Fiber treatment agent

Abstract

The present invention provides a fiber treatment agent which contains the following components (A) and (B) and is used in the treatment of fibers having a fiber swelling ratio in water of 200% or more as calculated by formula (1). (A) A compound having a coordinating functional group and a molecular weight of 1500 or more (B) Water. The swelling ratio (%) of the fiber in water is equal to [(w1-w2) / w2] * 100 (1), in the formula, w1 represents the mass (g) of the fiber measured by putting 1.0 g of the fiber into a container filled with 100g of ion exchange water, sealing the container, dipping the container into a water bath at 40 DEG C for 30 minutes, taking out the fiber from the container, and centrifugally dewatering for 1 minute at a centrifugal force of 220 [* g]; and w2 represents the mass of the fiber measured after the fiber with the measured mass (w1) is placed on filter paper and dried at 105 DEG C for 3 hours.

Description

Technical Field

[0001] This invention relates to fiber treatment agents. Background Technology

[0002] Naturally derived fibers typically differ from synthetic fibers, possessing a natural feel and appearance derived from natural materials. Regenerated protein fibers, such as regenerated collagen fibers, are typically manufactured by dissolving acid-soluble or insoluble collagen with alkali or enzymes to create a spinning solution. This solution is then extruded from a spinning nozzle into a coagulation bath for fiberization, and finally dried in a final process.

[0003] However, compared to synthetic fibers, naturally derived fibers are generally more hydrophilic, resulting in higher water absorption rates. When containing a large amount of water, their mechanical strength is typically lower, especially that of regenerated protein fibers, which have extremely low mechanical strength. Therefore, during washing, the mechanical strength decreases significantly due to the high water absorption rate, leading to breakage during subsequent drying with a hair dryer, thus reducing their suitability for use in hair accessories. Furthermore, regenerated protein fibers also suffer from low heat resistance. For example, when heat-setting with hair curlers at the same high temperature as human hair, they shrink or curl, compromising their appearance. Additionally, while synthetic fibers made of plastic retain their shape after heat-setting with hair curlers (possessing thermal shape memory), naturally derived fibers lose their shape after a single wash (lacking thermal shape memory). Therefore, compared to existing synthetic fibers made of plastic, they are less flexible in terms of styling. These problems are the main reasons hindering the widespread adoption of naturally derived fibers, especially regenerated protein fibers, in hair accessories and other fiber products.

[0004] Therefore, various studies have been conducted to address the aforementioned technical problems with naturally derived fibers. For example, it has been reported that crosslinking the wool with acrylic resin in fabrics containing at least 10% by weight of wool can suppress wear (pilling) caused by friction during washing (Patent Document 1). It has also been reported that treating naturally derived fibers with a fiber treatment agent containing specific hydroxymethyl compounds and specific phenolic compounds can solve the aforementioned technical problems related to water resistance, heat resistance, and thermal shape memory inherent in naturally derived fibers (Patent Document 2).

[0005] Patent Document 1: Japanese Patent Application Publication No. 1-260062

[0006] Patent Document 2: Japanese Patent Application Publication No. 2022-103113 Summary of the Invention

[0007] The present invention provides the following [1] to

[12] .

[0008] [1] A fiber treatment agent, wherein the fiber treatment agent contains the following components (A) and (B) for use in the treatment of fibers with a water swelling rate of 200% or more as calculated according to the following formula (1),

[0009] (A) Compounds with coordinating functional groups and a molecular weight of 1500 or more.

[0010] (B) Water.

[0011] Fiber swelling rate in water (%) = [(w1-w2) / w2]×100 (1)

[0012] [In the formula, w1 represents the mass (g) of the fiber after 1.0g of fiber is placed in a container filled with 100g of ion-exchange water, the container is sealed, and the fiber is immersed in a water bath at 40°C for 30 minutes. After that, the fiber is taken out of the container and centrifuged at 220 [×g] for 1 minute to remove water.]

[0013] w2 represents the mass of the fiber after it has been measured (w1) is placed on filter paper and dried at 105°C for 3 hours.

[0014] [2] The fiber treatment agent as described in [1] above, wherein the fiber is a regenerated protein fiber.

[0015] [3] The fiber treatment agent as described in [1] or [2] above, wherein the coordination functional group is a group comprising a hard base or a cross-base in the hard acid-base rule (HSAB rule).

[0016] [4] The fiber treatment agent as described in any one of [1] to [3] above, wherein the coordinating functional group comprises a group selected from components (a-1), (a-2) and (a-3),

[0017] (a-1) A group having a carboxyl group or a salt thereof,

[0018] (a-2) Groups having hydroxyl, alkoxy, alkoxide anion, or metal alkoxide groups,

[0019] (a-3) A group having a sulfonic acid group or a salt thereof.

[0020] [5] The fiber treatment agent as described in any one of [1] to [4] above, wherein component (A) contains one or more selected from (A-1) and (A-2) below.

[0021] (A-1) A polymer comprising structural units derived from unsaturated monomers having coordinating functional groups, wherein the polymer has a weight-average molecular weight of 1500 or more.

[0022] (A-2) A condensate of a compound having a coordinating functional group, wherein the molecular weight of the condensate is greater than 1500.

[0023] [6] The fiber treatment agent as described in [5] above, wherein the (A-1) polymer further comprises structural units derived from unsaturated hydrocarbon compounds.

[0024] [7] The fiber treatment agent as described in [5] or [6] above, wherein the (A-1) polymer contains one or more selected from (A-1-1), (A-1-2) and (A-1-3).

[0025] (A-1-1) is a copolymer comprising structural units derived from unsaturated monomers having coordinating functional groups and structural units derived from aromatic vinyl compounds, wherein the copolymer has a weight-average molecular weight of 1500 or more.

[0026] (A-1-2) comprises a copolymer containing structural units derived from an unsaturated monomer having a coordinating functional group and structural units derived from an unsaturated aliphatic hydrocarbon compound, wherein the copolymer has a weight-average molecular weight of 1500 or more.

[0027] (A-1-3) A polymer comprising a structural unit derived from an aromatic vinyl compound having a coordinating functional group or a polymer comprising a structural unit derived from an unsaturated aliphatic hydrocarbon compound having a coordinating functional group, wherein the polymer has a weight average molecular weight of 1500 or more (excluding copolymers (A-1-1) and (A-1-2)).

[0028] [8] The fiber treatment agent as described in [5] above, wherein the (A-2) condensate is a condensate with a molecular weight of 1500 or more, and contains one or more condensates selected from (A-2-1) and (A-2-2) below.

[0029] (A-2-1) A condensate of sulfonic acid or a salt thereof.

[0030] (A-2-2) condensate of gallic acid ester.

[0031] [9] The fiber treatment agent as described in any one of [1] to [8] above, wherein it further contains the following component (C).

[0032] (C) Polyvalent metal elements

[0033]

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

[0034]

[11] A fiber treatment kit, wherein:

[0035] A first fiber treatment agent containing the following components (A) and (B); and

[0036] A second fiber treatment agent containing the following components (A) and (B), wherein the pH of the second fiber treatment agent is more than 1.0 lower than the pH of the first fiber treatment agent.

[0037] The fiber treatment kit is used for the treatment of fibers with a water swelling rate of 200% or more, calculated according to the following formula (1).

[0038]

[12] A fiber treatment kit, wherein:

[0039] A fiber treatment agent containing the following components (A) and (B); and

[0040] Additional fiber treatment agents containing the following component (D),

[0041] The fiber treatment kit is used for treating fibers with a water swelling rate of 200% or more, calculated according to the following formula (1).

[0042] (D) The hydrogen bonding term δH of Hansen's solubility parameter is 18.3 MPa. 1 / 2 The following are compounds or salts thereof having at least one carboxyl group or a salt thereof and not having a fused ring (excluding component (A)).

[0043] (A) Compounds with coordinating functional groups and a molecular weight of 1500 or more.

[0044] (B) Water,

[0045] Fiber swelling rate in water (%) = [(w1-w2) / w2]×100 (1)

[0046] In the formula,

[0047] w1 represents the mass (g) of fiber obtained by placing 1.0g of fiber into a container filled with 100g of ion-exchanged water, sealing the container, immersing the fiber together in a 40°C water bath for 30 minutes, removing the fiber from the container, centrifuging it at 220 [×g] for 1 minute to remove water.

[0048] w2 represents the mass of the fiber after it has been measured (w1) is placed on filter paper and dried at 105°C for 3 hours. Attached Figure Description

[0049] Figure 1 It is a fluorescence imaging image of a fiber cross-section treated with the fiber treatment agent of Example 37. Detailed Implementation

[0050] While Patent Document 1 proposes a technique for modifying fibers using compounds with a certain molecular weight, it merely involves cross-linking the polymer compound with wool to achieve surface coverage. That is, prior to this application, there was a technical problem that compounds with a certain molecular weight could not penetrate the fibers from natural sources. On the other hand, Patent Document 2 describes a technique for modifying fibers using compounds with a certain molecular weight by impregnating hydroxymethyl and phenolic compounds into the fibers, coordinating phenolic hydroxyl groups within the fibers, and using hydroxymethyl compounds to condense the phenolic compounds together. This technique utilizes polymerized condensates to modify the fibers from within. However, when using this technique to modify fibers from within, the steps of monomer impregnation into the fibers and monomer polymerization within the fibers are essential, making the process cumbersome and limiting its application to large quantities of naturally sourced fibers.

[0051] Therefore, the present invention relates to a novel fiber treatment agent capable of impregnating a compound having a certain amount or more of molecular weight into the fiber.

[0052] In view of the above-mentioned technical problems, the inventors of the present invention have conducted in-depth research and found that compounds containing specific characteristic groups and having a certain molecular weight can specifically penetrate natural source fibers with specific properties, and the specific characteristic groups are coordinated with the fibers, thus solving the above-mentioned technical problems unique to natural source fibers, thereby completing the present invention.

[0053] According to the present invention, a novel fiber treatment agent is provided that allows compounds having a certain or higher molecular weight to penetrate into fibers and modify the fibers from within. Furthermore, by treating fibers with the fiber treatment agent of the present invention, water resistance and thermal shape memory can be improved, and the treatment process is simple. Therefore, it is useful as a fiber treatment agent for naturally derived fibers used in headwear products such as wigs and hair extensions.

[0054] [Fiber treatment agent]

[0055] The fiber treatment agent of the present invention contains components (A) and (B) as constituent components, and is suitable for fibers having specific properties.

[0056] <Fibers to which the fiber treatment agent of the present invention is applicable>

[0057] The fibers of the fiber treatment agent to which the present invention is applicable need to have a water swelling rate of 200% or more as calculated according to the following formula (1).

[0058] The fiber swelling rate in water, S (%) = [(w1-w2) / w2] × 100 (1)

[0059] In the formula,

[0060] w1 represents the mass (g) of fiber obtained by placing 1.0g of fiber into a container filled with 100g of ion-exchanged water, sealing the container, immersing the fiber together in a 40°C water bath for 30 minutes, removing the fiber from the container, centrifuging it at 220 [×g] for 1 minute to remove water.

[0061] w2 represents the mass of the fiber after it has been measured (w1) is placed on filter paper and dried at 105°C for 3 hours.

[0062] The centrifugal force [×g] is calculated according to the following formula.

[0063] Centrifugal force [×g] = 1.118 × centrifugal radius (m) × [rotation speed (min)] -1 )] 2 ×10 -3

[0064] Even when commercially available and readily available fibers are treated with fiber treatment agents containing compounds with a certain molecular weight or higher, the compounds merely coat the surface of the fibers and cannot penetrate into the fiber interior. This technical problem has long been recognized by those skilled in the art but remained unsolved prior to the filing of this application. Therefore, the inventors of this invention focused on the maximum swelling rate of fibers in water and explored fibers capable of penetrating into the fiber interior. They discovered that if a fiber has a specific property such that its swelling rate in water is 200% or higher as calculated according to the following formula (1), even compounds with a certain molecular weight or higher can penetrate into the fiber interior. Furthermore, it was found that by introducing coordination functional groups into the compound and setting the molecular weight to 1500 or higher, the compound can be retained in the fiber after penetration, thus solving the aforementioned technical problem unique to regenerated collagen fibers.

[0065] The fiber swelling rate in water of the fiber treated with the fiber treatment agent of the present invention is 200% or more, and from the viewpoint of promoting fiber penetration, it is preferably 250% or more, more preferably 300% or more, and even more preferably 350% or more. Furthermore, from the viewpoint of avoiding fiber breakage during the fiber treatment process due to excessive swelling (from the viewpoint of the operability of the fiber treatment process), 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 rate in water of the applicable fiber is preferably 250–1000%, more preferably 300–800%, even more preferably 350–600%, and even more preferably 350–500%.

[0066] Furthermore, there are no particular limitations on the applicable fibers as long as the fiber swelling rate in water is within the aforementioned range. Fibers containing metals are preferred, and naturally derived fibers or synthetic fibers containing metals are even more preferred. Among these, naturally derived fibers containing metals are preferred. Naturally derived fibers refer to fibers obtained from natural plants and animals, or fibers artificially manufactured using polymers or oligomers of proteins or polysaccharides derived from keratin, collagen, casein, soybeans, peanuts, corn, silk flakes, silk protein (e.g., silk fibroin), etc., as raw materials. Among these, fibers artificially manufactured from polymers or oligomers of proteins or polysaccharides derived from keratin, collagen, casein, soybeans, peanuts, corn, silk flakes, and silk proteins (e.g., silk fibroin) are preferred. Regenerated protein fibers derived from proteins derived from keratin, collagen, casein, soybean protein, peanut protein, corn protein, and silk proteins (e.g., silk fibroin) are even more preferred. Regenerated collagen fibers derived from collagen and regenerated silk fibers derived from silk fibroin are even more preferred. Regenerated collagen fibers are even more preferred.

[0067] Regenerated collagen fibers only need to have a fiber swelling rate within the above-mentioned range in water; they do not need to be 100% collagen and may contain natural or synthetic polymers or additives for quality improvement. They can also be fibers obtained by further processing regenerated collagen fibers. As for the form of regenerated collagen fibers, filaments are preferred. Filaments are usually taken out in spools or boxes.

[0068] Preferred regenerated collagen fibers are artificially manufactured fibers made from polymers or oligomers derived from collagen, i.e., regenerated collagen fibers made from collagen, and are regenerated collagen fibers with a fiber swelling rate in water within the aforementioned range.

[0069] Regenerated collagen fibers are typically manufactured by preparing a spinning solution from a solubilized collagen raw material, then extruding it from a spinning nozzle into a coagulation bath for fiberization, followed by drying the fibrous collagen in a final process. However, the undried regenerated collagen fibers before the drying process meet the aforementioned requirement of fiber swelling rate in water. Such undried regenerated collagen fibers can be manufactured using existing known methods before the drying process. For example, an example is the undried regenerated collagen fibers recovered without drying after solubilizing insoluble collagen fibers made from animal hides, extruding the resulting collagen aqueous solution through a spinning nozzle or slit, immersing it in an inorganic salt aqueous solution, and then retrieving it. Specific details are provided below.

[0070] As a raw material for collagen, the hide portion is preferred. The hide can be obtained, for example, from fresh hides or salted raw hides obtained from slaughtering livestock such as cattle. These hides are mostly composed of insoluble collagen fibers and are usually used after the reticular attached meat parts and the salt used to prevent spoilage have been removed.

[0071] The insoluble collagen fibers contain impurities such as lipids (glycerides, phospholipids, free fatty acids, etc.) and proteins (glycoproteins, albumin, etc.) other than collagen. These impurities significantly affect the spinning stability, luster, tensile strength, and other qualities, as well as odor, during fiberization. Therefore, it is preferable to pre-treat these impurities by hydrolyzing the fatty components in the insoluble collagen fibers, such as by lime impregnation, to loosen the collagen fibers, followed by conventional leather treatments in the prior art, such as acid-alkali treatment, enzyme treatment, and solvent treatment.

[0072] For insoluble collagen that has undergone this treatment, a solubilization process is performed to cleave the cross-linked peptides. Commonly known methods for this solubilization include alkali dissolution and enzymatic dissolution, or a combination of both.

[0073] When using the alkaline dissolution method, neutralization is preferably performed using an acid such as hydrochloric acid. Alternatively, as an improvement to the alkaline dissolution method known in the prior art, the method described in, for example, Japanese Patent Publication No. 46-15033 can be employed.

[0074] Enzymatic dissolution has the advantage of obtaining solubilized collagen with uniform molecular weight, and is the preferred method adopted in this invention. Such enzymatic dissolution methods can be those described in, for example, Japanese Patent Publication Nos. 43-25829 and 43-27513.

[0075] By further performing pH adjustment, salting out, washing, and solvent treatment on collagen that has undergone such solubilization treatment, high-quality regenerated collagen fibers can be obtained, and therefore these treatments are preferred.

[0076] Soluble collagen is dissolved using acids such as hydrochloric acid, acetic acid, or lactic acid, and adjusted to an aqueous collagen solution with a pH of 2–4.5 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 can be degassed under reduced pressure or filtered to remove fine impurities that are water-insoluble components, as needed. Furthermore, appropriate amounts of stabilizers, water-soluble polymers, and other additives can be added to the collagen aqueous solution as needed, for example, to improve mechanical strength, water and heat resistance, gloss, spinnability, prevent coloring, and prevent corrosion.

[0077] Collagen aqueous solution is sprayed through, for example, a spinning nozzle or slit, and then immersed in an inorganic salt aqueous solution, thereby obtaining undried regenerated collagen fibers. As the inorganic salt aqueous solution, aqueous solutions of water-soluble inorganic salts such as sodium sulfate, sodium chloride, and ammonium sulfate can be used. Typically, the concentration of inorganic salts in these aqueous solutions is adjusted to 10-40% by mass. The pH of the inorganic salt aqueous solution is preferably 2 or higher, more preferably 4 or higher, and preferably 13 or lower, more preferably 12 or lower. This pH adjustment can be achieved using metal salts such as sodium borate and sodium acetate, or hydrochloric acid, boric acid, acetic acid, and sodium hydroxide. When the pH of the inorganic salt aqueous solution is within the above range, the peptide bonds of collagen are less likely to hydrolyze, making it easier to obtain the target fibers. Furthermore, the temperature of the inorganic salt aqueous solution is not particularly limited, but from the viewpoint of preventing denaturation of soluble collagen, maintaining the strength of the fibers after spinning, and easily producing stable yarns, a temperature of 35°C or lower is generally preferred. Moreover, the lower limit of the temperature of the inorganic salt aqueous solution is not particularly limited, and is usually adjusted appropriately according to the solubility of the inorganic salts.

[0078] Undried regenerated collagen fibers can be pretreated (crosslinked) by impregnating them with 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, further preferably 1 equivalent or more, and preferably 500 equivalents or less, more preferably 100 equivalents or less, and further preferably 50 equivalents or less, with the epoxy compound monomer amount within the above range being sufficient to impart water-insoluble properties to the regenerated collagen fibers, and is also preferred in terms of industrial operability and environmental impact.

[0079] Epoxy monomers can be used directly or dissolved in various solvents. Examples of solvents include: water; alcohols such as methanol, ethanol, 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 can be used alone or in combination. When using water as a solvent, aqueous solutions of inorganic salts such as sodium sulfate, sodium chloride, and ammonium sulfate can be used as needed. Typically, the concentration of inorganic salts in the aqueous solution is adjusted to 10–40% by mass. Furthermore, the pH of the aqueous solution can be adjusted using metal salts such as sodium borate and sodium acetate, or hydrochloric acid, boric acid, acetic acid, and sodium hydroxide. In this case, from the viewpoint that the reaction between the epoxy groups of the epoxy monomers and the amino groups of collagen is not slowed down and that water insolubility is sufficient, the pH of the aqueous solution is preferably 6 or higher, and more preferably 8 or higher. In addition, since the pH of aqueous solutions of inorganic salts tends to decrease over time, buffers can be used as needed.

[0080] Regarding the processing temperature of undried regenerated collagen fibers using epoxy compound monomers, from the viewpoint that the regenerated collagen fibers do not degrade, the strength of the obtained fibers does not decrease, and it is easy to manufacture stable filaments, it is preferably below 50°C.

[0081] Furthermore, fibers to which the fiber treatment agent of the present invention is applicable are preferably made, from the viewpoint of improving water resistance, containing a polyvalent metal, or a salt thereof, or a complex thereof. Examples include one or more polyvalent metals, or salts thereof, or complexes thereof, selected from calcium, magnesium, strontium, barium, zinc, chromium, aluminum, titanium, zirconium, tin, lead, antimony, iron, and copper. From the viewpoint of ease of formulation and improved water resistance, heat resistance, and thermal shape memory, one or more polyvalent metals, or salts thereof, or complexes thereof, selected from aluminum, zirconium, and titanium are preferred, and aluminum, or salts thereof, or complexes thereof are more preferred. From the viewpoint of easy compatibility and improved water resistance, heat resistance, and thermal shape memory, the content of polyvalent metals, or their salts or complexes, in regenerated collagen fibers is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, further preferably 3.0% by mass or more, and even more preferably 5.0% by mass or more, in terms of elemental mass. Furthermore, from the viewpoint of improving the tactile feel of the fiber surface, it is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and even more preferably 10% by mass or less. That is, the content of polyvalent metals, or their salts or complexes, in applicable fibers is preferably 1.0 to 40% by mass, more preferably 2.0 to 30% by mass, further preferably 3.0 to 20% by mass, and even more preferably 5.0 to 10% by mass, in terms of elemental mass. In this specification, the "amount of elemental mass" can be quantified using ICP emission spectroscopy analysis. For example, an iCAP6500Duo (manufactured by Thermo Fisher Scientific Inc.) can be used as the ICP emission analysis device during ICP emission spectroscopy analysis. Furthermore, the measurement conditions for ICP emission spectroscopy analysis are as follows: the optimal analytical wavelength for the target metal can be determined by confirming the spectral pattern. For example, for aluminum, it is 396.152 nm. Additionally, the analytical sample can be pretreated according to the methods described in the examples, and calibration curves can be prepared for each target metal.

[0082] <Measurement Conditions>

[0083] •RF power: 1150W

[0084] • Cooling gas flow rate: 12L / min

[0085] • Atomizer flow rate: 0.70L / min

[0086] • Assist gas: 0.5 L / min

[0087] • Pump flow rate: 50 rpm

[0088] Furthermore, the undried regenerated collagen fibers are in a state of swelling with water or an aqueous solution of inorganic salts. This swelling can be in a state where the water or inorganic salt solution contains 4 to 15 times its mass relative to the regenerated collagen fibers. When the water or inorganic salt solution content is less than 4 times, the aluminum salt content in the regenerated collagen fibers is low, and there is a tendency for insufficient water resistance; while when it exceeds 15 times, the fiber strength deteriorates, and there is a tendency for handling to become difficult. Therefore, metals can be included in such a manner that the amount of metal element is within the above-mentioned range. For example, the following treatment can be performed.

[0089] First, the undried regenerated collagen fibers are impregnated in an aqueous solution of an aluminum salt. The preferred aluminum salts are basic aluminum chloride or basic aluminum sulfate, as shown in the following formula.

[0090] Al(OH) n Cl 3-n or Al2(OH) 2n (SO4) 3-n

[0091] [In the formula, n is 0.5 to 2.5.]

[0092] Specific examples include aluminum sulfate, aluminum chloride, and alum. Aluminum salts can be used alone or in combination of two or more.

[0093] The aluminum salt concentration in the aluminum salt aqueous solution, converted to alumina, is preferably 0.3 to 5% by mass. When the aluminum salt concentration is below 0.3% by mass, the aluminum salt content in the regenerated collagen fiber is low, and there is a tendency for insufficient water resistance; while when it exceeds 5% by mass, the treated fiber becomes hard, and there is a tendency for it to affect the feel.

[0094] The pH of aluminum salt aqueous solutions is typically 2.5–5. It can be adjusted using, for example, hydrochloric acid, sulfuric acid, acetic acid, sodium hydroxide, sodium carbonate, etc. Below 2.5, there is a tendency to damage the structure of collagen and cause denaturation; while above 5, aluminum salt precipitation occurs, making it difficult to penetrate the fibers. For pH, it is preferable to initially adjust to 2.2–3.5 to allow the aluminum salt aqueous solution to fully penetrate the regenerated collagen fibers, and then add, for example, sodium hydroxide or sodium carbonate, to adjust to 3.5–5 to complete the treatment. When using highly alkaline aluminum salts, an initial pH adjustment to 2.5–5 may also be performed.

[0095] Furthermore, the temperature of the aluminum salt aqueous solution is not particularly limited, but is preferably below 50°C. When the temperature exceeds 50°C, there is a tendency for modification of regenerated collagen fibers.

[0096] The immersion time of undried regenerated collagen fibers in an aqueous aluminum salt solution is typically 3 hours or more, preferably 6 to 25 hours. When the immersion time is less than 3 hours, the reaction of the aluminum salt is difficult to proceed, and there is a tendency for the water resistance of the regenerated collagen fibers to become insufficient. Furthermore, there is no particular upper limit to the immersion time; the reaction of the aluminum salt can proceed sufficiently within 25 hours, and the water resistance is also good.

[0097] In addition, to prevent uneven concentration of aluminum salts from being rapidly absorbed in regenerated collagen fibers, inorganic salts such as sodium chloride, sodium sulfate, and potassium chloride can be appropriately added to the aluminum salt aqueous solution.

[0098] After treating the regenerated collagen fibers with epoxy monomers or aluminum salts, they can be washed with water. Washing can be done, for example, by rinsing with running water for 10 minutes to 4 hours.

[0099] <Components>

[0100] [Ingredients (A)]

[0101] In the fiber treatment agent of the present invention, component (A) contains a compound having a coordinating functional group and a molecular weight of 1500 or more. Component (A) may be contained alone or in combination of two or more compounds.

[0102] In the prior art, compounds with a molecular weight of 1500 or higher are difficult to penetrate fibers, especially those of natural origin. However, the inventors of this invention unexpectedly discovered that, if it is component (A), it can penetrate into the interior of the fibers with the specific properties described above, and can modify the fibers by coordinating the coordinating functional groups within the fibers. Therefore, the fiber treatment agent of this invention should be called a fiber-penetrating treatment agent, which is completely different from conventional surface-coating fiber treatment agents.

[0103] (Coordination functional groups)

[0104] As a coordinating functional group, from the viewpoint of promoting penetration and coordination into fibers, and improving water resistance, heat resistance, and thermal shape memory, groups containing hard bases or borderline bases as defined in the HSAB rule are preferred. Here, in this specification, the "HSAB rule (Hard and Soft Acids and Bases rule)" refers to the classification of acid and base strength proposed by R.Pearson, which is based on the viewpoint of hardness and softness (J. Am. Chem. Soc. 1967, 89, 8, 1827-1836). Furthermore, "Pearson's hard base" refers to Lewis bases classified as hard bases in the concept of the HSAB rule introduced by Pearson in the 1960s, which are considered to readily react with Lewis acids classified as hard acids. As a hard base, functional groups equivalent to those of a hard base can be listed 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. Additionally, a borderline base is any type of base that is not classified as either a hard or soft base, meaning its strength lies between that of a hard and a soft base.

[0105] As a hard base, examples that can be listed include those containing hydroxide ions (OH-). - ), fluoride ions (F) - ), carboxyl group (COOH), carboxyl anion (COO) - ), carboxylates (COOM), phosphate ions (PO4) 3- ), sulfate ions (SO4) 2- ), chloride ions (Cl) - ), carbonate ions (CO3) 3- ), perchlorate ions (ClO4) - ), hydroxyl (OH), alkoxy groups with ether bonds (-O-) i.e., alkoxy groups (OR), alkoxide anions (O - The group consists of a metal alkoxide (OM), an ammonia (NH3), or an imino group (NH2). M represents a metal, preferably an alkali metal.

[0106] As a boundary base, examples that include bromide ions (Br) can be listed. - ), sulfite ions (SO3) 2-), azide ions (N 3- ), sulfonic acid group (SO3H), sulfonate group (SO3M, where M has the same meaning as above).

[0107] Among them, as a coordinating functional group, from the viewpoint of promoting penetration and coordination into the fiber, and improving water resistance, heat resistance and thermal shape memory ability, it is preferable to include a base group selected from (a-1), (a-2) and (a-3) below.

[0108] (a-1) A group having a carboxyl group or a salt thereof

[0109] (a-2) Groups having hydroxyl, alkoxy, alkoxide anion, or metal alkoxide salts

[0110] (a-3) A group having a sulfonic acid group or a salt thereof

[0111] 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; examples of alkaline earth metal salts include calcium salts and magnesium salts. From the viewpoint of dispersibility, sodium salts are preferred.

[0112] Specifically, (a-1) a group having a carboxyl group or its salt can dissociate into a carboxyl anion; additionally, if (a-2) is a phenolic hydroxyl group, it can dissociate into a phenol oxide. Furthermore, (a-3) a group having a sulfonic acid group or its salt can dissociate into a sulfonate anion.

[0113] There are no particular limitations on the type of compound with coordinating functional groups as long as the molecular weight is above 1500. However, from the viewpoint of promoting penetration and coordination into fibers, as well as improving water resistance, heat resistance and thermal shape memory, it is preferable to contain one or more of the following (A-1) and (A-2). (A-1) and (A-2) may each be contained individually or in combination of two or more.

[0114] (A-1) A polymer comprising structural units derived from unsaturated monomers having coordinating functional groups, wherein the polymer has a weight-average molecular weight of 1500 or more.

[0115] (A-2) A condensate of a compound having a coordinating functional group, wherein the molecular weight of the condensate is greater than 1500.

[0116] (polymer)

[0117] In polymer (A-1), unsaturated monomers having coordinating functional groups can include, for example, unsaturated monomers having one or more coordinating functional groups selected from (a-1) to (a-3) above. Furthermore, the unsaturated monomer having coordinating functional groups may have substituents. Examples of substituents include halogen groups, alkyl groups, cyano groups, nitro groups, amino groups, dialkylamino groups, alkoxyoxy groups, alkylthio groups, arylthio groups, and trialkylsilyl groups. The position and number of substituents are arbitrary; when two or more substituents are present, the substituents may be the same or different.

[0118] When the unsaturated monomer having (a-1) above is an unsaturated monomer having a carboxyl group or a salt thereof, specific examples include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, or their salts. The unsaturated monocarboxylic acid can be an unsaturated aliphatic monocarboxylic acid or an aromatic monocarboxylic acid containing an unsaturated group. Similarly, the unsaturated dicarboxylic acid can be an unsaturated aliphatic dicarboxylic acid or an aromatic dicarboxylic acid containing an unsaturated group. The unsaturated monomer having (a-1) as a coordinating functional group can be used alone or in combination of two or more.

[0119] Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, oleic acid, cyclopentenylacetic acid, and other unsaturated aliphatic monocarboxylic acids, as well as aromatic monocarboxylic acids containing unsaturated groups such as vinyl benzoic acid and cinnamic acid. Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesoconic acid, itaconic acid, methylene succinic acid, and other unsaturated aliphatic dicarboxylic acids, as well as aromatic dicarboxylic acids containing unsaturated groups such as vinyl terephthalic acid, vinyl isophthalic acid, and vinyl naphthalenedicarboxylic acid. When the unsaturated monocarboxylic acid or unsaturated dicarboxylic acid is in the form of a salt, the specific examples of the equilibrium ions of the salt are described above. Furthermore, unsaturated dicarboxylic acids can also be obtained by using unsaturated dicarboxylic anhydrides, which are then hydrolyzed using a base or similar solution to produce an acid. Examples of unsaturated dicarboxylic anhydrides include maleic anhydride and citraconic anhydride.

[0120] When the unsaturated monomer having (a-2) above is an unsaturated monomer having a phenolic hydroxyl group, specific examples include hydroxystyrene, isopropenylphenol, hydroxyphenyl (meth)acrylate, and hydroxyphenyl maleimide. Here, in this specification, "(meth)acrylate" means acrylate or methacrylate. Unsaturated monomers having (a-2) as a coordinating functional group can be used alone or in combination of two or more.

[0121] When the unsaturated monomer having (a-3) described above is an unsaturated monomer having a sulfonic acid group or a salt thereof, specific examples include vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, (meth)acryloyloxyethyl sulfonic acid, or their salts. Here, in this specification, "(meth)allyl" means allyl or methylallyl, and "(meth)acryloyl" means acryloyl or methacryloyl. Unsaturated monomers having (a-3) as a coordinating functional group can be used alone or in combination of two or more. Where the unsaturated monomer having a sulfonic acid group is in the form of a salt, the specific examples of the salt's equilibrium ion are described above.

[0122] Furthermore, as unsaturated monomers having coordination functional groups other than those described above, examples include unsaturated monomers in which the coordination functional groups described above are replaced with coordination functional groups other than those described above. Unsaturated monomers having coordination functional groups other than (a-1) to (a-3) can be used alone or in combination of two or more.

[0123] In the (A-1) polymer, the proportion of structural units derived from unsaturated monomers having coordinating functional groups is preferably 10 mol% or more, more preferably 15 mol% or more, and even more preferably 20 mol% or more. Furthermore, the proportion of structural units derived from unsaturated monomers having coordinating functional groups in the (A-1) polymer may also be 100 mol%.

[0124] (A-1) The polymer may also contain structural units other than those derived from unsaturated monomers with coordinating functional groups. There may also be more than two other structural units.

[0125] As other structural units, from the viewpoint of hydrophobizing the polymer and improving the water resistance and heat resistance of the fiber, it is preferable to further include structural units derived from unsaturated hydrocarbon compounds. As unsaturated hydrocarbon compounds, 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 substituents. The position and number of substituents are arbitrary; when there are two or more substituents, the substituents may be the same or different. Specific examples of substituents can be listed as described above.

[0126] Examples of aromatic vinyl compounds include styrene, methylstyrene, dimethylstyrene, chloromethylstyrene, vinylnaphthalene, and vinylanthracene. Among these, styrene and vinylnaphthalene are preferred from the viewpoint of hydrophobizing the polymer and improving the water resistance and heat resistance of the fiber, effectively increasing the elastic modulus of the fiber in water by utilizing the rigidity of the aromatic ring, and achieving good residual efficiency in the fiber by utilizing the large volume of the aromatic ring. Styrene and vinylnaphthalene are preferred, and styrene is more preferred.

[0127] Unsaturated aliphatic hydrocarbon compounds can be chain-like, branched, or cyclic.

[0128] Examples of unsaturated aliphatic hydrocarbon compounds that are either chain-like or branched include propylene, isobutylene, diisobutylene, triisobutylene, tripropylene, and tetrapropylene. Among these, diisobutylene and triisobutylene are preferred from the viewpoint of hydrophobizing the polymer and improving the water resistance and heat resistance of the fiber, and diisobutylene is more preferred.

[0129] Examples of cyclic unsaturated aliphatic hydrocarbon compounds include cyclopentene, cyclohexene, and cyclooctene. Among these, cyclopentene and cyclohexene are preferred from the viewpoint of hydrophobizing the polymer and improving the water resistance and heat resistance of the fiber, and cyclohexyl is more preferred.

[0130] Among them, aromatic vinyl compounds are preferred as unsaturated hydrocarbon compounds, and styrene is more preferred, from the viewpoint that they hydrophobize the polymer and improve the water resistance and heat resistance of the fiber, while effectively increasing the elastic modulus of the fiber in water by utilizing the rigidity of the aromatic ring and making good residual efficiency in the fiber by utilizing the large volume of the aromatic ring.

[0131] Among them, as the (A-1) polymer, from the viewpoint of promoting the penetration and coordination into the fiber, and improving water resistance, heat resistance and thermal shape memory ability, it is preferred to contain one or more of (A-1-1), (A-1-2) and (A-1-3) selected below.

[0132] (A-1-1) is a copolymer comprising structural units derived from unsaturated monomers having coordinating functional groups and structural units derived from aromatic vinyl compounds, wherein the copolymer has a weight-average molecular weight of 1500 or more.

[0133] (A-1-2) comprises a copolymer containing structural units derived from an unsaturated monomer having a coordinating functional group and structural units derived from an unsaturated aliphatic hydrocarbon compound, wherein the copolymer has a weight-average molecular weight of 1500 or more.

[0134] (A-1-3) A polymer comprising a structural unit derived from an aromatic vinyl compound having a coordinating functional group or a polymer comprising a structural unit derived from an unsaturated aliphatic hydrocarbon compound having a coordinating functional group, wherein the polymer has a weight average molecular weight of 1500 or more (excluding copolymers (A-1-1) and (A-1-2)).

[0135] The (A-1-1) copolymer, (A-1-2) copolymer, and (A-1-3) polymer may contain two or more of them individually or in combination. In addition, in the copolymers of (A-1-1) and (A-1-2), the monomers providing each structural unit may be in a block, random, or combination thereof.

[0136] As for the (A-1-1) copolymer, there are no particular limitations as long as the weight average molecular weight is 1500 or more. From the viewpoint of promoting the penetration and coordination into the fiber, as well as improving water resistance, heat resistance and thermal shape memory, copolymers containing structural units derived from aromatic vinyl compounds and structural units derived from unsaturated monomers having carboxyl groups or their salts are preferred. Copolymers containing structural units derived from aromatic vinyl compounds and structural units derived from one or more structural units selected from unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and their salts are more preferred. Specifically, the preferred selection is one or more carboxyl-modified products of styrene-maleic acid copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, vinylbenzoic acid-maleic acid copolymers, vinylbenzoic acid-acrylic acid copolymers, vinylbenzoic acid-methacrylic acid copolymers, styrene-4-vinylbenzoic acid copolymers, butadiene-4-vinylbenzoic acid copolymers, styrene-butadiene copolymers, and their salts; more preferably, one or more carboxyl-modified products of styrene-maleic acid copolymers, styrene-butadiene copolymers, and their salts; and even more preferably, styrene-maleic acid copolymers or their salts. When the (A-1-1) copolymer is in the form of a salt, the equilibrium ion of the salt is not particularly limited; examples include sodium salts, potassium salts, magnesium salts, calcium salts, ammonium salts, etc., with sodium salts being preferred.

[0137] Furthermore, regarding carboxyl-modified styrene-maleic acid copolymers or styrene-butadiene copolymers, maleic anhydride-modified styrene-maleic anhydride copolymers or styrene-butadiene copolymers can also be used, after generating carboxyl-modified styrene-maleic acid copolymers or styrene-butadiene copolymers using alkali or the like. As carboxyl-modified styrene-butadiene copolymers, SBL0696, SBL0533, SBL0545, SBL0548, SBL0568, SBL0569V, SBL0573, SBL0597C, SBL0850Z, and SBL2527A manufactured by ENEOS Materials Corporation are preferred, SBL0696, SBL0548, SBL0568, and SBL2527A are more preferred, and SBL0696 is even more preferred.

[0138] As for the (A-1-2) copolymer, there are no particular limitations as long as the weight average molecular weight is 1500 or above. From the viewpoint of promoting the penetration and coordination into the fiber, as well as improving water resistance, heat resistance and thermal shape memory, a copolymer containing structural units derived from unsaturated aliphatic hydrocarbon compounds and structural units derived from unsaturated monomers having carboxyl groups or their salts is preferred. A copolymer containing structural units derived from unsaturated aliphatic hydrocarbon compounds and structural units derived from one or more structural units selected from unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and their salts is more preferred. Specifically, the preferred selection is one or more of the following: 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 polymers, and their salts. More preferably, the selection is one or more of the following: diisobutylene-maleic acid copolymer, butadiene-maleic acid copolymer, maleic acid modified butadiene polymers, and their salts. When the (A-1-2) copolymer is in the form of a salt, the equilibrium ion of the salt is not particularly limited; examples include sodium salts, potassium salts, magnesium salts, calcium salts, and ammonium salts, with sodium salts being preferred.

[0139] Furthermore, regarding maleic acid modified products of diisobutylene-maleic acid copolymers, butadiene-maleic acid copolymers, and butadiene polymers, maleic anhydride modified products of diisobutylene-maleic anhydride copolymers, butadiene-maleic anhydride copolymers, or butadiene polymers can also be used, after generating maleic acid modified products of diisobutylene-maleic acid copolymers, butadiene-maleic acid copolymers, or butadiene polymers using alkali or the like. As maleic anhydride modified products of butadiene polymers or their salts, Ricon130MA8, Ricon130MA13, Ricon131MA5, Ricon131MA10, Ricon131MA17, and Ricon131MA20 manufactured by Cray Valley are preferred, Ricon130MA13 and Ricon131MA20 are more preferred, and Ricon130MA13 is even more preferred.

[0140] As for the polymer (A-1-3), there are no particular limitations as long as the weight average molecular weight is 1500 or more. From the viewpoint of promoting penetration and coordination into the fiber, and improving water resistance, heat resistance and thermal shape memory, it is preferable to select one or more polymers selected from the homopolymers of aromatic vinyl compounds having carboxyl groups, sulfonic acid groups or their salts, or hydroxyl groups, and homopolymers of unsaturated aliphatic hydrocarbon compounds having carboxyl groups, sulfonic acid groups or their salts, or hydroxyl groups. More preferably, it is preferable to select one or more polymers selected from the homopolymers of aromatic vinyl compounds having carboxyl groups or their salts, and homopolymers of unsaturated aliphatic hydrocarbon compounds having carboxyl groups or their salts. Even more preferably, it is preferable to select homopolymers of unsaturated aliphatic hydrocarbon compounds having carboxyl groups or their salts. Specifically, the polymer is preferably selected from one or more of poly(vinylbenzoic acid), poly(cinnamic acid), polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid or their salts, and polyvinyl alcohol; more preferably selected from one or more of polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid or their salts, and polyvinyl alcohol; even more preferably selected from one or more of polyacrylic acid, polymethacrylic acid and their salts; and even more preferably polyacrylic acid or its salts. When the polymer in (A-1-3) is in the form of a salt, the equilibrium ion of the salt is not particularly limited; examples include sodium salts, potassium salts, magnesium salts, calcium salts, ammonium salts, etc., with sodium salts being preferred. Polyvinyl alcohol may, for example, use vinyl acetate monomer as an unsaturated monomer, polymerize it to obtain polyvinyl acetate, and then saponify it.

[0141] In the (A-1-1) copolymer, from the viewpoint of promoting impregnation and coordination into the fiber, and improving water resistance, heat resistance and thermal shape memory, the ratio of structural units (u1) derived from aromatic vinyl compounds to structural units (u2) derived from unsaturated monomers having coordinating functional groups in the 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.

[0142] In the (A-1-2) copolymer, from the viewpoint of promoting penetration and coordination into the fiber, and improving water resistance, heat resistance and thermal shape memory, the ratio of structural units (u3) derived from unsaturated aliphatic hydrocarbon compounds to structural units (u4) derived from unsaturated monomers having coordinating functional groups in the molar ratio (u3 / u4) is preferably 1 / 5 to 5 / 1, more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1.

[0143] (A-1) The polymer can be manufactured, for example, by using unsaturated monomers capable of incorporating the structural units described above, in a suitable solvent, and in the presence of a polymerization initiator, by conventional methods such as free radical polymerization. The reaction conditions can be appropriately selected from commonly used conditions and are not particularly limited. Polymer separation can be carried out, for example, by injecting the reaction solution into a large amount of unsuitable solvent and drying the resulting precipitate under reduced pressure, or by distilling the reaction solution under reduced pressure using a rotary evaporator, or by other known separation methods. Alternatively, commercially available polymers or copolymers can be used.

[0144] (Condensate)

[0145] (A-2) A condensate is a condensate of a compound having a coordinating functional group. There are no particular limitations as long as the molecular weight is 1500 or higher. From the viewpoint of promoting penetration and coordination into fibers, and improving water resistance, heat resistance and thermal shape memory, it is preferred that the condensate has a molecular weight of 1500 or higher and contains one or more condensates selected from (A-2-1) and (A-2-2) below. (A-2-1) and (A-2-2) may each contain two or more, either alone or in combination.

[0146] (A-2-1) Condensates of sulfonic acids or their salts

[0147] (A-2-2) Condensate of gallic acid ester

[0148] As a sulfonic acid condensate or salt thereof, as in (A-2-1), aromatic sulfonic acid formaldehyde condensates or salts thereof may be listed, for example. Specific examples may include one or more selected from benzenesulfonic acid formaldehyde condensates, naphthalenesulfonic acid formaldehyde condensates, phenolsulfonic acid formaldehyde condensates, and their salts. Among these, from the viewpoint of promoting penetration and coordination into fibers, and improving water resistance, heat resistance, and thermal shape memory, naphthalenesulfonic acid formaldehyde condensates or salts thereof are preferred, and β-naphthalenesulfonic acid formaldehyde condensates or salts thereof are more preferred.

[0149] 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; examples of alkaline earth metal salts include calcium salts and magnesium salts. From a dispersive perspective, sodium salts are preferred.

[0150] Examples of (A-2-2) gallic acid ester condensates include hydrolyzable tannins. Tannins are classified into two types: condensed tannins formed by the polymerization of compounds with a flavanol backbone, and hydrolyzable tannins that form ester bonds between aromatic compounds such as gallic acid or ellagic acid and sugars such as glucose. Condensed tannins consist of bonds that do not undergo hydrolysis, while hydrolyzable tannins consist of ester bonds that readily undergo hydrolysis; in this respect, they differ as chemical substances. Tannic acid is a specific example of a hydrolyzable tannin.

[0151] The condensate of sulfonic acid (A-2-1) or its salt can be manufactured, for example, by methods already known. For instance, in the case of naphthalenesulfonic acid formaldehyde condensate, the naphthalenesulfonic acid formaldehyde condensate can be obtained by the condensation reaction of naphthalenesulfonic acid with formaldehyde. Then, by partially neutralizing the sulfonic acid with a base, for example, a naphthalenesulfonate formaldehyde condensate can be produced. After the reaction, purification can be carried out by dialysis, ultrafiltration, and reprecipitation. Furthermore, commercially available condensates of sulfonic acid or their salts can also be used.

[0152] When the condensate of (A-2-2) gallate is tannic acid, it can be extracted, for example, from gall (the gall of an oak tree) or gallnut (the gall of a sagebrush tree). After extraction, the extract can be purified by fractionation or concentration. Alternatively, commercially available gallate condensates can be used.

[0153] (Molecular weight)

[0154] In this specification, the molecular weight of component (A) is defined as follows: Specifically, when component (A) is a polymer of (A-1), or a condensate of (A-2-1) sulfonic acid or a salt thereof, the molecular weight refers to the weight-average molecular weight of polystyrene as determined by gel permeation chromatography (GPC), which can be specifically determined using the methods described in the examples. Furthermore, when component (A) is a condensate of (A-2-2) gallic ester, and this condensate is composed of a mixture, the molecular weight, as described above, refers to the weight-average molecular weight. On the other hand, when the (A-2-2) gallic ester condensate is a single compound, the molecular weight refers to the sum of the atomic weights of the atoms constituting the molecule.

[0155] When component (A) is a polymer of (A-1) or a condensate of (A-2-1) sulfonic acid or a salt thereof, the weight-average molecular weight is 1500 or more. However, from the viewpoint of promoting penetration and coordination into the fiber, and improving water resistance, heat resistance, and thermo-shape memory, it is preferably 1600 or more, more preferably 2000 or more, further preferably 3000 or more, even more preferably 4000 or more, and preferably 100,000 or less, more preferably 30,000 or less, further preferably 15,000 or less, even more preferably 10,000 or less, and even more preferably 8,000 or less. That is, such a weight-average molecular weight is preferably 1600 to 100,000, more preferably 2000 to 30,000, further preferably 3000 to 30,000, further preferably 3000 to 15,000, further preferably 3000 to 10,000, and even more preferably 4000 to 8000.

[0156] When the condensate of (A-2-2) gallic acid ester is a single compound, the molecular weight is 1500 or more. However, from the viewpoint of promoting penetration and coordination into fibers, and improving water resistance, heat resistance, and thermal shape memory, it is preferable to have a molecular weight of 1600 or more, more preferably 1700 or more, and more preferably 10000 or less, more preferably 5000 or less. That is, such a molecular weight is preferably 1600 to 10000, more preferably 1700 to 5000.

[0157] (Hydrogen bond term δH in Hansen solubility parameter)

[0158] Regarding component (A), a suitable compound was selected from the viewpoint of promoting fiber penetration and coordination, using the hydrogen bonding term δH of the Hansen solubility parameter as an indicator. Here, in this specification, the hydrogen bonding term of the Hansen solubility parameter refers to δH (MPa) calculated at 25°C 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, in the DIY program. 1 / 2 (Energy term arising from intermolecular hydrogen bonds). When component (A) is a salt, use the δH of the free acid (non-dissociated acid).

[0159] The hydrogen bonding term δH of the Hansen solubility parameter for component (A) is preferably 5.0 MPa. 1 / 2 The above, and more preferably 7.0 MPa 1 / 2 The above, and more preferably 9.0 MPa 1 / 2 The above, and preferably 20.0 MPa 1 / 2 The following, or more preferably, is 16.0 MPa 1 / 2 The following, and more preferably, is 13.0 MPa 1 / 2 Specifically, the hydrogen bonding term δH for such Hansen solubility parameters is preferably 5.0–20.0 MPa. 1 / 2 More preferably 7.0–16.0 MPa 1 / 2 A further preferred value is 9.0–13.0 MPa. 1 / 2 .

[0160] Specific examples of components (A) whose hydrogen bond term δH value, which is a Hansen solubility parameter, falls within the above range, include the following compounds.

[0161] • Styrene-maleic acid copolymer

[0162] (Styrene / maleic acid (molar ratio) = 1 / 1) 11.5 MPa 1 / 2

[0163] • Styrene-maleic acid copolymer

[0164] (Styrene / maleic acid (molar ratio) = 2 / 1) 9.2 MPa 1 / 2

[0165] • Styrene-maleic acid copolymer

[0166] (Styrene / maleic acid (molar ratio) = 3 / 1) 7.9 MPa 1 / 2

[0167] • Diisobutylene-maleic acid copolymer

[0168] (Diisobutylene / maleic acid (molar ratio) = 1 / 1) 9.4 MPa 1 / 2

[0169] • Polyacrylic acid 14.3MPa 1 / 2

[0170] • β-Naphthalenesulfonic acid formaldehyde condensate 17.8 MPa 1 / 2

[0171] (Acid value)

[0172] Furthermore, when component (A) has (a-1) or (a-3) as coordinating functional groups as described above, a suitable compound is selected from the viewpoint of promoting fiber penetration and coordination, using acid value as an indicator. Here, in this specification, "acid value" refers to the number of milligrams (mg) of potassium hydroxide required to neutralize the acidic components contained in 1g of sample, which can be determined by potentiometric titration according to JIS K 0070. When component (A) is a salt, the acid value of the free acid (non-dissociated acid) is used.

[0173] Regarding the acid value of component (A), from the viewpoint of promoting penetration and coordination into the fiber, and improving water resistance, heat resistance, and thermomorphic memory, it is preferably 100 mg KOH / g or more, more preferably 200 mg KOH / g or more, further preferably 300 mg KOH / g or more, even more preferably 400 mg KOH / g or more, and preferably 1000 mg KOH / g or less, more preferably 800 mg KOH / g or less, and even more preferably 600 mg KOH / g or less. That is, such an acid value is preferably 100–1000 mg KOH / g, more preferably 200–800 mg KOH / g, even more preferably 300–600 mg KOH / g, and even more preferably 400–600 mg KOH / g.

[0174] Specific examples of components (A) with acid values ​​within the above range can be listed below, such as the following compounds.

[0175] • Styrene-maleic acid copolymer

[0176] (Styrene / maleic acid (molar ratio) = 1 / 1) 475 mg KOH / g

[0177] • Styrene-maleic acid copolymer

[0178] (Styrene / maleic acid (molar ratio) = 2 / 1) 355mgKOH / g

[0179] • Styrene-maleic acid copolymer

[0180] (Styrene / maleic acid (molar ratio) = 3 / 1) 285 mg KOH / g

[0181] • Diisobutylene-maleic acid copolymer

[0182] (Diisobutylene / maleic acid (molar ratio) = 1 / 1) > 100 mg KOH / g

[0183] • Polyacrylic acid (Mw 5000) 757mgKOH / g

[0184] • β-Naphthalenesulfonic acid formaldehyde condensate (Mw > 1500) > 100 mg KOH / g

[0185] (Hydroxy valence)

[0186] When component (A) has the aforementioned (a-2) as a coordinating functional group, a suitable compound is selected from the viewpoint of promoting fiber penetration and coordination, using the hydroxyl valence as an indicator. Here, in this specification, "hydroxyl valence" refers to the number of milligrams (mg) of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group when 1g of sample is acetylated, which can be determined by potentiometric titration according to JIS K0070.

[0187] The hydroxyl value of component (A) is preferably 100 mg KOH / g or more, more preferably 200 mg KOH / g or more, even more preferably 300 mg KOH / g or more, and preferably 2000 mg KOH / g or less, more preferably 1500 mg KOH / g or less, even more preferably 1000 mg KOH / g or less. That is, the acid value is preferably 100 to 2000 mg KOH / g, more preferably 200 to 1500 mg KOH / g, and even more preferably 300 to 1000 mg KOH / g.

[0188] Specific examples of components (A) with hydroxyl valence within the above range can be listed below, such as the following compounds.

[0189] • Tannic acid (M 1701) 757 mg KOH / g

[0190] (content)

[0191] From the viewpoint of promoting the penetration and coordination of fibers, and improving water resistance, heat resistance, and thermoshape memory, the 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, further preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, even more preferably 2.3% by mass or more, even more preferably 3.0% by mass or more, and preferably 60% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 15% by mass or less, and even 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, even more preferably 0.5 to 15% by mass, even more preferably 1.0 to 15% by mass, even more preferably 2.3 to 15% by mass, and even more preferably 3.0 to 10% by mass. In this specification, when component (A) is a salt, the content of component (A) is a value converted to free acid.

[0192] Furthermore, in this invention, the content of component (A) in the fiber treatment agent is set to the range shown below, depending on the type of component (A) in the fiber treatment agent. That is, when component (A) is a condensate of (A-1) polymer or (A-2-1) sulfonic acid or a salt thereof, from the viewpoint of promoting penetration and coordination into the fiber, and improving water resistance, heat resistance and thermal shape memory ability, the content of component (A) in the fiber treatment agent of this invention is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, further preferably 1.0% by mass or more, even more preferably 2.3% by mass or more, even more preferably 3.0% by mass or more, and preferably 60% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, even more preferably 15% by mass or less, and even 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% by mass, more preferably 0.5 to 40% by mass, even more preferably 1.0 to 30% by mass, even more preferably 2.3 to 20% by mass, even more preferably 3.0 to 15% by mass, and even more preferably 3.0 to 10% by mass.

[0193] When component (A) is a condensate of (A-2-2) gallic acid ester, from the viewpoint of promoting penetration and coordination into fibers, and improving water resistance, heat resistance, and thermal shape memory, 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, further preferably 0.4% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1.0% by mass or less. 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, and further preferably 0.20 to 1.0% by mass.

[0194] (pH)

[0195] Regarding the pH of the fiber treatment agent of the present invention, from the viewpoint of promoting penetration and coordination into the fibers, and improving water resistance, heat resistance, and thermomorphic memory, it is preferably 2.0 or higher, more preferably 3.0 or higher, further preferably 3.5 or higher, and preferably 11.0 or lower, more preferably 10.0 or lower, further preferably 9.0 or lower, further preferably 7.0 or lower, further preferably 6.5 or lower, and further 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, further preferably 3.5 to 9.0, further preferably 3.5 to 7.0, further preferably 3.5 to 6.5, and further preferably 3.5 or higher and less than 5.5. Furthermore, the pH can be adjusted within the above range according to the content of component (A) in the fiber treatment agent. In this specification, "pH" refers to the value at 25°C, which can be measured using a pH meter.

[0196] In addition, in this invention, the content of component (A) in the fiber treatment agent can be set to the range shown below, depending on the pH of the fiber treatment agent and the type of component (A).

[0197] When component (A) is a condensate of (A-1) polymer or (A-2-1) sulfonic acid or a salt thereof, and the pH of the fiber treatment agent is less than 5.5, from the viewpoint of promoting penetration and coordination into the fiber, and improving water resistance, heat resistance, and thermo-shape memory, 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. Furthermore, from the viewpoint of improving the tactile feel of the fiber surface, it is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less. That is, when component (A) is a condensate of (A-1) polymer or (A-2-1) 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% by mass, more preferably 0.8 to 20% by mass, and even more preferably 1.3 to 10% by mass.

[0198] When component (A) is a condensate of (A-1) polymer or (A-2-1) sulfonic acid or a salt thereof, and the pH of the fiber treatment agent is 5.5 or higher, from the viewpoint of promoting penetration and coordination into the fiber, and improving water resistance, heat resistance, and thermal shape memory, 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 viewpoint of improving the tactile 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 condensate of (A-1) polymer or (A-2-1) 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% by mass, more preferably 2.0 to 50% by mass, and even more preferably 3.0 to 40% by mass.

[0199] When component (A) is a condensate of (A-2-2) gallic acid ester, from the viewpoint of promoting penetration and coordination into the fiber, and improving water resistance, heat resistance, and thermal shape memory, the content of component (A) in the fiber treatment agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.4% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1.0% by mass or less. That is, when component (A) is a condensate of (A-2-2) 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 further preferably 0.4 to 1.0% by mass.

[0200] Furthermore, the content of component (A) in the fiber treatment agent of the present invention can also be determined by the content of component (A) in the fiber treated with the fiber treatment agent of the present invention. For example, from the viewpoint of promoting retention and coordination in the fiber, and improving water resistance, heat resistance and thermal shape memory ability, it is preferable that the content of component (A) in the fiber treated with the fiber treatment agent of the present invention is 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 preferably 70% by mass or less, even 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, 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. Regarding the quantification of component (A), a suitable method that does not decompose component (A) and can dissolve the fiber is selected to dissolve and extract the fiber. After appropriately diluting the extraction solution, the absorbance is measured using, for example, a UV-Vis-NIR spectrophotometer (e.g., V-560 (manufactured by Nippon Spectrophotometer Co., Ltd.) at an absorbance wavelength suitable for quantifying component (A), and the content of component (A) is calculated based on the absorbance. Alternatively, HPLC / UV or gel permeation chromatography (GPC) can be used to measure the peak area of ​​a chromatogram plotted at an absorbance wavelength suitable for quantifying component (A), and the content of component (A) is calculated based on the peak area.

[0201] Furthermore, regarding the impregnation distribution of component (A) within the fiber cross-section, the fiber cross-section can be cut using a slicer, scalpel, razor, etc., based on the characteristics of component (A). Then, the cross-section can be evaluated using line or surface analysis employing methods such as optical microscopy, fluorescence microscopy, confocal laser microscopy with fluorescence imaging, TOF-SIMS, EPMA, TEM / SEM-EDS, microscopic IR, and microscopic laser Raman spectroscopy. More specifically, the evaluation can be performed, for example, by the following methods.

[0202] The cross-section of the treated fiber is measured using a confocal laser microscope via fluorescence imaging. If a significant difference in fluorescence intensity within the fiber is observed compared to the untreated fiber in the fluorescence imaging image, it is determined that component (A) has penetrated into the fiber. For example, since fibers treated with styrene-maleic acid copolymer or its salt as component (A) have a wavelength characteristic of styrene-maleic acid copolymer at 400 nm, fluorescence imaging can be performed using an excitation wavelength of 400 nm and a detection wavelength of 425–475 nm. For example, an AIRHD25 (manufactured by Nikon Corporation) can be used as the confocal laser microscope.

[0203] [Ingredient (B)]

[0204] In the fiber treatment agent of the present invention, water is contained as component (B).

[0205] The content of component (B) is the balance excluding component (A) and any other components described later. For example, in the fiber treatment agent of the present invention, the content of component (B) is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, further more preferably 40% by mass or more, and preferably 98% by mass or less, more preferably 97% by mass or less, further preferably 96% by mass or less, further more preferably 95% by mass or less, further more preferably 90% by mass or less, and further 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, further preferably 30 to 96% by mass, further more preferably 40 to 95% by mass, further more preferably 40 to 90% by mass, and further more preferably 40 to 85% by mass.

[0206] [Ingredient (C)]

[0207] In the fiber treatment agent of the present invention, from the viewpoint of improving the water resistance, heat resistance, and thermal shape memory of the fiber, it is preferable to further contain a polyvalent metal element as component (C). The larger the molecular weight of component (A) that modifies the fiber interior, the stronger its interaction with the fiber, and a higher modification effect can be expected; on the other hand, when the molecular weight is too large, penetration into the fiber interior becomes difficult. In contrast, it can be considered that by allowing component (A) and component (C) to penetrate into the fiber interior separately, component (A) undergoes salt cross-linking with each other within the fiber due to component (C), and interacts strongly with the fiber as a larger structural body, a high modification effect can be obtained.

[0208] As a multivalent metal element, metals (e.g., ultrafine metal particles), ions, salts, complexes, etc., can be used. As a salt of the multivalent metal, any salt of organic or inorganic metals can be used. Among these, inorganic salts of multivalent metals are preferred, and multivalent metal salts of hard acids and boundary acids that readily interact with the coordinating functional groups (hard bases, boundary bases) of component (A) are more preferred. More preferably, multivalent metal salts of hard acids and boundary acids are also preferred. Specifically, aluminum salts and zirconium salts are preferred, and aluminum sulfate, aluminum chloride, and zirconium sulfate are more preferred.

[0209] Regarding the content of component (C) in the fiber treatment agent of the present invention, from the viewpoint of increasing the effect of component (C) on salt cross-linking of components (A) in the fiber and improving the water resistance, heat resistance and thermal shape memory of the fiber, the content is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, further preferably 0.001% by mass or more, and even more preferably 0.007% by mass or more, in terms of metal element content. Furthermore, from the viewpoint of preventing the precipitation of components (A) and (C) in the fiber treatment agent or reducing the penetration efficiency into the fiber, the content is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, further 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, further preferably 0.001 to 0.10% by mass, and even more preferably 0.007 to 0.07% by mass.

[0210] <Other Ingredients>

[0211] The fiber treatment agent of the present invention may contain a pH adjuster as another component.

[0212] (pH adjuster)

[0213] As a pH adjuster, there are no particular limitations as long as it can adjust to the desired pH. Examples include bases such as sodium hydroxide and potassium hydroxide, and acids such as phosphoric acid, sulfuric acid, and hydrochloric acid.

[0214] [Fiber Treatment Kit]

[0215] The fiber treatment kit of the first embodiment includes the fiber treatment agent of the present invention (hereinafter also referred to as "agent 1a") and a fiber treatment agent of the present invention having a pH that is 1.0 or lower than that of agent 1a (hereinafter also referred to as "agent 2a"). The specific composition and applicable fibers of the fiber treatment agents in agent 1a and agent 2a are as described above.

[0216] The pH of agents 1a and 2a can be adjusted to the desired pH using the aforementioned pH adjuster.

[0217] Regarding the pH of the first agent, from the viewpoint of promoting penetration and coordination into the fibers, improving water resistance, heat resistance, and thermoshape memory, and from the viewpoint of adjusting the pH of the second agent to be 1.0 or lower than that of the first agent to improve the modification effect, it is preferably 3.0 or higher, more preferably 4.0 or higher, further preferably 4.5 or higher, 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 the second agent is preferably 3.0 to 11.0, more preferably 4.0 to 9.0, further preferably 4.5 to 8.0, and even more preferably 5.5 to 7.0.

[0218] Regarding the pH of the second agent, from the viewpoints of promoting penetration and coordination into the fibers, improving water resistance, heat resistance, and thermoshape memory, and from the viewpoint of adjusting the pH of the second agent to be 1.0 or lower than that of the first agent to improve the modification effect, it is preferably 2.0 or higher, more preferably 3.0 or higher, further preferably 3.5 or higher, and preferably 10.0 or lower, more preferably 8.0 or lower, further preferably 7.0 or lower, and further more preferably lower than 5.5. That is, the pH of the second agent is preferably 2.0 to 10.0, more preferably 3.0 to 8.0, further preferably 3.5 to 7.0, and further more preferably 3.5 or higher and lower than 5.5.

[0219] Regarding the ratio of agent 1a to agent 2a in the fiber treatment kit, from the viewpoint of promoting penetration and coordination into the fiber, as well as improving water resistance, heat resistance and thermal shape memory ability, the mass ratio (agent 1a / agent 2a) is preferably 1 / 5 to 5 / 1, more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1.

[0220] Furthermore, the fiber treatment kit of the first embodiment can also involve a final step of treating the naturally sourced fibers with agent 2a, followed by repeated treatment with agent 1a. Specifically, for example, the naturally sourced fibers are treated with agent 1a, then treated with agent 1a two to three or more times, and then treated with agent 2a.

[0221] The fiber treatment kit of the first embodiment may be a kit that houses agent 1a and agent 2a in separate containers, or it may be a kit that houses them in separate areas within a container using partitions.

[0222] The fiber treatment kit of the second embodiment includes the fiber treatment agent of the present invention (hereinafter also referred to as "Agent 1b") and an additional fiber treatment agent (hereinafter also referred to as "Agent 2b"), wherein the additional fiber treatment agent contains a hydrogen bonding term δH of 18.3 MPa as a Hansen solubility parameter of component (D). 1 / 2 The following are compounds or salts thereof that have at least one carboxyl group or a salt thereof and do not have a fused ring (excluding component (A)).

[0223] Agent 1b can be either a single agent or a two-agent agent. When Agent 1b is a single agent, its specific composition is as described above. In this case, a fiber treatment kit is formed that has both Agent 1b and Agent 2b.

[0224] Furthermore, when the first agent (1b) is a two-component form, for example, similar to the first embodiment described above, the fiber treatment agent of the present invention can be composed of a fiber treatment agent (hereinafter also referred to as "first agent (1b-1)") and a fiber treatment agent with a pH that is 1.0 or lower than that of the first agent (hereinafter also referred to as "first agent (1b-2)"). The specific composition of the first agent (1b-1) and the first agent (1b-2) is as described in the first embodiment. In this case, a fiber treatment kit having a three-component form having the first agent (1b-1), the first agent (1b-2), and the second agent (2b) is formed. Furthermore, the fibers to which the fiber treatment kit of this embodiment is applicable are as described above.

[0225] Compounds that are components (D) can be listed as (D1) and (D2) below.

[0226] (D1) The hydrogen bonding term δH of Hansen's solubility parameter is 18.3 MPa. 1 / 2 The following are aromatic compounds having at least one carboxyl group or its salt and not having a fused ring.

[0227] (D2) The hydrogen bonding term δH of Hansen's solubility parameter is 11.0 MPa. 1 / 2 Above 18.3MPa 1 / 2 The following are compounds that have at least one carboxyl group or its salt and do not have a fused ring (excluding aromatic compounds).

[0228] When component (D) is in the form of a salt, the salt is preferably an alkali metal salt, more preferably a sodium or potassium salt, and even more preferably a sodium salt.

[0229] Aromatic compounds that are components (D1) can be, for example, compounds or salts thereof represented by the following general formula (1) or general formula (2).

[0230]

[0231] [In the formula, =X represents methylene or oxo group, R] 1R represents a hydrogen atom, a hydroxyl group, or an alkyl, aryl, alkoxy, aryloxy, or arylalkoxy group that may have substituents. 2 This indicates ortho-phenylene, meta-phenylene, para-phenylene, benzylene, or alkylene that may have substituents. Wherein, in R... 2 Without an aryl group, R 1 It can be aryl, aryloxy, or arylalkoxy. [In the formula, A] 1 ~A 5 Each of these can independently represent a hydrogen atom, an acetyl group, a halogen atom, or a straight-chain or branched alkyl, alkenyl, alkoxy, or alkenyloxy group having 1 to 6 carbon atoms.

[0232] As aromatic compounds represented by the above general formula (1), compounds represented by the general formulas (1A), (1B) or (1C) shown below can be listed.

[0233] [In the formula, B] 1 ~B 4 Each of the following groups independently represents a hydrogen atom, an acetyl group, a halogen atom, or a straight-chain or branched alkyl, alkenyl, alkoxy, or alkenyloxy group having 1 to 6 carbon atoms; R 3 This refers to a hydroxyl group, or a group represented by the following general formula (1A)-a or (1A)-b. [In the formula, B] 5 ~B 9 Indicates the above B 1 ~B 4 Similarly, R 4 [This represents a hydrogen atom or a methyl group, where n represents an integer from 0 to 2.]

[0234] [In the formula, D] 1 ~D 4 Each of the following groups independently represents a hydrogen atom, an acetyl group, a halogen atom, or a straight-chain or branched alkyl, alkenyl, alkoxy, or alkenyloxy group having 1 to 6 carbon atoms. E 1 ~E 5 Represent D independently. 1 ~D 4 The same group or the group represented by general formula (1B)-a. [In the formula, m represents an integer from 0 to 4.]

[0235]

[0236] In the formula, R 6 G represents a hydrogen atom or a group represented by the general formula (1C)-a. 1 and G 2Each of these groups independently represents a hydrogen atom, an acetyl group, a halogen atom, an aryl group that may have substituents, an aralkyl or arylene group with 7 to 12 carbon atoms, or a straight-chain or branched alkyl, alkenyl, alkoxy, alkenyloxy, or aryloxy group with 1 to 6 carbon atoms. In R... 6 In the case of hydrogen atoms, G 1 and G 2 At least one of them is an aryl group, an aralkyl group having 7 to 12 carbon atoms, an arene group, or an aryloxy group, which may have substituents.

[0237]

[0238] [In the formula, J] 1 ~J 5 Each of these can independently represent a hydrogen atom, an acetyl group, a halogen atom, or a straight-chain or branched alkyl, alkenyl, alkoxy, or alkenyloxy group having 1 to 6 carbon atoms.

[0239] In the compounds represented by general formula (1A), as R 3 Compounds containing hydroxyl groups include 2-carboxybenzoic acid (phthalic acid) (Hansen solubility parameter hydrogen bond term δH: 13.4 MPa). 1 / 2 (The values ​​in parentheses after each compound name below represent the hydrogen bond term δH calculated using the above method.)

[0240] In the compounds represented by general formula (1A), as R 3 Compounds with the group represented by the general formula (1A)-a can be listed as 2-[[(4-vinylbenzyl)oxy]carbonyl]benzoic acid (7.0 MPa) 1 / 2 ).

[0241] In the compounds represented by general formula (1A), as R 3 Compounds with the group represented by general formula (1A)-b can be listed as 2-[[2-(acryloyloxy)ethoxy]carbonyl]benzoic acid (9.1 MPa) 1 / 2 ), 2-[[2-(methacryloyloxy)ethoxy]carbonyl]benzoic acid (8.4 MPa) 1 / 2 ).

[0242] As a compound represented by general formula (1B), 2-benzoylbenzoic acid (7.5 MPa) can be listed. 1 / 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 ).

[0243] In the compounds represented by general formula (1C), as R 6 Compounds containing hydrogen atoms include phenylsuccinic acid (15.8 MPa). 1 / 2 ), 2,3-diphenylsuccinic acid (11.9MPa 1 / 2 (+)-Di-p-toluyl-D-tartaric acid (10.2 MPa) 1 / 2 ).

[0244] In the compounds represented by general formula (1c), as R 6 Compounds with the group represented by the general formula (1c)-a can be listed as 4-oxo-4-[(4-vinylbenzyl)oxo]butyric acid (10.1 MPa). 1 / 2 ).

[0245] Furthermore, as a compound that does not belong to any of the general formulas (1A), (1B), and (1C) but belongs to general formula (1), 3-carboxybenzoic acid (isophthalic acid) (12.9 MPa) can be listed. 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 values ​​in parentheses after each compound name are the hydrogen bond terms δH calculated using the method described above.

[0246] As a specific example of the aromatic compound represented by the above general formula (2), benzoic acid (9.5 MPa) can be cited. 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 them, 4-ethylbenzoic acid, 4-vinylbenzoic acid, and benzoic acid are preferred.

[0247] In addition, phenylbutyric acid can be listed as a compound other than general formulas (1) and (2) that are components (D1).

[0248] Compounds that can be used as components (D2) include, for example, potassium 2,4-hexadienoate (12.5 MPa). 1 / 2 ).

[0249] Regarding the hydrogen bond term δH of the aromatic compound in component (D1), from the viewpoint of moderately hydrophobicizing the fiber interior, it is preferably 16.0 MPa. 1 / 2 The following, or more preferably, is 13.5 MPa1 / 2 The following, and more preferably, is 12.0 MPa 1 / 2 The following, and more preferably, is 10.0 MPa 1 / 2 Below, and preferably 3.0 MPa 1 / 2 The above, and more preferably 4.0 MPa 1 / 2 The above, and more preferably 5.0 MPa 1 / 2 above.

[0250] Regarding the hydrogen bond term δH of the compound containing component (D2), from the viewpoint of moderately hydrophobicizing the fiber interior, a value of 16.0 MPa is preferred. 1 / 2 The following, more preferably, is 15.0 MPa 1 / 2 The following, and more preferably, is 14.0 MPa 1 / 2 The following, and more preferably, is 13.0 MPa 1 / 2 Below, and preferably 11.0 MPa 1 / 2 The above, and more preferably 11.5 MPa 1 / 2 The above, and more preferably 12.0 MPa 1 / 2 above.

[0251] Regarding the pH of the second agent, from the viewpoint of promoting penetration and coordination into the fibers, and improving water resistance, heat resistance, and thermoforming properties, it is preferably 4.0 or higher, more preferably 5.0 or higher, and even more preferably 5.5 or higher, and preferably 9.0 or lower, more preferably 8.0 or lower, and even more preferably 7.0 or lower. That is, the pH of the second agent is preferably 4.0 to 9.0, more preferably 5.0 to 8.0, and even more preferably 5.5 to 7.0.

[0252] Regarding the content of component (D) in agent 2b, from the viewpoint of promoting penetration and coordination into the fiber, and improving water resistance, heat resistance, and thermoforming properties, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, further 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 agent 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. Wherein, when component (D) is a salt, the content of component (D) is the value converted to free acid.

[0253] Furthermore, the content of component (D) in agent 2b can be determined by the content of component (D) in the fiber treated with the additional fiber treatment agent of the present invention. For example, from the viewpoint of promoting retention and coordination in the fiber, and improving water resistance, heat resistance and thermal shape memory, it is preferable that the content of component (D) in the fiber treated with the additional fiber treatment agent of the present invention is 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less. That is, it is preferable that the content of component (D) in the fiber treated with the additional fiber treatment agent is 1 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 10 to 30% by mass. Regarding the quantification of component (D), a suitable method that does not decompose component (D) and can dissolve the fiber is selected to dissolve and extract the fiber. Next, after appropriately diluting the extraction solution, the absorbance is measured using an ultraviolet-visible-near-infrared spectrometer (e.g., V-560 (manufactured by Nippon Spectroscopy Co., Ltd.)) at an absorbance wavelength suitable for quantifying component (D), and the content of component (D) is calculated based on the absorbance.

[0254] Regarding the ratio of agent 1b to agent 2b in the fiber treatment kit, from the viewpoint of promoting penetration and coordination into the fiber, as well as improving water resistance, heat resistance and thermal shape memory ability, the 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.

[0255] When the first dose is a two-component formulation, the proportions of each agent in the first dose can be appropriately selected. For example, when it consists of the first dose-1 and the first dose-2, the mass ratio (total of the first dose-1 and the first dose-2 / the second dose) is preferably twice the mass ratio of the first dose. That is, the mass ratio (total of the first dose-1 and the first dose-2 / the second dose) is preferably 2 / 5 to 10 / 1, more preferably 2 / 3 to 6 / 1, and even more preferably 2 / 2 to 4 / 1.

[0256] The fiber treatment kit of the second embodiment can be a kit that houses agent 1b and agent 2b in separate containers, or it can be a kit that houses them in separate areas within a container using a divider. Furthermore, if agent 1b is a two-component formulation, for example, agent 1b-1, agent 1b-2, and agent 2b can be housed in separate containers, or they can be housed in separate areas within a single container.

[0257] [Storage methods for fiber treatment agents and fiber treatment kits]

[0258] When transporting or storing the fiber treatment agent and fiber treatment kit of the present invention before applying them to fibers, or when transporting or storing the raw materials before preparing the fiber treatment agent and fiber treatment kit, from the viewpoint of stability, the storage temperature can be set to a low temperature or a high temperature, or nitrogen can be filled into the void portion of the storage container.

[0259] Regarding the storage temperature of the fiber treatment agent and the fiber treatment kit, from the viewpoint of stability, it is preferably 1°C or higher, more preferably 2°C or higher, even more preferably 5°C or higher, and preferably 80°C or lower, more preferably 70°C or lower, even more preferably 60°C or lower.

[0260] [Fiber treatment methods]

[0261] <Basic Processing>

[0262] Using the fiber treatment agent of the present invention, natural source fibers are treated by a method including the following step (i), thereby promoting the penetration and coordination of component (A) into the natural source fibers and improving the water resistance and thermal shape memory ability, which are technical problems unique to natural source fibers.

[0263] Step (i): The step of immersing natural source fibers with a water swelling rate of 200% or more calculated by the above formula (1) in the fiber treatment agent of the present invention.

[0264] In this process, there is no particular limitation on the natural source fibers impregnated in the fiber treatment agent, as long as the fiber swelling rate in water calculated by the above formula (1) is 200% or more. Among them, the preferred fiber swelling rate in water for natural source fibers is as described above. For example, regarding undried regenerated collagen fibers, collagen raw materials can be solubilized to prepare a spinning solution, which is then sprayed from the spinning nozzle into a coagulation bath for fiberization, and the undried regenerated collagen fibers are then used.

[0265] Regarding the amount of fiber treatment agent used to impregnate naturally sourced fibers, the bath ratio (mass of fiber treatment agent / mass of naturally sourced fibers) relative to the mass of the naturally sourced fibers is preferably 2 or more, more preferably 3 or more, further preferably 5 or more, further more preferably 10 or more, further more preferably 20 or more, and preferably 500 or less, more preferably 250 or less, further preferably 100 or less, and further more preferably 50 or less. That is, the above-mentioned bath ratio is preferably 2 to 500, more preferably 3 to 250, further preferably 5 to 100, further more preferably 10 to 100, further more preferably 20 to 100, and further more preferably 20 to 50.

[0266] The impregnation of the natural-sourced fibers in this process in the fiber treatment agent can be carried out at room temperature (20℃±15℃), but heating is also acceptable. This heating can be achieved by raising the temperature of the fiber treatment agent. This heating can be done by impregnating the natural-sourced fibers in a heated fiber treatment agent, or by impregnating the natural-sourced fibers in a low-temperature fiber treatment agent followed by heating. Regarding the temperature of the fiber treatment agent, in order to allow component (A) to penetrate into the natural-sourced fibers and increase the interaction with the fiber constituent molecules, such as protein molecules, thereby achieving the effects of the present invention, a temperature of 20℃ or higher is preferred, more preferably 25℃ or higher, and even more preferably 30℃ or higher is preferred. Furthermore, to prevent the natural-sourced fibers from being modified and deteriorated due to heat, a temperature below 100℃ is preferred, more preferably below 80℃, even more preferably below 70℃, even more preferably below 60℃, and even more preferably below 50℃. That is, the above-mentioned temperature is preferably above 20°C and below 100°C, more preferably 25-80°C, even more preferably 30-70°C, even more preferably 30-60°C, and even more preferably 30-50°C.

[0267] The impregnation time in this process can be appropriately adjusted according to the heating temperature. For example, from the viewpoint of improving the elasticity of naturally derived fibers, it is preferably 15 minutes or more, more preferably 30 minutes or more, further preferably 1 hour or more, even more preferably 3 hours or more, even more preferably 5 hours or more, and even more preferably 10 hours or more. Furthermore, in order to suppress damage to the naturally derived fibers, it is preferably 48 hours or less, more preferably 33 hours or less, and even more preferably 30 hours or less. That is, the impregnation time is preferably 15 minutes or more and 48 hours or less, more preferably 30 minutes or more and 33 hours or less, further preferably 1 hour or more and 30 hours or less, even more preferably 3 hours or more and 30 hours or less, even more preferably 5 hours or more and 30 hours or less, and even more preferably 10 hours or more and 30 hours or less.

[0268] This process is preferably carried out in an environment where moisture evaporation is suppressed. Specific methods for suppressing moisture evaporation include covering a container impregnated with a fiber treatment agent made of a membrane, cap, or lid made of a water vapor-impermeable material.

[0269] After this process, the natural fiber may be rinsed or not, but rinsing is preferred from the viewpoint of preventing the natural fiber surface from becoming less tactile due to the remaining component (A).

[0270] It can be assumed that through these treatments, component (A) permeates into the naturally derived fibers and strongly coordinates with the metals within the fibers, such as polyvalent metals, thereby producing various effects.

[0271] When using the fiber treatment kit of the present invention, the natural source fibers can be treated by the agents contained in the kit in the same manner as described above, including step (i). There is no particular limitation on the order of application of the agents; the natural source fibers can be treated in any order.

[0272] <Further processing can be added>

[0273] In addition to the above-described step (i), one or more treatments selected from decolorization, dyeing, drying, surface finishing, heat treatment for further improving fiber elasticity (toughness), and inhibiting or removing coloring may be performed. Decolorization and dyeing may use known decolorizing and dyeing agents, and the methods for decolorization, dyeing, drying, surface finishing, heat treatment, or inhibiting or removing coloring may employ existing known methods.

[0274] At this point, the decolorization and dyeing processes can be performed before or after the aforementioned step (i). Additionally, multiple processes can be combined. When both decolorization and dyeing are added, decolorization must be performed before dyeing; any other process can be performed first, or between decolorization and dyeing.

[0275] On the other hand, drying, surface finishing, heat treatment to further improve fiber elasticity (toughness), and suppression or removal of coloring must be performed after the above-mentioned step (i), but there is no particular limitation on the order of these processes with decolorization and dyeing. In addition, drying, surface finishing, heat treatment to further improve fiber elasticity (toughness), and suppression or removal of coloring can be performed in any order.

[0276] (Decolorization)

[0277] Bleaching is performed by impregnating naturally sourced fibers into a bleaching agent composition containing an alkali, an oxidizing agent, and water. The bleaching agent composition is typically a two-component formulation, with the first component containing an alkali and water, and the second component containing an oxidizing agent and water. These two components are usually stored separately and mixed before impregnating the naturally sourced fibers.

[0278] Preferred alkaline agents include, for example: ammonia and its salts; alkanolamines (monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol, etc.) and their salts; alkyldiamines (1,3-propanediamine, etc.) and their salts; and carbonates (guanidine carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.); and mixtures thereof, but are not limited to these.

[0279] The content of alkali in the decolorizing agent composition (or a mixture of agent 1 and agent 2 in the case of a two-component formulation) 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 preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 7.5% by mass or less.

[0280] Preferred oxidizing agents include, but are not limited to, hydrogen peroxide, urea peroxide, melamine peroxide, and sodium bromate. Among these oxidizing agents, hydrogen peroxide is preferred.

[0281] The content of oxidant in the decolorizing agent composition is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 9% by mass or less.

[0282] 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 using a suitable buffer. The pH of the decolorizing agent composition at 25°C is preferably 6 or higher, more preferably 6.5 or higher, further preferably 6.8 or higher, and preferably 11 or lower, more preferably 10.5 or lower, and further preferably 10 or lower.

[0283] (dyeing)

[0284] Dyeing is performed by impregnating naturally sourced fibers into a dyeing agent composition. The dyeing agent composition contains dyes and may optionally contain alkalis, acids, oxidizing agents, etc. Examples of dyes include direct dyes, oxidative dyes, and combinations thereof.

[0285] There are no particular limitations on the types of direct dyes; any direct dye suitable for dyeing can be used. Examples of direct dyes include anionic dyes, nitro dyes, disperse dyes, cationic dyes, and dyes with an azophenol structure selected from HC Red 18, HC Blue 18, and HC Yellow 16, as well as their salts and mixtures thereof.

[0286]

[0287] HC Red 18, HC Blue 18, HC Yellow 16

[0288] Examples of cationic dyes include, but are not limited to, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 99, Basic Brown 4, Basic Brown 16, Basic Brown 17, Natural Brown 7, Basic Green 1, Basic Orange 31, Basic Red 2, Basic Red 12, Basic Red 22, Basic Red 51, Basic Red 76, Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 10, Basic Violet 14, Basic Yellow 57, and Basic Yellow 87, as well as mixtures thereof. Basic Red 51, Basic Orange 31, Basic Yellow 87, and mixtures thereof are particularly preferred.

[0289] As anionic dyes, examples 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, D D&C Brown No. 1, D&C Green No. 5, D&C Green No. 8, D&C Orange No. 4, D&C Orange No. 10, D&C Orange No. 11, D&C Red No. 21, D&C Red No. 27, D&C Red No. 33, D&C Purple No. 2, D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, FD&C Red No. 2, FD&C Red No. 40, FD&C Red No. 4, FD&C Yellow No. 6, FD&C Blue No. 1, Food Black No. 1, Food Black No. 2, and their alkali metal salts (sodium salts, potassium salts, etc.), and mixtures thereof, but not limited to these.

[0290] Among these, preferred anionic dyes are Acid Black 1, Acid Red 52, Acid Violet 2, Acid Violet 43, Acid Red 33, Acid Orange 4, Acid Orange 7, Acid Red 27, Acid Yellow 3, and Acid Yellow 10, as well as their salts. More preferred anionic dyes are Acid Red 52, Acid Violet 2, Acid Red 33, Acid Orange 4, and Acid Yellow 10, as well as their salts and mixtures thereof.

[0291] Examples of nitro dyes include HC Blue No. 2, HC Blue No. 4, HC Blue No. 5, HC Blue No. 6, HC Blue No. 7, HC Blue No. 8, HC Blue No. 9, HC Blue No. 10, HC Blue No. 11, HC Blue No. 12, HC Blue No. 13, HC Brown No. 1, HC Brown No. 2, HC Green No. 1, HC Orange No. 1, HC Orange No. 2, HC Orange No. 3, HC Orange No. 5, HC Red BN, HC Red No. 1, HC Red No. 3, HC Red No. 7, HC Red No. 8, HC Red No. 9, HC Red No. 10, HC Red No. 11, HC Red No. 13, and HC Red No. 54. HC Red No. 14, HC Purple BS, HC Purple No. 1, HC Purple No. 2, HC Yellow No. 2, HC Yellow No. 4, HC Yellow No. 5, HC Yellow No. 6, HC Yellow No. 7, HC Yellow No. 8, HC Yellow No. 9, HC Yellow No. 10, HC Yellow No. 11, HC Yellow No. 12, HC Yellow No. 13, HC Yellow No. 14, HC Yellow No. 15, 2-amino-6-chloro-4-nitrophenol, picric acid, 1,2-diamino-4-nitrobenzene, 1,4-diamino-2-nitrobenzene, 3-nitro-4-aminophenol, 1-hydroxy-2-amino-3-nitrobenzene and 2-hydroxyethylpicric acid, and mixtures thereof, but not limited to these.

[0292] Examples of disperse dyes include, but are not limited to, Disperse Blue 1, Disperse Black 9, and Disperse Violet 1, as well as mixtures thereof.

[0293] These direct dyes can be used alone, or in combination of two or more, or in combination of direct dyes with different ionic properties.

[0294] Regarding the content of direct dye in the dyeing composition, from the viewpoint of obtaining sufficient dyeability, it 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; and from the viewpoint of compatibility, it is preferably 10% by mass or less, more preferably 7.5% by mass or less, even more preferably 5.0% by mass or less, and even more preferably 3.0% by mass or less.

[0295] When the dyeing agent composition contains only a direct dye as the dye, an oxidizing agent is not required when dyeing naturally sourced fibers. However, if the goal is to brighten the color of the naturally sourced fibers, the composition may contain an oxidizing agent.

[0296] When the dyeing composition contains oxidative dyes, it is usually formulated as a two-component mixture. The first component contains an oxidative dye intermediate (precursor and coupling agent) and an alkali, while the second component contains an oxidizing agent such as hydrogen peroxide. The two components are usually stored separately and mixed before impregnating naturally sourced fibers.

[0297] As an intermediate for oxidative dyes, there are no particular restrictions, and any known precursors and coupling agents commonly used in dyeing products can be used appropriately.

[0298] Examples of precursors include p-phenylenediamine, toluene-2,5-diamine, 2-chloro-p-phenylenediamine, N-methoxyethyl-p-phenylenediamine, N-phenyl-p-phenylenediamine, N,N-bis(2-hydroxyethyl)p-phenylenediamine, 2-(2-hydroxyethyl)p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 4,4'-diaminodiphenylamine, 1,3-bis(N-(2-hydroxyethyl)-N-(4-aminophenyl)amino)-2-propanol, PEG-3,3,2'-p-phenylenediamine, p-aminophenol, p-methylaminophenol, and 3-methyl-4-aminophenol. 2-Aminomethyl-4-aminophenol, 2-(2-hydroxyethylaminomethyl)-4-aminophenol, o-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 2-amino-5-acetamidephenol, 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, but not limited to these.

[0299] Examples of coupling agents include m-phenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4-(2-hydroxyethylamino)anisole, 2,4-diamino-5-methylphenethyl ether, 2,4-diamino-5-(2-hydroxyethoxy)toluene, 2,4-dimethoxy-1,3-diaminobenzene, 2,6-bis(2-hydroxyethylamino)toluene, 2,4-diamino-5-fluorotoluene, and 1,3-bis(2,4- Diaminophenoxy propane, m-aminophenol, 2-methyl-5-aminophenol, 2-methyl-5-(2-hydroxyethylamino)phenol, 2,4-dichloro-3-aminophenol, 2-chloro-3-amino-6-methylphenol, 2-methyl-4-chloro-5-aminophenol, N-cyclopentyl-m-aminophenol, 2-methyl-4-methoxy-5-(2-hydroxyethylamino)phenol, 2-methyl-4-fluoro-5-aminophenol, p-aminophenol o-Cresol, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1-naphthol, 1,5-dihydroxynaphthol, 1,7-dihydroxynaphthol, 2,7-dihydroxynaphthol, 2-isopropyl-5-methylphenol, 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 6-hydroxybenzomorpholine, 3,4-methylenedioxyphenol, 2-bromo-4,5-methylenedioxyphenol, 3,4-methylenedioxy The substances include, but are not limited to, phenylene, 1-(2-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-diaminopyridine, 2,3-diamino-6-methoxypyridine, 2-methylamino-3-amino-6-methoxypyridine, 2-amino-3-hydroxypyridine, 2,6-diaminopyridine, salts of these substances, and mixtures thereof.

[0300] The content of the precursor and coupling agent in the dyeing composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 10% by mass or less, more preferably 7.5% by mass or less, and even more preferably 5.0% by mass or less.

[0301] In the case where the dyeing composition contains an oxidizing dye, it also contains an alkali agent. Preferred alkali agents include, for example: ammonia and its salts; alkanolamines (monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol, etc.) and their salts; alkyldiamines (1,3-propanediamine, etc.) and their salts; and carbonates (guanidine carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.); and mixtures thereof, but are not limited to these.

[0302] The content of alkali in the dyeing 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 preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 7.5% by mass or less.

[0303] When the dyeing agent composition contains an oxidizing dye, the composition containing the oxidizing agent (agent 2) is stored separately from the composition containing the oxidizing dye (agent 1) and mixed before impregnation of naturally sourced fibers. Preferred oxidizing agents include, for example, hydrogen peroxide, urea peroxide, melamine peroxide, and sodium bromate, but are not limited to these. Among these oxidizing agents, hydrogen peroxide is preferred.

[0304] The content of oxidant in the dyeing composition is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 9% by mass or less.

[0305] 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 using a suitable buffer. The pH of the dye composition formed by mixing the first and second agents at 25°C is preferably 6 or higher, more preferably 6.5 or higher, further preferably 6.8 or higher, and preferably 11 or lower, more preferably 10.5 or lower, and further preferably 10 or lower.

[0306] In the case where the dyeing composition contains oxidative dyes, it may also contain the direct dyes exemplified above.

[0307] The dye composition preferably also contains surfactants, conditioning ingredients, etc., as shown below, and is preferably formulated as a solution, emulsion, cream, paste, or mousse.

[0308] From the viewpoint of enabling the dye composition to efficiently penetrate and diffuse into the interior of naturally derived fibers and further improve the dyeing effect, the temperature of the dye composition is preferably 0°C or higher, more preferably 10°C or higher, even more preferably 20°C or higher, and preferably 90°C or lower, more preferably 80°C or lower.

[0309] (dry)

[0310] Regarding the fibers treated by the above-described step (i), from the viewpoint of improving subsequent workability and the adhesion of component (A) to the fibers, drying is preferable. The drying temperature is preferably 100°C or less, more preferably 80°C or less.

[0311] (Surface finishing)

[0312] Surface finishing is performed by impregnating naturally sourced fibers with a surface finishing agent. The surface finishing agent may contain cationic surfactants, silicones, or cationic polymers. In this specification, "cationic polymer" refers to a polymer having cationic groups or groups that can be ionized into cationic groups, and also includes amphoteric polymers that are cationic overall. Furthermore, the content of other components can be appropriately selected without impairing the effects of the invention.

[0313] (Catonic surfactant)

[0314] Without impairing the effects of the invention, the fiber treatment agent of the present invention may contain a cationic surfactant. The cationic surfactant is preferably a single 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.

[0315] Preferably, at least one single long-chain alkyl quaternary ammonium surfactant is selected from compounds represented by the following general formula (6).

[0316] In the formula, R 5 R represents saturated or unsaturated straight-chain or branched alkyl groups with 8 to 22 carbon atoms. 9 -CO-NH-(CH2) p -or R 9 -CO-O-(CH2) p -(R) 9 Represents a saturated or unsaturated straight-chain or branched alkyl chain with 7 to 21 carbon atoms (p represents an integer from 1 to 4), R 6 R 7 and R 8 Independently representing alkyl groups having 1 to 4 carbon atoms, and hydroxyalkyl groups having 1 to 4 carbon atoms, An - This indicates chloride ions, bromide ions, methyl sulfate ions, or ethyl sulfate ions.

[0317] Preferred cationic surfactants include, for example, long-chain quaternary ammonium compounds such as cetyltrimethylammonium chloride, myristyltrimethylammonium chloride, behenyltrimethylammonium chloride, cetyltrimethylammonium bromide, and stearamidopropyltrimethylammonium chloride. These compounds can be used alone or in mixtures.

[0318] Regarding the content of cationic surfactant in the fiber treatment agent of the present invention, from the viewpoint of improving the tactile feel of the surface of the treated natural fiber and further improving the effect of the present invention, it is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, and preferably 10% by mass or less, more preferably 5.0% by mass or less.

[0319] (Silicone)

[0320] Furthermore, from the viewpoint of improving the surface feel of the treated natural-source fibers and enhancing their combability, the fiber treatment agent of the present invention may contain silicone. Preferably, the silicone is selected from one or more of dimethylpolysiloxane and amino-modified silicone.

[0321] As dimethyl polysiloxane, any cyclic or acyclic dimethyl polysiloxane polymer can also be used. Examples include the SH200 series, BY22-019, BY22-020, BY11-026, B22-029, BY22-034, BY22-050A, BY22-055, BY22-060, BY22-083, FZ-4188 (the above are products of Toray Industries, Inc.), KF-9088, KM-900 series, MK-15H, and MK-88 (the above are products of Shin-Etsu Chemical Co., Ltd.).

[0322] As amino-modified silicones, all silicones having amino or ammonium groups can be used. Examples include amino-modified silicone oils with all or part of their terminal hydroxyl groups capped by methyl groups and uncapped amino-terminated polydimethylsiloxanes. From the viewpoint of improving the surface feel of treated natural-source fibers and enhancing combability, preferred amino-modified silicones include, for example, compounds represented by the following formula.

[0323]

[0324] In the formula, R' represents a hydrogen atom, a hydroxyl group, or R X R X J represents a monovalent hydrocarbon group with 1 to 20 carbon atoms, whether substituted or unsubstituted; J represents R. X R"-(NHCH2CH2) a NH2, OR X Or hydroxyl group, R" represents a divalent hydrocarbon group with 1 to 8 carbon atoms, a represents a number from 0 to 3, b and c represent numbers whose sum is 10 or more and less than 20,000, preferably 20 or more and less than 3,000, more preferably 30 or more and less than 1,000, and even more preferably 40 or more and less than 800.

[0325] Specific examples of commercially available amino-modified silicones include amino-modified silicone oils such as SF8452c, SS3551 (all products of Toray D. Corning Co., Ltd.), KF-8004, KF-867S, and KF-8015 (all products of Shin-Etsu Chemical Co., Ltd.), and amino-terminated polydimethylsiloxane emulsions such as SM8704c, SM8904, BY22-079, FZ-4671, and FZ4672 (all products of Toray D. Corning Co., Ltd.).

[0326] From the viewpoint of improving the surface feel of the treated natural fiber and further enhancing the effect of the present invention, the content of silicone in the fiber treatment agent of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, and more preferably 5.0% by mass or less.

[0327] (Catonic polymer)

[0328] Furthermore, from the viewpoint of improving the surface feel of treated natural-derived fibers, the fiber treatment agent of the present invention may contain cationic polymers.

[0329] Cationic polymers refer to polymers having cationic groups or groups that can be ionized into cationic groups, and also include amphoteric polymers that are cationic overall. Specifically, examples include polymers whose side chains contain amino or ammonium groups, or whose aqueous solutions contain 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 viewpoint of improving the softness, smoothness, and finger accessibility during rinsing or shampooing, as well as the combability and moisturizing properties during drying, and from the viewpoint of formulation stability, polymers containing diallyl quaternary ammonium salts as structural units, quaternized polyvinylpyrrolidone derivatives, and cationic cellulose derivatives are preferred; more preferably, polymers or copolymers of diallyl quaternary ammonium salts and cationic cellulose derivatives are preferred.

[0330] Specific examples of preferred diallyl quaternary ammonium salt polymers or copolymers include dimethyl diallyl ammonium chloride polymers (polyquaternary ammonium salt-6, e.g., Merquat 100, Lubrizol Advanced Materials), dimethyl diallyl ammonium chloride / acrylic acid copolymers (polyquaternary ammonium salt-22, e.g., Merquat 280, Merquat 295, Lubrizol Advanced Materials), and dimethyl diallyl ammonium chloride / acrylamide copolymers (polyquaternary ammonium salt-7, e.g., Merquat 550, Lubrizol Advanced Materials).

[0331] As a specific example of a preferred quaternized polyvinylpyrrolidone derivative, polymers obtained by polymerizing vinylpyrrolidone copolymers with dimethylaminoethyl methacrylate (polyquaternium salt 11, such as GAFQUAT 734, GAFQUAT 755, GAFQUAT 755N (all products of Ashland Corporation)) can be listed.

[0332] Specific examples of preferred cationic cellulose include polymers formed by adding glycidyl trimethylammonium chloride to hydroxycellulose (polyquaternium salt 10, such as LEOGARD G, LEOGARD GP (all products of Lion Corporation), POLYMER JR-125, POLYMER JR-400, POLYMER JR-30M, POLYMER LR-400, POLYMER LR-30M (all products of Amerchol Corporation)), and hydroxyethyl cellulose dimethyl diallyl ammonium chloride (polyquaternium salt 4, such as CELQUAT H-100, CELQUAT L-200 (all products of Akzo Nobel Corporation)).

[0333] From the viewpoint of improving the surface feel of treated natural-derived fibers, the content of 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 preferably 20% by mass or less, more preferably 10% by mass or less.

[0334] (Post-heating: a heat treatment used to further improve the fiber's elasticity (toughness))

[0335] From the viewpoint of more effectively improving the elasticity of naturally derived fibers, the fibers can be stretched while being heated. In this heating process, when the amount of naturally derived fibers is small, a hair curler or steam iron is preferred; for large quantities, equivalent results can be obtained by applying tension using a winding machine while heating with warm air or high-temperature steam.

[0336] Regarding the fiber elongation rate during heating, from the viewpoint of more effectively improving fiber elasticity, it is preferably 0.1% or more, more preferably 0.2% or more, and even more preferably 0.5% or more; in addition, from the viewpoint of suppressing damage to the fiber, it is preferably 10% or less, more preferably 5.0% or less, and even more preferably 2.0% or less.

[0337] Regarding the heating temperature, from the viewpoint of more effectively improving the fiber elasticity, it is preferably 60°C or higher, more preferably 80°C or higher, and even more preferably 100°C or higher; in addition, from the viewpoint of suppressing damage to the fiber, it is preferably 240°C or lower, more preferably 180°C or lower, and even more preferably 150°C or lower.

[0338] Regarding the heating time, from the viewpoint of more effectively improving fiber elasticity, it is preferably 1 second or more, more preferably 10 seconds or more, and even more preferably 1 minute or more; in addition, from the viewpoint of suppressing damage to the fiber, it is preferably 1 hour or less, more preferably 30 minutes or less, and even more preferably 5 minutes.

[0339] From the perspective of more effectively improving fiber elasticity, after heating, the naturally derived fibers can be stretched while being left to stand in water under tension.

[0340] Regarding the elongation rate at this time, from the viewpoint of more effectively improving the fiber elasticity, it is preferably 0.1% or more, more preferably 0.2% or more, and even more preferably 0.5% or more; in addition, from the viewpoint of suppressing damage to the fiber, it is preferably 10% or less, more preferably 5.0% or less, and even more preferably 2.0% or less.

[0341] Regarding the water temperature, from the viewpoint of more effectively improving the elasticity of the fibers, it is preferably 5°C or higher, more preferably 20°C or higher, and even more preferably 30°C or higher; in addition, from the viewpoint of suppressing damage to the fibers, it is preferably 80°C or lower, more preferably 60°C or lower, and even more preferably 50°C or lower.

[0342] Regarding the settling time in water, from the viewpoint of more effectively improving fiber elasticity, it is preferably 1 minute or more, more preferably 5 minutes or more, and even more preferably 30 minutes or more; in addition, from the viewpoint of suppressing damage to the fibers, it is preferably 48 hours or less, more preferably 24 hours or less, and even more preferably 3 hours or less.

[0343] Through this operation, depending on the processing conditions of step (i), elasticity comparable to human hair can be achieved during fiber drying.

[0344] (Suppress or remove staining)

[0345] Furthermore, the coordination functional groups of component (A) are those with OH and O. -In the case of a group, in order to suppress or remove the coloring of natural-derived fibers treated with the fiber treatment agent of the present invention, a salt-containing composition can be used for treatment. As the salt, any type of organic salt or inorganic salt can be used. Specifically, as organic salts, in addition to chelating organic salts such as disodium etidronate, disodium ethylenediaminetetraacetate, disodium catechol-3,5-disulfonic acid monohydrate, and sodium phytate, sodium mercaptoethanesulfonate and sodium 2-naphthalenesulfonate can also be listed. As inorganic salts, in addition to sulfites such as sodium sulfite, sodium chloride and aluminum chlorohydroxyl can also be listed. As preferred salts for this purpose, organic salts can include reducing salts (such as salts of thiols) and salts with metal chelating properties (such as sodium salts of edetate such as disodium ethylenediaminetetraacetate and sodium salts of etidronate such as disodium etidronate); inorganic salts can include reducing salts (such as sodium sulfite). More preferably, a reducing salt and a salt with metal chelating properties can be used together.

[0346] The fiber coloring caused by treatment with the fiber treatment agent of the present invention can be considered as both brownish-red oxidative coloring (which can be addressed by treatment with reducing salts) and yellowish-red coloring by metal complexes (which can be addressed by treatment with chelating agents). By performing corresponding decolorization treatments, fiber coloring can be better suppressed.

[0347] The salt-containing composition is preferably an aqueous solution. Furthermore, regarding the pH of the composition, from the viewpoint of not reducing the water resistance, elasticity (toughness, i.e., high elongation at break when the fiber is stretched), and heat resistance of the naturally derived fibers, it is preferably 2.0 or higher, more preferably 3.0 or higher, even more preferably 4.0 or higher, and preferably 9.0 or lower, more preferably 7.0 or lower, even more preferably 6.0 or lower.

[0348] Regarding the salt content in the above composition, from the viewpoint of suppressing or removing the coloring of naturally sourced fibers, it 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 not causing a decrease in the water resistance, elasticity (toughness, i.e., high elongation at break when the fiber is stretched) and heat resistance of the naturally sourced fibers due to the reducing effect, it is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5.0% by mass or less.

[0349] Regarding the temperature of treatment using the salt-containing composition, from the viewpoint of exhibiting the effect of inhibiting or removing the coloring of naturally sourced fibers, it is preferably 5°C or higher, more preferably 10°C or higher, and even more preferably 20°C or higher; in addition, from the viewpoint of avoiding fiber damage, it is preferably 100°C or lower, more preferably 60°C or lower, and even more preferably 40°C or lower.

[0350] Regarding the treatment time using the salt-containing composition, from the viewpoint of exhibiting the effect of inhibiting or removing the coloring of naturally sourced fibers, it is preferably 1 second or more, more preferably 30 seconds or more, and even more preferably 1 minute or more; in addition, from the viewpoint of avoiding fiber damage, it is preferably 60 minutes or less, more preferably 30 minutes or less, and even more preferably 15 minutes or less.

[0351] For fibers that have undergone the above treatments, the feel can be improved by using common fiber post-treatments, such as fiber treatment agents like softeners, or hair care products like conditioning agents or hair conditioners.

[0352] By using the above fiber treatment methods to treat natural-source fibers, component (A) penetrates into the fiber, and the coordination functional groups of component (A) coordinate with the fiber, thereby solving the technical problems unique to natural-source fibers. As a result, it is possible to manufacture fibers with excellent water resistance and thermal shape memory, to appropriately manufacture fibers for headwear products, and to use these fibers to manufacture various fiber products and appropriately manufacture headwear products.

[0353] In addition, in this invention, preferred headwear products include, for example, hair wigs, wigs, weaving, hair extensions, braids, hair accessories, and doll hair.

[0354] Regarding the embodiments described above, preferred embodiments of the present invention are further disclosed below.

[0355] <1> A fiber treatment agent, wherein the fiber treatment agent contains the following components (A) and (B) for use in the treatment of fibers with a water swelling rate of 200% or more as calculated according to the following formula (1).

[0356] <2> A fiber treatment kit, wherein the fiber treatment kit comprises: 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), wherein the pH of the second fiber treatment agent is more than 1.0 lower than the pH of the first fiber treatment agent, and the fiber treatment kit is used for treating fibers with a water swelling rate of more than 200% calculated according to the following formula (1).

[0357] <3> A fiber treatment kit, wherein the fiber treatment kit comprises: a fiber treatment agent containing components (A) and (B) below, and an additional fiber treatment agent containing component (D) below, the fiber treatment kit being used for treating fibers with a water swelling rate of 200% or more as calculated according to the following formula (1),

[0358] (A) Compounds with coordinating functional groups and a molecular weight of 1500 or more

[0359] (B) Water

[0360] Fiber swelling rate in water (%) = [(w1-w2) / w2]×100 (1)

[0361] In the formula,

[0362] w1 represents the mass (g) of fiber obtained by placing 1.0g of fiber into a container filled with 100g of ion-exchanged water, sealing the container, immersing the fiber together in a 40°C water bath for 30 minutes, removing the fiber from the container, centrifuging it at 220 [×g] for 1 minute to remove water.

[0363] w2 represents the mass of the fiber after its mass (w1) has been measured, placed on filter paper, and dried at 105°C for 3 hours.

[0364] (D) The hydrogen bonding term δH of Hansen's solubility parameter is 18.3 MPa. 1 / 2 The following are compounds or salts thereof having at least one carboxyl group or a salt thereof and not having a fused ring (excluding component (A)).

[0365] <4> The fiber treatment agent as described in <1> above, or the fiber treatment kit as described in <2> or <3> above, wherein the fiber swelling rate in water is preferably 250% or more, more preferably 300% or more, further preferably 350% or more, and preferably 1000% or less, more preferably 800% or less, further preferably 600% or less, and further preferably 500% or less.

[0366] <5> The fiber treatment agent as described in <1> above, or the fiber treatment kit as described in <2> or <3> above, wherein the fiber swelling rate in water is preferably 250-1000%, more preferably 300-800%, further preferably 350-600%, and even more preferably 350-500%.

[0367] <6> The fiber treatment agent as described in any one of <1>, <4> and <5> above, or the fiber treatment kit as described in any one of <2> to <5> above, wherein the fiber is preferably a regenerated protein fiber, more preferably a regenerated collagen fiber or a regenerated silk fiber, and even more preferably a regenerated collagen fiber.

[0368] <7> The fiber treatment agent as described in any one of <1>, <4> to <6> above, or the fiber treatment kit as described in any one of <2> to <6> above, wherein the fiber is preferably a polyvalent metal, or its salt or complex.

[0369] <8> The fiber treatment agent or the fiber treatment kit described in <7> above, wherein the polyvalent metal is preferably selected from one or more of calcium, magnesium, strontium, barium, zinc, chromium, aluminum, titanium, zirconium, tin, lead, antimony, iron and copper, more preferably selected from one or more of aluminum, zirconium and titanium, and even more preferably aluminum.

[0370] <9> The fiber treatment agent or the fiber treatment kit described in <7> or <8> above, wherein the content of the polyvalent metal, or its salt or complex in the fiber is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, further preferably 3.0% by mass or more, even more preferably 5.0% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and even more preferably 10% by mass or less.

[0371] <10> The fiber treatment agent as described in <7> or <8> above, or the fiber treatment kit as described in <7> or <8> above, wherein the content of the polyvalent metal, or its salt or complex in the fiber is preferably 1.0 to 40% by mass, more preferably 2.0 to 30% by mass, further preferably 3.0 to 20% by mass, and even more preferably 5.0 to 10% by mass, in terms of metal element content.

[0372] <11> The fiber treatment agent as described in any one of <1>, <4> to <10> above, or the fiber treatment kit as described in any one of <2> to <10> above, wherein component (A) preferably contains one or more selected from (A-1) and (A-2) below,

[0373] (A-1) A polymer comprising structural units derived from unsaturated monomers having coordinating functional groups, wherein the polymer has a weight-average molecular weight of 1500 or more.

[0374] (A-2) A condensate of a compound having a coordinating functional group, wherein the molecular weight of the condensate is greater than 1500.

[0375] <12> The fiber treatment agent as described in <11> above, or the fiber treatment kit as described in <11> above, wherein the (A-1) polymer preferably contains one or more selected from (A-1-1), (A-1-2), and (A-1-3) below.

[0376] (A-1-1) is a copolymer comprising structural units derived from unsaturated monomers having coordinating functional groups and structural units derived from aromatic vinyl compounds, wherein the copolymer has a weight-average molecular weight of 1500 or more.

[0377] (A-1-2) comprises a copolymer containing structural units derived from an unsaturated monomer having a coordinating functional group and structural units derived from an unsaturated aliphatic hydrocarbon compound, wherein the copolymer has a weight-average molecular weight of 1500 or more.

[0378] (A-1-3) is a polymer comprising a structural unit derived from an aromatic vinyl compound having a coordinating functional group or a polymer comprising a structural unit derived from an unsaturated aliphatic hydrocarbon compound having a coordinating functional group, wherein the weight average molecular weight of the copolymer is 1500 or more (excluding copolymers (A-1-1) and (A-1-2)).

[0379] <13> The fiber treatment agent as described in <11> or <12> above, or the fiber treatment kit as described in <11> or <12> above, wherein, in all structural units, the proportion of structural units derived from unsaturated monomers having coordination functional groups is preferably 10 mol% or more, more preferably 15 mol% or more, and even more preferably 20 mol% or more.

[0380] <14> The fiber treatment agent as described in any one of <1>, <4> to <13> above, or the fiber treatment kit as described in any one of <2> to <13> above, wherein the coordination functional group is preferably a group containing a hard base or a cross-base in the HSAB rule.

[0381] <15> The fiber treatment agent as described in any one of <1>, <4> to <14> above, or the fiber treatment kit as described in any one of <2> to <14> above, wherein the coordination functional group preferably comprises a base group selected from (a-1), (a-2) and (a-3) below,

[0382] (a-1) A group having a carboxyl group or its salt (carboxylate), preferably a carboxyl anion.

[0383] (a-2) A group having a hydroxyl, alkoxy, alkoxide anion, or metal alkoxide group; if the hydroxyl group is a phenolic hydroxyl group, it can be a phenol oxide.

[0384] (a-3) has a sulfonic acid group or its salt (sulfonate), and can be a sulfonate anion.

[0385] <16> The fiber treatment agent as described in any one of <12> to <15> above, or the fiber treatment kit as described in any one of <12> to <15> above, wherein, in the (A-1-1) copolymer, the ratio of structural units (u1) derived from aromatic vinyl compounds to structural units (u2) derived from unsaturated monomers having coordinating functional groups is preferably 1 / 5 to 5 / 1, more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1 in molar ratio (u1 / u2).

[0386] <17> The fiber treatment agent as described in any one of <12> to <16> above, or the fiber treatment kit as described in any one of <12> to <16> above, wherein, in the (A-1-2) copolymer, the ratio of structural units (u3) derived from unsaturated aliphatic hydrocarbon compounds to structural units (u4) derived from unsaturated monomers having coordinating functional groups is preferably 1 / 5 to 5 / 1, more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1 in molar ratio (u3 / u4).

[0387] <18> The fiber treatment agent as described in any one of <12> to <17> above, or the fiber treatment kit as described in any one of <12> to <17> above, wherein the (A-1-1) copolymer is a copolymer with a weight average molecular weight of 1500 or more, preferably a copolymer comprising structural units derived from aromatic vinyl compounds and structural units derived from unsaturated monomers having carboxyl groups or their salts, more preferably a copolymer comprising structural units derived from aromatic vinyl compounds and structural units derived from one or more structural units selected from unsaturated monocarboxylic acids, saturated dicarboxylic acids and their salts, and even more preferably a copolymer selected from styrene-maleic acid copolymers. The copolymers are selected from one or more of the following: styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, vinylbenzoic acid-maleic acid copolymers, vinylbenzoic acid-acrylic acid copolymers, vinylbenzoic acid-methacrylic acid copolymers, styrene-4-vinylbenzoic acid copolymers, butadiene-4-vinylbenzoic acid copolymers, carboxyl-modified styrene-butadiene copolymers, and their salts; more preferably, styrene-maleic acid copolymers or their salts.

[0388] <19> The fiber treatment agent as described in any one of <12> to <18> above, or the fiber treatment kit as described in any one of <12> to <18> above, wherein the (A-1-2) copolymer is a copolymer with a weight average molecular weight of 1500 or more, preferably a copolymer comprising structural units derived from unsaturated aliphatic hydrocarbon compounds and structural units derived from unsaturated monomers having carboxyl groups or their salts, more preferably a copolymer comprising structural units derived from unsaturated aliphatic hydrocarbon compounds and structural units derived from one or more structural units selected from unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and their salts, and even more preferably... The copolymer is selected from one or more copolymers chosen 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 products of butadiene polymers, and their salts, and is more preferably selected from one or more copolymers chosen from diisobutylene-maleic acid copolymer, butadiene-maleic acid copolymer, maleic acid modified products of butadiene polymers, and their salts.

[0389] <20> The fiber treatment agent as described in any one of <12> to <19> above, or the fiber treatment kit as described in any one of <12> to <19> above, wherein the (A-1-3) polymer is a polymer with a weight average molecular weight of 1500 or more, preferably one or more polymers selected from homopolymers of aromatic vinyl compounds having carboxyl groups, sulfonic acid groups or their salts, or hydroxyl groups, and homopolymers of unsaturated aliphatic hydrocarbon compounds having carboxyl groups, sulfonic acid groups or their salts, or hydroxyl groups, more preferably polymers selected from aromatic vinyl compounds having carboxyl groups or their salts. The polymer is selected from one or more of the following: homopolymers of vinyl compounds and homopolymers of unsaturated aliphatic hydrocarbon compounds having carboxyl groups or their salts; more preferably, homopolymers of unsaturated aliphatic hydrocarbon compounds having carboxyl groups or their salts; even more preferably, polymers selected from one or more of poly(vinylbenzoic acid), poly(cinnamic acid), polyacrylic acid and polymethacrylic acid or their salts, and polyvinyl alcohol; even more preferably, polymers selected from one or more of polyacrylic acid, polymethacrylic acid and their salts; and even more preferably, polyacrylic acid or its salts.

[0390] <21> The fiber treatment agent as described in any one of <12> to <20> above, or the fiber treatment kit as described in any one of <12> to <20> above, wherein the (A-1-3) polymer is preferably one or more polymers selected from poly(vinylbenzoic acid), poly(cinnamic acid), polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid or their salts, and polyvinyl alcohol, more preferably one or more polymers selected from polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid or their salts, and polyvinyl alcohol, further preferably one or more polymers selected from polyacrylic acid, polymethacrylic acid and their salts, and even more preferably polyacrylic acid or its salts.

[0391] <22> The fiber treatment agent as described in <11> above, or the fiber treatment kit as described in <11> above, wherein the (A-2) condensate is a condensate with a molecular weight of 1500 or more, and preferably contains one or more condensates selected from (A-2-1) and (A-2-2) below.

[0392] (A-2-1) A condensate of sulfonic acid or a salt thereof.

[0393] (A-2-2) condensate of gallic acid ester.

[0394] <23> The fiber treatment agent or the fiber treatment kit described in <22> above, wherein the (A-2-1) condensate is a condensate with a weight-average molecular weight of 1500 or more, preferably an aromatic sulfonic acid formaldehyde condensate or a salt thereof, more preferably a condensate selected from one or more of benzenesulfonic acid formaldehyde condensate, naphthalenesulfonic acid formaldehyde condensate, phenolsulfonic acid formaldehyde condensate and their salts, and even more preferably a naphthalenesulfonic acid formaldehyde condensate or a salt thereof.

[0395] <24> The fiber treatment agent as described in <22> or <23> above, or the fiber treatment kit as described in <22> or <23> above, wherein the (A-2-2) condensate is a condensate with a molecular weight of 1500 or more, preferably a hydrolyzable tannin, and more preferably tannic acid.

[0396] <25> The fiber treatment agent as described in any one of <11> to <24> above, or the fiber treatment kit as described in any one of <11> to <24> above, wherein, when component (A) is a condensate of (A-1) polymer or (A-2-1) sulfonic acid or a salt thereof, the weight-average molecular weight is preferably 1600 or more, more preferably 2000 or more, further preferably 3000 or more, even more preferably 4000 or more, and preferably 100000 or less, more preferably 30000 or less, even more preferably 15000 or less, even more preferably 10000 or less, and even more preferably 8000 or less.

[0397] <26> The fiber treatment agent as described in any one of <11> to <24> above, or the fiber treatment kit as described in any one of <11> to <24> above, wherein, when component (A) is a condensate of (A-1) polymer or (A-2-1) sulfonic acid or a salt thereof, the weight-average molecular weight is preferably 1600 to 100000, more preferably 2000 to 30000, further preferably 3000 to 30000, further preferably 3000 to 15000, further preferably 3000 to 10000, and even more preferably 4000 to 8000.

[0398] <27> The fiber treatment agent as described in any one of <22> to <26> above, or the fiber treatment kit as described in any one of <22> to <26> above, wherein component (A) is a condensate of (A-2-2) gallic acid ester, and when it is a single compound, the molecular weight is preferably 1600 or more, more preferably 1700 or more, and preferably 10000 or less, more preferably 5000 or less.

[0399] <28> The fiber treatment agent as described in any one of <22> to <26> above, or the fiber treatment kit as described in any one of <22> to <26> above, wherein component (A) is a condensate of (A-2-2) gallic acid ester, and when it is a single compound, the molecular weight is preferably 1600 to 10000, more preferably 1700 to 5000.

[0400] <29> The fiber treatment agent as described in any one of <1>, <4> to <28> above, or the fiber treatment kit as described in any one of <2> to <28> above, wherein the hydrogen bonding term δH of the Hansen solubility parameter of component (A) is preferably 5.0 MPa. 1 / 2 The above, and more preferably 7.0 MPa 1 / 2 The above, and more preferably 9.0 MPa 1 / 2 The above, and preferably 20.0 MPa 1 / 2 The following, or more preferably, is 16.0 MPa 1 / 2The following, and more preferably, is 13.0 MPa 1 / 2 the following.

[0401] <30> The fiber treatment agent as described in any one of <1>, <4> to <28> above, or the fiber treatment kit as described in any one of <1> to <28> above, wherein the hydrogen bonding term δH of the Hansen solubility parameter of component (A) is preferably 5.0 to 20.0 MPa. 1 / 2 More preferably 7.0–16.0 MPa 1 / 2 A further preferred value is 9.0–13.0 MPa. 1 / 2 .

[0402] <31> The fiber treatment agent as described in any one of <15> to <30> above, or the fiber treatment kit as described in any one of <15> to <30> above, wherein, when component (A) has (a-1) or (a-3) as a coordinating functional group, the acid value of component (A) is preferably 100 mg KOH / g or more, more preferably 200 mg KOH / g or more, further preferably 300 mg KOH / g or more, even more preferably 400 mg KOH / g or more, and preferably 1000 mg KOH / g or less, more preferably 800 mg KOH / g or less, and even more preferably 600 mg KOH / g or less.

[0403] <32> The fiber treatment agent as described in any one of <15> to <30> above, or the fiber treatment kit as described in any one of <15> to <30> above, wherein, when component (A) has (a-1) or (a-3) as a coordinating functional group, the acid value of component (A) is preferably 1600 to 100000, more preferably 2000 to 30000, further preferably 3000 to 10000, and even more preferably 4000 to 8000.

[0404] <33> The fiber treatment agent as described in any one of <15> to <32> above, or the fiber treatment kit as described in any one of <15> to <32> above, wherein, when component (A) has the above-described (a-2) as a coordinating functional group, the hydroxyl value of component (A) is preferably 100 mg KOH / g or more, more preferably 200 mg KOH / g or more, further preferably 300 mg KOH / g or more, and preferably 2000 mg KOH / g or less, more preferably 1500 mg KOH / g or less, and further preferably 1000 mg KOH / g or less.

[0405] <34> The fiber treatment agent as described in any one of <15> to <32> above, or the fiber treatment kit as described in any one of <15> to <32> above, wherein, when component (A) has the above-described (a-2) as a coordinating functional group, the hydroxyl value of component (A) is preferably 100 to 1000 mg KOH / g, more preferably 200 to 800 mg KOH / g, further preferably 300 to 600 mg KOH / g, and even more preferably 400 to 600 mg KOH / g.

[0406] <35> The fiber treatment agent as described in any one of <1>, <4> to <34> above, or the fiber treatment kit as described in any one of <2> to <34> above, wherein component (A) in the fiber treatment agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, even more preferably 2.3% by mass or more, even more preferably 3.0% by mass or more, and preferably 60% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 15% by mass or less, even more preferably 10% by mass or less.

[0407] <36> The fiber treatment agent as described in any one of <1>, <4> to <34> above, or the fiber treatment kit as described in any one of <2> to <34> above, wherein component (A) in the fiber treatment agent 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, even more preferably 0.5 to 15% by mass, even more preferably 1.0 to 15% by mass, even more preferably 2.3 to 15% by mass, and even more preferably 3.0 to 10% by mass.

[0408] <37> The fiber treatment agent as described in any one of <11> to <36> above, or the fiber treatment kit as described in any one of <11> to <36> above, wherein, when component (A) is a condensate of (A-1) polymer or (A-2-1) 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, further preferably 1.0% by mass or more, even more preferably 2.3% by mass or more, even more preferably 3.0% by mass or more, and preferably 60% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, even more preferably 20% by mass or less, even more preferably 15% by mass or less, even more preferably 10% by mass or less.

[0409] <38> The fiber treatment agent as described in any one of <11> to <36> above, or the fiber treatment kit as described in any one of <11> to <36> above, wherein, when component (A) is a condensate of (A-1) polymer or (A-2-1) sulfonic acid or a salt thereof, the content of component (A) in the fiber treatment agent is preferably 0.3 to 60% by mass, more preferably 0.5 to 40% by mass, even more preferably 1.0 to 30% by mass, even more preferably 2.3 to 20% by mass, even more preferably 3.0 to 15% by mass, and even more preferably 3.0 to 10% by mass.

[0410] <39> The fiber treatment agent as described in any one of <21> to <38> above, or the fiber treatment kit as described in any one of <22> to <38> above, wherein, when component (A) is a condensate of (A-2-2) 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, further preferably 0.4% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1.0% by mass or less.

[0411] <40> The fiber treatment agent as described in any one of <21> to <38> above, or the fiber treatment kit as described in any one of <22> to <38> above, wherein, when component (A) is a condensate of (A-2-2) 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, and even more preferably 0.20 to 1.0% by mass.

[0412] <41> The fiber treatment agent as described in any one of <1>, <4> to <40> above, or the fiber treatment kit as described in any one of <2> to <40> above, wherein the pH of the fiber treatment agent is preferably 2.0 or higher, more preferably 3.0 or higher, even more preferably 3.5 or higher, and 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, even more preferably less than 5.5.

[0413] <42> The fiber treatment agent as described in any one of <1>, <4> to <40> above, or the fiber treatment kit as described in 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, further preferably 3.5 to 9.0, further more preferably 3.5 to 7.0, further more preferably 3.5 to 6.5, and further more preferably 3.5 or more and less than 5.5.

[0414] <43> The fiber treatment agent as described in any one of <11> to <42> above, or the fiber treatment kit as described in any one of <11> to <42> above, wherein, when component (A) is a condensate of (A-1) polymer or (A-2-1) 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% by mass or more, more preferably 0.8% by mass or more, further preferably 1.3% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less.

[0415] <44> The fiber treatment agent as described in any one of <11> to <42> above, or the fiber treatment kit as described in any one of <11> to <42> above, wherein, when component (A) is a condensate of (A-1) polymer or (A-2-1) 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% by mass, more preferably 0.8 to 20% by mass, and even more preferably 1.3 to 10% by mass.

[0416] <45> The fiber treatment agent as described in any one of <11> to <44> above, or the fiber treatment kit as described in any one of <11> to <44> above, wherein, when component (A) is a condensate of (A-1) polymer or (A-2-1) 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 higher, more preferably 2.0% by mass or higher, further preferably 3.0% by mass or higher, and preferably 60% by mass or lower, more preferably 50% by mass or lower, further preferably 40% by mass or lower.

[0417] <46> The fiber treatment agent as described in any one of <11> to <44> above, or the fiber treatment kit as described in any one of <11> to <44> above, wherein, when component (A) is a condensate of (A-1) polymer or (A-2-1) 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% by mass, more preferably 2.0 to 50% by mass, and even more preferably 3.0 to 40% by mass.

[0418] <47> The fiber treatment agent as described in any one of <21> to <46> above, or the fiber treatment kit as described in any one of <22> to <46> above, wherein, when component (A) is a condensate of (A-2-2) 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, further preferably 0.4% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1.0% by mass or less.

[0419] <48> The fiber treatment agent as described in any one of <21> to <46> above, or the fiber treatment kit as described in any one of <22> to <46> above, wherein, when component (A) is a condensate of (A-2-2) 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.

[0420] <49> The fiber treatment agent as described in any one of <1>, <4> to <48> above, or the fiber treatment kit as described in any one of <2> to <48> above, wherein the content of component (A) in 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 preferably 70% by mass or less, even 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, even more preferably 45% by mass or less.

[0421] <50> The fiber treatment agent as described in any one of <1>, <4> to <48> above, or the fiber treatment kit as described in any one of <2> to <48> above, wherein the content of component (A) in 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, even more preferably 10 to 45% by mass.

[0422] <51> The fiber treatment agent as described in any one of <1>, <4> to <50> above, and the fiber treatment kit as described in any one of <2> to <50> above, 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, further preferably 30% by mass or more, further more preferably 40% by mass or more, and preferably 98% by mass or less, more preferably 97% by mass or less, further preferably 96% by mass or less, further more preferably 95% by mass or less, further more preferably 90% by mass or less, and further more preferably 85% by mass or less.

[0423] <52> The fiber treatment agent as described in any one of <1>, <4> to <50> above, or the fiber treatment kit as described in any one of <2> to <50> above, wherein the content of component (B) in the fiber treatment agent is preferably the balance after removing component (A) and the 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, even more preferably 40 to 95% by mass, even more preferably 40 to 90% by mass, even more preferably 40 to 85% by mass.

[0424] <53> The fiber treatment agent as described in any one of <1>, <4> to <52> above, and the fiber treatment kit as described in any one of <2> to <52> above, wherein preferably, it further contains a polyvalent metal element as component (C).

[0425] <54> The fiber treatment agent or the fiber treatment kit described in <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 cross-linked acid that readily interacts with the coordination functional group (hard base, cross-linked base) of component (A), even more preferably a polyvalent metal salt of a hard acid or a cross-linked acid, even more preferably one or more selected from aluminum salts and zirconium salts, even more preferably one or more selected from aluminum sulfate, aluminum chloride and zirconium sulfate.

[0426] <55> The fiber treatment agent as described in <53> or <54> above, or the fiber treatment kit as described in <53> or <54> above, wherein the content of component (C) in the fiber treatment agent, in terms of metal element content, is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, further preferably 0.001% by mass or more, even more preferably 0.007% by mass or more, and preferably 1.0% by mass or less, more preferably 0.5% by mass or less, further preferably 0.10% by mass or less, and even more preferably 0.07% by mass or less.

[0427] <56> The fiber treatment agent as described in <53> or <54> above, or the fiber treatment kit as described in <53> or <54> above, wherein the content of component (C) in the fiber treatment agent, in terms of metal element content, is preferably 0.0001 to 1.0% by mass, more preferably 0.0005 to 0.5% by mass, further preferably 0.001 to 0.10% by mass, and even more preferably 0.007 to 0.07% by mass.

[0428] <57> The fiber treatment kit as described in any one of <2>, <4> to <56> above, wherein the pH of the first fiber agent is preferably 3.0 or higher, more preferably 4.0 or higher, further preferably 4.5 or higher, 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, even more preferably 7.0 or lower.

[0429] <58> The fiber treatment kit as described in any one of <2>, <4> to <56> above, wherein the pH of the first fiber agent is preferably 3.0 to 11.0, more preferably 4.0 to 9.0, further preferably 4.5 to 8.0, and even more preferably 5.5 to 7.0.

[0430] <59> The fiber treatment kit as described in any one of <2>, <4> to <58> above, wherein the pH of the second fiber agent is preferably 2.0 or higher, more preferably 3.0 or higher, even more preferably 3.5 or higher, and preferably 10.0 or lower, more preferably 8.0 or lower, even more preferably 7.0 or lower, even more preferably less than 5.5.

[0431] <60> The fiber treatment kit as described in any one of <2>, <4> to <58> above, wherein the pH of the second fiber agent is preferably 2.0 to 10.0, more preferably 3.0 to 8.0, further preferably 3.5 to 7.0, and even more preferably 3.5 or more and less than 5.5.

[0432] <61> The fiber treatment kit as described in any one of <2>, <4> to <60> above, wherein the ratio of the first fiber treatment agent to the second fiber treatment agent in the fiber treatment kit is preferably 1 / 5 to 5 / 1, more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1 by mass ratio (first fiber treatment agent / second fiber treatment agent).

[0433] <62> The fiber treatment kit as described in any one of <2>, <4> to <61> above, wherein preferably, after treatment with the first fiber treatment agent once or twice or more, the second fiber treatment agent is used for final treatment.

[0434] <63> The fiber treatment kit as described in any one of <3> to <56> above, wherein the fiber treatment agent is preferably a single-agent or two-agent type.

[0435] <64> The fiber treatment kit described in <63> above, wherein, in the case of a two-agent fiber treatment agent, it is preferably composed of a fiber treatment agent (agent 1b-1) and a fiber treatment agent (agent 1b-2) with a pH 1.0 or lower than that of the fiber treatment agent.

[0436] <65> The fiber treatment kit as described in any one of <3> to <56> and <63> to <64> above, wherein component (D) is preferably selected from at least one of (D1) and (D2) below.

[0437] (D1) The hydrogen bonding term δH of Hansen's solubility parameter is 18.3 MPa. 1 / 2 The following are aromatic compounds having at least one carboxyl group or its salt and not having a fused ring:

[0438] (D2) The hydrogen bonding term δH of Hansen's solubility parameter is 11.0 MPa. 1 / 2 Above 18.3MPa 1 / 2 The following are compounds that have at least one carboxyl group or its salt and do not have a fused ring (excluding aromatic compounds).

[0439] <66> The fiber treatment kit described in <65> above, wherein component (D1) is preferably a compound or a salt thereof represented by general formula (1) or general formula (2).

[0440]

[0441] [In the formula, =X represents methylene or oxo group, R] 1 R represents a hydrogen atom, a hydroxyl group, or an alkyl, aryl, alkoxy, aryloxy, or arylalkoxy group that may have substituents. 2 This indicates ortho-phenylene, meta-phenylene, para-phenylene, benzylene, or alkylene that may have substituents. Wherein, in R... 2 Without an aryl group, R 1 [It is aryl, aryloxy, or arylalkoxy]

[0442] [In the formula, A] 1 ~A 5 Each of these can independently represent a hydrogen atom, an acetyl group, a halogen atom, or a straight-chain or branched alkyl, alkenyl, alkoxy, or alkenyloxy group having 1 to 6 carbon atoms.

[0443] <67> The fiber treatment kit described in <66> above, wherein the aromatic compound represented by general formula (1) is preferably a compound represented by general formula (1A), (1B) or (1C) below, [In the formula, B] 1 ~B 4 Each of the following groups independently represents a hydrogen atom, an acetyl group, a halogen atom, or a straight-chain or branched alkyl, alkenyl, alkoxy, or alkenyloxy group having 1 to 6 carbon atoms; R 3 [This represents a hydroxyl group, or a group represented by the following general formula (1A)-a or (1A)-b,]

[0444]

[0445] [In the formula, B] 5 ~B 9 Indicates the above B 1 ~B 4 The same meaning, R 4 [This represents a hydrogen atom or a methyl group, where n represents an integer from 0 to 2.]

[0446]

[0447] [In the formula, D] 1 ~D 4 Each of the following groups independently represents a hydrogen atom, an acetyl group, a halogen atom, or a straight-chain or branched alkyl, alkenyl, alkoxy, or alkenyloxy group having 1 to 6 carbon atoms. E 1 ~E 5 Represent D independently. 1 ~D 4 The same group or the group represented by general formula (1B)-a,

[0448] [In the formula, m represents an integer from 0 to 4,]

[0449] In the formula, R 6 G represents a hydrogen atom or a group represented by the general formula (1C)-a. 1 and G 2 Each of the following groups independently represents a hydrogen atom, an acetyl group, a halogen atom, an aryl group that may have substituents, an aralkyl or arylene group having 7 to 12 carbon atoms, or a straight-chain or branched alkyl, alkenyl, alkoxy, alkenyloxy, or aryloxy group having 1 to 6 carbon atoms, wherein, in R 6 In the case of hydrogen atoms, G 1 and G 2 At least one of them may be an aryl group, an aralkyl group having 7 to 12 carbon atoms, an arene group, or an aryloxy group having a substituent.

[0450] [In the formula, J]1 ~J 5 Each of these can independently represent a hydrogen atom, an acetyl group, a halogen atom, or a straight-chain or branched alkyl, alkenyl, alkoxy, or alkenyloxy group having 1 to 6 carbon atoms.

[0451] <68> The fiber treatment kit described in <67> above, 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.

[0452] <69> The fiber treatment kit described in <67> above, 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.

[0453] <70> The fiber treatment kit described in <67> above, wherein the compound represented by general formula (1c) is preferably phenylsuccinic acid, 2,3-diphenylsuccinic acid, (+)-di-p-toluamide-D-tartaric acid, or 4-oxo-4-[(4-vinylbenzyl)oxy]butyric acid.

[0454] <71> The fiber treatment kit as described in any one of <66> to <70> above, wherein the compound represented by 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, 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 or 4-bromobenzoic acid, more preferably 4-ethylbenzoic acid, 4-vinylbenzoic acid or benzoic acid.

[0455] <72> The fiber treatment kit as described in any one of <65> to <71> above, wherein the hydrogen bond term δH of the aromatic compound of component (D1) is preferably 16.0 MPa. 1 / 2 The following, or more preferably, is 13.5 MPa 1 / 2 The following, and more preferably, is 12.0 MPa 1 / 2 The following, and more preferably, is 10.0 MPa 1 / 2 Below, and preferably 3.0 MPa 1 / 2 The above, and more preferably 4.0 MPa 1 / 2 The above, and more preferably 5.0 MPa 1 / 2 above.

[0456] <73> The fiber treatment kit as described in any one of <65> to <71> above, wherein the hydrogen bond term δH of the aromatic compound of component (D1) is preferably 3.0 to 16.0 MPa. 1 / 2 More preferably, 4.0–13.5 MPa 1 / 2 A further preferred value is 5.0–12.0 MPa. 1 / 2 A further preferred value is 5.0–10.0 MPa. 1 / 2 the following.

[0457] <74> The fiber treatment kit as described in any one of <65> to <73> above, wherein the hydrogen bond term δH of the compound of component (D2) is preferably 16.0 MPa. 1 / 2 The following, more preferably, is 15.0 MPa 1 / 2 The following, and more preferably, is 14.0 MPa 1 / 2 The following, and more preferably, is 13.0 MPa 1 / 2 Below, and preferably 11.0 MPa 1 / 2 The above, and more preferably 11.5 MPa 1 / 2 The above, and more preferably 12.0 MPa 1 / 2 above.

[0458] <75> The fiber treatment kit as described in any one of <65> to <73> above, wherein the hydrogen bond term δH of the compound of component (D2) is preferably 11.0 to 16.0 MPa. 1 / 2 More preferably, it is 11.5–15.0 MPa. 1 / 2 A further preferred value is 12.0–14.0 MPa. 1 / 2 .

[0459] <76> The fiber treatment kit as described in any one of <65> to <75> above, wherein component (D2) is preferably potassium 2,4-hexadienoate.

[0460] <77> The fiber treatment kit as described in any one of <3> to <56> and <65> to <76> above, wherein the pH of the added fiber treatment agent 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.

[0461] <78> The fiber treatment kit as described in 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, and even more preferably 5.5 to 7.0.

[0462] <79> The fiber treatment kit as described in 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, further preferably 5% by mass or more, 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.

[0463] <80> The fiber treatment kit as described in 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, even more preferably 10 to 40% by mass, and even more preferably 20 to 35% by mass.

[0464] <81> The fiber treatment kit as described in any one of <3> to <56> and <65> to <80> above, wherein the content of component (D) in the additional fiber treatment agent is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

[0465] <82> The fiber treatment kit as described in any one of <3> to <56> and <65> to <80> above, wherein the content of component (D) in 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 in the fiber treated with the fiber treatment kit.

[0466] <83> The fiber treatment kit as described in any one of <3> to <56> and <65> to <82> above, wherein the ratio of the fiber treatment agent (first agent) to the additional fiber treatment agent (second agent) in the fiber treatment kit is preferably 1 / 5 to 5 / 1 by mass ratio (first agent / second agent), more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1.

[0467] <84> The fiber treatment kit as described in any one of <3> to <56> and <65> to <82> above, wherein, when the fiber treatment agent (first agent 1b) is a two-agent type and consists of two agents, first agent 1b-1 and first agent 1b-2, the ratio of the fiber treatment agent (first agent 1b) to the additional fiber treatment agent (second agent 2b) by mass ratio (total of first agent 1b-1 and first agent 1b-2 / second 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.

[0468] <85> The fiber treatment agent as described in any one of <1>, <4> to <55> above, or the fiber treatment kit as described in any one of <2> to <84> above, wherein the fiber treatment kit is a fiber-impregnating type.

[0469] <86> The fiber treatment agent as described in any one of <15> to <23>, <25> to <26>, <29> to <37>, <40> to <46> and <49> to <85> above, or the fiber treatment kit as described in any one of <15> to <23>, <25> to <26>, <29> to <37>, <40> to <46> and <49> to <85> above, 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.

[0470] <87> The fiber treatment kit as described in any one of <3> to <56> and <63> to <86> above, 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 potassium salt, and even more preferably a sodium salt.

[0471] <88> A fiber treatment method, wherein the fiber treatment method includes the following step (i):

[0472] Step (i): A step of impregnating natural source fibers with a water swelling rate of 200% or more, calculated according to the following formula (1), in a fiber treatment agent containing the following components (A) and (B).

[0473] (A) Compounds with coordinating functional groups and a molecular weight of 1500 or more.

[0474] (B) Water,

[0475] Fiber swelling rate in water (%) = [(w1-w2) / w2]×100 (1)

[0476] In the formula,

[0477] w1 represents the mass (g) of fiber obtained by placing 1.0g of fiber into a container filled with 100g of ion-exchanged water, sealing the container, immersing the fiber together in a 40°C water bath for 30 minutes, removing the fiber from the container, centrifuging it at 220 [×g] for 1 minute to remove water.

[0478] w2 represents the mass of the fiber after it has been measured (w1) is placed on filter paper and dried at 105°C for 3 hours.

[0479] <89> A fiber treatment method, wherein the fiber treatment method includes the following step (i):

[0480] Step (i): A step of impregnating natural source fibers with a water swelling rate of 200% or more, calculated according to the following formula (1), in a fiber treatment agent containing the following components (A) and (B).

[0481] (A) Compounds having a coordinating functional group and a molecular weight of 1500 or more (excluding copolymers derived from structural units of unsaturated monomers having a carboxyl group or its salt and structural units derived from aromatic vinyl compounds, having an acid value of 100 mg KOH / g or more, and a weight-average molecular weight of 1500 to 15000).

[0482] (B) Water,

[0483] Fiber swelling rate in water (%) = [(w1-w2) / w2]×100 (1)

[0484] In the formula,

[0485] w1 represents the mass (g) of fiber obtained by placing 1.0g of fiber into a container filled with 100g of ion-exchanged water, sealing the container, immersing the fiber together in a 40°C water bath for 30 minutes, removing the fiber from the container, centrifuging it at 220 [×g] for 1 minute to remove water.

[0486] w2 represents the mass of the fiber after it has been measured (w1) is placed on filter paper and dried at 105°C for 3 hours.

[0487] <90> A method for treating a fiber, wherein the fiber treatment method uses a fiber treatment kit, wherein the fiber has a water swelling rate of 200% or more as calculated by the following formula (1).

[0488] Fiber swelling rate in water (%) = [(w1-w2) / w2]×100 (1)

[0489] In the formula,

[0490] w1 represents the mass (g) of fiber obtained by placing 1.0g of fiber into a container filled with 100g of ion-exchanged water, sealing the container, immersing the fiber together in a 40°C water bath for 30 minutes, removing the fiber from the container, centrifuging it at 220 [×g] for 1 minute to remove water.

[0491] w2 represents the mass of the fiber after its mass (w1) has been measured, placed on filter paper, and dried at 105°C for 3 hours.

[0492] <Fiber Treatment Kit>

[0493] This fiber treatment kit features:

[0494] A fiber treatment agent containing the following components (A) and (B); and

[0495] A second fiber treatment agent containing the following components (A) and (B), wherein the pH of the second fiber treatment agent is more than 1.0 lower than the pH of the first fiber treatment agent.

[0496] (A) Compounds with coordinating functional groups and a molecular weight of 1500 or more.

[0497] (B) Water.

[0498] <91> A method for treating fibers, wherein the method uses a fiber treatment kit, and the fiber has a water swelling rate of 200% or more as calculated by the following formula (1).

[0499] Fiber swelling rate in water (%) = [(w1-w2) / w2]×100 (1)

[0500] In the formula,

[0501] w1 represents the mass (g) of fiber obtained by placing 1.0g of fiber into a container filled with 100g of ion-exchanged water, sealing the container, immersing the fiber together in a 40°C water bath for 30 minutes, removing the fiber from the container, centrifuging it at 220 [×g] for 1 minute to remove water.

[0502] w2 represents the mass of the fiber after its mass (w1) has been measured, placed on filter paper, and dried at 105°C for 3 hours.

[0503] <Fiber Treatment Kit>

[0504] This fiber treatment kit features:

[0505] A fiber treatment agent containing the following components (A) and (B); and

[0506] Additional fiber treatment agents containing the following component (D),

[0507] (A) Compounds with coordinating functional groups and a molecular weight of 1500 or more.

[0508] (B) Water,

[0509] (D) The hydrogen bonding term δH of Hansen's solubility parameter is 18.3 MPa. 1 / 2 The following are compounds or salts thereof having at least one carboxyl group or a salt thereof and not having a fused ring (excluding component (A)).

[0510] <92> The processing method as described in any one of <89> to <91> above, wherein the coordinating functional group is preferably a base group selected from (a-1), (a-2) and (a-3):

[0511] (a-1) A group having a carboxyl group or its salt (carboxylate), preferably a carboxyl anion.

[0512] (a-2) A group having a hydroxyl, alkoxy, alkoxide anion, or metal alkoxide group; if the hydroxyl group is a phenolic hydroxyl group, it can be a phenol oxide.

[0513] (a-3) has a sulfonic acid group or its salt (sulfonate), and can be a sulfonate anion.

[0514] <93> In the processing method described in <92> above, the salt is preferably an alkali metal salt, an alkaline earth metal salt or an ammonium salt, more preferably a sodium salt, lithium salt, potassium salt, calcium salt or magnesium salt, and even more preferably a sodium salt.

[0515] <94> The processing method described in <91> above, 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 potassium salt, and even more preferably a sodium salt.

[0516] [Example]

[0517] <Analytical Methods>

[0518] 1. Determination of the water-soluble swelling rate of regenerated collagen fibers

[0519] The fiber swelling rate in water is calculated according to the following formula (1).

[0520] The fiber swelling rate in water, S (%) = [(w1-w2) / w2] × 100 (1)

[0521] The definitions of each symbol in equation (1) are as follows.

[0522] w1: Immerse 1.0g of regenerated collagen fiber in a container with 100g of ion-exchanged water, seal the container, and immerse the container together in a water bath set to 40°C (model: TBS221FA, manufacturer: Toyo Seisakusho Co., Ltd.) for 30 minutes. After heating, remove the regenerated collagen fiber from the container and place it in a small centrifuge (H-112, KOKUSAN Co. Ltd.). Centrifuge at a centrifugal force of 220 [×g] (speed knob "4" (2000rpm)) for 1 minute to dehydrate, and then immediately measure its weight and set it as weight w1.

[0523] w2: Place the regenerated collagen fiber, after the weight w1 has been measured, on filter paper, put it in a dryer (SOFW-450SB, AS ONE Corporation) set to 105℃ and dry for 3 hours. Take it out and immediately measure its weight, and set it as weight w2.

[0524] 2. Determination of the weight-average molecular weight of component (A)

[0525] The weight-average molecular weight (Mw) of polystyrene was determined by gel permeation chromatography (GPC) under the following conditions.

[0526] (1) Sample

[0527] • Ultrapure water: Water produced by the Milli-Q ultrapure water manufacturing system, manufactured by Millipore.

[0528] • Dimethylformamide (DMF): Premium grade, manufactured by Kanto Chemical Co., Ltd.

[0529] • Lithium bromide monohydrate (LiBr): Premium grade, manufactured by Kanto Chemical Co., Ltd.

[0530] • Phosphoric acid: Extra grade, manufactured by Sigma-Aldrich

[0531] (2) Sample pretreatment method

[0532] Accurately weigh approximately 50 mg of the sample, add 0.5 mL of ultrapure water, and then add 10 mL of the mobile phase (described later) to dissolve it. Filter the solution to prepare the sample solution.

[0533] (3) Measurement

[0534] Using the sample solution and standard solution, GPC determination was performed under the following conditions to determine the converted weight-average molecular weight of polystyrene.

[0535] • Flow rate: 1 mL / min

[0536] • Mobile phase: DMF containing 60 mM phosphoric acid and 50 mM LiBr

[0537] • Column: TSKgel α (α) column (manufactured by Tosoh Corporation)

[0538] • Detector: RI (Differential Refraction Detector)

[0539] •Standard reference: Monodisperse polystyrene

[0540] 3. Aluminum quantification method in fibers

[0541] The aluminum content in the treated regenerated collagen fibers was quantified using the following method.

[0542] (1) Sample

[0543] • Sulfuric acid: For precision analysis, manufactured by Fujifilm and Koden Chemical Co., Ltd.

[0544] • Hydrochloric acid: Used for metal analysis, manufactured by Kanto Chemical Co., Ltd.

[0545] • Sodium carbonate: Premium grade, manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.

[0546] • Boric acid: Premium grade, manufactured by Fujifilm and Kojun Chemical Co., Ltd.

[0547] • Aluminum standard solution: 1000 mg / L for atomic absorption spectrometry analysis, manufactured by Kanto Chemical Co., Ltd.

[0548] • Ultrapure water: Water produced by the Milli-Q ultrapure water manufacturing system, manufactured by Millipore.

[0549] (2) Sample pretreatment method

[0550] The fiber bundle was suspended in a dryer (SOFW-450SB, AS ONE Corporation) set to 60°C, with a 250g weight installed at the lower end of the fiber bundle, and dried for 1 hour under tension.

[0551] Accurately weigh 0.1 g of the sample into a platinum crucible, heat until no more white fumes are produced, add a few drops of sulfuric acid, and heat again until no more white fumes are produced. Then, thoroughly ashing the sample using a 550°C electric furnace. Next, add 1 g of alkaline melting agent (sodium carbonate:boric acid = 1:0.4) and melt using a 950°C electric furnace. Cover with a watch glass, add 5 mL of ultrapure water and hydrochloric acid (6 mol / L), and heat to dissolve on a hot plate at 70–80°C. After cooling, dilute to 50 mL with ultrapure water. Use this diluted solution as the assay solution.

[0552] (3) Preparation of calibration curve solution

[0553] Calibration curve solutions of 0.1–20 mg / L were prepared using an aluminum standard solution (1000 mg / L). An equivalent amount of alkaline flux and hydrochloric acid was added to each solution.

[0554] (4) Measurement

[0555] The obtained sample was analyzed using an ICP emission spectrometer under the following conditions to determine each element.

[0556] • Analytical apparatus: iCAP6500Duo (manufactured by Thermo Fisher Scientific Inc.)

[0557] • Wavelength: Al 396.152nm

[0558] •RF power: 1150W

[0559] • Cooling gas flow rate: 12L / min

[0560] • Atomizer flow rate: 0.70L / min

[0561] • Assist gas: 0.5 L / min

[0562] • Pump flow rate: 50 rpm

[0563] 4. The hydrogen bonding term δH in Hansen's solubility parameter

[0564] The temperature was calculated at 25°C using the HSPiP 4th Edition 4.1.07 software package in the DIY program.

[0565] 5. Determination of acid value and hydroxyl value

[0566] The determination was performed by potentiometric titration according to JIS K 0070.

[0567] 6. pH Measurement

[0568] Each composition was directly measured at 25°C using a pH meter (F-52, manufactured by HORIBA).

[0569] 7. Quantitative method for component (A) in fibers

[0570] A quantitative method for indicating component (A) in modified regenerated collagen fibers when styrene-maleic acid copolymer or its salt is used as component (A).

[0571] (1) Sample

[0572] • 1 mol / L sodium hydroxide aqueous solution: for volumetric analysis, manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.

[0573] • Ultrapure water: Water produced by the Milli-Q ultrapure water manufacturing system, manufactured by Millipore.

[0574] • Dimethylformamide (DMF): Premium grade, manufactured by Kanto Chemical Co., Ltd.

[0575] • Lithium bromide monohydrate (LiBr): Premium grade, manufactured by Kanto Chemical Co., Ltd.

[0576] • Phosphoric acid: Extra grade, manufactured by Sigma-Aldrich

[0577] (2) Sample solution

[0578] After conditioning the sample at 20℃ and 65% relative humidity for 24 hours, finely chop it and accurately weigh approximately 50 mg. Add 10 mL of 1 mol / L sodium hydroxide aqueous solution and heat at 50℃ for 3 hours to dissolve. Adjust the pH of the solution to 4.7–5.3. Add 0.5 mL of ultrapure water to the freeze-dried sample, then add 9.5 mL of the mobile phase (described later) for dilution. Filter the diluted solution to prepare the sample solution.

[0579] (3) Preparation of calibration curve solution

[0580] Separately, the styrene-maleic acid copolymer or its salt is dissolved in the mobile phase described later, and a concentration of 0.25–5.0 mg / mL is prepared based on the non-dissociated styrene-maleic acid copolymer to prepare a standard solution for the preparation of a calibration curve.

[0581] (4) Measurement

[0582] Using the sample solution and standard solution, perform gel permeation chromatography (GPC) under the following conditions to determine the peak areas of the sample solution and the standard solution. Then, construct a calibration curve based on the peak area results of the standard solution.

[0583] • Flow rate: 0.8 mL / min

[0584] • Mobile phase: DMF containing 60 mM phosphoric acid and 50 mM LiBr

[0585] • Column: TSKgel α (α) column (manufactured by Tosoh Corporation)

[0586] • Detector: Ultraviolet-Vis spectrophotometer

[0587] • Measurement wavelength: 267nm

[0588] (5) Calculation of the amount of styrene-maleic acid copolymer

[0589] The amount of styrene-maleic acid copolymer per unit fiber mass was calculated using a calibration curve based on the peak area of ​​the styrene-maleic acid copolymer contained in the modified regenerated collagen fiber.

[0590] 8. Quantitative method for the composition (D) in fibers

[0591] The amount of component (D) contained in the treated regenerated collagen fibers was quantified according to the following method.

[0592] (1) Sample

[0593] • 6N hydrochloric acid: titrant for volumetric analysis, manufactured by Kanto Chemical Co., Ltd.

[0594] • Sodium acetate: Premium grade, manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.

[0595] • Acetic acid: Premium grade, manufactured by Fujifilm and Kojun Chemical Co., Ltd.

[0596] • Acetonitrile: For LC / MS, manufactured by Kanto Chemical Co., Ltd.

[0597] • Sodium benzoate: Premium grade, manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.

[0598] • Ultrapure water: Water produced by the Milli-Q ultrapure water manufacturing system, manufactured by Millipore.

[0599] (2) Sample pretreatment method

[0600] The sample was finely chopped, and approximately 10 mg was accurately weighed. Then, 3 mL of 6N hydrochloric acid was added, and the mixture was heated at 50°C for 15 hours to dissolve it. After cooling, the solution was filtered to obtain the sample solution.

[0601] (3) Preparation of calibration curve solution

[0602] Separately, component (A) is dissolved in the mobile phase, and for components with dissociation sites such as acid groups, it is prepared to a concentration of 0.1 to 100 μg / mL based on the non-dissociated component (A) to prepare a standard solution for the preparation of calibration curves.

[0603] (4) Measurement

[0604] For the sample solution and the standard solution, the peak area of ​​the sample solution and the peak area of ​​the standard solution were determined by liquid chromatography under the following conditions.

[0605] • Detector: Ultraviolet-Vis spectrometer

[0606] • Measurement wavelength: 230nm

[0607] • Column: A stainless steel tube with an inner diameter of 21 mm and a length of 150 mm is filled with 5 μm of octadecylsilanized silica gel for liquid chromatography.

[0608] • Column temperature: a constant temperature of around 40℃

[0609] • Mobile phase: Dissolve approximately 0.68 g of sodium acetate and 0.91 g of acetic acid in 750 mL of ultrapure water, then add 250 mL of acetonitrile and mix.

[0610] (5) HPLC / UV conditions

[0611] • Device: UltiMate3000 system (manufactured by Thermo Fisher Scientific Inc.)

[0612] • Column: L-column2 ODS, particle size 5μm, 2.1×150mm (Chemical Substance Evaluation Research Institute)

[0613] • Column temperature: 40℃

[0614] • Mobile phase: 20mM ammonium acetate 25% acetonitrile buffer

[0615] •Analysis time: 10 minutes

[0616] • Detector: DAD (Diode Array Detector)

[0617] • Detection wavelength: 230nm

[0618] • Flow rate: 0.3 mL / min (isocratic elution)

[0619] • Injection volume: 10μL

[0620] <Raw Materials Used>

[0621] The materials used in this embodiment are as follows.

[0622] (1) Regenerated collagen fibers

[0623] (i) Regenerated collagen fiber A

[0624] Manufacturing Example 1

[0625] The cowhide sheet is dissolved in alkali using conventional methods to prepare a spinning solution. This solution is then sprayed from a spinning nozzle into a coagulation bath for fiberization and epoxy compound treatment to produce regenerated collagen fibers. For this regenerated collagen fiber, one part by weight (relative to the dry weight of the fiber) is converted to 30 parts by weight of an aqueous solution containing 5.0% by weight of aluminum sulfate tetradecahydrate, 0.65% by weight of citric acid monohydrate, and 1.3% by weight of sodium hydroxide. The temperature is adjusted to 30°C, and the solution is immersed while circulating. Then, 5% sodium hydroxide aqueous solution is added in batches over approximately 1-5 hours. After 5 hours, the final pH of the solution is adjusted to 4.5-5.0. The solution is then maintained for 3 hours, followed by thorough washing to obtain regenerated collagen fiber A.

[0626] The water swelling rate of regenerated collagen fiber A is 435%.

[0627] The preparation of the coagulation bath was carried out in accordance with International Publication No. 2017 / 159565, and the treatment of the epoxy compound was carried out in accordance with International Publication No. 2014 / 132889.

[0628] (ii) Regenerated collagen fiber B

[0629] 300 bundles of regenerated collagen fiber A, each 30cm in length, were prepared (weighing 1.5g after drying at 60°C for 1 hour and then at 20°C and 65%RH for 12 hours). Each bundle was suspended individually in a dryer (SOFW-450SB, AS ONE Corporation) set to 60°C, with a 250g weight attached to the bottom of each bundle. The bundles were dried under tension for 1 hour and used as regenerated collagen fiber B.

[0630] • Shape: Straight bar

[0631] • Fiber swelling rate in water: 113%

[0632] • Aluminum content: 6.8% by mass

[0633] (iii) Regenerated collagen fiber C

[0634] Manufacturing Example 2

[0635] The cowhide sheet was prepared into a spinning solution by alkali solubilization using conventional methods. The solution was then sprayed from the spinning nozzle into a coagulation bath for fiberization. After treatment with an epoxy compound, the solution was thoroughly washed with water to obtain regenerated collagen fiber C.

[0636] The water swelling rate of regenerated collagen fiber C was 692%. The coagulation bath was prepared in accordance with International Publication No. 2017 / 159565, and the epoxy compound treatment was carried out in accordance with International Publication No. 2014 / 132889.

[0637] (2) (A-1-1) copolymer

[0638] (i) Sodium salt of styrene-maleic acid copolymer A

[0639] Use XIRAN1000HNa (manufactured by Polyscope).

[0640] •Weight-average molecular weight (Mw): 9195

[0641] • The hydrogen bonding term δH value of Hansen's solubility parameter: 11.5

[0642] • Acid value: 475 mg KOH / g

[0643] • Molar ratio of styrene to maleic acid: 1 / 1

[0644] (ii) Sodium salt of styrene-maleic acid copolymer B

[0645] Use XIRAN2000HNa (manufactured by Polyscope).

[0646] •Weight-average molecular weight (Mw): 8143

[0647] • The hydrogen bonding term δH value of Hansen's solubility parameter: 9.2

[0648] • Acid value: 355 mg KOH / g

[0649] • Molar ratio of styrene to maleic acid: 2 / 1

[0650] (iii) Sodium salt of styrene-maleic acid copolymer C

[0651] Use XIRAN3000HNa (manufactured by Polyscope).

[0652] •Weight-average molecular weight (Mw): 13803

[0653] • The hydrogen bonding term δH value of Hansen's solubility parameter: 7.9

[0654] • Acid value: 285 mg KOH / g

[0655] • Molar ratio of styrene to maleic acid: 3 / 1

[0656] (iv) Sodium salt of styrene-maleic acid copolymer D

[0657] Use XIRAN3500HNa (manufactured by Polyscope).

[0658] •Weight-average molecular weight (Mw): 71785

[0659] • The hydrogen bonding term δH value of Hansen's solubility parameter: 7.9

[0660] • Acid value: 285 mg KOH / g

[0661] • Molar ratio of styrene to maleic acid: 3 / 1

[0662] (v) Sodium salt of styrene-maleic acid copolymer E

[0663] Styrene-maleic anhydride copolymer was synthesized according to the literature (Gunji et al., Color Materials, 75(10), 463-460(2002)), and then used after hydrolysis with sodium hydroxide aqueous solution.

[0664] •Weight-average molecular weight (Mw): 17448

[0665] • The hydrogen bonding term δH value of Hansen's solubility parameter: 11.5

[0666] • Acid value: 475 mg KOH / g

[0667] • Molar ratio of styrene to maleic acid: 1 / 1

[0668] (vi) Sodium salt of styrene-maleic acid copolymer F

[0669] Styrene-maleic anhydride copolymer was synthesized according to the literature (Gunji et al., Color Materials, 75(10), 463-460(2002)), and then used after hydrolysis with sodium hydroxide aqueous solution.

[0670] •Weight-average molecular weight (Mw): 7049

[0671] • The hydrogen bonding term δH value of Hansen's solubility parameter: 11.5

[0672] • Acid value: 475 mg KOH / g

[0673] • Molar ratio of styrene to maleic acid: 1 / 1

[0674] (vii) Sodium salt of styrene-maleic acid copolymer G

[0675] Styrene-maleic anhydride copolymer was synthesized according to the literature (Gunji et al., Color Materials, 75(10), 463-460(2002)), and then used after hydrolysis with sodium hydroxide aqueous solution.

[0676] •Weight-average molecular weight (Mw): 27302

[0677] • The hydrogen bonding term δH value of Hansen's solubility parameter: 11.5

[0678] • Acid value: 475 mg KOH / g

[0679] • Molar ratio of styrene to maleic acid: 1 / 1

[0680] (viii) Sodium salt of styrene-maleic acid copolymer H

[0681] Styrene-maleic anhydride copolymer was synthesized according to the literature (Gunji et al., Color Materials, 75(10), 463-460(2002)), and then used after hydrolysis with sodium hydroxide aqueous solution.

[0682] •Weight-average molecular weight (Mw): 3829

[0683] • The hydrogen bonding term δH value of Hansen's solubility parameter: 11.5

[0684] • Acid value: 475 mg KOH / g

[0685] • Molar ratio of styrene to maleic acid: 1 / 1

[0686] (ix) Sodium salt of styrene-maleic acid copolymer I

[0687] Styrene-maleic anhydride copolymer was synthesized according to the literature (Gunji et al., Color Materials, 75(10), 463-460(2002)), and then used after hydrolysis with sodium hydroxide aqueous solution.

[0688] •Weight-average molecular weight (Mw): 10530

[0689] • The hydrogen bonding term δH value of Hansen's solubility parameter: 11.5

[0690] • Acid value: 475 mg KOH / g

[0691] • Molar ratio of styrene to maleic acid: 1 / 1

[0692] (x) Sodium salt of styrene-maleic acid copolymer J

[0693] Sodium salt of styrene-maleic anhydride copolymer was synthesized according to the literature (Gunji et al., Color Materials, 75(10), 463-460(2002)), and then used after hydrolysis with sodium hydroxide aqueous solution.

[0694] •Weight-average molecular weight (Mw): 3288

[0695] • The hydrogen bonding term δH value of Hansen's solubility parameter: 11.5

[0696] • Acid value: 475 mg KOH / g

[0697] • Molar ratio of styrene to maleic acid: 1 / 1

[0698] (3) (A-1-2) copolymer

[0699] (i) Sodium salt of diisobutylene-maleic acid copolymer

[0700] Use DEMOL EP (manufactured by Kao Corporation).

[0701] •Weight-average molecular weight (Mw): >1500

[0702] • The hydrogen bonding term δH value of Hansen's solubility parameter: 9.4

[0703] • Acid value: >100mgKOH / g

[0704] • Molar ratio of diisobutylene to maleic acid: 1 / 1

[0705] (ii) Sodium salt of butadiene-maleic acid copolymer

[0706] As a butadiene-maleic anhydride copolymer, Ricon130MA13 (manufactured by Cray Valley) was purchased and used after hydrolysis with sodium hydroxide.

[0707] •Weight-average molecular weight (Mw): >1500

[0708] • Acid value: 74 mg KOH / g

[0709] (iii) Sodium salt of styrene-butadiene copolymer (carboxyl modified)

[0710] Use SBL0696 (manufactured by ENEOS Materials Corporation).

[0711] •Weight-average molecular weight (Mw): >1500

[0712] (4) (A-1-3) polymer

[0713] (i) Polyacrylic acid

[0714] Polyacrylic acid 5000 (manufactured by Kao Corporation) was used.

[0715] •Weight-average molecular weight (Mw): 5000

[0716] • The hydrogen bonding term δH value of Hansen's solubility parameter: 14.3

[0717] • Acid value: 757 mg KOH / g

[0718] (ii) Sodium polystyrene sulfonate

[0719] The reagent “poly(sodium styrene sulfonate), analytical standard, for GPC, 4,300” was purchased and used from Sigma-Aldrich.

[0720] •Weight-average molecular weight (Mw): 4300

[0721] • The hydrogen bonding term δH value of Hansen's solubility parameter: 13.7 (based on polystyrene sulfonic acid).

[0722] (iii) Sodium polyvinyl sulfonate

[0723] The reagent “sodium poly(vinyl sulfonate), 25% aqueous solution (manufactured by Polysciences, Inc.)” was purchased and used from Fujifilm and Kojun Pharmaceutical Co., Ltd.

[0724] •Weight-average molecular weight (Mw): >4000

[0725] • The hydrogen bonding term δH value of Hansen's solubility parameter: 18.1 (based on polyvinylsulfonic acid).

[0726] (iv) Polyvinyl alcohol

[0727] The reagent “Poly(vinyl alcohol), MW 6000, 80% hydrolyzed (manufactured by Polysciences, Inc.)” was purchased and used by Fujifilm and Koujun Pharmaceutical Co., Ltd.

[0728] •Weight-average molecular weight (Mw): 6000

[0729] • The hydrogen bonding term δH value of Hansen's solubility parameter: 17.0

[0730] (5) Condensates of (A-2-1) sulfonic acids or their salts

[0731] (i) Sodium salt of β-naphthalenesulfonic acid formaldehyde condensate

[0732] Use DEMOL N (manufactured by Kao Corporation).

[0733] •Weight-average molecular weight (Mw): >1500

[0734] • The hydrogen bonding term δH value of Hansen's solubility parameter: 17.8

[0735] • Acid value: >100mgKOH / g

[0736] (6) Condensate of (A-2-2) gallic acid ester

[0737] (i) Tannic acid

[0738] Use chemically grade reagents (manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.).

[0739] • Molecular weight (M): 1701

[0740] • Hydroxyl value: 825 mg KOH / g

[0741] (7) Sodium benzoate

[0742] Use Wako Special Grade reagents (manufactured by Fujifilm Wako Pure Chemicals Co., Ltd.).

[0743] • Molecular weight (M): 122

[0744] • The hydrogen bonding term δH value of Hansen's solubility parameter: 9.5

[0745] • Acid value: 460 mg KOH / g

[0746] Examples 1-34 and Comparative Examples 1-3

[0747] Using the compositions formulated in Table 1, regenerated collagen fibers were treated according to the following methods, and various evaluations were performed. In Comparative Example 1, only steps (1) and (6) of treatment method A were performed for evaluation. The results of Examples 1-11 and Comparative Examples 1-2 are shown in Table 1; the results of Examples 12-22, and the results of Examples 1 and Comparative Examples 1-2 are shown in Table 2; and the results of Examples 23-34, Comparative Example 3, and the results of Comparative Example 1 are shown in Table 3.

[0748] <Handling Method>

[0749] (1) Processing method A

[0750] Process regenerated collagen fiber A according to the following steps.

[0751] (Step 1)

[0752] In each embodiment and comparative example, 10 fiber bundles with a length of 30 cm were made from regenerated collagen fiber A (the weight of which reached 1.5 g after drying at 60°C for 1 hour and placing at 20°C and 65%RH for 12 hours).

[0753] (Step 2)

[0754] The fiber bundles are impregnated with a amount of fiber treatment agent that reaches the liquor ratio shown in the table (the liquor ratio is calculated based on the dried weight of 1.5g in step 1 above). Each bundle is impregnated in a separate container, and the openings of each container are sealed.

[0755] (Step 3)

[0756] Immerse the container together in a water bath (TBS221FA, Toyo Seisakusho Co., Ltd.) set to the temperature shown in the table and let it stand for 5 minutes. After raising the temperature of the liquid in the container to the temperature shown in the table, remove the container from the water bath.

[0757] (Step 4)

[0758] Place the container containing the fiber bundle on the stirring rotor (VMR-5R, AS ONE Corporation) inside a dryer (SOFW-450SB, AS ONE Corporation) set to the temperature shown in the table, and rotate the container at 80 rpm for the heating and stirring time shown in the table.

[0759] (Step 5)

[0760] Remove the container containing the fiber bundles from the dryer and allow it to return to room temperature. Then, remove the fiber bundles from the container, rinse them with 30°C tap water for 30 seconds, and comb them to guide the direction of the hair.

[0761] (Step 6)

[0762] The fiber bundles are suspended one by one in a dryer set to the temperature recorded in the table. A 250g weight is installed at the lower end of each fiber bundle, and the fibers are dried for the time recorded in the table while the fibers are under tension.

[0763] (Step 7)

[0764] Remove the fiber bundle from the dryer, allow it to return to room temperature, and remove the weights.

[0765] (2) Treatment method B

[0766] Regenerated collagen fiber B is processed according to the following steps.

[0767] (Step 1)

[0768] In each of the embodiments and comparative examples, 10 bundles of 1.5g each (measured after being placed at 20°C and 65%RH for 12 hours) and 30cm in length were made from regenerated collagen fiber B.

[0769] (Step 2)

[0770] The fiber bundles are impregnated in a amount of fiber treatment agent that reaches the bath ratio shown in the table (the bath ratio is calculated based on the fiber weight of 1.5g in step 1 above). Each bundle is impregnated in a separate container, and the openings of each container are sealed.

[0771] (Step 3)

[0772] Immerse the container together in a water bath (TBS221FA, Toyo Seisakusho Co., Ltd.) set to the temperature shown in the table and let it stand for 5 minutes. After raising the temperature of the liquid in the container to the temperature shown in the table, remove the container from the water bath.

[0773] (Step 4)

[0774] Place the container containing the fiber bundle on the stirring rotor (VMR-5R, AS ONE Corporation) inside a dryer (SOFW-450SB, AS ONE Corporation) set to the temperature shown in the table, and rotate the container at 80 rpm for the heating and stirring time shown in the table.

[0775] (Step 5)

[0776] Remove the container containing the fiber bundles from the dryer and allow it to return to room temperature. Then, remove the fiber bundles from the container, rinse them with 30°C tap water for 30 seconds, and comb them to straighten the direction of the hair.

[0777] (Step 6)

[0778] The fiber bundles were suspended one by one in a dryer set to 60°C, and a 250g weight was installed at the bottom of each fiber bundle. The fibers were dried for 1 hour under tension.

[0779] (Step 7)

[0780] Remove the fiber bundle from the dryer, allow it to return to room temperature, and remove the weights.

[0781] <Evaluation>

[0782] 1. Quantitative

[0783] (i) Weight increase (%)

[0784] The weight (W) of the treated fiber bundle was measured after 12 hours of exposure at 20°C and 65%RH, and the weight gain relative to the initial fiber bundle weight of 1.5g was calculated.

[0785] Weight increase [%] = [(W-1.5) / 1.5] × 100

[0786] The greater the weight increase (%), the more component (A) has penetrated into the fiber. When the weight increase (%) is 0%, it can be considered that no component (A) has actually penetrated into the fiber.

[0787] (ii) Amount (%) of component (A) (Mw≥1500) contained within the fiber

[0788] Based on the chromatogram obtained by GPC as described in "7. Quantitative Method of Component (A) in Fiber" of the <Analytical Methods>, the amount of component (A) in the fiber, "GPC Quantitative Value Y (%)", is calculated. Here, "GPC Quantitative Value Y (%)" is the mass percentage of component (A) in the fiber, which is not consistent with the measured weight increase (%). That is, regarding the "GPC Quantitative Value Y (%)" mentioned here, since the weight average molecular weight of the copolymers involved in component (A) is 1500 or higher, it does not refer to the amount of fractions with a molecular weight of 1500 or higher in the GPC chromatogram, but rather to the quantitative value of all copolymers involved in component (A), including fractions with a molecular weight of less than 1500. Therefore, in the case of copolymers with a weight average molecular weight of less than 1500, since this copolymer does not belong to component (A), its quantitative value as component (A) is 0.

[0789] Then, the "theoretical weight increase X (%)" is obtained from the "GPC quantitative value Y (%)" using the following method.

[0790] (iii) Theoretical weight increase (%)

[0791] Based on the GPC quantification value Y (%) calculated from (ii) above, the theoretical weight gain X (%) is calculated using the following formula. Wherein, the theoretical weight gain X (%) is the maximum value assuming no loss of components due to dissolution from fibers, etc.

[0792] Weight increase X [%] = 100Y / (100-Y)

[0793] 2. Water resistance

[0794] (1) Elastic modulus of fiber under water tension (MPa)

[0795] The elastic modulus of the fibers under tensile stress in water was determined as described below. Evaluation was performed using fiber bundles that had just been treated using the aforementioned <treatment method>. Furthermore, the average value obtained from evaluating multiple fibers (5 fibers) was used. A higher value indicates better stiffness, resistance to stretching under external forces, and superior durability. The evaluation was conducted according to the following steps.

[0796] (Step 1)

[0797] Five fibers were cut from the fiber bundle, and a 3cm fiber piece was taken from each fiber, resulting in a total of five 3cm fiber pieces.

[0798] (Step 2)

[0799] The fiber sheet was mounted on an automatic fiber tensile testing machine (MTT690, manufactured by DIA-STRON Limited). After the fiber was immersed in water for 30 minutes, the automatic tensile test was started to determine the elastic modulus of the fiber under water tension. The cross-sectional area of ​​the fiber in water necessary for determining the elastic modulus was measured directly by observation using an optical microscope.

[0800] (2) The rate of increase in average breaking elongation during fiber stretching (%)

[0801] As an indicator of the fiber's water resistance and elasticity (toughness) during stretching, the average elongation at break is used, that is, the percentage of the original fiber length at which the fiber breaks after stretching. This is the average value obtained by evaluating multiple (10) fibers. The evaluation is conducted using fiber bundles that have just been treated using the above-described <treatment method> according to the following steps.

[0802] (Step 1)

[0803] Cut 10 fibers from the root of the fiber bundle. Take a 3cm fiber piece from the middle of the root and tip of each fiber, resulting in 10 3cm hair pieces.

[0804] (Step 2)

[0805] The fiber sheet was mounted on an automatic fiber tensile testing machine (MTT690, manufactured by DIA-STRON Limited). After being immersed in water for 30 minutes, the machine automatically measured and calculated the average elongation at break of the fiber in the water-immersed state. A higher value indicates higher elasticity, better toughness, and excellent durability.

[0806] According to the following formula, based on the average elongation at break (A%) of the fiber when stretched, the extent to which the average elongation at break (B%) of the treated fiber bundle increased (C%) relative to the untreated state is recorded in the table as the "increase rate (%) of average elongation at break of fiber when stretched".

[0807] The increase rate of average breaking elongation during fiber stretching, C (%) = B (%) - A (%)

[0808] (3) The increase in average breaking load (gf) during fiber stretching

[0809] The average breaking load of the fiber during tensile testing was used as an indicator of its water resistance. The evaluation was conducted using fiber bundles that had just been treated using the aforementioned <treatment method>. Furthermore, the average value was used when evaluating multiple fibers (10 fibers). The evaluation was performed according to the following steps.

[0810] (Step 1)

[0811] Cut 10 fibers from the root of the fiber bundle. Take a 3cm fiber piece from the middle of the root and tip of each fiber, resulting in 10 3cm hair pieces.

[0812] (Step 2)

[0813] The fiber sheet was mounted on an automatic fiber tensile testing machine (MTT690, manufactured by DIA-STRON Limited). After being immersed in water for 30 minutes, the machine automatically measured and determined the breaking load of the fiber when stretched while immersed in water. The higher the value, the less likely it is to break under external force, and the better its durability.

[0814] According to the following formula, based on the average breaking load (W0 (gf)) of the fiber under dry state (untreated fiber (Comparative Example 1)) without chemical treatment, the extent to which the average breaking load (W1 (gf)) of the treated fiber bundle increased relative to the untreated state (Y (gf)) is recorded in the table as "the increase in average breaking load [gf] of fiber under stretching".

[0815] Y(gf)=W1(gf)-W0(gf)

[0816] (4) Concentration (ppm) of component (A) in the fiber cleaning solution

[0817] The concentration of component (A) in the fiber cleaning solution was determined according to the following steps. Evaluation was performed using fiber bundles that had just been treated using the above-described <treatment method>, i.e., using fiber bundles obtained in Example 1 and Comparative Example 3.

[0818] (i) Preparation of fiber cleaning solution

[0819] Cut fibers from the root of the fiber bundle to make a 1.0g fiber bundle. Immerse this 1.0g fiber bundle in a container containing 100g of ion-exchanged water, seal the container, and immerse the container together in a water bath set to 40°C (model: TBS221FA, manufacturer: Toyo Seisakusho Co., Ltd.) for 1 hour. Then remove the fiber from the container. Use the remaining ion-exchanged water in the container as a fiber cleaning solution.

[0820] (ii) Quantification of component (A) in fiber cleaning solution

[0821] Quantification was performed by measuring the absorbance at a suitable wavelength using a UV-Vis-NIR spectrophotometer. For example, when component (A) is sodium styrene-maleic acid copolymer (XIRAN1000HNa, manufactured by Polyscope), the absorbance at 258 nm was measured using a UV-Vis-NIR spectrophotometer (V-560, manufactured by Nippon Spectrophotometer Co., Ltd.), and the concentration of component (A) was calculated based on this absorbance. A calibration curve was prepared by diluting the Polyscope-manufactured "XIRAN1000HNa" with deionized water.

[0822] 3. Thermal shape memory capability

[0823] The thermal shape memory capability was evaluated using fiber bundles that had just been treated using the above-described processing method. 0.5g of fiber was cut from the root of the fiber bundle to create a 22cm long fiber bundle. In the evaluation of "(I) Shape Imparting (Curling)," if the curling rate I was below 7%, it was considered ineffective, and no further processing or evaluation was performed.

[0824] (I) Shape given (curl)

[0825] (Step 1)

[0826] After wetting the 22cm long fiber bundle with 30℃ tap water for 30 seconds, wrap the wetted fiber bundle around a 14mm diameter plastic rod and fix it with a clip.

[0827] (Step 2)

[0828] The entire fiber bundle wound on the rod is immersed in a 60°C water bath (TBS221FA, Toyo Seisakusho Co., Ltd.) and heated for 1 minute.

[0829] (Step 3)

[0830] Remove the fiber bundle from the water bath, immerse it in water at 20°C for 1 minute, remove it from the water and allow it to return to room temperature.

[0831] (Step 4)

[0832] Remove the fiber bundle from the rod, comb it three times, then take it out of the water. Three minutes after taking it out, take a photo from the front and side while it is suspended.

[0833] (Step 5)

[0834] Measure the length L of the fiber bundle when it is suspended vertically based on the photograph (the distance from the top of the fiber bundle to the farthest point 1).

[0835] (Evaluation Criteria)

[0836] The length of the fiber bundle when it is stretched into a straight line is set as L0, the length of the fiber bundle after the shape is assigned is set as L, and the curling rate = fiber bundle length reduction rate (I) (%) calculated according to the following formula is defined as the curling strength.

[0837] Roll-up rate I (%) = [(L0-L) / L0] × 100

[0838] (II) Reshape (straighten)

[0839] (Step 1)

[0840] After combing the fiber bundles evaluated in (1) above to straighten the hair flow direction, use a straightener (AHI-938, manufactured by Miki Electric Industry Co., Ltd.) set to 180°C to slide 6 times at a speed of 5cm / sec.

[0841] (Step 2)

[0842] Rinse with running tap water at 30°C for 30 seconds, then dry with a towel.

[0843] (Step 3)

[0844] Hang and air dry at 20°C and 65%RH for 12 hours. After combing three times, take photos from the front and side while hanging.

[0845] (Step 4)

[0846] Measure the length L of the fiber bundle when it is suspended vertically based on the photograph (the distance from the top of the fiber bundle to the farthest point 1).

[0847] (Evaluation Criteria)

[0848] Let L0 be the length of the fiber bundle when it is stretched into a straight line, and L be the length of the fiber bundle after the shape assignment operation. Let the straightening rate (ST) (%) calculated according to the following formula be defined as the degree of straightening achievement. When ST=100%, the fiber bundle is completely straightened.

[0849] Straightening rate ST (%) = [1 - [(L0 - L) / L0]] × 100

[0850] (III) Reshape (curl)

[0851] (Step 1)

[0852] After wetting the fiber bundle evaluated in (2) above with tap water at 30°C for 30 seconds, the wetted fiber bundle is wrapped around a plastic rod with a diameter of 14 mm and fixed with a clip.

[0853] (Step 2)

[0854] The entire fiber bundle wound on the rod is immersed in a 60°C water bath (TBS221FA, Toyo Seisakusho Co., Ltd.) and heated for 1 minute.

[0855] (Step 3)

[0856] Remove the fiber bundle from the water bath, immerse it in water at 20°C for 1 minute, remove it from the water and allow it to return to room temperature.

[0857] (Step 4)

[0858] Remove the fiber bundle from the rod, comb it three times, then take it out of the water. Three minutes after taking it out, take a photo from the front and side while it is suspended.

[0859] (Step 5)

[0860] Measure the length L of the fiber bundle when it is suspended vertically based on the photograph (the distance from the top of the fiber bundle to the farthest point 1).

[0861] (Evaluation Criteria)

[0862] The length of the fiber bundle when it is stretched into a straight line is set as L0, the length of the fiber bundle after the shape is assigned is set as L, and the curling rate = fiber bundle length reduction rate (I) (%) calculated according to the following formula is defined as the curling strength.

[0863] Roll-up rate I (%) = [(L0-L) / L0] × 100

[0864] 4. Fiber swelling rate in water (%)

[0865] The fiber swelling rate in water was calculated according to the following formula (1). The evaluation was conducted using fiber bundles that had just been treated using the above-described treatment method.

[0866] The fiber swelling rate in water, S (%) = [(w1-w2) / w2] × 100 (1)

[0867] The definitions of each symbol in equation (1) are as follows.

[0868] w1: Cut the fiber from the root of the fiber bundle to make a 1.0g fiber bundle. Immerse the 1.0g fiber bundle in a container with 100g of ion-exchanged water, seal the container, and immerse the container together in a water bath set to 40°C (model: TBS221FA, manufacturer: Toyo Seisakusho Co., Ltd.) for 30 minutes. Remove the fiber from the container and place it in a small centrifuge (H-112, KOKUSAN Co. Ltd.). Centrifuge at a centrifugal force of 220 [×g] (speed knob "4" (2000rpm)) for 1 minute to dehydrate the fiber. Immediately weigh the fiber and record it as weight w1.

[0869] w2: After the weight w1 has been measured, the fiber is placed on filter paper and dried in a dryer set at 105°C (SOFW-450SB, AS ONE Corporation) for 3 hours. The fiber is then removed and its weight is measured immediately. This weight is recorded as w2.

[0870] 5. Excellent surface feel

[0871] Regarding the evaluation of surface feel, using fiber bundles that have just been treated using the <treatment method>, five professionals evaluated the smoothness of the feel when touched by hand according to the following criteria, and the total value of the five professionals was taken as the evaluation result.

[0872] (Evaluation Criteria)

[0873] 5: Compared to untreated fibers (Comparative Example 1), the texture is extremely smooth to the touch.

[0874] 4: Compared to untreated fibers (Comparative Example 1), the texture is smoother to the touch.

[0875] 3: Compared to untreated fibers (Comparative Example 1), the texture feels slightly smoother to the touch.

[0876] 2: The tactile sensation of the hand was unchanged compared to that of the untreated fiber (Comparative Example 1).

[0877] 1: It is rougher and drier than untreated fibers (Comparative Example 1), and has a poorer tactile feel.

[0878] 6. Heat resistance

[0879] (1) Shrinkage rate (%) after contact with water vapor at 110℃

[0880] The shrinkage rate after contact with 110°C water vapor was determined according to the following steps. The evaluation was performed using fiber bundles that had just been treated using the above-described treatment method.

[0881] (Step 1)

[0882] Cut the fibers from the fiber bundles and fix the ends of the five fiber bundles with tape (Scholes tape, 3M) to make a sample. At this time, the length of the fiber between the tapes is set to 10.0 cm.

[0883] (Step 2)

[0884] Place the sample into an autoclave (model: LSX-700, manufactured by TOMY KOGYO CO.,LTD.) and heat at 110°C for 10 minutes.

[0885] (Step 3)

[0886] Remove the sample and measure the length h of the fibers between the tapes. Calculate the percentage of shrinkage compared to the length before heating, and use this as the shrinkage rate H (%) after contact with 110℃ water vapor. The closer H is to 0%, the less likely the material will shrink due to heat, indicating superior heat resistance.

[0887] Shrinkage rate H (%) after contact with water vapor at 110℃ = [(10-h) / 10]×100

[0888] [In the formula, h represents the length (cm) of the sample after heating at 110℃ for 10 minutes.]

[0889] Then, the heat resistance of the fiber is judged according to the following criteria.

[0890] Based on the shrinkage rate H0 (%) of the untreated regenerated collagen fiber A after contact with water vapor at 110°C, the value of ΔH calculated by ΔH=H0-H is evaluated using scores from A to E.

[0891] (Evaluation Criteria)

[0892] A: 6 < ΔH

[0893] B: 4 < ΔH ≤ 6

[0894] C: 2 < ΔH ≤ 4

[0895] D: 0 < ΔH ≤ 2

[0896] E: ΔH≤0

[0897] 7. Inhibits fiber staining

[0898] Regarding the suppression of coloration in fibers, the following steps are performed for evaluation. The evaluation uses fiber bundles that have just been treated using the above-described <treatment method>.

[0899] (Step 1)

[0900] For the surface of the fiber bundle, the color of the fiber near the root, near the middle, and near the tip was measured using a spectrophotometer (CR-400 colorimeter, manufactured by Konica Minolta). The average value of the six points was taken as the colorimetric value (L, a, b).

[0901] (Step 2)

[0902] Regarding the degree of coloring, using white untreated fiber (Comparative Example 1) as a benchmark, ΔE was used... *ab An evaluation will be conducted. Furthermore, colorimetric measurements will be performed on the same day the processing begins.

[0903] ΔE *abThe following definition applies: when the measured values ​​of the untreated white fiber (Comparative Example 1) are set as (L0, a0, b0) and the measured values ​​of the treated fiber bundle are set as (L1, a1, b1), the result is determined by [(L1-L0)]. 2 +(a1-a0) 2 +(b1-b0) 2 ] 1 / 2 The shading suppression effect is defined and determined according to the following criteria.

[0904] (Evaluation Criteria)

[0905] 5: ΔE *ab ≤5.0

[0906] 4:5.0<ΔE *ab ≤10.0

[0907] 3: 10.0 < ΔE *ab ≤15.0

[0908] 2:15.0<ΔE *ab ≤20.0

[0909] 1:20.0<ΔE *ab

[0910] 8. Fluorescence Imaging Measurement

[0911] Regenerated collagen fibers treated with the composition of Example 37 were embedded in resin, then cut, and the exposed surfaces were subjected to fluorescence imaging measurements using a confocal laser microscope (A1RHD25, Nikon Corporation) (excitation wavelength 400 nm, fluorescence detection wavelength 425–475 nm). The results are shown below. Figure 1 .

[0912] [Table 1]

[0913]

[0914] [Table 2]

[0915]

[0916] [Table 3]

[0917]

[0918] Examples 35-38 and Comparative Example 4

[0919] Using the composition formulated in Table 4, regenerated collagen fibers were treated and evaluated in various ways as follows. In the case of an additional fiber treatment agent (agent 3) containing component (D), after treatment with agent 2, the process was repeated with agent 3 (steps 2) to (steps 5), followed by (step 7).

[0920] <Handling Method>

[0921] (1) Processing method C

[0922] Follow these steps to process regenerated collagen fiber A or regenerated collagen fiber C.

[0923] (Step 1)

[0924] In each embodiment, 10 fiber bundles with a length of 30 cm were made from regenerated collagen fibers (the weight of which reached 1.5 g after drying at 60°C for 1 hour and placing at 20°C and 65%RH for 12 hours).

[0925] First, use the first agent shown in the table to perform the following steps (2) to (5).

[0926] (Step 2)

[0927] Impregnate the fiber bundles with the amount of fiber treatment agent or additional fiber treatment agent that meets the liquor ratio shown in the table (the liquor ratio is calculated based on the dried weight of 1.5g in step 1 above). Impregnate each bundle using a separate container and seal the opening of each container.

[0928] (Step 3)

[0929] Immerse the container together in a water bath (TBS221FA, Toyo Seisakusho Co., Ltd.) set to the temperature shown in the table and let it stand for 5 minutes. After raising the temperature of the liquid in the container to the temperature shown in the table, remove the container from the water bath.

[0930] (Step 4)

[0931] Place the container containing the fiber bundle on the stirring rotor (VMR-5R, AS ONE Corporation) inside a dryer (SOFW-450SB, AS ONE Corporation) set to the temperature shown in the table, and rotate the container at 80 rpm for the heating and stirring time shown in the table.

[0932] (Step 5)

[0933] Remove the container containing the fiber bundles from the dryer and allow it to return to room temperature. Then, remove the fiber bundles from the container, rinse them with 30°C tap water for 30 seconds, and comb them to guide the direction of the hair.

[0934] (Step 6)

[0935] Using the second agent shown in the table, repeat steps (2) to (5).

[0936] (Step 7)

[0937] The fiber bundles are suspended one by one in a dryer set to the temperature recorded in the table. A 250g weight is installed at the lower end of each fiber bundle, and the fibers are dried for the time recorded in the table while the fibers are under tension.

[0938] (Step 8)

[0939] Remove the fiber bundle from the dryer, allow it to return to room temperature, and remove the weights.

[0940] <Evaluation>

[0941] The evaluation was based on the following criteria: “1. Weight gain”, “2. Water resistance” (1) to (3), “3. Thermal shape memory ability”, “4. Fiber swelling rate in water”, “5. Surface feel quality”, “6. Heat resistance” and “7. Inhibition of fiber staining”.

[0942] [Table 4]

[0943]

Claims

1. A fiber treatment agent, wherein, The fiber treatment agent contains the following components (A) and (B) and is used for the treatment of fibers with a water swelling rate of 200% or more, calculated according to the following formula (1). (A) Compounds with coordinating functional groups and a molecular weight of 1500 or more. (B) Water, Fiber swelling rate in water (%) = [(w1-w2) / w2]×100 (1) In the formula, w1 indicates that 1.0g of fiber was placed in a container filled with 100g of ion-exchanged water, the container was sealed, and the fiber was immersed in a water bath at 40°C for 30 minutes. Afterward, the fiber was removed from the container and centrifuged at 220 ×g for 1 minute to remove water, and the mass of the fiber (in grams) was measured. w2 represents the mass of the fiber measured after placing the fiber with mass w1 on filter paper and drying it at 105°C for 3 hours.

2. The fiber treatment agent as described in claim 1, wherein, The fiber is a regenerated protein fiber.

3. The fiber treatment agent as described in claim 1 or 2, wherein, Coordination functional groups are groups that contain hard bases or boundary bases in the hard and soft acid-base rules.

4. The fiber treatment agent according to any one of claims 1 to 3, wherein, The coordination functional group comprises groups selected from components (a-1), (a-2), and (a-3). (a-1) A group having a carboxyl group or a salt thereof, (a-2) Groups having hydroxyl, alkoxy, alkoxide anion, or metal alkoxide groups, (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) contains one or more of the following: (A-1) and (A-2). (A-1) A polymer comprising structural units derived from unsaturated monomers having coordinating functional groups, wherein the polymer has a weight-average molecular weight of 1500 or more. (A-2) A condensate of a compound having a coordinating functional group, wherein the molecular weight of the condensate is greater than 1500.

6. The fiber treatment agent as described in claim 5, wherein, (A-1) The polymer also contains structural units derived from unsaturated hydrocarbon compounds.

7. The fiber treatment agent as described in claim 5 or 6, wherein, (A-1) The polymer contains one or more of the following: (A-1-1), (A-1-2), and (A-1-3). (A-1-1) is a copolymer comprising structural units derived from unsaturated monomers having coordinating functional groups and structural units derived from aromatic vinyl compounds, wherein the copolymer has a weight-average molecular weight of 1500 or more. (A-1-2) comprises a copolymer containing structural units derived from an unsaturated monomer having a coordinating functional group and structural units derived from an unsaturated aliphatic hydrocarbon compound, wherein the copolymer has a weight-average molecular weight of 1500 or more. (A-1-3) A polymer comprising a structural unit derived from an aromatic vinyl compound having a coordinating functional group or a polymer comprising a structural unit derived from an unsaturated aliphatic hydrocarbon compound having a coordinating functional group, wherein the polymer has a weight average molecular weight of 1500 or more, but excludes copolymers (A-1-1) and (A-1-2).

8. The fiber treatment agent as described in claim 5, wherein, (A-2) A condensate is a condensate with a molecular weight of 1500 or more, and contains one or more condensates selected from (A-2-1) and (A-2-2) below. (A-2-1) A condensate of sulfonic acid or a salt thereof. (A-2-2) condensate of gallic acid ester.

9. The fiber treatment agent according to any one of claims 1 to 8, wherein, The fiber treatment agent also contains the following component (C). (C) Polyvalent metal elements.

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

11. A fiber treatment kit, wherein, The fiber treatment kit has: 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), wherein the pH of the second fiber treatment agent is more than 1.0 lower than the pH of the first fiber treatment agent. The fiber treatment kit is configured for use in the treatment of fibers with a water swelling rate of 200% or more, calculated according to the following formula (1). (A) Compounds with coordinating functional groups and a molecular weight of 1500 or more. (B) Water, Fiber swelling rate in water (%) = [(w1-w2) / w2]×100 (1) In the formula, w1 indicates that 1.0g of fiber was placed in a container filled with 100g of ion-exchanged water, the container was sealed, and the fiber was immersed in a water bath at 40°C for 30 minutes. Afterward, the fiber was removed from the container and centrifuged at 220 ×g for 1 minute to remove water, and the mass of the fiber (in grams) was measured. w2 represents the mass of the fiber measured after placing the fiber with mass w1 on filter paper and drying it at 105°C for 3 hours.

12. A fiber treatment kit, wherein, The fiber treatment kit has: A fiber treatment agent containing the following components (A) and (B); and Additional fiber treatment agents containing the following component (D), The fiber treatment kit is used for treating fibers with a water swelling rate of 200% or more, calculated according to the following formula (1). (D) The hydrogen bonding term δH of Hansen's solubility parameter is 18.3 MPa. 1 / 2 The following are compounds or salts of compounds having at least one carboxyl group or a salt thereof and not having a fused ring, but excluding component (A). (A) Compounds with coordinating functional groups and a molecular weight of 1500 or more. (B) Water, Fiber swelling rate in water (%) = [(w1-w2) / w2]×100 (1) In the formula, w1 indicates that 1.0g of fiber was placed in a container filled with 100g of ion-exchanged water, the container was sealed, and the fiber was immersed in a water bath at 40°C for 30 minutes. Afterward, the fiber was removed from the container and centrifuged at 220 ×g for 1 minute to remove water, and the mass of the fiber (in grams) was measured. w2 represents the mass of the fiber measured after placing the fiber with mass w1 on filter paper and drying it at 105°C for 3 hours.

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