Fiber dyeing agent composition for head decorative products

Abstract

To provide a fiber dyeing agent composition for a head ornament product, which contains an oxidation dye intermediate, is excellent in dyeability of a fiber for a head ornament product such as a regenerated collagen fiber, does not impair good combability even after dyeing, and gives a colored fiber having good compatibility with hair.SOLUTION: A fiber dyeing agent composition for head decorative products, which is used by mixing at least a first agent and a second agent, wherein the first agent contains an oxidation dye intermediate (A), an alkali agent, and water, the second agent contains hydrogen peroxide and water, and the pH of the dyeing agent composition obtained by mixing the first agent and the second agent is 9.5 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a dye composition for use in dyeing fibers for head accessories. [Background technology]

[0002] Regenerated collagen fiber, a protein fiber, is suitable for use as a raw material for artificial hair because its properties are similar to those of human hair. Fibers used as raw materials for artificial hair are required to have high aesthetic qualities, such as color development and texture.

[0003] Fibers for head accessories include both naturally-derived and synthetic fibers, but naturally-derived fibers generally have the natural texture and appearance that comes from natural materials, unlike synthetic fibers. Among naturally-derived fibers, regenerated protein fibers, such as regenerated collagen fibers, are obtained by solubilizing acid-soluble or insoluble collagen with alkali or enzymes to form a spinning solution, which is then extruded through a spinning nozzle into a coagulation bath for fiberization.

[0004] However, when using regenerated collagen fibers, which are naturally derived fibers, as fibers for head accessories, it is particularly necessary to improve various properties such as water resistance, heat resistance, and extensibility during the production of fibers for head accessories. Therefore, treatment agents for modifying fibers such as regenerated collagen fibers have also been studied. For example, Patent Document 1 discloses a fiber treatment agent that is used to treat regenerated collagen fibers and the like, improves water resistance and heat resistance, which are problems with naturally derived fibers, and can impart thermal shape memory ability, as well as improves stretchability (tenacity) and surface feel, without discoloring naturally derived fibers. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2023-171307 Summary of the Invention [Problem to be solved by the invention]

[0006] Patent Document 1 describes that in addition to treatment with the above-mentioned fiber treatment agent, treatments such as bleaching and dyeing may also be performed. Direct dyes, oxidative dyes, etc. are used to dye fibers. However, regenerated collagen fibers sometimes exhibit a different degree of dyeing than human hair. Furthermore, dyeing treatments can cause crimping of the regenerated collagen fibers, widening the fiber bundle, and impairing texture. As a result, when a head accessory containing dyed regenerated collagen fibers is worn on the hair, it becomes difficult to comb the fibers, resulting in poor compatibility with the hair. In particular, the present inventors have found that dye compositions using oxidative dyes tend to reduce compatibility of dyed regenerated collagen fibers with the hair. Patent Document 1 does not suggest or discuss these issues.

[0007] The present invention relates to a fiber dye composition for head accessories, which contains an oxidation dye intermediate and has excellent dyeability for fibers for head accessories such as regenerated collagen fibers, and which gives colored fibers that are easy to comb even after dyeing and that blend well with hair. [Means for solving the problem]

[0008] The present inventors have discovered that a multi-component dye composition for dyeing fibers for headwear products, which contains an oxidation dye intermediate and has a pH value below a predetermined value, can solve the above-mentioned problems. That is, the present invention relates to the following. [1] A fiber dye composition for headwear products, which is used by mixing at least a first agent and a second agent, wherein the first agent contains an oxidation dye intermediate (A), an alkaline agent, and water, and the second agent contains hydrogen peroxide and water, and the pH of the dye composition obtained by mixing the first agent and the second agent is 9.5 or less. [2] A method for dyeing fibers for head accessories, comprising the following steps (I) and (II) in this order: Step (I): Mixing at least the first and second agents to prepare a fiber dye composition for headwear. Here, the first agent contains the oxidation dye intermediate (A), an alkaline agent, and water, the second agent contains hydrogen peroxide and water, and the pH of the dye composition obtained by mixing the first agent and the second agent is 9.5 or less. Step (II) A step of applying the fiber dye composition for head accessories to the fiber for head accessories. [3] [1] A colored fiber for a headwear product dyed using the fiber dye composition for a headwear product. [4] A head accessory comprising the colored head accessory fiber according to [3]. [Effects of the Invention]

[0009] According to the present invention, there can be provided a fiber dye composition for head accessories, which contains an oxidation dye intermediate, has excellent dyeability for fibers for head accessories such as regenerated collagen fibers, does not impair ease of combing even after dyeing, and can give colored fibers that blend well with hair. DETAILED DESCRIPTION OF THE INVENTION

[0010] [Definition] As used herein, "head accessories" refers to, for example, hair wigs, hairpieces, weaving, hair extensions, braided hair, hair accessories, doll hair, etc. Furthermore, "fibers for head accessories" refers to fibers used in the head accessories. Human hair is excluded from the fibers for head accessories that are to be dyed with the dye composition of the present invention, but human hair may be mixed with the fibers for head accessories in the head accessories. In this specification, "excellent dyeability of fibers for head accessories" means that there is a large change in color of the fibers for head accessories before and after dyeing with the dye composition for fibers for head accessories. In this specification, "good compatibility with hair after dyeing" means that there is little change in appearance such as widening of the fiber bundle due to crimping of the fiber for a head accessory after dyeing, the fiber is well aligned with the hair, and the hair can be easily combed when attached to the hair. The dyeability and compatibility with hair can be specifically evaluated by the method described in the examples.

[0011] [Textile dye composition for head accessories] The fiber dye composition for head accessories of the present invention is a fiber dye composition for head accessories that uses a mixture of at least a first agent and a second agent, the first agent contains an oxidation dye intermediate (A), an alkali agent, and water; the second agent contains hydrogen peroxide and water; The stain composition obtained by mixing the first agent and the second agent has a pH of 9.5 or less. In the following description, the fiber dye composition for head accessories may be simply referred to as the "composition (of the present invention)" or "dye composition (of the present invention)." By virtue of the above-described constitution, the composition of the present invention can provide colored fibers for head accessories, such as regenerated collagen fibers, that have excellent dyeability, do not lose combability even after dyeing, and blend well with hair.

[0012] The reason why the composition of the present invention exhibits the above-mentioned effects is not clear, but is presumed to be as follows. The composition of the present invention is a multi-component staining composition that uses a mixture of a first component containing at least an alkaline agent and a second component containing hydrogen peroxide. The oxidative dye intermediate (A) is a low-molecular-weight compound, and when a dye composition containing this oxidative dye intermediate is applied to fibers for headwear, such as regenerated collagen fibers, it easily penetrates into the fibers. The penetration of the oxidative dye intermediate (A) into the fibers is promoted by the alkaline agent contained in the first agent. After penetration into the fibers, the oxidative dye intermediate (A) reacts with its couplers or with its precursor due to the action of hydrogen peroxide contained in the second agent to form a reaction product, which develops color and exhibits dyeability. Here, when regenerated collagen fibers are dyed using the composition of the present invention, by adjusting the pH of the composition to a predetermined value or less, the penetration of the oxidation dye intermediate (A) into the regenerated collagen fibers and the reactivity within the fibers are controlled within an appropriate range, which is thought to ensure both good dyeability and ease of compatibility with hair after dyeing. The mechanism of action of the present invention is not limited to the above.

[0013] <First agent> The first agent contains the oxidation dye intermediate (A), an alkaline agent, and water.

[0014] (Oxidation dye intermediate (A)) The oxidation dye intermediate (A) preferably comprises a coupler known as an oxidation dye intermediate. Examples of couplers include metaphenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4-(2-hydroxyethylamino)anisole [=2-amino-4-(β-hydroxyethyl)aminoanisole], 2,4-diamino-5-methylphenetole, 2,4-diamino-5-(2-hydroxyethoxy)toluene, 2,4-dimethoxy-1,3-diaminobenzene, 2,6-bis(2-hydroxyethylamino)toluene, and 2,4-diamino-5-fluorotoluene. , 1,3-bis(2,4-diaminophenoxy)propane, meta-aminophenol, 2-methyl-5-aminophenol [=5-aminoorthocresol], 2-methyl-5-(2-hydroxyethylamino)phenol, 2,4-dichloro-3-aminophenol, 2-chloro-3-amino-6-methylphenol, 2-methyl-4-chloro-5-aminophenol, N-cyclopentyl-meta-aminophenol, 2-methyl-4-methoxy-5-(2-hydroxyethylamino)phenol, 2 -Methyl-4-fluoro-5-aminophenol, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-isopropyl-5-methylphenol, 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 6-hydroxybenzomorpholine, 3,4-methylenedioxyphenol, 2-bromo-4,5- Examples of suitable salts include one or more selected from the group consisting of methylenedioxyphenol, 3,4-methylenedioxyaniline, 1-(2-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-diaminopyridine, 2,3-diamino-6-methoxypyridine, 2-methylamino-3-amino-6-methoxypyridine, 2-amino-3-hydroxypyridine, 2,6-diaminopyridine, and salts thereof. The salt is not particularly limited, but examples thereof include, in the case of a compound having a nitrogen atom, inorganic acid salts such as hydrochlorides and sulfates, and organic acid salts such as acetic acid and citric acid.

[0015] In this specification, the term "coupler" does not include compounds having a catechin structure. The "catechin structure" used here specifically refers to a structure represented by the following general formula (I):

[0016] [ka]

[0017] (In the formula, R A and R B are each independently a hydrogen atom or a hydroxy group. C is a hydrogen atom or an acyl group, and R D is a hydrogen atom or a ring-containing group.

[0018] R C The acyl group in the formula (II) is preferably a group represented by the following formula (II), and R D The ring structure-containing group in the formula (III) is preferably a group represented by the following formula (III).

[0019] [ka]

[0020] [ka]

[0021] (In the above formula, * indicates a bond. R A ~R C is the same as above.)

[0022] From the viewpoint of improving dyeability and fastness, the oxidation dye intermediate (A) used in the first agent more preferably contains one or more selected from the group consisting of the following components (A1) and (A2): Note that components (A1) and (A2) may be in the form of a salt, and the type of salt is not particularly limited. (A1) One or more couplers selected from the group consisting of couplers (A1-1) having a benzene ring, electron-donating groups at the 1st and 3rd positions on the benzene ring, and hydrogen atoms at the 4th and 6th positions; couplers (A1-2) having a pyridine ring, electron-donating groups at the 2nd and 6th positions on the pyridine ring, and hydrogen atoms at the 3rd and 5th positions; and couplers (A1-3) represented by the following general formula (A13):

[0023] [ka]

[0024] (In formula (A13), R 11 is -O-(CH2) n R is a divalent group represented by -O- (n is a number of 2 or more and 10 or less). 12 , R 14 , R 22 and R 24 is an electron-donating group, and R 15 and R 25 is a hydrogen atom. 13 , R 16 , R 23 and R 26 are each independently a hydrogen atom, an alkyl group, or an electron-donating group.

[0025] (A2) One or more couplers other than the component (A1), selected from the group consisting of couplers (A2-1) having a benzene ring, electron-donating groups at the 1st and 2nd positions on the benzene ring, and hydrogen atoms at two or more of the 3rd to 6th positions, and couplers (A2-2) having a pyridine ring, electron-donating groups at the 2nd and 3rd positions on the pyridine ring, and hydrogen atoms at two or more of the 4th to 6th positions. Because component (A1) has the above structure, it easily forms a reaction product of a trimer or higher. Similarly, because the coupler, component (A2), has a specific structure, it easily forms a reaction product of a dimer or higher. Therefore, when one or more oxidation dye intermediates (A) selected from the group consisting of components (A1) and (A2) are used, high-molecular-weight reaction products are easily generated inside the fiber, which is thought to improve fastness.

[0026] [Component (A1)] Component (A1) is one or more selected from the group consisting of couplers (A1-1) having a benzene ring, electron-donating groups at the 1- and 3-positions on the benzene ring, and hydrogen atoms at the 4- and 6-positions, couplers (A1-2) having a pyridine ring, electron-donating groups at the 2- and 6-positions on the pyridine ring, and hydrogen atoms at the 3- and 5-positions, and couplers (A1-3) represented by the following general formula (A13): Couplers (A1-1) to (A1-3) may be in the form of a salt, and the type of salt is not particularly limited.

[0027] [ka]

[0028] (In formula (A13), R 11 is -O-(CH2) n R is a divalent group represented by -O- (n is a number of 2 or more and 10 or less). 12 , R 14 , R 22 and R 24 is an electron-donating group, and R 15 and R 25 is a hydrogen atom. 13 , R 16 , R 23 and R 26 are each independently a hydrogen atom, an alkyl group, or an electron-donating group.

[0029] Examples of the electron-donating group in component (A1) include a hydroxy group, a hydroxyalkyl group, an alkoxy group, a hydroxyalkoxy group, a primary to tertiary amino group, an alkylamino group, and an aromatic hydrocarbon ring structure.

[0030] <Coupler (A1-1)> The coupler (A1-1) preferably includes a compound represented by the following general formula (A11) or a salt thereof.

[0031] [ka]

[0032] (In formula (A11), R 1 is an electron donating group attached to the carbon atom at position 1, R 2 is a hydrogen atom attached to the carbon atom at the 2nd position, an alkyl group or an electron-donating group, R 3 is an electron donating group attached to the 3-carbon atom, R 4 is a hydrogen atom, an alkyl group, or an electron-donating group bonded to the carbon atom at the 5-position. 2 and R 3 may be bonded to each other to form a hydrocarbon ring structure having aromaticity.

[0033] The electron-donating group in general formula (A11) preferably includes at least one selected from the group consisting of a hydroxy group, a hydroxyalkyl group, an alkoxy group, a hydroxyalkoxy group, a primary to tertiary amino group, an alkylamino group, and a hydrocarbon ring structure having aromaticity, more preferably includes at least one selected from the group consisting of a hydroxy group, a hydroxyalkyl group having from 2 to 8 carbon atoms, an alkoxy group having from 1 to 8 carbon atoms, a hydroxyalkoxy group having from 2 to 8 carbon atoms, a primary amino group (-NH2), and an alkylamino group having from 1 to 8 carbon atoms, and even more preferably includes at least one selected from the group consisting of a hydroxy group and a primary amino group (-NH2). The alkyl group preferably includes an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group. The aromatic hydrocarbon ring structure is represented by R 2 and R 3 are bonded to each other to form an aromatic hydrocarbon ring structure, the ring structure preferably includes an aromatic hydrocarbon ring structure having 5 to 8 ring carbon atoms, more preferably includes an aromatic hydrocarbon ring structure having 5 to 6 ring carbon atoms, and even more preferably includes an aromatic hydrocarbon ring structure having 6 ring carbon atoms.

[0034] In the general formula (A11), R 1is preferably a hydroxy group or a primary amino group (-NH). 2 is preferably a hydrogen atom or a methyl group, R 3 is preferably a hydroxy group or a primary amino group (-NH). 2 and R 3 are bonded to each other to form an aromatic hydrocarbon ring structure with 6 ring carbon atoms. 4 is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0035] Specific examples of the compound represented by the general formula (A11) include one or more compounds selected from the group consisting of meta-aminophenol, resorcinol, meta-phenylenediamine, 2-methylresorcinol, 1-naphthol, and salts thereof, and preferably include one or more compounds selected from the group consisting of meta-aminophenol, resorcinol, 2-methylresorcinol, 1-naphthol, and salts thereof.

[0036] <Coupler (A1-2)> The coupler (A1-2) preferably includes a compound represented by the following general formula (A12) or a salt thereof.

[0037] [ka]

[0038] (In formula (A12), R 5 is an electron donating group attached to the 2nd carbon atom, R 6 represents a hydrogen atom, an alkyl group, or an electron-donating group bonded to the 4-carbon atom; R 7 is an electron-donating group attached to the 6-carbon atom.)

[0039] The electron-donating group in general formula (A12) preferably includes one or more selected from the group consisting of a hydroxy group, a hydroxyalkyl group, an alkoxy group, a hydroxyalkoxy group, a primary to tertiary amino group, and an alkylamino group, more preferably includes one or more selected from the group consisting of a hydroxy group, a hydroxyalkyl group having from 2 to 8 carbon atoms, an alkoxy group having from 1 to 8 carbon atoms, a hydroxyalkoxy group having from 2 to 8 carbon atoms, a primary amino group (-NH2), and an alkylamino group having from 1 to 8 carbon atoms, and even more preferably includes one or more selected from the group consisting of a hydroxy group and a primary amino group (-NH2). The alkyl group preferably includes an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.

[0040] In the general formula (A12), R 5 is preferably a hydroxy group or a primary amino group (—NH), and R 6 is preferably a hydrogen atom or a methyl group. 7 is preferably a primary amino group (-NH2). Specific examples of the compound represented by the general formula (A12) include 2,6-diaminopyridine and salts thereof.

[0041] <Coupler (A1-3)> The coupler (A1-3) includes a compound represented by the following general formula (A13) or a salt thereof.

[0042] [ka]

[0043] (In formula (A13), R 11 is -O-(CH2) n R is a divalent group represented by -O- (n is a number of 2 or more and 10 or less). 12 , R 14 , R 22 and R 24 is an electron-donating group, and R 15 and R25 is a hydrogen atom. 13 , R 16 , R 23 and R 26 are each independently a hydrogen atom, an alkyl group, or an electron-donating group.

[0044] The electron-donating group, the alkyl group, and preferred embodiments thereof in formula (A13) are the same as those in formula (A12).

[0045] In general formula (A13), R 11 In the formula, n is preferably 2 or more and 8 or less, and more preferably 2 or more and 4 or less. R 12 , R 14 , R 22 and R 24 The electron donating group in R preferably comprises a hydroxy group or a primary amino group (-NH), more preferably a primary amino group (-NH). 13 , R 16 , R 23 and R 26 preferably contains a hydrogen atom or a methyl group, and more preferably is a hydrogen atom. Specific examples of the coupler represented by the general formula (A13) include 1,3-bis(2,4-diaminophenoxy)propane and salts thereof.

[0046] As the component (A1), one or more members selected from the group consisting of the couplers (A1-1), (A1-2), and (A1-3) can be used. Among the above, component (A1) preferably contains one or more compounds selected from the group consisting of compounds represented by general formula (A11), compounds represented by general formula (A12), compounds represented by general formula (A13), and salts thereof, more preferably contains one or more compounds selected from the group consisting of meta-aminophenol, resorcinol, meta-phenylenediamine, 2-methylresorcinol, 1-naphthol, 2,6-diaminopyridine, 1,3-bis(2,4-diaminophenoxy)propane, and salts thereof, and even more preferably contains one or more compounds selected from the group consisting of meta-aminophenol, resorcinol, 2-methylresorcinol, 1-naphthol, and salts thereof.

[0047] [Component (A2)] Component (A2) is a coupler other than component (A1), and is at least one selected from the group consisting of couplers (A2-1) having a benzene ring, electron-donating groups at the 1- and 2-positions on the benzene ring, and hydrogen atoms at two or more of the 3- to 6-positions, and couplers (A2-2) having a pyridine ring, electron-donating groups at the 2- and 3-positions on the pyridine ring, and hydrogen atoms at two or more of the 4- to 6-positions.

[0048] 《Coupler (A2-1)》 The coupler (A2-1) preferably includes a compound represented by the following general formula (A21) or a salt thereof, excluding couplers corresponding to the above component (A1).

[0049] [ka]

[0050] (In formula (A21), R 31 is an electron donating group attached to the carbon atom at position 1, R 32 is an electron donating group attached to the 2nd carbon atom, R 33 ~R 36 are hydrogen atoms, alkyl groups, or electron-donating groups bonded to the 3-, 4-, 5-, and 6-position carbons, respectively. 33 ~R 36 At least two of these are hydrogen atoms.)

[0051] The electron-donating group in general formula (A21) preferably includes one or more selected from the group consisting of a hydroxy group, a hydroxyalkyl group, an alkoxy group, a hydroxyalkoxy group, a primary to tertiary amino group, and an alkylamino group, more preferably includes one or more selected from the group consisting of a hydroxy group, a hydroxyalkyl group having from 2 to 8 carbon atoms, an alkoxy group having from 1 to 8 carbon atoms, a hydroxyalkoxy group having from 2 to 8 carbon atoms, a primary amino group (-NH2), and an alkylamino group having from 1 to 8 carbon atoms, and even more preferably includes one or more selected from the group consisting of a hydroxy group, a hydroxyalkoxy group having from 2 to 8 carbon atoms, and a primary amino group (-NH2). The alkyl group preferably includes an alkyl group having 1 to 8 carbon atoms, more preferably includes an alkyl group having 1 to 3 carbon atoms, and further preferably includes a methyl group.

[0052] In general formula (A21), R 31 is preferably a hydroxy group, a hydroxyalkoxy group having from 2 to 8 carbon atoms, or a primary amino group (-NH), and more preferably a hydroxy group, a hydroxyethoxy group, or a primary amino group (-NH). 32 is preferably a hydroxy group or a primary amino group (-NH2), more preferably a primary amino group (-NH2).

[0053] Specific examples of the compound represented by general formula (A21) include ortho-aminophenol, 2,4-diaminophenoxyethanol, and salts thereof.

[0054] 《Coupler (A2-2)》 The coupler (A2-2) preferably includes a compound represented by the following general formula (A22) or a salt thereof.

[0055] [ka]

[0056] (In formula (A22), R 37 is an electron donating group attached to the 2nd carbon atom, R 38 is an electron donating group attached to the 3-carbon atom. 39 ~R 41 are hydrogen atoms, alkyl groups, or electron-donating groups bonded to the 4-, 5-, and 6-position carbons, respectively. 39 ~R 41 At least two of these are hydrogen atoms.)

[0057] The electron-donating group, the alkyl group, and preferred embodiments thereof in formula (A22) are the same as those in formula (A21).

[0058] In the general formula (A22), R 37 is preferably a hydroxy group or a primary amino group (—NH), and R 38 is preferably a hydroxy group or a primary amino group (-NH), more preferably a primary amino group (-NH). 39 ~R 41 are each independently preferably a hydrogen atom or a methyl group, more preferably R 39 ~R 41 All of these are hydrogen atoms. Specific examples of the compound represented by the general formula (A22) include 2,3-diaminopyridine, 2-amino-3-hydroxypyridine, and salts thereof.

[0059] As the component (A2), one or more members selected from the group consisting of the above couplers (A2-1) and (A2-2) can be used. Among the above, component (A2) preferably contains one or more compounds selected from the group consisting of compounds represented by general formula (A21) above, compounds represented by general formula (A22) above, and salts thereof, and more preferably contains one or more compounds selected from the group consisting of ortho-aminophenol, 2,4-diaminophenoxyethanol, 2-amino-3-hydroxypyridine, and salts thereof.

[0060] Among the above, from the viewpoint of improving dyeability and fastness, the oxidation dye intermediate (A) preferably contains one or more selected from component (A1) and component (A2), more preferably component (A1). In this case, component (A1) preferably contains one or more selected from the group consisting of compounds represented by general formula (A11), compounds represented by general formula (A12), compounds represented by general formula (A13), and salts thereof, and component (A2) preferably contains one or more selected from the group consisting of compounds represented by general formula (A21), compounds represented by general formula (A22), and salts thereof. A more preferred embodiment includes one containing as component (A1) one or more members selected from the group consisting of meta-aminophenol, resorcinol, meta-phenylenediamine, 2-methylresorcinol, 1-naphthol, 2,6-diaminopyridine, 1,3-bis(2,4-diaminophenoxy)propane, and salts thereof, and one or more members selected from the group consisting of ortho-aminophenol, 2,4-diaminophenoxyethanol, 2-amino-3-hydroxypyridine, and salts thereof, as component (A2).

[0061] From the viewpoint of improving dyeability and fastness, the total content of components (A1) and (A2) in the oxidative dye intermediate (A) is preferably 30% by mass or more, more preferably 40% by mass or more, and 100% by mass or less. Furthermore, when the oxidative dye intermediate (A) contains another oxidative dye intermediate (e.g., a precursor of component (A3) described below), the total content of components (A1) and (A2) in the oxidative dye intermediate (A) may be, for example, 90% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less. That is, the total content of components (A1) and (A2) in the oxidative dye intermediate (A) is preferably 30% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 80% by mass or less, even more preferably 30% by mass or more and 70% by mass or less, and even more preferably 40% by mass or more and 60% by mass or less.

[0062] From the viewpoint of improving dyeability and fastness, the content of component (A1) in the oxidation dye intermediate (A) is preferably 30% by mass or more, more preferably 40% by mass or more and 100% by mass or less. The content of component (A1) in the oxidation dye intermediate (A) may be, for example, 90% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less. That is, the content of component (A1) in the oxidation dye intermediate (A) is preferably 30% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 80% by mass or less, even more preferably 40% by mass or more and 70% by mass or less, and even more preferably 40% by mass or more and 60% by mass or less.

[0063] (Component (A3): Precursor) From the viewpoint of further improving dyeability and fastness, the oxidation dye intermediate (A) preferably further contains component (A3): precursor as an oxidation dye intermediate other than the components (A1) and (A2). The precursor can be any compound known as a precursor of an oxidation dye intermediate, and examples thereof include paraphenylenediamine, toluene-2,5-diamine, orthochloroparaphenylenediamine, N-phenylparaphenylenediamine, N,N-bis(hydroxyethyl)paraphenylenediamine, 3-methyl-4-aminophenol, 2-hydroxyethylparaphenylenediamine, paraaminophenol, paramethylaminophenol, 4-amino-metacresol, and salts thereof. The salt is not particularly limited, and examples thereof include inorganic acid salts such as hydrochlorides and sulfates, and organic acid salts such as acetic acid and citric acid.

[0064] Among the above, from the viewpoint of further improving fastness when used in combination with the couplers of components (A1) and (A2), component (A3) preferably includes one or more members selected from the group consisting of toluene-2,5-diamine, para-aminophenol, 4-amino-metacresol, 1-hydroxyethyl-4,5-diaminopyrazole, and salts thereof.

[0065] When the oxidation dye intermediate (A) contains component (A3), the content of component (A3) in the oxidation dye intermediate (A) is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and is preferably 70% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 60% by mass or less, from the viewpoint of further improving dyeability and fastness. That is, the content of component (A3) in the oxidation dye intermediate (A) is preferably 20% by mass or more and 70% by mass or less, more preferably 30% by mass or more and 65% by mass or less, and even more preferably 40% by mass or more and 60% by mass or less.

[0066] The oxidation dye intermediate (A) may further contain a coupler other than the components (A1) and (A2). However, from the viewpoint of further improving dyeability and fastness, the total content of the components (A1) to (A3) in the oxidation dye intermediate (A) is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, still more preferably 95% by mass or more, and even more preferably 98% by mass or more, but not more than 100% by mass. That is, the content of couplers other than the components (A1) and (A2) in the oxidation dye intermediate (A) is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, still more preferably 5% by mass or less, and even more preferably 2% by mass or less, and may be 0% by mass.

[0067] From the viewpoint of further improving dyeability and fastness, the molecular weight of the oxidation dye intermediate (A) as a non-dissociated type is preferably 95 or more, more preferably 100 or more, and even more preferably 105 or more, and from the viewpoint of efficiently penetrating into the interior of the fiber to further improve dyeability, the molecular weight of the oxidation dye intermediate (A) as a non-dissociated type is preferably 500 or less, more preferably 300 or less, and even more preferably 200 or less. That is, the molecular weight of the oxidation dye intermediate (A) as a non-dissociated type is preferably 95 or more and 500 or less, more preferably 100 or more and 300 or less, and even more preferably 105 or more and 200 or less. The molecular weight of the oxidative dye intermediate (A) refers to the molecular weight of each oxidative dye intermediate in the oxidative dye intermediate (A), and it is preferable that the molecular weights of the components (A1), (A2), and (A3) in their undissociated form are all within the above range. Furthermore, the molecular weight of the oxidative dye intermediate (A) in its undissociated form refers to the molecular weight of the oxidative dye intermediate (A) in its non-ionic state, even when the oxidative dye intermediate (A) is a salt, and does not include the molecular weight of the counter ion. This also includes cases where the oxidative dye intermediate (A) has an onium group such as a quaternary ammonium group, and in such cases, the counter ion is similarly not included in the molecular weight.

[0068] (Alkaline agent) The alkaline agent used in the first agent may be either an inorganic alkaline agent or an organic alkaline agent. Examples of the alkaline agent include ammonia; alkanolamines such as mono-, di-, or trimethanolamine, and mono-, di-, or triethanolamine; alkylamines such as methylamine, dimethylamine, ethylamine, diethylamine, N-methylethylamine, propylamine, and butylamine; aralkylamines such as benzylamine; and inorganic alkali compounds such as sodium hydroxide and potassium hydroxide, and one or more of these can be used. From the viewpoint of water solubility, the number of carbon atoms in the alkanolamine, alkylamine, or aralkylamine is preferably 10 or less, and more preferably 8 or less. Among the above, from the viewpoint of efficiently penetrating the oxidation dye intermediate (A) into the interior of the fiber to further improve dyeability and fastness, the alkaline agent preferably contains one or more selected from the group consisting of ammonia, alkanolamine, alkylamine, aralkylamine, sodium hydroxide, and potassium hydroxide, and more preferably contains one or more selected from the group consisting of ammonia and alkanolamine.

[0069] (water) The water used in the first agent is not particularly limited, and for example, ion-exchanged water, pure water, distilled water, etc. can be used.

[0070] (Other ingredients) In addition to the above ingredients, the first agent may contain antioxidants, chelating agents, fragrances, preservatives, thickeners, pH adjusters, surfactants, texture improvers, and the like.

[0071] (Content) The content of each component in the first agent is preferably within the following ranges. From the viewpoint of improving dyeability, the content of component (A) in the first pack is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, even more preferably 0.05% by mass or more, still more preferably 0.10% by mass or more, still more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, and still more preferably 0.5% by mass or more, and from the viewpoint of improving formulation stability and improving compatibility of the head accessory fiber with hair after dyeing, it is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less. That is, the content of component (A) in the first pack is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.02% by mass or more and 5% by mass or less, even more preferably 0.05% by mass or more and 5% by mass or less, still more preferably 0.10% by mass or more and 3% by mass or less, still more preferably 0.2% by mass or more and 3% by mass or less, still more preferably 0.3% by mass or more and 3% by mass or less, and still more preferably 0.5% by mass or more and 2% by mass or less.

[0072] From the viewpoint of improving dyeability, the total content of component (A1) and component (A2) in the first agent is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, even more preferably 0.05% by mass or more, still more preferably 0.10% by mass or more, still more preferably 0.2% by mass or more, and still more preferably 0.25% by mass or more; from the viewpoint of improving formulation stability and improving compatibility of the fiber for a head accessory with the hair after dyeing, the total content is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2.0% by mass or less, still more preferably 1.5% by mass or less, and still more preferably 1.0% by mass or less. That is, the total content of component (A1) and component (A2) in the first agent is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.02% by mass or more and 3% by mass or less, even more preferably 0.05% by mass or more and 3% by mass or less, still more preferably 0.10% by mass or more and 2.0% by mass or less, even more preferably 0.2% by mass or more and 1.5% by mass or less, and still more preferably 0.25% by mass or more and 1.0% by mass or less.

[0073] The content of the alkaline agent in the first agent is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, in terms of the amount of active ingredient, from the viewpoint of improving dyeability and fastness. Furthermore, from the viewpoint of maintaining constant reactivity and ensuring dyeability, and from the viewpoint of improving compatibility of the dyed head accessory fiber with hair, the content is preferably 10% by mass or less, more preferably 7.5% by mass or less, and even more preferably 5% by mass or less. That is, the content of the alkaline agent in the first agent is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 7.5% by mass or less, even more preferably 0.5% by mass or more and 7.5% by mass or less, even more preferably 1.0% by mass or more and 7.5% by mass or less, and even more preferably 1.0% by mass or more and 5% by mass or less, in terms of the amount of active ingredient.

[0074] The content of water in the first agent is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more, and preferably 99.98% by mass or less, from the viewpoint of improving the solubility of the oxidation dye intermediate (A) and the alkaline agent, and from the viewpoint of improving the ease of handling when mixed with the second agent. The content of water in the first agent may be the balance of the oxidation dye intermediate (A) and the alkaline agent.

[0075] (pH) From the viewpoint of improving dyeability and fastness, the pH of the first agent is preferably 6 or higher, more preferably 6.5 or higher, even more preferably 7.0 or higher, and even more preferably 7.5 or higher. Furthermore, from the viewpoint of maintaining constant reactivity and ensuring dyeability, and from the viewpoint of improving compatibility of the head accessory fiber with hair after dyeing, the pH is preferably 10.5 or lower, more preferably 10.0 or lower, even more preferably 9.5 or lower, even more preferably 9.2 or lower, even more preferably 9.0 or lower, and even more preferably 8.5 or lower. That is, the pH of the first agent is preferably 6 or higher and 10.5 or lower, more preferably 6.5 or higher and 10.0 or lower, even more preferably 7.0 or higher and 9.5 or lower, even more preferably 7.0 or higher and 9.2 or lower, even more preferably 7.0 or higher and 9.0 or lower, and even more preferably 7.5 or higher and 8.5 or lower. The pH can be measured at 25°C by the method described in the Examples.

[0076] (Dosage form, manufacturing method) The dosage form of the first agent is not particularly limited, and can be liquid, paste, cream, gel, foam, spray, wax, or other dosage form depending on the product form, with liquid being preferred. The method for producing the first agent is not particularly limited, and it can be produced by mixing the respective components by any method. The first agent of this embodiment can be preferably obtained by mixing a medium (e.g., water), the oxidative dye intermediate (A), and other components under heating (e.g., 60 to 80°C) to uniformly dissolve or disperse the oxidative dye intermediate (A) and other components, and then adding an alkali agent at room temperature and mixing uniformly.

[0077] <Second agent> The second agent contains hydrogen peroxide and water. The content of hydrogen peroxide in the second agent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, in terms of the amount of active ingredient, from the viewpoint of improving dyeability and fastness, and is preferably 10% by mass or less, more preferably 8% by mass or less, in terms of improving compatibility of the dyed head accessory fiber with hair. That is, the content of hydrogen peroxide in the second agent is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, and even more preferably 1.0% by mass or more and 8% by mass or less, in terms of the amount of active ingredient. From the viewpoint of ease of handling, hydrogen peroxide is preferably blended in the form of an aqueous solution.

[0078] (water) The water used in the second agent is not particularly limited, and for example, ion-exchanged water, pure water, distilled water, etc. can be used. From the viewpoint of improving the ease of handling when mixed with the first agent, the water content in the second agent is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more, and is preferably 99.99% by mass or less. The content of water in the second agent comprises the remainder of the hydrogen peroxide.

[0079] (Other ingredients) In addition to the above components, the second agent may contain antioxidants, chelating agents, fragrances, preservatives, thickeners, pH adjusters, surfactants, texture improvers, and the like.

[0080] (pH) The pH of the second agent is preferably 2.5 or higher, more preferably 3.0 or higher, and is preferably 6 or lower, more preferably 5 or lower, and even more preferably 4 or lower. That is, the pH of the second agent is preferably 2.5 or higher and 6 or lower, more preferably 3.0 or higher and 5 or lower, and even more preferably 3.0 or higher and 4 or lower. The pH can be measured at 25°C by the method described in the Examples.

[0081] (Dosage form, manufacturing method) The dosage form of the second agent is not particularly limited, and can be liquid, paste, cream, gel, foam, spray, wax, or other dosage form depending on the product form, with liquid being preferred. The first and second agents may be in the same or different dosage forms, but from the viewpoint of ease of handling during use, it is preferable that they be in the same dosage form. The method for producing the second agent is not particularly limited, and it can be produced by mixing the components by any method. The second agent of this embodiment can be preferably obtained by mixing a medium (e.g., water) and other components under heating (e.g., 60 to 80°C) to dissolve them uniformly, and then adding hydrogen peroxide at room temperature and mixing them uniformly.

[0082] The composition of the present invention is used by mixing at least the first agent and the second agent. The mixing may be carried out at the time of use, or a mixture that has been mixed in advance may be used, but it is preferable to mix them at the time of use. Note that the composition of the present invention may be used by mixing at least the first agent and the second agent, and may further include, for example, a third agent or more containing other components. The mixing ratio of the first agent to the second agent varies depending on the concentrations of the oxidative dye intermediate (A) and alkaline agent in the first agent and the hydrogen peroxide in the second agent, but the first agent:second agent (mass ratio) is preferably in the range of 1:0.1 to 1:10, more preferably 1:0.2 to 1:5, and even more preferably 1:0.5 to 1:3.

[0083] (pH) The pH of the dye composition obtained by mixing the first and second agents is 9.5 or less, preferably 9.0 or less, more preferably 8.7 or less, even more preferably 8.5 or less, and even more preferably 8.2 or less, from the viewpoint of improving compatibility of the dyed head accessory fiber with the hair. Furthermore, from the viewpoint of improving dyeability, the pH is preferably 6.0 or more, more preferably 6.5 or more, even more preferably 7.0 or more, and even more preferably 7.5 or more. The pH of the dye composition is preferably 6.0 to 9.5, more preferably 6.0 to 9.0, even more preferably 6.0 to 8.7, even more preferably 6.0 to 8.5, even more preferably 6.5 to 8.2, even more preferably 7.0 to 8.2, and even more preferably 7.5 to 8.2. The pH is measured at 25° C. and can be measured by the method described in the Examples. After the first and second parts are mixed, the pH may be adjusted to the above range using a pH adjuster or the like.

[0084] (Content) The content of each component in the fiber dye composition for head accessories, obtained by mixing at least the first and second agents, is preferably within the following ranges. From the viewpoint of improving dyeability, the content of component (A) or a reaction product of component (A) in the composition is preferably 0.005% by mass or more, more preferably 0.010% by mass or more, even more preferably 0.02% by mass or more, still more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, still more preferably 0.10% by mass or more, and still more preferably 0.2% by mass or more; from the viewpoint of improving formulation stability and improving compatibility of the fiber for a head accessory with the hair after dyeing, the content is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. That is, the content in the composition is preferably 0.005% by mass or more and 3% by mass or less, more preferably 0.010% by mass or more and 3% by mass or less, even more preferably 0.02% by mass or more and 3% by mass or less, still more preferably 0.03% by mass or more and 2% by mass or less, even more preferably 0.05% by mass or more and 2% by mass or less, still more preferably 0.10% by mass or more and 2% by mass or less, and still more preferably 0.2% by mass or more and 1% by mass or less.

[0085] From the viewpoint of improving dyeability and fastness, the content of the alkaline agent in the composition is preferably 0.005% by mass or more, more preferably 0.010% by mass or more, even more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. Furthermore, from the viewpoint of maintaining constant reactivity and improving compatibility of the dyed head accessory fiber with hair, the content is preferably 5.0% by mass or less, more preferably 3.5% by mass or less, even more preferably 2.5% by mass or less, and even more preferably 1.5% by mass or less. That is, the content of the alkaline agent in the composition is preferably 0.005% by mass or more and 5.0% by mass or less, more preferably 0.010% by mass or more and 3.5% by mass or less, even more preferably 0.1% by mass or more and 2.5% by mass or less, and even more preferably 0.5% by mass or more and 1.5% by mass or less.

[0086] The content of hydrogen peroxide in the composition is preferably 5% by mass or less, more preferably 4.0% by mass or less, even more preferably 3.5% by mass or less, still more preferably 2.5% by mass or less, still more preferably 1.0% by mass or less, still more preferably 0.1% by mass or less, still more preferably 0.01% by mass or less, and still more preferably none.

[0087] The mass ratio of component (A) to hydrogen peroxide in the composition [oxidative dye intermediate (A) / hydrogen peroxide] is preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.010 or more, still more preferably 0.06 or more, and even more preferably 0.10 or more, from the viewpoint of suppressing damage to fibers caused by hydrogen peroxide. Furthermore, from the viewpoint of improving dyeability and fastness, it is preferably 50 or less, more preferably 20 or less, even more preferably 5 or less, still more preferably 2 or less, and even more preferably 1 or less. That is, the mass ratio [oxidative dye intermediate (A) / hydrogen peroxide] is preferably 0.001 or more and 50 or less, more preferably 0.005 or more and 20 or less, even more preferably 0.010 or more and 5 or less, still more preferably 0.06 or more and 2 or less, and even more preferably 0.10 or more and 1 or less. The mass of hydrogen peroxide refers to the amount of active ingredient.

[0088] The water content in the composition is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more, and is preferably 99.9% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less. That is, the water content in the composition is preferably 70% by mass or more and 99.9% by mass or less, more preferably 80% by mass or more and 97% by mass or less, and even more preferably 85% by mass or more and 95% by mass or less.

[0089] <Fiber for headdress products> The fibers for head accessories to be dyed with the dye composition of the present invention are fibers other than human hair and may be either naturally-derived or synthetic, although naturally-derived fibers are preferred. Naturally-derived fibers refer to fibers collected from natural plants and animals, or artificially produced fibers made from proteins derived from collagen, casein, soybeans, peanuts, corn, silk waste, silk proteins (e.g., silk fibroin), etc., or polymers or oligomers such as polysaccharides. Among these, artificially produced fibers made from animal hair, or polymers or oligomers such as proteins derived from keratin, collagen, casein, soybeans, peanuts, corn, silk waste, silk proteins (e.g., silk fibroin), etc., are preferred. Regenerated protein fibers made from proteins derived from keratin, collagen, casein, soybean proteins, peanut proteins, corn proteins, silk proteins (e.g., silk fibroin), etc. are more preferred. Regenerated protein fibers, such as regenerated collagen fibers made from collagen and regenerated silk fibers made from silk fibroin, are even more preferred, with regenerated collagen fibers being even more preferred. Regenerated collagen fibers can be produced by known techniques. The composition of regenerated collagen fibers does not need to be 100% collagen, and they may contain natural polymers, synthetic polymers, additives, etc. to improve quality. Furthermore, regenerated collagen fibers may be post-processed or post-treated. Filaments are preferred as the form of regenerated collagen fibers. Filaments are generally removed from bobbins or boxes. In addition, filaments emerging from the drying process in the regenerated collagen fiber production process can also be used directly.

[0090] Examples of synthetic fibers include fibers containing a synthetic resin as a main component. From the viewpoint of ease of production of synthetic fibers and of obtaining a texture similar to that of human hair, the synthetic resin is preferably a thermoplastic resin, more preferably one or more selected from the group consisting of polyester resin, polyamide resin, polyimide resin, polyamideimide resin, vinyl chloride resin, polycarbonate resin, polyphenylene sulfide resin, and modacrylic resin (a copolymer of acrylonitrile and vinyl chloride). Here, the term "main component" refers to a component whose content in the synthetic fiber is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, still more preferably 80% by mass or more, and even more preferably 90% by mass or more, but not more than 100% by mass. In addition to the above synthetic resins, the synthetic fibers may further contain various additives such as flame retardants, flame retardant auxiliaries, light or heat stabilizers, fluorescent agents, antioxidants, antistatic agents, and ultraviolet absorbers, as long as the effects of the present invention are not impaired.

[0091] The fibers for head accessories to be dyed with the dye composition of the present invention preferably contain regenerated collagen fibers. From the viewpoint of improving the dyeability of the fibers for head accessories and improving compatibility with hair after dyeing, the fibers for head accessories to be dyed with the dye composition of the present invention are more preferably fibers consisting of only regenerated collagen fibers.

[0092] [Dyeing method] The present invention provides a method for dyeing fibers for head accessories, which comprises the following steps (I) and (II) in this order: Step (I): Mixing at least the first and second agents to prepare a fiber dye composition for headwear. Here, the first agent contains the oxidation dye intermediate (A), an alkaline agent, and water, the second agent contains hydrogen peroxide and water, and the pH of the dye composition obtained by mixing the first agent and the second agent is 9.5 or less. Step (II) A step of applying the fiber dye composition for head accessories to the fiber for head accessories. In the following description, the method for dyeing fibers for head accessories will also be simply referred to as the "dyeing method of the present invention." The dye composition, the fiber for head accessories, and the preferred embodiments thereof are the same as those described above.

[0093] <Process (I)> In step (I), at least the first and second parts are mixed to prepare a fiber dye composition for head accessories. Here, the first agent contains the oxidation dye intermediate (A), an alkaline agent, and water, the second agent contains hydrogen peroxide and water, and the pH of the dye composition obtained by mixing the first agent and the second agent is 9.5 or less. The preferred embodiments of the first and second agents, their mixing ratio, and the pH of the dye composition are the same as those described for the fiber dye composition for head accessories.

[0094] <Process (II)> In step (II), the fiber dye composition for head accessories is applied to the fiber for head accessories. The fiber for head accessories and preferred embodiments thereof are the same as those described above.

[0095] The method for applying the fiber dye composition for head accessories to the fiber for head accessories may be any method that can bring the dye composition into contact with the fiber for head accessories, and examples thereof include a method of applying the composition to the fiber for head accessories in a dry or wet state, and a method of immersing the fiber for head accessories in the composition. Among the above, the method of applying the dye composition to the fiber for head accessories in a dry state is preferred. From the viewpoint of a balance between dyeability, fastness, and economy, the amount of dye composition applied to the fiber for headwear products is preferably such that the bath ratio (dry mass of fiber for headwear products:mass of dye composition) is 1:0.2 to 1:500, when the mass of the fiber after conditioning at 20°C and a relative humidity of 65% for 24 hours is taken as the dry mass. When the dye composition is applied to the fiber for head accessories, the amount of the dye composition to be applied to the fiber for head accessories is, from the viewpoint of balancing dyeability and economy, preferably 1:0.2 to 1:200, even more preferably 1:0.2 to 1:100, still more preferably 1:0.2 to 1:50, even more preferably 1:0.2 to 1:20, even more preferably 1:0.5 to 1:10, even more preferably 1:0.5 to 1:5, and even more preferably 1:0.8 to 1:3 in terms of the bath ratio (dry mass of fiber for head accessories:mass of dye composition), when the mass of the fiber after conditioning at 20°C and a relative humidity of 65% for 24 hours is taken as the dry mass. Furthermore, when immersing fibers for head accessories in the dye composition, when the mass of the fibers after conditioning for 24 hours at 20°C and a relative humidity of 65% is taken as the dry mass, the bath ratio (dry mass of fibers for head accessories:mass of dye composition) is more preferably 1:2 to 1:500, even more preferably 1:3 to 1:250, still more preferably 1:5 to 1:100, still more preferably 1:10 to 1:50, and even more preferably 1:10 to 1:20.

[0096] In step (II), when the dye composition is applied to the fiber for a head accessory, the application time is preferably 10 seconds or more, more preferably 20 seconds or more, from the viewpoint of further improving dyeability and fastness, and is preferably 10 minutes or less, more preferably 5 minutes or less, from the viewpoint of improving productivity and improving compatibility of the fiber for a head accessory with hair after dyeing. That is, the application time is preferably 10 seconds or more and 10 minutes or less, more preferably 20 seconds or more and 5 minutes or less. In step (II), it is preferable to further carry out a step of leaving the dye composition after applying it to the fiber for a head accessory. The leaving time is preferably 1 minute or more, more preferably 3 minutes or more, and even more preferably 5 minutes or more, from the viewpoint of further improving dyeability and fastness, and is preferably 1 hour or less, more preferably 30 minutes or less, from the viewpoint of improving productivity and improving compatibility of the dyed fiber for a head accessory with hair. That is, the leaving time is preferably 1 minute or more and 1 hour or less, more preferably 3 minutes or more and 30 minutes or less, and even more preferably 5 minutes or more and 30 minutes or less.

[0097] When the fiber for head accessories is immersed in the dye composition, the immersion time is preferably 10 seconds or more, more preferably 30 seconds or more, from the viewpoint of further improving dyeability and fastness, and is preferably 3 hours or less, more preferably 2 hours or less, and even more preferably 1 hour or less, from the viewpoint of improving productivity and improving compatibility of the fiber for head accessories with hair after dyeing. That is, the immersion time is preferably 10 seconds or more and 3 hours or less, more preferably 30 seconds or more and 2 hours or less, and even more preferably 30 seconds or more and 1 hour or less.

[0098] The temperature at which step (II) is carried out is not particularly limited, but from the viewpoint of improving the handleability of the dye composition and improving the compatibility of the dyed head accessory fiber with the hair, it is preferably 40° C. or lower, more preferably 35° C. or lower. Furthermore, from the viewpoint of further improving dyeability and fastness, it is preferably 5° C. or higher, more preferably 10° C. or higher. That is, the temperature in step (II) is preferably 5° C. or higher and 40° C. or lower, more preferably 10° C. or higher and 35° C. or lower.

[0099] (Rinse process) The dyeing method of the present invention preferably includes a step of rinsing the dye composition applied to the headwear fiber after step (II) (hereinafter simply referred to as the "rinsing step"). The rinsing step is carried out, for example, by rinsing the dye composition applied to the headwear fiber with water. The temperature of the water is not particularly limited, but warm water of 35 to 45°C is preferred.

[0100] (drying process) The dyeing method of the present invention preferably includes a step of drying the fiber for head accessories after the rinsing step (hereinafter also simply referred to as a "drying step"). The step of drying the fiber for head accessories is a step of reducing the moisture content of the fiber for head accessories, and includes, for example, towel drying, drying with a dryer (cold air or hot air), air drying, and a combination of two or more of these drying treatments in order to actively reduce the moisture content of the fiber for head accessories.

[0101] [Colored fibers for headdress products, headdress products] The present invention further provides a colored fiber for head accessories dyed with the fiber dye composition for head accessories, and a head accessory comprising the colored fiber for head accessories. The colored fiber for head accessories is the fiber for head accessories colored with the oxidation dye intermediate (A), and is preferably obtained by applying the dye composition to the fiber for head accessories using the dyeing method of the present invention. The colored fiber for head accessories can be suitably used for head accessories. The head accessories may contain the colored fiber for head accessories at least in part, and may contain the colored fiber for head accessories and human hair.

[0102] With respect to the above-mentioned embodiments, the present invention discloses the following.

[0103] <1> A fiber dye composition for headwear products, which is used by mixing at least a first agent and a second agent, the first agent contains an oxidation dye intermediate (A), an alkali agent, and water; the second agent contains hydrogen peroxide and water; A fiber dye composition for headwear products, wherein the dye composition obtained by mixing the first agent and the second agent has a pH of 9.0 or less.

[0104] <2> A method for dyeing fibers for head accessories, comprising the following steps (I) and (II) in this order: Step (I): Mixing at least the first and second agents to prepare a fiber dye composition for headwear. Here, the first agent contains the oxidation dye intermediate (A), an alkaline agent, and water, the second agent contains hydrogen peroxide and water, and the pH of the dye composition obtained by mixing the first agent and the second agent is 9.0 or less. Step (II) A step of applying the fiber dye composition for head accessories to the fiber for head accessories.

[0105] <3> The oxidation dye intermediate (A) contains one or more selected from the following components (A1) and (A2): <1> The fiber dye composition for head accessories described above, or <2> The dyeing method described. (A1) One or more couplers selected from the group consisting of couplers (A1-1) having a benzene ring, electron-donating groups at the 1st and 3rd positions on the benzene ring, and hydrogen atoms at the 4th and 6th positions; couplers (A1-2) having a pyridine ring, electron-donating groups at the 2nd and 6th positions on the pyridine ring, and hydrogen atoms at the 3rd and 5th positions; and couplers (A1-3) represented by the following general formula (A13): [ka] (In formula (A13), R 11 is -O-(CH2) n R is a divalent group represented by -O- (n is a number of 2 or more and 10 or less). 12 , R 14 , R 22 and R 24 is an electron-donating group, and R 15 and R 25 is a hydrogen atom. 13 , R 16 , R 23 and R 26 are each independently a hydrogen atom, an alkyl group, or an electron-donating group. (A2) One or more couplers other than the component (A1), selected from the group consisting of couplers (A2-1) having a benzene ring, electron-donating groups at the 1st and 2nd positions on the benzene ring, and hydrogen atoms at two or more of the 3rd to 6th positions, and couplers (A2-2) having a pyridine ring, electron-donating groups at the 2nd and 3rd positions on the pyridine ring, and hydrogen atoms at two or more of the 4th to 6th positions.

[0106] <4> The component (A1) contains at least one compound selected from the group consisting of a compound represented by the following general formula (A11), a compound represented by the following general formula (A12), a compound represented by the following general formula (A13), and salts thereof: The component (A2) contains at least one compound selected from the group consisting of a compound represented by the following general formula (A21), a compound represented by the following general formula (A22), and salts thereof: The aforementioned <1> or <3> The fiber dye composition for head accessories described above, or <2> or <3> The dyeing method described.

[0107] [ka]

[0108] (In formula (A11), R 1 is an electron donating group attached to the carbon atom at position 1, R 2 is a hydrogen atom attached to the carbon atom at the 2nd position, an alkyl group or an electron-donating group, R 3 is an electron donating group attached to the 3-carbon atom, R 4 is a hydrogen atom, an alkyl group, or an electron-donating group bonded to the carbon atom at the 5-position. 2 and R 3 may be bonded to each other to form a hydrocarbon ring structure having aromaticity. In formula (A12), R 5 is an electron donating group attached to the 2nd carbon atom, R 6 represents a hydrogen atom, an alkyl group, or an electron-donating group bonded to the 4-carbon atom; R 7 is an electron donating group attached to the 6-carbon atom. In formula (A13), R 11 is -O-(CH2) n R is a divalent group represented by -O- (n is a number of 2 or more and 10 or less). 12 , R 14 , R 22 and R 24 is an electron-donating group, and R 15 and R 25 is a hydrogen atom. 13 , R 16 , R 23 and R 26 are each independently a hydrogen atom, an alkyl group, or an electron-donating group. In formula (A21), R 31 is an electron donating group attached to the carbon atom at position 1, R 32 is an electron donating group attached to the 2nd carbon atom, R33 ~R 36 are hydrogen atoms, alkyl groups, or electron-donating groups bonded to the 3-, 4-, 5-, and 6-position carbons, respectively. 33 ~R 36 At least two of these are hydrogen atoms. In formula (A22), R 37 is an electron donating group attached to the 2nd carbon atom, R 38 is an electron donating group attached to the 3-carbon atom. 39 ~R 41 are hydrogen atoms, alkyl groups, or electron-donating groups bonded to the 4-, 5-, and 6-position carbons, respectively. 39 ~R 41 At least two of these are hydrogen atoms.)

[0109] <5> The component (A1) contains one or more selected from meta-aminophenol, resorcinol, meta-phenylenediamine, 2-methylresorcinol, 1-naphthol, 2,6-diaminopyridine, 1,3-bis(2,4-diaminophenoxy)propane, 1-naphthol, and salts thereof; The component (A2) contains one or more selected from ortho-aminophenol, 2,4-diaminophenoxyethanol, 2-amino-3-hydroxypyridine, and salts thereof. The aforementioned <1> and <3> ~ <4> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <4> The dyeing method according to any one of the above.

[0110] <6> The oxidation dye intermediate (A) contains a component (A1). <1> , <3> ~ <5> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <5> The dyeing method according to any one of the above.

[0111] <7> The oxidation dye intermediate (A) further contains a precursor as component (A3), and the precursor contains one or more selected from toluene-2,5-diamine, para-aminophenol, 4-amino-metacresol, 1-hydroxyethyl-4,5-diaminopyrazole, and salts thereof. <1> , <3> ~ <6> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <6> The dyeing method according to any one of the above.

[0112] <8> The pH of the fiber dye composition for headwear is 6.0 or more and 9.0 or less. <1> , <3> ~ <7> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <7> The dyeing method according to any one of the above. <9> The pH of the fiber dye composition for headwear is 6.0 or more and 8.5 or less. <1> , <3> ~ <8> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <8> The dyeing method according to any one of the above. <10> The pH of the fiber dye composition for headwear products is 6.5 or more and 8.2 or less. <1> , <3> ~ <9> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <9> The dyeing method according to any one of the above.

[0113] <11> The content of the oxidation dye intermediate (A) in the first agent is 0.5% by mass or more and 2% by mass or less. <1> , <3> ~ <10> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <10> The dyeing method according to any one of the above. <12> The total content of the component (A1) and the component (A2) in the first agent is 0.25% by mass or more and 1.0% by mass or less. <1> , <3> ~ <11> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <11> The dyeing method according to any one of the above. <13> The mixing ratio of the first agent to the second agent (first agent:second agent (mass ratio)) is 1:0.5 to 1:3. <1> , <3> ~ <12> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <12> The dyeing method according to any one of the above.

[0114] <14> The fiber for headwear products contains regenerated collagen fiber. <1> , <3> ~ <13> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <13> The dyeing method according to any one of the above.

[0115] <15> the mass ratio of the oxidation dye intermediate (A) to hydrogen peroxide in the fiber dye composition for headwear [oxidation dye intermediate (A) / hydrogen peroxide] is 0.06 or more and 2 or less; <1> , <3> ~ <14> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <14> The dyeing method according to any one of the above. <16> the mass ratio of the oxidation dye intermediate (A) to hydrogen peroxide in the fiber dye composition for headwear [oxidation dye intermediate (A) / hydrogen peroxide] is 0.10 or more and 1 or less; <1> , <3> ~ <15> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <15> The dyeing method according to any one of the above.

[0116] <17> The aforementioned <1> , <3> ~ <16> A colored fiber for head accessories dyed using the fiber dye composition for head accessories described in any one of the above. <18> The fiber for headwear products contains regenerated collagen fiber. <17> The fiber for colored headwear products described in 1. <19> The aforementioned <17> or <18> A headwear product comprising the colored headwear fiber described above. [Example]

[0117] The present invention will be described below with reference to examples, but the present invention is not limited to the scope of the examples. In this example, various measurements and evaluations were performed by the following methods.

[0118] <pH measurement> The pH at 25°C was measured using a pH meter (F-72, manufactured by Horiba, Ltd.).

[0119] In the evaluation of this example, the regenerated collagen fibers were purchased in the form of a commercially available extension product of regenerated collagen fibers manufactured by Kaneka Corporation, and the fibers were cut therefrom and divided into small tufts of hair for use in the evaluation. In this evaluation, the extension product was marked as using 100% Ultima as the fiber type, and a white one with a color number of 30 and a straight shape was used.

[0120] <Preparation and evaluation of the dye composition for regenerated collagen fibers> Examples 1 to 4, Comparative Examples 1 to 2 Each component shown in the "First Agent" in Table 1 was blended at the blending ratio described in the table and mixed until uniform to prepare the first agent. Similarly, each component shown in the "Second Agent" in Table 1 was blended at the blending ratio described in Table 1 and mixed until uniform to prepare the second agent. Next, the first agent and the second agent were mixed at the mass ratio described in Table 1 to prepare a dye composition for regenerated collagen fibers. Using the dye composition obtained by the above method, the dyeability and the compatibility with hair were evaluated by the following method. The results are shown in Table 1.

[0121] <Dyeability (color difference ΔE * ab) before and after dyeing> Using the above regenerated collagen fibers (100% Ultima used, white with a color number of 30, straight shape), a fiber bundle with a length of 10 cm and a mass of 1 g was prepared. After washing the fiber bundle with a plain shampoo having the following composition, it was rinsed with warm water at 40°C and thoroughly dried with a dryer. The hue (L0 * , a0 * , b0 * ) of the fiber bundle (fiber bundle before dyeing) was measured using a color difference meter (CR-400, manufactured by Konica Minolta Co., Ltd.). L0* ,a0 * ,b0 * The values ​​were measured at six points per fiber bundle and the average value was calculated. Next, 2 g of a dye composition prepared by mixing the first and second agents shown in Table 1 in the ratios shown in Table 1 was applied to the fiber bundle, which was then placed in a glass petri dish, the opening of which was covered with aluminum foil, and the fiber bundle was left floating in a water bath (TBS221FA, Toyo Seisakusho Co., Ltd.) set to 30°C for 30 minutes. After leaving for 30 minutes, the fiber bundle was rinsed with 40°C warm water for 30 seconds to wash away the dye composition, and a plain shampoo having the following composition was lathered for 15 seconds and then rinsed with 40°C warm water for 15 seconds, this operation being repeated twice. Next, a plain conditioner having the following composition was applied for 15 seconds, followed by rinsing with 40°C warm water for 15 seconds, and the fiber bundle was thoroughly dried with cold air from a dryer. The dried fiber bundle (dyed fiber bundle) was measured for hue (L1 * ,a1 * ,b1 * ) was measured. The color difference ΔE before and after dyeing of the fiber bundle is calculated using the following formula: * ab was calculated and shown in Table 1. ΔE * A larger ab value means higher staining.

[0122] ΔE * ab=〔(L1 * -L0 * ) 2 +(a1 * -a0 * ) 2 +(b1 * -b0 * ) 2 〕 1 / 2

[0123] (Plain shampoo composition) Ingredients (mass %) Polyoxyethylene (2) lauryl ether sodium sulfate (*1) 15.5 Lauric acid diethanolamide (*2) 1.5 edetic acid tetrasodium salt 0.3 Sodium benzoate 1.43 Refined water residue Total 100.0 *1: 57.4% by mass of Emar 227 (manufactured by Kao Corporation, active ingredient 27% by mass) *2: Aminone L-02 (Kao Corporation)

[0124] (Plain conditioner composition) Ingredients (mass %) Trimethylstearylammonium chloride (*1) 1.01 Distearyldimethylammonium chloride (*2) 2.0 Propylene glycol 5.0 Cetyl alcohol (*3) 2.0 Isopropyl alcohol 0.4 Methyl parahydroxybenzoate(*4) 0.1 Refined water residue Total 100.0 *1: 3.6% by mass of Kotamin 86W (manufactured by Kao Corporation, active ingredient 28% by mass) *2: 2.7% by mass of Kotamin D86P (manufactured by Kao Corporation, active ingredient 75% by mass) *3: Kalcol 6870 (Kao Corporation) *4: Mekkinsu M (manufactured by Ueno Pharmaceutical Co., Ltd.)

[0125] <Fits well with hair> The fiber bundle of the regenerated collagen fibers dyed by the method described in the "Dyeability" section above was placed on hair, and five expert monitors performed a sensory evaluation of the compatibility of the regenerated collagen fibers with the hair, including how well the regenerated collagen fibers aligned with the hair and how easily the hair could be combed. The expert monitors scored the compatibility with the hair from 5 to 1, with the number of expert monitors who scored 3 or higher representing the evaluation score. The results are shown in Table 1.

[0126] <Width change rate of fiber bundle (%)> For the fiber bundle of the regenerated collagen fibers (length 10 cm, mass 1 g), the width (W0 (cm)) was measured at a position 5 cm from the base of the fiber bundle toward the tip. Then, for the regenerated collagen fiber bundle dyed by the method described in the "Dyeability" section above, the width [W1 (cm)] was measured at a position 5 cm from the base of the fiber bundle toward the tip, and the width change rate (%) of the fiber bundle was calculated using the following formula. The results are shown in Table 1. A small width change rate of the fiber bundle indicates that the width of the fiber bundle is suppressed even after dyeing, and the fibers are well aligned with the hair, resulting in excellent compatibility with the hair.

[0127] Fiber bundle width change rate (%) = (W1-W0) / W0 x 100

[0128] Reference example 1 Instead of regenerated collagen fibers, human hair (manufactured by Viewlux Co., Ltd.) was used to prepare a hair bundle for evaluation, 10 cm in length and 1 g in mass. Using this hair bundle and the dye composition of Comparative Example 1, various evaluations were carried out in the same manner as above. The results are shown in Table 1. The blending amounts (mass %) shown in Table 1 are all amounts in their original form.

[0129] [Table 1]

[0130] Table 1 shows that the dye composition of the present invention exhibits the same level of dyeability for regenerated collagen fibers as the dye compositions of Comparative Examples 1 and 2, which have pH values ​​outside the range specified in the present invention, and also exhibits good compatibility with hair. Furthermore, according to Reference Example 1, even when human hair is treated with the dye composition of Comparative Example 1, which has a pH outside the range specified in the present invention, both the dyeability and compatibility with human hair and scalp hair are good, and it is clear that the hair behaves differently from regenerated collagen fibers.

[0131] The effects of the present invention can also be achieved by using the fiber dye compositions for head accessories shown in Table 2.

[0132] [Table 2] [Industrial Applicability]

[0133] According to the present invention, there can be provided a fiber dye composition for head accessories, which contains an oxidation dye intermediate, has excellent dyeability for fibers for head accessories such as regenerated collagen fibers, does not impair ease of combing even after dyeing, and can give colored fibers that blend well with hair.

Claims

1. A fiber dye composition for headwear products, which comprises a mixture of at least a first agent and a second agent, the first agent contains an oxidation dye intermediate (A), an alkali agent, and water; the second agent contains hydrogen peroxide and water; A fiber dye composition for head accessories, wherein the dye composition obtained by mixing the first agent and the second agent has a pH of 9.5 or less.

2. 2. The fiber dye composition for head accessories according to claim 1, wherein the pH of the dye composition is 6 or more.

3. 3. The fiber dye composition for head accessories according to claim 1, wherein the oxidation dye intermediate (A) comprises one or more components selected from the group consisting of the following components (A1) and (A2): (A1) One or more couplers selected from the group consisting of couplers (A1-1) having a benzene ring, electron-donating groups at the 1st and 3rd positions on the benzene ring, and hydrogen atoms at the 4th and 6th positions; couplers (A1-2) having a pyridine ring, electron-donating groups at the 2nd and 6th positions on the pyridine ring, and hydrogen atoms at the 3rd and 5th positions; and couplers (A1-3) represented by the following general formula (A13): 【Chemistry 1】 (In formula (A13), R １１ is -O-(CH ２ ) ｎ R is a divalent group represented by —O— (n is a number of 2 or more and 10 or less). １２ , R １４ , R ２２ and R ２４ is an electron donating group, R １５ and R ２５ is a hydrogen atom. １３ , R １６ , R ２３ and R ２６ are each independently a hydrogen atom, an alkyl group, or an electron-donating group. (A2) One or more couplers other than the component (A1), selected from the group consisting of couplers (A2-1) having a benzene ring, electron-donating groups at the 1- and 2-positions on the benzene ring, and hydrogen atoms at two or more of the 3- to 6-positions, and couplers (A2-2) having a pyridine ring, electron-donating groups at the 2- and 3-positions on the pyridine ring, and hydrogen atoms at two or more of the 4- to 6-positions.

4. The fiber dye composition for headwear products according to claim 3, wherein the oxidation dye intermediate (A) comprises the component (A1).

5. 4. The fiber dye composition for head accessories according to claim 3, wherein the component (A1) comprises one or more members selected from the group consisting of meta-aminophenol, resorcinol, meta-phenylenediamine, 2-methylresorcinol, 1-naphthol, 2,6-diaminopyridine, and 1,3-bis(2,4-diaminophenoxy)propane.

6. The fiber dye composition for head accessories according to claim 3, wherein the oxidation dye intermediate (A) further contains a precursor as component (A3), and the precursor contains one or more members selected from the group consisting of toluene-2,5-diamine, para-aminophenol, 4-amino-metacresol, 1-hydroxyethyl-4,5-diaminopyrazole, and salts thereof.

7. The fiber dye composition for headwear products according to claim 1, wherein the fiber for headwear products comprises regenerated collagen fiber.

8. A method for dyeing fibers for head accessories, comprising the following steps (I) and (II) in this order: Step (I) A step of mixing at least the first agent and the second agent to prepare a fiber dye composition for headwear products. Here, the first agent contains an oxidation dye intermediate (A), an alkaline agent, and water, the second agent contains hydrogen peroxide and water, and the dye composition obtained by mixing the first agent and the second agent has a pH of 9.5 or less. Step (II) A step of applying the fiber dye composition for head accessories to the fiber for head accessories.

9. A colored fiber for head accessories dyed with the fiber dye composition for head accessories according to any one of claims 1 to 7.

10. A head accessory comprising the colored head accessory fiber according to claim 9.

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