JP2008297265A - Hair dye composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a non-oxidative hair dye composition having favorable hair-dyeing capacity and enabling the hair to have flexibility or the like. <P>SOLUTION: The hair dye composition comprises (A) a direct dye, (B) an etheramine of formula (1) or a salt thereof, (C) an organic solvent such as an aromatic alcohol of formula (2), and (D) a branched fatty acid of formula (5) or a salt thereof. In the formula (1), R<SP>1</SP>to R<SP>4</SP>are each an alkyl or the like. In the formula (2), R<SP>5</SP>is H, methyl or methoxy; Y is a single bond; Z is H or OH; and c and d are each 0-5. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a hair dye composition.

  Hair is always affected by sunlight, ultraviolet rays, heat, drying, and the like, and tends to be pricked by daily hair washing, brushing, the heat of a dryer, and the like. In particular, it has been elucidated that damage such as loss of hair gloss and dryness due to drying of the hair dryer after shampooing is caused by cavitation inside the hair due to the heat of the hair dryer. In recent years, it has become common to enjoy changes in the appearance of hair, such as dyeing hair brightly or changing the hairstyle, and the frequency of these treatments has increased. In this way, hair subjected to oxidative hair dyeing treatment or permanent wave treatment is considered to easily cause internal cavitation due to chemical factors of the oxidative hair dye or permanent wave agent used. Furthermore, daily hair care actions (hair washing process, hand rush, brushing) continue to repeatedly give small distortion to the hair, and it is considered that cracks, gaps, cracks, cuts, etc. inside the hair grow and progress.

  Accordingly, various attempts have been made for the purpose of repairing hair damage. For example, as a technique for repairing or preventing damage to hair and imparting a good feel, hair cosmetics using ether type tertiary amine, higher alcohol and organic solvent (Patent Document 1), containing branched fatty acids Hair cosmetics (Patent Document 2) and the like have been proposed. In addition, non-oxidative hair dyes that are less damaging to hair than oxidative hair dyes and directly penetrate the hair into the hair are also widely used. Hair dyes (Patent Documents 3 and 4) have also been proposed.

  However, these hair dyes and hair cosmetics are insufficient to repair or inhibit fatigue destruction (split hairs and cut hairs) caused by oxidative hair dyes and permanent wave agents.

JP 2004-67534 A Japanese Unexamined Patent Publication No. 4-137719 Japanese Patent Laid-Open No. 2003-327519 JP2003-40746

  The present invention is excellent in hair dyeing power, repairs or inhibits hair damage and fatigue destruction due to chemical treatment, dryer drying, and daily hair care behavior, and has good flexibility and supple feel from wet to dry. An object of the present invention is to provide a non-oxidative hair dye composition that can be imparted with hair color.

  The inventor of the present invention uses a direct dye, an ether-type amine compound (hereinafter referred to as “ether amine”), an organic solvent such as an aromatic alcohol, and a branched fatty acid in combination to satisfy the above requirements. It has been found that a hair composition can be obtained.

  That is, the present invention provides a hair dye composition containing components (A), (B), (C), (D) and water.

(A) Direct dye

(B) Etheramine represented by the general formula (1) or a salt thereof

[Wherein R ¹ represents a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, R ² represents a linear or branched alkylene group having 2 to 5 carbon atoms, R ³ and R ⁴ is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or — (AO) _b H (A is an alkylene group having 2 to 4 carbon atoms, b is a number of 1 to 6; A may be the same or different, and the arrangement thereof is arbitrary.), And a represents an integer of 1 to 8. ]

(C) Organic solvent selected from the following (c1) to (c4)
(c1) Aromatic alcohol represented by general formula (2)

[Wherein R ⁵ represents a hydrogen atom, a methyl group or a methoxy group, Y represents a single bond or a linear or branched divalent hydrocarbon group having 1 to 3 carbon atoms, and Z represents a hydrogen atom or a hydroxyl group. C and d each represent a number from 0 to 5. However, c is not 0 when Y is a single bond. ]

  (c2) N-alkylpyrrolidone having a C1-6 alkyl group bonded to a nitrogen atom

  (c3) Alkylene carbonate having an alkylene group having 2 to 4 carbon atoms

(c4) Lactone represented by general formula (3) or (4)

[Wherein, R ⁶ and R ⁷ represent an alkyl group having 1 to 6 carbon atoms, and e and f represent 0 or 1. ]

(D) Branched fatty acid represented by the general formula (5) or a salt thereof

Wherein, R ⁸ represents a methyl group or an ethyl group, g is an integer of 3 to 36. ]

  The hair dye composition of the present invention has excellent hair dyeing power, repairs or inhibits hair damage and fatigue destruction, and can impart good flexibility and a supple feel from wet to dry. .

  Examples of the direct dye of component (A) used in the present invention include nitro dyes, anthraquinone dyes, acid dyes, oil-soluble dyes, basic dyes and the like.

  Examples of the nitro dye include HC blue 2, HC orange 1, HC red 1, HC red 3, HC yellow 2, and HC yellow 4.

  Examples of the anthraquinone dye include 1-amino-4-methylaminoanthraquinone and 1,4-diaminoanthraquinone.

  Acid dyes include Red No. 2, Red No. 3, Red No. 102, Red No. 104, Red No. 105, Red No. 106, Red No. 201, Red No. 227, Red No. 230, Red No. 232, Red No. 401, Red 502, Red 503, Red 504, Red 506, Orange 205, Orange 206, Orange 207, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Yellow 402, Yellow 403 , Yellow 406, Yellow 407, Green 3, Green 201, Green 204, Green 205, Green 401, Green 402, Blue 1, Blue 2, Blue 202, Blue 205, Purple 401, Black 401, Acid Blue 1, Acid Blue 3, Acid Blue 62, Acid Black 52, Acid Brown 13, Acid Green 50, Acid Orange 6, Acid Red 14, Acid Red 35, Acid Red 73, Acid Red 184 , Brilliant Black 1 and the like.

  As oil-soluble dyes, Red No. 215, Red No. 218, Red No. 225, Orange No. 201, Orange No. 206, Yellow No. 201, Yellow No. 204, Green No. 202, Purple No. 201, Red No. 501, Red No. 505, Examples include orange 403, yellow 404, yellow 405, and blue 403.

  Basic dyes include Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 99, Basic Brown 4, Basic Brown 16, Basic Brown 17, Basic Green 1, Basic Red 2, Basic Red 12, Basic Red 22, Basic Red 51, Basic Red 76, Basic Violet 1, Basic Violet 3, Basic Violet 10, Basic Violet 14, Basic Violet 57, Basic Yellow 57, Basic Yellow 87, Basic Orange 31, etc. It is done.

  Of these, acid dyes are preferred, and in particular, Yellow No. 4, Yellow No. 203, Yellow No. 403, Orange No. 205, Green No. 3, Green No. 201, Green No. 204, Red No. 2, Red No. 104, Red No. 106, Red 201, red 227, blue 1, blue 205, purple 401 and black 401 are preferred.

  One or more of the direct dyes can be used, and the content in the hair dye composition of the present invention is preferably 0.005 to 5% by mass, particularly 0.01 to 2% by mass.

In the ether amine of component (B) used in the present invention, R ¹ is a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, and has good flexibility and slipperiness from wet to dry. In particular, a linear or branched alkyl or alkenyl group having 12 to 24 carbon atoms, particularly 14 to 22 carbon atoms is preferable, and an alkyl group is particularly preferable from the viewpoint of excellent slipperiness after drying. .

R ² is a linear or branched alkylene group having 2 to 5 carbon atoms, can give good flexibility and slipperiness from wet to dryness, and is particularly straightforward from the viewpoint of excellent slipperiness after drying. Are preferred, and an alkylene group having 3 to 4 carbon atoms is particularly preferred. Moreover, a is an integer of 1-8, and it is especially preferable that it is 1-3.

R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or — (AO) _b H (A and b are as defined above), and from wet to dry From the viewpoint of providing good flexibility and slipperiness and excellent slipperiness after drying, the alkyl group having 1 to 6 carbon atoms and — (CH ₂ CH ₂ O) _b H (b is 1 to 3, particularly 1 It is preferable that at least one of R ² and R ³ is an alkyl group having 1 to 6 carbon atoms, particularly a methyl group or an ethyl group, and it is particularly preferable that both are the same.

  Preferable specific examples of the ether amine include N, N-dimethyl-3-hexadecyloxypropylamine and N, N-dimethyl-3-octadecyloxypropylamine.

  Moreover, it is preferable that the ether amine used for this invention is neutralized all or part by the inorganic acid or the organic acid.

  Examples of inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid and the like. Organic acids include monocarboxylic acids such as acetic acid and propionic acid; dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid and phthalic acid; polycarboxylic acids such as polyglutamic acid; glycolic acid And hydroxycarboxylic acids such as lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid and citric acid; and acidic amino acids such as glutamic acid and aspartic acid. Among these, inorganic acids, dicarboxylic acids, hydroxycarboxylic acids, and acidic amino acids are preferable, and hydrochloric acid is particularly preferable as the inorganic acid. As the dicarboxylic acid, maleic acid and succinic acid are particularly preferable. As the hydroxycarboxylic acid, glycolic acid, lactic acid, and malic acid are particularly preferable. As the acidic amino acid, glutamic acid is particularly preferable.

  Here, the branched fatty acid of component (D) may be used as the organic acid. Alternatively, ether amine and branched fatty acid may be mixed and neutralized in advance, and used as an acid addition salt. In the hair cosmetic composition of the present invention, it is presumed that component (B) and component (D) form a hydrophobic complex.

  The compounding amount of the inorganic acid and / or organic acid is 0.1 to 10 times mol, and further 0.3 to 4 times mol, with respect to the ether amine. This is preferable from the viewpoint of enhancing the conditioning effect.

  The ether amine of component (B) or a salt thereof may be used in combination of two or more, and the content in the hair dye composition of the present invention provides good flexibility and slipperiness during use. The ether amine is preferably 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, and particularly preferably 0.5 to 10% by mass.

  Among the organic solvents as component (C), the aromatic alcohol of (c1) includes benzyl alcohol, cinnamyl alcohol, phenethyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, 2-benzyloxyethanol. Etc. Of these, benzyl alcohol and 2-benzyloxyethanol are particularly preferable.

  Examples of the N-alkylpyrrolidone in (c2) include N-methylpyrrolidone, N-ethylpyrrolidone, N-butylpyrrolidone and the like.

  Examples of the alkylene carbonate (c3) include ethylene carbonate and propylene carbonate.

In the lactone of (c4), R ⁶ and R ⁷ in the general formula (3) or (4) are alkyl groups having 1 to 6 carbon atoms, and in the case of γ-lactone, the γ-position, δ- In the case of a lactone, a linear or branched alkyl group having 1 to 6 carbon atoms substituted at the δ position (that is, adjacent methylene of a hetero oxygen atom), for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group Etc. are preferred. Examples of these lactones include γ-butyrolactone, γ-caprolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, and δ-heptanolactone. From the viewpoint of lactone stability, γ-lactone In particular, γ-butyrolactone and γ-caprolactone are preferred.

  The organic solvent of component (C) may be used in combination of two or more, and the content in the hair dye composition of the present invention has good hair dyeing power, good flexibility and supple feel when used. From the point to provide, 0.1-30 mass%, Furthermore, 1-20 mass%, Especially 3-10 mass% is preferable.

  The branched fatty acid of component (D) can be separated and extracted from hair or the like according to the description of LIPIDS, vol.23, No.9, 878-881 (1988), for example. Patent Document 2, WO98 / 30532 Can also be synthesized according to The branched fatty acid is represented by the general formula (5) and preferably has a total carbon number of 7 to 40, more preferably 8 to 30, particularly 10 to 22, and specifically 18-methyleicosane. Acid, 14-methylpentadecanoic acid, 14-methylhexadecanoic acid, 15-methylhexadecanoic acid, 15-methylheptadecanoic acid, 16-methylheptadecanoic acid, 16-methyloctadecanoic acid, 17-methyloctadecanoic acid, 17-methylnonadecanoic acid Is mentioned. The branched fatty acid salts include alkali metal salts such as sodium salt, lithium salt and potassium salt; alkaline earth metal salts such as calcium salt and magnesium salt; ammonium salt; triethanolamine salt, diethanolamine salt and monoethanol. Organic amine salts such as amine salts; basic amino acid salts such as lysine salts and arginine salts.

  Examples of the extract include an extract from lanolin, that is, lanolin fatty acid and salts thereof. Lanolin fatty acid contains about 50% by mass of methyl branched long chain fatty acid called iso fatty acid or anteiso fatty acid. Specific examples include Crodacid 18-MEA [Crowda Japan Co., Ltd.], Scrairo [Crowda Japan Co., Ltd.], and FA-NH [Nippon Seika Co., Ltd.].

  Two or more kinds of component (D) branched fatty acids or salts thereof may be used in combination. Moreover, you may mix and use a synthetic product and an extract. The content in the hair dye composition of the present invention is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, from the viewpoint of the effect of recovering or suppressing hair damage.

  Ingredient ratio (B) / (D) of component (B) and component (D) is sufficient for the hair dyeing effect, the effect of repairing / suppressing damage to hair and fatigue destruction, and the effect of imparting flexibility and suppleness. On the other hand, from the viewpoint of ensuring good stability and usability, it is preferably in the range of 20/1 to 1/10, more preferably 10/1 to 1/5, especially 5/1 to 1/2. It is preferable to set it as the range.

  The amount of water contained in the hair dye composition of the present invention is preferably 50 to 98% by mass, particularly preferably 60 to 90% by mass.

  The hair dye composition of the present invention may further contain an amphiphilic amide lipid as component (E) in order to improve the effect of repairing from the outside of the hair. Examples of the amphiphilic amide lipid include those selected from diamide compounds represented by the general formula (6) and ceramides represented by the general formula (7).

(i) Diamide compound represented by the general formula (6)

[Wherein R ⁹ represents a linear or branched hydrocarbon group having 1 to 12 carbon atoms which may be substituted by a hydroxyl group and / or an alkoxy group, and R ¹⁰ represents a linear or branched chain having 1 to 5 carbon atoms. A branched divalent hydrocarbon group is represented, and R ¹¹ represents a linear or branched divalent hydrocarbon group having 1 to 22 carbon atoms. ]

In General Formula (6), R ⁹ is a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted with 1 to 3 groups selected from a hydroxyl group and an alkoxy group having 1 to 6 carbon atoms. Is preferred. Among them, an unsubstituted alkyl group having 1 to 12 carbon atoms, or 1 to 2 hydroxyl groups, one alkoxy group having 1 to 6 carbon atoms, or one hydroxyl group and one alkoxy group having 1 to 6 carbon atoms. A substituted alkyl group having 2 to 12 carbon atoms is more preferred. Specifically, methyl group, ethyl group, propyl group, butyl group, hexyl group, dodecyl group, 2-methylpropyl group, 2-ethylhexyl group, 2-hydroxyethyl group, 9-hydroxynonyl group, 2,3- Examples include dihydroxypropyl group, 2-methoxyethyl group, 2-hydroxy-3-methoxypropyl group, 9-methoxynonyl group, among which 2-hydroxyethyl group, methyl group, dodecyl group, 2-methoxyethyl group preferable.

In the general formula (6), R ¹⁰ is preferably a linear or branched alkylene group having 2 to 5 carbon atoms, more preferably 2 to 3 carbon atoms. Specifically, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, 1-methylethylene group, 2-methylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethyl Examples thereof include an ethylene group and a 2-ethyltrimethylene group, and among them, an ethylene group and a trimethylene group are preferable.

In the general formula (6), R ¹¹ is preferably a linear or branched divalent hydrocarbon group having 2 to 22 carbon atoms, more preferably a linear or branched alkylene group having 11 to 22 carbon atoms, and Alkenylene groups having 1 to 4 double bonds are preferred. Specifically, ethylene group, trimethylene group, tetramethylene group, hexamethylene group, heptamethylene group, octamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, hexa Decamethylene group, octadecamethylene group, 1-methylethylene group, 2-ethyltrimethylene group, 1-methylheptamethylene group, 2-methylheptamethylene group, 1-butylhexamethylene group, 2-methyl-5-ethyl Heptamethylene group, 2,3,6-trimethylheptamethylene group, 6-ethyldecamethylene group, 7-methyltetradecamethylene group, 7-ethylhexadecamethylene group, 7,12-dimethyloctadecamethylene group, 8, 11-dimethyloctadecamethylene group, 7,10-dimethyl-7-ethylhexadecamethylene group, 1-octadecylethylene group, ethenylene group, 1- Octadecenylethylene group, 7,11-octadecadienylene group, 7-ethenyl-9-hexadecamethylene group, 7,12-dimethyl-7,11-octadecadienylene group, 8,11-dimethyl- Examples include 7,11-octadecadienylene group. Of these, 7,12-dimethyloctadecamethylene group, 7,12-dimethyl-7,11-octadecadienylene group, octadecamethylene group, undecamethylene group, and tridecamethylene group are preferable.

A more preferred diamide compound (6) is a compound in which the above-mentioned preferred groups are combined as R ⁹ , R ¹⁰ and R ¹¹ , and specific examples thereof include the following compounds.

(ii) Ceramides represented by the general formula (7)

[Wherein R ¹² represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 4 to 30 carbon atoms which may be substituted by a hydroxy group, an oxo group or an amino group, and W represents a methylene group. , A methine group or an oxygen atom, a broken line indicates the presence or absence of a π bond, X ¹ represents a hydrogen atom, an acetyl group or a glyceryl group, or forms an oxo group with an adjacent oxygen atom, X ² , X ³ and X ⁴ each independently represent a hydrogen atom, a hydroxy group or an acetoxy group (provided that when W is a methine group, one of X ² and X ³ is a hydrogen atom and the other does not exist; When O—X ¹ is an oxo group, X ⁴ is not present), R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a hydroxy group, a hydroxymethyl group or an acetoxymethyl group, and R ¹⁵ represents a hydroxy group or 5 to 35 carbon atoms that the amino group may be substituted A linear, branched or cyclic saturated hydrocarbon group, or a linear, branched or cyclic saturated or unsaturated fatty acid having 8 to 22 carbon atoms, which may be substituted with a hydroxy group at the ω position of the hydrocarbon group. An ester-bonded group, R ¹⁶ represents a hydrogen atom, or may have a substituent selected from a hydroxy group, a hydroxyalkoxy group, an alkoxy group, and an acetoxy group; Indicates a saturated or unsaturated hydrocarbon group in the chain. ]

In the general formula (7), R ¹² is preferably a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 7 to 22 carbon atoms which may be substituted by a hydroxy group. X ¹ is preferably a hydrogen atom or a glyceryl group. The X ^2, X ³ and X ^4, is the 0-1 is hydroxy group, preferably the remainder is a hydrogen atom. As R ¹³ and R ¹⁴ , one is preferably a hydrogen atom or a hydroxymethyl group, and the other is preferably a hydrogen atom. As the fatty acid that may be ester-bonded or amide-bonded to the ω position of the saturated hydrocarbon group for R ¹⁵ , isostearic acid, 12-hydroxystearic acid, and linoleic acid are preferable. R ¹⁶ is preferably a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms in which 1 to 3 groups selected from a hydroxy group, a hydroxyalkoxy group and an alkoxy group may be substituted.

  Preferred ceramides (7) are natural ceramides or natural ceramides represented by the following general formula (7a) and derivatives thereof (hereinafter referred to as “natural ceramides (7a)”), and general formulas Pseudo-ceramides represented by (7b) (hereinafter referred to as “pseudo-ceramides (7b)”).

  (ii-1) Natural ceramides (7a)

[Wherein, R ^12a represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 7 to 19 carbon atoms which may be substituted by a hydroxy group, and W ¹ represents a methylene group or a methine group. , The broken line indicates the presence or absence of a π bond, X ^1a represents a hydrogen atom, or an oxo group is formed with an adjacent oxygen atom, and X ^2a , X ^3a and X ^4a are each independently a hydrogen atom, A hydroxy group or an acetoxy group (provided that when W ¹ is a methine group, one of X ^2a and X ^3a is a hydrogen atom and the other is not present, and when —O—X ^1a is an oxo group, X ^4a R ^13a represents a hydroxymethyl group or an acetoxymethyl group, R ^15a represents a linear, branched or cyclic saturated hydrocarbon group having 5 to 30 carbon atoms which may be substituted by the hydroxy group, or The number of carbon atoms that may be substituted with a hydroxy group at the ω-terminal of the alkyl group 8 to 22 linear or branched saturated or unsaturated fatty acid represents an ester-bonded group, and R ^16a represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

Preferably, R ^12a is a linear alkyl group having 7 to 19 carbon atoms, more preferably 13 to 15 carbon atoms; W ¹ is a methine group and ^one of X ^2a and X ^3a is a hydrogen atom; R ^15a is 9 to 9 carbon atoms Examples thereof include compounds in which 27 hydroxy groups are linear alkyl groups that may be substituted. X ^1a is preferably a hydrogen atom or forms an oxo group together with an oxygen atom. R ^15a is preferably a tricosyl group, a 1-hydroxypentadecyl group, a 1-hydroxytricosyl group, a heptadecyl group, a 1-hydroxyundecyl group, or a nonacosyl group in which linoleic acid is ester-bonded to the ω position.

  Specific examples of natural ceramides include ceramides Type 1 to 7 in which sphingosine, dihydrosphingosine, phytosphingosine, or sphingadienin is amidated (for example, J. Lipid Res., 24: 759 (1983) in FIG. 2 and J. Lipid. Res., 35: 2069 (1994) in FIG. 4 and porcine and human ceramides), and these N-alkyl compounds (for example, N-methyl compounds) Can be mentioned. These may be any of natural extracts and synthetic products, and commercially available products can be used.

  (ii-2) Pseudoceramides (7b)

[Wherein, R ^12b represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 10 to 22 carbon atoms which may be substituted by a hydroxy group, and X ^1b represents a hydrogen atom, an acetyl group or glyceryl. R ^15b is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 5 to 22 carbon atoms which may be substituted by a hydroxyl group or an amino group, or the hydrocarbon group Represents a group in which a linear or branched saturated or unsaturated fatty acid having 8 to 22 carbon atoms, which may be substituted with a hydroxyl group at the ω-terminal, is ester-bonded, and R ^16b represents a hydrogen atom or a hydroxy group , A hydroxyalkoxy group, an alkoxy group or an acetoxy group, an alkyl group having 1 to 8 carbon atoms which may be substituted. ]

R ^15b includes a nonyl group, a tridecyl group, a pentadecyl group, an undecyl group in which linoleic acid is ester-bonded to the ω position, a pentadecyl group in which linoleic acid is ester-bonded to the ω position, and 12-hydroxystearic acid is ester-bonded to the ω position. A pentadecyl group and an undecyl group in which methyl branched isostearic acid is amide-bonded at the ω position are preferred. The hydroxyalkoxy group or alkoxy group for R ^16b is preferably a group having 1 to 8 carbon atoms.

Pseudoceramides (7b) include those in which R ^12b is a hexadecyl group, X ^1b is a hydrogen atom, R ^15b is a pentadecyl group, and R ^16b is a hydroxyethyl group; R ^12b is a hexadecyl group, X ^1b is a hydrogen atom, R Preferably, ^15b is a nonyl group and R ^16b is a hydroxyethyl group; or R ^12b is a hexadecyl group, X ^1b is a glyceryl group, R ^15b is a tridecyl group, and R ^16b is a 3-methoxypropyl group. R ^12b is more preferably a hexadecyl group, X ^1b is a hydrogen atom, R ^15b is a pentadecyl group, and R ^16b is a hydroxyethyl group. Preferable specific examples include the following.

  Two or more amphiphilic amide lipids may be used in combination, and the content thereof is 0.01 to 10% by mass in the hair dye composition of the present invention from the viewpoint of the effect of recovering or suppressing damage. More preferably, it is 0.05 to 5% by mass.

  In order to further improve the feel imparted to the hair, silicones, oil components, cationic surfactants, and the like can be added to the hair dye composition of the present invention. Examples of silicones include the following.

(i) Highly polymerized dimethylpolysiloxane Examples include BY11-026, BY22-19 (Toray Dow Corning), FZ-3125 (Nihon Unicar).
Highly polymerized dimethylpolysiloxane is also used which is dissolved or dispersed in liquid oil (for example, (ii) dimethylpolysiloxane oil below, (iii) liquid silicone oil such as cyclic silicone, or liquid hydrocarbon oil such as isoparaffin). be able to.

(ii) Dimethylpolysiloxane oil represented by the following general formula

[In formula, h shows the integer of 0-650. ]

  Specifically, commercially available products such as SH200C series, viscosities 1 cs, 50 cs, 200 cs, 1000 cs, 5000 cs (Toray Dow Corning) are included.

(iii) Cyclic silicone represented by the following general formula

[In formula, i shows the integer of 3-7. ]

  Specific examples include dodecamethylcyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like. Commercially available products include SH244 and SH245 (Toray Dow Corning).

(iv) Amino-modified silicone represented by the following general formula

Wherein, R ¹⁷ represents the same group or a methyl or hydroxyl group and R ^18, 2 divalent hydrocarbon group R ¹⁸ is -R ¹⁹ -Q (wherein R ¹⁹ is 3 to 6 carbon atoms, Q is 1 -Represents a tertiary amino group-containing group or an ammonium group-containing group.), J and k are each a positive integer, and j + k depends on the molecular weight. A preferable average molecular weight is 3000 to 100,000. ]

  Examples include SS-3551, SF8452C, DC929, DC8500 (above, Toray Dow Corning), KT 1989 (GE Toshiba). When amino-modified silicone is used as an aqueous emulsion, the amount of amino-modified silicone contained in the aqueous emulsion is preferably 20 to 60% by mass, and more preferably 30 to 50% by mass. A preferred amino-modified silicone aqueous emulsion is SM8704C (Toray Dow Corning).

(v) Polyether-modified silicone A polyoxyalkylene group, preferably a polyoxyethylene group or a polyoxypropylene group, is bonded to the main chain of dimethylpolysiloxane.

  Specific examples include Silicone KF6011, KF6012, KF6013, KF351A, KF351A, KF352A, KF615A (Shin-Etsu Chemical), Silicone SH3746, SH3771C, SH3749 (Toray Dow Corning). It is done.

(vi) Other silicones In addition to the above, methylphenylpolysiloxane, fatty acid-modified silicone, alcohol-modified silicone, alkoxy-modified silicone, epoxy-modified silicone, fluorine-modified silicone, alkyl-modified silicone and the like can be mentioned.

  When the silicone compound is contained, the content thereof is preferably 0.1 to 15% by mass, and particularly preferably 0.5 to 10% by mass in the hair dye composition of the present invention.

  In addition, as the oil component, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, coconut oil fatty acid and other higher fatty acids, paraffin, liquid paraffin, liquid isoparaffin, Examples include hydrocarbon oils such as petrolatum, squalene, squalane, microcrystalline wax, and α-olefin oligomer. Natural oils such as camellia oil, macadamia nut oil, corn oil, olive oil, avocado oil, castor oil, safflower oil, jojoba oil, sunflower oil, rapeseed oil, sesame oil, soybean oil, and meadow foam oil; isopropyl myristate, palmitic acid Isopropyl acid, myristyl myristate, octyl palmitate, stearyl stearate, isocetyl stearate, isononyl isononanoate, isotridecyl isononanoate, stearic acid hydrogenated castor oil, hydroxystearic acid hardened castor oil, glyceryl tri-2-ethylhexanoate, tetra-2 -Mixed fatty acids such as pentaerythritol ethylhexanoate, neopentyl glycol dicaprate, diglyceryl diisostearate, dipentaerythritol and hydroxystearic acid / stearic acid / rosin acid And ester oils such as esters.

  Examples of the cationic surfactant include the following compounds (i) to (vi).

(i) Alkyltrimethylammonium salt Examples include compounds represented by the following general formula.
R ²⁰ −N ⁺ (CH ₃ ) ₃ X ⁻
[Wherein R ²⁰ represents an alkyl group having 12 to 22 carbon atoms, and X ⁻ represents a halogen (chlorine or bromine) ion or an alkyl sulfate ion having 1 to 2 carbon atoms. ]

(ii) Alkoxytrimethylammonium salt For example, the compound represented by the following general formula is mentioned.
R ²¹ —O—R ²² —N ⁺ (CH ₃ ) ₃ X ⁻
[Wherein R ²¹ represents an alkyl group having 12 to 22 carbon atoms, R ²² represents an ethylene group or a propylene group, and X ⁻ is the same as above. ]

(iii) Dialkyldimethylammonium salt Examples include compounds represented by the following general formula.
(R ²³ ) ₂ N ⁺ (CH ₃ ) ₂ X ⁻
[Wherein R ²³ represents an alkyl group having 12 to 22 carbon atoms or a benzyl group, and X ⁻ is the same as described above. ]

(iv) Alkyldimethylamine (and its salts)
For example, the compound represented by the following general formula and its salt are mentioned.
R ²⁴ -N (CH ₃ ) ₂
[Wherein R ²⁴ represents an alkyl group having 12 to 22 carbon atoms. ]

(v) Alkylamidoamine (and its salt)
For example, the compound represented by the following general formula and its salt are mentioned.
^{_{R 25 -CONH- (CH 2) m}} -N (R 26) 2
[Wherein, R ²⁵ represents an aliphatic hydrocarbon group having 11 to 23 carbon atoms, R ²⁶ is the same or different and represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m represents a number of 2 to 4] Indicates. ]

(vi) Hydroxy ether alkyl amines (and their salts)
For example, the compound represented by the following general formula and its salt are mentioned.

[Wherein R ²⁷ represents a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, and R ²⁸ and R ²⁹ are the same or different alkyl groups having 1 to 6 carbon atoms or — (A 'O) _p H (A' is an alkylene group having 2 to 4 carbon atoms, p is a number of 1 to 6, and p A's may be the same or different, and the arrangement thereof is arbitrary). Show. n shows the number of 1-5. ]

Examples of cationic surfactants other than the above (i) to (vi) include ethyl sulfate lanolin fatty acid aminopropylethyldimethylammonium (alkanoylaminopropyldimethylethylammonium ethyl sulfate, alkanoyl group derived from lanolin), ethyl sulfate lanolin fatty acid aminoethyl triethylammonium, ethyl lanolin fatty acid aminopropyl triethylammonium sulfate, methyl sulfate lanolin fatty acid aminoethyl trimethylammonium methyl sulfate lanolin fatty acid aminopropyl ethyl dimethyl ammonium ethyl sulfate isoalkanes acid (C ₁₄ ~C ₂₀₎ aminopropyl dimethylammonium, ethyl sulfate isoalkanes acid (C ₁₈ ~C ₂₂₎ aminopropyl dimethylammonium, aminopropyl ethylsulfate isostearate Examples include ruethyldimethylammonium, aminopropylethyldimethylammonium isononanoate ethyl sulfate, and alkyltrimethylammonium saccharin.

  Two or more kinds of cationic surfactants may be used in combination, and the content thereof is preferably 0.01 to 20% by mass, and more preferably 0.1 to 15% from the viewpoint of imparting good flexibility and slipperiness during use. % By mass, particularly 0.5 to 10% by mass is preferred.

  The hair dye composition of the present invention may further contain other components generally used in hair cosmetics depending on the purpose. For example, polymer compounds such as cationized cellulose, hydroxylated cellulose, xanthan gum, labor gum, highly polymerized polyethylene oxide; polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxy Nonionic surfactants such as ethylene hydrogenated castor oil, sucrose fatty acid esters, polyglycerin alkyl ethers, fatty acid alkanolamides and alkyl glycosides; antidandruff agents such as zinc pyrithione and benzalkonium chloride; amino acids; vitamins; Antibacterial agent; anti-inflammatory agent; antiseptic agent; chelating agent; moisturizer such as panthenol; pigment; eucalyptus polar solvent extract, shells or nacres with nacre, or hydrolyzate thereof, Protein obtained from cucumber or hydrolyzate thereof, protein-containing extract obtained from legume seeds, ginseng extract, rice germ extract, hibamata extract, camellia extract, aloe extract, moon peach leaf extract, Extracts such as chlorella extract; Pearl powder such as titanium oxide; Fragrance; Ultraviolet absorber; Antioxidant

  The hair dye composition of the present invention preferably has a pH (25 ° C.) of 1 to 5.5 when diluted 20 times by mass with water. Within this range, it has a function of recovering damage such as hair color, and is excellent in a function capable of imparting good flexibility and a supple feel from wet to dry. The pH value is particularly preferably adjusted to 2.0 to 5.0, more preferably 2.5 to 4.5 from the viewpoint of the effect of recovering damaged hair. For adjusting the pH, acidic substances such as inorganic acids and organic acids, and sodium hydroxide as a basic substance can be used in combination. Inorganic acids and organic acids include those used for neutralization of the ether amine of component (B) described above.

  In the hair dye composition of the present invention, components (A) to (D) and other optional components are added with water and ethanol, 2-propanol, glycerin, diglycerin, propylene glycol, dipropylene glycol and the like as necessary. It is manufactured by dissolving in a solvent. Examples of the product form include color rinse, color conditioner, hair manicure and the like.

  The pH of the hair dye composition shown below is a value at 25 ° C. when diluted 20 times by mass with water.

Examples 1-9 and Comparative Examples 1-3
A hair dye composition (color rinse) having the composition shown in Table 1 was produced, and “hair dyeability”, “flexibility”, “smoothness”, “moist feeling”, “smoothness” according to the following methods and standards. Evaluated. In addition, a fatigue resistance test was performed.

Evaluation method 20 g (about 15 to 20 cm) of hair of a Japanese woman that had been subjected to bleaching treatment (twice for 30 minutes with PRETIA HYBRICH (Kao)) was bundled and washed with shampoo. 2 g of the hair dye composition having the composition shown in Table 1 is uniformly applied to the hair, left for 5 minutes, rinsed with running water for 30 seconds, then towel-dried and further dried with a dryer. Sensory evaluation was performed for hair dyeability, flexibility, smoothness, moist feeling, and suppleness. The evaluation was performed by five people, and the total value of the evaluation was shown.

・ Evaluation criteria
4: Densely dyed 3: Slightly dyed 2: Not dyed very much 1: Not dyed

"Flexibility"
4: Very soft 3: Slightly soft 2: Not very soft 1: Not soft

"Smoothness"
4: Very slipping 3: Slightly slipping 2: Not slipping very much 1: Not slipping

"Moist feeling"
4: very moist 3: slightly moist 2: not very moist 1: not moist

"Flexible"
4: very supple 3: supple supple 2: not supple 1: not supple

"Fatigue resistance test"
According to the method described in YK Kamath, SB Hornby, HD Weigmann and S. Ruetsch, J. Cos. Sci., 50, 198-200 (1999), a load of 50 g / hair was repeatedly applied, and the number of repetitions until breakage Counted. Based on the obtained data, the fatigue resistance parameter (characteristic life) was calculated as follows.
In order to statistically handle the fatigue failure phenomenon, the “Weibull distribution” that can evaluate the characteristics of variation over a wide range was used. In the equation (a) of the Weibull distribution, the parameter θ (characteristic life) is obtained from the equation (b) obtained by taking the natural logarithm of both sides twice. The x axis is ln x, the y axis is ln ln [1 / [1-F (x)]], each data is plotted to obtain an approximate straight line, and the parameter θ is calculated from intercept = b lnθ and slope = b. (Formula (c)).

F (x) = 1−exp [-(x / θ) ^b ] (a)
ln ln [1 / [1−F (x)]] ＝ b ln x−b lnθ (b)
θ (characteristic life) = exp (− intercept / slope) (c)
x: Number of times of cutting, F (x): Order of cutting / number of samples b: Shape parameter θ: Characteristic life (number of times until 63.2% of samples are destroyed)

Example 10 Color conditioner (pH 3.3)
(mass%)
Orange 205 No. 0.05
Black 401 No. 0.02
N, N-dimethyl-3-octadecyloxypropylamine 2.0
Stearyl alcohol 5.0
Dipropylene glycol 1.0
N-methylpyrrolidone 5.0
Phenoxyethanol 0.1
Glycerin 5.0
Polypropylene glycol 2.5
18-methyleicosanoic acid 0.5
Amphiphilic amide lipid A 0.1
Sunflower oil 0.5
Methylpolysiloxane mixture 2.5
Lactic acid 1.5
Fragrance 0.4
Sodium hydroxide Appropriate amount Ion exchange water Remaining amount

  The above color conditioner has good hair dyeing properties, can repair or inhibit hair damage / fatigue destruction, and can impart good flexibility and a supple feel from wet to dry.

Example 11 Color conditioner (pH 3.3)
(mass%)
Orange 205 No. 0.07
Purple 401 0.01
N, N-dimethyl-3-octadecyloxypropylamine 0.5
Stearic acid dimethylaminopropylamide 2.0
Stearyl alcohol 5.0
Dipropylene glycol 1.0
Propylene carbonate 7.0
Phenoxyethanol 0.1
Glycerin 5.0
Polypropylene glycol 2.5
18-methyleicosanoic acid 0.5
Amphiphilic amide lipid B 0.1
Sunflower oil 0.5
Methylpolysiloxane mixture 2.5
Lactic acid 1.5
Fragrance 0.4
Sodium hydroxide Appropriate amount Ion exchange water Remaining amount

  The above-mentioned color conditioner has good hair dyeing properties, can repair or suppress hair damage and fatigue destruction, and can impart a good flexibility and a supple feel from wet to dry.

Example 12 Color conditioner (pH 3.3)
(mass%)
Red No. 106 0.05
N, N-dimethyl-3-octadecyloxypropylamine 1.5
N-stearyl poly (4) oxyethylene-
N, N, N-trimethylammonium chloride 0.1
Stearyl alcohol 5.0
Dipropylene glycol 1.0
γ-Caprolactone 5.0
Phenoxyethanol 0.1
Glycerin 5.0
Polypropylene glycol 2.5
18-methyleicosanoic acid 0.5
Amphiphilic amide lipid A 0.1
Sunflower oil 0.5
Methylpolysiloxane mixture 2.5
Lactic acid 1.5
Fragrance 0.4
Sodium hydroxide Appropriate amount Ion exchange water Remaining amount

  The above color conditioner has good hair dyeing properties, can repair or inhibit hair damage / fatigue destruction, and can impart good flexibility and a supple feel from wet to dry.

Example 13 Hair nail polish (pH 3.0)
(mass%)
Orange 205 No.0.2
Black 401 No. 0.1
Red No. 227 0.2
N, N-dimethyl-3-octadecyloxypropylamine 1.0
Dipropylene glycol 0.5
Ethanol 10.0
Benzyl alcohol 5.0
Phenoxyethanol 0.1
Amphiphilic amide lipid A 0.1
18-methyleicosanoic acid 0.5
Xanthan gum 2.0
Squalane 3.0
Polyoxyalkylene-modified dimethylpolysiloxane ^{* 5} 2.0
Lactic acid 4.0
Fragrance 0.3
Sodium hydroxide appropriate amount Ion-exchanged water remaining amount * 5: Silicone KF6011 (Shin-Etsu Chemical Co., Ltd.)

  The hair manicure has good hair dyeing properties, can repair or suppress damage and fatigue destruction of hair, and can impart good flexibility and a supple feel from the time of wet to the time of drying.

Example 14 Hair nail polish (pH 3.0)
(mass%)
Orange 205 No.0.2
Black 401 No. 0.1
Red No. 227 0.2
N, N-dimethyl-3-octadecyloxypropylamine 1.0
Dipropylene glycol 0.5
Ethanol 10.0
Benzyl alcohol 5.0
Phenoxyethanol 0.1
Amphiphilic amide lipid A 0.1
16-methyloctadecanoic acid 0.5
Xanthan gum 2.0
Squalane 3.0
Polyoxyalkylene-modified dimethylpolysiloxane ^{* 5} 2.0
Lactic acid 4.0
Fragrance 0.3
Sodium hydroxide appropriate amount Ion-exchanged water remaining amount * 5: Silicone KF6011 (Shin-Etsu Chemical Co., Ltd.)

  The hair manicure has good hair dyeing properties, can repair or suppress damage and fatigue destruction of hair, and can impart good flexibility and a supple feel from the time of wet to the time of drying.

Claims (3)

A hair dye composition comprising components (A), (B), (C), (D) and water.
(A) Direct dye
(B) Etheramine represented by the general formula (1) or a salt thereof

[Wherein R ¹ represents a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, R ² represents a linear or branched alkylene group having 2 to 5 carbon atoms, R ³ and R ⁴ is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or — (AO) _b H (A is an alkylene group having 2 to 4 carbon atoms, b is a number of 1 to 6; A may be the same or different, and the arrangement thereof is arbitrary.), And a represents an integer of 1 to 8. ]
(C) Organic solvent selected from the following (c1) to (c4)
(c1) Aromatic alcohol represented by general formula (2)

[Wherein R ⁵ represents a hydrogen atom, a methyl group or a methoxy group, Y represents a single bond or a linear or branched divalent hydrocarbon group having 1 to 3 carbon atoms, and Z represents a hydrogen atom or a hydroxyl group. C and d each represent a number from 0 to 5. However, c is not 0 when Y is a single bond. ]
(c2) N-alkylpyrrolidone having a C1-6 alkyl group bonded to a nitrogen atom
(c3) Alkylene carbonate having an alkylene group having 2 to 4 carbon atoms
(c4) Lactone represented by general formula (3) or (4)

[Wherein, R ⁶ and R ⁷ represent an alkyl group having 1 to 6 carbon atoms, and e and f represent 0 or 1. ]
(D) Branched fatty acid represented by the general formula (5) or a salt thereof

Wherein, R ⁸ represents a methyl group or an ethyl group, g is an integer of 3 to 36. ]   The hair dye composition according to claim 1, wherein the mass ratio (B) / (D) of the component (B) to the component (D) is in the range of 20/1 to 1/10.   The hair dye composition according to claim 1 or 2, further comprising an amphiphilic amide lipid as component (E).