JP2002047151A - Hairdye composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hairdye composition having high hair-dyeing and perfume- retention performances, and capable of providing gloss and smooth feeling to the hair. SOLUTION: This hairdye composition contains (A) a perfume compound having >1.5 Clog P value, (B) a silicone compound and (C) a cationic direct dye represented by formulas (1), (2), (3) or (4) (wherein, R1 to R4, and R9 to R12 are each a lower alkyl group or the like; Z, Z1 and Z2 are each a nitrogen atom or a methine group; Q/ Q', Q" and Q''' are each a cationic heterocyclic group; T and L are each a substituted phenyl group or the like; and X- is an anion).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hair dye composition having both high hair dyeing performance and residual scent.

[0002]

BACKGROUND OF THE INVENTION In the field of hair dyes, direct dyes are used in semi-permanent and permanent hair dyes. It is used as a main colorant in semi-permanent hair dyes and as an auxiliary colorant in permanent hair dyes to change the color tone due to oxidation dyes. And as a hair dyeing effect,
What is desired is a more intense coloring that evenly dyes the hair and that is resistant to light, sweat, shampoo washing, etc., to which the hair is exposed after dyeing.

[0003] Fragrance is also a very important factor for personal care products, and plays a role in imparting olfactory appeal to the product and increasing its value. In addition, soaps, shampoos, and the like that tend to leave a fragrance on the skin after bathing and the hair after shampooing tend to be preferred. Therefore, products that impart fragrance to skin and hair and have long-lasting properties are desired, and research is being continued to enhance such effects.

In the case of semi-permanent dyeing, hair dyes are applied to hair, and then the hair is optionally rinsed, and optionally washed with shampoo.
Then, a method of rinsing and drying the shampoo has been taken, but in any case, imparting a scent to the hair,
Moreover, the importance of having long-term sustainability is increasing. Further, in the case of performing permanent dyeing, there is a problem that an unpleasant odor such as an altered odor of protein remains after hair dyeing because an oxidation reaction under alkaline conditions is usually performed in hair. Therefore, it is very important to mask such an unpleasant odor and to impart a pleasant fragrance to the hair and to have a long-lasting property.

[0005]

SUMMARY OF THE INVENTION However, in the field of hair dyes, it is necessary to achieve both high hair dyeing performance and imparting fragrance to hair and having long lasting properties. There are few studies. Examples of the hair dye having a high residual fragrance include, in claim 8 of PCT Publication No. WO9841185, (A) a surfactant and (B) an aromatic ring, a pyran ring or a furan ring, a carbonyl group, an ether bond, and a carboxyl group. A hair dye composition having a structure having a group or a non-aromatic unsaturated bond and containing 0.00025 to 1% by weight of a fragrance substance having a ClogP value of 1.5 or less is disclosed. However, WO9841158 discloses that ClogP
Perfume substances with a value of more than 1.5 do not give any indication of increasing the lingering scent, and thus the fragrance remaining on the hair is limited.

[0006] An object of the present invention is to provide a hair dye composition having both high hair dyeing performance and residual fragrance.

[0007]

SUMMARY OF THE INVENTION By combining a specific fragrance compound, a silicone compound and a specific cationic direct dye, the present inventors can dye hair intensely and uniformly, and furthermore, light, sweat and shampoo. It has a high hair dyeing performance that is resistant to washing, etc., and also gives the hair a glossy and smooth feel, and gives a pleasant scent to the hair, and has a large degree of freedom in selecting the fragrance tone you want to leave on the hair It has been found that a hair dye composition can be obtained that can mask unpleasant odors such as denatured odor of protein and can maintain the scent for a long time.

[0008] The present invention provides a hair dye composition containing the following components (A), (B) and (C). (A) a fragrance compound having a ClogP value of more than 1.5 (B) a silicone compound (C) a cationic direct dye represented by the following general formula (1), (2), (3) or (4)

[0009]

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Wherein Z represents a nitrogen atom or a methine group, and R ¹ and R ² independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyethyl group, a cyanoethyl group, an aminoethyl group or By showing a 4-aminophenyl group or bonding to a benzene ring in the formula, an alkyl group having 1 to 4 carbon atoms may be substituted together with an adjacent nitrogen atom and a carbon atom of the benzene ring. Forms a nitrogen-containing heterocyclic ring which may have a nitrogen atom or an oxygen atom as a hetero atom of R ³ and R ⁴ are independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms Represents an alkoxy group or an acetyloxy group having 1 to 4 carbon atoms, and Q represents the following Q _{1 to} Q ₁₃ :

[0011]

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(Wherein, R ⁵ represents an alkyl group having 1 to 4 carbon atoms or hydroxyethyl group, R ⁶ and R ⁷ independently represent a hydrogen atom or the same group as R ^5, and R ⁸ represents Carbon number 1
And represents 4 to 4 alkoxy groups. ) Represents a group selected from
X ^- represents an anion. However, when Z is a methine group, Q is Q ₁ or Q ₂ , and R ³ is a group other than an alkoxy group, R ¹ and R ² are not simultaneously hydrogen atoms. ]

[0013]

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Wherein R ⁹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁰ is a hydrogen atom or a 1 to 4 carbon atoms.
4 represents an alkyl group, a cyanoethyl group, an aminoethyl group or a 4-aminophenyl group, or R ⁹ and R ¹⁰ may be substituted by an alkyl group having 1 to 4 carbon atoms together with an adjacent nitrogen atom; Forming a nitrogen-containing heterocyclic ring which may have a nitrogen atom or an oxygen atom as a hetero atom other than the nitrogen atom, wherein R ¹¹ and R ¹² independently represent a hydrogen atom, a halogen atom, an alkyl having 1 to 4 carbon atoms; A group, an alkoxy group having 1 to 4 carbon atoms or a cyano group, and Q ′ represents the following Q ′ _{1 to} Q ′ ₅

[0015]

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(Wherein, R ¹³ represents an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ represents an amino group, a methylamino group, a dimethylamino group, or the same group as R ¹³ ). And X ^- represents an anion. ]

[0017]

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[Wherein Z ₁ and Z ₂ independently represent a nitrogen atom or a methine group, and T represents the following T ₁ and T ₂

[0019]

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(Wherein, R ¹⁵ is a hydrogen atom or a carbon atom 1)
An alkyl group having 1 to 4 carbon atoms may be substituted together with an adjacent nitrogen atom and a carbon atom of the benzene ring by showing an alkyl group of 4 to 4 or bonding to a benzene ring in the formula; To form a nitrogen-containing heterocyclic ring which may have a nitrogen atom or an oxygen atom as a hetero atom, R ¹⁶ represents a hydrogen atom, a halogen atom, an amino group or an alkoxy group having 1 to 4 carbon atoms, and R ¹⁷ represents A hydrogen atom or a halogen atom, and R ¹⁸ and R ^{19 each} independently represent a hydrogen atom or
4 represents an alkyl group, and m represents 0 or 1. However,
When R ¹⁶ is an amino group, m is 0, and Z ₁ and Z ₂ simultaneously represent a methine group. And Q '' represents the following Q ″ _{1 to} Q ″ ₈ when T is T ₁ , m is 0, and Z ₁ is a nitrogen atom; Then the following Q '' _{1 to} Q '' ₇ :

[0021]

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(Wherein, R ²⁰ represents an alkyl group having 1 to 4 carbon atoms, and R ²¹ represents a hydrogen atom or the same group as R ²⁰ ).
And X ^- represents an anion. However, when Q ″ is Q ″ ₇ , Z ₁ and Z ₂ are not simultaneously nitrogen atoms. ]

[0023]

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[Wherein Q ′ ″ is the following Q ′ ″ _{1 to} Q ′ ″ ₇ :

[0025]

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(Where R^{twenty two}Is alkyl having 1 to 4 carbon atoms
Group, phenyl group, halogenated phenyl group or methylphen
A nyl group;^{twenty three}Is an alkyl group having 1 to 4 carbon atoms or
A phenyl group;^{twenty four}Is a hydrogen atom, an alkyl having 1 to 4 carbon atoms
A kill group or a phenyl group is represented by R ^{twenty five}Is a group having 1 to 4 carbon atoms.
Represents a alkyl group or a phenyl group;^{twenty four}And R^{twenty five}But
The number of carbon atoms as substituents, together with the adjacent carbon atoms
An alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms
Or a benzene ring which may have a nitro group,²⁶
Is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms
Si group or O^-And R²⁷And R²⁸Is an independent hydrogen source
Atom, halogen atom, nitro group, alkyl having 1 to 4 carbon atoms
A group or an alkoxy group having 1 to 4 carbon atoms. However,
Q '' '₁, Q '' '_Five, Q '' '₆And Q '' '₇Then, R^{twenty four}Is hydrogen
Indicates an atom other than an atom, and Q '' '_ThreeThen, R^{twenty two}Represents an alkyl group
When R^{twenty four}Is an alkyl group having 1 to 4 carbon atoms or phenyl
Represents a group. ) Represents a group selected from the group consisting of the following L₁~
L_Four

[0027]

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(Where R²⁹Is a hydrogen atom, a hydroxy group
Or group NR³⁶R³⁷(R³⁶And R³⁷Is an independent hydrogen source
, An alkyl group having 1 to 4 carbon atoms, a hydroxyethyl group or
Represents a phenyl group),³⁰Is a hydrogen atom, a halogen atom
, Hydroxy group, nitro group, alkyl having 1 to 4 carbon atoms
Group, alkoxy group having 1 to 4 carbon atoms, group NR³⁸R³⁹(R³⁸
And R³⁹Is independently a hydrogen atom, an alkyl having 1 to 4 carbons
Group, hydroxyethyl group or phenyl group)
Represents an acetamino group, R³¹Is a hydrogen atom, a halogen atom,
An alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms
Represents a oxy group, or R³⁰And R³⁶There are jointly adjacent charcoal
Together with an elemental atom or R³⁰And R³¹Are jointly adjacent
Along with carbon atoms, nitrogen atoms and oxygen atoms
Or a 5- or 6-membered ring which may contain a sulfur atom,
³²And R³³Is independently a hydrogen atom, phenyl group or carbon number
Represents an alkyl group of 1 to 4;³⁴And R³⁵Is independently water
A hydrogen atom, an amino group, a phenyl group or an alkyl group having 1 to 4 carbon atoms
Represents a kill group. X) represents a group selected from^-Is ani
Indicates on and n is R²⁶Is O^-0 if it is
Otherwise, 1 is indicated. Where R²⁹Is NR³⁶R³⁷In
Q '' '_TwoR^{twenty two}~ R^{twenty five}At least one of the
Other than a kill group, Q '' '_FiveAnd Q '' '₇R²⁷And R ²⁸But
It does not become a hydrogen atom at the same time. ]

[0029]

DETAILED DESCRIPTION OF THE INVENTION The fragrance compound of component (A) has a ClogP value of more than 1.5, particularly preferably 3 or more. By using such a fragrance compound in combination with the silicone compound of the component (B) and the cationic direct dye of the component (C), the fragrance remaining on the hair can be significantly improved. Here, the fragrance compound is a compound having a fragrance, and refers to a compound blended in a compounded fragrance composition used for imparting a fragrance to a product. The ClogP value refers to a common logarithmic value of the 1-octanol / water partition coefficient P indicating the ratio between the equilibrium concentrations of the compound in 1-octanol and in water. This ClogP value is calculated using a fragment approach (A. Leo, Comp.
rehensive Medical Chemistry, Vol. 4; C. Hansch, P.
G. Sammens, JB Taylor and CA Ramden, Eds.,
p.295, Pergramon Press, 1990) and is defined by values calculated with the "CLOGP" program available from Daylight Chemical Information Systems.

The fragrance compounds having a ClogP value exceeding 1.5 include 3,7-dimethyloctane-3-ol (1.530), p-methoxyphenylbutanone (1.658), benzylacetone (1.739), and 3-ethoxy-4-hydroxy. Benzaldehyde (1.804), benzyl acetate (1.960), 1,8-p-menthadien-6-one (2.013), 2-phenylethyl acetate (2.12
9), 1,7,7-trimethylbicyclo [2.2.1] heptan-2-one (2.177), 1-octen-3-ol (2.235), γ-octalactone (2.243), 1-phenylethyl acetate ( 2.26
9), 2-methoxy-4-allylphenol (2.397), methyl 3-oxo-2-pentylcyclopentylacetate (2.419),
Methyl cinnamate (2.465), Allyl 2-pentyloxyglycolate (2.507), 3,7-Dimethyl-1,6-octadiene
-3-ol (2.549), 2-methoxy-4- (1-propenyl) phenol (2.577), 3,7-dimethyl-4,6-octadiene-3
-All (2.609), p-menthan-8-ol (2.629), 3-
Methyl-2- (2-cis-penten-1-yl) -2-cyclopentene-
1-one (2.642), 1,8-cineole (2.755), 2-acetonaphthone (2.755), 3,7-dimethyl-cis-2,6-octadien-1-ol (2.769), 3,7-dimethyl- trans-2,6-octadien-1-ol (2.769), methyl N-methylanthranilate (2.791), 4-methyl-2- (2-methyl-1-propenyl) tetrahydropyran (2.896), 2,6 -Dimethyl-2-heptanol (2.988), nonanal (2.995), 2,6-dimethyl-7-octen-2-ol (3.033), methyl octynecarboxylate (3.097), estragole (3.134), 3-methyl- 5-phenyl-1-pentanol (3.169), β-naphthyl methyl ether (3.235), 2-butyl-4,4,6-trimethyl-1,3-dioxane (3.244), 3,7-dimethyl-6- Octen-1-ol (3.253), anethole (3.314), ethyl tricyclo [5.2.1.0 ^2,6 ] decane-2-ylcarboxylate (3.3
70), 2-methyl-5-isopropylphenol (3.401),
3,7-dimethyl-1,6-octadien-3-yl acetate (3.49
5), 3,7-dimethyloctane-3-ol (3.517), isobornyl acetate (3.525), p-menten-8-yl acetate (3.57)
5), 1- (4-isopropylcyclohexyl) ethanol (3.642), 5- (2,6,6-trimethyl-2-cyclohexene-1-
Yl) -4-pentan-3-one (3.710), 3,7-dimethyl acetate
-2,6-Octadien-1-yl (3.715), 4-cyclohexyl-4-methyl-2-pentanone (3.769), 4- (2,2,6-trimethyl-1-cyclohexen-1-yl) -3 -Buten-2-one (3.7
70), 2,5,5-trimethyl-1,2,3,4,4α, 5,6,7-octahydro-2-naphthalenol (3.772), 2,6-dinitro-3,5-
Dimethyl-4-t-butylbenzene (3.782), δ-undecalactone (3.860), 2-methyl-4- (2,2,3-trimethyl-3-
Cyclopenten-1-yl) -2-buten-1-ol (3.90
2), α-santalol (3.906), allyl 3-cyclohexylpropionate (3.935), 1- (2-t-butylcyclohexyloxy) -2-butanol (3.969), 2-heptylcyclopentanone (3.999), 5- (2,6,6-trimethyl-2-cyclohexen-1-yl) -3-methyl-3-buten-2-one (4.01
9), phenylethyl benzoate (4.058), diphenylmethane (4.059), ot-butylcyclohexyl acetate (4.05
9), pt-butylcyclohexyl acetate (4.059), p-methyl-isopropylbenzene (4.068), 4- (2,2,5,6-tetramethyl-2-cyclohexen-1-yl) -3-butene-2 -One (4.229), diphenyl oxide (4.240), p-mentha-
1,8-diene (4.352), 2,2,5-trimethyl-5-pentylcyclopentanone (4.498), cedrol (4.530), patchouli alcohol (4.530), 7-acetyl-1,2,3,4, 5,6,7,
8-octahydro-1,1,6,7-tetramethylnaphthalene (4.6
50), bisabolol (4.660), 1- (2,6,6-trimethyl-1
-Cyclohexen-1-yl) -2-buten-1-one (4.710),
3,7,11-trimethyl-2,6,10-dodecatrien-12-ol (4.800), vetiveryl acetate (5.092), sedolyl methyl ether (5.106), 3α, 6,6,9α-tetramethyldodecahydro Naphtho [2,1-b] furan (5.266), 6-acetyl-1,
1,2,3,3,5-hexamethylindane (5.688), 1- (2,2,6-
Trimethylcyclohexyl) -3-hexanol (5.86
8), 4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydrocyclopentabenzopyran (6.062), α-sedrene (6.133), 7-cyclohexade Senolide (6.361), 3-methylcyclopentadecanone (6.415), 9-cyclopentadecene-1-one (6.530), hexadecanolide (6.84)
5), rabdenol (7.228), 3,7,11,15-tetramethyl
2-hexadecene-1-ol (8.283) and the like (numerical values in parentheses indicate ClogP values).

Two or more kinds of the fragrance compounds of the component (A) may be used in combination, and the content thereof is 60% by weight in the prepared fragrance composition.
(Hereinafter simply referred to as%), more preferably 70% or more, particularly preferably 80% or more. Further, the content of the compounded flavor composition is 0.01 to 2% in the hair dye composition, and more preferably 0.05 to 2%.
To 1.5%, particularly preferably 0.1 to 1%. ClogP value is
A fragrance compound of 1.5 or less does not show remarkable improvement in residual scent by combined use with other components, but since the residual scent is not inhibited, by appropriately combining with the fragrance compound of component (A), The degree of freedom of incense tone remaining on the hair can be expanded. However, from the viewpoint of residual odor, it is more preferable to use only a fragrance compound having a ClogP value of 1.5 or less.

The silicone compound (B) is an organopolysiloxane derivative such as dimethylpolysiloxane, methylphenylpolysiloxane, polyether-modified silicone, amino-modified silicone, or poly (N-acylalkyleneimine) -modified silicone. Can be mentioned.

The polyether-modified silicone used in the present invention includes an organopolysiloxane side chain and / or
Or as a terminal group, a group -C _a H _2a- (C ₂ H ₄ O) _b- (C ₃ H ₆ O) _c -R
⁴⁰ (R ⁴⁰ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group having 1 to 30 carbon atoms, a represents an integer of 0 to 4, b represents an integer of 0 to 50 , C is 0
Represents an integer of ５０50. However, b and c do not become 0 at the same time. ). As the alkyl group for R ⁴⁰ , a methyl group, an ethyl group, a propyl group,
A butyl group and the like are mentioned, and an acyl group is an acetyl group and the like.

The amino-modified silicone used in the present invention has an amino group or an ammonium group as a side chain and / or a terminal group of the organopolysiloxane via a divalent group which may contain a hetero atom. And those obtained by bonding. Examples of such a divalent group include a group —C _d H _2d —NH
_{- (CH 2) e - (} d is an integer of 2 to 4, e represents an integer of 2 to 4.) And the like. Specific examples of the side chain and / or end _{groups, - (CH 2) 3 -NH-} (CH 2) 2 -NH 2, -CH 2 CH (CH 3) CH 2 -NH- (CH 2) 2 -NH ₂ ,-(CH ₂ ) ₃ -O- (C ₂ H ₄ O) ₈ -CO-CH ₂ -N ⁺ (CH ₃ ) _2- (CH ₂ ) ₃ -NH-CO- (C
H ₂ ) ₁₂ -CH ₃ Cl- ^{and the} like.

As the poly (N-acylalkyleneimine) -modified silicone used in the present invention, the side chain and / or the terminal group of the organopolysiloxane is represented by the general formula: Examples include those obtained by bonding poly (N-acylalkyleneimine) composed of the repeating unit represented by (5). Equation (5):

[0036]

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Wherein R ⁴¹ is a hydrogen atom, having 1 to 2 carbon atoms.
2 represents an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group, and n represents 2 or 3. ]

As the poly (N-acylalkylenimine) -modified silicone, the weight ratio of the poly (N-acylalkylenimine) segment to the organopolysiloxane segment is 1/20 to 20/1, and the molecular weight is 5%.
It is preferably from 00 to 5,000,000. As a divalent group containing a hetero atom,

[0039]

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(Wherein, X ⁻ represents a counter ion of a quaternary ammonium salt). The terminal group of the repeating unit of the formula (5) is a residue of a polymerization initiator used for obtaining a poly (N-acylalkyleneimine) segment, and examples thereof include an alkyl group such as a methyl group and an ethyl group. . These poly (N-acylalkyleneimine) -modified silicones are known compounds.
No. 76824, JP-A-4-85334 and the like.

The silicone compound of the component (B) is "Internat
ional Cosmetic Ingredient Dictionary and Handbook
Eighth Edition "on pages 1707-1709. Specific examples include dimethicone, phenylmethicone, phenyltrimethicone, amodimethicone, dimethicone copolyol,
Amodimethicone / dimethicone copolyol, dimethicone copolyol butyl ether, polysilicone, silicone quaternium and the like.

Two or more types of the silicone compound (B) may be used in combination.
It is preferably 1 to 10%, more preferably 0.1 to 5%, particularly preferably 0.5 to 3%.

Component (C), a cationic direct dye (1) to (4)
Are known compounds, and are cationic direct dyes.
(1) to (3) are WO 95/01772, WO 95/15144, EP 714954, etc., and cationic direct dyes (4) are U.S. Pat. No. 395591
No. 8, No. 4025301 and the like.

In each of the substituents in the general formulas (1) to (4), examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. Examples of the alkoxy group of Formulas 1 to 4 include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0045] In the general formula (1) ~ (4), X - as an anion represented by a chloride ion, bromide ion, iodide ion, trichloroacetic zincate ions, tetrachlorophthalic zincate ion, sulfate Examples include hydrogen ion, methyl sulfate ion, phosphate ion, formate ion, and acetate ion.

Specific examples of the cationic direct dyes (1) to (4) are shown below.

[0047]

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[0048]

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Two or more cationic direct dyes (1) to (4) of the component (C) may be used in combination, and the content thereof is 0.001 to 10%, particularly 0.005 to 5% in the hair dye composition. Is preferred. Further, other direct dyes can be used in combination.

The hair dye composition of the present invention comprises
Water or organic solvents are used. As the organic solvent, ethanol, lower alkanols such as 2-propanol, benzyl alcohol, aromatic alcohols such as 2-benzyloxyethanol, propylene glycol, 1,3-butanediol, polyols such as diethylene glycol, ethyl cellosolve, Cellosolves such as butyl cellosolve,
Carbitols such as ethyl carbitol and butyl carbitol; In particular, when an aromatic alcohol such as benzyl alcohol or 2-benzyloxyethanol is contained in the hair dye composition in an amount of 2 to 30%, it is effective and preferable for hair dyeing properties and residual fragrance.

The pH of the hair dye composition of the present invention is preferably from 2 to 11, particularly preferably from 5 to 10. Examples of the pH adjuster include inorganic acids such as hydrochloric acid and phosphoric acid, organic acids such as citric acid, glycolic acid and lactic acid, organic amines such as monoethanolamine and 2-amino-2-methylpropanol, ammonium carbonate, sodium carbonate and the like. Carbonates, bicarbonates such as sodium bicarbonate and ammonium bicarbonate, hydrochlorides such as ammonium chloride, phosphates such as monopotassium dihydrogen phosphate and disodium monohydrogen phosphate, and hydroxylation such as sodium hydroxide And aqueous ammonia.

The hair dye composition of the present invention can be used by mixing it with an oxidizing agent at the time of use. In this case, since the hair can be bleached at the same time, more vivid hair dyeing is possible. Examples of the oxidizing agent include hydrogen peroxide, ammonium persulfate, potassium persulfate, persulfates such as sodium persulfate, perborates such as sodium perborate, percarbonates such as sodium percarbonate, sodium bromate, and bromine. Examples thereof include bromates such as potassium acid, and hydrogen peroxide is particularly preferable. In addition, in the case of using such a mixture with an oxidizing agent at the time of use, an oxidation dye can be used together. When an oxidation dye is used, oxidation may be performed using an oxidase such as laccase, choline oxidase, and uricase.

Specific examples of the oxidation dye are shown below. As the precursor, paraphenylenediamine, toluene-
2,5-diamine, 2-chloro-paraphenylenediamine, N-methoxyethyl-paraphenylenediamine,
N, N-bis (2-hydroxyethyl) -paraphenylenediamine, 2- (2-hydroxyethyl) -paraphenylenediamine, 2,6-dimethyl-paraphenylenediamine, 4,4′-diaminodiphenylamine, 1,3
-Bis (N- (2-hydroxyethyl) -N- (4-aminophenyl) amino) -2-propanol, PEG-
3,2,2'-paraphenylenediamine, paraaminophenol, paramethylaminophenol, 3-methyl-
4-aminophenol, 2-aminomethyl-4-aminophenol, 2- (2-hydroxyethylaminomethyl) -4-aminophenol, orthoaminophenol, 2-amino-5-methylphenol, 2-amino-
6-methylphenol, 2-amino-5-acetamidophenol, 3,4-diaminobenzoic acid, 5-aminosalicylic acid, 2,4,5,6-tetraaminopyrimidine,
2,5,6-triamino-4-hydroxypyrimidine,
4,5-diamino-1- (4′-chlorobenzyl) pyrazole, and salts thereof. Examples of the coupler include metaphenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) anisole, 2,4-diamino-5-methylphenetol, and 2,4-diamino-5- (2-hydroxyethoxy) toluene, 2,4-dimethoxy-1,3
-Diaminobenzene, 2,6-bis (2-hydroxyethylamino) toluene, 2,4-diamino-5-fluorotoluene, 1,3-bis (2,4-diaminophenoxy) propane, metaaminophenol, Methyl-5
-Aminophenol, 2-methyl-5- (2-hydroxyethylamino) phenol, 2,4-dichloro-3-
Aminophenol, 2-chloro-3-amino-6-methylphenol, 2-methyl-4-chloro-5-aminophenol, N-cyclopentyl-metaaminophenol, 2-methyl-4-methoxy-5- (2- (Hydroxyethylamino) phenol, 2-methyl-4-fluoro-5-aminophenol, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1-naphthol, 1,
5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-isopropyl-5-methylphenol, 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 6- Hydroxybenzomorpholine, 3,4-methylenedioxyphenol, 2-bromo-4,5-methylenedioxyphenol, 3,4-methylenedioxyaniline, 1- (2-hydroxyethyl) amino-3,4-methylene Dioxybenzene, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-diaminopyridine, 2,3-diamino-6-methoxypyridine, 2-methylamino-3-amino- 6-methoxypyridine, 2-
Examples include amino-3-hydroxypyridine, 2,6-diaminopyridine, and salts thereof.

By containing a cationic polymer in the hair dye composition of the present invention, the hair dyeing effect and the conditioning effect of the hair after hair dyeing can be improved. Examples of the cationic polymer include a cationized cellulose derivative, a cationized guar gum derivative, a cationized polysaccharide, a diallyldialkyl quaternary ammonium salt derivative, a cationized polyvinyl pyrrolidone derivative, and the like. Among them, a diallyldialkyl quaternary ammonium salt derivative is preferable. Two or more of these cationic polymers may be used in combination, and the content thereof is 0.1% in the hair dye composition.
1-3%, especially 0.3-1%, is preferable for obtaining a sufficient effect.

The dye composition of the present invention can have a viscosity which can be easily applied to hair using a thickener, for example, 500 to 100,000 mPa · s. Examples of the thickener include carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, gum arabic, carrageenan, karaya gum, tragacanth gum, carob gum, quince seed (quince), casein, dextrin, gelatin, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, and hydroxyethyl cellulose. Propyl cellulose, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, polyacrylamide, locust bean gum, guar gum, hydroxypropyl guar gum, tamarint gum, dialkyldimethylammonium cellulose sulfate, xanthan gum, hydroxypropyl xanthan gum, gellan gum, welan gum, bentonite, etc. Can be

The form of the hair dye composition of the present invention is suitable for dyeing hair such as powder, transparent liquid, emulsion, cream, gel, paste, aerosol and aerosol foam. Dosage form.

The dyeing of the hair using the hair dye composition of the present invention is carried out by applying the composition to the hair, and for a time sufficient for the desired color tone to appear on the hair (1 to 60 minutes, especially 5 to 60 minutes). 40 min), then rinse the hair, optionally rinse with shampoo and rinse again, then dry the hair. There is also a method in which only the hair dye composition of the present invention is applied to hair, and rinsing is not required.

[0058]

EXAMPLES The cationic direct dye of the component (C) used in each of the examples is as follows.

[0059]

Embedded image

Example 1 Hair dyes shown in Table 1 were prepared, and their hair dyeing power and residual fragrance were evaluated. (Evaluation method) 15cm long with American blonde hair,
Six hair bundles weighing 20 g are made, and each of the present invention products 1 to
3. 15 g of the hair dye of any of Comparative Products 1 to 3 was applied so as to be sufficiently spread. After leaving them in a thermostat at 30 ° C. for 20 minutes, the hair tresses were thoroughly rinsed with warm water at 36 ° C. and dried. These hair bundles were observed by 20 panelists, and the hair dyeing power and the residual odor were evaluated according to the following criteria. Table 1 shows the total score.

(Evaluation Criteria) i) Hair dyeing power (the color of the product of the present invention and the comparative product is red for 1 to 3 and yellow for 4 to 5) Strong color is felt: 3 points Slightly strong color Feel: 2 points A little color is felt: 1 point Almost no color is felt: 0 point

Ii) Remaining scent property Immediately after the treatment (immediately after drying), a strong scent is recognized: 2 points Immediately after the treatment (immediately after drying): Slight scent is recognized: 1 point Immediately after the treatment (immediately after drying), almost no scent is recognized: 0 points

[0063]

[Table 1]

Each of the hair dye compositions of the present invention has a hair dyeing power,
Excellent lingering scent.

Example 2 Using 15 g of a mixture of 1 and 2 hair dyes shown in Table 2 in a weight ratio of 1: 1, the hair dyeing power and residual odor were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0066]

[Table 2]

Each of the hair dyes of the present invention is excellent in hair dyeing power and lingering scent.

Example 3 The following hair dye was prepared. Basic Red 51 0.01% Basic Yellow 87 0.04 Anethole (ClogP = 3.314) 0.1 Phenylethyl alcohol (ClogP = 1.183) 0.1 Silicone compound a (Japanese Unexamined Patent Application Publication No. H2-276824, Example 1) 1 ( Block copolymer of polydimethylsiloxane with poly (N-acetylethyleneimine) chains at both ends) Ethanol 15 Propylene glycol 5 Hydroxypropyl guar gum 1 Gafquat 734 (ISB Japan) 1 (Vinylpyrrolidone N, N- Dimethylaminoethyl methacrylic acid copolymer diethyl sulfate solution) Monoethanolamine 0.1 Phosphoric acid Adjusted to pH 9 Water Balance

This hair dye was applied to semi-dry light brown hair immediately after shampooing, left at room temperature (25 ° C.) for 5 minutes, rinsed with warm water, and dried. Hair is
It was colored in a clear orange color, and the aroma of anethole was strongly felt as a residual scent. The dyed hair had a smooth and smooth feel.

Example 4 The following hair dye was prepared. Basic Orange 31 (the cationic direct dye of the present invention (a)) 0.25% pt-butylcyclohexyl acetate (ClogP = 4.059) 0.1 Phenylethyl alcohol (ClogP = 1.183) 0.1 Silicone compound a (Example) 1 Ethanol 15 Propylene glycol 5 Hydroxypropyl guar gum 1 Catinal LC100 (Toho Chemical) 1 (O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose) Monoethanolamine 0.1 Phosphorus Acid pH adjusted to 9 Water balance

Applying this hair dye to light brown hair,
After standing at room temperature for 15 minutes, the hair was rinsed with warm water, then shampooed and rinsed, and the hair was dried. The hair was strongly orange-colored, and the scent of pt-butylcyclohexyl acetate was strongly felt as a residual scent.

Example 5 The following two-part hair dye was produced. First agent Basic Red 51 0.2% 2-butyl 4,4,6-trimethyl-1,3-dioxane (ClogP = 3.244) 0.2 Cetyltrimethylammonium chloride 1 28% ammonia water 5 Monoethanolamine 2 Propylene glycol 8 Polyoxyethylene (20) isostearyl ether 24 Polyoxyethylene (2) isostearyl ether 20 Mercoat 280 (35% aqueous solution) 8 Amodimethicone SM8702C (40% solution) 0.5 (Toray Dako Corning Silicone) (Aminoethyl propyl) Siloxane / dimethylsiloxane copolymer emulsion) Polyether-modified silicone KF6005 0.2 Tetrasodium edetate 0.1 Ammonium chloride Adjusted to pH 10 Water balance Second agent 35% Hydrogen peroxide 17.1% Methyl paraben 0.1 Phosphorus Acid pH adjusted to 3.5 Water balance

A mixture of the first and second agents in a weight ratio of 1: 1 was applied to light brown hair, left at room temperature for 15 minutes, and rinsed with warm water. Further, the hair was dried after shampooing and rinsing. The hair is strongly colored red, 2
The odor of -butyl 4,4,6-trimethyl-1,3-dioxane was strongly felt as a residual scent.

Example 6 The following two-part hair dye was produced. First agent Paraaminophenol 0.45% Paraaminoorthocresol 0.5 Basic Yellow 87 0.2 3,7-dimethyl-6-octen-1-ol (ClogP = 3.253) 0.1 2-methoxy-4-allylphenol (ClogP = 2.397) 0.15 dodecyldimethylethylammonium chloride 1 28% ammonia water 5 monoethanolamine 2 propylene glycol 8 polyoxyethylene (20) isostearyl ether 24 polyoxyethylene (2) isostearyl ether 20 mercoat 280 (35 % Aqueous solution) 8 Amodimethicone SM8702C (40% solution) 0.5 Sodium sulfite 0.05 Ascorbic acid 0.5 Tetrasodium edetate 0.1 Ammonium chloride Adjusted to pH 10 Water balance Second agent 35% Hydrogen peroxide 17.1 % Methyl paraben 0.1 Phosphoric acid Adjusted to pH 3.5 Lance

A mixture of the first and second agents in a weight ratio of 1: 1 was applied to light brown hair, left at room temperature for 30 minutes, and rinsed with warm water. Further, the hair was dried after shampooing and rinsing. The hair is strongly colored yellow-orange,
The scent of 3,7-dimethyl-6-octen-1-ol and 2-methoxy-4-allylphenol was strongly felt as a residual scent.

Example 7 The following two-part hair dye was produced. First agent Toluene-2,5-diamine 0.25% Para-aminophenol 0.16 Para-amino orthocresol 0.45 Basic Yellow 87 0.2 p-mentha-1,8-diene (ClogP = 4.352) 0.2 28% Aqueous ammonia 5 Monoethanolamine 2 Cetanol 8.5 Polyoxyethylene (40) cetyl ether 3 Polyoxyethylene (2) cetyl ether 3.5 Silicone compound a (identical to Example 3) 1 Liquid paraffin 0.5 Sodium sulfite 0.05 Ascorbic acid 0.5 Tetrasodium edetate 0.1 Perfume Appropriate amount Ammonium chloride Adjusted to pH 10 Water balance Second agent 35% Hydrogen peroxide 17.1% Methyl paraben 0.1 Phosphoric acid Adjusted to pH 3.5 Water Balance

A mixture of the first and second agents in a weight ratio of 1: 1 was applied to light brown hair, left at room temperature for 10 minutes, and rinsed with warm water. Further, the hair was dried after shampooing and rinsing. The hair is strongly colored red-orange,
The scent of p-mentha-1,8-diene was strongly felt as a residual scent.

[0078]

EFFECT OF THE INVENTION The hair dye composition of the present invention can strongly and uniformly dye hair, and has high hair dyeing performance that is resistant to light, sweat, washing, etc., and has a glossy and smooth feel to hair. And a preferable scent that can be selected from a wide range of scents can be imparted to hair, and the scent lasts for a long time.

 ──────────────────────────────────────────────────続 き Continued on front page F-term (reference) 4C083 AB012 AB082 AB172 AB282 AB352 AB412 AC012 AC022 AC072 AC102 AC122 AC182 AC212 AC342 AC352 AC472 AC482 AC532 AC542 AC552 AC692 AC732 AC842 AC851 AC852 AC861 AC862 AD072 AD132 AD151 AD162 AD282 AD352 AD532 AD64224 CC36 EE06 EE07 EE26

Claims (1)

[Claims] 1. A dye containing the following components (A), (B) and (C):
Hair composition. (A) a fragrance compound having a ClogP value of more than 1.5 (B) a silicone compound (C)
Direct dyesWherein Z represents a nitrogen atom or a methine group;¹as well as
R^TwoIs independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
Hydroxyethyl group, cyanoethyl group, aminoethyl group
Or a 4-aminophenyl group;
Adjacent nitrogen atom and ben by bonding to the zen ring
Together with the carbon atom of the zen ring, an alkyl group having 1 to 4 carbon atoms
May be replaced with nitrogen as a hetero atom other than the nitrogen atom.
A nitrogen-containing heterocyclic ring which may have an element atom or an oxygen atom
Forming, R^ThreeAnd R^FourIs independently a hydrogen atom or a halogen atom
, Cyano group, alkyl group having 1 to 4 carbon atoms, 1 to carbon atoms
4 represents an alkoxy group or an acetyloxy group, and Q is
Next Q₁~ Q₁₃:(Where R^FiveIs an alkyl group having 1 to 4 carbon atoms or hydroxy
Represents a ethyl group;⁶And R⁷Is independently a hydrogen atom or
R^FiveRepresents the same group as⁸Is alkoxy having 1 to 4 carbon atoms
Represents a group. X) represents a group selected from^-Is an anion
Is shown. Where Z is a methine group and Q is Q₁Or Q_Two
And R^ThreeIs a group other than an alkoxy group,¹When
R^TwoAre not simultaneously hydrogen atoms. [Chemical formula 3][Wherein, R⁹Is a hydrogen atom or an alkyl having 1 to 4 carbon atoms
The kill group is represented by R^TenIs a hydrogen atom, an alkyl having 1 to 4 carbon atoms
Group, cyanoethyl group, aminoethyl group or 4-amino
Represents a phenyl group, or R⁹And R^TenAre jointly adjacent
Even if the alkyl group having 1 to 4 carbon atoms is substituted together with the nitrogen atom,
Often, a nitrogen atom is a heteroatom other than the nitrogen atom.
Or a nitrogen-containing heterocyclic ring optionally having an oxygen atom;
¹¹And R¹²Is independently a hydrogen atom, halogen atom, carbon number
An alkyl group having 1 to 4, an alkoxy group having 1 to 4 carbon atoms, or
Represents a cyano group, and Q ′ represents the following Q ′₁~ Q '_Five:(Where R¹³Represents an alkyl group having 1 to 4 carbon atoms;¹⁴
Is an amino group, a methylamino group, a dimethylamino group, or
R¹³And the same group. X) represents a group selected from^-
Represents an anion. [Chemical formula 5][Wherein, Z₁And Z_TwoIndependently represents a nitrogen atom or a methine group.
Where T is the next T₁And T_Two Embedded image(Where R^FifteenIs a hydrogen atom or an alkyl having 1 to 4 carbon atoms
By bonding to the benzene ring in the formula
Together with the adjacent nitrogen atom and the carbon atom of the benzene ring,
The alkyl group having 1 to 4 carbon atoms may be substituted,
Having a nitrogen atom or an oxygen atom as a hetero atom other than the atom
To form a nitrogen-containing heterocyclic ring,¹⁶Is a hydrogen atom, halo
A gen atom, an amino group or an alkoxy group having 1 to 4 carbon atoms
And R¹⁷Represents a hydrogen atom or a halogen atom;¹⁸Passing
And R¹⁹Is independently a hydrogen atom or an alkyl having 1 to 4 carbon atoms
And m represents 0 or 1. Where R¹⁶Is amino
When m is 0, Z is₁And Z_TwoAt the same time
Shows a tin group. ) Represents a group selected from
T₁Where m is 0 and Z₁Is a nitrogen atom
Next Q ''₁~ Q ''₈Otherwise, the next Q ''₁~
Q ''₇:(Where R²⁰Represents an alkyl group having 1 to 4 carbon atoms;^{twenty one}
Is a hydrogen atom or R²⁰And the same group. Selected from)
X represents a group^-Represents an anion. However, Q ''
Q ''₇, Z₁And Z_TwoIs simultaneously a nitrogen atom
Absent. Embedded image[Where Q ′ ″ is the next Q ′ ″₁~ Q '' '₇:(Where R^{twenty two}Is an alkyl group having 1 to 4 carbon atoms, phenyl
Group, halogenated phenyl group or methylphenyl group
Then R^{twenty three}Represents an alkyl group having 1 to 4 carbon atoms or a phenyl group.
And R^{twenty four}Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
Or a phenyl group, ^{twenty five}Is an alkyl group having 1 to 4 carbon atoms
Or a phenyl group, or R^{twenty four}And R^{twenty five}Are next to each other
Along with the carbon atoms in contact therewith, a substituent having 1 to 4 carbon atoms
Alkyl group, alkoxy group having 1 to 4 carbon atoms or nitro
Forming a benzene ring which may have a group,²⁶Is 1 carbon
To 4 alkyl groups, alkoxy groups having 1 to 4 carbon atoms or O
^-And R²⁷And R²⁸Is independently a hydrogen atom or a halogen
Atom, nitro group, alkyl group having 1 to 4 carbon atoms or carbon number
1 to 4 represent an alkoxy group. However, Q '' '₁,
Q '' '_Five, Q '' '₆And Q '' '₇Then, R^{twenty four}Is other than a hydrogen atom
And Q '' '_ThreeThen, R^{twenty two}Represents an alkyl group;
^{twenty four}Represents an alkyl group having 1 to 4 carbon atoms or a phenyl group.
You. ) Represents a group selected from the group consisting of the following L₁~ L_Four Embedded image(Where R²⁹Is a hydrogen atom, a hydroxy group or a group NR
³⁶R³⁷(R³⁶And R³⁷Is independently a hydrogen atom, carbon number 1 to
4 alkyl group, hydroxyethyl group or phenyl group
Is shown), R³⁰Is hydrogen atom, halogen atom, hydroxy
Group, nitro group, alkyl group having 1 to 4 carbon atoms, 1 to 1 carbon atom
4 alkoxy group, group NR³⁸R³⁹(R³⁸And R³⁹Is German
A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, hydroxy
Ethyl group or phenyl group) or acetamino
A group represented by R³¹Is a hydrogen atom, a halogen atom, a C1-4
Represents an alkyl group or an alkoxy group having 1 to 4 carbon atoms.
Or R³⁰And R³⁶Together with adjacent carbon atoms
Or R³⁰And R³¹Are cooperating with adjacent carbon atoms
Both are nitrogen, oxygen or sulfur as hetero atoms
Forming a 5- to 6-membered ring which may contain atoms,³²And R³³
Is independently a hydrogen atom, a phenyl group or an alkyl group having 1 to 4 carbon atoms.
A alkyl group;³⁴And R³⁵Is independently a hydrogen atom,
A mino group, a phenyl group or an alkyl group having 1 to 4 carbon atoms
You. X) represents a group selected from^-Indicates an anion
And n is R²⁶Is O^-If 0, 0 otherwise
In the case, it indicates 1. Where R²⁹Is NR³⁶R³⁷When
Is Q '' '_TwoR^{twenty two}~ R^{twenty five}At least one is an alkyl group
Other than Q '' '_FiveAnd Q '' '₇R²⁷And R ²⁸But at the same time
It does not become a hydrogen atom. ]