JPH06264301A - Water - Google Patents

Abstract

PURPOSE:To obtain swimsuit excellent in resistance to discoloration due to chlorine by using stretchable interknitted fabric containing a polyurethane-based elastic fiber, a polyamide-based fiber and a normal pressure cation-dyeable polyester-based fiber and containing a mono- or polyhydroxybenzene derivative. CONSTITUTION:The swimsuit having excellent resistance to discoloration due to chlorine is obtained by sewing stretchable interknitted fabric containing a dyed polyurethane-based elastic fiber, a polyamide-based fiber and/or a normal pressure cation-dyeable polyester-based fiber and containing 0.1-20wt.% mono- and/or polyhydroxybenzene derivative of formula I [Z1 and Z2 are aromatic groups; A is alkylene, etc.; B1 is alkyl, etc.; B2 is H, alkyl, etc.; R1 is alkyl, etc.; R2 is alkylene, etc.; R3 is carboxylic acid metallic salt, etc.; 0<=(k), (m)<=4; 1<=(k+l) and (m+n)<=5], formula II (Z3 and Z4 are aromatic groups; B3 and B4 are same as B1; 0<=(s) and (u)<=4; 1<=(s+t) and (u+v)<=5] and formula III [Z5 is aromatic group; B5 is same as B1; 1<=(x)<=4; 1<=(x+y)<=5].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a swimsuit made of stretch-knitted knitted fabric having excellent durability. More specifically, regarding the improvement of chlorine fading resistance of a swimsuit made of a dyed stretchable knitted fabric containing polyurethane-based elastic fibers and polyamide-based fibers and / or polyester-based fibers, the knitted knitted fabric has the general formula 1, 0.1 to 20 with respect to the fiber weight, at least one or more of the mono- and / or polyhydroxybenzene derivatives mainly consisting of phenol represented by Chemical formula 2 and Chemical formula 3
%, The present invention relates to a swimsuit comprising a dyed stretchable knitted knitted fabric which has a significantly improved chlorine fading resistance when worn in various chlorine-containing environments without impairing the color of the dyed fabric.

[0002]

2. Description of the Related Art Dyeing products that have been dyed with compounded dyes such as acid dyes, disperse dyes, metal-containing dyes, reactive dyes and direct dyes have been discolored in chlorine-containing environments such as chlorine bleaching. Is known to do. In particular, a swimsuit made of stretchable interwoven knitted fabric composed of polyurethane elastic fibers and polyamide synthetic fibers dyed with acid dyes, disperse dyes, metal-containing dyes, reactive dyes, etc., is used as a swimming pool with an active chlorine concentration of 0. When worn in chlorine water containing 5 to 3 ppm for a long time, the color of the swimsuit is discolored, discolored such as yellowing, and dull, especially in fluorescent colors and vivid colors, and its value is greatly impaired. Conventionally, as a method for improving such chlorine discoloration resistance, a method of using a dye having a good chlorine discoloration resistance to the interwoven fabric, a method of imparting water repellency to a fiber or a cloth by some method, Although methods such as post-treatment of dyed products to improve chlorine discoloration resistance have been proposed and studied, until now there is a method that satisfies chlorine discoloration resistance without damaging the color of the fabric immediately after dyeing. Not developed.

[0003]

As a method for improving the resistance to chlorine fading, tannic acid, which is usually used as a dyeing fastness improver as disclosed in JP-A-57-14358, is obtained by using a polyamide-based synthetic fiber. A method of imparting the knitted fabric including the fabric has been proposed. However, natural tannic acid itself is a compound colored yellowish brown, and therefore, when it is used for a dyed product of a vivid color or a light color, especially a vivid blue color, the original color or vividness of the dye is greatly impaired. In addition, since tannic acid is a polyphenol compound containing a large number of galloyl groups in its molecule, the presence of a basic additive in the fiber oxidizes two adjacent hydroxyl groups contained in the galloyl group to cause irreversible It has a quinone structure and may be colored in a dark color such as brown to change the color of the dyed product.

[0004]

In view of the above situation, the present inventor has earnestly studied based on a new idea, and as a result, has arrived at an epoch-making present invention that solves the above problems. That is, the present invention relates to a polyurethane-based elastic fiber and a polyamide-based fiber and / or a polyester-based fiber dyed with at least one dye selected from acid dyes, disperse dyes, metal-containing dyes, reactive dyes and direct dyes. A swimsuit comprising a stretchable interwoven knitted fabric containing at least the following: at least one mono- and / or polyhydroxybenzene derivative mainly containing phenol represented by the general formulas 1, 2 and 3 in the knitted fabric. By soaking the seeds or more in a high-temperature bath for 0.1-20% of the weight of the fiber, the chlorine-resistant change in various chlorine-containing environments without impairing the original color of the dyed product. Provided is a stretchable knitted knitted fabric with significantly improved fading and a swimsuit made of the knitted knitted fabric. The present invention improves the resistance to chlorine fading and discoloration by incorporating the compound group at the time of dyeing and / or before and after dyeing, and contributes to the improvement of the durability of the product. The present invention is described in detail below, but the present invention is not limited thereto.

The mono- and / or polyhydroxybenzene derivative containing phenol as the main component in the present invention is 4,4 as a group of compounds represented by the general formula 1.
′ -Methylenebisphenol, 4,4 ′-(1-methylethylidene) bisphenol, 4,4′-ethylidenebisphenol, 4,4 ′-(1-α-methylbenzylidene) bisphenol, 4,4′-cyclohexylidenebisphenol , 4,4 '-[1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylidene] bisphenol, 4,4'-[(4-hydroxyphenyl) methylene] bis (methylphenol ), 4,
4 '-[(4-hydroxyphenyl) methylene] bis (2,6-dimethylphenol), 4,4'-methylenebis (2,6-dimethylphenol), 4,4'-(1
-Methylethylidene) bis (2-methylphenol),
4,4 ', 4 "-Ethirizine trisphenol, 4,4
′, 4 ″ -Methylidine trisphenol, 2,2′-methylenebis (4-methylphenol), 4,4 ′-(1
-Methylethylidene) bis (2,6-dimethylphenol), phenolphthalein, 1,4-phenylene-
4,4'-bisphenol, 1,4-bis (4-hydroxyphenyl) cyclohexane, bis (3,5-dihydroxyphenyl) methane, 2,2'-bis (4-hydroxynaphthyl) methane, 2,2'- Bis (5-hydroxynaphthyl) methane, 2,2'-bis (6-hydroxynaphthyl) methane, 2,2'-bis (7-hydroxynaphthyl) methane, 2,2'-bis (8-hydroxynaphthyl) methane , 2,2'-bis (4,7-dihydroxynaphthyl) methane, 2,2'-bis (3,6-dihydroxynaphthyl) methane, and other diphenylmethane derivatives having hydroxyl groups introduced, and multimers of these as monomers , Bis (4-hydroxyphenyl) sulfone, bis (3,5
-A diphenylsulfone derivative having a hydroxyl group introduced therein such as dihydroxyphenyl) sulfone and a polymer having these as monomers, and a hydroxyl group introduced such as 4,4'-dihydroxydiphenylsulfide and bis (3,5-dihydroxyphenyl) sulfide. Diphenyl sulfide derivatives and multimers using them as monomers, diphenyl ether derivatives having hydroxyl groups introduced such as 4,4'-dihydroxydiphenyl ether and bis (3,5-dihydroxyphenyl) ether, and multimers using these as monomers ,
4,4'-dihydroxyazobenzene, bis (3,5-
Examples thereof include azobenzene derivatives having a hydroxyl group introduced such as dihydroxy) azobenzene and multimers using these as monomers.

The mono- and / or polyhydroxyphenylcarboxylic acid metal salt derivative mainly containing 4-hydroxyphenyl, which is a group of compounds represented by the above chemical formula 1, in the present invention is sodium 4-hydroxyphenylacetate,
Sodium bis (4-hydroxyphenyl) acetate, 1,
Sodium 1-bis (4-hydroxyphenyl) propionate, Sodium 1,2-bis (4-hydroxyphenyl) propionate, Sodium 2,2-bis (4-hydroxyphenyl) propionate, 1,1-Bis (4 −
Hydroxyphenyl) sodium butyrate, 1,2-bis (4-hydroxyphenyl) sodium butyrate, 2,2-
Sodium bis (4-hydroxyphenyl) butyrate, 1,
Sodium 3-bis (4-hydroxyphenyl) butyrate,
Sodium 3,3-bis (4-hydroxyphenyl) butyrate, Sodium 1,1-bis (4-hydroxyphenyl) valerate, Sodium 1,2-bis (4-hydroxyphenyl) valerate, 1,3-bis ( 4-hydroxyphenyl) sodium valerate, 1,4-bis (4-hydroxyphenyl) sodium valerate, 2,2-bis (4-hydroxyphenyl) sodium valerate, 2,3-bis (4
-Hydroxyphenyl) sodium valerate, 2,4-bis (4-hydroxyphenyl) sodium valerate, 3,
Sodium 3-bis (4-hydroxyphenyl) valerate, Sodium 3,4-bis (4-hydroxyphenyl) valerate, Sodium 4,4-bis (4-hydroxyphenyl) valerate, 1,1-Bis (4 -Sodium hydroxyphenyl) hexanoate, sodium 1,2-bis (4-hydroxyphenyl) hexanoate, sodium 1,3-bis (4-hydroxyphenyl) hexanoate,
Sodium 1,4-bis (4-hydroxyphenyl) hexanoate, Sodium 1,5-bis (4-hydroxyphenyl) hexanoate, Sodium 2,2-bis (4-hydroxyphenyl) hexanoate, 2,3-bis Sodium (4-hydroxyphenyl) hexanoate, sodium 2,4-bis (4-hydroxyphenyl) hexanoate,
Sodium 2,5-bis (4-hydroxyphenyl) hexanoate, Sodium 3,3-bis (4-hydroxyphenyl) hexanoate, Sodium 3,4-bis (4-hydroxyphenyl) hexanoate, 3,5-bis Sodium (4-hydroxyphenyl) hexanoate, sodium 4,4-bis (4-hydroxyphenyl) hexanoate,
4-hydroxyphenyl and / or polyhydroxyphenyl monoalkylcarboxylic acid sodium salt derivatives such as sodium 4,5-bis (4-hydroxyphenyl) hexanoate and sodium 5,5-bis (4-hydroxyphenyl) hexanoate, Examples thereof include magnesium monocarboxylic acid salts thereof, and / or multimers of these as monomers.

The mono- and / or polyhydroxyphenyl sulfonic acid metal salt derivative mainly containing 4-hydroxyphenyl, which is a group of compounds represented by the above chemical formula 2, is 1
-(4-hydroxyphenyl) ethanesulfonic acid sodium salt, 2- (4-hydroxyphenyl) ethanesulfonic acid sodium salt, 2,2-bis (4-hydroxyphenyl) ethanesulfonic acid sodium salt, 1,1-bis (4-
Hydroxyphenyl) propane sulfonic acid sodium salt,
Sodium 1,2-bis (4-hydroxyphenyl) propane sulfonate, Sodium 1,3-bis (4-hydroxyphenyl) propane sulfonate, Sodium 2,2-bis (4-hydroxyphenyl) propane sulfonate, 2, Sodium 3-bis (4-hydroxyphenyl) propanesulfonate, Sodium 3,3-bis (4-hydroxyphenyl) propanesulfonate, 1,1-
Sodium bis (4-hydroxyphenyl) butanesulfonate, sodium 1,2-bis (4-hydroxyphenyl) butanesulfonate, sodium 1,3-bis (4-hydroxyphenyl) butanesulfonate, 1,4-bis ( Sodium 4-hydroxyphenyl) butanesulfonate, Sodium 2,2-bis (4-hydroxyphenyl) butanesulfonate, Sodium 2,3-bis (4-hydroxyphenyl) butanesulfonate, 2,4-bis (4- Sodium hydroxyphenyl) butane sulfonate, sodium 3,3-bis (4-hydroxyphenyl) butane sulfonate, sodium 3,4-bis (4-hydroxyphenyl) butane sulfonate, 4,4-bis (4-hydroxyphenyl) ) Sodium butanesulfonate, 1,1-bis ( Sodium -hydroxyphenyl) pentanesulfonate, sodium 1,2-bis (4-hydroxyphenyl) pentanesulfonate, sodium 1,3-bis (4-hydroxyphenyl) pentanesulfonate, 1,4-bis (4-hydroxy) Sodium phenyl) pentanesulfonate, sodium 1,5-bis (4-hydroxyphenyl) pentanesulfonate, 2,2
-Sodium bis (4-hydroxyphenyl) pentanesulfonate, 2,3-bis (4-hydroxyphenyl)
Sodium pentanesulfonate, Sodium 2,4-bis (4-hydroxyphenyl) pentanesulfonate,
Sodium 2,5-bis (4-hydroxyphenyl) pentanesulfonate, Sodium 3,3-bis (4-hydroxyphenyl) pentanesulfonate, Sodium 3,4-bis (4-hydroxyphenyl) pentanesulfonate, 3, 5-bis (4-hydroxyphenyl) pentanesulfonic acid sodium salt, 4,4-bis (4-hydroxyphenyl) pentanesulfonic acid sodium salt, 4,5-
4-hydroxyphenyl and / or polyhydroxyphenyl monoalkylsulfonic acid sodium salt derivatives such as sodium bis (4-hydroxyphenyl) pentanesulfonate and sodium 5,5-bis (4-hydroxyphenyl) pentanesulfonate, and these Examples of the monocarboxylic acid magnesium salts and / or multimers of these as monomers.

As the compound group represented by the general formula 2, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3,3'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 3,
5-dihydroxybiphenyl, 2,4-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 2,3
′ -Dihydroxybiphenyl, 3,5,4′-trihydroxybiphenyl, 2,4,4′-trihydroxybiphenyl, 2,6,4′-trihydroxybiphenyl,
Biphenyl derivatives having a hydroxyl group introduced therein such as 3,3 ′, 5,5′-tetrahydroxybiphenyl and multimers using these as monomers, 2,2′-bis (4-hydroxynaphthyl), 2,2′- Bis (5-hydroxynaphthyl), 2,2'-bis (6-hydroxynaphthyl),
3,3'-bis (6-hydroxynaphthyl), 2,2 '
-Bis (8-hydroxynaphthyl), 1,1'-bis (3-hydroxynaphthyl), 1,1'-bis (4-hydroxynaphthyl), 1,1'-bis (5-hydroxynaphthyl), 1, 1'-bis (6-hydroxynaphthyl), 1,1'-bis (7-hydroxynaphthyl),
Examples thereof include a binaphthyl derivative into which a hydroxyl group such as 1,1′-bis (8-hydroxynaphthyl) is introduced, and a multimer including these as monomers.

As a group of compounds represented by the above general formula 3, 3-hydroxybenzoic acid and / or methyl, ethyl, isopropyl, t-butyl containing the same as an acid component,
Amyl and stearyl esters and multimers of these as monomers, 4-hydroxybenzoic acid and / or methyl, ethyl, isopropyl, and t containing these as acid components
-Butyl, amyl and stearyl esters and multimers using these as monomers, 3,5-dihydroxybenzoic acid and / or methyl, ethyl having this as an acid component,
Isopropyl, t-butyl, amyl and stearyl esters and multimers using these as monomers, 2,4-dihydroxybenzoic acid and / or methyl, ethyl, isopropyl, t-butyl, amyl and stearyl containing the same as an acid component Esters and multimers using them as monomers, hydroxyacetophenones such as 3-hydroxyacetophenone, 4-dihydroxyacetophenone, 3,5-dihydroxyacetophenone, and 2,4-dihydroxyacetophenone, and multimers using these as monomers , 3-hydroxybenzyl ethyl ketone, 4-hydroxybenzyl ethyl ketone, 3-hydroxybenzyl-
Isoropyrketone, 4-hydroxybenzyl-isolopyrketone, 3-hydroxybenzyl butyl ketone, 4-
Hydroxybenzyl ketones such as hydroxybenzyl butyl ketone, 3-hydroxybenzyl amyl ketone, 4-hydroxybenzyl amyl ketone, 4-hydroxybenzyl stearyl ketone and 3-hydroxybenzyl stearyl ketone, and multimers using these as monomers, isopropyl Examples thereof include alkylphenols such as phenol, butylphenol and amylphenol, and multimers using these as monomers.

Polymers represented by the above general formulas 1, 2, and 3 containing a phenol-based mono- and / or polyhydroxybenzene derivative as a monomer are obtained by oxidizing these monomers oxidatively. The aromatic nucleus-direct aromatic nucleus conjugate produced by coupling is more preferable. The multimer is produced by a known method, for example, Horse-radi.
It is carried out by oxidative coupling of phenolic compounds with sh peroxidase enzyme. Further, a formalin condensate obtained from the above-mentioned phenols as a raw material such as a conventional novolac resin may be used.

When the mono- and / or polyhydroxybenzene derivative mainly containing phenol of the present invention is used, it may be used alone or in combination of two or more kinds. The polyhydroxybenzene derivative in the present invention is a polyhydroxybenzene derivative that reacts with a basic additive contained in a polyamide fiber and / or a polyester fiber or a polyurethane elastic fiber to form a quinone structure and thus develops a color. Benzene derivatives (hydroquinone, catechol, pyrogallol, etc.) are not preferable because they impair the hue of the dyed product, and polyhydroxybenzene derivatives (phenol, resorcin, phloroglucin, etc.) that do not take a quinone structure when oxidized are preferable.

The polyamide fiber in the present invention is not particularly limited, but is represented by 6 nylon and 6.6 nylon. The atmospheric pressure cationic dyeable polyester fiber in the present invention is not particularly limited, but in order to impart atmospheric pressure cationic dyeability, for example, sodium 5-sulfoisophthalate or long-chain alkylene glycol is used together. It is represented by a polyester fiber produced by melt spinning a polymerized polyester.

The polyurethane elastic fiber in the present invention is an elastic fiber obtained by spinning a polymer composition mainly composed of the following polyurethane. As the polyurethane in the present invention, a polymer diol having a number average molecular weight of 600 or more, preferably 1000 to 5000 and a melting point of 60 ° C. or less, an isocyanate mainly composed of an organic diisocyanate, and a polyfunctional active hydrogen compound having a molecular weight of 400 or less are used. The polymer obtained by reacting is mentioned.

As the polymer diol, at least one kind of polytetramethylene glycol, polyether glycols such as polyethylene propylene glycol, ethylene glycol, 1,6-hexanediol, 1,4-butanediol and neopentyl glycols is used. Adipic acid, suberic acid, azelaic acid, sebacic acid, β-
Polyester glycols obtained by reacting with at least one dicarboxylic acid such as methyladipic acid and isophthalic acid, polymer diols such as polycaprolactone glycol and polyhexamethylene dicarbonate glycol, or two or more thereof. A mixture or a copolymer can be illustrated.

The organic diisocyanate is 4,4
′ -Diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 4,4
One or a mixture of two or more kinds of organic diisocyanates such as'-dicyclohexylmethane diisocyanate and isophorone diisocyanate can be exemplified. Furthermore, a small amount of triisocyanate may be used in combination.

As the polyfunctional active hydrogen compound, ethylenediamine, 1,2-propylenediamine, hexamethylenediamine, xylylenediamine, 4,4'-diphenylmethanediamine, hydrazine, 1,4-diaminopiperazine, ethylene glycol, 1 Examples include 1,4-butanediol, 1,6-hexanediol, water and the like, or a mixture of two or more thereof. If desired, these compounds may be used in a small amount in combination with a terminating agent such as monoamine or monoalcohol. However, preferred are diamines alone or mainly.

The polyurethane-based composition is spun into elastic fibers, but it is preferable that the polyurethane-based composition is dissolved in a solvent and dry-spun. Examples of the solvent include, but are not limited to, N, N-dimethylformamide, N, N-dimethylacetamide, tetramethylurea and hexamethylphosphonamide. Compositions other than polyurethane that make up polyurethane-based compositions include stabilizers such as lubricants, UV absorbers, anti-yellowing agents, pigments, antistatic agents, surface treatment agents, flame retardants, antifungal agents, reinforcing agents and chlorine. A water deterioration inhibitor is exemplified. In particular, as chlorine water deterioration inhibitors, magnesium oxide, zinc oxide, aluminum oxide,
Examples thereof include metal oxides and metal hydroxides such as magnesium hydroxide, zinc hydroxide, aluminum hydroxide, and hydrotalcite compounds, and these may be used alone or as a mixture of two or more kinds. Particularly preferred is magnesium oxide or zinc oxide. Addition to these polyurethane solutions is not particularly limited, but the average particle size is 0.0
It is preferably added as particles of 5 to 3 μm.

The polyurethane elastic fiber used in the present invention preferably has a denier in the range of 20 to 100, preferably 40 to 80. These elastic fibers are used in the state of covering yarn or bare yarn. The stretchable knitted fabric targeted in the present invention is a knitted fabric knitted by using the polyurethane elastic fiber and the polyamide fiber, and the knitted fabric may be a weft knitted fabric even if it is warp knitted fabric. It may be a knitted fabric, a tricot knitted fabric, or a Raschel knitted fabric, and is not limited. The knitting structure can be exemplified by half knitting, reverse half knitting, double atlas knitting, double denby knitting, etc., but is not particularly limited. In addition, it is preferable that the surface of the knitted fabric is composed of a polyamide fiber from the viewpoint of texture.

The knitted fabric is refined, relaxed and dried under normal conditions. Heat set temperature is 150-1
The temperature is 90 ° C, preferably 160 to 180 ° C. The dyeing conditions are 20 to 120 minutes in the dye bath, preferably 40 to 60
Minutes. The dyeing machine may be a Wins dyeing machine, a jet dyeing machine or the like which is normally used. The dye may be any of acid dyes, metal-containing dyes, fluorescent dyes and disperse dyes, as long as they are ordinary dyes selected by dye manufacturers for dyeing polyamide fibers. At the time of dyeing, organic acid esters such as formic acid ester, acetic acid ester, butyric acid ester, etc. were added to the dyeing bath in order to prevent the pH of the dyeing bath from 4.5 to less than 4.5 from the start of dyeing to the end of dyeing. Good. By adding the organic acid ester to the dye bath, it is possible to minimize the dropping of the basic additive from the fiber due to dyeing.

As the method of incorporating the compounds represented by the above Chemical Formula 1, Chemical Formula 2 and Chemical Formula 3 into the dyed interlaced knitted fabric, a method of mixing at the time of fiber production, a method of dissolving in an organic solvent and dipping, padding and There are methods such as spraying for attachment, but generally, the same method as in the case of dyeing with a disperse dye may be used. The method is illustrated below, but the production method is not limited thereto. If necessary, a predetermined amount of at least one of the compounds is dispersed using a commercially available anionic dispersant such as a naphthalenesulfonic acid formalin condensate and a dispersing machine such as a ball mill, a dyno mill or an attritor. . A stretchable interlaced knitted fabric containing polyamide-based fibers and polyurethane-based elastic fibers is dipped in the previously-heated compound dispersion, and the mixture is bathed for 20 to 120 minutes, preferably 40 to 60 minutes, and a bath temperature of 40 to Treatment at 95 ° C, preferably 60-85 ° C,
The compound is attached to the fiber surface. Further, in order to increase the yield of adhesion, a carrier agent such as orthophenylphenol may be added to the treatment bath at the same time for treatment. Further, the application of the compound to the knitted or knitted fabric may be carried out before dyeing, may be carried out at the same time as dyeing, and is usually carried out after dyeing for the purpose of improving various dyeing fastness by anionic polyphenol or the like. It is preferable to perform it at the same time as the dye fixing treatment or after the fixing treatment.

[0021]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto. The following examples are dyed polyurethane elastic fibers and polyamide fibers containing a mono- and / or polyhydroxybenzene derivative mainly containing phenol represented by the general formulas 1, 2 and 3. An example is a swimsuit comprising a stretched knitted knitted fabric containing at least polyester fiber and / or having improved chlorine discoloration resistance of the dyed product in chlorine water. Moreover, the part in an Example means a weight part. -Example 1-A polytetramethylene ether glycol having hydroxyl groups at both ends and a number average molecular weight of 2000 and 4,4'-diphenylmethane diisocyanate are reacted at a molar ratio of 1: 2 to produce a prepolymer, and then ethylenediamine is used. Chain extension is carried out with a polymer concentration of 30% (solvent is N, N-
With dimethylacetamide), a polyurethane solution having a viscosity of 2000 poise (30 ° C.) was obtained. 3% magnesium oxide (average particle size 0.1
~ 2.0 μm) is dispersed in dimethylacetamide with an attritor and added, and then a whiteness improver, an antioxidant, an ultraviolet absorber and a gas yellowing inhibitor are added and mixed to obtain a spinning dope. It was

After defoaming, the spinning solution was spun out from a spinneret having a hole diameter of 0.2 mm and a number of holes of 5 and extruded into a spinning cylinder in which heated air of 180 ° C. was flowed to perform false twisting at a rotation speed of 10,000 rpm, A 6 denier polyurethane elastic fiber (A) of 40 denier was wound at a spinning speed of 500 m / min while applying 6% of the oil agent to the yarn. As the polyamide fiber, a denier of 50 denier and 12 filaments of 6.6 nylon fiber (B) produced by melt spinning was prepared. As polyester fibers, there were prepared 50 denier and 10 filament normal pressure cationic dyeable polyester fibers (C) produced by melt spinning. A raw machine was knitted using a 28 gauge, tricot machine manufactured by KARL MAYER as a knitting machine. (A) 100% fiber draft,
The knitting conditions are (A) fiber braid length 70 cm / 480
Course, (B) and (C) Fiber braid length 160 cm
/ 480 course, (55 courses on board), the knitting structure is half knitting.

The raw fabric containing (A) and (B) thus obtained was refined, relaxed, dried, and heat set to dye each knitted fabric. 0.4% acetic acid in the dye bath
g / L, ammonium sulfate 2 g / L, anionic level dye 1.2 g / L
Is dissolved in a bath ratio of 1:13 and dye: Kayacyl Bl
ue BR, 5% owf (acid dye), 40 ° C to 95
It was carried out under the condition of 60 ° C. for 60 minutes. After washing with hot water at 50 ° C for 10 minutes, the chlorine fading inhibitor: bisphenol A, 5% owf is dyed and the knitted fabric is dipped in the dispersion liquid at 40 ° C.
To 80 ° C. for 50 minutes. Further, dye fixing treatment was performed using an anionic polyphenol which was not tannic acid. The obtained dyed knitted fabric was stretched and dehydrated, drained with a mangle, dried at 160 ° C. with a pin tenter and set.

The fading of the hue of the stretched interwoven knitted fabric obtained by the above-mentioned method with chlorine water was measured. The conditions of this chlorine fading test are as follows: 1 part of the knitted fabric is subjected to 400 parts of chlorine water having an effective chlorine concentration of 100 ppm and pH = 7.0 at a bath temperature of 40 ° C. for 30 minutes so that the chlorine water flow may hit the knitted fabric surface vertically. It is dipped and treated with chlorine water. The color fading was measured by measuring the hue of the dyed cross-knitted fabric, and the difference in hue before and after the treatment with chlorine water was obtained, and the chlorine fastness (color fading grade) was determined from the result. The results are shown in Table 1.

The dyed stretchable interwoven knitted fabric thus obtained was sewn to prepare a general one-piece swimsuit. A pool for competition (length 25m, width 12m, water depth), in which 5 swimmers with standard swimming ability actually wear the swimwear, effective chlorine concentration 0.5ppm, pH 6.5-7.5, water temperature 30 ° C. 1.6m)
Was continuously used for 100 hours, and the hues before and after the test were compared. The results are shown in Table 1.

-Example 2- An interwoven knitted fabric dyed with the same prescription as in Example 1 except that the interwoven knitted fabric containing (A) and (C) is used and treated with chlorine water. It was The results are shown in Table 1.

Example 3-A knitted and knitted fabric dyed with the same formulation as in Example 1 except that sodium 2,2-bis (4-hydroxyphenyl) valerate, 5% owf is used as a chlorine fading inhibitor. Is made,
Chlorine water treatment was performed. The results are shown in Table 1.

Example 4-A knitted knitted fabric dyed in the same manner as in Example 1 except that sodium 2,2-bis (4-hydroxyphenyl) butanesulfonate, 5% owf is used as a chlorine fading inhibitor. The ground was prepared and treated with chlorine water. The results are shown in Table 1.

-Example 5- 4,4'-biphenol as a chlorine fading inhibitor, 5%
A mixed knitted fabric dyed with the same formulation as in Example 1 except that owf was used was prepared and treated with chlorine water. The results are shown in Table 1.

Example 6 A chlorine knitted fabric was dyed with the same prescription as in Example 1 except that 3,5-dihydroxybenzyl ethyl ketone and 5% owf were used as the chlorine fading-inhibiting agent. Water treatment was performed. The results are shown in Table 1.

Example 7 As a chlorine fading inhibitor, bisphenol A was used as a monomer and Horsera-dish peroxidase was used.
Bisphenol A polymer (average molecular weight 1000) produced by reacting an enzyme as a catalyst, 5% o
A knitted and knitted fabric that was dyed with the same formulation as in Example 1 except that wf was used was prepared and treated with chlorine water. The results are shown in Table 1.

Example 8-A knitted and knitted fabric dyed with the same formulation as in Example 1 except that sodium 2,2-bis (4-hydroxyphenyl) valerate and 2% owf are used as a chlorine fading inhibitor. Is made,
Chlorine water treatment was performed. The results are shown in Table 1.

-Example 9- 4,4'-biphenol, 2 as a chlorine fading inhibitor
A knitted and knitted fabric dyed with the same formulation as in Example 1 except that% owf was used was prepared and treated with chlorine water. The results are shown in Table 1.
Shown in.

-Example 10- 4,4'-biphenol, 1 as a chlorine fading inhibitor
A mixed knitted fabric dyed with the same formulation as in Example 1 except that 0% owf was used was prepared and treated with chlorine water. The results are shown in Table 1.

Comparative Example 1 A mixed knitted fabric dyed with the same prescription as in Example 1 was prepared without using any chlorine fading inhibitor, and was treated with chlorine water. The results are shown in Table 1.

Comparative Example 2 A cross dyed with the same formulation as in Example 1 except that no chlorine fading inhibitor was used and a cross knitted fabric containing (A) and (C) was used. A knitted fabric was prepared and treated with chlorine water.
The results are shown in Table 1.

Comparative Example 3-A chlorine-fading inhibitor and a tannic acid as a dye-fixing agent were used without using any chlorine fading inhibitor, using a knitted knitted fabric containing (A) and (C). A knitted and knitted fabric dyed with the same formulation as in Example 1 except that the tartar treatment was performed, was prepared and was treated with chlorine water. The results are shown in Table 1.

Comparative Example 4-Dyeing was carried out with the same formulation as in Example 1 except that no chlorine fading inhibitor was used and tannic acid / tartar treatment was carried out as a chlorine fading inhibitor and dye fixing agent. A mixed knitted fabric was prepared and treated with chlorine water. The results are shown in Table 1.

[0039]

[Table 1] In Table 1, (A) fibers are polyurethane elastic fibers, (B) fibers are polyamide fibers, (C) fibers are atmospheric pressure cationic dyeable polyester fibers, and the adhered amount is owf.

[0040]

EFFECT OF THE INVENTION According to the present invention, the chlorine-resistant fading resistance of a swimsuit comprising a stretchable knitted fabric containing at least dyed polyurethane elastic fibers and polyamide fibers and / or atmospheric pressure cationic dyeable polyester fibers. The dyeability can be improved without impairing the color of the dyed product, and a product having excellent chlorine resistance can be provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location D06M 13/152 D06P 5/00 DBC 9356-4H DBG 9356-4H DBH 9356-4H 102 9356-4H 5 / 04 DBC 9356-4H DBG 9356-4H DBH 9356-4H // D01F 6/70 Z 7199-3B D06P 1/64 9356-4H (72) Inventor Koji Shirahaku 2-1-1 Katata, Otsu, Shiga Prefecture Toyobo Co., Ltd. Research Institute (72) Inventor Hajime Hajime 2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo Co., Ltd. Research Institute

Claims (2)

[Claims] 1. A polyurethane-based elastic fiber and a polyamide-based fiber and / or a normal pressure cation dyeable with at least one dye selected from acid dyes, disperse dyes, metal-containing dyes, reactive dyes and direct dyes. A stretchable interlaced knitted fabric containing at least dyed polyester fiber, wherein the knitted fabric has at least one mono- and / or polyhydroxybenzene derivative mainly containing phenol represented by Chemical formula 1, Chemical formula 2, and Chemical formula 3. A swimsuit made of stretchable interwoven knitted fabric, characterized in that 0.1 to 20% of the seeds are contained in the fiber weight. [Chemical 1] [Chemical 2] [Chemical 3] (Wherein Z1 is an aromatic group, Z2, Z3, Z4, and Z
5 is an aromatic group which is the same as or different from Z1, respectively, A is a divalent group such as an alkylene group, an ether group, a sulfonyl group, a sulfide group and an azo group, and B1 is an alkyl group, an alkoxy group, a nitro group, a sulfone group and an amino group. A monovalent group or hydrogen atom, B2, B3, B4 and B5 are the same or different monovalent groups or hydrogen atoms as B1, respectively, R
1 represents an alkyl group or aryl group, R2 represents an alkylene or arylene group, and R3 represents a metal salt of a carboxyl group or a metal salt of a sulfonic acid group. Also, k, l,
m, n, s, t, u, v, x and y are the following (Q)
Indicates a positive integer that satisfies the formula group. ) 0 ≦ k ≦ 4 1 ≦ k + l ≦ 5 (Q-1) 0 ≦ m ≦ 4 1 ≦ m + n ≦ 5 (Q-2) 0 ≦ s ≦ 4 1 ≦ s + t ≦ 5 (Q-3) 0 ≦ u ≦ 4 1 ≦ u + v ≦ 5 (Q-4) 1 ≦ x ≦ 4 1 ≦ x + y ≦ 6 (Q-5) 2. The method according to claim 1, wherein after the compounds represented by the general formulas 1, 2, and 3 are contained, they are further treated with an anionic polyphenol to improve various dye fastnesses. A swimsuit made of elastic stretch knitted fabric.