JPWO1997040227A1 - Fiber treatment materials and fibers and products treated with fiber treatment materials - Google Patents

Abstract

(57) [Abstract] A first fiber treatment material of the present invention comprises a functional protein obtained by treating a protein such as collagen with a crosslinking agent, and a solvent-based resin. A second fiber treatment material comprises the functional protein and a water-based resin. A third fiber treatment material comprises a water-soluble organic substance with an average molecular weight of 100 to 20,000, and a reactive modifier. A fourth fiber treatment material comprises the functional protein and a reactive modifier. Products such as fibers or textiles are treated with any of the above fiber treatment materials.

Description

Detailed Description of the Invention

Fiber Treatment Materials and Fibers and Products Treated with the Fiber Treatment Materials Technical Field The present invention relates to fiber treatment materials containing proteins or water-soluble organic substances, and fibers and textile products treated with the fiber treatment materials. Background Art Various techniques have been proposed to impart moisture absorbency to synthetic fibers, such as polyester fibers, and textile products made from such fibers. For example, Method (I) treats synthetic fibers with a treatment solution containing an acrylic or urethane emulsion and a fine powder of natural organic substances such as collagen. In Method (I), the synthetic fibers and the fine powder of natural organic substances are only physically bonded via the emulsion, which acts as a binder. This treatment method, however, can result in the powder falling off during washing, resulting in durability issues. Furthermore, increasing the proportion of emulsion to improve durability, results in the synthetic fibers becoming stiffer, making them unsuitable for practical use. Another method, Method (II), treats synthetic fibers with a treatment solution containing a modifier (monomer) that enhances moisture absorbency, such as a polyethylene glycol-based compound. This treatment method (II) provides excellent durability because the modifier forms a hydrophilic layer inside and on the surface of synthetic fibers, but only slightly improves moisture absorption. Also proposed is a method (III) in which synthetic fibers are treated with a treatment solution containing an aqueous protein solution and the modifier. Such an aqueous protein solution is obtained, for example, by dissolving silk fibers in a calcium chloride solution and dialyzing the solution through cellophane tubing. This treatment method (III) improves moisture absorption to some extent because the protein adheres to the synthetic fibers. However, increasing the amount of protein to a level that achieves sufficient moisture absorption results in a stiff texture. On the other hand, maintaining texture requires limited protein addition, which results in insufficient moisture absorption. Furthermore, in addition to moisture absorption and texture, improvements in water absorbency, antistatic properties, durability, and other properties are also desired for fibers and textile products. DISCLOSURE OF THE INVENTION A first fiber treatment material of the present invention is characterized by comprising a functional protein obtained by treating a protein with a crosslinking agent and a solvent-based resin. More specifically, the functional protein is obtained by the following process: (1) A protein-containing aqueous solution is reacted with a crosslinking agent dissolved in an organic solvent, and the aqueous protein phase containing the crosslinking agent is separated. (2) An acid is added to the protein solution containing the crosslinking agent to lower the pH below the isoelectric point of the protein, and the precipitate is separated, dried, and powdered. The protein can be selected arbitrarily. For example, egg white from chicken, quail, duck, or goose eggs, whey, casein, serum protein, collagen, gelatin, fibroin, sericin, etc. can be used. The crosslinking agent can be a diisocyanate compound, a dialdehyde compound, a diketone compound, etc. The diisocyanate compounds include toluene isocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), naphthalene diisocyanate (NDI), etc. Chloroform, hexane, toluene, etc. can be used as the organic solvent for dissolving the crosslinker. Acids that can be used include acetic acid, citric acid, succinic acid, lactic acid, tartaric acid, fumaric acid, etc. The solvent-based resin is a resin obtained by dissolving a urethane-based resin, an acrylic-based resin, a vinyl chloride-based resin, etc. in a solvent consisting of one or more of dimethylformamide (DMF), methyl ethyl ketone (MEK), toluene, cyclohexane, butyl acetate, etc. The functional protein obtained by the above treatment is soluble in organic solvents and insoluble in water. The fiber treatment material of the present invention can be prepared by dissolving the functional protein and then mixing it with a solvent-based resin. Specifically, the functional protein is dissolved by dispersing the protein powder in an organic solvent (e.g., DMF) at room temperature, heating the mixture to 60-80°C while stirring, and completely dissolving the protein until the solution becomes transparent. The mixture is then cooled to room temperature. The functional protein is mixed with the solvent-based resin by gradually adding the functional protein solution to the stirred solvent-based resin. The functional protein content is, for example, 0.1-50 wt%, preferably 1-30 wt%. Less than 0.1 wt% results in insufficient effectiveness, while more than 50 wt% results in peeling and reduced transparency. In the fiber treatment material of the present invention, the functional protein is mixed with the solvent-based resin at the molecular level, thereby improving the touch, moisture absorption/desorption, durability, transparency, etc., without degrading the physical properties of the resin. A second fiber treatment material of the present invention is characterized by comprising a functional protein obtained by treating a protein with a crosslinking agent and a water-based resin. More specifically, the functional protein of this second fiber treatment material is obtained by the following steps: (1) Reacting a protein-containing aqueous solution with a crosslinking agent dissolved in an organic solvent and separating the aqueous protein phase containing the crosslinking agent. (2) Adjusting the pH of the protein solution containing the crosslinking agent to a value equal to or higher than the isoelectric point of the protein, Isolating the modified protein, drying it, and powdering it. The protein can be selected arbitrarily. For example, egg white from chicken, quail, duck, or goose eggs, whey, casein, serum protein, collagen, gelatin, fibroin, sericin, etc. can be used. The crosslinking agent can be a diisocyanate compound, a dialdehyde compound, a diketone compound, etc. The diisocyanate compounds include toluene isocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), naphthalene diisocyanate (NDI), etc. Chloroform, hexane, toluene, etc. can be used as organic solvents for dissolving the crosslinker. The water-based resin refers to a resin whose solvent is water, and includes emulsions and water-soluble resins. Emulsions include silicone-based, acrylic-based, urethane-based, vinyl acetate-based, and vinyl chloride-based emulsions. Water-soluble resins include polyvinyl alcohol, cellulose-based polymers, polyethyleneimine, and polyethylene oxide. The functional protein obtained by the above treatment is water-soluble, but becomes water-insoluble after thermal fixation. The fiber treatment material of the present invention can be prepared by dissolving the functional protein and then mixing it with the water-based resin. Specifically, the functional protein is dissolved by dispersing the protein powder in water at room temperature, heating the mixture to 60-80°C while stirring, and completely dissolving the solution until it becomes transparent, after which it is cooled to room temperature. The functional protein is mixed with the water-based resin by adding the functional protein solution to the water-based resin in an appropriate ratio. The functional protein content is, for example, 0.1-50 wt%, preferably 1-30 wt%. If it is less than 0.1 wt%, sufficient effect cannot be obtained, while if it is more than 50 wt%, the product may peel easily or become less transparent. A third fiber treatment material of the present invention is characterized by containing a water-soluble organic substance with an average molecular weight of 100-20,000 and a reactive modifier. The water-soluble organic substance includes not only natural water-soluble organic substances themselves, but also derivatives of these substances that have been subjected to decomposition, modification, or other processes. If the average molecular weight of the water-soluble organic substance is less than 100, durability will be poor. Conversely, if the content exceeds 200,000 and sufficient functionality is achieved, the texture will become stiff. The average molecular weight can be adjusted by common methods such as hydrolysis using acids or alkalis. When treating fibers with this fiber treatment agent, the water-soluble organic substance and reactive modifier are thought to polymerize upon heating, forming a durable hydrophilic layer on the surface and interior of the fiber. The water-soluble organic substance can be a protein or a protein derivative. The protein derivative can be obtained by decomposing or modifying a protein. Specific examples of proteins include fibroin, collagen, and wool, and combinations of these may also be used. Fibroin is preferred as the protein due to its availability and cost, but is not limited to these specific examples. Other proteins such as egg white and whey can also be used. Examples of reactive modifiers include hydrophilic compounds having a polymerizable vinyl group in the molecule, monomers containing a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, or a phosphate group, hydrophilic compounds having an epoxy group, and compounds having an aziridine group. Specific examples of such reactive modifiers include polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, bisphenol A polyethylene glycol diacrylate, bisphenol A polyethylene glycol dimethacrylate, and bisphenol S polyethylene glycol dimethacrylate. Specific examples of such reactive modifiers include acrylic acid, methacrylic acid, maleic acid, itaconic acid, acrylamide, methacrylamide, vinyl sulfonic acid, and hydroxypropyl methacrylate. Specific examples of such reactive modifiers include polyethylene glycol diglycidyl ether. Specific examples of such reactive modifiers include compounds having the following chemical formula 1:

[Chemical formula 1] This third fiber treatment material may contain chitosan in addition to the water-soluble organic substance and reactive modifier. The chitosan does not need to have an average molecular weight of 100 to 20,000. The inclusion of chitosan improves moisture absorption. A fourth fiber treatment material of the present invention is characterized by comprising a functional protein obtained by treating a protein with a crosslinking agent and a reactive modifier. The functional protein of this fourth fiber treatment material is the same as the functional protein of the second fiber treatment material. The reactive modifier of this fourth fiber treatment material is the same as the reactive modifier of the third fiber treatment material. The fibers of the present invention are treated with any of the first to fourth fiber treatment materials. The fibers include commonly known synthetic fibers such as nylon, polyester, and polyurethane. The products of the present invention are treated with any of the first to fourth fiber treatment materials. The textile products include yarns, woven fabrics, knitted fabrics, nonwoven fabrics, etc., made of the synthetic fibers. They may also be composites of natural fibers such as cotton, wool, and hemp. Specific examples of the products include blouses, dress shirts, pants, skirts, linings, and upholstery materials for furniture such as chairs. The treatment method for the fiber treatment material may be any method, including immersion and padding. Immersion methods include room temperature standing and heating and stirring. Padding methods include pad drying and pad steaming, with pad steaming being preferred. In the case of textile products, proteins become insoluble in water after the fiber treatment material is thermally fixed, preventing protein loss even after repeated washing. Therefore, such textile products have excellent durability and can maintain good touch, water absorbency, moisture permeability, transparency, and the like even after long-term use. Examples of products other than textiles include films, sheets, and leather. Leather includes PVC leather, synthetic leather, artificial leather, split leather, and resin-coated fabric. Surface treatment methods for films, sheets, or leather include spray coating, gravure coating, and knife coating. The surface finishing layer formed on a product using a fiber treatment material can impart excellent surface smoothness and a pleasant touch. Furthermore, due to its excellent transparency, it does not impair the transparency of the underlying printed pattern, transparent film, or leather. Alternatively, a film made of the fiber treatment material can be prepared and then attached to the surface of a product to form a surface finishing layer. BRIEF DESCRIPTION OF THE DRAWINGS: Figure 1 shows the FTIR measurement results for the functional protein obtained in Example 1. Figure 2 shows the FTIR measurement results for the pantyhose of Example 3 washed 10 times. Figure 3 shows the FTIR measurement results for the pantyhose of Comparative Example 7. Figure 4 shows the FTIR measurement results for the pantyhose of Comparative Example 8 washed 5 times. BEST MODE FOR CARRYING OUT THE INVENTION [First Embodiment] The fiber treatment material of this embodiment corresponds to the first fiber treatment material described above and can be prepared as follows. First, the functional protein is prepared as follows. A protein-containing aqueous solution is reacted with a crosslinker dissolved in an organic solvent, and the aqueous protein solution containing the crosslinker is separated. Acid is then added to the crosslinker-containing protein solution to lower the pH below the isoelectric point of the protein. The precipitate is then separated and dried to obtain a functional protein powder. The resulting protein powder is then dispersed in an organic solvent at room temperature, heated to 60-80°C with stirring, and completely dissolved until the solution becomes transparent. The solution is then cooled to room temperature. The functional protein solution is then gradually added to a stirred solvent-based resin to obtain the fiber treatment material of this embodiment. This fiber treatment material is used to surface treat leather or other materials to form a surface finish layer. Alternatively, this fiber treatment material can be used to create a film, which is then applied to a product to form a surface finish layer. [Example 1] Whey protein powder was diluted with water to a protein concentration of 3.5%, and the pH was adjusted to 12 with sodium hydroxide. A solution of 2,4-toluenediisocyanate (TDI) in chloroform was added to this protein solution and reacted at 45°C for 2 hours. After the reaction, the reaction solution was left at room temperature for 2 hours to separate into an aqueous layer and a chloroform layer. The chloroform layer was then removed by filtration, and the aqueous layer was separated. The pH of the resulting aqueous layer was adjusted to 3.5 to precipitate the crosslinked protein, which was then collected by filtration and lyophilized to obtain a functional protein powder. Next, 150 g of the resulting functional protein powder was dispersed in dimethylformamide (DMF) at room temperature with stirring. The dispersion was then placed in an 80°C water bath for 15 minutes with stirring to completely dissolve the functional protein powder, and then allowed to cool to room temperature to obtain a functional protein solution. The functional protein content in this solution was 15 wt%. Next, a urethane-based resin (CRISBON S-750 (product name), manufactured by Dainippon Ink & Chemicals, Inc.) dissolved in DMF was used as the solvent-based resin. The functional protein solution was gradually poured into the stirred solvent-based resin solution and mixed to obtain a solution of the fiber treatment material of this embodiment. The functional protein content of the fiber treatment material was 10 wt% of the total solids. Next, the fiber treatment material solution was applied to release paper using a bar coater and dried at 80°C to produce a 20 μm-thick film. [Comparative Example 1] A resin solution was prepared by adding only DMF to the solvent-based resin to achieve a resin solids content of 20% without blending the functional protein. This resin solution was used to produce a 20 μm-thick film in the same manner as in Example 1. [Comparative Example 2] In Example 1, insoluble collagen powder (average particle size 5 μm) mechanically pulverized from cowhide shavings was used instead of the functional protein, and a solution with a collagen powder content of 10 wt% of the total solids was obtained. Next, a 20 μm thick film was produced using this solution in the same manner as in Example 1. [Example 2] In Example 1, Luxkin U-65 (trade name, manufactured by Seiko Chemical Co., Ltd.) was used as the urethane resin, and the other conditions were the same to obtain a solution of the fiber treatment material of this embodiment. Next, this fiber treatment material solution was used as a surface treatment material to coat vinyl chloride leather for notebook covers using a gravure coating machine to form a surface finishing layer. The application amount of this solution was 20 g/ ^m2 . [Comparative Example 3] In Example 2, a solution containing no functional protein was prepared. Next, this solution was used to coat vinyl chloride leather in the same manner as in Example 2 to form a surface finishing layer. [Comparative Example 4] In Example 2, insoluble collagen powder (average particle size 5 μm) mechanically pulverized from cowhide shavings was used instead of the functional protein, and a solution with a collagen powder content of 10 wt% of the total solids was obtained. Next, this solution was used to coat vinyl chloride leather in the same manner as in Example 2 to form a surface finishing layer. [Example 3] In Example 1, a solution of the fiber treatment material of this embodiment was obtained using the same conditions as in Example 1, except that Luxkin U-15 (trade name, manufactured by Seiko Chemical Co., Ltd.) was used as the urethane resin. This fiber treatment solution was then used as a surface treatment material to coat enamel-finish vinyl chloride leather for bags using a gravure coating machine to form a surface finish layer. The application amount of this solution was 20 g/ ^m² . [Comparative Example 5] In Example 3, a solution containing no functional protein was prepared. This solution was then used to coat enamel-finish vinyl chloride leather in the same manner as in Example 3 to form a surface finish layer. [Comparative Example 6] In Example 3, collagen powder was used instead of the functional protein to obtain a solution with a collagen powder content of 10 wt% of the total solids. This solution was then used to coat enamel-finish vinyl chloride leather in the same manner as in Example 3 to form a surface finish layer. [Comparative Example 7] Enamel-finish vinyl chloride leather was used for evaluation as this comparative example. [Evaluation of Properties] For each of Examples 1 to 3 and Comparative Examples 1 to 7, at least one of moisture permeability, tensile strength, and elongation was measured, and at least one of surface touch and glossiness was evaluated. Practical Tests A and B were also conducted and the results evaluated. The results are shown in Tables 1 to 3. The moisture permeability was measured in accordance with JIS L 1099-A. The tensile strength and elongation were measured in accordance with JIS K-7311. The surface touchiness was evaluated by having 20 people evaluate the feel of the sample surface when touched with their hands according to the following criteria, and the average of the 20 evaluations was taken. The glossiness was measured in accordance with the 60-degree specular reflection method of JIS K-7105. 5 points: very good touchability; 4 points: good touchability; 3 points: average; 2 points: poor touchability; 1 point: very poor touchability. Practical Test A was conducted by making a notebook from the obtained leather and observing the changes in the folded section. In the practical test B, the obtained leather was sewn, and 10 randomly selected people were asked to evaluate it according to the following criteria, and the average of the 10 people's evaluations was taken: 5 points: Good slipperiness, very easy to sew with a sewing machine 4 points: Moderate slipperiness, easy to sew with a sewing machine 3 points: Average 2 points: Tacky, difficult to sew with a sewing machine 1 point: Strong tacky, very difficult to sew with a sewing machine

[Table 1] From Table 1, it can be seen that the film of Example 1 contains functional protein, and therefore has good tensile strength and elongation. It also has good moisture permeability and a good touch. On the other hand, the film of Comparative Example 1 does not contain functional protein, and therefore, although it has good tensile strength and elongation, it is inferior to the film of Example 1 in terms of moisture permeability and a good touch. Furthermore, the film of Comparative Example 2 contains collagen powder instead of functional protein, and therefore, although it has good moisture permeability and a good touch, it is inferior to the film of Example 1 in terms of tensile strength and elongation.

[Table 2] From Table 2, it can be seen that the vinyl chloride leather of Example 2 has a good feel to the touch because the surface finish layer contains functional proteins. Furthermore, the practical test also showed no abnormalities and the durability was high. On the other hand, the vinyl chloride leather of Comparative Example 3 did not contain functional proteins in the surface finish layer, so the practical test showed no abnormalities, but the feel was poor. Furthermore, the vinyl chloride leather of Comparative Example 4, whose surface finish layer contains insoluble collagen powder instead of functional proteins, has a good feel to the touch, but suffers from whitening of the folded portions, which is a problem.

[Table 3] Table 3 shows that the enamel-finish vinyl chloride leather of Example 3 has a good feel and gloss due to the inclusion of functional protein in the surface finish layer. It also has good slipperiness and is easy to sew. On the other hand, the enamel-finish vinyl chloride leather of Comparative Example 5 does not contain functional protein in the surface finish layer, resulting in poor feel and practical test results. Furthermore, the enamel-finish vinyl chloride leather of Comparative Example 6, whose surface finish layer contains collagen powder instead of functional protein, has a good feel and practical test results, but poor gloss. Comparative Example 7 is an enamel-finish vinyl chloride leather without a surface finish layer, so it has good gloss but very poor feel and practical test results. [Second Embodiment] The fiber treatment material of the second embodiment corresponds to the second fiber treatment material and can be prepared as follows. First, a functional protein is prepared as follows. A protein-containing aqueous solution is reacted with a crosslinker dissolved in an organic solvent, and the aqueous protein solution containing the crosslinker is separated. It is preferable to improve the water solubility of the protein by pretreatment such as hydrolysis before use. The pH of the protein solution containing the crosslinker is then adjusted to a value equal to or higher than the isoelectric point of the protein. The modified protein is then separated and dried to obtain a functional protein powder. The resulting protein powder is then dispersed in water at room temperature, heated to, for example, 60-80°C while stirring, until the solution becomes transparent and completely dissolved, and then cooled to room temperature. The functional protein solution is then added to an aqueous resin in an appropriate ratio and mixed to obtain the fiber treatment material according to this embodiment. This fiber treatment material is used to surface treat films, sheets, leather, knitted fabrics, woven fabrics, or nonwoven fabrics to form a surface treatment layer. [Example 4] Whey protein powder was diluted with water to a protein concentration of 3.5% and adjusted to pH 12 with sodium hydroxide. A solution of 2,4-toluene diisocyanate (TDI) in chloroform was added to this protein solution and allowed to react at 45°C for 2 hours. After the reaction, the reaction mixture was left at room temperature for 2 hours to separate into an aqueous layer and a chloroform layer. The chloroform layer was then removed by filtration, and the aqueous layer was collected. The pH of the resulting aqueous layer was adjusted to 7 and then dried to obtain a functional protein powder. Next, 50 g of the resulting functional protein powder was dispersed in 950 g of water, and the dispersion was stirred in an 80°C water bath for 20 minutes to completely dissolve the functional protein powder, yielding a 5 wt% solution. After allowing the solution to cool naturally, 82 g of the solution was mixed with 100 g of an acrylic emulsion (Yodozol 2D540 (trade name), Kaneho NSC Co., Ltd.) and uniformly mixed using a propeller stirrer to obtain a fiber treatment solution. The fiber treatment solution was then gravure coated onto a transparent polyvinyl chloride sheet at a coverage of 10 g/ ^m² and dried at 120°C to obtain a sheet with a surface finish layer. Comparative Example 8: Instead of the functional protein used in the Examples, insoluble collagen powder (average particle size 5 μm) prepared by mechanically pulverizing cowhide shavings was used. This collagen powder was then blended with an acrylic emulsion (Yodozol 2D540 (trade name)) to a collagen powder content of 10 wt% of the total solids (collagen powder and resin solids) to obtain a fiber treatment solution. The fiber treatment solution was then applied to a polyvinyl chloride sheet and dried in the same manner as in Example 4 to obtain a sheet with a surface finish layer. Comparative Example 9: Instead of the functional protein used in Example 4, water-soluble gelatin (average molecular weight 3000) was used. This water-soluble gelatin was then blended with an acrylic emulsion to obtain a fiber treatment solution. The fiber treatment solution was then applied to a polyvinyl chloride sheet and dried in the same manner as in Example 4 to obtain a sheet with a surface finish layer. [Comparative Example 10] A protein-free acrylic emulsion (Yodozol 2D540 (trade name)) was applied to a polyvinyl chloride sheet in the same manner as in Example 4, followed by drying to obtain a sheet with a surface finish layer. [Example 5] The sheet with the surface finish layer obtained in Example 4 was laminated to an enamel-finish polyvinyl chloride leather using an adhesive to obtain an enamel-finish polyvinyl chloride leather with a surface finish layer. [Comparative Example 11] The enamel-finish polyvinyl chloride leather was used as this comparative example for evaluation. [Evaluation of Properties] The surface touch, stain resistance (water resistance), and transparency of Example 4 and Comparative Examples 4-10 were evaluated. For Example 5 and Comparative Example 11, gloss and practical test results were also measured. The results are shown in Table 4. The surface touch was evaluated by having 20 people evaluate the feel of the surface of the evaluation sample using their hands according to the following criteria, and the average of the 20 evaluations was taken. 5 points: very good touch; 4 points: good touch; 3 points: average; 2 points: poor touch; 1 point: very poor touch. The stain resistance (water resistance) was evaluated by dropping a drop of water, soy sauce, or dishwashing detergent (concentration 1 g/1000 ml) onto the evaluation sample, wiping it off with a dry cloth after 24 hours, and observing the surface condition. The transparency was evaluated by visual inspection. The gloss was evaluated according to the 60-degree specular reflection method of JIS K 7105. In the practical test, the obtained leather was sewn, and 10 randomly selected people evaluated it according to the following criteria, and the average of the 10 evaluations was taken. 5 points: good slipperiness, very easy to sew; 4 points: moderate slipperiness, easy to sew; 3 points: average; 2 points: tacky, difficult to sew; 1 point: strong tacky, very difficult to sew.

[Table 4] Table 4 shows that the polyvinyl chloride sheet of Example 4, containing functional protein in the surface finishing layer, exhibits excellent surface feel, stain resistance, and transparency. Therefore, this polyvinyl chloride sheet is suitable for use as, for example, a tablecloth. On the other hand, the polyvinyl chloride sheet of Comparative Example 8, containing insoluble collagen powder in the surface finishing layer, exhibits satisfactory surface feel and stain resistance, but exhibits a frosted glass-like haze, resulting in a poor appearance. The polyvinyl chloride sheet of Comparative Example 9, containing water-soluble gelatin in the surface finishing layer, exhibits satisfactory surface feel and transparency, but exhibits poor stain resistance. Furthermore, the water-soluble gelatin dissolves when exposed to water, creating practical problems. The polyvinyl chloride sheet of Comparative Example 10, containing no protein in the surface finishing layer, exhibits satisfactory stain resistance and transparency, but exhibits poor surface feel. The enamel-like polyvinyl chloride leather of Example 5, containing functional protein in the surface finishing layer, exhibits excellent surface feel and gloss. It was also very easy to sew and performed well in practical tests. On the other hand, the patent-finish polyvinyl chloride sheet leather of Comparative Example 11, which does not contain protein in the surface finish layer, had good gloss but poor surface feel. It was also very difficult to sew and performed poorly in practical tests. [Example 6] 4 parts by weight of the 5 wt% functional protein solution obtained in Example 4, 2 parts by weight of a urethane emulsion [UN-11 (trade name), manufactured by Kyoeisha Chemical Co., Ltd.], and 94 parts by weight of water were added to a drum dyeing machine. The dyed pantyhose were then placed in the dyeing machine at a bath ratio of 1:20, immersed at 40°C for 15 minutes, and then centrifuged to achieve a pickup rate of 30%. The pantyhose were then steam-dried and heat-set to obtain pantyhose with protein adhered to the fiber surface. [Comparative Example 12] This comparative example used commercially available pantyhose with the same yarn composition as the pantyhose used in Example 6. [Comparative Example 13] The dyed pantyhose of Example 6 was used as this comparative example. [Comparative Example 14] In Example 6, 2 parts by weight of a urethane emulsion [UN-11 (trade name)] and 98 parts by weight of water were added to the drum dyeing machine. Otherwise, the pantyhose were processed in the same manner as in Example 6. [Comparative Example 15] Water-soluble fibroin (average molecular weight 4800) was used instead of the functional protein of Example 6, and pantyhose with fibroin adhered to the fiber surface were obtained in the same manner as in Example 6. [Evaluation of Properties] The pantyhose of Example 6 and Comparative Examples 12 to 15 were evaluated for water absorbency and surface feel, and frictional electrification voltage was measured. The results are shown in Table 5. The state of protein adhesion was also confirmed for the pantyhose of Example 6 and Comparative Examples 14 and 15. The results are shown in Figures 2 to 4. The water absorbency was measured in accordance with JIS L 1096-A. The surface feel was evaluated using the same method as in Example 1. The frictional charging voltage was measured in accordance with JIS L 1094-B. The protein adhesion state was measured by vigorously stirring the pantyhose in 1 liter of water at 40°C for 24 hours to forcibly extract the deposits, then evaporating the water and measuring the residue using FTIR (Fourier transform infrared spectroscopy). The protein adhesion state was measured after 10 washes for Example 6 and 5 washes for Comparative Example 15. The washing was performed using a household single-layer fully automatic washing machine, using 2 g/liter of household laundry detergent (Monogen Uni (trade name), manufactured by P&G) and washing for 5 minutes, rinsing twice, and spin-drying for 4 minutes. The pantyhose were placed in a laundry net during this washing. The results of FTIR measurement of the dried and solidified 5 wt% functional protein solution obtained in Example 4 are shown in Figure 1. As shown in Figure 1, protein peaks due to amide bonds are observed around 1550 cm ^-1 and 1650 cm ^-1 .

[Table 5] Table 5 shows that the pantyhose of Example 6 have a good surface feel due to the functional protein adhered to the fiber surface. They also have good water absorbency and can quickly absorb sweat, quickly eliminating stuffiness. Furthermore, they also have excellent antistatic properties. These effects are similarly achieved when a surface finish layer containing functional protein is formed on a fabric substrate such as polyester. Furthermore, the FTIR measurement results in Figure 2 show protein peaks near 1550 cm ^-1 and 1650 cm ^-1 , indicating that the functional protein is retained on the fiber surface even after 10 washes. The pantyhose of Comparative Examples 12 and 13 are commercially available products without protein adhered to the fiber surface, and therefore have a normal surface feel, but poor water absorbency, are unable to quickly absorb sweat, and remain stuffy. They also have poor antistatic properties. The pantyhose of Comparative Example 14 also have poor water absorbency and antistatic properties due to the lack of protein adhered to the fiber surface. The pantyhose of Comparative Example 15, which uses water-soluble fibroin as the protein, exhibited excellent surface feel, absorbency, and antistatic properties, as shown in Table 5. However, as shown in Figure 4, no peak characteristic of protein was observed, and it was clear that the water-soluble fibroin had leached from the surface of the fibers after five washes. [Third Embodiment] The fiber treatment material of the third embodiment corresponds to the third fiber treatment material described above and contains a solvent and the following components: Water-soluble organic substance: 1-15 wt% Reactive modifier: 0.1-10 wt% Other: 0-10 wt% The solvent can be water, alcohols, dimethylformamide, acetone, dimethyl sulfoxide, or a mixture thereof. Other components, such as a polymerization initiator and a carrier for the reactive modifier, may be added as needed. The polymerization initiator can include peroxides, azo compounds, metal salts, etc. The carrier allows the reactive modifier to penetrate deeper into the fibers than the surface layer. Specific examples of the carrier include chlorobenzenes, methylnaphthalenes, diphenyls, aromatic esters, aliphatic halogenated hydrocarbons, etc. [Example 7] In the third embodiment, specific examples and concentrations of each component in the fiber treatment material are as follows: Silk fibroin hydrolysate: 5 wt% Compound of chemical formula 2: 5 wt% Water: 89 wt% Zn( _BF4 ) ₂ : 1 wt%

[Chemical formula 2] The silk fibroin hydrolysate of Example 7 was obtained as follows. Specifically, silk fibroin yarn, from which sericin had been removed by a conventional method, was dissolved in 2N-HCl solution at 70°C for 1 hour, and then neutralized with caustic soda to obtain a fibroin hydrolysate solution. This fibroin solution was spray-dried to prepare fibroin powder. This fibroin powder had an average molecular weight of approximately 4800 and was water-soluble. Next, this fiber treatment material was used to impregnate a 100% polyester taffeta fabric (120 g/ ^m3 basis weight) and then squeezed to a 70% pick-up using a mangle. This was followed by a steam heat treatment at 105°C for 10 minutes, followed by hot water washing (40°C for 10 minutes), drying, and heat setting. [Example 8] In the third embodiment, the specific components and concentrations of each fiber treatment material were as follows. Silk fibroin hydrolysate: 2 wt% Collagen: 3 wt% Compound of formula 1: 2 wt% Compound of formula 3: 4 wt% Water: 88.5 wt% (NH ₄ ) ₂ S ₂ O ₈ : 0.5 wt%

[Chemical formula 3] The collagen used was Nutrilan (trade name, manufactured by Henkel Hakusui), a powdered collagen with an average molecular weight of approximately 1500. The treatment of taffeta fabric using this fiber treatment material was the same as in Example 1. [Example 9] In the above embodiment, the specific components and concentrations of each component in the fiber treatment material were as follows: Silk fibroin hydrolysate...4 _{wt% Compound of chemical formula 3...2 wt% Compound of chemical formula 4...4 wt% Water...39.5 wt% (NH4)2S2O8 ... 0.5} wt% 1% aqueous chitosan solution...50 _wt %

[Chemical formula 4] The chitosan used was CTA-1 lactic acid (trade name, manufactured by Kataoka Chikkarin Co., Ltd.) with an average molecular weight of approximately 300,000. The treatment of taffeta fabric using this fiber treatment material was the same as in Example 7. [Comparative Example 16] The amount of silk fibroin hydrolyzate in the fiber treatment material of Example 7 was 0, and the water content was 94 wt%. The other components and concentrations were the same as in Example 7. The treatment of taffeta fabric using this fiber treatment material was the same as in Example 7. [Comparative Example 17] The amount of silk fibroin hydrolyzate and collagen in the fiber treatment material of Example 8 was 0, and the water content was 93.5 wt%. The other components and concentrations were the same as in Example 7. The treatment of taffeta fabric using this fiber treatment material was the same as in Example 7. [Comparative Example 18] The amount of silk fibroin hydrolyzate and chitosan in the fiber treatment material of Example 9 was 0, and the water content was 93.5 wt%. The other components and concentrations were the same as in Example 7. The treatment of taffeta fabric using this fiber treatment material was the same as in Example 7. Comparative Example 19: High-molecular-weight silk fibroin was used instead of the silk fibroin hydrolysate in the fiber treatment material of Example 7. Other components and concentrations were the same as in Example 7. The high-molecular-weight silk fibroin in this comparative example was obtained as follows: Silk fibroin yarn, from which sericin had been removed by a conventional method, was heated and dissolved in a 50 wt% calcium chloride aqueous solution, and the resulting solution was dialyzed and desalted using a cellulose tube. The fibroin concentration of the resulting fibroin aqueous solution was 4.2 wt%. The molecular weight of the fibroin in this solution was approximately 100,000. Note that this solution was not very stable (it gelled within a few days), so it was used on the day it was prepared. The treatment of taffeta fabric using this fiber treatment material was the same as in Example 7. Comparative Example 20: Untreated polyester fabric was used as this comparative example. Characteristic Evaluation: The moisture absorption and frictional electrification voltage were measured for the treated taffeta fabrics obtained in Examples 7-9 and Comparative Examples 16-20, initially and after washing. Furthermore, the texture was evaluated. The results are shown in Tables 6 and 7. The moisture absorption was measured by conditioning a sample of the processed taffeta fabric in a 23°C, 30% RH atmosphere for 12 hours, then placing the sample in a 30°C, 80% RH atmosphere and measuring the weight change. The washing was performed in accordance with JIS L-0217 103. The frictional electrification voltage was measured in accordance with JIS L-1094 B. Twenty randomly selected people touched the samples and evaluated the texture, assuming it was a dress shirt fabric, according to the following criteria: 5 points: soft and very good texture; 4 points: soft and good texture; 3 points: average; 2 points: stiff and poor texture; 1 point: stiff and very poor texture. In the texture column of the tables, ◎ indicates an average of 4 to 5 points, ○ indicates an average of 3 to less than 4 points, △ indicates an average of 2 to less than 3 points, and × indicates an average of 1 to less than 2 points.

[Table 6]

[Table 7] Table 6 shows that the processed taffeta fabrics of Examples 7 to 9 were treated with a fiber treatment containing a water-soluble organic substance with an average molecular weight of 100 to 20,000 and a reactive modifier, and therefore exhibited high moisture absorption and good moisture absorption both initially before and after washing. Therefore, these processed taffeta fabrics can reduce stuffiness when worn as apparel. In particular, Example 9 contains chitosan, which significantly improves moisture absorption. The texture of the processed taffeta fabrics of the Examples is soft and very good. Furthermore, the processed taffeta fabrics of the Examples exhibited low triboelectric charging potential, making them less likely to cause discomfort due to static electricity. Furthermore, the processed taffeta fabric of Example 8, which was treated with a fiber treatment containing silk fibroin and collagen as water-soluble organic substances and the compounds of Chemical Formulas 1 and 3 as reactive modifiers, exhibited improved moisture absorption and triboelectric charging properties compared to Example 1. On the other hand, Table 7 shows that the processed taffeta fabric of Comparative Example 16 was treated with the fiber treatment material of Example 1, which does not contain water-soluble organic substances, and therefore had low moisture absorption both initially and after washing, indicating poor moisture absorption. It also had a high frictional electrification voltage, making it a material that is prone to discomfort due to static electricity. The processed taffeta fabric of Comparative Example 17 was treated with the fiber treatment material of Example 8, which does not contain water-soluble organic substances, and therefore had low moisture absorption and high frictional electrification. The processed taffeta fabric of Comparative Example 18 was treated with the fiber treatment material of Example 9, which does not contain water-soluble organic substances, and therefore had low moisture absorption and high frictional electrification. The processed taffeta fabric of Comparative Example 19 was treated with the fiber treatment material of Example 7, which contains high-molecular-weight silk fibroin instead of silk fibroin hydrolysate, and therefore had poor texture. The polyester cloth of Comparative Example 20 was untreated, and therefore had very low moisture absorption and very high frictional electrification. [Fourth Embodiment] This fiber treatment material corresponds to the fourth fiber treatment material and contains the functional protein of the second fiber treatment material and the reactive modifier of the third fiber treatment material. [Example 10] Whey protein powder and hydrolyzed silk fibroin (weight ratio 8:2) were diluted with water to a protein concentration of 3.5%, and the pH was adjusted to 12 with sodium hydroxide. 2,4-toluene diisocyanate (TDI) dissolved in chloroform was added to this protein solution and reacted at 45°C for 2 hours. After the reaction, the reaction solution was left at room temperature for 2 hours to separate into an aqueous layer and a chloroform layer. The chloroform layer was then removed by filtration, and the aqueous layer was separated. The pH of the resulting aqueous layer was adjusted to 7 and then dried to obtain a functional protein powder. Specific examples and concentrations of each component in the fiber treatment material are as follows: Functional protein powder: 5 wt% Compound of Chemical Formula 5: 4 wt% Compound of Chemical Formula 6: 3 wt% Water: 88 wt%

[Chemical formula 5]

[Chemical formula 6] Polyester fibers (100d/2-ply yarn, 48 filaments) were treated using the fiber treatment material of this example as described below. Socks were also made using this treated fiber. The treated fiber was then wrapped in cheesecloth, dyed, and dried. The dyed cheese-wrapped fiber was placed in an Overmeyer dyeing machine, and the treatment material was added to the fiber at a bath ratio of 1:20. The treatment was carried out at 20°C for 20 minutes. The treated fiber was dehydrated in a centrifugal dehydrator to a pickup rate of 100%. The dehydrated fiber was placed in a pressure vessel, filled with steam, and heat-treated at 100°C for 20 minutes. The heat-treated fiber was washed and then dried. Socks were made from the treated fiber using a circular knitting machine. [Comparative Example 21] The fiber of Example 10 was dyed only, and socks were made using this fiber in the same manner as in Example 10. [Evaluation of Properties] The moisture absorption amount, water absorption rate, and frictional charging voltage of the socks obtained in Example 10 and Comparative Example 21 were measured after washing. The results are shown in Table 8. The washing was performed 50 times according to JIS L-0217 103 method. The moisture absorption amount was measured by leaving the sample in a 23°C, 30% RH atmosphere for 12 hours to condition the moisture, then transferring it to a 30°C, 80% RH atmosphere and measuring the weight change before and after conditioning. The water absorption rate was measured by dropping a water drop of about 40 mg onto the sock from a height of 3 cm and measuring the time until the water was completely absorbed. The frictional electrification voltage was measured according to JIS L-1094.

[Table 8] From Table 8, it can be seen that the sock of Example 10 was made from fibers treated with the fourth fiber treatment material, and therefore had good moisture absorption amount, water absorption rate, and frictional electrification voltage. On the other hand, the sock of Comparative Example 21 was made from fibers not treated with the fourth fiber treatment material, and therefore had problems with moisture absorption amount, water absorption rate, and frictional electrification voltage. INDUSTRIAL APPLICABILITY The present invention relates to a fiber treatment material that can improve moisture absorption and release properties, and can be used as a fiber treatment material for, for example, yarn, knitted fabric, woven fabric, nonwoven fabric, etc.

───────────────────────────────────────────────────── Continued from the front page (81) Designated States: EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), CA, JP, KR, US (Note) This publication is based on the publication of the internationally published patent application by the International Bureau of Patents (WIPO). The effect of the international publication of the Japanese patent application (Japanese utility model registration application) related to this publication arises pursuant to Article 184-10, Paragraph 1 of the Patent Act (Article 48-13, Paragraph 2 of the Utility Model Act) and is unrelated to this publication.

Claims (9)

[Claims] 1. A fiber treatment material comprising a functional protein obtained by treating a protein with a crosslinking agent and a solvent-based resin. 2. A fiber treatment material comprising a functional protein obtained by treating a protein with a crosslinking agent and an aqueous resin. 3. A fiber treatment material comprising a water-soluble organic substance having an average molecular weight of 100 to 20,000 and a reactive modifier. 4. The fiber treatment material according to claim 3, characterized in that it contains chitosan in addition to the water-soluble organic substance and the reactive modifier. 5. The fiber treatment material according to claim 3 or 4, wherein the water-soluble organic matter is at least one of a protein, a protein derivative, and a polysaccharide. 6. The fiber treatment material according to claim 5, wherein the protein is at least one selected from the group consisting of fibroin, collagen, and wool. 7. A fiber treatment material comprising a functional protein obtained by treating a protein with a crosslinking agent and a reactive modifier. 8. Fibers treated with the fiber treatment material according to any one of claims 1 to 7. 9. A product treated with the fiber treatment material according to any one of claims 1 to 7.