JP2959034B2 - Dyed product and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a dyed knitted fabric containing polyurethane elastic fibers and a method for producing the same. More specifically, the present invention provides a dyed fabric of a cross-knitted fabric containing a polyurethane elastic fiber containing a specific metal compound which has prevented deterioration in various chlorine-containing environments, and a method for producing the same.

(Prior art) Polyurethane elastic yarn obtained from 4,4-diphenylmethane diisocyanate, a polyhydroxy polymer having a relatively low degree of polymerization and a polyfunctional active hydrogen compound has a high degree of rubber elasticity, tensile stress, recoverability, etc. Because of its excellent mechanical properties and its excellent thermal behavior, it has attracted much attention as a functional material for clothing such as foundations, socks and sportswear. However,
It is known that the use of chlorine bleaching for such predominantly long-chain synthetic elastic segmented polyurethane products results in a substantial reduction in the physical properties of the segmented polyurethane. Also, swimwear made of polyurethane elastic fiber and polyamide, when exposed to chlorine water containing active chlorine concentration of 0.5 to 3 ppm in the swimming pool,
It is known that a reduction in the physical properties of the fibers occurs.
Improvements in resistance to such chlorine-induced degradation have been conventionally made. For example, zinc oxide (JP-B-60-43444), magnesium oxide, and aluminum oxide (JP-B-61-35283) are known as chlorine degradation inhibitors. Have been.

(Problems to be Solved by the Invention) Dyeing a fabric such as a chlorine-resistant polyurethane elastic fiber containing a metal compound such as zinc oxide, magnesium oxide or aluminum oxide or a cross-knitted fabric containing the fiber, and fixing the dye. When a dye fixing agent such as tannin or tannin-bite tartar, which is commonly used, is used, the polyurethane elastic fiber turns brown, which significantly impairs the quality of the dyed product.

(Means for Solving the Problems) The present inventors have solved the above problems and dyed a knitted knitted fabric containing a polyurethane elastic fiber having resistance to a chlorine environment to obtain a high quality dyed product (color clarity). Etc.), the invention has been made to provide a dyed product of a specific knitted knitted fabric excellent in the above. That is, the present invention is a dyed fabric of a cross-knitted fabric containing polyurethane elastic fibers, wherein the polyurethane elastic fibers contain a metal oxide or a metal hydroxide, and the dyed product is an alkali dye as a dye fixing agent. A dyed material characterized by possessing an anionic phenolic compound which does not take a quinone structure upon contact, and also dyes a knitted and knitted fabric containing polyurethane elastic fibers containing a metal oxide or a metal hydroxide. A method for producing a dyed fabric of a cross-knitted fabric containing polyurethane elastic fibers, characterized in that an anionic phenol compound which does not form a quinone structure in contact with an alkali is used as a dye fixing agent when fixing a dye.

As the polyurethane in the present invention, a polymer diol having a molecular weight of 600 or more, preferably 1,000 to 5,000, and a melting point of 60 ° C. or less, an organic diisocyanate and a molecular weight of 40
Polymers obtained by reacting 0 or less polyfunctional active hydrogen compounds are exemplified. Examples of the polymer diol include polytetramethylene ether glycol, polyether glycols such as polyethylene propylene ether glycol, glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol. Polyester glycols, polycaprolactone glycol, polyhexamethylene obtained by reacting at least one kind with at least one kind of dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, β-methyladipic acid, and isophthalic acid One type of polymer diol such as dicarbonate glycol or a mixture or copolymer of two or more types thereof is exemplified. As organic diisocyanates, 4,4-
Such as diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4-dicyclohexylmethane diisocyanate, and isophorone diisocyanate One or a mixture of two or more organic diisocyanates is exemplified.
The polyfunctional active hydrogen compounds include ethylenediamine, 1,
2-propylenediamine, hexamethylenediamine, xylylenediamine, 4,4-diphenylmethanediamine,
Examples include one or a mixture of two or more of hydrazine, 1,4-diaminopiperazine, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, water, and, if desired, a terminating agent such as a monoamine. Is done. However, particularly preferred are polyfunctional active hydrogen compounds composed mainly of diamines or diamines. Examples of the polyurethane solvent include N, N-dimethylformamide, N, N-dimethylacetamide, tetramethylurea, hexamethylphosphonamide and the like. In the present invention, the metal oxide or metal hydroxide contained in the polyurethane may be magnesium oxide, zinc oxide, aluminum oxide, magnesium hydroxide, zinc hydroxide, aluminum hydroxide or a hydrotalcite compound {Mg _X Al _Y ( OH)
It is a one or a mixture of two or more of these _{Z CO 3 · lH 2 O}} , particularly preferred are magnesium oxide, zinc oxide. These amounts are preferably from 0.5 to 5% to the total amount of polyurethane, but are particularly preferably from 1 to 3%. The denier of the polyurethane elastic fiber is suitably from 20 to 100 denier, preferably from 40 to 70 denier. Also,
Either covering yarn or bare yarn may be used. The knitted knitted fabric in the present invention is knitted from the polyurethane elastic fiber and other fibers, and is not particularly limited as the other fiber. Silk, wool, polyamide fiber, promix fiber Are preferable, and a polyamide fiber is particularly preferable. The polyurethane elastic fibers are knitted with polyamide fibers to form a knitted fabric. The knitted knitted fabric may be a horizontal knitted fabric or a warp knitted fabric. Further, the knitted fabric may be knitted with a tricot knit or a raschel knit. The knitting structure may be any knitting structure such as half knitting, reverse half knitting, double atlas knitting, and double Denby knitting. Also,
It is preferable that the surface of the knitted fabric is made of a fiber other than the polyurethane elastic fiber, in particular, a polyamide fiber in terms of a feeling. Hereinafter, the knitted fabric with polyamide fibers will be described. The knitted fabric is scoured, relaxed and dried under normal conditions. The heat setting temperature is suitably from 150 to 190 ° C, preferably from 160 to 180 ° C. Dyeing conditions are in dyeing bath 20
120120 minutes, preferably 40-60 minutes. The dyeing machine may be a conventional one such as a win dyeing machine or a jet dyeing machine. The dye may be an acid dye, a gold-containing dye, or a fluorescent dye as long as it is a normal dye selected by a dye maker for polyamide. The dye fixing agent used in the present invention is an anionic phenol compound which does not take a quinone structure upon contact with an alkali. Examples of the phenol compound include a phenolsulfonic acid formaldehyde resin, a novolak type resin sulfone compound, and a novolak type phenol compound. Examples of resins include methanesulfonic acid, benzylated phenolsulfonic acid, thiophenol compounds, dihydroxydiphenylsulfone compounds, ligand compounds, and metal chelate compounds thereof. The amount of the anionic phenol compound used is in the range of 1 to 20% owf, preferably 3 to 10% owf, based on the polyamide fiber. When the amount of the anionic phenol compound is 1% owf or less, a durable dye fixing effect is not achieved. When the amount is 20% owf or more, the fixing effect is good but the texture becomes hard, which is not preferable. As a method of applying the anionic phenol compound to the knitted fabric, a method of immersing the dyed knitted fabric in the anionic phenol compound solution, a method of padding the anionic phenol compound solution to the knitted fabric, or a method of knitting the knitted fabric However, from the viewpoint that the dye fixing agent can be efficiently applied to the knitted fabric with as few steps as possible including the dyeing process, and the dispersion of the performance can be reduced, the method of applying by dipping is preferred. Is preferred. The dye fixing temperature is 40 to 100
° C, preferably 70-90 ° C. Further, according to the method of the present invention, a resin processing agent, a softening agent, an antistatic agent, a water repellent, and the like can be added to the treatment liquid used for immersion, padding, or spraying.

(Examples) Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the examples. In addition, the part in an Example means a weight part.

<Examples 1-3, Comparative Examples 1-4> Polytetramethylene ether glycol having a hydroxyl group at both ends and having a molecular weight of about 2,000 was reacted with 4,4-diphenylmethane diisocyanate at a molar ratio of 1: 2 to prepare a prepolymer. A polymer was produced, and a chain extension reaction was performed with 1,2-propylenediamine to obtain a polyurethane solution having a polymer concentration of 30% and a viscosity of 2000 poise. 3% by weight of magnesium oxide (average particle size: 0.1 to
2μ) was added in a state of being dispersed in advance by an attractor, and at the same time, an antioxidant, an ultraviolet absorber and a gas yellowing inhibitor were added, and the mixture was stirred to obtain a spinning stock solution. Vacuum defoaming of the spinning stock solution from a nozzle with a diameter of 0.2 mm and 5 holes
Extruded into a spinning cylinder with heated air at 80 ° C, 10,000 rpm
The yarn was false-twisted at a rotation speed of, and wound at a spinning speed of 500 m / min while applying an oil agent to the yarn at a rate of 6% to obtain a 40 denier polyurethane elastic fiber (A). As a comparative sample, a yarn (B) to which no magnesium oxide was added was produced in the same manner. Using the polyurethane elastic fibers (A) and (B) having the denier and the number of filaments shown in Table 1, and the polyamide fiber (C), a greige fabric was knitted under the following conditions.

○ (A), (B) warping draft of yarn: 100% ○ Knitting machine: 28 gauge tricot machine manufactured by KARL MAYER ○ Warp knitting conditions: (A), (B) knitting length of yarn 70cm / 480 course (C) Yarn knitting length 160cm / 480 course On-machine course 55 courses ○ Knitting structure: Half Front reed 1-0 / 2-3 (C) Yarn Back reed 1-2 / 1-0 (A), (B ) Yarn Using the dough, scouring, relaxing, drying,
Heat setting and staining were performed.

○ scouring, relaxing machine, wide-width relaxer scouring aid: Marbon T 2g / (Matsumoto Yushi Seiyaku Co., Ltd.-anionic activator) temperature × time: 80 ° C × 30 seconds ○ drying: pin tenter 120 ° C × 40 seconds ○ heat setting: pin tenter 180 ° C × 30 seconds ○ Dyeing dye: Solor Rhodanine B15% owf (acid dye manufactured by Sumitomo Chemical Co., Ltd.) Acetic acid 1.3g / 50 ° C × 10 minutes After washing with hot water, dye fixing treatment was carried out according to the method shown in Table 1. . The obtained dough was centrifugally dehydrated, dehydrated with a mangle, and dried and set with a pin tenter at 160 ° C. for 30 seconds.

A: 5% formalin condensate of bisphenol sulfone and aromatic sulfonic acid (Nylon Super N manufactured by Nissei Kasei)
owf80 ° C × 30 minutes B: Chelated product of formaldehyde condensate of sulfonated dihydrooxydiphenyl sulfone (Dainippon Pharmaceutical Co., Ltd.)
Hyfix GM) 5% owf 80 ° C x 30 minutes C: Formaldehyde condensate of sulfonated dihydrooxydiphenyl sulfone (FK70 manufactured by Fuji Chemical Industry Co., Ltd.)
7) 5% owf at 80 ° C x 30 minutes D: Natural tannin 3% owf (acetic acid 1g /) 60 ° C x 20 minutes E: Natural tannin-tartar D
5 g / (acetic acid 1 g /) 60 ° C x 20 minutes Light fastness: JIS L 0842 Third exposure method Water fastness: JIS L 0846 B method 16 hours Seawater fastness: JIS L 0847 Embrittlement of fabric with chlorinated water: The cloth stretched 40% in the direction is immersed in 30 ppm chlorine water for 6 hours, and the stress before and after immersion is compared.

(Effects of the Invention) According to the method of the present invention, after dyeing a knitted and knitted fabric of polyurethane elastic fibers containing a metal oxide or a metal hydroxide, when fixing the dye, a quinone structure is formed by contact with an alkali as a dye fixing agent. By using an anionic phenolic compound which does not remove the water, it is possible to provide a cross-knitted fabric of polyurethane elastic fiber which is free from polyurethane discoloration and reduced fastness and has excellent resistance to exposure to chlorine water.

Claims (2)

(57) [Claims] 1. A dyed fabric of a knitted and knitted fabric containing polyurethane elastic fibers, wherein the polyurethane elastic fibers contain a metal oxide or a metal hydroxide, and the dyed product is made of an alkali as a dye fixing agent. A dyed material characterized by possessing an anionic phenolic compound which does not take a quinone structure upon contact, and without causing brown discoloration or deterioration in fastness of polyurethane. 2. An anionic system which does not form a quinone structure in contact with an alkali as a dye fixing agent when dyeing and fixing a cross-knitted fabric containing a polyurethane elastic fiber containing a metal oxide or a metal hydroxide. A method for producing a dyed fabric of a knitted and knitted fabric containing polyurethane elastic fibers, wherein a phenolic compound is used and brown discoloration of the polyurethane and deterioration of fastness are not caused.