Novel blue pigment and red pigment, and dyeing composition

Abstract

The purpose 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 fading resistance. The blue pigment according to the present invention is obtained by reacting a mixture of an iridoid glycoside-containing aglycone and a nitrogen-containing compound, the nitrogen-containing compound having two or more nitrogen-containing groups, at least one of the nitrogen-containing groups being a primary amino group or a primary ammonium group, and the nitrogen-containing compound not having a carboxyl group. Furthermore, the red pigment according to the present invention is obtained by reacting a mixture of an aglycone comprising an ester hydrolysate of iridoid glycoside and a nitrogen-containing compound, the nitrogen-containing compound having two or more nitrogen-containing groups, at least one of the nitrogen-containing groups being a primary amino group or a primary ammonium group, and the nitrogen-containing compound not having a carboxyl group.

Description

Technical Field

[0001] This invention relates to novel blue and red pigments, and dyeing compositions containing the blue and / or red pigments. Background Technology

[0002] While hair dyeing products using synthetic dyes are the mainstream, in recent years, hair dyeing compositions using safe natural pigments have received much attention due to concerns about hair damage and allergic reactions.

[0003] Gardenia pigment is a natural pigment obtained from the fruit of Gardenia augusta Merrill or Gardenia jasminoides Ellis, belonging to the Rubiaceae family. Depending on the manufacturing method, it exists in three colors: blue, red, and yellow. Gardenia blue pigment is produced by adding iridoid glycosides and protein breakdown products obtained from gardenia fruit to... β The pigment is obtained by β-glucosidase. Additionally, gardenia red pigment is produced by adding β-glucosidase to a mixture of ester hydrolysates and protein hydrolysates of iridoid glycosides obtained from gardenia fruit. β Gardenia pigments, obtained by β-glucosidase (Food Additives Code, 9th Edition, 2018, Ministry of Health, Labour and Welfare, Consumer Affairs Agency), are widely used as coloring materials in food and other products. These gardenia pigments are also sometimes used as hair dyes.

[0004] For example, Patent Document 1 reports a hair dye containing gardenia blue pigment, a reducing agent with a thiol group, and an alkali that can deepen the color of hair. Patent Document 2 reports a hair dye composition containing gardenia blue pigment liquid containing genipin and a cationic polymer, which has high dyeing properties in the range of chestnut to dark brown. Patent Document 3 reports a hair dye composition containing gardenia blue pigment liquid containing genipin, a nitro-based direct dye, and a cationic surfactant, which has high dyeing properties in the range of chestnut to dark brown.

[0005] Furthermore, Patent Document 4 discloses a hair dyeing composition containing (i) gardenia blue pigment, wherein the recovery rate of pigment components that are not adsorbed by a sodium ion-type methacrylic acid-based weak acid cation exchange resin and flow out is 85% or less when the gardenia blue pigment is passed through the resin; or (ii) gardenia red pigment, wherein the recovery rate of pigment components that are not adsorbed by a sodium ion-type methacrylic acid-based weak acid cation exchange resin and flow out is 60% or less when the gardenia red pigment is passed through the resin. Moreover, Patent Document 4 describes that by using the gardenia blue pigment (i) or gardenia red pigment (ii) as a direct dye, the fixation on hair is improved even without the use of dyeing auxiliaries, resulting in excellent hair dyeing effects; the gardenia blue pigment (i) is obtained by mixing arginine with iridoid glycosides obtained from the fruit of Gardenia jasminoides (Rubiaceae family) and subjecting it to a prescribed enzyme reaction; the gardenia red pigment (ii) is obtained by mixing arginine with an ester hydrolysate of iridoid glycosides obtained from the fruit of Gardenia jasminoides (Rubiaceae family) and subjecting it to a prescribed enzyme reaction.

[0006] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2013-133320 Patent Document 2: Japanese Patent Application Publication No. 2000-53544 Patent Document 3: Japanese Patent Application Publication No. 2000-95654 Patent Document 4: International Publication No. 2018 / 181008 Summary of the Invention

[0007] The technical problem that the invention aims to solve However, gardenia pigment is difficult to fix to hair, resulting in insufficient hair dyeing properties even when used in hair dyeing products. Furthermore, in conventional hair dyeing products using gardenia pigment, dyeing aids (reducing agents, alkalis, penetration enhancers, etc.) are indispensable to improve the dyeing properties and achieve excellent dyeing results, or the composition is limited by factors such as the inclusion of cationic substances. Additionally, the hair dyeing composition proposed in Patent Document 4 is prone to fading after shampooing, indicating room for improvement in fading resistance.

[0008] The purpose of this invention is to provide a novel blue pigment and a red pigment, as well as a dyeing composition containing the blue pigment and / or the red pigment with excellent colorfastness.

[0009] Technical solutions for solving technical problems In order to solve the above-mentioned technical problems, the inventors conducted in-depth research and discovered that by using a blue pigment obtained by reacting a mixture of an aglycone containing iridoid glycosides and a nitrogen-containing compound with a specific chemical structure, or a red pigment obtained by reacting an aglycone containing an ester hydrolysate of iridoid glycosides and a nitrogen-containing compound with a specific chemical structure, as a dye for dyeing compositions, it is possible to obtain dyeing compositions with excellent colorfastness. This invention was completed based on further repeated research based on the above insights.

[0010] That is, the present invention provides an invention in the manner disclosed below.

[0011] Item 1. A blue pigment obtained by reacting a mixture of an aglycone containing an iridoid glycoside and a nitrogen-containing compound, said nitrogen-containing compound having two or more nitrogen-containing groups, at least one of said nitrogen-containing groups being a primary amino or primary ammonium group, and said nitrogen-containing compound not having a carboxyl group.

[0012] Item 2. The blue pigment according to Item 1, wherein the nitrogen-containing compound has a primary amino or primary ammonium group, and a guanidine or nitrogen-containing heterocycle.

[0013] Item 3. The blue pigment according to Item 1, wherein the nitrogen-containing compound is selected from at least one of guanidine, aminoguanidine, histamine, alkyl arginine esters and their salts.

[0014] Item 4. A red pigment obtained by reacting an aglycone comprising an ester hydrolysate of an iridoid glycoside with a nitrogen-containing compound, said nitrogen-containing compound having two or more nitrogen-containing groups, at least one of said nitrogen-containing groups being a primary amino or primary ammonium group, and said nitrogen-containing compound not having a carboxyl group.

[0015] Item 5. The red pigment according to Item 4, wherein the nitrogen-containing compound has a primary amino or primary ammonium group, and a guanidine group or a nitrogen-containing heterocycle.

[0016] Item 6. The red pigment according to Item 4, wherein the nitrogen-containing compound is selected from at least one of guanidine, aminoguanidine, histamine, alkyl arginine esters and their salts.

[0017] Item 7. A dyeing composition comprising any one of items 1 to 3 blue pigment and / or any one of items 4 to 6 red pigment.

[0018] Item 8. The dyeing composition according to Item 7, wherein the dyeing composition is a hair dyeing composition.

[0019] Item 9. The dyeing composition according to Item 8, wherein the dyeing composition is used for dyeing gray hair.

[0020] Item 10. The dyeing composition according to Item 7, wherein the dyeing composition is a fiber dyeing composition.

[0021] Item 11. A dyeing method for dyeing hair or fibers using the dyeing composition described in Item 8 or 10.

[0022] Item 12. Use of the blue pigment of any one of Items 1 to 3 and / or the red pigment of any one of Items 4 to 6 for the manufacture of hair dyeing compositions or fiber dyeing compositions.

[0023] Invention Effects The blue or red pigment of the present invention has good dyeing properties when used as a dye, and exhibits excellent colorfastness in the washing treatment of dyed or dyed fibers using cleaning agents such as shampoo and soap.

[0024] Furthermore, when the dyeing composition of the present invention is used as a hair dyeing composition, by containing the blue pigment and / or red pigment of the present invention, the colorfastness during the washing process of dyed hair using shampoo is significantly improved. Therefore, compared with conventional hair dyeing products using gardenia blue or red pigment, the hair color can be maintained for a longer time. As a result, the frequency of hair dyeing can be reduced.

[0025] Furthermore, when the dyeing composition of the present invention is used as a hair dyeing composition, it can exhibit good hair dyeing properties by containing the blue pigment and / or red pigment of the present invention. Therefore, it can reduce the amount of dyeing auxiliary agents used in the past, or suppress damage to hair and scalp, or suppress dyeing of skin, etc. during hair dyeing.

[0026] Furthermore, when the dyeing composition of the present invention is used as a hair dyeing composition, the blue pigment and / or red pigment of the present invention, which have good hair dyeing properties, are used as direct dyes. Therefore, it also has the advantage of fewer compositional limitations and can provide hair dyeing products with various compositions and forms. Attached Figure Description

[0027] Figure 1 A graph showing the degree of color fading after shampoo washing of blue-dyed goat hair bundles dyed with a blue dye solution containing the blue pigment manufactured in Example 1 (from left to right: undyed goat hair bundles, before shampoo washing, after one shampoo washing, and after seven shampoo washings). The following... Figures 2-10 Similarly.

[0028] Figure 2 A graph showing the degree of color fading after shampooing treatment of blue-dyed goat hair bundles dyed with a blue dye solution containing the blue pigment manufactured in Example 2.

[0029] Figure 3 A graph showing the degree of color fading after shampooing treatment of blue-dyed goat hair bundles dyed with a blue dye solution containing the blue pigment manufactured in Example 3.

[0030] Figure 4 A graph showing the degree of color fading after shampooing treatment of blue-dyed goat hair bundles dyed with a blue dye solution containing the blue pigment manufactured in Example 4.

[0031] Figure 5 A graph showing the degree of color fading after shampooing treatment of blue-dyed goat hair bundles dyed with a blue dye solution containing the blue pigment manufactured in Example 5.

[0032] Figure 6 A graph showing the degree of color fading after shampooing treatment of blue-dyed goat hair bundles dyed with a blue dye solution containing the blue pigment manufactured in Example 6.

[0033] Figure 7 A graph showing the degree of color fading after shampooing treatment of blue-dyed goat hair bundles dyed with a blue dye solution containing the blue pigment manufactured in Example 7.

[0034] Figure 8 A graph showing the degree of color fading after shampooing treatment of blue-dyed goat hair bundles dyed with a blue dye solution containing the blue pigment manufactured in Example 8.

[0035] Figure 9 A graph showing the degree of color fading after shampooing treatment of blue-dyed goat hair bundles dyed with a blue dye solution containing the blue pigment manufactured in Example 9.

[0036] Figure 10 A graph showing the degree of color fading after washing with shampoo on a blue-dyed goat hair bundle dyed with a blue dye solution containing gardenia blue pigment manufactured in Comparative Example 1.

[0037] Figure 11 A graph showing the ΔL and ΔE values ​​of blue-dyed goat hair bundles dyed with a blue dye solution containing the blue pigment manufactured in Example 1 before shampoo washing treatment (0 times), after 1 shampoo washing treatment, and after 7 shampoo washing treatments.

[0038] Figure 12 A graph showing the ΔL and ΔE values ​​of blue-dyed goat hair bundles dyed with a blue dye solution containing the blue pigment manufactured in Example 2 before shampoo washing treatment (0 times), after 1 shampoo washing treatment, and after 7 shampoo washing treatments.

[0039] Figure 13A graph showing the ΔL and ΔE values ​​of blue-dyed goat hair bundles dyed with a blue dye solution containing the blue pigment manufactured in Example 3 before shampoo washing treatment (0 times), after 1 shampoo washing treatment, and after 7 shampoo washing treatments.

[0040] Figure 14 A graph showing the ΔL and ΔE values ​​of blue-dyed goat hair bundles dyed with a blue dye solution containing the blue pigment manufactured in Example 4 before shampoo washing treatment (0 times), after 1 shampoo washing treatment, and after 7 shampoo washing treatments.

[0041] Figure 15 A graph showing the ΔL and ΔE values ​​of blue-dyed goat hair bundles dyed with a blue dye solution containing the blue pigment manufactured in Example 5 before shampoo washing treatment (0 times), after 1 shampoo washing treatment, and after 7 shampoo washing treatments.

[0042] Figure 16 A graph showing the ΔL and ΔE values ​​of blue-dyed goat hair bundles dyed with a blue dyeing solution containing gardenia blue pigment manufactured in Comparative Example 1 before shampoo washing treatment (0 times), after 1 shampoo washing treatment, and after 7 shampoo washing treatments.

[0043] Figure 17 A graph showing the degree of color fading after shampoo washing of red-dyed goat hair bundles dyed with a red dye solution containing the red pigment manufactured in Example 10 (from left to right: undyed goat hair bundles, before shampoo washing, after one shampoo washing, and after seven shampoo washings). The following... Figures 18-20 Similarly.

[0044] Figure 18 A graph showing the degree of color fading after shampooing treatment of red-dyed goat hair bundles dyed with a red dye solution containing the red pigment manufactured in Example 11.

[0045] Figure 19 A graph showing the degree of color fading after shampooing treatment of red-dyed goat hair bundles dyed with a red dye solution containing the red pigment manufactured in Example 12.

[0046] Figure 20 A graph showing the degree of color fading after washing with shampoo on a red dye solution containing gardenia red pigment manufactured in Comparative Example 2, which was used to dye a red-dyed goat hair bundle.

[0047] Figure 21 A graph showing the ΔL and ΔE values ​​of red-dyed goat hair bundles dyed with a red dyeing solution containing the red pigment manufactured in Example 10 before shampoo washing treatment (0 times), after 1 shampoo washing treatment, and after 7 shampoo washing treatments.

[0048] Figure 22 A graph showing the ΔL and ΔE values ​​of red-dyed goat hair bundles dyed with a red dyeing solution containing gardenia red pigment manufactured in Comparative Example 2 before shampoo washing treatment (0 times), after 1 shampoo washing treatment, and after 7 shampoo washing treatments.

[0049] Figure 23 The graph shows the degree of staining and fading when the color treatment and shampoo washing operations are repeated 3 times each using the color treatment made with gardenia blue pigment obtained in Comparative Example 1.

[0050] Figure 24 The graph shows the degree of staining and fading when the dyeing operation and shampoo washing operation are repeated 3 times each using the coloring care agent made with the blue pigment obtained in Example 1.

[0051] Figure 25 A graph showing the ΔE values ​​when the dyeing operation and shampoo washing operation were repeated 3 times each using the coloring care agent made with gardenia blue pigment obtained in Comparative Example 1.

[0052] Figure 26 A graph showing the ΔE value when the coloring and shampooing operations are repeated 3 times each using the coloring care agent made with the blue pigment obtained in Example 1.

[0053] Figure 27 A graph illustrating the degree of color fading after hand washing of polyester fabric dyed with a blue dye solution containing the blue pigment manufactured in Example 1 (from left to right: undyed polyester fabric, dyed polyester fabric, and hand-washed polyester fabric). The following... Figures 28-34 Similarly.

[0054] Figure 28 A graph showing the degree of color fading after hand washing of nylon fabric dyed with a blue dye solution containing the blue pigment manufactured in Example 1.

[0055] Figure 29 A graph showing the degree of color fading after hand washing of silk fabric dyed with a blue dye solution containing the blue pigment manufactured in Example 1.

[0056] Figure 30 A graph showing the degree of color fading after hand washing of cotton fabric dyed with a blue dye solution containing the blue pigment manufactured in Example 1.

[0057] Figure 31 A graph showing the degree of color fading after hand washing of polyester fabric dyed with a red dye solution containing the red pigment manufactured in Example 12.

[0058] Figure 32A graph showing the degree of color fading after hand washing of nylon fabric dyed with a red dye solution containing the red pigment manufactured in Example 10.

[0059] Figure 33 A graph showing the degree of color fading after hand washing of silk fabric dyed with a red dye solution containing the red pigment manufactured in Example 10.

[0060] Figure 34 A graph showing the degree of color fading after hand washing of cotton fabric dyed with a red dye solution containing the red pigment manufactured in Example 10.

[0061] Figure 35 A graph showing the degree of color fading after shampooing treatment of blue-dyed human hair strands dyed with a blue dye solution containing the blue pigment manufactured in Example 1 (from left to right: undyed human hair strand, before shampooing treatment, after one shampooing treatment, and after seven shampooing treatments). The following... Figures 36-41 Similarly.

[0062] Figure 36 A graph showing the degree of color fading after shampooing of a strand of blue-dyed human hair dyed with a blue dye solution containing the blue pigment manufactured in Example 13.

[0063] Figure 37 A graph showing the degree of color fading after shampooing of a human hair strand dyed with a blue dye solution containing the blue pigment manufactured in Example 14.

[0064] Figure 38 A graph showing the degree of color fading after shampooing of a human hair strand dyed with a blue dye solution containing the blue pigment manufactured in Example 15.

[0065] Figure 39 A graph showing the degree of color fading after washing a strand of blue-dyed human hair dyed with a blue dye solution containing gardenia blue pigment manufactured in Comparative Example 1.

[0066] Figure 40 A graph showing the degree of color fading after shampooing treatment of a red-dyed human hair strand dyed with a red dye solution containing the red pigment manufactured in Example 10.

[0067] Figure 41 A graph showing the degree of color fading after washing a red-dyed human hair strand dyed with a red dye solution containing gardenia red pigment manufactured in Comparative Example 2. Detailed Implementation

[0068] 1. Blue pigment The novel blue pigment of the present invention is characterized by being obtained by reacting a mixture of an aglycone containing an iridoid glycoside and a nitrogen-containing compound, wherein the nitrogen-containing compound has two or more nitrogen-containing groups, at least one of which is a primary amino or primary ammonium group, and the nitrogen-containing compound does not have a carboxyl group. In particular, it is obtained by using the above-mentioned nitrogen-containing compound instead of the protein hydrolysate or amino acid used in the conventional manufacture of gardenia blue pigment. When used as a direct dye in hair dyeing compositions or fiber dyeing compositions, the novel blue pigment of the present invention can impart good dyeing properties and excellent colorfastness to the hair dyeing compositions or fiber dyeing compositions. The novel blue pigment of the present invention will be described in detail below.

[0069] 1-1. Methods for manufacturing blue pigment The method for manufacturing the blue pigment of the present invention is as long as it is a method of reacting a mixture containing an aglycone of an iridoid glycoside and a nitrogen-containing compound, wherein the nitrogen-containing compound has two or more nitrogen-containing groups, at least one of which is a primary amino or primary ammonium group, and the nitrogen-containing compound does not have a carboxyl group. There are no other particular limitations, and known methods can be used. For example, the following methods can be used: (1) obtaining an aglycone of an iridoid glycoside and then reacting a mixture containing the aglycone and the above-mentioned nitrogen-containing compound (hereinafter also referred to as "manufacturing method A") and (2) a method of causing β-glucosidase to function in a mixture containing an iridoid glycoside and the above-mentioned nitrogen-containing compound (hereinafter also referred to as "manufacturing method B"). Hereinafter, manufacturing methods A and B of the blue pigment of the present invention will be described in detail.

[0070] 1-1-1. Method A for manufacturing blue pigment Method A for manufacturing the blue pigment of the present invention is a method of obtaining an aglycone of an iridoid glycoside and then reacting a mixture containing the aglycone and the above-mentioned nitrogen-containing compound.

[0071] <Aglycones of iridoid glycosides> There are no particular limitations on iridoid glycosides, for example: iridoid glycosides that can be used as raw materials for the manufacture of common gardenia blue pigment, and iridoid glycosides obtained from indigo olive (Genipa Americana) (known as huito or jagua).

[0072] There are no particular restrictions on the methods for obtaining iridoid glycosides. For example, methods can be used to extract iridoid glycosides from plants containing iridoid glycosides, such as the fruit of Gardenia jasminoides (Rubiaceae family) and the fruit of Gynostemma pentaphyllum (Rubiaceae family). The following is a representative example of a method for obtaining iridoid glycosides from the fruit of Gardenia jasminoides (Rubiaceae family) through extraction.

[0073] The fruit of Gardenia jasminoides, a member of the Rubiaceae family, used as a raw material for extraction can be dried, finely chopped, or pulverized as needed.

[0074] The extraction solvent used in the extraction process is limited to the ability to dissolve iridoid glycosides, and there are no particular limitations. Examples include water, alcohol (preferably ethanol), or mixtures thereof.

[0075] The temperature and time during extraction can be set appropriately according to the type of extraction solvent used. For example, 0.5 to 24 hours at around 20 to 100°C can be used.

[0076] After extraction, the solid components are removed to obtain an extract containing iridoid glycosides. This extract can be used directly as iridoid glycosides, or it can be concentrated or dried before use. It should be noted that this extract contains a yellow pigment in addition to iridoid glycosides; therefore, the yellow pigment can be removed from the extract as needed. The removal of the yellow pigment can be carried out using known methods employing adsorption resins. Furthermore, the iridoid glycoside can be a single component or contain two or more components, but from the viewpoint of further improving colorfastness, genipin is preferred.

[0077] There are no particular restrictions on the methods for obtaining the aglycones of iridoid glycosides; for example, they can be obtained by utilizing... β - It is obtained by treating iridoid glycosides with glucosidase.

[0078] As β - Glucosidase, without particular restrictions, can be used as commonly used in the manufacture of gardenia blue pigment. β - Glucosidases, for example, can be derived from Aspergillus niger, Trichoderma reesei, Trichoderma viride, almond kernels, etc. β -Glucosidase. As... β - Glucosidases can also be commercially available products such as Sumizyme C6000, Sumizyme AC, Sumizyme C, Sumizyme X, Sumizyme BGT, Sumizyme BGA (trade name; manufactured by Shin Nippon Chemical Co., Ltd.), Cellulosin AC40, Cellulosin T3, Cellulosin AL (trade name; manufactured by HBI Co., Ltd.), Onozuka 3S, Y-NC (trade name; manufactured by Yakult Pharmaceutical Co., Ltd.), Cellulase A "Amano" 3, Cellulase T "Amano" 4 (trade name; manufactured by Amano Enzyme Products Co., Ltd.).

[0079] useβ - There are no particular restrictions on the enzymatic treatment with glucosidase, as long as the conditions are suitable for generating the aglycone of iridoid glycosides. For example, in an aqueous solution containing iridoid glycosides, the concentration can be approximately 1–500 U relative to 1 g of iridoid glycoside. β - Glucosidase can coexist.

[0080] Regarding the temperature conditions required for β-glucosidase to function, β - The effective temperature range of glucosidase can be set appropriately, for example, around 20 to 70°C, preferably around 40 to 60°C.

[0081] Regarding the pH conditions for β-glucosidase to function, β The effective pH range for glucosidase can be set appropriately, for example, around pH 4 to 5, with pH 4.2 to 4.8 being the preferred range.

[0082] Thus, by activating β-glucosidase to act on iridoid glycosides, the aglycone of the iridoid glycoside is obtained. Furthermore, the resulting solution can be purified using conventional methods such as resin treatment or membrane treatment, if necessary.

[0083] <Nitrogen-containing compounds> The nitrogen-containing compound used to obtain the blue pigment of the present invention is characterized by having two or more nitrogen-containing groups, at least one of which is a primary amino or primary ammonium group, and the nitrogen-containing compound does not have a carboxyl group. Conventional gardenia blue pigments are manufactured using protein hydrolysates or amino acids, but in the present invention, by using the aforementioned nitrogen-containing compound instead of these, a novel blue pigment different from conventional gardenia blue pigments can be obtained. Furthermore, when used as a dye, the blue pigment of the present invention exhibits superior colorfastness in the washing treatment of dyed or dyed fibers using shampoos, soaps, or other cleaning agents compared to conventional gardenia blue pigments.

[0084] Nitrogen-containing groups refer to groups containing one or more nitrogen atoms and without a carbonyl group. Examples include: primary amino groups, acyclic secondary or tertiary amino groups containing one nitrogen atom, guanidinyl, hydrazine, hydrazone, amidine, azo, diazonyl, and nitro groups; aliphatic heterocycles containing one nitrogen atom, such as pyrrolidine rings, pyrrololine rings, and piperidine rings (e.g., 5-membered rings, 6-membered rings); aliphatic heterocycles containing two nitrogen atoms, such as imidazoline rings, imidazoline rings, and piperazine rings (e.g., 5-membered rings, 6-membered rings); and aliphatic heterocycles containing three nitrogen atoms, such as hexahydrotriazine rings. Aromatic heterocycles containing one nitrogen atom, such as pyrrole rings and pyridine rings; aromatic heterocycles containing two nitrogen atoms, such as imidazole rings, pyrazole rings, pyridazine rings, pyrimidine rings, and pyrazine rings; aromatic heterocycles containing three nitrogen atoms, such as triazole rings and triazine rings; and fused heterocycles containing one to four nitrogen atoms, such as indole, isoindole, benzimidazole, benzotriazole, purine, quinoline, and isoquinoline. It should be noted that the nitrogen-containing groups mentioned above can be in the form of ammonium groups (ammonium ions) (e.g., primary amino groups can be in the form of primary ammonium groups). These nitrogen-containing groups can be located at the end of the molecular backbone, outside the end of the molecular backbone, or constitute part of the molecular backbone. Examples of secondary or tertiary amine groups include: straight-chain or branched aliphatic saturated hydrocarbon groups with 1 to 24 carbon atoms; straight-chain or branched aliphatic unsaturated hydrocarbon groups with 2 to 12 carbon atoms; alicyclic saturated hydrocarbon groups with 5 to 12 carbon atoms forming the ring; alicyclic unsaturated hydrocarbon groups with 5 to 12 carbon atoms forming the ring; aromatic hydrocarbon groups (e.g., phenyl, tolyl, xylyl, naphthyl, and biphenyl); or groups formed by bonding one or more of these groups to a nitrogen atom. Furthermore, the hydrogen atom in the nitrogen-containing group can be replaced by substituents such as alkyl, alkenyl, alkynyl, aryl, hydroxyl, alkoxy, or halogen groups. Additionally, the nitrogen-containing compound may have one or more of the aforementioned nitrogen-containing groups. Furthermore, the nitrogen-containing compound has two or more of the aforementioned nitrogen-containing groups (at least one of which is a primary amino or primary ammonium group), preferably four or fewer, more preferably three or fewer, and even more preferably two. Examples of nitrogen-containing compounds having four of the aforementioned nitrogen-containing groups include spermine. Examples of nitrogen-containing compounds having three of the aforementioned nitrogen-containing groups include spermidine. Among the aforementioned nitrogen-containing groups, from the viewpoint of obtaining a blue pigment with even better colorfastness and excellent staining properties, guanidine groups and nitrogen-containing heterocycles (more preferably aromatic heterocycles containing two nitrogen atoms (5-membered or 6-membered rings), and even more preferably imidazole rings) are preferred.

[0085] In nitrogen-containing compounds, two or more nitrogen-containing groups can be directly bonded or bonded via a linking group (a group that connects the nitrogen-containing groups to each other). There are no particular limitations on the linking group; examples include: straight-chain or branched aliphatic saturated hydrocarbon groups with 1 to 20 carbon atoms; straight-chain or branched aliphatic unsaturated hydrocarbon groups with 2 to 12 carbon atoms; alicyclic saturated hydrocarbon groups with 5 to 12 carbon atoms forming the ring; alicyclic unsaturated hydrocarbon groups with 5 to 12 carbon atoms forming the ring; aromatic hydrocarbon groups (e.g., phenyl, tolyl, xylyl, naphthyl, and biphenyl); and groups formed by the bonding of two or more of these. Furthermore, nitrogen-containing compounds may have other substituents or functional groups besides the aforementioned nitrogen-containing groups in the molecule. Examples of other substituents or functional groups include hydroxyl groups, alkoxy groups, halogen groups, ketone groups, ester bonds, amide bonds, imide bonds, ether bonds, thioether bonds, carbamate bonds, and urea bonds. In addition, nitrogen-containing compounds can be in the form of salts such as sulfates and hydrochlorides.

[0086] From the viewpoint of obtaining a blue pigment with even better colorfastness and excellent staining properties, compounds of the following general formula (1), general formula (2), general formula (3), general formula (4), 4-(aminoalkyl)pyridine, 4-(aminoalkyl)piperidine, 4-(aminoalkyl)aniline, alkylene diamine, N-alkylalkylene diamine, N,N-dialkylalkylene diamine, N-(hydroxyalkyl)alkylene diamine and their salts (e.g., sulfuric acid) are preferred as nitrogen-containing compounds. At least one of the following (salts and hydrochlorides, etc.), more preferably selected from guanidine, aminoguanidine, histamine, arginine methyl ester, arginine ethyl ester, 4-aminomethylpyridine, 4-(aminomethyl)piperidine, 2-(4-aminophenyl)ethylamine, cadaverine, N-ethylethylenediamine, N,N-diethyl-1,3-diaminopropane, N-(2-hydroxypropyl)ethylenediamine and their salts, further preferably selected from guanidine, aminoguanidine, histamine, cadaverine, N-(2-hydroxypropyl)ethylenediamine and their salts, particularly preferably guanidine and / or their salts.

[0087] [Chemistry 1] (where R is in the formula) 1 It is a straight-chain or branched alkylene group having 2 to 18 carbon atoms. [Chemistry 2] (where R is in the formula) 2 It is an alkyl group consisting of 1 to 4 carbon atoms in a straight-chain or branched form, or an alkenyl group consisting of 2 to 4 carbon atoms in a straight-chain or branched form. [Chemistry 3] (where R is in the formula) 3 It is a single bond, or a straight-chain or branched alkylene group having 1 to 3 carbon atoms. [Chemistry 4] (where R is in the formula) 4 R is a straight-chain or branched alkylene group having 3 to 4 carbon atoms. 5 It is an alkyl group that has 1 to 8 carbon atoms and is either straight-chain or branched. <Manufacturing Method A> The method A for manufacturing the blue pigment of the present invention is not particularly limited except for reacting a mixture containing the aglycone of the iridoid glycoside and the nitrogen-containing compound. For example, a method can be described as adding the nitrogen-containing compound to an aqueous solution containing the aglycone of the iridoid glycoside and reacting it.

[0088] The amount of nitrogen-containing compound added needs to be appropriately adjusted according to the content of the aglycone of the iridoid glycoside in the mixture (e.g., aqueous solution). For example, it is about 0.2 to 2 moles relative to 1 mole of the aglycone of the iridoid glycoside, preferably 0.4 to 1.5 moles, and more preferably 0.8 to 1.2 moles. It should be noted that, to the extent that it does not impair the effects of the present invention, the mixture may contain not only the above-mentioned nitrogen-containing compound, but may also contain at least one selected from amine compounds, protein decomposition products, and amino acids other than the above-mentioned nitrogen-containing compounds.

[0089] The pH during the reaction needs to be adjusted appropriately according to the nitrogen-containing compound used, for example, around 5.5 to 8.5, preferably 6.0 to 8.0.

[0090] The reaction temperature needs to be adjusted appropriately according to the reactivity of the nitrogen-containing compound used, for example, around 20 to 80°C. From the viewpoint of promoting the reaction and inhibiting the formation of byproducts, 30 to 50°C is preferred.

[0091] The reaction time needs to be adjusted appropriately based on the type and amount of the aglycone and nitrogen-containing compound used in the iridoid glycoside, as well as the temperature conditions. For example, it is approximately 5 to 72 hours, preferably 20 to 40 hours. It should be noted that, from the viewpoint of promoting the reaction, stirring or shaking is preferred during the reaction.

[0092] After the reaction is complete, solid components are removed by solid-liquid separation processes such as centrifugation and filtration, thereby obtaining 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 can be used directly in the dyeing composition of the present invention, or it can be concentrated as needed to prepare a concentrated solution, or it can be dried to prepare a powder for use.

[0093] In addition, the blue pigment obtained by the present invention can be refined as needed to remove unnecessary components other than the blue pigment.

[0094] 1-1-2. Method B for manufacturing blue pigment Method B for manufacturing the blue pigment of the present invention is a method of making β-glucosidase function in a mixture containing iridoid glycosides and the above-mentioned nitrogen-containing compounds.

[0095] <Iridoid Glycosides> As the iridoid glycoside used in manufacturing method B, the iridoid glycoside described in the above-mentioned "1-1-1. Manufacturing method A of blue pigment" column is used.

[0096] <Nitrogen-containing compounds> The nitrogen-containing compound used in manufacturing method B is the nitrogen-containing compound described in the "1-1-1. Manufacturing method A of blue pigment" section above.

[0097] < β -Glucosidase> As used in manufacturing method B β - Glucosidase, which can be used as described in the "1-1-1. Method A for Manufacturing Blue Pigment" section above. β - Glucosidase.

[0098] <Manufacturing Method B> Method B for producing the blue pigment of the present invention is not particularly limited except for the method of enabling β-glucosidase to function in a mixture containing the above-mentioned iridoid glycosides and the above-mentioned nitrogen-containing compounds. It should be noted that, to the extent that it does not impair the effects of the present invention, the mixture may contain not only the above-mentioned nitrogen-containing compounds, but may also contain at least one of amine compounds, protein decomposition products, and amino acids other than the above-mentioned nitrogen-containing compounds.

[0099] The treatment to activate β-glucosidase can be carried out under conditions that allow the blue pigment of the present invention to be generated in a mixture containing the above-mentioned iridoid glycoside and the above-mentioned nitrogen-containing compound. For example, it can be added to a mixture obtained by mixing the above-mentioned iridoid glycoside and the above-mentioned nitrogen-containing compound in water. β -Glucosidase and incubate under aerobic conditions.

[0100] Regarding the treatment used to activate β-glucosidase, specifically, it is sufficient to achieve a concentration of approximately 1-50% by mass of the aforementioned iridoid glycoside, 1-50% by mass of the aforementioned nitrogen-containing compound, and approximately 1-500 U relative to 1 g of the aforementioned iridoid glycoside. β - Glucosidase can coexist under aerobic conditions.

[0101] Regarding the temperature conditions required for β-glucosidase to function, β - The effective temperature range of glucosidase can be set appropriately, for example, around 20 to 70°C, preferably around 40 to 60°C.

[0102] Regarding the pH conditions for β-glucosidase to function, β The effective pH range for glucosidase can be set appropriately, for example, around pH 3 to 6.5, with pH 4 to 5 being preferred.

[0103] Regarding the timing of β-glucosidase activation, it depends on the method used. β The amount of glucosidase, the above-mentioned iridoid glycosides, and the temperature conditions can be set appropriately. For example, an hour of 1 to 100 hours is acceptable, and an hour of 10 to 80 hours is preferred.

[0104] There are no particular limitations on the methods for setting aerobic conditions to enable β-glucosidase to function. Examples include mechanical methods such as stirring and shaking; methods such as blowing oxygen-containing gases such as air into the system; and combinations of these methods.

[0105] Thus, the blue pigment of the present invention is generated by activating β-glucosidase. After activating β-glucosidase, solid components are removed by solid-liquid separation processes such as centrifugation and filtration, thereby obtaining 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 can be used directly in the dyeing composition of the present invention, or it can be concentrated as needed and used as a concentrated solution, or it can be dried and used as a powder.

[0106] In addition, the blue pigment obtained by the present invention can also be refined as needed to remove unnecessary components other than the blue pigment.

[0107] 1-2. Uses of blue pigment The blue pigment of this invention can be used in food coloring materials and dyes, and is particularly suitable as a dye for dyeing hair or fibers.

[0108] 2. Red pigment The novel red pigment of the present invention is characterized by being obtained by reacting an aglycone containing an ester hydrolysate of a cycloalkenyl ether glycoside with a nitrogen-containing compound, wherein the nitrogen-containing compound has two or more nitrogen-containing groups, at least one of which is a primary amino or primary ammonium group, and the nitrogen-containing compound does not have a carboxyl group. In particular, it is obtained by using the above-mentioned nitrogen-containing compound instead of the protein hydrolysate or amino acid used in the manufacture of conventional gardenia red pigment. When used as a direct dye in hair dyeing compositions or fiber dyeing compositions, the novel red pigment of the present invention can impart good dyeing properties and excellent colorfastness to the hair dyeing compositions or fiber dyeing compositions. The novel red pigment of the present invention will be described in detail below.

[0109] 2-1. Methods for manufacturing red pigment The method for producing the red pigment of the present invention is simply a method of reacting a mixture of an aglycone containing an ester hydrolysate of an iridoid glycoside and a nitrogen-containing compound, wherein the nitrogen-containing compound has two or more nitrogen-containing groups, at least one of which is a primary amino or primary ammonium group, and the nitrogen-containing compound does not have a carboxyl group. There are no other particular limitations, and known methods can be used. For example, the following methods can be used: (1) obtaining an aglycone containing an ester hydrolysate of an iridoid glycoside, and then reacting a mixture containing the aglycone and the above-mentioned nitrogen-containing compound (hereinafter also referred to as "Production Method C"), and (2) a method of causing β-glucosidase to function in a mixture containing an ester hydrolysate of an iridoid glycoside and the above-mentioned nitrogen-containing compound (hereinafter also referred to as "Production Method D"). Hereinafter, the production methods C and D of the red pigment of the present invention will be described in detail.

[0110] 2-1-1. Methods for manufacturing red pigment C The red pigment manufacturing method C of the present invention is a method of obtaining the aglycone of the ester hydrolysate of iridoid glycosides, and then reacting a mixture containing the aglycone and the above-mentioned nitrogen-containing compound.

[0111] <Aglycones of ester hydrolysates of iridoid glycosides> As the iridoid glycoside used in manufacturing method C, the iridoid glycoside described in the above-mentioned "1-1-1. Manufacturing method A of blue pigment" column is used.

[0112] Ester hydrolysates of iridoid glycosides refer to compounds in which the 4-position group of the iridoid skeleton is a carboxyl group. There are no particular limitations on the types of ester hydrolysates of iridoid glycosides; examples include ester hydrolysates of iridoid glycosides that can be used as raw materials for the manufacture of common gardenia red pigment, and ester hydrolysates of iridoid glycosides obtained from Genipa Americana.

[0113] There are no particular limitations on the method for obtaining the ester hydrolysate of iridoid glycosides. For example, a method can be given by hydrolyzing the ester bond at position 4 of the iridoid skeleton of the iridoid glycoside to convert it into a carboxyl group.

[0114] There are no particular limitations on the method for hydrolyzing the ester bond at the 4-position of the iridoid skeleton of iridoid glycosides. For example, the method commonly used in the production of gardenia red pigment can be used. Specifically, alkaline hydrolysis, acid hydrolysis, and enzymatic hydrolysis can be cited.

[0115] There are no particular restrictions on the types of alkali used in alkaline hydrolysis; examples include sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. One type of alkali can be used alone, or two or more can be used in combination.

[0116] There are no particular restrictions on the types of acids used in acid hydrolysis. Examples include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; and organic acids such as citric acid, formic acid, acetic acid, oxalic acid, ascorbic acid, tartaric acid, and fumaric acid. One type of acid can be used alone, or two or more can be used in combination.

[0117] Regarding the type of enzyme used in enzymatic hydrolysis, there are no particular restrictions as long as it can hydrolyze the ester bond at the 4-position of the iridoid skeleton of the iridoid glycoside; for example, esterases can be cited.

[0118] Among these hydrolysis methods, alkaline hydrolysis is preferred. The conditions for alkaline hydrolysis can be any conditions used in the usual production of gardenia red pigment; for example, coexisting iridoid glycosides and excess alkali in an aqueous solution at approximately 10–80°C, preferably 30–60°C, for approximately 1–72 hours, preferably 20–48 hours. After alkaline hydrolysis, it is preferable to pre-add acid to adjust the pH to below neutral.

[0119] There are no particular limitations on the method for obtaining the aglycone of the ester hydrolysate of iridoid glycosides; for example, it can be obtained by utilizing... β - It is obtained by enzymatic treatment of the ester hydrolysate of iridoid glycosides with glucosidase. Specifically, in the above "1-1-1. Method A for manufacturing blue pigment", the same method can be used except that the ester hydrolysate of iridoid glycosides is used instead of iridoid glycosides.

[0120] <Manufacturing Method C> The method C for producing the red pigment of the present invention is not particularly limited except for reacting the aglycone of the ester hydrolysate containing the iridoid glycoside with the mixture of the above-mentioned nitrogen-containing compound. For example, a method can be described by adding the above-mentioned nitrogen-containing compound to an aqueous solution containing the aglycone of the ester hydrolysate containing the iridoid glycoside and reacting it.

[0121] <Nitrogen-containing compounds> The nitrogen-containing compound used in manufacturing method C is the same as the one described in section "1-1-1. Manufacturing Method A of Blue Pigment". By using this nitrogen-containing compound, a novel red pigment, different from conventional gardenia red pigment, can be obtained. Furthermore, when used as a dye, the red pigment of the present invention exhibits superior colorfastness compared to conventional gardenia red pigment during the washing treatment of dyed or dyed fibers using detergents such as shampoo and soap.

[0122] From the viewpoint of obtaining a red pigment with even better colorfastness and excellent staining properties, compounds selected from the above general formula (1), the above general formula (2), the above general formula (3), the above general formula (4), 4-(aminoalkyl)pyridine, 4-(aminoalkyl)piperidine, 4-(aminoalkyl)aniline, alkylene diamine, N-alkylalkylene diamine, N,N-dialkylalkylene diamine, N-(hydroxyalkyl)alkylene diamine and their salts (e.g., sulfuric acid) are preferred as nitrogen-containing compounds. At least one of the following (salts and hydrochlorides, etc.), more preferably selected from guanidine, aminoguanidine, histamine, arginine methyl ester, arginine ethyl ester, 4-aminomethylpyridine, 4-(aminomethyl)piperidine, 2-(4-aminophenyl)ethylamine, cadaverine, N-ethylethylenediamine, N,N-diethyl-1,3-diaminopropane, N-(2-hydroxypropyl)ethylenediamine and their salts, further preferably selected from guanidine, aminoguanidine, histamine, cadaverine, N-(2-hydroxypropyl)ethylenediamine and their salts, particularly preferably guanidine and / or their salts.

[0123] The amount of nitrogen-containing compound added needs to be appropriately adjusted according to the content of the aglycone in the ester hydrolysate of the iridoid glycoside in the mixture (e.g., aqueous solution). For example, it is about 0.5 to 10 moles relative to 1 mole of the aglycone in the ester hydrolysate of the iridoid glycoside, preferably 1 to 8 moles, and more preferably 2 to 6 moles. It should be noted that, to the extent that it does not impair the effects of the present invention, the mixture may contain not only the above-mentioned nitrogen-containing compound, but also at least one selected from amine compounds, protein decomposition products, and amino acids other than the above-mentioned nitrogen-containing compounds.

[0124] The pH during the reaction needs to be adjusted appropriately depending on the nitrogen-containing compound used, for example, around 3.0 to 7.0, preferably 4.0 to 5.0.

[0125] The reaction temperature needs to be adjusted appropriately according to the reactivity of the nitrogen-containing compound used, for example, around 20 to 70°C. From the viewpoint of promoting the reaction and inhibiting the formation of byproducts, 30 to 60°C is preferred.

[0126] The reaction time needs to be adjusted appropriately based on the type and amount of aglycone and nitrogen-containing compounds in the hydrolysate of the iridoid glycoside used, as well as temperature conditions. For example, it is approximately 10 to 100 hours, preferably 20 to 80 hours. It should be noted that, from the viewpoint of promoting the reaction, stirring or shaking is preferred during the reaction.

[0127] After the reaction is complete, solid components are removed by solid-liquid separation processes such as centrifugation and filtration, thereby obtaining 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 can be used directly in the dyeing composition of the present invention, or it can be concentrated to prepare a concentrated solution as needed, or it can be dried to prepare a powder for use.

[0128] In addition, the red pigment obtained by the present invention can be refined as needed to remove unnecessary components other than the red pigment.

[0129] 2-1-2. Methods for manufacturing red pigment (D) The red pigment manufacturing method D of the present invention is a method of making β-glucosidase function in a mixture of an ester hydrolysate containing iridoid glycosides and the above-mentioned nitrogen-containing compound.

[0130] <Ester hydrolysates of iridoid glycosides> As the ester hydrolysate of the iridoid glycoside used in manufacturing method D, the ester hydrolysate of the iridoid glycoside described in the "2-1-1. Manufacturing method C of red pigment" section above is used.

[0131] <Nitrogen-containing compounds> The nitrogen-containing compound used in manufacturing method D is the same as the one described in section "1-1-1. Manufacturing Method A of Blue Pigment". By using this nitrogen-containing compound, a novel red pigment, different from conventional gardenia red pigment, can be obtained. Furthermore, when used as a dye, the red pigment of the present invention exhibits superior colorfastness compared to conventional gardenia red pigment during the washing treatment of dyed or dyed fibers using detergents such as shampoo and soap.

[0132] From the viewpoint of obtaining a red pigment with even better colorfastness and excellent staining properties, compounds selected from the above general formula (1), the above general formula (2), the above general formula (3), the above general formula (4), 4-(aminoalkyl)pyridine, 4-(aminoalkyl)piperidine, 4-(aminoalkyl)aniline, alkylene diamine, N-alkylalkylene diamine, N,N-dialkylalkylene diamine, N-(hydroxyalkyl)alkylene diamine and their salts (e.g., sulfuric acid) are preferred as nitrogen-containing compounds. At least one of the following (salts and hydrochlorides, etc.), more preferably selected from guanidine, aminoguanidine, histamine, arginine methyl ester, arginine ethyl ester, 4-aminomethylpyridine, 4-(aminomethyl)piperidine, 2-(4-aminophenyl)ethylamine, cadaverine, N-ethylethylenediamine, N,N-diethyl-1,3-diaminopropane, N-(2-hydroxypropyl)ethylenediamine and their salts, further preferably selected from guanidine, aminoguanidine, histamine, cadaverine, N-(2-hydroxypropyl)ethylenediamine and their salts, particularly preferably guanidine and / or their salts.

[0133] < β -Glucosidase> As used in manufacturing method D β - Glucosidase, which can be used as described in the "1-1-1. Method A for Manufacturing Blue Pigment" section above. β - Glucosidase.

[0134] <Manufacturing Method D> The method D for producing the red pigment of the present invention is simply a method of inducing β-glucosidase to function in a mixture containing the ester hydrolysate of the above-mentioned iridoid glycoside and the above-mentioned nitrogen-containing compound, and there are no particular limitations thereto. It should be noted that, to the extent that it does not impair the effects of the present invention, the mixture may contain not only the above-mentioned nitrogen-containing compound, but may also contain at least one selected from amine compounds, protein decomposition products, and amino acids other than the above-mentioned nitrogen-containing compounds.

[0135] The treatment to activate β-glucosidase can be carried out under conditions that allow the red pigment of the present invention to be generated in a mixture containing the ester hydrolysate of the above-mentioned iridoid glycoside and the above-mentioned nitrogen-containing compound. For example, it can be added to a mixture obtained by mixing the ester hydrolysate of the above-mentioned iridoid glycoside and the above-mentioned nitrogen-containing compound in water. β - Incubation with glucosidase is sufficient.

[0136] Regarding the treatment used to activate β-glucosidase, specifically, it is necessary to achieve a concentration of approximately 1-50% by mass of the ester hydrolysate of the aforementioned iridoid glycoside, 1-50% by mass of the aforementioned nitrogen-containing compound, and approximately 1-500 U relative to 1 g of the ester hydrolysate of the aforementioned iridoid glycoside.β - Glucosidase can coexist.

[0137] Regarding the temperature conditions required for β-glucosidase to function, β - The effective temperature range of glucosidase can be set appropriately, for example, around 20 to 70°C, preferably around 40 to 60°C.

[0138] Regarding the pH conditions for β-glucosidase to function, β The effective pH range for glucosidase can be set appropriately, for example, around pH 4 to 5, with pH 4.2 to 4.8 being the preferred range.

[0139] Regarding the timing of β-glucosidase activation, it depends on the method used. β - The amount of glucosidase, the ester hydrolysate of the above-mentioned iridoid glycosides, and the temperature conditions can be set appropriately, for example, about 10 to 100 hours, preferably about 20 to 80 hours.

[0140] Thus, the red pigment of the present invention is generated by activating β-glucosidase. After activating β-glucosidase, solid components are removed by solid-liquid separation processes such as centrifugation and filtration, thereby obtaining 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 can be used directly in the dyeing composition of the present invention, or it can be concentrated as needed and used as a concentrated solution, or it can be dried and used as a powder.

[0141] In addition, the red pigment obtained by the present invention can be refined as needed to remove unnecessary components other than the red pigment.

[0142] 2-2. Uses of Red Pigment The red pigment of the present invention can be used in food coloring materials and dyes, and is particularly suitable as a dye for dyeing hair or fibers.

[0143] 3. Dyeing composition The dyeing composition of the present invention contains the blue and / or red pigments 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 linen. Examples of animal fibers include wool, goat hair, and silk. Examples of chemical fibers include synthetic fibers, semi-synthetic fibers, and regenerated fibers. The choice of pigment is determined appropriately based on the desired color to be imparted to the hair or fiber.

[0144] The dyeing composition of the present invention is preferably a hair dyeing composition or a fiber dyeing composition. By incorporating the blue and / or red pigments of the present invention, the hair dyeing composition or fiber dyeing composition of the present invention exhibits significantly improved colorfastness during the washing process of dyed hair or dyed fibers using shampoos, soaps, or other cleaning agents. Therefore, compared to conventional hair dyes or fiber dyes using gardenia blue or red pigments, it has the characteristic of maintaining the color tone of dyed hair or dyed fibers for a longer period of time.

[0145] <Blue pigment content> In the hair dyeing composition or fiber dyeing composition of the present invention, the content of the blue pigment can be appropriately set according to the product form of the hair dyeing composition or fiber dyeing composition, the concentration of color to be imparted to the hair or fiber, etc. For example, the color value E of the hair dyeing composition or fiber dyeing composition... 10% 1cm The amount is 0.01 or more, preferably 0.01 to 40, more preferably 0.5 to 30, and even more preferably 1.0 to 20.

[0146] In this invention, "color value E" 10% 1cm "I" is a unit representing the concentration of pigment color. It refers to the value obtained by converting the absorbance of the maximum absorption wavelength measured using an absorbance meter within a reliable concentration range with a cuvette with an optical path length of 1 cm into the value in a 10% by mass solution.

[0147] The maximum absorption wavelength of the blue pigment of this invention is around 590 nm, therefore the color value E of the blue pigment of this invention is... 10% 1cm The absorbance can be determined by identifying the maximum absorption wavelength around 590 nm and measuring its absorbance. In the absence of a maximum absorption wavelength, it is sufficient to measure the absorbance at 590 nm. In the determination of the color value of the blue pigment of the present invention, citrate buffer (pH 7.0) (the solution described in the Ninth Edition of the Food Additives Standard) is used as the dilution solvent for the pigment solution used for absorbance measurement.

[0148] Furthermore, in the hair dyeing composition or fiber dyeing 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.

[0149] <Content of red pigment> In the hair dyeing composition or fiber dyeing composition of the present invention, the content of the red pigment of the present invention can be appropriately set according to the product form of the hair dyeing composition or fiber dyeing composition, the concentration of color to be imparted to the hair or fiber, etc. For example, the color value E of the hair dyeing composition or fiber dyeing composition... 10% 1cm The amount is 0.1 or more, preferably 0.1 to 40, more preferably 0.1 to 30, and even more preferably 0.2 to 10.

[0150] The maximum absorption wavelength of the red pigment in this invention is located near 535 nm, therefore the color value E of the red pigment in this invention is... 10% 1cm The absorbance can be determined by identifying the maximum absorption wavelength around 535 nm and measuring its absorbance. In the absence of a maximum absorption wavelength, it is sufficient to measure the absorbance at 535 nm. In the determination of the color value of the red pigment of the present invention, an acetate buffer (pH 4.0) (the solution described in the Eighth Edition of the Food Additives Standard) is used as the dilution solvent for the pigment solution used for absorbance measurement.

[0151] Furthermore, in the hair dyeing composition or fiber dyeing 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.

[0152] <Penetration enhancer (dyeing aid)> The blue and red pigments of the present invention have good dyeing properties and provide sufficient dyeing effect even without the use of a penetration enhancer. Therefore, the hair dyeing composition or fiber dyeing composition of the present invention may not contain a penetration enhancer. However, a penetration enhancer may be included to further improve the dyeing properties of the pigment on hair or fiber by further promoting penetration into the hair or fiber.

[0153] As a penetration enhancer, any penetration enhancer that can promote the penetration of direct dyes into the hair or fiber is acceptable. Examples include: aromatic alcohols such as benzyl alcohol, 2-phenylethanol, cinnamyl alcohol, phenylpropanol, α-methylbenzyl alcohol, dimethylbenzylmethanol, benzyloxyethanol, phenoxyethanol, and p-anisole; lower monohydric alcohols such as ethanol and isopropanol; polyols such as ethylene glycol, propylene glycol, and 1,3-butanediol; and alkyl carbonates such as ethylene carbonate and propylene carbonate. These penetration enhancers can be used alone or in combination of two or more.

[0154] There are no particular limitations on the content of the penetration enhancer in the hair dyeing composition or fiber dyeing composition of the present invention. For example, 0 to 10% by mass, preferably 0 to 5.0% by mass, and more preferably 0 to 0.4% by mass can be cited. In conventional hair dyeing compositions or fiber dyeing compositions that use direct dyes, the content of the penetration enhancer is usually set to 0.5% by mass or more when it is combined with the dye. However, in the hair dyeing composition or fiber dyeing composition of the present invention, since the blue and red pigments of the present invention have high dyeing properties, the content of the penetration enhancer can be set to 0% by mass or a small amount, thereby eliminating or reducing safety concerns caused by the combination of the penetration enhancer.

[0155] <Reducing agent (dyeing aid)> The hair dyeing composition or fiber dyeing composition of the present invention may not contain a reducing agent. However, a reducing agent may be included to further improve the dyeing properties of the pigment on hair or fiber.

[0156] There are no particular restrictions on the types of reducing agents; examples include sulfites such as sodium sulfite and sodium bisulfite, sodium L-ascorbate, and compounds with thiol groups. These reducing agents can be used alone or in combination of two or more.

[0157] There are no particular limitations on the content of the reducing agent in the hair dyeing composition or fiber dyeing composition of the present invention. For example, 0 to 1% by mass, preferably 0 to 0.8% by mass, and more preferably 0 to 0.2% by mass can be cited. In conventional hair dyeing compositions or fiber dyeing compositions that use direct dyes, the content of the reducing agent is usually set to 0.3% by mass or more when it is combined with the dye. However, in the hair dyeing composition or fiber dyeing composition of the present invention, since the blue and red pigments of the present invention have high dyeing properties, the content of the penetration promoter can be set to 0% by mass or a small amount, thereby eliminating or reducing safety concerns caused by the combination with the reducing agent.

[0158] <Alkali (Dyeing Auxiliary Agent)> The hair dyeing composition or fiber dyeing composition of the present invention may not contain an alkali agent. However, an alkali agent may be included in order to further improve the dyeability of the pigment on the hair or fiber by opening the epidermis.

[0159] There are no particular restrictions on the types of alkali agents. Examples include: alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkyl alcohol amines and their salts 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 its salts; alkyl diamines and their salts 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 alkali agents can be used individually or in combination of two or more.

[0160] There are no particular limitations on the content of the alkali agent in the hair dyeing composition or fiber dyeing composition of the present invention, as long as it is appropriately set in a manner that can satisfy the pH range described later. For example, 0 to 1.5% by mass, preferably 0 to 1.0% by mass, and more preferably 0 to 0.4% by mass can be cited. In conventional hair dyeing compositions or fiber dyeing compositions that use direct dyes, the content of the alkali agent is usually set to 0.5% by mass or more when it is added. However, in the hair dyeing composition or fiber dyeing composition of the present invention, since the blue and red pigments of the present invention have high dyeing properties, the content of the alkali agent can be set to 0% by mass or a small amount, thereby eliminating or reducing safety concerns caused by the addition of the alkali agent.

[0161] <Other Ingredients> In addition to the blue and / or red pigments of the present invention, the hair dyeing composition or fiber dyeing composition of the present invention may, as needed, include direct dyes such as acid dyes, natural dyes, nitro dyes, and disperse dyes; reactive dyes such as oxidative dyes. The presence or absence of such other dyes depends on the desired hue to be imparted to the hair or fiber.

[0162] In addition to the components described above, the hair dyeing composition of the present invention may also contain other components commonly used in hair dyeing compositions. Such components may include, for example, higher alcohols, organosilicones, hydrocarbons, waxes, animal and vegetable oils, 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, humectants, pH adjusters, animal extracts, plant extracts, yeast extracts, vitamins, pigments, fragrances, ultraviolet absorbers, hair growth ingredients, hair nourishing ingredients, anti-dandruff ingredients, etc. The content of these components may be appropriately set according to the type of ingredients used and the product form of the hair dyeing composition.

[0163] <ph> The pH of the hair dyeing composition or the fiber dyeing composition of the present application is not particularly limited, and for example, it is appropriately set within a range of 3.0 to 11.0, preferably 3.0 to 9.0, more preferably 5.0 to 8.0, and further preferably 6.5 to 7.5, from the viewpoint of further improving the color loss resistance in the washing treatment of the dyed hair or the dyed fiber using a cleansing agent such as a shampoo or a soap.

[0164] <Application Object, Product Form, and the Like> The hair dyeing composition of the present application is used for dyeing hair. The hair dyeing composition of the present application can be applied to any one of white hair, black hair, brown hair, blond hair, and the like, but white hair is a preferable application object because the hair dyeing effect of the hair dyeing composition of the present application is easily exhibited. In addition, the hair dyeing composition of the present application can be a shampoo, a rinse, a conditioner, or a hair cream. In addition, the hair dyeing composition of the present application can also be incorporated in a shampoo, a rinse, a conditioner, or a hair cream.

[0165] In addition, the hair dyeing composition of the present application can be any one of a permanent hair dye, a semi-permanent hair dye, and the like, but a semi-permanent hair dye is preferable.

[0166] The permanent hair dye refers to a hair dye (in Japan, classified as a quasi drug) using a reactive dye such as an oxidative dye. In the case where the hair dyeing composition of the present application is formulated into the product form of a permanent hair dye, a reactive dye such as an oxidative dye can be incorporated in addition to the blue pigment and / or the red pigment of the present application as a dye.

[0167] The semi-permanent hair dye refers to a hair dye (in Japan, classified as a cosmetic material) using a direct dye, and in the case where the hair dyeing composition of the present application is formulated into the product form of a semi-permanent hair dye, the blue pigment and / or the red pigment of the present application is used as a direct dye, and other direct dyes can also be added as needed, and formulated.

[0168] 4. Dyeing Method To dye hair using the hair dyeing composition of the present application, it is only necessary to use a method corresponding to the product form of the hair dyeing composition, such as, for example, to apply it to the hair to be dyed and leave it for a prescribed period of time, and then rinse it with water or the like. If desired, it can also be rinsed using a shampoo. In addition, as to the temperature conditions when dyeing hair using the hair dyeing composition of the present application, it is only necessary to be at ordinary temperature, but there is a tendency for the higher the temperature at the time of dyeing, the more the dyeing effect is improved, and therefore it is only necessary to be appropriately set in accordance with the composition of the hair dyeing composition, the concentration of the color that should be imparted to the hair, and the like. In addition, as a method of dyeing fibers using the fiber dyeing composition of the present application, for example, there can be mentioned a method of immersing a fiber bundle or cloth in the fiber dyeing composition and leaving it for a prescribed period of time, and then rinsing it with water or the like. If desired, it can also be rinsed using a detergent.

[0169] Example The present application will be described more specifically below by way of examples, but the present application is not limited to these examples.

[0170] 1-1. Production of blue pigment A geniposide aqueous solution having a color value of about 1250 was measured out in such a way that the total color value (color value (E 10% 1cm A geniposide aqueous solution having a color value of about 1250 was measured out in such a way that the total color value (color value (E β - Glucosidase (1000 U / g, "Sumizyme C", manufactured by Shin Nippon Chemical Industry Co., Ltd.) was mixed with an appropriate amount of ion exchange water so that the total amount was 180 g (color value of geniposide: 300). This aqueous solution was heated to 50°C, the pH was adjusted to 4.5 with an aqueous sodium hydroxide solution, and enzyme reaction was performed for 20 hours to obtain a genipin aqueous solution (color value of genipin: about 240).

[0171] Next, 155 g of the genipin aqueous solution was measured out, and each of the nitrogen-containing compounds or arginine shown in Table 1 was added to the genipin aqueous solution in the amounts shown in Table 1, and the total amount was made 180 g with ion exchange water to prepare a pigment raw solution.

[0172] The pH of the prepared pigment raw solution was adjusted to 7.0 with an aqueous hydrochloric acid or sodium hydroxide solution, and oscillatory stirring was performed in a constant-temperature bath set to 35°C.

[0173] The pigment reaction solution was taken out from the constant-temperature bath 24 hours after the start of the reaction, and filtration was performed to separate the solid and the liquid to obtain a blue pigment solution. The obtained blue pigment solution was powderized by freeze-drying to obtain each blue pigment.

[0174] 1-2. Test of colorfastness to washing of blue pigment to goat hair Dissolve each blue pigment (equivalent to 0.5% based on a color value of 400) in water, and adjust the pH to 7.0 using sodium hydroxide solution or hydrochloric acid to obtain the respective blue staining solutions.

[0175] Mix 2 mL of each blue staining solution with 1 g of goat hair bundles, rinse with running water after 10 minutes, and dry with a dryer to obtain each blue-stained hair bundle.

[0176] For each blue-stained hair tuft and the unstained hair tuft without dyeing solution, a spectrophotometer (CM-5, Konica Minolta Japan Co., Ltd.) was used to determine... value, Value and Values ​​in the CIELAB color space ( Colors were represented in a color space. Measurement conditions were set as follows: light source D65 during reflection, field of view 10°, and measurement diameter 3mm. Three hair tufts were measured, and the average value was taken as the measured value.

[0177] Here, the CIELAB color space refers to the color space formed by representing chromaticity. axis, Orthogonal coordinates formed by axes and perpendicular coordinates to them The color-forming system of the color-forming three-dimensional structure composed of axes means When the value increases on the positive side, the red tone increases; when it increases on the negative side, the green tone increases. Additionally... When the value increases on the positive side, the yellow tone increases; when the value increases on the negative side, the blue tone increases. The value corresponds to brightness. =100 is white. =0 is black. The higher the value, the more likely it is to brighten.

[0178] Then, calculate the undyed hair tufts. value, Value and The values ​​are the ΔL and ΔE values ​​of each blue-dyed hair tuft at the baseline. The sign is chosen so that the ΔL value is positive. Here, the ΔL and ΔE values ​​refer to... value, value.

[0179] In addition, 2 mL of shampoo diluted 10 times with water was mixed with each of the above-mentioned blue-dyed hair tufts, rinsed with running water after 2 minutes, and dried with a dryer. This shampoo treatment was repeated 7 times. Then, after 1 or 7 shampoo treatments, the results were measured using the same method as above. value, Value and Calculate the values ​​of ΔL and ΔE.

[0180] In addition, the ΔL and ΔE values ​​after 7 shampoo washes were divided by the ΔL and ΔE values ​​after 1 shampoo wash to obtain the color retention rate (%), which is used as an indicator of colorfastness. It can be said that the higher the color retention rate (%), the less likely the hair will fade in shampoo, and the better the colorfastness. The results are shown in Table 1.

[0181] It should be noted that, in the initial shampooing process, insufficient pigment fixation and loss of hair hair can lead to less pigment loss in subsequent shampooing processes. Therefore, to evaluate from the perspective of pigment fixation, the color tone after one shampooing process is used as the benchmark.

[0182] [Table 1] As shown in Table 1, Figures 1-16 As shown, it was confirmed that the blue pigments of the present invention obtained in Examples 1-9, compared with the gardenia blue pigment obtained in Comparative Example 1, had larger ΔL and ΔE values ​​after 7 shampoo washes (higher hue retention rate) and excellent colorfastness. In particular, it was confirmed that the blue pigments of the present invention obtained in Examples 1, 7, or 9 using guanidine sulfate, cadaverine dihydrochloride, or N-(2-hydroxypropyl)ethylenediamine had very large ΔL and ΔE values ​​after 7 shampoo washes (very high hue retention rate) and excellent colorfastness compared with the gardenia blue pigment obtained in Comparative Example 1.

[0183] 2-1. Production of Red Pigment Measure 100g of color value (E) 10% 1cm A solution of approximately 1250 mL of genipin was mixed with 40 mL of a 30% sodium hydroxide aqueous solution. The resulting mixture was heated to 45°C for 24 hours to undergo a hydrolysis reaction, yielding an aqueous solution of genipin.

[0184] Then, an aqueous solution obtained by dissolving 151g of ascorbic acid and each nitrogenous compound or arginine shown in Table 2 in 400ml of ion-exchanged water was added to the above genipin acid aqueous solution, and the pH was adjusted to 4.5 with sodium hydroxide aqueous solution or hydrochloric acid. Further additives were then added to the resulting aqueous solution. β The mixture obtained by mixing 10g of glucosidase (1000U / g, "Sumizyme C", manufactured by Shin Nippon Chemical Industry Co., Ltd.) with 30ml of ion-exchanged water was then adjusted to pH 4.5 with sodium hydroxide aqueous solution to obtain the pigment reaction solution.

[0185] The obtained pigment reaction solution was shaken and stirred in a constant temperature bath set at 50°C. After 20 hours, the pigment reaction solution was removed from the constant temperature bath, heated to 90°C, and subjected to an enzyme inactivation reaction for 1 hour. Then, it was cooled with ice water and subjected to solid-liquid separation and filtration to obtain a red pigment solution.

[0186] The obtained red pigment solution was diluted with deionized water to obtain a 0.5% solution with a color value of 400, thus obtaining various red staining solutions.

[0187] 2-2. Test on the colorfastness of red pigment to goat hair Mix 2 mL of each red staining solution with 1 g of goat hair bundles, rinse with running water after 10 minutes, and dry with a dryer to obtain each red-stained hair bundle.

[0188] For each red-dyed hair tuft and the undyed hair tuft that was not treated with the dye solution, a colorimeter (CM-5, Konica Minolta Japan Co., Ltd.) was used to measure the color difference. value, Value and Values ​​in the CIELAB color space ( Colors were represented in a color space. Measurement conditions were set as follows: light source D65 during reflection, field of view 10°, and measurement diameter 3mm. Three hair tufts were measured, and the average value was taken as the measured value.

[0189] Then, calculate the undyed hair tufts. value, Value and The values ​​are the ΔL and ΔE values ​​of each red-dyed hair tuft when the baseline is reached. The sign is chosen so that the ΔL value is positive. Here, the ΔL and ΔE values ​​refer to... value, value.

[0190] Additionally, 2 mL of shampoo diluted 10 times with water was mixed with each of the aforementioned red-dyed hair tufts. After 2 minutes, the mixture was rinsed with running water and dried using a dryer. This shampoo treatment was repeated 7 times. Then, after one or seven shampoo treatments, the hair was tested using the same method as described above. value, Value and Calculate the values ​​of ΔL and ΔE.

[0191] In addition, the ΔL and ΔE values ​​after 7 shampoo washes were divided by the ΔL and ΔE values ​​after 1 shampoo wash to obtain the color retention rate (%), which is used as an indicator of colorfastness. It can be said that the higher the color retention rate (%), the less likely the hair will fade in shampoo, and the better the colorfastness. The results are shown in Table 2.

[0192] [Table 2] As shown in Table 2, Figures 17-22 As shown, the red pigments of the present invention obtained in Examples 10-12 showed higher ΔL and ΔE values ​​(higher hue retention rate) and better colorfastness compared to the gardenia red pigment obtained in Comparative Example 2 after 7 shampoo washes.

[0193] 3-1. Manufacturing of hair color treatment products Hair coloring and conditioning agents were manufactured using the blue pigment obtained in Example 1 or Comparative Example 1, according to the formulations described in Table 3.

[0194] [Table 3] 3-2. Tests on the dyeing properties and colorfastness of hair coloring treatments Mix 2 mL of the above hair coloring and conditioning agent with 1 g of goat hair bundle moistened with water. After 10 minutes, rinse with running water and dry in a dryer to obtain individual colored hair bundles. Then, mix 2 mL of shampoo diluted 10 times with water with each of the above colored hair bundles, rinse with running water after 2 minutes, and dry in a dryer. Repeat the hair coloring and conditioning agent dyeing and shampooing process 3 times.

[0195] For each dyed and washed goat hair bundle, a two-dimensional colorimeter (PPLB-410, manufactured by Papalab Co., Ltd.) was used to measure... value, Value and Values ​​in the CIELAB color space ( Colors are represented in a color space. Calculations are made using undyed hair tufts. value, Value and The values ​​represent the ΔE values ​​of each dyed and washed hair tuft as a baseline. Here, the ΔE values ​​refer to... The value of ΔE is generally considered to be larger, indicating better staining. The results are shown in Table 4.

[0196] [Table 4] As shown in Table 4, Figures 23-26 As shown, it was confirmed that the coloring and conditioning agent made with the blue pigment of the present invention obtained in Example 1 has a larger ΔE value after dyeing and washing, better dyeing properties and colorfastness, and better colorfastness during repeated washing compared with the coloring and conditioning agent made with the gardenia blue pigment obtained in Comparative Example 1.

[0197] 4-1. Tests on the dyeing properties and colorfastness of blue pigment on fabrics Undyed fabrics (polyester, nylon, silk, or cotton) were immersed in the blue dyeing solution (25°C) prepared in Example 1 for 10 minutes, then rinsed with running water and dried to obtain dyed fabrics. The dyed fabrics were then hand-washed with detergent and allowed to air dry.

[0198] For each dyed fabric after dyeing and after hand washing, a two-dimensional colorimeter (PPLB-410, manufactured by Papalab Co., Ltd.) was used to measure... value, Value and Values ​​in the CIELAB color space ( Colors are represented in a color space. Calculations are performed using undyed fabric. value, Value and The values ​​represent the ΔE values ​​of each dyed fabric after dyeing and after hand washing, with the values ​​serving as the baseline. Here, the ΔE values ​​refer to... The value was calculated by dividing the ΔE value after hand washing by the ΔE value after dyeing, and the resulting value was used as the color retention rate (%). This color retention rate is used as an indicator of colorfastness. Generally speaking, a higher color retention rate (%) indicates less fading in detergents and better colorfastness. The results are shown in Table 5.

[0199] [Table 5] As shown in Table 5, Figures 27-30 As shown, the blue pigment of the present invention obtained in Example 1 has been confirmed to have good dyeing properties on various fabrics, and in addition, it has excellent resistance to fading.

[0200] 4-2. Tests on the dyeing properties and colorfastness of red pigment on fabric Undyed fabrics (polyester, nylon, silk, or cotton) were immersed in the red dyeing solution (25°C) prepared in Example 10. After 10 minutes, they were rinsed with running water and dried to obtain dyed fabrics. Then, each dyed fabric was hand-washed with detergent and allowed to air dry.

[0201] For each dyed fabric after dyeing and after hand washing, a two-dimensional colorimeter (PPLB-410, manufactured by Papalab Co., Ltd.) was used to measure... value, Value and Values ​​in the CIELAB color space ( Colors are represented in a color space. Calculations are performed using undyed fabric. value, Value and The values ​​represent the ΔE values ​​of each dyed fabric after dyeing and after hand washing, with the values ​​serving as the baseline. Here, the ΔE values ​​refer to... The value was calculated by dividing the ΔE value after hand washing by the ΔE value after dyeing, and this value was used as the color retention rate (%). The color retention rate is used as an indicator of colorfastness. It can be said that the higher the color retention rate (%), the less likely the color will fade in detergent, and the better the colorfastness. The results are shown in Table 6.

[0202] [Table 6] As shown in Table 6, Figures 31-34 As shown, the red pigment of the present invention obtained in Example 10 has been confirmed to have good dyeing properties on various fabrics, and in addition, it has excellent resistance to fading.

[0203] 5-1. Test on the colorfastness of blue pigment on human hair As the blue staining solution, the blue staining solutions prepared in Example 1 and Comparative Example 1 were used. In addition, 2-(4-aminophenyl)ethylamine (4.90 g), N-ethylethylenediamine (3.17 g), or 4-aminomethylpyridine (3.89 g) were used instead of guanidine sulfate (8.22 g), and the blue staining solutions were prepared by the same method as in Example 1 (Examples 13-15).

[0204] Using these blue dye solutions, human hair bundles (bleached and washed with shampoo) were used instead of goat hair bundles. Otherwise, the colorfastness was evaluated using the same method as described in "1-2. Test on the colorfastness of blue dye on goat hair" above. The results are shown in Table 7.

[0205] [Table 7] As shown in Table 7, Figures 35-39 As shown, it was confirmed that the blue pigment of the present invention obtained in Examples 1, 13-15 had a larger ΔL value and ΔE value (higher hue retention rate) after 7 shampoo washing treatments compared with the gardenia blue pigment obtained in Comparative Example 1, and also had excellent resistance to fading in human hair.

[0206] 5-2. Test on the colorfastness of red pigment in human hair The red staining solution prepared in Example 10 and Comparative Example 2 was used as the red staining solution.

[0207] Using these red dye solutions, human hair bundles (bleached and washed with shampoo) were used instead of goat hair bundles. Otherwise, the colorfastness was evaluated using the same method as described in "2-2. Test on the colorfastness of red dye on goat hair". The results are shown in Table 8.

[0208] [Table 8] As shown in Table 8, Figure 40 and 41 As shown, the red pigment of the present invention obtained in Example 10, compared with the gardenia red pigment obtained in Comparative Example 2, has a larger ΔL value and ΔE value after 7 shampoo washes (higher hue retention rate) and excellent resistance to fading in human hair.< / ph>

Claims

1. A blue pigment, characterized in that it is It is obtained by reacting a mixture of an aglycone containing iridoid glycosides and a nitrogen-containing compound. The nitrogen-containing compound has two or more nitrogen-containing groups, at least one of which is a primary amino or primary ammonium group, and the nitrogen-containing compound does not have a carboxyl group.

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

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

4. A red pigment, characterized in that it is It is obtained by reacting an aglycone containing an ester hydrolysate of iridoid glycosides with a mixture of nitrogen-containing compounds. The nitrogen-containing compound has two or more nitrogen-containing groups, at least one of which is a primary amino or primary ammonium group, and the nitrogen-containing compound does not have a carboxyl group.

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

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

7. A dyeing composition, characterized in that, It contains the blue pigment as described in any one of claims 1 to 3 and / or the red pigment as described in any one of claims 4 to 6.

8. The dyeing composition according to claim 7, wherein, The dyeing composition is a hair dyeing composition.

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

10. The dyeing composition according to claim 7, wherein, The dyeing composition is a fiber dyeing composition.

11. A staining method, characterized in that, Hair or fibers are dyed using the dyeing composition according to claim 8 or 10.

12. Use of the blue pigment of any one of claims 1 to 3 and / or the red pigment of any one of claims 4 to 6 for the manufacture of hair dyeing compositions or fiber dyeing compositions.

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