JP2006124872A - Multipurpose natural polymer conjugate fiber and textile thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide technologies for spinning a water-insoluble conjugate fiber from water-soluble polymer materials especially natural polysaccharide and polyamino acid aqueous solutions and producing textiles from the obtained conjugate fiber. <P>SOLUTION: The conjugate fiber is obtained by mixing an anionic polymer electrolytic aqueous solution and a cationic polymer aqueous solution and using polymer conjugate formation at the interface of the both aqueous solutions. The conjugate fiber and the textiles have practical strength, dye-affinity, edibility, chemical substance adsorptivity/permeability, and perfect biodegradability, that is, even if disposed in natural environment, the fiber and the textiles are decomposed into carbon dioxide and water. The natural polymer conjugate fiber and textiles thereof can be applied to general purpose applications such as fiber industry products, foods, medical care, agriculture and sanitary goods. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a fabric produced from a novel natural polymer conjugate fiber. The natural polymer conjugate fiber in the present invention is a conjugate fiber produced by the inventor of the present invention using the raw materials and production methods described in Japanese Patent Publication 2002-339155. In the present application, this production method is referred to as “aqueous solution interspinning method”. Natural polymer composite fibers produced by the aqueous interfacial spinning method are safe in the manufacturing process, use only water with no environmental pollution and dilute acetic acid as solvents, and have the characteristics that can be produced continuously without using special equipment. It can be used for general industrial production of water-soluble polymer composite fibers and woven fabrics. In addition, it is a particularly effective technique for reducing the manufacturing cost due to the use of water as a solvent, improving the safety of the manufacturing process, and reducing waste liquid during manufacturing.

  It is well known that synthetic fiber nylon was born from imitation of natural raw silk. Aiming at the industrialization of synthetic silk that exceeds the performance of nylon fibers, polyamino acid fibers have been extensively studied for about 25 years since about 1945, and were expected as promising new fibers. However, the high cost of raw material amino acids and dichloroacetic acid as a spinning solvent and the safety of the solvent have been problems. Some polyamino acid fibers, especially polyglutamic acid, were the most promising candidates for industrialization, but the high water solubility of this product itself was a drawback, and there was no use that could make use of the performance of polyglutamic acid fibers. Was abandoned. In the current textile industry, direct spinning of composite fibers from aqueous solutions of polyamino acids or polysaccharides is one of the most ideal but difficult technical challenges.

  As the above background shows, the water-soluble natural polymer compound is expected to be widely used as a useful fiber over silk if it can be made into a fiber. There have been two problems in the past to achieve this. One is the solvent, and the other is the non-water resistance of the fiber derived from the water solubility of the starting polymer.

  In principle, water-insoluble fibers cannot be created from aqueous solutions of water-soluble polymers. Therefore, a technique for spinning a water-soluble polymer in water to form a water-insoluble fiber has not been reported so far. The “aqueous solution interspinning method” developed by the present inventor is a method using a natural polymer aqueous solution and utilizing a polymer reaction at the interface between aqueous solutions or between water and a water-soluble solvent. The greatest advantage is that it enables efficient production of polymer fibers.

  In the methods described in Patent Publications H10-279604 and 2002-339155, for example, chitosan and anionic polysaccharide (especially gellan gum) which are cationic polysaccharides are water-soluble polymers that can be used for polymer reaction at the solution interface. ), A composite fiber of chitosan and gellan can be spun continuously from the interface of both aqueous solutions.

Patent Publication H10-279604 Patent Publication 2002-339155

  As a result of intensive studies on the above-described continuous spinning method of natural polymer composite fibers from water, the present inventors have conducted a spinning technique for continuously producing natural polymer composite fibers and the post-spinning that enables the spinning technology. Was developed and described in patent publication 2002-339155. The fiber production method by the interfacial reaction of water-soluble polymers uses water as a medium, so the temperature is about room temperature and the pH is near neutral, that is, under mild conditions close to the living body or the natural environment. . In addition, there is an advantage that the physical shape of the fiber can be easily controlled by changing the type of polymer electrolyte such as natural polysaccharide or polyamino acid.

  Regarding the primary quality of natural polymer conjugate fibers, there are a series of consecutive holidays reported by the present inventors. The most important ones are listed. (i) Renewable materials, biomass and raw material production by fermentation, (ii) Water-insoluble fiber formation from water-soluble polyelectrolyte, (iii) Low cost interfacial reaction solvent (water, dilute acetic acid), (iv) Simple Continuous spinning, (v) low-cost dehydration solvents (methanol, ethanol, acetone), (vi) fiber strength improvement by crosslinking (chemical crosslinking agent, photocrosslinking, enzyme crosslinking), (vii) good dyeing properties, ( viii) Biodegradation in the natural environment.

  As described above, natural polymer composite fibers produced by aqueous solution interfacial spinning have a production method that is harmless to safety and the environment, ease of mass spinning equipment, practical mechanical properties, and complete biodegradability. Because it combines, it is a new multipurpose and core fiber material.

  An object of the present invention is to provide a technique for producing a natural polymer conjugate fiber, for example, a conjugate fiber spun from chitosan and gellan on a large scale, and producing a fabric from the obtained conjugate fiber.

  The present application relates to a water-soluble natural polymer composite fiber produced by a solution interface spinning method characterized by the use of cationic polyelectrolytes such as polyamino acids and natural polysaccharides, anionic polyelectrolytes, and aqueous solutions thereof. The present invention relates to a fabric manufactured from fibers, and a manufacturing technique thereof.

  When a polyamino acid is used as the anionic polymer electrolyte, it is a polyglutamic acid having a carboxyl group. When a polyamino acid is used as the cationic polyelectrolyte, it is polylysine or polyornithine having an amino group. As anionic polyelectrolytes other than polyamino acids, a variety of composite fibers are spun using chitosan, a natural polysaccharide as a cationic polyelectrolyte, gellan as an anionic natural polysaccharide, and polyacrylic acid, a kind of vinyl polymer. be able to.

  Polylysine-gellan gum composite fiber, polyornithine-gellan gum fiber, chitosan-polyglutamic acid composite fiber, polylysine-polyglutamic acid composite fiber, polyornithine-polyglutamic acid composite fiber can be spun using the water-soluble polyelectrolytes listed above. is there. Further, chitosan-polyacrylic acid fiber can be spun as a composite fiber not containing a polyamino acid as a polymer electrolyte component.

  From the above physical property tests, the PIC fabric is completely inferior in terms of performance as a fabric even when compared with both PE, which is the current main textile material, and silk, which is the finest natural fiber. From the quantified physical properties, it was found that PIC fabric is a textile material with a new texture different from PE fabric and silk fabric. It can be concluded that PIC fabric is a new natural fabric that combines the comfort and breathability of natural materials with the touch of skin.

  The natural conjugate fiber fabric of the present invention can be applied to all conjugate fibers listed in [0007] in addition to chitosan-gellan conjugate fibers.

BEST MODE FOR CARRYING OUT THE INVENTION

[Example 1]
By using the above-mentioned techniques, water-insoluble fibers can be obtained from these aqueous solutions using chitosan and gellan gum, which have not been able to be directly converted into fibers from aqueous solutions, and polylysine and polyglutamic acids, which are polyamino acids. Can now. As a production example, FIG. 1 shows chitosan-gellan conjugate fiber spun using the apparatus disclosed in Japanese Patent Publication No. 2002-33915 and wound on a bobbin.

Example of production of natural polymer composite fiber fabric

[Example 2]
Examples of use of the present invention will be described in more detail by the following examples. However, this example does not limit the effectiveness of the present invention.

  A large amount of chitosan-gellan composite fiber was spun and wound around four bobbins each with the same length. Four fibers were simultaneously wound on one bobbin using a re-recycler. The combined fibers were processed using a ring spinning machine to create a twisted yarn. Fabrics using chitosan-gellan composite fibers (hereinafter abbreviated as PIC fibers) were made with a rapier loom. In the rapier loom, polyester (hereinafter abbreviated as PE), silk, cotton, and PIC were used as warp yarns. Eight kinds of fabrics were made using four kinds of fibers. There are four types of fabrics that contain PIC in warp and / or weft, PIC × PIC fabric, PIC × PE fabric, PIC × cotton fabric, and PIC × silk fabric. The fiber length of the chitosan-gellan composite fiber necessary for making a 10 cm × 10 cm PIC × PIC fabric was about 130 m for the warp and about 120 m for the weft. The weaving density of the produced fabric was 63 vertical and 58 horizontal per inch. Since weaving at the same time using an automatic loom, weaving density showed the same value for all four PIC fabrics.

Kawabata, who was developed by Kawabata et al. In 1972 as a device for measuring mechanical properties, mainly for measuring the texture of fabrics
The mechanical properties and texture of fabrics made by Evaluation System (KES) were evaluated. As a comparative sample of PIC x PIC fabric, silk x silk fabric and PE x PE fabric were used.

[Example 3]
As for compression recovery, the resilience due to compression was equivalent because all three types of samples showed almost the same numerical value. The compression linearity is compressibility with a small force, and corresponds to the texture of the fabric at the moment of touching with the skin. PIC × PIC <PE × PE
<It increased in the order of silk x silk. The work of compression was the ease with which the fabric was compressed, and the result was that it was easier to compress in the order of silk x silk <PE x PE <PIC x PIC.

  The bending stiffness of the sample in which PIC is woven in the warp or weft of the fabric is much larger than that of silk and PE, suggesting that bending is difficult. Bending hysteresis represents the elasticity to bending, and as the value increases, the resilience to bending decreases. The numbers increased in the order of silk x silk <PE x PE <PIC x PIC.

  Regarding the average surface friction coefficient, PIC x PIC fabric shows a smaller value than other fabrics. Since PE fibers and silk fibers are twisted a large number of fine diameter fibers, the friction coefficient of the surface of the twisted yarn is large. This is considered to occur due to the difference in the form of twisted yarns of PIC fiber, PE fiber and silk fiber. In the case of PIC fiber, the surface of the twisted yarn was smooth.

The cold feeling of contact is a thermal physical property when touched by the skin. A large value indicates a strong cold feeling, and a small value indicates a strong warm feeling. PIC x PIC <Silk x Silk
<From PE x PE, it was found that PIC x PIC fabric has a strong feeling of warmth. The steady thermal conductivity of PIC × PIC and silk × silk fabric showed the same value, and the value of PE × PE fabric was large. It was found that PIC x PIC fabric has the same thermal conductivity as silk.

  PIC fabrics could be woven by automatic looms as well as polyester and silk. This directly indicates that PIC fabric can be dressed. Furthermore, chitosan, one of the main components of PIC fabric, has antibacterial properties, so it can be applied to medical clothing. Regarding the production of natural polysaccharides, chitosan is the second largest after cellulose (cotton), and is produced from shrimp husks and rice husks, which are industrial wastes. From the viewpoint of recycling waste, PIC fabrics are expected to be applied to various fields as a new generation textile material.

  Natural polymer composite fibers produced by the aqueous interfacial spinning method have practical strength, dyeability, edible properties, adsorption / permeability of chemical substances, and even when discarded in the natural environment, they are converted into carbon dioxide and water by microorganisms. Has complete biodegradability to be degraded. Therefore, the natural polymer conjugate fiber and the woven fabric shown in the present invention can be used for various purposes such as food, medicine, agriculture, sanitary goods as well as the textile industry.

2 is a photograph of a chitosan-gellan composite fiber according to the present invention.

It is a schematic diagram of a PIC fabric sample according to the present invention.

Claims (5)

A method for producing a composite fiber comprising mixing an aqueous solution of an anionic polyelectrolyte and an aqueous solution of a cationic polyelectrolyte and utilizing formation of a polymer complex at the interface between the two aqueous solutions, and a woven fabric obtained from the composite fiber . 2. The composite fiber and the woven fabric thereof according to claim 1, wherein the anionic polymer electrolyte is polyglutamic acid or gellan. 2. The composite fiber and the woven fabric thereof according to claim 1, wherein the cationic polyelectrolyte is polylysine, polyornithine or chitosan. The combination of cationic and anionic polyelectrolytes is chitosan-gellan, polylysine-gellan, polyornithine-gellan, chitosan-polyglutamic acid, polylysine-polyglutamic acid, and polyornithine-polyglutamic acid 1. The composite fiber and woven fabric thereof according to 1. 5. A method for producing a conjugate fiber and a woven fabric thereof according to claim 4.