Novel blue dye, novel red dye, and dyeing composition

Abstract

The present invention addresses the problem of providing: a novel blue dye and a novel red dye; and a dyeing composition that contains the blue dye and / or the red dye and has excellent color-fastness. This blue dye is produced by reacting a mixture that contains an aglycone of an iridoid glycoside and a nitrogenated compound having two or more nitrogenated groups and having no carboxy group, wherein at least one of the nitrogenated groups is a primary amino group or a primary ammonium group. This red dye is produced by reacting a mixture that contains an aglycone of an ester hydrolysate of an iridoid glycoside and a nitrogenated compound having two or more nigrogenated groups and having no carboxy group, wherein at least one of the nitrogenated groups is a primary amino group or a primary ammonium group.

Description

Novel blue and red dyes and dyeing compositions

[0001] The present invention relates to novel blue and red pigments, and dyeing compositions containing the blue and / or red pigments.

[0002] Hair coloring products using synthetic dyes are the mainstream for dyeing hair. However, due to concerns about damage to hair and allergic reactions, hair coloring compositions using highly safe natural pigments have been attracting attention in recent years.

[0003] Gardenia pigment is a natural pigment obtained from the fruit of the Rubiaceae plant (Gardenia augusta Merrill or Gardenia jasminoides Ellis). Depending on the production method, it comes in three colors: blue, red, and yellow. Gardenia blue pigment is obtained by adding β-glucosidase to a mixture of iridoid glycosides and proteolysates obtained from gardenia fruit. Gardenia red pigment is obtained by adding β-glucosidase to a mixture of ester hydrolysates of iridoid glycosides and proteolysates obtained from gardenia fruit (Food Additives Official Standards, 9th Edition, 2018, Ministry of Health, Labor, and Welfare, Consumer Affairs Agency). These pigments are widely used as food coloring agents. These gardenia pigments are also sometimes used as hair dyes.

[0004] For example, Patent Document 1 reports that a hair dye containing a gardenia blue pigment, a reducing agent having a thiol group, and an alkaline agent can dye hair deeply. Patent Document 2 reports that a hair dye composition containing a gardenia blue pigment solution containing genipin and a cationic polymer has high dyeing properties, dyeing hair in chestnut to dark brown. Patent Document 3 reports that a hair dye composition containing a gardenia blue pigment solution containing genipin, a nitro-based direct dye, and a cationic surfactant has high dyeing properties, dyeing hair in chestnut to dark brown.

[0005] Furthermore, Patent Document 4 proposes a hair coloring composition containing (i) a gardenia blue pigment that, when passed through a sodium ion-type methacrylic acid-based weakly acidic cation exchange resin, results in a recovery rate of 85% or less of the pigment components that are not adsorbed by the resin and flow out, or (ii) a gardenia red pigment that, when passed through a sodium ion-type methacrylic acid-based weakly acidic cation exchange resin, results in a recovery rate of 60% or less of the pigment components that are not adsorbed by the resin and flow out. Patent Document 4 also describes that by using the gardenia blue pigment (i) or the gardenia red pigment (ii) directly as a dye, fixation to hair is improved and an excellent hair dyeing effect can be obtained without using a dyeing adjuvant; that the gardenia blue pigment (i) is obtained by mixing arginine with an iridoid glycoside obtained from the fruit of gardenia jasmine (Rubiaceae) and subjecting the mixture to a predetermined enzymatic reaction; and that the gardenia red pigment (ii) is obtained by mixing arginine with an ester hydrolysate of an iridoid glycoside obtained from the fruit of gardenia jasmine (Rubiaceae) and subjecting the mixture to a predetermined enzymatic reaction.

[0006] JP 2013-133320 A JP 2000-53544 A JP 2000-95654 A International Publication No. 2018 / 181008

[0007] However, gardenia pigments have the drawback that they are difficult to fix to hair, and even when used in hair coloring products, they do not provide sufficient hair dyeing properties. Furthermore, conventional hair coloring products using gardenia pigments have the drawback that dyeing auxiliaries (reducing agents, alkali agents, penetration enhancers, etc.) are necessary to enhance the hair dyeing properties of the gardenia pigments and achieve excellent hair dyeing effects, and that there are compositional limitations, such as the inclusion of cationic substances. Furthermore, the hair coloring composition proposed in Patent Document 4 is prone to fading when the dyed hair is washed with shampoo after dyeing, and there is room for improvement in color fading resistance.

[0008] An object of the present invention is to provide a novel blue pigment and a novel red pigment, and a dyeing composition containing the blue pigment and / or the red pigment and having excellent color fading resistance.

[0009] The present inventors have conducted extensive research to solve the above problems and have found that a dyeing composition excellent in color fading resistance can be obtained by using, as a dye for a dyeing composition, a blue pigment obtained by reacting a mixture containing an aglycone of an iridoid glycoside with a nitrogen-containing compound having a specific chemical structure, or a red pigment obtained by reacting an aglycone of an ester hydrolysate of an iridoid glycoside with a mixture containing a nitrogen-containing compound having a specific chemical structure. The present invention was completed through further research based on this finding.

[0010] That is, the present invention provides the following aspects of the invention: Item 1. A blue pigment obtainable by reacting a mixture containing an aglycone of an iridoid glycoside with a nitrogen-containing compound having two or more nitrogen-containing groups, at least one of which is a primary amino group or a primary ammonium group, and having no carboxy group. Item 2. The blue pigment according to Item 1, wherein the nitrogen-containing compound has a primary amino group or a primary ammonium group and a guanidino group or a nitrogen-containing heterocycle. Item 3. The blue pigment according to Item 1, wherein the nitrogen-containing compound is at least one selected from the group consisting of agmatine, aminoguanidine, histamine, arginine alkyl ester, and salts thereof. Item 4. A red pigment obtainable by reacting a mixture containing an aglycone of an ester hydrolysate of an iridoid glycoside with a nitrogen-containing compound having two or more nitrogen-containing groups, at least one of which is a primary amino group or a primary ammonium group, and having no carboxy group. Item 5. Item 4. The red pigment according to Item 4, wherein the nitrogen-containing compound has a primary amino group or a primary ammonium group and a guanidino group or a nitrogen-containing heterocycle. Item 6. The red pigment according to Item 4, wherein the nitrogen-containing compound is at least one selected from the group consisting of agmatine, aminoguanidine, histamine, arginine alkyl esters, and salts thereof. Item 7. A dyeing composition comprising the blue pigment according to any one of Items 1 to 3 and / or the red pigment according to any one of Items 4 to 6. Item 8. The dyeing composition according to Item 7, which is a hair coloring composition. Item 9. The dyeing composition according to Item 8, which is used for dyeing gray hair. Item 10. The dyeing composition according to Item 7, which is a fiber dyeing composition. Item 11. A dyeing method, comprising dyeing hair or fibers with the dyeing composition according to Item 8 or 10. Item 12. Use of the blue pigment according to any one of Items 1 to 3 and / or the red pigment according to any one of Items 4 to 6, for producing a hair coloring composition or a fiber dyeing composition.

[0011] When used as a dye, the blue or red dye of the present invention has good dyeability and excellent colorfastness in washing treatment of dyed hair or dyed fibers using detergents such as shampoo and soap.

[0012] Furthermore, when the dye composition of the present invention is used as a hair coloring composition, the inclusion of the blue pigment and / or red pigment of the present invention significantly improves color fading resistance during washing treatment of dyed hair with shampoo, and therefore the color tone of dyed hair can be maintained for a longer period of time than hair coloring products using conventional gardenia blue or red pigments, thereby reducing the frequency of hair coloring.

[0013] Furthermore, when the dyeing composition of the present invention is used as a hair coloring composition, it can exhibit good hair dyeing properties by containing the blue pigment and / or red pigment of the present invention, so that the amount of dyeing auxiliary agents conventionally used can be reduced or they can be omitted, thereby suppressing damage to the hair and scalp and suppressing staining of the skin, etc. during hair dyeing.

[0014] Furthermore, when the dyeing composition of the present invention is used as a hair coloring composition, the blue pigment and / or red pigment of the present invention, which has good hair dyeing properties in itself, is used as a direct dye, so there is an advantage that there are fewer restrictions on the composition, making it possible to provide hair coloring products with a variety of compositions and forms.

[0015] 1 is a diagram showing the degree of color fading after shampoo washing of a blue-dyed goat hair bundle dyed using the blue dye solution containing a blue pigment produced in Example 1 (from left: undyed goat hair bundle, before shampoo washing, after one shampoo washing, and after seven shampoo washings; the same applies to Figures 2 to 10 below). FIG. 1 is a diagram showing the degree of color fading after shampoo washing of a blue-dyed goat hair bundle dyed using the blue dye solution containing a blue pigment produced in Example 2. FIG. 2 is a diagram showing the degree of color fading after shampoo washing of a blue-dyed goat hair bundle dyed using the blue dye solution containing a blue pigment produced in Example 3. FIG. 3 is a diagram showing the degree of color fading after shampoo washing of a blue-dyed goat hair bundle dyed using the blue dye solution containing a blue pigment produced in Example 4. FIG. 4 is a diagram showing the degree of color fading after shampoo washing of a blue-dyed goat hair bundle dyed using the blue dye solution containing a blue pigment produced in Example 5. FIG. 5 is a diagram showing the degree of color fading after shampoo washing of a blue-dyed goat hair bundle dyed using the blue dye solution containing a blue pigment produced in Example 6.

[0033] Figure 1 is a graph showing the degree of color fading after shampooing of a blue-dyed goat hair bundle dyed with the blue dye solution containing a blue pigment produced in Example 7.

[0034] Figure 2 is a graph showing the degree of color fading after shampooing of a blue-dyed goat hair bundle dyed with the blue dye solution containing a blue pigment produced in Example 8.

[0035] Figure 3 is a graph showing the degree of color fading after shampooing of a blue-dyed goat hair bundle dyed with the blue dye solution containing a blue pigment produced in Example 9.

[0036] Figure 4 is a graph showing the degree of color fading after shampooing of a blue-dyed goat hair bundle dyed with the blue dye solution containing a blue pigment produced in Comparative Example 1.

[0037] Figure 5 is a graph showing the ΔL value and ΔE value of a blue-dyed goat hair bundle dyed with the blue dye solution containing a blue pigment produced in Example 1 before shampooing (0 times), after 1 shampooing, and after 7 shampooings.

[0038] Figure 6 is a graph showing the ΔL value and ΔE value of a blue-dyed goat hair bundle dyed with the blue dye solution containing a blue pigment produced in Example 2 before shampooing (0 times), after 1 shampooing, and after 7 shampooings. 1 is a graph showing the ΔL value and ΔE value of a blue-dyed goat hair bundle dyed with the blue dye solution containing the blue pigment produced in Example 3 before shampoo washing (0 times), after 1 shampoo washing treatment, and after 7 shampoo washing treatments.1 is a graph showing the ΔL value and ΔE value of a blue-dyed goat hair bundle dyed with the blue dye solution containing the blue pigment produced in Example 4 before shampooing (0 times), after one shampooing, and after seven shampooings. 2 is a graph showing the ΔL value and ΔE value of a blue-dyed goat hair bundle dyed with the blue dye solution containing the blue pigment produced in Example 5 before shampooing (0 times), after one shampooing, and after seven shampooings. 3 is a graph showing the ΔL value and ΔE value of a blue-dyed goat hair bundle dyed with the blue dye solution containing the gardenia blue pigment produced in Comparative Example 1 before shampooing (0 times), after one shampooing, and after seven shampooings. 1 is a diagram showing the degree of color fading after shampooing of a red-dyed goat hair bundle dyed using a red dye solution containing a red pigment produced in Example 10 (from left: undyed goat hair bundle, before shampooing, after one shampooing, and after seven shampooings; the same applies to Figures 18 to 20 below). FIG. 1 is a diagram showing the degree of color fading after shampooing of a red-dyed goat hair bundle dyed using a red dye solution containing a red pigment produced in Example 11. FIG. 2 is a diagram showing the degree of color fading after shampooing of a red-dyed goat hair bundle dyed using a red dye solution containing a red pigment produced in Example 12. FIG. 3 is a diagram showing the degree of color fading after shampooing of a red-dyed goat hair bundle dyed using a red dye solution containing a red pigment produced in Comparative Example 2. FIG. 4 is a graph showing the ΔL value and ΔE value of a red-dyed goat hair bundle dyed using a red dye solution containing a red pigment produced in Example 10 before shampooing (0 times), after one shampooing, and after seven shampooings. 1 is a graph showing the ΔL value and ΔE value of a red-dyed goat hair bundle dyed with a red dye solution containing the gardenia red pigment produced in Comparative Example 2 before shampoo washing (0 times), after one shampoo washing, and after seven shampoo washings. 2 is a graph showing the degree of dyeing and color fading when the dyeing operation and shampoo washing operation are repeated three times each using the color treatment prepared with the gardenia blue pigment obtained in Comparative Example 1. 3 is a graph showing the degree of dyeing and color fading when the dyeing operation and shampoo washing operation are repeated three times each using the color treatment prepared with the blue pigment obtained in Example 1.2 is a graph showing the ΔE value when a dyeing operation and a shampoo-washing operation are repeated three times each using a color treatment prepared using the gardenia blue pigment obtained in Comparative Example 1. FIG. 3 is a graph showing the ΔE value when a dyeing operation and a shampoo-washing operation are repeated three times each using a color treatment prepared using the blue pigment obtained in Example 1. FIG. 4 is a diagram showing the degree of color fading after hand-washing of polyester fabric dyed with a blue dyeing solution containing the blue pigment prepared in Example 1 (from left: undyed polyester fabric, dyed polyester fabric, polyester fabric after hand-washing; the same applies to Figures 28 to 34 below). FIG. 5 is a diagram showing the degree of color fading after hand-washing of nylon fabric dyed with a blue dyeing solution containing the blue pigment prepared in Example 1. FIG. 6 is a diagram showing the degree of color fading after hand-washing of silk fabric dyed with a blue dyeing solution containing the blue pigment prepared in Example 1. FIG. 7 is a diagram showing the degree of color fading after hand-washing of cotton fabric dyed with a blue dyeing solution containing the blue pigment prepared in Example 1. 1 is a graph showing the degree of color fading after hand washing of a polyester fabric dyed using a red dye solution containing a red pigment produced in Example 12. FIG. 1 is a graph showing the degree of color fading after hand washing of a nylon fabric dyed using a red dye solution containing a red pigment produced in Example 10. FIG. 1 is a graph showing the degree of color fading after hand washing of a silk fabric dyed using a red dye solution containing a red pigment produced in Example 10. FIG. 1 is a graph showing the degree of color fading after hand washing of a cotton fabric dyed using a red dye solution containing a red pigment produced in Example 10. FIG. 1 is a graph showing the degree of color fading after shampoo washing of a blue-dyed human hair bundle dyed using a blue dye solution containing a blue pigment produced in Example 1 (from left: undyed human hair bundle, before shampoo washing, after one shampoo washing, and after seven shampoo washings; the same applies to Figures 36 to 41 below). FIG. 2 is a graph showing the degree of color fading after shampoo washing of a blue-dyed human hair bundle dyed using a blue dye solution containing a blue pigment produced in Example 13. 12A and 12B are graphs showing the degree of color fading after shampooing treatment of a blue-dyed human hair bundle dyed with the blue dye solution containing the blue pigment produced in Example 14. FIG. 12B are graphs showing the degree of color fading after shampooing treatment of a blue-dyed human hair bundle dyed with the blue dye solution containing the blue pigment produced in Example 15.1 is a diagram showing the degree of color fading after shampooing of a blue-dyed human hair bundle dyed with a blue dyeing solution containing a gardenia blue pigment prepared in Comparative Example 1. 2 is a diagram showing the degree of color fading after shampooing of a red-dyed human hair bundle dyed with a red dyeing solution containing a red pigment prepared in Example 10. 3 is a diagram showing the degree of color fading after shampooing of a red-dyed human hair bundle dyed with a red dyeing solution containing a gardenia red pigment prepared in Comparative Example 2.

[0016] 1. Blue Pigment The novel blue pigment of the present invention is obtainable by reacting a mixture containing an aglycone of an iridoid glycoside with a nitrogen-containing compound having two or more nitrogen-containing groups, at least one of which is a primary amino group or a primary ammonium group, and which does not have a carboxy group. In particular, the novel blue pigment is characterized by being obtainable by using the nitrogen-containing compound in place of a protein hydrolysate or amino acid used in the conventional production of gardenia blue pigments. When used as a direct dye in a hair coloring composition or a fiber dyeing composition, the novel blue pigment of the present invention can impart good dyeability and excellent colorfastness to the hair coloring composition or fiber dyeing composition. The novel blue pigment of the present invention is described in detail below.

[0017] 1-1. Method for Producing Blue Pigment The method for producing the blue pigment of the present invention is not particularly limited as long as it involves reacting a mixture containing an aglycone of an iridoid glycoside with a nitrogen-containing compound having two or more nitrogen-containing groups, at least one of which is a primary amino group or a primary ammonium group, and which does not have a carboxy group, and any known method can be used. Examples include (1) a method of obtaining an aglycone of an iridoid glycoside and then reacting the aglycone with a mixture containing the nitrogen-containing compound (hereinafter also referred to as "Production Method A"), and (2) a method of treating a mixture containing an iridoid glycoside and the nitrogen-containing compound with β-glucosidase (hereinafter also referred to as "Production Method B"). Methods A and B for producing the blue pigment of the present invention are described in detail below.

[0018] 1-1-1. Method A for Producing Blue Pigment Method A for producing a blue pigment of the present invention is a method in which an aglycone of an iridoid glycoside is obtained, and then a mixture containing the aglycone and the nitrogen-containing compound is reacted.

[0019] <Aglycone of Iridoid Glycoside> The iridoid glycoside is not particularly limited, and examples thereof include those that can be used as raw materials for producing ordinary gardenia blue pigments, and those obtained from Genipa Americana (also known as wito or jagua).

[0020] The method for obtaining iridoid glycosides is not particularly limited, and examples thereof include a method in which plants containing iridoid glycosides, such as the fruit of Gardenia jasmine (Rubiaceae) and the fruit of Jagua, are subjected to an extraction treatment to obtain iridoid glycosides. As a representative example, a method for obtaining iridoid glycosides from the fruit of Gardenia jasmine (Rubiaceae) by extraction treatment will be described below.

[0021] The fruits of Gardenia jasmine (Rubiaceae) used as the extraction raw material may be dried, chopped, crushed, etc., as necessary.

[0022] The extraction solvent used in the extraction treatment is not particularly limited as long as it can dissolve the iridoid glycoside, and examples thereof include water, alcohol (preferably ethanol), and a mixture thereof.

[0023] The temperature and time during extraction may be appropriately set depending on the type of extraction solvent used, and examples include temperatures of about 20 to 100° C. for 0.5 to 24 hours.

[0024] After the extraction treatment, the solids are removed to obtain an extract containing iridoid glycosides. The extract may be used as the iridoid glycoside as is, or may be concentrated or dried before use. Since the extract also contains yellow pigments in addition to the iridoid glycosides, the yellow pigments may be removed from the extract as needed. Removal of the yellow pigments can be carried out by a known method using an adsorption resin. The iridoid glycoside may be a single component or may contain two or more components. However, it is preferable to use geniposide in order to further improve colorfastness.

[0025] The method for obtaining the aglycone of the iridoid glycoside is not particularly limited, and for example, it can be obtained by enzymatically treating the iridoid glycoside with β-glucosidase.

[0026] The β-glucosidase is not particularly limited, and can be one typically used in the production of gardenia blue pigment, such as those derived from Aspergillus niger, Trichoderma reesei, Trichoderma viride, almonds, etc. Commercially available β-glucosidases include Sumiteam C6000, Sumiteam AC, Sumiteam C, Sumiteam X, Sumiteam BGT, and Sumiteam BGA (trade names; manufactured by Shin Nippon Chemical Industry Co., Ltd.), Cellulosin AC40, Cellulosin T3, and Cellulosin AL (trade names; manufactured by HIBI Corporation), Onozuka 3S and Y-NC (trade names; manufactured by Yakult Pharmaceutical Co., Ltd.), Cellulase A "Amano" 3, and Cellulase T "Amano" 4 (trade names; manufactured by Amano Enzyme Inc.).

[0027] The enzymatic treatment with β-glucosidase is not particularly limited as long as it is carried out under conditions that allow the production of an aglycone of an iridoid glycoside. For example, β-glucosidase may be coexisted in an aqueous solution containing an iridoid glycoside at a concentration of about 1 to 500 U per 1 g of the iridoid glycoside.

[0028] The temperature conditions for the action of β-glucosidase may be appropriately set within the temperature range in which β-glucosidase acts, for example, about 20 to 70°C, preferably about 40 to 60°C.

[0029] The pH conditions for the action of β-glucosidase may be appropriately set within the pH range in which β-glucosidase acts, for example, about pH 4 to 5, preferably about pH 4.2 to 4.8.

[0030] Thus, the aglycone of the iridoid glycoside can be obtained by treating the iridoid glycoside with β-glucosidase. If necessary, the obtained solution may be further purified by a conventional method such as resin treatment or membrane treatment.

[0031] <Nitrogen-Containing Compound> The nitrogen-containing compound used to obtain the blue pigment of the present invention has two or more nitrogen-containing groups, at least one of which is a primary amino group or a primary ammonium group, and is characterized by the absence of a carboxy group. Conventional gardenia blue pigments are produced using protein hydrolysates or amino acids. However, in the present invention, the nitrogen-containing compound is used instead of these to obtain a novel blue pigment that differs from conventional gardenia blue pigments. Furthermore, when used as a dye, the blue pigment of the present invention exhibits superior colorfastness in washing dyed hair or dyed fabrics with detergents such as shampoos and soaps, compared to conventional gardenia blue pigments.

[0032] The nitrogen-containing group is a group that contains one or more nitrogen atoms and does not have a carbonyl group, and examples thereof include a primary amino group, an acyclic secondary or tertiary amino group containing one nitrogen atom, a guanidino group, a hydrazino group, a hydrazono group, an amidino group, an azo group, a diazo group, and a nitro group; an aliphatic heterocycle containing one nitrogen atom such as a pyrrolidine ring, a pyrroline ring, and a piperidine ring (for example, a 5-membered ring, a 6-membered ring, etc.); an aliphatic heterocycle containing two nitrogen atoms such as an imidazolidine ring, an imidazoline ring, and a piperazine ring (for example, a 5-membered ring, a 6-membered ring, etc.); and an aliphatic heterocycle containing three nitrogen atoms such as a hexahydrotriazine ring (for example, a 5-membered ring, a 6-membered ring, etc.). Examples of the nitrogen-containing heterocyclic group include aromatic heterocycles containing one nitrogen atom (e.g., 5-membered ring, 6-membered ring, etc.), pyrrole ring, and pyridine ring, aromatic heterocycles containing two nitrogen atoms (e.g., 5-membered ring, 6-membered ring, etc.), imidazole ring, pyrazole ring, pyridazine ring, pyrimidine ring, and pyrazine ring, aromatic heterocycles containing two nitrogen atoms (e.g., 5-membered ring, 6-membered ring, etc.), triazole ring, and triazine ring, aromatic heterocycles containing three nitrogen atoms (e.g., 5-membered ring, 6-membered ring, etc.), and fused heterocycles containing one to four nitrogen atoms, such as indole, isoindole, benzimidazole, benzotriazole, purine, quinoline, and isoquinoline. The nitrogen-containing group may be in the form of an ammonium group (ammonium ion) (e.g., a primary amino group may be in the form of a primary ammonium group). The nitrogen-containing group may be located at the terminal of the molecular main chain, at a location other than the terminal of the molecular main chain, or may constitute part of the molecular main chain. Examples of the secondary or tertiary amino group include a linear or branched aliphatic saturated hydrocarbon group having 1 to 24 carbon atoms, a linear or branched aliphatic unsaturated hydrocarbon group having 2 to 12 carbon atoms, an alicyclic saturated hydrocarbon group having 5 to 12 ring carbon atoms, an alicyclic unsaturated hydrocarbon group having 5 to 12 ring carbon atoms, an aromatic hydrocarbon group (e.g., a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group, etc.), or a group in which two or more of these groups are bonded to a nitrogen atom. In addition, the hydrogen atom in the nitrogen-containing group may be substituted with a substituent such as an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxy group, an alkoxy group, or a halogen group.The nitrogen-containing compound may have one type of nitrogen-containing group, or two or more types. The nitrogen-containing compound has two or more nitrogen-containing groups (at least one of which is a primary amino group or a primary ammonium group), preferably four or less, more preferably three or less, and even more preferably two. An example of a nitrogen-containing compound having four nitrogen-containing groups is spermine. An example of a nitrogen-containing compound having three nitrogen-containing groups is spermidine. Of the nitrogen-containing groups, the nitrogen-containing groups other than primary amino groups and primary ammonium groups are preferably guanidino groups and nitrogen-containing heterocycles (more preferably aromatic heterocycles (five- or six-membered rings) containing two nitrogen atoms, and even more preferably imidazole rings) from the viewpoint of obtaining a blue pigment having even better colorfastness and excellent dyeability.

[0033] In a nitrogen-containing compound, two or more nitrogen-containing groups may be bonded directly or via a linking group (a group that links nitrogen-containing groups together). The linking group is not particularly limited, and examples thereof include linear or branched aliphatic saturated hydrocarbon groups having 1 to 20 carbon atoms, linear or branched aliphatic unsaturated hydrocarbon groups having 2 to 12 carbon atoms, alicyclic saturated hydrocarbon groups having 5 to 12 ring carbon atoms, alicyclic unsaturated hydrocarbon groups having 5 to 12 ring carbon atoms, aromatic hydrocarbon groups (e.g., phenyl, tolyl, xylyl, naphthyl, and biphenyl groups), and groups in which two or more of these groups are bonded. Furthermore, the nitrogen-containing compound may have a substituent or functional group other than the nitrogen-containing group in the molecule. Examples of such a substituent or functional group include a hydroxy group, an alkoxy group, a halogen group, a ketone group, an ester bond, an amide bond, an imide bond, an ether bond, a thioether bond, a urethane bond, and a urea bond. Furthermore, the nitrogen-containing compound may be in the form of a salt such as a sulfate or a hydrochloride.

[0034] From the viewpoint of obtaining a blue pigment having even more excellent colorfastness and excellent dyeability, the nitrogen-containing compound is preferably at least one selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), a compound represented by the following general formula (4), 4-(aminoalkyl)pyridine, 4-(aminoalkyl)piperidine, 4-(aminoalkyl)aniline, alkylenediamine, N-alkylalkylenediamine, N,N-dialkylalkylenediamine, N-(hydroxyalkyl)alkylenediamine, and salts thereof (for example, sulfates and hydrochlorides), and more preferably agmatine. , aminoguanidine, histamine, arginine methyl ester, arginine ethyl ester, 4-picolylamine, 4-(aminomethyl)piperidine, 2-(4-aminophenyl)ethylamine, cadaverine, N-ethylethylenediamine, N,N-diethyl-1,3-diaminopropane, N-(2-hydroxypropyl)ethylenediamine, and salts thereof, more preferably at least one selected from the group consisting of agmatine, aminoguanidine, histamine, cadaverine, N-(2-hydroxypropyl)ethylenediamine, and salts thereof, and particularly preferably agmatine and / or a salt thereof. (In the formula, R 1 is a linear or branched alkylene group having 2 to 18 carbon atoms. (In the formula, R 2 is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkenyl group having 2 to 4 carbon atoms. (In the formula, R 3 is a single bond or a linear or branched alkylene group having 1 to 3 carbon atoms. (In the formula, R 4 is a linear or branched alkylene group having 3 to 4 carbon atoms, and R 5 is a linear or branched alkyl group having 1 to 8 carbon atoms.

[0035] <Production Method A> The production method A of the blue pigment of the present invention is not particularly limited except that it comprises reacting a mixture containing the aglycone of the iridoid glycoside with the nitrogen-containing compound, and examples thereof include a method in which the nitrogen-containing compound is added to an aqueous solution containing the aglycone of the iridoid glycoside and reacted.

[0036] The amount of the nitrogen-containing compound added needs to be adjusted appropriately depending on the content of the aglycone of the iridoid glycoside in the mixture (e.g., aqueous solution), and is, for example, about 0.2 to 2 mol, preferably 0.4 to 1.5 mol, and more preferably 0.8 to 1.2 mol per mol of the aglycone of the iridoid glycoside. The mixture may contain, together with the nitrogen-containing compound, at least one compound other than the nitrogen-containing compound selected from the group consisting of amine compounds, protein hydrolysates, and amino acids, within a range that does not impair the effects of the present invention.

[0037] The pH during the reaction must be adjusted appropriately depending on the nitrogen-containing compound used, but is, for example, about 5.5 to 8.5, preferably 6.0 to 8.0.

[0038] The temperature during the reaction needs to be adjusted appropriately depending on the reactivity of the nitrogen-containing compound used, but is, for example, about 20 to 80°C, and from the viewpoints of promoting the reaction and suppressing the production of by-products, it is preferably 30 to 50°C.

[0039] The reaction time needs to be adjusted appropriately depending on the types and amounts of the aglycone of the iridoid glycoside and the nitrogen-containing compound used, the temperature conditions, etc., but is, for example, about 5 to 72 hours, preferably 20 to 40 hours. From the viewpoint of accelerating the reaction, it is preferable to carry out stirring or shaking during the reaction.

[0040] After the reaction is completed, solids are removed by solid-liquid separation such as centrifugation, filtration, etc., to obtain a composition (aqueous solution) containing the blue pigment of the present invention. The obtained composition (aqueous solution) containing the blue pigment of the present invention may be used as is for the dye composition of the present invention, but may also be concentrated to form a concentrated liquid, or may be dried to form a powder for use.

[0041] Furthermore, the obtained blue pigment of the present invention may be subjected to a purification treatment as needed to remove unnecessary components other than the blue pigment.

[0042] 1-1-2. Method B for Producing Blue Pigment Method B for producing a blue pigment of the present invention is a method in which β-glucosidase is allowed to act on a mixture containing an iridoid glycoside and the nitrogen-containing compound.

[0043] <Iridoid glycoside> As the iridoid glycoside used in production method B, those described in the above section "1-1-1. Production method A of blue pigment" are used.

[0044] <Nitrogen-containing compound> As the nitrogen-containing compound used in production method B, those described in the section "1-1-1. Production method A of blue pigment" above are used.

[0045] <β-Glucosidase> As the β-glucosidase used in production method B, those described in the above section "1-1-1. Production method A of blue pigment" can be used.

[0046] <Production Method B> The method for producing a blue pigment of the present invention is not particularly limited as long as it involves the action of β-glucosidase in a mixture containing the iridoid glycoside and the nitrogen-containing compound. The mixture may contain, together with the nitrogen-containing compound, at least one compound selected from the group consisting of an amine compound other than the nitrogen-containing compound, a protein hydrolysate, and an amino acid, within a range that does not impair the effects of the present invention.

[0047] The treatment for allowing β-glucosidase to act may be carried out under conditions that allow the blue pigment of the present invention to be produced in a mixture containing the iridoid glycoside and the nitrogen-containing compound. For example, β-glucosidase may be added to a mixture obtained by mixing the iridoid glycoside and the nitrogen-containing compound in water, and the mixture may be incubated under aerobic conditions.

[0048] Specifically, the treatment for allowing the β-glucosidase to act thereon may be carried out by allowing 1 to 50% by mass of the iridoid glycoside, 1 to 50% by mass of the nitrogen-containing compound, and β-glucosidase at a concentration of about 1 to 500 U per 1 g of the iridoid glycoside to coexist under aerobic conditions.

[0049] The temperature conditions for the action of β-glucosidase may be appropriately set within the temperature range in which β-glucosidase acts, for example, about 20 to 70°C, preferably about 40 to 60°C.

[0050] The pH conditions for the action of β-glucosidase may be appropriately set within the pH range in which β-glucosidase acts, for example, about pH 3 to 6.5, preferably about pH 4 to 5.

[0051] The time for which β-glucosidase is allowed to act may be appropriately determined depending on the amount of β-glucosidase and the iridoid glycoside used, the temperature conditions, etc., and may be, for example, about 1 to 100 hours, preferably about 10 to 80 hours.

[0052] The method for creating aerobic conditions when allowing β-glucosidase to act is not particularly limited, and examples thereof include mechanical methods such as stirring and shaking; methods in which an oxygen-containing gas such as air is blown into the system; and combinations thereof.

[0053] Thus, the blue pigment of the present invention is produced by the action of β-glucosidase. After the action of β-glucosidase, solids are removed by solid-liquid separation treatment such as centrifugation or filtration to obtain a composition (aqueous solution) containing the blue pigment of the present invention. The obtained composition (aqueous solution) containing the blue pigment of the present invention may be used as is in the dye composition of the present invention, or, if necessary, may be concentrated and used in the form of a concentrated liquid, or may be dried to form a powder and used.

[0054] Furthermore, the obtained blue pigment of the present invention may be subjected to a purification treatment as needed to remove unnecessary components other than the blue pigment.

[0055] 1-2. Uses of Blue Pigment The blue pigment of the present invention can be used as a food coloring agent, dye, etc., and is particularly suitable for use as a dye for dyeing hair or fibers.

[0056] 2. Red Pigment The novel red pigment of the present invention is obtainable by reacting a mixture containing an aglycone of an ester hydrolysate of an iridoid glycoside with a nitrogen-containing compound having two or more nitrogen-containing groups, at least one of which is a primary amino group or a primary ammonium group, and which does not have a carboxy group. In particular, the novel red pigment is characterized by being obtainable by using the nitrogen-containing compound instead of a protein hydrolysate or amino acid used in the conventional production of gardenia red pigments. When used as a direct dye in a hair coloring composition or a fiber dyeing composition, the novel red pigment of the present invention can impart good dyeability and excellent colorfastness to the hair coloring composition or fiber dyeing composition. The novel red pigment of the present invention is described in detail below.

[0057] 2-1. Method for Producing Red Pigment The method for producing the red pigment of the present invention is not particularly limited as long as it involves reacting a mixture containing an aglycone of an ester hydrolysate of an iridoid glycoside with a nitrogen-containing compound having two or more nitrogen-containing groups, at least one of which is a primary amino group or a primary ammonium group, and which does not have a carboxy group, and any known method can be used. Examples include (1) a method of obtaining an aglycone of an ester hydrolysate of an iridoid glycoside and then reacting the aglycone with a mixture containing the nitrogen-containing compound (hereinafter also referred to as "Production Method C"), and (2) a method of treating a mixture containing an ester hydrolysate of an iridoid glycoside and the nitrogen-containing compound with β-glucosidase (hereinafter also referred to as "Production Method D"). Methods C and D for producing the red pigment of the present invention are described in detail below.

[0058] 2-1-1. Method C for Producing Red Pigment Method C for producing a red pigment of the present invention is a method in which an aglycone of an ester hydrolyzate of an iridoid glycoside is obtained, and then the aglycone is reacted with a mixture containing the nitrogen-containing compound.

[0059] <Aglycone of ester hydrolysate of iridoid glycoside> As the iridoid glycoside used in production method C, the one described in the above section "1-1-1. Production method A of blue pigment" is used.

[0060] The ester hydrolysate of an iridoid glycoside is a compound in which the group bonded to the 4-position of the iridoid skeleton in the iridoid glycoside is a carboxyl group. The ester hydrolysate of an iridoid glycoside is not particularly limited, and examples thereof include those that can be used as raw materials for producing conventional gardenia red pigments and those obtained from jagua (Genipa Americana).

[0061] The method for obtaining an ester hydrolysate of an iridoid glycoside is not particularly limited, and examples thereof include a method in which the ester bond at the 4-position of the iridoid skeleton of an iridoid glycoside is hydrolyzed to convert it into a carboxy group.

[0062] The method for hydrolyzing the ester bond at the 4-position of the iridoid skeleton of the iridoid glycoside is not particularly limited, and for example, a method that is commonly employed in the production of gardenia red pigments can be used, and specific examples thereof include alkaline hydrolysis, acid hydrolysis, and enzymatic hydrolysis.

[0063] The type of alkali used in the alkaline hydrolysis is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. These alkalis may be used alone or in combination of two or more.

[0064] The type of acid used for acid hydrolysis is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, etc., and organic acids such as citric acid, formic acid, acetic acid, oxalic acid, ascorbic acid, tartaric acid, fumaric acid, etc. These acids may be used alone or in combination of two or more.

[0065] The type of enzyme used for enzymatic hydrolysis is not particularly limited as long as it can hydrolyze the ester bond at the 4-position of the iridoid skeleton of the iridoid glycoside, and examples thereof include esterase.

[0066] Among these hydrolysis methods, alkaline hydrolysis is preferred. The conditions for alkaline hydrolysis may be any conditions that are commonly used in the production of gardenia red pigment, and examples include hydrolysis in an aqueous solution in the presence of an iridoid glycoside and an excess amount of alkali at about 10 to 80°C, preferably about 30 to 60°C, for about 1 to 72 hours, preferably about 20 to 48 hours. After alkaline hydrolysis, it is preferable to add an acid to adjust the pH to neutral or below.

[0067] The method for obtaining the aglycone of an ester hydrolysate of an iridoid glycoside is not particularly limited, and for example, the aglycone can be obtained by enzymatically treating an ester hydrolysate of an iridoid glycoside with β-glucosidase. Specifically, the same method as in the above section "1-1-1. Method A for producing a blue pigment" can be employed, except that an ester hydrolysate of an iridoid glycoside is used instead of the iridoid glycoside.

[0068] <Production Method C> The production method C of the red pigment of the present invention is not particularly limited except that it comprises reacting a mixture containing an aglycone of an ester hydrolysate of an iridoid glycoside with the nitrogen-containing compound, and examples thereof include a method in which the nitrogen-containing compound is added to an aqueous solution containing the aglycone of an ester hydrolysate of an iridoid glycoside and reacted.

[0069] <Nitrogen-Containing Compound> The nitrogen-containing compound used in Production Method C is the one described in the section "1-1-1. Production Method A of Blue Pigment." By using this nitrogen-containing compound, a novel red pigment different from conventional gardenia red pigments can be obtained. When used as a dye, the red pigment of the present invention has superior color fading resistance in washing treatments of dyed hair or dyed fibers using detergents such as shampoo and soap, compared to conventional gardenia red pigments.

[0070] From the viewpoint of obtaining a red pigment having even more excellent colorfastness and excellent dyeability, the nitrogen-containing compound is preferably at least one selected from the group consisting of compounds represented by the above general formula (1), compounds represented by the above general formula (2), compounds represented by the above general formula (3), compounds represented by the above general formula (4), 4-(aminoalkyl)pyridines, 4-(aminoalkyl)piperidines, 4-(aminoalkyl)anilines, alkylenediamines, N-alkylalkylenediamines, N,N-dialkylalkylenediamines, N-(hydroxyalkyl)alkylenediamines, and salts thereof (for example, sulfates and hydrochlorides), and more preferably agmatine. , aminoguanidine, histamine, arginine methyl ester, arginine ethyl ester, 4-picolylamine, 4-(aminomethyl)piperidine, 2-(4-aminophenyl)ethylamine, cadaverine, N-ethylethylenediamine, N,N-diethyl-1,3-diaminopropane, N-(2-hydroxypropyl)ethylenediamine, and salts thereof, more preferably at least one selected from the group consisting of agmatine, aminoguanidine, histamine, cadaverine, N-(2-hydroxypropyl)ethylenediamine, and salts thereof, and particularly preferably agmatine and / or a salt thereof.

[0071] The amount of the nitrogen-containing compound added needs to be adjusted appropriately depending on the content of the aglycone of the ester hydrolysate of the iridoid glycoside in the mixture (e.g., aqueous solution), and is, for example, about 0.5 to 10 mol, preferably 1 to 8 mol, and more preferably 2 to 6 mol, per mol of the aglycone of the ester hydrolysate of the iridoid glycoside. Note that the mixture may contain, together with the nitrogen-containing compound, at least one compound other than the nitrogen-containing compound selected from the group consisting of amine compounds, protein hydrolysates, and amino acids, within a range that does not impair the effects of the present invention.

[0072] The pH during the reaction must be adjusted appropriately depending on the nitrogen-containing compound used, but is, for example, about 3.0 to 7.0, preferably 4.0 to 5.0.

[0073] The temperature during the reaction needs to be adjusted appropriately depending on the reactivity of the nitrogen-containing compound used, but is, for example, about 20 to 70°C, and from the viewpoints of promoting the reaction and suppressing the production of by-products, it is preferably 30 to 60°C.

[0074] The reaction time needs to be appropriately adjusted depending on the types and amounts of the aglycone and nitrogen-containing compound of the ester hydrolysate of the iridoid glycoside used, the temperature conditions, etc., but is, for example, about 10 to 100 hours, preferably 20 to 80 hours. Note that, from the viewpoint of accelerating the reaction, it is preferable to carry out stirring or shaking during the reaction.

[0075] After the reaction is completed, solids are removed by solid-liquid separation such as centrifugation, filtration, etc., to obtain a composition (aqueous solution) containing the red pigment of the present invention. The obtained composition (aqueous solution) containing the red pigment of the present invention may be used as is for the dye composition of the present invention, but may also be concentrated to form a concentrated liquid, or may be dried to form a powder for use.

[0076] Furthermore, the obtained red pigment of the present invention may be subjected to a purification treatment as needed to remove unnecessary components other than the red pigment.

[0077] 2-1-2. Method D for Producing Red Pigment Method D for producing a red pigment of the present invention is a method in which β-glucosidase is allowed to act on a mixture containing an ester hydrolysate of an iridoid glycoside and the nitrogen-containing compound.

[0078] <Ester Hydrolysate of Iridoid Glycoside> As the ester hydrolysate of iridoid glycoside used in Production Method D, the one described in the above section "2-1-1. Production Method C of Red Pigment" is used.

[0079] <Nitrogen-Containing Compound> The nitrogen-containing compound used in Production Method D is the one described in the section "1-1-1. Production Method A of Blue Pigment." By using this nitrogen-containing compound, a novel red pigment different from conventional gardenia red pigments can be obtained. When used as a dye, the red pigment of the present invention has superior color fading resistance in washing treatments of dyed hair or dyed fibers using detergents such as shampoo and soap, compared to conventional gardenia red pigments.

[0080] From the viewpoint of obtaining a red pigment having even more excellent colorfastness and excellent dyeability, the nitrogen-containing compound is preferably at least one selected from the group consisting of compounds represented by the above general formula (1), compounds represented by the above general formula (2), compounds represented by the above general formula (3), compounds represented by the above general formula (4), 4-(aminoalkyl)pyridines, 4-(aminoalkyl)piperidines, 4-(aminoalkyl)anilines, alkylenediamines, N-alkylalkylenediamines, N,N-dialkylalkylenediamines, N-(hydroxyalkyl)alkylenediamines, and salts thereof (for example, sulfates and hydrochlorides), and more preferably agmatine. , aminoguanidine, histamine, arginine methyl ester, arginine ethyl ester, 4-picolylamine, 4-(aminomethyl)piperidine, 2-(4-aminophenyl)ethylamine, cadaverine, N-ethylethylenediamine, N,N-diethyl-1,3-diaminopropane, N-(2-hydroxypropyl)ethylenediamine, and salts thereof, more preferably at least one selected from the group consisting of agmatine, aminoguanidine, histamine, cadaverine, N-(2-hydroxypropyl)ethylenediamine, and salts thereof, and particularly preferably agmatine and / or a salt thereof.

[0081] <β-Glucosidase> As the β-glucosidase used in Production Method D, those described in the above section "1-1-1. Production Method A of Blue Pigment" can be used.

[0082] <Production Method D> The method for producing the red pigment of the present invention is not particularly limited as long as it involves the action of β-glucosidase in a mixture containing the ester hydrolysate of the iridoid glycoside and the nitrogen-containing compound. The mixture may contain, together with the nitrogen-containing compound, at least one compound selected from the group consisting of an amine compound other than the nitrogen-containing compound, a protein hydrolysate, and an amino acid, within a range that does not impair the effects of the present invention.

[0083] The treatment for allowing β-glucosidase to act may be carried out under conditions under which the red pigment of the present invention can be produced in a mixture containing the ester hydrolysate of the iridoid glycoside and the nitrogen-containing compound. For example, β-glucosidase may be added to a mixture obtained by mixing the ester hydrolysate of the iridoid glycoside and the nitrogen-containing compound in water, and the mixture may be incubated.

[0084] Specifically, the treatment for allowing the β-glucosidase to act thereon may be carried out by allowing 1 to 50% by mass of the ester hydrolysate of the iridoid glycoside, 1 to 50% by mass of the nitrogen-containing compound, and β-glucosidase at a concentration of about 1 to 500 U per 1 g of the ester hydrolysate of the iridoid glycoside to coexist.

[0085] The temperature conditions for the action of β-glucosidase may be appropriately set within the temperature range in which β-glucosidase acts, for example, about 20 to 70°C, preferably about 40 to 60°C.

[0086] The pH conditions for the action of β-glucosidase may be appropriately set within the pH range in which β-glucosidase acts, for example, about pH 4 to 5, preferably about pH 4.2 to 4.8.

[0087] The time for which the β-glucosidase is allowed to act may be appropriately determined depending on the amount of β-glucosidase and the ester hydrolysate of the iridoid glycoside used, the temperature conditions, etc., and may be, for example, about 10 to 100 hours, preferably about 20 to 80 hours.

[0088] Thus, the red pigment of the present invention is produced by the action of β-glucosidase. After the action of β-glucosidase, solids are removed by solid-liquid separation treatment such as centrifugation or filtration to obtain a composition (aqueous solution) containing the red pigment of the present invention. The obtained composition (aqueous solution) containing the red pigment of the present invention may be used as is for the dye composition of the present invention, but may also be concentrated as necessary and used in the form of a concentrated liquid, or may be dried to form a powder and used.

[0089] Furthermore, the obtained red pigment of the present invention may be subjected to a purification treatment as needed to remove unnecessary components other than the red pigment.

[0090] 2-2. Uses of the Red Pigment The red pigment of the present invention can be used as a food coloring agent, dye, etc., and is particularly suitable for use as a dye for dyeing hair or fibers.

[0091] 3. Dyeing Composition The dyeing composition of the present invention contains the blue pigment and / or the red pigment of the present invention. The dyeing composition of the present invention is used for dyeing hair and fibers (natural fibers such as plant fibers and animal fibers, chemical fibers, etc.). Examples of plant fibers include cotton and hemp. Examples of animal fibers include wool, goat hair, and silk. Examples of chemical fibers include synthetic fibers, semi-synthetic fibers, and recycled fibers. The dye to be used can be appropriately determined depending on the color to be imparted to the hair or fiber.

[0092] The dyeing composition of the present invention is preferably a hair coloring composition or a fiber dyeing composition. By incorporating the blue pigment and / or red pigment of the present invention, the hair coloring composition or fiber dyeing composition of the present invention has a significantly improved color fading resistance in washing treatments of dyed hair or dyed fibers with detergents such as shampoos and soaps, and is therefore characterized by being able to maintain the color tone of dyed hair or dyed fibers for a longer period of time than hair coloring agents or fiber dyeing agents that use conventional gardenia blue or red pigments.

[0093] <Content of Blue Pigment> In the hair coloring composition or fiber dyeing composition of the present invention, the content of the blue pigment of the present invention may be appropriately set depending on the product form of the hair coloring composition or fiber dyeing composition, the color depth to be imparted to hair or fibers, etc. 10% 1cm is 0.01 or more, preferably 0.01 to 40, more preferably 0.5 to 30, and even more preferably 1.0 to 20.

[0094] In the present invention, "color value E 10% 1cm " is a unit that expresses the color intensity of a dye, and refers to the value obtained by converting the absorbance at the maximum absorption wavelength when measured using a cell with an optical path length of 1 cm in a reliable concentration range with an absorptiometer into a value for a 10 mass % solution.

[0095] The maximum absorption wavelength of the blue dye of the present invention is around 590 nm, so the color value E 10% 1cm can be determined by identifying a maximum absorption wavelength near 590 nm and measuring the absorbance at that wavelength, but if there is no maximum absorption wavelength, the absorbance at 590 nm may be measured. In measuring the color value of the blue pigment of the present invention, a citrate buffer solution (pH 7.0) (described in the 9th edition of the Japanese Standards of Food Additives) is used as a diluting solvent for the pigment solution used to measure the absorbance.

[0096] Furthermore, in the hair coloring composition or fiber dye composition of the present invention, the content of the blue pigment of the present invention is, for example, 0.01% by mass or more, preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, and particularly preferably 1.0 to 10% by mass.

[0097] <Content of Red Pigment> In the hair coloring composition or fiber dyeing composition of the present invention, the content of the red pigment of the present invention may be appropriately set depending on the product form of the hair coloring composition or fiber dyeing composition, the color depth to be imparted to hair or fibers, etc. For example, 10% 1cmis 0.1 or more, preferably 0.1 to 40, more preferably 0.1 to 30, and even more preferably 0.2 to 10.

[0098] The maximum absorption wavelength of the red dye of the present invention is around 535 nm, so the color value E 10% 1cm can be determined by identifying a maximum absorption wavelength near 535 nm and measuring the absorbance at that wavelength, but if there is no maximum absorption wavelength, the absorbance at 535 nm may be measured. In measuring the color value of the red pigment of the present invention, an acetate buffer solution (pH 4.0) (described in the Official Standards of Food Additives, 8th Edition) is used as a dilution solvent for the pigment solution used to measure absorbance.

[0099] Furthermore, in the hair coloring composition or fiber dye composition of the present invention, the content of the red pigment of the present invention is, for example, 0.1% by mass or more, preferably 0.1 to 40% by mass, more preferably 0.1 to 30% by mass, and particularly preferably 0.2 to 10% by mass.

[0100] <Penetration enhancer (dyeing auxiliary)> The blue and red pigments of the present invention have good dyeing properties and provide sufficient dyeing effects without the use of a penetration enhancer, so the hair coloring composition or fiber dyeing composition of the present invention does not need to contain a penetration enhancer. However, a penetration enhancer may be contained in order to further promote penetration into hair or fibers, thereby further improving the dyeing properties of the pigment on hair or fibers.

[0101] The penetration enhancer may be any that can promote the penetration of the direct dye into the hair or fiber, and examples thereof include aromatic alcohols such as benzyl alcohol, 2-phenylethyl alcohol, cinnamyl alcohol, phenylpropanol, α-methylbenzyl alcohol, dimethylbenzyl carbinol, benzyloxyethanol, phenoxyethanol, and p-anisyl alcohol; lower monohydric alcohols such as ethanol and isopropanol; polyhydric alcohols such as ethylene glycol, propylene glycol, and 1,3-butylene glycol; alkylene carbonates such as ethylene carbonate and propylene carbonate; etc. These penetration enhancers may be used alone or in combination of two or more.

[0102] The content of the penetration enhancer in the hair coloring composition or fiber dyeing composition of the present invention is not particularly limited, and may be, for example, 0 to 10% by mass, preferably 0 to 5.0% by mass, and more preferably 0 to 0.4% by mass. In conventional hair coloring compositions or fiber dyeing compositions that use direct dyes, when a penetration enhancer is incorporated, the content is usually set to 0.5% by mass or more. However, in the hair coloring composition or fiber dyeing composition of the present invention, because the dyeing properties of the blue pigment and red pigment of the present invention are high, the content of the penetration enhancer can be set to 0% by mass or a small amount, and safety concerns due to the incorporation of a penetration enhancer can be eliminated or reduced.

[0103] <Reducing Agent (Dyeing Auxiliary Agent)> The hair coloring composition or fiber dyeing composition of the present invention does not necessarily contain a reducing agent, but may contain a reducing agent in order to further improve the dyeability of the dye on hair or fibers.

[0104] The type of reducing agent is not particularly limited, and examples thereof include sulfites such as sodium sulfite and sodium hydrogen sulfite, sodium L-ascorbate, compounds having a thiol group, etc. These reducing agents may be used alone or in combination of two or more.

[0105] The content of the reducing agent in the hair coloring composition or fiber dyeing composition of the present invention is not particularly limited, and may be, for example, 0 to 1 mass %, preferably 0 to 0.8 mass %, and more preferably 0 to 0.2 mass %. In conventional hair coloring compositions or fiber dyeing compositions that use direct dyes, the content of a reducing agent, when blended, is usually set to 0.3 mass % or more. However, in the hair coloring composition or fiber dyeing composition of the present invention, because the dyeability of the blue pigment and red pigment of the present invention is high, the content of the penetration enhancer can be set to 0 mass % or a small amount, and safety concerns due to the blending of a reducing agent can be eliminated or reduced.

[0106] <Alkaline Agent (Dyeing Auxiliary Agent)> The hair coloring composition or fiber dyeing composition of the present invention does not necessarily contain an alkaline agent, but may contain an alkaline agent in order to further improve the dyeability of the dye on the hair or fiber by opening the cuticle.

[0107] The type of alkaline agent is not particularly limited, and examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkanolamines and salts thereof such as monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, isopropanolamine, dipropanolamine, tripropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, and 2-amino-2-hydroxymethyl-1,3-propanediol; ammonia and salts thereof; alkanediamines and salts thereof such as 1,3-propanediamine; and carbonates such as guanidine carbonate, guanidine bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, and lithium carbonate. These alkaline agents may be used alone or in combination of two or more.

[0108] The content of the alkaline agent in the hair coloring composition or fiber dyeing composition of the present invention is not particularly limited and may be set appropriately so as to satisfy the pH range described below, and may be, for example, 0 to 1.5% by mass, preferably 0 to 1.0% by mass, and more preferably 0 to 0.4% by mass. In conventional hair coloring compositions or fiber dyeing compositions that use direct dyes, when an alkaline agent is incorporated, the content is usually set to 0.5% by mass or more. However, in the hair coloring composition or fiber dyeing composition of the present invention, because the dyeability of the blue pigment and red pigment of the present invention is high, the content of the alkaline agent can be set to 0% by mass or a small amount, thereby eliminating or reducing safety concerns due to the incorporation of an alkaline agent.

[0109] <Other Components> In addition to the blue pigment and / or red pigment of the present invention, the hair coloring composition or fiber dyeing composition of the present invention may contain, as necessary, direct dyes such as acid dyes, natural dyes, nitro dyes, disperse dyes, etc.; reactive dyes such as oxidation dyes, etc. Whether or not such other dyes are blended can be determined depending on the color tone to be imparted to hair or fibers, etc.

[0110] In addition to the above-mentioned components, the hair coloring composition of the present invention may contain other components commonly used in hair coloring compositions.Such components can be appropriately blended, for example, higher alcohols, silicones, hydrocarbons, waxes, animal and vegetable oils and fats, higher fatty acids, organic solvents, thickeners, organic acids, cationic surfactants, amphoteric surfactants, nonionic surfactants, anionic surfactants, cationic polymers, anionic polymers, amphoteric polymers, proteins, protein hydrolysates, amino acids, preservatives, chelating agents, stabilizers, antioxidants, antibacterial agents, moisturizers, pH adjusters, animal extracts, plant extracts, yeast extracts, vitamins, pigments, fragrances, UV absorbers, hair growth ingredients, wool ingredients, anti-dandruff ingredients, etc.The content of these ingredients can be appropriately set depending on the type of ingredients used, the product form of the hair coloring composition, etc.

[0111] <pH> The pH of the hair coloring composition or fiber dyeing composition of the present invention is not particularly limited and may be set appropriately within the range of, for example, pH 3.0 to 11.0. From the viewpoint of further improving color fading resistance in washing treatment of dyed hair or dyed fibers using a detergent such as shampoo or soap, the pH is preferably 3.0 to 9.0, more preferably 5.0 to 8.0, and even more preferably 6.5 to 7.5.

[0112] <Applications, Product Form, etc.> The hair coloring composition of the present invention is used to dye hair. The hair coloring composition of the present invention may be applied to any hair, such as gray hair, black hair, brown hair, or blonde hair, but gray hair is a preferred application target because the hair coloring effect of the hair coloring composition of the present invention is more likely to be achieved. The hair coloring composition of the present invention may also be a shampoo, rinse, conditioner, or hair milk. The hair coloring composition of the present invention may also be incorporated into a shampoo, rinse, conditioner, or hair milk.

[0113] The hair coloring composition of the present invention may be in the form of any product such as a permanent hair dye or a semi-permanent hair dye, but is preferably in the form of a semi-permanent hair dye.

[0114] A permanent hair dye is a hair dye that uses a reactive dye such as an oxidation dye (classified as a quasi-drug in Japan). When the hair coloring composition of the present invention is made into a permanent hair dye product, it can be formulated by blending a reactive dye such as an oxidation dye in addition to the blue dye and / or red dye of the present invention.

[0115] A semi-permanent hair dye is a hair dye that uses a direct dye (in Japan, it is classified as a cosmetic product). When the hair coloring composition of the present invention is made into a semi-permanent hair dye product, the blue pigment and / or red pigment of the present invention can be used as the direct dye, and other direct dyes can be added as necessary to form the formulation.

[0116] 4. Dyeing Method Hair dyeing using the hair coloring composition of the present invention may be performed using a method appropriate for the product form of the hair coloring composition. For example, the composition may be applied to the hair to be dyed, left for a predetermined time, and then rinsed off with water or the like. If necessary, the composition may be rinsed off with shampoo. Furthermore, the temperature conditions for dyeing hair using the hair coloring composition of the present invention may be room temperature. However, the higher the temperature during dyeing, the better the hair dyeing effect tends to be, so the temperature may be appropriately set depending on the composition of the hair coloring composition, the color intensity to be imparted to the hair, and the like. Furthermore, a method for dyeing fibers using the fiber dye composition of the present invention may, for example, be a method in which a fiber bundle or fabric is immersed in the fiber dye composition, left for a predetermined time, and then rinsed off with water or the like. If necessary, the composition may be rinsed off with a detergent.

[0117] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0118] 1-1. Production of blue pigment Total color value (color value (E 10% 1cm A geniposide aqueous solution with a color value of approximately 1250 was measured so that the mass (%) × mass (g) was 54,000, and 1 / 10 of that mass was mixed with β-glucosidase (1000 U / g, "Sumiteam C", manufactured by Shin-Nippon Chemical Industry Co., Ltd.) and an appropriate amount of ion-exchanged water to a total volume of 180 g (geniposide color value: 300). This aqueous solution was heated to 50 ° C, the pH was adjusted to 4.5 with aqueous sodium hydroxide, and the enzyme reaction was carried out for 20 hours to obtain a genipin aqueous solution (genipin color value: approximately 240). Then, 155 g of the genipin aqueous solution was measured, and each nitrogen-containing compound or arginine shown in Table 1 was added to the genipin aqueous solution in the amounts shown in Table 1, and then the total volume was adjusted to 180 g with ion-exchanged water to prepare a dye raw solution. The pH of the prepared dye raw solution was adjusted to 7.0 with hydrochloric acid or aqueous sodium hydroxide, and the solution was shaken and stirred in a thermostatic chamber set at 35 ° C. After 24 hours from the start of the reaction, the dye reaction solution was removed from the thermostatic bath and subjected to solid-liquid separation filtration to obtain a blue dye solution, which was then freeze-dried to powder to obtain each blue dye.

[0119] 1-2. Test of color fading resistance of blue dye on goat hair Each blue dye was dissolved in water at 0.5% (calculated as a color value of 400) and the pH was adjusted to 7.0 with aqueous sodium hydroxide solution or hydrochloric acid to obtain each blue dye solution. 2 mL of each blue dye solution was applied to 1 g of goat hair bundle, and after 10 minutes, the hair was washed with running water and dried with a hair dryer to obtain each blue-dyed hair bundle. Each blue-dyed hair bundle and an undyed hair bundle that had not been treated with the dye solution were measured using a spectrophotometer (CM-5, Konica Minolta Japan, Inc.) to measure the L * Value, a * value, and b * values ​​were measured and expressed in the CIELAB color space (CIE 1976 L * a * b * The measurement conditions were set to reflectance, light source D65, field of view 10°, and measurement diameter 3 mm. The hair bundle was measured at three points, and the average value was taken as the measurement value. Here, the CIELAB color space is a * axis, b * The Cartesian coordinate system consists of two axes, and the L * It is a color system that forms a color solid composed of a * Increasing the value on the positive side increases redness, increasing the value on the negative side increases greenness, and * An increase in the value on the positive side means an increase in yellowness, and an increase in the value on the negative side means an increase in blueness. * The value corresponds to the lightness, and the L * = 100 is white, L * When L = 0, it becomes black, * The larger the value, the brighter the hair tends to be. * Value, a * value, and b * The ΔL value and ΔE value of each blue-dyed hair bundle were calculated using the standard value. However, the sign of the ΔL value was selected so that it would be a positive value. Here, the ΔL value and ΔE value were respectively * value, ΔE * The ab value is used to indicate the value of the shampoo. 2 mL of shampoo diluted 10 times with water was applied to each of the blue-dyed hair bundles, and after 2 minutes, the hair was washed with running water and dried with a hair dryer. This shampoo washing treatment was repeated 7 times. After the first or seventh shampoo washing treatment, the L * Value, a* value, and b * The values ​​were measured, and the ΔL value and ΔE value were calculated. The ΔL value and ΔE value after seven shampooing treatments were divided by the ΔL value and ΔE value after one shampooing treatment to obtain a value that was defined as color retention (%), and the color retention was used as an index of color fading resistance. The higher the color retention (%), the more resistant the color to fading by shampooing and the more excellent the color fading resistance. The above results are shown in Table 1. It is considered that pigments that are not sufficiently fixed to the hair fall off in the first shampooing treatment, and that only a small amount of pigment falls off in subsequent shampooing treatments. Therefore, in order to evaluate from the perspective of pigment fixation, the color tone after one shampooing treatment was used as the standard for evaluation.

[0120]

[0121] 1 to 16, the blue pigments of the present invention obtained in Examples 1 to 9 had larger ΔL and ΔE values ​​(higher color retention) after seven shampoo washing treatments, demonstrating excellent color fading resistance, compared to the gardenia blue pigment obtained in Comparative Example 1. In particular, the blue pigments of the present invention obtained in Examples 1, 7, and 9 using agmatine sulfate, cadaverine dihydrochloride, or N-(2-hydroxypropyl)ethylenediamine had significantly larger ΔL and ΔE values ​​(higher color retention) after seven shampoo washing treatments, demonstrating excellent color fading resistance, compared to the gardenia blue pigment obtained in Comparative Example 1.

[0122] 2-1. Production of red pigment Color value (E 10% 1cm100 g of a geniposide aqueous solution with a pH of approximately 1250 was weighed out and mixed with 40 ml of 30% aqueous sodium hydroxide. The resulting mixture was heated to 45°C and hydrolyzed for 24 hours to obtain a geniposidic acid aqueous solution. An aqueous solution was then prepared by dissolving 151 g of ascorbic acid and each of the nitrogen-containing compounds shown in Table 2 or arginine in 400 ml of ion-exchanged water in the amounts shown in Table 2. This aqueous solution was then added to the geniposidic acid aqueous solution, and the pH was adjusted to 4.5 with aqueous sodium hydroxide or hydrochloric acid. A mixture of 10 g of β-glucosidase (1000 U / g, "Sumiteam C," manufactured by Shin-Nippon Chemical Industry Co., Ltd.) in 30 ml of ion-exchanged water was then added to the resulting solution, and the pH was again adjusted to 4.5 with aqueous sodium hydroxide to obtain a dye reaction solution. The resulting dye reaction solution was shaken and stirred in a thermostatic chamber set at 50°C. After 20 hours, the dye reaction solution was removed from the thermostatic bath, heated to 90°C, and subjected to an enzyme inactivation reaction for 1 hour. After that, the dye reaction solution was cooled with ice water and subjected to solid-liquid separation filtration to obtain a red dye solution. The obtained red dye solution was diluted with ion-exchanged water to a 0.5% solution with a color value of 400, to obtain each red dye solution.

[0123] 2-2. Test of colorfastness of red dye on goat hair 2 mL of each red dye solution was applied to 1 g of goat hair bundle, and after 10 minutes, the hair was washed with running water and dried with a hair dryer to obtain each red-dyed hair bundle. Each red-dyed hair bundle and an undyed hair bundle that had not been treated with the dye solution were measured using a color difference meter (CM-5, Konica Minolta Japan, Inc.) to measure the L * Value, a * value, and b * values ​​were measured and expressed in the CIELAB color space (CIE 1976 L * a * b * The color was expressed in a color space. The measurement conditions were set to reflectance, light source D65, field of view 10°, and measurement diameter 3 mm. The hair bundle was measured at three points, and the average value was taken as the measurement value. Then, the L of the undyed hair bundle was * Value, a * value, and b * The ΔL value and ΔE value of each red-dyed hair bundle were calculated using the standard value. However, the sign of the ΔL value was selected so that it would be a positive value. Here, the ΔL value and ΔE value were respectively * value, ΔE* The ab value is used to indicate the value of the shampoo. 2 mL of shampoo diluted 10 times with water was applied to each of the red-dyed hair bundles, and after 2 minutes, the hair was washed with running water and dried with a hair dryer. This shampoo washing treatment was repeated 7 times. After the first or seventh shampoo washing treatment, the L * Value, a * value, and b * The values ​​were measured, and the ΔL value and ΔE value were calculated. The ΔL value and ΔE value after seven shampooing treatments were divided by the ΔL value and ΔE value after one shampooing treatment to obtain the color retention rate (%), which was used as an index of color fading resistance. The higher the color retention rate (%), the more resistant the color to fading with shampooing and the more excellent the color fading resistance. The above results are shown in Table 2.

[0124]

[0125] As shown in Table 2 and FIGS. 17 to 22, the red pigments of the present invention obtained in Examples 10 to 12 had larger ΔL and ΔE values ​​(higher color tone retention) after seven shampoo washing treatments than the gardenia red pigment obtained in Comparative Example 2, confirming that they were excellent in color fading resistance.

[0126] 3-1. Preparation of Hair Color Treatment Hair color treatments were prepared according to the formulations shown in Table 3 using the blue pigment obtained in Example 1 or Comparative Example 1.

[0127]

[0128] 3-2. Test of dyeability and color fading resistance of hair color treatment 2 mL of the hair color treatment was applied to 1 g of goat hair bundle moistened with water, and after 10 minutes, it was washed with running water and dried with a hair dryer to obtain each dyed hair bundle. Then, 2 mL of shampoo diluted 10 times with water was applied to each dyed hair bundle, and after 2 minutes, it was washed with running water and dried with a hair dryer. The hair color treatment dyeing operation and shampoo washing operation were repeated three times. For each goat hair bundle after dyeing and washing, the L * Value, a * value, and b *values ​​were measured and expressed in the CIELAB color space (CIE 1976 L * a * b * The color was expressed in the color space. * Value, a * value, and b * The ΔE values ​​of the hair bundles after each dyeing and washing were calculated using the standard values. * This refers to the ab value. The larger the ΔE value, the better the dyeing. The results are shown in Table 4.

[0129]

[0130] As shown in Table 4 and Figures 23 to 26, the color treatment prepared using the blue pigment of the present invention obtained in Example 1 had larger ΔE values ​​after dyeing and washing than the color treatment prepared using the gardenia blue pigment obtained in Comparative Example 1, confirming that it had superior dyeability and colorfastness, as well as superior colorfastness after repeated washing.

[0131] 4-1. Test of dyeability and colorfastness of blue dye on fabric Each undyed fabric (polyester fabric, nylon fabric, silk fabric, or cotton fabric) was immersed in the blue dye solution (25°C) prepared in Example 1, washed with running water after 10 minutes, and dried to obtain each dyed fabric. Thereafter, each dyed fabric was hand-washed with detergent and air-dried. For each dyed fabric after dyeing and hand-washing, the L * Value, a * value, and b * values ​​were measured and expressed in the CIELAB color space (CIE 1976 L * a * b * The color was expressed in the L color space. * Value, a * value, and b * The ΔE values ​​of the dyed fabrics after dyeing and after hand-washing were calculated based on the standard value. *The color retention rate (%) refers to the ab value. The ΔE value after hand washing was divided by the ΔE value after dyeing to obtain the color retention rate, which was used as an index of color fading resistance. The higher the color retention rate (%), the more resistant the fabric to color fading with detergent, and the better the color fading resistance. The results are shown in Table 5.

[0132]

[0133] As shown in Table 5 and FIGS. 27 to 30, it was confirmed that the blue colorant of the present invention obtained in Example 1 has good dyeability for various fabrics and is excellent in colorfastness.

[0134] 4-2. Test of dyeability and colorfastness of red dye on fabric Each undyed fabric (polyester fabric, nylon fabric, silk fabric, or cotton fabric) was immersed in the red dye solution (25°C) prepared in Example 10, washed with running water after 10 minutes, and dried to obtain each dyed fabric. Thereafter, each dyed fabric was hand-washed with detergent and air-dried. For each dyed fabric after dyeing and hand-washing, the L * Value, a * value, and b * values ​​were measured and expressed in the CIELAB color space (CIE 1976 L * a * b * The color was expressed in the L color space. * Value, a * value, and b * The ΔE values ​​of the dyed fabrics after dyeing and after hand-washing were calculated based on the standard value. * The color retention rate (%) refers to the ab value. The ΔE value after hand washing was divided by the ΔE value after dyeing to obtain the color retention rate, which was used as an index of color fading resistance. The higher the color retention rate (%), the more resistant the fabric to color fading with detergent, and the better the color fading resistance. The results are shown in Table 6.

[0135]

[0136] As shown in Table 6 and FIGS. 31 to 34, it was confirmed that the red dye of the present invention obtained in Example 10 has good dyeability for various fabrics and is excellent in colorfastness.

[0137] 5-1. Test of Color Fading Resistance of Blue Dye on Human Hair The blue dye solutions prepared in Example 1 and Comparative Example 1 were used as the blue dye solutions. Furthermore, blue dye solutions were prepared in the same manner as in Example 1 (Examples 13 to 15), except that 2-(4-aminophenyl)ethylamine (4.90 g), N-ethylethylenediamine (3.17 g), or 4-picolylamine (3.89 g) was used instead of agmatine sulfate (8.22 g). Using these blue dye solutions, color fading resistance was evaluated in the same manner as in "1-2. Test of Color Fading Resistance of Blue Dye on Goat Hair" above, except that a bundle of human hair (bleached and washed with shampoo) was used instead of a bundle of goat hair. The results are shown in Table 7.

[0138]

[0139] As shown in Table 7 and Figures 35 to 39, the blue pigments of the present invention obtained in Examples 1 and 13 to 15 had larger ΔL and ΔE values ​​(higher color tone retention) after seven shampoo washing treatments than the gardenia blue pigment obtained in Comparative Example 1, and were confirmed to have excellent color fading resistance even on human hair.

[0140] 5-2. Test of color fading resistance of red dye on human hair The red dye solutions prepared in Example 10 and Comparative Example 2 were used as the red dye solutions. Color fading resistance was evaluated using these red dye solutions in the same manner as in "2-2. Test of color fading resistance of red dye on goat hair" above, except that a bundle of human hair (bleached and washed with shampoo) was used instead of a bundle of goat hair. The results are shown in Table 8.

[0141]

[0142] As shown in Table 8 and Figures 40 and 41, the red pigment of the present invention obtained in Example 10 had larger ΔL and ΔE values ​​(higher color tone retention) after seven shampoo washing treatments than the gardenia red pigment obtained in Comparative Example 2, and was confirmed to have excellent color fading resistance even on human hair.

Claims

1. A blue pigment obtained by reacting a mixture containing an aglycone of an iridoid glycoside with a nitrogen-containing compound having two or more nitrogen-containing groups, at least one of which is a primary amino group or a primary ammonium group, and which has no carboxy group.

2. The blue dye according to claim 1, wherein the nitrogen-containing compound has a primary amino group or a primary ammonium group, and a guanidino group or a nitrogen-containing heterocycle.

3. The blue pigment according to claim 1, wherein the nitrogen-containing compound is at least one selected from the group consisting of agmatine, aminoguanidine, histamine, arginine alkyl esters, and salts thereof.

4. A red pigment obtained by reacting a mixture containing an aglycone of an ester hydrolysate of an iridoid glycoside with a nitrogen-containing compound having two or more nitrogen-containing groups, at least one of which is a primary amino group or a primary ammonium group, and which has no carboxy group.

5. The red pigment according to claim 4, wherein the nitrogen-containing compound has a primary amino group or a primary ammonium group, and a guanidino group or a nitrogen-containing heterocycle.

6. The red pigment according to claim 4, wherein the nitrogen-containing compound is at least one selected from the group consisting of agmatine, aminoguanidine, histamine, arginine alkyl esters, and salts thereof.

7. A dyeing composition comprising the blue pigment according to any one of claims 1 to 3 and / or the red pigment according to any one of claims 4 to 6.

8. A dye composition according to claim 7, which is a hair colouring composition.

9. The dye composition according to claim 8, which is used for dyeing gray hair.

10. A dyeing composition according to claim 7, which is a textile dyeing composition.

11. A dyeing method comprising dyeing hair or fibers with the dyeing composition according to claim 8 or 10.

12. Use of a blue pigment according to any one of claims 1 to 3 and / or a red pigment according to any one of claims 4 to 6 for the preparation of a hair colouring composition or a textile dyeing composition.

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