Fiber-treating agent

Abstract

To provide a regenerated protein fiber-treating agent that improves the water resistance and heat resistance of regenerated protein fiber; can form the regenerated protein fiber into a specific shape by heat-setting; also improves the elasticity (tenacity) of the regenerated protein fiber; and enables these performance given to the regenerated protein fiber to be gradually removed by washing, the regenerated protein fiber-treating agent usable to make fibers for hair-dressing products.SOLUTION: A regenerated protein fiber-treating agent contains following components (A) to (C). (A): A specific phenol compound. (C): Water.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a regenerated protein fiber treatment agent for imparting water resistance, heat resistance, and heat-shape resistance to washing to regenerated protein fibers used in headwear products such as wigs and extensions. [Background technology]

[0002] Naturally derived fibers have applications such as wigs and hair extensions, and unlike synthetic fibers, they possess a natural texture and appearance derived from natural materials. Among naturally derived fibers, regenerated protein fibers, such as regenerated collagen fibers, are obtained by solubilizing acid-soluble or insoluble collagen with alkali or enzymes to create a spinning solution, which is then extruded through a spinning nozzle into a coagulation bath to form fibers.

[0003] However, regenerated collagen fibers generally have higher hydrophilicity than synthetic fibers, resulting in a high water absorption rate and extremely low mechanical strength when saturated with water. Therefore, during shampooing, the high water absorption rate significantly reduces mechanical strength, leading to breakage during subsequent drying with a hairdryer, thus reducing their suitability as headwear products.

[0004] Furthermore, regenerated collagen fibers have a problem with low heat resistance. When styling with a hair iron, if they are styled at the same high temperatures as human hair, they will shrink and become frizzy, spoiling their appearance.

[0005] Furthermore, while plastic synthetic fibers retain their shape after heat styling with a hair iron, etc., even after subsequent washing (they have thermal shape memory), regenerated collagen fibers lose their shape after a single subsequent wash (they lack thermal shape memory). Therefore, they are inferior to conventional plastic synthetic fibers in terms of styling flexibility.

[0006] The three points mentioned above were factors hindering the widespread use of regenerated collagen fibers for headwear products. In particular, the impact of water resistance, i.e., the decrease in mechanical strength when wet, was significant. On the other hand, in the field of human hair fibers, which are also used in headwear products, a method is known in which specific aldehyde derivatives and phenolic compounds are applied to human hair fibers that do not inherently possess thermal shape memory ability in order to impart this ability to the fibers (Patent Document 1). [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2019-143281 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] However, in the manufacturing of headwear products, fibers are sometimes stretched strongly, and the technology described in Patent Document 1 sometimes did not result in sufficient elasticity (toughness) of the treated fibers. Therefore, there was a need to improve the elasticity of the treated fibers to prevent breakage during stretching. On the other hand, unlike the aforementioned thermal shape memory ability, if a new shape and elasticity can be imparted to regenerated collagen fibers by heat setting, and this is not removed after several washes, but can be gradually returned to its original state by repeated washing, it would be possible to impart other properties to the regenerated collagen fibers.

[0009] Therefore, the present invention relates to a regenerated protein fiber treatment agent for manufacturing fibers for headwear products, which improves the water resistance and heat resistance of regenerated protein fibers, such as regenerated collagen fibers, imparts the property of retaining the shape imparted by heat setting even after several washes (heat shape wash resistance), has excellent elasticity (toughness) and feel, and moreover, allows the imparted properties such as water resistance, heat resistance, shape, elasticity, and feel to be gradually removed by repeated washing. [Means for solving the problem]

[0010] As a result of intensive research, the present inventors have found that by treating regenerated protein fibers with a composition containing a specific phenolic compound, the water resistance and heat resistance of the regenerated protein fibers are improved, and not only can a shape be imparted by heat setting, but unexpectedly, the elasticity (toughness) of the regenerated protein fibers is improved compared to before treatment and can be increased to a level close to human hair. Furthermore, it has been found that the performance imparted to the regenerated protein fibers after this treatment is gradually removed by washing, and the present invention has been completed.

[0011] The present invention provides a regenerated protein fiber treatment agent containing the following components (A) and (C). (A): A phenolic compound selected from the group consisting of the following components (a1) to (a5) (a1) 2,3,3',4,4',5'-hexahydroxybenzophenone (a2) 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane (a3) A resorcin derivative represented by the general formula (1)

[0012]

Chemical formula

[0016]

Chemical formula

[0017] 〔In the formula, R 3 represents a hydrogen atom or a methyl group, X represents a hydrogen atom, a hydroxyl group or a methoxy group, R 4 represents an aromatic hydrocarbon group which may be substituted by up to 3 hydroxyl or methoxy groups and may form a condensed ring with 1,3-dioxolane, R 5This represents an aromatic hydrocarbon group which may be substituted with a hydroxyl group, a methoxy group, or up to three hydroxyl or methoxy groups which may form a condensed ring with 1,3-dioxolane, or an arylcarbonyloxy group which may be substituted with up to three hydroxyl or methoxy groups. (C):Water

[0018] Furthermore, the present invention provides a method for processing regenerated protein fibers, which includes the following step (i). (i) The step of immersing the fibers in the regenerated protein fiber treatment agent.

[0019] Furthermore, the present invention provides a method for producing fibers for headwear products, which includes a step of treating regenerated protein fibers by the fiber processing method described above.

[0020] Furthermore, the present invention provides a method for manufacturing headwear products, which includes a step of treating regenerated protein fibers by the fiber processing method described above.

[0021] Furthermore, the present invention provides regenerated protein fibers for headwear products containing the above-mentioned component (A).

[0022] Furthermore, the present invention provides a headwear product comprising regenerated protein fibers containing the above-mentioned component (A) as a constituent element. [Effects of the Invention]

[0023] According to the present invention, it is possible to provide a regenerated protein fiber treatment agent for producing fibers for headwear products that have improved water resistance and heat resistance, can be given shape by heat setting, have improved elasticity (toughness) and feel, and can also have these imparted properties gradually removed by washing. [Modes for carrying out the invention]

[0024] [Fibers to be processed in this invention] The regenerated protein fibers to be treated with the fiber treatment agent of the present invention are preferably those made from naturally derived proteins such as keratin, collagen, casein, soy protein, peanut protein, corn protein, and silk protein (e.g., silk fibroin), more preferably regenerated collagen fibers made from collagen, more preferably regenerated silk fibers made from silk fibroin, and even more preferably regenerated collagen fibers.

[0025] Regenerated protein fibers can be manufactured using known technologies, and their composition does not need to be 100% naturally derived protein; they may contain natural or synthetic polymers or additives for quality improvement. Furthermore, they may be post-processed regenerated protein fibers. Filaments are preferred as the form of regenerated protein fibers. Filaments are generally taken from bobbins or boxes. Alternatively, filaments that come out of the drying process during the manufacturing of regenerated protein fibers can be used directly.

[0026] [Component (A): A specific phenolic compound] Component (A) is a phenol compound selected from the group consisting of the following components (a1) to (a5). The molecular weight of component (A) is preferably 110 or more, preferably 1000 or less, more preferably 700 or less, and even more preferably 500 or less, from the viewpoint of good permeability into the regenerated protein fibers. (a1) 2,3,3',4,4',5'-Hexahydroxybenzophenone (a2) 5,5',6,6'-Tetrahydroxy-3,3,3',3'-Tetramethyl-1,1'-Spirobindan (a3) Resorcinol derivatives represented by general formula (1)

[0027] [ka]

[0028] [During the ceremony, A 1 ~A 4These may be the same or different, and represent a hydrogen atom, a hydroxyl group, a halogen atom, a sulfonic acid group or its salt, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms. (a4) Naphthol derivatives represented by general formula (2) or (3)

[0029] [ka]

[0030] [During the ceremony, R 1 This represents a hydrogen atom or a methyl group. A 5 This includes a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, an optionally substituted aralkyl or arylalkenyl group having 7 to 12 carbon atoms, a linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms, a halogen atom, or -CO-R 2 (R 2 (represents a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, an aralkyl or arylalkenyl group having 7 to 12 carbon atoms which may have substituents, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have substituents) D represents a hydrogen atom, a hydroxyl group, a methyl group, or a linear or branched alkoxy or alkenyloxy group having 1 to 12 carbon atoms. E represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms. G represents a hydroxyl group, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer from 0 to 2. (a5) Flavan-3-ol derivatives represented by general formula (4)

[0031] [ka]

[0032] [During the ceremony, R 3 This represents a hydrogen atom or a methyl group. X represents a hydrogen atom, a hydroxyl group, or a methoxy group. R 4 This represents an aromatic hydrocarbon group which may be substituted with up to three hydroxyl or methoxy groups and may form a condensed ring with 1,3-dioxolane. R 5 This represents an aromatic hydrocarbon group which may be substituted with a hydroxyl group, a methoxy group, or up to three hydroxyl or methoxy groups which may form a condensed ring with 1,3-dioxolane, or an arylcarbonyloxy group which may be substituted with up to three hydroxyl or methoxy groups.

[0033] Examples of resorcinol derivatives represented by general formula (1) of component (a3) ​​include resorcinol, 2-methylresorcinol, 4-chlororesorcinol, and pyrogallol.

[0034] The naphthol derivative of component (a4) represented by general formula (2) or (3) is, in general formula (2) or (3), R 1 Preferably, the atom is a hydrogen atom or an alkyl group or alkenyl having 1 to 4 carbon atoms, and more preferably a hydrogen atom. Also, A 5 Preferably, the component is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; more preferably, it is a hydrogen atom or a hydroxyl group. Furthermore, it is preferable that D is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Furthermore, it is preferable that E is a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

[0035] Examples of such compounds include 1-naphthol, 2-naphthol, 3-methylnaphthalene-1-ol, naphthalene-1,5-diol, and naphthalene-1,8-diol.

[0036] The molecular weight of the flavan-3-ol derivative represented by general formula (4) of component (a5) is preferably 150 or more. Furthermore, from the viewpoint of good penetration into the interior of the fiber, a molecular weight of 1000 or less, more preferably 700 or less, and more preferably 500 or less is preferred.

[0037] Examples of component (a5) include catechin, epicatechin, epigallocatechin, gallocatechin, catechin gallate, epicatechin gallate, gallocatechin gallate, and epigallocatechin gallate (hereinafter collectively referred to as "catechins"). Of these, one or more selected from catechin, epigallocatechin, and epigallocatechin gallate are preferred. Alternatively, a mixture containing the above compounds, such as a tea extract, can also be used.

[0038] The analysis of catechins in a mixture can be performed using an analytical method suitable for the sample from among the commonly known analytical methods for nonpolymeric catechins. For example, it can be performed by liquid chromatography (HPLC). During measurement, the sample may be freeze-dried to match the detection range of the instrument, or impurities may be removed from the sample to match the separation capabilities of the instrument, as appropriate treatment may be performed as needed.

[0039] Among the components (A), the following are selected from the viewpoint of making the change in shape of the regenerated protein fibers after treatment with the fiber treatment agent of the present invention more pronounced, more appropriately controlling the heat shape resistance and washability of the regenerated protein fibers, and further improving the natural appearance and feel: resorcinol, 1-naphthol, 2-naphthol, 3-methylnaphthalene-1-ol, naphthalene-1,5-diol, naphthalene-1,8-diol, catechin, epicatechin, epigallocatechin, gallocatechin, catechin gallate, epicatechin gallate, gallocatechin gallate, epigallocatechin gallate Preferably, one or more selected from tea extracts, and more preferably, one or more selected from resorcinol, catechin, epicatechin, gallocatechin, epigallocatechin, catechin gallate, epicatechin gallate, gallocatechin gallate, epigallocatechin gallate, and tea extracts.

[0040] Component (A) can be used alone or in combination of two or more types. From the viewpoint of being able to more appropriately control the heat shape resistance, washability and durability of the regenerated protein fibers and improving the feel, one or more selected from (a1), (a2), (a3), and (a5) is preferred, and from the viewpoint of being able to slightly color the fibers and being more suitable for headwear product applications, one or more selected from (a1), (a2), and (a5) is more preferred.

[0041] The content of component (A) in the fiber treatment agent of the present invention is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 2.5% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of imparting appropriate heat shape resistance and washability and strength to the regenerated protein fibers after treatment. Furthermore, in addition to the above viewpoint, from the viewpoint of improving the feel of the fiber surface, the content is preferably 80% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 40% by mass or less, even more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0042] In other words, the content of component (A) in the fiber treatment agent of the present invention is preferably 0.1 to 80% by mass, more preferably 1 to 60% by mass, even more preferably 2.5 to 50% by mass, even more preferably 5 to 40% by mass, even more preferably 5 to 35% by mass, and even more preferably 5 to 30% by mass, from the viewpoint of imparting appropriate heat shape resistance and washability and strength to the treated fibers and improving the feel of the fiber surface.

[0043] [Ingredient (B): Salt] The fiber treatment agent of the present invention may further contain a salt as component (B) in order to further improve the washability and removal of components adsorbed in the fibers after treatment. Either an organic salt or an inorganic salt can be used as component (B). From the viewpoint of washability and removal, it is preferable that the fiber treatment agent of the present invention does not contain a component corresponding to component (D) described below. For this reason, it is preferable that component (B) is a salt other than the salt corresponding to component (D), i.e., a salt other than glyoxylate. Specifically, examples of organic salts include chelating organic salts such as sodium citrate, sodium lactate, disodium etidronate, disodium ethylenediaminetetraacetate, disodium catechol-3,5-disulfonate monohydrate, and sodium phytate, as well as sodium mercaptoethanesulfonate and sodium 2-naphthalenesulfonate. Examples of inorganic salts include sulfites such as sodium sulfite, as well as sodium chloride and aluminum chlorohydrate.

[0044] Of these, salts of organic or inorganic acids with low reducing activity, such as sodium citrate, sodium lactate, disodium etidronate, disodium ethylenediaminetetraacetate, disodium catechol-3,5-disulfonic acid monohydrate, sodium phytate, sodium 2-naphthalenesulfonate, sodium chloride, and aluminum chlorohydrate are preferred; salts of organic acids with low reducing activity, such as sodium citrate, sodium lactate, disodium etidronate, disodium ethylenediaminetetraacetate, disodium catechol-3,5-disulfonic acid monohydrate, sodium phytate, and sodium 2-naphthalenesulfonate are more preferred; and organic salts with low reducing activity and chelating properties, or with a total of two or more hydroxyl groups, carboxyl groups, and phosphate groups, such as sodium citrate, sodium lactate, disodium etidronate, disodium ethylenediaminetetraacetate, disodium catechol-3,5-disulfonic acid monohydrate, and sodium phytate are even more preferred.

[0045] Here, an organic or inorganic acid with low reducing activity refers to an organic or inorganic acid whose standard oxidation-reduction potential (25°C) in aqueous solution is -0.5V or higher. The standard oxidation-reduction potential (25°C) of an organic or inorganic acid in aqueous solution is preferably -0.3V or higher, and more preferably -0.1V or higher. Note that the standard oxidation-reduction potential (25°C) in aqueous solution refers to the value when the standard pressure is 101325 Pa.

[0046] The content of component (B) in the fiber treatment agent of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, and even more preferably 3% by mass or more, from the viewpoint of making it easier to remove components sorbed to regenerated protein fibers in a shorter period of time, and from the viewpoint of a good feel, it is preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0047] Furthermore, with respect to the chelating organic salt among component (B), the content in the fiber treatment agent of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.10% by mass or more, from the viewpoint of making it easier to remove components sorbed to regenerated protein fibers in a shorter period of time, and from the viewpoint of a good feel, it is preferably 10% by mass or less, more preferably 5.0% by mass or less, and even more preferably 2.5% by mass or less.

[0048] The molar ratio (B) / (A) of component (B) to component (A) in the fiber treatment agent of the present invention is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.10 or more, even more preferably 0.30 or more, and even more preferably 0.50 or more, from the viewpoint of facilitating the removal of components during washing. Furthermore, from the viewpoint of formulation stability, it is preferably less than 20, more preferably 10 or less, even more preferably 5 or less, and even more preferably 3 or less. In other words, the molar ratio (B) / (A) of component (B) to component (A) is preferably 0.01 or more and less than 20, more preferably 0.05 or more and less than 20, even more preferably 0.10 to 10, even more preferably 0.30 to 5, and even more preferably 0.50 to 3, from the viewpoint of facilitating the removal of components during washing.

[0049] [Component (C): Water] The fiber treatment agent of the present invention uses water as a medium. The content of component (C) in the fiber treatment agent of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 40% by mass or more, and also preferably 99% by mass or less, more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less. In other words, the content of component (C) in the fiber treatment agent of the present invention is preferably 10 to 99% by mass, more preferably 20 to 98% by mass, even more preferably 30 to 97% by mass, and even more preferably 40 to 95% by mass.

[0050] [Cationic surfactants] The fiber treatment agent of the present invention may contain a cationic surfactant to the extent that it does not impair the effects of the present invention. The cationic surfactant is preferably a monolong-chain alkylquaternary ammonium salt having one C8-C24 alkyl group and three C1-C4 alkyl groups.

[0051] Preferably, at least one monolong-chain alkylquaternary ammonium surfactant is selected from compounds represented by the following general formula.

[0052] [ka]

[0053] [In the formula, R 6 R is a saturated or unsaturated linear or branched alkyl group having 8 to 22 carbon atoms. 10 -CO-NH-(CH2) m - or R 8 -CO-O-(CH2) m -(R 10 (where m represents an integer from 1 to 4, and R represents a saturated or unsaturated linear or branched alkyl chain having 7 to 21 carbon atoms.) 7 , R 8 and R 9 These independently represent an alkyl group having 1 to 4 carbon atoms, or a hydroxylalkyl group having 1 to 4 carbon atoms, and An - This represents chloride ions, bromide ions, metosulfate ions, or ethosulfate ions.

[0054] Suitable cationic surfactants include, for example, long-chain quaternary ammonium compounds such as cetyltrimethylammonium chloride, myristyltrimethylammonium chloride, behentrimonium chloride, cetyltrimethylammonium bromide, and stearamidopropyltrimonium chloride, which can be used individually or as mixtures thereof.

[0055] The content of the cationic surfactant in the fiber treatment agent of the present invention is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of improving the feel of the regenerated protein fibers after treatment and further enhancing the effects of the present invention.

[0056] 〔silicone〕 Furthermore, the fiber treatment agent of the present invention may contain silicone to improve the feel and cohesiveness of the regenerated protein fibers after treatment. Preferably, one or more silicones are selected from dimethylpolysiloxane and amino-modified silicones.

[0057] Any cyclic or acyclic dimethylpolysiloxane polymer can be used as the dimethylpolysiloxane, and examples include the SH200 series, BY22-019, BY22-020, BY11-026, B22-029, BY22-034, BY22-050A, BY22-055, BY22-060, BY22-083, FZ-4188 (all from Toray Dow Corning Co., Ltd.), KF-9088, KM-900 series, MK-15H, and MK-88 (all from Shin-Etsu Chemical Co., Ltd.).

[0058] Any silicone having an amino group or an ammonium group can be used as the amino-modified silicone. Examples include amino-modified silicone oils in which all or some of the terminal hydroxyl groups are terminally encapsulated with methyl groups, etc., and amodimethicones that are not terminally encapsulated. From the viewpoint of improving the feel and cohesiveness of the regenerated protein fibers after treatment, preferred amino-modified silicones include, for example, the compounds shown in the following formula.

[0059] [ka]

[0060] [In the formula, R' is a hydrogen atom, a hydroxyl group or R X Show, R Xrepresents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and J is R X , R"-(NHCH2CH2) a NH2, OR X Or it represents a hydroxyl group, R'' represents a divalent hydrocarbon group having 1 to 8 carbon atoms, a represents a number from 0 to 3, and b and c represent a number such that their sum is number-average of 10 or more and less than 20,000, preferably 20 or more and less than 3,000, more preferably 30 or more and less than 1,000, and even more preferably 40 or more and less than 800.

[0061] Suitable commercially available amino-modified silicones include amino-modified silicone oils such as SF8452C and SS3551 (both from Toray Dow Corning Co., Ltd.), KF-8004, KF-867S, and KF-8015 (all from Shin-Etsu Chemical Co., Ltd.), and amodimethicone emulsions such as SM8704C, SM8904, BY22-079, FZ-4671, and FZ4672 (all from Toray Dow Corning Co., Ltd.).

[0062] The silicone content in the fiber treatment agent of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, and also preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of improving the feel of the regenerated protein fibers after treatment and further enhancing the effects of the present invention.

[0063] [Cationic polymers] Furthermore, the fiber treatment agent of the present invention may contain a cationic polymer from the viewpoint of improving the feel of the regenerated protein fibers after treatment.

[0064] Cationic polymers are polymers having a cationic group or a group that can be ionized into a cationic group, and also include amphoteric polymers that are cationic overall. Specifically, they are aqueous solutions containing an amino group or an ammonium group in the side chain of the polymer chain, or containing diallyl quaternary ammonium salt as a constituent unit, such as cationized cellulose derivatives, cationic starch, cationized guar gum derivatives, polymers or copolymers of diallyl quaternary ammonium salt, and quaternized polyvinylpyrrolidone derivatives. Of these, from the viewpoint of improving the softness, smoothness and ease of handling during rinsing and shampooing, ease of manageability and moisturizing properties during drying, and the stability of the agent, one or more selected from polymers containing diallyl quaternary ammonium salt as a constituent unit, quaternized polyvinylpyrrolidone derivatives, and cationized cellulose derivatives are preferred, and one or more selected from polymers or copolymers of diallyl quaternary ammonium salt and cationized cellulose derivatives are more preferred.

[0065] Specific examples of suitable polymers or copolymers of diallyl quaternary ammonium salts include dimethyldiallylammonium chloride polymer (Polyquaternium-6, e.g., Merquart 100; Lubrizol Advanced Materials), dimethyldiallylammonium chloride / acrylic acid copolymer (Polyquaternium-22, e.g., Merquart 280, 295; Lubrizol Advanced Materials), and dimethyldiallylammonium chloride / acrylamide copolymer (Polyquaternium-7, e.g., Merquart 550; Lubrizol Advanced Materials).

[0066] Specific examples of suitable quaternized polyvinylpyrrolidone derivatives include polymers obtained by polymerizing vinylpyrrolidone copolymer and dimethylaminoethyl methacrylate (polyquaternium-11, e.g., Gaffcut 734, Gaffcut 755, Gaffcut 755N (all from Ashland)).

[0067] Suitable examples of cationized cellulose include polymers obtained by loading hydroxycellulose with glycidyltrimethylammonium chloride (Polyquaternium-10, e.g., Leoguard G, GP (both from Lion Corporation), Polymer JR-125, JR-400, JR-30M, LR-400, LR-30M (all from Amarcol)), and hydroxyethylcellulose dimethyldiallylammonium chloride (Polyquaternium-4, e.g., Cellcoat H-100, L-200 (both from AkzoNobel)).

[0068] The content of the cationic polymer in the fiber treatment agent of the present invention is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, and also preferably 20% by mass or less, more preferably 10% by mass or less, from the viewpoint of improving the feel of the regenerated protein fibers after treatment.

[0069] Furthermore, the fiber treatment agent of the present invention may contain antioxidants such as ascorbic acid; and pH adjusters such as sodium hydroxide, potassium hydroxide, phosphoric acid, and hydrochloric acid.

[0070] Furthermore, from the viewpoint of maintaining cleaning and removal properties, it is preferable that the fiber treatment agent of the present invention does not contain component (D) described below.

[0071] [Iss] The pH of the fiber treatment agent of the present invention is preferably 3.0 or higher, more preferably 3.5 or higher, even more preferably 4.0 or higher, and also preferably 11.0 or lower, more preferably 9.0 or lower, and even more preferably 7.0 or lower, from the viewpoint of suppressing damage to regenerated protein fibers. Note that the pH values ​​in the present invention are those at 25°C. In other words, the pH of the fiber treatment agent of the present invention is preferably 3.0 to 11.0, more preferably 3.5 to 9.0, and even more preferably 4.0 to 7.0, from the viewpoint of suppressing damage to regenerated protein fibers.

[0072] [Storage method for fiber treatment agents] When transporting and storing the fiber treatment agent manufactured as described above before applying it to fibers, or when transporting and storing the raw materials before preparing the fiber treatment agent, the storage temperature can be kept low or nitrogen can be filled into the voids in the storage container to prevent oxidative discoloration of component (A) and unintended reaction progression during transport. The storage temperature is preferably 1°C or higher, more preferably 2°C or higher, and even more preferably 5°C or higher, from the viewpoint of preventing freezing and recrystallization, and is preferably 25°C or lower, more preferably 20°C or lower, and even more preferably 15°C or lower, from the viewpoint of preventing oxidative discoloration and unintended reaction progression.

[0073] [Fiber processing method] (Basic procedures) By treating regenerated protein fibers using the fiber treatment agent of the present invention in a method including the following step (i), it is possible to impart heat shape resistance and high durability to the regenerated protein fibers while maintaining their elasticity (toughness) to a high degree. Step (i) Step of immersing regenerated protein fibers in the fiber treatment agent of the present invention.

[0074] In step (i), the regenerated protein fibers to be immersed in the fiber treatment agent may be dry or wet. The amount of fiber treatment agent to be immersed in the regenerated protein fibers is preferably 2 or more, more preferably 3 or more, even more preferably 5 or more, even more preferably 10 or more, even more preferably 20 or more, and also preferably 500 or less, more preferably 250 or less, and even more preferably 100 or less, in terms of the bath ratio (mass of fiber treatment agent / mass of regenerated protein fibers) to the mass of the regenerated protein fibers. In other words, the bath ratio is preferably 2 to 500, more preferably 3 to 250, even more preferably 5 to 100, even more preferably 10 to 100, and even more preferably 20 to 100.

[0075] Furthermore, in step (i), the regenerated protein fibers may be fixed in advance with a curler or the like, and then immersed in the fiber treatment agent of the present invention under heating. By doing so, the regenerated protein fibers can be given heat shape resistance, high durability, and the desired shape simultaneously.

[0076] In step (i), the immersion of the regenerated protein fibers into the fiber treatment agent is preferably carried out under heating, and this heating is performed by warming the fiber treatment agent. This heating may be carried out by immersing the regenerated protein fibers in the heated fiber treatment agent, or by immersing the regenerated protein fibers in the low-temperature fiber treatment agent and then heating it. The temperature of the fiber treatment agent is preferably 20°C or higher, more preferably 35°C or higher, and even more preferably 45°C or higher, in order to obtain the effects of the present invention by increasing the interaction between component (A) and the fiber constituent molecules in the regenerated protein fibers, such as protein molecules. Furthermore, in order to prevent the regenerated protein fibers from denature and degrading due to heat, the temperature is preferably less than 100°C, more preferably 80°C or lower, even more preferably 70°C or lower, and even more preferably 60°C or lower.

[0077] The immersion time in step (i) is adjusted as appropriate depending on the heating temperature, but for example, from the viewpoint of exhibiting an effect of improving the elasticity of the regenerated protein fibers, it is preferably 15 minutes or more, more preferably 30 minutes or more, and even more preferably 1 hour or more, and in order to suppress damage to the regenerated protein fibers, it is preferably 48 hours or less, more preferably 24 hours or less, and even more preferably 12 hours or less.

[0078] Step (i) is preferably carried out in an environment in which the evaporation of moisture is suppressed. Specific means of suppressing the evaporation of moisture include covering the container of the fiber treatment agent in which the regenerated protein fibers are immersed with a film-like substance, cap, lid, etc., made of a material that does not allow water vapor to pass through.

[0079] After step (i), the regenerated protein fibers may be rinsed or not, but rinsing is preferable from the viewpoint of preventing a decrease in the feel of the regenerated protein fibers due to excess component (A).

[0080] These processes are thought to cause components (A) and (B) to penetrate into the regenerated protein fibers, leading to interactions with the fiber constituent molecules within the regenerated protein fibers, such as protein molecules.

[0081] By performing crosslinking treatment after step (i), or after step (ii-a) or step (ii-b), the water resistance of the regenerated protein fibers can be improved (the mechanical strength when wet is increased).

[0082] Step (ii-a): A step of immersing regenerated protein fibers in a post-crosslinking agent (I) containing components (D) and (C). (D): At least one formaldehyde derivative selected from formaldehyde, formaldehyde hydrate, glyoxylic acid, glyoxylic acid hydrate, glyoxylate, glyoxal, glyoxal hydrate, glutaraldehyde, and glutaraldehyde hydrate. (C):Water

[0083] As for component (D), from the viewpoint of improving the water resistance of the regenerated protein fibers, that is, increasing the mechanical strength when wet, formaldehyde, formaldehyde hydrate, glyoxal, glyoxal hydrate, glutaraldehyde, and glutaraldehyde hydrate are preferred, and formaldehyde and formaldehyde hydrate are more preferred.

[0084] The content of component (D) in the post-crosslinking agent (I) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, and also preferably 60% by mass or less, more preferably 40% by mass or more, and even more preferably 20% by mass or less, from the viewpoint of improving the water resistance of the regenerated protein fibers, that is, increasing the mechanical strength when wet. In other words, the content of component (D) in the post-crosslinking agent (I) is preferably 0.01 to 60% by mass, more preferably 0.1 to 40% by mass, and even more preferably 1 to 20% by mass.

[0085] Step (ii-b) A step of immersing regenerated protein fibers in a post-crosslinking agent (II) containing components (E) and (C). (E): Compounds having a structure in which methylol groups are bonded to each of the two nitrogen atoms in the molecule. (C):Water

[0086] Examples of component (E) include the compounds (E1) to (E4) shown below, of which compounds (E3) and (E4) are preferred, and compound (E3) is more preferred.

[0087] [ka]

[0088] The content of component (E) in the post-crosslinking agent (II) is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 2.5% by mass or more, even more preferably 5% by mass or more, even more preferably 10% by mass or more, and also preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less, and even more preferably 40% by mass or less, from the viewpoint of improving the water resistance of the regenerated protein fibers, that is, increasing the mechanical strength when wet. In other words, the content of component (E) in the post-crosslinking agent (II) is preferably 0.1 to 80% by mass, more preferably 1 to 70% by mass, even more preferably 2.5 to 60% by mass, even more preferably 5 to 50% by mass, and even more preferably 10 to 40% by mass.

[0089] Furthermore, the post-crosslinking agent may contain pH adjusters such as sodium hydroxide, potassium hydroxide, phosphoric acid, hydrochloric acid, and organic acids.

[0090] The pH of the post-crosslinking agent is preferably 11.0 or lower, more preferably 10.0 or lower, even more preferably 9.0 or lower, and also preferably 2.0 or higher, more preferably 3.0 or higher, and even more preferably 4.0 or higher, from the viewpoint of suppressing damage to the regenerated protein fibers. In other words, the pH of the post-crosslinking agent is preferably 2.0 to 11.0, more preferably 3.0 to 10.0, and even more preferably 4.0 to 9.0, from the viewpoint of suppressing damage to the regenerated protein fibers.

[0091] The temperature of the post-crosslinking agent used in step (ii-a) or (ii-b) is preferably 20°C or higher, more preferably 35°C or higher, and even more preferably 45°C or higher, from the viewpoint of controlling the effects of the present invention (removable deformation and strength) by ensuring that the interaction between the components sorbed to the regenerated protein fibers and the fiber constituent molecules within the regenerated protein fibers, such as protein molecules, is appropriate. Furthermore, from the viewpoint of preventing the regenerated protein fibers from denatured and degraded by heat, the temperature is preferably less than 100°C, more preferably 80°C or lower, even more preferably 70°C or lower, and even more preferably 60°C or lower.

[0092] In step (ii-a) or (ii-b), the regenerated protein fibers immersed in the post-crosslinking agent may be dry or wet. The amount of post-crosslinking agent used to immerse the regenerated protein fibers is preferably 2 or more, more preferably 3 or more, even more preferably 5 or more, even more preferably 10 or more, even more preferably 20 or more, and also preferably 500 or less, more preferably 250 or less, and even more preferably 100 or less, in terms of the bath ratio (mass of post-crosslinking agent / mass of fibers treated in step (i)) to the mass of the regenerated protein fibers. In other words, the bath ratio is preferably 2 to 500, more preferably 3 to 250, even more preferably 5 to 100, even more preferably 10 to 100, and even more preferably 20 to 100.

[0093] The immersion time of the regenerated protein fibers in the post-crosslinking agent in step (ii-a) or (ii-b) is preferably 1 minute or more, more preferably 3 minutes or more, even more preferably 5 minutes or more, and also preferably 5 hours or less, more preferably 3 hours or less, and even more preferably 1 hour or less, in order to allow the post-crosslinking agent to penetrate and diffuse into the regenerated protein fibers.

[0094] [Further processing may be added] The fiber processing method of the present invention may further include, in addition to the above-described steps (i) to (ii-a) or steps (i) to (ii-b), one or more additional treatments selected from decolorization, dyeing, surface finishing for imparting hydrophobicity and reducing friction, and heat treatment for further improving fiber elasticity (toughness).

[0095] In this case, the decolorization and dyeing processes may be performed before or after the aforementioned steps (i) to (ii-a) or (ii-b), or they may be performed between each of the steps (i) to (ii-a) or (ii-b). Furthermore, multiple processes can be combined and added, and if both decolorization and dyeing are added, the order of the processes may vary, except that decolorization must be performed before dyeing, and another process may be performed between decolorization and dyeing.

[0096] On the other hand, surface finishing for hydrophobicity and friction reduction, and heat treatment for further improvement of fiber elasticity (toughness) must be performed after the aforementioned steps (i) to (ii-a) or (ii-b). Furthermore, if the surface finishing for hydrophobicity and friction reduction, and heat treatment for further improvement of fiber elasticity (toughness) are performed after steps (i) to (ii-a) or (ii-b) as described above, the order of processing with decolorization and dyeing is not particularly limited. Also, the order in which the surface finishing for hydrophobicity and friction reduction, and heat treatment for further improvement of fiber elasticity (toughness) are performed may be either first or second.

[0097] (bleaching) Decolorization is performed by immersing regenerated protein fibers in a decolorizing agent composition containing an alkaline agent, an oxidizing agent, and water. The decolorizing agent composition is usually in two parts: the first part contains an alkaline agent and water, and the second part contains an oxidizing agent and water. These two parts are typically stored separately and mixed before immersing the regenerated protein fibers.

[0098] Suitable alkaline agents include, but are not limited to, ammonia and its salts; alkanolamines (monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol, etc.) and their salts; alkanediamines (1,3-propanediamine, etc.) and their salts; and carbonates (guanidine carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.) and mixtures thereof.

[0099] The alkaline agent content in the decolorizing agent composition (in the case of a two-part type, a mixture of the first and second components) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and also preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 7.5% by mass or less.

[0100] Suitable oxidizing agents include, but are not limited to, hydrogen peroxide, urea peroxide, melamine peroxide, and sodium bromate. Among these oxidizing agents, hydrogen peroxide is preferred.

[0101] The content of the oxidizing agent in the decolorizing agent composition is preferably 1% by mass or more, more preferably 2% by mass or more, and also preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 9% by mass or less.

[0102] When the first and second agents are stored separately, the pH of the second agent at 25°C is preferably 2 or higher, more preferably 2.5 or higher, and also preferably 6 or lower, more preferably 4 or lower. This pH can be adjusted with a suitable buffer. The pH of the decolorizing agent composition at 25°C is preferably 6 or higher, more preferably 6.5 or higher, even more preferably 6.8 or higher, and also preferably 11 or lower, more preferably 10.5 or lower, and even more preferably 10 or lower.

[0103] (staining) Dyeing is carried out by immersing regenerated protein fibers in a dyeing composition. The dyeing composition contains dyes and may optionally contain alkaline agents, acids, oxidizing agents, etc. Examples of dyes include direct dyes, oxidation dyes, and combinations thereof.

[0104] The type of direct dye is not particularly limited, and any direct dye suitable for dyeing can be used. Examples of direct dyes include anionic dyes, nitro dyes, disperse dyes, cationic dyes, and dyes having an azophenol structure selected from the group consisting of HC Red 18, HC Blue 18, and HC Yellow 16, as well as salts thereof and mixtures thereof.

[0105] [ka]

[0106] Examples of cationic dyes include, but are not limited to, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 99, Basic Brown 4, Basic Brown 16, Basic Brown 17, Natural Brown 7, Basic Green 1, Basic Orange 31, Basic Red 2, Basic Red 12, Basic Red 22, Basic Red 51, Basic Red 76, Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 10, Basic Violet 14, Basic Yellow 57, and Basic Yellow 87, as well as mixtures thereof. Basic Red 51, Basic Orange 31, Basic Yellow 87, and mixtures thereof are particularly preferred.

[0107] Examples of anionic dyes include Acid Black 1, Acid Blue 1, Acid Blue 3, Acid Blue 5, Acid Blue 7, Acid Blue 9, Acid Blue 74, Acid Orange 3, Acid Orange 4, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Red 1, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 33, Acid Red 50, Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 88, Acid Red 92, Acid Red 155, Acid Red 180, Acid Violet 2, Acid Violet 9, Acid Violet 43, Acid Violet 49, Acid Yellow 1, Acid Examples include, but are not limited to, Yellow 10, Acid Yellow 23, Acid Yellow 3, Food Yellow No. 8, D&C Brown No. 1, D&C Green No. 5, D&C Green No. 8, D&C Orange No. 4, D&C Orange No. 10, D&C Orange No. 11, D&C Red No. 21, D&C Red No. 27, D&C Red No. 33, D&C Violet 2, D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, FD&C Red 2, FD&C Red 40, FD&C Red No. 4, FD&C Yellow No. 6, FD&C Blue 1, Food Black 1, Food Black 2, as well as alkali metal salts of these (sodium salts, potassium salts, etc.) and mixtures thereof.

[0108] Among these, preferred anionic dyes are Acid Black 1, Acid Red 52, Acid Violet 2, Acid Violet 43, Acid Red 33, Acid Orange 4, Acid Orange 7, Acid Red 27, Acid Yellow 3, and Acid Yellow 10, as well as their salts. More preferred anionic dyes are Acid Red 52, Acid Violet 2, Acid Red 33, Acid Orange 4, and Acid Yellow 10, as well as their salts and mixtures.

[0109] Examples of nitro dyes include HC Blue No. 2, HC Blue No. 4, HC Blue No. 5, HC Blue No. 6, HC Blue No. 7, HC Blue No. 8, HC Blue No. 9, HC Blue No. 10, HC Blue No. 11, HC Blue No. 12, HC Blue No. 13, HC Brown No. 1, HC Brown No. 2, HC Green No. 1, HC Orange No. 1, HC Orange No. 2, HC Orange No. 3, HC Orange No. 5, HC Red BN, HC Red No. 1, HC Red No. 3, HC Red No. 7, HC Red No. 8, HC Red No. 9, HC Red No. 10, HC Red No. 11, HC Red No. 13, HC Red No. 54, HC Red No. 14, HC Violet BS, HC Examples include, but are not limited to, Violet No. 1, HC Violet No. 2, HC Yellow No. 2, HC Yellow No. 4, HC Yellow No. 5, HC Yellow No. 6, HC Yellow No. 7, HC Yellow No. 8, HC Yellow No. 9, HC Yellow No. 10, HC Yellow No. 11, HC Yellow No. 12, HC Yellow No. 13, HC Yellow No. 14, HC Yellow No. 15, 2-amino-6-chloro-4-nitrophenol, picramic acid, 1,2-diamino-4-nitrobenzol, 1,4-diamino-2-nitrobenzol, 3-nitro-4-aminophenol, 1-hydroxy-2-amino-3-nitrobenzol, and 2-hydroxyethylpicramic acid, as well as mixtures thereof.

[0110] Examples of disperse dyes include, but are not limited to, Disperse Blue 1, Disperse Black 9, and Disperse Violet 1, and mixtures thereof.

[0111] These direct dyes can be used individually or in combination of two or more, and direct dyes with different ionic properties can also be used together.

[0112] From the viewpoint of obtaining sufficient dyeing properties, the content of direct dyes in the dyeing agent composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.05% by mass or more. From the viewpoint of compatibility, it is preferably 10% by mass or less, more preferably 7.5% by mass or less, even more preferably 5.0% by mass or less, and even more preferably 3.0% by mass or less.

[0113] If the dyeing composition contains only direct dyes as dyes, an oxidizing agent is not necessary to dye the regenerated protein fibers. However, if it is desired to lighten the color of the regenerated protein fibers, an oxidizing agent can be included in the composition.

[0114] When a dyeing composition contains an oxidative dye, it is usually a two-part system. The first part contains an oxidative dye intermediate (precursor and coupler) and an alkaline agent, while the second part contains an oxidizing agent such as hydrogen peroxide. These two parts are usually stored separately and mixed before immersing the regenerated protein fibers.

[0115] There are no particular restrictions on the oxidation dye intermediate; any known precursor and coupler commonly used in dyed products can be suitably used.

[0116] Precursors include, for example, paraphenylenediamine, toluene-2,5-diamine, 2-chloro-paraphenylenediamine, N-methoxyethyl-paraphenylenediamine, N-phenylparaphenylenediamine, N,N-bis(2-hydroxyethyl)-paraphenylenediamine, 2-(2-hydroxyethyl)-paraphenylenediamine, 2,6-dimethyl-paraphenylenediamine, 4,4'-diaminodiphenylamine, 1,3-bis(N-(2-hydroxyethyl)-N-(4-aminophenyl)amino)-2-propanol, PEG-3,3,2'-paraphenylenediamine, para-aminophenol, para-methylaminophenol, 3 Examples include, but are not limited to, methyl-4-aminophenol, 2-aminomethyl-4-aminophenol, 2-(2-hydroxyethylaminomethyl)-4-aminophenol, orthoaminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 2-amino-5-acetamidophenol, 3,4-diaminobenzoic acid, 5-aminosalicylic acid, 2,4,5,6-tetraaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine, 4,5-diamino-1-(4'-chlorobenzyl)pyrazole, 4,5-diamino-1-hydroxyethylpyrazole, and salts of these substances and mixtures thereof.

[0117] Examples of couplers include metaphenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4-(2-hydroxyethylamino)anisole, 2,4-diamino-5-methylphenethole, 2,4-diamino-5-(2-hydroxyethoxy)toluene, 2,4-dimethoxy-1,3-diaminobenzene, 2,6-bis(2-hydroxyethylamino)toluene, 2,4-diamino-5-fluorotoluene, 1,3-bis(2,4-diaminophenoxy)propane, metaaminophenol, 2-methyl-5-aminophenol, 2-methyl-5-(2-hydroxyethylamino)phenol, 2,4-dichloro-3-aminophenol, 2-chloro-3-amino-6-methylphenol, 2-methyl-4-chloro-5-aminophenol, N-cyclopentyl-methaminophenol, 2-methyl-4-methoxy-5-(2-hydroxyethylamino)phenol, 2-methyl-4-fluoro-5-aminophenol, para-amino-o-toxylethanolamine Zol, 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-methylenedioxyphenol Examples include, but are not limited to, 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 of these substances and mixtures thereof.

[0118] The content of precursor and coupler in the dyeing agent composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 10% by mass or less, more preferably 7.5% by mass or less, and even more preferably 5% by mass or less.

[0119] If the dyeing composition contains an oxidation dye, it further contains an alkaline agent. Suitable alkaline agents include, but are not limited to, ammonia and its salts; alkanolamines (monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol, etc.) and their salts; alkanediamines (1,3-propanediamine, etc.) and their salts; and carbonates (guanidine carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.); and mixtures thereof.

[0120] The content of the alkaline agent in the dyeing agent composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and also preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 7.5% by mass or less.

[0121] When the dyeing composition contains an oxidative dye, the oxidizing agent composition (second agent) is stored separately from the oxidative dye composition (first agent) and mixed before immersing the regenerated protein fibers. Suitable oxidizing agents include, but are not limited to, hydrogen peroxide, urea peroxide, melamine peroxide, and sodium bromate. Among these oxidizing agents, hydrogen peroxide is preferred.

[0122] The content of the oxidizing agent in the dyeing agent composition is preferably 1% by mass or more, more preferably 2% by mass or more, and also preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 9% by mass or less.

[0123] When the first and second agents are stored separately, the pH of the second agent at 25°C is preferably 2 or higher, more preferably 2.5 or higher, and also preferably 6 or lower, more preferably 4 or lower. This pH can be adjusted with a suitable buffer. The pH of the dyeing composition obtained by mixing the first and second agents at 25°C is preferably 6 or higher, more preferably 6.5 or higher, even more preferably 6.8 or higher, and also preferably 11 or lower, more preferably 10.5 or lower, and even more preferably 10 or lower.

[0124] If the dyeing composition contains an oxidation dye, it may further contain the direct dyes exemplified above.

[0125] The dyeing composition may preferably further contain the following surfactants, conditioning components, etc., and may preferably take the form of a solution, emulsion, cream, paste, or mousse.

[0126] The temperature of the dyeing agent composition is preferably 0°C or higher, more preferably 10°C or higher, even more preferably 20°C or higher, and also preferably 90°C or lower, more preferably 80°C or lower, from the viewpoint of efficiently penetrating and diffusing the dyeing agent composition into the regenerated protein fibers and further enhancing the dyeing effect.

[0127] (Surface finish for imparting hydrophobicity and reducing friction) Surface finishing for hydrophobicity and friction reduction is performed in a step after the aforementioned steps (i), (II-a), or (II-b) by immersing the regenerated protein fibers in the surface finishing agent shown below.

[0128] The surface finishing agent contains the following components (F) and (C). (F) Epoxyaminosilane copolymer, which is the reaction product of the following compounds (a) to (d) (a) Polysiloxane having at least two oxyranyl groups or oxetanyl groups (b) Polyether having at least two oxyranyl or oxetanyl groups (c) Aminopropyltrialkoxysilane (d) Compounds selected from the group consisting of the following primary and secondary amines Primary amines: Methylamine, ethylamine, propyleneamine, ethanolamine, isopropylamine, butylamine, isobutylamine, hexylamine, dodecylamine, oleylamine, aniline, aminopropyltrimethylsilane, aminopropyltriethylsilane, aminomorpholine, aminopropyldiethylamine, benzylamine, naphthylamine, 3-amino-9-ethylcarbazole, 1-aminoheptafluorohexane, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octaneamine Secondary amines: Methylethylamine, methyloctadecylamine, diethanolamine, dibenzylamine, dihexylamine, dicyclohexylamine, piperidine, pyrrolidine, phthalimide, polymeramines (C) Water

[0129] [Ingredient (F): Epoxyaminosilane copolymer] The epoxyaminosilane copolymer of component (F) is the reaction product of the compounds (a) to (d) shown below.

[0130] <Compounds (a), (b)> Compound (a) is a polysiloxane containing at least two oxiranyl groups or oxetanyl groups, for example, one represented by the following general formula (5).

[0131] [ka]

[0132] [In the formula, R represents a C1-C6 hydrocarbon group that may contain heteroatoms and has an oxyranyl or oxetanyl group at its terminus, and x represents a number from 1 to 1000.]

[0133] Compound (b) is a polyether containing at least two oxyranyl groups or oxetanyl groups, for example, one represented by the following general formula (6).

[0134] [ka]

[0135] [In the formula, R has the same meaning as above, y is between 1 and 100, z is between 0 and 100, and y+z is between 1 and 200.]

[0136] In general formulas (5) and (6), an oxygen atom is preferred as the heteroatom that R may contain. Examples of R include oxyranylmethyl group (glycidyl group), oxyranylmethoxy group (glycidyloxy group), oxyranylmethoxypropyl group (glycidyloxypropyl group), oxetanylmethyl group, oxetanylmethoxy group, oxetanylmethoxypropyl group, 3-ethyloxetanylmethyl group, etc., and among these, a hydrocarbon group having 1 to 4 carbon atoms that has an oxyranyl group and may contain a heterooxygen atom is preferred, and at least one selected from oxyranylmethyl group (glycidyl group), oxyranylmethoxy group (glycidyloxy group), and oxyranylmethoxypropyl group (glycidyloxypropyl group) is even more preferred.

[0137] <Compound (c)> Compound (c) is aminopropyltrialkoxysilane. The alkoxy group in compound (c) may have 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and more preferably 3 carbon atoms, with isopropoxy being particularly preferred. Examples of compound (c) include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltripropoxysilane, aminopropyltriisopropoxysilane, aminopropyltributoxysilane, and aminopropyltritert-butoxysilane, with aminopropyltriisopropoxysilane being particularly preferred. Compound (c) can be used individually or in combination of two or more.

[0138] <Compound (d)> Compound (d) is a compound selected from the group consisting of the following primary and secondary amines. Primary amines: Methylamine, ethylamine, propyleneamine, ethanolamine, isopropylamine, butylamine, isobutylamine, hexylamine, dodecylamine, oleylamine, aniline, aminopropyltrimethylsilane, aminopropyltriethylsilane, aminomorpholine, aminoethyldimethylamine, aminoethyldiethylamine, aminoethyldibutylamine, aminopropyldimethylamine, aminopropyldiethylamine, aminopropyldibutylamine, benzylamine, naphthylamine, 3-amino-9-ethylcarbazole, 1-aminoheptafluorohexane, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octaneamine Secondary amines: Methylethylamine, methyloctadecylamine, diethanolamine, dibenzylamine, dihexylamine, dicyclohexylamine, piperidine, pyrrolidine, phthalimide, polymeramines

[0139] Of these, primary amines are preferred, and one selected from aminopropyldiethylamine, aminopropyldimethylamine, and aminopropyldibutylamine is even more preferred. Compound (d) can be used individually or in combination of two or more.

[0140] The reaction of compounds (a) to (d) is carried out, for example, by refluxing in a solvent such as isopropanol for a certain period of time. Here, the molar ratio of the oxyranyl group or oxetanyl group of compounds (a) and (b) to the amino group of compound (c) is preferably 1 or more, more preferably 1.1 or more, even more preferably 1.2 or more, and also preferably 4 or less, more preferably 3.9 or less, and even more preferably 3.8 or less.

[0141] Component (F) may include those with the INCI name polysilicone-29, and an example of a commercially available product is Silsoft CLX-E from Momentive Performance Materials (15% by mass of active ingredient, containing dipropylene glycol and water).

[0142] The content of component (F) in the surface finishing agent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.10% by mass or more, and even more preferably 0.20% by mass or more, from the viewpoint of providing sufficient hydrophobicity to the regenerated protein fibers, and from the viewpoint of not giving a sticky feeling, it is preferably 15.00% by mass or less, more preferably 10.00% by mass or less, even more preferably 8.00% by mass or less, and even more preferably 6.00% by mass or less.

[0143] The pH of the surface finishing agent at 25°C is preferably within the following ranges from the viewpoint of increasing the reaction rate of the trialkoxysilane portion of component (F) in the acidic or basic range. When the surface finishing agent is in the acidic range, it is preferably 1.0 or higher, more preferably 1.5 or higher, even more preferably 2.0 or higher, preferably 5.0 or lower, more preferably 4.0 or lower, and even more preferably 3.5 or lower. When the surface finishing agent is in the basic range, it is preferably 7.0 or higher, more preferably 7.5 or higher, even more preferably 8.0 or higher, preferably 11 or lower, more preferably 10.5 or lower, and even more preferably 10 or lower. To adjust the pH of the surface finishing agent to the above ranges, the surface finishing agent may contain a pH adjusting agent as appropriate. As pH adjusters, alkaline agents such as alkanolamines or their salts, including monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, and 2-aminobutanol; alkanediamines or their salts, including 1,3-propanediamine; carbonates such as guanidine carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; and hydroxides such as sodium hydroxide and potassium hydroxide can be used. As acidic agents, inorganic acids such as hydrochloric acid and phosphoric acid, hydrochloride salts such as monoethanolamine hydrochloride, phosphates such as monopotassium dihydrogen phosphate and disodium monohydrogen phosphate, and organic acids such as lactic acid and malic acid can be used.

[0144] The amount of surface finishing agent used to immerse the regenerated protein fibers is preferably 2 or more, more preferably 5 or more, even more preferably 10 or more, and also preferably 100 or less, more preferably 50 or less, and even more preferably 20 or less, in terms of the bath ratio (mass of surface finishing agent / mass of regenerated protein fibers) relative to the mass of the regenerated protein fibers.

[0145] (Post-heating: Heat treatment to further improve fiber elasticity (toughness)) Furthermore, to more effectively improve the elasticity of the regenerated protein fibers, they can be heated while being stretched under tension. For small quantities of regenerated protein fibers, it is preferable to use a hair iron for this heating, while for large quantities, equivalent results can be obtained by applying tension with a winding machine while heating with hot air.

[0146] The fiber stretch rate during heating is preferably 0.1% or more, more preferably 0.2% or more, and even more preferably 0.5% or more, from the viewpoint of more effectively improving the elasticity of the fibers, and from the viewpoint of suppressing damage to the fibers, it is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less.

[0147] The heating temperature is preferably 120°C or higher, more preferably 140°C or higher, and even more preferably 160°C or higher, from the viewpoint of more effectively improving the elasticity of the fibers, and preferably 240°C or lower, more preferably 220°C or lower, and even more preferably 200°C or lower, from the viewpoint of suppressing damage to the fibers.

[0148] The heating time is preferably 1 second or more, more preferably 3 seconds or more, and even more preferably 5 seconds or more, from the viewpoint of more effectively improving the elasticity of the fibers, and from the viewpoint of suppressing damage to the fibers, it is preferably 60 seconds or less, more preferably 30 seconds or less, and even more preferably 20 seconds or less.

[0149] After heating, the regenerated protein fibers can be subjected to tension and stretched while being left to stand in water, in order to more effectively improve the elasticity of the fibers.

[0150] The elongation rate in this case is preferably 0.1% or more, more preferably 0.2% or more, and even more preferably 0.5% or more, from the viewpoint of more effectively improving the elasticity of the fibers, and preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less, from the viewpoint of suppressing damage to the fibers.

[0151] From the viewpoint of more effectively improving the elasticity of the fibers, the water temperature is preferably 5°C or higher, more preferably 20°C or higher, and even more preferably 30°C or higher. Furthermore, from the viewpoint of suppressing damage to the fibers, the water temperature is preferably 80°C or lower, more preferably 60°C or lower, and even more preferably 50°C or lower.

[0152] The standing time in water is preferably 1 minute or more, more preferably 5 minutes or more, and even more preferably 30 minutes or more, from the viewpoint of more effectively improving the elasticity of the fibers, and from the viewpoint of suppressing damage to the fibers, it is preferably 48 hours or less, more preferably 24 hours or less, and even more preferably 3 hours or less.

[0153] This operation, depending on the processing conditions in steps (i) to (ii-a) or (ii-b), can enable the fibers to achieve elasticity comparable to human hair during drying.

[0154] (Suppression or removal of discoloration) Furthermore, to suppress or remove discoloration in regenerated protein fibers treated with the fiber treatment agent of the present invention, the fibers can be treated with a composition containing the aforementioned component (B). Preferred components (B) for this purpose include, among organic salts, reducing salts (such as salts of thiol compounds) and salts with metal chelating properties (such as sodium salts of edetate, such as disodium ethylenediaminetetraacetate, and sodium salts of etidronic acid, such as disodium etidronate), and among inorganic salts, reducing salts (such as sulfites, such as sodium sulfite). In particular, it is more preferable to use a reducing salt and a salt with metal chelating properties in combination.

[0155] The fiber discoloration resulting from treatment with the fiber treatment agent of the present invention is thought to consist of both brownish oxidative discoloration (which can be treated with reducing salts) and yellowish catechin metal complex coloration (which can be treated with chelating agents). It is believed that the discoloration of the fibers can be better suppressed by performing decolorization treatments corresponding to each type of discoloration.

[0156] The composition containing the above component (B) is preferably an aqueous solution. Furthermore, from the viewpoint of not reducing the strength of the regenerated protein fibers, the pH of this composition is preferably 2.0 or higher, more preferably 3.0 or higher, even more preferably 4.0 or higher, and also preferably 9.0 or lower, more preferably 7.0 or lower, and even more preferably 6.0 or lower.

[0157] The content of component (B) in the composition containing component (B) is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 2.0% by mass or more, from the viewpoint of exhibiting the effect of suppressing or removing the discoloration of regenerated protein fibers, and preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5.0% by mass or less, from the viewpoint of not reducing the strength of regenerated protein fibers due to the reducing action.

[0158] The processing temperature with the composition containing component (B) is preferably 5°C or higher, more preferably 10°C or higher, and even more preferably 20°C or higher, from the viewpoint of exhibiting the effect of suppressing or removing the discoloration of the regenerated protein fibers, and is preferably 100°C or lower, more preferably 60°C or lower, and even more preferably 40°C or lower, from the viewpoint of avoiding damage to the fibers.

[0159] The processing time with the composition containing component (B) is preferably 1 second or more, more preferably 30 seconds or more, and even more preferably 1 minute or more, from the viewpoint of exhibiting the effect of suppressing or removing the discoloration of the regenerated protein fibers, and from the viewpoint of avoiding damage to the fibers, it is preferably 60 minutes or less, more preferably 30 minutes or less, and even more preferably 15 minutes or less.

[0160] By processing regenerated protein fibers as described above, it is possible to manufacture fibers for headwear products that contain component (A) within the fibers, which allows for shape impartment by heat setting, exhibits excellent tensile modulus, and significantly improves the elasticity (toughness) of the regenerated protein fibers, while also allowing these imparted properties to be gradually removed by washing. Furthermore, headwear products can be manufactured using these fibers. In this invention, examples of headwear products include hair wigs, hairpieces, weaving, hair extensions, braided hair, hair accessories, doll hair, and the like. [Examples]

[0161] Examples 1-6, Comparative Example 1 The compositions shown in Table 1 were used to treat regenerated collagen fibers according to the method described below, and various evaluations were performed. The pH of each composition was measured directly using a pH meter (HORIBA F-52) at room temperature (25°C) after preparation.

[0162] <Processing method> 1. A 22cm long bundle of 0.50g of regenerated collagen fiber (*) was immersed in a container containing 40g of fiber treatment agent. The container was sealed, and the entire container was immersed in a 50°C water bath (manufacturer: Toyo Seisakusho Co., Ltd. / model number: TBS221FA) and heated for 18 hours. * Kaneka Corporation's regenerated collagen fibers were purchased in the form of commercially available hair extension products, and the fibers were cut and divided into small bundles for evaluation. For this evaluation, the extension products used were those labeled as using 100% Ultima fiber, with a color count of 3 (brown), and a straight shape. 2. Remove the container containing the hair bundles from the water bath and allow them to return to room temperature. 3. Remove the hair bundles from the container, rinse them with 30°C running tap water for 30 seconds, lather them with the evaluation shampoo for 60 seconds, rinse them again with 30°C running tap water for 30 seconds, lightly towel dry them, then dry them with a hot air dryer (Tescom Nobby White NB3000) while combing, and measure the weight of the hair bundles (W1).

[0163] <Formula for the evaluation shampoo> Ingredients (mass%) Sodium laureth sulfate 15.5 Lauramide DEA 1.5 Sodium benzoate 0.5 EDTA-2Na 0.3 Amount for adjusting phosphoric acid to pH 7 Ion-exchanged water balance Total 100

[0164] <Removability by washing> 1. After the above treatment, continue to immerse the hair bundle in a container containing 40 g of ion-exchanged water, seal the mouth of the container, and immerse the whole container in a water bath at 50 °C (manufacturer: Toyo Seisakusho Co., Ltd. / model number: TBS221FA) and heat for 18 hours. 2. Take out the container containing the hair bundle from the water bath and let it return to room temperature. 3. Take out the hair bundle from the container, rinse it with running water at 30 °C for 30 seconds, foam it with the shampoo for evaluation for 60 seconds, rinse it with running water at 30 °C for 30 seconds, gently squeeze out the moisture with a towel, and then dry the hair bundle while combing it with a warm air dryer (manufactured by Tescom Co., Nobby White NB3000), and measure the weight of the hair bundle (W2).

[0165] The removal rate R of the components adsorbed by washing was defined as follows and evaluated in three grades A to C according to the removal rate. R = [(W1 - W2) / (W1 - 0.50)] × 100 [%] W1 - 0.50: Indicates how many grams of the components in the fiber treatment agent are adsorbed in the fiber. W1 - W2: Indicates how many grams of the components adsorbed in the fiber can be removed by washing. R: Indicates "what percentage" of the components adsorbed in the fiber can be removed by washing.

[0166] Furthermore, regarding the improvement of removability by adding component (B), it was evaluated according to the following criteria. A: 45 < R The removability has been greatly improved B: 40 < R ≤ 45 The removability has been improved C: R ≤ 40 There is no change or a decrease in removability (less than or equal to the treatment with component (A) alone (= Example 6))

[0167] <Increase in elongation at break during fiber tension> As an indicator of the elasticity (toughness) of fibers under tension, the average elongation at break, that is, the percentage of the original fiber length at which break occurs when the fiber is stretched under tension, was evaluated using the average value obtained from multiple fibers. The evaluation was performed using hair bundles immediately after being treated with the above <treatment method>, following the procedure below. 1. Ten fibers were cut from the base of the hair bundle. A 3cm fiber piece was taken from the middle of the base and tip of each fiber, resulting in a total of 10 3cm hair pieces. 2. The fiber samples were placed in a DIA-STRON limited "MTT690 Automatic Fiber Tensile Tester" and automatic measurement was started to determine the average elongation at break when the fibers were wet. A higher value indicates greater elasticity, superior toughness, and superior durability. The table shows the percentage increase in elongation at break under tensile strength, compared to the baseline of 18.20% for untreated fibers (i.e., those cut directly from commercially available products). Specifically, the break elongation when the fibers are pulled taut in their untreated, as-cut state from a commercially available product was set as the baseline (A%), and the break elongation of the hair bundle immediately after treatment was set as B%. The increase in the break elongation from the untreated state (C(%)) is indicated in the table as "Increase in break elongation when fibers are pulled taut [%]". C(%) = B(%) - A(%)

[0168] <Increase in breaking load during fiber tension> The evaluation of the breaking load during fiber tensile stress was performed using fiber bundles immediately after treatment according to the above-described <treatment method>. The average value obtained from evaluations of multiple fibers was used as the numerical value. The evaluation was performed according to the following procedure. 1. Ten fibers were cut from the base of the hair bundle. A 3cm fiber piece was taken from the middle of the base and tip of each fiber, resulting in a total of 10 3cm hair pieces. 2. The fiber samples were placed in the DIA-STRON limited "MTT690 Automatic Fiber Tensile Testing Machine" and automatic measurement was started to determine the breaking load when the fiber was stretched while wet. A higher value indicates greater stiffness and resilience, making the fiber more resistant to stretching by external forces and demonstrating superior durability. The table shows the increase in the breaking load during fiber tensile stress [gf], compared to the breaking load (70.79 gf) of the untreated fiber, i.e., the fiber in its original, unprocessed state as cut from a commercially available product.

[0169] <Good surface texture> For the tactile evaluation, five expert panelists evaluated the smoothness of the hair when touched by hand using hair strands immediately after processing according to the <processing method>, and the sum of the five panelists' evaluations was used as the final result. (Evaluation Criteria) 5: It has an extremely smooth texture compared to untreated fibers. 4: It has a smoother feel compared to untreated fibers. 3: It has a slightly smoother feel compared to untreated fibers. 2: The texture is the same as untreated fibers. 1: It is rougher and has a less pleasant feel than untreated fibers.

[0170] [Table 1]

[0171] Example 7 The compositions shown in Table 2 were used to treat regenerated collagen fibers according to the method described below, and various evaluations were performed. The pH of each composition was measured directly using a pH meter (HORIBA F-52) at room temperature (25°C) after preparation.

[0172] <Processing method> 1. A 22cm long bundle of 0.50g of regenerated collagen fiber (*) was immersed in a container containing 5g of fiber treatment agent. The container was sealed, and the entire container was immersed in a 50°C water bath (manufacturer: Toyo Seisakusho Co., Ltd. / model number: TBS221FA) and heated for 40 hours. * Kaneka Corporation's regenerated collagen fibers were purchased in the form of commercially available hair extension products, and the fibers were cut and divided into small bundles for evaluation. For this evaluation, the extension products used were those labeled as using 100% Ultima fiber, with a color count of 3 (brown), and a straight shape. 2. Remove the container containing the hair bundles from the water bath and allow them to return to room temperature. 3. Remove the hair bundles from the container, rinse them with 30°C running tap water for 30 seconds, lather them with the aforementioned evaluation shampoo for 60 seconds, rinse them again with 30°C running tap water for 30 seconds, lightly towel dry them, then dry them with a hot air dryer (Tescom Nobby White NB3000) while combing, and measure the weight of the hair bundles (W1).

[0173] <Evaluation Method> Using the same method as described above, the removal rate R (%) by washing, the rate of increase in elongation at break during fiber tension (%), and the increase in breaking load (gf) during fiber tension were calculated, and the quality of the surface feel was evaluated.

[0174] [Table 2]

[0175] Examples 8-10 Using the compositions shown in Table 3, regenerated collagen fibers were treated in the same manner as in Examples 1 to 6, and evaluated for "removability by washing" and "good surface feel."

[0176] [Table 3]

[0177] Prescription examples The same effect as described above can also be obtained by immersing fibers (regenerated collagen fibers) in the fiber treatment agent, of which Table 4 shows example formulations.

[0178] [Table 4]

[0179] Furthermore, the hair bundles processed in the above embodiments can all be used as extensions by securing them to the hair with pins or the like, and can perform adequately on a human head.

Claims

1. A regenerated protein fiber treatment agent comprising the following components (A) and (C): (A): A phenolic compound selected from the group consisting of the following components (a1) to (a5): (a1) 2,3,3',4,4',5'-Hexahydroxybenzophenone (a2) 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindan (a3) Resorcinol or its derivative represented by the general formula (1) 【Chemistry 1】 [During the ceremony, A 1 ~A 4 may be the same or different, and each represents a hydrogen atom, a hydroxyl group, a halogen atom, a sulfonic acid group or a salt thereof, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms. (a4) Naphthol derivative represented by general formula (2) or (3) 【Chemistry 2】 [During the ceremony, R 1 represents a hydrogen atom or a methyl group, A 5 is a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, an aralkyl or arylalkenyl group having 7 to 12 carbon atoms which may have a substituent, a linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms, a halogen atom, or -CO-R 2 (R 2 represents a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, an aralkyl or arylalkenyl group having 7 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, D represents a hydrogen atom, a hydroxyl group, a methyl group, or a linear or branched alkoxy or alkenyloxy group having 1 to 12 carbon atoms; E represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms; G represents a hydroxyl group, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 2. (a5) Flavan-3-ol derivative represented by general formula (4) 【Chemistry 3】 [During the ceremony, R 3 represents a hydrogen atom or a methyl group, X represents a hydrogen atom, a hydroxyl group, or a methoxy group; R4 represents an aromatic hydrocarbon group which may be substituted with up to three hydroxyl or methoxy groups and which may form a condensed ring with 1,3-dioxolane; R 5 represents a hydroxyl group, a methoxy group, an aromatic hydrocarbon group which may be substituted with up to three hydroxyl groups or methoxy groups and which may form a condensed ring with 1,3-dioxolane, or an arylcarbonyloxy group or aralkylcarbonyloxy group which may be substituted with up to three hydroxyl groups or methoxy groups. (C):Water

2. The regenerated protein fiber treatment agent according to claim 1, wherein component (A) is a phenol compound selected from components (a3) ​​to (a5).

3. 3. The regenerated protein fiber treatment agent according to claim 1, wherein the content of component (A) in the regenerated protein fiber treatment agent is 0.1% by mass or more and 80% by mass or less.

4. The regenerated protein fiber treatment agent according to any one of claims 1 to 3, further comprising the following component (B): (B) Salt

5. 5. The regenerated protein fiber treatment agent according to claim 4, wherein the content of component (B) in the regenerated protein fiber treatment agent is from 0.01% by mass to 25% by mass.

6. 6. The regenerated protein fiber treatment agent according to claim 4 or 5, wherein the molar ratio (B) / (A) of component (B) to component (A) is 0.01 or more and less than 20.

7. A method for treating regenerated protein fibers, comprising the following step (i): Step (i) A step of immersing regenerated protein fibers in the regenerated protein fiber treatment agent according to any one of claims 1 to 6.

8. The method for treating regenerated protein fibers according to claim 7, wherein the following step (ii-a) is carried out after step (i). Step (ii-a): A step of immersing the regenerated protein fiber in a post-crosslinking agent containing components (D) and (C). (D): at least one formaldehyde derivative selected from formaldehyde, formaldehyde hydrate, glyoxylic acid, glyoxylic acid hydrate, glyoxylate, glyoxal, glyoxal hydrate, glutaraldehyde, and glutaraldehyde hydrate (C):Water

9. The method for treating regenerated protein fibers according to claim 7, wherein the following step (ii-b) is carried out after step (i). Step (ii-b) A step of immersing the regenerated protein fiber in a post-crosslinking agent containing components (E) and (C). (E): A compound with a structure in which a methylol group is bonded to each of the two nitrogen atoms in the molecule. (C):Water

10. A method for treating regenerated protein fibers described in any one of claims 7 to 9, further comprising one or more treatments selected from bleaching and dyeing before or after steps (i) to (ii-a) or (ii-b), or between each of steps (i) to (ii-a) or (ii-b).

11. The method for treating regenerated protein fibers according to any one of claims 7 to 10, further comprising, after step (i), step (ii-a) or step (ii-b), a step of immersing the regenerated protein fibers in a surface finishing agent containing the following components (F) and (C). (F) An epoxyaminosilane copolymer which is a reaction product of the following compounds (a) to (d): (a) A polysiloxane having at least two oxiranyl or oxetanyl groups. (b) Polyethers containing at least two oxiranyl or oxetanyl groups. (c) Aminopropyltrialkoxysilane (d) Compounds selected from the group consisting of primary and secondary amines: Primary amines: methylamine, ethylamine, propyleneamine, ethanolamine, isopropylamine, butylamine, isobutylamine, hexylamine, dodecylamine, oleylamine, aniline, aminopropyltrimethylsilane, aminopropyltriethylsilane, aminomorpholine, aminopropyldiethylamine, benzylamine, naphthylamine, 3-amino-9-ethylcarbazole, 1-aminoheptafluorohexane, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octanamine Secondary amines: methylethylamine, methyloctadecylamine, diethanolamine, dibenzylamine, dihexylamine, dicyclohexylamine, piperidine, pyrrolidine, phthalimide, polymeric amines (C) Water

12. A method for treating regenerated protein fibers described in any one of claims 7 to 11, further comprising applying tension to the treated regenerated protein fibers and heating them while stretching them.

13. A method for treating regenerated protein fibers described in any one of claims 7 to 12, further comprising treating the treated regenerated protein fibers with a composition containing a salt selected from a reducing organic salt, an organic salt having a metal chelating activity, and a reducing inorganic salt.

14. A method for producing regenerated protein fibers for head ornament products, comprising a step of treating regenerated protein fibers by the regenerated protein fiber treatment method according to any one of claims 7 to 13.

15. A method for producing a head accessory product, comprising a step of treating regenerated protein fibers by the regenerated protein fiber treatment method according to any one of claims 7 to 13.

16. A regenerated protein fiber for headwear products, comprising the following component (A): (A): A phenolic compound selected from the group consisting of the following components (a1) to (a5): (a1) 2,3,3',4,4',5'-Hexahydroxybenzophenone (a2) 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindan (a3) Resorcinol or its derivative represented by the general formula (1) 【Chemistry 4】 [During the ceremony, A 1 ~A 4 may be the same or different, and each represents a hydrogen atom, a hydroxyl group, a halogen atom, a sulfonic acid group or a salt thereof, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms. (a4) Naphthol derivative represented by general formula (2) or (3) 【Chemistry 5】 [During the ceremony, R 1 represents a hydrogen atom or a methyl group, A 5 is a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, an aralkyl or arylalkenyl group having 7 to 12 carbon atoms which may have a substituent, a linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms, a halogen atom, or -CO-R 2 (R 2 represents a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, an aralkyl or arylalkenyl group having 7 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, D represents a hydrogen atom, a hydroxyl group, a methyl group, or a linear or branched alkoxy or alkenyloxy group having 1 to 12 carbon atoms; E represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms; G represents a hydroxyl group, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 2. (a5) Flavan-3-ol derivative represented by general formula (4) 【Chemistry 6】 [During the ceremony, R 3 represents a hydrogen atom or a methyl group, X represents a hydrogen atom, a hydroxyl group, or a methoxy group; R 4 represents an aromatic hydrocarbon group which may be substituted with up to three hydroxyl or methoxy groups and which may form a condensed ring with 1,3-dioxolane, R 5 represents a hydroxyl group, a methoxy group, an aromatic hydrocarbon group which may be substituted with up to three hydroxyl groups or methoxy groups and which may form a condensed ring with 1,3-dioxolane, or an arylcarbonyloxy group or aralkylcarbonyloxy group which may be substituted with up to three hydroxyl groups or methoxy groups.

17. The regenerated protein fiber for head accessories according to claim 16, wherein the component (A) is a phenolic compound selected from the components (a3) ​​to (a5).

18. A head accessory product comprising, as a component, a regenerated protein fiber containing the following component (A): (A): A phenolic compound selected from the group consisting of the following components (a1) to (a5): (a1) 2,3,3',4,4',5'-Hexahydroxybenzophenone (a2) 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindan (a3) Resorcinol or its derivative represented by the general formula (1) 【Chemistry 7】 [During the ceremony, A 1 ~A 4 may be the same or different, and each represents a hydrogen atom, a hydroxyl group, a halogen atom, a sulfonic acid group or a salt thereof, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms. (a4) Naphthol derivative represented by general formula (2) or (3) 【Chemistry 8】 [During the ceremony, R 1 represents a hydrogen atom or a methyl group, A 5 is a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, an aralkyl or arylalkenyl group having 7 to 12 carbon atoms which may have a substituent, a linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms, a halogen atom, or -CO-R 2 (R 2 represents a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms, an aralkyl or arylalkenyl group having 7 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, D represents a hydrogen atom, a hydroxyl group, a methyl group, or a linear or branched alkoxy or alkenyloxy group having 1 to 12 carbon atoms; E represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy or alkenyloxy group having 1 to 6 carbon atoms; G is a hydroxyl group, a linear or branched alkyl group or an alkenyl group having 1 to 6 carbon atoms. or an alkoxy group having 1 to 6 carbon atoms, and n is an integer of 0 to 2. (a5) Flavan-3-ol derivative represented by general formula (4) 【Chemistry 9】 [During the ceremony, R 3 represents a hydrogen atom or a methyl group, X represents a hydrogen atom, a hydroxyl group, or a methoxy group; R 4 represents an aromatic hydrocarbon group which may be substituted with up to three hydroxyl or methoxy groups and which may form a condensed ring with 1,3-dioxolane, R 5 represents a hydroxyl group, a methoxy group, an aromatic hydrocarbon group which may be substituted with up to three hydroxyl groups or methoxy groups and which may form a condensed ring with 1,3-dioxolane, or an arylcarbonyloxy group or aralkylcarbonyloxy group which may be substituted with up to three hydroxyl groups or methoxy groups.

19. The head accessory product according to claim 18, wherein the component (A) is a phenolic compound selected from the components (a3) ​​to (a5).

20. The head accessory product according to claim 18 or 19, which is selected from a hair wig, a toupee, a weaving, a hair extension, a braided hair, a hair accessory, and a doll hair.

Images