JP2009074201A - Method for producing modified polyamide-based fiber material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for screening a processing agent having excellent economical efficiency, large functionality-imparting effects, excellent durability and high practical values and to provide a method for processing by paying attention to points at issue that improving processing of moisture retaining properties of nylon easily causes problems in feeling with insufficient durability of processing effects and a plurality of kinds of processing agents are expensive causing problems in economical efficiency with difficulty in obtaining reproducibility in quality of processed products etc. <P>SOLUTION: The method for producing a modified polyamide-based fiber material uses a polyfunctional type cationizing agent as a binder for animal and vegetable proteins and reacting a polyamide-based fiber material with the animal and vegetable proteins in water solvent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a method for producing a modified polyamide fiber material that has been modified so as to impart functionality such as moisture retention, wearing comfort, and texture to the polyamide fiber material.

In recent years, with the improvement of quality of life and increasing interest in environmental, safety and health issues, shape memory fibers, flame retardant and flame retardant fibers, UV shielding fibers, insect and mite fibers, antibacterial fibers and deodorant fibers Functional fibers such as high-texture / high-quality fibers and skin damage prevention fibers have been developed one after another, attracting the attention of the textile industry.

On the other hand, in order for the Japanese textile industry, which is being overwhelmed by China, to survive and coexist with China, it is considered indispensable to develop functional fibers with added value to the fibers. Development and commercialization of this is an extremely important issue for the Japanese textile industry.

In such a situation, the skin material is provided with a protein material such as sericin, silk fibroin, collagen, keratin, and soy protein on a synthetic fiber that is inferior in hygroscopicity due to poor hygroscopicity. Research that is gentle to the skin, that is, a texture that feels good to the skin, absorbs and releases moisture, deodorant, antistatic, antioxidant, ultraviolet shielding, antibacterial, skin damage prevention, etc. Some have been put to practical use.

As a known document of functional processing related to nylon, as described in Patent Document 1 or Non-Patent Document 1, a cross-section variation of the fiber such as a horizontal striped groove on the fiber surface or a tripod-type cross section is used. There is a description of the development of moisture absorbing and releasing nylon materials with changes.

Patent Document 2 describes a method of hydrophilizing a polyamide-based synthetic fiber by treating with an aqueous acid solution, followed by treatment with an aqueous solution of a crosslinking reagent having a plurality of glycidyl ether groups or carboxyl groups, and further treating with an aqueous polysaccharide solution. Has been.

Further, Patent Document 3 describes a functional processing method in which a nylon fiber is supported by a dyeing method in which tea extract, catechin, saponin and tannin are treated at a high temperature of 100 ° C. or higher.

As seen in these examples, there have been many studies on the practical application of nylon fiber modification processing methods, but each has its own merits and demerits. There is still room for research.

For example, the method of changing the cross-sectional variation of the fiber is insufficient and insufficient in terms of improving the moisture retention and feeling. The processing method using the cross-linking agent has complicated processes, and the processing cost increases because of processing using many expensive chemicals. When resin is used for coating, there is a concern about its harmfulness.

Furthermore, Patent Document 4 discloses a modified processing method characterized in that a synthetic fiber is treated using a solution comprising a sericin aqueous solution and a fixing agent as a treatment liquid. In this case, the sericin is insolubilized by chemically reacting water-soluble sericin with an insolubilizing agent, and the idea is to physically impart the insolubilized sericin to the hydrophobic synthetic fiber.

Therefore, in this case, there is a problem that sericin is gradually removed by washing. Moreover, although this patent document 4 does not include the concept of processing a yarn, there is a problem that if the yarn is processed according to this patent, the yarn turns yellow. Although there is a description that an insolubilizing agent is used, for example, aldehydes have a problem of generating formalin, and there is a problem that the use of a resinizing agent impairs the texture of fibers.

There is also the idea of reacting cyanuric chloride with polyamide fibers in an organic solvent, but in that case, the process and equipment for excluding severe irritating odors are complicated, and a solvent recovery process is also required, which is a special case. Since capital investment is required, a significant increase in cost is inevitable, making it economically impossible.
Japanese Patent No. 3281477 "Fiber and Industry" Vol.61, No.3, P-63 (2005) JP-A-9-296369 JP 2000-328469 A Japanese Patent No. 2588445

As described above, the moisture retention improvement processing method of nylon is likely to cause a problem in the texture, the durability of the processing effect is insufficient, the variety of processing chemicals is expensive and there is a problem in economy, processed products Focusing on issues such as the inability to obtain reproducibility in product quality, we screened high-practical value processing chemicals with excellent economic efficiency, large functionality, and excellent durability, and the practical use of processing methods Chemical research was conducted.

Polyamide-based fiber material, commonly known as nylon, is often used for clothing that touches the skin directly, such as pantyhose, innerwear, and sporting goods, and imparting functionality represented by wearing comfort is an extremely important issue. It is.

The present invention is a method for producing a modified polyamide fiber material, wherein a polyfunctional cationizing agent is used as a binder for animal and plant proteins, and the polyamide fiber material is reacted with the animal and plant proteins in an aqueous solvent. (Claim 1).

The present invention also provides a polyfunctional cationizing agent comprising a quaternary ammonium group as a cation group and having two or more epoxy groups or chlorohydrin groups as a reactive group in one molecule. The method for producing a modified polyamide fiber material according to claim 1 (claim 2).

Furthermore, the present invention is characterized in that the animal or plant protein is selected from sericin, silk fibroin, collagen, keratin, chitosan, chitin, gelatin, soybean protein, and a hydrolysis product thereof alone or as a mixture. A method for producing a modified polyamide fiber material according to any one of Items 2 (Claim 3).

Next, according to the present invention, the polyamide fiber material is 6,6-nylon, 6-nylon, 6,10-nylon, 11-nylon, 9-nylon and 4-nylon alone or as a mixture, or synthesized. 4. The method for producing a modified polyamide fiber material according to any one of claims 1 to 3, wherein the material is selected from a blended and woven fiber material with fibers and / or natural fibers (claim 4). .

Next, the present invention is a modified polyamide fiber material produced by the method according to any one of claims 1 to 4 (claim 5).

As a result of promoting development research on functional fiber-friendly functional fibers with excellent quality, such as economy, environment / safety, texture, durability, and processing effects of processed products, It has been found that functionalities such as moisture retention, wearing comfort and texture can be imparted to the polyamide fiber material by the method.

That is, the polyamide-based fiber material processed and modified by the method of the present invention becomes a functional fiber excellent in moisture retention and wearing comfort, is given a warm texture that is gentle to the skin, and is repeatedly durable and economical. In addition, excellent functional fibers can be obtained. Furthermore, since the method of the present invention can be processed by a simple operation method using an inexpensive drug, it is excellent in economic efficiency and has a high practical value.

The present invention is characterized in that a polyfunctional cationizing agent is used as a binder for animal and vegetable proteins, and the animal and vegetable proteins are reacted with a polyamide fiber material in an aqueous solvent. In other words, the present invention enables the functional cationizing agent and the animal and vegetable protein to be cross-linked with the polyamide fiber material in an aqueous solvent and simultaneously cationized to bind the animal and vegetable protein to the polyamide fiber material and simultaneously cationize. This is a method for modifying a polyamide-based fiber material, characterized in that it is subjected to a modification process on the basis of excellent economic efficiency, such as moisture retention and texture.

In order to achieve the object, the case of processing a yarn will be described as an example. The polyfunctional cationizing agent, the deaerating agent for eliminating foam, specifically, for example, Taspon SN- 1 (manufactured by LANXESS), an inside / outside difference preventing agent for eliminating processing spots on the inside and outside of the cheese, specifically, for example, MIRALAN QJ (manufactured by CIBA) etc. is added to the dyeing bath (in an aqueous solvent), A small amount of catalyst, specifically, for example, an epoxidation catalyst such as ammonium persulfate, zinc borofluoride, and tungsten complex, and a polyamide fiber material. Can be modified.

Examples of animal and plant proteins that can be used in the present invention include those selected from sericin, silk fibroin, collagen, keratin, chitosan, chitin, gelatin, soybean protein, and hydrolyzed products thereof alone or as a mixture.

Examples of the cationizing agent that can be used in the present invention include the industry magazine “Processing Technology” Vol. 26, no. 12 (1991) "Cationizing agents and their applications" Among low molecular weight compounds described in Table 1 on page 802, those having two or more reactive groups can be used. That is, a polyfunctional cationizing agent having two or more chlorohydrin groups or epoxy groups in one molecule, specifically, for example, Cationone UK (manufactured by Yushi Kogyo Co., Ltd.) can be mentioned. In this case, the cationizing agent can be used in combination with a monofunctional cationizing agent such as 3-chloro-2-hydroxypropyltrimethylammonium chloride in addition to the polyfunctional cationizing agent.

The embodiment of the present invention will be described in more detail in the case of processing a yarn.
In an aqueous solvent having a bath ratio of 1:10 to 1:30, 0.1 to 5% owf of degassing / foaming agent, 1 to 10% owf of inside / outside difference preventing agent, and 5 polyfunctional cationizing agent -20% owf, 1-10% owf of animal and plant protein and 0.1-1.0% catalyst are added at room temperature and stirred, dispersed or dissolved. Nylon fiber (yarn) is added to this, and the temperature is raised while circulating the liquid, and the temperature is kept at 100 to 150 ° C. for 0.5 to 3 hours. Then, it may be cooled, drained, washed with water, soaped with warm water and dried.

The fiber material to be processed of the present invention is a polyamide-based synthetic fiber generally called nylon, specifically 6,6-nylon, 6-nylon, 6,10-nylon, 11-nylon, 9- Nylon and 4-nylon alone or as a mixture, but other synthetic or semi-synthetic fibers such as polyurethane, polyester, polyacrylonitrile, acetate, polylactic acid, viscose rayon and natural fibers such as silk, wool, cotton, etc. It may be a blended / unwoven fiber. Further, the present invention can be applied to all forms of fiber materials such as yarn, woven fabric, knitted fabric, and non-woven fabric.

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these examples. In the examples,% means% by weight.

Example 1
A 1 kg cheese dyeing machine is charged with 12 L of water, and 1 kg of a 6,6 nylon cheese-wound thread (70d) is set. Then, while circulating the liquid, 10 g (1% owf) of Taspon SN-1 (manufactured by LANXESS) as a degassing agent, 30 g of MIRALAN QJ (manufactured by CIBA) as an internal / external difference inhibitor, and cationone as a polyfunctional cationizing agent -Dissolve by adding 100 g of UK (manufactured by Yushi Kogyo Co., Ltd.), 30 g of collagen (water-soluble collagen powder having an average molecular weight of about 10,000) as animal and plant protein, and 2 g of ammonium persulfate as a catalyst. The temperature is raised at 1.5 ° C./min. In a sealed state, and the temperature is maintained at 120 ° C. for 2 hours. Next, the temperature is lowered to 70 ° C., the liquid is drained, and washing with water is repeated twice.

Comparative Example 1
In place of the cationizing agent (Cathionone-UK) in Example 1, an equivalent amount of a polyfunctional epoxidizing agent having no cationic group, Epolite 40E (Kyoeisha Chemical Co., Ltd., ethylene glycol diglycidyl ether) was used under the same conditions. processed.

Comparison of effects:
(1) Moisturizing properties:
When the nylon thread thus modified was knitted into pantyhose and a moisture retention test was performed at 20 ° C. × 65% RH,
Comparative Example 1 was 4.5%, while Example 1 was 5.0%.
As is clear from the test results, it was confirmed that the processed product of the present invention has excellent moisture retention.

(2) Wear comfort test:
Examples of the above-mentioned processed and unprocessed products on the monitor were as follows: 1) feel, 2) smoothness, 3) suppleness, 4) dullness, 5) dampness, and wearing sensory tests. 1 was clearly superior to Comparative Example 1. Moreover, the evaluation after 20 times of washing was equally excellent.

(3) Yellowing:
In Example 1, no yellowing of the yarn was observed, but in the case of Comparative Example 1, the yellowing of the yarn was large, and the processed yarn of Comparative Example 1 was difficult to use in the field of white or light color. Met.

(4) Dyeability:
As a result of dyeing under the same conditions using an acid dye (Aminyl Red E-2BL (Taoka Chemical Co., Ltd.)), Example 1 was superior to Comparative Example 1 in dyeing density by about 20%.

Example 2
When the processing temperature in Example 1 was carried out at 130 ° C. for 2 hours, the moisture retention, wearing comfort, and dyeability were all excellent as in Example 1.

Example 3
A 1 kg cheese dyeing machine is charged with 12 L of water, and 1 kg of a 6,6 nylon cheese-wound thread (70d) is set. Next, while circulating the liquid, 10 g (1% owf) of Taspon SN-1 (manufactured by LANXESS) as a degassing agent, 30 g of MIRALAN QJ (manufactured by CIBA) as an inner / outer layer difference preventing agent, and a polyfunctional cationizing agent 100 g of cationonone-UK (manufactured by Yushi Kogyo Co., Ltd.), 30 g of sericin (water-soluble sericin powder having an average molecular weight of about 10,000) as animal and plant protein, and 2 g of ammonium persulfate as a catalyst are added and dissolved. The temperature is raised at 1.5 ° C./min in a sealed state, and the temperature is maintained at 130 ° C. for 2 hours. Next, the temperature is lowered to 70 ° C., the liquid is drained, and washing with water is repeated twice.

(1) Moisturizing properties:
When the nylon thread thus modified was knitted into pantyhose and tested for moisture retention at 20 ° C. × 65% RH, the unprocessed product was 4.1%. The quality processed product was 5.4%. As is clear from the test results, it was confirmed that the processed product of the present invention has excellent moisture retention.

(2) Wear comfort test:
As a result of wearing sensory tests on the above processed and unprocessed products on monitors, 1) feel, 2) smoothness, 3) suppleness, 4) dryness, and 5) stuffiness The example product was clearly superior to the unprocessed product. Moreover, the evaluation after 20 times of washing was equally excellent.

Example 4
When the processing temperature in Example 3 was performed at 120 ° C. for 2 hours, both the moisture retention and wearing comfort were excellent in the same manner as in Example 3.

According to the present invention, it is possible to firmly bind animal and plant proteins to a polyamide fiber material using a polyfunctional cationizing agent, and a fiber material excellent in moisture retention, wearing comfort, texture, durability, and dyeability. Can be obtained. Furthermore, since the method of the present invention can be processed by a simple operation method using an inexpensive drug, it is excellent in economic efficiency and has a high practical value.

Claims (5)

A method for producing a modified polyamide fiber material, wherein a polyfunctional cationizing agent is used as a binder for animal and vegetable proteins, and the animal and vegetable protein is reacted with the polyamide fiber material in an aqueous solvent. The polyfunctional cationizing agent is a polyfunctional cationizing agent containing a quaternary ammonium group as a cation group and having two or more epoxy groups or chlorohydrin groups as a reactive group in one molecule. A method for producing a modified polyamide fiber material according to claim 1. The animal or plant protein is selected from sericin, silk fibroin, collagen, keratin, chitosan, chitin, gelatin, soybean protein, and a hydrolyzate thereof alone or as a mixture thereof. The manufacturing method of the modified polyamide fiber material as described in 2. The polyamide fiber material is 6,6-nylon, 6-nylon, 6,10-nylon, 11-nylon, 9-nylon and 4-nylon alone or as a mixture, or synthetic fiber and / or natural fiber The method for producing a modified polyamide fiber material according to any one of claims 1 to 3, characterized in that the material is selected from the following blended / woven fabric materials. A modified polyamide fiber material produced by the method according to any one of claims 1 to 4.