WO2016093189A1

WO2016093189A1 - Hair dye composition

Info

Publication number: WO2016093189A1
Application number: PCT/JP2015/084251
Authority: WO
Inventors: 志保中岡; 昌良野尻; 由紀直井
Original assignee: 花王株式会社
Priority date: 2014-12-09
Filing date: 2015-12-07
Publication date: 2016-06-16
Also published as: TW201627412A

Abstract

(First invention) A hair dye composition containing components (A), (B), and (C-1). (A) A direct dye, (B) a sulfonated polysaccharide, (C-1) a cationic polymer having a charge density of 3-24 meq/g. (Second invention) A hair dye composition containing components (A), (B), and (C-2), the charge ratio (C-2)/(B) of component (B) and component (C-2) is from 0.5 to 30. (A) A direct dye, (B) a sulfonated polysaccharide, (C-2) a cationic surfactant selected from the group consisting of monoalkyl (C_8-22) quaternary ammonium salts, monoalkyl (C_8-22) ether amines, monoalkylamide (C_8-22) amines, and salts of these amines.

Description

Hair dye composition

The present invention relates to a hair dye composition.

About 1st invention The hair cosmetics containing a cationic polymer are used widely as what maintains a natural state of hair, or recovers from a damaged state. Further, a composition obtained by adding a dye directly to such a composition is generally called a color treatment as a composition having both hair dyeing property and conditioning property, and has attracted attention in recent years.

For example, hair dye compositions containing a cationic direct dye and a cationic or amphoteric polymer have been proposed as being excellent in hair dyeability and fastness (Patent Document 1 and Patent Document 2).

On the other hand, the polysaccharide derivative described in Patent Document 3 is not easily affected by inorganic metal salts, organic metal salts, pH, temperature, etc., exhibits a stable thickening property, and has an emulsion stabilizing action. When used for toiletry products, it is considered to be less sticky to the skin and excellent in usability (Patent Document 3).

(Patent Document 1) JP 11-343218 (Patent Document 2) JP 2000-7542 (Patent Document 3) JP 10-25301

● About the second invention Hair dyes using direct dyes are accepted by users because they are safer and more convenient than hair dyes using oxidative dyes and have less hair damage. Various products have been proposed with names such as hair nail polish, color treatment, and color hair conditioner.

For example, Patent Document 4 proposes a hair conditioner that combines a basic dye and a neutral dye in a specific ratio with a cationic surfactant and a fatty alcohol to enable quick and uniform hair dyeing and has a conditioning effect. Has been.

On the other hand, Patent Document 5 proposes a hair cosmetic comprising an acid dye in combination with a film-forming polymer and a specific polysaccharide derivative as a thickening agent. This hair cosmetic has good spread and is easy to apply to hair. It is said that it has excellent usability.

(Patent Document 4) JP-A-01-132512 (Patent Document 5) JP-A-11-012139

About 1st invention 1st invention provides the hair dye composition containing the following component (A), (B) and (C-1).
(A) Direct dye (B) Sulfonated polysaccharide (C-1) Cationic polymer with charge density of 3 meq / g or more and 24 meq / g or less

● About the Second Invention The second invention contains the components (A), (B) and (C-2), and the charge ratio (C-2) between the components (B) and (C-2). / (B) provides a hair dye composition having 0.5 or more and 30 or less.
(A) Direct dye (B) Sulfonated polysaccharide (C-2) _Monoalkyl (C _8-22 ) quaternary ammonium salt, monoalkyl (C _8-22 ) ether amine, monoalkyl amide (C _8-22 ) Cationic surfactants selected from the group consisting of amines and salts of these amines

It is a figure which shows the persistence of the friction reduction effect of the hair by the hair dye composition of 1st invention. It is a figure which shows the persistence of the friction reduction effect of the hair by the hair dye composition of 1st invention.

Detailed Description of the Invention

About the 1st invention The hair dye composition as proposed in Patent Document 1 or 2 was not satisfactory in dyeability, feel after dyeing treatment, and dyeing fastness. Further, in Patent Document 3, the polysaccharide derivative is not used for the hair dye composition, and temporarily contains a cationic direct dye as proposed in Patent Document 1 or 2 and a cationic or amphoteric polymer. Even when the polysaccharide derivative described in Patent Document 3 is to be added to the hair dye composition, complex ions are generated between the cationic direct dye and the polysaccharide derivative, or between the cationic or amphoteric polymer and the polysaccharide derivative. Because of the formation of a sex complex, a decrease in dyeability and a significant deterioration in touch are expected.

Therefore, according to the first invention, good dyeability and dyeing fastness can be obtained regardless of the ionicity of the direct dye, and the excellent feeling improvement effect after the treatment is maintained, and the excellent feeling is maintained even after repeated shampoo washing. Furthermore, the present invention relates to a stable hair dye composition that does not produce precipitates.

The present inventors have found that the above problem can be solved by using a sulfonated polysaccharide and a cationic polymer having a charge density within a certain range together with a direct dye.

In the first invention, the charge density of the cationic polymer refers to the number of moles of cationic groups per 1 g of the polymer including counter ions in the polymer obtained as a raw material × 1000 (meq / g). In the present invention, the charge density of the anionic polymer means the number of moles of anionic group per 1 g of the polymer including the counter ion in the polymer obtained as a raw material × 1000 (meq / g). The cationic polymer in the present invention includes a polymer that has a cationic group and an anionic group and becomes cationic as a whole. The polymer in such a case shall consider only the charge density of the cationic group.

[Component (A): Direct dye]
The direct dye of component (A) is selected from the group consisting of the following azo dyes (A-1), (A-2) and (A-3), acid dyes, basic dyes, nitro dyes and disperse dyes At least one kind or two or more dyes can be used.

Examples of the acid dye include Blue No. 1, Purple No. 401, Black No. 401, Orange No. 205, Red No. 227, Red No. 106, Yellow No. 203, and Acid Orange 3.
Examples of the basic dye include basic red 51, basic blue 99, basic brown 16, basic brown 17, basic red 76, basic yellow 57, and the like.
Nitro dyes include 2-nitro-p-phenylenediamine, 2-amino-6-chloro-4-nitrophenol, 3-nitro-p-hydroxyethylaminophenol, 4-nitro-o-phenylenediamine, 4-amino -3-nitrophenol, 4-hydroxypropylamino-3-nitrophenol, N, N-bis (2-hydroxyethyl) -2-nitro-p-phenylenediamine, HC Blue 2, HC Orange 1, HC Red 1, HC red 3, HC yellow 2, HC yellow 4, HC yellow 5, etc. are mentioned.
Examples of the disperse dye include disperse purple 1, disperse blue 1, and disperse black 9.

When the hair dye composition of the first invention is a two-part type or a three-part type, the component (A) may be contained in any of the first agent, the second agent, and the third agent. From the viewpoint of stability, it is preferably contained in the first agent or the third agent, and more preferably contained in the first agent. The content of the component (A) in the hair dye composition of the first invention is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more, and preferably It is 2 mass% or less, More preferably, it is 1 mass% or less, More preferably, it is 0.5 mass% or less.

[Oxidative dye]
When the hair dye composition of the first invention is a two-component or three-component system, the first agent can contain an oxidation dye in addition to the direct dye of component (A). As an oxidation dye, the well-known precursor and coupler normally used for the hair dye can be used.

Examples of the precursor include paraphenylenediamine, toluene-2,5-diamine, 2-chloroparaphenylenediamine, paraaminophenol, paramethylaminophenol, orthoaminophenol, N-phenylparaphenylenediamine, N, N-bis (2 -Hydroxyethyl) paraphenylenediamine, 1-hydroxyethyl-4,5-diaminopyrazole and salts thereof.

Examples of couplers include metaphenylenediamine, 2,4-diaminophenoxyethanol, metaaminophenol, 2-methyl-5-aminophenol, 2-methyl-5- (2-hydroxyethylamino) phenol, resorcin, 1- Examples thereof include naphthol, 1,5-dihydroxynaphthalene, hydroquinone and their salts.

The precursor and coupler may be used alone or in combination of two or more. The total content of the precursor and the coupler in the entire composition of the first invention is preferably a content that does not affect the dyeability of the component (A), preferably 0.01% by mass or more, more preferably Is 0.1% by mass or more, preferably 5% by mass or less, more preferably 3% by mass, still more preferably 2% by mass or less, still more preferably 1% by mass or less, and further preferably 0.5% by mass or less.

[Component (B): Sulfonated polysaccharide]
The sulfonated polysaccharide of component (B) is an anionic polymer, but even when used in combination with the cationic polymer of component (C-1), precipitation is difficult to occur, and the hair due to component (C-1) is difficult to entangle. The sustainability of the touching effect can be improved. Moreover, the hair dyeing property by the component (A) is also improved by blending the component (B).

As the component (B), a water-soluble alkyl-substituted polysaccharide in which part or all of the hydrogen atoms of the hydroxy group in the polysaccharide are substituted with the following substituent (b1) is preferable. The term “water-soluble” as used herein means that 0.001% by mass or more dissolves in water at 25 ° C.
(b1) a sulfoalkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxy group or a salt thereof

Specific examples of the substituent (b1) include 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfo-2-hydroxypropyl group, 2-sulfo-1- (hydroxymethyl) ethyl group, and the like. Part or all of them may be a salt with an alkali metal such as sodium or potassium, an alkaline earth metal such as calcium or magnesium, an organic cationic group such as amines, or an ammonium ion. Among these, a sodium salt of a 3-sulfo-2-hydroxypropyl group is preferable.

In Component (B), it is preferable that part or all of the hydrogen atoms of the hydroxy group in the polysaccharide are further substituted with the following substituent (b2) in addition to the substituent (b1).
(b2) an alkyl glyceryl ether group having a linear or branched alkyl group having 10 to 40 carbon atoms and / or an alkenyl glyceryl ether group having a linear or branched alkenyl group having 10 to 40 carbon atoms

Specific examples of the substituent (b2) include 2-hydroxy-3-alkoxypropyl group, 2-alkoxy-1- (hydroxymethyl) ethyl group, 2-hydroxy-3-alkenyloxypropyl group, 2-alkenyloxy- Examples thereof include 1- (hydroxymethyl) ethyl group, and these groups may be substituted with a hydrogen atom of a hydroxy group of hydroxyethyl group or hydroxypropyl group bonded to a polysaccharide molecule. The alkyl group or alkenyl group having 10 to 40 carbon atoms substituted on the glyceryl ether group is preferably a linear or branched alkyl group or alkenyl group having 12 to 36 carbon atoms, more preferably 16 to 24 carbon atoms, From the viewpoint of storage stability of the hair dye composition, an alkyl group, more preferably a linear alkyl group, is preferable, and a linear alkyl group having 18 carbon atoms is particularly preferable.

In addition, when the substituent (b1) or (b2) has a hydroxy group, the hydrogen atom of the hydroxy group may be further substituted with another substituent (b1) or (b2).

The degree of substitution with the substituent (b1) per constituent monosaccharide residue is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.1 or more, and preferably 2.5 or less, more preferably 2 or less, Preferably it is 1.5 or less. The degree of substitution with the substituent (b2) per constituent monosaccharide residue is preferably 0.001 or more, more preferably 0.002 or more, still more preferably 0.003 or more, and preferably 1 or less, more preferably 0.5 or less. More preferably, it is 0.1 or less. Furthermore, the ratio (b1) / (b2) of the number of substituents (b1) and substituents (b2) is preferably 1000 or less, more preferably 500 or less, still more preferably 300 or less, and 1/100 Above, more preferably 1/10 or more. Note that the component (B) does not necessarily have the substituent (b1) in each repeating unit of the polysaccharide, and if the substituent (b1) is introduced as a whole molecule, It is preferable that the degree of substitution with the substituents (b1) and (b2) is within the above range on average.

In addition, as the polysaccharide which is the basic skeleton of the sulfonated polysaccharide of component (B), cellulose, guar gum, starch, hydroxyethyl cellulose, hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch, ethyl cellulose, ethyl guar gum, ethyl Starch, hydroxypropyl cellulose, hydroxypropyl guar gum, hydroxypropyl starch, hydroxyethyl methyl cellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, hydroxypropyl methyl cellulose, hydroxypropyl methyl guar gum, hydroxypropyl methyl starch, etc., among others, cellulose, Hydroxyethyl cellulose, methyl cellulose, ethyl cellulose , Hydroxypropylcellulose is preferable. Substitution by methyl group, ethyl group, hydroxyethyl group, hydroxypropyl group, etc. in these polysaccharide derivatives may be substitution by a single substituent or substitution by plural substituents, and the degree of substitution per constituent monosaccharide residue Is preferably 0.1 or more, more preferably 0.5 or more, and is preferably 10 or less, more preferably 5 or less. The weight average molecular weight of these polysaccharides is preferably 10,000 or more, more preferably 100,000 or more, further preferably 300,000 or more, and preferably 10 million or less, more preferably 5 million or less, and still more preferably Less than 2 million.

The sulfonated polysaccharide of component (B) is obtained by sulfonating a part or all of the hydrogen atoms of the hydroxyl group of the polysaccharide (introducing a substituent (b1) having a sulfonic acid group), or the hydrogen atom of the hydroxyl group of the polysaccharide. After sulfonation of a part, hydrophobization (introduction of substituent (b2)) of some or all of the remaining hydrogen atoms of the hydroxyl group, or after hydrophobization of some of the hydroxyl groups of the polysaccharide It can be produced by sulfonating a part or all of the remaining hydrogen atoms of the hydroxyl group, or simultaneously hydrophobizing and sulfonating.

The substituents (b1) and (b2) in the sulfonated polysaccharide may be substituted not only with the hydroxy group of the polysaccharide used as a raw material, but also with the hydroxy group of the other substituent (b1) or the substituent (b2). In addition, such substitution may occur in a superimposed manner. That is, in addition to the compound in which only the hydrogen atom of the hydroxy group of the polysaccharide is substituted with the substituents (b1) and (b2), and the sulfonation (b1) after the hydrophobization (b2), the substituent (b2) Further, the substituent (b2) or (b1) may be substituted, and the substituent (b1) may be further substituted with the substituent (b1). In the case of hydrophobization (b2) after sulfonation (b1), substituent (b2) is further substituted with substituent (b2), and substituent (b1) is further substituted with substituent (b1) or (b2). ) May be substituted. Further, when the hydrophobization and sulfonation are performed simultaneously, the substituent (b2) or (b1) is further substituted on the substituent (b2), and the substituent (b2) or (b1) is further substituted on the substituent (b1). ) May be included, and further, substitution to such other substituents may be included. In the first invention, any of such polysaccharides can be used.

Specific examples of component (B) include stearoxy PG hydroxyethyl cellulose sulfonic acid Na, hydroxyethyl cellulose sulfonic acid or a salt thereof.

The sulfonated polysaccharide of component (B) can be used singly or in combination of two or more, and the content in the hair dye composition of the first invention is a viscosity that is difficult to drip at the time of application and easy to use. From the viewpoint of improving the hair dyeing property, and from the viewpoint of the sustainability of the feel improvement effect by the component (C-1), preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass. % Or more, preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.

[Component (C-1): Cationic polymer having a charge density of 3 meq / g to 24 meq / g]
The charge density of the cationic polymer of component (C-1) is preferably 3.5 meq / g or more, more preferably 4 meq / g or more, and still more preferably 4.5 meq, from the viewpoint of the effect of making hair feel less tangled and smooth. From the viewpoint of sustaining the above effect, it is preferably 10 meq / g or less, more preferably 7 meq / g or less, still more preferably 6.5 meq / g or less.

As the cationic polymer of component (C-1), any of (C-1-1) non-crosslinked type and (C-1-2) crosslinked type can be used. It is excellent in touching effect, and the non-crosslinked type is excellent in effect sustainability. In the first invention, it is more preferable to use a crosslinked cationic polymer and a non-crosslinked cationic polymer in combination as the component (C-1). While being excellent in the sustainability of the touching effect, these effects can be further improved.

Examples of the non-crosslinked cationic polymer of the component (C-1-1) include a polymer containing a diallyl quaternary ammonium salt as a structural unit, a quaternized polyvinyl imidazolium derivative, polyethyleneimine, and the like.

As the polymer containing a diallyl quaternary ammonium salt as a structural unit, a polymer having a skeleton represented by the following general formula (1) or (2) is preferable.

[In the formula, R ¹ and R ² may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group (such as a phenyl group), a hydroxyalkyl group, an amidoalkyl group, a cyanoalkyl group, an alkoxy group. Represents an alkyl group or a carboalkoxyalkyl group, R ³ and R ⁴ may be the same or different, each represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, and X ⁻ represents an anion (chloride ion, Bromide ion, iodide ion, sulfate anion, sulfonate anion, methyl sulfate anion, phosphate anion, nitrate anion, etc.). ]

The polymer containing diallyl quaternary ammonium salt as a structural unit is a structural unit represented by the formula (1) or (2) from the viewpoint of further enhancing the effect of improving the conditioning effect sustainability in combination with the component (B). In one molecule, it is preferably contained in an amount of 65 to 100 mol%, more preferably 90 to 100 mol%, still more preferably 95 to 100 mol%.

Specific examples of the polymer containing diallyl quaternary ammonium salt as a structural unit include those represented by the following general formula (3) or (4).

[Wherein R ¹ , R ² and X ⁻ represent the same meaning as described above. p, q and r represent molar ratios, and p + q + r = 100. ]

p is preferably 0 to 50, more preferably 0 to 25, still more preferably 0 to 10, still more preferably 0 to 5, and q is preferably 50 to 100, more preferably 65 to 100, still more preferably 75. -100, more preferably 90-100, still more preferably 95-100, r is preferably 0-50, more preferably 0-25, still more preferably 0-10, still more preferably 0-5.

Among these, a homopolymer of diallyl quaternary ammonium salt, a copolymer of diallyl quaternary ammonium salt and acrylic acid, and a copolymer of diallyl quaternary ammonium salt and acrylamide are preferable. Specific examples of homopolymers of diallyl quaternary ammonium salts include Marquat 100 (INCI name: Polyquaternium-6, manufactured by Lubrizol Advanced Materials, Inc., charge density 6.2 meq / g, weight average molecular weight 150,000), etc. Specific examples of copolymers of quaternary ammonium salts and acrylic acid include Marquat 295 (INCI name: Polyquaternium-22, manufactured by Lubrizol Advanced Materials, Inc., charge density 6.0 meq / g, weight average molecular weight 190,000), Marcoat 280 ( INCI name: Polyquaternium-22, manufactured by Lubrizol Advanced Materials, Inc., charge density 5.0 meq / g, weight average molecular weight 450,000), specific examples of copolymers of diallyl quaternary ammonium salt and acrylamide include Marquat 550 (INCI name: Polyquaternium-7, manufactured by Lubrizol Advanced Materials, Inc., charge density 3.1 meq / g, weight average molecular weight 1,600,000).

As the quaternized polyvinyl imidazolium derivative, for example, a compound represented by the following general formula (5) is preferable.

[Wherein, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Y ⁻ represents a chloride ion, bromide ion, iodide ion, sulfate anion, sulfonate anion, alkyl sulfate anion having 1 to 4 carbon atoms. , Phosphate anions, nitrate anions and the like, and s and t are molar ratios, and s + t = 100. ]

From the viewpoint of further enhancing the effect of improving the sustaining effect of the conditioning effect by the combined use with the component (B), t, which is the molar ratio of the monomer exhibiting cationic property, is preferably 73 or more, more preferably 90 or more, and still more preferably 93 or more. And preferably 99 or less.

Specific examples of such quaternized polyvinyl imidazolium derivatives include rubicut excellence (BASF, charge density 6.7 meq / g, weight average molecular weight 40,000), which is a copolymer of vinylpyrrolidone and methylvinylimidazolium chloride. Is mentioned.

Specific examples of polyethyleneimine include polyethyleneimine having a charge density of 23.2 meq / g and a weight average molecular weight of 10,000 sold by Wako Pure Chemical Industries, Ltd.

Examples of the crosslinked cationic polymer of component (C-1-2) include a polymer of methacryloyloxyethylenetrimonium chloride.

Specific examples of the polymer of methacryloyloxyethylenetrimonium chloride include (INCI name: Polyquaternium-37, BASF: Cosmedia Ultragel 300, charge density 4.8).

The weight average molecular weight of the component (C-1) is preferably 10,000 or more, more preferably 50,000 or more, and still more preferably from the viewpoint of forming a water-insoluble complex with the component (B) and easily remaining on the hair. It is 100,000 or more, preferably 10,000,000 or less, more preferably 1,000,000 or less, and still more preferably 800,000 or less.

Here, the weight average molecular weight can be measured under the following conditions, for example, by gel permeation chromatography (GPC).
Moving bed: 50 mM LiBr, 1% CH ₃ COOH / ethanol: water = 3: 7
Column: TSK gel α-M (two in series)
Reference material: Polyethylene glycol

The cationic polymer of component (C-1) having a charge density of 3 meq / g or more and 24 meq / g or less can be used alone or in combination of two or more, and is contained in the hair dye composition of the first invention. The amount is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.3% by mass or more, and preferably from the viewpoint of the effect of making the hair feel less tangled and smooth and its durability. It is 20 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 6 mass% or less.

The charge ratio (C-1) / (B) between the component (C-1) and the component (B) in the hair dye composition of the first invention is a water-insoluble complex formed from both components during rinsing. Is preferably 0.001 or more, more preferably 0.1 or more, still more preferably 1 or more, and preferably 40 or less, more preferably 20 or less, and still more preferably, from the viewpoint of adsorbing to the hair surface and improving shampoo resistance. It is 12 or less, more preferably 11 or less, more preferably 10 or less, more preferably 9.5 or less, and further preferably 9 or less. Furthermore, dyeability can be improved by using this charge ratio. Moreover, with this charge ratio, it is difficult to form a precipitate due to a water-insoluble complex in the preparation. Here, the charge ratio (C-1) / (B) can be calculated according to the following equation.

Charge ratio (C-1) / (B)
= (Content of component (C-1) x charge density of component (C-1)) / (content of component (B) x charge density of component (B))

[Component (D): Cationic polymer with a charge density of less than 3 meq / g]
The hair dye composition of the first invention can further improve the feel of the hair by further containing a cationic polymer having a charge density of less than 3 meq / g as component (D).

As the component (D), either a non-crosslinked type or a crosslinked type can be used, but it is more preferable to use a crosslinked type from the viewpoint of smoothness during rinsing. Examples of such a crosslinked cationic polymer having a charge density of less than 3 meq / g include N, N-dimethylaminoethyl diethyl sulfate methacrylate / N, N-dimethylacrylamide / polyethylene glycol dimethacrylate (INCI). Name: Polyquaternium-52, Sofcare KG-101W-E, manufactured by Kao Corporation, charge density 0.83 meq / g). Examples of the non-crosslinked cationic polymer having a charge density of less than 3 meq / g include cationized cellulose such as hydroxyethylcellulose hydroxypropyltrimethylammonium chloride ether (INCI name: polyquaternium-10). Examples of the cationized cellulose include Caticello M-80 (manufactured by Kao Corporation, charge density 1.1 meq / g), Caticello L-150 (manufactured by Kao Corporation, charge density 0.9 meq / g), and the like.

The content of component (D) in the hair dye composition of the first invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.3% by mass or more, and preferably It is 20 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 6 mass% or less.

[Component (E): Sodium chloride]
The hair dye composition of the first invention preferably further contains sodium chloride as the component (E). By containing sodium chloride, it is possible to increase the viscosity of the hair dye composition and to make it easy to handle, such as suppressing dripping during application.

The content of component (E) in the hair dye composition of the first invention is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and preferably It is 3 mass% or less, More preferably, it is 2.5 mass% or less, More preferably, it is 2 mass% or less.

[Surfactant]
The hair dye composition of the first invention can contain a surfactant. Surfactants include cationic surfactants, nonionic surfactants, amphoteric surfactants, and anionic surfactants. Among these, anionic surfactants and nonionic surfactants are preferable from the viewpoint of the stability of the formulation.

Anionic surfactants include alkyl benzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, Examples include α-sulfo fatty acid salts, N-acyl amino acid salts, phosphoric acid mono- or diesters, and sulfosuccinic acid esters. Examples of the alkyl ether sulfate include polyoxyethylene alkyl ether sulfate. Of these, alkyl sulfates, alkyl ether sulfates, saturated fatty acid salts, and alkyl ether carboxylates are preferred. Counter ions of the anionic group of these anionic surfactants include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; alkanol group having 2 or 3 carbon atoms And alkanolamine salts having 1 to 3 (for example, monoethanolamine salt, diethanolamine salt, triethanolamine salt, triisopropanolamine salt, etc.).

As the cationic surfactant, monoalkyltrimethylammonium chloride, dialkyldimethylammonium chloride and monoalkyltrimethylammonium bromide are preferable from the viewpoint of imparting an excellent feel to the hair after dyeing, and stearyltrimethylammonium chloride is particularly preferable. (Steartrimonium chloride), cetyltrimethylammonium chloride (cetrimonium chloride), and lauryltrimethylammonium chloride (lauryltrimonium chloride) are more preferable, and it is also preferable to mix two or more.

Nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, higher fatty acid sucrose ester, polyglycerin fatty acid ester, higher fatty acid mono- or diethanolamide, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid Examples thereof include esters, polyoxyethylene sorbite fatty acid esters, alkyl saccharides, alkylamine oxides, and alkylamidoamine oxides. Of these, polyoxyalkylene alkyl ether, polyoxyethylene hydrogenated castor oil, and alkyl saccharide are preferred, and polyoxyethylene alkyl (12-14) ether and alkyl polyglucoside are more preferred.

Examples of amphoteric surfactants include imidazoline, carbobetaine, amide betaine, sulfobetaine, hydroxysulfobetaine, amide sulfobetaine, and the like, and betaine surfactants such as alkyldimethylaminoacetic acid betaine and fatty acid amidopropyl betaine are more preferable. Fatty acid amidopropyl betaine is more preferred.

The surfactant may be contained in any of the first agent, the second agent, and the third agent when the hair dye composition of the first invention is a two-part or three-part type.

These surfactants can be used alone or in combination of two or more, and the content in the whole composition of the first invention is preferably from the viewpoint of good feel and emulsification performance. 0.01% by mass, more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, further preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and further preferably 1.5% by mass or less.

[Higher alcohol]
The hair dye composition of the first invention preferably contains a higher alcohol having 12 or more carbon atoms from the viewpoint of improving touch and improving stability. The higher alcohol may be contained in any one of the first agent, the second agent, and the third agent when the hair dye composition of the first invention is a two-part or three-part type.

As the higher alcohol, those having 12 or more carbon atoms, more preferably 16 or more, and 30 or less carbon atoms, and further 22 or less are preferable. Specifically, myristyl alcohol, cetyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol , Isostearyl alcohol, 2-octyldodecanol, oleyl alcohol and the like.

The higher alcohol may be used in combination of two or more, and the content in the total composition of the first invention is 3% by mass or more from the viewpoint of the viscosity and stability of the hair dye composition, 4 mass% or more is preferable, 11 mass% or less, Furthermore, 9 mass% or less is preferable.

〔Organic solvent〕
The hair dye composition of the first invention may contain an organic solvent. Examples of organic solvents include lower alkanols such as ethanol, 1-propanol, and 2-propanol; aromatic alcohols such as benzyl alcohol, 2-benzyloxyethanol, and phenoxyethanol; propylene glycol, 1,3-butanediol, diethylene glycol, glycerin, and the like. Polyols; Ether alcohols such as ethoxyethanol, ethoxydiglycol and methoxyethanol; N-alkylpyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone; alkylene carbonates such as propylene carbonate; lactones such as γ-valerolactone and γ-caprolactone Is mentioned.

These organic solvents can be used alone or in combination of two or more, and the content in the total composition of the first invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, More preferably, it is 1% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and further preferably 5% by mass or less.

[Alkaline agent]
The hair dye composition of the first invention can further contain an alkali agent. When the hair dye composition of the first invention is a two-part or three-part type, the alkaline agent is contained in the first agent. Examples of such alkali agents include ammonia and salts thereof; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, and 2-aminobutanol. Alkane diamines and salts thereof; alkane diamines such as 1,3-propanediamine and salts thereof; carbonates such as guanidine carbonate, guanidine bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, and lithium carbonate . Among these alkaline agents, at least one selected from the group consisting of ammonia and salts thereof, monoethanolamine and salts thereof, and 2-amino-2-methylpropanol is preferable, and among these, 2-amino-2- More preferred is methylpropanol.

Two or more alkali agents may be used in combination, and the content in the total composition of the first invention is 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of sufficient hair dyeing effect. Is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further 0.5% by mass or more, and further preferably 1% by mass or more, and from the viewpoint of reducing hair damage and scalp irritation, 20% by mass or less, and further % By mass or less, further 5% by mass or less, further 4% by mass or less, more preferably 3% by mass or less.

〔hydrogen peroxide〕
When the hair dye composition of the first invention is a two-part hair dye or a three-part hair dye, the second agent can contain hydrogen peroxide. The content of hydrogen peroxide in the total composition of the first invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more from the viewpoint of sufficient hair dyeing effect. From the viewpoint of reducing hair damage and scalp irritation, it is preferably 12% by mass or less, more preferably 9% by mass or less, further 6% by mass or less, and still more preferably 4% by mass or less.

(PH adjuster)
The hair dye composition of the first invention is a pH adjuster, in addition to the above-mentioned alkaline agents, inorganic acids such as hydrochloric acid and phosphoric acid, organic acids such as citric acid, glycolic acid, malic acid and lactic acid, hydrochloric acid Hydrochlorides such as monoethanolamine, phosphates such as monopotassium dihydrogen phosphate and disodium monohydrogen phosphate can be used.

These pH adjusting agents may be contained in any one of the first agent, the second agent, and the third agent in the two-component or three-component hair dye. In addition, the content in the entire composition of the first invention is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of sufficient dyeing effect and reduction of hair damage and scalp irritation. More preferably, it is 0.2% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and further preferably 3% by mass or less.

[Medium]
In the hair dye composition of the first invention, water is used as a medium. The content of water in the hair dye composition of the first invention is 10% by mass or more, further 20% by mass or more, further 30% by mass or more, further 40% by mass or more, and further 50% by mass or more. It is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less.

[Other optional ingredients]
In addition to the above components, other components that are usually used as cosmetic raw materials can be added to the hair dye composition of the first invention.

Examples of the purpose of blending such optional components include pearling, antiseptic, metal sequestering, stabilization, antioxidant, ultraviolet absorption, moisture retention, product coloring, fragrance, etc. As specific optional components, Examples include animal and vegetable oils and fats, higher fatty acids, protein hydrolysates, protein derivatives, amino acids, plant extracts, vitamins, pigments, and fragrances.

[PH]
In the case of a one-component hair dye, the pH (25 ° C.) of the hair dye composition of the first invention can be appropriately adjusted depending on the direct dye used. When an acidic dye is used as the direct dye, the pH (25 ° C.) of the hair dye composition of the first invention is preferably 2 or more from the viewpoint of improving the stability of the dye and the adsorption to the hair. Preferably it is 2.5 or more, More preferably, it is 3 or more, Preferably it is 6.5 or less, More preferably, it is 6 or less, More preferably, it is 5.5 or less, More preferably, it is 5 or less. When the azo dye (A-1), (A-2) or (A-3), or the basic dye is used as the direct dye, the pH (25 ° C.) of the hair dye composition of the first invention is the dye From the viewpoint of improving the stability of the hair and the adsorption to the hair, it is preferably 7 or more, more preferably 8 or more, still more preferably 8.5 or more, still more preferably 9 or more, and preferably 12 or less, more preferably 11.5 or less, more preferably 11 or less, and further preferably 10.5 or less. When a nitro dye or disperse dye is used as the direct dye, the pH (25 ° C.) of the hair dye composition of the first invention is preferably 2.5 or more, more preferably 3 or more, and preferably 12 or less. More preferably, it is 11.5 or less, More preferably, it is 11 or less.

When the hair dye composition of the first invention is a two-component hair dye, the pH (25 ° C.) of the first agent is preferably 8 to 12, and the pH (25 ° C.) of the second agent is preferably Is 2-5. The pH (25 ° C.) during use of the mixture of the first agent and the second agent of the first invention is preferably 8 or more, more preferably 8.5 or more, and still more preferably, from the viewpoint of hair dyeing effect and skin irritation. It is 9 or more, preferably 11.5 or less, more preferably 11 or less, and further preferably 10.5 or less.

In the present specification, the pH of the hair dye composition of the first invention is a value measured at room temperature (25 ° C.) using a pH meter F-22 manufactured by Horiba, Ltd.

[Drug type]
The hair dye composition of 1st invention can be used as various hair dyes of 1 agent type, 2 agent type, or 3 agent type. The one-component hair dye composition is composed of a single agent containing the components (A), (B) and (C-1). The two-component hair dye composition preferably comprises a first agent containing component (A) and an alkaline agent, and a second agent containing hydrogen peroxide. The three-component hair dye composition comprises a first agent containing an alkaline agent, a second agent containing hydrogen peroxide, and a third agent containing component (A), or component (A) And a first agent containing an alkali agent, a second agent containing hydrogen peroxide, and a third agent containing other components. As the third agent containing the above-mentioned other components, a powdery oxidizer made of a granulated material such as persulfate (ammonium persulfate, potassium persulfate, sodium persulfate, etc.) may be used to improve decolorization power. preferable.
In the first invention, the “total composition” refers to the entire composition at the time of use of the hair dyeing treatment. In the above-mentioned two-component hair dye, the first agent and the second agent are mixed. In the case of a three-component hair dye, it means a mixture after mixing the first agent, the second agent and the third agent.

The hair dye composition of the first invention can be used, for example, in the form of liquid, emulsion, cream, gel, paste, mousse, etc., and can also be in the form of an aerosol. . It is desirable to adjust the viscosity of the entire composition in these cases so that it does not easily drip when applied to the hair. The viscosity (25 ° C.) of this whole composition was rotated at 10 rpm for 1 minute using a rotor TC by a B-type rotational viscometer with a helical stand (model; digital viscometer TVB-10, Toki Sangyo Co., Ltd.). The subsequent measured value is preferably 2,000 to 200,000 mPa · s, more preferably 4,000 to 150,000 mPa · s, still more preferably 6,000 to 100,000 mPa · s, and further preferably 8,000 to 80,000 mPa · s. In addition, in the case of a two-part type or a three-part type, the measurement shall be made after 3 minutes have elapsed since the mixing of each agent.

The hair dye composition of the first invention can also be used as a foam by discharging it from a non-aerosol-type former container when applied to the hair, or by shaking and foaming in a cup. it can. In this case, the viscosity of the entire composition before foaming is also preferably adjusted so that it does not easily drip when applied to the hair as a foam. The viscosity (25 ° C.) of this entire composition was rotated for 1 minute at 30 rpm using a rotor No. 1 with a B-type rotational viscometer (model; Digital Viscometer TV-10, Toki Sangyo Co., Ltd.) The measured value (however, when the viscosity exceeds 160 mPa · s, the measured value after rotating at 12 rpm for 1 minute) is preferably 1 to 800 mPa · s, more preferably 1 to 600 mPa · s, still more preferably 1 to 500 mPa · s, more preferably 1 to 300 mPa · s. In addition, in the case of a two-part type or a three-part type, the measurement shall be made after 3 minutes have elapsed since the mixing of each agent.

[Hair dyeing method]
In order to carry out a hair dyeing treatment using the hair dye composition of the first invention, for example, the hair dye composition of the first invention (in the case of the two-agent or three-agent system, the first to third agents are used). After mixing just before use) is applied to the hair, allowed to stand for a predetermined time, rinsed with water and dried. The application temperature to hair is preferably 15 to 45 ° C., and the application time is preferably 1 to 60 minutes, more preferably 5 to 45 minutes, and further preferably 10 to 30 minutes.

With respect to the embodiment described above, preferred aspects of the first invention will be further disclosed below.

<1> A hair dye composition containing the following components (A), (B) and (C-1).
(A) Direct dye (B) Sulfonated polysaccharide (C-1) Cationic polymer with charge density of 3 meq / g or more and 24 meq / g or less

<2> Component (A) is selected from the group consisting of azo dyes (A-1), (A-2) and (A-3), acid dyes, basic dyes, nitro dyes and disperse dyes or The hair dye composition according to <1>, which is two or more kinds of dyes.

<3> Component (A) is one or more azo dyes selected from the group consisting of the following (A-1), (A-2) and (A-3), and pH at 25 ° C. However, it is preferably 7 or more, more preferably 8 or more, still more preferably 8.5 or more, still more preferably 9 or more, preferably 12 or less, more preferably 11.5 or less, still more preferably 11 or less, still more preferably Is 10.5 or less, The hair dye composition as described in <2>.

<4> Component (A) is an acid dye, and the pH at 25 ° C. is preferably 2 or more, more preferably 2.5 or more, still more preferably 3 or more, and preferably 6.5 or less, more preferably 6 or less. More preferably, the hair dye composition according to <2>, which is 5.5 or less, more preferably 5 or less.

<5> Two-component or three-component hair dye composition, preferably containing component (A) in the first agent or the third agent according to any one of <1> to <4> Hair dye composition.

<6> The content of component (A) is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more, and preferably 2% by mass or less, more preferably 1 The hair dye composition according to any one of <1> to <5>, which is not more than mass%, more preferably not more than 0.5 mass%.

<7> Component (B) is preferably a water-soluble alkyl-substituted polysaccharide in which some or all of the hydrogen atoms of the hydroxy group in the polysaccharide are substituted with the following substituent (b1) <1> to <6> A hair dye composition according to any one of the above.
(b1) a sulfoalkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxy group or a salt thereof

<8> The substituent (b1) is preferably a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfo-2-hydroxypropyl group, a 2-sulfo-1- (hydroxymethyl) ethyl group and a salt thereof. The hair dye composition according to <7>, which is selected from the group consisting of:

<9> The degree of substitution with the substituent (a1) per constituent monosaccharide residue is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.1 or more, and preferably 2.5 or less, more preferably 2 The hair dye composition according to <7> or <8>, further preferably 1.5 or less.

<10> Component (B) is preferably a water-soluble alkyl-substituted polysaccharide in which some or all of the hydrogen atoms of the hydroxy group in the polysaccharide are further substituted with the following substituent (b2) <7> to <9> The hair dye composition according to any one of the above.
(a2) an alkyl glyceryl ether group having a linear or branched alkyl group having 10 to 40 carbon atoms and / or an alkenyl glyceryl ether group having a linear or branched alkenyl group having 10 to 40 carbon atoms

<11> Substituent (b2) is preferably 2-hydroxy-3-alkoxypropyl, 2-alkoxy-1- (hydroxymethyl) ethyl, 2-hydroxy-3-alkenyloxypropyl and 2-alkenyloxy The hair dye composition according to <10>, which is selected from the group consisting of -1- (hydroxymethyl) ethyl groups.

<12> The degree of substitution with the substituent (b2) per constituent monosaccharide residue is preferably 0.001 or more, more preferably 0.002 or more, still more preferably 0.003 or more, and preferably 1 or less, more preferably 0.5. The hair dye composition according to <10> or <11>, further preferably 0.1 or less.

<13> The ratio (b1) / (b2) of the number of substituents (b1) and substituents (b2) is preferably 1000 or less, more preferably 500 or less, and even more preferably 300 or less. The hair dye composition according to any one of <10> to <12>, which is 100 or more, more preferably 1/10 or more.

<14> The polysaccharide that is the basic skeleton of the sulfonated polysaccharide of component (B) is preferably cellulose, guar gum, starch, hydroxyethyl cellulose, hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch, ethyl cellulose, ethyl guar gum , Ethyl starch, hydroxypropyl cellulose, hydroxypropyl guar gum, hydroxypropyl starch, hydroxyethyl methylcellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, hydroxypropyl methylcellulose, hydroxypropyl methyl guar gum and hydroxypropyl methyl starch < The hair dye composition according to any one of 1> to <13>.

<15> The weight average molecular weight of the polysaccharide which is the basic skeleton of the sulfonated polysaccharide of component (B) is preferably 10,000 or more, more preferably 100,000 or more, and even more preferably 300,000 or more, and preferably The hair dye composition according to <14>, which is 10 million or less, more preferably 5 million or less, and still more preferably 2 million or less.

<16> The dye according to any one of <1> to <15>, wherein the component (B) is preferably hydroxyethyl cellulose hydroxypropyl stearyl ether hydroxypropyl sulfonate (INCI name: sodium stearoxy PG hydroxyethyl cellulose sulfonate Na) Hair composition.

<17> The content of component (B) is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and preferably 10% by mass or less, more preferably 5%. The hair dye composition according to any one of <1> to <16>, which is not more than mass%, more preferably not more than 3 mass%.

<18> The charge density of the component (C-1) is preferably 3.5 meq / g or more, more preferably 4 meq / g or more, further preferably 4.5 meq / g or more, and preferably 10 meq / g or less. The hair dye composition according to any one of <1> to <17>, more preferably 7 meq / g or less, and still more preferably 6.5 meq / g or less.

<19> Component (C-1) is preferably at least one selected from (C-1-1) non-crosslinked cationic polymer and (C-1-2) crosslinked cationic polymer <1> ~ Hair dye composition according to any one of <18>.

<20> Component (C-1) is preferably a combination of (C-1-1) non-crosslinked cationic polymer and (C-1-2) crosslinked cationic polymer <19> The hair dye composition as described.

<21> The non-crosslinked cationic polymer of component (C-1-1) is preferably a polymer comprising a diallyl quaternary ammonium salt as a constituent unit, a group consisting of a quaternized polyvinyl imidazolium derivative, polyethyleneimine, and the like. The hair dye composition according to <19> or <20>, which is selected.

<22> The hair dye composition according to <21>, wherein the polymer containing a diallyl quaternary ammonium salt as a constituent unit preferably has a skeleton represented by the following general formula (1) or (2): object.

<23> The polymer containing a diallyl quaternary ammonium salt as a constituent unit is preferably 65 to 100 mol%, more preferably 90, preferably the constituent unit represented by the formula (1) or (2) in one molecule. The hair dye composition according to <22>, which is contained in an amount of ˜100 mol%, more preferably 95 to 100 mol%.

<24> The polymer containing a diallyl quaternary ammonium salt as a constituent unit is preferably selected from the group consisting of polyquaternium-6, polyquaternium-22, and polyquaternium-7. The hair dye composition as described.

<25> The hair dye composition according to <21>, wherein the quaternized polyvinyl imidazolium derivative is preferably represented by the following general formula (5).

<26> The hair dye composition according to <19> or <20>, wherein the crosslinked cationic polymer of component (C-1-2) is preferably a polymer of methacryloyloxyethylenetrimonium chloride.

<27> The hair dye composition according to <26>, wherein the crosslinked cationic polymer of component (C-1-2) is preferably polyquaternium-37.

<28> The weight average molecular weight of the component (C-1) is preferably 10,000 or more, more preferably 50,000 or more, further preferably 100,000 or more, preferably 10,000,000 or less, more preferably 1,000,000 or less, and still more preferably. The hair dye composition according to any one of <1> to <27>, which is 800,000 or less.

<29> The content of the component (C-1) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.3% by mass or more, and preferably 20% by mass or less, more preferably The hair dye composition according to any one of <1> to <28>, wherein is 8% by mass or less, more preferably 6% by mass or less.

<30> The charge ratio (C-1) / (B) between the component (C-1) and the component (B) is preferably 0.001 or more, more preferably 0.1 or more, still more preferably 1 or more. <1> to <29>, preferably 40 or less, more preferably 20 or less, further preferably 12 or less, further preferably 11 or less, further preferably 10 or less, further preferably 9.5 or less, and further preferably 9 or less. The hair dye composition in any one.

<31> The hair dye composition according to any one of <1> to <30>, which preferably further contains a component (D).
(D) Cationic polymer with a charge density of less than 3 meq / g

<32> The hair dye composition according to <31>, wherein the component (D) is preferably selected from polyquaternium-52 and polyquaternium-10.

<33> The content of component (D) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.3% by mass or more, and preferably 20% by mass or less, more preferably 8% by mass. The hair dye composition according to <31> or <32>, which is not more than mass%, more preferably not more than 6 mass%.

<34> The hair dye composition according to any one of <1> to <33>, preferably further containing a component (E).
(E) Sodium chloride

<35> The content of the component (E) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and preferably 3% by mass or less, more preferably 2.5% by mass. <29> The hair dye composition according to <29>, wherein the hair dye composition is not more than mass%, more preferably not more than 2 mass%.

<36> A hair coloring method in which the hair dye composition according to any one of <1> to <35> is applied to hair, left for 1 to 60 minutes, rinsed with water, and dried.

Regarding the second invention In the hair conditioner described in Patent Document 4, when an anionic acid dye is used as a direct dye instead of a basic dye (cationic dye) or a neutral dye, an acid dye and a cation There is a problem that the surfactant forms an ion-binding complex, and the hair dyeability is lowered or a stable composition cannot be obtained.

Moreover, in the hair cosmetics described in Patent Document 5, when other direct dyes are used in place of the acid dyes, the feeling of use cannot be improved, and compared with the hair conditioner described in Patent Document 4 above. In addition, sufficient applicability and a touch improvement effect could not be obtained.

Therefore, according to the second invention, regardless of the ionicity of the direct dye, the hair dyeing property and the coating property are maintained as before, and the feeling improvement effect after the treatment is excellent, and the excellent feeling is maintained even after repeated shampoo washing. Furthermore, the present invention relates to a stable hair dye composition that does not produce precipitates during storage.

The present inventors have found that the above-mentioned problem can be solved by combining a cationic surfactant and a sulfonated polysaccharide so that the charge ratio of both is within a certain range.

When the hair dye composition of the second invention is a two-part type or a three-part type, the component (A) may be contained in any of the first agent, the second agent, and the third agent. From the viewpoint of stability, it is preferably contained in the first agent or the third agent, and more preferably contained in the first agent. The content of component (A) in the hair dye composition of the second invention is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, and still more preferably 0.005% by mass from the viewpoint of the stability of the formulation. % Or more, more preferably 0.01% by mass or more, preferably 2% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less.

[Oxidative dye]
When the hair dye composition of the second invention is a two-component or three-component system, the first agent can contain an oxidation dye in addition to the direct dye of component (A). As an oxidation dye, the well-known precursor and coupler normally used for the hair dye can be used.

The precursor and coupler may be used alone or in combination of two or more. The total content of the precursor and the coupler in the entire composition of the second invention is preferably a content that does not affect the dyeability of the component (A), preferably 0.01% by mass or more, more preferably Is 0.1% by mass or more, preferably 5% by mass or less, more preferably 3% by mass, still more preferably 2% by mass or less, still more preferably 1% by mass or less, and further preferably 0.5% by mass or less.

[Component (B): Sulfonated polysaccharide]
As the component (B), a water-soluble alkyl-substituted polysaccharide in which part or all of the hydrogen atoms of the hydroxy group in the polysaccharide are substituted with the following substituent (b1) is preferable. The term “water-soluble” as used herein means that 0.001% by mass or more dissolves in water at 25 ° C.
(b1) a sulfoalkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxy group or a salt thereof

Specific examples of the substituent (b2) include 2-hydroxy-3-alkoxypropyl group, 2-alkoxy-1- (hydroxymethyl) ethyl group, 2-hydroxy-3-alkenyloxypropyl group, 2-alkenyloxy- Examples thereof include 1- (hydroxymethyl) ethyl group, and these groups may be substituted with a hydrogen atom of a hydroxy group of hydroxyethyl group or hydroxypropyl group bonded to a polysaccharide molecule. The alkyl group or alkenyl group having 10 to 40 carbon atoms substituted on the glyceryl ether group is preferably a linear or branched alkyl group or alkenyl group having 12 to 36 carbon atoms, more preferably 16 to 24 carbon atoms, From the viewpoint of the formulation stability during storage of the hair dye composition, an alkyl group, more preferably a linear alkyl group, is preferable, and a linear alkyl group having 18 carbon atoms is particularly preferable.

In addition, as the polysaccharide that is the basic skeleton of the sulfonated polysaccharide of component (B), cellulose, guar gum, starch, hydroxyethyl cellulose, hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch, ethyl cellulose, ethyl guar gum, ethyl Starch, hydroxypropyl cellulose, hydroxypropyl guar gum, hydroxypropyl starch, hydroxyethyl methyl cellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, hydroxypropyl methyl cellulose, hydroxypropyl methyl guar gum, hydroxypropyl methyl starch, etc., among others, cellulose, Hydroxyethyl cellulose, methyl cellulose, ethyl cellulose , Hydroxypropylcellulose is preferable. Substitution by methyl group, ethyl group, hydroxyethyl group, hydroxypropyl group, etc. in these polysaccharide derivatives may be substitution by a single substituent or substitution by plural substituents, and the degree of substitution per constituent monosaccharide residue Is preferably 0.1 or more, more preferably 0.5 or more, and is preferably 10 or less, more preferably 5 or less. The weight average molecular weight of these polysaccharides is preferably 10,000 or more, more preferably 100,000 or more, further preferably 300,000 or more, and preferably 10 million or less, more preferably 5 million or less, and still more preferably Less than 2 million.

The substituents (b1) and (b2) in the sulfonated polysaccharide may be substituted not only with the hydroxy group of the polysaccharide used as a raw material, but also with the hydroxy group of the other substituent (b1) or the substituent (b2). In addition, such substitution may occur in a superimposed manner. That is, in addition to the compound in which only the hydrogen atom of the hydroxy group of the polysaccharide is substituted with the substituents (b1) and (b2), and the sulfonation (b1) after the hydrophobization (b2), the substituent (b2) Further, the substituent (b2) or (b1) may be substituted, and the substituent (b1) may be further substituted with the substituent (b1). In the case of hydrophobization (b2) after sulfonation (b1), substituent (b2) is further substituted with substituent (b2), and substituent (b1) is further substituted with substituent (b1) or (b2). ) May be substituted. Further, when the hydrophobization and sulfonation are performed simultaneously, the substituent (b2) or (b1) is further substituted on the substituent (b2), and the substituent (b2) or (b1) is further substituted on the substituent (b1). ) May be included, and further, substitution to such other substituents may be included. In the second invention, any of such polysaccharides can be used.

The sulfonated polysaccharide of component (B) is an anionic polymer, but even when used in combination with the cationic surfactant of component (C-2), precipitation is difficult to occur, and the hair due to component (C-2) is difficult to entangle. It is possible to improve the sustainability of the effect of making a pleasant feel. Moreover, the hair dyeing property by component (A) can also be improved by blending component (B).

The sulfonated polysaccharide of component (B) can be used alone or in combination of two or more, and the content in the hair dye composition of the second invention is good operability at the time of coating (paint spreading) From the viewpoints of ease, dripping difficulty, shape retention as a hair dye), improvement of hair dyeing properties, and the sustainability of the touch improvement effect by component (C-2), It is 0.05 mass% or more, More preferably, it is 0.1 mass% or more, More preferably, it is 0.2 mass% or more, Preferably it is 5 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 2 mass% or less.

[Component (C-2): Cationic surfactant]
The cationic surfactant of component (C-2) in the second invention includes monoalkyl (C _8-22 ) quaternary ammonium salts, monoalkyl (C _8-22 ) ether amines, monoalkyl amides (C _{8- 22} ) One or more compounds selected from the group consisting of amines and salts of these amines. Among these, a monoalkyl (C _8-22 ) quaternary ammonium salt is preferable from the viewpoint of formulation stability during storage.

(I) The monoalkyl (C _8-22 ) quaternary ammonium salt includes a compound represented by the following general formula (6).

Wherein, R ⁵ represents a linear or branched chain alkyl group having 8 to 22 carbon atoms, R ⁶ ~ R ^8, which may be the same or different, represent a hydrogen atom or a methyl group, An ^- Indicates an anion. ]

In the general formula (6), the carbon number of the alkyl group represented by R ⁵ is 8 or more, preferably 12 or more, more preferably 16 or more, and 22 or less, preferably 20 or less. . R ⁵ is preferably a linear alkyl group. Examples of An ⁻ include halide ions such as chloride ion and bromide ion, and chloride ion is more preferable.

Specific examples of the monoalkyl quaternary ammonium salt represented by the general formula (6) include alkyltrimethylammonium chlorides such as behenyltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, among which behenyltrimethylammonium chloride. Stearyltrimethylammonium chloride is preferred.

(Ii) Examples of the monoalkyl (C _8-22 ) ether amine include compounds represented by the following general formula (7).

[In the formula, R ⁹ represents a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, and R ¹⁰ and R ¹¹ may be the same or different, and have 1 to 6 carbon atoms. Indicates an alkyl group. ]

In the general formula (7), the carbon number of the alkyl group represented by R ⁹ is 8 or more, preferably 12 or more, more preferably 16 or more, and 22 or less, preferably 20 or less, more Preferably it is 18 or less. R ⁹ is preferably a linear alkyl group. R ¹⁰ and R ¹¹ are preferably methyl groups.

The monoalkyl ether amine reacts with an acid to form a quaternary ammonium salt, which becomes a surfactant. In the second invention, the content of the monoalkyl ether amine salt as the component (C-2) is the converted amount as the monoalkyl ether amine.

Examples of the salt include salts with organic acids or inorganic acids. Examples of the inorganic acid include salts with hydrochloric acid, sulfuric acid, phosphoric acid and the like. Examples of organic acids include salts with monocarboxylic acids such as acetic acid and propionic acid; salts with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, and phthalic acid; and polyglutamic acid. Examples include salts with polycarboxylic acids; salts with hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid, and citric acid; salts with acidic amino acids such as glutamic acid and aspartic acid. Among these, as the inorganic acid salt, a salt with hydrochloric acid is more preferable. The organic acid salt is preferably a salt of dicarboxylic acid, hydroxycarboxylic acid, or acidic amino acid. As a salt by dicarboxylic acid, a salt by maleic acid or succinic acid is more preferable. As a salt by hydroxycarboxylic acid, a salt by glycolic acid, lactic acid or malic acid is more preferable. As a salt of an acidic amino acid, a salt of glutamic acid is more preferable.

Specific examples of the monoalkyl (C _8-22 ) ether amine represented by the general formula (7) include N, N-dimethyl-3-hexadecyloxypropylamine and N, N-dimethyl-3-octadecyloxypropyl. Examples of such salts include organic acid salts such as N, N-dimethyl-3-hexadecyloxypropylamine lactate and N, N-dimethyl-3-octadecyloxypropylamine lactate.

(Iii) Examples of monoalkylamide (C _8-22 ) amines include compounds represented by the following general formula (8).

[In the formula, R ¹² CO represents a linear or branched alkanoyl group or alkenoyl group having 8 to 22 carbon atoms, and R ¹³ and R ¹⁴ may be the same or different, and have 1 to 4 carbon atoms. Represents an alkyl group, and b represents a number of 2 or more and 4 or less. ]

In the general formula (8), R ¹² CO has 8 or more carbon atoms, preferably 12 or more, more preferably 16 or more, still more preferably 18 or more, and 22 or less carbon atoms, preferably 20 or less. R ¹² CO is preferably a linear alkanoyl group or alkenoyl group. R ¹³ and R ¹⁴ are preferably methyl groups.

The monoalkylamidoamine reacts with an acid to form a quaternary ammonium salt, which becomes a surfactant. In the second invention, the content of the monoalkylamidoamine salt as the component (C-2) is the converted amount as the monoalkylamidoamine.

Examples of the monoalkylamide (C _8-22 ) amine represented by the general formula (8) include docosanamidopropyldimethylamine and stearamidopropyldimethylamine, and the salt is preferably an organic acid salt, for example, docosa Examples thereof include namidpropyldimethylamine lactate and stearamidepropyldimethylamine lactate.

The cationic surfactant of component (C-2) can be used alone or in combination of two or more, and the content in the hair dye composition of the second invention is determined by the formulation at the time of storage of the composition From the viewpoint of stability, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably. Is 2% by mass or less, more preferably 1% by mass or less.

The charge ratio (C-2) / (B) between the component (C-2) and the component (B) in the hair dye composition of the second invention is a water-insoluble complex formed from both components during rinsing. Is 0.5 or more, preferably 1 or more, more preferably 1.5 or more, still more preferably 2 or more, and further preferably 2.5 or more, from the viewpoint of promptly adsorbing to the hair surface and enhancing the sustainability of the touch improvement effect. Also, it is 30 or less, preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, still more preferably 8 or less. Furthermore, dyeability can be improved by using this charge ratio. Moreover, if it is this charge ratio, it will be difficult to form the deposit by a water-insoluble complex in a hair dye composition. Here, the charge ratio (C-2) / (B) can be calculated according to the following equation. In the second invention, the charge density of the anionic polymer such as component (B) is the number of moles of anionic group per gram of the polymer including the counter ion in the polymer obtained as a raw material × 1000 (meq / g The charge density of the cationic surfactant of component (C-2) shall mean the number of moles of cationic groups per gram of cationic surfactant including counter ions x 1000 (meq / g). .

Charge ratio (C-2) / (B)
= (Content of component (C-2) x charge density of component (C-2)) / (content of component (B) x charge density of component (B))

Total mass ratio of component (B) and component (C-2) to component (A) in the hair dye composition of the second invention [(B) + (C-2)] / (A) Is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, still more preferably 6.5 or more, still more preferably 7.5 or more, from the viewpoint of achieving both improved feeling during rinsing and prescription stability during storage. In addition, it is preferably 50 or less, more preferably 40 or less, still more preferably 35 or less, still more preferably 30 or less, still more preferably 25 or less, still more preferably 15 or less, and further preferably 14.5 or less.

[Component (F): Higher alcohol]
The hair dye composition of the second invention preferably contains a higher alcohol having 12 or more carbon atoms from the viewpoint of improving the feel during rinsing and improving the formulation stability during storage. The higher alcohol may be contained in any of the first agent, the second agent, and the third agent when the hair dye composition of the second invention is a two-part or three-part type.

As the higher alcohol, those having 16 or more carbon atoms are preferable, those having 30 or less carbon atoms, and further 22 or less carbon atoms are preferable. Specific examples include myristyl alcohol, cetyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol, isostearyl alcohol, 2-octyldodecanol, and oleyl alcohol. These can be used alone or in combination of two or more.

The content of the component (F) in the hair dye composition of the second invention is preferably 3% by mass or more, preferably 11% by mass or less, more preferably 9% by mass or less, and still more preferably. 7% by mass or less.

The mass ratio (C-2) / (F) of the component (C-2) to the component (F) in the hair dye composition of the second invention is an improvement in the feel during rinsing and the formulation stability during storage. From the standpoint of coexistence, it is preferably 0.02 or more, more preferably 0.03 or more, still more preferably 0.05 or more, still more preferably 0.1 or more, and preferably 2 or less, more preferably 1 or less, still more preferably 0.6 or less. More preferably, it is 0.5 or less, more preferably 0.3 or less, and still more preferably 0.25 or less.

[Surfactants other than component (C-2)]
The hair dye composition of the second invention may further contain a nonionic surfactant, an amphoteric surfactant or an anionic surfactant. Among these, anionic surfactants and nonionic surfactants are preferable from the viewpoint of the stability of the formulation.

As anionic surfactants, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, olefin sulfonate, alkane sulfonate, saturated or unsaturated fatty acid salt, alkyl or alkenyl ether carboxylate, α-sulfo fatty acid salt N-acyl amino acid salts, phosphoric acid mono- or diesters, sulfosuccinic acid esters and the like. Examples of the alkyl ether sulfate include polyoxyethylene alkyl ether sulfate. Of these, alkyl sulfates, alkyl ether sulfates, saturated fatty acid salts, and alkyl ether carboxylates are preferred. Counter ions of the anionic group of these anionic surfactants include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; alkanol group having 2 or 3 carbon atoms And alkanolamine salts having 1 to 3 (for example, monoethanolamine salt, diethanolamine salt, triethanolamine salt, triisopropanolamine salt, etc.).

Surfactants other than these components (C-2) are contained in any of the first agent, the second agent, and the third agent when the hair dye composition of the second invention is a two-part or three-part type. You may let them.

Surfactants other than these components (C-2) can be used either alone or in combination of two or more thereof, and the content in the total composition of the second invention has a good feel, From the viewpoint of emulsification performance, it is preferably 0.01% by mass, more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, further preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, still more preferably 3% by mass or less, further preferably 1.5% by mass. % Or less.

[Cationic polymer]
The hair dye composition of the second invention can further contain a cationic polymer. The cationic polymer refers to a polymer having a cationic group or a group that can be ionized into a cationic group, and includes an amphoteric polymer that becomes cationic as a whole. As the cationic polymer, a water-soluble one containing an amino group or an ammonium group in the side chain of the polymer chain or containing a diallyl quaternary ammonium salt as a structural unit, such as cationized cellulose, cationic starch, cationic guar gum, Examples include polymers or copolymers of diallyl quaternary ammonium salts and quaternized polyvinyl pyrrolidone. Of these, diallyl is advantageous in terms of the softness, smoothness and ease of fingering after rinsing after hair dyeing, the ease of grouping and moisture retention during drying, and the stability of the formulation during storage. A quaternary ammonium salt polymer or copolymer, quaternized polyvinylpyrrolidone and cationized cellulose are preferred, and a diallyl quaternary ammonium salt polymer or copolymer and cationized cellulose are more preferred.

Specific examples of the cationic polymer include dimethyldiallylammonium chloride polymer (polyquaternium-6, such as Marquat 100; Lubrizol Advanced Materials), dimethyldiallylammonium chloride / acrylic acid copolymer (polyquaternium-22, MERCOAT 280, ND 295; Lubrizol Advanced Materials), dimethyldiallylammonium chloride / acrylamide copolymer (Polyquaternium-7, eg, Marquat 550; Lubrizol Advanced Materials), quaternized polyvinylpyrrolidone derivatives (Polyquaternium-11, such as Guffcut 734, 755, 755N; Ashland), cationized cellulose derivatives (Polyquaternium-10, such as Leogard G, GP; Lion, Polymer) JR-125, the JR-400, the JR-30M, the LR-400, the LR-30M; above, Dow Chemical Company) and the like.

These cationic polymers may be used in combination of two or more, and the content thereof is preferably 0.001% by mass or more in the total composition of the second invention from the viewpoint of reducing hair damage and scalp irritation, More preferably, it is 0.01 mass% or more, More preferably, it is 0.05 mass% or more, Preferably it is 20 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less.

〔Organic solvent〕
The hair dye composition of the second invention may contain an organic solvent. Examples of organic solvents include lower alkanols such as ethanol, 1-propanol, and 2-propanol; aromatic alcohols such as benzyl alcohol, 2-benzyloxyethanol, and phenoxyethanol; propylene glycol, 1,3-butanediol, diethylene glycol, glycerin, and the like. Polyols; Ether alcohols such as ethoxyethanol, ethoxydiglycol and methoxyethanol; N-alkylpyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone; alkylene carbonates such as propylene carbonate; lactones such as γ-valerolactone and γ-caprolactone Is mentioned.

These organic solvents can be used alone or in combination of two or more kinds, and the content in the total composition of the second invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, More preferably, it is 1% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and further preferably 8% by mass or less.

[Alkaline agent]
The hair dye composition of the second invention may further contain an alkali agent. When the hair dye composition of the second invention is a two-part or three-part type, the alkaline agent is contained in the first agent. Examples of such alkali agents include ammonia and salts thereof; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, and 2-aminobutanol. Alkane diamines and salts thereof; alkane diamines such as 1,3-propanediamine and salts thereof; carbonates such as guanidine carbonate, guanidine bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, and lithium carbonate . Among these alkaline agents, at least one selected from the group consisting of ammonia and salts thereof, monoethanolamine and salts thereof, and 2-amino-2-methylpropanol is preferable, and among these, 2-amino-2- More preferred is methylpropanol.

Two or more alkali agents may be used in combination, and the content in the total composition of the second invention is 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of sufficient hair dyeing effect. Is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further 0.5% by mass or more, and further preferably 1% by mass or more, and from the viewpoint of reducing hair damage and scalp irritation, 20% by mass or less, and further 10% % By mass or less, further 5% by mass or less, further 4% by mass or less, more preferably 3% by mass or less.

〔hydrogen peroxide〕
When the hair dye composition of the second invention is a two-component hair dye or a three-component hair dye, hydrogen peroxide can be contained in the second agent. The content of hydrogen peroxide in the total composition of the second invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more from the viewpoint of sufficient hair dyeing effect. From the viewpoint of reducing hair damage and scalp irritation, it is preferably 12% by mass or less, more preferably 9% by mass or less, further 6% by mass or less, and still more preferably 4% by mass or less.

[Medium]
In the hair dye composition of the second invention, water is used as a medium. The content of water in the hair dye composition of the second invention is 10% by mass or more, further 20% by mass or more, further 30% by mass or more, further 40% by mass or more, and further 50% by mass or more. It is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less.

(PH adjuster)
The hair dye composition of the second invention is used as a pH adjuster in addition to the above-mentioned alkaline agents, inorganic acids such as hydrochloric acid and phosphoric acid, organic acids such as citric acid, glycolic acid, malic acid and lactic acid, hydrochloric acid Hydrochlorides such as monoethanolamine, phosphates such as monopotassium dihydrogen phosphate and disodium monohydrogen phosphate can be used.

These pH adjusting agents may be contained in any one of the first agent, the second agent, and the third agent in the two-component or three-component hair dye. The content in the total composition of the second invention is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of sufficient dyeing effect and reduction of hair damage and scalp irritation. More preferably, it is 0.2% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and further preferably 3% by mass or less.

[PH]
In the case of a one-component hair dye, the pH (25 ° C.) of the hair dye composition of the second invention can be appropriately adjusted depending on the direct dye used. When an acid dye is used as a direct dye, the pH (25 ° C.) of the hair dye composition of the second invention is preferably 2 or more from the viewpoint of improving dye stability and hair adsorption. Preferably it is 2.5 or more, More preferably, it is 3 or more, Preferably it is 6.5 or less, More preferably, it is 6 or less, More preferably, it is 5.5 or less, More preferably, it is 5 or less. When the azo dye (A-1), (A-2) or (A-3), or the basic dye is used as the direct dye, the pH (25 ° C.) of the hair dye composition of the second invention is the dye From the viewpoint of improving the stability of the hair and the adsorption to the hair, it is preferably 7 or more, more preferably 8 or more, still more preferably 8.5 or more, still more preferably 9 or more, and preferably 12 or less, more preferably 11.5 or less, more preferably 11 or less, and further preferably 10.5 or less. When a nitro dye or a disperse dye is used as the direct dye, the pH (25 ° C.) of the hair dye composition of the second invention is preferably 2.5 or more, more preferably 3 or more, and preferably 12 or less. More preferably, it is 11.5 or less, More preferably, it is 11 or less.

In addition, when the hair dye composition of the second invention is a two-component hair dye, the pH of the first agent is preferably 8 to 12 and the pH of the second agent is preferably 25 ° C. Is 2-5. The pH (25 ° C.) at the time of use of the mixture of the first agent and the second agent of the second invention is preferably 8 or more, more preferably 8.5 or more, and still more preferably from the viewpoint of hair dyeing effect and skin irritation. It is 9 or more, preferably 11.5 or less, more preferably 11 or less, and further preferably 10.5 or less.

In the present specification, the pH of the hair dye composition of the second invention is a value measured at room temperature (25 ° C.) using a pH meter F-22 manufactured by Horiba, Ltd.

[Other optional ingredients]
In addition to the above components, other components that are usually used as cosmetic raw materials can be added to the hair dye composition of the second invention.

Examples of the purpose of blending such optional ingredients include pearlization, antiseptic, metal sequestration, antioxidant, ultraviolet absorption, moisturizing, product coloring, flavoring, etc. Specific optional ingredients include animal and vegetable fats and oils, Examples include higher fatty acids, protein hydrolysates, protein derivatives, amino acids, plant extracts, vitamins, flavors, and the like.

[Drug type]
The hair dye composition of 2nd invention can be used as various hair dyes of 1 agent type, 2 agent type, or 3 agent type. The one-component hair dye composition comprises a single agent containing components (A), (B) and (C-2). The two-component hair dye composition preferably comprises a first agent containing component (A) and an alkaline agent, and a second agent containing hydrogen peroxide. The three-component hair dye composition comprises a first agent containing an alkaline agent, a second agent containing hydrogen peroxide, and a third agent containing component (A), or component (A) And a first agent containing an alkali agent, a second agent containing hydrogen peroxide, and a third agent containing other components. As the third agent containing the above-mentioned other components, a powdery oxidizer made of a granulated material such as persulfate (ammonium persulfate, potassium persulfate, sodium persulfate, etc.) may be used to improve decolorization power. preferable.
In the second invention, the “total composition” refers to the entire composition at the time of use of the hair dyeing treatment. In the above-mentioned two-component hair dye, the first agent and the second agent are mixed. In the case of a three-component hair dye, it means a mixture after mixing the first agent, the second agent and the third agent.

The hair dye composition of the second invention can be used, for example, in the form of liquid, emulsion, cream, gel, paste, mousse, etc., and can also be in the form of an aerosol. . It is desirable to adjust the viscosity of the entire composition in these cases so that it does not easily drip when applied to the hair. The viscosity (25 ° C.) of this whole composition was rotated for 1 minute at 10 rpm using a rotor TC by a B-type rotational viscometer with a helical stand (model; digital viscometer TVB-10, manufactured by Toki Sangyo Co., Ltd.). The subsequent measured value is preferably 2,000 to 200,000 mPa · s, more preferably 4,000 to 150,000 mPa · s, still more preferably 6,000 to 100,000 mPa · s, and further preferably 8,000 to 80,000 mPa · s. In addition, in the case of a two-part type or a three-part type, the measurement shall be made after 3 minutes have elapsed since the mixing of each agent.

The hair dye composition of the second invention can also be used as a foam by discharging it from a non-aerosol-type former container when applied to the hair, or by shaking and foaming in a cup. it can. In this case, the viscosity of the entire composition before foaming is also preferably adjusted so that it does not easily drip when applied to the hair as a foam. The viscosity (25 ° C.) of this whole composition was rotated for 1 minute at 30 rpm using a rotor No. 1 with a B-type rotational viscometer (model; digital viscometer TV-10, manufactured by Toki Sangyo Co., Ltd.). The measured value (however, when the viscosity exceeds 160 mPa · s, the measured value after rotating at 12 rpm for 1 minute) is preferably 1 to 800 mPa · s, more preferably 1 to 600 mPa · s, still more preferably 1 to 500 mPa · s, more preferably 1 to 300 mPa · s. In addition, in the case of a two-part type or a three-part type, the measurement shall be made after 3 minutes have elapsed since the mixing of each agent.

[Hair dyeing method]
In order to carry out a hair dyeing treatment using the hair dye composition of the second invention, for example, the hair dye composition of the second invention (in the case of the two-agent type or the three-agent type, the first to third agents are used). After mixing just before use) is applied to the hair, allowed to stand for a predetermined time, rinsed with water and dried. The application temperature to hair is preferably 15 to 45 ° C., and the application time is preferably 1 to 60 minutes, more preferably 5 to 45 minutes, and further preferably 10 to 30 minutes.

With respect to the embodiment described above, a preferred aspect of the second invention will be further disclosed below.

<1> A hair dye composition containing the following components (A), (B) and (C-2).
(A) Direct dye (B) Sulfonated polysaccharide (C-2) _Monoalkyl (C _8-22 ) quaternary ammonium salt, monoalkyl (C _8-22 ) ether amine, monoalkyl amide (C _8-22 ) Cationic surfactants selected from the group consisting of amines and salts of these amines

<2> Component (A) is preferably selected from the group consisting of azo dyes (A-1), (A-2) and (A-3), acid dyes, basic dyes, nitro dyes and disperse dyes The hair dye composition according to <1>, which is one or more dyes.

<3> Component (A) is preferably one or more azo dyes selected from the group consisting of the following (A-1), (A-2) and (A-3), The pH at 0 ° C. is preferably 7 or more, more preferably 8 or more, still more preferably 8.5 or more, still more preferably 9 or more, preferably 12 or less, more preferably 11.5 or less, still more preferably 11 or less. The hair dye composition according to <2>, more preferably 10.5 or less.

<6> The content of component (A) is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, still more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more, and preferably 2 The hair dye composition according to any one of <1> to <5>, wherein the hair dye composition is 1% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less.

<9> The degree of substitution with the substituent (b1) per constituent monosaccharide residue is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.1 or more, and preferably 2.5 or less, more preferably 2 The hair dye composition according to <7> or <8>, further preferably 1.5 or less.

<17> The content of component (B) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and preferably 5% by mass or less, more preferably 3%. The hair dye composition according to any one of <1> to <16>, which is not more than mass%, more preferably not more than 2 mass%.

<18> The monoalkyl (C _8-22 ) quaternary ammonium salt in the component (C-2) is preferably a compound represented by the general formula (6), according to any one of <1> to <17> Hair dye composition.

<19> The dye according to any one of <1> to <18>, wherein the monoalkyl (C _8-22 ) ether amine in the component (C-2) is preferably a compound represented by the general formula (7) Hair composition.

<20> The dye according to any one of <1> to <19>, wherein the monoalkylamide (C _8-22 ) amine in the component (C-2) is preferably a compound represented by the general formula (8) Hair composition.

[In the formula, R ¹² represents a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, and R ¹³ and R ¹⁴ may be the same or different, and are alkyl having 1 to 4 carbon atoms. Represents a group, and b represents a number of 2 or more and 4 or less. ]

<21> The content of component (C-2) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 5% by mass or less, more preferably The hair dye composition according to any one of <1> to <20>, wherein is 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less.

<22> The charge ratio (C-2) / (B) between component (C-2) and component (B) is preferably 1 or more, more preferably 1.5 or more, still more preferably 2 or more, and even more preferably 2.5. The hair dye composition according to any one of <1> to <21>, which is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, and still more preferably 8 or less.

<23> The hair dye composition according to any one of <1> to <22>, preferably further containing a component (F).
(F) Higher alcohols with 12 or more carbon atoms

<24> The hair dye composition according to <23>, wherein the component (F) preferably has 16 or more carbon atoms, preferably 30 or less carbon atoms, more preferably 22 or less carbon atoms.

<25> The content of the component (F) is preferably 3% by mass or more, preferably 11% by mass or less, more preferably 9% by mass or less, and further preferably 7% by mass or less <23> Or the hair dye composition as described in <24>.

<26> The mass ratio (C-2) / (F) of the component (C-2) to the component (F) is preferably 0.02 or more, more preferably 0.03 or more, still more preferably 0.05 or more, still more preferably 0.1. Or more, preferably 2 or less, more preferably 1 or less, still more preferably 0.6 or less, still more preferably 0.5 or less, still more preferably 0.3 or less, and further preferably 0.25 or less, from <23> to <25> The hair dye composition in any one.

<27> A hair coloring method in which the hair dye composition according to any one of <1> to <26> is applied to hair, left for 1 to 60 minutes, rinsed with water, and dried.

● Production Example 1 for the first invention
The sulfonated polysaccharide of component (B) was obtained by the following method.
In a 1 L kneader, 100 g of hydroxyethyl cellulose (manufactured by Union Carbide, QP15000H, LOT.W8077P, hereinafter “HEC”) and 0.61 g of stearyl glycidyl ether (0.45 mol% to HEC) were charged. The apparatus was sealed, and the apparatus was degassed (13.3 kPa) and replaced with nitrogen three times to remove oxygen in the reaction system. After purging with nitrogen, 50 g of isopropyl alcohol (0.5 mass times vs. HEC) was added at room temperature while stirring the powder. After 5 minutes, a mixed solution of 6.67 g (20 mol%) of 48 mass% sodium hydroxide aqueous solution and 36.5 g of ion-exchanged water (total water volume 0.4 mass times to HEC) was gradually added while stirring the powder. After stirring at room temperature for 30 minutes, the temperature was raised to 80 ° C., and a hydrophobization reaction was carried out at 80 ° C. for 3 hours. After completion of the hydrophobization reaction, the mixture was cooled to 50 ° C, and 31.2 g (20 mol% vs. HEC) of 2,3-epoxypropane sodium sulfonate aqueous solution (41.1% by mass) prepared separately was slowly added while stirring. The sulfonation reaction was carried out for 5 hours. After completion of the sulfonation reaction, 4.8 g of acetic acid was slowly added for neutralization. After stirring for 30 minutes, drying under reduced pressure (90 ° C./100 mmHg) was performed for 6 hours in a kneader to obtain 110 g of stearoxy PG hydroxyethyl cellulose sulfonate Na as a yellowish white powder.
The obtained stearoxy PG hydroxyethyl cellulose sulfonate Na had a degree of substitution of 3-stearyloxy-2-hydroxypropyl group of 0.0033, a degree of substitution of 3-sulfo-2-hydroxypropyl group of 0.139, and a charge density of 0.54 meq / g. there were.

Examples 1 to 14 and Comparative Examples 1 to 5
A color treatment (pH 10.01) having the composition shown in Tables 2 to 3 was prepared. The obtained color treatment was evaluated for dyeability, feel after treatment, and formulation stability according to the following methods. These results are also shown in Tables 2 to 3. Moreover, about Example 5 and the comparative example 1, evaluation of touch persistence was also performed and the result is shown in FIG.

[Dyeability]
Apply color treatment to 1g of Chinese white hair (approx. 10cm) at a bath ratio (water: hair: agent) = 1: 1: 0.5 (mass ratio), leave at 40 ° C for 5 minutes, then about 40 ° C Rinse with water, wipe with a towel, and dry with a dryer.
The color of the resulting hair bundle immediately after dyeing is measured with a CIE color system (L ^* , a ^* , b ^* ) using a color difference meter (manufactured by Konica Minolta Sensing Co., Ltd., color difference meter CR-400), The difference from the color before dyeing was determined by the following formula and was defined as dyeability ΔE ^* . The results are shown in Tables 2-3. The larger ΔE ^{*, the} better the dyeability.

[In the formula, L ^* ₀ , a ^* ₀ and b ^* ₀ represent the values of L ^* , a ^* and b ^* of the hair bundle before dyeing, respectively, L ^* ₁ , a ^* ₁ and b ^* ₁ are The values of L ^* , a ^* and b ^* immediately after staining are shown, respectively. ]

[Feel after drying (sensory evaluation)]
Apply color treatment to 1g of European hair with a bath ratio (water: hair: agent) = 1: 1: 0.5, leave at 40 ° C for 5 minutes, rinse with water at about 40 ° C and wipe with a towel And dried with a dryer. The fingers after drying were subjected to sensory evaluation in the following five stages using Comparative Example 3 as a control. The results are shown in Tables 2-3.
+2: Fingering is significantly better than Comparative Example 3 +1: Fingering is better than Comparative Example 3 0: Fingering is almost equivalent to Comparative Example 3 -1: Fingering is better than Comparative Example 3 -2: Compared to Comparative Example 3, the fingering is significantly worse

[Prescription stability]
When preparing the color treatment, it was visually observed according to the following criteria to evaluate the formulation stability of the hair dye composition. The results are shown in Tables 2-3.
1: Dye easily dissolves, and no precipitate is present even after one week 0: Complex of dye and polymer is precipitated after one week of blending

[Feeling Persistence (Coming Force)]
Apply the color treatment of Example 5 or Comparative Example 2 at a bath ratio (water: hair: agent) = 1: 1: 0.5 (mass ratio) to 10 g of European hair 10 g (length 23 cm), 40 ° C. After leaving it for 5 minutes, it was rinsed with about 40 ° C. water, wiped with a towel, and dried with a dryer.
The above two types of tresses were subjected to hair washing treatment 6 times including “pre-washing” → “shampoo frothing” → “shampoo rinse” → “towel dry” → “dry”. As the shampoo, 1 g of the evaluation shampoo shown in Table 1 was used with respect to the tres.
At this time, the combing force in “shampooing” was measured by a dynamic combing force measurement method (J. Soc. Cosmet. Chem. Japan. Vol. 27, No. 1, P11-13 1993).
For shampoo frothing, after suspending the tress coated with 1g of the shampoo for evaluation shown in Table 1 on the force gauge, sandwich the hair tress with the two hair brushes from front and back or from both sides, combing 30 times, and applying the force applied during each combing It was measured. Combing was performed at a rate of about 1 per second. Of the measured combing force, the combing force was evaluated by the average value of 25 times excluding the first 5 times. As the hair brush, Kao Lunet (manufactured by Kao Corporation, total length: about 20 cm, comb size: about 4 × 10 cm, comb tooth density: 6 / cm) was used. The average of 25 measurements is shown in FIG.

* 3: Polymer synthesized in Production Example 1
* 4: Hydroxyethyl cellulose sulfonic acid
* 5: Serogen F-5A (Daiichi Kogyo Seiyaku Co., Ltd.)
* 6: Marcoat 100 (Lubrizol Advanced Materials, Inc.)
* 7: Kosmedia Ultra Gel 300 (BASF)
* 8: Polyethyleneimine (manufactured by Wako Pure Chemical Industries, average molecular weight about 10,000)
* 9: Sofcare KG-101W-E (Kao Corporation)
* 10: Cachisero L-150 (manufactured by Kao Corporation)

Examples 15 to 26 and Comparative Examples 6 to 10
A color treatment (pH 3.50) having the composition shown in Table 4 was prepared. The obtained color treatment was evaluated for dyeability, feel after treatment, and formulation stability according to the following methods. Moreover, about Example 19 and the comparative example 7, evaluation of touch persistence was also performed.

[Dyeability]
Evaluation was performed according to the method described above. The results are shown in Table 4.

[Feel after drying (sensory evaluation)]
Evaluation was performed according to the method described above except that Comparative Example 8 was used as a control. The results are shown in Table 4.

[Prescription stability]
Evaluation was performed according to the method described above. The results are shown in Table 4.

[Feeling Persistence (Coming Force)]
Evaluation was performed according to the above-described method except that the color treatments of Example 19 and Comparative Example 7 were used. The average value of 25 measurements is shown in FIG.

* 11: pH adjustment amount

● Production Example 2 for the second invention
The sulfonated polysaccharide of component (B) was obtained by the following method.
In a 1 L kneader, 100 g of hydroxyethyl cellulose (manufactured by Union Carbide, QP15000H, LOT.W8077P, hereinafter “HEC”) and 0.61 g of stearyl glycidyl ether (0.45 mol% to HEC) were charged. The apparatus was sealed, and the apparatus was degassed (13.3 kPa) and replaced with nitrogen three times to remove oxygen in the reaction system. After purging with nitrogen, 50 g of isopropyl alcohol (0.5 mass times vs. HEC) was added at room temperature while stirring the powder. After 5 minutes, a mixed solution of 6.67 g (20 mol%) of 48 mass% sodium hydroxide aqueous solution and 36.5 g of ion-exchanged water (total water volume 0.4 mass times to HEC) was gradually added while stirring the powder. After stirring at room temperature for 30 minutes, the temperature was raised to 80 ° C., and a hydrophobization reaction was carried out at 80 ° C. for 3 hours. After completion of the hydrophobization reaction, the mixture was cooled to 50 ° C, and 31.2 g (20 mol% vs. HEC) of 2,3-epoxypropane sodium sulfonate aqueous solution (41.1% by mass) prepared separately was slowly added while stirring. The sulfonation reaction was carried out for 5 hours. After completion of the sulfonation reaction, 4.8 g of acetic acid was slowly added for neutralization. After stirring for 30 minutes, drying under reduced pressure (90 ° C./100 mmHg) was performed for 6 hours in a kneader to obtain 110 g of stearoxy PG hydroxyethyl cellulose sulfonate Na as a yellowish white powder.
The obtained stearoxy PG hydroxyethyl cellulose sulfonate Na had a degree of substitution of 3-stearyloxy-2-hydroxypropyl group of 0.0033, a degree of substitution of 3-sulfo-2-hydroxypropyl group of 0.139, and a charge density of 0.54 meq / g. there were.

Examples 27 to 34 and Comparative Examples 11 to 13
A color treatment (pH 9.1) having the composition shown in Table 6 was prepared. The resulting color treatment was evaluated for formulation stability and feel sustainability according to the following methods. These results are also shown in Table 6.

[Prescription stability during storage]
The color treatment was placed in a glass bottle, stored at 50 ° C. for 1 day, and visually observed according to the following criteria to evaluate the prescription stability during storage of the color treatment.
1: The dye is dissolved and no water-insoluble complex exists. 0: The water-insoluble complex of the dye and the cationic surfactant exists.

[Feeling Persistence (Coming Force)]
Chinese hair (Burelux Co., Ltd., weight 25g, length 26cm) treated twice with powder bleach (using Silk Lift made by KAO Germany, powder: 2 liquids mixed at 5: 7 (mass ratio) Was applied at a bath ratio of 1: 1 (mass ratio), allowed to stand for 30 minutes, washed and dried, and then subjected to the color treatment shown in Table 6 with a bath ratio (water: hair: agent) = 1: 1: 0.5 (mass) Ratio), left at room temperature for 5 minutes, wiped with a towel, and dried with a dryer.
The above-mentioned tress was subjected to a hair washing treatment of 5 cycles of “prewash (rinse with water)” → “shampoo application” → “shampoo rinse” → “towel dry” → “dry”. As the shampoo, 2.5 g of the evaluation shampoo shown in Table 5 was used with respect to the tres.
At this time, the combing force in “shampoo rinse” was measured by a dynamic combing force measurement method (J. Soc. Cosmet. Chem. Japan. Vol. 27, No. 1, P11-13 1993). In accordance with this measurement method, after applying shampoo and suspending the foamed hair on the force gauge, while applying tap water at a flow rate of about 2170 mL / min in the shower, sandwich the hair tress with two hair brushes from the front and back or both sides, Combing was performed 25 times, and the force applied during each combing was measured. Combing was performed at a rate of about 1 per second. Of the measured combing force, the combing force was evaluated by the average value of 20 times excluding the first 5 times. As the hair brush, Kao Lunet (manufactured by Kao Corporation, total length: about 20 cm, comb size: about 4 × 10 cm, comb tooth density: 6 / cm) was used.

The color treatments of Examples 27 to 34 were excellent in prescription stability during storage, and the combing force remained low even after 5 times of shampooing, and a good feeling was maintained.

Formulation Examples 1-20
Table 7 shows an example of pH9.1 color treatment, and Table 8 shows an example of pH3.5 color treatment.

The color treatments of Formulation Examples 1 to 20 have good hair dyeing properties, are excellent in formulation stability during storage, and maintain a good feel after shampooing.

Claims

A hair dye composition containing the following components (A), (B) and (C-1).
(A) Direct dye (B) Sulfonated polysaccharide (C-1) Cationic polymer with charge density of 3 meq / g or more and 24 meq / g or less
Component (A) is one or more selected from the group consisting of azo dyes (A-1), (A-2) and (A-3), acid dyes, basic dyes, nitro dyes and disperse dyes The hair dye composition according to claim 1, wherein
Component (A) is one or more azo dyes selected from the group consisting of the following (A-1), (A-2) and (A-3), and has a pH of 7 or more at 25 ° C. The hair dye composition according to claim 2, which is 12 or less.
The hair dye composition according to claim 2, wherein the component (A) is an acid dye, and the pH at 25 ° C is 2 or more and 6.5 or less.
The dye according to any one of claims 1 to 4, wherein the component (B) is a water-soluble alkyl-substituted polysaccharide in which part or all of the hydrogen atoms of the hydroxy group in the polysaccharide are substituted with the following substituent (b1). Hair composition.
(b1) a sulfoalkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxy group or a salt thereof
The component (C-1) is a combination of (C-1-1) a non-crosslinked cationic polymer and (C-1-2) a crosslinked cationic polymer. The hair dye composition as described.
The hair dye composition according to any one of claims 1 to 6, further comprising a component (D).
(D) Cationic polymer with a charge density of less than 3 meq / g
The hair dye composition according to any one of claims 1 to 7, further comprising a component (E).
(E) Sodium chloride
The hair dye composition according to any one of claims 1 to 8, wherein the charge ratio (C-1) / (B) of the component (B) to the component (C-1) is 0.001 or more and 40 or less.
Dye containing components (A), (B) and (C-2) and having a charge ratio (C-2) / (B) between component (B) and component (C-2) of 0.5 to 30 Hair composition.
(A) Direct dye (B) Sulfonated polysaccharide (C-2) Monoalkyl (C 8-22 ) quaternary ammonium salt, monoalkyl (C 8-22 ) ether amine, monoalkyl amide (C 8-22 ) Cationic surfactants selected from the group consisting of amines and salts of these amines
Component (A) is one or more selected from the group consisting of azo dyes (A-1), (A-2) and (A-3), acid dyes, basic dyes, nitro dyes and disperse dyes 11. The hair dye composition according to claim 10, wherein
Component (A) is one or more azo dyes selected from the group consisting of the following (A-1), (A-2) and (A-3), and has a pH of 7 or more at 25 ° C. 12. The hair dye composition according to claim 11, which is 12 or less.
12. The hair dye composition according to claim 11, wherein the component (A) is an acid dye, and the pH at 25 ° C. is 2 or more and 6.5 or less.
The dye according to any one of claims 10 to 13, wherein the component (B) is a water-soluble alkyl-substituted polysaccharide in which part or all of the hydrogen atoms of the hydroxy group in the polysaccharide are substituted with the following substituent (b1). Hair composition.
(b1) a sulfoalkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxy group or a salt thereof
The hair dye composition according to any one of claims 10 to 14, further comprising a component (F).
(F) Higher alcohols with 12 or more carbon atoms
The hair dye composition according to claim 15, wherein the mass ratio (C-2) / (F) of the component (C-2) to the component (F) is 0.02 or more and 2 or less.