JP2011178718A - Hair dye containing silicon compound and basic dye - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair dye having an improved dyeing property and suppressed skin staining. <P>SOLUTION: The hair dye includes a silicon compound comprising a block copolymer having a specific structure, a silicon compound having a specific structure with phenyl group, and a basic dye. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a hair dye containing a silicon compound and a basic dye. More specifically, the present invention relates to a hair dye having improved dyeability and skin coloration suppressed.

  Silicone compounds are useful as hair conditioning agents for improving the touch, gloss and smoothness in hair cosmetics. For example, Patent Document 1 describes that hair conditioning is improved by using a specific organopolysiloxane copolymer. However, as an effect of the organopolysiloxane copolymer, only an improvement in hair conditioning is shown, and no further effect has been found.

  Patent Document 2 describes that the use of a basic dye, a nonionic dye, and a neutral dye improves hair feel while suppressing skin contamination. However, when the hair dyeing property of the hair is improved, the skin contamination is worsened, which is not sufficient.

  Patent Documents 3, 4 and 5 describe that each silicon compound exhibits the effect of improving the feel of hair and imparting gloss, but no further effect is shown.

Japanese Patent Laid-Open No. 2004-231607 JP 2004-26690 A WO2004 / 058198 JP 63-183517 A Japanese Unexamined Patent Publication No. 63-243018

  When the hair dyeing property is improved by using a direct dye, the deterioration of skin contamination is a point that should be improved in the past in hair dyes. This invention made it the subject which should be solved to provide the hair dye from which the dyeability improved and skin coloring was suppressed.

  As a result of intensive studies to solve the above problems, the present inventors have used a combination of a basic dye and a silicon compound having a specific structure, thereby improving dyeability and suppressing skin coloring. The present invention has been completed.

（式中、Ｒ³は、互いに独立してそれぞれ同一でも異なっていてもよく、メチル基またはフェニル基（但し、Ｒ³が全てメチル基である場合、及びＲ³が全てフェニル基である場合を除く）を示し、Ｒ⁴は、互いに独立してそれぞれ同一でも異なっていてもよく、メチル基または水酸基を表す。また、ｍは1000〜20000の整数である。） That is, according to the present invention,
(A) a silicon compound represented by the following formula (A);
(B) a silicon compound represented by the following formula (B); and (c) a basic dye:
A hair dye containing is provided.
Formula (A): R ² -A ¹ -R ²
(In the formula, A ¹ represents Formula A-1:-(Si (R ¹ ) ₂ O) _a Si (R ¹ ) _2-
Formula A-2: -Y ^1-
Formula A-3: —O (CH ₂ CH ₂ O) _n —
Formula _{A-4: -O (CH 2} CH 2 CH 2 O) n -
[Wherein, R ^{1 s} may be the same or different from each other independently and each represents a saturated aliphatic monovalent hydrocarbon group, a hydroxyl group, or an alkoxy group, and Y ¹ represents an alkylene group. a represents an integer of 1 to 1350. N in Formula A-3 and n in Formula A-4 each independently represent an integer of 0 to 220, provided that both n in Formula A-3 and n in Formula A-4 are 0. No]
Among the monomer units A-1 to A-4 represented by the formula, a block copolymer comprising at least the formula A-1 and the formula A-3 and / or the formula A-4 is shown, and both ends are bonded to R ² . is doing.
R ² may be the same or different independently of each other and each independently represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted monovalent hydrocarbon group, or an alkoxy group. )
Formula (B):

(In the formula, R ³ may be the same or different independently from each other, and may be a methyl group or a phenyl group (provided that R ³ is all methyl groups and R ³ is all phenyl groups). R ^{4 s} may be the same or different and each independently represents a methyl group or a hydroxyl group, and m is an integer of 1000 to 20000.)

〔式中、Ｒ¹は、互いに独立してそれぞれ同一でも異なっていてもよく、飽和脂肪族１価の炭化水素基、水酸基、又はアルコキシ基を表し、Ｙ¹は、互いに独立してそれぞれ同一でも異なっていてもよく、アルキレン基を表す。Ｒ²は、互いに独立してそれぞれ同一でも異なっていてもよく、水素原子、水酸基、置換または無置換の１価の炭化水素基、アルコキシ基、あるいは式：−Ｙ^1A−Ｏ−（Ｃ₂Ｈ₄Ｏ）_b1A（Ｃ₃Ｈ₆Ｏ）_b2A−Ｙ²（Ｙ^1Aはアルキレン基を示し、Ｙ²は、水素原子、又は置換もしくは無置換の１価の炭化水素基を示す。ｂ１Ａ及びｂ２Ａはそれぞれ独立に、0〜220の整数を示す（但しｂ１Ａ及びｂ２Ａの両方が０であることはない）で表される基であり、
ａは、1〜1350の整数を示し、
ｂ１およびｂ２は、それぞれ独立に0〜220の整数を示し（但しｂ１およびb２の両方が０であることはない）、
ｃは、0〜50の整数である。但しｃが0であるとき、Ｒ¹またはＲ²で表される基の少なくとも１つの基は−Ｙ^1A−Ｏ−（Ｃ₂Ｈ₄Ｏ）_b1A（Ｃ₃Ｈ₆Ｏ）_b2A−Ｙ²で表される基である。
式：−（Ｓｉ(Ｒ¹）₂Ｏ）_aＳｉ(Ｒ¹）₂−で表されるポリオルガノシロキサンブロックの平均分子量は134〜10000であり、
式：−（Ｓｉ(Ｒ¹）₂Ｏ）_aＳｉ(Ｒ¹）₂−で表されるポリオルガノシロキサンブロックは、式（Ａ−１）で表されるシリコン化合物の0.7〜97.5質量％を構成し、
式：−（Ｃ ₂Ｈ ₄Ｏ）_b1（Ｃ ₃Ｈ ₆Ｏ）_b2−で表されるポリオキシアルキレンブロックの平均分子量は130〜10000であり、
式（Ａ−１）で表されるシリコン化合物の平均分子量は650〜100000である。〕 Preferably, the silicon compound represented by the formula (A) is a silicon compound represented by the following formula (A-1).
Formula (A-1)

[In the formula, R ¹ may be the same as or different from each other, independently of one another, represent a saturated aliphatic monovalent hydrocarbon group, a hydroxyl group, or an alkoxy group, Y ¹ is also respectively identical, independently of one another It may be different and represents an alkylene group. R ² may be the same or different from each other independently of each other, and may be a hydrogen atom, a hydroxyl group, a substituted or unsubstituted monovalent hydrocarbon group, an alkoxy group, or a formula: —Y ^1A —O— (C ₂ H _{4 O) b1A (C 3 H} 6 O) b2A -Y 2 (Y 1A is an alkylene group, Y ² is, .B1A and B2a represents a hydrogen atom, or a substituted or unsubstituted monovalent hydrocarbon group Each independently represents an integer of 0 to 220 (provided that both b1A and b2A are not 0),
a represents an integer of 1 to 1350,
b1 and b2 each independently represent an integer of 0 to 220 (provided that both b1 and b2 are not 0);
c is an integer of 0-50. However, when c is 0, at least one group represented by R ¹ or R ² is —Y ^1A —O— (C ₂ H ₄ O) _b1A (C ₃ H ₆ O) _b2A —Y ² . It is a group represented.
The average molecular weight of the polyorganosiloxane block represented by the formula:-(Si (R ¹ ) ₂ O) _a Si (R ¹ ) _2- is 134 to 10,000,
The polyorganosiloxane block represented by the formula:-(Si (R ¹ ) ₂ O) _a Si (R ¹ ) ₂ -constitutes 0.7 to 97.5% by mass of the silicon compound represented by the formula (A-1). And
The average molecular weight of the polyoxyalkylene block represented by the formula: — (C ₂ H ₄ O) _b1 (C ₃ H ₆ O) _b2 — is 130 to 10,000.
The average molecular weight of the silicon compound represented by the formula (A-1) is 650 to 100,000. ]

Preferably, content of the silicon compound represented by Formula (A) is 1-10 mass% with respect to the mass of hair dye.
Preferably, content of the silicon compound represented by Formula (B) is 1-10 mass% with respect to the mass of a hair dye.

Preferably, the total content of the silicon compound represented by the formula (A) and the silicon compound represented by the formula (B) is 3 to 15% by mass with respect to the mass of the hair dye.
Preferably, the total content of the silicon compound represented by the formula (A) and the silicon compound represented by the formula (B) is 9 to 15% by mass with respect to the mass of the hair dye.

Preferably, the basic dye is basic blue (basic blue), basic violet (basic purple), basic brown (basic brown), basic red (basic red), basic yellow (basic) Yellow) or basic dyes belonging to basic green.
Preferably, the basic dye is basic blue 99 (8-amino-2-bromo-5-hydroxy-4-imino-6-[(3- (trimethylammonio) phenyl) amino] -1 (4H)- Naphthalinone-chloride).

  According to the present invention, there is further provided a hair coloring method comprising applying the above-described hair dye of the present invention to hair.

  The hair dye of the present invention has improved dyeability and suppressed skin coloring.

Hereinafter, embodiments of the present invention will be described in detail.
The hair dye of the present invention is
(A) a silicon compound represented by the formula (A);
(B) a silicon compound represented by the formula (B); and (c) a basic dye:
It is characterized by containing. In the hair dye of the present invention, by blending both the silicon compound represented by the formula (A) and the silicon compound represented by the formula (B), two effects of improving dyeability and suppressing skin coloring are obtained. Can be achieved at the same time. In addition, the silicon compound said in this specification is synonymous with a silicone compound.

The first silicon compound used in the present invention is a silicon compound represented by the following formula (A).
Formula (A): R ² -A ¹ -R ²
(In the formula, A ¹ represents Formula A-1:-(Si (R ¹ ) ₂ O) _a Si (R ¹ ) _2-
Formula A-2: -Y ^1-
Formula A-3: —O (CH ₂ CH ₂ O) _n —
Formula _{A-4: -O (CH 2} CH 2 CH 2 O) n -
[Wherein, R ^{1 s} may be the same or different from each other independently and each represents a saturated aliphatic monovalent hydrocarbon group, a hydroxyl group, or an alkoxy group, and Y ¹ represents an alkylene group. a represents an integer of 1 to 1350. N in Formula A-3 and n in Formula A-4 each independently represent an integer of 0 to 220, provided that both n in Formula A-3 and n in Formula A-4 are 0. No]
Among the monomer units A-1 to A-4 represented by the formula, a block copolymer comprising at least the formula A-1 and the formula A-3 and / or the formula A-4 is shown, and both ends are bonded to R ² . is doing.
R ² may be the same or different independently of each other and each independently represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted monovalent hydrocarbon group, or an alkoxy group. )

  Regarding the formulas A-1 to A-4, the silicon compound represented by the formula (A) includes a plurality of monomer units represented by the formulas A-1 to A-4. It may be the same or different independently. That is, the silicon compound represented by the formula (A) includes a plurality of monomer units represented by the formula A-1 having different structures, a plurality of monomer units represented by the formula A-2 having different structures, A monomer unit represented by the formula A-3 having a different structure or a plurality of monomer units represented by the formula A-4 having a different structure may be contained.

A ¹ represents a block copolymer composed of at least Formula A-1 and Formula A-3 and / or Formula A-4 among monomer units A-1 to A-4. That is, among formulas A-1 to A-4, the essential ones are (i) a monomer unit represented by formula A-1 and (ii) a formula A-3 and / or formula A-4. It is a monomer unit, and the monomer unit represented by the formula A-2 is not necessarily present. Preferably, A ¹ is composed of four monomer units of formula A-1, formula A-2, formula A-3 and formula A-4.

〔式中、Ｒ¹は、互いに独立してそれぞれ同一でも異なっていてもよく、飽和脂肪族１価の炭化水素基、水酸基、又はアルコキシ基を表し、Ｙ¹は、互いに独立してそれぞれ同一でも異なっていてもよく、アルキレン基を表す。Ｒ²は、互いに独立してそれぞれ同一でも異なっていてもよく、水素原子、水酸基、置換または無置換の１価の炭化水素基、アルコキシ基、あるいは式：−Ｙ^1A−Ｏ−（Ｃ₂Ｈ₄Ｏ）_b1A（Ｃ₃Ｈ₆Ｏ）_b2A−Ｙ²（Ｙ^1Aはアルキレン基を示し、Ｙ²は、水素原子、又は置換もしくは無置換の１価の炭化水素基を示す。ｂ１Ａ及びｂ２Ａはそれぞれ独立に、0〜220の整数を示す（但しｂ１Ａ及びｂ２Ａの両方が０であることはない）で表される基であり、
ａは、1〜1350の整数を示し、
ｂ１およびｂ２は、それぞれ独立に0〜220の整数を示し（但しｂ１およびb２の両方が０であることはない）、
ｃは、0〜50の整数である。但しｃが0であるとき、Ｒ¹またはＲ²で表される基の少なくとも１つの基は−Ｙ^1A−Ｏ−（Ｃ₂Ｈ₄Ｏ）_b1A（Ｃ₃Ｈ₆Ｏ）_b2A−Ｙ²で表される基である。
式：−（Ｓｉ(Ｒ¹）₂Ｏ）_aＳｉ(Ｒ¹）₂−で表されるポリオルガノシロキサンブロックの平均分子量は134〜10000であり、
式：−（Ｓｉ(Ｒ¹）₂Ｏ）_aＳｉ(Ｒ¹）₂−で表されるポリオルガノシロキサンブロックは、式（Ａ−１）で表されるシリコン化合物の0.7〜97.5質量％を構成し、
式：−（Ｃ ₂Ｈ ₄Ｏ）_b1（Ｃ ₃Ｈ ₆Ｏ）_b2−で表されるポリオキシアルキレンブロックの平均分子量は130〜10000であり、
式（Ａ−１）で表されるシリコン化合物の平均分子量は650〜100000である。〕 The silicon compound represented by the formula (A) is preferably a silicon compound represented by the following formula (A-1).
Formula (A-1)

[In the formula, R ¹ may be the same as or different from each other, independently of one another, represent a saturated aliphatic monovalent hydrocarbon group, a hydroxyl group, or an alkoxy group, Y ¹ is also respectively identical, independently of one another It may be different and represents an alkylene group. R ² may be the same or different from each other independently of each other, and may be a hydrogen atom, a hydroxyl group, a substituted or unsubstituted monovalent hydrocarbon group, an alkoxy group, or a formula: —Y ^1A —O— (C ₂ H _{4 O) b1A (C 3 H} 6 O) b2A -Y 2 (Y 1A is an alkylene group, Y ² is, .B1A and B2a represents a hydrogen atom, or a substituted or unsubstituted monovalent hydrocarbon group Each independently represents an integer of 0 to 220 (provided that both b1A and b2A are not 0),
a represents an integer of 1 to 1350,
b1 and b2 each independently represent an integer of 0 to 220 (provided that both b1 and b2 are not 0);
c is an integer of 0-50. However, when c is 0, at least one group represented by R ¹ or R ² is —Y ^1A —O— (C ₂ H ₄ O) _b1A (C ₃ H ₆ O) _b2A —Y ² . It is a group represented.
The average molecular weight of the polyorganosiloxane block represented by the formula:-(Si (R ¹ ) ₂ O) _a Si (R ¹ ) _2- is 134 to 10,000,
The polyorganosiloxane block represented by the formula:-(Si (R ¹ ) ₂ O) _a Si (R ¹ ) ₂ -constitutes 0.7 to 97.5% by mass of the silicon compound represented by the formula (A-1). And
The average molecular weight of the polyoxyalkylene block represented by the formula: — (C ₂ H ₄ O) _b1 (C ₃ H ₆ O) _b2 — is 130 to 10,000.
The average molecular weight of the silicon compound represented by the formula (A-1) is 650 to 100,000. ]

  The silicon compound represented by the above formula (A) (preferably, the silicon compound represented by the following formula (A-1)) is a polyorganosiloxane-polyoxyalkylene block block copolymer, and is disclosed in International Publication WO2004. / 058198 publications can be used. Specific examples of the silicon compound represented by the formula (A) (preferably the silicon compound represented by the following formula (A-1)) include trade names FZ-2222, FZ-2233, FZ-2231, FZ- Examples include 2250 (Toray Dow Corning), but are not limited thereto.

（式中、Ｒ³は、互いに独立してそれぞれ同一でも異なっていてもよく、メチル基またはフェニル基（但し、Ｒ³が全てメチル基である場合、及びＲ³が全てフェニル基である場合を除く）を示し、Ｒ⁴は、互いに独立してそれぞれ同一でも異なっていてもよく、メチル基または水酸基を表す。また、ｍは1000〜20000の整数である。） The second silicon compound used in the present invention is a phenyl-modified silicon compound represented by the following formula (B).
Formula (B):

(In the formula, R ³ may be the same or different independently from each other, and may be a methyl group or a phenyl group (provided that R ³ is all methyl groups and R ³ is all phenyl groups). R ^{4 s} may be the same or different and each independently represents a methyl group or a hydroxyl group, and m is an integer of 1000 to 20000.)

  As the silicon compound represented by the formula (B), those described in JP-A-63-183517 and JP-A-63-243018 can be used. Specific examples of the silicon compound represented by the formula (B) include, but are not limited to, trade names SH556 and PH-1555 (Toray Dow Corning).

  The content of the silicon compound represented by the formula (A) is preferably 1 to 10% by mass, more preferably 2 to 10% by mass with respect to the mass of the hair dye, and 3 to 10% by mass. It is particularly preferred that

  The content of the silicon compound represented by the formula (B) is preferably 1 to 10% by mass, more preferably 2 to 10% by mass with respect to the mass of the hair dye, and 3 to 10% by mass. It is particularly preferred that

  The total content of the silicon compound represented by the formula (A) and the silicon compound represented by the formula (B) is preferably 3 to 15% by mass with respect to the mass of the hair dye, and 5 to 15 mass. %, More preferably 7 to 15% by mass, and particularly preferably 9 to 15% by mass.

  The hair dye of the present invention may further contain other silicon compounds other than the silicon compound represented by the formula (A) and the silicon compound represented by the formula (B). Examples of other silicon compounds include dimethicone, highly polymerized dimethylpolysiloxane, dimethylpolysiloxane, amino-modified silicon, and cyclic silicon. Silicon compounds do not depend on polymers or monomers. In addition, there are lubricants that have a cationic site in the molecule, thereby improving the residual amount on the hair, and are not particularly limited. When blending other silicon compounds as described above, the blending amount is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 0.5 to 5% by mass in the hair preparation of the present invention. . Specific examples of other silicon compounds include, but are not limited to, the following silicon.

<Linear dimethyl silicon>
A silicon compound represented by the following structure (n represents an integer of 5 or more). Specific examples include SH200 C series and SH200Fluid series (made by Toray Dow Silicone), but are not limited thereto.

<Circular silicon>
Silicon compounds represented by the following structure (n is an integer of 1 to 20), and specific examples include SH245 Fluid, DC345 Fluid, DC246 Fluid, etc. (manufactured by Toray Dow Silicone Co., Ltd.). Is not to be done.

<Amino-modified silicon>
Silicon compounds containing the following monomer units in the molecule, specifically, SM8904, BY22-079, SILSTYLE104, etc. (manufactured by Toray Dow Silicone Co., Ltd.), etc., are not limited thereto.

  The basic dye used in the present invention is not particularly limited as long as it can be added to the hair dye. Examples of the basic dye used in the present invention include basic blue (basic blue), basic violet (basic purple), basic brown (basic brown), basic red (basic red), and basic dye. Basic dyes belonging to yellow (basic yellow) and basic green (basic green) can be used. Specific examples of the basic dye include, for example, 9- (dimethylamino) -benzo [a] phenoxadi-7-ium chloride (CI51175; basic blue No. 6), di [4- (diethylamino) phenyl] [ 4- (Ethylamino) naphthyl] carbenium chloride (CI42595; Basic Blue No. 7), 3,7-di (dimethylamino) phenothiazine-5-ium chloride (CI522015; Basic Blue No.9), di [4- (Dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium chloride (CI44045; Basic Blue No. 26), 2-[(4- (ethyl (2-hydroxyethyl) amino) phenyl) Azo] -6-methoxy-3-methyl-benzothiazoliu -Methyl sulfate (CI11154; Basic Blue No. 41), 8-amino-2-bromo-5-hydroxy-4-imino-6-[(3- (trimethylammonio) phenyl) amino] -1 (4H) Naphthalinone chloride (CI 56059; basic blue No. 99), bis [4- (dimethylamino) -phenyl] [4- (methylamino) phenyl] carbenium chloride (CI 42535; basic violet No. 1), Tris (4-amino-3-methylphenyl) -carbenium-chloride (CI42520; basic violet No. 2), tris [4- (dimethylamino) phenyl] carbenium-chloride (CI42555; basic violet No. 3), 2 -[3,6- (die Ruamino) dibenzopyranium-9-yl] -benzoic acid chloride (CI45170; basic violet No. 10), di (4-aminophenyl) (4-amino-3-methylphenyl) carbenium chloride (CI42510; basic) Violet No. 14), 1,3-bis [(2,4-diamino-5-methylphenyl) azo] -3-methylbenzene (CI21010; Basic Brown No. 4), 1-[(4-amino Phenyl) azo] -7- (trimethylammonio) -2-naphthol-chloride (CI12250; Basic Brown No. 16), 1-[(4-amino-3-nitrophenyl) azo] -7- (trimethylammoni E) -2-Naphthol-chloride (CI12251; Basic Round No. 17), 3,7-diamino-2,8-dimethyl-5-phenyl-phenazinium chloride (CI 50240; Basic Red No. 2), 1,4-dimethyl-5-[(4- (dimethylamino) phenyl ) Azo] -1,2,4-triazolium chloride (CI11055; Basic Red No. 22), 2-hydroxy-1-[(2-methoxyphenyl) azo] -7- (trimethylammonio) -naphthalene- Chloride (CI12245; Basic Red No. 76), 2- [2 ((2,4-dimethoxyphenyl) amino) ethenyl] -1,3,3-trimethyl-3H-indole-1-ium-chloride (CI48055; Basic Yellow No. 11), 3-methyl-1-phenyl-4-[(3- (trimethyl) Ammonio) phenyl) azo] -pyrazol-5-one-chloride (CI12719; basic yellow No. 57), bis [4- (diethylamino) phenyl] phenylcarbenium-hydrogen sulfate (1: 1) (CI41040; basic -Green No. 1) etc. are mentioned.

  The content of the basic dye is preferably 0.01 to 5% by mass and more preferably 0.05 to 2% by mass with respect to the mass of the hair dye.

  The hair dye of the present invention includes, in addition to the basic dyes described above, oxidation dyes, chelate dyes, acid dyes, nonionic dyes and neutral dyes, which are classified into permanent hairs, semi-permanent hairs, and temporary hairs. And carbon black may be mixed as appropriate. Further, a nitro dye (HC dye), a paraphenylenediamine compound or the like may be appropriately mixed.

  In addition to the above, various additives may be added to the hair dye of the present invention. Additives include base materials, surfactants, fats and oils, solvents, thickeners, organic acids, preservatives, antioxidants, pH adjusters, wetting agents, fragrances, metal odor masking agents, and product colorants. And UV absorbers for products. In addition, as additives, components used in ordinary cosmetics and the like within the range not impairing the object of the present invention, such as emollients, treatment agents, moisturizers, softeners, lubricants, moisturizers, hair restorers, hair nourishing agents, Hair growth agent, anti-dandruff agent, anti-whitening agent, anti-aging agent, active oxygen remover, antioxidant, collagen synthesis accelerator, vitamin agent, fragrance, coloring agent, antiperspirant, cooling sensation agent, warming sensation agent, etc. Can be mentioned. In addition, antibacterial agent, antimicrobial agent, antibiotic agent, anti-inflammatory agent, antiallergic agent, hormone agent, skin disease treatment agent, antifungal agent, antipruritic agent, sweating agent, antiperspirant, vasoconstrictor, vasodilator, Vitamins, silicones, minerals, hydrolyzed proteins, amino acids, emollients, and the like can be appropriately blended. The usage-amount of these additives can be suitably set within the range with the effect of this invention.

  Examples of the base include higher alcohols, hydrocarbons, fatty acid esters, vegetable oils, fatty acids and the like.

  As the surfactant, a cationic surfactant is preferably contained in order to further improve the feel given to the hair. As the cationic surfactant, mono long-chain alkyl quaternary ammonium salts are preferable, and specific examples include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, and behenyltrimethylammonium chloride. Behenyltrimethylammonium is preferred. Two or more surfactants may be used in combination, and the content thereof is 0.01 to 20.0% by mass of the cosmetic of the present invention from the viewpoint of further flexibility, smoothness, stability and the like, In particular, 0.1 to 10.0% by mass is preferable.

Examples of the antioxidant include ascorbic acid and derivatives thereof, sodium sulfite and the like.
pH adjusters include citric acid, phosphoric acid, ammonia, ammonium bicarbonate, ammonium carbonate, potassium hydroxide, sodium hydroxide, monoethanolamine, isopropanolamine, ammonium phosphate, diammonium phosphate monobasic, sodium citrate , Ammonium citrate, potassium phosphate, sodium phosphate and the like can be used.

Examples of the wetting agent include 1,3-butylene glycol, propylene glycol, glycerin, sorbitol, sodium pyrrolidonecarboxylate, amino acid, vegetable oil and the like.
Examples of the thickener include xanthan gum, polyethylene glycol, hydroxyethyl cellulose and the like.

  Solvents include water, ethanol, isopropyl alcohol, 1,3 butylene glycol, 1,2-pentanediol, 2-methyl-2,4-pentanediol, glycerin, diglycerin, propylene glycol. -Dipropylene glycol, dipropylene glycol and the like.

  The pH of the hair dye of the present invention is preferably pH 5 to 10, more preferably pH 5 to 8, more preferably 5 to 7, and further preferably 6 to 7.

  The dosage form of the hair dye of the present invention is not particularly limited, and specifically, a shampoo, a treatment, a conditioner, a hair manicure and the like containing a basic dye, a non-washing type hair oil, a retouch, and a hair mascara. Mousses, hair waxes, hair styling gels and the like.

By applying the hair dye of the present invention to hair, hair can be dyed.
The coating amount of the hair dye of the present invention is preferably about 20 g to 100 g, more preferably about 40 g to 80 g of hair dye of the present invention is applied to hair having a length of about 20 cm.

  The following examples further illustrate the present invention, but the present invention is not limited to the examples.

<Preparation of oil phase A>
The following components were mixed to prepare an oil phase A.
Cetanol 1.5g
Stearyl alcohol 3.5g
Glyceryl stearate 0.5g
1g PEG-20 tristearate
Stearic acid polyglyceride 2g
Kachinar DC-80 (Toho Chemical Co., Ltd.) 2.5g
Katchinal BHC-60BE (Toho Chemical Co., Ltd.) 3.7g

<Used silicon>
As the silicon compound represented by the formula (A) of the present invention, FZ-2233 (manufactured by Toray Dow Corning) was used, and as the silicon compound represented by the formula (B) of the present invention, SH556 (Toray Dow Corning) Made). Moreover, the following compounds were used as other silicon.
DC246 Fluid (Toray Dow Silicone; cyclic silicon)
SILSTYLE104, etc. (made by Toray Dow Silicone; amino-modified silicone)
SH200 C, Fluid200 10CS (manufactured by Toray Dow Silicone; linear dimethyl silicon)
SH200 C, Fluid200 1000CS (manufactured by Toray Dow Silicone; linear dimethylsilicone)

<Preparation of hair dye>
Hair dyes having the compositions shown in Table 1 were prepared by the following method.
The oil phase A and the aqueous phase (glycerin and water) are heated to 80 ° C. When the temperature reaches 80 ° C., the oil phase is mixed with the aqueous phase and homogenized at 2500 rpm for 4 minutes. Silicon was mixed with oil phase A before homogenization, and basic blue 99 was added to the aqueous phase before homogenization. The amount of water added was adjusted so that the total amount was 100 g.

<Determination of skin coloring>
After washing with shampoo, 0.5 g of hair dye (shown in Table 1) was applied to 1 cm ² on the inner side of the upper arm and left for 5 minutes. Then, it washed with hand soap and warm water for 2 minutes, and judged the coloring degree. The results are shown in Table 1.
X: The boundary is clearly understood.
Δ: It can be seen that it is dyed.
○: Vaguely stained.
A: If you look closely, you can see that it is dyed.

<Determination of hair dyeing properties>
The goat hair was washed with shampoo, and 2 g of hair dye (shown in Table 1) was applied to 1 g of the goat hair that had been drained of water, and allowed to stand for 5 minutes. Then, it rinsed with warm water, and judged with the color degree ((DELTA) E) with the color difference meter CR-400 (made by Konica Minolta).
ΔE is produced from the color difference ΔL ^* a ^* b ^* with the following formula:
ΔE ＝ [(ΔL *) 2+ (Δa *) 2+ (Δb *) 2] 1/2
In general, when the same dye is used, if ΔE is increased, the hair dyeing property is improved (dye well), and if ΔE is decreased, the hair dyeing property is deteriorated (not dyed).
The results are shown in Table 1.

  From the results shown in Table 1, by blending both the silicon compound represented by the formula (A) and the silicon compound represented by the formula (B), the hair dyeing property can be improved without deteriorating skin coloring. Proven. Moreover, it was demonstrated that skin coloring can be further suppressed by increasing the compounding quantity of the silicon compound represented by Formula (A) and the silicon compound represented by Formula (B).

Claims (9)

(A) a silicon compound represented by the following formula (A);
(B) a silicon compound represented by the following formula (B); and (c) a basic dye:
Hair dye containing.
Formula (A): R ² -A ¹ -R ²
(In the formula, A ¹ represents Formula A-1:-(Si (R ¹ ) ₂ O) _a Si (R ¹ ) _2-
Formula A-2: -Y ^1-
Formula A-3: —O (CH ₂ CH ₂ O) _n —
Formula _{A-4: -O (CH 2} CH 2 CH 2 O) n -
[Wherein, R ^{1 s} may be the same or different from each other independently and each represents a saturated aliphatic monovalent hydrocarbon group, a hydroxyl group, or an alkoxy group, and Y ¹ represents an alkylene group. a represents an integer of 1 to 1350. N in Formula A-3 and n in Formula A-4 each independently represent an integer of 0 to 220, provided that both n in Formula A-3 and n in Formula A-4 are 0. No]
Among the monomer units A-1 to A-4 represented by the formula, a block copolymer comprising at least the formula A-1 and the formula A-3 and / or the formula A-4 is shown, and both ends are bonded to R ² . is doing.
R ² may be the same or different independently of each other and each independently represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted monovalent hydrocarbon group, or an alkoxy group. )
Formula (B):

(In the formula, R ³ may be the same or different independently from each other, and may be a methyl group or a phenyl group (provided that R ³ is all methyl groups and R ³ is all phenyl groups). R ^{4 s} may be the same or different and each independently represents a methyl group or a hydroxyl group, and m is an integer of 1000 to 20000.) The hair dye according to claim 1, wherein the silicon compound represented by the formula (A) is a silicon compound represented by the following formula (A-1).
Formula (A-1)

[In the formula, R ¹ may be the same as or different from each other, independently of one another, represent a saturated aliphatic monovalent hydrocarbon group, a hydroxyl group, or an alkoxy group, Y ¹ is also respectively identical, independently of one another It may be different and represents an alkylene group. R ² may be the same or different from each other independently of each other, and may be a hydrogen atom, a hydroxyl group, a substituted or unsubstituted monovalent hydrocarbon group, an alkoxy group, or a formula: —Y ^1A —O— (C ₂ H _{4 O) b1A (C 3 H} 6 O) b2A -Y 2 (Y 1A is an alkylene group, Y ² is, .B1A and B2a represents a hydrogen atom, or a substituted or unsubstituted monovalent hydrocarbon group Each independently represents an integer of 0 to 220 (provided that both b1A and b2A are not 0),
a represents an integer of 1 to 1350,
b1 and b2 each independently represent an integer of 0 to 220 (provided that both b1 and b2 are not 0);
c is an integer of 0-50. However, when c is 0, at least one group represented by R ¹ or R ² is —Y ^1A —O— (C ₂ H ₄ O) _b1A (C ₃ H ₆ O) _b2A —Y ² . It is a group represented.
The average molecular weight of the polyorganosiloxane block represented by the formula:-(Si (R ¹ ) ₂ O) _a Si (R ¹ ) _2- is 134 to 10,000,
The polyorganosiloxane block represented by the formula:-(Si (R ¹ ) ₂ O) _a Si (R ¹ ) ₂ -constitutes 0.7 to 97.5% by mass of the silicon compound represented by the formula (A-1). And
The average molecular weight of the polyoxyalkylene block represented by the formula: — (C ₂ H ₄ O) _b1 (C ₃ H ₆ O) _b2 — is 130 to 10,000.
The average molecular weight of the silicon compound represented by the formula (A-1) is 650 to 100,000. ] The hair dye according to claim 1 or 2, wherein the content of the silicon compound represented by the formula (A) is 1 to 10% by mass with respect to the mass of the hair dye. The hair dye according to any one of claims 1 to 3, wherein the content of the silicon compound represented by the formula (B) is 1 to 10% by mass with respect to the mass of the hair dye. The total content of the silicon compound represented by the formula (A) and the silicon compound represented by the formula (B) is 3 to 15% by mass with respect to the mass of the hair dye, Hair dye according to claim 1. The total content of the silicon compound represented by the formula (A) and the silicon compound represented by the formula (B) is 9 to 15% by mass with respect to the mass of the hair dye, Hair dye according to claim 1. Basic dyes are basic blue (basic blue), basic violet (basic purple), basic brown (basic brown), basic red (basic red), basic yellow (basic yellow), Or the hair dye of any one of Claim 1 to 6 which is a basic dye which belongs to basic green (basic green). The basic dye is basic blue 99 (8-amino-2-bromo-5-hydroxy-4-imino-6-[(3- (trimethylammonio) phenyl) amino] -1 (4H) -naphthalinone-chloride. The hair dye according to any one of claims 1 to 7, wherein A hair dyeing method comprising applying the hair dye according to any one of claims 1 to 8 to hair.