Fiber treatment agent

Abstract

This fiber treatment agent is used for the treatment of fibers, contains the following components (A) and (B), and has an underwater fiber swelling rate of 200% or greater as calculated by the following formula (1). (A) A compound having a coordinating functional group and a molecular weight of 1500 or greater (B) Water (1): Underwater fiber swelling rate (%) = [(w1 - w2) / w2] × 100 [wherein w1 represents a mass (g) of the fiber measured after placing 1.0 g of the fiber in a container filled with 100 g of ion-exchanged water, sealing the container, immersing the entire container in a water bath at 40 °C for 30 minutes, taking out the fiber from the container, and subjecting the fiber to centrifugal dehydration for 1 minute with a centrifugal force of 220 [× g], and w2 represents a mass of the fiber measured after measuring the mass (w1) of the fiber, placing the fiber on filter paper, and drying the fiber at 105 °C for 3 hours.]

Description

Fiber treatment agents

[0001] The present invention relates to a fiber treatment agent.

[0002] Naturally-derived fibers generally have a natural texture and appearance derived from natural materials, unlike synthetic fibers. Among naturally-derived fibers, regenerated protein fibers, for example, regenerated collagen fibers, are usually produced by solubilizing acid-soluble or insoluble collagen with alkali or enzymes to prepare a spinning dope, discharging the dope from a spinning nozzle into a coagulation bath to form fibers, and then drying the fibrous collagen in the final step.

[0003] However, naturally-derived fibers generally have higher water absorption rates than synthetic fibers due to their higher hydrophilicity. Therefore, they generally have low mechanical strength when wet, and recycled protein fibers, in particular, have extremely low mechanical strength. As a result, their high water absorption significantly reduces their mechanical strength during shampooing, leading to breakage during subsequent drying with a hair dryer, reducing their suitability as head accessories. Additionally, recycled protein fibers suffer from poor heat resistance. For example, when heat-set using a hair iron or similar device at high temperatures similar to those used with human hair, they can shrink and crimp, resulting in a poor appearance. Furthermore, while plastic synthetic fibers retain their shape after heat-setting using an iron or similar device even after subsequent washing (they have thermal shape memory), naturally-derived fibers lose their shape after heat-setting using an iron or similar device after a single subsequent washing (they lack thermal shape memory). Therefore, they are inferior to conventional plastic synthetic fibers in terms of flexibility in shape setting. These issues have hindered the widespread use of naturally-derived fibers, particularly recycled protein fibers, in textile products such as head accessories.

[0004] Therefore, various studies have been conducted to solve the above-mentioned problems of naturally derived fibers. For example, it has been reported that in a fabric containing at least 10% by weight of wool, cross-linking the wool with an acrylic resin can suppress wear (puffing) due to friction during washing (Patent Document 1). It has also been reported that treating naturally derived fibers with a fiber treatment agent containing a specific methylol compound and a specific phenol compound can solve the above-mentioned problems related to water resistance, heat resistance, and thermal shape memory ability that are specific to naturally derived fibers (Patent Document 2).

[0005] (Patent Document 1) JP 1-260062 A (Patent Document 2) JP 2022-103113 A

[0006] The present invention provides the following [1] to

[12] . [1] A fiber treatment agent for use in treating a fiber having a swelling ratio in water of 200% or more, calculated by the following formula (1), comprising the following components (A) and (B): (A) a compound having a coordinating functional group and a molecular weight of 1,500 or more; (B) water. Fiber swelling ratio in water (%) = [(w1 - w2) / w2] × 100 (1) [In the formula, w1 represents the mass (g) of the fiber measured by placing 1.0 g of fiber in a container filled with 100 g of ion-exchanged water, sealing the container, immersing the container in a water bath at 40°C for 30 minutes, removing the fiber from the container, and centrifuging for 1 minute at a centrifugal force of 220 [×g]. w2 represents the mass of the fiber measured after placing the fiber, whose mass (w1) has been measured, on filter paper and drying it at 105°C for 3 hours. [2] The fiber treating agent according to [1] above, wherein the fiber is a regenerated protein fiber. [3] The fiber treating agent according to [1] or [2] above, wherein the coordinating functional group is a group containing a hard base or an intermediate base according to the HSAB rule. [4] The fiber treating agent according to any one of [1] to [3] above, wherein the coordinating functional group comprises one selected from the following components (a-1), (a-2), and (a-3): (a-1) a group having a carboxy group or a salt thereof (a-2) a group having a hydroxyl group, an alkoxy group, an alkoxide anion, or a metal alcoholate (a-3) a group having a sulfonic acid group or a salt thereof [5] The fiber treating agent according to any one of [1] to [4] above, wherein component (A) comprises one or more selected from the following (A-1) and (A-2). (A-1) A polymer containing a structural unit derived from an unsaturated monomer having a coordinating functional group, the polymer having a weight average molecular weight of 1500 or more. (A-2) A condensate of a compound having a coordinating functional group, the condensate having a molecular weight of 1500 or more. [6] The fiber treating agent according to [5] above, wherein the polymer (A-1) further contains a structural unit derived from an unsaturated hydrocarbon compound. [7] The fiber treating agent according to [5] above or [6] above, wherein the polymer (A-1) contains one or more selected from the following (A-1-1), (A-1-2), and (A-1-3):(A-1-1) A copolymer containing a structural unit derived from an unsaturated monomer having a coordinating functional group and a structural unit derived from an aromatic vinyl compound, the copolymer having a weight-average molecular weight of 1500 or more. (A-1-2) A copolymer containing a structural unit derived from an unsaturated monomer having a coordinating functional group and a structural unit derived from an unsaturated aliphatic hydrocarbon compound, the copolymer having a weight-average molecular weight of 1500 or more. (A-1-3) A polymer containing a structural unit derived from an aromatic vinyl compound having a coordinating functional group or a polymer containing a structural unit derived from an unsaturated aliphatic hydrocarbon compound having a coordinating functional group, the polymer having a weight-average molecular weight of 1500 or more (excluding copolymers (A-1-1) and (A-1-2)). [8] The fiber treatment agent according to item [5] above, wherein the condensate (A-2) is a condensate having a molecular weight of 1500 or more and comprises one or more condensates selected from the following (A-2-1) and (A-2-2): (A-2-1) A condensate of sulfonic acid or a salt thereof (A-2-2) A condensate of a gallic acid ester [9] The fiber treatment agent according to any one of [1] to [8] above, further comprising the following component (C): (C) a polyvalent metal element

[10] The fiber treatment agent according to [9] above, wherein the content of component (C) in the fiber treatment agent is 0.0001% by mass or more and 1% by mass or less.

[0007]

[11] A fiber treatment kit for use in treating a fiber having a swelling rate in water of 200% or more as calculated by the following formula (1), comprising: a first fiber treatment agent containing the following components (A) and (B); and a second fiber treatment agent containing the following components (A) and (B), the second fiber treatment agent having a pH that is 1.0 or more lower than that of the first fiber treatment agent.

[0008]

[12] A fiber treatment kit for use in treating fibers having a swelling rate in water of 200% or more calculated by the following formula (1), the fiber treatment kit comprising: a fiber treatment agent containing the following components (A) and (B); and an additional fiber treatment agent containing the following component (D): (D) a fiber having a hydrogen bond term δH of the Hansen solubility parameter of 18.3 MPa. 1 / 2 A compound or a salt thereof having at least one carboxy group or a salt thereof and no fused ring, which is as follows (excluding component (A)):

[0009] (A) a compound having a coordinating functional group and a molecular weight of 1500 or more; (B) water;

[0010] Fiber swelling ratio in water (%) = [(w1 - w2) / w2] × 100 (1) (wherein w1 represents the mass (g) of the fiber measured after placing 1.0 g of fiber in a container filled with 100 g of ion-exchanged water, sealing the container, immersing the container in a water bath at 40°C for 30 minutes, removing the fiber from the container, and centrifuging for 1 minute at a centrifugal force of 220 [×g]. w2 represents the mass of the fiber measured after placing the fiber whose mass (w1) has been measured on filter paper and drying it at 105°C for 3 hours.)

[0011] 10 is a fluorescent image of a cross section of a fiber treated with the fiber treatment agent of Example 37. Detailed Description of the Invention

[0012] Patent Document 1 proposes a technology for modifying fibers with a compound having a molecular weight above a certain level, but it merely involves crosslinking wool with a polymeric compound to coat the surface. Prior to the filing of this application, there was a problem with the inability of compounds having a molecular weight above a certain level to penetrate naturally derived fibers. Meanwhile, Patent Document 2 proposes a technology for modifying fibers with a compound having a molecular weight above a certain level by penetrating a methylol compound and a phenolic compound into the fiber, coordinating phenolic hydroxyl groups within the fiber, and condensing the phenolic compounds with the methylol compound, thereby modifying the fiber from within with the polymerized condensate. However, this technology for modifying fibers from within requires the steps of penetrating a monomer into the fiber and polymerizing the monomer within the fiber, which makes the treatment process complicated and limits the ability to treat large quantities of naturally derived fibers. Therefore, the present invention relates to a novel fiber treatment agent capable of penetrating a compound having a molecular weight above a certain level into the fiber.

[0013] The inventors have conducted research in light of the above-mentioned problems and have found that a compound containing a specific characteristic group and having a molecular weight of a certain level or more can specifically penetrate naturally-derived fibers having specific properties, and that the specific characteristic group can be coordinated to the fiber, thereby solving the above-mentioned problems specific to naturally-derived fibers, and have completed the present invention.

[0014] According to the present invention, a novel fiber treatment agent can be provided that can modify fibers from the inside by penetrating a compound having a certain molecular weight or more into the fibers. Furthermore, by treating fibers with the fiber treatment agent of the present invention, water resistance and thermal shape memory ability can be improved, and the treatment process is simple, so that the fiber treatment agent is useful as a fiber treatment agent for naturally derived fibers used in head accessories such as wigs and extensions.

[0015] [Fiber Treating Agent] The fiber treating agent of the present invention contains components (A) and (B) as constituents, and is applied to fibers having specific properties.

[0016] <Fibers to which the fiber treating agent of the present invention is applied> The fibers to which the fiber treating agent of the present invention is applied must have a swelling ratio in water calculated by the following formula (1) of 200% or more.

[0017] Fiber swelling ratio in water S (%) = [(w1 - w2) / w2] × 100 (1)

[0018] (Wherein, w1 represents the mass (g) of the fiber measured after placing 1.0 g of fiber in a container filled with 100 g of ion-exchanged water, sealing the container, immersing the container in a water bath at 40°C for 30 minutes, removing the fiber from the container, and centrifuging and dehydrating it for 1 minute at a centrifugal force of 220 [×g]. w2 represents the mass (g) of the fiber measured after placing the fiber whose mass (w1) has been measured on filter paper and drying it at 105°C for 3 hours.)

[0019] The centrifugal force [×g] is a value calculated by the following formula.

[0020] Centrifugal force [× g] = 1.118 × centrifugal radius (m) × [rotation speed (min -1 )] 2 x10 -3

[0021] Even when fiber treatment agents containing compounds with molecular weights above a certain level are applied to fibers commonly available on the market, the compounds merely coat the fiber surface and fail to penetrate into the fiber interior. This problem has long been recognized by those skilled in the art and remained unsolved even prior to the filing of this application. Therefore, the present inventors focused on the maximum swelling ratio of fibers in water and searched for fibers capable of penetrating into the fiber interior. They found that even compounds with molecular weights above a certain level can penetrate into the fiber interior as long as the fibers have a specific property of a fiber swelling ratio in water of 200% or more, as calculated by the following formula (1). Furthermore, they found that by introducing a coordinating functional group into the compound and increasing the molecular weight to 1500 or more, the compound can be retained in the fiber after penetration, thereby solving the above-mentioned problem specific to regenerated collagen fibers.

[0022] The fibers to which the fiber treating agent of the present invention is applied have a fiber swelling ratio in water of 200% or more, but from the viewpoint of promoting penetration into the fibers, it is preferably 250% or more, more preferably 300% or more, and even more preferably 350% or more. Furthermore, from the viewpoint of avoiding easy fiber breakage in the fiber treatment step due to excessive swelling (from the viewpoint of workability in the fiber treatment step), it is preferably 1000% or less, more preferably 800% or less, even more preferably 600% or less, and even more preferably 500% or less. That is, the fiber swelling ratio in water of the applied fibers is preferably 250 to 1000%, more preferably 300 to 800%, even more preferably 350 to 600%, and even more preferably 350 to 500%.

[0023] The applicable fibers are not particularly limited as long as their swelling ratio in water is within the above-mentioned range, but metal-containing fibers are preferred, and metal-containing naturally derived fibers or metal-containing synthetic fibers are more preferred. Of these, metal-containing naturally derived fibers are preferred. Naturally derived fibers refer to fibers collected from natural plants and animals, or artificially produced fibers using polymers or oligomers of proteins and polysaccharides derived from keratin, collagen, casein, soybeans, peanuts, corn, silk waste, silk proteins (e.g., silk fibroin), etc. Among these, artificially produced fibers are preferred, using polymers and oligomers of proteins and polysaccharides derived from keratin, collagen, casein, soybeans, peanuts, corn, silk waste, silk proteins (e.g., silk fibroin), etc. as raw materials; regenerated protein fibers are more preferred, using proteins derived from keratin, collagen, casein, soybeans, peanuts, corn proteins, silk proteins (e.g., silk fibroin), etc. as raw materials; regenerated protein fibers such as regenerated collagen fibers derived from collagen and regenerated silk fibers derived from silk fibroin are even more preferred, with regenerated collagen fibers being even more preferred.

[0024] As long as the fiber swelling rate in water is within the above-mentioned range, the regenerated collagen fiber does not need to be 100% collagen, and may contain natural or synthetic polymers or additives to improve quality. Furthermore, the regenerated collagen fiber may be post-processed. The preferred form of regenerated collagen fiber is filament. Filaments are generally taken out from bobbins or boxes.

[0025] Suitable regenerated collagen fibers are artificially produced using collagen-derived polymers or oligomers as raw materials, i.e., regenerated collagen fibers made from collagen, which have a fiber swelling ratio in water within the above-mentioned range. Regenerated collagen fibers are typically produced by using a solubilized collagen raw material as a spinning solution, discharging this solution from a spinning nozzle into a coagulation bath to fiberize it, and then drying the fibrous collagen in the final step. Undried regenerated collagen fibers before the drying step satisfy the above-mentioned fiber swelling ratio in water requirement. Such undried regenerated collagen fibers can be produced by conventional methods up to the drying step. For example, undried regenerated collagen fibers can be produced by discharging an aqueous collagen solution obtained by solubilizing insoluble collagen fibers made from the split hides of livestock animals through a spinning nozzle or slit, immersing the resulting solution in an aqueous inorganic salt solution, and then recovering the resultant fibers without drying. This method is described in detail below.

[0026] The preferred collagen raw material is split skin. Split skin is obtained from fresh split skin obtained by slaughtering livestock animals such as cattle, or from salted raw hides. These split skins are mostly composed of insoluble collagen fibers, but are usually used after removing the fleshy part that is usually attached in a mesh-like form and removing the salt used to prevent spoilage and deterioration.

[0027] These insoluble collagen fibers contain impurities such as lipids (e.g., glycerides, phospholipids, and free fatty acids), glycoproteins, albumin, and other proteins other than collagen. These impurities have a significant effect on spinning stability, quality (e.g., gloss and strength and elongation), odor, and other factors during fiberization. Therefore, it is preferable to remove these impurities in advance by, for example, soaking the insoluble collagen fibers in lime to hydrolyze the fat in the fibers and loosen the collagen fibers, and then subjecting the fibers to conventional leather treatments such as acid / alkali treatment, enzyme treatment, and solvent treatment.

[0028] The insoluble collagen thus treated is then subjected to a solubilization treatment to cleave the cross-linked peptide moieties. As a method for such solubilization, a commonly used known alkali solubilization method, an enzyme solubilization method, etc., can be used. Furthermore, the alkali solubilization method and the enzyme solubilization method may be used in combination.

[0029] When the alkali solubilization method is applied, it is preferable to neutralize with an acid such as hydrochloric acid. Note that, as an improved version of the conventional alkali solubilization method, for example, the method described in JP-B-46-15033 may be used.

[0030] The enzymatic solubilization method has the advantage of being able to obtain solubilized collagen with a uniform molecular weight, and is a method that can be suitably employed in the present invention. Examples of such enzymatic solubilization methods that can be employed include those described in Japanese Patent Publication Nos. 43-25829 and 43-27513.

[0031] If the collagen that has been solubilized in this way is further subjected to operations such as pH adjustment, salting out, water washing, and solvent treatment, it is possible to obtain regenerated collagen fibers with excellent quality, and therefore it is preferable to perform these treatments.

[0032] Solubilized collagen is dissolved in an acid such as hydrochloric acid, acetic acid, or lactic acid to obtain a collagen aqueous solution having a pH of 2 to 4.5 and a collagen concentration of 1% by mass or more, preferably 2% by mass or more, and 15% by mass or less, preferably 10% by mass or less. The collagen aqueous solution may be degassed under reduced pressure and stirred, as needed, or filtered to remove water-insoluble fine particles. Furthermore, the collagen aqueous solution may contain appropriate amounts of additives such as stabilizers and water-soluble polymers, as needed, for purposes such as improving mechanical strength, water resistance and heat resistance, gloss, spinnability, coloration prevention, and preservative properties.

[0033] Undried regenerated collagen fibers can be obtained by discharging an aqueous collagen solution through, for example, a spinning nozzle or slit and immersing the resulting solution in an aqueous inorganic salt solution. Examples of aqueous inorganic salt solutions include aqueous solutions of water-soluble inorganic salts such as sodium sulfate, sodium chloride, and ammonium sulfate. Typically, the concentration of the inorganic salt in these aqueous inorganic salt solutions is adjusted to 10 to 40% by mass. The pH of the aqueous inorganic salt solution is preferably 2 or higher, more preferably 4 or higher, and preferably 13 or lower, more preferably 12 or lower. To adjust the pH, for example, metal salts such as sodium borate and sodium acetate, hydrochloric acid, boric acid, acetic acid, and sodium hydroxide can be used. When the pH of the aqueous inorganic salt solution is within the above range, the collagen peptide bonds are less susceptible to hydrolysis, making it easier to obtain the desired fibers. The temperature of the aqueous inorganic salt solution is not particularly limited, but is typically 35°C or lower, which prevents denaturation of soluble collagen, prevents a decrease in the strength of the spun fibers, and facilitates the production of stable threads. The lower limit of the temperature of the aqueous inorganic salt solution is not particularly limited, but can typically be adjusted appropriately depending on the solubility of the inorganic salt.

[0034] The regenerated collagen fibers may be pretreated (crosslinked) by immersing the undried regenerated collagen fibers in an epoxy compound monomer or a solution thereof. The amount of epoxy compound monomer is preferably 0.1 equivalents or more, more preferably 0.5 equivalents or more, and even more preferably 1 equivalent or more, relative to the amount of amino groups in the regenerated collagen fibers that can react with the epoxy groups of the epoxy compound, as measured by amino acid analysis, and is also preferably 500 equivalents or less, more preferably 100 equivalents or less, and even more preferably 50 equivalents or less. By using an epoxy compound monomer in this range, the regenerated collagen fibers can be sufficiently insolubilized in water, and this is also preferable from an industrial handleability and environmental standpoint.

[0035] The epoxy compound monomer may be used as is or dissolved in various solvents. Examples of solvents include water; alcohols such as methyl alcohol, ethyl alcohol, and isopropanol; ethers such as tetrahydrofuran and dioxane; halogenated organic solvents such as dichloromethane, chloroform, and carbon tetrachloride; and neutral organic solvents such as dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). These solvents may be used alone or in combination of two or more. When water is used as the solvent, an aqueous solution of an inorganic salt such as sodium sulfate, sodium chloride, or ammonium sulfate may be used as needed. Typically, the concentration of the inorganic salt in the aqueous solution is adjusted to 10 to 40% by mass. The pH of the aqueous solution may also be adjusted with, for example, a metal salt such as sodium borate or sodium acetate, or hydrochloric acid, boric acid, acetic acid, or sodium hydroxide. In this case, the pH of the aqueous solution is preferably 6 or higher, more preferably 8 or higher, from the viewpoint of preventing the reaction between the epoxy groups of the epoxy compound monomer and the amino groups of collagen from slowing down and ensuring sufficient insolubilization in water. Furthermore, since the pH of an aqueous solution of an inorganic salt tends to decrease over time, a buffer may be used if necessary.

[0036] The treatment temperature for undried regenerated collagen fibers with epoxy compound monomer is preferably 50°C or lower, from the viewpoints of preventing denaturation of the regenerated collagen fibers, preventing a decrease in the strength of the resulting fibers, and facilitating stable production of threads.

[0037] Furthermore, from the viewpoint of improving water resistance, the fibers to which the fiber treatment agent of the present invention is applied preferably contain a polyvalent metal, or a salt or complex thereof. Examples include one or more polyvalent metals selected from calcium, magnesium, strontium, barium, zinc, chromium, aluminum, titanium, zirconium, tin, lead, antimony, iron, and copper, or a salt or complex thereof. Among these, from the viewpoint of improving ease of coordination, water resistance, heat resistance, and thermal shape memory ability, one or more polyvalent metals selected from aluminum, zirconium, and titanium, or a salt or complex thereof, are preferred, and aluminum, a salt or complex thereof is more preferred. The content of polyvalent metals, or salts or complexes thereof in regenerated collagen fibers is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, even more preferably 3.0% by mass or more, and even more preferably 5.0% by mass or more, in terms of metal element content, from the viewpoint of improving ease of coordination, water resistance, heat resistance, and thermal shape memory ability; and from the viewpoint of improving the feel of the fiber surface, it is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and even more preferably 10% by mass or less. That is, the content of polyvalent metals, or salts or complexes thereof in the applicable fibers is preferably 1.0 to 40% by mass, more preferably 2.0 to 30% by mass, even more preferably 3.0 to 20% by mass, and even more preferably 5.0 to 10% by mass, in terms of metal element content. Note that, in this specification, the "metal element content" is determined by ICP atomic emission spectroscopy. For ICP optical emission spectroscopy, an ICP optical emission analyzer such as an iCAP6500Duo (manufactured by Thermo Fisher Scientific) can be used. The measurement conditions for ICP optical emission spectroscopy are as follows: The wavelength is selected by checking the spectral profile and selecting the optimal analysis wavelength for the target metal. For example, for aluminum, it is 396.152 nm. The analytical sample is pretreated using the method described in the examples, and a calibration curve is created for each target metal.

[0038] <Measurement conditions> RF power: 1150 W Coolant gas flow rate: 12 L / min Nebulizer flow rate: 0.70 L / min Auxiliary gas: 0.5 L / min Pump flow rate: 50 rpm

[0039] Furthermore, undried regenerated collagen fibers are in a swollen state with water or an aqueous solution of inorganic salts. This swelling is preferably achieved by adding 4 to 15 times the mass of the regenerated collagen fibers with water or an aqueous solution of inorganic salts. If the content of water or an aqueous solution of inorganic salts is less than 4 times, the aluminum salt content in the regenerated collagen fibers tends to be low, resulting in insufficient water resistance. If the content of water or an aqueous solution of inorganic salts is more than 15 times, the strength of the fibers tends to be weak, making them difficult to handle. Therefore, metals may be added so that the amount of metal element falls within the above range. For example, the following treatment can be performed.

[0040] First, the undried regenerated collagen fibers are immersed in an aqueous solution of an aluminum salt, preferably basic aluminum chloride or basic aluminum sulfate represented by the following formula:

[0041] Al(OH) n Cl 3-n , or Al 2 (OH) 2n (SO4) 3-n

[0042] [In the formula, n is 0.5 to 2.5.]

[0043] Specific examples include aluminum sulfate, aluminum chloride, and alum. Aluminum salts can be used alone or in combination of two or more. The aluminum salt concentration in the aluminum salt aqueous solution is preferably 0.3 to 5 mass% in terms of aluminum oxide. If the aluminum salt concentration is less than 0.3 mass%, the aluminum salt content in the regenerated collagen fibers will be low, and water resistance will tend to be insufficient. If the aluminum salt concentration is more than 5 mass%, the treated fibers will tend to become hard and lose their texture.

[0044] The pH of the aluminum salt aqueous solution is usually 2.5 to 5. It can be adjusted using, for example, hydrochloric acid, sulfuric acid, acetic acid, sodium hydroxide, sodium carbonate, etc. If the pH is less than 2.5, the collagen structure tends to be destroyed and denatured, while if it exceeds 5, aluminum salt precipitation occurs, making it difficult to penetrate into the fibers. It is preferable to initially adjust the pH to 2.2 to 3.5 to allow the aluminum salt aqueous solution to sufficiently penetrate into the regenerated collagen fibers, and then add, for example, sodium hydroxide, sodium carbonate, etc. to adjust the pH to 3.5 to 5 to complete the treatment. If a highly basic aluminum salt is used, only the initial pH adjustment to 2.5 to 5 is sufficient.

[0045] The temperature of the aluminum salt aqueous solution is not particularly limited, but is preferably not higher than 50° C. If the temperature exceeds 50° C., the regenerated collagen fibers tend to denature.

[0046] The time for immersing undried regenerated collagen fibers in the aqueous aluminum salt solution is usually 3 hours or more, preferably 6 to 25 hours. If the immersion time is less than 3 hours, the reaction of the aluminum salt will not proceed easily, and the water resistance of the regenerated collagen fibers will tend to be insufficient. There is no particular upper limit to the immersion time, but if the immersion time is within 25 hours, the reaction of the aluminum salt will proceed sufficiently and water resistance will be good.

[0047] In order to prevent the aluminum salt from being rapidly absorbed into the regenerated collagen fibers and causing uneven concentration, an inorganic salt such as sodium chloride, sodium sulfate, or potassium chloride may be added to the aqueous aluminum salt solution as appropriate.

[0048] After treating the regenerated collagen fibers with the epoxy compound monomer or aluminum salt, they may be washed with water, for example, by washing with running water for 10 minutes to 4 hours.

[0049] <Constituent Components> [Component (A)] The fiber treatment agent of the present invention contains, as component (A), a compound having a coordinating functional group and a molecular weight of at least 1500. Component (A) may be contained alone or in combination of two or more types.

[0050]

[0003] Conventionally, compounds with a molecular weight of 1500 or more have had difficulty penetrating into fibers, particularly naturally occurring fibers. However, the present inventors have unexpectedly discovered that component (A) can penetrate into fibers having the specific properties described above and can modify the fibers by coordinating functional groups within the fibers. Therefore, the fiber treatment agent of the present invention can be called a fiber-penetrating treatment agent, and is completely different from conventional surface-coating fiber treatment agents.

[0051] (Coordinating Functional Group) From the viewpoints of promoting penetration and coordination into fibers and improving water resistance, heat resistance, and thermal shape memory ability, the coordinating functional group is preferably a group containing a hard base or a borderline base in the HSAB rule. Here, the "HSAB rule (Hard and Soft Acids and Bases principle)" as used herein is a classification of acid-base strength proposed by R. G. Pearson, which is based on hardness and softness (J. Am. Chem. Soc. 1967, 89, 8, 1827-1836). Furthermore, "Pearson's hard base" refers to a Lewis base classified as a hard base in the concept of the HSAB rule introduced by Pearson in the 1960s, and is said to be reactive with Lewis acids classified as hard acids. Examples of hard bases include functional groups corresponding to the hard bases described in "Application of the Principle of Hard and Soft Acids and Bases to Organic Chemistry," Ralp G. Pearson and Jon. Songstad, J. Am. Chem. Soc. 1967, 89, 8, 1827-1836. Note that an intermediate base (borderline base) is a base that is not classified as either a hard base or a soft base, and means that the strength of the base is intermediate between that of a hard base and a soft base.

[0052] Examples of hard bases include hydroxide ions (OH - ), fluoride ion (F -), carboxy group (COOH), carboxy anion (COO - ), carboxylate (COOM), phosphate ion (PO4 3- ), sulfate ions (SO4 2- ), chloride ions (Cl - ), carbonate ions (CO3 3- ), perchlorate ion (ClO - ), a hydroxyl group (OH), a group having an ether bond (—O—), i.e., an alkoxy group (OR), an alkoxide anion (O - ), metal alcoholate (OM), ammonia (NH3) or a group containing an imino group (NH2). M represents a metal, preferably an alkali metal. Examples of intermediate bases include bromide ion (Br - ), sulfite ions (SO3 2- ), azide ion (N 3- ), a group containing a sulfonic acid group (SO3H), or a group containing a sulfonate salt (SO3M, where M has the same meaning as defined above).

[0053] Among these, from the viewpoints of promoting penetration and coordination into fibers, and improving water resistance, heat resistance, and thermal shape memory ability, the coordinating functional group is preferably a group containing a base selected from the following (a-1), (a-2), and (a-3):

[0054] (a-1) A group having a carboxy group or a salt thereof; (a-2) A group having a hydroxyl group, an alkoxy group, an alkoxide anion, or a metal alcoholate; (a-3) A group having a sulfonic acid group or a salt thereof.

[0055] Examples of salts include alkali metal salts, alkaline earth metal salts, and ammonium salts. Examples of alkali metal salts include sodium salts, lithium salts, and potassium salts, and examples of alkaline earth metal salts include calcium salts and magnesium salts. Among these, sodium salts are preferred from the viewpoint of dispersibility. Note that (a-1) a group having a carboxy group or a salt thereof may be dissociated into a carboxy anion, and (a-2) when the hydroxyl group is a phenolic hydroxyl group, it may be dissociated into a phenoxide. Furthermore, (a-3) a group having a sulfonic acid group or a salt thereof may be dissociated into a sulfonate anion.

[0056] The compound having such a coordinating functional group is not particularly limited as long as it has a molecular weight of 1,500 or more, but from the viewpoints of promoting penetration and coordination into fibers and improving water resistance, heat resistance, and thermal shape memory ability, it is preferable that the compound contain one or more selected from the following (A-1) and (A-2). (A-1) and (A-2) can be contained either alone or in combination of two or more.

[0057] (A-1) A polymer containing a structural unit derived from an unsaturated monomer having a coordinating functional group, the polymer having a weight-average molecular weight of 1500 or more. (A-2) A condensation product of a compound having a coordinating functional group, the condensation product having a molecular weight of 1500 or more.

[0058] (Polymer) In the polymer (A-1), examples of the unsaturated monomer having a coordinating functional group include unsaturated monomers having one or more coordinating functional groups selected from the above-described (a-1) to (a-3). The unsaturated monomer having a coordinating functional group may have a substituent. Examples of the substituent include a halo group, an alkyl group, a cyano group, a nitro group, an amino group, a dialkylamino group, an alkoxycarbonyl group, an alkylthio group, an arylthio group, and a trialkylsilyl group. The position and number of the substituent are optional, and when two or more substituents are present, the substituents may be the same or different.

[0059] Specific examples of the unsaturated monomer having (a-1) above that is an unsaturated monomer having a carboxy group or a salt thereof include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and salts thereof. The unsaturated monocarboxylic acid may be an unsaturated aliphatic monocarboxylic acid or an unsaturated group-containing aromatic monocarboxylic acid. The unsaturated dicarboxylic acid may be an unsaturated aliphatic dicarboxylic acid or an unsaturated group-containing aromatic dicarboxylic acid. The unsaturated monomer having (a-1) as a coordinating functional group may be used alone or in combination of two or more.

[0060] Examples of unsaturated monocarboxylic acids include unsaturated aliphatic monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, oleic acid, and cyclopentenylacetic acid, and unsaturated group-containing aromatic monocarboxylic acids such as vinylbenzoic acid and cinnamic acid. Examples of unsaturated dicarboxylic acids include unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and methylenesuccinic acid, and unsaturated group-containing aromatic dicarboxylic acids such as vinylterephthalic acid, vinylisophthalic acid, and vinylnaphthalenedicarboxylic acid. When the unsaturated monocarboxylic acid or unsaturated dicarboxylic acid is in the form of a salt, specific examples of the counter ion of the salt are as described above. The unsaturated dicarboxylic acid can also be used in the acid form by using an unsaturated dicarboxylic acid anhydride and hydrolyzing it with an alkali or the like. Examples of unsaturated dicarboxylic acid anhydrides include maleic anhydride and citraconic anhydride.

[0061] Specific examples of the unsaturated monomer having (a-2) above that is an unsaturated monomer having a phenolic hydroxyl group include hydroxystyrene, isopropenylphenol, hydroxyphenyl(meth)acrylate, and hydroxyphenylmaleimide. Here, in this specification, "(meth)acrylate" means acrylate or methacrylate. The unsaturated monomer having (a-2) as a coordinating functional group can be used alone or in combination of two or more types.

[0062] Specific examples of the unsaturated monomer having (a-3) that is an unsaturated monomer having a sulfonic acid group or a salt thereof include vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, (meth)acryloyloxyethyl sulfonic acid, and salts thereof. Herein, "(meth)allyl" means allyl or methallyl, and "(meth)acryloyl" means acryloyl or methacryloyl. The unsaturated monomer having (a-3) as a coordinating functional group can be used alone or in combination of two or more. When the unsaturated monomer having a sulfonic acid group is in the form of a salt, specific examples of the counter ion of the salt are as explained above.

[0063] Examples of unsaturated monomers having a coordinating functional group other than those described above include unsaturated monomers in which the coordinating functional group described above is substituted with a coordinating functional group other than the coordinating functional group. Unsaturated monomers having a coordinating functional group other than (a-1) to (a-3) can be used alone or in combination of two or more.

[0064] In the polymer (A-1), the proportion of the structural units derived from the unsaturated monomer having a coordinating functional group is preferably 10 mol % or more, more preferably 15 mol % or more, and even more preferably 20 mol % or more. The proportion of the structural units derived from the unsaturated monomer having a coordinating functional group in the polymer (A-1) may be 100 mol %.

[0065] The polymer (A-1) may contain structural units other than the structural units derived from the unsaturated monomer having a coordinating functional group. The polymer may contain two or more of the other structural units. As the other structural units, it is preferable to further contain a structural unit derived from an unsaturated hydrocarbon compound, from the viewpoint of hydrophobizing the polymer and improving the water resistance and heat resistance of the fiber. As the unsaturated hydrocarbon compound, aromatic vinyl compounds and unsaturated aliphatic hydrocarbon compounds are preferred, from the viewpoint of hydrophobizing the polymer and improving the water resistance and heat resistance of the fiber. The unsaturated hydrocarbon compound may have a substituent. The position and number of the substituents are optional, and when two or more substituents are present, the substituents may be the same or different. Specific examples of the substituent include those similar to those mentioned above.

[0066] Examples of aromatic vinyl compounds include styrene, methylstyrene, dimethylstyrene, chloromethylstyrene, vinylnaphthalene, and vinylanthracene. Among these, styrene and vinylnaphthalene are preferred, and styrene is more preferred, from the viewpoints of hydrophobizing the polymer and improving the water resistance and heat resistance of the fiber, effectively improving the underwater elastic modulus of the fiber due to the rigidity of the aromatic ring, and improving the retention efficiency in the fiber due to the bulkiness of the aromatic ring. The unsaturated aliphatic hydrocarbon compound may be linear, branched, or cyclic. Examples of linear or branched unsaturated aliphatic hydrocarbon compounds include propylene, isobutylene, diisobutylene, triisobutylene, tripropylene, and tetrapropylene. Among these, diisobutylene and triisobutylene are preferred, and diisobutylene is more preferred, from the viewpoint of hydrophobizing the polymer and improving the water resistance and heat resistance of the fiber. Examples of cyclic unsaturated aliphatic hydrocarbon compounds include cyclopentene, cyclohexene, and cyclooctene. Among these, from the viewpoint of hydrophobizing the polymer and improving the water resistance and heat resistance of the fiber, cyclopentene and cyclohexene are preferred, and cyclohexene is more preferred.

[0067] Among these, as the unsaturated hydrocarbon compound, aromatic vinyl compounds are preferred, and styrene is more preferred, from the viewpoints that they hydrophobize the polymer to improve the water resistance and heat resistance of the fiber, the rigidity of the aromatic rings can effectively improve the modulus of elasticity in water of the fiber, and the bulkiness of the aromatic rings improves the efficiency of retention in the fiber.

[0068] Among these, from the viewpoints of promoting penetration and coordination into fibers, and improving water resistance, heat resistance, and thermal shape memory ability, it is preferable that the polymer (A-1) contains one or more selected from the following (A-1-1), (A-1-2), and (A-1-3):

[0069] (A-1-1) A copolymer containing a structural unit derived from an unsaturated monomer having a coordinating functional group and a structural unit derived from an aromatic vinyl compound, the copolymer having a weight-average molecular weight of 1500 or more. (A-1-2) A copolymer containing a structural unit derived from an unsaturated monomer having a coordinating functional group and a structural unit derived from an unsaturated aliphatic hydrocarbon compound, the copolymer having a weight-average molecular weight of 1500 or more. (A-1-3) A polymer containing a structural unit derived from an aromatic vinyl compound having a coordinating functional group or a polymer containing a structural unit derived from an unsaturated aliphatic hydrocarbon compound having a coordinating functional group, the polymer having a weight-average molecular weight of 1500 or more (however, excluding copolymers (A-1-1) and (A-1-2)).

[0070] The copolymer (A-1-1), copolymer (A-1-2), and polymer (A-1-3) may be contained alone or in combination of two or more. In the copolymers (A-1-1) and (A-1-2), the bonding state of the monomers that give each structural unit may be block bonding, random bonding, or a combination thereof.

[0071] The copolymer (A-1-1) is not particularly limited as long as it has a weight-average molecular weight of 1,500 or more. From the viewpoints of promoting penetration and coordination into fibers, and improving water resistance, heat resistance, and thermal shape memory ability, however, a copolymer containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from an unsaturated monomer having a carboxy group or a salt thereof is preferred, and a copolymer containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from one or more selected from an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, and a salt thereof is more preferred. Specifically, for example, one or more selected from styrene-maleic acid copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, vinylbenzoic acid-maleic acid copolymer, vinylbenzoic acid-acrylic acid copolymer, vinylbenzoic acid-methacrylic acid copolymer, styrene-4-vinylbenzoic acid copolymer, butadiene-4-vinylbenzoic acid copolymer, carboxy-modified products of styrene-butadiene copolymers and salts thereof are preferred, more preferably one or more selected from styrene-maleic acid copolymer, carboxy-modified products of styrene-butadiene copolymers and salts thereof, and even more preferably styrene-maleic acid copolymer or a salt thereof. When the (A-1-1) copolymer is in the form of a salt, the counter ion of the salt is not particularly limited, and examples include sodium salt, potassium salt, magnesium salt, calcium salt, ammonium salt, etc., with sodium salt being preferred. Furthermore, the carboxy-modified product of styrene-maleic acid copolymer or styrene-butadiene copolymer can be prepared by using a styrene-maleic anhydride copolymer or a maleic anhydride-modified styrene-butadiene copolymer and generating a carboxy-modified product of styrene-maleic acid copolymer or styrene-butadiene copolymer with an alkali or the like. Preferred carboxy-modified products of styrene-butadiene copolymers include SBL0696, SBL0533, SBL0545, SBL0548, SBL0568, SBL0569V, SBL0573, SBL0597C, SBL0850Z, and SBL2527A manufactured by ENEOS Material Corporation, with SBL0696, SBL0548, SBL0568, and SBL2527A being more preferred, and SBL0696 being even more preferred.

[0072] The copolymer (A-1-2) is not particularly limited as long as it has a weight-average molecular weight of 1,500 or more. From the viewpoints of promoting penetration and coordination into fibers, and improving water resistance, heat resistance, and thermal shape memory ability, however, a copolymer containing a structural unit derived from an unsaturated aliphatic hydrocarbon compound and a structural unit derived from an unsaturated monomer having a carboxy group or a salt thereof is preferred, and a copolymer containing a structural unit derived from an unsaturated aliphatic hydrocarbon compound and a structural unit derived from one or more selected from unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and salts thereof is more preferred. Specifically, for example, one or more selected from diisobutylene-maleic acid copolymer, diisobutylene-acrylic acid copolymer, diisobutylene-methacrylic acid copolymer, diisobutylene-4-vinylbenzoic acid copolymer, butadiene-maleic acid copolymer, butadiene-acrylic acid copolymer, butadiene-methacrylic acid copolymer, butadiene-4-vinylbenzoic acid copolymer, maleic acid-modified butadiene polymer, and salts thereof are preferred, and one or more selected from diisobutylene-maleic acid copolymer, butadiene-maleic acid copolymer, maleic acid-modified butadiene polymer, and salts thereof are more preferred. When the (A-1-2) copolymer is in the form of a salt, the counter ion of the salt is not particularly limited, and examples include sodium salt, potassium salt, magnesium salt, calcium salt, ammonium salt, etc., with sodium salt being preferred. Furthermore, as for the diisobutylene-maleic acid copolymer, butadiene-maleic acid copolymer, or maleic acid-modified butadiene polymer, a diisobutylene-maleic anhydride copolymer, a butadiene-maleic anhydride copolymer, or a maleic anhydride-modified butadiene polymer can be used, and a maleic acid-modified diisobutylene-maleic acid copolymer, butadiene-maleic acid copolymer, or butadiene polymer can be produced with an alkali or the like and used. As the maleic anhydride-modified butadiene polymer or a salt thereof, Ricon 130MA8, Ricon 130MA13, Ricon 131MA5, Ricon 131MA10, Ricon 131MA17, and Ricon 131MA20 manufactured by Cray Valley are preferred, Ricon 130MA13 and Ricon 131MA20 are more preferred, and Ricon 130MA13 is even more preferred.

[0073] The polymer (A-1-3) is not particularly limited as long as it has a weight-average molecular weight of 1,500 or more. From the viewpoints of promoting penetration and coordination into fibers, and improving water resistance, heat resistance, and thermal shape memory ability, however, one or more polymers selected from homopolymers of aromatic vinyl compounds having a carboxy group, a sulfonic acid group, or a salt thereof, or a hydroxyl group, and homopolymers of unsaturated aliphatic hydrocarbon compounds having a carboxy group, a sulfonic acid group, or a salt thereof, or a hydroxyl group are preferred; one or more polymers selected from homopolymers of aromatic vinyl compounds having a carboxy group or a salt thereof, and homopolymers of unsaturated aliphatic hydrocarbon compounds having a carboxy group or a salt thereof are more preferred, and homopolymers of unsaturated aliphatic hydrocarbon compounds having a carboxy group or a salt thereof are even more preferred. Specifically, for example, one or more selected from poly(vinyl benzoic acid), poly(cinnamic acid), polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid or a salt thereof, and polyvinyl alcohol are preferred; one or more selected from polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid or a salt thereof, and polyvinyl alcohol are more preferred; one or more selected from polyacrylic acid, polymethacrylic acid, and a salt thereof are even more preferred; and polyacrylic acid or a salt thereof is even more preferred. When the polymer (A-1-3) is in the form of a salt, the counter ion of the salt is not particularly limited, but examples include sodium salt, potassium salt, magnesium salt, calcium salt, and ammonium salt, with sodium salt being preferred. Note that polyvinyl alcohol may be prepared, for example, by using vinyl acetate monomer as the unsaturated monomer, polymerizing this to obtain polyvinyl acetate, and then saponifying the resulting polyvinyl acetate.

[0074] In the copolymer (A-1-1), the molar ratio (u1 / u2) of the structural unit (u1) derived from an aromatic vinyl compound to the structural unit (u2) derived from an unsaturated monomer having a coordinating functional group is preferably 1 / 5 to 5 / 1, more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1, from the viewpoints of promoting penetration and coordination into fibers and improving water resistance, heat resistance, and thermal shape memory. In the copolymer (A-1-2), the molar ratio (u3 / u4) of the structural unit (u3) derived from an unsaturated aliphatic hydrocarbon compound to the structural unit (u4) derived from an unsaturated monomer having a coordinating functional group is preferably 1 / 5 to 5 / 1, more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1, from the viewpoints of promoting penetration and coordination into fibers and improving water resistance, heat resistance, and thermal shape memory.

[0075] The polymer (A-1) can be produced, for example, by a conventionally known method such as radical polymerization using an unsaturated monomer capable of introducing each of the structural units described above in an appropriate solvent in the presence of a polymerization initiator. The reaction conditions are not particularly limited and may be appropriately selected from commonly used conditions. The polymer can be isolated by a known isolation method, such as a method of pouring the reaction solution into a large amount of poor solvent and drying the resulting precipitate under reduced pressure, or a method of distilling the reaction solution under reduced pressure using an evaporator. Alternatively, commercially available polymers or copolymers may be used.

[0076] (Condensate) The (A-2) condensate is a condensate of a compound having a coordinating functional group and is not particularly limited as long as it has a molecular weight of 1500 or more, but from the viewpoints of promoting penetration and coordination into fibers and improving water resistance, heat resistance, and thermal shape memory ability, it is preferable that the condensate has a molecular weight of 1500 or more and contains one or more condensates selected from the following (A-2-1) and (A-2-2). (A-2-1) and (A-2-2) can be contained either alone or in combination of two or more.

[0077] (A-2-1) Condensate of sulfonic acid or its salt (A-2-2) Condensate of gallic acid ester

[0078] The sulfonic acid condensate or salt thereof in (A-2-1) may, for example, be an aromatic sulfonic acid-formalin condensate or a salt thereof. Specific examples include one or more selected from benzenesulfonic acid-formalin condensates, naphthalenesulfonic acid-formalin condensates, phenolsulfonic acid-formalin condensates, and salts thereof. Among these, from the viewpoints of promoting penetration and coordination into fibers and improving water resistance, heat resistance, and thermal shape memory ability, naphthalenesulfonic acid-formalin condensates or salts thereof are preferred, and β-naphthalenesulfonic acid-formalin condensates or salts thereof are more preferred. Examples of salts include alkali metal salts, alkaline earth metal salts, and ammonium salts. Examples of alkali metal salts include sodium salts, lithium salts, and potassium salts, and examples of alkaline earth metal salts include calcium salts and magnesium salts. Among these, sodium salts are preferred from the viewpoint of dispersibility.

[0079] (A-2-2) Examples of condensates of gallic acid esters include hydrolyzable tannins. Tannins are classified into two types: condensed tannins formed by polymerizing compounds having a flavanol skeleton, and hydrolyzable tannins formed by ester bonds between aromatic compounds such as gallic acid or ellagic acid and sugars such as glucose. The two types differ as chemical substances in that condensed tannins are formed by bonds that do not undergo hydrolysis, whereas hydrolyzable tannins are formed by ester bonds that are easily hydrolyzed. A specific example of a hydrolyzable tannin is tannic acid.

[0080] The sulfonic acid condensate or salt thereof in (A-2-1) can be produced, for example, by a conventionally known method. For example, in the case of a naphthalenesulfonic acid-formalin condensate, a naphthalenesulfonic acid-formalin condensate can be obtained by the condensation reaction of naphthalenesulfonic acid and formaldehyde. Then, for example, the sulfonic acid moiety is neutralized with an alkali to produce a naphthalenesulfonate-formalin condensate. After the reaction, the product can be purified by dialysis, ultrafiltration, or reprecipitation. Alternatively, commercially available sulfonic acid condensates or salts thereof may be used.

[0081] When the (A-2-2) condensate of gallic acid ester is tannic acid, it can be obtained by extraction from, for example, gall nuts (an insect of the genus Quercus) or Chinese gallnuts (an insect of the genus Rhus). After extraction, the extract may be purified by fractionation or the like, or may be concentrated. Alternatively, commercially available condensates of gallic acid ester may be used.

[0082] (Molecular Weight) In this specification, the molecular weight of component (A) is specified as follows. That is, when component (A) is (A-1) a polymer or (A-2-1) a sulfonic acid condensate or a salt thereof, the molecular weight refers to the weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC), and specifically, can be measured by the method described in the Examples. Furthermore, when component (A) is (A-2-2) a gallic acid ester condensate and the condensate is composed of a mixture, the molecular weight refers to the weight-average molecular weight as described above. On the other hand, when (A-2-2) a gallic acid ester condensate is a single compound, the molecular weight refers to the sum of the atomic weights of the atoms constituting the molecule.

[0083] When component (A) is (A-1) a polymer or (A-2-1) a sulfonic acid condensate or a salt thereof, the weight-average molecular weight is 1,500 or more, but from the viewpoints of promoting penetration and coordination into fibers and improving water resistance, heat resistance, and thermal shape memory ability, it is preferably 1,600 or more, more preferably 2,000 or more, even more preferably 3,000 or more, and still more preferably 4,000 or more, and is preferably 100,000 or less, more preferably 30,000 or less, even more preferably 15,000 or less, even more preferably 10,000 or less, and still more preferably 8,000 or less. That is, the weight-average molecular weight is preferably 1,600 to 100,000, more preferably 2,000 to 30,000, even more preferably 3,000 to 30,000, even more preferably 3,000 to 15,000, even more preferably 3,000 to 10,000, and still more preferably 4,000 to 8,000.

[0084] When the condensate of gallic acid ester (A-2-2) is a single compound, its molecular weight is 1,500 or more, but from the viewpoints of promoting penetration and coordination into fibers and improving water resistance, heat resistance, and thermal shape memory ability, it is preferably 1,600 or more, more preferably 1,700 or more, and preferably 10,000 or less, more preferably 5,000 or less. That is, the molecular weight is preferably 1,600 to 10,000, more preferably 1,700 to 5,000.

[0085] (Hydrogen bond term δH of Hansen solubility parameter) A suitable compound can be selected for component (A) from the viewpoint of promoting penetration and coordination into fibers, using the hydrogen bond term δH of Hansen solubility parameter as an index. Here, in this specification, "hydrogen bond term of Hansen solubility parameter" refers to δH (MPa) calculated at 25°C in a DIY program using the software package HSPiP 4th Edition 4.1.07 based on Hansen Solubility Parameters: A User's Handbook, CRC Press, Boca Raton FL, 2007. 1 / 2 ) (energy term due to intermolecular hydrogen bonds). When component (A) is a salt, the δH of the free acid (undissociated acid) is used.

[0086] The hydrogen bond term δH of the Hansen solubility parameter of component (A) is preferably 5.0 MPa. 1 / 2 More preferably, 7.0 MPa 1 / 2 More preferably, 9.0 MPa 1 / 2 and preferably 20.0 MPa or more. 1 / 2 or less, more preferably 16.0 MPa 1 / 2 More preferably, 13.0 MPa or less 1 / 2 That is, the hydrogen bond term δH of the Hansen solubility parameter is preferably 5.0 to 20.0 MPa. 1 / 2 , more preferably 7.0 to 16.0 MPa 1 / 2 , more preferably 9.0 to 13.0 MPa 1 / 2 is.

[0087] Specific examples of component (A) having a hydrogen bond parameter δH value of Hansen solubility parameter within the above range include the following compounds: Styrene-maleic acid copolymer (styrene / maleic acid (molar ratio) = 1 / 1) 11.5 MPa 1 / 2 Styrene-maleic acid copolymer (styrene / maleic acid (molar ratio) = 2 / 1) 9.2 MPa 1 / 2 Styrene-maleic acid copolymer (styrene / maleic acid (molar ratio) = 3 / 1) 7.9 MPa 1 / 2 Diisobutylene-maleic acid copolymer (diisobutylene / maleic acid (molar ratio) = 1 / 1) 9.4 MPa 1 / 2 ・Polyacrylic acid 14.3 MPa 1 / 2 β-naphthalenesulfonic acid formalin condensate 17.8 MPa 1 / 2

[0088] (Acid Value) Furthermore, when component (A) has the above-described (a-1) or (a-3) as a coordinating functional group, a suitable compound can be selected from the viewpoint of promoting penetration into fibers and coordination, using the acid value as an indicator. Here, in this specification, the "acid value" refers to the number of milligrams (mg) of potassium hydroxide required to neutralize the acidic components contained in 1 g of sample, and can be determined by potentiometric titration in accordance with JIS K 0070. When component (A) is a salt, the acid value of the free acid (undissociated acid) is used.

[0089] From the viewpoints of promoting penetration and coordination into fibers and improving water resistance, heat resistance, and thermal shape memory ability, the acid value of component (A) is preferably 100 mgKOH / g or more, more preferably 200 mgKOH / g or more, even more preferably 300 mgKOH / g or more, still more preferably 400 mgKOH / g or more, and is preferably 1000 mgKOH / g or less, more preferably 800 mgKOH / g or less, even more preferably 600 mgKOH / g or less. That is, the acid value is preferably 100 to 1000 mgKOH / g, more preferably 200 to 800 mgKOH / g, even more preferably 300 to 600 mgKOH / g, and still more preferably 400 to 600 mgKOH / g.

[0090] Specific examples of component (A) having an acid value within the above range include the following compounds: Styrene-maleic acid copolymer (styrene / maleic acid (molar ratio) = 1 / 1) 475 mg KOH / g Styrene-maleic acid copolymer (styrene / maleic acid (molar ratio) = 2 / 1) 355 mg KOH / g Styrene-maleic acid copolymer (styrene / maleic acid (molar ratio) = 3 / 1) 285 mg KOH / g Diisobutylene-maleic acid copolymer (diisobutylene / maleic acid (molar ratio) = 1 / 1) > 100 mg KOH / g Polyacrylic acid (Mw 5000) 757 mg KOH / g β-naphthalenesulfonic acid formalin condensate (Mw > 1500) > 100 mg KOH / g

[0091] (Hydroxyl value) When component (A) has the above-described (a-2) as a coordinating functional group, a suitable compound can be selected from the viewpoint of promoting penetration into fibers and coordination, using the hydroxyl value as an indicator. Here, in this specification, the "hydroxyl value" means the number of milligrams (mg) of potassium hydroxide required to neutralize acetic acid bonded to hydroxyl groups when 1 g of a sample is acetylated, and can be determined by potentiometric titration in accordance with JIS K 0070.

[0092] The hydroxyl value of component (A) is preferably 100 mgKOH / g or more, more preferably 200 mgKOH / g or more, even more preferably 300 mgKOH / g or more, and is preferably 2000 mgKOH / g or less, more preferably 1500 mgKOH / g or less, even more preferably 1000 mgKOH / g or less. That is, the acid value is preferably 100 to 2000 mgKOH / g, more preferably 200 to 1500 mgKOH / g, even more preferably 300 to 1000 mgKOH / g.

[0093] Specific examples of component (A) having a hydroxyl value within the above range include the following compounds: Tannic acid (M 1701) 757 mg KOH / g

[0094] From the viewpoints of promoting penetration and coordination into fibers and improving water resistance, heat resistance, and thermal shape memory ability, the content of component (A) 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 0.3% by mass or more, still more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, still more preferably 2.3% by mass or more, still more preferably 3.0% by mass or more, and preferably 60% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, still more preferably 15% by mass or less, and still more preferably 10% by mass or less. That is, the content of component (A) in the fiber treatment agent of the present invention is preferably 0.1 to 60% by mass, more preferably 0.2 to 40% by mass, even more preferably 0.3 to 30% by mass, still more preferably 0.5 to 15% by mass, still more preferably 1.0 to 15% by mass, still more preferably 2.3 to 15% by mass, and still more preferably 3.0 to 10% by mass. In this specification, when component (A) is a salt, the content of component (A) is expressed as a value converted into the free acid.

[0095] Furthermore, in the present invention, depending on the type of component (A) in the fiber treatment agent, the content of component (A) in the fiber treatment agent can be set within the ranges shown below. That is, when component (A) is (A-1) a polymer or (A-2-1) a sulfonic acid condensate or a salt thereof, the content of component (A) in the fiber treatment agent of the present invention is, from the viewpoints of promoting penetration and coordination into fibers and improving water resistance, heat resistance, and thermal shape memory ability, preferably 0.3% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, still more preferably 2.3% by mass or more, still more preferably 3.0% by mass or more, and preferably 60% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferably 15% by mass or less, and still more preferably 10% by mass or less. That is, the content of component (A) in the fiber treatment agent of the present invention is preferably 0.3 to 60 mass%, more preferably 0.5 to 40 mass%, even more preferably 1.0 to 30 mass%, still more preferably 2.3 to 20 mass%, even more preferably 3.0 to 15 mass%, and still more preferably 3.0 to 10 mass%.

[0096] When component (A) is (A-2-2) a condensate of a gallic acid ester, the content of component (A) 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 0.4% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1.0% by mass or less, from the viewpoints of promoting penetration and coordination into fibers and improving water resistance, heat resistance, and thermal shape memory ability. That is, the content of component (A) in the fiber treatment agent of the present invention is preferably 0.05 to 10% by mass, more preferably 0.10 to 5% by mass, even more preferably 0.20 to 1.0% by mass.

[0097] (pH) From the viewpoints of promoting penetration and coordination into fibers and improving water resistance, heat resistance, and thermal shape memory, the pH of the fiber treatment agent of the present invention is preferably 2.0 or higher, more preferably 3.0 or higher, and even more preferably 3.5 or higher. It is also preferably 11.0 or lower, more preferably 10.0 or lower, even more preferably 9.0 or lower, even more preferably 7.0 or lower, even more preferably 6.5 or lower, and even more preferably less than 5.5. That is, 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, even more preferably 3.5 to 9.0, even more preferably 3.5 to 7.0, even more preferably 3.5 to 6.5, and even more preferably 3.5 or higher but less than 5.5. The pH can also be adjusted within the above range depending on the content of component (A) in the fiber treatment agent. In this specification, "pH" refers to the value at 25°C and can be measured using a pH meter.

[0098] Furthermore, in the present invention, the content of component (A) in the fiber treatment agent can be set within the range shown below, depending on the pH of the fiber treatment agent and the type of component (A). When component (A) is (A-1) a polymer or (A-2-1) a sulfonic acid condensate or a salt thereof, and the pH of the fiber treatment agent is less than 5.5, the content of component (A) in the fiber treatment agent is preferably 0.3% by mass or more, more preferably 0.8% by mass or more, and even more preferably 1.3% by mass or more, from the viewpoints of promoting penetration and coordination into the fiber and improving water resistance, heat resistance, and thermal shape memory ability, and is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, from the viewpoint of improving the feel of the fiber surface. That is, when component (A) is (A-1) a polymer or (A-2-1) a condensate of sulfonic acid or a salt thereof, and the pH of the fiber treatment agent is less than 5.5, the content of component (A) in the fiber treatment agent is preferably 0.3 to 30 mass%, more preferably 0.8 to 20 mass%, and even more preferably 1.3 to 10 mass%.

[0099] When component (A) is a polymer (A-1) or a condensate of sulfonic acid (A-2-1) or a salt thereof, and the pH of the fiber treatment agent is 5.5 or higher, the content of component (A) in the fiber treatment agent is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, and even more preferably 3.0% by mass or more, from the viewpoints of promoting penetration and coordination into fibers and improving water resistance, heat resistance, and thermal shape memory ability. Furthermore, from the viewpoint of improving the feel of the fiber surface, it is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less. That is, when component (A) is a polymer (A-1) or a condensate of sulfonic acid (A-2-1) or a salt thereof, and the pH of the fiber treatment agent is 5.5 or higher, the content of component (A) in the fiber treatment agent is preferably 1.0 to 60% by mass, more preferably 2.0 to 50% by mass, and even more preferably 3.0 to 40% by mass.

[0100] When component (A) is (A-2-2) a condensate of a gallic acid ester, from the viewpoints of promoting penetration and coordination into fibers and improving water resistance, heat resistance, and thermal shape memory ability, 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, even more preferably 0.4% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1.0% by mass or less. That is, when component (A) is (A-2-2) a condensate of a gallic acid ester, the content of component (A) in the fiber treatment agent is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and even more preferably 0.4 to 1.0% by mass.

[0101] Furthermore, the content of component (A) in the fiber treatment agent of the present invention may be determined using the content of component (A) in fibers treated with the fiber treatment agent of the present invention as an index. For example, from the viewpoints of promoting retention and coordination in the fiber and improving water resistance, heat resistance, and thermal shape memory ability, the content of component (A) in fibers treated with the fiber treatment agent of the present invention can be set to an amount that is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, even more preferably 3.0% by mass or more, even more preferably 5.0% by mass or more, and even more preferably 10% by mass or more, and is preferably 70% by mass or less, more preferably 65% ​​by mass or less, even more preferably 60% by mass or less, even more preferably 55% by mass or less, even more preferably 50% by mass or less, and even more preferably 45% by mass or less. That is, the content of component (A) in the fiber treated with the fiber treatment agent is preferably 0.1 to 70% by mass, more preferably 0.5 to 65% by mass, even more preferably 1.0 to 60% by mass, even more preferably 3.0 to 55% by mass, even more preferably 5.0 to 50% by mass, and even more preferably 10 to 45% by mass. The amount of component (A) is determined by selecting an appropriate method that does not decompose component (A) and can dissolve the fiber, and then dissolving and extracting the fiber. After appropriately diluting the extracted solution, the absorbance is measured using an ultraviolet-visible-near-infrared spectrophotometer (e.g., V-560 (manufactured by JASCO Corporation)) at an absorption wavelength suitable for the quantification of component (A), and the content of component (A) is calculated from the absorbance. Alternatively, the peak areas of a chromatogram drawn at an absorption wavelength suitable for the quantification of component (A) using HPLC / UV or gel permeation chromatography (GPC) are measured, and the content of component (A) is calculated from the peak areas.

[0102] The penetration distribution of component (A) into the fiber cross section can be evaluated by cutting out a fiber cross section with a microtome, knife, razor, or the like, depending on the characteristics of component (A), and then performing linear or area analysis of the cross section using an optical microscope, a fluorescence microscope, a fluorescence imaging method using a confocal laser microscope, TOF-SIMS, EPMA, TEM / SEM-EDS, microscopic IR, microscopic laser Raman spectroscopy, or the like. More specifically, the penetration distribution can be evaluated, for example, by the following method. The cross section of the treated fiber is measured by a fluorescence imaging method using a confocal laser microscope, and if a clear difference in fluorescence intensity inside the fiber is observed in the fluorescence imaging image compared to an untreated fiber, it can be determined that component (A) has penetrated into the fiber. For example, a fiber treated with a styrene-maleic acid copolymer or a salt thereof as component (A) has a wavelength of 400 nm that is specific to styrene-maleic acid copolymers, and therefore, fluorescence imaging can be performed at an excitation wavelength of 400 nm and a detection wavelength of 425 to 475 nm. As the confocal laser microscope, for example, AIRHD25 (manufactured by Nikon Corporation) can be used.

[0103] [Component (B)] The fiber treatment agent of the present invention contains water as component (B). The content of component (B) is the remainder excluding component (A) and the optional components described below. For example, the content of component (B) in the fiber treatment agent of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and even more preferably 40% by mass or more, and is preferably 98% by mass or less, more preferably 97% by mass or less, even more preferably 96% by mass or less, even more preferably 95% by mass or less, even more preferably 90% by mass or less, and even more preferably 85% by mass or less. That is, the content of component (B) in the fiber treatment agent of the present invention is preferably 10 to 98% by mass, more preferably 20 to 97% by mass, even more preferably 30 to 96% by mass, even more preferably 40 to 95% by mass, even more preferably 40 to 90% by mass, and even more preferably 40 to 85% by mass.

[0104] [Component (C)] From the viewpoint of improving the water resistance, heat resistance, and thermal shape memory ability of fibers, the fiber treatment agent of the present invention preferably further contains a polyvalent metal element as component (C). The larger the molecular weight of component (A), which modifies the interior of a fiber, the stronger the interaction with the fiber, and a high modifying effect is expected. However, if the molecular weight is too large, penetration into the interior of the fiber becomes difficult. In contrast, it is believed that by allowing component (A) and component (C) to penetrate into the interior of the fiber, the components (A) are salt-bridged by component (C) within the fiber, and a larger structure that interacts strongly with the fiber can be formed, resulting in a high modifying effect.

[0105] The polyvalent metal element may be, for example, a metal (e.g., ultrafine metal particle), an ion, or a salt, complex, or the like. As the salt of the polyvalent metal, either an organic salt or an inorganic salt may be used. Among these, inorganic salts of polyvalent metals are preferred, and polyvalent metal salts of hard acids or intermediate acids that easily interact with the coordinating functional group (hard base, intermediate base) of component (A) are more preferred, and polyvalent metal salts of hard acids or intermediate acids are even more preferred. Specifically, for example, aluminum salts and zirconium salts are preferred, and aluminum sulfate, aluminum chloride, and zirconium sulfate are even more preferred.

[0106] The content of component (C) in the fiber treatment agent of the present invention is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, even more preferably 0.001% by mass or more, and even more preferably 0.007% by mass or more, in terms of metal element amount, from the viewpoints of enhancing the salt-bridge action of component (C) between components (A) in the fiber and improving the water resistance, heat resistance, and thermal shape memory ability of the fiber; and from the viewpoints of preventing precipitation of components (A) and (C) in the fiber treatment agent and a decrease in the penetration efficiency into the fiber, the content is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.10% by mass or less, and even more preferably 0.07% by mass or less. That is, the content of component (C) in the fiber treatment agent is preferably 0.0001 to 1.0% by mass, more preferably 0.0005 to 0.5% by mass, even more preferably 0.001 to 0.10% by mass, and even more preferably 0.007 to 0.07% by mass.

[0107] <Other Components> The fiber treating agent of the present invention may contain a pH adjuster as another component.

[0108] (pH Adjusting Agent) The pH adjusting agent is not particularly limited as long as it can adjust the pH to the desired level, and examples thereof include alkalis such as sodium hydroxide and potassium hydroxide, and acids such as phosphoric acid, sulfuric acid and hydrochloric acid.

[0109] [Fiber Treatment Kit] The fiber treatment kit according to the first embodiment includes the fiber treatment agent of the present invention (hereinafter also referred to as "Agent 1a") and another fiber treatment agent of the present invention having a pH 1.0 or more lower than that of Agent 1a (hereinafter also referred to as "Agent 2a"). The specific configurations of the fiber treatment agents in Agents 1a and 2a and the applicable fibers are as described above. The pH of Agents 1a and 2a may be adjusted to the desired pH using the pH adjuster described above. From the viewpoints of promoting penetration and coordination into fibers, improving water resistance, heat resistance, and thermal shape memory, and adjusting the pH of Agent 2a to be 1.0 or more lower than that of Agent 1a to enhance the modifying effect, the pH of Agent 1a is preferably 3.0 or higher, more preferably 4.0 or higher, even more preferably 4.5 or higher, and even more preferably 5.5 or higher; and preferably 11.0 or lower, more preferably 9.0 or lower, even more preferably 8.0 or lower, and even more preferably 7.0 or lower. That is, the pH of Agent 2a is preferably 3.0 to 11.0, more preferably 4.0 to 9.0, even more preferably 4.5 to 8.0, and even more preferably 5.5 to 7.0. From the viewpoints of promoting penetration and coordination into fibers, improving water resistance, heat resistance, and thermal shape memory ability, and of adjusting the pH of Agent 2a to be 1.0 or more lower than Agent 1a to enhance the modifying effect, the pH of Agent 2a is preferably 2.0 or higher, more preferably 3.0 or higher, and even more preferably 3.5 or higher, and is also preferably 10.0 or lower, more preferably 8.0 or lower, even more preferably 7.0 or lower, and even more preferably less than 5.5. That is, the pH of Agent 2a is preferably 2.0 to 10.0, more preferably 3.0 to 8.0, even more preferably 3.5 to 7.0, and even more preferably 3.5 or higher but less than 5.5.

[0110] The ratio of Agent 1a to Agent 2a in the fiber treatment kit is preferably 1 / 5 to 5 / 1 by mass (Agent 1a / Agent 2a), from the viewpoints of promoting penetration and coordination into the fiber and improving water resistance, heat resistance, and thermal shape memory ability. Furthermore, the fiber treatment kit according to the first embodiment can also be used to repeatedly treat naturally derived fibers with Agent 1a by finally performing a step of treating the naturally derived fibers with Agent 2a. Specifically, for example, naturally derived fibers can be treated with Agent 1a, and then further treated with Agent 1a two or three or more times, and then treated with Agent 2a.

[0111] The fiber treatment kit of the first embodiment may contain the first a agent and the second a agent in separate containers, or may contain them individually in independent areas separated by partitions within a single container.

[0112] The fiber treatment kit according to the second embodiment comprises the fiber treatment agent of the present invention (hereinafter also referred to as "agent 1b") and a component (D) having a hydrogen bond term δH of the Hansen solubility parameter of 18.3 MPa. 1 / 2 The fiber treatment kit further comprises an additional fiber treatment agent (hereinafter also referred to as "agent 2b") containing a compound or salt thereof having at least one carboxy group or salt thereof and no fused ring, which is as follows (excluding component (A)). Agent 1b may be a single-component or a two-component type. When agent 1b is a single-component type, the specific configuration of agent 1b is as described above. In this case, the fiber treatment kit is a two-component type comprising agents 1b and 2b. Furthermore, when agent 1b is a two-component type, for example, as in the first embodiment, the fiber treatment agent of the present invention can be composed of a fiber treatment agent (hereinafter also referred to as "agent 1b-1") and a fiber treatment agent (hereinafter also referred to as "agent 1b-2") having a pH 1.0 or more lower than that of agent 1b-1. The specific configurations of agents 1b-1 and 1b-2 are as described in the first embodiment. In this case, the fiber treatment kit is a three-component type comprising agents 1b-1, 1b-2, and 2b. The fibers to which the fiber treatment kit according to this embodiment is applicable are as described above.

[0113] Examples of the compound of component (D) include the following (D1) and (D2): (D1) A compound having a hydrogen bond term δH of the Hansen solubility parameter of 18.3 MPa. 1 / 2 An aromatic compound (D2) having at least one carboxy group or a salt thereof and no condensed ring, wherein the hydrogen bond term δH of the Hansen solubility parameter is 11.0 MPa or less. 1 / 2 Over 18.3 MPa 1 / 2 When component (D) is in the form of a salt, the salt is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt, and even more preferably a sodium salt.

[0114] Examples of the aromatic compound of component (D1) include compounds represented by the following general formula (1) or general formula (2) or salts thereof.

[0115]

[0116] [wherein =X represents a methylidene group or an oxo group, and R 1 represents a hydrogen atom, a hydroxyl group, or an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an aralkyloxy group which may have a substituent, and R 2 represents an o-phenylene group, an m-phenylene group, a p-phenylene group, a benzylidene group, or an alkylene group which may have a substituent, 2 does not have an aryl group, R 1 is an aryl group, an aryloxy group, or an aralkyloxy group.

[0117]

[0118] [In the formula, A 1 ~A 5 each independently represents a hydrogen atom, 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.

[0119] Examples of the aromatic compound represented by the general formula (1) include compounds represented by the following general formula (1A), (1B) or (1C).

[0120]

[0121] [In the formula, B 1 ~B 4 each independently represents a hydrogen atom, 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; R 3 represents a hydroxy group or a group represented by the following general formula (1A)-a or (1A)-b.

[0122]

[0123] [In the formula, B 5 ~B 9 is the above B 1 ~B 4 has the same meaning as 4 represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 2.

[0124]

[0125] [In the formula, D 1 ~D 4 each independently represents a hydrogen atom, 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; E 1 ~E 5 are each independently 1 ~D 4 or a group represented by general formula (1B)-a.]

[0126]

[0127] (wherein m represents an integer of 0 to 4.)

[0128]

[0129] [In the formula, R 6 represents a hydrogen atom or a group represented by general formula (1C)-a, G 1 and G 2each independently represents a hydrogen atom, an acetyl group, a halogen atom, an aryl group which may have a substituent, an aralkyl group or an arylalkenyl group having 7 to 12 carbon atoms, or a linear or branched alkyl group, alkenyl group, alkoxy group, alkenyloxy group or aroyloxy group having 1 to 6 carbon atoms. 6 is a hydrogen atom, G 1 and G 2 At least one of the groups is an aryl group, an aralkyl group having 7 to 12 carbon atoms, an arylalkenyl group, or an aroyloxy group, each of which may have a substituent.]

[0130]

[0131] [In the ceremony, J 1 ~J 5 each independently represents a hydrogen atom, 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.

[0132] Among the compounds represented by general formula (1A), R 3 The compound in which is a hydroxy group is 2-carboxybenzoic acid (phthalic acid) (Hansen solubility parameter hydrogen bond term δH: 13.4 MPa) 1 / 2 ) (Hereinafter, the numerical value in parentheses after each compound name indicates the hydrogen bond parameter δH calculated by the above-mentioned method). Among the compounds represented by general formula (1A), R 3 As a compound in which is a group represented by general formula (1A)-a, 2-[[(4-vinylbenzyl)oxy]carbonyl]benzoic acid (7.0 MPa 1 / 2 Among the compounds represented by general formula (1A), R 3 As a compound in which is a group represented by general formula (1A)-b, 2-[[2-(acryloyloxy)ethoxy]carbonyl]benzoic acid (9.1 MPa 1 / 2 ), 2-[[2-(methacryloyloxy)ethoxy]carbonyl]benzoic acid (8.4 MPa 1 / 2 ) are listed.

[0133] The compound represented by the general formula (1B) is 2-benzoylbenzoic acid (7.5 MPa1 / 2 ), 2-(2-methylbenzoyl)benzoic acid (6.9 MPa 1 / 2 ), 2-(3-methylbenzoyl)benzoic acid (6.6 MPa 1 / 2 ), 2-(4-methylbenzoyl)benzoic acid (7.2 MPa 1 / 2 ), 2-(2-chlorobenzoyl)benzoic acid (7.1 MPa 1 / 2 ), 2-(3-chlorobenzoyl)benzoic acid (6.9 MPa 1 / 2 ), 2-(4-chlorobenzoyl)benzoic acid (7.5 MPa 1 / 2 ), 2-[4-[2-(2-(acryloyloxy)ethoxy)ethoxy]benzoyl]benzoic acid (8.7 MPa 1 / 2 ) are listed.

[0134] Among the compounds represented by general formula (1C), R 6 As a compound in which is a hydrogen atom, phenylsuccinic acid (15.8 MPa 1 / 2 ), 2,3-diphenylsuccinic acid (11.9 MPa 1 / 2 ), (+)-di-p-toluoyl-D-tartaric acid (10.2 MPa 1 / 2 Among the compounds represented by general formula (1c), R 6 As a compound in which is a group represented by general formula (1c)-a, 4-oxo-4-[(4-vinylbenzyl)oxy]butanoic acid (10.1 MPa 1 / 2 ) are listed.

[0135] In addition, as a compound that is not included in any of the general formulas (1A), (1B), and (1C) but is included in the general formula (1), there is 3-carboxybenzoic acid (isophthalic acid) (12.9 MPa 1 / 2 ), 4-carboxybenzoic acid (terephthalic acid) (13.7 MPa 1 / 2 ), 3-benzoylbenzoic acid (7.2 MPa 1 / 2 ), 4-benzoylbenzoic acid (7.9 MPa 1 / 2 The number in parentheses after each compound name is the hydrogen bond parameter δH calculated by the method described above.

[0136] Specific examples of the aromatic compound represented by the general formula (2) include benzoic acid (9.5 MPa) 1 / 2), 2-methylbenzoic acid (8.4 MPa 1 / 2 ), 3-methylbenzoic acid (8.0 MPa 1 / 2 ), 4-methylbenzoic acid (8.8 MPa 1 / 2 ), 2-ethylbenzoic acid (7.7 MPa 1 / 2 ), 3-ethylbenzoic acid (7.4 MPa 1 / 2 ), 4-ethylbenzoic acid (8.1 MPa 1 / 22 ), 2-propylbenzoic acid (7.0 MPa 1 / 2 ), 3-propylbenzoic acid (6.7 MPa 1 / 2 ), 4-propylbenzoic acid (7.4 MPa 1 / 2 ), 2-isopropylbenzoic acid (6.7 MPa 1 / 2 ), 3-isopropylbenzoic acid (6.5 MPa 1 / 2 ), 4-isopropylbenzoic acid (7.1 MPa 1 / 2 ), 2-n-butylbenzoic acid (6.8 MPa 1 / 2 ), 3-n-butylbenzoic acid (6.5 MPa 1 / 2 ), 4-n-butylbenzoic acid (7.2 MPa 1 / 2 ), 2-tert-butylbenzoic acid (6.1 MPa 1 / 2 ), 3-tert-butylbenzoic acid (5.9 MPa 1 / 2 ), 4-tert-butylbenzoic acid (6.5 MPa 1 / 2 ), 2-vinylbenzoic acid (8.0 MPa 1 / 2 ), 3-vinylbenzoic acid (7.7 MPa 1 / 2 ), 4-vinylbenzoic acid (8.5 MPa 1 / 2 ), 2-acetylbenzoic acid (8.6 MPa 1 / 2 ), 3-acetylbenzoic acid (8.2 MPa 1 / 2 ), 4-acetylbenzoic acid (8.9 MPa 1 / 2 ), 2-methoxybenzoic acid (9.7 MPa 1 / 2 ), 3-methoxybenzoic acid (9.3 MPa 1 / 2 ), 4-methoxybenzoic acid (10.1 MPa 1 / 2 ), 2-chlorobenzoic acid (8.7 MPa 1 / 2 ), 3-chlorobenzoic acid (8.4 MPa 1 / 2 ), 4-chlorobenzoic acid (9.2 MPa 1 / 2 ), 2-bromobenzoic acid (9.1 MPa 1 / 2), 3-bromobenzoic acid (8.8 MPa 1 / 2 ), 4-bromobenzoic acid (10.1 MPa 1 / 2 Among these, 4-ethylbenzoic acid, 4-vinylbenzoic acid, and benzoic acid are preferred.

[0137] Furthermore, an example of the compound of component (D1) other than the compounds of general formulas (1) and (2) is phenylbutanoic acid.

[0138] Examples of the compound of component (D2) include potassium 2,4-hexadienoate (12.5 MPa 1 / 2 ) can be mentioned.

[0139] The hydrogen bond parameter δH of the aromatic compound of component (D1) is preferably 16.0 MPa from the viewpoint of appropriately hydrophobizing the inside of the fiber. 1 / 2 Less than or equal to 13.5 MPa, more preferably 1 / 2 More preferably, 12.0 MPa or less 1 / 2 More preferably, 10.0 MPa or less 1 / 2 is preferably 3.0 MPa or less. 1 / 2 More preferably, 4.0 MPa 1 / 2 More preferably, 5.0 MPa 1 / 2 That's all.

[0140] The hydrogen bond parameter δH of the compound of component (D2) is preferably 16.0 MPa from the viewpoint of appropriately hydrophobizing the inside of the fiber. 1 / 2 Not more than 15.0 MPa, more preferably 1 / 2 More preferably, 14.0 MPa or less 1 / 2 More preferably, 13.0 MPa or less 1 / 2 and preferably 11.0 MPa or less. 1 / 2 More preferably, 11.5 MPa 1 / 2 More preferably, 12.0 MPa 1 / 2 That's all.

[0141] From the viewpoints of promoting penetration and coordination into fibers and improving water resistance, heat resistance, and thermal shape memory ability, the pH of agent 2b is preferably 4.0 or higher, more preferably 5.0 or higher, even more preferably 5.5 or higher, and preferably 9.0 or lower, more preferably 8.0 or lower, even more preferably 7.0 or lower. That is, the pH of agent 2b is preferably 4.0 to 9.0, more preferably 5.0 to 8.0, even more preferably 5.5 to 7.0.

[0142] From the viewpoints of promoting penetration and coordination into fibers and improving water resistance, heat resistance, and thermal shape memory ability, the content of component (D) in component 2b is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 20% by mass or more, and preferably 60% by mass or less, more preferably 55% by mass or less, even more preferably 50% by mass or less, even more preferably 40% by mass or less, and even more preferably 35% by mass or less. That is, the content of component (D) in component 2b is preferably 0.1 to 60% by mass, more preferably 1 to 55% by mass, even more preferably 5 to 50% by mass, even more preferably 10 to 40% by mass, and even more preferably 20 to 35% by mass. Note that when component (D) is a salt, the content of component (D) is expressed as a value converted to the free acid.

[0143] The content of component (D) in agent 2b may be determined based on the content of component (D) in fibers treated with the additional fiber treatment agent of the present invention. For example, from the viewpoint of promoting retention and coordination in the fibers and improving water resistance, heat resistance, and thermal shape memory ability, the content of component (D) in fibers treated with the additional fiber treatment agent of the present invention is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. That is, the content of component (D) in fibers treated with the additional fiber treatment agent is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass. The amount of component (D) is quantified by selecting an appropriate method that does not decompose component (D) and can dissolve the fibers, and then dissolving and extracting the fibers. Next, after appropriately diluting the extracted solution, the absorbance is measured using an ultraviolet-visible-near-infrared spectrophotometer (for example, V-560 (manufactured by JASCO Corporation)) at an absorption wavelength suitable for the quantitative determination of component (D), and the content of component (D) is calculated from the absorbance.

[0144] The ratio of Agent 1b to Agent 2b in the fiber treatment kit is preferably 1 / 5 to 5 / 1 by mass (Agent 1b / Agent 2b), from the viewpoints of promoting penetration and coordination into fibers and improving water resistance, heat resistance, and thermal shape memory ability. When Agent 1b is a two-component type, the ratio of each component in Agent 1b can be selected appropriately. For example, when Agent 1b is composed of Agents 1b-1 and 1b-2, the mass ratio (total of Agents 1b-1 and 1b-2 / Agent 2b) is preferably twice the mass ratio of Agent 1b. That is, the mass ratio (total of Agents 1b-1 and 1b-2 / Agent 2b) is preferably 2 / 5 to 10 / 1, more preferably 2 / 3 to 6 / 1, and even more preferably 2 / 2 to 4 / 1.

[0145] The fiber treatment kit according to the second embodiment may contain agents 1b and 2b in separate containers, or may contain them in separate areas separated by a partition within a single container. Furthermore, when agent 1b is a two-component type, for example, the three agents, agent 1b-1, agent 1b-2, and agent 2b, may be contained in separate containers or may be contained in separate areas separated within a single container.

[0146] [Storage method for fiber treatment agent and fiber treatment kit] When transporting and storing the fiber treatment agent and fiber treatment kit of the present invention before application to fibers, or when transporting and storing raw materials before preparing the fiber treatment agent and fiber treatment kit, from the standpoint of stability, the storage temperature can be set to low or high, or nitrogen can be filled into the void space in the storage container.

[0147] From the viewpoint of stability, the storage temperature of the fiber treatment agent and fiber treatment kit is preferably 1°C or higher, more preferably 2°C or higher, even more preferably 5°C or higher, and is preferably 80°C or lower, more preferably 70°C or lower, even more preferably 60°C or lower.

[0148] [Textile Treatment Method] <Basic Treatment> By treating naturally-derived fibers with the fiber treatment agent of the present invention using a method including the following step (i), the penetration and coordination of component (A) into naturally-derived fibers is promoted, and water resistance and thermal shape memory ability, which are problems specific to naturally-derived fibers, can be improved. Step (i) A step of immersing naturally-derived fibers having a fiber swelling rate in water of 200% or more calculated by the above formula (1), in the fiber treatment agent of the present invention.

[0149] In this step, the naturally derived fibers to be immersed in the fiber treatment agent are not particularly limited as long as they have a fiber swelling ratio in water of 200% or more as calculated by the above formula (1). The preferred fiber swelling ratio in water for naturally derived fibers is as described above. For example, undried regenerated collagen fibers can be used, preferably undried regenerated collagen fibers that are prepared by solubilizing a collagen raw material to prepare a spinning solution, ejecting this from a spinning nozzle into a coagulation bath to form fibers, and then recovering them without drying.

[0150] The amount of fiber treatment agent in which the naturally-derived fibers are immersed, expressed as a liquor ratio to the mass of the naturally-derived fibers (mass of fiber treatment agent / mass of naturally-derived fibers), is preferably 2 or more, more preferably 3 or more, even more preferably 5 or more, even more preferably 10 or more, even more preferably 20 or more, and is preferably 500 or less, more preferably 250 or less, even more preferably 100 or less, and even more preferably 50 or less. That is, the liquor ratio is preferably 2 to 500, more preferably 3 to 250, even more preferably 5 to 100, even more preferably 10 to 100, even more preferably 20 to 100, and even more preferably 20 to 50.

[0151] In this step, the naturally derived fibers can be immersed in the fiber treatment agent at room temperature (20°C ± 15°C), or they may be heated. This heating is carried out by heating the fiber treatment agent. This heating may be carried out by immersing the naturally derived fibers in a heated fiber treatment agent, or by immersing the naturally derived fibers in a low-temperature fiber treatment agent and then heating them. The temperature of the fiber treatment agent is preferably 20°C or higher, more preferably 25°C or higher, and even more preferably 30°C or higher, in order to achieve the effects of the present invention by allowing component (A) to penetrate into the naturally derived fibers and increasing the interaction with the fiber-constituting molecules of the fibers, such as protein molecules. Furthermore, in order to prevent the naturally derived fibers from being denatured and degraded by heat, the temperature is preferably less than 100°C, more preferably 80°C or lower, even more preferably 70°C or lower, even more preferably 60°C or lower, and even more preferably 50°C or lower. That is, the temperature is preferably 20°C or higher and lower than 100°C, more preferably 25 to 80°C, even more preferably 30 to 70°C, still more preferably 30 to 60°C, and even more preferably 30 to 50°C.

[0152] The immersion time in this step is adjusted appropriately depending on the heating temperature, but is, for example, preferably 15 minutes or more, more preferably 30 minutes or more, even more preferably 1 hour or more, still more preferably 3 hours or more, still more preferably 5 hours or more, and still more preferably 10 hours or more from the viewpoint of exhibiting the effect of improving the stretchability of the naturally derived fiber, and is preferably 48 hours or less, more preferably 33 hours or less, and still more preferably 30 hours or less to suppress damage to the naturally derived fiber. That is, the immersion time is preferably 15 minutes to 48 hours, more preferably 30 minutes to 33 hours, still more preferably 1 hour to 30 hours, still more preferably 3 hours to 30 hours, still more preferably 5 hours to 30 hours, and still more preferably 10 hours to 30 hours.

[0153] This step is preferably carried out in an environment in which evaporation of water is suppressed. Specific means for suppressing evaporation of water include covering the container of the fiber treatment agent in which the naturally derived fibers are immersed with a film-like substance, cap, lid, or the like made of a material that is impermeable to water vapor.

[0154] After this step, the naturally-derived fibers may or may not be rinsed, but rinsing is preferred from the viewpoint of preventing deterioration of the feel of the surface of the naturally-derived fibers due to excess component (A).

[0155] These treatments are believed to allow component (A) to penetrate into the naturally occurring fibers and to strongly coordinate with metals, such as polyvalent metals, within the fibers, thereby producing various effects.

[0156] When using the fiber treatment kit of the present invention, the naturally-derived fiber may be treated with each agent contained in the kit by a method including step (i) as described above. The order in which the agents are applied is not particularly limited, and the naturally-derived fiber may be treated in any order.

[0157] <Additional Treatments That May Be Implemented> In addition to the above-described step (i), one or more treatments selected from bleaching, dyeing, drying, surface finishing, heat treatment for further improving fiber stretchability (tenacity), and suppression or removal of coloring may be additionally carried out. Note that known bleaching agents and dyeing agents can be used for bleaching and dyeing, and conventionally known methods can be adopted for each of the bleaching, dyeing, drying, surface finishing, heat treatment, and suppression or removal of coloring.

[0158] In this case, the bleaching and dyeing treatments may be performed before or after the above-mentioned step (i). Furthermore, a combination of multiple treatments may be added. When both bleaching and dyeing are added, any of the treatments may be performed first, except that bleaching must be performed before dyeing, and another treatment may be performed between bleaching and dyeing.

[0159] On the other hand, drying, surface finishing, heat treatment for further improving fiber stretchability (tenacity), and suppression or removal of coloring must be performed after the above-mentioned step (i), but the order of the treatments with bleaching and dyeing is not particularly limited. Moreover, drying, surface finishing, heat treatment for further improving fiber stretchability (tenacity), and suppression or removal of coloring may be performed in any order.

[0160] (Bleaching) Bleaching is carried out by immersing the naturally derived fiber in a bleaching composition containing an alkaline agent, an oxidizing agent, and water. The bleaching composition is usually a two-component composition, with the first component containing an alkaline agent and water, and the second component containing an oxidizing agent and water. These two components are usually stored separately and mixed before immersing the naturally derived fiber.

[0161] Suitable alkaline agents include, but are not limited to, for example, ammonia and its salts; alkanolamines (monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol, etc.) and their salts; alkanediamines (1,3-propanediamine, etc.) and their salts; and carbonates (guanidine carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.); and mixtures thereof.

[0162] The content of the alkaline agent in the bleaching composition (in the case of a two-component type, a mixture of the first and second agents) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 7.5% by mass or less.

[0163] Suitable oxidizing agents include, but are not limited to, hydrogen peroxide, urea peroxide, melamine peroxide, and sodium bromate, with hydrogen peroxide being preferred.

[0164] The content of the oxidizing agent in the bleaching 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 even more preferably 9% by mass or less.

[0165] When the first and second agents are stored separately, the pH of the second agent at 25°C is preferably 2 or higher, more preferably 2.5 or higher, and preferably 6 or lower, more preferably 4 or lower. This pH can be adjusted with a suitable buffer. The pH of the bleaching composition at 25°C is preferably 6 or higher, more preferably 6.5 or higher, even more preferably 6.8 or higher, and preferably 11 or lower, more preferably 10.5 or lower, even more preferably 10 or lower.

[0166] (Dyeing) Dyeing is carried out by immersing the naturally occurring fiber in the 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.

[0167] The type of direct dye is not particularly limited, and any direct dye suitable for dyeing can be used. Examples of direct dyes include anionic dyes, nitro dyes, disperse dyes, cationic dyes, and dyes having an azophenol structure selected from the group consisting of HC Red 18, HC Blue 18, and HC Yellow 16 below, as well as salts thereof, and mixtures thereof.

[0168]

[0169] Examples of cationic dyes include, but are not limited to, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 99, Basic Brown 4, Basic Brown 16, Basic Brown 17, Natural Brown 7, Basic Green 1, Basic Orange 31, Basic Red 2, Basic Red 12, Basic Red 22, Basic Red 51, Basic Red 76, Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 10, Basic Violet 14, Basic Yellow 57, and Basic Yellow 87, and mixtures thereof. Basic Red 51, Basic Orange 31, Basic Yellow 87, and mixtures thereof are particularly preferred.

[0170] Examples of anionic dyes 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, Food Yellow No. 8, and D&C Brown No. Examples of suitable dyes include, but are not limited to, D&C Green 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 thereof (sodium salts, potassium salts, etc.), and mixtures thereof.

[0171] Among these, preferred anionic dyes are Acid Black 1, Acid Red 52, Acid Violet 2, Acid Violet 43, Acid Red 33, Acid Orange 4, Acid Orange 7, Acid Red 27, Acid Yellow 3, and Acid Yellow 10, as well as salts thereof. More preferred anionic dyes are Acid Red 52, Acid Violet 2, Acid Red 33, Acid Orange 4, and Acid Yellow 10, as well as salts and mixtures thereof.

[0172] Examples of nitro dyes include HC Blue No. 2, HC Blue No. 4, HC Blue No. 5, HC Blue No. 6, HC Blue No. 7, HC Blue No. 8, HC Blue No. 9, HC Blue No. 10, HC Blue No. 11, HC Blue No. 12, HC Blue No. 13, HC Brown No. 1, HC Brown No. 2, HC Green No. 1, HC Orange No. 1, HC Orange No. 2, HC Orange No. 3, HC Orange No. 5, HC Red BN, HC Red No. 1, HC Red No. 3, HC Red No. 7, HC Red No. 8, HC Red No. 9, HC Red No. 10, and HC Red No. 11, HC Red No. 13, HC Red No. 54, HC Red No. 14, HC Violet BS, HC Violet No. 1, HC Violet No. 2, HC Yellow No. 2, HC Yellow No. 4, HC Yellow No. 5, HC Yellow No. 6, HC Yellow No. 7, HC Yellow No. 8, HC Yellow No. 9, HC Yellow No. 10, HC Yellow No. 11, HC Yellow No. 12, HC Yellow No. 13, HC Yellow No. 14, HC Yellow No. Examples of suitable amines include, but are not limited to, 15,2-amino-6-chloro-4-nitrophenol, picramic acid, 1,2-diamino-4-nitrobenzole, 1,4-diamino-2-nitrobenzole, 3-nitro-4-aminophenol, 1-hydroxy-2-amino-3-nitrobenzole, and 2-hydroxyethylpicramic acid, and mixtures thereof.

[0173] Disperse dyes include, but are not limited to, for example, Disperse Blue 1, Disperse Black 9, and Disperse Violet 1, and mixtures thereof.

[0174] These direct dyes can be used alone or in combination of two or more kinds, and direct dyes having different ionic properties can also be used in combination.

[0175] 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 even more preferably 0.05% by mass or more, from the viewpoint of obtaining sufficient dyeability, 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 even more preferably 3.0% by mass or less, from the viewpoint of blendability.

[0176] When the dye composition contains only direct dyes as dyes, an oxidizing agent is not required to dye naturally occurring fibers, but if it is desired to lighten the color of naturally occurring fibers, an oxidizing agent can also be included in the composition.

[0177] When the dye composition contains an oxidation dye, it is usually in a two-component form, with the first component containing an oxidation dye intermediate (precursor and coupler) and an alkali agent, and the second component containing an oxidizing agent such as hydrogen peroxide. These two components are usually stored separately and mixed before soaking the naturally derived fiber.

[0178] The oxidation dye intermediate is not particularly limited, and any known precursors and couplers that are commonly used in dyed products can be suitably used.

[0179] Examples of precursors include paraphenylenediamine, toluene-2,5-diamine, 2-chloro-paraphenylenediamine, N-methoxyethyl-paraphenylenediamine, N-phenyl-paraphenylenediamine, N,N-bis(2-hydroxyethyl)paraphenylenediamine, 2-(2-hydroxyethyl)paraphenylenediamine, 2,6-dimethyl-paraphenylenediamine, 4,4'-diaminodiphenylamine, 1,3-bis(N-(2-hydroxyethyl)-N-(4-aminophenyl)amino)-2-propanol, PEG-3,3,2'-paraphenylenediamine, paraaminophenol, paramethylaminophenol, 3- Examples of suitable amino acids include, but are not limited to, methyl-4-aminophenol, 2-aminomethyl-4-aminophenol, 2-(2-hydroxyethylaminomethyl)-4-aminophenol, orthoaminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 2-amino-5-acetamidophenol, 3,4-diaminobenzoic acid, 5-aminosalicylic acid, 2,4,5,6-tetraaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine, 4,5-diamino-1-(4'-chlorobenzyl)pyrazole, 4,5-diamino-1-hydroxyethylpyrazole, and salts of these substances and mixtures thereof.

[0180] Examples of couplers include metaphenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4-(2-hydroxyethylamino)anisole, 2,4-diamino-5-methylphenetole, 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, meta-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-meta-aminophenol, 2-methyl-4-methoxy-5-(2-hydroxyethylamino)phenol, 2-methyl-4-fluoro-5-aminophenol, and para-amino ortho-cresol. sol, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-isopropyl-5-methylphenol, 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 6-hydroxybenzomorpholine, 3,4-methylenedioxyphenol, 2-bromo-4,5-methylenedioxyphenol Examples of suitable hydroxybenzoates include, but are not limited to, 3,4-methylenedioxyaniline, 1-(2-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-diaminopyridine, 2,3-diamino-6-methoxypyridine, 2-methylamino-3-amino-6-methoxypyridine, 2-amino-3-hydroxypyridine, 2,6-diaminopyridine, and salts of these substances and mixtures thereof.

[0181] The contents of the precursor and the coupler in the dye composition are each preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 10% by mass or less, more preferably 7.5% by mass or less, and even more preferably 5.0% by mass or less.

[0182] When the dye composition contains an oxidation dye, it further contains an alkaline agent. Suitable alkaline agents include, but are not limited to, ammonia and its salts, alkanolamines (monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol, etc.) and their salts, alkanediamines (1,3-propanediamine, etc.) and their salts, and carbonates (guanidine carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.), and mixtures thereof.

[0183] The content of the alkaline agent in the dye composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 7.5% by mass or less.

[0184] When the dye composition contains an oxidation dye, the composition containing the oxidizing agent (second agent) is stored separately from the composition containing the oxidation dye (first agent), and they are mixed before immersing the naturally derived fiber. Suitable oxidizing agents include, but are not limited to, hydrogen peroxide, urea peroxide, melamine peroxide, and sodium bromate. Among these oxidizing agents, hydrogen peroxide is preferred.

[0185] 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 even more preferably 9% by mass or less.

[0186] 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, more preferably 4 or less. This pH can be adjusted with a suitable buffer. The pH of the staining composition obtained by mixing the first and second agents at 25°C is preferably 6 or more, more preferably 6.5 or more, even more preferably 6.8 or more, and preferably 11 or less, more preferably 10.5 or less, even more preferably 10 or less.

[0187] When the dye composition contains an oxidation dye, it may further contain a direct dye as exemplified above.

[0188] The dye composition may preferably further contain surfactants, conditioning components, etc., as described below, and may preferably take the form of a solution, emulsion, cream, paste, or mousse.

[0189] The temperature of the dye composition is preferably 0°C or higher, more preferably 10°C or higher, and even more preferably 20°C or higher, from the viewpoint of efficiently penetrating and diffusing the dye composition into the naturally-derived fiber and further enhancing the dyeing effect, and is preferably 90°C or lower, and more preferably 80°C or lower.

[0190] (Drying) The fibers treated in the above step (i) are preferably dried to improve subsequent handling properties and to improve fixation of component (A) to the fibers. The drying temperature is preferably 100°C or lower, more preferably 80°C or lower.

[0191] (Surface Finishing) Surface finishing is performed by immersing the naturally derived fibers in a surface finishing agent. The surface finishing agent may contain a cationic surfactant, silicone, or cationic polymer. In this specification, the term "cationic polymer" refers to a polymer having a cationic group or a group that can be ionized to a cationic group, and also includes amphoteric polymers that are cationic as a whole. The content of other components can be appropriately selected within a range that does not impair the effects of the present invention.

[0192] (Cationic Surfactant) 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 mono-long-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.

[0193] Preferably, the at least one mono-long chain alkyl quaternary ammonium surfactant is selected from compounds represented by the following general formula (6):

[0194]

[0195] [In the formula, R 5 is a saturated or unsaturated, straight-chain 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, and p represents an integer of 1 to 4), R 6 , R 7 and R 8 each independently represents an alkyl group having 1 to 4 carbon atoms or a hydroxylalkyl group having 1 to 4 carbon atoms; An - represents a chloride ion, a bromide ion, a methosulfate ion, or an ethosulfate ion.

[0196] Suitable cationic surfactants include, for example, long-chain quaternary ammonium compounds such as cetyltrimethylammonium chloride, myristyltrimethylammonium chloride, behentrimonium chloride, cetyltrimethylammonium bromide, and stearamidopropyltrimonium chloride, which can be used alone or in mixtures thereof.

[0197] 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, from the viewpoint of improving the feel of the surface of naturally-derived fibers after treatment and further enhancing the effects of the present invention.

[0198] (Silicone) The fiber treatment agent of the present invention may contain silicone to improve the feel of the surface of naturally-derived fibers after treatment and to improve the manageability of the fibers. The silicone is preferably at least one selected from dimethylpolysiloxane and amino-modified silicone.

[0199] As the dimethylpolysiloxane, any cyclic or acyclic dimethylpolysiloxane polymer can be used, and examples thereof include the SH200 series, BY22-019, BY22-020, BY11-026, B22-029, BY22-034, BY22-050A, BY22-055, BY22-060, BY22-083, and FZ-4188 (all manufactured by Dow Corning Toray Co., Ltd.), and KF-9088, KM-900 series, MK-15H, and MK-88 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0200] 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 oil in which all or part of the terminal hydroxyl groups are end-capped with methyl groups or the like, and amodimethicone that is not end-capped. From the viewpoint of improving the feel of the surface of naturally-derived fibers after treatment and improving the manageability, preferred amino-modified silicones include, for example, compounds represented by the following formula:

[0201]

[0202] [wherein R′ is a hydrogen atom, a hydroxyl group, or R X indicates 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 a hydroxyl group, R" represents a divalent hydrocarbon group having 1 to 8 carbon atoms, a represents a number from 0 to 3, and b and c represent numbers whose sum is, on a number average, 10 or more and less than 20,000, preferably 20 or more and less than 3,000, more preferably 30 or more and less than 1,000, and even more preferably 40 or more and less than 800.

[0203] Specific examples of suitable commercially available amino-modified silicone products include amino-modified silicone oils such as SF8452c and SS3551 (both manufactured by Dow Corning Toray Co., Ltd.), and KF-8004, KF-867S, and KF-8015 (both manufactured by Shin-Etsu Chemical Co., Ltd.), and amodimethicone emulsions such as SM8704c, SM8904, BY22-079, FZ-4671, and FZ4672 (both manufactured by Dow Corning Toray Co., Ltd.).

[0204] From the viewpoint of improving the feel of the surface of naturally-derived fibers after treatment and further enhancing the effects 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.

[0205] (Cationic Polymer) The fiber treating agent of the present invention may contain a cationic polymer from the viewpoint of improving the feel of the surface of naturally occurring fibers after treatment.

[0206] The 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 are cationic as a whole. That is, examples include aqueous solutions containing amino groups or ammonium groups in the side chains of the polymer chain, or containing diallyl quaternary ammonium salts as structural units, such as cationic cellulose derivatives, cationic starch, cationic guar gum derivatives, polymers or copolymers of diallyl quaternary ammonium salts, and quaternized polyvinylpyrrolidone derivatives. Among these, from the viewpoints of improving the effects of softness, smoothness, and ease of combing during rinsing and shampooing, ease of manageability and moisturizing properties during drying, and the stability of the agent, one or more selected from polymers containing diallyl quaternary ammonium salts as structural units, quaternized polyvinylpyrrolidone derivatives, and cationic cellulose derivatives are preferred, and one or more selected from polymers or copolymers of diallyl quaternary ammonium salts and cationized cellulose derivatives are more preferred.

[0207] Specific examples of suitable diallyl quaternary ammonium salt polymers or copolymers include dimethyldiallylammonium chloride polymers (Polyquaternium-6, e.g., Marcoat 100; Lubrizol Advanced Materials), dimethyldiallylammonium chloride / acrylic acid copolymers (Polyquaternium-22, e.g., Marcoat 280, Marcoat 295; Lubrizol Advanced Materials), and dimethyldiallylammonium chloride / acrylamide copolymers (Polyquaternium-7, e.g., Marcoat 550; Lubrizol Advanced Materials).

[0208] A specific example of a suitable quaternized polyvinylpyrrolidone derivative is a polymer obtained by polymerizing a vinylpyrrolidone copolymer and dimethylaminoethyl methacrylate (Polyquaternium 11, for example, Gafcut 734, Gafcut 755, Gafcut 755N (all manufactured by Ashland)).

[0209] Specific examples of suitable cationized cellulose include polymers in which hydroxycellulose is loaded with glycidyltrimethylammonium chloride (Polyquaternium 10, for example, Leoguard G and Leoguard GP (both manufactured by Lion Corporation), Polymer JR-125, JR-400, JR-30M, LR-400, and LR-30M (both manufactured by Amerchol)), and hydroxyethylcellulose dimethyl diallylammonium chloride (Polyquaternium-4, for example, Cellcoat H-100 and Cellcoat L-200 (both manufactured by Akzo Nobel)).

[0210] From the viewpoint of improving the feel of the surface of naturally-derived fibers 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, even more preferably 0.05% by mass or more, and is preferably 20% by mass or less, more preferably 10% by mass or less.

[0211] (Post-heating: Heat treatment for further improving fiber stretchability (tenacity)) Furthermore, from the viewpoint of more effectively improving the stretchability of naturally-derived fibers, the naturally-derived fibers can be heated while being stretched under tension. For this heating, if the amount of naturally-derived fibers is small, it is preferable to use a hair iron or steam iron, but if the amount is large, equivalent results can be obtained by heating with hot air or high-temperature steam while applying tension with a winding machine.

[0212] The fiber draw ratio during heating is preferably 0.1% or more, more preferably 0.2% or more, and even more preferably 0.5% or more, from the viewpoint of more effectively improving the stretchability of the fiber, and is preferably 10% or less, more preferably 5.0% or less, and even more preferably 2.0% or less, from the viewpoint of suppressing damage to the fiber.

[0213] The heating temperature is preferably 60°C or higher, more preferably 80°C or higher, and even more preferably 100°C or higher, from the viewpoint of more effectively improving the stretchability of the fiber, and is preferably 240°C or lower, more preferably 180°C or lower, and even more preferably 150°C or lower, from the viewpoint of suppressing damage to the fiber.

[0214] The heating time is preferably 1 second or more, more preferably 10 seconds or more, and even more preferably 1 minute or more, from the viewpoint of more effectively improving the stretchability of the fiber, and is preferably 1 hour or less, more preferably 30 minutes or less, and even more preferably 5 minutes or less, from the viewpoint of suppressing damage to the fiber.

[0215] After heating, the naturally occurring fibers can be left standing in water while being stretched by applying tension, in order to more effectively improve the stretchability of the fibers.

[0216] The stretching ratio at this time is preferably 0.1% or more, more preferably 0.2% or more, and even more preferably 0.5% or more, from the viewpoint of more effectively improving the stretchability of the fiber, and is preferably 10% or less, more preferably 5.0% or less, and even more preferably 2.0% or less, from the viewpoint of suppressing damage to the fiber.

[0217] The water temperature is preferably 5°C or higher, more preferably 20°C or higher, and even more preferably 30°C or higher, from the viewpoint of more effectively improving the stretchability of the fibers, and is preferably 80°C or lower, more preferably 60°C or lower, and even more preferably 50°C or lower, from the viewpoint of suppressing damage to the fibers.

[0218] The standing time in water is preferably 1 minute or more, more preferably 5 minutes or more, and even more preferably 30 minutes or more, from the viewpoint of more effectively improving the stretchability of the fiber, and is preferably 48 hours or less, more preferably 24 hours or less, and even more preferably 3 hours or less, from the viewpoint of suppressing damage to the fiber.

[0219] Depending on the treatment conditions in step (i), this operation can make the fibers stretchable to a level comparable to that of human hair when dried.

[0220] (Suppression or removal of coloration) Furthermore, the coordinating functional group of component (A) is OH, O -In the case where the group is a group having the formula (I), the fiber can be treated with a composition containing a salt for the purpose of suppressing or removing discoloration in naturally occurring fibers that have been treated with the fiber treatment agent of the present invention. The salt may be either an organic or inorganic salt. Specific examples of the organic salt include organic salts with chelating activity such as disodium etidronate, disodium ethylenediaminetetraacetate, disodium catechol-3,5-disulfonate monohydrate, and sodium phytate, as well as sodium mercaptoethanesulfonate and sodium 2-naphthalenesulfonate. Examples of the inorganic salt include sulfites such as sodium sulfite, as well as sodium chloride and aluminum chlorohydrate. Examples of preferred salts for this purpose include, in the case of organic salts, reducing salts (such as salts of thiol compounds) and salts with metal chelating activity (such as sodium salts of edetic acid such as disodium ethylenediaminetetraacetate, and sodium salts of etidronic acid such as disodium etidronate), and in the case of inorganic salts, reducing salts (such as sulfites such as sodium sulfite). Among these, it is more preferable to use a reducing salt and a metal chelating salt in combination.

[0221] The discoloration of fibers caused by treatment with the fiber treatment agent of the present invention is thought to be both brownish oxidation discoloration (which can be dealt with by treatment with a reducing salt) and yellowish metal complex discoloration (which can be dealt with by treatment with a chelating agent), and it is thought that fiber discoloration can be better suppressed by carrying out a decolorization treatment corresponding to each of these.

[0222] The salt-containing composition is preferably an aqueous solution, and the pH of the composition is preferably 2.0 or more, more preferably 3.0 or more, and even more preferably 4.0 or more, from the viewpoint of not reducing the water resistance, stretchability (tenacity, i.e., high breaking elongation when the fiber is pulled), and heat resistance of the naturally derived fiber, and is preferably 9.0 or less, more preferably 7.0 or less, and even more preferably 6.0 or less.

[0223] The content of the salt in the composition is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 2.0% by mass or more, from the viewpoint of exhibiting the effect of suppressing or removing discoloration of naturally derived fibers, and is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5.0% by mass or less, from the viewpoint of not reducing the water resistance, stretchability (tenacity, i.e., high breaking elongation when the fiber is pulled), and heat resistance of the naturally derived fibers.

[0224] The treatment temperature with the salt-containing composition is preferably 5°C or higher, more preferably 10°C or higher, and even more preferably 20°C or higher, from the viewpoint of exerting the effect of suppressing or removing discoloration of naturally-occurring fibers, and is preferably 100°C or lower, more preferably 60°C or lower, and even more preferably 40°C or lower, from the viewpoint of avoiding damage to the fibers.

[0225] The treatment time with the salt-containing composition is preferably 1 second or more, more preferably 30 seconds or more, and even more preferably 1 minute or more, from the viewpoint of exerting the effect of suppressing or removing discoloration of naturally derived fibers, and is preferably 60 minutes or less, more preferably 30 minutes or less, and even more preferably 15 minutes or less, from the viewpoint of avoiding damage to the fibers.

[0226] The feel of the fibers that have been subjected to the various treatments described above can then be improved by a commonly used 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 hair treatment.

[0227] By treating naturally derived fibers with the above-described fiber treatment method, component (A) penetrates into the fibers and the coordinating functional groups of component (A) coordinate to the fibers, thereby solving problems specific to naturally derived fibers, and it is therefore possible to produce fibers with excellent water resistance and thermal shape memory ability, preferably fibers for head accessories, etc., and further, various textile products, preferably head accessories, etc., can be produced using the fibers. Note that examples of head accessories suitable in the present invention include hair wigs, hairpieces, weaving, hair extensions, braided hair, hair accessories, and doll hair.

[0228] With respect to the above-described embodiment, further preferred aspects of the present invention will be disclosed below.

[0229] <1> A fiber treatment agent for use in treating fibers having a fiber swelling rate in water of 200% or more as calculated by the following formula (1), comprising the following components (A) and (B):

[0230] <2> A fiber treatment kit for use in treating a fiber having a swelling rate in water of 200% or more as calculated by the following formula (1), comprising: a first fiber treatment agent containing the following components (A) and (B); and a second fiber treatment agent containing the following components (A) and (B), the second fiber treatment agent having a pH that is 1.0 or more lower than that of the first fiber treatment agent.

[0231] <3> A fiber treatment kit for use in treating a fiber having a swelling rate in water of 200% or more as calculated by the following formula (1), the fiber treatment kit comprising: a fiber treatment agent containing the following components (A) and (B); and an additional fiber treatment agent containing the following component (D).

[0232] (A) a compound having a coordinating functional group and a molecular weight of 1500 or more; (B) water;

[0233] Fiber swelling ratio in water (%) = [(w1 - w2) / w2] × 100 (1) (wherein w1 represents the mass (g) of the fiber measured after placing 1.0 g of fiber in a container filled with 100 g of ion-exchanged water, sealing the container, immersing the container in a water bath at 40°C for 30 minutes, removing the fiber from the container, and centrifuging for 1 minute at a centrifugal force of 220 [×g]. w2 represents the mass of the fiber measured after placing the fiber whose mass (w1) has been measured on filter paper and drying it at 105°C for 3 hours.)

[0234] (D) The hydrogen bond term δH of the Hansen solubility parameter is 18.3 MPa. 1 / 2 A compound or a salt thereof having at least one carboxy group or a salt thereof and no fused ring, which is the following (excluding component (A)):

[0235] <4> The fiber treatment agent according to <1> above, or the fiber treatment kit according to <2> or <3> above, having a fiber swelling rate in water of preferably 250% or more, more preferably 300% or more, even more preferably 350% or more, and preferably 1000% or less, more preferably 800% or less, even more preferably 600% or less, and even more preferably 500% or less. <5> The fiber treatment agent according to <1> above, or the fiber treatment kit according to <2> or <3> above, having a fiber swelling rate in water of preferably 250 to 1000%, more preferably 300 to 800%, even more preferably 350 to 600%, and still more preferably 350 to 500%.

[0236] <6> The fiber treatment agent according to any one of <1>, <4> and <5>, or the fiber treatment kit according to any one of <2> to <5>, wherein the fibers are preferably regenerated protein fibers, more preferably regenerated collagen fibers or regenerated silk fibers, and even more preferably regenerated collagen fibers.

[0237] <7> The fiber treatment agent according to any one of <1> and <4> to <6> above, or the fiber treatment kit according to any one of <2> to <6> above, wherein the fiber preferably contains a polyvalent metal, or a salt or complex thereof. <8> The fiber treatment agent according to <7> above, or the fiber treatment kit according to <7> above, wherein the polyvalent metal is preferably one or more selected from calcium, magnesium, strontium, barium, zinc, chromium, aluminum, titanium, zirconium, tin, lead, antimony, iron, and copper, more preferably one or more selected from aluminum, zirconium, and titanium, and even more preferably aluminum.

[0238] <9> The fiber treatment agent according to <7> or <8>, or the fiber treatment kit according to <7> or <8>, wherein the content of the polyvalent metal, or its salt or complex in the fiber is, in terms of the amount of metal element, preferably 1.0% by mass or more, more preferably 2.0% by mass or more, even more preferably 3.0% by mass or more, still more preferably 5.0% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and still more preferably 10% by mass or less. <10> The fiber treatment agent according to <7> or <8>, or the fiber treatment kit according to <7> or <8>, wherein the content of the polyvalent metal, or its salt or complex in the fiber is, in terms of the amount of metal element, preferably 1.0 to 40% by mass, more preferably 2.0 to 30% by mass, even more preferably 3.0 to 20% by mass, and still more preferably 5.0 to 10% by mass.

[0239] <11> The fiber treatment agent according to any one of <1> and <4> to <10>, or the fiber treatment kit according to any one of <2> to <10>, wherein the component (A) preferably includes one or more selected from the following (A-1) and (A-2):

[0240] (A-1) A polymer containing a structural unit derived from an unsaturated monomer having a coordinating functional group, the polymer having a weight-average molecular weight of 1500 or more. (A-2) A condensation product of a compound having a coordinating functional group, the condensation product having a molecular weight of 1500 or more.

[0241] <12> The fiber treatment agent according to <11> above, or the fiber treatment kit according to <11> above, wherein the polymer (A-1) preferably includes one or more selected from the following (A-1-1), (A-1-2), and (A-1-3):

[0242] (A-1-1) A copolymer containing a structural unit derived from an unsaturated monomer having a coordinating functional group and a structural unit derived from an aromatic vinyl compound, the copolymer having a weight-average molecular weight of 1500 or more. (A-1-2) A copolymer containing a structural unit derived from an unsaturated monomer having a coordinating functional group and a structural unit derived from an unsaturated aliphatic hydrocarbon compound, the copolymer having a weight-average molecular weight of 1500 or more. (A-1-3) A polymer containing a structural unit derived from an aromatic vinyl compound having a coordinating functional group or a polymer containing a structural unit derived from an unsaturated aliphatic hydrocarbon compound having a coordinating functional group, the polymer having a weight-average molecular weight of 1500 or more (however, excluding copolymers (A-1-1) and (A-1-2)).

[0243] <13> The fiber treatment agent according to <11> or <12>, or the fiber treatment kit according to <11> or <12>, wherein the proportion of structural units derived from unsaturated monomers having a coordinating functional group is preferably 10 mol % or more, more preferably 15 mol % or more, and even more preferably 20 mol % or more, of all structural units.

[0244] <14> The fiber treatment agent according to any one of <1> and <4> to <13>, or the fiber treatment kit according to any one of <2> to <13>, wherein the coordinating functional group is preferably a group containing a hard base or an intermediate base according to the HSAB rule.

[0245] <15> The fiber treatment agent according to any one of the above <1> and <4> to <14>, or the fiber treatment kit according to any one of the above <2> to <14>, wherein the coordinating functional group is preferably a group containing a base selected from the following (a-1), (a-2), and (a-3):

[0246] (a-1) A group having a carboxy group or a salt thereof (carboxylate), which may be a carboxy anion. (a-2) A group having a hydroxy group, an alkoxy group, an alkoxide anion, or a metal alcoholate, which may be a phenoxide when the hydroxy group is a phenolic hydroxy group. (a-3) A group having a sulfonic acid group or a salt thereof (sulfonate), which may be a sulfonate anion.

[0247] <16> The fiber treatment agent according to any one of the above <12> to <15> or the fiber treatment kit according to any one of the above <12> to <15>, wherein in the (A-1-1) copolymer, the ratio of the structural unit (u1) derived from an aromatic vinyl compound to the structural unit (u2) derived from an unsaturated monomer having a coordinating functional group, expressed as a molar ratio (u1 / u2), is preferably 1 / 5 to 5 / 1, more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1.

[0248] <17> The fiber treatment agent according to any one of the above <12> to <16> or the fiber treatment kit according to any one of the above <12> to <16>, wherein in the (A-1-2) copolymer, the molar ratio (u3 / u4) of the structural unit (u3) derived from an unsaturated aliphatic hydrocarbon compound to the structural unit (u4) derived from an unsaturated monomer having a coordinating functional group is preferably 1 / 5 to 5 / 1, more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1.

[0249] <18> The copolymer (A-1-1) is a copolymer having a weight-average molecular weight of 1,500 or more, preferably a copolymer containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from an unsaturated monomer having a carboxy group or a salt thereof, more preferably a copolymer containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from one or more selected from an unsaturated monocarboxylic acid, a saturated dicarboxylic acid, and a salt thereof, and even more preferably a styrene-maleic acid copolymer, a styrene-acrylic acid copolymer, a styrene-methacrylic acid copolymer, a vinylbenzoic acid-maleic acid copolymer, a vinylbenzoic acid-acrylic ... The fiber treatment agent according to any one of the above <12> to <17>, or the fiber treatment kit according to any one of the above <12> to <17>, which is one or more copolymers selected from benzoic acid-methacrylic acid copolymer, styrene-4-vinylbenzoic acid copolymer, butadiene-4-vinylbenzoic acid copolymer, carboxy-modified products of styrene-butadiene copolymers, and salts thereof, more preferably one or more copolymers selected from styrene-maleic acid copolymer, carboxy-modified products of styrene-butadiene copolymers, and salts thereof, and even more preferably styrene-maleic acid copolymer or a salt thereof.

[0250] <19> The copolymer (A-1-2) is a copolymer having a weight-average molecular weight of 1,500 or more, and is preferably a copolymer containing a structural unit derived from an unsaturated aliphatic hydrocarbon compound and a structural unit derived from an unsaturated monomer having a carboxy group or a salt thereof, more preferably a copolymer containing a structural unit derived from an unsaturated aliphatic hydrocarbon compound and a structural unit derived from one or more selected from the group consisting of an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, and a salt thereof, and even more preferably a copolymer containing a structural unit derived from a diisobutylene-maleic acid copolymer, a diisobutylene-acrylic acid copolymer, a diisobutylene-methacrylic acid copolymer, or a diisobutylene-4-vinylbenzoic acid copolymer. The fiber treatment agent according to any one of <12> to <18>, or the fiber treatment kit according to any one of <12> to <18>, wherein the copolymer is one or more copolymers selected from diisobutylene-maleic acid copolymer, butadiene-acrylic acid copolymer, butadiene-methacrylic acid copolymer, butadiene-4-vinylbenzoic acid copolymer, maleic acid-modified butadiene polymers, and salts thereof, and more preferably one or more copolymers selected from diisobutylene-maleic acid copolymer, butadiene-maleic acid copolymer, maleic acid-modified butadiene polymers, and salts thereof.

[0251] <20> The polymer (A-1-3) is a polymer having a weight-average molecular weight of 1,500 or more, and is preferably one or more polymers selected from homopolymers of aromatic vinyl compounds having a carboxy group, a sulfonic acid group or a salt thereof, or a hydroxyl group, and homopolymers of unsaturated aliphatic hydrocarbon compounds having a carboxy group, a sulfonic acid group or a salt thereof, or a hydroxyl group, more preferably one or more polymers selected from homopolymers of aromatic vinyl compounds having a carboxy group or a salt thereof, and homopolymers of unsaturated aliphatic hydrocarbon compounds having a carboxy group or a salt thereof, and even more preferably one or more polymers selected from homopolymers of aromatic vinyl compounds having a carboxy group or a salt thereof, and homopolymers of unsaturated aliphatic hydrocarbon compounds having a carboxy group or a salt thereof, and The fiber treatment agent according to any one of <12> to <19>, or the fiber treatment kit according to any one of <12> to <19>, is a homopolymer of an unsaturated aliphatic hydrocarbon compound having a group or a salt thereof, more preferably one or more polymers selected from poly(vinyl benzoic acid), poly(cinnamic acid), polyacrylic acid, polymethacrylic acid or salts thereof, and polyvinyl alcohol, even more preferably one or more polymers selected from polyacrylic acid, polymethacrylic acid, and salts thereof, and particularly preferably polyacrylic acid or a salt thereof. <21> The fiber treatment agent according to any one of the above <12> to <20>, or the fiber treatment kit according to any one of the above <12> to <20>, wherein the polymer (A-1-3) is preferably one or more polymers selected from poly(vinyl benzoic acid), poly(cinnamic acid), polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid or a salt thereof, and polyvinyl alcohol, more preferably one or more polymers selected from polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid or a salt thereof, and polyvinyl alcohol, even more preferably one or more polymers selected from polyacrylic acid, polymethacrylic acid, and a salt thereof, and still more preferably polyacrylic acid or a salt thereof.

[0252] <22> The fiber treatment agent according to <11> or the fiber treatment kit according to <11>, wherein the (A-2) condensate has a molecular weight of 1,500 or more and preferably includes one or more condensates selected from the following (A-2-1) and (A-2-2):

[0253] (A-2-1) Condensate of sulfonic acid or its salt (A-2-2) Condensate of gallic acid ester

[0254] <23> The fiber treatment agent according to <22> above, or the fiber treatment kit according to <22> above, wherein the (A-2-1) condensate is a condensate having a weight-average molecular weight of 1,500 or more, preferably an aromatic sulfonic acid-formalin condensate or a salt thereof, more preferably one or more condensates selected from a benzenesulfonic acid-formalin condensate, a naphthalenesulfonic acid-formalin condensate, a phenolsulfonic acid-formalin condensate, and salts thereof, and even more preferably a naphthalenesulfonic acid-formalin condensate or a salt thereof.

[0255] <24> The fiber treatment agent according to the above item <22> or <23>, or the fiber treatment kit according to the above item <22> or <23>, wherein the (A-2-2) condensate has a molecular weight of 1,500 or more, and is preferably a hydrolyzable tannin, and more preferably tannic acid.

[0256] <25> The fiber treatment agent according to any one of the above <11> to <24> or the fiber treatment kit according to any one of the above <11> to <24>, wherein when component (A) is (A-1) a polymer or (A-2-1) a condensate of sulfonic acid or a salt thereof, the weight-average molecular weight is preferably 1,600 or more, more preferably 2,000 or more, even more preferably 3,000 or more, still more preferably 4,000 or more, and preferably 100,000 or less, more preferably 30,000 or less, even more preferably 15,000 or less, still more preferably 10,000 or less, and still more preferably 8,000 or less. <26> The fiber treatment agent according to any one of the above <11> to <24> or the fiber treatment kit according to any one of the above <11> to <24>, wherein when component (A) is (A-1) a polymer or (A-2-1) a condensate of sulfonic acid or a salt thereof, the weight-average molecular weight is preferably 1,600 to 100,000, more preferably 2,000 to 30,000, even more preferably 3,000 to 30,000, even more preferably 3,000 to 15,000, even more preferably 3,000 to 10,000, and still more preferably 4,000 to 8,000.

[0257] <27> The fiber treatment agent according to any one of the above <22> to <26> or the fiber treatment kit according to any one of the above <22> to <26>, wherein, when component (A) is (A-2-2) a condensate of a gallic acid ester and is a single compound, the molecular weight is preferably 1,600 or more, more preferably 1,700 or more, and preferably 10,000 or less, more preferably 5,000 or less. <28> The fiber treatment agent according to any one of the above <22> to <26> or the fiber treatment kit according to any one of the above <22> to <26>, wherein, when component (A) is (A-2-2) a condensate of a gallic acid ester and is a single compound, the molecular weight is preferably 1,600 to 10,000, more preferably 1,700 to 5,000.

[0258] <29> The hydrogen bond term δH of the Hansen solubility parameter of the component (A) is preferably 5.0 MPa 1 / 2 More preferably, 7.0 MPa 1 / 2 More preferably, 9.0 MPa 1 / 2 and preferably 20.0 MPa or more.1 / 2 or less, more preferably 16.0 MPa 1 / 2 More preferably, 13.0 MPa or less 1 / 2 The fiber treatment agent according to any one of the above items <1> and <4> to <28>, or the fiber treatment kit according to any one of the above items <2> to <28>. <30> The hydrogen bond term δH of the Hansen solubility parameter of the component (A) is preferably 5.0 to 20.0 MPa. 1 / 2 , more preferably 7.0 to 16.0 MPa 1 / 2 , more preferably 9.0 to 13.0 MPa 1 / 2 The fiber treatment agent according to any one of <1> and <4> to <28>, or the fiber treatment kit according to any one of <1> to <28>,

[0259] <31> The fiber treatment agent according to any one of the above <15> to <30> or the fiber treatment kit according to any one of the above <15> to <30>, wherein, when component (A) has (a-1) or (a-3) as a coordinating functional group, component (A) has an acid value of preferably 100 mgKOH / g or more, more preferably 200 mgKOH / g or more, even more preferably 300 mgKOH / g or more, still more preferably 400 mgKOH / g or more, and preferably 1000 mgKOH / g or less, more preferably 800 mgKOH / g or less, even more preferably 600 mgKOH / g or less. <32> The fiber treatment agent according to any one of the above <15> to <30> or the fiber treatment kit according to any one of the above <15> to <30>, wherein when component (A) has (a-1) or (a-3) as the coordinating functional group, component (A) preferably has an acid value of 1,600 to 100,000, more preferably 2,000 to 30,000, even more preferably 3,000 to 10,000, and still more preferably 4,000 to 8,000.

[0260] <33> The fiber treatment agent according to any one of the above <15> to <32> or the fiber treatment kit according to any one of the above <15> to <32>, wherein, when component (A) has (a-2) as a coordinating functional group, component (A) has a hydroxyl value of preferably 100 mgKOH / g or more, more preferably 200 mgKOH / g or more, even more preferably 300 mgKOH / g or more, and preferably 2000 mgKOH / g or less, more preferably 1500 mgKOH / g or less, even more preferably 1000 mgKOH / g or less. <34> The fiber treatment agent according to any one of the above <15> to <32> or the fiber treatment kit according to any one of the above <15> to <32>, wherein, when component (A) has (a-2) as a coordinating functional group, component (A) has a hydroxyl value of preferably 100 to 1,000 mgKOH / g, more preferably 200 to 800 mgKOH / g, even more preferably 300 to 600 mgKOH / g, and still more preferably 400 to 600 mgKOH / g.

[0261] <35> The fiber treatment agent according to any one of <1> and <4> to <34> above, or the fiber treatment kit according to any one of <2> to <34> above, wherein 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, even more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, still more preferably 2.3% by mass or more, still more preferably 3.0% by mass or more, and is preferably 60% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, still more preferably 15% by mass or less, and still more preferably 10% by mass or less. <36> The fiber treatment agent according to any one of <1> and <4> to <34> above, or the fiber treatment kit according to any one of <2> to <34> above, wherein the fiber treatment agent contains component (A) in an amount of preferably 0.1 to 60 mass%, more preferably 0.2 to 40 mass%, even more preferably 0.3 to 30 mass%, still more preferably 0.5 to 15 mass%, still more preferably 1.0 to 15 mass%, still more preferably 2.3 to 15 mass%, and still more preferably 3.0 to 10 mass%.

[0262] <37> The fiber treatment agent according to any one of the above <11> to <36>, or the fiber treatment kit according to any one of the above <11> to <36>, wherein, when component (A) is (A-1) a polymer or (A-2-1) a condensate of sulfonic acid or a salt thereof, the content of component (A) in the fiber treatment agent is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, still more preferably 2.3% by mass or more, still more preferably 3.0% by mass or more, and is preferably 60% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferably 15% by mass or less, and still more preferably 10% by mass or less. <38> The fiber treatment agent according to any one of the above <11> to <36>, or the fiber treatment kit according to any one of the above <11> to <36>, wherein, when component (A) is (A-1) a polymer or (A-2-1) a condensate of sulfonic acid or a salt thereof, the content of component (A) in the fiber treatment agent is preferably 0.3 to 60 mass%, more preferably 0.5 to 40 mass%, even more preferably 1.0 to 30 mass%, still more preferably 2.3 to 20 mass%, still more preferably 3.0 to 15 mass%, and still more preferably 3.0 to 10 mass%.

[0263] <39> The fiber treatment agent according to any one of the above <21> to <38> or the fiber treatment kit according to any one of the above <22> to <38>, wherein, when component (A) is (A-2-2) a condensate of a gallic acid ester, 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, even more preferably 0.4% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1.0% by mass or less. <40> The fiber treatment agent according to any one of the above <21> to <38> or the fiber treatment kit according to any one of the above <22> to <38>, wherein, when component (A) is (A-2-2) a condensate of a gallic acid ester, the content of component (A) in the fiber treatment agent is preferably 0.05 to 10% by mass, more preferably 0.10 to 5% by mass, even more preferably 0.20 to 1.0% by mass.

[0264] <41> The fiber treatment agent according to any one of <1> and <4> to <40> above, or the fiber treatment kit according to any one of <2> to <40> above, wherein the pH of the fiber treatment agent is preferably 2.0 or more, more preferably 3.0 or more, even more preferably 3.5 or more, and preferably 11.0 or less, more preferably 10.0 or less, even more preferably 9.0 or less, even more preferably 7.0 or less, even more preferably 6.5 or less, and even more preferably less than 5.5. <42> The fiber treatment agent according to any one of <1> and <4> to <40> above, or the fiber treatment kit according to any one of <2> to <40> above, wherein the pH of the fiber treatment agent is preferably 2.0 to 11.0, more preferably 3.0 to 10.0, even more preferably 3.5 to 9.0, even more preferably 3.5 to 7.0, even more preferably 3.5 to 6.5, and even more preferably 3.5 or more and less than 5.5.

[0265] <43> The fiber treatment agent according to any one of the above <11> to <42> or the fiber treatment kit according to any one of the above <11> to <42>, wherein component (A) is (A-1) a polymer or (A-2-1) a condensate of sulfonic acid or a salt thereof, and wherein, when the fiber treatment agent has a pH of less than 5.5, the content of component (A) in the fiber treatment agent is preferably at least 0.3% by mass, more preferably at least 0.8% by mass, even more preferably at least 1.3% by mass, and preferably at most 30% by mass, more preferably at most 20% by mass, even more preferably at most 10% by mass. <44> The fiber treatment agent according to any one of the above <11> to <42> or the fiber treatment kit according to any one of the above <11> to <42>, wherein the component (A) is (A-1) a polymer or (A-2-1) a condensate of sulfonic acid or a salt thereof, and when the pH of the fiber treatment agent is less than 5.5, the content of component (A) in the fiber treatment agent is preferably 0.3 to 30 mass%, more preferably 0.8 to 20 mass%, and even more preferably 1.3 to 10 mass%.

[0266] <45> The fiber treatment agent according to any one of the above <11> to <44> or the fiber treatment kit according to any one of the above <11> to <44>, wherein, when component (A) is (A-1) a polymer or (A-2-1) a condensate of sulfonic acid or a salt thereof, and the pH of the fiber treatment agent is 5.5 or higher, the content of component (A) in the fiber treatment agent is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, even more preferably 3.0% by mass or more, and is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less. <46> The fiber treatment agent according to any one of the above <11> to <44> or the fiber treatment kit according to any one of the above <11> to <44>, wherein, when component (A) is (A-1) a polymer or (A-2-1) a condensate of sulfonic acid or a salt thereof, and the pH of the fiber treatment agent is 5.5 or higher, the content of component (A) in the fiber treatment agent is preferably 1.0 to 60 mass%, more preferably 2.0 to 50 mass%, and even more preferably 3.0 to 40 mass%.

[0267] <47> The fiber treatment agent according to any one of the above <21> to <46> or the fiber treatment kit according to any one of the above <22> to <46>, wherein, when component (A) is (A-2-2) a condensate of a gallic acid ester, 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, even more preferably 0.4% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1.0% by mass or less. <48> The fiber treatment agent according to any one of the above <21> to <46> or the fiber treatment kit according to any one of the above <22> to <46>, wherein, when component (A) is (A-2-2) a condensate of a gallic acid ester, the content of component (A) in the fiber treatment agent is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, even more preferably 0.4 to 1.0% by mass.

[0268] <49> The fiber treatment agent according to any one of <1> and <4> to <48>, or the fiber treatment kit according to any one of <2> to <48>, wherein the content of component (A) in the fiber treatment agent is such that the content of component (A) in fibers treated with the fiber treatment agent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, even more preferably 3.0% by mass or more, even more preferably 5.0% by mass or more, even more preferably 10% by mass or more, and is preferably 70% by mass or less, more preferably 65% ​​by mass or less, even more preferably 60% by mass or less, even more preferably 55% by mass or less, even more preferably 50% by mass or less, and even more preferably 45% by mass or less. <50> The fiber treatment agent according to any one of <1> and <4> to <48>, or the fiber treatment kit according to any one of <2> to <48>, wherein the content of component (A) in the fiber treatment agent is such that the content of component (A) in fibers treated with the fiber treatment agent is preferably 0.1 to 70 mass%, more preferably 0.5 to 65 mass%, even more preferably 1.0 to 60 mass%, even more preferably 3.0 to 55 mass%, even more preferably 5.0 to 50 mass%, and even more preferably 10 to 45 mass%.

[0269] <51> The fiber treatment agent according to any one of <1> and <4> to <50>, or the fiber treatment kit according to any one of <2> to <50>, wherein the content of component (B) in the fiber treatment agent is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, still more preferably 40% by mass or more, and is preferably 98% by mass or less, more preferably 97% by mass or less, even more preferably 96% by mass or less, still more preferably 95% by mass or less, even more preferably 90% by mass or less, and still more preferably 85% by mass or less. <52> The fiber treatment agent according to any one of <1> and <4> to <50> above, or the fiber treatment kit according to any one of <2> to <50> above, wherein the content of component (B) in the fiber treatment agent is preferably the remainder excluding component (A) and any optional components described below, more preferably 10 to 98% by mass, more preferably 20 to 97% by mass, even more preferably 30 to 96% by mass, still more preferably 40 to 95% by mass, even more preferably 40 to 90% by mass, and still more preferably 40 to 85% by mass.

[0270] <53> The fiber treatment agent according to any one of <1> and <4> to <52> above, or the fiber treatment kit according to any one of <2> to <52> above, preferably further containing a polyvalent metal element as component (C). <54> The fiber treatment agent according to <53> above, or the fiber treatment kit according to <53> above, wherein component (C) is preferably an inorganic salt of a polyvalent metal, more preferably a polyvalent metal salt of a hard acid or a medium acid that easily interacts with the coordinating functional group (hard base, medium base) of component (A), even more preferably a polyvalent metal salt of a hard acid or a medium acid, even more preferably one or more selected from aluminum salts and zirconium salts, and even more preferably one or more selected from aluminum sulfate, aluminum chloride, and zirconium sulfate.

[0271] <55> The fiber treatment agent according to <53> or <54>, or the fiber treatment kit according to <53> or <54>, wherein the content of component (C) in the fiber treatment agent is, as the amount of metal element, preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, even more preferably 0.001% by mass or more, still more preferably 0.007% by mass or more, and preferably 1.0% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.10% by mass or less, and still more preferably 0.07% by mass or less. <56> The fiber treatment agent according to <53> or <54>, or the fiber treatment kit according to <53> or <54>, wherein the content of component (C) in the fiber treatment agent is, as the metal element amount, preferably 0.0001 to 1.0 mass%, more preferably 0.0005 to 0.5 mass%, even more preferably 0.001 to 0.10 mass%, and still more preferably 0.007 to 0.07 mass%.

[0272] <57> The fiber treatment kit according to any one of <2> and <4> to <56> above, wherein the pH of the first fibrous agent is preferably 3.0 or more, more preferably 4.0 or more, even more preferably 4.5 or more, still more preferably 5.5 or more, and preferably 11.0 or less, more preferably 9.0 or less, even more preferably 8.0 or less, and still more preferably 7.0 or less. <58> The fiber treatment kit according to any one of <2> and <4> to <56> above, wherein the pH of the first fibrous agent is preferably 3.0 to 11.0, more preferably 4.0 to 9.0, even more preferably 4.5 to 8.0, and still more preferably 5.5 to 7.0.

[0273] <59> The fiber treatment kit according to any one of <2> and <4> to <58> above, wherein the pH of the second fibrous agent is preferably 2.0 or more, more preferably 3.0 or more, even more preferably 3.5 or more, and preferably 10.0 or less, more preferably 8.0 or less, even more preferably 7.0 or less, and even more preferably less than 5.5. <60> The fiber treatment kit according to any one of <2> and <4> to <58> above, wherein the pH of the second fibrous agent is preferably 2.0 to 10.0, more preferably 3.0 to 8.0, even more preferably 3.5 to 7.0, and even more preferably 3.5 or more and less than 5.5.

[0274] <61> The fiber treatment kit according to any one of <2> and <4> to <60> above, wherein the ratio of the first fiber treatment agent to the second fiber treatment agent in the fiber treatment kit, in terms of mass ratio (first fiber treatment agent / second fiber treatment agent), is preferably 1 / 5 to 5 / 1, more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1.

[0275] <62> The fiber treatment kit according to any one of <2> and <4> to <61>, preferably comprising treating the fibers once or twice or more times with the first fiber treatment agent, and then finally treating the fibers with the second fiber treatment agent.

[0276] <63> The fiber treatment kit according to any one of <3> to <56> above, wherein the fiber treatment agent is preferably a one-component or two-component type. <64> The fiber treatment kit according to <63> above, wherein when the fiber treatment agent is a two-component type, the fiber treatment kit preferably comprises a fiber treatment agent (agent 1b-1) and a fiber treatment agent (agent 1b-2) having a pH 1.0 or more lower than that of the fiber treatment agent.

[0277] <65> The fiber treatment kit according to any one of the above items <3> to <56> and <63> to <64>, wherein the component (D) is preferably one or more selected from the following (D1) and (D2):

[0278] (D1) The hydrogen bond term δH of the Hansen solubility parameter is 18.3 MPa 1 / 2 (D2) Aromatic compounds having at least one carboxy group or a salt thereof and no condensed ring, wherein the hydrogen bond term δH of the Hansen solubility parameter is 11.0 MPa or less. 1 / 2 Over 18.3 MPa 1 / 2 A compound (excluding aromatic compounds) having at least one carboxy group or a salt thereof and no condensed ring, which is:

[0279] <66> The fiber treatment kit according to the above item <65>, wherein the component (D1) is preferably a compound represented by the following general formula (1) or general formula (2) or a salt thereof:

[0280]

[0281] [wherein =X represents a methylidene group or an oxo group, and R1 represents a hydrogen atom, a hydroxyl group, or an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an aralkyloxy group which may have a substituent, and R 2 represents an o-phenylene group, an m-phenylene group, a p-phenylene group, a benzylidene group, or an alkylene group which may have a substituent, 2 does not have an aryl group, R 1 is an aryl group, an aryloxy group, or an aralkyloxy group.

[0282] [In the formula, A 1 ~A 5 each independently represents a hydrogen atom, 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.

[0283] <67> The fiber treatment kit according to the above <66>, wherein the aromatic compound represented by the general formula (1) is preferably a compound represented by the following general formula (1A), (1B) or (1C):

[0284]

[0285] [In the formula, B 1 ~B 4 each independently represents a hydrogen atom, 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; R 3 represents a hydroxy group or a group represented by the following general formula (1A)-a or (1A)-b.

[0286]

[0287] [In the formula, B 5 ~B 9 is the above B 1 ~B 4 has the same meaning as 4 represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 2.

[0288]

[0289] [In the formula, D 1 ~D4 each independently represents a hydrogen atom, 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; E 1 ~E 5 are each independently 1 ~D 4 or a group represented by general formula (1B)-a.]

[0290]

[0291] (wherein m represents an integer of 0 to 4.)

[0292]

[0293] [In the formula, R 6 represents a hydrogen atom or a group represented by general formula (1C)-a, G 1 and G 2 each independently represents a hydrogen atom, an acetyl group, a halogen atom, an aryl group which may have a substituent, an aralkyl group or an arylalkenyl group having 7 to 12 carbon atoms, or a linear or branched alkyl group, alkenyl group, alkoxy group, alkenyloxy group or aroyloxy group having 1 to 6 carbon atoms. 6 is a hydrogen atom, G 1 and G 2 At least one of the groups is an aryl group, an aralkyl group having 7 to 12 carbon atoms, an arylalkenyl group, or an aroyloxy group, each of which may have a substituent.]

[0294]

[0295] [In the ceremony, J 1 ~J 5 each independently represents a hydrogen atom, 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.

[0296] <68> The fiber treatment kit according to the above <67>, wherein the compound represented by general formula (1A) is preferably 2-carboxybenzoic acid (phthalic acid), 2-[[(4-vinylbenzyl)oxy]carbonyl]benzoic acid, 2-[[2-(acryloyloxy)ethoxy]carbonyl]benzoic acid, or 2-[[2-(methacryloyloxy)ethoxy]carbonyl]benzoic acid. <69> The fiber treatment kit according to the above item <67>, wherein the compound represented by general formula (1B) is preferably 2-benzoylbenzoic acid, 2-(2-methylbenzoyl)benzoic acid, 2-(3-methylbenzoyl)benzoic acid, 2-(4-methylbenzoyl)benzoic acid, 2-(2-chlorobenzoyl)benzoic acid, 2-(3-chlorobenzoyl)benzoic acid, 2-(4-chlorobenzoyl)benzoic acid, or 2-[4-[2-(2-(acryloyloxy)ethoxy)ethoxy]benzoyl]benzoic acid. <70> The fiber treatment kit according to the above item <67>, wherein the compound represented by general formula (1c) is preferably phenylsuccinic acid, 2,3-diphenylsuccinic acid, (+)-di-p-toluoyl-D-tartaric acid, or 4-oxo-4-[(4-vinylbenzyl)oxy]butanoic acid.

[0297] <71> The compound represented by the general formula (2) is benzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 2-ethylbenzoic acid, 3-ethylbenzoic acid, 4-ethylbenzoic acid, 2-propylbenzoic acid, 3-propylbenzoic acid, 4-propylbenzoic acid, 2-isopropylbenzoic acid, 3-isopropylbenzoic acid, 4-isopropylbenzoic acid, 2-n-butylbenzoic acid, 3-n-butylbenzoic acid, 4-n-butylbenzoic acid, 2-tert-butylbenzoic acid, 3-tert-butylbenzoic acid, 4-tert-butylbenzoic acid The fiber treatment kit according to any one of the above <66> to <70>, wherein the benzoic acid is selected from the group consisting of benzoic acid, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 2-acetylbenzoic acid, 3-acetylbenzoic acid, 4-acetylbenzoic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, 4-methoxybenzoic acid, 2-chlorobenzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, 2-bromobenzoic acid, 3-bromobenzoic acid, and 4-bromobenzoic acid, and more preferably 4-ethylbenzoic acid, 4-vinylbenzoic acid, and benzoic acid.

[0298] <72> The hydrogen bond parameter δH of the aromatic compound of component (D1) is preferably 16.0 MPa 1 / 2 Less than or equal to 13.5 MPa, more preferably 1 / 2 More preferably, 12.0 MPa or less 1 / 2 More preferably, 10.0 MPa or less 1 / 2 and preferably 3.0 MPa or less. 1 / 2 More preferably, 4.0 MPa 1 / 2 More preferably, 5.0 MPa 1 / 2 <73> The fiber treatment kit according to any one of the above items <65> to <71>, wherein the hydrogen bond parameter δH of the aromatic compound of component (D1) is preferably 3.0 to 16.0 MPa. 1 / 2 , more preferably 4.0 to 13.5 MPa 1 / 2 , more preferably 5.0 to 12.0 MPa 1 / 2 , more preferably 5.0 to 10.0 MPa 1 / 2 The fiber treatment kit according to any one of <65> to <71>, which is:

[0299] <74> The hydrogen bond parameter δH of the compound of component (D2) is preferably 16.0 MPa 1 / 2 Not more than 15.0 MPa, more preferably 1 / 2 More preferably, 14.0 MPa or less 1 / 2 More preferably, 13.0 MPa or less 1 / 2 is not more than 11.0 MPa, and preferably 1 / 2 More preferably, 11.5 MPa 1 / 2 More preferably, 12.0 MPa 1 / 2 <75> The fiber treatment kit according to any one of the above items <65> to <73>. <75> The hydrogen bond parameter δH of the compound of component (D2) is preferably 11.0 to 16.0 MPa. 1 / 2 , more preferably 11.5 to 15.0 MPa 1 / 2 , more preferably 12.0 to 14.0 MPa 1 / 2 The fiber treatment kit according to any one of <65> to <73>,

[0300] <76> The fiber treatment kit according to any one of the above items <65> to <75>, wherein the component (D2) is preferably potassium 2,4-hexadienoate.

[0301] <77> The fiber treatment kit according to any one of <3> to <56> and <65> to <76> above, wherein the pH of the additional fiber treatment agent is preferably 4.0 or more, more preferably 5.0 or more, even more preferably 5.5 or more, and preferably 9.0 or less, more preferably 8.0 or less, even more preferably 7.0 or less. <78> The fiber treatment kit according to any one of <3> to <56> and <65> to <76> above, wherein the pH of the additional fiber treatment agent is preferably 4.0 to 9.0, more preferably 5.0 to 8.0, even more preferably 5.5 to 7.0.

[0302] <79> The fiber treatment kit according to any one of <3> to <56> and <65> to <78> above, wherein the content of component (D) in the additional fiber treatment agent is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and preferably 60% by mass or less, more preferably 55% by mass or less, even more preferably 50% by mass or less, still more preferably 40% by mass or less, and still more preferably 35% by mass or less. <80> The fiber treatment kit according to any one of <3> to <56> and <65> to <78> above, wherein the content of component (D) in the additional fiber treatment agent is preferably 0.1 to 60% by mass, more preferably 1 to 55% by mass, even more preferably 5 to 50% by mass, still more preferably 10 to 40% by mass, and still more preferably 20 to 35% by mass.

[0303] <81> The fiber treatment kit according to any one of <3> to <56> and <65> to <80> above, wherein the content of component (D) in the additional fiber treatment agent is such that the content of component (D) in fibers treated with the fiber treatment kit is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less. <82> The fiber treatment kit according to any one of <3> to <56> and <65> to <80> above, wherein the content of component (D) in the additional fiber treatment agent is such that the content of component (D) in fibers treated with the fiber treatment kit is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, even more preferably 10 to 30% by mass.

[0304] <83> The fiber treatment kit according to any one of <3> to <56> and <65> to <82> above, wherein the ratio of the fiber treatment agent (agent 1b) to the additional fiber treatment agent (agent 2b) in the fiber treatment kit, expressed as a mass ratio (agent 1b / agent 2b), is preferably 1 / 5 to 5 / 1, more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1. <84> The fiber treatment kit according to any one of <3> to <56> and <65> to <82>, wherein when the fiber treatment agent (agent 1b) is a two-component type consisting of agents 1b-1 and 1b-2, the ratio of the fiber treatment agent (agent 1b) to the additional fiber treatment agent (agent 2b) is preferably 2 / 5 to 10 / 1, more preferably 2 / 3 to 6 / 1, and even more preferably 2 / 2 to 4 / 1, by mass ratio (total of agents 1b-1 and 1b-2 / agent 2b).

[0305] <85> The fiber treatment agent according to any one of <1> and <4> to <55>, or the fiber treatment kit according to any one of <2> to <84>, which is a fiber-penetrating type.

[0306] <86> The fiber treatment agent according to any one of the above <15> to <23>, <25> to <26>, <29> to <37>, <40> to <46>, and <49> to <85>, or the fiber treatment kit according to any one of the above <15> to <23>, <25> to <26>, <29> to <37>, <40> to <46>, and <49> to <85>, wherein, when component (A) is in the form of a salt, the salt is preferably an alkali metal salt, an alkaline earth metal salt, or an ammonium salt, more preferably a sodium salt, a lithium salt, a potassium salt, a calcium salt, or a magnesium salt, and even more preferably a sodium salt. <87> The fiber treatment kit according to any one of the above <3> to <56> and <63> to <86>, wherein, when component (D) is in the form of a salt, the salt is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt, and even more preferably a sodium salt.

[0307] <88> A fiber treatment method including the following step (i): Step (i) is a step of immersing a naturally occurring fiber, the fiber swelling ratio in water of which is calculated by the following formula (1) of 200% or more, in a fiber treatment agent containing the following components (A) and (B): (A) a compound having a coordinating functional group and a molecular weight of 1,500 or more, (B) water Fiber swelling ratio in water (%) = [(w1 - w2) / w2] × 100 (1) (wherein w1 represents the mass (g) of the fiber measured after placing 1.0 g of fiber in a container filled with 100 g of ion-exchanged water, sealing the container, immersing the container in a water bath at 40°C for 30 minutes, removing the fiber from the container, and centrifuging and dehydrating it for 1 minute at a centrifugal force of 220 [×g]; and w2 represents the mass of the fiber measured after placing the fiber, whose mass (w1) has been measured, on filter paper and drying it at 105°C for 3 hours.)

[0308] <89> A fiber treatment method including the following step (i): Step (i): Immersing a naturally occurring fiber, the fiber swelling ratio in water of which is calculated by the following formula (1) of 200% or more, in a fiber treatment agent containing the following components (A) and (B): (A) a compound having a coordinating functional group and a molecular weight of 1,500 or more (excluding copolymers containing a structural unit derived from an unsaturated monomer having a carboxy group or a salt thereof and a structural unit derived from an aromatic vinyl compound, the copolymer having an acid value of 100 mg KOH / g or more and a weight average molecular weight of 1,500 to 15,000), (B) water Fiber swelling ratio in water (%)=[(w1-w2) / w2]×100 (1) [wherein, w1 indicates the mass (g) of the fiber measured after placing 1.0 g of fiber in a container filled with 100 g of ion-exchanged water, sealing the container, immersing the container in a water bath at 40°C for 30 minutes, removing the fiber from the container, and centrifuging and dehydrating it for 1 minute at a centrifugal force of 220 [×g]. w2 indicates the mass (g) of the fiber measured after placing the fiber whose mass (w1) has been measured on filter paper and drying it at 105°C for 3 hours.

[0309] <90> A method for treating fibers that have a swelling rate in water of 200% or more, calculated by the following formula (1), using the following fiber treatment kit: Fiber swelling rate in water (%) = [(w1 - w2) / w2] × 100 (1) (wherein w1 represents the mass (g) of the fiber measured after placing 1.0 g of fiber in a container filled with 100 g of ion-exchanged water, sealing the container, immersing the container in a water bath at 40°C for 30 minutes, removing the fiber from the container, and centrifuging for 1 minute at a centrifugal force of 220 [×g]. w2 represents the mass of the fiber measured after placing the fiber whose mass (w1) has been measured on filter paper and drying it at 105°C for 3 hours. <Fiber treatment kit> A fiber treatment kit comprising: a fiber treatment agent containing the following components (A) and (B); and a second fiber treatment agent containing the following components (A) and (B), the second fiber treatment agent having a pH lower than that of the first fiber treatment agent by 1.0 or more: (A) a compound having a coordinating functional group and a molecular weight of 1,500 or more; (B) water;

[0310] <91> A method for treating fibers having a swelling rate in water of 200% or more, calculated by the following formula (1), using the following fiber treatment kit: Fiber swelling rate in water (%) = [(w1 - w2) / w2] × 100 (1) (wherein w1 represents the mass (g) of the fiber measured after placing 1.0 g of fiber in a container filled with 100 g of ion-exchanged water, sealing the container, immersing the container in a water bath at 40°C for 30 minutes, removing the fiber from the container, and centrifuging for 1 minute at a centrifugal force of 220 [×g]. w2 represents the mass of the fiber measured after placing the fiber whose mass (w1) has been measured on filter paper and drying it at 105°C for 3 hours.) <Fiber treatment kit> A fiber treatment kit comprising: a fiber treatment agent containing the following components (A) and (B); and an additional fiber treatment agent containing the following component (D). (A) A compound having a coordinating functional group and a molecular weight of 1500 or more. (B) Water. (D) The hydrogen bond term δH of the Hansen solubility parameter is 18.3 MPa. 1 / 2 A compound or a salt thereof having at least one carboxy group or a salt thereof and no fused ring, which is the following (excluding component (A)):

[0311] <92> The treatment method according to any one of the above items <89> to <91>, wherein the coordinating functional group is preferably a group containing a base selected from the following (a-1), (a-2) and (a-3):

[0312] (a-1) A group having a carboxy group or a salt thereof (carboxylate), which may be a carboxy anion. (a-2) A group having a hydroxy group, an alkoxy group, an alkoxide anion, or a metal alcoholate, which may be a phenoxide when the hydroxy group is a phenolic hydroxy group. (a-3) A group having a sulfonic acid group or a salt thereof (sulfonate), which may be a sulfonate anion.

[0313] <93> The treatment method according to <92> above, wherein the salt is preferably an alkali metal salt, an alkaline earth metal salt, or an ammonium salt, more preferably a sodium salt, a lithium salt, a potassium salt, a calcium salt, or a magnesium salt, and even more preferably a sodium salt.

[0314] <94> The treatment method according to the above <91>, wherein when the component (D) is in the form of a salt, the salt is preferably an alkali metal salt, more preferably a sodium salt or potassium salt, and even more preferably a sodium salt.

[0315] <Analysis Method> 1. Measurement of fiber swelling ratio of regenerated collagen fiber in water The fiber swelling ratio in water was calculated according to the following formula (1).

[0316] Fiber swelling ratio in water S (%) = [(w1 - w2) / w2] × 100 (1)

[0317] The definitions of each symbol in formula (1) are as follows. w1: 1.0 g of regenerated collagen fibers were immersed in a container containing 100 g of ion-exchanged water, the container was sealed, and the entire container was immersed in a water bath (model number: TBS221FA, manufacturer: Toyo Seisakusho Co., Ltd.) set to 40°C and heated for 30 minutes. The regenerated collagen fibers were then removed from the container and placed in a small centrifuge (H-112, Kokusan Co., Ltd.) and centrifuged for 1 minute at a centrifugal force of 220 [×g] (rotation speed dial "4" (2000 rpm)). The fibers were then removed and immediately weighed, and this weight was recorded as weight w1. w2: The regenerated collagen fibers after measuring weight w1 were placed on filter paper and placed in a dryer (SOFW-450SB, AS ONE Corporation) set to 105°C and dried for 3 hours. The fibers were then removed and immediately weighed, and this weight was recorded as weight w2.

[0318] 2. Measurement of Weight-Average Molecular Weight of Component (A) The weight-average molecular weight (Mw) in terms of polystyrene was measured by gel permeation chromatography (GPC) under the following conditions. (1) Reagents: Ultrapure water: Milli-Q ultrapure water production system, manufactured by Millipore Corporation; Dimethylformamide (DMF): Special grade, manufactured by Kanto Chemical Co., Ltd.; Lithium bromide monohydrate (LiBr): Special grade, manufactured by Kanto Chemical Co., Ltd.; Phosphoric acid: Special grade, manufactured by Sigma-Aldrich Co., Ltd. (2) Sample Pretreatment Method: Approximately 50 mg of sample was precisely weighed, 0.5 mL of ultrapure water was added, and 10 mL of the mobile phase described below was added. The resulting solution was filtered to obtain a sample solution. (3) Measurement: GPC measurement was performed using the sample solution and standard solution under the following conditions to determine the weight-average molecular weight in terms of polystyrene. Flow rate: 1 mL / min Mobile phase: DMF containing 60 mM phosphoric acid and 50 mM LiBr Column: TSKgel α (Alpha) column (manufactured by Tosoh Corporation) Detector: RI (differential refractometer) Standard material: monodisperse polystyrene

[0319] 3. Method for Determining Aluminum in Fibers The amount of aluminum contained in the regenerated collagen fibers after treatment was determined using the following method. (1) Reagents: Sulfuric acid: for precision analysis, Fujifilm Wako Pure Chemical Industries, Ltd. Hydrochloric acid: for metal analysis, Kanto Chemical Co., Ltd. Sodium carbonate: special grade, Fujifilm Wako Pure Chemical Industries, Ltd. Boric acid: special grade, Fujifilm Wako Pure Chemical Industries, Ltd. Aluminum standard solution: for atomic absorption analysis 1000 mg / L, Kanto Chemical Co., Ltd. Ultrapure water: water produced by ultrapure water production system Milli-Q, Millipore Corporation (2) Sample Pretreatment Method: The fiber bundle was hung in a dryer (SOFW-450SB, AS ONE Corporation) set to 60°C, a 250 g weight was attached to the bottom end of the fiber bundle, and the fiber was dried for 1 hour with tension applied to the entire fiber. 0.1 g of sample was weighed into a platinum crucible and heated until no white smoke was produced. A few drops of sulfuric acid were added, and the mixture was heated again until no white smoke was produced. It was then thoroughly incinerated in a 550°C electric furnace. 1 g of alkaline flux (sodium carbonate:boric acid = 1:0.4) was then added and melted in a 950°C electric furnace. A watch glass was placed over the sample, and 5 mL of ultrapure water and hydrochloric acid (6 mol / L) were added. The mixture was heated and dissolved on a hot plate at 70-80°C. After cooling, the solution was adjusted to a constant volume of 50 mL with ultrapure water. This solution was used as the measurement solution. (3) Preparation of Calibration Solutions: Calibration solutions ranging from 0.1 to 20 mg / L were prepared using an aluminum standard solution (1000 mg / L). Alkaline flux and hydrochloric acid were added to each solution to achieve the same concentration as the sample. (4) Measurement: The prepared samples were measured for each element using an ICP atomic emission spectrometer under the following conditions. Analysis device: iCAP6500Duo (manufactured by Thermo Fisher Scientific) Wavelength: Al 396.152 nm RF power: 1150 W Coolant gas flow rate: 12 L / min Nebulizer flow rate: 0.70 L / min Auxiliary gas: 0.5 L / min Pump flow rate: 50 rpm

[0320] 4. The hydrogen bond term δH of the Hansen solubility parameter was calculated at 25°C in the DIY program using the software package HSPiP 4th Edition 4.1.07.

[0321] 5. Measurement of Acid Value and Hydroxyl Value Measured by potentiometric titration in accordance with JIS K 0070.

[0322] 6. Measurement of pH Each composition was measured as it was at 25° C. using a pH meter (F-52, manufactured by HORIBA).

[0323] 7. Quantitative Method for Component (A) in Fibers The following describes the quantitative method for the amount of component (A) in modified regenerated collagen fibers when styrene-maleic acid copolymer or its salt is used as component (A). (1) Reagents: 1 mol / L aqueous sodium hydroxide solution: for volumetric analysis, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; Ultrapure water: water produced by an ultrapure water production system, Milli-Q, manufactured by Millipore; Dimethylformamide (DMF): special grade, manufactured by Kanto Chemical Co., Inc.; Lithium bromide monohydrate (LiBr): special grade, manufactured by Kanto Chemical Co., Inc.; Phosphoric acid: special grade, manufactured by Sigma-Aldrich. (2) Sample Solution: The sample was conditioned at 20°C and 65% relative humidity for 24 hours, then finely chopped. Approximately 50 mg of the sample was precisely weighed, and 10 mL of 1 mol / L aqueous sodium hydroxide solution was added and the mixture was dissolved by heating at 50°C for 3 hours. The pH of the solution was adjusted to 4.7-5.3, and the freeze-dried sample was diluted with 0.5 mL of ultrapure water and 9.5 mL of the mobile phase described below. The diluted solution was filtered to prepare the sample solution. (3) Preparation of Calibration Curve Solution Separately, styrene-maleic acid copolymer or its salt was dissolved in the mobile phase described below to prepare a concentration of 0.25-5.0 mg / mL of undissociated styrene-maleic acid copolymer, which was used as the standard solution for drawing the calibration curve. (4) Measurement Gel permeation chromatography (GPC) measurements were performed using the sample solution and the standard solution under the following conditions, and the peak areas of the sample solution and the standard solution were determined. A calibration curve was also prepared based on the peak area results of the standard solution. Flow rate: 0.8 mL / min Mobile phase: DMF containing 60 mM phosphoric acid and 50 mM LiBr Column: TSKgel α (Alpha) column (manufactured by Tosoh Corporation) Detector: UV-visible spectrophotometer Measurement wavelength: 267 nm (5) Calculation of the amount of styrene-maleic acid copolymer The amount of styrene-maleic acid copolymer per mass of fiber was calculated using a calibration curve created based on the peak area derived from the styrene-maleic acid copolymer contained in the modified regenerated collagen fibers.

[0324] 8. Quantitative Method for Component (D) in Fiber The amount of component (D) contained in the regenerated collagen fibers after treatment is quantified using the following method. (1) Reagents: 6N hydrochloric acid: titrant for volumetric analysis, manufactured by Kanto Chemical Co., Ltd.; Sodium acetate: special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; Acetic acid: special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; Acetonitrile: for LC / MS, manufactured by Kanto Chemical Co., Ltd.; Sodium benzoate: special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; Ultrapure water: water produced by ultrapure water production system Milli-Q, manufactured by Millipore Corporation. (2) Sample Pretreatment Method: The sample is finely chopped, and approximately 10 mg is precisely weighed out. 3 mL of 6N hydrochloric acid is added and the mixture is dissolved by heating at 50°C for 15 hours. After cooling, the mixture is filtered to obtain the sample solution. (3) Preparation of Calibration Curve Solution: Separately, dissolve component (A) in the mobile phase. If there is a dissociation site, such as an acid group, prepare a non-dissociated component (A) at a concentration of 0.1 to 100 μg / mL to prepare a standard solution for drawing a calibration curve. (4) Measurement: Test the sample solution and standard solution using liquid chromatography under the following conditions, and measure the peak area of ​​the sample solution and the peak area of ​​the standard solution. Detector: UV-visible spectrophotometer Measurement wavelength: 230 nm Column: A stainless steel tube with an inner diameter of 21 mm and a length of 150 mm is packed with 5 μm octadecylsilylated silica gel for liquid chromatography. Column temperature: A constant temperature of around 40°C Mobile phase: Dissolve approximately 0.68 g of sodium acetate and 0.91 g of acetic acid in 750 mL of ultrapure water, add 250 mL of acetonitrile, and mix. (5) HPLC / UV Conditions Apparatus: UltiMate 3000 system (manufactured by Thermo Fisher Scientific) Column: L-column 2 ODS, particle size 5 μm, 2.1 × 150 mm (Chemicals Evaluation and Research Institute, Japan) Column temperature: 40°C Mobile phase: 20 mM ammonium acetate, 25% acetonitrile buffer Analysis time: 10 minutes Detector: DAD (diode array detector) Detection wavelength: 230 nm Flow rate: 0.3 mL / min (isocratic elution) Injection volume: 10 μL

[0325] <Raw Materials Used> The materials used in this example are as follows. (1) Regenerated Collagen Fiber (i) Regenerated Collagen Fiber A Production Example 1: Cow split hide was solubilized with alkali according to standard methods to prepare a spinning dope. This was then extruded from a spinning nozzle into a coagulation bath for fiberization, followed by treatment with an epoxy compound to produce regenerated collagen fibers. The regenerated collagen fibers were immersed in 30 parts by mass of an aqueous solution containing 5.0% by mass of aluminum sulfate 14-18 hydrate, 0.65% by mass of citric acid monohydrate, and 1.3% by mass of sodium hydroxide per part by mass of the regenerated collagen fibers (equivalent to the dry weight of the fibers) at a temperature adjusted to 30°C while circulating the solution. A 5% aqueous sodium hydroxide solution was then added in portions over approximately 1 to 5 hours to adjust the final pH of the solution after 5 hours to 4.5 to 5.0. The regenerated collagen fibers were then retained in the solution for another 3 hours and thoroughly washed with water to obtain regenerated collagen fiber A. Regenerated collagen fiber A had a fiber swelling ratio in water of 435%. The preparation of the coagulation bath was carried out in accordance with WO 2017 / 159565, and the epoxy compound treatment was carried out in accordance with WO 2014 / 132889.

[0326] (ii) Regenerated Collagen Fiber B 300 fiber bundles (amount that would weigh 1.5 g when dried at 60°C for 1 hour and then left at 20°C and 65% RH for 12 hours) with a length of 30 cm were prepared from regenerated collagen fiber A. Each fiber bundle was hung individually in a dryer (SOFW-450SB, AS ONE Corporation) set to 60°C, a 250 g weight was attached to the bottom end of each fiber bundle, and the fiber was dried for 1 hour with tension applied to the entire fiber, which was used as regenerated collagen fiber B. Shape: Straight Fiber swelling rate in water: 113% Aluminum content: 6.8% by mass

[0327] (iii) Regenerated Collagen Fiber C Production Example 2 Cow split hide was solubilized with alkali according to a conventional method to prepare a spinning dope, which was then discharged from a spinning nozzle into a coagulation bath to form fibers, which were then treated with an epoxy compound and thoroughly washed with water to obtain regenerated collagen fiber C. The regenerated collagen fiber C had a fiber swelling rate in water of 692%. The coagulation bath was prepared according to WO 2017 / 159565, and the epoxy compound treatment was carried out according to WO 2014 / 132889.

[0328] (2) (A-1-1) Copolymer (i) Styrene-maleic acid copolymer sodium salt A XIRAN1000HNa (manufactured by Polyscope) was used. Weight average molecular weight (Mw): 9195 Hydrogen bond term δH value of Hansen solubility parameter: 11.5 Acid value: 475 mg KOH / g Molar ratio of styrene / maleic acid: 1 / 1

[0329] (ii) Styrene-maleic acid copolymer sodium salt B XIRAN2000HNa (manufactured by Polyscope) was used. Weight average molecular weight (Mw): 8143 Hydrogen bond term δH value of Hansen solubility parameter: 9.2 Acid value: 355 mg KOH / g Molar ratio of styrene / maleic acid: 2 / 1

[0330] (iii) Styrene-maleic acid copolymer sodium salt C XIRAN3000HNa (manufactured by Polyscope) was used. Weight average molecular weight (Mw): 13,803 Hydrogen bond term δH value of Hansen solubility parameter: 7.9 Acid value: 285 mg KOH / g Molar ratio of styrene / maleic acid: 3 / 1

[0331] (iv) Styrene-maleic acid copolymer sodium salt D XIRAN3500HNa (manufactured by Polyscope) was used. Weight average molecular weight (Mw): 71,785 Hydrogen bond term δH value of Hansen solubility parameter: 7.9 Acid value: 285 mg KOH / g Molar ratio of styrene / maleic acid: 3 / 1

[0332] (v) Styrene-maleic acid copolymer sodium salt E Styrene-maleic anhydride copolymer was synthesized according to the literature (Gunji et al., Color Materials, 75(10), 463-460 (2002)) and used after hydrolyzing with an aqueous sodium hydroxide solution. Weight average molecular weight (Mw): 17,448 Hydrogen bond term δH value of Hansen solubility parameter: 11.5 Acid value: 475 mg KOH / g Molar ratio of styrene / maleic acid: 1 / 1

[0333] (vi) Styrene-maleic acid copolymer sodium salt F Styrene-maleic anhydride copolymer was synthesized according to the literature (Gunji et al., Color Materials, 75(10), 463-460 (2002)) and used after hydrolyzing with an aqueous sodium hydroxide solution. Weight average molecular weight (Mw): 7049 Hydrogen bond term δH value of Hansen solubility parameter: 11.5 Acid value: 475 mg KOH / g Molar ratio of styrene / maleic acid: 1 / 1

[0334] (vii) Styrene-maleic acid copolymer sodium salt G Styrene-maleic anhydride copolymer was synthesized according to the literature (Gunji et al., Color Materials, 75(10), 463-460 (2002)) and used after hydrolyzing with an aqueous sodium hydroxide solution. Weight average molecular weight (Mw): 27,302 Hydrogen bond term δH value of Hansen solubility parameter: 11.5 Acid value: 475 mg KOH / g Molar ratio of styrene / maleic acid: 1 / 1

[0335] (viii) Styrene-maleic acid copolymer sodium salt H Styrene-maleic anhydride copolymer was synthesized according to the literature (Gunji et al., Color Materials, 75(10), 463-460 (2002)) and used after hydrolyzing with an aqueous sodium hydroxide solution. Weight average molecular weight (Mw): 3829 Hansen solubility parameter hydrogen bond term δH value: 11.5 Acid value: 475 mg KOH / g Molar ratio of styrene / maleic acid: 1 / 1

[0336] (ix) Styrene-maleic acid copolymer sodium salt I Styrene-maleic anhydride copolymer was synthesized according to the literature (Gunji et al., Color Materials, 75(10), 463-460 (2002)) and used after hydrolyzing with an aqueous sodium hydroxide solution. Weight average molecular weight (Mw): 10,530 Hydrogen bond term δH value of Hansen solubility parameter: 11.5 Acid value: 475 mg KOH / g Molar ratio of styrene / maleic acid: 1 / 1

[0337] (x) Sodium salt of styrene-maleic acid copolymer J Sodium salt of styrene-maleic anhydride copolymer was synthesized according to the literature (Gunji et al., Color Materials, 75(10), 463-460 (2002)) and used after hydrolyzing with an aqueous sodium hydroxide solution. Weight average molecular weight (Mw): 3288 Hydrogen bond term δH value of Hansen solubility parameter: 11.5 Acid value: 475 mg KOH / g Molar ratio of styrene / maleic acid: 1 / 1

[0338] (3) (A-1-2) Copolymer (i) Diisobutylene-Maleic Acid Copolymer Sodium Salt Demol EP (manufactured by Kao Corporation) was used. Weight average molecular weight (Mw): >1500 Hydrogen bond term δH value of Hansen solubility parameter: 9.4 Acid value: >100 mg KOH / g Diisobutylene / maleic acid molar ratio: 1 / 1

[0339] (ii) Butadiene-maleic acid copolymer sodium salt Ricon 130MA13 (manufactured by Cray Valley) was purchased as a butadiene-maleic anhydride copolymer and hydrolyzed with sodium hydroxide before use. Weight average molecular weight (Mw): >1500 Acid value: 74 mg KOH / g

[0340] (iii) Styrene-butadiene copolymer (carboxy-modified) sodium salt SBL0696 (manufactured by ENEOS Material Corporation) was used. Weight average molecular weight (Mw): >1500

[0341] (4) (A-1-3) Polymer (i) Polyacrylic acid Polyacrylic acid 5000 (manufactured by Kao Corporation) was used. Weight average molecular weight (Mw): 5000 Hydrogen bond term δH value of Hansen solubility parameter: 14.3 Acid value: 757 mg KOH / g

[0342] (ii) Polystyrene sulfonate sodium salt: The reagent "Poly(styrene sulfonate sodium salt), analytical standard, for GPC, 4,300" was purchased from Sigma-Aldrich and used. Weight average molecular weight (Mw): 4,300. Hansen solubility parameter, hydrogen bond term δH value: 13.7 (as polystyrene sulfonate).

[0343] (iii) Sodium polyvinyl sulfonate: The reagent "Poly(vinyl sulfonic acid) sodium salt, 25% aqueous solution (Polysciences, Inc.)" was purchased from Fujifilm Wako Pure Chemical Industries, Ltd. and used. Weight average molecular weight (Mw): >4000 Hydrogen bond term δH value of Hansen solubility parameter: 18.1 (as polyvinyl sulfonic acid).

[0344] (iv) Polyvinyl alcohol: The reagent "Poly(vinyl alcohol), MW 6000, 80% hydrolyzed (Polysciences, Inc.)" was purchased from Fujifilm Wako Pure Chemical Industries, Ltd. Weight-average molecular weight (Mw): 6000 Hydrogen bond term δH value of Hansen solubility parameter: 17.0

[0345] (5) (A-2-1) Condensate of sulfonic acid or its salt (i) β-naphthalenesulfonic acid formalin condensate sodium salt Demol N (manufactured by Kao Corporation) was used. Weight average molecular weight (Mw): >1500 Hydrogen bond term δH value of Hansen solubility parameter: 17.8 Acid value: >100 mg KOH / g

[0346] (6) (A-2-2) Condensate of Gallic Acid Ester (i) Tannic Acid Chemical Practical Grade Reagent (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used. Molecular weight (M): 1701 Hydroxyl value: 825 mg KOH / g

[0347] (7) Sodium benzoate: Wako Special Grade Reagent (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used. Molecular weight (M): 122; Hansen solubility parameter (hydrogen bond term δH value): 9.5; Acid value: 460 mg KOH / g

[0348] Examples 1 to 34 and Comparative Examples 1 to 3 Regenerated collagen fibers were treated according to the methods below using the compositions formulated as shown in Table 1, and various evaluations were carried out. In Comparative Example 1, only (Procedure 1) and (Procedure 6) of the treatment method A below were carried out and evaluated. The results of Examples 1 to 11 and Comparative Examples 1 and 2 are shown in Table 1, the results of Examples 12 to 22 are shown in Table 2 together with the results of Example 1 and Comparative Examples 1 and 2, and the results of Examples 23 to 34 and Comparative Example 3 are shown in Table 3 together with the result of Comparative Example 1.

[0349] <Treatment Method> (1) Treatment Method A Regenerated collagen fiber A was treated according to the following procedure. (Procedure 1) Ten 30 cm long fiber bundles (amounts that would weigh 1.5 g when dried at 60°C for 1 hour and then left at 20°C and 65% RH for 12 hours) were prepared from regenerated collagen fiber A for each Example and Comparative Example. (Procedure 2) Each fiber bundle was immersed in a separate container in an amount of fiber treatment agent at the bath ratio shown in the table (calculated based on the 1.5 g weight after drying in Procedure 1 above), and the opening of each container was sealed. (Procedure 3) The container was immersed in a water bath (TBS221FA, Toyo Seisakusho Co., Ltd.) set at the temperature shown in the table and allowed to stand for 5 minutes. The liquid temperature in the container was then raised to the temperature shown in the table, and the container was then removed from the water bath. (Procedure 4) The container containing the fiber bundle was placed on a stirring rotor (VMR-5R, AS ONE Corporation) installed in a dryer (SOFW-450SB, AS ONE Corporation) set to the temperature shown in the table, and the container was rotated at a rotation speed of 80 rpm, followed by heating and stirring for the time shown in the table. (Procedure 5) The container containing the fiber bundle was removed from the dryer and returned to room temperature, after which the fiber bundle was removed from the container and rinsed with running tap water at 30°C for 30 seconds, and the hair flow was adjusted with a comb. (Procedure 6) The fiber bundles were hung one by one in a dryer set to the temperature shown in the table, and a 250 g weight was attached to the bottom end of each fiber bundle. Drying was performed for the time shown in the table with tension applied to the entire fiber. (Procedure 7) The fiber bundles were removed from the dryer, returned to room temperature, and the weight was removed.

[0350] (2) Treatment Method B Regenerated collagen fiber B was treated according to the following procedure. (Procedure 1) Ten 30 cm long fiber bundles each weighing 1.5 g (measured after standing for 12 hours at 20°C and 65% RH) were prepared from regenerated collagen fiber B for each Example and Comparative Example. (Procedure 2) Each fiber bundle was immersed in a separate container in an amount of fiber treatment agent at the bath ratio shown in the table (the bath ratio was calculated based on the 1.5 g fiber weight obtained in Procedure 1 above), and the opening of each container was sealed. (Procedure 3) The container was immersed in a water bath (TBS221FA, Toyo Seisakusho Co., Ltd.) set at the temperature shown in the table and allowed to stand for 5 minutes. The liquid temperature in the container was then raised to the temperature shown in the table, after which the container was removed from the water bath. (Procedure 4) The container containing the fiber bundle was placed on a stirring rotor (VMR-5R, AS ONE Corporation) installed in a dryer (SOFW-450SB, AS ONE Corporation) set to the temperature shown in the table, and the container was rotated at a rotation speed of 80 rpm, followed by heating and stirring for the time shown in the table. (Procedure 5) The container containing the fiber bundle was removed from the dryer and returned to room temperature, after which the fiber bundle was removed from the container and rinsed with running tap water at 30°C for 30 seconds, and the hair flow was adjusted with a comb. (Procedure 6) The fiber bundles were hung one by one in a dryer set to 60°C, and a 250g weight was attached to the bottom end of each fiber bundle. Drying was performed for 1 hour with tension applied to the entire fiber. (Procedure 7) The fiber bundles were removed from the dryer, returned to room temperature, and the weight was removed.

[0351] <Evaluation> 1. Quantitation (i) Weight Increase (%) The weight (W) of the fiber bundle after treatment was measured after leaving it at 20°C and 65% RH for 12 hours, and the weight increase rate from the initial fiber bundle weight of 1.5 g was calculated.

[0352] Weight increase [%] = [(W - 1.5) / 1.5] x 100

[0353] A larger weight increase (%) indicates that a larger amount of component (A) has penetrated into the interior of the fiber, and a weight increase (%) of 0% is considered to indicate that substantially no penetration of component (A) has occurred into the interior of the fiber.

[0354] (ii) Amount (%) of component (A) (Mw≧1500) contained within the fiber: The amount of component (A) in the fiber, "GPC quantitative value Y (%)," was calculated based on the chromatogram obtained by GPC measurement described in "7. Quantitative Method for Component (A) in Fiber" under <Analysis Methods>. Note that "GPC quantitative value Y (%)" is the mass percent of component (A) in the fiber and does not correspond to the measured weight increase (%). That is, since the weight-average molecular weight of the copolymer related to component (A) is 1500 or more, "GPC quantitative value Y (%)" here does not refer to the amount of the fraction with a molecular weight of 1500 or more in the GPC chromatogram, but rather to the quantitative value of the entire copolymer related to component (A), including the fraction with a molecular weight less than 1500. Therefore, in the case of a copolymer with a weight-average molecular weight less than 1500, the copolymer does not fall under component (A), and therefore the quantitative value for component (A) is 0. Then, the "theoretical weight increase X (%)" calculated from the "GPC quantitative value Y (%)" was calculated by the following method.

[0355] (iii) Theoretical weight gain (%) Based on the GPC quantitative value Y (%) calculated in (ii) above, the theoretical weight gain X (%) was calculated using the following formula. The theoretical weight gain X (%) is the maximum value when it is assumed that no components are lost from the fiber due to elution or the like.

[0356] Weight increase X [%] = 100Y / (100-Y)

[0357] 2. Water Resistance (1) Elastic Modulus (MPa) When Fibers are Tensioned in Water The elastic modulus when fibers are tensioned in water was measured as follows. Evaluation was performed using a fiber bundle immediately after treatment using the above-mentioned <Treatment Method>. The average value when multiple (five) fibers were evaluated was used as the numerical value. A higher numerical value indicates firmness, resistance to stretching due to external force, and superior durability. Evaluation was performed using the following procedure. (Procedure 1) Five fibers were cut from the fiber bundle, and 3 cm fiber pieces were taken from each, resulting in a total of five 3 cm fiber pieces. (Procedure 2) The fiber pieces were placed in an automatic fiber tensile tester (MTT690, manufactured by DIA-STRON Limited). After the fibers were left immersed in water for 30 minutes, automatic tensile measurement was started to determine the elastic modulus when the fibers were tensioned in water. The cross-sectional area of ​​the fiber in water, which is necessary for determining the elastic modulus, was separately measured directly by optical microscopy.

[0358] (2) Increase in Average Breaking Elongation During Fiber Pulling (%) As an index of water resistance and stretchability (tenacity) during fiber pulling, the average breaking elongation, i.e., the percentage of stretching relative to the original fiber length at which the fiber breaks when pulled, was evaluated for multiple (10) fibers and the average value was used. The evaluation was performed using a fiber bundle immediately after the above-mentioned <Processing Method> treatment, as follows: (Procedure 1) Ten fibers were cut from the base of the fiber bundle. A 3 cm fiber piece was taken from the midpoint between the base and the tip of each fiber, resulting in a total of 10 3 cm hair pieces. (Procedure 2) The fiber pieces were placed in an automatic fiber tensile tester (MTT690, manufactured by DIA-STRON Limited). After leaving the fiber immersed in water for 30 minutes, automatic measurement was started, and the average breaking elongation was determined for the fiber immersed in water. The higher the value, the more elastic, tough and durable the material is.

[0359] According to the following formula, the average breaking elongation (A%) when the regenerated collagen fiber A was pulled without being treated with any chemicals and only dried (only the above-mentioned treatment method A (Step 1) and (Step 6) were performed, hereinafter also referred to as "untreated fiber (Comparative Example 1)") was used as the standard, and the increase (C%) in the average breaking elongation (B%) of the treated fiber bundle from the untreated state was recorded in the table as "increase rate (%) in average breaking elongation when the fiber was pulled."

[0360] Increase in average breaking elongation during fiber tension C (%) = B (%) - A (%)

[0361] (3) Increase in average breaking load when fiber is stretched (gf) The average breaking load when fiber is stretched was used as an index of water resistance when fiber is stretched. Evaluation was performed using a fiber bundle immediately after treatment with the above-mentioned <Treatment Method>. The numerical value was the average value when multiple fibers (10 fibers) were evaluated. The evaluation was performed using the following procedure. (Procedure 1) Ten fibers were cut from the base of the fiber bundle. A 3 cm fiber piece was taken from near the middle between the base and the tip of each fiber, resulting in a total of 10 3 cm hair pieces. (Procedure 2) The fiber pieces were placed in an automatic fiber tensile tester (MTT690, manufactured by DIA-STRON Limited). After leaving the fiber immersed in water for 30 minutes, automatic measurement was started to determine the breaking load when the fiber was stretched while immersed in water. A higher numerical value indicates resistance to breakage due to external force and superior durability.

[0362] According to the following formula, the average breaking load (W0 (gf)) when the regenerated collagen fiber A was pulled after drying without any chemical treatment [untreated fiber (Comparative Example 1)] was used as the standard, and the increase (Y (gf)) in the average breaking load (W1 (gf)) of the treated fiber bundle from the untreated state was recorded in the table as "Increase in average breaking load when the fiber was pulled [gf]".

[0363] Y(gf)=W1(gf)-W0(gf)

[0364] (4) Concentration (ppm) of Component (A) in Fiber Cleaning Solution The concentration of component (A) in the fiber cleaning solution was measured using the following procedure. The evaluation was performed using fiber bundles obtained in Example 1 and Comparative Example 3 immediately after treatment using the above-mentioned <Treatment Method>. (i) Preparation of Fiber Cleaning Solution Fibers were cut from the base of the fiber bundle to prepare 1.0 g of fiber bundle. This 1.0 g of fiber bundle was immersed in a container containing 100 g of ion-exchanged water, the container was sealed, and the container was immersed in a water bath (model number: TBS221FA, manufacturer: Toyo Seisakusho Co., Ltd.) set at 40°C and heated for 1 hour, after which the fibers were removed from the container. The ion-exchanged water remaining in the container was used as the fiber cleaning solution. (ii) Quantification of Component (A) in Fiber Cleaning Solution Quantification was performed by measuring the absorbance at a suitable wavelength using an ultraviolet-visible-near-infrared spectrophotometer. For example, when component (A) was a styrene-maleic acid copolymer sodium salt (XIRAN1000HNa, manufactured by Polyscope), the absorbance at 258 nm was measured using an ultraviolet-visible-near-infrared spectrophotometer (V-560, manufactured by JASCO Corporation), and the concentration of component (A) was calculated from the absorbance. A calibration curve was prepared by diluting "XIRAN1000HNa" manufactured by Polyscope with ion-exchanged water.

[0365] 3. Thermal Shape Memory Ability The thermal shape memory ability was evaluated using a fiber bundle immediately after the treatment described above. 0.5 g of fiber was cut from the base of the fiber bundle to prepare a 22 cm long fiber bundle. In the evaluation of "(I) Shaping (Curl)," if the curl-up ratio I was 7% or less, the treatment was deemed ineffective and subsequent treatments and evaluations were not performed. (I) Shaping (Curl) (Procedure 1) The prepared 22 cm long fiber bundle was wetted with 30°C tap water for 30 seconds, and then the wet fiber bundle was wrapped around a 14 mm diameter plastic rod and secured with a clip. (Procedure 2) The fiber bundle wrapped around the rod was immersed in a 60°C water bath (TBS221FA, Toyo Seisakusho Co., Ltd.) and heated for 1 minute. (Procedure 3) The fiber bundle was removed from the water bath, immersed in 20°C water for 1 minute, removed from the water, and allowed to return to room temperature. (Step 4) The fiber bundle was removed from the rod, combed three times, and then photographed from the side while hanging, 3 minutes after it was removed from the water. (Step 5) From the photograph, the length L of the fiber bundle when it was hung vertically (the distance from the top end of the fiber bundle to the furthest point) was measured.

[0366] (Evaluation Criteria) The length of the fiber bundle when stretched in a straight line was defined as L0, and the length of the fiber bundle after the shaping operation was defined as L. The curl-up ratio calculated according to the following formula = fiber bundle length reduction ratio (I) (%) was defined as the curl winding strength.

[0367] Curl-up ratio I (%) = [(L0 - L) / L0] x 100

[0368] (II) Reshaping (Straightening) (Procedure 1) The fiber bundle evaluated in (1) above was combed to straighten the hair flow, and then slid six times at a speed of 5 cm / sec with a flat iron (AHI-938, manufactured by Miki Electric Industrial Co., Ltd.) set at 180°C. (Procedure 2) Rinse with running tap water at 30°C for 30 seconds and towel dry. (Procedure 3) Hang and air dry for 12 hours at 20°C and 65% RH, then comb through three times, and photograph from the side while hanging. (Procedure 4) From the photograph, the length L (the distance from the top end of the fiber bundle to the furthest point) when the fiber bundle was hung vertically was measured.

[0369] (Evaluation Criteria) The length of the fiber bundle when stretched straight is L0, and the length of the fiber bundle after the shaping operation is L. The straightening rate (ST) (%) calculated according to the following formula was defined as the degree of achievement of straightening. When ST = 100%, the fiber bundle is completely straightened.

[0370] Straightening rate ST (%) = [1 - [(L0 - L) / L0]] x 100

[0371] (III) Reshaping (Curling) (Procedure 1) The fiber bundle evaluated in (2) above was wetted with 30°C tap water for 30 seconds, and then the wet fiber bundle was wound around a 14 mm diameter plastic rod and secured with a clip. (Procedure 2) The fiber bundle wound around the rod was immersed in a 60°C water bath (TBS221FA, Toyo Seisakusho Co., Ltd.) and heated for 1 minute. (Procedure 3) The fiber bundle was removed from the water bath, immersed in 20°C water for 1 minute, removed from the water, and allowed to return to room temperature. (Procedure 4) The fiber bundle was removed from the rod, combed three times, and then photographed from the side while hanging 3 minutes after removal from the water. (Procedure 5) The length L of the fiber bundle when hanging vertically (the distance from the top end of the fiber bundle to the furthest point) was measured from the photograph.

[0372] (Evaluation Criteria) The length of the fiber bundle when stretched in a straight line was defined as L0, and the length of the fiber bundle after the shaping operation was defined as L. The curl-up ratio calculated according to the following formula = fiber bundle length reduction ratio (I) (%) was defined as the curl winding strength.

[0373] Curl-up ratio I (%) = [(L0 - L) / L0] x 100

[0374] 4. Fiber swelling ratio in water (%) The fiber swelling ratio in water was calculated by the following formula (1): Evaluation was carried out using the fiber bundle immediately after treatment by the above-mentioned <Treatment method>.

[0375] Fiber swelling ratio in water S (%) = [(w1 - w2) / w2] × 100 (1)

[0376] The definitions of each symbol in formula (1) are as follows. w1: Fibers were cut from the base of the fiber bundle to prepare a 1.0 g fiber bundle. This 1.0 g fiber bundle was immersed in a container containing 100 g of ion-exchanged water, the container was sealed, and the entire container was immersed in a water bath (model number: TBS221FA, manufacturer: Toyo Seisakusho Co., Ltd.) set to 40 ° C. and heated for 30 minutes. The fibers were then removed from the container and placed in a small centrifuge (H-112, Kokusan Co., Ltd.) and centrifuged for 1 minute at a centrifugal force of 220 [× g] (rotation speed dial "4" (2000 rpm)). The fibers were then removed and immediately weighed, and this was designated weight w1. w2: The fibers after measuring weight w1 were placed on filter paper and placed in a dryer (SOFW-450SB, AS ONE Corporation) set to 105 ° C., dried for 3 hours, and then removed. The weight was immediately measured and designated weight w2.

[0377] 5. Surface feel: The surface feel was evaluated by five expert panelists using the fiber bundle immediately after treatment with the <Treatment method> to evaluate the smoothness of the feel when touched with the hand according to the following criteria, and the total value of the five panelists was used as the evaluation result.

[0378] (Evaluation criteria) 5: Extremely smooth to the touch compared to untreated fiber (Comparative Example 1) 4: Smoother to the touch compared to untreated fiber (Comparative Example 1) 3: Slightly smoother to the touch compared to untreated fiber (Comparative Example 1) 2: No difference in the touch from untreated fiber (Comparative Example 1) 1: Rougher and squeakier than untreated fiber (Comparative Example 1), and the touch is inferior

[0379] 6. Heat Resistance (1) Shrinkage (%) after Contact with Water Vapor at 110°C The shrinkage after contact with water vapor at 110°C was measured using the following procedure. Evaluation was performed using a fiber bundle immediately after treatment using the above-mentioned <Treatment Method>. (Procedure 1) Fibers were cut from the fiber bundle, and both ends of each five-fiber bundle were fixed with tape (Scotch tape, manufactured by 3M) to prepare a sample. At this time, the length of the fibers between the tapes was set to 10.0 cm. (Procedure 2) The sample was placed in an autoclave (model number: LSX-700, manufactured by Tomy Kogyo Co., Ltd.) and heated at 110°C for 10 minutes. (Procedure 3) The sample was removed, and the length h of the fibers between the tapes was measured. The percentage of shrinkage compared to the length before heating was calculated, and this was taken as the shrinkage H (%) after contact with water vapor at 110°C. The closer H is to 0%, the less likely the sample is to shrink due to heat, indicating better heat resistance.

[0380] Shrinkage rate after contact with water vapor at 110°C H (%) = [(10 - h) / 10] x 100

[0381] (wherein h represents the length (cm) of the sample after heating at 110°C for 10 minutes.)

[0382] The heat resistance of the fibers was evaluated according to the following criteria: The shrinkage rate H0 (%) of regenerated collagen fiber A after contact with water vapor at 110°C in a state where it was dried without any chemical treatment [untreated fiber (Comparative Example 1)] was used as the standard. The heat resistance was evaluated with a score of A to E according to the value of ΔH calculated by ΔH = H0 - H.

[0383] (Evaluation criteria) A: 6<ΔH B: 4<ΔH≦6 C: 2<ΔH≦4 D: 0<ΔH≦2 E: ΔH≦0

[0384] 7. Suppression of Fiber Coloring Suppression of fiber coloring was evaluated by the following procedure. The evaluation was carried out using a fiber bundle immediately after treatment with the above-mentioned <Treatment Method>. (Procedure 1) The color of the fiber near the root, midpoint, and tip on both the front and back of the fiber bundle was measured using a spectrophotometer (color difference meter CR-400, manufactured by Konica Minolta), and the average value of a total of six points was taken as the color measurement value (L, a, b). (Procedure 2) The degree of coloring was evaluated by ΔE using white untreated fiber (Comparative Example 1) as the standard. *abThe color was also measured on the same day that the treatment was carried out.

[0385] ΔE *ab is the value of (L1-L0) where the measured values ​​of the white untreated fiber (Comparative Example 1) are (L0, a0, b0) and the measured values ​​of the treated fiber bundle are (L1, a1, b1). 2 + (a1-a0) 2 +(b1-b0) 2 〕 1 / 2 The coloring suppression effect was evaluated according to the following criteria.

[0386] (Evaluation criteria) 5: ΔE *ab ≦5.0 4:5.0<ΔE *ab ≦10.0 3:10.0<ΔE *ab ≦15.0 2:15.0<ΔE *ab ≦20.0 1:20.0<ΔE *ab

[0387] 8. Fluorescence Imaging Measurement The regenerated collagen fibers treated with the composition of Example 37 were embedded in resin and then cut, and the exposed surface was subjected to fluorescence imaging measurement (excitation wavelength 400 nm, fluorescence detection wavelength 425 to 475 nm) using a confocal laser microscope (A1RHD25, manufactured by Nikon Corporation). The results are shown in Figure 1.

[0388]

[0389]

[0390]

[0391] Examples 35 to 38 and Comparative Example 4 Regenerated collagen fibers were treated and evaluated according to the methods described below using the compositions formulated as shown in Table 4. When an additional fiber treatment agent (third agent) containing component (D) was used, after treatment with the second agent, (Procedures 2) to (Procedure 5) were repeated using the third agent, and then (Procedure 7) was carried out.

[0392] <Treatment Method> (1) Treatment Method C Regenerated collagen fiber A or regenerated collagen fiber C was treated according to the following procedure. (Procedure 1) Ten 30 cm long fiber bundles (amount that would weigh 1.5 g when dried at 60°C for 1 hour and then left at 20°C and 65% RH for 12 hours) were prepared from the regenerated collagen fiber for each Example. First, the following (Procedure 2) to (Procedure 5) were performed using the first agent shown in the table. (Procedure 2) Each fiber bundle was immersed in a separate container in an amount of fiber treatment agent or additional fiber treatment agent at the bath ratio shown in the table (the bath ratio was calculated based on the 1.5 g weight after drying in Step 1 above), and the opening of each container was sealed. (Procedure 3) The container was immersed in a water bath (TBS221FA, Toyo Seisakusho Co., Ltd.) set at the temperature shown in the table and left to stand for 5 minutes. The liquid temperature in the container was then raised to the temperature shown in the table, and the container was then removed from the water bath. (Procedure 4) The container containing the fiber bundle was placed on a stirring rotor (VMR-5R, AS ONE Corporation) installed in a dryer (SOFW-450SB, AS ONE Corporation) set to the temperature shown in the table, and the container was rotated at a rotation speed of 80 rpm, followed by heating and stirring for the time shown in the table. (Procedure 5) The container containing the fiber bundle was removed from the dryer and returned to room temperature. The fiber bundle was then removed from the container and rinsed with running tap water at 30°C for 30 seconds, and the hair flow was adjusted with a comb. (Procedure 6) Using the second agent shown in the table, (Procedure 2) to (Procedure 5) were repeated. (Procedure 7) The fiber bundles were hung one by one in a dryer set to the temperature shown in the table, and a 250 g weight was attached to the bottom end of each fiber bundle. The fiber bundles were dried for the time shown in the table with tension applied to the entire fiber. (Procedure 8) The fiber bundles were removed from the dryer, returned to room temperature, and the weight was removed.

[0393] <Evaluation> Evaluation was carried out in accordance with the above-mentioned "1. Weight gain", "2. Water resistance" (1) to (3), "3. Thermal shape memory ability", "4. Fiber swelling ratio in water", "5. Good surface feel", "6. Heat resistance", and "7. Suppression of fiber coloration".

[0394]

Claims

1. A fiber treatment agent for use in treating fibers having a fiber swelling rate in water of 200% or more as calculated by the following formula (1), comprising the following components (A) and (B): (A) a compound having a coordinating functional group and a molecular weight of 1500 or more (B) water Fiber swelling rate in water (%) = [(w1 - w2) / w2] x 100 (1) (wherein w1 represents the mass (g) of the fiber measured after placing 1.0 g of fiber in a container filled with 100 g of ion-exchanged water, sealing the container, immersing the container in a water bath at 40°C for 30 minutes, removing the fiber from the container, and centrifuging for 1 minute at a centrifugal force of 220 [x g]. w2 represents the mass of the fiber measured after placing the fiber whose mass (w1) has been measured on a filter paper and drying it at 105°C for 3 hours.) 2. The fiber treatment agent according to claim 1, wherein the fiber is a regenerated protein fiber.

3. The fiber treatment agent according to claim 1 or 2, wherein the coordinating functional group is a group containing a hard base or an intermediate base according to the HSAB rule.

4. The fiber treatment agent according to any one of claims 1 to 3, wherein the coordinating functional group comprises one selected from the following components (a-1), (a-2) and (a-3): (a-1) a group having a carboxy group or a salt thereof, (a-2) a group having a hydroxyl group, an alkoxy group, an alkoxide anion or a metal alcoholate, and (a-3) a group having a sulfonic acid group or a salt thereof.

5. The fiber treatment agent according to any one of claims 1 to 4, wherein component (A) comprises one or more selected from the following (A-1) and (A-2): (A-1) A polymer containing a structural unit derived from an unsaturated monomer having a coordinating functional group, the polymer having a weight average molecular weight of 1500 or more; (A-2) A condensate of a compound having a coordinating functional group, the condensate having a molecular weight of 1500 or more.

6. The fiber treatment agent according to claim 5, wherein the polymer (A-1) further contains a structural unit derived from an unsaturated hydrocarbon compound.

7. The fiber treatment agent according to claim 5 or 6, wherein the polymer (A-1) comprises one or more selected from the following (A-1-1), (A-1-2), and (A-1-3): (A-1-1) A copolymer containing a structural unit derived from an unsaturated monomer having a coordinating functional group and a structural unit derived from an aromatic vinyl compound, and having a weight-average molecular weight of 1500 or more; (A-1-2) A copolymer containing a structural unit derived from an unsaturated monomer having a coordinating functional group and a structural unit derived from an unsaturated aliphatic hydrocarbon compound, and having a weight-average molecular weight of 1500 or more; (A-1-3) A polymer containing a structural unit derived from an aromatic vinyl compound having a coordinating functional group or a polymer containing a structural unit derived from an unsaturated aliphatic hydrocarbon compound having a coordinating functional group, and having a weight-average molecular weight of 1500 or more (excluding the copolymers (A-1-1) and (A-1-2)).

8. The fiber treatment agent according to claim 5, wherein the condensate (A-2) is a condensate having a molecular weight of 1,500 or more and includes one or more condensates selected from the following (A-2-1) and (A-2-2): (A-2-1) A condensate of sulfonic acid or a salt thereof (A-2-2) A condensate of a gallic acid ester 9. The fiber treatment agent according to any one of claims 1 to 8, further comprising the following component (C): (C) a polyvalent metal element.

10. The fiber treatment agent according to claim 9, wherein the content of component (C) in the fiber treatment agent is 0.0001% by mass or more and 1% by mass or less.

11. A fiber treatment kit comprising a first fiber treatment agent containing the following components (A) and (B), and a second fiber treatment agent containing the following components (A) and (B), the second fiber treatment agent having a pH at least 1.0 lower than that of the first fiber treatment agent, for use in treating a fiber having a swelling rate in water of 200% or more as calculated by the following formula (1): (A) a compound having a coordinating functional group and a molecular weight of 1500 or more (B) water Fiber swelling rate in water (%) = [(w1 - w2) / w2] x 100 (1) (wherein w1 represents the mass (g) of the fiber measured after placing 1.0 g of fiber in a container filled with 100 g of ion-exchanged water, sealing the container, immersing the container in a water bath at 40°C for 30 minutes, removing the fiber from the container, and centrifuging for 1 minute at a centrifugal force of 220 [x g]. w2 indicates the mass of the fiber measured after the mass (w1) was measured and the fiber was placed on a filter paper and dried at 105° C. for 3 hours.

12. A fiber treatment kit for use in treating a fiber having a swelling rate in water of 200% or more calculated by the following formula (1), comprising a fiber treatment agent containing the following components (A) and (B) and an additional fiber treatment agent containing the following component (D). (D) A fiber treatment kit for use in treating a fiber having a swelling rate in water of 200% or more calculated by the following formula (1), comprising the following components (A) and (B): 1 / 2 (A) A compound having at least one carboxy group or a salt thereof and having no condensed ring, which is equal to or less than the above (excluding component (A)). (A) A compound having a coordinating functional group and a molecular weight of 1,500 or more. (B) Water. Fiber swelling ratio in water (%) = [(w1 - w2) / w2] x 100 (1) (wherein w1 represents the mass (g) of the fiber measured after placing 1.0 g of fiber in a container filled with 100 g of ion-exchanged water, sealing the container, immersing the container in a water bath at 40°C for 30 minutes, removing the fiber from the container, and centrifuging for 1 minute at a centrifugal force of 220 [x g]. w2 represents the mass of the fiber measured after placing the fiber whose mass (w1) has been measured on a filter paper and drying it at 105°C for 3 hours.)

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