JP2864256B2 - FIBER STRUCTURE CONTAINING ELASTIC YARN EXCELLENT IN DURATION AND PROCESS FOR PRODUCING THE SAME - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention is to improve the durability of elastic recovery force of a fiber structure containing an elastic yarn by improving light-resistant deterioration and chlorine-resistant deterioration. is there.

(Prior art) Elastic yarn is a fiber with elasticity like rubber, nylon,
These fibers are distinctly different from ordinary fibers typified by polyester.

The elastic yarn is usually composed of a high melting point high crystalline portion (hard segment) and a low melting point amorphous portion (soft segment) in a block copolymer having high elasticity,
Various elastic yarns are formed by a combination of the two. When the connection between the hard segment and the soft segment is a urethane bond or an ester bond, they are called a urethane elastic yarn and a polyester elastic yarn, respectively. The purpose of using the elastic yarn in a woven or knitted fabric is to make a fabric having elasticity. By using the elastic yarn, remarkable elongation and recovery can be obtained.

Elastic yarns are rarely used by themselves,
Many are used as cross-woven knitted articles by combining with other fibers such as nylon and cotton polyester. These elastic yarns or the knitted material containing the elastic yarns have a reduced durability (doughness or stretch of the fabric) due to a decrease in the resilience during use, so that the service life of the product is shorter than that of general clothing. The main causes of the decrease in resilience are the molecular deterioration of the elastic yarn by various environmental stamps such as light deterioration by light and oxygen in the atmosphere, chlorine deterioration by washing water or pool water, and hydrolysis by fungi. It is considered that this is because the molecular weight at which cleaved was reduced.

A method for preventing a decrease in the resilience has been intensively studied at the yarn production stage, and the performance thereof has been improving year by year. However, countermeasures at the yarn production stage are naturally limited by constraints and economics resulting from the production process conditions. Also, no effective countermeasures have been found at the dyeing stage. Therefore, the durability of the elastic yarn or the product containing the elastic yarn is still inferior to other synthetic resins, and measures to improve the durability are desired from various fields.

(Problems to be Solved by the Invention) An object of the present invention is to improve the light resistance deterioration and the chlorine resistance deterioration of a fiber structure containing an elastic yarn, thereby improving the elastic recovery performance of the elastic yarn and improving the durability of the product. To improve it.

(Means for Solving the Problems) The present invention relates to a fiber structure containing an elastic yarn, in which an antioxidant is diffused and permeated into the fiber to form a polyoxyphenol film on the fiber surface, thereby deteriorating chlorine resistance. The present invention is characterized by reducing the light resistance and light deterioration resistance and remarkably improving the durability of the product.

That is, the present invention diffuses and penetrates an antioxidant into a fiber structure including an elastic yarn dyed with any dye that can be dyed, such as an acid dye, a metal complex hydrochloric acid dye, a slender dye, a disperse dye, and a cationic dye. Further, it has been found that by further treating with a polyoxyphenol-based compound, synergistically excellent durable light and chlorine resistance can be obtained.

The elastic yarn in the elastic yarn-containing fiber structure according to the present invention may be essentially any as long as its molecular structure is composed of a soft segment and a hard segment,
Preferable specific examples include polyurethane elastic yarns, polyester elastic yarns, and other ones composed of a soft segment and a hard segment. These are used alone or in the form of a composite fiber in which two or more kinds are mixed.

Next, examples of the antioxidant for treating the elastic yarn-containing fiber structure include a hydroxybenzophenone-based compound, a benzotriazole-based compound, and an oxalic acid adoanilide-based compound.

More detailed examples of antioxidants used in the present invention include:
2,4-dihydroxybenzophenone, 2-hydroxy-
4-methoxybenzophenone, 2,2'-dihydroxy-
4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzopheno, 5-sulfonic acid, 2
-Hydroxy-4-n-octoxybenzophenenone,
2- (2'-hydroxy-3'-tert-butyl-5'-
Methoxyphenyl) -5-chlorobenzotriazole,
2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2-
(2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-bentylphenyl) -benzotriazole,
-(2'-hydroxy-3 ', 5'-di-tert-octylphenyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) -benzotriazole, 2- (2'- Hydroxy-3 ', 5'-di-tert-
Butylphenyl) -benzotriazole, 2- (2'-
Hydroxy-3 ', 5'-di-tert-bentylphenyl)
-Benzotriazole, 2-ethoxy-2'-ethyloxalic acid bisanilide, 2-ethoxy-5
There are tert-butyl-2'-ethyloxalic acid bisanilide and the like, but other chemicals can be used as long as they have a light stabilizing action and an active chlorine neutralizing action by adsorbing on the fiber. . A single compound or a combination of two or more compounds are selected from these compounds.

The amount of antioxidant used is usually 0.1 to 10% of fiber weight
wf, preferably 0.5 to 5% owf.

Next, examples of the polyoxyphenol-based compound for treating the elastic yarn include a phenolsulfonic acid formaldehyde resin, a novolak type resin sulfonate, a resole resin metasulfonate, a benzylated phenolsulfonate, a thiophenol compound, and a dihydroxydiol compound. There are compounds generally called synthetic tannins such as phenylsulfone compounds and natural tannic acids. In particular, when natural tannic acid is used, excellent elastic recovery performance with excellent durability can be obtained. The application of these polyoxyphenol compounds is sufficient to form a uniform film on the fiber surface, and is usually 0.5 to 1
0% owf, preferably in the range of 1-5% owf.

By forming a polyphenol film on the fiber surface, the antioxidant inside the fiber is prevented from diffusing to the outside of the fiber, and the antioxidant action of phenol works synergistically to provide light and chlorine resistance. It is thought that it improves.

Since the antioxidant does not dissolve in water or only a very small amount thereof, the treatment liquid is preferably prepared as a hydrophilic organic solvent liquid, a mixed solution of water and a hydrophilic organic solvent or an aqueous dispersion. Examples of the hydrophilic organic solvent solution include methanol, ethanol, ethylene glycol, N, N'-dimethylformamide and the like.

Next, as a method of treating the fiber structure with an antioxidant solution, a method of adsorbing simultaneously with the dye at the time of dyeing, a method of immersing in a separate bath after dyeing, a method of immersing simultaneously with the polyoxyphenol compound, a padkia method, There are a pad batching method, a spraying method, a method of adding a color paste and printing, and the like, but any method may be used, and the method is not particularly limited.

The immersion treatment method has a treatment temperature of 40 ° C. to 130 ° C., and the treatment liquid is most efficiently absorbed by the fiber at 60 ° C. to 90 ° C.
The pH of the processing solution is usually adjusted in the range of 3 to 5. The processing time is usually from 5 to 60 minutes, preferably from 10 to 30 minutes.

The dyed material thus treated alone improves the chlorine and light degradation performance of the fiber alone, but the durability of the dyed product is markedly improved by adding a polyoxyphenol compound. Above all, if natural tannin and tartar are treated according to a known method, their performance is dramatically improved. This is probably because the antioxidant action of natural tannin works synergistically. The formation of a film of natural tannin also improves the wet fastness.

In the case where the elastic yarn-containing fiber structure obtained by the practice of the present invention is a cross-knitted or mixed woven material, the antioxidant is also adsorbed to the mating fiber. That is, in the case of the immersion treatment, the antioxidant is first adsorbed to the elastic yarn first. This is presumably because the soft segment portion of the elastic yarn has a large gap between molecular structures even at a low temperature, and is physically adsorbed in the gap. However, as the temperature rises, the gap in the amorphous portion of the mating fiber expands, so that a part of the antioxidant adsorbed on the elastic yarn is desorbed and the phenomenon of adsorption to the mating fiber occurs. When the mating fiber is nylon 6, adsorption to nylon starts around 60 ° C., which is the secondary transition point. 70 ℃
If the treatment is performed at 9090 ° C. for 30 to 60 minutes, the adsorption distribution ratio of the antioxidant to the elastic yarn and the mating fiber reaches equilibrium.

The elastic fiber-containing colored fiber structure treated by the method of the present invention has surprisingly improved light fastness and chlorine fastness even with respect to the mating fiber blended with the elastic yarn.
This is considered to prevent gas-phase oxidative decomposition and liquid-phase oxidative decomposition of the dyeing dye by a light stabilizing action and an antioxidant action with the antioxidant adsorbed on the partner fiber.

In this manner, the fiber structure containing the elastic yarn obtained in the practice of the present invention has improved light fastness and chlorine fastness, so that power down (decrease in elastic recovery force) occurs during use and discoloration occurs. The appearance quality and physical properties of the product are not impaired, and the product life can be significantly improved.

Accordingly, the present invention is applicable to a wide range of medical clothing such as sports clothing such as leotards, swimwear, and ski wear, women's fashion clothing such as brassieres and girdles, pantyhose-socks, gloves, underwear, hands, and bandages. It can be expected to contribute to improving durability in the product field.

 Next, the present invention will be specifically described with reference to examples.

Example 1 Refined polyamide fiber (6 nylon 50d / 13)
t) and polyurethane-based elastic fiber (40d) knitted material (knitting ratio nylon / polyurethane = 8/2) with Kyanol Milling Blue 2RW2% owf (Nippon Kayaku Co., Ltd.) New Bonn TS (Nissaku Chemical Co., Ltd.) ) 2% owf with acetic acid
After dyeing in a treatment bath adjusted to H4 at a temperature of 95 ° C. for 40 minutes, washing and drying were performed. Next, each post-treatment was performed using the following post-treatment agents.

Treatment 1. Antioxidant only 2,2'-dihydroxy-4,4'-2% owf dimethoxybenzophenone (DHB) 2,2 ', 4,4'-tetrahydroxy 2% owf benzophenone (THB) Acetic acid (90%) 1 cc / L bath ratio 1:30 Washing and drying at 80 ° C for 20 minutes.

The benzophenone-based antioxidant was used to prepare a uniform aqueous dispersion using a dispersant and added to the treatment bath.

Treatment 2. Hyfic GM (synthetic tannin, manufactured by Dainippon Pharmaceutical Co., Ltd.) + DHB + THB Hyfic GM 3% DHB 2% THB 2% Bath ratio 1:30 Treatment temperature 80 ° C. Washing and drying for 20 minutes in 20 minutes.

Treatment 3. Natural tannin and tartar + DHB + THB Natural tannin 3% DHB 2% THB 2% Acetic acid (90%) 1cc / L Bath ratio 1:30 The following treatment is performed at a treatment temperature of 80 ° C for 20 minutes.

 Tartaric 1.5% Acetic acid 1cc / L Bath ratio 1:30 Washing and drying at a treatment temperature of 60 ° C for 20 minutes.

Comparative Example 1. As a comparative example, post-treatment was performed as follows using the dyed product of Example 1.

 Hyficus GM 3% owf Treatment temperature 80 ° C, time 20 minutes, then rinse and dry.

 The results are summarized in FIG.

Example 2. A scouring set cationically dyeable polyester (50d / 13
t) and polyurethane elastic fiber (40d) mixed knitting material (knitting ratio cationic dyeable / polyurethane = 8/2) Kayacryl Pink B-ED 1% owf (Nippon Kayaku Co., Ltd.) 3 g / L with acetic acid and sodium acetate
After dyeing in a dyeing bath adjusted to a temperature of 120 ° C. for a time of 50 minutes, it was washed with water. Next, tannic acid 3% owf, 2- (2 '
-Hydroxy-3'-tbutyl-5'-methoxyphenyl) -5-chlorobenzotriazole 1% owf, 2-
1% owf of (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -benzotriazole was adjusted to pH 4 with acetic acid.
The dyed cloth was heat-treated at a temperature of 80 ° C. for 20 minutes. Further, 2% owf of antimony potassium tartrate was immersed at a high temperature for 20 minutes at 60 ° C. in a treatment bath adjusted to pH 4 using acetic acid. The benzotriazole-based compound was prepared into a uniform aqueous dispersion using a dispersant and added to the treatment bath. The results are summarized in FIG.

Comparative Example 2. As a comparative example, the dyed fabric of Example 2 was treated with tannic acid and quarry stone without using a benzotriazole-based compound.

 The results are summarized in FIG.

Light embrittlement test method Sample: 30% elongation in measurement direction Light irradiation condition: irradiate for 20, 40, 60, 80, 100 hours using JIS L0842 carbon arc lamp type light resistance tester.

Strength measures the stress at the time of 80% extension.

Chlorine embrittlement test method Sample: 30% elongation in measurement direction Chlorine treatment condition: Effective chlorine 300ppm pH unadjusted (approximately 9.8 when using sodium hypochlorite)
Treat for 1 hour, dehydrate and air dry to give 1 day (test solution is always stirred).

The treatment is repeated for 2, 5, 10, and 15 days in this repetition.

[Brief description of the drawings]

FIGS. 1A and 1B and FIGS. 2A and 2B are graphs showing light embrittlement (A) and chlorine embrittlement of Examples and Comparative Examples, respectively.

Claims (4)

(57) [Claims] 1. A dyed fiber structure comprising an elastic yarn composed of a soft segment and a hard segment, wherein the fiber structure contains an antioxidant diffused and penetrated into the fiber, and the fiber surface is coated with a polyoxyphenol film. A colored fiber structure comprising an elastic yarn having excellent elastic recovery power durability. 2. The fibrous structure according to claim 1, wherein the elastic yarn essentially comprises a polyurethane elastic fiber or a polyester elastic fiber. 3. The antioxidant is a hydroxybenzophenone compound, a benzotriazole compound or an oxalic acid anilide compound, and the polyoxyphenol compound is a phenolsulfonic acid formaldehyde resin.
A compound generally referred to as a synthetic tannin or a natural tannic acid, such as a sulfonated product of a novolak type resin, metasulfonic acid of a resole resin, benzylated phenolsulfonic acid, a thiophenol compound, a dihydroxydiphenylsulfone compound, and the like. Textile structure. 4. A method for producing a colored fiber structure by dyeing a fiber structure containing an elastic yarn composed of a soft segment and a hard segment, wherein the fiber structure contains an antioxidant during or after dyeing. By treating with a treatment liquid and a treatment liquid containing a polyoxyphenol compound,
A method for producing a colored fiber structure comprising an elastic yarn which contains an antioxidant diffused and infiltrated into the inside of a fiber, and has an excellent elastic recovery strength and a fiber surface coated with a polyoxyphenol film.