阅读说明：本技术 含有碱性染料和氨基酸的化合物、染发用染料以及染发用组合物 (Compound containing basic dye and amino acid, dye for hair dyeing and composition for hair dyeing ) 是由 内藤慧悟 宮崎泰彰 沼泽成能 阿部胜美 于 2019-08-30 设计创作，主要内容包括：本发明提供一种染发能力优异、水溶性和发泡性良好、清洗时和干燥后保持毛发的顺滑且耐汗性优异、抑制染色毛发褪色的染发用染料及其染发用组合物,所述化合物由下述通式(1)表示,化1：(X)(Z) (1),式中,X表示至少含有一个可具有取代基的碳原子数为0～20的氨基酸的碱性染料,Z表示含有氨基酸的非显色阴离子。(The present invention provides a hair dye and a hair dye composition, which have excellent hair dyeing ability, good water solubility and foamability, keep hair smooth during cleaning and after drying, have excellent perspiration resistance, and inhibit fading of dyed hair, wherein the compound is represented by the following general formula (1) formula 1: (X) (Z) (1), wherein X represents a basic dye containing at least one amino acid having 0-20 carbon atoms which may have a substituent, and Z represents a non-color-developing anion containing the amino acid.)

1. A compound represented by the following general formula (1),

1, preparation:

(X)(Z) (1)，

wherein X represents a basic dye containing at least one amino acid having 0 to 20 carbon atoms which may have a substituent,

z represents a non-chromogenic anion containing an amino acid.

2. The compound of claim 1, wherein,

in the general formula (1), X is a basic dye represented by the following general formula (2),

and (3) conversion 2:

in the formula, R¹And R²Each independently represent

An amino group having 0 to 20 carbon atoms which may have a substituent,

A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,

An optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or

A heterocyclic group having 2 to 30 carbon atoms which may have a substituent.

3. The compound of claim 1, wherein,

in the general formula (1), X is a basic dye represented by the following general formula (3),

and (3) conversion:

in the formula, R³～R¹⁸Each independently represents-H, halogen atom, -NO₂、-NO、-CN、-OH、

An amino group having 0 to 20 carbon atoms which may have a substituent,

A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,

A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,

A cycloalkyl group having 3 to 20 carbon atoms which may have a substituent,

A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent,

A cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent,

An acyl group having 1 to 20 carbon atoms which may have a substituent,

An optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or

A heterocyclic group having 2 to 30 carbon atoms which may have a substituent,

R³～R¹⁸can be bonded to each other between adjacent groups to form a ring.

4. The compound of claim 1, wherein,

in the general formula (1), X is a basic dye represented by the following general formula (4),

and (4) conversion:

in the formula, R¹⁹～R²⁷Each independently represents-H, halogen atom, -NO₂、-NO、-CN、-OH、

An amino group having 0 to 20 carbon atoms which may have a substituent,

A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,

A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,

A cycloalkyl group having 3 to 20 carbon atoms which may have a substituent,

A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent,

A cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent,

An acyl group having 1 to 20 carbon atoms which may have a substituent,

An optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or

A heterocyclic group having 2 to 30 carbon atoms which may have a substituent,

R¹⁹～R²³and R²⁴～R²⁷Can be bonded to each other between adjacent groups to form a ring.

5. The compound of claim 1, wherein,

in the general formula (1), X is a basic dye represented by the following general formula (5),

and (5) conversion:

in the formula, R²⁸～R³⁰Each independently represent

An amino group having 0 to 20 carbon atoms which may have a substituent,

A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,

A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,

A cycloalkyl group having 1 to 20 carbon atoms which may have a substituent,

A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent,

A cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent,

An acyl group having 1 to 20 carbon atoms which may have a substituent,

An optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or

A heterocyclic group having 2 to 30 carbon atoms which may have a substituent,

R²⁹and R³⁰Can bond to each other to form a ring.

6. The compound according to any one of claims 1 to 5, wherein,

in the general formula (1), the amino acid-containing non-coloring anion represented by Z is an amino acid-based anionic surfactant.

7. A dye for hair dyeing comprising the compound according to any one of claims 1 to 6.

8. A hair coloring composition comprising:

a dye for hair dyeing according to claim 7;

at least one auxiliary selected from the group consisting of wetting agents, swelling agents, penetrating agents, solvents, pH adjusting agents, surfactants, fragrances, and thickeners; and

and (3) water.

Technical Field

The present invention relates to a compound containing a basic dye and an amino acid, a dye for hair dyeing, and a composition for hair dyeing. More particularly, the present invention relates to a hair dye and a hair dye composition which have excellent hair dyeing ability, good water solubility and foamability, excellent perspiration resistance and can effectively suppress fading of dyed hair while keeping the hair smooth during and after washing and drying.

Background

In recent years, in a wide range of age groups, people who enjoy various hair colors by dyeing black hair and white hair are increasing, and many hair dyes such as a coloring agent (sometimes referred to as "hair dye"), a hair repair essence, a hair color care agent, and a color hair conditioner are sold as a hair dye. In hair dyeing treatment, an oxidation hair dye (permanent hair dye) using an oxidation dye having high dyeing ability and good coloring is mainly used, but there is a problem that skin irritation such as hair damage and allergy is easily caused. Therefore, hair dyes using a highly safe basic dye have been proposed instead of the oxidation dye (patent documents 1 to 5).

The semi-permanent hair dyes (hair color conditioners and color conditioners) using the basic dyes have a problem that dyeing is discolored due to the influence of daily hair washing, sun exposure, and the like, and it is necessary to repeatedly dye hair many times in order to maintain dyeing. Since repeated hair dyeing causes great damage to the hair, the hair may be more likely to fade, and development of a basic dye having a fading-inhibiting effect has been an important issue.

Disclosure of Invention

The invention provides a dye for hair dyeing and a composition for hair dyeing, which have excellent hair dyeing ability, good water solubility and foamability, smooth property during cleaning and after drying, excellent sweat resistance and inhibition of fading of dyed hair.

As a result of intensive studies to solve the above problems, the present invention is mainly as follows.

1. A compound represented by the following general formula (1),

1, preparation:

(X)(Z) (1)，

wherein X represents a basic dye containing at least one amino acid having 0 to 20 carbon atoms which may have a substituent, and Z represents a non-coloring anion containing the amino acid.

2. In the compound, in the general formula (1), X is a basic dye represented by the following general formula (2),

and (3) conversion 2:

in the formula, R¹And R²Each independently represent

An amino group having 0 to 20 carbon atoms which may have a substituent,

A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,

An optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or

A heterocyclic group having 2 to 30 carbon atoms which may have a substituent.

3. In the compound, in the general formula (1), X is a basic dye represented by the following general formula (3),

and (3) conversion:

in the formula, R³～R¹⁸Each independently represents-H, halogen atom, -NO₂a-NO, -CN, -OH, an amino group having 0 to 20 carbon atoms which may have a substituent,

A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,

A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,

A cycloalkyl group having 3 to 20 carbon atoms which may have a substituent,

A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent,

A cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent,

An acyl group having 0 to 20 carbon atoms which may have a substituent,

An optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or

A heterocyclic group having 2 to 30 carbon atoms which may have a substituent,

R³～R¹⁸can be bonded to each other between adjacent groups to form a ring.

4. In the compound, in the general formula (1), X is a basic dye represented by the following general formula (4),

and (4) conversion:

in the formula, R¹⁹～R²⁷Each independently represents-H, halogen atom, -NO₂a-NO, -CN, -OH, an amino group having 0 to 20 carbon atoms which may have a substituent,

A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,

A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,

A cycloalkyl group having 3 to 20 carbon atoms which may have a substituent,

A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent,

A cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent,

An acyl group having 1 to 20 carbon atoms which may have a substituent,

An optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or

A heterocyclic group having 2 to 30 carbon atoms which may have a substituent,

R¹⁹～R²³and R²⁴～R²⁷Can be bonded to each other between adjacent groups to form a ring.

5. In the compound, in the general formula (1), X is a basic dye represented by the following general formula (5),

and (5) conversion:

in the formula, R²⁸～R³⁰Each independently represents an amino group having 0 to 20 carbon atoms which may have a substituent,

A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,

A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,

A cycloalkyl group having 1 to 20 carbon atoms which may have a substituent,

A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent,

A cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent,

An acyl group having 1 to 20 carbon atoms which may have a substituent,

An optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or

A heterocyclic group having 2 to 30 carbon atoms which may have a substituent,

R²⁹and R³⁰Can bond to each other to form a ring.

6. In the compound, in the general formula (1), the non-color-developing anion containing an amino acid represented by Z is an amino acid-based anionic surfactant.

7. A dye for hair dyeing comprising the compound.

8. A hair coloring composition comprising: the dye for hair dyeing; at least one auxiliary selected from the group consisting of wetting agents, swelling agents, penetrating agents, solvents, pH adjusting agents, surfactants, fragrances, and thickeners; and water.

The compound and the dye for hair dyeing of the present invention can provide a composition for hair dyeing which is excellent in hair dyeing ability, good in water solubility and foamability, free from hair drying during and after washing, free from hair fluffiness, capable of keeping smooth and excellent in perspiration resistance, and can effectively suppress fading of dyed hair.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention. First, the compound represented by the general formula (1) is specifically described, but the present invention is not limited thereto.

In the general formula (1), "basic dye" in "basic dye containing at least one amino group having 0 to 20 carbon atoms which may have a substituent" represented by "X" is also represented by a cationic dye, and the basic dye represents a dye composed of a compound having an onium group representing basicity (cationic property) in a molecular structure. As an example of the onium group contained in the dye molecule represented by "X", an ammonium group (-NH-) can be mentioned₃ ⁺) Phosphorus radical (-PH)₃ ⁺) Oxygen onium group (-OH)₂ ⁺) Thio (-SH), thio (-SH)₂ ⁺) Imino (═ NH)₂ ⁺) Nitrile group (-C [ identical to ] NH)⁺) And the like, typically those having the quaternary ammonium groups described below. The moiety "-H" in these groups may be substituted by a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent orAromatic hydrocarbon groups and the like, and these groups may contain one or more groups in one dye molecule. Further, these basic dyes "X" are preferably water-soluble dyes.

In the general formula (1), the "amino group" in the "basic dye containing an amino group having 0 to 20 carbon atoms which may have at least one substituent" represented by "X" includes a quaternary ammonium group (-N)⁺RR 'R', R, R 'and R' are H or an optional substituent), "- (N)⁺N or⁺RR '"(R, R' is H or any substituent), unsubstituted amino (-NH)₂) A mono-substituted amino group (-NHR, R is an optional substituent) or a di-substituted amino group (-NHRR ', R and R' are optional substituents). However, it is preferably X sulfonic acid group (-SO)₃H) Carboxyl group (-COOH), phosphoric acid group (-O-PO (OH)₂) Hydroxamic acid (-CO-NH-OH), phosphonic acid (-PO (OH))₂) Boronic acid group (-O-B) (OH)₂) Phosphinic acid group (-O-POH)₂) Silanol (-SiH)₂-OH or-Si (OH)₃) Etc. which do not contain an acidic group.

In the general formula (1), "Z" represents "a non-coloring anion containing an amino acid". In the general formula (1), "Z" is a counter ion of the aforementioned "X", and is capable of forming a compound (complex) represented by the general formula (1). In the present invention, "non-chromogenic anion containing an amino acid" means a compound that contains an "amino acid" or an "amino acid" structure and is capable of becoming an anion. In general, the amino acid is a compound having an amino group (-NHRR ', R and R' represent H or any group which may be the same or different) and a carboxyl group (-COOH, -COO)^-) Specific examples of the amino acid include α -amino acids mainly containing glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, cystine, methionine, aspartic acid, glutamic acid, asparagine, glutamine, lysine, arginine, phenylalanine, tyrosine, tryptophan, and histidine, and in the present invention, "a non-color-developing anion containing an amino acid" may contain these amino acids in the molecular structure, and therefore, may have a structure in which an amino group or the like in the amino acid is substituted.

In "Z" in the general formula (1), the amino group and the carboxyl group may be one or more. When "non-color-developing anion containing amino acid" represented by "Z" is in "anion" state, "Z" is an anion forming a complex with cation "X". Therefore, it is preferable that the valency of "X" and the valency of "Z" are the same, more preferably, 1 or 2 valencies, respectively, and particularly preferably, 1 valency, respectively.

In "X" and "Z" represented by the general formula (1), the "X" and "Z" may be one kind or a mixture of two or more kinds, respectively, in order to make the general formula (1) neutral as a whole, but preferably, the kind of X is one kind, and also preferably, the kind of "Z" is one kind.

In the general formula (1), "X" may be a commercially available basic dye. Further, in the general formula (1), "X" is preferably a compound represented by one of the general formulae (2) to (5).

In the general formula (1), R is contained in "X" or represented by¹～R³⁰The "amino group having 0 to 20 carbon atoms which may have a substituent" may include-NH₂A mono-substituted amino group such as an ethylamino group, an acetylamino group, or a phenylamino group; and disubstituted amino groups such as diethylamino, diphenylamino, and acetylaminol. In addition, the quaternary amino group which may have a substituent such as a trialkylamino (or trialkylamino) group, a triethylamino (or triethylamino) group or a trialkylamino (or trialkylamino) group, a triphenylamino (or trimethylamino) group, and the like, having a group bonded to these amino groups, is also included in the "amino group having 0 to 20 carbon atoms which may have a substituent", and these substituents may be the same or different from each other.

In the general formula (1), as represented by R¹～R³⁰The "linear or branched alkenyl group having 2 to 20 carbon atoms" in the "linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent(s)" includes, specifically, a vinyl group, an allyl group, an isopropenyl group, a 2-butenyl group, a 1-hexenyl group, or a linear or branched group in which a plurality of these alkenyl groups are bonded.

In the general formula (1) above,as a group consisting of R¹～R³⁰The "aromatic hydrocarbon group having 6 to 30 carbon atoms" in the "aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent" includes, specifically, phenyl, biphenyl, triphenyl, tetraphenyl, styryl, naphthyl, anthryl, acenaphthenyl, phenanthryl, fluorenyl, indenyl, pyrenyl, triphenylenyl and the like, and an acyl group and an amino group may be inserted. The term "aromatic hydrocarbon group" as used herein means an aromatic hydrocarbon group or a condensed polycyclic aromatic group.

In the general formula (1), as represented by R¹～R³⁰The "heterocyclic group having 2 to 30 carbon atoms" in the "heterocyclic group having 2 to 30 carbon atoms which may have a substituent" includes, specifically, triazinyl, pyridyl, pyrimidinyl, imidazolyl, furyl, pyrrolyl, thienyl, quinolyl, isoquinolyl, benzofuryl, benzothienyl, indolyl, carbazolyl, carbolinyl, pyridoindolyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, quinoxalyl, benzimidazolyl, pyrazolyl, dibenzofuryl, dibenzothienyl, naphthyridinyl, phenanthrolinyl, acridinyl, hydantoin and the like, and may be bonded through an acyl group and an amino group.

In the general formulae (3) and (4), as represented by R³～R²⁷Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. In the present invention, the "halogen atom" is preferably a fluorine atom or a chlorine atom.

In the general formulae (3) to (5), R is represented by³～R³⁰The "linear or branched alkyl group having 1 to 20 carbon atoms" in the "linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent(s)" may specifically include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and the like; a branched alkyl group such as an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isooctyl group, and a tert-octyl group.

In the general formulae (3) to (5), R is represented by³～R³⁰The "carbon atom which may have a substituent(s)" representedThe "cycloalkyl group having 3 to 20 carbon atoms" in the "cycloalkyl groups having 3 to 20 carbon atoms" includes, specifically, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl and the like.

In the general formulae (3) to (5), R is represented by³～R³⁰The "linear or branched alkoxy group having 1 to 20 carbon atoms" in the "linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent(s)" includes, specifically, linear alkoxy groups such as methoxy, ethoxy, propoxy, n-butoxy, n-pentoxy, n-hexoxy, heptoxy, octoxy, nonoxy, and decyloxy; a branched alkoxy group such as an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an isooctyloxy group, and a tert-octyloxy group.

In the general formulae (3) to (5), R is represented by³～R³⁰The "cycloalkoxy group having 3 to 20 carbon atoms" in the "cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent" includes, specifically, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy and the like.

In the general formulae (3) to (5), R is represented by³～R³⁰The "acyl group having 1 to 20 carbon atoms" in the "acyl group having 1 to 20 carbon atoms which may have a substituent" includes, specifically, formyl group, acetyl group, propionyl group, acryloyl group, benzoyl group and the like.

The "substituent" in the "amino group having 0 to 20 carbon atoms which may have a substituent" in X of the general formula (1) or R in the general formulae (2) to (5)¹～R³⁰Of the representation

An amino group having 0 to 20 carbon atoms which may have a substituent,

"optionally substituted straight-chain or branched alkenyl group having 2 to 20 carbon atoms

"optionally substituted straight-chain or branched alkyl group having 1 to 20 carbon atoms

A cycloalkyl group having 3 to 20 carbon atoms which may have a substituent,

"optionally substituted straight-chain or branched alkoxy group having 1 to 20 carbon atoms

A cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent,

An optionally substituted acyl group having 1 to 20 carbon atoms,

An "optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms" or

The "substituent" of the "heterocyclic group having 5 to 30 carbon atoms which may have a substituent",

specific examples thereof include nitro group (-NO2), nitroso group (-NO), cyano group (-CN), and hydroxyl group (-OH); halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom;

an unsubstituted amino group; a mono-or di-substituted amino group having a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, such as a methylamino group, dimethylamino group, diethylamino group, ethylmethylamino group, methylpropylamino group, di-tert-butylamino group, or diphenylamino group;

sulfonamide (-O)₂-NRR ') (where "-NRR'" in the group is unsubstituted amino; a mono-or di-substituted amino group having a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, such as a methylamino group, dimethylamino group, diethylamino group, ethylmethylamino group, methylpropylamino group, di-t-butylamino group, or diphenylamino group);

a linear or branched alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an n-hexyl group, an isohexyl group, a heptyl group, an n-octyl group, a tert-octyl group, an isooctyl group, a nonyl group, a decyl group, or the like;

cycloalkyl groups having 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, and the like;

a linear or branched alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a tert-butoxy group, a n-pentyloxy group, or a n-hexyloxy group;

a cycloalkoxy group having 3 to 20 carbon atoms such as a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, etc.; a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentylene group, a 1-hexenyl group, an isopropenyl group, an isobutenyl group, or a linear or branched alkenyl group having 2 to 20 carbon atoms to which a plurality of these alkenyl groups are bonded;

acyl groups having 1 to 20 carbon atoms such as formyl group, acetyl group, propionyl group, acryloyl group, and benzoyl group; an aromatic hydrocarbon group having 6 to 30 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a triphenylene group, an indenyl group, a fluorenyl group, a styryl group, or the like;

a heterocyclic group having 2 to 30 carbon atoms such as a pyridyl group, a pyrimidyl group, a triazinyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, a pyrazinyl group, a pyridazinyl group, a piperidyl group, a piperazinyl group, a quinolyl group, an isoquinolyl group, a naphthyridinyl group, an indolyl group, a benzimidazolyl group, a carbazolyl group, a carbolinyl group, a pyridoindolyl group, an acridinyl group, a phenanthrolinyl group, a phenanthridinyl group, a hydantoinyl group, a furyl group, a benzofuryl group, a dibenzofuryl group, a pyranyl group, a coumaroyl group, an isobenzofuryl group, a xanthenyl group, an xanthenyl group, a thienyl group, a thiopyranyl group, a benzothienyl group, a dibenzothienyl group, a thioxanthyl group;

and a cyclic alkylene group having 3 to 30 carbon atoms such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentylene group, a cyclohexenyl group, a cycloheptenyl group, (1, 3-or 1, 4-) cyclohexadienyl group, and 1, 5-cyclooctadienyl group. These "substituents" may include only one or a plurality of substituents, and when a plurality of substituents are included, they may be the same or different. These "substituents" may have the substituents exemplified above, and further, these substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

In the general formula (2), as R¹Or R²Preferably, it is

An optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms or

A heterocyclic group having 2 to 30 carbon atoms which may have a substituent.

In the general formula (3), as R³～R¹⁸Preferably, the alkyl group is-H, a halogen atom, an optionally substituted amino group having 0 to 20 carbon atoms, or an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms.

In the general formula (3), R³～R¹⁸May be bonded to each other between adjacent groups to form a ring, and when forming a ring, preferably, R³And R⁴、R⁵And R⁶、R⁷～R¹¹、R¹²～R¹⁶、R¹⁷And R¹⁸Bonded to each other to form a ring, which is preferably a five-membered ring or a six-membered ring.

In the general formula (4), as R³～R¹⁸preferably-H,

An amino group having 0 to 20 carbon atoms which may have a substituent or

An optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms.

In the general formula (4), R¹⁹～R²⁷It is also possible that adjacent groups are bonded to each other to form a ring, and when forming a ring, preferably R²⁰And R²¹、R²²And R²³、R²⁴～R²⁷Bonded to each other to form a ring, which is preferably a five-membered ring or a six-membered ring.

In the general formula (5), as R²⁸～R³⁰Preferably, it is

A linear or branched cycloalkyl group having 1 to 20 carbon atoms which may have a substituent,

An optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms or

A heterocyclic group having 2 to 30 carbon atoms which may have a substituent.

In the general formula (5), R²⁹And R³⁰The ring may be bonded to each other to form a ring, and when the ring is formed, a five-membered ring or a six-membered ring is preferable.

In the general formula (1), "non-color-developing anion containing amino acid" represented by "Z" is preferably in the molecular structureThe surfactant is preferably an amino acid anionic surfactant because it contains an amino acid. Specific examples thereof include N-acyl-N-alkylglycinates (N-C such as N-cocoyl-N-methylglycinate)₈～C₂₂alkanoyl-N-alkanoyl glycinates) and,

N-C of N-acyl-N-alkylglutamate (N-cocoyl-N-methylglutamate or the like)₈～C₂₂alkanoyl-N-alkylglutamates) and,

N-C of N-acyl-N-alkyl alaninate (N-cocoyl-N-methyl alaninate, N-lauroyl-N-methyl- β -alaninate, etc.)₈～C₂₂alkanoyl-N-alkyl-alaninates) and,

N-acyl-N-alkyl aspartate (N-C of N-cocoyl-N-methyl aspartate and the like)₈～C₂₂alkanoyl-N-alkylaspartate) and,

N-acyl glycinate (N-C of N-cocoyl glycinate and the like)₈～C₂₂Alkanoyl glycinate) salts,

N-acyl glutamates (N-C of sodium lauroyl glutamate, N-cocoyl glutamate, etc.)₈～C₂₂Alkanoyl glutamate)

N-Acylacrylates (N-C of N-cocoylacrylaluminate and the like)₈～C₂₂Alkanoyl alaninates) and (C) alkanoyl alaninates,

N-ACYL ASPARTATE (N-C OF N-lauroyl ASPARTATE AND the like)₈～C₂₂Alkanoyl aspartate) salts,

N-acyl sarcosinates (N-C of N-cocoyl sarcosinate and the like)₈～C₂₂Alkanoyl sarcosinates) and the like. Examples of such salts include alkali metal salts of lithium, sodium, potassium, cesium, and the like; trialkylamine salts such as triethanolamine; and a salt amino acid salt of arginine and the like.

In the general formula (1), the amino acid anionic surfactant represented by "Z" is preferably N-acyl-N-alkyl glutamate, N-acyl-N-alkyl alanate such as N-lauroyl-N-methyl- β -alanate, N-acyl glutamate such as sodium lauroyl glutamate, or N-acyl alanate.

Specific examples of preferred compounds of the present invention represented by the general formula (1) are shown below, but the present invention is not limited to these compounds. In the following structural formulae, some hydrogen atoms are omitted, and even if stereoisomers exist, a planar structural formula is described.

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The compound represented by the general formula (1) can be synthesized, for example, by using a basic dye represented by (X) and a salt such as a sodium salt of an amino acid represented by (Z) in the general formula (1) as starting materials. Specifically, the basic dye is dissolved in water, an organic solvent, or the like, and a sodium salt of an amino acid or the like is added thereto under appropriate temperature conditions to carry out a reaction, and the obtained solid is purified under appropriate solvent, temperature, or the like conditions, whereby the compound of the dye for hair dyeing of the present invention (dye having an amino acid as a counter ion) can be obtained.

The compound of the present invention represented by the general formula (1) can be purified by column chromatography; adsorption purification by silica gel, activated carbon, activated clay, or the like; purification is carried out by a known method such as recrystallization from a solvent or crystallization. In addition, identification of compounds and analysis of physical properties can be performed by ultraviolet-visible absorption spectroscopy (UV-Vis), thermogravimetric analysis-differential thermal analysis (TG-DTA), Gas Chromatography (GC), nuclear magnetic resonance analysis (NMR), and the like.

The compounds according to the invention are preferably used in the form of so-called hair dyes. The compound represented by the general formula (1) is preferably used as a dye for hair dyeing, and can be used as a dye for hair dyeing containing the compound represented by the general formula (1) by mixing other dyes with components such as additives and auxiliaries. An embodiment of the hair dye suitable for the present invention is a hair dye composition comprising a hair dye represented by the general formula (1) and at least one auxiliary selected from the group consisting of a wetting agent, a swelling agent, a penetrating agent, a solvent, a pH adjuster, a surfactant, a perfume and a thickener, and water.

Examples of the humectant include glycerin, propylene glycol, sorbitol, 1, 3-butylene glycol, and polyethylene glycols. When the wetting agent is used, the content thereof is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, based on the total amount of the hair dyeing composition.

Examples of the swelling agent include an alkaline aqueous solution containing ammonia (ammonium hydroxide) or Monoethanolamine (MEA). When the swelling agent is used, the content thereof is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, based on the total amount of the hair dyeing composition.

Examples of the penetrating agent and the solvent include monovalent alcohols having an alkyl group having 1 to 6 carbon atoms such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, butoxyethanol, polyvalent alcohols having 3 to 8 carbon atoms such as propylene glycol, butylene glycol, pentanediol, hexanediol, hexanetriol, heptanediol, heptatriol, octanediol, octatriol, isoprene glycol, propylene glycol, glycerin, diethylene glycol monoethyl ether, and ethers thereof, N-alkylpyrrolidones such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone which are liquid at room temperature (25 ℃ ± 2 ℃), alkylene carbonates such as ethylene carbonate and propylene carbonate (lower alkylene carbonates), benzyloxyethoxyethanol, benzyl alcohol, benzyloxyethanol, cinnamyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, 2-benzylalcohol, and β -benzyl alcohol, and the total amount of the penetrating agent and the penetrating agent is preferably 20 to 40% by weight, more preferably, the total amount of the penetrating agent and the penetrating agent are preferably 20 to 40% by weight of the N-alkyl alcohol.

Examples of the pH adjuster include acids such as phosphoric acid, sodium lactate-lactic acid, and sodium citrate-citric acid; ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, and the like. When the pH adjuster is used, the content thereof is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the total amount of the hair dyeing composition.

As the surfactant, a cationic surfactant or a nonionic surfactant is mainly used. Specific examples thereof include, but are not limited to, silicon compounds such as polysiloxanes, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyglycerol fatty acid esters, sugar alcohol ethers such as fatty amines and quaternary ammonium salts thereof (e.g., trimethyl stearyl ammonium chloride), sorbitol alkyl ethers, and polyoxyethylene sorbitan fatty acid esters. Among them, polyoxyethylene sorbitan fatty acid esters are preferable. By using the polyoxyethylene sorbitan fatty acid ester, the effect of reducing skin contamination (the ability to prevent skin contamination) is further improved.

The polyoxyethylene sorbitan fatty acid ester is preferably at least one selected from the group consisting of polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate.

When the surfactant is used, the content thereof is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, based on the total amount of the hair-dyeing composition, from the viewpoint of reducing skin contamination.

Examples of the perfume include vanillin, synthetic alcohol, piperonal, coumarin, 2-methyl-3- (3, 4-methylenedioxy-phenyl) -propionaldehyde, 4- (4-hydroxyphenyl) -2-butanone, benzaldehyde, anisyl alcohol, 3, 4-dimethoxybenzaldehyde, piperonyl acetate, phenylacetaldehyde dimethyl acetal, phenoxyethanol, phenylacetaldehyde glycerol acetal, furan alcohol, sugar lactone, maltol, ethyl diglycol, benzyl acetate, linalool, camphor, terpineol, citronellol, geraniol, 2, 6-nonadiene, methyl octyl carbonate, 3, 7-dimethyl-2, 6-octadienal, nonanal, and the like. When the perfume is used, the content thereof is preferably 0.00001 to 2 wt% based on the total amount of the hair dyeing composition.

Examples of the thickener include thickeners derived from guar gum and derivatives thereof, hydroxyethyl cellulose, xanthan gum, collagen, gelatin, sodium carboxymethyl cellulose, carboxyvinyl polymer (registered trademark, Carbopol), sodium alginate, gum arabic (Gumarabic), cellulose derivatives, and polymer (ethylene oxide). These thickeners have the effect of making the hair dye composition highly viscous and forming a gel in a form that is easy to handle. When the thickener is used, the content thereof is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, based on the total amount of the hair dyeing composition.

The water used in the hair dyeing composition of the present invention is not particularly limited, and ion-exchanged water, purified water, and the like can be used.

The dye for hair dyeing of the present invention containing the compound represented by the general formula (1) is excellent in dyeing ability and robustness as a dye for hair dyeing itself, and can dye hair uniformly. Further, the hair dye containing the compound represented by the general formula (1) can be combined with other hair dyes to adjust the color to yellow, brown or black.

For example, examples of the combination basic dye include a direct dye having an amino group or a substituted amino group in the molecule, specifically, red No. 213 (c.i. basic violet 10, rhodamine B), red No. 214 (c.i. basic violet, rhodamine B acetate); basic blue (c.i. basic blue) 7, 9, 26, 75, 99; basic red (c.i. basic red) 2, 22, 51, 76; basic yellow (c.i. basic yellow) 57, 87; basic orange (c.i. basic orange) 31; alkaline brown (c.i. basic brown) 16, 17; basic violet (c.i. basic violet) 2, 3, 4, 14, etc. Further, "c.i." means a color index.

Examples of the combined HC dye include direct dyes having a nitro group in the molecule, and specifically, c.i. HC blue 2, 15; hc red 1,3, 7, 11, 13; hc yellow 2, 4, 5, 9, 11, 13; hc orange 1, 2; hc violet 1, 2; 4-hydroxypropylamino-3-nitrophenol, and the like.

In an embodiment of the hair dyeing composition of the present invention, the hair dyeing dye containing the compound represented by the general formula (1) is preferably 0.001 to 5% by weight based on the total amount of the hair dyeing composition, and the remainder is preferably a material containing at least one auxiliary selected from the group consisting of a wetting agent, a swelling agent, a penetrating agent, a solvent, a pH adjuster, a surfactant, a perfume, and a thickener, and water. If the content of the dye for hair dyeing is less than 0.001 wt%, it is difficult to obtain the effect of maintaining the color tone and the leveling property, and even if the amount exceeds 5 wt%, the effect of improving the dyeing or the like is reduced. The content of the dye for hair dyeing is preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight, based on the total amount of the composition for hair dyeing.

The pH value of the hair dyeing composition is preferably 4 to 9, and more preferably 5 to 7. The pH of the hair dye composition can be adjusted by a known method, but is preferably adjusted by using a pH adjuster such as citric acid monohydrate or trisodium citrate dihydrate. That is, for example, when a hair dye composition having a pH of 6 is prepared, an aqueous solution having a pH of 6 is prepared in advance by dissolving citric acid monohydrate and trisodium citrate dihydrate in water, and then a hair dye containing the compound represented by the general formula (1) and other additives (auxiliaries and the like) are added to the aqueous solution as needed, whereby a hair dye composition having a pH of 6 can be obtained.

The hair dye composition of the present invention may contain known cosmetic ingredients within a range not to impair the effects of the present invention. Examples of the cosmetic ingredients that can be added include higher alcohols, vaseline, polyvalent alcohols, esters, preservatives, bactericides, silicone derivatives, and water-soluble polymers.

Specifically, for example, the hair dyeing method using the hair dyeing composition of the present invention can be carried out by contacting a hair dyeing subject such as human hair or livestock hair with the hair dyeing composition of the present invention. The hair dyeing temperature is preferably 5 to 60 ℃ and, in view of being carried out near the scalp, more preferably 15 to 45 ℃. The hair dyeing time is preferably 5 to 60 minutes, more preferably 10 to 30 minutes.

After dyeing, post-treatments such as rinsing and drying are usually performed. The washing may be carried out until the color of the hair dye is completely insoluble, and for example, the hair dye is washed at 5 to 40 ℃ under running water of 5 to 15L/min every 0.5 to 2 minutes. The drying after the washing may be natural drying (usually at 5 to 40 ℃ for 10 minutes to 10 hours), or a hot air dryer (usually at 40 to 60 ℃ for 10 minutes to 10 hours) may be used as necessary.

After the washing, soaping may be performed. The soaping is performed, for example, by washing the surface of the substrate with a proper amount of soaping liquid (a mixed solution of shampoo and warm water) at a temperature of usually 15 to 50 ℃ for 1 to 10 minutes until the soaping liquid is completely removed.

As described above, the dye for hair dyeing and the composition for hair dyeing containing the compound according to the present invention can exhibit an excellent dyeing effect even in any one of a coloring agent, a hair restorer essence, and a hair color care agent. In particular, the composition can exert an effect on a color-developing care agent having a weak dyeing ability.