Fiber treatment agent

Abstract

The present invention relates to a fiber treatment agent which improves water resistance and heat resistance, which are problems of naturally derived fibers, imparts thermal shape memory ability, and also improves stretchability (flexibility) and surface tactile sensation. This fiber treatment agent is a single-agent-type fiber treatment agent comprising a single composition or a multi-agent-type fiber treatment agent comprising a plurality of compositions, and contains the following components (A) to (C) in the entire composition. (A): an aromatic compound having one or more vinyl groups or vinylidene groups and a coordinating functional group; (B): a radical initiator; (C): water.

Description

Technical Field

[0001] The present invention relates to a fiber treatment agent for imparting water resistance, heat resistance and thermal shape memory to natural-origin fibers, and relates to a fiber treatment agent suitable for treating natural-origin fibers used for fiber products such as wigs, hair extensions and other headdresses. Background Art

[0002] Natural fibers are generally different from synthetic fibers and have a natural feel and appearance formed by natural materials. Regenerated protein fibers among natural fibers, such as regenerated collagen fibers, are obtained by dissolving acid-soluble collagen or insoluble collagen with alkali or enzyme to prepare a spinning solution, and then ejecting it from a spinning nozzle into a coagulation bath for fiberization.

[0003] However, compared with synthetic fibers, natural fibers are generally more hydrophilic and therefore have a high water absorption rate. When containing a large amount of water, they generally have low mechanical strength, and regenerated protein fibers in particular have extremely low mechanical strength. Therefore, when washed, the mechanical strength is significantly reduced due to the high water absorption rate, and they break during subsequent drying, which reduces their applicability as fiber products.

[0004] In addition, regenerated protein fibers among natural fibers have a problem of low heat resistance. For example, when heat-setting using a hair iron or the like is performed at a high temperature similar to that of human hair, shrinkage or curling may occur, thereby impairing the aesthetics.

[0005] In addition, in the case of synthetic fibers made of plastic, when heat-set using a hair iron, the shape can continue to be remembered even after subsequent washing (having thermal shape memory ability), but in the case of fibers of natural origin, when heat-set using a hair iron, the shape will disappear in the next washing (having no thermal shape memory ability). Therefore, compared with existing synthetic fibers made of plastic, there are some deficiencies in terms of styling freedom.

[0006] The above-mentioned factors have become the main reasons that hinder the popularization of natural-origin fibers, especially regenerated protein fibers, in fiber products such as headwear products. In particular, the influence of the reduction in water resistance, that is, the mechanical strength when wet, is significant.

[0007] On the other hand, in the field of human hair fibers, which are natural fibers, there is known a method of allowing a specific aldehyde derivative to act with a phenol compound in order to impart thermal shape memory capability to human hair fibers that do not originally have thermal shape memory capability (Patent Document 1).

[0008] (Patent Document 1) Japanese Patent Application Publication No. 2019-143281 Summary of the invention

[0009] The present invention provides a single-component fiber-treating agent consisting of a single composition or a multi-component fiber-treating agent consisting of a plurality of compositions, wherein the fiber-treating agent contains the following components (A) to (C) in its entire composition.

[0010] (A): Aromatic compound having one or more vinyl or vinylidene groups and a coordinating functional group

[0011] (B): Free radical initiator

[0012] (C) Water

[0013] The present invention also provides a fiber treating agent kit comprising a composition containing the following components (A) and (C), and a composition containing the following components (B) and (C).

[0014] (A): Aromatic compound having one or more vinyl or vinylidene groups and a coordinating functional group

[0015] (B): Free radical initiator

[0016] (C) Water DETAILED DESCRIPTION

[0017] When manufacturing fiber products such as headwear products, fibers are sometimes strongly stretched, and the stretchability (flexibility) of the treated fibers is sometimes insufficient in the technology described in Patent Document 1. Therefore, in order to prevent breakage during stretching, it is required to improve the stretchability of the treated fibers.

[0018] Therefore, the present invention relates to a fiber treating agent that improves water resistance and heat resistance, which are problematic aspects of natural-origin fibers, imparts thermal shape memory capability, and also improves stretchability (flexibility) and surface feel.

[0019] The inventors of the present invention have conducted intensive studies and have found that, by treating natural fibers with a composition containing an aromatic compound having a vinyl or vinylidene group and a coordinating functional group and a radical initiator, the aromatic compound that has penetrated into the fibers is polymerized, and its coordinating functional group is strongly coordinated with a metal (mainly a polyvalent metal) in the natural fibers, thereby improving the strength or heat resistance of the fibers in water and preventing the aromatic compound or its polymer from leaking out of the fibers. Furthermore, as a result, it has been found that the water resistance and heat resistance of the natural fibers in both dry and wet conditions are improved, and not only can the natural fibers be given a shape by heat setting, but the elasticity (flexibility) of the natural fibers is unexpectedly improved compared to before the treatment, and can be improved to a level close to that of human hair, thereby completing the present invention.

[0020] The present invention can provide a fiber treatment agent that can improve the water resistance and heat resistance of natural-origin fibers in both dry and wet conditions, impart thermal shape memory capability, and improve stretchability (flexibility) and surface feel.

[0021] [Single-dose and multiple-dose]

[0022] The fiber treatment agent of the present invention also includes any form of a single-component fiber treatment agent composed of a single composition, a two-component fiber treatment agent composed of multiple compositions and a multi-component fiber treatment agent in which fibers are sequentially impregnated with these multiple compositions. In addition, the above-mentioned single-component fiber treatment agent also includes a form in which multiple compositions are mixed into a single composition when used.

[0023] In the present invention, the content in the fiber-treating agent refers to the content in a single composition used in the case of a one-dose fiber-treating agent, and refers to the content in each treatment agent used in each stage in the case of a multi-dose fiber-treating agent.

[0024] [Fibers to be treated in the present invention]

[0025] The fiber of the treatment object of the fiber treatment agent of the present invention preferably contains metal fiber, preferably natural fiber containing metal or synthetic fiber containing metal, wherein, preferably natural fiber containing metal. Natural fiber refers to fiber obtained from natural animals and plants, or artificial fiber made of polymers or oligomers such as proteins or polysaccharides from keratin, collagen, casein, soybean, peanut, corn, silk scraps, silk protein (such as silk protein), etc. as raw materials. Among these, preferably artificial fiber made of polymers or oligomers such as proteins or polysaccharides from keratin, collagen, casein, soybean, peanut, corn, silk scraps, silk protein (such as silk protein), etc., more preferably regenerated protein fiber made of protein from keratin, collagen, casein, soybean protein, peanut protein, corn protein, silk protein (such as silk protein), etc., more preferably regenerated collagen fiber made of collagen, regenerated protein fiber such as regenerated silk fiber made of silk protein, and further preferably regenerated collagen fiber.

[0026] Regenerated collagen fibers can be manufactured using known techniques, and the composition does not have to be 100% collagen, and may contain natural or synthetic polymers or additives for quality improvement. It may also be a material obtained by post-processing the regenerated collagen fibers. As the form of the regenerated collagen fibers, filaments are preferred. The filaments are usually taken out from a reel or a box. In addition, the filaments obtained by the drying process in the manufacturing process of the regenerated collagen fibers may also be directly used.

[0027] The synthetic fiber containing metal may be a synthetic fiber treated with metal. The natural fiber containing metal also includes a fiber that originally contains metal, such as a fiber obtained from natural animals and plants. In this case, it is not necessary to make it contain metal again. For example, it may be a fiber treated with a metal salt, such as a fiber treated with aluminum salt for water resistance as described in Japanese Patent Publication No. 2003-027318.

[0028] [Component (A): an aromatic compound having a vinyl group or a vinylidene group and a coordinating functional group]

[0029] Component (A) is an aromatic compound having one or more vinyl or vinylidene groups and a coordinating functional group. As the coordinating functional group in component (A), it is preferred to include Pearson's hard base (Hard Base). Pearson's hard base (Hard Base) refers to a Lewis base classified as a hard base in the concept of HSAB (Hard and Soft Acids and Bases, hard and soft acids and bases) proposed by Pearson (RGPearson) in the 1960s, and is easy to react with a Lewis acid classified as a hard acid.

[0030] Examples of the hard base contained in the coordinating functional group of the aromatic compound of component (A) include functional groups corresponding to the hard base described in Application of the Principle of Hard and Soft Acids and Bases to Organic Chemistry, Ralph G. Pearson and Jon. Songstad, J. Am. Chem. Soc. 1967, 89, 8, 1827-1836, such as COO - , O - , COOH, OH, NH2, etc. Among these, COO - , O - , COOH, OH. From the viewpoint of further reducing fiber coloration and improving the fixation of the fiber after treatment (inhibiting elution during washing), COO - , COOH. The coordinating functional group in the component (A) is preferably a functional group containing a carboxyl group or a group obtained by removing one hydrogen atom from the benzene ring of catechol (1,2-dihydroxybenzene).

[0031] Hereinafter, the aromatic compound of component (A) is divided into (A-1) aromatic compounds having coordinating functional groups including COOH, COO - or COOH salts, and (A-2) the coordinating functional groups include OH, O -The case of a salt of or OH is exemplified.

[0032] (A-1) Coordinating functional groups include COOH, COO - or COOH salts

[0033] As (A-1), there can be mentioned (A-1-a) aromatic compounds having a vinyl group or a vinylidene group as part of a styrene skeleton, and (A-1-b) aromatic compounds having a vinyl group or a vinylidene group as part of an acryloyl group or a methacryloyl group. In addition, as examples of the case where component (A-1) is a salt, there can be mentioned alkali metal salts such as sodium salts and potassium salts.

[0034] (A-1-a) The coordinating functional groups include COOH, COO - or COOH salts and vinyl or vinylidene is part of the styrene skeleton

[0035] Examples of the aromatic compound (A-1-a) include compounds represented by the following general formula (1).

[0036]

[0037] [In formula (1), R 1 A represents a hydrogen atom or a methyl group. 1 ~A 5 Each independently represents a hydrogen atom, a carboxyl group, a group represented by the general formula (2), an acetyl group, a halogen atom, or a linear or branched alkyl group, alkenyl group, alkoxy group or alkenyloxy group having 1 to 6 carbon atoms. 2 represents a linear or branched saturated or unsaturated divalent hydrocarbon group or divalent hydrocarbonoxy group having 1 to 6 carbon atoms, o-phenylene, m-phenylene, p-phenylene, benzylidene or phenyl C2-C4 alkylene. 1 ~A 5 Contains at least one carboxyl group or a group represented by the general formula (2).

[0038] In (A-1-a), as A 1 ~A 5 Specific examples of aromatic compounds containing at least one carboxyl group include 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, and mixtures of two or three selected from these. From the viewpoint of easy availability and excellent surface feel of the treated fiber, a mixture of the three is preferred. On the other hand, from the viewpoint of imparting water resistance, 4-vinylbenzoic acid is preferred.

[0039] In (A-1-a), as A 1 ~A 5Specific examples of the aromatic compound containing at least one group represented by the general formula (2) include 4-oxo-4-((4-vinylbenzyl)oxy)butyric acid and 2-(((4-vinylbenzyl)oxy)carbonyl)benzoic acid.

[0040] (A-1-b) Coordinating functional groups include COOH, COO - or COOH salts and the vinyl or vinylidene group is part of an acryloyl group or a methacryloyl group

[0041] Examples of the aromatic compound (A-1-b) include compounds represented by the following general formula (3).

[0042]

[0043] In formula (3), R 3 represents a hydrogen atom or a methyl group, B 1 ~B 4 Each independently represents a hydrogen atom, a carboxyl group, an acetyl group, a halogen atom, or a linear or branched alkyl group, alkenyl group, alkoxy group or alkenyloxy group having 1 to 6 carbon atoms, Ph represents a phenylene group, n represents an integer of 0 to 2, and m represents 0 or 1.]

[0044] Specific examples of the aromatic compound represented by the general formula (3) include 2-((2-(acryloyloxy)ethoxy)carbonyl)benzoic acid, 2-((2-(methacryloyloxy)ethoxy)carbonyl)benzoic acid, and 2-(4-(2-(2-(acryloyloxy)ethoxy)ethoxy)benzoyl)benzoic acid.

[0045] (A-2) Its coordinating functional groups include OH, O - Or the case of OH salts

[0046] Examples of (A-2) include compounds represented by the following general formula (4).

[0047]

[0048] [In formula (4), R 4 represents a hydrogen atom or a methyl group, E 1 ~E 5 Each independently represents a hydrogen atom, a hydroxyl group, a group represented by the general formula (5), an acetyl group, a halogen atom, or a linear or branched alkyl group, alkenyl group, alkoxy group or alkenyloxy group having 1 to 6 carbon atoms, 1 ~G 5 Each independently represents a hydrogen atom, a hydroxyl group, an acetyl group, a halogen atom, or a linear or branched alkyl group, alkenyl group, alkoxy group or alkenyloxy group having 1 to 6 carbon atoms. 1 ~E 5Contains at least one group represented by the general formula (5).

[0049] Specific examples of the aromatic compound represented by the general formula (4) include 4-vinylbenzyl 3,4,5-trihydroxybenzoate.

[0050] As component (A), a compound corresponding to (A-1) is more preferred from the viewpoint of further reducing fiber coloring and improving the fixation after fiber treatment (suppression of elution during washing).

[0051] Component (A) can be used alone or in combination of two or more. The content of component (A) in the fiber treatment agent of the present invention varies depending on the pH range of the fiber treatment agent, and is preferably in the range shown below. Among them, the content of component (A) when component (A) is a salt refers to the content of the corresponding non-dissociated form. The non-dissociated form refers to the state in which the counter ion is replaced by hydrogen in the case of an acid, such as acid COOH in the case of a COO-salt; and the state in which the proton is removed in the case of a base, such as the state of an amine in the case of an ammonium salt. Among them, in the case where the fiber treatment agent is a multi-dose type, the so-called "pH of the fiber treatment agent" here refers to the pH of the treatment agent containing component (A). In the case where there are multiple treatment agents containing component (A), the preferred content range is determined according to the pH of each treatment agent. In addition, as described above, the form in which multiple compositions are mixed into a single composition when used is included in the single-dose fiber treatment agent, and the "pH of the fiber treatment agent" refers to the pH after mixing.

[0052] When the pH of the fiber-treating agent is 2.0 or more and less than 6.5, the content of the component (A) in the fiber-treating agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.5% by mass or more, and further preferably 1.0% by mass or more in the case of a salt in a non-dissociated form, from the viewpoint of imparting higher shape retention, water resistance, stretchability (flexibility, i.e., high elongation at break when the fiber is stretched) and heat resistance to the natural-origin fiber after the treatment, and is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, further more preferably 20% by mass or less, and further more preferably 15% by mass or less in terms of improving the touch of the fiber surface.

[0053] That is, when the pH of the fiber treatment agent is 2.0 or more and less than 6.5, from the above viewpoint, the content of component (A) in the fiber treatment agent of the present invention is preferably 0.1 to 40% by mass in a non-dissociated form when it is a salt, more preferably 0.2 to 30% by mass, further preferably 0.5 to 25% by mass, further more preferably 1.0 to 20% by mass, and further more preferably 1.0 to 15% by mass.

[0054] When the pH of the fiber treatment agent is 6.5 or more and 11.0 or less, the content of the component (A) in the fiber treatment agent is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, further preferably 5.0% by mass or more, and further preferably 10% by mass or more in the case of a salt in a non-dissociated form, from the viewpoint of imparting higher shape retention, water resistance, stretchability (flexibility, i.e., high elongation at break when the fiber is stretched) and heat resistance to the natural-origin fiber after the treatment, and is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and further preferably 60% by mass or less in terms of improving the touch of the fiber surface.

[0055] That is, when the pH of the fiber treatment agent is 6.5 or more and 11.0 or less, from the above viewpoint, the content of component (A) in the fiber treatment agent of the present invention is preferably 1.0 to 90% by mass, more preferably 2.0 to 80% by mass, further preferably 5.0 to 70% by mass, and further preferably 10 to 60% by mass in a non-dissociated form when the fiber treatment agent is a salt.

[0056] [Component (B): free radical initiator]

[0057] Component (B) is a free radical initiator for polymerizing component (A). Component (B) may be contained in the same composition as component (A), or the fiber treatment agent used may be made into a multi-dose formula, for example, a two-dose formula, and contained in a composition (second agent) different from the composition (first agent) containing component (A). Examples of component (B) include peroxide initiators, azo initiators, and the like. In addition, a combination of an oxidizing agent and a reducing agent may also be used as a redox initiator.

[0058] Examples of the peroxide initiator include sodium persulfate, potassium persulfate, ammonium persulfate, tert-butyl hydroperoxide, tert-amyl hydroperoxide, p-diisopropylbenzene hydroperoxide, cumene hydroperoxide, pinane hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, benzoyl peroxide, t-butyl perbenzoate, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxyneodecanoate, and tert-butyl peroxyneodecanoate. peroxyneodecanoate), t-butylperoxypivalate, (3,5,5-trimethylhexanoyl peroxide), dipropionyl peroxide, diacetyl peroxide, etc.

[0059] Examples of the azo initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-hydroxymethylpropionitrile), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 4,4'-azobis(4-cyanovaleric acid) acid), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine], 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, etc.

[0060] As the oxidizing agent used in the redox initiator, in addition to the compounds listed as the peroxide initiator mentioned above, hydrogen peroxide, sodium hypochlorite, potassium hypochlorite, oxygen, ozone, etc. can be listed. In addition, as the reducing agent used in the redox initiator, sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium pyrosulfite, potassium pyrosulfite, ferrous ion, chromium ion, ascorbic acid, formaldehyde sulfoxylate, tetramethylenediamine, sodium hydroxymethanesulfinate, etc. can be listed.

[0061] From the viewpoint of promoting the penetration of the compound in the solution into the fiber, the fiber treatment agent for hydrophilic natural-origin fiber is preferably an aqueous solution, and therefore, as the free radical initiator formulated in the fiber treatment agent, a water-soluble free radical initiator is also preferred. As the water-soluble azo initiator, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine], 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, etc. are preferred.

[0062] The water-soluble free radical initiator refers to a free radical initiator which, when 1 g of the powder of the free radical initiator is added to water and vigorously shaken and mixed every 5 minutes at 20°C±5°C for 30 seconds, is preferably "poorly soluble" to "very soluble", more preferably "slightly poorly soluble" to "very soluble", further preferably "slightly soluble" to "very soluble", further more preferably "soluble" to "very soluble", and further more preferably "very soluble" in the following terms indicating the degree of solubility specified for the volume of water (mL) required to dissolve within 30 minutes.

[0063] 〈Amount of water required to dissolve 1g of free radical initiator〉

[0064] Very soluble: less than 1mL;

[0065] Soluble: more than 1mL and less than 10mL;

[0066] Slightly soluble: more than 10mL and less than 30mL;

[0067] Slightly insoluble: more than 30mL and less than 100mL;

[0068] Insoluble: more than 100mL and less than 1000mL;

[0069] Very difficult to dissolve: more than 1000mL and less than 10000mL;

[0070] Almost insoluble: more than 10000mL.

[0071] In addition, as a treatment agent for natural-origin fibers with low heat resistance, it is more preferable to use a free radical initiator with a low 10-hour half-life temperature that can be effectively decomposed even at a low treatment temperature and function as a free radical initiator. Among them, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] (10-hour half-life temperature: 61°C), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] (10-hour half-life temperature: 57°C), 2,2'-azobis(2-methylpropionamidine) dihydrochloride (10-hour half-life temperature: 56°C), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (10-hour half-life temperature: 44°C) are preferred.

[0072] The 10-hour half-life temperature of the radical initiator refers to the temperature at which 50% of the radical initiator decomposes after 10 hours. The 10-hour half-life temperature of the radical initiator is preferably 80°C or less, more preferably 70°C or less, further preferably 60°C or less, and further preferably 50°C or less, from the viewpoint of not causing damage to natural-origin fibers that are not resistant to high temperatures and being able to react effectively at low temperatures. In addition, from the viewpoint of not showing excessive reactivity during storage at room temperature and being advantageous for storage and transportation, it is preferably 0°C or more, more preferably 10°C or more, and further preferably 20°C or more.

[0073] The component (B) may be used alone or in combination of two or more. The content of the component (B) 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, further preferably 0.1% by mass or more, and further more preferably 0.5% by mass or more, in terms of effectively reacting and imparting higher shape durability, water resistance, elasticity (flexibility, i.e., high elongation at break when the fiber is stretched) and heat resistance to the treated natural-origin fiber, in the case of a salt or a complex, in terms of the non-dissociated form of the compound that becomes the main body of the reaction, for example, in the case of a peroxide initiator, in terms of the peroxide, in the case of an azo initiator, in terms of the azo compound, in the case of a redox initiator, in terms of the non-dissociated form of each of the oxidizing agent and the reducing agent, and in terms of preventing the molecular weight of the polymer generated due to excessive concentration from becoming too small, preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 40% by mass or less, and further more preferably 20% by mass or less. When a redox initiator is used as the component (B), the content of the component (B) refers to the total amount of the non-dissociated compounds of the oxidizing agent and the reducing agent.

[0074] From the viewpoint of efficiently reacting and imparting higher shape retention, water resistance, stretchability (flexibility, i.e., high elongation at break when the fiber is stretched) and heat resistance to the treated natural-origin fiber, the mass ratio (B) / (A) of the component (B) to the component (A) is preferably 0.001 or more, more preferably 0.01 or more, and is preferably 200 or less, more preferably 50 or less. However, in the case of a multi-component fiber treatment agent in which the component (A) and the component (B) are contained in different treatment agents, the mass ratio (B) / (A) in a mixed solution obtained by virtually mixing the two preparations may be within the above range.

[0075] [Ingredient (C): Water]

[0076] The fiber treatment agent of the present invention uses water as a medium. The content of the 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, further preferably 30% by mass or more, further more preferably 40% by mass or more, and preferably 98% by mass or less, more preferably 97% by mass or less, further preferably 96% by mass or less, further more preferably 95% by mass or less, further more preferably 90% by mass or less, further more preferably 85% by mass or less.

[0077] That is, the content of component (C) in the fiber treatment agent of the present invention is preferably 10 to 98 mass %, more preferably 20 to 97 mass %, further preferably 30 to 96 mass %, further more preferably 40 to 95 mass %, further more preferably 40 to 90 mass %, further more preferably 40 to 85 mass %.

[0078] 〔Cationic surfactant〕

[0079] The fiber treatment agent of the present invention may contain a cationic surfactant within a range that does not impair the effects of the present invention. The cationic surfactant is preferably a monolong chain alkyl quaternary ammonium salt having one alkyl group having 8 to 24 carbon atoms and three alkyl groups having 1 to 4 carbon atoms.

[0080] It is preferred that at least one mono-long chain alkyl quaternary ammonium surfactant is selected from the compounds represented by the following general formula (6).

[0081]

[0082] 〔In the formula, R 5 represents a saturated or unsaturated linear or branched alkyl group having 8 to 22 carbon atoms, R 9 -CO-NH-(CH2) p - or R 9 -CO-O-(CH2) p -(R 9 represents a saturated or unsaturated linear or branched alkyl chain having 7 to 21 carbon atoms, p represents an integer of 1 to 4), R 6 , R 7 and R 8 An independently represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, - represents chloride, bromide, methylsulfate or ethylsulfate. ]

[0083] Preferred cationic surfactants include long-chain quaternary ammonium compounds such as cetyl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, and stearamidopropyl trimethyl ammonium chloride. These may be used alone or in the form of a mixture thereof.

[0084] From the viewpoint of improving the touch of the surface of the natural-origin fiber after treatment and further enhancing the effect of the present invention, 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 0.10% by mass or more, and is preferably 10% by mass or less, more preferably 5.0% by mass or less.

[0085] 〔Silicone〕

[0086] The fiber treatment agent of the present invention may contain silicone from the viewpoint of improving the touch of the treated natural fiber surface and improving combing properties. The silicone is preferably at least one selected from dimethylpolysiloxane and amino-modified silicone.

[0087] As the dimethylpolysiloxane, any kind of cyclic or non-cyclic dimethylpolysiloxane polymers may be used, and examples thereof include SH200 series, BY22-019, BY22-020, BY11-026, B22-029, BY22-034, BY22-050A, BY22-055, BY22-060, BY22-083, FZ-4188 (all from Dow Corning Toray Corporation), KF-9088, KM-900 series, MK-15H, and MK-88 (all from Shin-Etsu Chemical Co., Ltd.).

[0088] As the amino-modified silicone, any silicone having an amino group or an ammonium group can be used, and examples thereof include amino-modified silicone oils in which all or part of the terminal hydroxyl groups are blocked with methyl groups or the like, and unblocked amino-terminated polydimethylsiloxanes. From the viewpoint of improving the touch of the surface of the treated natural fiber and improving the combing properties, preferred amino-modified silicones include, for example, compounds represented by the following formula.

[0089]

[0090] [wherein, R' represents a hydrogen atom, a hydroxyl group or R X , R X represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and J represents R X 、R"-(NHCH2CH2) a NH2、OR Xor hydroxyl, 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 whose sum is 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 further preferably 40 or more and less than 800 in number average.]

[0091] Specific examples of commercially available products of preferred amino-modified silicones include amino-modified silicone oils such as SF8452C, SS3551 (all from Dow Corning Toray Corporation), KF-8004, KF-867S, and KF-8015 (all from Shin-Etsu Chemical Co., Ltd.), and aminodimethicone emulsions such as SM8704C, SM8904, BY22-079, FZ-4671, and FZ4672 (all from Dow Corning Toray Corporation).

[0092] From the viewpoint of improving the touch of the surface of the natural-origin fiber after treatment and further enhancing the effect of the present invention, the content of silicone 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 is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5.0% by mass or less.

[0093] 〔Cationic polymer〕

[0094] Furthermore, from the viewpoint of improving the touch of the surface of the natural-origin fiber after treatment, the fiber treatment agent of the present invention may contain a cationic polymer.

[0095] Cationic polymer refers to a polymer having a cationic group or a group that can be ionized into a cationic group, and also includes amphoteric polymers that present cationicity as a whole. That is, polymers containing amino or ammonium groups or containing diallyl quaternary ammonium salt as a structural unit in the side chain of the polymer chain can be listed, for example, cationized cellulose derivatives, cationic starch, cationized guar gum derivatives, polymers or copolymers of diallyl quaternary ammonium salts, quaternized polyvinyl pyrrolidone derivatives, etc. can be listed. Among these, from the perspective of improving the softness, smoothness and easy passability of fingers when rinsing or shampooing, the effect of easy combing and moisture retention when drying and the stability of the formulation, preferably selected from polymers containing diallyl quaternary ammonium salt as a structural unit, quaternized polyvinyl pyrrolidone derivatives, cationized cellulose derivatives One or more, more preferably selected from polymers or copolymers of diallyl quaternary ammonium salts, cationized cellulose derivatives One or more.

[0096] Specific examples of preferred diallyl quaternary ammonium salt polymers or copolymers include dimethyldiallylammonium chloride polymers (polyquaternium-6, such as Merquat 100; Lubrizol Advanced Materials), dimethyldiallylammonium chloride / acrylic acid copolymers (polyquaternium-22, such as Merquat 280 and Merquat 295; Lubrizol Advanced Materials), and dimethyldiallylammonium chloride / acrylamide copolymers (polyquaternium-7, such as Merquat 550; Lubrizol Advanced Materials).

[0097] Specific examples of preferred quaternized polyvinyl pyrrolidone derivatives include polymers obtained by polymerizing a vinyl pyrrolidone copolymer with dimethylaminoethyl methacrylate (polyquaternium salt 11, such as GAFQUAT 734, GAFQUAT 755, and GAFQUAT 755N (all from Ashland)).

[0098] Specific examples of preferred cationized cellulose include polymers obtained by adding glycidyl trimethylammonium chloride to hydroxycellulose (polyquaternium 10, such as LEOGARD G and LEOGARD GP (all from Lion), POLYMER JR-125, POLYMER JR-400, POLYMER JR-30M, POLYMER LR-400, POLYMER LR-30M (all from Amerchol)), hydroxyethylcellulose dimethyl diallylammonium chloride (polyquaternium-4, such as CELQUATH-100 and CELQUAT L-200 (all from Akzo Nobel)), and the like.

[0099] From the viewpoint of improving the touch of the surface of the natural-origin fiber after treatment, 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, further preferably 0.05% by mass or more, and is preferably 20% by mass or less, more preferably 10% by mass or less.

[0100] The fiber treatment agent of the present invention may further contain: an antioxidant such as ascorbic acid; a pH adjuster such as sodium hydroxide, potassium hydroxide, phosphoric acid, hydrochloric acid, etc.

[0101] 〔pH〕

[0102] From the viewpoint of suppressing damage to natural-origin fibers and improving durability, the pH of the fiber treatment agent of the present invention is preferably 2.0 or more, more preferably 3.0 or more, further preferably 3.5 or more, further more preferably 4.0 or more, and is preferably 11.0 or less, more preferably 10.0 or less, further preferably 9.0 or less. However, the pH of the present invention is a value at 25°C.

[0103] That is, from the viewpoint of suppressing damage to natural fibers and improving durability, the pH of the fiber treatment agent of the present invention is preferably 2.0 to 11.0, more preferably 3.0 to 10.0, further preferably 3.5 to 9.0, and further more preferably 4.0 to 9.0.

[0104] In the case of a multi-component fiber treatment agent, the pH of each component satisfies the above-mentioned conditions. However, the pH of each component is preferably close to each other. Specifically, the pH difference between the highest pH formulation and the lowest pH formulation is preferably 3.0 or less, more preferably 2.0 or less, further preferably 1.0 or less, and further preferably 0.5 or less. As described above, the form in which a plurality of compositions are mixed into a single composition when used is included in the single-component fiber treatment agent, and the "pH of the fiber treatment agent" refers to the pH after mixing.

[0105] [Storage of fiber treatment agents]

[0106] When the fiber treatment agent produced as described above is transported and stored before being applied to fibers, or when the raw materials before preparing the fiber treatment agent are transported and stored, in order to prevent oxidative coloration of the polymer of component (A) or unintentional reaction and recrystallization during transportation, the storage temperature may be set to a low or high temperature, or the voids in the storage container may be filled with nitrogen.

[0107] The storage temperature of the fiber treatment agent is preferably 1°C or higher, more preferably 2°C or higher, and further preferably 5°C or higher from the viewpoint of preventing freezing or recrystallization, and is preferably 25°C or lower, more preferably 20°C or lower, and further preferably 15°C or lower from the viewpoint of preventing oxidative coloration or unintentional reaction.

[0108] In addition, the storage temperature of the fiber treatment agent is preferably 20°C or higher, more preferably 30°C or higher, and further preferably 40°C or higher from the viewpoint of preventing recrystallization of a high concentration solution, and is preferably 80°C or lower, more preferably 70°C or lower, and further preferably 60°C or lower from the viewpoint of preventing oxidative coloration or unintentional reaction.

[0109] 〔Fiber processing method〕

[0110] (Basic processing)

[0111] By using the fiber treatment agent of the present invention to treat natural fibers by a method including the following step (i), water resistance and heat resistance, which are problematic points of natural fibers, can be improved, thermal shape memory can be imparted, and stretchability (flexibility) and surface feel can be improved.

[0112] Step (i) A step of impregnating natural-origin fibers in the fiber-treating agent of the present invention

[0113] When the fiber treatment agent of the present invention is a multi-component type, examples of the multi-component fiber treatment agent include a two-component fiber treatment agent consisting of a first component containing component (A) and a second component containing component (B). When such a multi-component fiber treatment agent is used, step (i) becomes a multi-stage treatment step of sequentially immersing the natural fiber in each component. For example, when the above-mentioned two-component fiber treatment agent is used, step (i) becomes: after immersing the natural fiber in the first component containing component (A), the natural fiber treated with the first component is immersed in the second component containing component (B); or after immersing the natural fiber in the second component containing component (B), the natural fiber treated with the second component is immersed in the first component containing component (A).

[0114] In step (i), the natural fiber impregnated with the fiber treatment agent may be dry or wet. From the viewpoint of improving water resistance, heat resistance, imparting thermal shape memory ability, improving elasticity (flexibility), and surface touch, the amount of the fiber treatment agent impregnated with the natural fiber is preferably 2.0 or more, more preferably 3.0 or more, further preferably 5.0 or more, further more preferably 10 or more, further more preferably 20 or more, and preferably 500 or less, more preferably 250 or less, and further preferably 100 or less in terms of the bath ratio relative to the mass of the natural fiber (mass of the fiber treatment agent / mass of the natural fiber).

[0115] That is, from the above viewpoints, the bath ratio is preferably 2.0 to 500, more preferably 3.0 to 250, further preferably 5.0 to 100, further more preferably 10 to 100, and further more preferably 20 to 100.

[0116] In step (i), the natural fiber may be fixed in advance with a curling iron or the like, and then immersed in the fiber treatment agent of the present invention under heating. By doing so, the natural fiber can be given a desired shape in addition to thermal shape memory and high durability.

[0117] The immersion of the natural fiber in the fiber treatment agent in step (i) is preferably carried out under heating, and the heating is carried out by warming the fiber treatment agent. In addition, the heating can also be carried out by immersing the natural fiber in the fiber treatment agent in a heated state, and can also be carried out by immersing the natural fiber in the fiber treatment agent at a low temperature and then heating it. Regarding the temperature of the fiber treatment agent, in order to obtain the effect of the present invention by increasing the interaction between component (A) and the fiber constituent molecules in the natural fiber, such as protein molecules, it is preferably 20°C or more, more preferably 35°C or more, and even more preferably 45°C or more. In addition, in order to prevent the natural fiber from being modified and deteriorated due to heat, it is preferably less than 100°C, more preferably 80°C or less, more preferably 70°C or less, and even more preferably 60°C or less.

[0118] The immersion time in step (i) can be appropriately adjusted according to the heating temperature. For example, from the viewpoint of improving the stretchability of natural fibers, the immersion time is preferably 15 minutes or more, more preferably 30 minutes or more, and even more preferably 1 hour or more. In order to suppress damage to natural fibers, the immersion time is preferably 48 hours or less, more preferably 24 hours or less, and even more preferably 12 hours or less.

[0119] Step (i) is preferably performed under an environment where water evaporation is suppressed. A specific method for suppressing water evaporation is to cover the container impregnated with the fiber treatment agent for natural fibers with a film-like material, a cap, a cover, etc. made of a material that does not permeate water vapor.

[0120] In the case of multi-stage treatment using a multi-agent fiber treatment agent, the aforementioned bath ratio, temperature, immersion time, and other conditions are adopted in each stage. In addition, in the case of multi-stage treatment, rinsing, drying, etc. can also be performed between each stage.

[0121] After step (i), the natural fiber may or may not be rinsed. However, rinsing is preferred from the viewpoint of preventing the deterioration of the texture of the natural fiber surface due to the excess component (A) or its polymer.

[0122] It is considered that by these treatments, the component (A) penetrates into the natural fiber and polymerizes, and strongly coordinates with the metal, for example, the polyvalent metal, in the fiber, thereby producing various effects.

[0123] [Additional processing is possible]

[0124] In addition to the above-mentioned step (i), one or more treatments selected from the group consisting of bleaching, dyeing, surface treatment for imparting hydrophobicity and reducing friction, and heat treatment for further improving the stretchability (flexibility) of the fiber may be additionally performed.

[0125] At this time, each treatment of bleaching and dyeing can be carried out before the aforementioned step (i), or it can be carried out afterwards. In addition, it is also possible to combine and add a plurality of treatments. When adding both bleaching and dyeing, except that it is necessary to bleach before dyeing, any treatment can be carried out first, and other treatments can also be carried out between bleaching and dyeing.

[0126] On the other hand, the surface treatment for imparting hydrophobicity and low friction and the heat treatment for further improving the elasticity (flexibility) of the fiber need to be performed after the aforementioned step (i), but the order of the treatments with bleaching and dyeing is not particularly limited. In addition, the surface treatment for imparting hydrophobicity and low friction and the heat treatment for further improving the elasticity (flexibility) of the fiber may be performed first.

[0127] (Decolorization)

[0128] Decolorization is performed by dipping the natural fiber in a decolorizing agent composition containing an alkali agent, an oxidant, and water. The decolorizing agent composition is usually a two-component form, with the first component containing an alkali agent and water and the second component containing an oxidant and water. The two components are usually kept separately and mixed before dipping the natural fiber.

[0129] Preferred alkali agents include, for example, ammonia and its salts; alkanolamines (monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol, etc.) and their salts; alkylenediamines (1,3-propylenediamine, etc.) and their salts; and carbonates (guanidine carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.); and mixtures thereof, but are not limited to these.

[0130] The content of the alkaline agent in the decolorizing agent composition (a mixture of the first agent and the second agent in the case of a two-part composition) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1.0% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 7.5% by mass or less.

[0131] Preferred 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.

[0132] 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 is preferably 15% by mass or less, more preferably 12% by mass or less, and further preferably 9% by mass or less.

[0133] When the first and second agents are stored separately, the pH of the second agent at 25°C is preferably 2 or more, more preferably 2.5 or more, and preferably 6 or less, and more preferably 4 or less. The pH can be adjusted using an appropriate buffer. The pH of the decolorizing agent composition at 25°C is preferably 6 or more, more preferably 6.5 or more, and further preferably 6.8 or more, and further preferably 11 or less, more preferably 10.5 or less, and further preferably 10 or less.

[0134] (dyeing)

[0135] Dyeing is performed by immersing the natural fiber in a dye composition. The dye composition contains a dye and may optionally contain an alkali agent, an acid, an oxidizing agent, etc. Examples of the dye include direct dyes, oxidation dyes, and combinations thereof.

[0136] The type of direct dye is not particularly limited, and any direct dye suitable for dyeing can be used. As examples of direct dyes, anionic dyes, nitro dyes, disperse dyes, cationic dyes, and dyes with azophenol structure selected from the following HC Red 18, HC Blue 18 and HC Yellow 16, and their salts, and their mixtures can be cited.

[0137]

[0138] As the cationic dye, for example, 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 and mixtures thereof can be listed, but are not limited to these. Particularly preferred are basic red 51, basic orange 31, basic yellow 87 and mixtures thereof.

[0139] Examples of the anionic dye include acid black 1, acid blue 1, acid blue 3, food 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 yellow 10, acid yellow 23, acid yellow 3, and 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, and alkali metal salts (sodium salt, potassium salt, etc.) thereof and mixtures thereof, but are not limited to these.

[0140] 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, and salts thereof. More preferred anionic dyes are acid red 52, acid violet 2, acid red 33, acid orange 4 and acid yellow 10, and salts thereof and mixtures thereof.

[0141] Examples of the nitro dye 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 Purple BS, HC Purple No. 1, HC Purple 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-nitrobenzene, 1,4-diamino-2-nitrobenzene, 3-nitro-4-aminophenol, 1-hydroxy-2-amino-3-nitrobenzene and 2-hydroxyethylpicramic acid and mixtures thereof, but are not limited thereto.

[0142] Examples of the disperse dye include Disperse Blue 1, Disperse Black 9, Disperse Violet 1, and mixtures thereof, but the present invention is not limited to these.

[0143] These direct dyes may be used alone or in combination of two or more, and direct dyes having different ionicity may be used in combination.

[0144] The content of the direct dye in the dye composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and further preferably 0.05% by mass or more from the viewpoint of obtaining sufficient dyeing properties, and 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 further preferably 3.0% by mass or less from the viewpoint of compatibility.

[0145] When the dye composition contains only a direct dye as a dye, an oxidizing agent is not required to dye the natural fiber. However, when the color of the natural fiber is to be brightened, the composition may contain an oxidizing agent.

[0146] When the dye composition contains an oxidation dye, it is usually prepared in two parts, the first part contains an oxidation dye intermediate (precursor and coupler) and an alkali agent, and the second part contains an oxidizing agent such as hydrogen peroxide. The two parts are usually kept separately and mixed before impregnating the natural fiber.

[0147] The oxidation dye intermediate is not particularly limited, and any known precursors and couplers commonly used in dyeing products can be appropriately used.

[0148] Examples of the precursor include p-phenylenediamine, toluene-2,5-diamine, 2-chloro-p-phenylenediamine, N-methoxyethyl-p-phenylenediamine, N-phenyl-p-phenylenediamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-(2-hydroxyethyl)-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 4,4'-diaminodiphenylamine, 1,3-bis(N-(2-hydroxyethyl)-N-(4-aminophenyl)amino)-2-propanol, PEG-3,3,2'-p-phenylenediamine, p-aminophenol, p-methylaminophenol, 3-methyl-4-aminophenol, Phenol, 2-aminomethyl-4-aminophenol, 2-(2-hydroxyethylaminomethyl)-4-aminophenol, o-aminophenol, 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, salts thereof, and mixtures thereof, but are not limited thereto.

[0149] Examples of the coupler include m-phenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4-(2-hydroxyethylamino)anisole, 2,4-diamino-5-methylphenethyl ether, 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, m-aminophenol, 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-m-aminophenol, 2-methyl-4-methoxy-5-(2-hydroxyethylamino)phenol, 2-methyl-4-fluoro-5-aminophenol, p-Amino-o-cresol, 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, 3,4-methylenedioxyphenol Oxyaniline, 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, salts thereof, and mixtures thereof, but are not limited thereto.

[0150] The content of the precursor and the coupler in the dye 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 further preferably 5.0% by mass or less.

[0151] When the dye composition contains an oxidative dye, it also contains an alkali agent. Preferred alkali agents include, for example, ammonia and its salts; alkanolamines (monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol, etc.) and their salts; alkanediamines (1,3-propylenediamine, etc.) and their salts; and carbonates (guanidine carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.); and mixtures thereof, but are not limited thereto.

[0152] The content of the alkali agent in the dye composition is preferably 0.1 mass % or more, more preferably 0.5 mass % or more, further preferably 1.0 mass % or more, and is preferably 15 mass % or less, more preferably 10 mass % or less, further preferably 7.5 mass % or less.

[0153] When the dye composition contains an oxidation dye, the composition containing the oxidation dye (second agent) is stored separately from the composition containing the oxidation dye (first agent) and mixed before impregnating the natural fiber. Preferred oxidants include, but are not limited to, hydrogen peroxide, urea peroxide, melamine peroxide, and sodium bromate. Among these oxidants, hydrogen peroxide is preferred.

[0154] The content of the oxidizing agent in the dye composition is preferably 1% by mass or more, more preferably 2% by mass or more, and is preferably 15% by mass or less, more preferably 12% by mass or less, and further preferably 9% by mass or less.

[0155] When the first and second agents are stored separately, the pH of the second agent at 25°C is preferably 2 or more, more preferably 2.5 or more, and preferably 6 or less, and more preferably 4 or less. The pH can be adjusted using a suitable buffer. The pH of the dye composition formed by mixing the first and second agents at 25°C is preferably 6 or more, more preferably 6.5 or more, and further preferably 6.8 or more, and further preferably 11 or less, more preferably 10.5 or less, and further preferably 10 or less.

[0156] When the dye composition contains an oxidation dye, it may further contain the direct dye exemplified above.

[0157] The dye composition may preferably further contain a surfactant, conditioning component, etc. as shown below, and may preferably be in the form of a solution, emulsion, cream, paste, or mousse.

[0158] From the viewpoint of allowing the dye composition to efficiently penetrate and diffuse into the interior of the natural-origin fiber and further improving the dyeing effect, the temperature of the dye composition is preferably above 0°C, more preferably above 10°C, further preferably above 20°C, and preferably below 90°C, more preferably below 80°C.

[0159] (Post-heating: heating treatment to further improve the elasticity (flexibility) of the fiber)

[0160] From the viewpoint of further effectively improving the elasticity of natural fibers, the natural fibers can be stretched by applying tension while being heated. In this heating, when the natural fibers are small in quantity, it is preferred to use a hair iron, and when the natural fibers are large in quantity, the same result can be obtained by applying tension by a winder while performing warm air heating.

[0161] Regarding the fiber elongation during heating, from the viewpoint of more effectively improving the elasticity of the fiber, it is preferably 0.1% or more, more preferably 0.2% or more, and further preferably 0.5% or more. From the viewpoint of suppressing damage to the fiber, it is preferably 10% or less, more preferably 5.0% or less, and further preferably 2.0% or less.

[0162] Regarding the heating temperature, from the viewpoint of more effectively improving the stretchability of the fiber, it is preferably above 120°C, more preferably above 140°C, and further preferably above 160°C. From the viewpoint of suppressing damage to the fiber, it is preferably below 240°C, more preferably below 220°C, and further preferably below 200°C.

[0163] Regarding the heating time, from the viewpoint of more effectively improving the elasticity of the fiber, it is preferably more than 1 second, more preferably more than 3 seconds, and further preferably more than 5 seconds. From the viewpoint of suppressing damage to the fiber, it is preferably less than 60 seconds, more preferably less than 30 seconds, and further preferably less than 20 seconds.

[0164] After heating, from the viewpoint of more effectively improving the stretchability of the fiber, the natural fiber may be left to stand in water while tension is applied to stretch it.

[0165] Regarding the elongation at this time, from the viewpoint of more effectively improving the stretchability of the fiber, it is preferably 0.1% or more, more preferably 0.2% or more, and further preferably 0.5% or more. In addition, from the viewpoint of suppressing damage to the fiber, it is preferably 10% or less, more preferably 5.0% or less, and further preferably 2.0% or less.

[0166] Regarding the water temperature, from the viewpoint of more effectively improving the stretchability of the fiber, it is preferably above 5°C, more preferably above 20°C, and further preferably above 30°C. From the viewpoint of suppressing damage to the fiber, it is preferably below 80°C, more preferably below 60°C, and further preferably below 50°C.

[0167] Regarding the standing time in water, from the viewpoint of more effectively improving the elasticity of the fiber, it is preferably more than 1 minute, more preferably more than 5 minutes, and further preferably more than 30 minutes. From the viewpoint of suppressing damage to the fiber, it is preferably less than 48 hours, more preferably less than 24 hours, and further preferably less than 3 hours.

[0168] By this operation, depending on the treatment conditions in step (i), the fibers can achieve elasticity equivalent to that of human hair when dried.

[0169] (Suppression or removal of coloration)

[0170] In addition, the coordinating functional group in component (A) is a functional group having OH or O - In the case of a group, in order to suppress or remove the coloring of the natural fiber after being treated with the fiber treatment agent of the present invention, a composition containing a salt can be used for treatment. As the salt, any of organic salts and inorganic salts can also be used. Specifically, as organic salts, in addition to organic salts with chelating effects such as disodium hydroxyethyl phosphonate, disodium ethylenediaminetetraacetic acid, disodium catechol-3,5-disulfonic acid monohydrate, and sodium phytate, sodium mercaptoethane sulfonate, sodium 2-naphthalene sulfonate, etc. can also be listed. As inorganic salts, in addition to sulfites such as sodium sulfite, sodium chloride, chlorohydroxyaluminum, etc. can also be listed. As preferred salts for this purpose, among organic salts, salts with reducing properties (salts of thiol compounds, etc.) and salts with metal chelating properties (sodium salts of ethylenediaminetetraacetic acid such as disodium ethylenediaminetetraacetic acid, sodium salts of hydroxyethyl phosphonic acid such as disodium hydroxyethyl phosphonate, etc.) can be listed. Among inorganic salts, salts with reducing properties (sulfites such as sodium sulfite) can be listed. Among these, it is more preferred to use a salt having a reducing property and a salt having a metal chelating effect in combination.

[0171] It is believed that the fiber coloring caused by treatment with the fiber treatment agent of the present invention is both brown-based oxidative coloring (which can be dealt with by treatment with a reducing salt) and yellow-based catechin metal complex coloring (which can be dealt with by treatment with a chelating agent), and it is believed that by implementing a corresponding bleaching treatment, the coloring of the fiber can be better suppressed.

[0172] The composition containing salt is preferably an aqueous solution. In addition, from the viewpoint of not reducing the water resistance, elasticity (flexibility, i.e., high elongation at break when the fiber is stretched) and heat resistance of the natural fiber, the pH of the composition is preferably 2.0 or more, more preferably 3.0 or more, further preferably 4.0 or more, and preferably 9.0 or less, more preferably 7.0 or less, and further preferably 6.0 or less.

[0173] The salt content in the above-mentioned composition is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and further preferably 2.0% by mass or more, from the viewpoint of expressing the effect of inhibiting or removing the coloring of the natural-origin fiber. From the viewpoint of not reducing the water resistance, stretchability (flexibility, i.e., high elongation at break when the fiber is stretched) and heat resistance of the natural-origin fiber due to the reducing effect, it is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5.0% by mass or less.

[0174] Regarding the treatment temperature using the salt-containing composition, from the viewpoint of expressing the effect of inhibiting or removing the coloring of natural-origin fibers, it is preferably 5°C or more, more preferably 10°C or more, and further preferably 20°C or more. From the viewpoint of avoiding fiber damage, it is preferably 100°C or less, more preferably 60°C or less, and further preferably 40°C or less.

[0175] The treatment time using the salt-containing composition is preferably 1 second or longer, more preferably 30 seconds or longer, and even more preferably 1 minute or longer from the viewpoint of expressing the effect of inhibiting or removing coloration of natural-origin fibers. From the viewpoint of avoiding fiber damage, the treatment time is preferably 60 minutes or shorter, more preferably 30 minutes or shorter, and even more preferably 15 minutes or shorter.

[0176] The fibers subjected to the above-mentioned various treatments can also be improved in texture by a common fiber post-treatment, for example, treatment with a fiber treatment agent such as a softener or treatment with a hair care agent such as a conditioner or a hair treatment agent.

[0177] By treating the natural source fiber using the above fiber processing method, the polymer of component (A) is contained in the fiber, which can be given a shape by heat setting, and it is possible to produce fibers with excellent water resistance, heat resistance, and tensile elastic modulus, and highly improved stretchability (flexibility) of the natural source fiber, which is suitable for producing fibers for headwear products, etc. In addition, the fiber can be used to produce various fiber products, which is suitable for producing headwear products, etc.

[0178] In the present invention, preferred headwear products include, for example, hair wigs, fake hair, weaving, hair extensions, braid hair, hair accessories, and doll hair.

[0179] With regard to the above-described embodiments, preferred aspects of the present invention will be further disclosed below.

[0180] <1> A fiber-treating agent, which is a one-component fiber-treating agent consisting of a single composition or a multi-component fiber-treating agent consisting of a plurality of compositions, and contains the following components (A) to (C) in its entirety.

[0181] (A): Aromatic compound having one or more vinyl or vinylidene groups and a coordinating functional group

[0182] (B): Free radical initiator

[0183] (C) Water

[0184] <2> The fiber treating agent according to <1>, wherein the coordinating functional group in the component (A) is preferably a group containing a Pearson's hard base.

[0185] <3> The fiber treating agent according to <1> or <2>, wherein the coordinating functional group in component (A) preferably includes COO - , O - , COOH, OH or NH2, more preferably a group containing COO - , O - The group is preferably a group containing a carboxyl group or a group obtained by removing one hydrogen atom from the benzene ring of catechol (1,2-dihydroxybenzene).

[0186] <4> The fiber treating agent according to any one of <1> to <3>, wherein the component (A) is the following component (A-1) or (A-2).

[0187] (A-1) The coordinating functional groups include COOH, COO - or COOH salts of aromatic compounds

[0188] (A-2) The coordinating functional group includes OH, O - or OH salts of aromatic compounds

[0189] <5> The fiber treating agent according to <4>, wherein the component (A-1) is preferably the following component (A-1-a) or (A-1-b).

[0190] (A-1-a) Aromatic compound having a vinyl group or a vinylidene group as part of the styrene skeleton

[0191] (A-1-b) Aromatic compound having a vinyl group or a vinylidene group as part of an acryloyl group or a methacryloyl group

[0192] <6> A fiber treatment agent as described in <5>, wherein component (A-1-a) is preferably a compound represented by the following general formula (1), and more preferably 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid or a mixture of two or three selected from these, 4-oxo-4-((4-vinylbenzyl)oxy)butyric acid or 2-(((4-vinylbenzyl)oxy)carbonyl)benzoic acid.

[0193]

[0194] [In formula (1), R 1 A represents a hydrogen atom or a methyl group. 1 ~A 5Each independently represents a hydrogen atom, a carboxyl group, a group represented by the general formula (2), an acetyl group, a halogen atom, or a linear or branched alkyl group, alkenyl group, alkoxy group or alkenyloxy group having 1 to 6 carbon atoms. 2 represents a linear or branched saturated or unsaturated divalent hydrocarbon group or divalent hydrocarbonoxy group having 1 to 6 carbon atoms, o-phenylene, m-phenylene, p-phenylene, benzylidene or phenyl C2-C4 alkylene. 1 ~A 5 Contains at least one carboxyl group or a group represented by the general formula (2).

[0195] <7> A fiber treatment agent as described in <5>, wherein component (A-1-b) is preferably a compound represented by the following general formula (3), more preferably 2-((2-(acryloyloxy)ethoxy)carbonyl)benzoic acid, 2-((2-(methacryloyloxy)ethoxy)carbonyl)benzoic acid or 2-(4-(2-(2-(acryloyloxy)ethoxy)ethoxy)benzoyl)benzoic acid.

[0196]

[0197] In formula (3), R 3 represents a hydrogen atom or a methyl group, B 1 ~B 4 Each independently represents a hydrogen atom, a carboxyl group, an acetyl group, a halogen atom, or a linear or branched alkyl group, alkenyl group, alkoxy group or alkenyloxy group having 1 to 6 carbon atoms, Ph represents a phenylene group, n represents an integer of 0 to 2, and m represents 0 or 1.]

[0198] <8> The fiber treating agent according to <4>, wherein the component (A-2) is preferably a compound represented by the following general formula (4), and more preferably 4-vinylbenzyl 3,4,5-trihydroxybenzoate.

[0199]

[0200] [In formula (4), R 4 represents a hydrogen atom or a methyl group, E 1 ~E 5 Each independently represents a hydrogen atom, a hydroxyl group, a group represented by the general formula (5), an acetyl group, a halogen atom, or a linear or branched alkyl group, alkenyl group, alkoxy group or alkenyloxy group having 1 to 6 carbon atoms, 1 ~G 5 Each independently represents a hydrogen atom, a hydroxyl group, an acetyl group, a halogen atom, or a linear or branched alkyl group, alkenyl group, alkoxy group or alkenyloxy group having 1 to 6 carbon atoms. 1 ~E 5 Contains at least one group represented by the general formula (5).

[0201] <9> The fiber treating agent according to any one of <1> to <8>, wherein the component (B) is a peroxide initiator, an azo initiator, or a redox initiator.

[0202] <10> The fiber treatment agent according to <9>, wherein the peroxide initiator is preferably at least one selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, tert-butyl hydroperoxide, tert-amyl hydroperoxide, p-diisopropyl hydroperoxide, isopropyl hydroperoxide, pinane hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, benzoyl peroxide, tert-butyl perbenzoate, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide and diacetyl peroxide.

[0203] <11> The fiber treating agent according to <9>, wherein the azo initiator is preferably selected from 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), ...,4-dimethylvaleroni bis(2-hydroxymethylpropionitrile), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine], 2,2'-azobis(2-methylpropionamidine) dihydrochloride and 2,2'-azobis[2-(2-imidazolin-2-yl)propane] More preferably, it is one or more selected from 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine], 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and 2,2'- One or more azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, more preferably one or more selected from 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine], 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride.

[0204] <12> The fiber treatment agent according to <9>, wherein the redox initiator is selected from sodium persulfate, potassium persulfate, ammonium persulfate, tert-butyl hydroperoxide, tert-amyl hydroperoxide, p-diisopropyl hydroperoxide, cumene hydroperoxide, pinane hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, benzoyl peroxide, tert-butyl perbenzoate, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, di-(2-ethoxyethyl)peroxydicarbonate, di-(2-ethoxyethyl)peroxydicarbonate, di-(2-ethoxyethyl)peroxydicarbonate, di-(2-ethoxyethyl)peroxydicarbonate, di-(2-ethoxyethyl)peroxydicarbonate, di-(2-ethoxyethyl)peroxydicarbonate, di- A combination of an oxidizing agent selected from the group consisting of tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide, hydrogen peroxide, sodium hypochlorite, potassium hypochlorite, oxygen, and ozone and a reducing agent selected from the group consisting of sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium pyrosulfite, potassium pyrosulfite, ferrous ion, chromium ion, ascorbic acid, formaldehyde sulfoxylate, tetramethylenediamine, and sodium hydroxymethylsulfinate.

[0205] <13> The fiber-treating agent according to any one of <1> to <12>, wherein the content of component (B) in the fiber-treating agent (in the case of a multi-dose fiber-treating agent, the content of component (B) in a composition containing component (B)) is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, further preferably 0.1% by mass or more, further more preferably 0.5% by mass or more, and is preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 40% by mass or less, further more preferably 20% by mass or less in terms of non-dissociated form.

[0206] <14> The fiber treatment agent according to any one of <1> to <13>, wherein the content of component (C) is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, further more preferably 40% by mass or more, and is preferably 98% by mass or less, more preferably 97% by mass or less, further preferably 96% by mass or less, further more preferably 95% by mass or less, further more preferably 90% by mass or less, and further more preferably 85% by mass or less.

[0207] <15> The fiber-treating agent according to any one of <1> to <14>, wherein the pH of the fiber-treating agent is preferably 2.0 or higher, more preferably 3.0 or higher, further preferably 3.5 or higher, further more preferably 4.0 or higher, and is preferably 11.0 or lower, more preferably 10.0 or lower, further preferably 9.0 or lower.

[0208] <16> The fiber treatment agent according to any one of <1> to <15>, wherein the pH of the treatment agent containing component (A) is 2.0 or more and less than 6.5, and the content of component (A) in the fiber treatment agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.5% by mass or more, further more preferably 1.0% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, further more preferably 20% by mass or less, and further more preferably 15% by mass or less in terms of non-dissociated form.

[0209] <17> A fiber treatment agent as described in any one of <1> to <15>, wherein the pH of the treatment agent containing component (A) is 6.5 or more and 11.0 or less, and the content of component (A) in the fiber treatment agent is preferably 1.0 mass% or more, more preferably 2.0 mass% or more, further preferably 5.0 mass% or more, further more preferably 10 mass% or more, and preferably 90 mass% or less, more preferably 80 mass% or less, further preferably 70 mass% or less, further more preferably 60 mass% or less in terms of non-dissociated form.

[0210] <18> A fiber treatment agent as described in any one of <1> to <17>, wherein the mass ratio (B) / (A) of component (B) to component (A) in the fiber treatment agent (when it is a multi-agent fiber treatment agent and component (A) and component (B) are contained in different treatment agents, the mass ratio (B) / (A) of component (B) to component (A) is preferably 0.001 or more, more preferably 0.01 or more, and preferably 200 or less, more preferably 50 or less.

[0211] <19> A fiber treating agent kit comprising a composition containing the following component (A) and component (C) and a composition containing the following component (B) and component (C).

[0212] (A): Aromatic compound having one or more vinyl or vinylidene groups and a coordinating functional group

[0213] (B): Free radical initiator

[0214] (C) Water

[0215] <20> A fiber processing method comprising the following step (i).

[0216] Step (i) A step of impregnating natural-derived fibers into a single composition or a plurality of compositions containing the following components (A) to (C) in total

[0217] (A): Aromatic compound having one or more vinyl or vinylidene groups and a coordinating functional group

[0218] (B): Free radical initiator

[0219] (C) Water

[0220] <21> A fiber processing method comprising the following step (i).

[0221] Step (i) A step of impregnating natural-derived fibers into a single composition or a plurality of compositions containing the following components (A) to (C) in total

[0222] (A): an aromatic compound having one or more vinyl or vinylidene groups and a coordinating functional group (excluding vinylbenzoic acid and its salts)

[0223] (B): Free radical initiator

[0224] (C) Water

[0225] <22> Use of a single composition or a plurality of compositions containing the following components (A) to (C) in the total composition as a fiber treating agent.

[0226] (A): Aromatic compound having one or more vinyl or vinylidene groups and a coordinating functional group

[0227] (B): Free radical initiator

[0228] (C) Water

[0229] <23> Use of a single composition or a plurality of compositions containing the following components (A) to (C) in the total composition as a fiber treating agent.

[0230] (A): an aromatic compound having one or more vinyl or vinylidene groups and a coordinating functional group (excluding vinylbenzoic acid and its salts)

[0231] (B): Free radical initiator

[0232] (C) Water

[0233] Example

[0234] Example 1, Comparative Examples 1 to 3

[0235] Regenerated collagen fibers were treated and various evaluations were performed by the following methods using the compositions of the formulations shown in Table 1. The pH of each prepared composition was measured directly at room temperature (25° C.) using a pH meter (F-52 manufactured by HORIBA).

[0236] <Handling method>

[0237] 1. Immerse 0.50 g of a 22 cm long bundle of regenerated collagen fiber (※) in a container to which a fiber treatment agent in the amount of bath ratio shown in the table has been added, seal the container mouth, and immerse the container in a water bath (manufacturer: Toyo Seisakusho Co., Ltd. / model: TBS221FA) at the temperature shown in the table, and heat for the time shown in the table.

[0238] ※: Regenerated collagen fibers manufactured by Kaneka were purchased in the form of commercially available hair extension products, and fibers were cut and divided into bundles for evaluation. In this evaluation, the hair extension products used were white, straight fibers with the Ultima 100% usage mark and color number 30.

[0239] 2. Take the container containing the hair bundle out of the water bath and return it to room temperature.

[0240] 3. The hair bundle was taken out of the container, rinsed with 30°C running tap water for 30 seconds, foamed with the evaluation shampoo for 60 seconds, rinsed with 30°C running tap water for 30 seconds, and the moisture was gently wiped off with a towel. Then, the hair bundle was combed and blown dry with a warm air hair dryer (manufactured by TESCOM, Nobby White NB3000).

[0241] <Evaluation of Shampoo Formulation>

[0242]

[0243]

[0244] <Increase in average elongation at break when stretching fibers>

[0245] As an index of water resistance and stretchability (flexibility), the average elongation at break when the fiber is stretched, that is, the average value of the fiber when it is stretched by stretching and then breaks after a few percent of the original fiber length, is used when evaluating multiple (10) fibers. The evaluation is performed using the hair bundle just after the treatment using the above-mentioned <treatment method> according to the following steps.

[0246] 1. Cut 10 fibers from the root of the hair bundle. Select a 3 cm fiber piece from the middle between the root and the tip of each fiber, and get a total of 10 3 cm hair pieces.

[0247] 2. Place the fiber sheet in the "MTT690 Fiber Automatic Tensile Tester" manufactured by DIA-STRON Limited. After being immersed in water for 30 minutes, start automatic measurement to find the average breaking elongation of the fiber in the state of being immersed in water. The higher the value, the higher the elasticity, the better the flexibility, and the better the durability.

[0248] According to the following formula, the average breaking elongation (A%) when the fiber is stretched in the original state (untreated; Comparative Example 1) cut from a commercial product is used as a reference, and the degree to which the average breaking elongation (B%) of the treated hair bundle increases from the untreated state (C%) is taken as the "increase rate of the average breaking elongation when the fiber is stretched [%]" and recorded in the table.

[0249] C(%)=B(%)-A(%)

[0250] <Increase in average breaking load when stretching fibers>

[0251] As an index of water resistance, the average breaking load when the fiber is stretched is used. The evaluation is performed using the hair bundle just after being treated by the above-mentioned <Treatment Method>. In addition, as a numerical value, the average value when evaluating using multiple (10) fibers is used. The evaluation is performed according to the following steps.

[0252] 1. Cut 10 fibers from the root of the hair bundle. Select a 3 cm fiber piece from the middle between the root and the tip of each fiber, and get a total of 10 3 cm hair pieces.

[0253] 2. Place the fiber sheet in the "MTT690 Fiber Automatic Tensile Tester" manufactured by DIA-STRON Limited. After being immersed in water for 30 minutes, start automatic measurement to find the breaking load when the fiber is extended while immersed in water. The higher the value, the more elastic it is, the stronger the extension caused by external force, and the better the durability.

[0254] According to the following formula, the average breaking load (W0 (gf)) when the fiber is stretched in the original state (untreated; Comparative Example 1) cut from a commercial product is used as a reference, and the degree to which the average breaking load (W1 (gf)) of the treated hair bundle increases from the untreated state (Y (gf)) is taken as the "increase in the average breaking load when the fiber is stretched [gf]" and recorded in the table.

[0255] Y(gf)=W1(gf)-W0(gf)

[0256] <Shrinkage rate during high temperature perming>

[0257] As an index of heat resistance, the shrinkage rate during high temperature hair curling was used. The evaluation was performed using the hair bundle just after being treated by the above-mentioned <Treatment Method>. In addition, as a numerical value, the average value when evaluating using multiple (5) fibers was used. The evaluation was performed according to the following steps.

[0258] 1. Cut 5 fibers from the roots of the hair bundle just treated in the above-mentioned <Treatment Method> and mark them. Measure the lengths of these 5 treated fibers and record the average value (set as length L1). Next, tie these 5 marked treated fibers together by sandwiching them between 2 hair bundles (1 g) of 0.5 g of untreated regenerated collagen fibers prepared separately to make a new hair bundle (hereinafter referred to as a large hair bundle), and apply a hair straightener set to 180°C (manufactured by Miki Electric Industry Co., Ltd. / Model: AHI-938) to the entire large hair bundle 10 times at a speed of 5 cm / sec.

[0259] 2. After the perming operation, take out 5 marked fibers from the large hair bundle, re-measure the length of each of the 5 marked fibers, and record the average value (referred to as length L2).

[0260] 3. Define the shrinkage rate S during high temperature perm setting dry ={1-(L2 / L1)}×100[%]. dry The closer to 0%, the less likely the shrinkage due to dry heat occurs, and the better the heat resistance.

[0261] <Shrinkage ratio when heated with hot water>

[0262] As an index of water resistance and heat resistance, the shrinkage rate when heated with hot water is used. The evaluation is performed using the hair bundle just after being treated by the above-mentioned <Treatment Method>. In addition, as a numerical value, the average value when evaluating using multiple (5) fibers is used. The evaluation is performed according to the following procedures.

[0263] 1. Five fibers were cut from the root of the hair bundle, and the average length of each fiber was recorded (referred to as length L1), and then immersed in a 90°C water bath (manufacturer: Toyo Seisakusho Co., Ltd. / model: TBS221FA) for 1 minute.

[0264] 2. After the heating operation, take out 5 fibers, gently wipe off the moisture with a towel, dry them at room temperature and humidity for 30 minutes, and then re-record the average length of each fiber (set as length L2).

[0265] 3. Definition of shrinkage rate when heated with hot water Swet = {1-(L2 / L1)}×100 [%] The closer Swet is to 0%, the less likely it is to shrink due to wet heat, and the better the heat resistance.

[0266] <Thermal shape memory capability>

[0267] The thermal shape memory ability was evaluated using the hair bundle immediately after being treated by the above-mentioned <Treatment Method>. If the result value of "I: Shape imparting (curls)" was 5% or less, it was considered that there was no effect, and subsequent treatment and evaluation were not performed.

[0268] I: Shape giving (curls)

[0269] 1. A 22 cm long bundle of 0.5 g of regenerated collagen fibers was moistened with 30°C tap water for 30 seconds, and then the moistened bundle was wound around a plastic rod with a diameter of 14 mm and fixed with a clip.

[0270] 2. The entire hair bundle wound around the rod was immersed in a 60° C. water bath (manufacturer: Toyo Seisakusho Co., Ltd. / model: TBS221FA) and heated for 1 minute.

[0271] 3. Take the hair bundle out of the water bath, immerse it in 25°C water for 1 minute, take it out of the water, and cool it back to room temperature.

[0272] 4. Remove the hair bundle from the rod, comb it 3 times, take it out of the water, and then take photos from the front and side in the hanging state after 3 minutes.

[0273] (Evaluation Criteria)

[0274] The untreated hair bundle length is defined as L0 (22 cm), the treated hair bundle length is defined as L, and the curl ratio = hair bundle length reduction ratio (I) (%) obtained by the following formula is defined as the curl strength of the curled hair.

[0275] I=[(L0-L) / L0]×100

[0276] II: Reshape (straighten)

[0277] 1. The hair bundle evaluated in I was combed into a lock and then slid six times at a speed of 5 cm / sec using a hair straightener (manufactured by Miki Electric Industry Co., Ltd., model: AHI-938) set at 180°C.

[0278] 2. Rinse with 30°C running tap water for 30 seconds, lather with the evaluation shampoo for 60 seconds, rinse with 30°C running tap water for 30 seconds, and dry with a towel.

[0279] 3. Hang it up and dry it naturally at 20°C 65% RH for 12 hours. After combing, visually observe it from the front and side while it is hung up.

[0280] (Evaluation Criteria)

[0281] The untreated hair bundle length is L0 (22 cm), the treated hair bundle length is L, and the straightening rate (ST) (%) obtained by the following formula is defined as the degree of straightening. When ST = 100%, the hair bundle is completely straightened.

[0282] ST=[1-(L0-L) / L0]×100

[0283] III: Reshape (curls)

[0284] 1. The hair bundle evaluated in II was moistened with tap water at 30°C for 30 seconds, and then the moistened hair bundle was wound around a plastic rod having a diameter of 14 mm and fixed with a clip.

[0285] 2. The entire hair bundle wound around the rod was immersed in a 60° C. water bath (manufacturer: Toyo Seisakusho Co., Ltd. / model: TBS221FA) and heated for 1 minute.

[0286] 3. Take the hair bundle out of the water bath, immerse it in 25°C water for 1 minute, take it out of the water, and cool it back to room temperature.

[0287] 4. Remove the hair bundle from the rod, comb it 3 times, take it out of the water, and then take photos from the front and side in the hanging state after 3 minutes.

[0288] (Evaluation Criteria)

[0289] The untreated hair bundle length is defined as L0 (22 cm), the treated hair bundle length is defined as L, and the curl ratio = hair bundle length reduction ratio (I) (%) obtained by the following formula is defined as the curl strength of the curled hair.

[0290] I=[(L0-L) / L0]×100

[0291] <Excellent surface feel>

[0292] Evaluation of Surface Feeling Using the hair bundles immediately after being treated by the <Treatment Method>, five professional panelists evaluated the smoothness of the feel when touching the hair bundles based on the following criteria, and the total value of the five panelists was used as the evaluation result.

[0293] (Evaluation Criteria)

[0294] 5: The texture is very smooth compared with the untreated fiber (Comparative Example 1).

[0295] 4: Smoother feel than the untreated fiber (Comparative Example 1).

[0296] 3: The texture is slightly smoother than that of the untreated fiber (Comparative Example 1).

[0297] 2: There is no difference in feel from the untreated fiber (Comparative Example 1).

[0298] 1: Compared with the untreated fiber (Comparative Example 1), the fiber had a rough and astringent feel and a poor texture.

[0299] <Suppression of fiber coloration>

[0300] 1. For the front and back sides of the hair bundle, measure the color near the root, near the middle, and near the tip of the hair using a colorimeter (CR-400, manufactured by Konica Minolta). The average value of the total of 6 points is taken as the color value (L, a, b).

[0301] 2. The untreated white hair bundle (*) of color number 30 (Comparative Example 1) was used as a reference, and the degree of coloration was evaluated using ΔE*ab. In addition, color measurement was performed on the day of treatment.

[0302] (※) Untreated color 30 white hair

[0303] Regenerated collagen fibers manufactured by Kaneka Co., Ltd. were purchased in the form of commercially available hair extension products, and fibers were cut and divided into bundles for evaluation. In this evaluation, a hair extension product with a white color number of 30 and a straight shape and having an Ultima 100% use mark was used as the fiber type.

[0304] When the measured value of the untreated white hair bundle of color number 30 is set to (L0, a0, b0), and the measured value of the treated hair bundle is set to (L1, a1, b1), [(L1-L0) 2 +(a1-a0) 2 +(b1-b0) 2 〕 1 / 2 ΔE*ab was defined, and the coloration suppressing effect was determined according to the following criteria.

[0305] 5: ΔE*ab≤5.0

[0306] 4: 5.0<ΔE*ab≤10.0

[0307] 3: 10.0<ΔE*ab≤15.0

[0308] 2: 15.0<ΔE*ab≤20.0

[0309] 1:20.0<ΔE*ab

[0310]

Table 1

[0311]

[0312] *: pH adjustment amount

[0313] Embodiments 2 to 11

[0314] Regenerated collagen fibers were treated and various evaluations were performed by the following methods using the first and second agents of the formulations shown in Table 2. The pH of each prepared composition was measured at room temperature (25° C.) using a pH meter (F-52 manufactured by HORIBA).

[0315] The concentrations of the components listed in the table are the concentrations in the first dose and the second dose, respectively.

[0316] <Handling method>

[0317] 1. Immerse 0.5 g of regenerated collagen fiber (※) with a length of 22 cm in a container containing the first dose in the amount of bath ratio shown in the table, seal the container mouth, and immerse the container in a water bath (manufacturer: Toyo Seisakusho Co., Ltd. / model: TBS221FA) at the temperature shown in the table, and heat for the time shown in the table.

[0318] ※: Regenerated collagen fibers manufactured by Kaneka were purchased in the form of commercially available hair extension products, and fibers were cut and divided into bundles for evaluation. In this evaluation, the hair extension products used were white, straight fibers with the Ultima 100% usage mark and color number 30.

[0319] 2. Take the container containing the hair bundle out of the water bath and return it to room temperature.

[0320] 3. The hair bundle was taken out of the container, rinsed with 30°C running tap water for 30 seconds, foamed with the evaluation shampoo for 60 seconds, rinsed with 30°C running tap water for 30 seconds, and the moisture was gently wiped off with a towel. Then, the hair bundle was combed and blown dry with a warm air hair dryer (manufactured by TESCOM, Nobby White NB3000).

[0321] 4. Immerse the hair bundle in a container containing the second agent in the amount of the bath ratio shown in the table, seal the container mouth, and immerse the container in a water bath (manufacturer: Toyo Seisakusho Co., Ltd. / model: TBS221FA) at the temperature shown in the table for the time shown in the table.

[0322] 5. Take the container containing the hair bundle out of the water bath and return it to room temperature.

[0323] 6. The hair bundle was taken out of the container, rinsed with 30°C running water of tap water for 30 seconds, foamed with the evaluation shampoo for 60 seconds, rinsed with 30°C running water of tap water for 30 seconds, and gently wiped off the moisture with a towel, and then the hair bundle was combed and blow-dried with a warm air hair dryer (manufactured by TESCOM, Nobby White NB3000). At this point, the hair bundle was still straight.

[0324]

[0325] Furthermore, the hair bundles treated in the above examples were visually observed, and no coloration was observed except for Examples 9 and 10. In Examples 9 and 10, slight coloration (light yellow) was observed, but ΔE*ab was 5.0 or less (evaluation 5).

[0326] Comparative Example 4

[0327] Using the following formulation, the regenerated collagen fibers were treated according to the <Treatment Method> in Example 1 and Comparative Examples 1 to 3. The treated hair bundles were evaluated for the degree of coloration of the fibers in the same manner as above, and brown coloration was observed (Evaluation 1).

[0328]

[0329] pH(25℃):5.5

[0330] Bath ratio: 40

[0331] Heating conditions: 50℃ for 3h.

Claims

1. A fiber treating agent, wherein The present invention is a single-component fiber treatment agent composed of a single composition or a multi-component fiber treatment agent composed of a plurality of compositions, and the entire composition thereof contains the following components (A) to (C), (A): an aromatic compound having one or more vinyl or vinylidene groups and a coordinating functional group; (B): free radical initiator; (C): Water.

2. The fiber treating agent according to claim 1, wherein The coordinating functional group in the component (A) is a group containing a Pearson's hard base.

3. The fiber treating agent according to claim 1 or 2, wherein The coordinating functional group in component (A) is a COO - , O - , COOH or OH groups.

4. The fiber treating agent according to claim 3, wherein Component (A) is the following component (A-1) or (A-2), (A-1) The coordinating functional groups include COOH, COO - or aromatic compounds containing a salt of COOH; (A-2) The coordinating functional group includes OH, O - Or an aromatic compound containing a salt of OH.

5. The fiber treating agent according to claim 4, wherein Component (A) is component (A-1).

6. The fiber treating agent according to any one of claims 1 to 5, wherein Component (B) is an azo initiator.

7. The fiber treating agent according to any one of claims 1 to 6, wherein The pH of the fiber treatment agent containing the component (A) is 2.0 or more and less than 6.5, and the content of the component (A) in the fiber treatment agent is 0.1 mass % or more and 40 mass % or less in terms of the non-dissociated form.

8. The fiber treating agent according to any one of claims 1 to 6, wherein The pH of the fiber treatment agent containing the component (A) is 6.5 or more and less than 11.0, and the content of the component (A) in the fiber treatment agent is 1.0 mass % or more and 90 mass % or less in terms of the non-dissociated form.

9. A fiber treatment agent kit, wherein: Comprising: a composition comprising the following components (A) and (C), and a composition comprising the following components (B) and (C), (A): an aromatic compound having one or more vinyl or vinylidene groups and a coordinating functional group; (B): free radical initiator; (C): Water.

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