represented by the general formula (1-1) is preferably a resorcinol derivative represented by the following general formula (1-1-3).

[ in the formula, A¹、A²B and E are as defined above.]

<19>

The hair deformation treating agent according to <18>, wherein the resorcinol derivative represented by the general formula (1-1-3) is preferably a resorcinol derivative represented by the following general formula (i).

[ in the formula, A¹、A²And B represents the same meaning as above, E¹Represents a hydroxyl group, a linear or branched alkyl group or alkenyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy group or alkenyloxy group having 1 to 6 carbon atoms.]

<20>

Such as<19>The hair deformation treating agent according to (1), wherein A¹And A²Preferably a hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, and more preferably a hydrogen atom.

<21>

Such as<19>Or<20>The hair-deforming agent according to the above, wherein B is preferably a hydrogen atom, an aralkyl OR aralkenyl group having 7 to 12 carbon atoms, which may have a substituent, OR-OR³(R³A hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 4 carbon atoms).

<22>

The hair deformation treatment agent according to any one of <18> to <21>, wherein E1 is preferably 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.

<23>

The hair deformation treatment agent according to any one of <19> to <22>, wherein the resorcinol derivative represented by the general formula (i) is preferably 2-alkylresorcinol, pyrogallol, 2-methoxyresorcinol, gallic acid or a gallic acid ester, more preferably 2-alkylresorcinol, gallic acid or a gallic acid ester.

<24>

The hair deformation treating agent according to <18>, wherein the resorcinol derivative represented by the general formula (1-1-3) is preferably a resorcinol derivative represented by the following formula (ii-1).

[ in the formula, A¹And A²The same meanings as described above are indicated.]

<25>

The hair deformation treating agent according to <24>, wherein the resorcinol derivative represented by the general formula (ii-1) is preferably 4-alkylresorcinol, 4-alkenylresorcinol, 4-aralkylresorcinol, 4-hydroxyalkylalkylresorcinol, 4-arylalkenylresorcinol, 4-hydroxyarylalkenylresorcinol, or 4- (1-methylnaphthyl) resorcinol, 4-alkoxyresorcinol, halogenated resorcinol, 4-alkanoyl resorcinol or 4-arylalkanoyl resorcinol, more preferably 4-alkylresorcinol, 4-arylalkyl resorcinol, halogenated resorcinol, 4-alkanoyl resorcinol or 4-arylalkanoyl resorcinol, and still more preferably 4-alkylresorcinol or 4-arylalkyl resorcinol.

<26>

The hair deformation treatment agent according to <18>, wherein the resorcinol derivative represented by the general formula (1-1-3) is preferably a resorcinol derivative represented by the following general formula (ii-2).

[ in the formula, A¹And A²Represents the same meaning as described above, B¹Represents a linear OR branched alkyl OR alkenyl group having 1 to 12 carbon atoms, an aralkyl OR arylalkenyl group having 7 to 12 carbon atoms and optionally having a substituent, -OR³or-COOR³(R³A hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms).]

<27>

The hair deformation treatment agent according to <26>, wherein the resorcinol derivative represented by the general formula (ii-2) is preferably a resorcinol derivative represented by the following general formula (ii-2-a).

[ in the formula, B¹The same meanings as described above are indicated.]

<28>

The hair deformation treatment agent according to <27>, wherein the resorcinol derivative represented by the general formula (ii-2-a) is preferably 5-alkylresorcinol, 5-alkenylresorcinol, phloroglucinol, 5-alkoxybenzene-1, 3-diol, 3, 5-dihydroxybenzoic acid, 3, 5-dihydroxybenzoate, 5-aralkylresorcinol, 5-hydroxyalkylalkylresorcinol, 5-arylalkenylresorcinol or 5-hydroxyarenylresorcinol, and more preferably 5-alkylresorcinol, 5-aralkylresorcinol, 5-hydroxyalkylalkylresorcinol or 5-hydroxyarenylresorcinol.

<29>

The hair deformation treating agent according to <26>, wherein the resorcinol derivative represented by (ii-2) is preferably a resorcinol derivative represented by the following general formula (ii-2-b).

[ in the formula, A¹、A²And B¹The same meanings as described above are indicated.]

<30>

Such as<29>The hair deformation treating agent according to (1), wherein A¹And A²Preferably 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.

<31>

The hair styling agent according to <30>, wherein the resorcinol derivative represented by the general formula (ii-2-b) is preferably 2-alkylbenzene-1, 3, 5-triphenol, phloroglucinol carboxylate, or 3, 5-dihydroxybenzoate, and more preferably phloroglucinol carboxylate.

<32>

The hair deformation treatment agent according to <9>, wherein the benzophenone derivative represented by the general formula (1-2) is preferably benzophenone-1, benzophenone-2, benzophenone-3, benzophenone-6, benzophenone-8, benzophenone-10 or benzophenone-12, more preferably benzophenone-12.

<33>

Such as<9>The hair styling agent according to (1-3-a) or (1-3-b), wherein the naphthol derivative represented by the general formula (1-3-a) or (1-3-b) is R¹Preferred are naphthol derivatives having a hydrogen atom or an alkyl group or alkenyl group having 1 to 4 carbon atoms, and more preferred is a hydrogen atom.

<34>

Such as<33>The hair styling agent according to (1-3-a) or (1-3-b), wherein the naphthol derivative represented by the general formula (1-3-a) or (1-3-b) is A in the general formula (1-3-a) or (1-3-b)¹And A²The naphthol derivative is preferably 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, and more preferably a hydrogen atom or a hydroxyl group.

<35>

The hair deformation treatment agent according to <33> or <34>, wherein the naphthol derivative represented by the general formula (1-3-a) or (1-3-b) is a naphthol derivative in which D in the general formula (1-3-a) or (1-3-b) is preferably 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.

<36>

The hair deformation treatment agent according to any one of <33> to <35>, wherein the naphthol derivative represented by the general formula (1-3-a) or (1-3-b) is a naphthol derivative in which E in the general formula (1-3-a) or (1-3-b) is preferably 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.

<37>

The hair deformation treatment agent according to any one of the items <33> to <36>, wherein the naphthol derivative represented by the general formula (1-3-a) or (1-3-b) is 1-naphthol, 2-naphthol, 3-methylnaphthalene-1-ol, 1, 4-naphthalenediol, 1, 5-naphthalenediol or 1, 8-naphthalenediol.

<38>

The hair deformation treatment agent according to any one of <5> to <37>, wherein the component (D) is preferably 1 or 2 or more selected from the group consisting of m-dimethoxybenzene derivatives represented by the general formula (1-1-1), resorcinol derivatives represented by the general formula (1-1-3), benzophenone derivatives represented by the general formula (1-2), and naphthol derivatives represented by the general formula (1-3-a) or (1-3-b), and more preferably selected from the group consisting of 2-methylresorcinol, 4-chlororesorcinol, 4-alkylresorcinol, 4-aralkylresorcinol, 4-acylated resorcinol, 5-alkylresorcinol, 5-aralkylresorcinol, 5-hydroxyarenylresorcinol, phloroglucinol carboxylate, resorcinol carboxylate, and mixtures thereof, 1 or 2 or more of gallic acid and gallic acid ester, more preferably 1 or 2 or more selected from 4-butylresorcinol (common name: Rucinol), 4- (1-phenylethyl) resorcinol (common name: pimecro 377(Symwhite377)), 5- (hydroxyphenylvinyl) resorcinol (common name: resveratrol (resveratrorol)), 3-hydroxyphenyl-1- (benzene-2, 4, 6-trisphenol) propan-1-one (common name: Phloretin (Phloretin), 4- (2, 4-dihydroxybenzoyl) resorcinol (common name: Benzophenone-2 (Benzophenone-2)), 5- (hydroxyphenylvinyl) -1, 3-dimethoxybenzene (common name: Pterostilbene (Pterostilbene)) and 1-naphthol, more preferably 1 or 2 or more selected from 4-butylresorcinol, 4- (1-phenylethyl) resorcinol and 4-n-hexylresorcinol.

<39>

The hair deformation treatment agent according to any one of <1> to <38>, wherein the pH of the hair deformation treatment agent is preferably 4 or less, more preferably 3 or less, further preferably 2.5 or less, further preferably 2 or less, and further preferably 1 or more, more preferably 1.2 or more, further preferably 1.5 or more.

<40>

The hair deformation treatment agent according to any one of <1> to <39>, wherein the molecular weight of the component (D) is preferably 120 or more, and the molecular weight of the component (D) is 1000 or less, further 500 or less, further 300 or less from the viewpoint of penetration into hair.

<41>

The hair styling agent according to any one of <1> to <40>, wherein the amount of the aromatic compound having at least one amino group, another amino group or a hydroxyl group in the ortho-position or para-position of the one amino group, and a closed-shell quinoid structure when oxidized is preferably less than 0.1% by mass, more preferably less than 0.01% by mass, and even more preferably the compound is not contained in the hair styling agent.

<42>

The hair deformation treatment agent according to any one of <1> to <41>, wherein the deformation of the hair is preferably not caused by cleavage and recombination of S-S bonds of hair proteins.

<43>

The hair deformation treatment agent according to any one of <1> to <42>, wherein the total amount of components that reduce proteins in hair is preferably less than 0.1% by mass, more preferably less than 0.01% by mass, and even more preferably the hair deformation treatment agent does not contain the compound.

<44>

The hair deformation treatment agent according to <43>, wherein the component that reduces proteins in hair is preferably a thiol, bisulfite or a salt thereof.

<45>

The hair styling agent according to <44>, wherein the thiol is preferably thioglycolic acid, dithioglycolic acid, cysteine, acetylcysteine, or butyrolactone thiol.

<46>

The hair styling agent according to any one of <1> to <45>, wherein the hair styling agent is preferably a multi-dose formula including a first dose containing the component (a) and a second dose containing the component (B).

<47>

The hair deformation treatment agent according to <46>, wherein the content of the component (A) in the first agent is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 2.5% by mass or more, further preferably 3% by mass or more, and further preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, further preferably 15% by mass or less, further preferably 12% by mass or less.

<48>

The hair deformation treatment agent according to <46> or <47>, wherein the content of the component (B) in the second agent is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, further preferably 4% by mass or more, further preferably 5% by mass or more, and further preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, further preferably 17% by mass or less.

<49>

The hair styling agent according to any one of <46> to <48>, wherein the hair styling agent is preferably a multi-dose type including a first dose containing the component (A) and a second dose containing the components (B) and (D).

<50>

The hair deformation treatment agent according to <49>, wherein the mass ratio (D)/(B) of the content of the component (D) to the content of the component (B) in the second agent is preferably 0.1 or more, more preferably 0.15 or more, further preferably 0.2 or more, and further preferably 3 or less, more preferably 2 or less, further preferably 1 or less, further preferably 0.4 or less.

<51>

The hair deformation treatment agent according to any one of <46> to <50>, wherein the pH of the first agent is preferably 4 or less, further 3 or less, further 2.5 or less, further 2 or less, and further preferably 1 or more, further 1.2 or more, further 1.5 or more.

<52>

The multi-dose hair styling agent according to any one of <46> to <51>, wherein the composition after mixing is the composition according to any one of <1> to <45 >.

<53>

A hair treatment method for deforming the shape of hair semi-permanently or permanently, comprising the following steps (i) and (ii),

(i) a step of applying the hair deformation treatment agent according to any one of <1> to <52> to hair and allowing the agent to penetrate into the hair,

(ii) and a step of shaping the hair impregnated with the hair deformation treatment agent by heating.

<54>

The method of hair modification according to <53>, wherein the step (i) is preferably a step of mixing a first agent and a second agent of the multi-agent hair modification treatment agent according to any one of <46> to <52>, and applying the mixture to the hair.

<55>

The hair modification method according to <53>, wherein the step (i) is preferably a step of applying one of the first and second doses of the multi-dose hair modification treatment agent according to any one of <46> to <52> to the hair and then applying another dose to the application part in a superposed manner.

<56>

The hair deformation method according to <55>, wherein the step (i) is preferably a step of applying the first dose containing the component (A) to the application part while overlapping the second dose containing the component (B) with the application part.

<57>

The hair treatment method according to <55> or <56>, wherein the molar ratio (B)/(a) of the amount of the component (B) contained in the second agent applied to the hair to the amount of the component (a) contained in the first agent applied to the hair is preferably 0.2 or more, more preferably 0.3 or more, further preferably 0.4 or more, further preferably 0.5 or more, further preferably 0.7 or more, and further preferably 5 or less, further preferably 2.5 or less, further preferably 2 or less, further preferably 1.5 or less, further preferably 1.2 or less.

<58>

The hair treatment method according to any one of <55> to <57>, wherein the molar ratio [ (B) + (D) ]/(A) of the total content of the components (B) and (D) in the second agent applied to the hair to the amount of the component (A) in the first agent applied to the hair is preferably 0.2 or more, preferably 0.3 or more, more preferably 0.4 or more, further preferably 0.5 or more, further preferably 0.7 or more, and further preferably 5 or less, preferably 2.5 or less, more preferably 2 or less, further preferably 1.5 or less, further preferably 1.2 or less.

<59>

The hair deformation method according to any one of <55> to <58>, wherein: the step of applying one of the first and second doses to the hair and the step of applying the other dose to the applicator in an overlapping manner include a step of placing the hair to which the one dose is applied.

<60>

The hair treatment method according to the above <59>, wherein when the hair applied with one dose is left to stand, the hair is preferably left to stand while being heated to 40 to 90 ℃.

<61>

The hair treatment method according to any one of <53> to <60>, which preferably comprises a step of wetting the hair before the step (i).

<62>

The hair treatment method according to any one of <53> to <61>, wherein the heating temperature in step (ii) is preferably 50 ℃ or higher, more preferably 60 ℃ or higher, further preferably 80 ℃ or higher, and further preferably 250 ℃ or lower, more preferably 240 ℃ or lower, further preferably 230 ℃ or lower.

<63>

The hair treatment method according to any one of <53> to <62>, wherein the step (ii) is preferably performed in an environment in which evaporation of water is suppressed.

<64>

The hair treatment method according to any one of <53> to <63>, preferably not comprising a step of applying a hair treatment agent containing a reducing agent or a strongly alkaline hair treatment agent having a pH of 12 to 14 to the hair.

<65>

The hair treatment method according to any one of <53> to <64>, wherein the mass of the hair deformation treatment agent applied to the hair in step (i) is preferably 0.05 or more, more preferably 0.1 or more, further preferably 0.25 or more, further preferably 0.5 or more, further preferably 5 or less, more preferably 3 or less, further preferably 2 or less, in terms of a bath ratio (mass of hair deformation treatment agent/mass of hair) to the mass of the hair.

<66>

The hair treatment method according to any one of <53> to <65>, wherein the heating time in step (ii) is preferably 1 second or more, further 5 seconds or more, further 1 minute or more, further 5 minutes or more, further 15 minutes or more, further 30 minutes or more, and further preferably 2 hours or less, further 1 hour or less, further 45 minutes or less.

<67>

The hair treatment method according to any one of <53> to <66>, wherein a step of placing the hair applied with the hair treatment agent is preferably included between the steps (i) and (ii).

<68>

The hair treatment method according to <67>, wherein the leaving time is preferably 1 minute or more, more preferably 3 minutes or more, further preferably 5 minutes or more, and further preferably 1 hour or less, more preferably 30 minutes or less, further preferably 20 minutes or less.

<69>

The hair treatment method according to <67> or <68>, wherein the hair is preferably heated to 40 to 90 ℃ during the leaving between the steps (i) and (ii).

<70>

The hair treatment method according to any one of <53> to <69>, wherein a step of rinsing the hair applied with the hair treatment agent is preferably not included between the steps (i) and (ii).

<71>

The hair treatment method according to any one of <53> to <70>, which preferably comprises a step of rinsing the hair after the step (ii).

<72>

The hair treatment method according to any one of <53> to <71>, wherein the hair is preferably reshaped into a different shape by heating after the step (ii).

<73>

The hair treatment method according to <72>, wherein the hair is preferably reshaped without applying a hair reshaping agent.

<74>

The hair treatment method according to <72> or <73>, wherein the heating temperature at the time of re-deforming the hair is preferably 30 ℃ or more, more preferably 40 ℃ or more, and 230 ℃ or less, more preferably 220 ℃ or less, and further preferably 210 ℃ or less.

<75>

Use of the composition according to any one of <1> to <52> for semi-permanent or permanent hair deformation.

[ examples ]

Examples 1 to 12 and comparative examples 1 to 6

The treatment agents shown in table 1 were prepared, and the following 3-stage hair treatment was performed to evaluate the respective shape-imparting effects. The results are shown in Table 1. The pH of each composition was measured directly at room temperature (25 ℃ C.) using a pH meter (HORIBA manufactured/model: F-52).

< I: imparting a semi-permanent curl shape >

1. After 0.5g of a 25cm long tress of caucasian straight hair (untreated hair) was wetted with 30 seconds of tap water at 30 ℃, the wet tress was wound around a plastic hair curling rod 14mm in diameter and fixed with a hair clip.

2. The treatment agent 1g was applied to the hair bundle wound on the hair curling rod, the whole hair curling rod was sealed by coating it with a wrap film, and heated in an oven set at 90 ℃ for 1 hour.

3. The strands were removed from the oven and allowed to return to room temperature.

4. The tresses were released from the curling iron, rinsed with running water at 30 ℃ for 30 seconds, and lathered by rubbing with shampoo for evaluation for 60 seconds.

5. After rinsing with running water at 30 ℃ for 30 seconds, the hair was immersed in running water at 30 ℃ for 60 seconds at an infinite bath ratio, and then the hair was pulled up from the water while grasping the root of the hair strand, and the hair strand was gently shaken to remove water.

6. The film was left standing in a laboratory for 2 hours, dried, combed through with a comb, hung, and a photograph was taken from the front side. From the photograph, the curvature radius of the portion where the curl of the hair bundle is strongest is obtained, and the curvature radius is multiplied by2 to obtain the curl diameter.

(evaluation criteria)

A: the curling diameter is 1 or more times and less than 2 times of the curling iron (diameter 14mm) used.

B: the curling diameter is more than 2 times and less than 3 times of the curling iron (diameter 14mm) used.

C: the curling diameter is more than 3 times and less than 4 times of the curling iron (diameter 14mm) used.

D: the curling diameter is more than 4 times and less than 50 times of the curling iron (diameter 14mm) used.

E: the hair is kept straight and the shape is unchanged compared with the shape before treatment.

< II: imparting a semi-permanent straight hair shape to hair having a semi-permanent curly hair shape >

1. For < I: imparting a semi-permanent curl > the hair tresses evaluated were combed through with a comb and after opening the tangles, slid 6 times at a speed of 5cm/sec using a hair iron with a measured temperature of 180 ℃.

2. Rinsed with running water at 30 deg.C for 30 seconds, kneaded with evaluation shampoo for 60 seconds, rinsed with running water at 30 deg.C for 30 seconds, and wiped with a towel.

3. The hair was dried while being vibrated (without using a hair dryer) to give a natural shape, combed through with a comb, and then hung and visually observed from the front side.

(evaluation criteria)

A: the hair curler has no residue, and completely realizes hair straightening.

B: the curl is weakened compared to the curler before treatment, but the straightening is not fully achieved.

C: the curly hair is kept unchanged, and the shape is unchanged compared with that before treatment.

< III: imparting a semi-permanent curl shape to hair having a semi-permanent straight hair shape >

1. The < II: after wetting the hair tresses evaluated in the section of hair with a semipermanent curly shape > were applied, the wet tresses were wound around a plastic hair roller 14mm in diameter and fixed with a hair clip.

2. The whole curling iron was sealed by coating it with a wrap film and heated in an oven set at 40 ℃ for 1 hour.

3. The strands were removed from the oven and allowed to return to room temperature.

4. The tresses were released from the curling iron, rinsed with running water at 30 ℃ for 30 seconds, and lathered by rubbing with shampoo for evaluation for 60 seconds.

5. After rinsing with running water at 30 ℃ for 30 seconds, the hair was immersed in running water at 30 ℃ for 60 seconds at an infinite bath ratio, and then the hair was pulled up from the water while grasping the root of the hair strand, and the hair strand was gently shaken to remove water.

6. The film was left standing in a laboratory for 2 hours, dried, combed through with a comb, hung, and a photograph was taken from the front side. From the photograph, the curvature radius of the portion where the curl of the hair bundle is strongest is obtained, and the curvature radius is multiplied by2 to obtain the curl diameter.

(evaluation criteria)

A: the curling diameter is 1 or more times and less than 2 times of the curling iron (diameter 14mm) used.

B: the curling diameter is more than 2 times and less than 3 times of the curling iron (diameter 14mm) used.

C: the curling diameter is more than 3 times and less than 4 times of the curling iron (diameter 14mm) used.

D: the curling diameter is more than 4 times and less than 50 times of the curling iron (diameter 14mm) used.

E: the hair is kept straight and the shape is unchanged compared with the shape before treatment.

< formulation of shampoo for evaluation >

Examples 13 to 14

The treatment agents shown in table 2 were prepared, and the following 3-stage hair treatment was performed to evaluate the respective shape-imparting effects. The results are shown in Table 2.

< I: imparting a semi-permanent curl shape >

1. After 0.5g of a 25cm long tress of caucasian straight hair (untreated hair) was wetted with 30 seconds of tap water at 30 ℃, the wet tress was wound around a plastic hair curling rod 14mm in diameter and fixed with a hair clip.

2. The tresses of hair wound around the curling iron were immersed in 40g of the treatment agent, and in this state, heated in an oven set at 90 ℃ for 3 hours.

3. The strands were removed from the oven and allowed to return to room temperature.

4. The tresses were released from the curling iron, rinsed with running water at 30 ℃ for 30 seconds, and lathered by rubbing with shampoo for evaluation for 60 seconds.

5. After rinsing with running water at 30 ℃ for 30 seconds, the hair was immersed in running water at 30 ℃ for 60 seconds at an infinite bath ratio, and then the hair was pulled up from the water while grasping the root of the hair strand, and the hair strand was gently shaken to remove water.

6. The film was left standing in a laboratory for 2 hours, dried, combed through with a comb, hung, and a photograph was taken from the front side. From the photograph, the curvature radius of the portion where the curl of the hair bundle is strongest is obtained, and the curvature radius is multiplied by2 to obtain the curl diameter.

(evaluation criteria)

A: the curling diameter is 1 or more times and less than 2 times of the curling iron (diameter 14mm) used.

B: the curling diameter is more than 2 times and less than 3 times of the curling iron (diameter 14mm) used.

C: the curling diameter is more than 3 times and less than 4 times of the curling iron (diameter 14mm) used.

D: the curling diameter is more than 4 times and less than 50 times of the curling iron (diameter 14mm) used.

E: the hair is kept straight and the shape is unchanged compared with the shape before treatment.

< II: imparting a semi-permanent straight hair shape to hair having a semi-permanent curly hair shape >

1. The hair tresses for which the effect of imparting the initial shape was evaluated were combed with a comb and opened to tangle, and then slid 6 times at a speed of 5cm/sec using a hair straightener with a measured temperature of 180 ℃.

2. Rinsed with running water at 30 deg.C for 30 seconds, kneaded with evaluation shampoo for 60 seconds, rinsed with running water at 30 deg.C for 30 seconds, and wiped with a towel.

3. The hair was dried while being vibrated (without using a hair dryer) to give a natural shape, combed through with a comb, and then hung and visually observed from the front side.

(evaluation criteria)

A: the hair curler has no residue, and completely realizes hair straightening.

B: the curl is weakened compared to the curler before treatment, but the straightening is not fully achieved.

C: the curly hair is kept unchanged, and the shape is unchanged compared with that before treatment.

< III: imparting a semi-permanent curl shape to hair having a semi-permanent straight hair shape >

1. The < II: after wetting the hair tresses evaluated in the section of hair with a semipermanent curly shape > were applied, the wet tresses were wound around a plastic hair roller 14mm in diameter and fixed with a hair clip.

2. The whole curling iron was sealed by coating it with a wrap film and heated in an oven set at 40 ℃ for 1 hour.

3. The strands were removed from the oven and allowed to return to room temperature.

4. The tresses were released from the curling iron, rinsed with running water at 30 ℃ for 30 seconds, and lathered by rubbing with shampoo for evaluation for 60 seconds.

5. After rinsing with running water at 30 ℃ for 30 seconds, the hair was immersed in running water at 30 ℃ for 60 seconds at an infinite bath ratio, and then the hair was pulled up from the water while grasping the root of the hair strand, and the hair strand was gently shaken to remove water.

6. The film was left standing in a laboratory for 2 hours, dried, combed through with a comb, hung, and a photograph was taken from the front side. From the photograph, the radius of curvature of the portion where the curl of the hair is strongest is determined, and the radius of curvature is multiplied by2 to determine the curl diameter.

(evaluation criteria)

A: the curling diameter is 1 or more times and less than 2 times of the curling iron (diameter 14mm) used.

B: the curling diameter is more than 2 times and less than 3 times of the curling iron (diameter 14mm) used.

C: the curling diameter is more than 3 times and less than 4 times of the curling iron (diameter 14mm) used.

D: the curling diameter is more than 4 times and less than 50 times of the curling rod (diameter is 14mm)

E: the hair is kept straight and the shape is unchanged compared with the shape before treatment.

[ Table 2]

*1: adjusting the pH value to 2.0

Example 15

The treatment agents shown in table 3 were prepared, and the following 3-stage hair treatment was performed to evaluate the respective shape-imparting effects. The results are shown in Table 3.

< I: imparting a semi-permanent straight hair shape >

1. After wetting a hair strand (untreated hair) from straight hair, which is slightly open at the ends of a caucasian, with tap water at 30 ℃ for 30 seconds (weight: 0.5 g/length: 25cm), the wet hair strand was wound around a plastic curling iron having a diameter of 14mm and fixed with a hair clip.

2. The treatment agent 1.0g was applied to the hair tresses wound on the hair curling rod, the whole hair curling rod was sealed by coating it with a wrap film, and heated in an oven set at 40 ℃ for 1 hour.

3. The strands were removed from the oven and allowed to return to room temperature.

4. The wrap was removed from the curling iron, and after wiping off the moisture with a towel, warm air drying was carried out with a hair dryer until completely dry.

5. After the hair strand was combed with a comb and opened to tangle, the hair was slid 6 times at a speed of 5cm/sec using a hair straightener whose measured temperature was 230 ℃ to produce a hair style in which the hair strand was completely straightened from the root to the tail.

6. The hair tresses were rinsed with running water at 30 ℃ for 30 seconds from tap water and lathered by rubbing with the evaluation shampoo for 60 seconds. Thereafter, the plate was rinsed with running water of 30 ℃ for 30 seconds and then wiped off with a towel.

7. The hair was dried while vibrating to naturally assume the shape it had, combed through with a comb, and then hung and visually observed from the front side.

(evaluation criteria)

A: the spread of the ends of the hair bundle disappears and a completely straight hair shape is maintained from the root to the tail.

B: the spread of the ends of the hair strands is suppressed and the hair is straightened, but still spread slightly.

C: the ends of the hair strands are splayed as in the untreated state.

< II: imparting a semi-permanent curl shape to hair having a semi-permanent straight hair shape >

1. The < I: after wetting the hair tresses evaluated in the section entitled "imparting a semi-permanent straight hair shape", the wet hair tresses were wound around a plastic hair roller having a diameter of 14mm and fixed with a hair clip.

2. The whole curling iron was sealed by coating it with a wrap film and heated in an oven set at 40 ℃ for 1 hour.

3. The strands were removed from the oven and allowed to return to room temperature.

4. The tresses were released from the curling iron, rinsed with running water at 30 ℃ for 30 seconds, and lathered by rubbing with shampoo for evaluation for 60 seconds.

5. After rinsing with running water at 30 ℃ for 30 seconds, the hair was immersed in running water at 30 ℃ for 60 seconds at an infinite bath ratio, and then the hair was pulled up from the water while grasping the root of the hair strand, and the hair strand was gently shaken to remove water.

6. The film was left standing in a laboratory for 2 hours, dried, combed through with a comb, hung, and a photograph was taken from the front side. From the photograph, the curvature radius of the portion where the curl of the hair bundle is strongest is obtained, and the curvature radius is multiplied by2 to obtain the curl diameter.

(evaluation criteria)

A: the curling diameter is 1 or more times and less than 2 times of the curling iron (diameter 14mm) used.

B: the curling diameter is more than 2 times and less than 3 times of the curling iron (diameter 14mm) used.

C: the curling diameter is more than 3 times and less than 4 times of the curling iron (diameter 14mm) used.

D: the curling diameter is more than 4 times and less than 50 times of the curling iron (diameter 14mm) used.

E: the hair is kept straight and the shape is unchanged compared with the shape before treatment.

< III: imparting a semi-permanent straight hair shape to hair having a semi-permanent curly hair shape >

1. For < II: the hair strand evaluated in the section of "imparting a semi-permanent curl shape" to the hair imparted with a semi-permanent straight shape was combed with a comb and opened to tangle, and then slid 6 times at a speed of 5cm/sec using a hair straightener with a measured temperature of 180 ℃.

2. Rinsed with running water at 30 deg.C for 30 seconds, kneaded with evaluation shampoo for 60 seconds, rinsed with running water at 30 deg.C for 30 seconds, and wiped with a towel.

3. The hair was dried while being vibrated (without using a hair dryer) to give a natural shape, combed through with a comb, and then hung and visually observed from the front side.

(evaluation criteria)

A: the hair curler has no residue, and completely realizes hair straightening.

B: the curl is weakened compared to the curler before treatment, but the straightening is not fully achieved.

C: the curly hair is kept unchanged, and the shape is unchanged compared with that before treatment.

[ Table 3]

*1: adjusting the pH value to 2.0

Example 16

Two-pack type treatment agents shown in table 4 were prepared, and the following 3-stage hair treatment was performed to evaluate the respective shape-imparting effects. The results are shown in Table 4.

< I: imparting a semi-permanent curl shape >

1. After 0.5g of a 25cm long tress of straight (untreated) caucasian hair was wetted with 30 seconds of tap water at 30 ℃, the wet tress was wound around a plastic hair curling iron 14mm in diameter and fixed with a hair clip.

2. The hair tresses wound on the hair curling bar were coated with one dose of the formulation 1g, the whole hair curling bar was sealed with a wrap film, and left at 25 ℃ for 5 minutes.

3. The hair tresses wound on the hair curling bar were coated with the formulation two 1g, the whole hair curling bar was sealed with a wrap film, and heated in an oven set at 90 ℃ for 1 hour.

4. The strands were removed from the oven and allowed to return to room temperature.

5. The tresses were released from the curling iron, rinsed with running water at 30 ℃ for 30 seconds, and lathered by rubbing with shampoo for evaluation for 60 seconds.

6. After rinsing with running water at 30 ℃ for 30 seconds, the hair was immersed in running water at 30 ℃ for 60 seconds at an infinite bath ratio, and then the hair was pulled up from the water while grasping the root of the hair strand, and the hair strand was gently shaken to remove water.

7. The film was left standing in a laboratory for 2 hours, dried, combed through with a comb, hung, and a photograph was taken from the front side. From the photograph, the curvature radius of the portion where the curl of the hair bundle is strongest is obtained, and the curvature radius is multiplied by2 to obtain the curl diameter.

(evaluation criteria for initial shape imparting Effect)

A: the curling diameter is 1 or more times and less than 2 times of the curling iron (diameter 14mm) used.

B: the curling diameter is more than 2 times and less than 3 times of the curling iron (diameter 14mm) used.

C: the curling diameter is more than 3 times and less than 4 times of the curling iron (diameter 14mm) used.

D: the curling diameter is more than 4 times and less than 50 times of the curling iron (diameter 14mm) used.

E: the hair is kept straight and the shape is unchanged compared with the shape before treatment.

< II: imparting a semi-permanent straight hair shape to hair having a semi-permanent curly hair shape >

1. For < I: imparting a semi-permanent curl > the hair tresses evaluated were combed through with a comb and after opening the tangles, slid 6 times at a speed of 5cm/sec using a hair straightener at a measured temperature of 180 ℃.

2. Rinsed with running water at 30 deg.C for 30 seconds, kneaded with evaluation shampoo for 60 seconds, rinsed with running water at 30 deg.C for 30 seconds, and wiped with a towel.

3. The hair was dried while being vibrated (without using a hair dryer) to give a natural shape, combed through with a comb, and then hung and visually observed from the front side.

(evaluation criteria for reshaping Effect)

A: the hair curler has no residue, and completely realizes hair straightening.

B: the curl is weakened compared to the curler before treatment, but the straightening is not fully achieved.

C: the curly hair is kept unchanged, and the shape is unchanged compared with that before treatment.

< III: imparting a semi-permanent curl shape to hair having a semi-permanent straight hair shape >

1. The < II: after wetting the hair tresses evaluated in the section of hair with a semipermanent curly shape > were applied, the wet tresses were wound around a plastic hair roller 14mm in diameter and fixed with a hair clip.

2. The whole curling iron was sealed by coating it with a wrap film and heated in an oven set at 40 ℃ for 1 hour.

3. The strands were removed from the oven and allowed to return to room temperature.

4. The tresses were released from the curling iron, rinsed with running water at 30 ℃ for 30 seconds, and lathered by rubbing with shampoo for evaluation for 60 seconds.

5. After rinsing with running water at 30 ℃ for 30 seconds, the hair was immersed in running water at 30 ℃ for 60 seconds at an infinite bath ratio, and then the hair was pulled up from the water while grasping the root of the hair strand, and the hair strand was gently shaken to remove water.

6. The film was left standing in a laboratory for 2 hours, dried, combed through with a comb, hung, and a photograph was taken from the front side. From the photograph, the curvature radius of the portion where the curl of the hair bundle is strongest is obtained, and the curvature radius is multiplied by2 to obtain the curl diameter.

(evaluation criteria for reshaping Effect)

A: the curling diameter is 1 or more times and less than 2 times of the curling iron (diameter 14mm) used.

B: the curling diameter is more than 2 times and less than 3 times of the curling iron (diameter 14mm) used.

C: the curling diameter is more than 3 times and less than 4 times of the curling iron (diameter 14mm) used.

D: the curling diameter is more than 4 times and less than 50 times of the curling iron (diameter 14mm) used.

E: the hair is kept straight and the shape is unchanged compared with the shape before treatment.

[ Table 4]

*1: adjusting the pH value to 2.0

Example 17

Evaluation was performed in the same manner as in example 16, except that the application order of the first formulation and the second formulation used in example 16 was changed. That is, at < I: evaluation of semipermanent curl formation > the procedure of example 16 was repeated except that 1g of the formulation was applied to the tress of hair wound on the hair curling rod, the whole hair curling rod was covered with a wrap film, the tress of hair was left at 25 ℃ for 5 minutes, then 1g of the formulation was applied to the tress of hair, the whole hair curling rod was covered with a wrap film and sealed, and the hair was heated in an oven set at 90 ℃ for 1 hour.

The treated tresses were observed with results < I: evaluation of imparting semi-permanent curl > was C, < II: the evaluation of hair imparted with a semi-permanent curly shape imparted with a semi-permanent straight shape > was a, < III: the hair given a semi-permanent straight hair shape was evaluated as "C".

Comparative example 7

A hair treatment agent was prepared according to patent document 3 (specification of U.S. patent No. 4278659), and the following treatment was performed: evaluation of imparting semi-permanent curl >. Specifically, hair treatment agents were prepared and evaluated in the following order.

< preparation of Hair treatment agent >

An aqueous solution having a pH of 2.0 and containing 5% by mass of glyceraldehyde and 5% by mass of resorcinol was prepared. The aqueous solution was heated under reflux for 1 hour to obtain a hair treatment agent.

< I: imparting a semi-permanent curl shape >

1. A tress of 25cm long, 0.5g of caucasian hair straightened by a person, was wetted with 30 seconds of tap water at 30 ℃ and then the wet tress was wound around a plastic hair curler 14mm in diameter and fixed with a hair clip.

2. The treatment agent 1g prepared in < preparation of hair treatment agent > was applied to the hair tresses wound on the hair curling bar, the whole hair curling bar was covered with a wrap film to be sealed, and heated in an oven set at 90 ℃ for 1 hour.

3. The strands were removed from the oven and allowed to return to room temperature.

4. The tresses were released from the curling iron, rinsed with running water at 30 ℃ for 30 seconds, and lathered by rubbing with shampoo for evaluation for 60 seconds.

5. After rinsing with running water at 30 ℃ for 30 seconds, the hair was immersed in running water at 30 ℃ for 60 seconds at an infinite bath ratio, and then the hair was pulled up from the water while grasping the root of the hair strand, and the hair strand was gently shaken to remove water.

6. The film was left standing in a laboratory for 2 hours, dried, combed through with a comb, hung, and a photograph was taken from the front side.

The hair treatment was performed in the above-described procedure, but the hair shape after the treatment with the hair treatment agent used in comparative example 7 was the same as that before the treatment, and no curl shape was imparted.

(method example 1)

The following treatments (I to II) were carried out.

< I: imparting a semi-permanent curl shape >

A tress of 25cm long, 0.5g of caucasian hair straightened by a person, was wetted with 30 seconds of tap water at 30 ℃ and then the wet tress was wound around a plastic hair curling rod 14mm in diameter and fixed with a hair clip.

The tresses of hair wound around the curling iron were applied with 0.5g of a 20 mass% aqueous solution of glyoxylic acid (pH 2.0) and allowed to stand at 25 ℃ for 5 minutes. Thereafter, 0.5g of resorcinol was applied in a 30 mass% aqueous solution (pH 2.0), the whole curling iron was covered with a wrap film to be sealed, and the hair was heated in an oven at a set temperature of 90 ℃ for 1 hour.

The strands were removed from the oven and allowed to return to room temperature. The tresses were released from the curling iron, rinsed with running water at 30 ℃ for 30 seconds, and lathered by rubbing with shampoo for evaluation for 60 seconds. After rinsing with running water at 30 ℃ for 30 seconds, the hair was immersed in running water at 30 ℃ for 60 seconds at an infinite bath ratio, and then the hair was pulled up from the water while grasping the root of the hair strand, and the hair strand was gently shaken to remove water. The sheet was left to stand in a laboratory for 2 hours while being hung, dried, combed through with a comb, hung, and visually observed from the front side, and it was found that a semi-permanent curled shape was successfully imparted.

< II: imparting a semi-permanent straight hair shape to hair having a semi-permanent curly hair shape >

For < I: imparting a semi-permanent curl > the hair tresses evaluated were combed through with a comb and after opening the tangles, slid 6 times at a speed of 5cm/sec using a hair straightener at a measured temperature of 140 ℃. Rinsed with running water at 30 deg.C for 30 seconds, kneaded with evaluation shampoo for 60 seconds, rinsed with running water at 30 deg.C for 30 seconds, and wiped with a towel. The hair was dried while being vibrated to give a natural shape, combed through with a comb, hung, and visually observed from the front side, and it was found that a semi-permanent straight hair shape was successfully given.

(method example 2)

The following treatments (I to II) were carried out.

< I: imparting a semi-permanent curl shape >

A tress of 25cm long, 0.5g of caucasian hair straightened by a person, was wetted with 30 seconds of tap water at 30 ℃ and then the wet tress was wound around a plastic hair curling rod 14mm in diameter and fixed with a hair clip.

A 30 mass% aqueous solution (pH 2.0) of resorcinol (0.5 g) was applied to the tresses of hair wound on the curling iron, and the tresses were allowed to stand at 25 ℃ for 5 minutes. Thereafter, 0.5g of a 20 mass% aqueous solution of glyoxylic acid (pH 2.0) was applied thereto, the whole hair curler was sealed by coating it with a wrap film, and the resultant was heated in an oven at a set temperature of 90 ℃ for 1 hour.

The strands were removed from the oven and allowed to return to room temperature. The tresses were released from the curling iron, rinsed with running water at 30 ℃ for 30 seconds, and lathered by rubbing with shampoo for evaluation for 60 seconds. After rinsing with running water at 30 ℃ for 30 seconds, the hair was immersed in running water at 30 ℃ for 60 seconds at an infinite bath ratio, and then the hair was pulled up from the water while grasping the root of the hair strand, and the hair strand was gently shaken to remove water. The sheet was left to stand in a laboratory for 2 hours while being hung, dried, combed through with a comb, hung, and visually observed from the front side, and it was found that a semi-permanent curled shape was successfully imparted.

< II: imparting a semi-permanent straight hair shape to hair having a semi-permanent curly hair shape >

For < I: imparting a semi-permanent curl > the hair tresses evaluated were combed through with a comb and after opening the tangles, slid 6 times at a speed of 5cm/sec using a hair straightener at a measured temperature of 140 ℃. Rinsed with running water at 30 deg.C for 30 seconds, kneaded with evaluation shampoo for 60 seconds, rinsed with running water at 30 deg.C for 30 seconds, and wiped with a towel. The hair was dried while being vibrated to give a natural shape, combed through with a comb, hung, and visually observed from the front side, and it was found that a semi-permanent straight hair shape was successfully given.

(method example 3)

The following processes (steps 1 to 3) are performed.

< step 1: imparting a semi-permanent straight hair shape >

A 20 mass% aqueous solution of glyoxylic acid (pH 2.0) and a 30 mass% aqueous solution of resorcinol (pH 2.0) were mixed in a ratio of 1: 1 to prepare a treating agent A. After a tress of 25cm long, 0.5g of Caucasian curly hair, was wetted with 30 seconds of tap water at 30 ℃, the tress was coated with the treating agent A1g, the whole tress was covered with a wrap film to seal it, and heated in an oven set at 40 ℃ for 1 hour.

The hair was taken out of the oven and allowed to return to room temperature, and after the wrap was removed, the remaining treatment agent on the hair was wiped off with a towel, and the hair was dried with a hair dryer while being combed with a comb.

This operation was performed 6 times by using a hair straightener (taiff titanium manufactured by daihatsu corporation) having a set temperature of 230 ℃ for hair strands blow-dried by a blower, and holding the hair strands with the hair strands held between the hair strands by the hair straightener jaws while sliding the hair strands from the hair root side to the hair tail side at a speed of 5 cm/sec.

The hair tresses treated with the hair iron were rinsed with running water at 30 ℃ for 30 seconds, rubbed with a shampoo for foaming for 60 seconds, rinsed with running water at 30 ℃ for 30 seconds, and then dried naturally with towel, and as a result, it was found that a semi-permanent straight hair shape was successfully imparted.

< step 2: imparting a semi-permanent curl shape >

After wetting the hair tresses evaluated in step 1 with tap water at 30 ℃ for 30 seconds, the wet tresses were wound on plastic hair curling rods 14mm in diameter and fixed with hair clips. The whole curling iron was sealed by coating it with a wrap film and heated in an oven set at 40 ℃ for 1 hour. The strands were removed from the oven and allowed to return to room temperature. The tresses were released from the curling iron, rinsed with running water at 30 ℃ for 30 seconds, and lathered by rubbing with shampoo for evaluation for 60 seconds. After rinsing with running water at 30 ℃ for 30 seconds, the hair was immersed in running water at 30 ℃ for 60 seconds at an infinite bath ratio, and then the hair was gently pulled up from the water by grasping the root of the hair strand, and the hair strand was gently shaken to remove water. The sheet was left to stand in a laboratory for 2 hours while being hung, dried, combed through with a comb, hung, and visually observed from the front side, and it was found that a semi-permanent curled shape was successfully imparted.

< step 3: imparting a semi-permanent straight hair shape >

For the hair tresses evaluated in step 2, after combing through with a comb and opening the tangles, 6 slides at a speed of 5cm/sec using a hair iron with a measured temperature of 180 ℃. Rinsed with running water at 30 deg.C for 30 seconds, kneaded with evaluation shampoo for 60 seconds, rinsed with running water at 30 deg.C for 30 seconds, and wiped with a towel. The hair was dried while being vibrated to give a natural shape, combed through with a comb, hung, and visually observed, and it was found that a semi-permanent straight hair shape was successfully given.

Claims (17)

1. A hair-setting treatment agent, wherein,

contains the following components (A), (B) and (C), and the molar ratio (B)/(A) of the content of the component (B) to the content of the component (A) is 0.2 to 5,

(A) glyoxylic acid or a hydrate or salt thereof,

(B) the resorcinol is a mixture of resorcinol and a water-soluble organic solvent,

(C) and (3) water.

2. The hair deformation treatment agent according to claim 1, wherein,

further containing a compound represented by the following general formula (1) as a component (D),

in the formula (I), the compound is shown in the specification,

R¹represents a hydrogen atom or a methyl group,

A¹and A²The same or different, represents a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, an aralkyl or arylalkenyl group having 7 to 12 carbon atoms, which may have a substituent, a linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms, a halogen atom or-CO-R²Wherein R is²Is a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, an aralkyl or arylalkenyl group having 7 to 12 carbon atoms and optionally having a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms and optionally having a substituent,

b represents a hydrogen atom, a linear OR branched alkyl OR alkenyl group having 1 to 12 carbon atoms, an aralkyl OR arylalkenyl group having 7 to 12 carbon atoms and optionally having a substituent, -OR³or-COOR³Wherein R is³Is 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 or alkenyloxy group having 1 to 12 carbon atoms,

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;

wherein A is¹、A²2 or 3 of B and E are hydrogen atoms, the remaining groups are not sulfo-containing groups; when D is a hydrogen atom or a methyl group, A¹And B, or A²And B, together with the 2 carbon atoms to which they are adjacent, form a benzene ring which is unsubstituted or substituted with a hydroxyl group.

3. The hair deformation treatment agent according to claim 2, wherein,

the molar ratio (D)/(B) of the content of the component (D) to the content of the component (B) is 0.1 to 3.

4. The hair deformation treating agent according to claim 2 or 3, wherein,

the component (D) is a compound represented by the general formula (1-1-3),

in the formula, A¹、A²B and E are as defined above.

5. The hair deformation treatment agent according to any one of claims 1 to 4,

the content of the component (a) as an acid is 1 to 30 mass%.

6. The hair deformation treatment agent according to any one of claims 1 to 5, wherein,

the content of the component (B) is 1 to 30% by mass.

7. The hair deformation treatment agent according to any one of claims 1 to 6,

the hair deformation treatment agent has a pH of 4 or less.

8. The hair deformation treatment agent according to any one of claims 1 to 7,

the amount of the aromatic compound having at least one amino group, having another amino group or hydroxyl group at the ortho-position or para-position to the one amino group, and having a closed-shell quinoid structure when oxidized is less than 0.1 mass%.

9. The hair deformation treatment agent according to any one of claims 1 to 8,

the total amount of the mercaptan, the bisulfite and the salt thereof is less than 0.1% by mass.

10. The hair deformation treatment agent according to any one of claims 1 to 9,

the hair deformation treatment agent is a multi-agent type comprising a first agent containing component (A) and a second agent containing component (B), and the pH value of the first agent is 4 or less.

11. Use of the treatment agent according to any one of claims 1 to 10 for hair deformation.

12. A method of treating hair, wherein,

the hair treatment process deforms the hair shape semi-permanently or permanently,

the hair treatment method comprises the following steps (i) and (ii),

(i) a step of applying the hair deformation treatment agent according to any one of claims 1 to 10 to hair and allowing the agent to penetrate into the hair,

(ii) and a step of shaping the hair impregnated with the hair deformation treatment agent by heating.

13. The hair treatment method according to claim 12,

step (i) is a step of applying one of the first and second agents of the hair deformation treatment agent according to claim 10 to hair and then applying the other agent to the application part in an overlapping manner.

14. The hair treatment method according to claim 12 or 13,

comprising the step of wetting the hair prior to step (i).

15. The hair treatment method according to any one of claims 12 to 14,

the heating temperature in step (ii) is 50 ℃ or more and 250 ℃ or less.

16. The hair treatment method according to any one of claims 12 to 15,

step (ii) is carried out in an environment in which evaporation of water is suppressed.

17. The hair treatment method according to any one of claims 12 to 16,

the method does not comprise the step of applying a hair treatment agent containing a reducing agent or a strongly alkaline hair treatment agent with a pH value of 12-14 to the hair.