Method for dyeing fibers for head decorative products containing regenerated collagen fibers

Abstract

To provide a method for dyeing a fiber for a head ornament product, capable of reducing a color difference between the hair and the fiber for the head ornament product containing a regenerated collagen fiber, and improving a color compatibility effect.SOLUTION: A method for dyeing a fiber for a head decorative product containing a regenerated collagen fiber, wherein the regenerated collagen fiber contains a modified regenerated collagen fiber containing a predetermined compound (X), and the dyeing method comprises a step (I) of attaching a head decorative product containing the fiber for a head decorative product to hair dyed with a hair dye B, and a step (II) of bringing the hair and the fiber for a head decorative product into a wet state in a state where the hair and the fiber for a head decorative product are in contact with each other, in this order, also disclosed is a method for dyeing a fiber for a hair ornamentation product, which comprises a step (III) of applying a dyeing agent (A) to the fiber for a hair ornamentation product, before the step (I) or between the step (I) and the step (II).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for dyeing fibers for head accessories containing regenerated collagen fibers. [Background technology]

[0002] Blended fibers containing cellulosic fibers and protein fibers are generally dyed with reactive dyes. For example, it is known that blended fibers containing rayon and wool can be dyed with reactive dyes to produce a solid color with no pattern (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 186580 / 1983 Summary of the Invention [Problem to be solved by the invention]

[0004] However, even in the case of blended fibers containing cellulosic fibers and protein-based fibers, when blended fibers containing cellulosic fibers and regenerated protein fibers are dyed with reactive dyes, there is a problem that mottled shades occur under normal dyeing conditions and a solid color cannot be obtained. Furthermore, the present inventors have found that this problem (the occurrence of mottled shades in dyeing) also occurs when dyeing hair and regenerated collagen fibers.

[0005] The present invention relates to a method for dyeing fibers for head accessories, which can reduce the color difference between hair and fibers for head accessories containing regenerated collagen fibers and improve the color matching effect. [Means for solving the problem]

[0006] The inventors have intensively studied methods for treating hair and fibers for head accessories containing specific modified regenerated collagen fibers, and have discovered that the above-mentioned problems can be solved, leading to the completion of the present invention. That is, the present invention relates to the following. [1] A method for dyeing fibers for head accessories containing regenerated collagen fibers, comprising: The regenerated collagen fibers contain one or more compounds (X) selected from the group consisting of the following components (X1) and (X2): (X1) Benzoic acid or its salts (X2) A copolymer containing a structural unit derived from an unsaturated monomer having a carboxy group and a structural unit derived from an aromatic vinyl compound, the copolymer having an acid value of 100 mgKOH / g or more and a weight average molecular weight of 1500 or more and 15000 or less, or a salt thereof. The modified regenerated collagen fiber contains The dyeing method includes the following steps (I) and (II) in this order: A method for dyeing fibers for head accessories, comprising the following step (III) before the step (I) or between the steps (I) and (II): Step (I) A step of attaching a head accessory containing the fiber for a head accessory to hair dyed with hair dye B. Step (II): A step of keeping the hair and the fiber for head accessories in a wet state while the hair and the fiber for head accessories are in contact with each other. Step (III) A step of applying dye A to the fiber for headwear products. [2] A dyeing kit comprising a dye A for dyeing fibers for head accessories containing regenerated collagen fibers and a hair dye B for dyeing hair, A dyeing kit comprising modified regenerated collagen fibers containing one or more compounds (X) selected from the group consisting of the following components (X1) and (X2): (X1) Benzoic acid or its salts (X2) A copolymer containing a structural unit derived from an unsaturated monomer having a carboxy group and a structural unit derived from an aromatic vinyl compound, the copolymer having an acid value of 100 mgKOH / g or more and a weight average molecular weight of 1500 or more and 15000 or less, or a salt thereof. [Effects of the Invention]

[0007] According to the present invention, a method for dyeing fibers for head accessories can be provided that can reduce the color difference between hair and fibers for head accessories containing specific modified regenerated collagen fibers and improve the color matching effect. DETAILED DESCRIPTION OF THE INVENTION

[0008] [Definition] As used herein, "reducing the color difference between hair and the fiber for head accessories containing regenerated collagen fibers and improving the color matching effect" means that the color difference between hair and the fiber for head accessories is reduced after step (II) defined in the present invention, which is a step of bringing the hair and the fiber for head accessories into a wet state while they are in contact with each other, compared to before step (II). This effect can be specifically evaluated by the method described in the examples.

[0009] [Dyeing method for fibers used in headwear products] The method for dyeing fibers for head accessories of the present invention (hereinafter also simply referred to as "the method of the present invention") is a method for dyeing fibers for head accessories containing regenerated collagen fibers, The regenerated collagen fibers contain one or more compounds (X) selected from the group consisting of the following components (X1) and (X2): (X1) Benzoic acid or its salts (X2) A copolymer containing a structural unit derived from an unsaturated monomer having a carboxy group and a structural unit derived from an aromatic vinyl compound, the copolymer having an acid value of 100 mgKOH / g or more and a weight average molecular weight of 1500 or more and 15000 or less, or a salt thereof. The modified regenerated collagen fiber contains The dyeing method includes the following steps (I) and (II) in this order: The method includes the following step (III) before the step (I) or between the step (I) and the step (II). Step (I) A step of attaching a head accessory containing the fiber for a head accessory to hair dyed with hair dye B. Step (II): A step of keeping the hair and the fiber for head accessories in a wet state while the hair and the fiber for head accessories are in contact with each other. Step (III) A step of applying dye A to the fiber for headwear products. The method of the present invention, having the above-described configuration, makes it possible to reduce the color difference between hair and the fiber for head accessories containing the specific modified regenerated collagen fiber, thereby improving the color matching effect.

[0010] The reason why the method of the present invention exhibits the above-mentioned effects is not clear, but is presumed to be as follows. The fibers for head accessories to be dyed according to the present invention are regenerated collagen fibers containing modified regenerated collagen fibers (hereinafter simply referred to as "modified regenerated collagen fibers") containing one or more compounds (X) selected from the group consisting of the above-mentioned components (X1) and (X2). Compound (X) acts as a modifier for the regenerated collagen fibers, improving their water resistance, strength, etc. On the other hand, for example, when a head accessory is attached to a portion of the hair, the hair and the modified regenerated collagen fiber are dyed differently even when the same dye is used. However, by using the method of the present invention, in step (II), the dye transfers from the hair dyed with hair dye B to the head accessory fiber containing the modified regenerated collagen fiber, which is thought to reduce the color difference between the hair and the head accessory fiber and improve the color matching effect. The mechanism of action of the present invention is not limited to the above.

[0011] <Headdress products> In this specification, the term "headwear product" refers to, for example, a hair wig, a toupee, a weaving, a hair extension, a braided hair, a hair accessory, a doll hair, etc. Among these, from the viewpoint of effectively exerting the effects of the present invention, the headwear product used in the present invention preferably includes one or more selected from the group consisting of a hair wig, a toupee, a weaving, and a hair extension, and more preferably includes a hair extension. The term "fiber for head accessories" refers to fibers used in the above-mentioned head accessories, and includes human hair. The head accessory product in this specification may contain at least a portion of modified regenerated collagen fiber as the fiber for the head accessory product, but from the viewpoint of effectively obtaining the effects of the present invention, it is preferable that the fiber for the head accessory product consists solely of modified regenerated collagen fiber.

[0012] <Modified regenerated collagen fiber> The fibers for head accessories to be dyed by the method of the present invention include regenerated collagen fibers, which include modified regenerated collagen fibers containing one or more compounds (X) selected from the group consisting of the following components (X1) and (X2): (X1) Benzoic acid or its salts (X2) A copolymer containing a structural unit derived from an unsaturated monomer having a carboxy group and a structural unit derived from an aromatic vinyl compound, the copolymer having an acid value of 100 mgKOH / g or more and a weight average molecular weight of 1500 or more and 15000 or less, or a salt thereof.

[0013] (Compound (X)) Compound (X) is one or more compounds selected from the group consisting of component (X1) and component (X2), and is a modifier for regenerated collagen fibers. The regenerated collagen fibers to be modified by compound (X) will be described later.

[0014] (Component (X1)) Component (X1) is benzoic acid or a salt thereof. When component (X1) is a salt, examples thereof include alkali metal salts such as sodium salts and potassium salts. Specific examples of component (X1) include one or more selected from the group consisting of benzoic acid, sodium benzoate, and potassium benzoate, and preferably include one or more selected from the group consisting of benzoic acid and sodium benzoate.

[0015] (Component (X2)) Component (X2) is a copolymer containing structural units derived from an unsaturated monomer having a carboxy group and structural units derived from an aromatic vinyl compound, and is a copolymer or a salt thereof having an acid value of 100 mgKOH / g or more and a weight average molecular weight of 1,500 or more and 15,000 or less.

[0016] In component (X2), the structural unit derived from an unsaturated monomer having a carboxy group may be derived from an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or a combination thereof. Specific examples of the unsaturated monomer having a carboxy group include unsaturated monocarboxylic acids and unsaturated dicarboxylic acids. Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, oleic acid, and cyclopentenylacetic acid, and examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and methylene succinic acid. Alternatively, an unsaturated dicarboxylic acid anhydride may be used as the unsaturated monomer having a carboxy group, and may be converted into an acid form by hydrolysis with an alkali, etc. Examples of unsaturated dicarboxylic acid anhydrides include maleic anhydride and citraconic anhydride. The unsaturated monomers having a carboxy group can be used alone or in combination of two or more kinds.

[0017] The structural unit derived from an aromatic vinyl compound in component (X2) is not particularly limited as long as it is derived from an aromatic compound substituted with at least a vinyl group. Specific examples of aromatic vinyl compounds include styrene, α-methylstyrene, p-methylstyrene, 3-vinyltoluene, dimethylstyrene, ethylvinylbenzene, chloromethylstyrene, vinylnaphthalene, and vinylanthracene. The aromatic vinyl compounds can be used alone or in combination of two or more kinds.

[0018] In the component (X2), the bonding state of the monomers that give rise to each structural unit may be block bonding, random bonding, or a combination thereof.

[0019] The component (X2) may contain structural units other than the above unsaturated monomers. Examples of other structural units include, but are not limited to, structural units derived from unsaturated aliphatic hydrocarbon compounds, such as linear, branched, or cyclic unsaturated aliphatic hydrocarbon compounds. Examples of the linear or branched unsaturated aliphatic hydrocarbon compound include propylene, isobutylene, diisobutylene, triisobutylene, tripropylene, and tetrapropylene. Examples of the cyclic unsaturated aliphatic hydrocarbon compound include cyclopentene, cyclohexene, and cyclooctene. The structural units derived from the unsaturated aliphatic hydrocarbon compound may include one or more types.

[0020] A suitable embodiment of component (X2) is, for example, a copolymer containing structural units derived from one or more selected from the group consisting of unsaturated monocarboxylic acids and unsaturated dicarboxylic acids, and structural units derived from an aromatic vinyl compound. Specific examples of the component (X2), from the viewpoint of further improving dyeability, fastness, and color compatibility, preferably include at least one selected from the group consisting of styrene-maleic acid copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, vinylbenzoic acid-maleic acid copolymer, vinylbenzoic acid-acrylic acid copolymer, vinylbenzoic acid-methacrylic acid copolymer, and styrene-4-vinylbenzoic acid copolymer, and more preferably include styrene-maleic acid copolymer.

[0021] In component (X2), the molar ratio (u1 / u2) of the structural unit (u1) derived from the unsaturated monomer having a carboxy group to the structural unit (u2) derived from the aromatic vinyl compound monomer is preferably 1 / 5 to 5 / 1, more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1.

[0022] The acid value of component (X2) is 100 mgKOH / g or more, and from the viewpoint of further improving dyeability, fastness, and color compatibility, it is preferably 200 mgKOH / g or more, more preferably 300 mgKOH / g or more, even more preferably 400 mgKOH / g or more, and preferably 1000 mgKOH / g or less, more preferably 800 mgKOH / g or less, even more preferably 600 mgKOH / g or less. That is, the acid value of component (X2) is preferably 100 mgKOH / g or more and 1000 mgKOH / g or less, more preferably 200 mgKOH / g or more and 800 mgKOH / g or less, even more preferably 200 mgKOH / g or more and 600 mgKOH / g or less, still more preferably 300 mgKOH / g or more and 600 mgKOH / g or less, and still more preferably 400 mgKOH / g or more and 600 mgKOH / g or less. Here, the acid value is the number of mg of potassium hydroxide required to neutralize 1 g of sample.

[0023] Specific examples of the component (X2) having an acid value within the above range include the following compounds. Styrene-maleic acid copolymer (Styrene / maleic acid (molar ratio) = 1 / 1) 475mgKOH / g Styrene-maleic acid copolymer (Styrene / maleic acid (molar ratio) = 2 / 1) 355mgKOH / g Styrene-maleic acid copolymer (Styrene / maleic acid (molar ratio) = 3 / 1) 285mgKOH / g

[0024] Component (X2) has a weight-average molecular weight of 1,500 or more and 15,000 or less, and from the viewpoint of further improving dyeability, fastness, and color matching effect, it is preferably 3,000 or more, more preferably 5,000 or more, even more preferably 6,000 or more, and preferably 10,000 or less, more preferably 9,500 or less, and even more preferably 9,000 or less. The weight-average molecular weight of component (X2) is preferably 1,500 or more and 10,000 or less, more preferably 3,000 or more and 10,000 or less, even more preferably 5,000 or more and 9,500 or less, and even more preferably 6,000 or more and 9,000 or less. The weight-average molecular weight of component (X2) may also be preferably 3,000 or more and 15,000 or less, more preferably 5,000 or more and 15,000 or less, even more preferably 6,000 or more and 10,000 or less. In this specification, the term "weight average molecular weight" refers to a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC), and specifically can be measured by the method described in the examples.

[0025] The compound (X) can be used alone or in combination of two or more. Among the above, from the viewpoint of further improving dyeability, fastness, and color matching effect, the compound (X) preferably contains one or more selected from the group consisting of benzoic acid, sodium benzoate, and a styrene-maleic acid copolymer, and more preferably contains a styrene-maleic acid copolymer.

[0026] (Content of Compound (X)) From the viewpoint of further improving dyeability, fastness, and color matching effects, the content of compound (X) in the modified regenerated collagen fiber is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, still more preferably 3.0% by mass or more, still more preferably 5.0% by mass or more, still more preferably 10% by mass or more, still more preferably 15% by mass or more, still more preferably 20% by mass or more, and is preferably 70% by mass or less, more preferably 65% ​​by mass or less, still more preferably 60% by mass or less, still more preferably 55% by mass or less, still more preferably 50% by mass or less, still more preferably 45% by mass or less, and still more preferably 40% by mass or less. The content of compound (X) in the modified regenerated collagen fibers is preferably 0.1% by mass or more and 70% by mass or less, more preferably 0.5% by mass or more and 65% by mass or less, even more preferably 1.0% by mass or more and 60% by mass or less, even more preferably 3.0% by mass or more and 55% by mass or less, even more preferably 5.0% by mass or more and 50% by mass or less, even more preferably 10% by mass or more and 45% by mass or less, even more preferably 15% by mass or more and 40% by mass or less, and even more preferably 20% by mass or more and 40% by mass or less.

[0027] When the modified regenerated collagen fibers contain component (X1) as compound (X), the content of component (X1) in the modified regenerated collagen fibers means the content converted into benzoic acid.

[0028] Furthermore, in this specification, the quantification of compound (X) in modified regenerated collagen fibers is carried out by selecting an appropriate method that does not decompose compound (X) and can dissolve the regenerated collagen fibers, and then dissolving and extracting the fibers. The extracted solution is then appropriately diluted, and the absorbance is measured using, for example, an ultraviolet-visible-near-infrared spectrophotometer (e.g., V-560 (manufactured by JASCO Corporation)) at an absorption wavelength suitable for quantifying compound (X), and the content of compound (X) is calculated from the absorbance. Alternatively, the peak area of ​​a chromatogram drawn at an absorption wavelength suitable for quantifying compound (X) using HPLC / UV or GPC / UV is measured, and the content of compound (X) is calculated from the peak area. The content of compound (X) in the modified regenerated collagen fibers can be specifically measured by the method described in the Examples.

[0029] (Component (Y): Polyvalent metal, its salt, or its complex) In order to firmly coordinate the compound (X) inside the fiber and further improve dyeability, fastness, and color compatibility, the modified regenerated collagen fiber preferably further contains a polyvalent metal, a salt thereof, or a complex thereof as a component (Y) in addition to the compound (X). Component (Y) also acts as a modifier for the regenerated collagen fiber. Examples of component (Y) include one or more polyvalent metals selected from the group consisting of calcium, magnesium, strontium, barium, zinc, chromium, aluminum, titanium, zirconium, tin, lead, antimony, iron, and copper, or salts or complexes thereof, which may be used alone or in combination of two or more. Among the above, from the viewpoint of improving water resistance and further improving dyeability, fastness, and color matching effects, component (Y) preferably contains one or more polyvalent metals selected from the group consisting of aluminum, zirconium, and titanium, or a salt or complex thereof, and more preferably contains aluminum, or a salt or complex thereof.

[0030] When the modified regenerated collagen fiber contains component (Y), the content of component (Y) in the modified regenerated collagen fiber is, in terms of the amount of metal element, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, even more preferably 2.0% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and even more preferably 10% by mass or less, from the viewpoints of improving water resistance and further improving dyeability, fastness, and color matching effects. The content of component (Y) in the modified regenerated collagen fiber is, in terms of the amount of metal element, preferably 0.1% by mass or more and 40% by mass or less, more preferably 0.5% by mass or more and 30% by mass or less, even more preferably 1.0% by mass or more and 20% by mass or less, and even more preferably 2.0% by mass or more and 10% by mass or less. The amount of component (Y) in the modified regenerated collagen fibers is quantified, for example, as follows: The modified regenerated collagen fibers are incinerated, alkali-fused, and dissolved in acid to prepare a solution. This solution is then appropriately diluted to prepare a measurement sample, and the amount of metal elements is quantified using an ICP atomic emission spectrometer. Specifically, the amount of the metal elements can be measured by the method described in the Examples.

[0031] (Method for manufacturing modified regenerated collagen fiber) The regenerated collagen fibers that are the raw material for modified regenerated collagen fibers do not need to be 100% collagen, and may contain natural or synthetic polymers or additives to improve quality. Furthermore, they may be post-processed regenerated collagen fibers. The preferred form of regenerated collagen fibers is filament. Filaments are generally taken out from bobbins or boxes.

[0032] Suitable regenerated collagen fibers are artificially produced fibers made from collagen-derived polymers and oligomers. Regenerated collagen fibers are typically produced by using a solubilized collagen raw material as a spinning dope, discharging this from a spinning nozzle into a coagulation bath to form fibers, and then drying the fibrous collagen in the final step. Regenerated collagen fibers before the drying step (hereinafter also referred to as "undried regenerated collagen fibers") can be produced by conventionally known methods. For example, undried regenerated collagen fibers can be obtained by discharging an aqueous collagen solution obtained by solubilizing insoluble collagen fibers made from the split hides of livestock animals through a spinning nozzle or slit, immersing the aqueous solution in an inorganic salt solution, and then recovering the fibers without drying. This method will be specifically described below.

[0033] The preferred collagen raw material for producing regenerated collagen fibers is split skin. Split skins are obtained from fresh split skins obtained by slaughtering livestock animals such as cows, or from salted raw hides. These split skins are mostly composed of insoluble collagen fibers, but they are used after removing the fleshy part that usually adheres to them in a mesh-like form, and removing the salt used to prevent spoilage and deterioration.

[0034] These insoluble collagen fibers contain impurities such as lipids (e.g., glycerides, phospholipids, and free fatty acids), glycoproteins, and proteins other than collagen (e.g., albumin). These impurities have a significant effect on spinning stability, quality (e.g., luster and strength / elongation), odor, and other factors during fiberization. Therefore, it is preferable to remove these impurities in advance by, for example, soaking in lime to hydrolyze the fat in the insoluble collagen fibers and loosen the collagen fibers, and then subjecting them to conventional leather treatments such as acid / alkali treatment, enzyme treatment, and solvent treatment.

[0035] The insoluble collagen thus treated is then subjected to a solubilization treatment to cleave the cross-linked peptide moieties. As a method for such solubilization, a commonly used known alkali solubilization method, an enzyme solubilization method, etc., can be used. Furthermore, the alkali solubilization method and the enzyme solubilization method may be used in combination.

[0036] When the alkali solubilization method is applied, it is preferable to neutralize with an acid such as hydrochloric acid. Note that, as an improved version of the conventional alkali solubilization method, for example, the method described in JP-B-46-15033 may be used.

[0037] The enzymatic solubilization method has the advantage of being able to obtain solubilized collagen with a uniform molecular weight, and is a method that can be suitably employed in the present invention. Examples of such enzymatic solubilization methods that can be employed include those described in Japanese Patent Publication Nos. 43-25829 and 43-27513.

[0038] If the collagen that has been solubilized in this way is further subjected to operations such as pH adjustment, salting out, water washing, and solvent treatment, it is possible to obtain regenerated collagen fibers with excellent quality, and therefore it is preferable to perform these treatments.

[0039] Solubilized collagen is dissolved in an acid such as hydrochloric acid, acetic acid, or lactic acid to obtain a collagen aqueous solution having a pH of 2 to 4.5 and a collagen concentration of 1% by mass or more, preferably 2% by mass or more, and 15% by mass or less, preferably 10% by mass or less. The collagen aqueous solution may be degassed under reduced pressure and stirred, or filtered to remove water-insoluble fine particles. Furthermore, the collagen aqueous solution may contain appropriate amounts of additives, such as stabilizers and water-soluble polymers, for purposes such as improving mechanical strength, water resistance, heat resistance, gloss, and spinnability, preventing coloration, and preserving properties.

[0040] The collagen aqueous solution is extruded through a spinning nozzle or a slit, for example, and immersed in an inorganic salt aqueous solution to obtain undried regenerated collagen fibers. Examples of the inorganic salt aqueous solution include aqueous solutions of water-soluble inorganic salts such as sodium sulfate, sodium chloride, and ammonium sulfate. Typically, the concentration of the inorganic salt in these inorganic salt aqueous solutions is adjusted to 10 to 40% by mass. The pH of the inorganic salt aqueous solution is preferably 2 or higher, more preferably 4 or higher, and preferably 13 or lower, more preferably 12 or lower. To adjust the pH, for example, metal salts such as sodium borate and sodium acetate, hydrochloric acid, boric acid, acetic acid, and sodium hydroxide can be used. When the pH of the inorganic salt aqueous solution is within the above range, the collagen peptide bonds are less susceptible to hydrolysis, making it easier to obtain the desired fibers. The temperature of the inorganic salt aqueous solution is not particularly limited, but is generally desirably 35°C or lower, since this prevents denaturation of soluble collagen, prevents a decrease in the strength of the spun fibers, and facilitates the production of stable threads. The lower limit of the temperature of the inorganic salt aqueous solution is not particularly limited, but can generally be adjusted appropriately depending on the solubility of the inorganic salt.

[0041] The undried regenerated collagen fibers may be pretreated (crosslinked) by immersing them in an epoxy compound or a solution thereof. The amount of the epoxy compound is preferably at least 0.1 equivalent, more preferably at least 0.5 equivalent, and even more preferably at least 1 equivalent, relative to the amount of amino groups in the regenerated collagen fibers that can react with the epoxy groups of the epoxy compound, as measured by amino acid analysis, and is preferably at most 500 equivalents, more preferably at most 100 equivalents, and even more preferably at most 50 equivalents. Having the amount of the epoxy compound within this range not only ensures a sufficient water-insolubilizing effect on the regenerated collagen fibers, but is also favorable from an industrial handleability and environmental standpoint.

[0042] The epoxy compound is used as is or dissolved in various solvents. Examples of solvents include water; alcohols such as methyl alcohol, ethyl alcohol, and isopropanol; ethers such as tetrahydrofuran and dioxane; halogenated organic solvents such as dichloromethane, chloroform, and carbon tetrachloride; and neutral organic solvents such as dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). These solvents may be used alone or in combination of two or more. When water is used as the solvent, an aqueous solution of an inorganic salt such as sodium sulfate, sodium chloride, or ammonium sulfate may be used as needed. Typically, the concentration of the inorganic salt in the aqueous solution is adjusted to 10 to 40% by mass. The pH of the aqueous solution may be adjusted with, for example, a metal salt such as sodium borate or sodium acetate, or hydrochloric acid, boric acid, acetic acid, or sodium hydroxide. In this case, the pH of the aqueous solution is preferably 6 or higher, more preferably 8 or higher, from the viewpoint of not slowing down the reaction between the epoxy groups of the epoxy compound and the amino groups of collagen and ensuring sufficient insolubilization in water. Furthermore, since the pH of an aqueous solution of an inorganic salt tends to decrease over time, a buffer may be used if necessary.

[0043] The temperature during treatment of undried regenerated collagen fibers with an epoxy compound is preferably 50°C or lower, from the viewpoints of preventing denaturation of the regenerated collagen fibers, preventing a decrease in the strength of the resulting fibers, and facilitating stable production of threads.

[0044] [Treatment with a fiber treatment agent containing component (Y)] Here, the modified regenerated collagen fiber used in the present invention preferably contains the above-mentioned component (Y) from the viewpoint of improving water resistance, and in producing the modified regenerated collagen fiber, it is preferable to treat the undried regenerated collagen fiber obtained by the above-mentioned method by the following method. First, undried regenerated collagen fibers are immersed in a fiber treatment agent containing component (Y). The fiber treatment agent containing component (Y) is preferably an aqueous solution containing a polyvalent metal salt or polyvalent metal complex corresponding to component (Y). The polyvalent metal salt or polyvalent metal complex preferably contains an aluminum salt or aluminum complex, more preferably contains an aluminum salt. The aluminum salt is preferably basic aluminum chloride or basic aluminum sulfate represented by the following formula: Al(OH) n Cl 3-n , or Al2(OH) 2n (SO4) 3-n [In the formula, n is 0.5 to 2.5] Specific examples of the aluminum salt include aluminum sulfate, aluminum chloride, and alum, and these can be used alone or in combination of two or more.

[0045] The content of the polyvalent metal salt and polyvalent metal complex in the fiber treatment agent is preferably 0.3 mass % or more and 5 mass % or less in terms of polyvalent metal oxide (aluminum oxide when the polyvalent metal is aluminum).

[0046] In order to prevent the polyvalent metal salt or polyvalent metal complex from being rapidly absorbed into the undried regenerated collagen fibers and causing uneven concentration, inorganic salts such as sodium chloride, sodium sulfate, and potassium chloride may be added to the fiber treatment agent as appropriate.

[0047] The pH of the fiber treatment agent at 25°C is preferably in the range of 2.5 or more and 5 or less, and can be adjusted using, for example, hydrochloric acid, sulfuric acid, acetic acid, sodium hydroxide, sodium carbonate, etc. A pH of 2.5 or more can suppress denaturation of the collagen structure, while a pH of 5 or less reduces the risk of precipitation of polyvalent metal salts or polyvalent metal complexes. It is preferable to initially adjust the pH to 2.2 or more and 3.5 or less to allow the aqueous solution of the polyvalent metal salt or polyvalent metal complex to sufficiently penetrate into the undried regenerated collagen fibers, and then add, for example, sodium hydroxide, sodium carbonate, etc. to adjust the pH to 3.5 or more and 5 or less to complete the treatment. When a highly basic polyvalent metal salt or polyvalent metal complex is used, only an initial pH adjustment of 2.5 or more and 5 or less is sufficient.

[0048] When treating with a fiber treatment agent containing component (Y), the bath ratio of regenerated collagen fibers or undried regenerated collagen fibers to the fiber treatment agent (dry mass of regenerated collagen fibers or undried regenerated collagen fibers:mass of the fiber treatment agent) is preferably 1:2 to 1:500, more preferably 1:3 to 1:250, even more preferably 1:5 to 1:100, and even more preferably 1:20 to 1:50, when the mass of the fibers after conditioning at 20°C and a relative humidity of 65% for 24 hours is taken as the dry mass.

[0049] The temperature during treatment with the fiber treatment agent containing component (Y) (liquid temperature of the fiber treatment agent) is not particularly limited, but is preferably 5°C or higher, more preferably 10°C or higher, and is preferably 50°C or lower, more preferably 45°C or lower.

[0050] The treatment time (immersion time) with the fiber treatment agent containing component (Y) is preferably 15 minutes or more, more preferably 30 minutes or more, even more preferably 1 hour or more, and even more preferably 3 hours or more, and is preferably 48 hours or less, more preferably 33 hours or less, and even more preferably 20 hours or less.

[0051] After treating the undried regenerated collagen fibers with an epoxy compound and / or the fiber treatment agent, they may be washed with water, for example, by washing with running water for 10 minutes to 4 hours.

[0052] [Treatment with a fiber treatment agent containing component (X)] Regenerated collagen fibers, or undried regenerated collagen fibers obtained by treatment with a fiber treatment agent containing component (Y), are treated with a fiber treatment agent containing component (X) to obtain modified regenerated collagen fibers that can be dyed with the dye composition of the present invention.

[0053] From the viewpoints of improving penetration into fibers and improving color matching effects, the content of component (X) in the fiber treatment agent is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, still more preferably 2.5% by mass or more, even more preferably 3.0% by mass or more, and preferably 60% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less. The content of component (X) in the fiber treatment agent is preferably 0.3% by mass or more and 60% by mass or less, more preferably 0.5% by mass or more and 60% by mass or less, even more preferably 1.0% by mass or more and 40% by mass or less, still more preferably 2.5% by mass or more and 40% by mass or less, and even more preferably 3.0% by mass or more and 35% by mass or less.

[0054] When component (X1) is used as component (X), the content of component (X1) in the fiber treatment agent, calculated as benzoic acid, is even more preferably 5.0% by mass or more, even more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, and even more preferably 30% by mass or less, from the viewpoints of improving penetration into fibers and improving color matching effect. When component (X1) is used as component (X), the content of component (X1) in the fiber treatment agent, calculated as benzoic acid, is preferably 0.3% by mass or more and 60% by mass or less, more preferably 0.5% by mass or more and 60% by mass or less, even more preferably 1.0% by mass or more and 40% by mass or less, still more preferably 2.5% by mass or more and 40% by mass or less, still more preferably 3.0% by mass or more and 35% by mass or less, still more preferably 5.0% by mass or more and 30% by mass or less, still more preferably 10% by mass or more and 30% by mass or less, still more preferably 15% by mass or more and 30% by mass or less, and still more preferably 20% by mass or more and 30% by mass or less.

[0055] When component (X2) is used as component (X), the content of component (X2) in the fiber treatment agent is even more preferably 4.0% by mass or more, and even more preferably 30% by mass or less, even more preferably 20% by mass or less, even more preferably 10% by mass or less, and even more preferably 5% by mass or less, from the viewpoints of improving penetration into fibers and improving color matching effect. When component (X2) is used as component (X), the content of component (X2) in the fiber treatment agent is preferably 0.3% by mass or more and 60% by mass or less, more preferably 0.5% by mass or more and 60% by mass or less, even more preferably 1.0% by mass or more and 40% by mass or less, still more preferably 2.5% by mass or more and 40% by mass or less, still more preferably 3.0% by mass or more and 35% by mass or less, still more preferably 4.0% by mass or more and 30% by mass or less, still more preferably 4.0% by mass or more and 20% by mass or less, still more preferably 4.0% by mass or more and 10% by mass or less, and still more preferably 4.0% by mass or more and 5% by mass or less.

[0056] The fiber treating agent containing component (X) preferably further contains a pH adjuster. The pH adjuster is not particularly limited as long as it can adjust the pH to the desired level, and examples thereof include alkalis such as sodium hydroxide and potassium hydroxide, and acids such as phosphoric acid, sulfuric acid and hydrochloric acid.

[0057] The fiber treating agent containing component (X) further contains water. The water content in the fiber treating agent is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and even more preferably 70% by mass or more, and is preferably 99.7% by mass or less.

[0058] The pH of the fiber treatment agent containing component (X) at 25°C is preferably 3.0 or higher, more preferably 3.5 or higher, and even more preferably 4.0 or higher, from the viewpoint of suppressing damage to fibers, and is preferably 7.5 or lower, more preferably 7.0 or lower, and even more preferably 6.5 or lower, from the viewpoint of suppressing damage to fibers. The pH of the fiber treatment agent containing component (X) at 25°C is preferably 3.0 or higher and 7.5 or lower, more preferably 3.5 or higher and 7.0 or lower, and even more preferably 4.0 or higher and 6.5 or lower. The pH can be measured by the method described in the Examples.

[0059] Treatment with a fiber treatment agent containing component (X) can be carried out by immersing regenerated collagen fibers, or undried regenerated collagen fibers obtained by treatment with a fiber treatment agent containing component (Y), in the fiber treatment agent containing component (X).

[0060] When treating with a fiber treatment agent containing component (X), the bath ratio of regenerated collagen fibers or undried regenerated collagen fibers to the fiber treatment agent (dry mass of regenerated collagen fibers or undried regenerated collagen fibers:mass of the fiber treatment agent) is preferably 1:2 to 1:500, more preferably 1:3 to 1:250, even more preferably 1:5 to 1:100, and even more preferably 1:20 to 1:50, when the mass of the fibers after conditioning at 20°C and a relative humidity of 65% for 24 hours is taken as the dry mass.

[0061] The temperature during treatment with a fiber treatment agent containing component (X) (the temperature of the fiber treatment agent) is preferably 20°C or higher, more preferably 25°C or higher, and even more preferably 30°C or higher, from the viewpoint of improving penetration into fibers, and from the viewpoint of suppressing damage to fibers, it is preferably less than 100°C, more preferably 90°C or lower, even more preferably 80°C or lower, still more preferably 70°C or lower, and even more preferably 60°C or lower. The temperature during treatment with a fiber treatment agent containing component (X) (the temperature of the fiber treatment agent) is preferably 20°C or higher and lower than 100°C, more preferably 20°C or higher and 90°C or lower, even more preferably 25°C or higher and 80°C or lower, still more preferably 25°C or higher and 70°C or lower, and even more preferably 30°C or higher and 60°C or lower. When treating with a heated fiber treatment agent, the regenerated collagen fibers or undried regenerated collagen fibers may be immersed in the heated fiber treatment agent, or the regenerated collagen fibers or undried regenerated collagen fibers may be immersed in a cold fiber treatment agent and then the fiber treatment agent may be heated.

[0062] The treatment time (immersion time) with the fiber treatment agent containing component (X) is preferably 15 minutes or more, more preferably 30 minutes or more, even more preferably 1 hour or more, and even more preferably 3 hours or more from the viewpoint of improving the treatment effect, and is preferably 48 hours or less, more preferably 33 hours or less, and even more preferably 20 hours or less from the viewpoint of suppressing damage to the fiber. The treatment time (immersion time) with the fiber treatment agent containing component (X) is preferably 15 minutes to 48 hours, more preferably 30 minutes to 33 hours, even more preferably 1 hour to 20 hours, and even more preferably 3 hours to 20 hours.

[0063] Treatment with the fiber treatment agent containing component (X) is preferably carried out in an environment in which evaporation of water is suppressed. Specific means for suppressing evaporation of water include covering the container of the fiber treatment agent in which the fibers are immersed with a film-like substance, cap, lid, or the like made of a material that is impermeable to water vapor.

[0064] After treatment with the fiber treatment agent, the resulting modified regenerated collagen fibers are preferably washed with water, for example, by washing with running water for 10 minutes to 4 hours.

[0065] When component (X2) is used as component (X), the treatment with the fiber treatment agent containing component (X2) may be carried out two or more times. Specifically, it is preferable to carry out the following steps (1) and (2) in this order two or more times. (1) A step of immersing regenerated collagen fibers or undried regenerated collagen fibers obtained by treatment with a fiber treatment agent containing component (Y) in a fiber treatment agent containing component (X1). (2) A step of removing the fibers immersed in the fiber treatment agent in (1) and rinsing them with water.

[0066] From the viewpoint of improving the treatment effect, the treatment conditions for the first treatment and the second and subsequent treatments are more preferably within the following ranges, with the other points remaining the same as above. In the first treatment, the pH at 25°C of the fiber treatment agent used in step (1) is preferably 4.5 or higher, more preferably 5.0 or higher, and is preferably 7.5 or lower, more preferably 7.0 or lower, and even more preferably 6.5 or lower, from the viewpoints of improving penetration into the fiber and suppressing damage to the fiber. In the first treatment, the pH at 25°C of the fiber treatment agent used in step (1) is preferably 4.5 or higher and 7.5 or lower, more preferably 5.0 or higher and 7.0 or lower, and even more preferably 5.0 or higher and 6.5 or lower. In the first treatment, the treatment time (immersion time) in step (1) is preferably 3 hours or more, more preferably 4 hours or more, and even more preferably 6 hours or more from the viewpoint of improving the treatment effect, and is preferably 48 hours or less, more preferably 33 hours or less, and even more preferably 20 hours or less from the viewpoint of suppressing damage to the fiber. In the first treatment, the treatment time (immersion time) in step (1) is preferably 3 hours or more and 48 hours or less, more preferably 4 hours or more and 33 hours or less, and even more preferably 6 hours or more and 20 hours or less.

[0067] In the second or subsequent treatments, the pH at 25°C of the fiber treatment agent used in step (1) is preferably 3.0 or higher, more preferably 3.5 or higher, and is preferably 6.0 or lower, more preferably 5.5 or lower, even more preferably 5.0 or lower, and still more preferably less than 4.5, from the viewpoint of improving the treatment effect. In the second or subsequent treatments, the pH at 25°C of the fiber treatment agent used in step (1) is preferably 3.0 or higher and 6.0 or lower, more preferably 3.0 or higher and 5.5 or lower, even more preferably 3.5 or higher and 5.0 or lower, and still more preferably 3.5 or higher and lower than 4.5. In the second or subsequent treatments, the treatment time (immersion time) in step (1) is preferably 15 minutes or more, more preferably 30 minutes or more, from the viewpoint of improving the treatment effect, and is preferably 5 hours or less, more preferably 3 hours or less, and even more preferably 2 hours or less, from the viewpoint of suppressing damage to the fibers. In the second or subsequent treatments, the treatment time (immersion time) in step (1) is preferably 15 minutes or more and 5 hours or less, more preferably 15 minutes or more and 3 hours or less, and even more preferably 30 minutes or more and 2 hours or less.

[0068] The number of treatments with the fiber treatment agent containing component (X2) is preferably 2 to 5 times, more preferably 2 to 3 times, from the viewpoint of improving the treatment effect and productivity. After the above treatment, the resulting modified regenerated collagen fibers are preferably dried. The drying temperature is preferably 40°C or higher, more preferably 50°C or higher, from the viewpoint of improving the drying rate, and is preferably 100°C or lower, more preferably 80°C or lower, from the viewpoint of suppressing damage to the fibers. The drying time is preferably 15 minutes or longer, more preferably 30 minutes or longer, and from the viewpoint of suppressing damage to the fibers, is preferably 48 hours or shorter, more preferably 33 hours or shorter, and even more preferably 20 hours or shorter.

[0069] By carrying out the above modification treatment, component (X) penetrates into the regenerated collagen fibers. Furthermore, when treatment is carried out with a fiber treatment agent containing component (Y), component (X) is strongly coordinated to polyvalent metals within the fibers. When fibers for head accessories containing the modified regenerated collagen fibers are dyed using the method of the present invention, the dyes in dyeing agent A and hair dye B, described below, interact with component (X) and component (Y), making them more likely to remain within the modified regenerated collagen fibers, further improving dyeability and fastness.

[0070] The regenerated collagen fibers to be dyed by the method of the present invention may be fibers that contain at least a portion of the modified regenerated collagen fibers, or may be fibers consisting of only modified regenerated collagen fibers. From the viewpoint of further improving dyeability, fastness, and color compatibility, the regenerated collagen fibers to be dyed by the method of the present invention are preferably fibers consisting of only modified regenerated collagen fibers.

[0071] The method of the present invention comprises the following steps (I), (II), and (III). Step (I) A step of attaching a head accessory containing the fiber for a head accessory to hair dyed with hair dye B. Step (II): A step of keeping the hair and the fiber for head accessories in a wet state while the hair and the fiber for head accessories are in contact with each other. Step (III) A step of dyeing the fiber for head accessories with dye A

[0072] The fiber for head accessories used in steps (I) and (II) contains the modified regenerated collagen fiber. In step (II), the dye migrates from the hair dyed with dye B to the fiber for head accessories containing the modified regenerated collagen fiber, dyeing the fiber for head accessories. This reduces the color difference between the hair and the fiber for head accessories containing the regenerated collagen fiber, improving the color matching effect.

[0073] Here, the fiber for head accessories used in the method of the present invention may be colored or uncolored, but from the viewpoint of improving the color compatibility between hair and the fiber for head accessories containing regenerated collagen fibers, it is preferable that the fiber be colored, for example with a pigment. The method of the present invention is either (1) a method having the steps (III), (I), and (II) in this order, or (2) a method having the steps (I), (III), and (II) in this order. In the method (1), dye A is applied to fibers for head accessories (step (III)) to obtain a head accessory containing the dyed fibers for head accessories. The head accessory is then attached to hair dyed with hair dye B (step (I)), and the hair and the dyed fibers for head accessories are then left in a wet state while in contact with each other (step (II)). A rinsing step or a washing step with a detergent may be included between steps (III) and (I), and a rinsing step is preferably included. In the method (2), a head accessory containing the head accessory fiber is attached to hair dyed with hair dye B (step (I)), and then, without removing the head accessory containing the head accessory fiber, dye A is applied to the head accessory fiber to obtain a head accessory containing the dyed head accessory fiber (step (III)). Next, the hair and the dyed head accessory fiber are kept in contact with each other and are kept in a wet state (step (II)). In step (III) of applying dye A to the head accessory fiber, a conventional method such as wrapping the head accessory fiber in aluminum foil or plastic wrap may be used. Among the above, the method (1) is preferred from the viewpoint of ease of dyeing treatment, that is, the step (III) is preferably carried out before the step (I).

[0074] <Process (III)> In step (III), the fiber for head accessories is applied with dye A. The fiber for head accessories contains regenerated collagen fibers including the modified regenerated collagen fibers.

[0075] (Dyeing agent A) From the viewpoint of dyeing by penetrating the interior of the modified regenerated collagen fibers, the dye A is preferably a dye containing one or more dyes selected from the group consisting of oxidative dyes, acid dyes, and basic dyes.

[0076] [Oxidation dyes] The oxidation dye preferably includes 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.

[0077] 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):

[0078] [ka]

[0079] (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. 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).

[0080] [ka]

[0081] [ka]

[0082] (In the above formula, * indicates a bond. R A ~R C is the same as above.)

[0083] From the viewpoint of improving the dyeability, fastness, and color compatibility of the modified regenerated collagen fiber, the oxidation dye is preferably an oxidation dye intermediate (A) containing one or more members 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):

[0084] [ka]

[0085] (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.

[0086] (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.

[0087] The components (A1) and (A2) and the couplers (A1-1) to (A1-3) and (A2-1) to (A2-2) may be in the form of a salt, and the type of salt is not particularly limited.

[0088] Component (A1) is a coupler having a specific structure, which makes it easy for component (A1) to form a trimer or higher reaction product. Similarly, component (A2), a coupler, also has a specific structure, which makes it easy for component (A2) to form a dimer or higher reaction product. 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 produced inside the fiber, which is thought to improve fastness.

[0089] [Component (A1)] Component (A1) is at least one 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):

[0090] [ka]

[0091] (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. 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.

[0092] <Coupler (A1-1)> The coupler (A1-1) preferably includes a compound represented by the following general formula (A11) or a salt thereof.

[0093] [ka]

[0094] (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.

[0095] 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 3are 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.

[0096] In the general formula (A11), R 1 is 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.

[0097] 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.

[0098] <Coupler (A1-2)> The coupler (A1-2) preferably includes a compound represented by the following general formula (A12) or a salt thereof.

[0099] [ka]

[0100] (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 7is an electron-donating group attached to the 6-carbon atom.) 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.

[0101] 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.

[0102] <Coupler (A1-3)> The coupler (A1-3) preferably includes a compound represented by the following general formula (A13) or a salt thereof.

[0103] [ka]

[0104] (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 R24 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.

[0105] The electron-donating group, the alkyl group, and preferred embodiments thereof in formula (A13) are the same as those in formula (A12).

[0106] 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.

[0107] 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.

[0108] [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.

[0109] 《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).

[0110] [ka]

[0111] (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.)

[0112] 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.

[0113] 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).

[0114] Specific examples of the compound represented by general formula (A21) include ortho-aminophenol, 2,4-diaminophenoxyethanol, and salts thereof.

[0115] 《Coupler (A2-2)》 The coupler (A2-2) preferably includes a compound represented by the following general formula (A22) or a salt thereof.

[0116] [ka]

[0117] (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.)

[0118] The electron-donating group, the alkyl group, and preferred embodiments thereof in formula (A22) are the same as those in formula (A21).

[0119] 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.

[0120] 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 a coupler (A2-1), and more preferably contains one or more selected from the group consisting of ortho-aminophenol, 2,4-diaminophenoxyethanol, and salts thereof.

[0121] Among the above, from the viewpoint of compatibility, the oxidation dye intermediate (A) preferably contains component (A1), and more preferably contains one or more 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. The oxidation dye intermediate (A) preferably contains a coupler (A1-1), more preferably one or more selected from the group consisting of meta-aminophenol, resorcinol, 2-methylresorcinol, 1-naphthol, and salts thereof.

[0122] From the viewpoint of improving dyeability, fastness, and color compatibility, the total content of components (A1) and (A2) 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. Furthermore, when the oxidation dye intermediate (A) contains another oxidation dye intermediate (for example, a precursor of component (A3) described below), the total content of components (A1) and (A2) 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.

[0123] From the viewpoint of improving dyeability, fastness, and color compatibility, 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.

[0124] [Component (A3): Precursor] From the viewpoint of further improving dyeability, fastness, and color compatibility, the oxidation dye intermediate (A) preferably further contains component (A3): a 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, without any limitation, 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.

[0125] Among the above, from the viewpoint of further improving dyeability, fastness, and color compatibility when used in combination with the couplers of components (A1) and (A2), component (A3) preferably contains one or more selected from the group consisting of toluene-2,5-diamine, para-aminophenol, 4-amino-metacresol, 1-hydroxyethyl-4,5-diaminopyrazole, and salts thereof.

[0126] 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, fastness, and color matching effects. 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 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.

[0127] 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, fastness, and color matching effects, 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.

[0128] From the viewpoint of further improving dyeability, fastness, and color compatibility, 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. 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 undissociated molecular weights of the components (A1), (A2), and (A3) are all within the above range. Furthermore, the undissociated molecular weight of the oxidative dye intermediate (A) refers to the molecular weight of the oxidative dye intermediate (A) in a 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.

[0129] When the dye used in staining agent A includes an oxidation dye, staining agent A is preferably a multi-component staining agent having at least a first component and a second component. Here, the first agent contains the oxidation dye intermediate (A), an alkaline agent, and water, and the second agent contains hydrogen peroxide and water.

[0130] [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, fastness, and color compatibility, 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.

[0131] 〔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.

[0132] [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.

[0133] The content of each component in the first agent is preferably within the following ranges. From the viewpoint of improving dyeability, the content of the oxidation dye intermediate (A) in the first agent 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 0.05% 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, it is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and still more preferably 2.0% by mass or less. The content of the oxidation dye intermediate (A) in the first agent is preferably 0.005% by mass or more and 5.0% by mass or less, more preferably 0.010% by mass or more and 3.0% by mass or less, even more preferably 0.02% by mass or more and 3.0% by mass or less, still more preferably 0.05% by mass or more and 3.0% by mass or less, still more preferably 0.10% by mass or more and 3.0% by mass or less, still more preferably 0.2% by mass or more and 3.0% by mass or less, still more preferably 0.3% by mass or more and 3.0% by mass or less, and still more preferably 0.5% by mass or more and 2.0% by mass or less.

[0134] From the viewpoint of improving dyeability, the total content of component (A1) and component (A2) in the first agent is preferably 0.003% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.02% by mass or more, still more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and still more preferably 0.25% by mass or more, and from the viewpoint of improving formulation stability, it is preferably 5.0% by mass or less, more preferably 3.0% 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. The total content of component (A1) and component (A2) in the first agent is preferably 0.003% by mass or more and 5.0% by mass or less, more preferably 0.01% by mass or more and 3.0% by mass or less, even more preferably 0.02% by mass or more and 3.0% by mass or less, still more preferably 0.05% by mass or more and 2.0% by mass or less, even more preferably 0.1% by mass or more and 1.5% by mass or less, still 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.

[0135] 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, from the viewpoint of improving dyeability, fastness, and color compatibility. Furthermore, from the viewpoint of maintaining constant reactivity, it is preferably 10% by mass or less, more preferably 7.5% by mass or less, and even more preferably 5.0% by mass or less. 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, and even more preferably 1.0% by mass or more and 5.0% by mass or less. The content of the alkaline agent herein means an effective amount of the alkaline agent.

[0136] 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.

[0137] (pH) From the viewpoint of improving dyeability, fastness, and color compatibility, the pH of the first agent is preferably 6 or more, more preferably 8 or more, and even more preferably 10 or more. From the viewpoint of maintaining constant reactivity, the pH is preferably 12 or less, more preferably 11.5 or less, and even more preferably 11.0 or less. The pH of the first agent is preferably 6 or more and 12.0 or less, more preferably 8 or more and 11.5 or less, and even more preferably 10 or more and 11.0 or less. The pH can be measured at 25°C by the method described in the Examples.

[0138] (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 components by any method. The first agent of this embodiment can be preferably obtained by mixing a medium (e.g., water), a dye, and other components under heating (e.g., 60 to 80°C) to uniformly dissolve or disperse the dye and other components, and then adding an alkaline agent at room temperature and mixing uniformly.

[0139] 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 from the viewpoint of improving dyeability, fastness, and color compatibility, and is preferably 10% by mass or less, more preferably 8.0% by mass or less from the viewpoint of suppressing damage to the fibers. 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 8.0% by mass or less. From the viewpoint of ease of handling, hydrogen peroxide is preferably blended in the form of an aqueous solution. In this specification, the content of hydrogen peroxide in the second agent means an effective amount of hydrogen peroxide.

[0140] 〔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 99.9% by mass or less. The content of water in the second agent comprises the remainder of the hydrogen peroxide.

[0141] [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.

[0142] (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. The pH of the second agent is preferably 2.5 or higher and 6 or lower, more preferably 2.5 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.

[0143] (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.

[0144] The multi-agent stain is used by mixing at least the first agent and the second agent. The mixing may be performed at the time of use, or a mixture that has been mixed in advance may be used, but a mixture that has been mixed in advance is preferably used. Note that the multi-agent stain may be a mixture of at least the first agent and the second agent, and may also include a mixture that further includes 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. After mixing the first and second agents, the pH may be adjusted before use. In this case, the pH is preferably 3.0 or higher, more preferably 3.5 or higher, even more preferably 4.0 or higher, from the viewpoints of suppressing damage to fibers and improving dyeability, fastness after dyeing, and color compatibility, and is preferably 7.5 or lower, more preferably 7.0 or lower, even more preferably 6.5 or lower. The pH of the composition after mixing the first and second agents is preferably 3.0 or higher and 7.5 or lower, more preferably 3.5 or higher and 7.0 or lower, even more preferably 4.0 or higher and 6.5 or lower, at 25°C. When the first and second agents are mixed in advance and used, they may be left to stand for a certain period of time before use. In this case, the standing time is preferably 1 hour or longer, more preferably 5 hours or longer, even more preferably 1 day or longer, and still more preferably 1 month or longer from the viewpoints of handling during use and improving dyeability, fastness after dyeing, and color compatibility, and is preferably 3 years or shorter, more preferably 2 years or shorter, even more preferably 1 year or shorter, and still more preferably 6 months or shorter from the viewpoints of improving dyeability, fastness, and color compatibility.

[0145] Furthermore, the mass ratio of the oxidative dye intermediate (A) to hydrogen peroxide in the multi-component dyeing agent [oxidative dye intermediate (A) / hydrogen peroxide] is preferably 0.0005 or more, more preferably 0.001 or more, even more preferably 0.01 or more, still more preferably 0.02 or more, and even more preferably 0.05 or more, from the viewpoint of suppressing damage to fibers caused by hydrogen peroxide. Furthermore, from the viewpoint of improving dyeability, fastness after dyeing, and color compatibility, it is preferably 50 or less, more preferably 20 or less, even more preferably 10 or less, still more preferably 5 or less, still more preferably 2 or less, and even more preferably 0.5 or less. That is, the mass ratio [oxidative dye intermediate (A) / hydrogen peroxide] is preferably 0.0005 or more and 50 or less, more preferably 0.001 or more and 20 or less, even more preferably 0.01 or more and 10 or less, still more preferably 0.02 or more and 5 or less, still more preferably 0.05 or more and 2 or less, and even more preferably 0.05 or more and 0.5 or less. The mass of hydrogen peroxide is the amount of active ingredient.

[0146] [Acid dye] As the acid dye, any known acid dye can be used without particular limitation. However, from the viewpoint of improving the fastness and color compatibility of the modified regenerated collagen fiber after dyeing, the acid dye preferably includes an acid dye (C) that has a sulfonic acid group and satisfies at least one of the following (3) and (4): (3) Molecular weight of 500 or more (4) When the molecular weight is Mw, the difference (ab) between the number of sulfonic acid groups (a) and the number of cationic sites (b) divided by Mw [(ab) / Mw] is 0.0045 or less. The molecular weight of the acid dye here refers to the molecular weight in an undissociated (acid) state. For example, even if at least a portion of the sulfonic acid groups in the acid dye are in the form of sulfonate salts, the molecular weight of the acid dye refers to the molecular weight in the undissociated sulfonic acid state, and does not include the molecular weight of the counter ion. This also includes cases where the acid dye has an onium group such as a quaternary ammonium group, but in such cases, the counter ion is similarly not included in the molecular weight. The acid dye (C) may be an acid dye that satisfies either one of the above (3) and (4), or may be an acid dye that satisfies both the above (3) and (4).

[0147] Because the acid dye (C) has a sulfonic acid group, it interacts with the structural moieties derived from the components (X) and (Y) inside the modified regenerated collagen fiber, making it easier for the acid dye (C) to remain inside the fiber, which is thought to further improve fastness. Furthermore, acid dyes that satisfy the above condition (3) have a large molecular weight, so that they are less likely to fade after dyeing and can improve color fastness. Furthermore, since the object to be dyed is regenerated collagen fibers, it is thought that, unlike hair, it will be possible to dye the fibers by penetrating the acid dye into the fibers. When an acid dye that satisfies the above condition (4) has a value [(ab) / Mw] obtained by dividing the difference (ab) between the number of sulfonic acid groups (a) and the number of cationic sites (b) in the acid dye by Mw, which is a predetermined value or less, the repulsion between the negative charges between the structural portion derived from compound (X) in the modified regenerated collagen fiber and the acid dye can be sufficiently reduced, and it is thought that this improves the fixation of the acid dye to the modified regenerated collagen fiber, thereby further improving the dyeability and fastness.

[0148] The number (a) of sulfonic acid groups in the acid dye (C) may be 1 or more, and from the viewpoint of improving the dyeability, fastness, and color compatibility of the modified regenerated collagen fibers, it is preferably 1 or more, more preferably 2 or more, and preferably 6 or less, more preferably 5 or less, even more preferably 4 or less, and still more preferably 3 or less. That is, the number (a) of sulfonic acid groups in the acid dye (C) is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, even more preferably 1 or more and 4 or less, still more preferably 1 or more and 3 or less, and still more preferably 2 or more and 3 or less. The "number (a) of sulfonic acid groups in the acid dye (C)" herein means the number of sulfonic acid groups in the acid dye (C) in a non-dissociated (acid) state.

[0149] The acid dye (C) may be at least partially in the form of a salt, and from the viewpoint of improving the dyeability, fastness, and color compatibility of the modified regenerated collagen fiber, the salt preferably includes an ammonium salt or a metal salt, more preferably an ammonium salt or one or more metal salts selected from the group consisting of alkali metals, alkaline earth metals, and transition metals, more preferably an ammonium salt or one or more metal salts selected from the group consisting of potassium, sodium, calcium, iron, and chromium, even more preferably an ammonium salt or one or more metal salts selected from the group consisting of sodium, calcium, iron, and chromium, and even more preferably a sodium salt.

[0150] From the viewpoint of improving the fastness of the modified regenerated collagen fibers, it is preferable that the acid dye (C) further has a cationic moiety. Examples of the cationic moiety include quaternary ammonium cationic moieties and iminium cationic moieties, and from the viewpoint of improving the robustness of the modified regenerated collagen fiber, it preferably contains an iminium cationic moiety.

[0151] The number of cationic moieties (b) in the acid dye (C) may be 0. When the acid dye (C) has cationic moieties, from the viewpoint of improving the fastness of the modified regenerated collagen fibers, the number of cationic moieties (b) in the acid dye (C) is preferably 1 or more and preferably 5 or less, more preferably 4 or less, even more preferably 3 or less, and still more preferably 2 or less. That is, it is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, even more preferably 1 or more and 3 or less, and still more preferably 1 or more and 2 or less. The number (b) of cationic moieties in the acid dye (C) is preferably 0 or more and 5 or less, more preferably 0 or more and 4 or less, even more preferably 0 or more and 3 or less, still more preferably 0 or more and 2 or less, and still more preferably 1 or more and 2 or less.

[0152] From the viewpoint of improving the fastness of the modified regenerated collagen fibers, the difference (ab) between the number of sulfonic acid groups (a) in the acid dye (C) and the number of cationic sites (b) in the acid dye (C) is preferably 1 or more, and preferably 5 or less, more preferably 4 or less, even more preferably 3 or less, and still more preferably 2 or less. That is, it is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, even more preferably 1 or more and 3 or less, and still more preferably 1 or more and 2 or less.

[0153] From the viewpoint of improving the dyeability, fastness, and color compatibility of the modified regenerated collagen fiber, it is preferable that the acid dye (C) has a small number of carboxy groups, and the number of carboxy groups in the acid dye (C) is preferably 2 or less, more preferably 1 or less, and even more preferably 0.

[0154] (Requirement (3)) The acid dye (C) that satisfies the above condition (3) has a sulfonic acid group and a molecular weight of 500 or more. When the acid dye (C) satisfies the above (3), the molecular weight of the acid dye (C) is preferably 520 or more, more preferably 540 or more, from the viewpoint of improving the fastness of the modified regenerated collagen fibers after dyeing, and is also preferably 1,500 or less, more preferably 1,200 or less, even more preferably 1,000 or less, still more preferably 900 or less, still more preferably 800 or less, still more preferably 780 or less, still more preferably 750 or less, still more preferably 700 or less, and still more preferably 650 or less. When the acid dye (C) satisfies the above (3), the molecular weight of the acid dye (C) is preferably 500 or more and 1,500 or less, more preferably 500 or more and 1,200 or less, even more preferably 500 or more and 1,000 or less, still more preferably 500 or more and 900 or less, still more preferably 500 or more and 800 or less, still more preferably 500 or more and 780 or less, still more preferably 520 or more and 750 or less, still more preferably 520 or more and 700 or less, and still more preferably 540 or more and 650 or less.

[0155] (Requirement (4)) When the acid dye (C) satisfies the above (4), the difference (ab) between the number of sulfonic acid groups in the acid dye (C) (a) and the number of cationic sites in the acid dye (C) (b), divided by Mw, where Mw is the molecular weight of the acid dye (C) (molecular weight in the undissociated (acid) state), is 0.0045 or less, preferably 0.0040 or less, more preferably 0.0030 or less, and even more preferably 0.0025 or less, from the viewpoint of improving the dyeability, fastness, and color compatibility of the modified regenerated collagen fibers. Furthermore, when the acid dye (C) satisfies the above (4), [(ab) / Mw] is preferably 0.0005 or more, more preferably 0.0010 or more. When the acid dye (C) satisfies the above (4), [(ab) / Mw] is preferably 0.0005 or more and 0.0045 or less, more preferably 0.0005 or more and 0.0040 or less, even more preferably 0.0010 or more and 0.0030 or less, and still more preferably 0.0010 or more and 0.0025 or less.

[0156] When the acid dye (C) satisfies the above (4), the molecular weight Mw is preferably 250 or more, more preferably 280 or more, even more preferably 300 or more, and still more preferably 320 or more. Also, it is preferably 1,500 or less, more preferably 1,200 or less, even more preferably 1,000 or less, still more preferably 900 or less, still more preferably 800 or less, still more preferably 780 or less, still more preferably 750 or less, still more preferably 700 or less, and still more preferably 650 or less. When the acid dye (C) satisfies the above (4), the molecular weight Mw is preferably 250 or more and 1,500 or less, more preferably 250 or more and 1,200 or less, even more preferably 250 or more and 1,000 or less, still more preferably 250 or more and 900 or less, still more preferably 280 or more and 800 or less, still more preferably 280 or more and 780 or less, still more preferably 280 or more and 750 or less, still more preferably 300 or more and 700 or less, and still more preferably 320 or more and 650 or less.

[0157] The acid dye (C) may satisfy both of the above (3) and (4), and in that case, the molecular weight of the acid dye (C) is 500 or more and [(ab) / Mw] is 0.0045 or less. The preferred ranges of the molecular weight and [(ab) / Mw] of the oxidation dye (C) are the same as those described above.

[0158] From the viewpoint of improving the dyeability, fastness, and color compatibility of the modified regenerated collagen fiber, the acid dye (C) is preferably Acid Black 52 (Color Index No. 15711), Acid Green 1 (Color Index No. 10020), Food Black 1 (Color Index No. 28440), Food Green 3 (Color Index No. 42053), Acid Green 5 (Color Index No. 42095), Acid Blue 9 (Color Index No. 42090), Acid Blue 5 (Color Index No. 42052), Acid Green 3 (Color Index No. 42085), Acid Green 25 (Color Index No. 61570), Acid Brown 13 (Color Index No. 10410), Acid Red 52 (Color Index No. 45100), Acid Black 1 (Color Index No. 20470), Acid Red 18 (Color Index No. 10410), Acid Red ... No.16255), Acid Red 27(Color Index No.16185), Acid Blue 3(Color Index No.42051), Acid Green 50(Color Index No.44090), Acid Red 73(Color Index No.27290), Acid Blue 1(Color Index No.42045), Acid Red 184(Color Index No.15685), Acid Red 35(Color Index No.18065), Acid Red 14(Color Index No.14720), Food Red 6(Color Index No.16155), Acid Orange 3(Color Index No.10385), Acid Orange 24(Color Index No.20170), Acid Violet 43(Color Index No.60730), Acid Blue 62(Color Index No.62045), Acid Red 88(Color Index No.15620)、Acid Yellow 11(Color Index No.18820)、Acid Yellow 36(Color Index No.13065)、Acid Yellow 1(Color Index No.10316)、Acid Orange 7(Color Index No.15510)、Acid Orange 20(Color Index No.14600)、Acid Orange 6(Color Index No.14270)、Food Red 17(Color Index No.16035)、Acid Red 41(Color Index No.16290)、Acid Red 1(Color Index No.18050)、Acid Red 155(Color Index No.18130)、Acid Red 180(Color Index No.18736)、Acid Yellow 17(Color Index No.18965)、Acid Yellow 23(Color Index No.19140)、Acid Red 163(Color Index No.24790)、Food Black 2(Color Index No.27755)、Direct Orange 39(Color Index No.40215)、Acid Blue 7(Color Index No.42080)、Acid Green 9(Color Index No.42100)、Acid Green 22(Color Index No.42170)、Acid Blue 104(Color Index No.42735)、Acid Violet 9(Color Index No.45190)、Acid Red 50(Color Index No.45220)、Acid Violet 50(Color Index No.50325)、Acid Black 2(Color Index No.50420)、Acid Blue 80(Color Index No.61585)、Acid Blue 87(Color Index No.74180)、Acid Red 195(Color Index No.18760)、Acid Red 249(Color Index No.The color may include one or more selected from the group consisting of Acid Red 131, Acid Red 337 (Color Index No. 17102), Acid Red 18134, Acid Red 131, and Acid Red 337 (Color Index No. 17102).

[0159] Acid dye (C) is more preferably Acid Black 52 (Color Index No. 15711), Acid Green 1 (Color Index No. 10020), Food Black 1 (Color Index No. 28440), Food Green 3 (Color Index No. 42053), Acid Green 5 (Color Index No. 42095), Acid Blue 9 (Color Index). No.42090), Acid Blue 5(Color Index No.42052), Acid Green 3(Color Index No.42085), Acid Green 25(Color Index No.61570), Acid Brown 13(Color Index No.10410), Acid Red 52(Color Index No.45100), Acid Black 1(Color Index No.20470), Acid Red 18(Color Index No.16255), Acid Red 27(Color Index No.16185), Acid Blue 3(Color Index No.42051), Acid Green 50(Color Index No.44090), Acid Red 73(Color Index No.27290), Acid Blue 1(Color Index No.42045), Acid Yellow 36(Color Index No.13065), Acid Yellow 1(Color Index No.10316), Acid Orange 7(Color Index No.15510), Acid Blue 7(Color Index No.42080), Acid Green 9(Color Index No.42100), Acid Blue 104(Color Index No.42735), Acid Violet 50(Color Index No.50325), Acid Red 249(Color Index No. 18134), Acid Red 131, and Acid Red 337 (Color Index No. 17102).

[0160] Among the above, from the viewpoint of improving the durability of the modified regenerated collagen fibers, the acid dye (C) preferably includes one or more dyes selected from the group consisting of Food Green 3 (Color Index No. 42053), Acid Green 5 (Color Index No. 42095), Acid Blue 9 (Color Index No. 42090), Acid Blue 5 (Color Index No. 42052), Acid Green 3 (Color Index No. 42085), Acid Red 52 (Color Index No. 45100), Acid Blue 3 (Color Index No. 42051), Acid Green 50 (Color Index No. 44090), and Acid Blue 1 (Color Index No. 42045), which have a cationic moiety number (b) of 1 or more, and even more preferably includes one or more dyes selected from the group consisting of Acid Blue 9 and Acid Red 52.

[0161] [Basic dyes] As the basic dye, any known basic dye can be used without particular limitation, but from the viewpoint of improving the dyeability and fastness of the modified regenerated collagen fiber, the basic dye preferably includes a basic dye (D) (hereinafter simply referred to as "basic dye (D)") in which the value obtained by dividing the number of cationic moieties (a) by Mw [(a) / Mw] is 0.00275 or more, where Mw is the molecular weight. Because the number of cationic moieties (a) per molecular weight of the basic dye (D) is a predetermined value or more, it is thought that this enhances the electrical interaction with component (X) in the modified regenerated collagen fiber, thereby improving the dyeability. Examples of the cationic moiety include quaternary ammonium cationic moieties, imidazolium cationic moieties, pyridinium cationic moieties, pyrrolidinium cationic moieties, piperidinium cationic moieties, iminium cationic moieties, and pyrylium cationic moieties. From the viewpoint of improving the dyeability of the modified regenerated collagen fiber, it preferably contains an imidazolium cationic moiety or a pyridinium cationic moiety.

[0162] From the viewpoint of improving fastness, the molecular weight Mw of the basic dye (D) is preferably 200 or more, more preferably 220 or more, even more preferably 240 or more, and still more preferably 250 or more, and from the viewpoint of improving dyeability, it is preferably 500 or less, more preferably 450 or less, even more preferably 400 or less, still more preferably 360 or less, and still more preferably 340 or less. The molecular weight Mw of the basic dye (D) is preferably 200 or more and 500 or less, more preferably 220 or more and 450 or less, even more preferably 240 or more and 400 or less, still more preferably 250 or more and 360 or less, and still more preferably 250 or more and 340 or less. In this specification, the molecular weight of a basic dye means a state in which the dye has chloride as a counter ion and the charge is neutralized, that is, the molecular weight of the chloride.

[0163] The number (a) of cationic moieties in the basic dye (D) may be 1 or more, and is preferably 5 or less, more preferably 4 or less, even more preferably 3 or less, and still more preferably 2 or less. The number (a) of cationic moieties in the basic dye (D) is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, even more preferably 1 or more and 3 or less, still more preferably 1 or more and 2 or less, and still more preferably 1.

[0164] Furthermore, when the molecular weight of the basic dye (D) is Mw, the value obtained by dividing the number of cationic sites (a) by Mw [(a) / Mw] is 0.00275 or more, preferably 0.00280 or more, and even more preferably 0.00290 or more, from the viewpoint of improving dyeability, and is preferably 0.010 or less, more preferably 0.008 or less, even more preferably 0.006 or less, even more preferably 0.005 or less, and even more preferably 0.004 or less. When the molecular weight of the basic dye (D) is Mw, the value obtained by dividing the number of cationic moieties (a) by Mw [(a) / Mw] is 0.00275 or more, preferably 0.00275 or more and 0.010 or less, more preferably 0.00275 or more and 0.008 or less, even more preferably 0.00275 or more and 0.006 or less, still more preferably 0.00275 or more and 0.005 or less, still more preferably 0.00280 or more and 0.005 or less, and still more preferably 0.00290 or more and 0.004 or less.

[0165] Among the above, from the viewpoint of improving the dyeability, fastness, and color compatibility of the modified regenerated collagen fiber, the basic dye (D) preferably includes one or more dyes selected from the group consisting of Basic Red 51, Basic Yellow 87, Basic Orange 31, Basic Blue 124, Basic Brown 16 (Color Index No. 12250), Basic Violet 14 (Color Index No. 42510), Basic Black 7 (Color Index No. 51215), Basic Blue 25 (Color Index No. 52025), Basic Blue 6 (Color Index No. 51175), Basic Red 2 (Color Index No. 50240), Basic Red 22 (Color Index No. 11055), Basic Blue 17 (Color Index No. 52040), and Basic Blue 9 (Color Index No. 52015), and more preferably includes one or more dyes selected from the group consisting of Basic Red 51, Basic Yellow 87, Basic Orange 31, Basic Blue 124, Basic Brown 16 (Color Index No. 12250), Basic Violet 14 (Color Index No. 42510), Basic Black 7 (Color Index No. 51215), Basic Blue 25 (Color Index No. 52025), Basic Blue 6 (Color Index No. 51175), Basic Red 2 (Color Index No. 50240), Basic Red 22 (Color Index No. 11055), Basic Blue 17 (Color Index No. 52040), and Basic Blue 9 (Color Index No. 52015). Preferably, the colorant contains one or more selected from the group consisting of Basic Red 51, Basic Yellow 87, Basic Orange 31, and Basic Blue 124, and more preferably, one or more selected from the group consisting of Basic Red 51, Basic Yellow 87, and Basic Orange 31.

[0166] When the dye used in the dye A is one or more dyes selected from the group consisting of acid dyes and basic dyes, the dye A is preferably a one-component dye containing one or more dyes selected from the group consisting of acid dyes and basic dyes and water.

[0167] The content of the dye in dye A (in the case of the multi-component dye, a dye prepared by mixing at least the first and second agents at the time of use or in advance) is, from the viewpoint of improving dyeability, preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, still 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 0.1% by mass or more, and still more preferably 0.2% by mass or more, and from the viewpoint of improving formulation stability, is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. The content of the dye in dyeing agent A is preferably 0.001% by mass or more and 3% by mass or less, more preferably 0.005% by mass or more and 3% by mass or less, even more preferably 0.01% by mass or more and 3% by mass or less, still more preferably 0.02% by mass or more and 3% by mass or less, still more preferably 0.03% by mass or more and 3% by mass or less, still more preferably 0.05% by mass or more and 3% by mass or less, still more preferably 0.1% 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. From the viewpoint of improving handleability, the water content in dye A 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 99.995% by mass or less.

[0168] In addition to the above components, dye A may contain antioxidants, penetration enhancers, chelating agents, fragrances, preservatives, thickeners, pH adjusters, surfactants, texture improvers, etc., within the scope of the invention. The formulation of dye A is not particularly limited, and can be liquid, paste, cream, gel, foam, spray, wax, or other formulation depending on the product form, with liquid being preferred. The method for producing the dye A is not particularly limited, and the dye A can be produced by mixing the components by any method. The dye A of this embodiment can be 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 the dye and mixing them uniformly. When the dye A is a multi-component dye, the first and second components are separately produced and applied at the time of use or by mixing them in advance.

[0169] (Dyeing method) The method for dyeing the fiber for headwear in step (III) is not particularly limited, and for example, dye A is applied to the fiber for headwear. When dye A is a multi-component dye, the first and second components are mixed together to prepare the dye at the time of use or in advance, and then the dye is applied to the fiber for headwear.

[0170] In step (III), the method of applying dye A to the fiber for head accessories may be any method that can bring dye A into contact with the fiber for head accessories, and examples thereof include a method of applying dye A to the fiber for head accessories in a dry or wet state, and a method of immersing the fiber for head accessories in dye A. Among the above, the method of applying or immersing dye A to the fiber for head accessories in a dry state is preferred. The term "wet state" as used herein refers to the state after a process for increasing the moisture content of the fiber for head accessories. The water content of the fiber for head accessories is not particularly limited, but when the mass of the fiber for head accessories after conditioning for 24 hours at 20°C and a relative humidity of 65% is taken as 1, the mass ratio (water / fiber for head accessories) is preferably 0.05 or more, more preferably 0.10 or more, even more preferably 0.2 or more, still more preferably 0.3 or more, still more preferably 0.5 or more, still more preferably 0.7 or more, still more preferably 1.0 or more, and is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less. The water content in the fiber for head accessories in a wet state is preferably a mass ratio (water / fiber for head accessories) of 0.05 or more and 5 or less, more preferably 0.10 or more and 5 or less, even more preferably 0.2 or more and 5 or less, still more preferably 0.3 or more and 5 or less, still more preferably 0.5 or more and 3 or less, still more preferably 0.7 or more and 2 or less, and still more preferably 1.0 or more and 2 or less, where the mass of the fiber for head accessories after conditioning at 20°C and a relative humidity of 65% for 24 hours is taken as 1. Furthermore, the term "dry state" as used herein refers to the state of the fiber for head accessories after a process for reducing the moisture content of the fiber for head accessories. The water content in the fiber for head accessories is not particularly limited, but when the mass of the fiber for head accessories after conditioning for 24 hours at 20°C and a relative humidity of 65% is taken as 1, the mass ratio (water / fiber for head accessories) is preferably 0.8 or less, more preferably 0.7 or less, even more preferably 0.5 or less, still more preferably 0.3 or less, still more preferably 0.2 or less, still more preferably 0.1 or less, and still more preferably less than 0.1.

[0171] From the viewpoint of dyeability and uniformity (even dyeing), the amount of dye A applied to the fiber for headwear products is preferably a liquor ratio (dry mass of fiber for headwear products:mass of dye A) of 1:0.2 to 1:500, where the mass of the fiber after conditioning for 24 hours at 20°C and a relative humidity of 65% is taken as the dry mass. When dye A is applied to the fiber for head accessories, the amount of dye A to be applied to the fiber for head accessories is, 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, a bath ratio (dry mass of fiber for head accessories:mass of dye A) of more 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. Furthermore, when immersing the fiber for head accessories in dye A, when the mass of the fiber 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 the fiber for head accessories:mass of dye A) 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.

[0172] Furthermore, in step (III), the dyeing conditions for the fiber for head accessories may be set using as an index the mass ratio [component (X) / dye] of component (X) in the fiber for head accessories to the dye in dyeing agent A. Specifically, for example, step (III) may be carried out under conditions such that the mass ratio [component (X) / dye] of component (X) in the fiber for head accessories to the dye in dyeing agent A is preferably 3 or more, more preferably 5 or more, even more preferably 10 or more, and still more preferably 20 or more, from the viewpoints of dye compatibility, storage stability of the dyeing agent, and level dyeing ability; and further, from the viewpoints of dyeability and level dyeing ability, it is preferably 20,000 or less, more preferably 10,000 or less, even more preferably 4,000 or less, even more preferably 2,000 or less, even more preferably 1,000 or less, even more preferably 500 or less, even more preferably 200 or less, and still more preferably 100 or less. That is, the mass ratio [component (X) / dye] is preferably 3 or more and 20,000 or less, more preferably 5 or more and 10,000 or less, even more preferably 10 or more and 10,000 or less, still more preferably 10 or more and 4,000 or less, still more preferably 10 or more and 2,000 or less, still more preferably 10 or more and 1,000 or less, still more preferably 10 or more and 500 or less, still more preferably 10 or more and 200 or less, and still more preferably 20 or more and 100 or less. Furthermore, the dyeing conditions for the fiber for head accessories can also be set using the mass ratio [component (Y) / dye] of component (Y) in the fiber for head accessories to the dye in dyeing agent A as an index. Specifically, for example, from the viewpoints of dye compatibility, storage stability of the dyeing agent, and dye levelness, the mass ratio [component (Y) / dye] of component (Y) in the fiber for head accessories to the dye in dyeing agent A is preferably 0.3 or more, more preferably 0.5 or more, even more preferably 1.0 or more, and still more preferably 2 or more, and from the viewpoints of dyeability and dye levelness, step (III) can also be carried out under conditions such that the mass ratio is preferably 5000 or less, more preferably 2000 or less, even more preferably 1000 or less, still more preferably 500 or less, even more preferably 200 or less, even more preferably 100 or less, still more preferably 50 or less, even more preferably 20 or less, and still more preferably 10 or less. That is, the mass ratio [component (Y) / dye] is preferably 0.3 or more and 5000 or less, more preferably 0.5 or more and 2000 or less, even more preferably 1.0 or more and 2000 or less, still more preferably 2 or more and 2000 or less, still more preferably 2 or more and 1000 or less, still more preferably 2 or more and 500 or less, still more preferably 2 or more and 200 or less, still more preferably 2 or more and 100 or less, still more preferably 2 or more and 50 or less, still more preferably 2 or more and 20 or less, and still more preferably 2 or more and 10 or less.

[0173] In step (III), when dye agent A is applied to the fiber for a head accessory product, the application time is preferably 10 seconds or more, more preferably 20 seconds or more, from the viewpoint of further improving dyeability, fastness, and color compatibility, and is preferably 10 minutes or less, more preferably 5 minutes or less, from the viewpoint of improving productivity. 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.

[0174] In step (III), it is preferable to further carry out a step of leaving the dye A after applying it to the fiber for head accessories. The leaving time is preferably 1 minute or more, more preferably 3 minutes or more, from the viewpoint of further improving dyeability, fastness, and color compatibility, and is preferably 1 hour or less, more preferably 30 minutes or less, from the viewpoint of improving productivity. 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.

[0175] The temperature in the leaving step after step (III) is not particularly limited, but is preferably 40° C. or lower, more preferably 35° C. or lower, from the viewpoint of improving the handleability of dye agent A. Moreover, from the viewpoint of further improving dyeability, fastness, and color compatibility, the temperature is preferably 25° C. or higher, more preferably 30° C. or higher.

[0176] When the fiber for head accessories is immersed in dye agent A, the immersion time is preferably 10 seconds or more, more preferably 30 seconds or more, from the viewpoint of further improving dyeability, fastness, and color compatibility, 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. The immersion time is preferably 10 seconds or more and 3 hours or less, more preferably 10 seconds or more and 2 hours or less, and even more preferably 30 seconds or more and 1 hour or less.

[0177] After step (III), it is preferable to carry out a step of washing away excess dye A with water. This step may be carried out as step (II) or may be carried out separately from step (II). The water referred to here may be water at room temperature (5°C or higher and 35°C or lower) or warm water above 35°C.

[0178] Furthermore, the fibers for head accessories after washing away dye A with water are preferably dried before being subjected to the next step. The drying step is a step of reducing the moisture content of the fibers for head accessories after washing away dye A with water. The water content in the fibers for head accessories after drying is not particularly limited, but preferably refers to a mass ratio (water / fiber for head accessories) of 0.8 or less, more preferably 0.7 or less, even more preferably 0.5 or less, even more preferably 0.3 or less, even more preferably 0.2 or less, even more preferably 0.1 or less, and even more preferably less than 0.1, when the mass of the fibers after conditioning at 20°C and 65% relative humidity for 24 hours is taken as 1. Drying methods include, for example, towel drying, drying with a hair dryer (cold or hot air), air drying, and combinations of two or more of these drying processes.

[0179] <Process (I)> In step (I), a head accessory containing fibers for head accessories is attached to hair dyed with hair dye B. The head accessory attached to the hair in step (I) may be one that has been dyed with dye A in step (III), or it may be a head accessory containing uncolored modified regenerated collagen fibers. The head accessory product can be attached to the hair by any known method appropriate for the type, shape, etc. of the head accessory product.

[0180] (Hair dye B) The hair to which the head accessory is attached in step (I) is hair dyed with hair dye B. The entire hair does not need to be dyed with hair dye B, as long as at least a portion is dyed with hair dye B. However, from the viewpoint of improving the color compatibility between the hair and the head accessory fiber containing the modified regenerated collagen fiber, it is preferable that the entire hair be dyed with hair dye B. Hair dye B can be any hair dye that can dye hair, and commercially available hair dyes may be used. However, from the viewpoint of easily penetrating the dye in hair dye B into the interior of the fibers when transferring it to and dyeing the fibers for head accessories containing modified regenerated collagen fibers, and from the viewpoint of improving the durability of the fibers for head accessories after dyeing, hair dye B is preferably a hair dye containing one or more dyes selected from the group consisting of oxidative dyes, acidic dyes, and basic dyes, and more preferably a hair dye containing an oxidative dye. The oxidative dyes, acid dyes, and basic dyes contained in hair dye B, as well as their preferred embodiments, are the same as the dyes used in dye A, from the viewpoint of improving the dyeability, fastness, and color compatibility of regenerated collagen fibers, including modified regenerated collagen fibers.

[0181] When the dye used in hair dye B includes an oxidation dye, hair dye B is preferably a multi-component hair dye comprising at least a first and a second agent. The oxidation dye, the multi-component hair dye comprising a first and a second agent, and preferred embodiments thereof are the same as those of the multi-component dye A.

[0182] When the dye used in hair dye B is an acid dye or a basic dye, hair dye B may be a one-component dye. The acid dye, basic dye, one-component hair dye, and preferred embodiments thereof are the same as those of the one-component dye A.

[0183] The dye content in hair dye B (in the case of the multi-component hair dye, the hair dye prepared by mixing at least the first and second components at the time of use) is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.02% by mass or more, even more preferably 0.03% by mass or more, even more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more, from the viewpoint of improving dyeability, and is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, from the viewpoint of improving formulation stability. The content of the dye in hair dye B is preferably 0.005% by mass or more and 3% by mass or less, more preferably 0.01% 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, even more preferably 0.03% 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, even more preferably 0.1% by mass or more and 2% by mass or less, and even more preferably 0.2% by mass or more and 1% by mass or less. From the viewpoint of improving handleability, the water content in hair dye B 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 99.995% by mass or less.

[0184] In addition to the above-mentioned components, hair dye B may contain antioxidants, penetration enhancers, chelating agents, fragrances, preservatives, thickeners, pH adjusters, surfactants, texture enhancers, etc., within the scope of the present invention. The formulation of hair dye B is not particularly limited, and can be in the form of liquid, paste, cream, gel, foam, spray, wax, or the like depending on the product form, with liquid being preferred. The method for producing hair dye B is not particularly limited, and it can be produced by mixing the respective components by any method. Hair dye B of this embodiment can be obtained by mixing a medium (e.g., water) and other components under heating (e.g., 60 to 80°C) until uniformly dissolved, then adding the dye and mixing uniformly. When hair dye B is a multi-component dye, a first component, a second component, etc. are separately produced and applied at the time of use or by mixing them in advance. The method for producing the first component is not particularly limited, and it can be produced by mixing the respective components by any method. The first component of this embodiment can be obtained by mixing a medium (e.g., water), the dye, and other components under heating (e.g., 60 to 80°C) until uniformly dissolved or dispersed, then adding an alkali agent at room temperature and mixing uniformly. The method for producing the second component is not particularly limited, and it can be produced by mixing the respective 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.

[0185] There are no particular limitations on the method for dyeing hair with hair dye B, and conventional methods can be used. When using a commercially available hair dye, it is preferable to dye the hair according to the method described in the instructions attached to the product.

[0186] Dye A and hair dye B may be the same or different. Furthermore, the dye contained in dye A and the dye contained in hair dye B may be the same type or different types. Here, "the same type" means, for example, when the dye contained in dye A and the dye contained in hair dye B are both oxidation dyes; when the dye contained in dye A and the dye contained in hair dye B are both acid dyes; when the dye contained in dye A and the dye contained in hair dye B are both basic dyes; etc. The dye contents contained in the dye A and the hair dye B may be different from each other.

[0187] <Process (II)> In step (II), the hair and the fiber for head accessories are kept in contact with each other and kept wet. By performing this step, the dye from the hair dyed with hair dye B is transferred to the fiber for head accessories containing the modified regenerated collagen fiber, thereby improving the color matching effect. The fibers for head accessories subjected to step (II) are uncolored modified regenerated collagen fibers, or fibers for head accessories containing modified regenerated collagen fibers dyed in step (III).

[0188] The term "wet state" as used herein refers to the state of the fiber for head accessories and the hair after a process for increasing the moisture content. The water content in the fiber for head accessories and the hair is not particularly limited, but when the weight of the fiber for head accessories after conditioning for 24 hours at 20°C and a relative humidity of 65% is taken as 1, the water content in the fiber for head accessories, expressed as a mass ratio (water / fiber for head accessories), is preferably 0.05 or more, more preferably 0.10 or more, even more preferably 0.2 or more, still more preferably 0.3 or more, still more preferably 0.5 or more, still more preferably 0.7 or more, and still more preferably 1.0 or more, from the viewpoint of improving color matching, and is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less, from the viewpoint of easy handling. The water content in the fiber for head accessories in a wet state is preferably a mass ratio (water / fiber for head accessories) of 0.05 or more and 5 or less, more preferably 0.10 or more and 5 or less, even more preferably 0.2 or more and 5 or less, still more preferably 0.3 or more and 5 or less, more preferably 0.5 or more and 3 or less, even more preferably 0.7 or more and 2 or less, and still more preferably 1.0 or more and 2 or less, where the mass of the fiber for head accessories after conditioning at 20°C and a relative humidity of 65% for 24 hours is taken as 1. The method for moistening the hair and the fiber for a head accessory is not particularly limited, and examples thereof include (i) immersing the hair in water, (ii) rinsing with water, (iii) washing with a hair wash composition, (iv) treating with a rinse-off conditioner or treatment and then rinsing with water, (v) spraying or misting the hair with a water-containing spray, (vi) applying steam, (vii) wrapping with a wet towel, or (vii) wrapping in plastic wrap, aluminum foil, or the like while wet with water, and one or more of these methods can be used.

[0189] Among the above, from the viewpoint of ease of processing and improving the color compatibility between the hair and the fiber for a head accessory containing modified regenerated collagen fibers, step (II) preferably includes one or more methods selected from the group consisting of (ii) a method of rinsing the hair to which the head accessory is attached with water, and (iii) a method of washing the hair with a hair wash composition, and more preferably includes a step of washing the hair and the fiber for a head accessory with a hair wash composition, followed by rinsing with water. The water referred to here may be water at room temperature (5° C. or higher and 35° C. or lower) or warm water above 35° C. The hair wash composition used in step (II) is not particularly limited, and a commercially available product may be used.

[0190] In step (II), the time for moistening the hair and the fiber for a head accessory product is not particularly limited and can be appropriately selected depending on the method for moistening the hair. From the viewpoint of improving the color matching effect between the hair and the fiber for a head accessory product containing regenerated collagen fibers, the time is preferably 1 second or more, more preferably 5 seconds or more. From the viewpoint of reducing the burden on the hairdresser and the patient, the time is preferably 6 hours or less, more preferably 3 hours or less, and even more preferably 2 hours or less. The time is preferably 1 second or more and 6 hours or less, more preferably 5 seconds or more and 3 hours or less, and even more preferably 5 seconds or more and 2 hours or less. In step (II), the temperature at which the hair and the fiber for a head accessory are moistened is not particularly limited and can be appropriately selected depending on the method for moistening. From the viewpoint of improving the color matching effect between the hair and the fiber for a head accessory containing regenerated collagen fibers, the time is preferably above 0°C, more preferably 5°C or higher, and from the viewpoint of reducing the burden on the hairdresser and the patient, the time is preferably 100°C or lower. The temperature here refers to the temperature of the water used to moisten the hair.

[0191] After step (II), it is preferable to carry out a step of drying the head accessory and the hair to which it is attached (hereinafter simply referred to as the "drying step"). The drying step is a step of reducing the moisture content of the head accessory and the hair to which it is attached. The water content in the head accessory fiber and hair after drying is not particularly limited, but the water content in the head accessory fiber is preferably a mass ratio (water / head accessory fiber) of 0.8 or less, more preferably 0.7 or less, even more preferably 0.5 or less, even more preferably 0.3 or less, even more preferably 0.2 or less, even more preferably 0.1 or less, and even more preferably less than 0.1, when the weight of the head accessory fiber after conditioning at 20°C and 65% relative humidity for 24 hours is taken as 1. Drying methods include, for example, towel drying, drying with a hair dryer (cold or hot air), air drying, and combinations of two or more of these drying processes.

[0192] [Staining kit] The present invention further provides a dyeing kit comprising a dye A for dyeing fibers for head accessories containing regenerated collagen fibers and a hair dye B for dyeing hair, The regenerated collagen fiber provides a dyeing kit containing modified regenerated collagen fiber containing one or more compounds (X) selected from the group consisting of the following components (X1) and (X2): (X1) Benzoic acid or its salts (X2) A copolymer containing a structural unit derived from an unsaturated monomer having a carboxy group and a structural unit derived from an aromatic vinyl compound, the copolymer having an acid value of 100 mgKOH / g or more and a weight average molecular weight of 1500 or more and 15000 or less, or a salt thereof.

[0193] The dye A in the dyeing kit and its preferred embodiments are the same as the dye A used in the step (III), and the hair dye B has the same preferred embodiments as the hair dye B used in the hair dyeing.

[0194] The staining kit can be used, for example, in the following manner. First, the hair is dyed with hair dye B. Meanwhile, a fiber for a head accessory is dyed with dye A according to the step (III), and a head accessory containing the fiber for a head accessory dyed with dye A according to the step (I) is attached to the hair. Next, according to the step (II), the hair and the fiber for a head accessory are kept in contact with each other and kept in a wet state. Alternatively, the hair is dyed with hair dye B, and a head accessory containing the undyed head accessory fiber is attached to the hair according to the step (I). Next, according to the step (III), the head accessory fiber is dyed with dye A. Furthermore, according to the step (II), the hair and the dyed head accessory fiber are kept in contact with each other and kept in a wet state. By using the dye kit of the present invention in the above-described manner, the color difference between the hair and the fiber for head accessories containing regenerated collagen fibers can be reduced, and the color matching effect can be improved.

[0195] With respect to the above-mentioned embodiments, the present invention discloses the following. <1> A method for dyeing fibers for head accessories containing regenerated collagen fibers, comprising: The regenerated collagen fibers contain one or more compounds (X) selected from the group consisting of the following components (X1) and (X2): (X1) Benzoic acid or its salts (X2) A copolymer containing a structural unit derived from an unsaturated monomer having a carboxy group and a structural unit derived from an aromatic vinyl compound, the copolymer having an acid value of 100 mgKOH / g or more and a weight average molecular weight of 1500 or more and 15000 or less, or a salt thereof. The modified regenerated collagen fiber contains The dyeing method includes the following steps (I) and (II) in this order: A method for dyeing fibers for head accessories, comprising the following step (III) before the step (I) or between the steps (I) and (II): Step (I) A step of attaching a head accessory containing the fiber for a head accessory to hair dyed with hair dye B. Step (II): A step of keeping the hair and the fiber for head accessories in a wet state while the hair and the fiber for head accessories are in contact with each other. Step (III) A step of applying dye A to the fiber for headwear products. <2> The head accessory product includes a hair wig, a toupee, a weaving, a hair extension, a braided hair, a hair accessory, or a doll hair, preferably includes one or more selected from the group consisting of a hair wig, a toupee, a weaving, and a hair extension, more preferably includes a hair extension; <1> Dyeing method. <3> The component (X1) contains one or more selected from the group consisting of benzoic acid, sodium benzoate, and potassium benzoate, and preferably contains one or more selected from the group consisting of benzoic acid and sodium benzoate. <1> or <2> Dyeing method. <4> the component (X2) comprises a copolymer containing structural units derived from one or more selected from the group consisting of unsaturated monocarboxylic acids and unsaturated dicarboxylic acids, and structural units derived from an aromatic vinyl compound, preferably one or more selected from the group consisting of styrene-maleic acid copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, vinylbenzoic acid-maleic acid copolymer, vinylbenzoic acid-acrylic acid copolymer, vinylbenzoic acid-methacrylic acid copolymer, and styrene-4-vinylbenzoic acid copolymer, more preferably a styrene-maleic acid copolymer; <1> ~ <3> One of the following dyeing methods. <5> In the component (X2), the molar ratio (u1 / u2) of the structural unit (u1) derived from the unsaturated monomer having a carboxy group to the structural unit (u2) derived from the aromatic vinyl compound monomer is preferably 1 / 5 to 5 / 1, more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1. <1> ~ <4> One of the following dyeing methods. <6> The acid value of the component (X2) is preferably 100 mgKOH / g or more and 1000 mgKOH / g or less, more preferably 200 mgKOH / g or more and 800 mgKOH / g or less, even more preferably 200 mgKOH / g or more and 600 mgKOH / g or less, still more preferably 300 mgKOH / g or more and 600 mgKOH / g or less, and still more preferably 400 mgKOH / g or more and 600 mgKOH / g or less. <1> ~ <5> One of the following dyeing methods. <7> The weight average molecular weight of the component (X2) is preferably 3,000 or more and 15,000 or less, more preferably 5,000 or more and 15,000 or less, even more preferably 6,000 or more and 15,000 or less, and still more preferably 6,000 or more and 10,000 or less. <1> ~ <6> One of the following dyeing methods. <8> The compound (X) preferably contains one or more selected from the group consisting of benzoic acid, sodium benzoate, and a styrene-maleic acid copolymer, and more preferably contains a styrene-maleic acid copolymer. <1> ~ <7> One of the following dyeing methods. <9> The content of compound (X) in the modified regenerated collagen fibers is preferably 0.1% by mass or more and 70% by mass or less, more preferably 0.5% by mass or more and 65% by mass or less, even more preferably 1.0% by mass or more and 60% by mass or less, still more preferably 3.0% by mass or more and 55% by mass or less, even more preferably 5.0% by mass or more and 50% by mass or less, still more preferably 10% by mass or more and 45% by mass or less, still more preferably 15% by mass or more and 40% by mass or less, and still more preferably 20% by mass or more and 40% by mass or less, <1> ~ <8> One of the following dyeing methods. <10> The modified regenerated collagen fibers further contain a polyvalent metal, a salt thereof, or a complex thereof as component (Y). <1> ~ <9> One of the following dyeing methods.

[0196] <11> the component (Y) comprises one or more polyvalent metals selected from the group consisting of calcium, magnesium, strontium, barium, zinc, chromium, aluminum, titanium, zirconium, tin, lead, antimony, iron, and copper, or salts thereof, or complexes thereof, preferably one or more polyvalent metals selected from the group consisting of aluminum, zirconium, and titanium, or salts thereof, or complexes thereof, and more preferably aluminum, or salts thereof, or complexes thereof; <10> Dyeing method. <12> The content of component (Y) in the modified regenerated collagen fibers is preferably 0.1% by mass or more and 40% by mass or less, more preferably 0.5% by mass or more and 30% by mass or less, even more preferably 1.0% by mass or more and 20% by mass or less, and even more preferably 2.0% by mass or more and 10% by mass or less, in terms of the amount of metal elements. <10> or <11> Dyeing method. <13> The fibers for head accessories subjected to the dyeing method are preferably colored. <1> ~ <12> One of the following dyeing methods. <14> The dyeing method is either (1) a method having the steps (III), (I), and (II) in this order, or (2) a method having the steps (I), (III), and (II) in this order. <1> ~ <13> One of the following dyeing methods. <15> In the method (1), a rinsing step is preferably included between the step (III) and the step (I). <14> Dyeing method. <16> The step (III) is carried out before the step (I). <1> ~ <15> One of the following dyeing methods. <17> The dye A is preferably a dye containing at least one dye selected from the group consisting of oxidation dyes, acid dyes, and basic dyes. <1> ~ <16> One of the following dyeing methods. <18> The oxidation dye contains a coupler, and is preferably an oxidation dye intermediate (A) containing one or more selected from the group consisting of the following components (A1) and (A2): <17> Dyeing method. (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. <19> The coupler (A1-1) preferably contains a compound represented by the following general formula (A11) or a salt thereof: <18> Dyeing method. [ka] (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. <20> In the general formula (A11), R 1 is preferably a hydroxy group or a primary amino group (—NH), and R 2 is preferably a hydrogen atom or a methyl group, R 3 is preferably a hydroxy group, a primary amino group (—NH), or R 2 and R 3 are bonded to each other to form an aromatic hydrocarbon ring structure having six ring carbon atoms, and R 4 is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom; <19> Dyeing method.

[0197] <21> The compound represented by the general formula (A11) is at least one selected from the group consisting of meta-aminophenol, resorcinol, meta-phenylenediamine, 2-methylresorcinol, and 1-naphthol, and preferably at least one selected from the group consisting of meta-aminophenol, resorcinol, 2-methylresorcinol, and 1-naphthol. <19> or <20> Dyeing method. <22> The coupler (A1-2) preferably contains a compound represented by the following general formula (A12) or a salt thereof: <18> ~ <21> One of the following dyeing methods. [ka] (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.) <23> 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, and R 7 is preferably a primary amino group (—NH), <22> Dyeing method. <24> The compound represented by the general formula (A12) contains 2,6-diaminopyridine or a salt thereof. <22> or <23> Dyeing method. <25> In the general formula (A13), R 11 n in the formula is preferably 2 or more and 8 or less, more preferably 2 or more and 4 or less, and R 12 , R 14 , R 22 and R 24 The electron donating group in preferably comprises a hydroxy group or a primary amino group (-NH), more preferably a primary amino group (-NH), and R 13 , R 16 , R 23 and R 26preferably contains a hydrogen atom or a methyl group, more preferably a hydrogen atom; <18> ~ <24> One of the following dyeing methods. <26> the coupler represented by general formula (A13) contains 1,3-bis(2,4-diaminophenoxy)propane or a salt thereof; <18> ~ <25> One of the following dyeing methods. <27> The component (A1) preferably contains one or more 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 more preferably contains one or more selected from the group consisting of meta-aminophenol, resorcinol, 2-methylresorcinol, 1-naphthol, and salts thereof. <18> ~ <26> One of the following dyeing methods. <28> The coupler (A2-1) preferably contains a compound represented by the following general formula (A21) or a salt thereof: <18> ~ <27> One of the following dyeing methods. [ka] (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.) <29> In the 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), more preferably a hydroxy group, a hydroxyethoxy group, or a primary amino group (-NH); R 32is preferably a hydroxy group or a primary amino group (-NH), more preferably a primary amino group (-NH), <28> Dyeing method. <30> The compound represented by the general formula (A21) contains one or more selected from the group consisting of ortho-aminophenol, 2,4-diaminophenoxyethanol, and salts thereof. <28> or <29> Dyeing method.

[0198] <31> The coupler (A2-2) preferably contains a compound represented by the following general formula (A22) or a salt thereof: <18> ~ <30> One of the following dyeing methods. [ka] (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.) <32> 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), and R 39 ~R 41 are each independently preferably a hydrogen atom or a methyl group, more preferably R 39 ~R 41 are all hydrogen atoms, <31> Dyeing method. <33> The compound represented by the general formula (A22) includes 2,3-diaminopyridine, 2-amino-3-hydroxypyridine, or a salt thereof. <31> or <32> Dyeing method. <34> The component (A2) preferably contains a coupler (A2-1), more preferably one or more selected from the group consisting of ortho-aminophenol, 2,4-diaminophenoxyethanol, and salts thereof. <18> ~ <33> One of the following dyeing methods. <35> The oxidation dye intermediate (A) preferably contains a component (A1), and more preferably contains one or more 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. <18> ~ <34> One of the following dyeing methods. <36> The oxidation dye intermediate (A) preferably contains a coupler (A1-1), more preferably contains one or more selected from the group consisting of meta-aminophenol, resorcinol, 2-methylresorcinol, 1-naphthol, and salts thereof. <18> ~ <34> One of the following dyeing methods. <37> The oxidation dye intermediate (A) further contains component (A3): precursor, <18> ~ <36> Either one of the following staining methods <38> the component (A3) comprises one or more members selected from the group consisting of 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, and preferably comprises one or more members selected from the group consisting of toluene-2,5-diamine, paraaminophenol, 4-amino-metacresol, 1-hydroxyethyl-4,5-diaminopyrazole, and salts thereof; <37> Dyeing method. <39> The molecular weight of the oxidation dye intermediate (A) 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, as a non-dissociated type. <18> ~ <38> One of the following dyeing methods. <40> The acid dye preferably includes an acid dye (C) having a sulfonic acid group and satisfying at least one of the following (3) and (4): <17> ~ <39> One of the following dyeing methods. (3) Molecular weight of 500 or more (4) When the molecular weight is Mw, the difference (ab) between the number of sulfonic acid groups (a) and the number of cationic sites (b) divided by Mw [(ab) / Mw] is 0.0045 or less.

[0199] <41> the number (a) of sulfonic acid groups in the acid dye (C) is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, even more preferably 1 or more and 4 or less, still more preferably 1 or more and 3 or less, and still more preferably 2 or more and 3 or less; <40> Dyeing method. <42> the cationic moiety comprises at least one selected from the group consisting of a quaternary ammonium cationic moiety and an iminium cationic moiety, and preferably comprises an iminium cationic moiety; <40> or <41> Dyeing method. <43> the number (b) of cationic moieties in the acid dye (C) is preferably 0 or more and 5 or less, more preferably 0 or more and 4 or less, even more preferably 0 or more and 3 or less, still more preferably 0 or more and 2 or less, and still more preferably 1 or more and 2 or less; <40> ~ <42> One of the following dyeing methods. <44> the difference (ab) between the number (a) of sulfonic acid groups in the acid dye (C) and the number (b) of cationic sites in the acid dye (C) is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, even more preferably 1 or more and 3 or less, and still more preferably 1 or more and 2 or less; <40> ~ <43> One of the following dyeing methods. <45> When the acid dye (C) satisfies the above (3), the molecular weight of the acid dye (C) is preferably 500 or more and 1,500 or less, more preferably 500 or more and 1,200 or less, even more preferably 500 or more and 1,000 or less, still more preferably 500 or more and 900 or less, still more preferably 500 or more and 800 or less, still more preferably 500 or more and 780 or less, still more preferably 520 or more and 750 or less, still more preferably 520 or more and 700 or less, and still more preferably 540 or more and 650 or less. <40> ~ <44> One of the following dyeing methods. <46> When the acid dye (C) satisfies the above (4), [(ab) / Mw] is preferably 0.0005 or more and 0.0045 or less, more preferably 0.0005 or more and 0.0040 or less, even more preferably 0.0010 or more and 0.0030 or less, and still more preferably 0.0010 or more and 0.0025 or less. <40> ~ <45> One of the following dyeing methods. <47> When the acid dye (C) satisfies the above (4), the molecular weight Mw is preferably 250 or more and 1,500 or less, more preferably 250 or more and 1,200 or less, even more preferably 250 or more and 1,000 or less, still more preferably 250 or more and 900 or less, still more preferably 280 or more and 800 or less, still more preferably 280 or more and 780 or less, still more preferably 280 or more and 750 or less, still more preferably 300 or more and 700 or less, and still more preferably 320 or more and 650 or less. <40> ~ <46> One of the following dyeing methods. <48> The acidic dye (C) is preferably Acid Black 52 (Color Index No. 15711), Acid Green 1 (Color Index No. 10020), Food Black 1 (Color Index No. 28440), Food Green 3 (Color Index No. 42053), Acid Green 5 (Color Index No. 42095), Acid Blue 9 (Color Index No. 42090), Acid Blue 5 (Color Index No. 42052), Acid Green 3 (Color Index No. 42085), Acid Green 25 (Color Index No. 61570), Acid Brown 13 (Color Index No. 10410), Acid Red 52 (Color Index No. 45100), Acid Black 1 (Color Index No. 20470), Acid Red 18 (Color Index No. 16255), Acid Red 27 (Color Index No. 16185), Acid Blue 3 (Color Index No. 42051), Acid Green 50 (Color Index No. 44090), Acid Red 73 (Color Index No. 27290), Acid Blue 1 (Color Index No. 42045), Acid Red 184 (Color Index No. 15685), Acid Red 35 (Color Index No. 18065), Acid Red 14 (Color Index No. 14720), Food Red 6 (Color Index No. 16155), Acid Orange 3 (Color Index No. 10385), Acid Orange 24 (Color Index No. 20170), Acid Violet 43 (Color Index No. 60730), Acid Blue 62 (Color Index No. 62045), Acid Red 88 (Color Index No. 15620), Acid Yellow 11 (Color Index No.18820)、Acid Yellow 36(Color Index No.13065)、Acid Yellow 1(Color Index No.10316)、Acid Orange 7(Color Index No.15510)、Acid Orange 20(Color Index No.14600)、Acid Orange 6(Color Index No.14270)、Food Red 17(Color Index No.16035)、Acid Red 41(Color Index No.16290)、Acid Red 1(Color Index No.18050)、Acid Red 155(Color Index No.18130)、Acid Red 180(Color Index No.18736)、Acid Yellow 17(Color Index No.18965)、Acid Yellow 23(Color Index No.19140)、Acid Red 163(Color Index No.24790)、Food Black 2(Color Index No.27755)、Direct Orange 39(Color Index No.40215)、Acid Blue 7(Color Index No.42080)、Acid Green 9(Color Index No.42100)、Acid Green 22(Color Index No.42170)、Acid Blue 104(Color Index No.42735)、Acid Violet 9(Color Index No.45190)、Acid Red 50(Color Index No.45220)、Acid Violet 50(Color Index No.50325)、Acid Black 2(Color Index No.50420)、Acid Blue 80(Color Index No.61585)、Acid Blue 87(Color Index No.74180)、Acid Red 195(Color Index No.18760)、Acid Red 249(Color Index No.and more preferably, one or more selected from the group consisting of Acid Black 52 (Color Index No. 15711), Acid Green 1 (Color Index No. 10020), Food Black 1 (Color Index No. 28440), Food Green 3 (Color Index No. 42053), Acid Green 5 (Color Index No. 42095), Acid Blue 9 (Color Index No. 42090), Acid Blue 5 (Color Index No. 42052), Acid Green 3 (Color Index No. 42085), Acid Green 25 (Color Index No. 61570), Acid Brown 13 (Color Index No. 10410), Acid Red 52 (Color Index No. 45100), Acid Black 1 (Color Index No. 17102). and Acid Red 18 (Color Index No. 16255), Acid Red 27 (Color Index No. 16185), Acid Blue 3 (Color Index No. 42051), Acid Green 50 (Color Index No. 44090), Acid Red 73 (Color Index No. 27290), Acid Blue 1 (Color Index No. 42045), Acid Blue 7 (Color Index No. 42080), Acid Green 9 (Color Index No. 42100), Acid Blue 104 (Color Index No. 42735), and Acid Violet 50 (Color Index No. 50325), more preferably Food Green 3 (Color Index No. 42053), Acid Green 5 (Color Index No. 42054), and the like, each of which has a cationic moiety (b) of 1 or more. No.42095), Acid Blue 9(Color Index No.42090), Acid Blue 5 (Color Index No. 42052), Acid Green 3 (Color Index No. 42085), Acid Red 52 (Color Index No. 45100), Acid Blue 3 (Color Index No. 42051), Acid Green 50 (Color Index No. 44090), and Acid Blue 1 (Color Index No. 42045), and even more preferably, at least one selected from the group consisting of Acid Blue 9 and Acid Red 52; <40> ~ <47> Either one of the dyeing methods. <49> The basic dye preferably contains a basic dye (D) in which the value obtained by dividing the number of cationic moieties (a) by Mw [(a) / Mw] is 0.00275 or more, where Mw is the molecular weight. <17> ~ <48> One of the following dyeing methods. <50> the cationic moiety comprises at least one selected from the group consisting of a quaternary ammonium cationic moiety, an imidazolium cationic moiety, a pyridinium cationic moiety, a pyrrolidinium cationic moiety, a piperidinium cationic moiety, an iminium cationic moiety, and a pyrylium cationic moiety, and preferably comprises an imidazolium cationic moiety or a pyridinium cationic moiety; <49> Dyeing method.

[0200] <51> The molecular weight Mw of the basic dye (D) is preferably 200 or more and 500 or less, more preferably 220 or more and 450 or less, even more preferably 240 or more and 400 or less, still more preferably 250 or more and 360 or less, and still more preferably 250 or more and 340 or less. <49> or <50> Dyeing method. <52> the number (a) of cationic moieties of the basic dye (D) is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, even more preferably 1 or more and 3 or less, still more preferably 1 or more and 2 or less, and still more preferably 1; <49> ~ <51> One of the following dyeing methods. <53> When the molecular weight of the basic dye (D) is Mw, the value obtained by dividing the number of cationic moieties (a) by Mw [(a) / Mw] is preferably 0.00275 or more and 0.010 or less, more preferably 0.00275 or more and 0.008 or less, even more preferably 0.00275 or more and 0.006 or less, still more preferably 0.00275 or more and 0.005 or less, still more preferably 0.00280 or more and 0.005 or less, and still more preferably 0.00290 or more and 0.004 or less. <49> ~ <52> One of the following dyeing methods. <54> The basic dye (D) preferably comprises one or more selected from the group consisting of Basic Red 51, Basic Yellow 87, Basic Orange 31, Basic Blue 124, Basic Brown 16 (Color Index No. 12250), Basic Violet 14 (Color Index No. 42510), Basic Black 7 (Color Index No. 51215), Basic Blue 25 (Color Index No. 52025), Basic Blue 6 (Color Index No. 51175), Basic Red 2 (Color Index No. 50240), Basic Red 22 (Color Index No. 11055), Basic Blue 17 (Color Index No. 52040), and Basic Blue 9 (Color Index No. 52015), and more preferably comprises one or more selected from the group consisting of Basic Red 51, Basic Yellow 87, Basic Orange 31, Basic Blue 124, and Basic Brown 16, more preferably comprising one or more selected from the group consisting of Basic Red 51, Basic Yellow 87, Basic Orange 31, and Basic Blue 124, and even more preferably comprising one or more selected from the group consisting of Basic Red 51, Basic Yellow 87, and Basic Orange 31; <49> ~ <53> One of the following dyeing methods. <55> The content of the dye in the dyeing agent A is preferably 0.001% by mass or more and 3% by mass or less, more preferably 0.005% by mass or more and 3% by mass or less, even more preferably 0.01% by mass or more and 3% by mass or less, still more preferably 0.02% by mass or more and 3% by mass or less, still more preferably 0.03% by mass or more and 3% by mass or less, still more preferably 0.05% by mass or more and 3% by mass or less, still more preferably 0.1% 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, <1> ~ <54> One of the following dyeing methods. <56> The content of water in the dye A 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 99.995% by mass or less. <1> ~ <55> One of the following dyeing methods. <57> The dye A is in the form of a liquid, paste, cream, gel, foam, spray, or wax, and is preferably in the form of a liquid. <1> ~ <56> One of the following dyeing methods. <58> In the step (III), the method of applying the dye A to the fiber for head accessories includes a method of applying the dye A to the fiber for head accessories in a dry or wet state, or a method of immersing the fiber for head accessories in the dye A, and preferably includes a method of applying or immersing the fiber for head accessories in a dry state. <1> ~ <57> One of the following dyeing methods. <59> The water content in the fiber for head accessories in the wet state is preferably a mass ratio (water / fiber for head accessories) of 0.05 or more and 5 or less, more preferably 0.10 or more and 5 or less, even more preferably 0.2 or more and 5 or less, still more preferably 0.3 or more and 5 or less, more preferably 0.5 or more and 3 or less, even more preferably 0.7 or more and 2 or less, and still more preferably 1.0 or more and 2 or less, when the mass of the fiber for head accessories after conditioning at 20°C and a relative humidity of 65% for 24 hours is taken as 1. <58> Dyeing method. <60> In the step (III), the amount of dye A applied to the fiber for headwear products is preferably 1:0.2 to 1:500 in terms of a bath ratio (dry mass of fiber for headwear products:mass of dye A) 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. <1> ~ <59> Either one of the staining methods.

[0201] <61> In the step (III), when dye agent A is applied to the fiber for a head accessory product, the amount of dye agent A applied to the fiber for a head accessory product is, 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, a bath ratio (dry mass of fiber for a head accessory product:mass of dye agent A) of more 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. <60> Dyeing method. <62> In the step (III), when the fiber for head accessories is immersed in dye A, the bath ratio (dry mass of fiber for head accessories:mass of dye A) 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 still more preferably 1:10 to 1:20, 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. <60> Dyeing method. <63> In the step (III), when the dye A is applied to the fiber for a head accessory product, 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. <58> ~ <61> Either one of the staining methods. <64> In the step (III), after the dye A is applied to the fiber for a head ornament product, a step of leaving the dye A to stand is further carried out, and 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. <58> ~ <61> , <63> Either one of the staining methods. <65> The temperature in the leaving step after the step (III) is preferably 40°C or less, more preferably 35°C or less, and is preferably 25°C or more, more preferably 30°C or more. <64> Dyeing method. <66> In the step (III), when the fiber for head accessories is immersed in the dye A, the immersion time is preferably from 10 seconds to 3 hours, more preferably from 10 seconds to 2 hours, and even more preferably from 30 seconds to 1 hour. <58> ~ <60> , <62> Either one of the staining methods. <67> After the step (III), a step of washing away excess dye A with water is carried out. <1> ~ <66> Either one of the staining methods. <68> After the dye A is washed away with water, the fiber for headwear products is subjected to a drying process and then to the next process. <67> Dyeing method. <69> The hair dye B is preferably a hair dye containing one or more dyes selected from the group consisting of oxidation dyes, acid dyes, and basic dyes, and more preferably a hair dye containing an oxidation dye. <1> ~ <68> Either one of the staining methods. <70> The wet state in step (II) is a state after a step of increasing the moisture content of the hair and the fiber for a head accessory, and the water content in the fiber for a head accessory in the wet state is, when the mass of the fiber for a head accessory after conditioning at 20°C and a relative humidity of 65% for 24 hours is taken as 1, preferably a mass ratio (water / fiber for a head accessory) of 0.05 to 5, more preferably 0.10 to 5, even more preferably 0.2 to 5, still more preferably 0.3 to 5, more preferably 0.5 to 3, even more preferably 0.7 to 2, and still more preferably 1.0 to 2. <1> ~ <69> Either one of the staining methods.

[0202] <71> In the step (II), the method of bringing the hair and the fiber for a head accessory into a wet state includes one or more of the following methods: (i) immersing the hair, to which the head accessory is attached, in a state where the hair and the fiber for a head accessory are in contact with each other, (ii) rinsing with water, (iii) washing with a hair cleanser composition, (iv) treating with a rinse-off conditioner or treatment and then rinsing with water, (v) applying a spray or mist containing water, (vi) applying steam, (vii) wrapping with a wet towel, or (vii) wrapping in plastic wrap, aluminum foil, or the like while wet with water. <1> ~ <70> Either one of the staining methods. <72> The step (II) preferably includes one or more methods selected from the group consisting of (ii) a method of rinsing the hair on which the head accessory is attached with water, and (iii) a method of washing the hair with a hair wash composition, and more preferably includes a step of washing the hair and the head accessory fiber with a hair wash composition, followed by rinsing with water. <71> Dyeing method. <73> In the step (II), the time for keeping the hair and the fiber for a head accessory in a wet state is preferably 1 second or more and 6 hours or less, more preferably 5 seconds or more and 3 hours or less, and even more preferably 5 seconds or more and 2 hours or less. <1> ~ <72> Either one of the staining methods. <74> In the step (II), the temperature at which the hair and the fiber for a head accessory are kept wet is preferably higher than 0°C, more preferably 5°C or higher, and preferably 100°C or lower. <1> ~ <73> Either one of the staining methods. <75> After carrying out the step (II), a step of drying the head accessory product and the hair to which it is attached is carried out. <1> ~ <74> Either one of the staining methods. <76> A dyeing kit comprising a dye A for dyeing fibers for head accessories containing regenerated collagen fibers and a hair dye B for dyeing hair, A dyeing kit comprising modified regenerated collagen fibers containing one or more compounds (X) selected from the group consisting of the following components (X1) and (X2): (X1) Benzoic acid or its salts (X2) A copolymer containing a structural unit derived from an unsaturated monomer having a carboxy group and a structural unit derived from an aromatic vinyl compound, the copolymer having an acid value of 100 mgKOH / g or more and a weight average molecular weight of 1500 or more and 15000 or less, or a salt thereof. <77> Use of composition A as a dye for fibers for headwear products containing regenerated collagen fibers, The composition A contains one or more dyes selected from the group consisting of oxidation dyes, acid dyes, and basic dyes, and water; The regenerated collagen fibers contain one or more compounds (X) selected from the group consisting of the following components (X1) and (X2): (X1) Benzoic acid or its salts (X2) A copolymer containing a structural unit derived from an unsaturated monomer having a carboxy group and a structural unit derived from an aromatic vinyl compound, the copolymer having an acid value of 100 mgKOH / g or more and a weight average molecular weight of 1500 or more and 15000 or less, or a salt thereof. The modified regenerated collagen fiber contains The method for dyeing the fiber for a head accessory with the composition A includes the following steps (I) and (II) in this order: The use, which comprises the following step (III) before the step (I) or between the step (I) and the step (II): Step (I) A step of attaching a head accessory containing the fiber for a head accessory to hair dyed with hair dye B. Step (II): A step of keeping the hair and the fiber for head accessories in a wet state while the hair and the fiber for head accessories are in contact with each other. Step (III) applying composition A to the fiber for headwear. <78> A dye composition for dyeing fibers for head accessories containing regenerated collagen fibers, comprising: The composition contains one or more dyes selected from the group consisting of oxidation dyes, acid dyes, and basic dyes, and water; The regenerated collagen fibers contain one or more compounds (X) selected from the group consisting of the following components (X1) and (X2): (X1) Benzoic acid or its salts (X2) A copolymer containing a structural unit derived from an unsaturated monomer having a carboxy group and a structural unit derived from an aromatic vinyl compound, the copolymer having an acid value of 100 mgKOH / g or more and a weight average molecular weight of 1500 or more and 15000 or less, or a salt thereof. The modified regenerated collagen fiber contains The method for dyeing the fiber for a head accessory product with the dye composition includes the following steps (I) and (II) in this order: A dye composition comprising the following step (III) before the step (I) or between the step (I) and the step (II): Step (I) A step of attaching a head accessory containing the fiber for a head accessory to hair dyed with hair dye B. Step (II): A step of keeping the hair and the fiber for head accessories in a wet state while the hair and the fiber for head accessories are in contact with each other. Step (III) applying the dye composition to the headwear fiber <79> The oxidation dye contains a coupler, and is preferably an oxidation dye intermediate (A) containing one or more selected from the group consisting of the following components (A1) and (A2): <77> Use of, or <78> A dye composition. (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 11is -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. R 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. <80> The coupler (A1-1) preferably contains a compound represented by the following general formula (A11) or a salt thereof: <79> Use of, or <79> A dye composition. [ka] (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. <81> In the general formula (A11), R 1 is preferably a hydroxy group or a primary amino group (—NH), and R 2 is preferably a hydrogen atom or a methyl group, R 3 is preferably a hydroxy group, a primary amino group (—NH), or R2 and R 3 are bonded to each other to form an aromatic hydrocarbon ring structure having six ring carbon atoms, and R 4 is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom; <80> Use of, or <80> A dye composition.

[0203] <82> The compound represented by the general formula (A11) is at least one selected from the group consisting of meta-aminophenol, resorcinol, meta-phenylenediamine, 2-methylresorcinol, 1-naphthol, and salts thereof, and preferably at least one selected from the group consisting of meta-aminophenol, resorcinol, 2-methylresorcinol, 1-naphthol, and salts thereof. <80> or <81> Use of, or <80> or <81> A dye composition. <83> The coupler (A1-2) preferably contains a compound represented by the following general formula (A12) or a salt thereof: <79> ~ <82> Use of any one of the following: <79> ~ <82> Any one of the dye compositions. [ka] (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.) <84> 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, and R 7 is preferably a primary amino group (—NH), <83> Use of, or <83> A dye composition. <85> The compound represented by the general formula (A12) contains 2,6-diaminopyridine or a salt thereof. <83> or <84> Use of, or <83> or <84> A dye composition. <86> In the general formula (A13), R 11 n in the formula is preferably 2 or more and 8 or less, more preferably 2 or more and 4 or less, and R 12 , R 14 , R 22 and R 24 The electron donating group in preferably comprises a hydroxy group or a primary amino group (-NH), more preferably a primary amino group (-NH), and R 13 , R 16 , R 23 and R 26 preferably contains a hydrogen atom or a methyl group, more preferably a hydrogen atom; <79> ~ <85> Use of any one of the following: <79> ~ <85> Any one of the dye compositions. <87> the coupler represented by general formula (A13) contains 1,3-bis(2,4-diaminophenoxy)propane or a salt thereof; <78> ~ <86> Use of any one of the following: <79> ~ <86> Any one of the dye compositions. <88> The component (A1) preferably contains one or more 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 more preferably contains one or more selected from the group consisting of meta-aminophenol, resorcinol, 2-methylresorcinol, 1-naphthol, and salts thereof. <79> ~ <87> Use of any one of the following: <79> ~ <87> Any one of the dye compositions. <89> The coupler (A2-1) preferably contains a compound represented by the following general formula (A21) or a salt thereof: <79> ~ <88> Use of any one of the following: <79> ~ <88> Any one of the dye compositions. [ka] (In formula (A21), R 31 is an electron donating group attached to the carbon atom at position 1, R 32is 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.) <90> In the 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), more preferably a hydroxy group, a hydroxyethoxy group, or a primary amino group (-NH); R 32 is preferably a hydroxy group or a primary amino group (-NH), more preferably a primary amino group (-NH), <89> Use of, or <89> A dye composition. <91> The compound represented by the general formula (A21) contains one or more selected from the group consisting of ortho-aminophenol, 2,4-diaminophenoxyethanol, and salts thereof. <89> or <90> Use of, or <89> or <90> A dye composition.

[0204] <92> The coupler (A2-2) preferably contains a compound represented by the following general formula (A22) or a salt thereof: <79> ~ <91> Use of any one of the following: <79> ~ <91> Any one of the dye compositions. [ka] (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.) <93> In the general formula (A22), R 37is 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), and R 39 ~R 41 are each independently preferably a hydrogen atom or a methyl group, more preferably R 39 ~R 41 are all hydrogen atoms, <92> Use of, or <92> A dye composition. <94> The compound represented by the general formula (A22) includes 2,3-diaminopyridine, 2-amino-3-hydroxypyridine, or a salt thereof. <92> or <93> Use of, or <92> or <93> A dye composition. <95> The component (A2) preferably contains a coupler (A2-1), more preferably one or more selected from the group consisting of ortho-aminophenol, 2,4-diaminophenoxyethanol, and salts thereof. <79> ~ <94> Use of any one of the following: <79> ~ <94> Any one of the dye compositions. <96> The oxidation dye intermediate (A) preferably contains a component (A1), and more preferably contains one or more 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. <79> ~ <95> Use of any one of the following: <79> ~ <95> Any one of the dye compositions. <97> The oxidation dye intermediate (A) preferably contains a coupler (A1-1), more preferably contains one or more selected from the group consisting of meta-aminophenol, resorcinol, 2-methylresorcinol, 1-naphthol, and salts thereof. <79> ~ <95> Use of any one of the following: <79> ~ <95> Any one of the dye compositions. <98> The oxidation dye intermediate (A) further contains component (A3): precursor, <79> ~ <97> Use of any one of the following: <79> ~ <97> Any one of the dye compositions. <99> the component (A3) comprises one or more members selected from the group consisting of 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, and preferably comprises one or more members selected from the group consisting of toluene-2,5-diamine, paraaminophenol, 4-amino-metacresol, 1-hydroxyethyl-4,5-diaminopyrazole, and salts thereof; <98> Use of, or <98> A dye composition. <100> The molecular weight of the oxidation dye intermediate (A) 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, as a non-dissociated type. <79> ~ <99> Use of any one of the following: <79> ~ <99> Any one of the dye compositions. <101> The acid dye preferably includes an acid dye (C) having a sulfonic acid group and satisfying at least one of the following (3) and (4): <77> ~ <100> Use of any one of the following: <78> ~ <100> Any one of the dye compositions. (3) Molecular weight of 500 or more (4) When the molecular weight is Mw, the difference (ab) between the number of sulfonic acid groups (a) and the number of cationic sites (b) divided by Mw [(ab) / Mw] is 0.0045 or less.

[0205] <102> the number (a) of sulfonic acid groups in the acid dye (C) is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, even more preferably 1 or more and 4 or less, still more preferably 1 or more and 3 or less, and still more preferably 2 or more and 3 or less; <101> Use of, or <101> A dye composition. <103> the cationic moiety comprises at least one selected from the group consisting of a quaternary ammonium cationic moiety and an iminium cationic moiety, and preferably comprises an iminium cationic moiety; <101> or <102> Use of, or <101> or <102> A dye composition. <104> the number (b) of cationic moieties in the acid dye (C) is preferably 0 or more and 5 or less, more preferably 0 or more and 4 or less, even more preferably 0 or more and 3 or less, still more preferably 0 or more and 2 or less, and still more preferably 1 or more and 2 or less; <101> ~ <103> Use of any one of the following: <101> ~ <103> Any one of the dye compositions. <105> the difference (ab) between the number (a) of sulfonic acid groups in the acid dye (C) and the number (b) of cationic sites in the acid dye (C) is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, even more preferably 1 or more and 3 or less, and still more preferably 1 or more and 2 or less; <101> ~ <104> Use of any one of the following: <101> ~ <104> Any one of the dye compositions. <106> When the acid dye (C) satisfies the above (3), the molecular weight of the acid dye (C) is preferably 500 or more and 1,500 or less, more preferably 500 or more and 1,200 or less, even more preferably 500 or more and 1,000 or less, still more preferably 500 or more and 900 or less, still more preferably 500 or more and 800 or less, still more preferably 500 or more and 780 or less, still more preferably 520 or more and 750 or less, still more preferably 520 or more and 700 or less, and still more preferably 540 or more and 650 or less. <101> ~ <105> Use of any one of the following: <101> ~ <105> Any one of the dye compositions. <107> When the acid dye (C) satisfies the above (4), [(ab) / Mw] is preferably 0.0005 or more and 0.0045 or less, more preferably 0.0005 or more and 0.0040 or less, even more preferably 0.0010 or more and 0.0025 or less. <101> ~ <106> Use of any one of the following: <101> ~ <106> Any one of the dye compositions. <108> When the acid dye (C) satisfies the above (4), the molecular weight Mw is preferably 250 or more and 1,500 or less, more preferably 250 or more and 1,200 or less, even more preferably 250 or more and 1,000 or less, still more preferably 250 or more and 900 or less, still more preferably 280 or more and 800 or less, still more preferably 280 or more and 780 or less, still more preferably 280 or more and 750 or less, still more preferably 300 or more and 700 or less, and still more preferably 320 or more and 650 or less. <101> ~ <107> Use of any one of the following: <101> ~ <107> Any one of the dye compositions. <109> The acidic dye (C) is preferably Acid Black 52 (Color Index No. 15711), Acid Green 1 (Color Index No. 10020), Food Black 1 (Color Index No. 28440), Food Green 3 (Color Index No. 42053), Acid Green 5 (Color Index No. 42095), Acid Blue 9 (Color Index No. 42090), Acid Blue 5 (Color Index No. 42052), Acid Green 3 (Color Index No. 42085), Acid Green 25 (Color Index No. 61570), Acid Brown 13 (Color Index No. 10410), Acid Red 52 (Color Index No. 45100), Acid Black 1 (Color Index No. 20470), Acid Red 18 (Color Index No. 16255), Acid Red 27 (Color Index No. 16185), Acid Blue 3 (Color Index No. 42051), Acid Green 50 (Color Index No. 44090), Acid Red 73 (Color Index No. 27290), Acid Blue 1 (Color Index No. 42045), Acid Red 184 (Color Index No. 15685), Acid Red 35 (Color Index No. 18065), Acid Red 14 (Color Index No. 14720), Food Red 6 (Color Index No. 16155), Acid Orange 3 (Color Index No. 10385), Acid Orange 24 (Color Index No. 20170), Acid Violet 43 (Color Index No. 60730), Acid Blue 62 (Color Index No. 62045), Acid Red 88 (Color Index No. 15620), Acid Yellow 11 (Color Index No.18820)、Acid Yellow 36(Color Index No.13065)、Acid Yellow 1(Color Index No.10316)、Acid Orange 7(Color Index No.15510)、Acid Orange 20(Color Index No.14600)、Acid Orange 6(Color Index No.14270)、Food Red 17(Color Index No.16035)、Acid Red 41(Color Index No.16290)、Acid Red 1(Color Index No.18050)、Acid Red 155(Color Index No.18130)、Acid Red 180(Color Index No.18736)、Acid Yellow 17(Color Index No.18965)、Acid Yellow 23(Color Index No.19140)、Acid Red 163(Color Index No.24790)、Food Black 2(Color Index No.27755)、Direct Orange 39(Color Index No.40215)、Acid Blue 7(Color Index No.42080)、Acid Green 9(Color Index No.42100)、Acid Green 22(Color Index No.42170)、Acid Blue 104(Color Index No.42735)、Acid Violet 9(Color Index No.45190)、Acid Red 50(Color Index No.45220)、Acid Violet 50(Color Index No.50325)、Acid Black 2(Color Index No.50420)、Acid Blue 80(Color Index No.61585)、Acid Blue 87(Color Index No.74180)、Acid Red 195(Color Index No.18760)、Acid Red 249(Color Index No.and more preferably, one or more selected from the group consisting of Acid Black 52 (Color Index No. 15711), Acid Green 1 (Color Index No. 10020), Food Black 1 (Color Index No. 28440), Food Green 3 (Color Index No. 42053), Acid Green 5 (Color Index No. 42095), Acid Blue 9 (Color Index No. 42090), Acid Blue 5 (Color Index No. 42052), Acid Green 3 (Color Index No. 42085), Acid Green 25 (Color Index No. 61570), Acid Brown 13 (Color Index No. 10410), Acid Red 52 (Color Index No. 45100), Acid Black 1 (Color Index No. 17102). and Acid Red 18 (Color Index No. 16255), Acid Red 27 (Color Index No. 16185), Acid Blue 3 (Color Index No. 42051), Acid Green 50 (Color Index No. 44090), Acid Red 73 (Color Index No. 27290), Acid Blue 1 (Color Index No. 42045), Acid Blue 7 (Color Index No. 42080), Acid Green 9 (Color Index No. 42100), Acid Blue 104 (Color Index No. 42735), and Acid Violet 50 (Color Index No. 50325), more preferably Food Green 3 (Color Index No. 42053), Acid Green 5 (Color Index No. 42054), and the like, each of which has a cationic moiety (b) of 1 or more. No.42095), Acid Blue 9(Color Index No.42090), Acid Blue 5 (Color Index No. 42052), Acid Green 3 (Color Index No. 42085), Acid Red 52 (Color Index No. 45100), Acid Blue 3 (Color Index No. 42051), Acid Green 50 (Color Index No. 44090), and Acid Blue 1 (Color Index No. 42045), and even more preferably, at least one selected from the group consisting of Acid Blue 9 and Acid Red 52; <101> ~ <108> Use of any one of the following: <101> ~ <108> Any one of the dye compositions. <110> The basic dye preferably contains a basic dye (D) in which the value obtained by dividing the number of cationic moieties (a) by Mw [(a) / Mw] is 0.00275 or more, where Mw is the molecular weight. <77> ~ <109> Use of any one of the following: <78> ~ <109> Any one of the dye compositions. <111> the cationic moiety comprises at least one selected from the group consisting of a quaternary ammonium cationic moiety, an imidazolium cationic moiety, a pyridinium cationic moiety, a pyrrolidinium cationic moiety, a piperidinium cationic moiety, an iminium cationic moiety, and a pyrylium cationic moiety, and preferably comprises an imidazolium cationic moiety or a pyridinium cationic moiety; <110> Use of, or <110> A dye composition.

[0206] <112> The molecular weight Mw of the basic dye (D) is preferably 200 or more and 500 or less, more preferably 220 or more and 450 or less, even more preferably 240 or more and 400 or less, still more preferably 250 or more and 360 or less, and still more preferably 250 or more and 340 or less. <110> or <111> Use of, or <110> or <111> A dye composition. <113> the number (a) of cationic moieties of the basic dye (D) is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, even more preferably 1 or more and 3 or less, still more preferably 1 or more and 2 or less, and still more preferably 1; <110> ~ <112> Use of any one of the following: <110> ~ <112> Any one of the dye compositions. <114> When the molecular weight of the basic dye (D) is Mw, the value obtained by dividing the number of cationic moieties (a) by Mw [(a) / Mw] is preferably 0.00275 or more and 0.010 or less, more preferably 0.00275 or more and 0.008 or less, even more preferably 0.00275 or more and 0.006 or less, still more preferably 0.00275 or more and 0.005 or less, still more preferably 0.00280 or more and 0.005 or less, and still more preferably 0.00290 or more and 0.004 or less. <110> ~ <113> Use of any one of the following: <110> ~ <113> Any one of the dye compositions. <115> The basic dye (D) preferably comprises one or more selected from the group consisting of Basic Red 51, Basic Yellow 87, Basic Orange 31, Basic Blue 124, Basic Brown 16 (Color Index No. 12250), Basic Violet 14 (Color Index No. 42510), Basic Black 7 (Color Index No. 51215), Basic Blue 25 (Color Index No. 52025), Basic Blue 6 (Color Index No. 51175), Basic Red 2 (Color Index No. 50240), Basic Red 22 (Color Index No. 11055), Basic Blue 17 (Color Index No. 52040), and Basic Blue 9 (Color Index No. 52015), and more preferably comprises one or more selected from the group consisting of Basic Red 51, Basic Yellow 87, Basic Orange 31, Basic Blue 124, and Basic Brown 16, more preferably comprising one or more selected from the group consisting of Basic Red 51, Basic Yellow 87, Basic Orange 31, and Basic Blue 124, and even more preferably comprising one or more selected from the group consisting of Basic Red 51, Basic Yellow 87, and Basic Orange 31; <110> ~ <114> Use of any one of the following: <110> ~ <114> Any one of the dye compositions.

[0207] <116> A method for dyeing fibers for head accessories containing regenerated collagen fibers, comprising: The regenerated collagen fibers contain one or more compounds (X) selected from the group consisting of the following components (X1) and (X2): (X1) Benzoic acid or its salts (X2) A styrene-maleic acid copolymer having an acid value of 200 mgKOH / g or more and 600 mgKOH / g or less and a weight average molecular weight of 3,000 or more and 15,000 or less. The modified regenerated collagen fiber contains The dyeing method includes the following steps (I) and (II) in this order: A method for dyeing fibers for head accessories, comprising the following step (III) before the step (I) or between the steps (I) and (II): Step (I) A step of attaching a head accessory containing the fiber for a head accessory to hair dyed with hair dye B. Step (II): A step of keeping the hair and the fiber for head accessories in a wet state while the hair and the fiber for head accessories are in contact with each other. Step (III) A step of applying dye A to the fiber for headwear products.

[0208] <117> A dyeing kit comprising a dye A for dyeing fibers for head accessories containing regenerated collagen fibers and a hair dye B for dyeing hair, A dyeing kit comprising modified regenerated collagen fibers containing one or more compounds (X) selected from the group consisting of the following components (X1) and (X2): (X1) Benzoic acid or its salts (X2) A styrene-maleic acid copolymer having an acid value of 200 mgKOH / g or more and 600 mgKOH / g or less and a weight average molecular weight of 3,000 or more and 15,000 or less.

[0209] <118> The modified regenerated collagen fiber contains, as component (X2), a styrene-maleic acid copolymer having an acid value of 200 mgKOH / g or more and 600 mgKOH / g or less and a weight-average molecular weight of 6,000 or more and 15,000 or less. <116> or <117> Dyeing kit. <119> The modified regenerated collagen fiber contains, as component (X2), a styrene-maleic acid copolymer having an acid value of 400 mgKOH / g or more and 600 mgKOH / g or less and a weight-average molecular weight of 6,000 or more and 10,000 or less. <116> or <118> or <117> or <118> Dyeing kit. <120> The modified regenerated collagen fiber contains aluminum or a salt or complex thereof as component (Y). <116> and <118> ~ <119> Any one of the staining methods, or <117> ~ <119> One of the staining kits.

[0210] <121> The content of compound (X) in the modified regenerated collagen fiber is 20% by mass or more and 40% by mass or less. <116> and <118> ~ <120> Any one of the staining methods, or <117> ~ <120> One of the staining kits. <122> The content of component (Y) in the modified regenerated collagen fiber is 2.0% by mass or more and 10% by mass or less in terms of the amount of metal elements. <120> or <121> or <120> or <121> Dyeing kit.

[0211] <123> The dye A contains one or more dyes selected from an oxidation dye, an acid dye, and a basic dye, Hair dye B contains one or more dyes selected from oxidation dyes, acid dyes, and basic dyes. <116> and <118> ~ <122> Any one of the staining methods, or <117> ~ <122> One of the staining kits. <124> The oxidation dye comprises one or more oxidation dye intermediates (A) selected from 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 precursors selected from toluene-2,5-diamine, para-aminophenol, 4-amino-metacresol, 1-hydroxyethyl-4,5-diaminopyrazole, and salts thereof; The acid dye contains one or more selected from the group consisting of Acid Black 52 (Color Index No. 15711), Acid Green 1 (Color Index No. 10020), Food Black 1 (Color Index No. 28440), Food Green 3 (Color Index No. 42053), Acid Green 5 (Color Index No. 42095), Acid Blue 9 (Color Index No. 42090), Acid Blue 5 (Color Index No. 42052), Acid Green 3 (Color Index No. 42085), Acid Green 25 (Color Index No. 61570), Acid Brown 13 (Color Index No. 10410), Acid Red 52 (Color Index No. 45100), Acid Black 1 (Color Index No. 20470), Acid Red 18 (Color Index No. 16255), Acid Red 27 (Color Index No. 16185), Acid Blue 3 (Color Index No. 42051), Acid Green 50 (Color Index No. 44090), Acid Red 73 (Color Index No. 27290), Acid Blue 1 (Color Index No. 42045), Acid Yellow 36 (Color Index No. 13065), Acid Yellow 1 (Color Index No. 10316), Acid Orange 7 (Color Index No. 15510), Acid Blue 7 (Color Index No. 42080), Acid Green 9 (Color Index No. 42100), Acid Blue 104 (Color Index No. 42735), Acid Violet 50 (Color Index No. 50325), Acid Red 249 (Color Index No. 18134), Acid Red 131, and Acid Red 337 (Color Index No. 17102). the basic dye includes one or more selected from Basic Red 51, Basic Yellow 87, Basic Orange 31, Basic Blue 124, Basic Brown 16 (Color Index No. 12250), Basic Violet 14 (Color Index No. 42510), Basic Black 7 (Color Index No. 51215), Basic Blue 25 (Color Index No. 52025), Basic Blue 6 (Color Index No. 51175), Basic Red 2 (Color Index No. 50240), Basic Red 22 (Color Index No. 11055), Basic Blue 17 (Color Index No. 52040), and Basic Blue 9 (Color Index No. 52015); , <123> or <123> Dyeing kit.

[0212] <125> The dyeing agent A is a multi-component dyeing agent containing at least an oxidative dye intermediate (A) containing the following as an oxidative dye, an alkaline agent, a first agent containing water, and a second agent containing hydrogen peroxide and water, wherein the mass ratio of the oxidative dye intermediate (A) to hydrogen peroxide in the multi-component dyeing agent [oxidative dye intermediate (A) / hydrogen peroxide] is 0.05 or more and 2 or less. <116> and <118> ~ <123> Either one of the staining methods. [Oxidation dye intermediate (A)] One or more selected from meta-aminophenol, resorcinol, meta-phenylenediamine, 2-methylresorcinol, 1-naphthol, 2,6-diaminopyridine, 1,3-bis(2,4-diaminophenoxy)propane, and salts thereof <126> The dyeing agent A is a multi-component dyeing agent containing at least an oxidative dye intermediate (A) containing the following as an oxidative dye, an alkaline agent, a first agent containing water, and a second agent containing hydrogen peroxide and water, wherein the mass ratio of the oxidative dye intermediate (A) to hydrogen peroxide in the multi-component dyeing agent [oxidative dye intermediate (A) / hydrogen peroxide] is 0.05 or more and 0.5 or less. <116> and <118> ~ <123> Either one of the staining methods. [Oxidation dye intermediate (A)] One or more selected from meta-aminophenol, resorcinol, meta-phenylenediamine, 2-methylresorcinol, 1-naphthol, 2,6-diaminopyridine, 1,3-bis(2,4-diaminophenoxy)propane, and salts thereof <127> The first agent further contains one or more precursors selected from toluene-2,5-diamine, para-aminophenol, 4-amino-metacresol, 1-hydroxyethyl-4,5-diaminopyrazole, and salts thereof. <125> or <126> Dyeing method. <128> Step (III) is carried out under conditions in which the mass ratio of component (X) in the fiber for headwear to the dye in dyeing agent A [component (X) / dye] is 10 or more and 10,000 or less. <116> and <118> ~ <127> Either one of the staining methods. <129> Step (III) is carried out under conditions in which the mass ratio of component (Y) in the fiber for headwear to the dye in the dyeing agent A [component (Y) / dye] is 2 or more and 2,000 or less. <120> ~ <128> Any one of the staining methods.

[0213] <130> Step (III), step (I), and step (II) are carried out in this order. <116> and <118> ~ <129> Any one of the staining methods. [Example]

[0214] 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 the examples, various measurements and evaluations were carried out by the following methods.

[0215] <pH measurement> The pH at 25 °C was measured using a pH meter (F-72, manufactured by Horiba, Ltd.).

[0216] <Quantification of benzoic acid in modified regenerated collagen fibers> In this specification, the quantification of benzoic acid contained in the modified regenerated collagen fiber X1 obtained in Production Example 2 was performed by the following method. · Reagents 6N hydrochloric acid: Titrant for volumetric analysis, manufactured by Kanto Chemical Co., Inc. Sodium acetate: Special grade, manufactured by FUJIFILM Wako Pure Chemical Corporation Acetic acid: Special grade, manufactured by FUJIFILM Wako Pure Chemical Corporation Acetonitrile: For LC / MS, manufactured by Kanto Chemical Co., Inc. Sodium benzoate: Special grade, manufactured by FUJIFILM Wako Pure Chemical Corporation Ultra-pure water: Milli-Q water produced by an ultra-pure water production apparatus, manufactured by Merck Millipore · Quantification method The sample (modified regenerated collagen fiber B1) was conditioned at 20 °C and 65% relative humidity for 24 hours, then cut into small pieces, precisely weighed about 10 mg, 3 mL of 6N hydrochloric acid was added, and it was heated and dissolved at 50 °C for 15 hours. After cooling, the filtered solution was used as the sample solution. Separately, sodium benzoate was dissolved in the mobile phase and prepared to a concentration of 0.1 - 100 μg / mL as benzoic acid, which was used as the standard solution for calibration curve plotting. Using the sample solution and the standard solution, liquid chromatography (HPLC) measurement was performed, and the amount of benzoic acid was calculated from the ratio of the peak area of the sample solution and the peak area of the standard solution. · Measurement conditions Detector: Ultraviolet-visible spectrophotometer Measurement wavelength: 230 nm Column: A stainless steel tube with an inner diameter of 21 mm and a length of 150 mm was filled with 5 μm octadecylsilylated silica gel for liquid chromatography. Column temperature: A constant temperature around 40 °C Mobile phase: Approximately 0.68 g of sodium acetate and 0.91 g of acetic acid were dissolved in 750 mL of ultra-pure water, then 250 mL of acetonitrile was added and mixed. ·HPLC / UV conditions Device: UltiMate 3000 system (Thermo Fisher Scientific) Column: L column 2 ODS 5 μm 2.1 × 150 mm (Chemicals Evaluation and Research Institute, Japan) Column temperature: 40℃ Mobile phase: 20 mM ammonium acetate, 25% acetonitrile buffer Analysis time: 10 minutes Detector: DAD (Diode Array Detector) Detection wavelength: 230 nm Flow rate: 0.3 mL / min (isocratic elution) Injection volume: 10μL

[0217] <Weight average molecular weight of styrene-maleic acid copolymer> In this specification, the weight average molecular weight of the styrene-maleic acid copolymer was measured under the following conditions, and the weight average molecular weight was calculated in terms of polystyrene. (1) Reagents Ultrapure water: Milli-Q ultrapure water production system, manufactured by Millipore Dimethylformamide (DMF): Special grade, manufactured by Kanto Chemical Co., Ltd. Lithium bromide monohydrate (LiBr): Special grade, manufactured by Kanto Chemical Co., Ltd. Phosphoric acid: Special grade, manufactured by Sigma-Aldrich (2) Sample pretreatment method Approximately 50 mg of sample was precisely weighed, 0.5 mL of ultrapure water was added, and 10 mL of the mobile phase described below was added to dissolve the solution, which was then filtered to prepare a sample solution. (3) Measurement Using the sample solution and the standard solution, gel permeation chromatography (GPC) measurement was carried out under the following conditions to determine the weight average molecular weight in terms of polystyrene. ·Flow rate: 1mL / min Mobile phase: 60 mM phosphoric acid, 50 mM LiBr in DMF Column: TSKgel α (Alpha) column (Tosoh Corporation) Detector: RI (Differential Refractive Index Detector)

[0218] <Quantitative determination of styrene-maleic acid copolymer in modified regenerated collagen fibers> In this specification, the amount of styrene-maleic acid copolymer in the modified regenerated collagen fiber X2 obtained in Production Example 3 was determined by the following method. (1) Reagents 1 mol / L sodium hydroxide solution: for volumetric analysis, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Ultrapure water: Milli-Q ultrapure water production system, manufactured by Millipore Dimethylformamide (DMF): Special grade, manufactured by Kanto Chemical Co., Ltd. Lithium bromide monohydrate (LiBr): Special grade, manufactured by Kanto Chemical Co., Ltd. Phosphoric acid: Special grade, manufactured by Sigma-Aldrich (2) Sample solution The sample (modified regenerated collagen fiber X2) was conditioned at 20°C and 65% relative humidity for 24 hours, then finely chopped, and approximately 50 mg was precisely weighed. 10 mL of 1 mol / L aqueous sodium hydroxide solution was added and the mixture was heated and dissolved at 50°C for 3 hours. The pH of the solution was adjusted to 4.7-5.3, and the freeze-dried sample was diluted with 0.5 mL of ultrapure water and 9.5 mL of the mobile phase described below. The diluted solution was filtered to prepare the sample solution. (3) Preparation of calibration curve solution Separately, styrene-maleic acid copolymer was dissolved in the mobile phase described below to prepare a non-dissociated styrene-maleic acid copolymer with a concentration of 0.25 to 5.0 mg / mL, which was used as a standard solution for drawing a calibration curve. (4) Measurement Using the sample solution and the standard solution, gel permeation chromatography (GPC) measurements were performed under the following conditions to determine the peak areas of the sample solution and the standard solution. A calibration curve was also created based on the peak area of ​​the standard solution. ·Flow rate: 0.8mL / min Mobile phase: 60 mM phosphoric acid, 50 mM LiBr in DMF Column: TSKgel α (Alpha) column (Tosoh Corporation) Detector: UV-visible spectroscopic detector ·Measurement wavelength: 267nm (5) Calculation of the amount of styrene-maleic acid copolymer The amount of styrene-maleic acid copolymer per fiber mass was calculated using a calibration curve created based on the peak area derived from the styrene-maleic acid copolymer contained in the modified regenerated collagen fiber.

[0219] <Quantitative determination of aluminum in modified regenerated collagen fibers> In this specification, the quantitative determination of aluminum in the modified regenerated collagen fibers was carried out by the following method. (1) Reagents Sulfuric acid: for precision analysis, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Hydrochloric acid: for metal analysis, manufactured by Kanto Chemical Co., Ltd. Sodium carbonate: Special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Boric acid: Special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Aluminum standard solution: 1000 mg / L for atomic absorption analysis, manufactured by Kanto Chemical Co., Ltd. Ultrapure water: Milli-Q ultrapure water production system, manufactured by Millipore (2) Sample pretreatment method The modified regenerated collagen fiber bundle was hung in a dryer (SOFW-450SB, AS ONE Corporation) set to 60°C, a 250g weight was attached to the bottom end of the fiber bundle, and the fiber was dried for 1 hour under tension. The fiber was then removed from the dryer and conditioned at 20°C and 65% relative humidity for 24 hours. 0.1 g of sample (modified regenerated collagen fiber) was precisely weighed into a platinum crucible and heated until no more white smoke was emitted. After adding several drops of sulfuric acid, the mixture was heated again until no more white smoke was emitted and thoroughly incinerated in an electric furnace at 550°C. 1 g of an alkaline flux (sodium carbonate:boric acid = 1:0.4) was then added and the mixture was melted in an electric furnace at 950°C. A watch glass was placed over the sample, and 5 mL of ultrapure water and hydrochloric acid (6 mol / L) were added. The mixture was heated and dissolved on a hot plate at 70-80°C. After cooling, the solution was adjusted to a constant volume of 50 mL with ultrapure water and used as the measurement solution. (3) Preparation of calibration curve solution Using an aluminum standard solution (1000 mg / L), calibration curve solutions of 0.1 to 20 mg / L were prepared. An alkali flux and hydrochloric acid were added to each solution so that the concentrations were the same as those of the measurement solutions. (4) Measurement Using the prepared measurement solution, each element was measured under the following conditions using an ICP emission spectrometer. Analytical equipment: iCAP6500Duo (Thermo Fisher Scientific) ·Wavelength: Al 396.152nm RF power: 1150W Coolant gas flow rate: 12L / min Nebulizer flow rate: 0.70L / min Auxiliary gas: 0.5L / min Pump flow rate: 50 rpm

[0220] Manufacturing Example 1 (Manufacturing of Regenerated Collagen Fiber X0) Cowhide split hide was solubilized with alkali according to standard methods to prepare a spinning solution, which was then extruded from a spinning nozzle into a coagulation bath to produce regenerated collagen fibers. The regenerated collagen fibers were immersed in 30 parts by mass of an aqueous solution containing 5.0% by mass of aluminum sulfate 14-18 hydrate, 0.65% by mass of citric acid monohydrate, and 1.3% by mass of sodium hydroxide (component (Y))) at 30°C with circulation, with the dry mass being the fiber mass after conditioning at 20°C and 65% relative humidity for 24 hours. A 5% aqueous solution of sodium hydroxide was then added in portions over approximately 1 to 5 hours to adjust the final pH of the solution to 4.5 to 5.0 after 5 hours. The fibers were then left in the solution for another 3 hours and thoroughly washed with water to obtain regenerated collagen fiber X0.

[0221] Manufacturing Example 2 (Manufacturing of Modified Regenerated Collagen Fiber X1) The regenerated collagen fiber X0 obtained in Production Example 1 was treated according to the following procedure to obtain modified regenerated collagen fiber X1. (Step 1) Ten 30 cm long fiber bundles (amount that would have a mass of 1.5 g when dried at 60°C for 1 hour and then left at 20°C and 65% RH for 12 hours) were prepared from regenerated collagen fiber X0 for each example and comparative example. (Step 2) Component (X1), benzoic acid (Wako Special Grade Reagent, Fujifilm Wako Pure Chemical Industries, Ltd., molecular weight: 122), was dissolved in water, and the pH was adjusted to 6.0 with a pH adjuster (sodium hydroxide) to prepare a fiber treatment agent containing 25.4% by mass of benzoic acid. The fiber bundles were immersed in a volume of fiber treatment agent such that the bath ratio (mass of fiber bundle after drying in step 1: mass of fiber treatment agent) was 1:30, using a separate container for each bundle, and the opening of each container was sealed. (Step 3) The container was immersed in a water bath (TBS221FA, Toyo Seisakusho Co., Ltd.) set at 40°C and left to stand for 5 minutes, and after the liquid temperature in the container was raised to 40°C, the container was removed from the water bath. (Step 4) The container containing the fiber bundle was placed on a stirring rotor (VMR-5R, AS ONE Corporation) installed in a dryer (SOFW-450SB, AS ONE Corporation) set at 40°C, and the container was rotated at a rotation speed of 80 rpm while being heated and stirred for 3 hours. (Step 5) The container containing the fiber bundle was removed from the dryer and returned to room temperature, after which the fiber bundle was taken out of the container, rinsed with running tap water at 30°C for 30 seconds, and the flow of the fibers was adjusted with a comb. (Step 6) Each fiber bundle was hung in a dryer set at 60°C, and a 250g weight was attached to the bottom end of each fiber bundle, followed by drying for 1 hour with tension applied to the entire fiber. (Step 7) The fiber bundle was removed from the dryer, allowed to cool to room temperature, and the weight was removed.

[0222] The modified regenerated collagen fiber X1 produced in Production Example 2 above had a benzoic acid content of 27.3% by mass calculated as benzoic acid, and an aluminum content of 5.7% by mass.

[0223] Manufacturing Example 3 (Manufacturing of Modified Regenerated Collagen Fiber X2) The regenerated collagen fiber X0 obtained in Production Example 1 was treated according to the following procedure to obtain modified regenerated collagen fiber X2. (Step 1) Ten 30 cm long fiber bundles (amount that would have a mass of 1.5 g when dried at 60°C for 1 hour and then left at 20°C and 65% RH for 12 hours) were prepared from regenerated collagen fiber X0 for each example. First, using the X2a agent shown in Table 1, the following steps 2 to 5 were carried out. Agents X2a and X2b shown in Table 1 were prepared by blending and mixing the components listed in Table 1 using styrene-maleic acid copolymer (XIRAN1000HNa, manufactured by Polyscope, weight average molecular weight (Mw): 9195, acid value: 475 mg KOH / g, styrene / maleic acid molar ratio: 1 / 1) as component (X2). (Step 2) The fiber bundles prepared in (Procedure 1) were immersed in an amount of X2a agent such that the bath ratio (mass of fiber bundle after drying in Procedure 1: mass of X2a agent) was 1:30, using a separate container for each bundle, and the opening of each container was sealed. (Step 3) The container was immersed in a water bath (TBS221FA, Toyo Seisakusho Co., Ltd.) set at 40°C and left to stand for 5 minutes, and after the liquid temperature in the container was raised to 40°C, the container was removed from the water bath. (Step 4) The container containing the fiber bundle was placed on a stirring rotor (VMR-5R, AS ONE Corporation) installed in a dryer (SOFW-450SB, AS ONE Corporation) set at 40°C, and the container was rotated at a rotation speed of 80 rpm while being heated and stirred for 6 hours. (Step 5) The container containing the fiber bundle was removed from the dryer and returned to room temperature, after which the fiber bundle was taken out of the container, rinsed with running tap water at 30°C for 30 seconds, and the fiber flow was adjusted with a comb. (Step 6) The fiber bundle obtained in (Procedure 5) was subjected to (Procedure 2) to (Procedure 5) again, using the agent X2b shown in Table 1 instead of the agent X2a. However, the heating and stirring time in (Procedure 4) was set to 1 hour. (Step 7) The fiber bundles obtained in (Step 6) were hung one by one in a dryer set at 60°C, and a 250 g weight was attached to the bottom end of each fiber bundle, followed by drying for 1 hour with tension applied to the entire fiber. (Step 8) The fiber bundle was removed from the dryer, allowed to cool to room temperature, and the weight was removed.

[0224] [Table 1]

[0225] The blending amounts (mass %) shown in Table 1 are all amounts of active ingredients. The modified regenerated collagen fiber X2 produced in Production Example 3 above had a styrene-maleic acid copolymer content of 31.4 mass % and an aluminum content of 5.5 mass %.

[0226] Production Example 4 (Preparation of Dye A1 Containing Acid Dye) The components shown in Table 2 were blended and mixed until uniform to prepare a stain A1 containing an acid dye.

[0227] Production Example 5 (Preparation of Hair Dye B1 Containing Acid Dye) The components shown in Table 2 were blended and mixed until uniform to prepare hair dye B1 containing an acid dye.

[0228] Production Example 6 (Preparation of dye A2 containing a basic dye) The components shown in Table 2 were blended and mixed until uniform to prepare dye A2 containing a basic dye.

[0229] Production Example 7 (Preparation of Hair Dye B2 Containing Basic Dye) The components shown in Table 2 were blended and mixed until uniform to prepare hair dye B2 containing a basic dye.

[0230] Production Example 8 (Preparation of dye A3 containing oxidation dye) The components shown in "Part 1" in Table 3 were blended and mixed until uniform to prepare Part 1. Similarly, the components shown in "Part 2" in Table 3 were blended and mixed until uniform to prepare Part 2. Before use, the first and second agents were mixed in a mass ratio of 1:1 to prepare a dye A3 containing an oxidation dye, which was used for the evaluation described below.

[0231] Production Example 9 (Preparation of dye A4 containing oxidation dye) The components shown in "Part 1" in Table 3 were blended and mixed until uniform to prepare Part 1. Similarly, the components shown in "Part 2" in Table 3 were blended and mixed until uniform to prepare Part 2. Before use, the first and second agents were mixed in a mass ratio of 1:1 to prepare a dye A4 containing an oxidation dye, which was used for the evaluation described below.

[0232] Production Example 10 (Preparation of Hair Dye B3 Containing Oxidative Dye) The components shown in "Part 1" in Table 3 were blended and mixed until uniform to prepare Part 1. Similarly, the components shown in "Part 2" in Table 3 were blended and mixed until uniform to prepare Part 2. Before use, the first and second agents were mixed at a mass ratio of 1:1 to prepare hair dye B3 containing an oxidation dye, which was used for the evaluation described below.

[0233] [Table 2]

[0234] [Table 3]

[0235] Examples 1 to 7, Comparative Examples 1 to 12 (Step (III): Dyeing of fiber bundles for headwear products) Fiber bundles corresponding to head accessories (extensions) were dyed in the following manner. A fiber bundle having a length of 10 cm and a mass of 1 g was prepared using the fibers for head accessories shown in Tables 4 to 7. The fiber bundle was washed with plain shampoo having the following composition, then rinsed with warm water at 40°C, and thoroughly dried with a hair dryer.

[0236] The fiber bundle was then dyed in the following manner. 2 g of dye 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 the fiber bundle for 30 minutes, the dye was washed away by rinsing with 40°C warm water for 30 seconds, and the fiber bundle was then lathered with a plain shampoo having the following composition 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 hair dryer.

[0237] The color (L0 * ,a0 * ,b0 * ) was measured using a color difference meter (CR-400, Konica Minolta, Inc.). * ,a0 * ,b0 * The values ​​were measured at six points per fiber bundle and the average value was calculated.

[0238] (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)

[0239] (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.)

[0240] (Hair dyeing) A hair bundle of 10 cm in length and 1 g in mass was prepared using white hair (Beaulux Co., Ltd.) equivalent to human hair. The hair bundle was washed with the plain shampoo of the above composition, rinsed with warm water at 40°C, and thoroughly dried with a hair dryer. The hair tresses were then dyed in the following manner. 2 g of hair dye was applied to the hair bundle. This was placed in a glass petri dish, the opening of which was covered with aluminum foil, and the hair 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 hair dye, and the operation of lathering with plain shampoo of the above composition for 15 seconds and rinsing with 40°C warm water for 15 seconds was repeated twice. Next, the plain conditioner of the above composition was applied for 15 seconds, followed by rinsing with 40°C warm water for 15 seconds, and then thoroughly dried with cold air from a hair dryer.

[0241] After dyeing, the color (L1 * ,a1 * ,b1 * ) was measured using a color difference meter (CR-400, Konica Minolta, Inc.). * ,a1 * ,b1 * Each measurement was taken at six points per hair bundle and the average value was calculated.

[0242] The color difference ΔE between the fiber bundle obtained in step (III) immediately after dyeing and the hair bundle after dyeing is calculated from the following formula: * ab1 was calculated and shown in Tables 4 to 7. ΔE * The larger the value of ab1, the greater the color difference between the fiber bundle immediately after dyeing and the hair bundle immediately after dyeing.

[0243] ΔE * ab1=〔(L1 * -L0 * ) 2 +(a1 * -a0 * ) 2 +(b1 * -b0 * ) 2 〕 1 / 2

[0244] (Process (I), Process (II)) The dyed fiber bundle obtained in step (III) and the dyed hair bundle were overlapped. The overlapped fiber bundle was immersed in a container containing 20 g of a solution prepared by diluting the plain shampoo 10 times with purified water. The container containing the fiber bundle was placed on a stirring rotor (VMR-5R, AS ONE Corporation) installed in a dryer (SOFW-450SB, AS ONE Corporation) set at 40°C, and the container was rotated at a rotation speed of 80 rpm and heated and stirred for 15 minutes. The container containing the fiber bundle was removed from the dryer and returned to room temperature, after which the fiber bundle was removed from the container, rinsed with running tap water at 40°C for 120 seconds, and thoroughly dried with cold air from a dryer. The color of the dried fiber bundle was measured using a color difference meter in the same manner as above. * ,a2 * ,b2 * The hue (L3 * ,a3 * ,b3 * ) was measured. According to the following formula, the color difference ΔE between the fiber bundle and the hair bundle after step (II) * ab2 was calculated and shown in Tables 4 to 7.

[0245] ΔE * ab2=〔(L3 * -L2 * ) 2 +(a3 * -a2 * ) 2 +(b3 * -b2 * ) 2 〕 1 / 2

[0246] (Color matching effect of headwear products) ΔE * ab1-ΔE * The values ​​of ab2 were calculated and are shown in Tables 4 to 7. The larger this value, the greater the color matching effect due to dye transfer from the hair bundle corresponding to the hair to the fiber bundle corresponding to the head accessory product in step (II).

[0247] [Table 4]

[0248] [Table 5]

[0249] [Table 6]

[0250] [Table 7]

[0251] In Tables 4 to 7, comparisons between Example 1 and Comparative Examples 1 and 2, Example 2 and Comparative Examples 3 and 4, Example 3 and Comparative Examples 5 and 6, Example 4 and Comparative Examples 7 and 8, Examples 5 and 6 and Comparative Examples 9 and 10, and Example 7 and Comparative Examples 11 and 12 show that the method of the present invention provides the greatest effect of color matching due to dye transfer from hair to fiber for head accessories. It also shows that similar effects can be obtained even when different types of dyes are used to dye the hair.

[0252] The effects of the present invention can also be achieved by using the modified regenerated collagen fibers shown in Formulation Example 1. Prescription example 1 Instead of XIRAN1000HNa (manufactured by Polyscope), XIRAN3000HNa (weight average molecular weight (Mw): 13803, acid value: 285 mg KOH / g, styrene / maleic acid molar ratio: 3 / 1, manufactured by Polyscope) was used, and the regenerated collagen fiber C0 obtained in Production Example 1 was treated in the same manner as in Production Example 3 to obtain modified regenerated collagen fiber X3. Next, the modified regenerated collagen fibers X3 are treated using the treatment composition shown in Table 1 in the same procedure as shown in (Fiber treatment).

[0253] The effects of the present invention can be achieved even when the dye compositions shown in Formulation Examples 2 to 7 are used.

[0254] [Table 8]

[0255] [Table 9]

[0256] [Table 10] [Industrial Applicability]

[0257] According to the present invention, a method for dyeing fibers for head accessories can be provided that can reduce the color difference between hair and fibers for head accessories containing specific modified regenerated collagen fibers and improve the color matching effect.

Claims

1. A method for dyeing fibers for head accessories containing regenerated collagen fibers, comprising: The regenerated collagen fibers contain one or more compounds (X) selected from the group consisting of the following components (X1) and (X2): (X1) Benzoic acid or its salt (X2) A copolymer containing a structural unit derived from an unsaturated monomer having a carboxy group and a structural unit derived from an aromatic vinyl compound, the copolymer having an acid value of 100 mgKOH / g or more and a weight average molecular weight of 1,500 or more and 15,000 or less, or a salt thereof. The modified regenerated collagen fiber contains The dyeing method includes the following steps (I) and (II) in this order: A method for dyeing fibers for head accessories, comprising the following step (III) before the step (I) or between the step (I) and the step (II): Step (I): A step of attaching a head accessory containing the fiber for a head accessory to hair dyed with hair dye B. Step (II): A step of keeping the hair and the fiber for head accessories in a wet state while the hair and the fiber for head accessories are in contact with each other. Step (III) A step of applying dye A to the fiber for head accessories.

2. 2. The method for dyeing fibers for head accessories according to claim 1, wherein the hair dye B contains one or more dyes selected from the group consisting of oxidation dyes, acid dyes, and basic dyes.

3. 2. The method for dyeing fibers for head accessories according to claim 1, wherein the dyeing agent A contains one or more dyes selected from the group consisting of oxidation dyes, acid dyes, and basic dyes.

4. The method for dyeing fibers for a head accessory according to any one of claims 1 to 3, wherein the step (II) comprises a step of washing the hair to which the head accessory is attached with a hair wash composition, and then rinsing with water.

5. The method for dyeing fibers for head accessories according to any one of claims 1 to 3, wherein the step (III) is carried out before the step (I).

6. A dyeing kit comprising a dye A for dyeing fibers for head accessories containing regenerated collagen fibers and a hair dye B for dyeing hair, The dyeing kit includes modified regenerated collagen fibers containing one or more compounds (X) selected from the group consisting of the following components (X1) and (X2): (X1) Benzoic acid or its salt (X2) A copolymer containing a structural unit derived from an unsaturated monomer having a carboxy group and a structural unit derived from an aromatic vinyl compound, the copolymer having an acid value of 100 mgKOH / g or more and a weight average molecular weight of 1,500 or more and 15,000 or less, or a salt thereof.

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