Protein coated yarn

Abstract

To provide protein coating finished yarn in which, in a chemical fiber which does not exhibit swelling property to water, a protein coating is formed and fixed on a fiber surface, for applying new functions (suppression of ultraviolet radiation deterioration, dyeing property of a natural dye, improvement of a wearing comfort, and the like) to the chemical fiber, and in fixing the protein to a natural fiber which exhibits swelling property to water, a coating of a non-water soluble protein is formed and fixed on a fiber front layer, the non-water soluble protein coating not eluting in water washing, for applying new functions (improvement of dyeing property and recovery from wrinkles).SOLUTION: The invention is configured so that, aluminum chloride hexahydrate Al(H2O)6Cl3 is hydrolyzed for finally forming a polymer of aluminum hydroxide, the polymer of aluminum hydroxide is fixed to a fiber surface by hydrogen bond for generating many OH groups on the fiber surface, through the OH groups, a protein or a protein hydrolyzate is fixed to the fiber surface through hydrogen bond and chelate bond (formation of chelate complex), then the protein or the protein hydrolyzate is made into a water insoluble state for forming a stable protein coating on the fiber surface.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to the discovery that the product obtained by hydrolysis of aluminum chloride hexahydrate is effective for forming a water-insoluble protein coating on the surface of natural and synthetic fibers. [Background technology]

[0002] Surface finishing processes for textiles have been used to impart new functionality to textiles and produce and supply high-value-added textile products. Focusing on the properties of proteins as finishing agents, the N-terminus, C-terminus, basic, and acidic amino acid residues are positively or negatively charged in aqueous solution, promoting the adsorption of dye molecules that ionize in water. Protein-coated fibers have been shown to improve the dyeability of direct dyes (Non-Patent Document 1). Meanwhile, because proteins contain many hydrophilic residues, they form hydrogen bonds and chelate complexes with metal ions in water, losing their water solubility and stabilizing their properties. For example, impregnating cotton fibers with low-molecular-weight protein and then infiltrating aluminum ions into the fibers connected the hydroxyl groups of cellulose and protein through hydrogen bonds and chelate complexes, resulting in the formation of crosslinks between molecular chains and improving the wrinkle recovery of cotton fabric (Patent Document 1). Furthermore, cotton fabric wrinkle recovery has been improved by impregnating cotton fibers with low-molecular-weight proteins and then reacting them with crosslinking agents such as butanetetracarboxylic acid or urethane resin to actively form crosslinks between molecular chains (Non-Patent Document 2).

[0003] However, because both of these methods require the penetration of low-molecular-weight proteins into the fiber, they are difficult to apply to coating synthetic fibers that do not swell in water. For example, Kevlar fibers exhibit high strength but are susceptible to degradation by UV radiation, requiring some kind of protection when exposed to sunlight for long periods outdoors (Non-Patent Document 3). On the other hand, keratin, a type of protein, contains amino acids that absorb UVA (320-400 nm) and carbonylate (Non-Patent Documents 4, 5). Therefore, a keratin protein coating can reduce the UV sensitivity of coated materials. Therefore, we developed a technology to fix a keratin protein coating to the surface of Kevlar fibers. On the other hand, polyester fibers have a standard moisture regain of only 0.4%, so when used in textiles, their low moisture absorption can lead to sweating and a stuffy feeling, making them uncomfortable to wear. Therefore, we developed a technology for coating polyester fibers with hydrophilic proteins, because coating fiber surfaces with hydrophilic materials improves comfort and enables the development of new functional polyester fibers. Conventional methods for immobilizing hydrophilic proteins on fibers using crosslinking agents such as urethane resins involve first coating the fiber with the protein and then crosslinking the protein with the resin to immobilize it. This method tends to result in a resin layer on the outermost layer of the fiber, which does not necessarily improve comfort. New processing techniques must be developed to create a protein layer on the outermost layer. Furthermore, when immobilizing hydrophilic proteins on natural cellulosic fibers such as cotton and linen, conventional crosslinking agents such as urethane resins tend to form a resin layer on the outermost layer of the fiber, potentially reducing the comfort of the natural fibers through processing (Non-Patent Documents 1 and 2). The method described in Patent Document 1 uses aluminum chloride instead of a crosslinking resin, which has relatively little effect on comfort. However, there are limitations on the amount of aluminum chloride that can be used, resulting in incomplete fixation and immobilization of the protein component. Furthermore, there are limitations on the control of the immobilization amount, so improvements are needed. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Yutaka Kawahara, Patent Application No. 6-339421, Method for treating natural fibers. [Non-patent literature] [Non-Patent Document 1] Yutaka Kawahara, Masatoshi Shioya, Akira Takaku, American Dyestuff Reporter, Vol. 85, No. 9, pp. 88-91 (1996), Effect of non-formaldehyde finishing using urethane and water-soluble silk powder compounds on dyeing and mechanical properties of cotton fabrics. [Non-patent document 2] Yutaka Kawahara, Hirokazu Furuta, Masatoshi Shioya, Journal of the Society of Fiber Science and Technology, Vol. 52, No. 10, pp. 562-565 (1996), Processing of cotton using water-soluble silk fibroin. [Non-patent document 3] Akinobu Yamaguchi, Tsuguo Nishimura, Taketo Uomoto, Proceedings of the Annual Meeting of the Concrete Institute, Vol. 18, No. 1, pp. 1161-1166 (1996), Fundamental Study on Evaluation Methods for Deterioration Phenomena of Various Fibers Caused by Ultraviolet Rays. [Non-patent document 4] Jens J. Thiele, Sherry N. Hsieh, Karlis Briviba, Helmut Sies, Journal of Investigative Dermatology, Vol. 113, No. 3, pp. 335-339 (1999), Protein oxidation in human stratum corneum: susceptibility of keratins to oxidation in vitro and presence of a keratin oxidation gradient in vivo. [Non-patent document 5] Toshihiro Fujii, Yumiko Ito, Journal of the Japanese Society of Cosmetic Chemists, Vol. 52, No. 2, pp. 99-104 (2018), Detection of carbonyl proteins induced by long-wavelength ultraviolet light and blue light using keratin film. [Non-patent document 6] Hideyuki Ikada, Yukihiko Takeuchi, Michio Ashida, Proceedings of the Polymer Research Society, Vol. 49, No. 6, pp. 527-533 (1992), Examination of the possibility of polylactic acid as a photodegradable polymer. [Non-Patent Document 7] Yutaka Kawahara, Motohiro Hanada, Shota Onosato, Wataru Takarada, Midori Takasaki, Koji Takeda, Yoshimitsu Ikeda, Takeshi Kikutani, Journal of Macromolecular Science, Part B, Volume 58, Issue 10, Pages 828-846 (2019), High-speed melt spinning of polylactide / poly(butyleneterephthalate) bicomponent fibers:mechanism of fiber structure development and dyeing behavior. Summary of the Invention [Problem to be solved by the invention]

[0005] For chemical fibers that do not swell in water, a protein film can be formed and fixed on the fiber surface, making it possible to impart new functions (suppression of deterioration due to UV radiation, improved comfort, etc.). Even when fixing proteins to natural fibers that swell in water, it is possible to form and fix a water-insoluble protein film on the fiber surface that will not dissolve in water when washed, making it possible to impart new functions (dyeability, wrinkle recovery, etc.). [Means for solving the problem]

[0006] When aluminum chloride hexahydrate Al(H2O)6Cl3 is hydrolyzed to an aqueous solution, the following reaction occurs, producing a polymer of basic aluminum chloride [Al2(OH) n Cl 6-n ] m is known to be formed. TIFF0007777270000001.tif25159Polymers of basic aluminum chloride are widely used as precipitants. Polymers of basic aluminum chloride are called polyaluminum chloride (PAC) and are commercially available. When this PAC is further dried, water-insoluble aluminum hydroxide Al(OH)3 is produced. Aluminum hydroxide reflects the structure of PAC and is a polymer [Al2(OH)6]. m The precipitated aluminum hydroxide polymer has the ability to fix proteins through hydrogen bonds and chelate bonds (formation of chelate complexes). When the above-mentioned aluminum chloride hexahydrate hydrolysis and drying reactions are carried out on the fiber surface, the hydrochloric acid generated by the hydrolysis of aluminum chloride hexahydrate can erode the fiber surface, forming fine grooves and pores on the fiber surface, even in synthetic fibers that do not swell in water. The erosive action is particularly intensified during the drying process, as the concentration of hydrochloric acid increases. The grooves and pores formed by erosion increase the surface area of ​​the fiber, making them convenient for the attachment of aluminum hydroxide polymers formed by the insolubilization of basic aluminum chloride polymers. Although aramid fibers such as Kevlar and polyester fibers do not swell in water, they absorb moisture from the atmosphere and form hydrogen bonds, allowing aluminum hydroxide polymers to be stably attached to the surface of these fibers (especially in the grooves and pores). As a result, the fiber surface becomes rich in OH groups of aluminum hydroxide, and the protein is stably fixed to the aluminum hydroxide through hydrogen bonds and chelate bonds (formation of chelate complexes), resulting in the fiber surface being coated with protein.

[0007] When treating natural cellulosic fibers such as cotton and hemp, glycosidic bonds are hydrolyzed by hydrochloric acid, so it is necessary to perform a treatment to remove the hydrochloric acid as needed. Specifically, by applying a sodium carbonate aqueous solution to the fibers before the drying process to perform a neutralization treatment, it is possible to prevent the hydrolysis reaction of cellulosic fibers caused by hydrochloric acid while fixing aluminum hydroxide polymers to the fiber surface. The fixed aluminum hydroxide polymers help to coat the fiber surface with proteins. Based on the above idea, the present invention was achieved through extensive research. [Effects of the Invention]

[0008] This makes it possible to impart the diverse functions of various proteins to synthetic fibers, facilitating the development of new functional textile products. For example, polylactic acid fibers, which are composed of ester bonds similar to polyester fibers, are susceptible to degradation by ultraviolet light from germicidal lamps and other sources (Non-Patent Document 6). By forming a coating of ultraviolet-absorbing proteins (e.g., keratin or sericin) on the fiber surface using the method of the present invention, degradation of polylactic acid fibers due to UV exposure can be reduced. Furthermore, because keratin and sericin are easily dyed with natural dyes, fibers coated with these proteins can be dyed using natural dyes at temperatures of approximately 40°C. For example, when polylactic acid fibers are dyed under industrial dyeing conditions (98–130°C), disperse dye fixation is poor and significant thermal shrinkage occurs after dyeing. Therefore, despite being a fiber that meets the SDGs, the use of polylactic acid fibers as clothing fibers is hindered by the inability to dye them (Non-Patent Document 7). If this invention is applied to polylactic acid fibers, the surface protein coating can be colored with natural dyes at around 40°C, overcoming the problem of thermal shrinkage of fibers during dyeing processes, and it is expected that polylactic acid fibers will be used in the general clothing field. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a diagram showing the difference in spectral reflectance curves between a Kevlar 29 fabric (treated fabric) that has been treated to form a feather keratin coating and an untreated Kevlar 29 fabric (untreated fabric) that does not have the coating formed thereon (Example 2). DETAILED DESCRIPTION OF THE INVENTION [Example]

[0010] A Kevlar 29 fabric sample was immersed in a 10% aqueous solution of aluminum chloride hexahydrate for 2 minutes, pulled out, and dried (105°C, 30 minutes). The fabric in this state was immersed in a 10% aqueous solution of water-soluble feather keratin hydrolyzate for 2 minutes, pulled out, and dried (105°C, 30 minutes), and then heat-treated at 170°C for 5 minutes. The fabric was then washed in hot water (80°C, 2 minutes) and dried (105°C, 30 minutes) to obtain a Kevlar 29 fabric with a feather keratin coating. The weight gain of the Kevlar 29 fabric after this series of operations was 15.4%. [Example]

[0011] The spectral reflectance curve of the Kevlar 29 fabric obtained in Example 1 was measured and compared with that of an untreated Kevlar 29 fabric not coated with feather keratin to examine the difference in ultraviolet absorption characteristics between the two (see Figure 1). In the range of 360 to 700 nm, the reflectance of the treated product was always low. [Example]

[0012] The Kevlar 29 fabric obtained in Example 1 and an untreated Kevlar 29 fabric without a feather keratin coating were subjected to ultraviolet irradiation treatment using a carbon arc lamp in accordance with JIS L0842 using an autofade meter (U48AU, Suga Testing Instruments Co., Ltd.) for 25 hours, and the tensile strength of the warp yarns constituting the fabric after irradiation was compared between the treated and untreated fabrics. As a result, the warp yarns of the treated fabric had a tensile strength of 13.19±0.98 gf / d, while the warp yarns of the untreated fabric had a tensile strength of 12.62±0.56 gf / d. [Example]

[0013] The Kevlar 29 fabric obtained in Example 1 and an untreated Kevlar 29 fabric without a feather keratin coating were subjected to ultraviolet irradiation treatment using a carbon arc lamp in accordance with JIS L0842 using an autofade meter (U48AU, Suga Testing Instruments Co., Ltd.) for 40 hours, and the tensile strength of the warp yarns constituting the woven fabric after irradiation was compared between the treated and untreated fabrics. As a result, the warp yarns of the treated fabric had a tensile strength of 13.33 ± 0.72 gf / d, while the warp yarns of the untreated fabric had a tensile strength of 11.63 ± 1.18 gf / d. [Example]

[0014] A polyester nonwoven fabric sample was immersed in a 10% aqueous solution of aluminum chloride hexahydrate for 2 minutes, pulled out, and dried at 30°C. The nonwoven fabric in this state was immersed in a 10% aqueous solution of water-soluble feather keratin hydrolyzate for 2 minutes, pulled out, and dried at 30°C. It was then washed with hot water (80°C, 2 minutes), and air-dried at room temperature to obtain a polyester nonwoven fabric with a feather keratin coating. The weight gain of the polyester nonwoven fabric after this series of operations was 12.1%. [Example]

[0015] A polyester nonwoven fabric sample was immersed in a 10% aqueous solution of aluminum chloride hexahydrate for 2 minutes, pulled out, and dried at 100°C. The nonwoven fabric in this state was immersed in a 10% aqueous solution of water-soluble feather keratin hydrolyzate for 2 minutes, pulled out, and dried at 100°C. It was then washed with hot water (80°C, 2 minutes), and air-dried at room temperature to obtain a polyester nonwoven fabric with a feather keratin coating. The weight gain of the polyester nonwoven fabric after this series of operations was 15.3%. [Example]

[0016] A 10% aqueous solution of aluminum chloride hexahydrate was sprayed on both sides of a cellulose nonwoven fabric sample, followed by a 10% aqueous solution of water-soluble feather keratin hydrolyzate, and finally a 10% aqueous solution of sodium carbonate, followed by drying at 30°C. The sample was then washed with hot water (80°C, 2 minutes) and air-dried at room temperature to obtain a cellulose nonwoven fabric coated with feather keratin. The weight gain of the cellulose nonwoven fabric after this series of operations was 31.5%. [Example]

[0017] A 10% aqueous solution of aluminum chloride hexahydrate was sprayed on both sides of a cellulose nonwoven fabric sample, followed by a 10% aqueous solution of water-soluble feather keratin hydrolyzate, and finally a 10% aqueous solution of sodium carbonate, followed by drying at 100°C. The sample was then washed with hot water (80°C, 2 minutes) and air-dried at room temperature to obtain a cellulose nonwoven fabric coated with feather keratin. The weight gain of the cellulose nonwoven fabric after this series of operations was 35.1%. [Example]

[0018] A 10% aqueous solution of aluminum chloride hexahydrate was sprayed on both sides of a cellulose nonwoven fabric sample, followed by a 10% aqueous solution of water-soluble feather keratin hydrolyzate, and finally a 10% aqueous solution of sodium carbonate, followed by drying at 160°C. The sample was then washed with hot water (80°C, 2 minutes) and air-dried at room temperature to obtain a cellulose nonwoven fabric coated with feather keratin. The weight gain of the cellulose nonwoven fabric after this series of operations was 36.0%.

Claims

1. A method for immobilizing proteins or protein hydrolysates on fibers by hydrolyzing aluminum chloride hexahydrate, immobilizing a portion of the product on the fiber surface, and forming hydrogen bonds or chelate complexes with the immobilized product.

2. 2. Fibers having proteins or protein hydrolysates immobilized thereon by the method of claim 1.

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