JPH0657530A - Polyamide fiber and its production - Google Patents

Abstract

PURPOSE:To obtain polyamide fiber excellent in resistance to change in color with chlorine by including a mono- or a polyhydroxybenzene derivative consisting essential of phenol in polyamide-based fiber. CONSTITUTION:The polyamide fiber is obtained by including a mono- and/or a polyhydroxybenzene derivative, consisting essentially of phenol and expressed by formulas I to III [Z1 is aromatic group; Z2 to Z5 each are aromatic group same as or different from R1; A, R1 and R2 form bivalent group such as alkylene or ether; B1 is alkyl, etc.; B2 to B5 each are monovalent group same as or different from B1 or H; 0<=(k)<=4; 1<=(k+1)<=5; 0<=(m)<=4; 1<=(m+n)<=5; 0<=(s)<=4; 1<=(s+t)<=5; 0<=(u)<=4; 1<=(u+v)<=5; 1<=(x)<=4; 1<=(x+y)<=6] in an amount of 0.1-20% based on the fiber weight. Thereby, the resistance to change in color of a woven or a knitted fabric with chlorine can be improved without impairing the color of the dyed fabric.

Description

Detailed Description of the Invention

[0001]

This invention relates to polyamide fibers. More specifically, at least one or more of the mono- and / or polyhydroxybenzene derivatives mainly containing the compound phenol represented by the general formulas 1, 2, and 3 is added to the polyamide in an amount of 0 to the fiber weight. ．
The present invention relates to a polyamide fiber obtained by adding 1 to 20% and spinning and preventing discoloration of the dyed fiber due to chlorine in various chlorine-containing environments, and a method for producing the same.

[0002]

2. Description of the Related Art Generally, as a method of imparting chlorine fading resistance to a polyamide fiber, a method of treating with a synthetic fixing agent (so-called synthetic tannin) such as an aromatic oxysulfonic acid condensate or a natural tannic acid is used. And how to use tartar is known. (JP-A-56-5329
1 gazette, JP-A-56-53293)

[0003]

[Problems to be Solved by the Invention] However, sterilization /
In a variety of chlorine-containing environments such as swimming pools that use chlorine as a disinfectant, chlorine dye fading resistance can be obtained by using dyed interwoven knitted fabrics that mainly use polyamide fibers treated with synthetic fix agent. However, there is a problem that the dye is deteriorated to cause discoloration or fading after long-term use. In addition, the dyed interlaced knitted fabric mainly using the polyamide fiber treated with natural tannic acid has a significantly higher chlorine fading resistance than the synthetic fix agent, but is of a raw material quality because it is a natural product. Since it is unstable and tannic acid itself is colored yellowish brown, there is a problem that when it is used for a bright color, a light color and a fluorescent color, the color of the dyed product is greatly impaired. Furthermore, since tannic acid is a compound having a galloyl group in the molecule, it reacts with a basic additive contained in the fibers of a polyamide fiber or a knitting partner material to irreversibly change to a quinone compound, Further, there is a problem that the color changes to dark brown.

[0004]

The present invention has been made in view of the above circumstances, and its object is to:
Polyamide fiber with excellent chlorine fading resistance, which exhibits excellent chlorine fading resistance stably for a long period of time in various chlorine-containing environments and does not impair the color during dyeing, and a method for producing the same. I will provide a.

[0005]

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 which solves the above problems. That is, according to the present invention, the fiber weight is obtained by kneading and adding at least one or more of mono- and / or polyhydroxybenzene derivatives mainly containing phenol represented by the general formulas 1, 2, and 3 at the time of spinning. Against 0.1
The present invention provides a polyamide fiber containing ~ 20%, capable of dyeing without impairing the color of the dye itself, and having significantly improved chlorine fading resistance in various chlorine-containing environments, and a method for producing the same. is there. In the present invention, the compound group is added and spun at the time of producing a polyamide fiber, or high temperature dipping is performed in a bath in which the compound group is dissolved or / and dispersed at the time of dyeing and / or before and after dyeing to contain the compound. It improves chlorine fading and contributes to the improvement of product quality. The present invention is described in detail below, but the present invention is not limited thereto.

As the mono- and / or polyhydroxybenzene derivative mainly containing phenol used as the chlorine fading inhibitor in the present invention, 4,4'-methylenebisphenol, which is a compound group represented by the general formula 1,
4,4 '-(1-methylethylidene) bisphenol,
4,4'-ethylidene bisphenol, 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 (2,2 6-dimethylphenol), 4,4 '-(1-methylethylidene) bis (2-methylphenol), 4,4', 4 "-ethylidyne trisphenol, 4,4 ', 4" -methylidyne 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)
Diphenylmethane derivatives having hydroxyl groups such as methane and multimers using these as monomers, diphenylsulfone derivatives having hydroxyl groups such as bis (4-hydroxyphenyl) sulfone and bis (3,5-dihydroxyphenyl) sulfone, and these Is a monomer,
Diphenyl sulfide derivatives such as 4,4′-dihydroxydiphenyl sulfide and bis (3,5-dihydroxyphenyl) sulfide, and multimers using these as monomers, 4,4′-dihydroxydiphenyl ether, bis (3 , 5-Dihydroxyphenyl) ether-containing diphenyl ether derivatives and multimers using these as monomers, 4,4 ′
Examples thereof include hydroxyl group-introduced azobenzene derivatives such as dihydroxyazobenzene and bis (3,5-dihydroxy) azobenzene, and multimers using these as monomers.

As a group of compounds 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, 3,3
Biphenyl derivatives having a hydroxyl group introduced therein such as ′, 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), 1,1 '
Examples thereof include a binaphthyl derivative having a hydroxyl group introduced such as -bis (8-hydroxynaphthyl), and a multimer using these as a monomer.

As a group of compounds represented by the general formula 3,
-Hydroxybenzoic acid and / or methyl, ethyl, isopropyl, t-butyl, amyl and stearyl esters containing the same as the acid component and multimers of these as monomers, 4-hydroxybenzoic acid and / or the acid component thereof , Methyl, ethyl, isopropyl, t-butyl, amyl and stearyl esters and multimers of these as monomers, 3,5-dihydroxybenzoic acid and / or methyl, ethyl, isopropyl, t containing these as acid components. -Butyl, amyl and stearyl esters and multimers using them as monomers, 2,4-dihydroxybenzoic acid and / or methyl, ethyl, isopropyl, t-butyl, amyl and stearyl esters containing these as acid components and these 3-Hydroxyl Hydroxyacetophenones such as tophenone, 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 general formulas (1), (2) and (3), which have a phenol-based mono- and / or polyhydroxybenzene derivative as a monomer, are oxidatively capped with these monomers. The aromatic nucleus-direct aromatic nucleus conjugate produced by ringing is more preferable. The production of the multimer is carried out by a known method, for example, by oxidative coupling of a phenol compound with a horseradish 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. Further, the polyhydroxybenzene derivative in the present invention is a polyhydroxybenzene which is colored by reacting with a basic additive contained in polyamide fibers or interwoven fibers (for example, polyurethane fibers) to form a quinone structure. Derivatives (hydroquinone, catechol, pyrogallol, etc. or their derivatives) are not preferable because they impair the color of the dye itself, and polyhydroxybenzene derivatives (phenol, resorcin, phloroglucin, etc., which do not take a quinone structure when oxidized, or their derivatives). ) Is preferred.

The substance used as a chlorine fading inhibitor in the present invention is preferably one which has a high whiteness or is colorless, in view of the influence on the color of the dyed product. It is preferable that the number of substituents other than the hydroxyl group introduced into the ring is as small as possible, and more preferably a substance that does not have an absorption maximum in the ultraviolet wavelength region of 350 nm or more when formed into an aqueous solution or an organic solvent solution, and particularly preferable in this respect. Is 4,4'-biphenol, bisphenol A, 4,
They are 4'-dihydroxydiphenyl sulfone and 4,4'-methylenebisphenol.

The polyamide fiber in the present invention is not particularly limited, but generally, the main raw material is polyamide synthesized by polycondensation reaction of diamine and dicarboxylic acid or ring-opening polycondensation reaction of lactam. Is. An example of the former is nylon 66 synthesized from adipic acid and hexamethylenediamine, and an example of the latter is nylon 6 synthesized from ε-caprolactam.

A chlorine fading inhibitor represented by the general formulas 1, 2, and 3 is kneaded into a polyamide to obtain a molten polyamide having a final content of the chlorine fading agent of 0.1 to 20% by weight. Prepare. The method of kneading the chlorine fading inhibitor is not particularly limited, but for example, it can be kneaded while adjusting the final content of the chlorine fading inhibitor by the master chip method. That is, a polyamide containing a large amount of a chlorine fading inhibitor was prepared by melt-kneading in advance, and this was used as a base polymer, and during melt spinning, by adding the polyamide to the base polymer, the content of the chlorine fading inhibitor was contained. Adjust the rate to be within the given range. In addition, a method in which a predetermined amount of polyamide having a final content within the above range and a chlorine fading inhibitor are simultaneously charged into a hopper and kneading is performed at the time of melt spinning, and the like can also be mentioned.

Upon melt-kneading, it is necessary to uniformly disperse the chlorine fading inhibitor in the polyamide in order to make the chlorine fading resistance of the resulting chlorine fading-resistant polyamide fiber uniform. In order to improve the dispersibility of the chlorine fading inhibitor in the polyamide, melt kneading is performed at a melt viscosity of 2000 poise or less. Here, the melt viscosity of the polyamide to which the chlorine fading inhibitor is added can be controlled by the melting temperature, the degree of polymerization of the polyamide, and the water content of the polyamide. In order to adjust the melt viscosity at the time of melt kneading to 2000 poises or less, the relative viscosity of 2.2 is taken into consideration in consideration of economical efficiency.
-2.5 polyamide is used, the moisture content of the polyamide to which the chlorine fading inhibitor is added is adjusted to 0.1-0.08%, and the temperature during kneading is set to 270-280 ° C. Is preferred. In addition, the humidity control of the moisture content is 0.1 to 0.0 in advance.
The polyamide whose humidity is adjusted to 8% and the chlorine fading inhibitor may be mixed, or the humidity may be adjusted to be within the above range after mixing.

The molten polyamide in which the chlorine fading preventing agent thus obtained is uniformly dispersed, that is, the molten polyamide containing the chlorine fading preventing agent is dried to obtain a water content of 0.05.
% Or less, preferably 0.02% or less. By setting the water content of the molten polyamide containing the chlorine fading inhibitor to 0.05%, the post-polymerization of the polyamide is promoted and the relative viscosity of the polyamide is increased. A chlorine-fading resistant polyamide fiber of the present invention can be produced by melt-spinning a moisture-adjusted molten polyamide at a temperature equal to or higher than the melting point of the polyamide, and spinning the obtained product to a predetermined fineness. . In the production method of the present invention, when a high-molecular weight polyamide obtained by solid-phase polymerization is used, chlorine-fading resistant polyamide fibers with further improved fiber strength can be obtained.

The chlorine fading-resistant polyamide fiber prepared by the above method is woven or knitted with other fibers to prepare a woven fabric or a knitted fabric. The method of knitting and knitting is not particularly limited, but it is considered that stretchability is indispensable when considering the use as a cloth for wearing in swimming pools. In this respect, polyurethane elastic fiber, etc. It is desirable to use the spandex fiber as the mating partner fiber. Hereinafter, the interwoven knitted fabric of the chlorine fading-resistant polyamide fiber and the spandex fiber will be described. The spandex fiber, which is the mating knitting fiber, is not particularly limited as long as it is an elastic fiber having effective elongation and recovery properties, and is generally synthesized from a polyalkylene glycol or polyether glycol component and a diisocyanate component. Polyurethane urea-based elastic fiber obtained by spinning a polyurethane urea synthesized by a method of extending the molecular chain of a polymer precursor with diamines or glycols, and further stopping the reaction of the molecular chain end with amines or alcohols. An example is a polyester ether elastic fiber obtained by spinning a polyester ether synthesized by copolymerizing a polyalkylene glycol or polyether glycol component with an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid and a glycol. To be done. An interlaced knitted fabric is created by knitting using these spandex fibers and the above chlorine fading-resistant polyamide fibers. The mixed knitted fabric may be a weft knitted fabric or a warp knitted fabric, and may be 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.

General formulas 1 and 2 are added to the dyed cross knitted fabric.
Examples of the method of incorporating the compound represented by Chemical Formula 3 include the method of adding the compound by melt-kneading at the time of producing the fiber, or the method of adding the compound to a cloth or knitted fabric containing chlorine-fading resistant polyamide fiber as a main component. Examples include a method of dissolving the group in an organic solvent and dipping, padding, and spraying to adhere it, and a method of dispersing the compound group using a suitable dispersant or emulsifier and then exhausting it by a known exhaustion method. . The following is an example of a method for exhausting a chlorine fading-preventing agent into a chlorine fading-resistant polyamide fiber knitted fabric, but the manufacturing method is not limited thereto. Using a commercially available anionic dispersant such as a naphthalene sulfonic acid formalin condensate, a predetermined amount of at least one compound selected from the compound group, and using a disperser such as a ball mill, a dyno mill or an attritor. Spread. The interlaced knitted fabric containing the polyamide fiber and the spandex fiber is dipped in the previously heated compound dispersion liquid, and is immersed in a bath for 20 to 12
0 minutes, preferably 40 to 60 minutes, bath temperature 40 to 95 ° C,
It is preferably treated at 60 to 85 ° C to allow the compound to adhere 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 fabric may be carried out before dyeing or at the same time as dyeing, and is usually carried out after dyeing for the purpose of improving dye fastness by various dyes such as anionic polyphenol. It may be performed simultaneously with the treatment or after the fixing treatment.

Hereinafter, the chlorine fading-resistant polyamide fiber of the present invention will be described with reference to Examples. In the following examples, relative viscosity (RV value) and chlorine fading resistance were evaluated as follows. RV value: Specific viscosity at 20 ° C. was obtained for a sample prepared by dissolving 0.2 g of sample in 20 cc of concentrated sulfuric acid.

Chlorine fading resistance: Chlorine fading resistance polyamide fibers are knitted into cylinders to prepare a sample cloth of chlorine fading resistance polyamide fibers, and after scouring, relaxing, drying and heat setting under normal conditions. Dyeing is carried out using dyes commonly used for polyamide fibers. Further, dye fixing treatment was performed using a synthetic fixing agent such as an aromatic oxysulfonic acid condensate. The dyed sample cloth thus obtained was immersed in an aqueous sodium hypochlorite solution under the following conditions, and the change in hue before and after the treatment was evaluated using a gray scale. Active chlorine concentration: 100 ppm Bath pH: 7.0 Bath ratio: 1: 400 Bath temperature: 40 ° C Immersion time: 30 minutes (after treatment, rinse with hot water and dry with air) The aqueous solution of sodium chlorite was acidified with acetic acid, and iodometry was performed using a normal solution of sodium thiosulfate.

[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 represented by the general formulas 1, 2, and 3.
By using a polyamide fiber characterized in that at least one or more mono- and / or polyhydroxybenzene derivative mainly containing phenol represented by An example of improving the chlorine discoloration resistance of a polyamide fiber dyeing product in an aqueous sodium chlorite solution will be illustrated. Moreover, the part in an Example means a weight part. -Example 1-Using nylon 6 (RV = 2.5) as polyamide,
The moisture content of this nylon 6 was adjusted to 0.08% or less.
Bisphenol A was added as a chlorine fading inhibitor so that the final content rate was 5%, and the melt viscosity after the addition was adjusted to 1850 poise. I made a chip. Next, this nylon 6 chip containing a chlorine fading inhibitor is dried, the moisture content is adjusted to 0.02%, melt-spun, and then stretched, followed by stretching to a 50 denier 12 filament chlorine-fading polyamide fiber (A). Got Further, no abnormality was found in the breaking strength and elongation of this chlorine fading-resistant polyamide fiber as compared with nylon 6 general products having the same fineness.

As spandex fiber, 40 denier and 5 filaments of polyurethane urea elastic fiber (B) produced by solution spinning were prepared, and a mixed knitted fabric composed of both fibers was prepared. Knitting machine A raw machine was knitted using a 28 gauge tricot machine manufactured by KARL MAYER. (B) 100% fiber draft, knitting conditions (A) fiber braid length 160 cm / 480 course, (machine course 55), (B) fiber braid length 70 cm / 480 course,
The knitting structure is half.

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. It was washed with hot water at 50 ° C. for 10 minutes. Subsequently, a dye fixing treatment was performed using a synthetic fixing agent (anionic polyphenol) that 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 dyed knitted fabric obtained by the above-mentioned method with chlorine-containing water was measured. The results of determination of chlorine fastness (discoloration grade) are shown in Table 1 below. About this dyed sample cloth, before washing and washing 10
The chlorine fading resistance after rotation was measured. The chlorine fading resistance was good both before and after washing, and no deterioration in chlorine fading resistance due to washing was observed. In Table 1,
(A) is a polyamide fiber containing a chlorine fading inhibitor,
(B) shows spandex fibers, and (C) shows ordinary nylon 6 fibers. The addition amount% indicates the weight% of polyamide fiber.

Example 2-A chlorine-fading-resistant polyamide fiber was produced in the same manner as in Example 1 except that 4,4'-biphenol, 5%, was used as the chlorine-fading inhibitor. Further, a dyed interwoven knitted fabric was produced using this fiber and treated with an aqueous solution of sodium hypochlorite. The results are shown in Table 1.

Example 3-A chlorine-fading-resistant polyamide fiber was produced in the same manner as in Example 1 except that 4,4'-dihydroxydiphenyl sulfone, 5%, was used as a chlorine-fading inhibitor. Further, a dyed interwoven knitted fabric was produced using this fiber and treated with an aqueous solution of sodium hypochlorite. The results are shown in Table 1.

Example 4-A chlorine fading-resistant polyamide fiber was produced in the same manner as in Example 1 except that 4,4'-methylenebisphenol, 5%, was used as a chlorine fading inhibitor. Further, a dyed interwoven knitted fabric was produced using this fiber and treated with an aqueous solution of sodium hypochlorite. The results are shown in Table 1.

Example 5-Bisphenol A produced by reacting bisphenol A as a monomer and using horseradish peroxidase enzyme as a catalyst as a chlorine fading inhibitor
A chlorine fading-resistant polyamide fiber was produced in the same manner as in Example 1 except that 5% of a polymer (average molecular weight 1000) was used. Further, a dyed interwoven knitted fabric was produced using this fiber and treated with an aqueous solution of sodium hypochlorite. The results are shown in Table 1.

Example 6 A chlorine fading-resistant polyamide fiber was produced in the same manner as in Example 1 except that 2% of bisphenol A was used as the chlorine fading preventive agent. Further, a dyed interwoven knitted fabric was produced using this fiber and treated with an aqueous solution of sodium hypochlorite. The results are shown in Table 1.

Comparative Example 1 Nylon 6 fiber (C) (50 denier 12 filaments) melt-spun by a known method was used as the polyamide fiber, and the polyurethane urea elastic fiber (B) was used in the same manner as in Example 1. A knitted knitted fabric was produced, and subsequently, a dyed knitted knitted fabric was produced and treated with an aqueous solution of sodium hypochlorite. The results are shown in Table 1.

Example 7 Bisphenol A 5% ow dispersed by using Dispa TL (Dye Dispersant manufactured by Meisei Chemical Industry Co., Ltd.) as a dispersant.
A dyeing bath containing f (the dyeing recipe is the same as in Example 1) was prepared, and a knitted fabric of nylon 6 fiber (C) and polyurethane urea elastic fiber (B) produced by the method shown in Comparative Example 1 was dipped. The dyeing was carried out at 95 ° C. for 30 minutes. Subsequently, a dye fixing treatment was carried out in the same manner as in Example 1 to produce a dyed interlaced knitted fabric. This knitted fabric was treated with an aqueous solution of sodium hypochlorite. The results are shown in Table 2. In Table 2, (B) indicates spandex fiber, (C) indicates ordinary nylon 6 fiber, and the amount of addition is% by weight of interlaced knitted fabric.
Indicates.

-Example 8- 4,4'-biphenol 5% o as a chlorine fading inhibitor
A dyed and knitted fabric was produced in the same manner as in Example 7 except that wf was used. This knitted fabric was treated with an aqueous solution of sodium hypochlorite. The results are shown in Table 2.

Example 9 A cross-knitted fabric dyed in the same manner as in Example 7 was prepared except that 4,4'-dihydroxydiphenylsulfone 5% owf was used as a chlorine fading inhibitor. This knitted fabric was treated with an aqueous solution of sodium hypochlorite. The results are shown in Table 2.

Example 10 A cross-knitted fabric dyed in the same manner as in Example 7 was prepared except that 4,4′-methylenebisphenol 5% owf was used as a chlorine fading inhibitor. This knitted fabric was treated with an aqueous solution of sodium hypochlorite. The results are shown in Table 2.

-Comparative Example 2-Nylon 6 fiber (C) dyed with the same formulation as in Comparative Example 1 except that tannic acid / tartar tar treatment is performed as a dye fixing agent.
And a polyurethane urea elastic fiber (B) were used as a knitted and knitted fabric, and treated with an aqueous solution of sodium hypochlorite. The results are shown in Table 2.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

According to the present invention, the chlorine and fading resistance of woven fabrics and knitted fabrics using polyamide fibers can be dramatically improved without impairing the color of the dyed product. It becomes possible to provide products with excellent chlorination.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location D06M 13/152 // D06M 101: 34 (72) Inventor Koji Shirahaku 2 Katata, Otsu City, Shiga Prefecture No. 1-1 Toyobo Co., Ltd. Research Institute (72) Inventor Hajime Hajime 2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo Co., Ltd. Research Institute

Claims (4)

[Claims] 1. A general formula 1, a chemical formula 2, and a chemical formula 3 shown below.
At least one or more mono- and / or polyhydroxybenzene derivatives mainly containing phenol represented by the formula (1) are contained in an amount of 0.1 to 20% with respect to 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 R1 and R2 and is a trivalent group such as an alkylene group, an ether group, a sulfonyl group, a sulfide group or an azo group, and B1 is an alkyl group, an alkoxy group or a nitro group. Group, sulfone group, monovalent group such as amino group or hydrogen atom, B2, B3, B4
And B5 each represent the same or different monovalent group or hydrogen atom as B1. Also, k, l, m, n, and
s, t, u, v, x and y are positive integers that satisfy the following formula (Q) 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 for producing a polyamide fiber according to claim 1, which is obtained by adding the compounds represented by the general formulas 1, 2, and 3 to polyamide and spinning the mixture. 3. The polyamide fiber according to claim 1, which is obtained by spinning a polyamide fiber, and then subjecting the compound represented by the general formulas 1, 2, and 3 to a high temperature immersion treatment to adhere the compound to the fiber. Manufacturing method. 4. The polyamide fiber according to claim 1, wherein the compound group contained is a multimer containing the compounds represented by the general formulas 1, 2, and 3 as monomers.