JP2007176887A - Hair dye composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair dye effective for restoring the springy or wavy hair generated at the tip of excessively damaged hair to the natural state, suppressing the generation of the springy or wavy hair, reducing the degradation of the feeling of the hair and uniformly dyeing the hair from the root to the tip. <P>SOLUTION: The hair dye composition contains the components (A) to (C) and has a pH of 8-12. (A) A quaternary ammonium salt expressed by general formula (1) (R<SP>1</SP>is a 6-12C saturated or unsaturated hydrocarbon group; R<SP>2</SP>and R<SP>3</SP>are each independently a 1-3C alkyl; n is an integer of 0-2; m is 1 or 2; and X<SP>-</SP>is halide ion, alkylsulfate ion or alkyl- or arylsulfonic acid ion), (B) an oxidizing agent and (C) toluene-2,5-diamine, p-aminophenol or their acid addition salts. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is a hair dye containing a specific quaternary ammonium salt, which restores the bounce and undulation generated at the hair tip due to the accumulation of hair damage and restores it to its original state, and suppresses its occurrence It is related with the hair dye composition which can suppress the deterioration of the hair touch by damage, and can dye | stain uniformly from a root to a hair tip.

  For dyeing hair, hair dyes using oxidative coupling reactions of oxidative dye intermediates (precursors and couplers) in the presence of an alkali agent, an oxidant and the like are widely used. However, hair dyes containing oxidants can cause hair damage, not only causing lift up and peeling of the cuticle, generation of cysteic acid, and reduction of lipids in the hair, Appearance tends to deteriorate. As a phenomenon of deterioration of touch and appearance, a finger catching feeling, a squeaky feeling, a feeling of firmness, etc. may occur during shampooing or drying, and hair color / glossiness and cohesion may deteriorate. Furthermore, such hair damage is remarkable in the hair tip portion because it accumulates when dyeing or decoloring is repeated, and as a symptom thereof, the hair tip portion is bounced or swelled. In addition, the difference in the degree of damage between the root portion and the hair tip portion also causes problems such as uneven dyeing easily occurring and the color of the hair tip portion being easily removed by washing with shampoo.

  Therefore, as one method for solving hair damage and feeling / appearance deterioration, an additive having a conditioning action is used. For example, it has been proposed to add a certain silicone derivative such as an amino-modified polysiloxane to an oxidative hair dye (see Patent Document 1), or to add a cationic polymer (see Patent Document 2). However, these conditioning components are not satisfactory because they have the drawback of reducing the dyeing power or decoloring power when added in an amount necessary to exert a sufficient effect.

  On the other hand, a method of using a specific organic acid, a sulfonic acid compound, and an organic solvent in combination has been proposed as a method for straightening hair (a method for straightening hair) (see Patent Document 3). However, it is not sufficient to suppress the bounce and undulation that occurs at the hair tip and restore it to its original state, and is not intended for dyeing or decoloring hair.

JP 63-51315 A U.S. Pat.No. 4,362,528 JP-A-8-92043

  Therefore, the present invention restores the bounce and undulation that occurs at the hair tip that has accumulated excessive damage and restores it to its original state, and can suppress its occurrence, while suppressing the deterioration of the feel of the hair and from the root. It aims at providing the hair dye which can be dye | stained uniformly to a hair end, and the method of dye | staining hair using the hair dye.

  This inventor discovered that the said subject was solved by using a specific ammonium salt, an oxidizing agent, and a specific precursor together.

  That is, the present invention provides a hair dye composition containing the following components (A), (B) and (C) and having a pH of 8-12.

  (A) Quaternary ammonium salt represented by general formula (1)

[Wherein, R ¹ represents a saturated or unsaturated hydrocarbon group having 6 to 12 carbon atoms, R ² and R ³ represent the same or different alkyl group having 1 to 3 carbon atoms, and n represents 0 Represents an integer of ˜2, m represents 1 or 2, and X ⁻ represents a halide ion, an alkyl sulfate ion, an alkyl or aryl sulfonate ion. ]

(B) Oxidizing agent
(C) Toluene-2,5-diamine, paraaminophenol or acid addition salts thereof

  Moreover, this invention has the 1st agent containing the alkaline agent and the 2nd agent containing a component (B), and the said hair dye composition mixes the 1st agent and the 2nd agent just before use. And a method of dyeing hair that is applied to hair, left for a predetermined time, and then washed away.

  The hair dye of the present invention restores the bounce and undulation that occurs at the hair tips due to the accumulation of damage to the hair, restores it to its original state, suppresses its occurrence, and reduces the feel of the hair due to damage. In addition, it can be dyed uniformly from the root to the hair tip.

  The hair dye of the present invention is a two-component type comprising a first agent containing an alkaline agent and a second agent containing an oxidizing agent such as hydrogen peroxide, or a persulfate as a third agent (for example, (Ammonium persulfate, potassium persulfate, sodium persulfate) and the like can be used in the form of a three-part type formed by combining powdered oxidizers made of a granulated product. Hereinafter, the “total composition” in the present invention refers to the whole composition immediately before use in which the first agent and the second agent are mixed in the case of the two-agent type, and in the case of the three-agent type, the first agent, The entire composition immediately before use in which the second agent and the third agent are mixed.

  The pH (25 ° C.) of the hair dye composition of the present invention is pH 8 to 12 at the time of use (mixing), and particularly preferably pH 9 to 11 from the viewpoint of hair dyeing / bleaching effect and skin irritation. The pH of the first agent before mixing is preferably pH 8-12, and the pH of the second agent before mixing is preferably 2-5. As pH adjusters, in addition to the alkaline agents shown below, inorganic acids such as hydrochloric acid and phosphoric acid, organic acids such as citric acid, glycolic acid and lactic acid, hydrochlorides such as monoethanolamine hydrochloride, monopotassium dihydrogen phosphate And phosphates such as disodium monohydrogen phosphate.

Examples of the X ⁻ halide ion of the quaternary ammonium salt represented by the general formula (1), which is the component (A), include chloride ion, iodide ion, bromide ion, and the like. Examples thereof include sulfate ions and ethyl sulfate ions, and examples of alkyl or aryl sulfonate ions include methane sulfonate ions and para-toluene sulfonate ions. Of these, halide ions are preferred.

Further, the carbon number of R ^{1 in} the general formula (1) is preferably 8 to 12, and R ² and R ³ are preferably the same. Specifically, as m = 1, octylcyclopentyldimethylammonium salt, 2-ethylhexylcyclopentyldimethylammonium salt, decylcyclopentyldimethylammonium salt (n = 0), octylcyclopentylmethyldimethylammonium salt, 2-ethylhexylcyclopentyl Examples thereof include methyldimethylammonium salt and decylcyclopentylmethyldimethylammonium salt (n = 1).

  Examples of m = 2 include octylcyclohexyldimethylammonium salt, 2-ethylhexylcyclohexyldimethylammonium salt, decylcyclohexyldimethylammonium salt, octylcyclohexyldiethylammonium salt, octylcyclohexylmethylethylammonium salt, octylcyclohexyldipropylammonium salt (above, n = 0), octylcyclohexylmethyldimethylammonium salt, 2-ethylhexylcyclohexylmethyldimethylammonium salt, decylcyclohexylmethyldimethylammonium salt, octylcyclohexylmethylmethylethylammonium salt (n = 1), octylcyclohexylethyldimethylammonium salt, Decylcyclohexylethyldimethylammonium salt, oct And lucyclohexylethyl diethylammonium salt (n = 2).

Among these, n is preferably 0 or 1, and R ¹ preferably has 8 to 10 carbon atoms.

  The quaternary ammonium salt of component (A) may be used in combination of two or more thereof, and the content thereof is from the viewpoint of the effect of suppressing waviness, the feel during hair dyeing treatment, and the stability of the composition. The content is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, and particularly preferably 0.1 to 2% by weight in the total composition.

  The oxidizing agent of component (B) is preferably included in the second agent. However, the oxidizing agent as component (B) does not include the persulfate used in the third agent. Examples of the oxidizing agent include hydrogen peroxide and urea peroxide that is a generator of hydrogen peroxide or oxygen, melamine peroxide, sodium perborate, potassium perborate, sodium percarbonate, potassium percarbonate, and the like. Hydrogen peroxide is particularly preferable. The content of the oxidizing agent is 0.1 to 12% by weight, more preferably 0.5 to 9% in terms of hydrogen peroxide, in terms of hydrogen peroxide, from the viewpoint of sufficient hair dyeing / bleaching effect and reduction of hair damage and scalp irritation. % By weight, especially 1 to 6% by weight is preferred.

  In the present invention, component 2, (C), toluene-2,5-diamine, paraaminophenol, or an acid addition salt thereof is an oxidation dye intermediate (precursor) and is preferably included in the first agent. The acid addition salt is not particularly limited as long as it is a physiologically acceptable acid addition salt, but preferred are hydrochloride, sulfate, and phosphate. These toluene-2,5-diamine, paraaminophenol or acid addition salts thereof may be used alone or in combination of two or more thereof, and the content thereof is 0.01 to 5% by weight in the total composition, Especially 0.1 to 4 weight% is preferable.

  When the hair dye of the present invention is used in a two-part type or a three-part type, the first agent further contains an alkali agent. Alkaline agents such as ammonia and salts thereof; alkanolamines such as monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol and 2-aminobutanol and salts thereof; alkanediamines such as 1,3-propanediamine and the like Salts: carbonates such as guanidine carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like. These alkaline agents may be used in combination of two or more, and the content thereof is 0.05% in the total composition from the viewpoint of sufficient hair dyeing / bleaching effect and reduction of hair damage and scalp irritation. Is preferably 15 to 15% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 0.2 to 5% by weight.

  Of the above alkaline agents, ammonia, alkanolamines and salts thereof are preferred. As the ammonium salt, ammonium carbonate and ammonium hydrogen carbonate are preferable, and as the alkanolamine and its salt, monoethanolamine and its salt are preferable. Furthermore, the content of these is most preferably in the following range. The sum of the content (X) when ammonia and its salt in all compositions are converted as ammonia and the content (Y) when monoethanolamine and its salt are converted as monoethanolamine is sufficient. From the viewpoint of hair / bleaching effect and reduction of hair damage, scalp stimulation, and olfactory stimulation, it is preferably 0.05 to 15% by weight, more preferably 0.1 to 10% by weight, particularly 0.2 to 5% in the total composition. It is preferable that it is weight%. The weight ratio of X / Y is preferably 0.01: 1 to 2: 1, more preferably 0.02: 1 to 1: 1, and particularly preferably 0.05: 1 to 0.5: 1.

  The hair dye of the present invention may contain a direct dye or an oxidation dye intermediate in the first agent.

  Examples of the direct dye include acid dyes, nitro dyes, disperse dyes, basic dyes, and direct dyes described in JP-A-2003-342139. Examples of acid dyes include blue No. 1, purple No. 401, black No. 401, orange color No. 205, red No. 227, red No. 106, yellow No. 203, acidic orange 3, etc., and nitro dyes include 2-nitro Paraphenylenediamine, 2-amino-6-chloro-4-nitrophenol, 3-nitro-p-hydroxyethylaminophenol, 4-nitroorthophenylenediamine, 4-amino-3-nitrophenol, 4-hydroxypropylamino- 3-nitrophenol, HC blue 2, HC orange 1, HC red 1, HC yellow 2, HC yellow 4, HC yellow 5, HC red 3, N, N-bis- (2-hydroxyethyl) -2-nitropara Examples include disperse dyes such as disperse purple 1, disperse blue 1, disperse black 9, etc., and basic dyes include basic blue 99, basic tea 16, basic tea 17, and base. Basic red 76, basic red 51, basic yellow 57, basic yellow 87, basic orange 31 and the like.

  Two or more direct dyes may be used in combination, or may be used in combination with an oxidation dye intermediate. The content thereof is preferably 0.001 to 5% by weight, particularly 0.01 to 3% by weight in the total composition.

  As the oxidation dye intermediate, known precursors and couplers that are usually used in hair dyes can be used. As the precursor, in addition to component (C), for example, paraphenylenediamine, 2-chloro-paraphenylenediamine, N-methoxyethylparaphenylenediamine, N, N-bis (2-hydroxyethyl) paraphenylenediamine, 2- ( 2-hydroxyethyl) paraphenylenediamine, 2,6-dimethylparaphenylenediamine, 4,4'-diaminodiphenylamine, 1,3-bis (N- (2-hydroxyethyl) -N- (4-aminophenyl) amino ) -2-propanol, PEG-3,3,2'-paraphenylenediamine, paramethylaminophenol, 3-methyl-4-aminophenol, 2-aminomethyl-4-aminophenol, 2- (2-hydroxyethyl) Aminomethyl) -4-aminophenol, orthoaminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 2-amino-5-acetamidophenol, 3,4-diaminobenzoic acid, Five -Aminosalicylic acid, 2,4,5,6-tetraaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5- Examples include diamino-1-hydroxyethylpyrazole and salts thereof.

  Examples of the coupler include metaphenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) anisole, 2,4-diamino-5-methylphenetole, and 2,4-diamino. -5- (2-hydroxyethoxy) toluene, 2,4-dimethoxy-1,3-diaminobenzene, 2,6-bis (2-hydroxyethylamino) toluene, 2,4-diamino-5-fluorotoluene, 1 , 3-Bis (2,4-diaminophenoxy) propane, metaaminophenol, 2-methyl-5-aminophenol, 2-methyl-5- (2-hydroxyethylamino) phenol, 2,4-dichloro-3- Aminophenol, 2-chloro-3-amino-6-methylphenol, 2-methyl-4-chloro-5-aminophenol, N-cyclopentyl-metaaminophenol, 2-methyl-4-methoxy-5- (2- Hydroxyethylamino) phenol, 2-methyl-4-fluoro-5- Minophenol, resorcin, 2-methylresorcin, 4-chlororesorcin, 1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-isopropyl-5-methylphenol, 4 -Hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 6-hydroxybenzomorpholine, 3,4-methylenedioxyphenol, 2-bromo-4,5-methylenedioxyphenol, 3,4 -Methylenedioxyaniline, 1- (2-hydroxyethyl) amino-3,4-methylenedioxybenzene, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-diaminopyridine 2,3-diamino-6-methoxypyridine, 2-methylamino-3-amino-6-methoxypyridine, 2-amino-3-hydroxypyridine, 2,6-diaminopyridine and the like And the like salts and the like of.

  Two or more precursors and couplers may be used in combination, and the content of the precursor is preferably 0.01 to 10% by weight, particularly 0.1 to 5% by weight in the total composition as the total amount with the component (C). The coupler is preferably 0.01 to 5% by weight, particularly 0.1 to 4% by weight, based on the total composition.

  The hair dye composition of the present invention may further contain a surfactant. As the surfactant, any of a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and an anionic surfactant can be used.

  As the cationic surfactant, mono long-chain alkyl quaternary ammonium salts are preferable, and specific examples include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, and behenyltrimethylammonium chloride. Stearyl trimethyl ammonium and behenyl trimethyl ammonium chloride are preferable.

  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 saccharide surfactants, alkyl amine oxides, and alkyl amido amine oxides. Of these, polyoxyalkylene alkyl ether and polyoxyethylene hydrogenated castor oil are preferable, and polyoxyethylene alkyl ether is particularly preferable.

  Examples of amphoteric surfactants include imidazoline series, carbobetaine series, amide betaine series, sulfobetaine series, hydroxysulfobetaine series, and amide sulfobetaine series.

  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-sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphate mono- or diester type surfactants, and sulfosuccinate esters. Counter ions of the anionic residue of the surfactant 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 Alkanolamine having 1 to 3 (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).

  Two or more kinds of these surfactants may be used in combination, and the content thereof is preferably 0.01 to 10% by weight in the total composition, particularly the stability of the composition (solubilization of the solvent, emulsification of the oil agent). Etc.) is preferably 0.05 to 5% by weight.

  In the hair dye of the present invention, a cationic polymer may be further contained in any one or more of the first agent, the second agent, and the third agent. 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. That is, as the cationic polymer, an aqueous solution 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 a cationized cellulose derivative, a cationic starch, a cationization Examples include guar gum derivatives, diallyl quaternary ammonium salt polymers or copolymers, and quaternized polyvinylpyrrolidone derivatives. Among these, diallyl quaternary ammonium salt is a constituent unit particularly in terms of softness, smoothness and ease of fingering during hair dyeing, ease of grouping and moisture retention during drying, and stability of the agent. Preferred is a polymer, a quaternized polyvinylpyrrolidone derivative or a cationized cellulose derivative, more preferably a diallyl quaternary ammonium salt polymer or copolymer, more preferably a cationized cellulose derivative, or a diallyl quaternary ammonium salt polymer or copolymer. The coalescence is most preferred.

  As the skeleton of the diallyl quaternary ammonium salt polymer, one represented by the following general formula (2) or (3) is preferable.

[In the formula, R ⁴ and R ⁵ 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 ⁶ and R ⁷ 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 An ⁻ represents an anion (chloride ion, Bromide ion, iodide ion, sulfate anion, sulfonate anion, methyl sulfate anion, phosphate anion, nitrate anion, etc.). ]

  Examples of the monomer constituting the copolymer with the diallyl quaternary ammonium salt include acrylic acid, methacrylic acid or salts thereof, and acrylamide, and acrylic acid, methacrylic acid or salts thereof are particularly preferable. A copolymer of acrylic acid, methacrylic acid or a salt thereof and a diallyl quaternary ammonium salt has a high constituent ratio of diallyl quaternary ammonium salt, and becomes a cationic polymer as a whole.

  Specific examples of the polymer or copolymer of diallyl quaternary ammonium salt include dimethyldiallylammonium chloride polymer (Polyquaternium-6, such as Marquat 100; ONDEO Nalco), dimethyldiallylammonium chloride / acrylic acid copolymer (Polyquaternium) -22, such as Marquat 280, 295; ONDEO Nalco), dimethyldiallylammonium chloride / acrylamide copolymer (Polyquaternium-7, such as Marquat 550; ONDEO Nalco), etc. preferable.

  As the quaternized polyvinylpyrrolidone derivative, those represented by the following general formula (4) are preferable.

[In the formula, R ⁸ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁹ , R ¹⁰ and R ¹¹ may be the same or different; a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, hydroxy An alkyl group, an amidoalkyl group, a cyanoalkyl group, an alkoxyalkyl group or a carboalkoxyalkyl group; B represents an oxygen atom or an imino group; r represents an integer of 1 to 10; Represents a number of ˜8000, and An ⁻ has the same meaning as described above. ]

  The molecular weight of the quaternized polyvinylpyrrolidone derivative used in the present invention is preferably 10,000 to 2,000,000, particularly preferably 50,000 to 1,500,000. Examples of commercially available products include Guffcoat 734, 755, and 755N [above, IS Japan Co., Ltd.].

  As the cationized cellulose derivative, for example, those represented by the following general formula (5) are preferable.

[Wherein, G represents a residue of an anhydroglucose unit, f represents an integer of 50 to 20,000, and R ¹² represents a substituent represented by the following general formula (6). ]

[Wherein R ¹³ and R ¹⁴ represent an alkylene group having 2 or 3 carbon atoms, g represents an integer of 0 to 10, h represents an integer of 0 to 3, and i represents an integer of 0 to 10] R ¹⁵ represents an alkylene group having 1 to 3 carbon atoms or a hydroxyalkylene group, R ¹⁶ , R ¹⁷ and R ¹⁸ may be the same or different and each represents an alkyl group, aryl group or aralkyl group having up to 10 carbon atoms, Moreover, you may form the heterocyclic ring containing the nitrogen atom in a formula. An ^- has the same meaning as above. ]

  The cation substitution degree of the cationized cellulose derivative, that is, the average value of h per anhydroglucose unit is preferably 0.01 to 1, particularly 0.02 to 0.5. Moreover, the sum total of g + i is 1-3 on average. If the degree of cation substitution is less than 0.01, it is not sufficient and may exceed 1, but 1 or less is preferable from the viewpoint of reaction yield. The molecular weight of the cationized cellulose derivative used here is preferably 100,000 to 3,000,000. Commercially available products include Leo Guard G, GP [above Lion Corporation], Polymer JR-125, JR-400, JR-30M, LR-400, LR-30M (above, Union Carbide) Etc. Examples of other cationized cellulose derivatives include hydroxyethyl cellulose dimethyl diallylammonium chloride, and examples of commercially available products include Cellcoat H-100 and L-200 (National Starch and Chemical Co., Ltd.).

  These cationic polymers may be used in combination of two or more, and the higher the content, the higher the effect. However, when the content is too large, the stability is poor and the viscosity of the agent alone or at the time of mixing is reduced. From these points, 0.001 to 20% by weight in the total composition is preferable, particularly 0.01 to 10% by weight, and particularly preferably 0.05 to 5% by weight from the viewpoint of improving the touch.

  The hair dye of the present invention preferably further contains silicones in order to impart an excellent usability. Examples of silicones include polysiloxanes, modified silicones (amino-modified silicones, fluorine-modified silicones, alcohol-modified silicones, polyether-modified silicones, epoxy-modified silicones, alkyl-modified silicones, etc.), and cyclic polysiloxanes. Amino-modified silicones are preferred, and it is particularly preferred to use dimethylpolysiloxane and amino-modified silicone in combination.

  Examples of polysiloxanes include, for example, highly polymerized silicones having a number average polymerization degree of 1000 or more, further 1500 or more, particularly 2000 or more and less than 20000, SH200-1,000,000cs (Toray Dow Corning Silicone Co., Ltd.), TSF451- 100MA [GE Toshiba Silicone Co., Ltd.], BY11-026 [Toray Dow Corning Silicone Co., Ltd .; dilute solution of highly polymerized silicone with low viscosity silicone], KF9008 [Shin-Etsu Silicone Co., Ltd.] Cyclic silicone of highly polymerized silicone Dilute solution], BY22-050A (Toray Dow Corning Silicone Co., Ltd .; cationic emulsion of highly polymerized silicone), BY22-060 [Toray Dow Corning Silicone Co., Ltd .; dilute highly polymerized silicone with low viscosity silicone Cationic emulsion of the solution], BY22-020 [Toray Dow Corning Silicone Co., Ltd .; highly polymerized silicone diluted with liquid paraffin It can be used those commercially available as such a highly polymerized silicone solution of a cationic emulsion diluted in low viscosity silicone]; cationic emulsion] of the liquid, KM904 [Shin-Etsu Silicone Corporation.

  The amino-modified silicone may be any silicone having an amino group or an ammonium group, such as amino-modified silicone oil in which all or part of the terminal hydroxyl groups are blocked with methyl groups, amodimethicone in which the terminals are not blocked, etc. There is. Preferred amino-modified silicones include those represented by the following general formula (7).

[Wherein R ¹⁹ represents a hydroxyl group, a hydrogen atom or R, R represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, D represents R, a group —R ′ — (NHCH ₂ CH ₂ ) _j NH _{2 represents} a group OR or a hydroxyl group, R ′ represents a divalent hydrocarbon group having 1 to 8 carbon atoms, j represents a number of 0 to 3, and p and q are the number average of the sum. 10 to less than 20000, preferably 10 to less than 3000, more preferably 30 to less than 1000, and still more preferably 40 to less than 800. The amino equivalent is 200 g / mol to 100,000 g / mol, preferably 200 g / mol to 30,000 g / mol, more preferably 400 g / mol to 10,000 g / mol, and still more preferably 600 g / mol to 5000 g / mol. . ]

Specific examples of suitable commercially available amino-modified silicones include SF8451C (Toray Dow Corning Silicone Co., Ltd., viscosity 600 mm ² / s, amino equivalent 1700 g / mol), SF8452C (Toray Dow Corning Silicone Co., Ltd.) , Viscosity 700mm ² / s, amino equivalent 6400g / mol], SF8457C [Toray Dow Corning Silicone Co., Ltd., viscosity 1200mm ² / s, amino equivalent 1800g / mol], KF8003 [GE Toshiba Silicone Co., Ltd. viscosity 1850mm ² / s, amino equivalent 2000 g / mol], KF867 [GE Toshiba Silicone Co., Ltd., viscosity 1300 mm ² / s, amino equivalent 1700 g / mol] and other amino-modified silicone oils, SM8704C [Toray Dow Corning Silicone Co., Ltd. ), Amino equivalent 1800 g / mol] and the like. The amino-modified silicone oil may be blended in the form of an emulsion. Emulsions of amino-modified silicones can be obtained by mechanical emulsification (high shear mechanical mixing of amino-modified silicone and water), chemical emulsification (emulsification of amino-modified silicone with water and emulsifier), or a combination thereof, or by emulsion polymerization. Can be prepared.

The total content of the silicones is preferably from 0.02 to 40% by weight, more preferably from 0.1 to 20% by weight, particularly preferably from 0.2 to 15% by weight, based on the total composition, from the viewpoint of sufficient effects and suppression of stickiness. The content ratio of each silicone is preferably such that the converted amino equivalent represented by the following formula is from 500 to 100,000 g / mol, more preferably from 1,000 to 80,000 g / mol, particularly from 2,000 to 50,000 g. A range of / mol is preferred.
Equivalent amino equivalent (g / mol) = [total weight of all silicones in 1 g of total composition (g / g)] / [total number of amino groups, imino groups and ammonium groups of amino-modified silicone in 1 g of total composition (Mol / g)].

  Here, “total weight of all silicones in 1 g of total composition (g / g)” and “moles of amino groups, imino groups and ammonium groups of amino-modified silicone in 1 g of total composition (mol / g)” Is obtained as follows.

  First, silicones are fractionated from each of the first agent and the second agent (in the case of a three-agent type, the third agent), and the total weight (g) of all silicones in each agent and amino-modified silicone The total number of moles (mol) of the amino group, imino group and ammonium group is determined. Next, considering the mixing ratio of each agent in the total composition, the total weight (g / g) of all silicones in 1 g of the total composition, and the amino group, imino group and ammonium group of the amino-modified silicone in 1 g of the total composition Calculate the total number of moles (mol / g). Finally, the converted amino equivalent (g / mol) is calculated using the converted amino equivalent calculation formula.

  In the case of containing silicones, the weight ratio of cationic polymer (active amount): silicones is preferably 50: 1 to 1:50, more preferably 50: 1 to 1:10.

  The composition of the present invention preferably contains a higher alcohol in any one or more of the first agent, the second agent, and the third agent from the viewpoint of improvement in feel and stability. These have the effect of forming a structure with a surfactant to prevent separation and improving the feel during rinsing.

  As the higher alcohol, those having 8 to 22 carbon atoms, particularly 16 to 22 carbon atoms are preferable, and specific examples thereof include cetyl alcohol, stearyl alcohol, behenyl alcohol, and the like, and mixtures thereof.

  Two or more higher alcohols may be used in combination, and the content thereof is preferably 0.01 to 20% by weight, particularly 0.1 to 10% by weight, based on the total composition.

  In the composition of the present invention, water and, if necessary, an organic solvent are used as a medium. Examples of organic solvents include lower alcohols such as ethanol and 2-propanol, aromatic alcohols such as benzyl alcohol and benzyloxyethanol, polyols such as propylene glycol, 1,3-butanediol, diethylene glycol, and glycerin, ethyl cellosolve, Examples thereof include cellosolves such as butyl cellosolve, and carbitols such as ethyl carbitol and butyl carbitol.

  In addition to the above components, other components that are usually used as cosmetic raw materials can be added to the composition of the present invention. Such optional components include hydrocarbons, animal and vegetable fats and oils, higher fatty acids, natural or synthetic polymers, ethers, protein derivatives, hydrolyzed proteins, amino acids, preservatives, chelating agents, stabilizers, oxidation Examples include inhibitors, botanical extracts, herbal extracts, vitamins, fragrances, and UV absorbers.

When the hair dye of the present invention is used in a two-part type or a three-part type, the first and second agent dosage forms are, for example, liquid, emulsion, cream, gel, paste, mousse, etc. Or an aerosol form. It is desirable to mix the first agent and the second agent (or the third agent in the case of the three-agent type), and to make the viscosity difficult to spill when applied to the hair, 25 ° C, type B with helical stand The viscosity measured by a rotational viscometer (B8R type viscometer, TOKIMEC) is preferably 2,000 to 100,000 mm ² / s. Here, the viscosity is a value after rotating at 10 rpm for 1 minute using a rotor TC.

  For the hair dyeing treatment using the composition of the present invention, for example, the first agent and the second agent of the composition of the present invention (or the third agent in the case of the three-component type) are mixed immediately before use, and then the hair. Apply to the above, and after washing for a predetermined time, wash away and dry. The application temperature to the hair is preferably 15 to 45 ° C. The standing time is preferably within 1 hour, preferably 3 to 45 minutes, more preferably 5 to 30 minutes, and particularly preferably 10 to 30 minutes. In this case, first, the hair dye is lightly washed with water, then washed with a shampoo containing an anionic surfactant, and then washed with water, the cationic polymer flows out moderately, and the silicones remain in the hair moderately. And a good conditioning effect. As the shampoo, a general aqueous shampoo containing about 5 to 20% by weight of an anionic surfactant such as sodium laureth-1 sulfate, sodium laureth-2 sulfate or sodium laureth-3 sulfate is suitable.

  A first agent shown in Tables 1 and 2, a second agent shown in Table 3, and a third agent shown in Table 4 were prepared.

<Smoothness during rinsing>
The first agent shown in Table 1 and the second agent shown in Table 3 are mixed at a weight ratio of 1: 2 into an unchemically treated hair bundle having a length of 20 cm, a width of 1.5 cm, and a weight of 1.0 g. Apply at a bath ratio (agent: hair) = 1: 1. After standing at 25 ° C for 30 minutes, rinse with about 40 ° C water, wash with a commercial shampoo, rinse with water, apply a commercial rinse, rinse with water, wipe with a towel and dry. Thereafter, hair washing and drying were repeated 90 times. This was repeated 8 times, and then shampooed again for about 15 seconds. Subsequently, the hair was rinsed with 40 ° C. hot water and the slip feeling was sensory evaluated. The evaluation was performed by five people, and the total value of the evaluation was shown.

・ Evaluation criteria 4: Slip well 3: Slightly slip 2: Not slippery 1: Not slippery

<Effects to restore the swell generated on the hair tip to the original state>
The first agent and the table shown in Table 1 are applied to a hair bundle of length 20 cm, width 1.5 cm, and weight 1.0 g, which was created using damaged hair that had been bleached 8 times and washed and dried 720 times in advance. The second agent shown in 3 is mixed at a weight ratio of 1: 2 and applied at a bath ratio (agent: hair) = 1: 1. After standing at 25 ° C for 30 minutes, rinse with about 40 ° C water, wash with a commercial shampoo, wash with water, apply a commercial rinse, rinse with water, wipe with a towel and dry. Thereafter, the degree of undulation of the hair tips was evaluated visually. Evaluation was performed by five panelists, and the total value of the evaluation is shown in Table 5.

・ Evaluation criteria 4: Swelling is removed 3: Slightly swelling is taken 2: Not much swelling is taken 1: Swelling is not taken

<Effect of suppressing the occurrence of swell due to accumulation of hair damage>
The first agent shown in Table 1 and the second agent shown in Table 3 are mixed at a weight ratio of 1: 2 into an unchemically treated hair bundle having a length of 20 cm, a width of 1.5 cm, and a weight of 1.0 g. Apply at a bath ratio (agent: hair) = 1: 1. After standing at 25 ° C for 30 minutes, rinse with about 40 ° C water, wash with a commercial shampoo, rinse with water, apply a commercial rinse, rinse with water, wipe with a towel and dry. Thereafter, hair washing and drying were repeated 90 times. This was repeated 8 times. The occurrence of undulation of the hair tips was evaluated visually. The evaluation was performed by five panelists, and the total value of the evaluation is shown in Table 5.

・ Evaluation criteria 4: No undulation 3: Less undulation 2: Some undulation 1: An undulation has occurred

<Dyeability evaluation>
The first agent shown in Table 1 (Example 1, Comparative Example 1) and the second agent shown in Table 3 were mixed at a weight ratio of 1: 2, respectively, and the bath ratio (agent: hair) = 1: 1. Apply to the hair bundle. After standing at 25 ° C for 30 minutes, rinse with about 40 ° C water, wash with a commercial shampoo, rinse with water, apply a commercial rinse, rinse with water, wipe with a towel and dry.

Dye hair made with goat hair, hair that has not yet undergone chemical treatment such as dyeing (untreated hair), and hair that has been damaged by repeated chemical treatment (damaged hair) according to the hair dyeing process described above, The color of these hair bundles was measured with a CIE color system (L ^* , a ^* , b ^* ) using a color difference meter (Konica Minolta Sensing Co., Ltd., color difference meter CR-400), according to the following formula: ΔE ^* was calculated. The larger ΔE ^{*, the} better the dyeability. The results are shown in Table 6.

[L ^* ₁ , a ^* ₁ , and b ^* ₁ are measured values before staining, and L ^* ₂ , a ^* ₂ , and b ^* ₂ are measured values after staining. ]

  In all cases of goat wool, untreated hair and damaged hair, the hair dye containing the component (A) was able to obtain the same or better dyeability as the hair dye not containing the component (A). . That is, the hair dye composition of the present invention can suppress the occurrence of waviness and remove the generated waviness without reducing the dyeability. Moreover, it turns out that it can dye | stain uniformly from a root to a hair tip from the dyeing | staining property of the damage hair which is a representative of a hair tip, and the unprocessed hair which is the representative of a root.

<Usage as a three-part type>
After mixing 1 part by weight of the first agent shown in Tables 1 and 2 with 1 part by weight of the second agent shown in Table 3 and 0.3 to 1 part by weight of the third agent shown in Table 5, Applied to wool, the hair was usually washed with shampoo and allowed to dry for 30 minutes working time.
As a result of observing the color tone of the obtained dyed hair, both dyeability and shampoo fastness were good.

Claims (4)

A hair dye composition containing the following components (A), (B) and (C) and having a pH of 8-12.
(A) Quaternary ammonium salt represented by general formula (1)

[Wherein, R ¹ represents a saturated or unsaturated hydrocarbon group having 6 to 12 carbon atoms, R ² and R ³ represent the same or different alkyl group having 1 to 3 carbon atoms, and n represents 0 Represents an integer of ˜2, m represents 1 or 2, and X ⁻ represents a halide ion, an alkyl sulfate ion, an alkyl or aryl sulfonate ion. ]
(B) Oxidizing agent
(C) Toluene-2,5-diamine, paraaminophenol or acid addition salts thereof   Ingredient (A) is 0.1 to 10% by weight in the total composition, Ingredient (B) is 0.1 to 12% by weight in the total composition with hydrogen peroxide equivalent, and Component (C) is 0.01 to 5% by weight in the total composition The hair dye composition according to claim 1, which is contained.   The hair dye composition according to claim 1 or 2, comprising a first agent containing an alkaline agent and a second agent containing a component (B).   A method for dyeing hair, wherein the first agent and the second agent of the hair dye composition according to claim 3 are mixed immediately before use, applied to the hair, allowed to stand for a predetermined time and then washed away.