JPH05195322A - Polyurethane elastic fiber - Google Patents

Abstract

PURPOSE:To improve the chlorine deterioration resistance of a polyurethane elastic fiber. CONSTITUTION:A polyurethane elastic fiber having excellent chlorine deterioration resistance is produced by adding at least one kind of substance having a chlorine-reaction quantity of 50 m-eq/g determined by the method described in the specification to a polyurethane or a polyurethane solution and spinning the mixture.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to polyurethane-based elastic fibers. More specifically, polyurethane (hereinafter, polyurethane is a generic term for polyurethane and polyurethaneurea in the present invention) or at least one kind of a polyurethane solution having a reaction amount of chlorine of 50 meq / g measured by the method shown in the text. The present invention relates to a polyurethane-based elastic fiber obtained by adding 0.1 to 20% by weight to the fiber weight and spinning the resulting fiber to prevent deterioration in various chlorine-containing environments.

[0002]

2. Description of the Related Art Polyurethane elastic fibers obtained from 4,4'-diphenylmethane diisocyanate, polyhydroxy polymers having a relatively low degree of polymerization and polyfunctional active hydrogen compounds have a high degree of rubber elasticity, and have tensile stress and recovery. Since it has excellent physical properties such as properties, and also has excellent properties regarding thermal behavior, it has received a great deal of attention as a functional material for clothing such as foundations, socks, and sportswear. However, it is known that washing with chlorine bleaching on such products consisting mainly of long-chain synthetic elastic segmented polyurethanes causes a considerable reduction in the physical properties of the segmented polyurethanes. A swimsuit made of segmented polyurethane elastic fiber and polyamide has an active chlorine concentration of 0.5 to 3 in the swimming pool.
It is known that exposure to chlorine water containing ppm results in a decrease in the physical properties of the fiber. The resistance to such chlorine-induced deterioration has been conventionally improved. For example, zinc oxide (Japanese Patent Publication No. Sho 6) is used as a chlorine deterioration inhibitor.
0-43444), magnesium oxide, and aluminum oxide (Japanese Patent Publication No. Sho 61-35283).

[0003]

In polyurethane elastic fibers containing an inorganic metal compound such as zinc oxide, magnesium oxide, aluminum oxide, etc., these additives do not dissolve in an organic solvent or polyurethane, so that they are compatible with each other. It has the disadvantage of not doing so, and the industrial productivity of polyurethanes or polyurethane solutions containing them is somewhat reduced. Further, when passing through post-processing such as dyeing, there is a possibility that these additives are dissolved or fallen off by dipping in a treatment bath, and effective chlorine deterioration resistance is impaired.
Further, tannic acid which is generally used as a dye fixing treatment and a discoloration fastness improving treatment for a dyed product by chlorine after dyeing a fabric obtained by interlacing fibers containing such a basic additive with an acid dye or the like. -When tartar treatment is carried out, the basic additive in the fiber oxidizes two adjacent hydroxyl groups contained in the galloyl group in the tannic acid molecule to irreversibly form a quinone structure, resulting in a dark color such as brown. Therefore, the conventional tannic acid treatment may be restricted because it is colored in the color and changes 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, in the present invention, the reaction amount of chlorine measured by the following method is 50
Provided is a polyurethane-based elastic fiber having excellent chlorine deterioration resistance, characterized in that at least one kind of substance having a milliequivalent / g is contained in an amount of 0.1 to 20% by weight based on the weight of the fiber. In the present invention, the compound group is added to polyurethane or a polyurethane solution, and spinning is carried out.
It improves the chlorine resistance of the polyurethane elastic fiber 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.

[0005]

[Measurement Method of Reaction Amount of Chlorine] A method of measuring the reaction amount of chlorine (hereinafter referred to as C) is shown below. In the measurement method,% is% by weight
Indicates. (1) Reagent and its preparation method Sodium hypochlorite solution Sodium hypochlorite manufactured by Nacalai Tesque, Inc. (special grade reagent)
Dilute 30 g to 1 liter with pure water. Dilute acetic acid aqueous solution (10%) Dilute 5 g of acetic acid with pure water to bring the total amount to 50 g. Starch indicator (5%) Soluble starch (1 g, manufactured by Nacalai Tesque, Inc.) is dissolved in pure water to make the total amount 20 g. Nacalai Tesque acetate special grade reagent is used as it is. Aqueous potassium iodide solution (20%) 100% potassium iodide (special grade reagent) manufactured by Nacalai Tesque, Inc.
g is dissolved in pure water to make the total amount 500 g. N / 10 sodium thiosulfate standard solution The standard solution manufactured by Nacalai Tesque, Inc. is used as it is. (Strength of defined solution; f) Solvent A proper solvent is selected according to the property of the substance (hereinafter referred to as sample) whose reaction amount of chlorine is measured. In this case, chloroform, methanol, ethanol, isopropyl alcohol, methyl isopropyl ketone (all above are special grade reagents manufactured by Nacalai Tesque, Inc.), pure water, etc., and / or
Or it mixed and used. (2) Preparation of sample solution A predetermined amount of the sample (Sg, preferably about 0.1 g) is precisely weighed with an analytical balance and dissolved in a solvent (selected in (1)-) in a 100 ml volumetric flask, 100 in total
ml. (3) Equipment used (numbers in parentheses are shown) 25 ml Burette (1) Whole pipette 25 ml (1), 10 ml (2), 5 ml
(1) 2 ml (1) Measuring pipette 10 ml (1) Erlenmeyer flask with stopper 100 ml (measurement number + 2 for blank test) Magnetic stirrer, stirrer (same number as Erlenmeyer flask) Clock (1) (4) Chlorine Reaction volume quantitative operation Put N / 10 sodium thiosulfate normal solution into a 25 ml buret. A 25 ml hole pipette is used to dispense a sodium hypochlorite solution into each 100 ml Erlenmeyer flask containing the stirrer for the number of measurements. Prepare two blank tests. Dispense the sample solution into an Erlenmeyer flask using a 10 ml hole pipette. 10 ml of solvent for blank test
Dispense. While stirring, 1 ml of 10% dilute acetic acid aqueous solution is added to all Erlenmeyer flasks using a 10 ml measuring pipette. The time when the dilute acetic acid aqueous solution is first added is set to 0 minutes, and the timing is started. After reaching the predetermined time, take one Erlenmeyer flask,
5 ml of 20% potassium iodide aqueous solution and 2 ml of acetic acid
Added. The standard reaction time is 5, 10, 20, 30, 40 minutes. With stirring, sodium thiosulfate normal solution is added dropwise until there is almost no color. Add a few drops of starch indicator,
Continue dripping until the purple color has completely disappeared. The point where the purple color has completely disappeared is used as the titration end point. Hereinafter, the titration amount is measured by the same operation at each predetermined time. (Required titration amount: Vm
l) For the blank test, perform the titration in the same manner as immediately after the addition of dilute acetic acid and after the titration of the sample containing the sample. The average value of these two times is used as the required titration amount (V ₀ ml) of the blank test. (5) Calculation of reaction amount (C) of chlorine Reaction time is x, (V ₀ -V) of each reaction time is y,
The correlation between x and y was obtained by the method of least squares in the form of the following equation (1). y = a + bx (correlation coefficient: r) Formula (1) The linear correlation coefficient is preferably 0.98 or more from the viewpoint of measurement accuracy. The reaction time (y) of the obtained straight line was extrapolated to 0 (that is, a), and C was calculated by the following equation (2). C = a × f ÷ S Formula (2) (unit of C; milliequivalent / g, f; titer of N / 10 sodium thiosulfate normal solution, S; sample amount (g))

In the present invention, the substance having a reaction amount of chlorine of 50 meq / g is 4,4'-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 "-
Ethyridine 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)
Diphenylmethane derivatives having a hydroxyl group introduced such as methane and 2,2'-bis (3,6-dihydroxynaphthyl) methane, and multimers using 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 multimer 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 these as monomers, diphenyl ether derivatives having a hydroxyl group introduced such as 4,4'-dihydroxydiphenyl ether and bis (3,5-dihydroxyphenyl) ether, 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.

Further, 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
Biphenyl derivatives having a hydroxyl group introduced therein such as ′ -trihydroxybiphenyl, 2,4,4′-trihydroxybiphenyl, 2,6,4′-trihydroxybiphenyl and 3,3 ′, 5,5′-tetrahydroxybiphenyl, and Polymers containing 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, Examples thereof include a binaphthyl derivative having a hydroxyl group introduced therein such as 1′-bis (7-hydroxynaphthyl) and 1,1′-bis (8-hydroxynaphthyl), and a multimer using these as a monomer.

Further, 3-hydroxybenzoic acid and / or methyl, ethyl, isopropyl, t-butyl, amyl and stearyl esters containing the same as an acid component and multimers of these as monomers, 4-hydroxybenzoic acid and / or Or methyl, ethyl, which uses this as an acid component
Isopropyl, t-butyl, amyl and stearyl esters and multimers of these as monomers, 3,5-dihydroxybenzoic acid and / or methyl, ethyl, isopropyl, t-butyl, amyl and stearyl containing the same as an acid component Esters and multimers of these as monomers, 2,4-dihydroxybenzoic acid and / or methyl, ethyl, isopropyl, t-containing the same as an acid component
Butyl, amyl and stearyl esters and multimers using them as monomers, hydroxyacetophenones such as 3-hydroxyacetophenone, 4-dihydroxyacetophenone, 3,5-dihydroxyacetophenone, and 2,4-dihydroxyacetophenone, and a single amount thereof Body multimers, 3-hydroxybenzyl ethyl ketone, 4-hydroxybenzyl ethyl ketone, 3-hydroxybenzyl-isolopyrketone, 4-hydroxybenzyl-isoropyl ketone, 3-hydroxybenzyl butyl ketone, 4-hydroxybenzyl butyl ketone,
Hydroxybenzyl ketones such as 3-hydroxybenzyl amyl ketone, 4-hydroxybenzyl amyl ketone, 4-hydroxybenzyl stearyl ketone, and 3-hydroxybenzyl stearyl ketone, and multimers using these as monomers, isopropylphenol, butylphenol, amyl Examples thereof include alkylphenols such as phenol, and multimers including these as monomers.

When a substance having a reaction amount of chlorine measured by the above method of the present invention of 50 meq / g or more is used, it may be used alone or in combination of two or more kinds. The substance used as a chlorine fading inhibitor in the present invention preferably has a reactivity with chlorine measured by the above method of 60 meq / g or more from the viewpoint of performance, and more preferably 70 mm. It is desirable that the dyed product contains an equivalent amount / g or more of the substance. Further, the substance used as a chlorine deterioration inhibitor in the present invention is preferably a substance having a high whiteness or being colorless, from the viewpoint of the influence on the color of the dyed product. It is more preferable that the number of substituents other than the hydroxyl group introduced in the above is smaller, and particularly preferable are 4,4′-biphenol, bisphenol A, 4,4′-dihydroxydiphenyl sulfone, and 4,4′-methylenebisphenol. Even if the substance has a reactivity with chlorine measured by the above method of 50 meq / g or more, hydroxybenzophenone derivatives, catechols, pyrogallols, and gallic acid esters, which are themselves colored, are not preferable. Of the substance group having a reactivity with chlorine measured by the above method of the present invention of 50 meq / g or more, it reacts with a basic additive contained in polyamide fiber and / or polyester fiber or polyurethane fiber. A polyhydroxybenzene derivative (hydroquinone, catechol, pyrogallol or a derivative thereof) in which a hydroxyl group is located in the ortho position and / or the para position, which develops a color when it becomes a quinone structure, is preferable because it impairs the hue of the fiber. However, polyhydroxybenzene derivatives (phenol, resorcin, phloroglucinol and their derivatives) having a monohydroxy and / or hydroxyl group in the meta position that does not take a quinone structure when oxidized are preferable.

The method of applying the chlorine deterioration inhibitor according to the present invention to polyurethane or a polyurethane solution may be carried out by a conventionally known method, for example, the polymer and each component of the additive may be sequentially mixed. Alternatively, each component of the additive may be prepared in advance as a solution and then mixed with the polymer.

The polyurethane-based 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, a small amount of a terminating agent such as monoamine or monoalcohol may be used in combination with these compounds. However, preferred are diamines alone or mainly.

The polyurethane-based composition is spun into elastic fibers, but is not particularly limited, but it is preferable to dissolve the polyurethane-based composition in a solvent and dry-spin it. 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. Further, these metal compounds may be supplementarily added and used together with the chlorine-reactive substance group according to the present invention. Particularly preferred is magnesium oxide or zinc oxide. The addition to these polyurethane solutions is not particularly limited, but the average particle size is 0.
It is preferably added as particles having a particle size of 05 to 3 μm, and the amount thereof is preferably 0.5 to 5.0% by weight based on the polyurethane.

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.

[0017]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto. In the following examples, the polyurethane elastic fiber is made to contain at least one kind of substance group having a reaction amount of chlorine of 50 meq / g measured by the above-mentioned method. An example of the improvement of chlorine deterioration will be described. In addition, parts and% in the examples
Means parts by weight and% by weight. -Example 1-A polytetramethylene ether glycol having hydroxyl groups at both ends and having a number average molecular weight of 2000 and 4,4'-diphenylmethane diisocyanate are reacted at a molar ratio of 1: 2 to prepare a prepolymer, and then 1 , 2-propylenediamine was subjected to chain extension to obtain a polyurethane solution having a polymer concentration of 30% (solvent is N, N-dimethylformamide) and a viscosity of 2000 poise (30 ° C.). 3% of 4,4'-dihydroxybiphenyl (reactive amount of chlorine; C = 98.7 meq /
g) was added as a dimethylformamide solution, and then a whiteness improver, an antioxidant, an ultraviolet absorber and a gas yellowing inhibitor were added and mixed with stirring to obtain a spinning dope.

After defoaming, the spinning dope 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 at 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.

After refining, relaxing, drying and heat setting the polyurethane elastic fiber thus obtained,
Dyeing was performed. For dyeing, 0.4 g / L of acetic acid, 2 g / L of ammonium sulfate and 1.2 g / L of anionic leveling agent were dissolved in a dyeing bath, and a bath ratio of 1:13 was used to dye: Kayacyl Blue BR,
It was carried out under the conditions of 5% owf (acid dye) and 40 ° C. to 95 ° C. for 60 minutes. It was washed with hot water at 50 ° C. for 10 minutes, and subsequently, a dye fixing treatment was performed using an anionic polyphenol which was not tannic acid. The resulting dyed polyurethane elastic fiber is stretched and dehydrated, and deliquored with a mangle, and then 1
By drying at 60 ° C. and setting, a dyed polyurethane elastic fiber (B) was obtained.

The obtained (A) fiber and (B) fiber are stretched in the yarn length direction by 40%, and the effective chlorine concentration is 30 pp.
Immersion in 800 parts of chlorine water having a pH of 7.0 and a bath temperature of 30 ° C. for 6 hours, and the deterioration resistance of the yarn due to the chlorine water was evaluated. The stress retention rate before and after immersion of each fiber is shown in Table 1 below.

Example 2-Polyurethane elastic fibers and dyed polyurethane elastic fibers were prepared by the same formulation as in Example 1 except that 4,4'-dihydroxybiphenyl, 1.5% was used as a chlorine deterioration inhibitor. Then, the deterioration resistance due to chlorine water was evaluated. The results are shown in Table 1 below.

Example 3-Polyurethane elastic fiber and polyurethane elastic fiber having the same formulation as in Example 1 except that bisphenol A (reaction amount of chlorine; C = 79.5 meq / g), 3%, is used as a chlorine deterioration inhibitor. A dyed polyurethane elastic fiber was prepared, and its deterioration resistance to chlorine water was evaluated. The results are shown in Table 1 below.

Example 4-Polyurethane elastic fibers and dyed polyurethane elastic fibers were prepared by the same formulation as in Example 1 except that bisphenol A, 1.5% was used as a chlorine deterioration inhibitor.
The deterioration resistance due to chlorine water was evaluated. The results are shown in Table 1 below.

-Example 5- 4,4'-dihydroxydiphenyl sulfone as a chlorine deterioration inhibitor (reaction amount of chlorine; C = 73.9 meq /
Polyurethane elastic fibers and dyed polyurethane elastic fibers were prepared with the same formulation as in Example 1 except that g) and 3% were used, and the deterioration resistance to chlorine water was evaluated. The results are shown in Table 1 below.

Example 6 3,5-dihydroxybenzyl ethyl ketone as a chlorine deterioration inhibitor (reaction amount of chlorine; C = 76.1 milliequivalent /
Polyurethane elastic fibers and dyed polyurethane elastic fibers were prepared with the same formulation as in Example 1 except that g) and 3% were used, and the deterioration resistance to chlorine water was evaluated. The results are shown in Table 1 below.

Example 7 As a chlorine deterioration inhibitor, bisphenol A was used as a monomer, and Horsera-dish peroxidase was used.
A bisphenol A polymer (average molecular weight 1000) (reaction amount of chlorine; C = 56.3 meq / g) produced by reacting with an enzyme as a catalyst, the same formulation as in Example 1 except that 3% was used. Polyurethane elastic fibers and dyed polyurethane elastic fibers were produced and evaluated for deterioration resistance to chlorine water. The results are shown in Table 2 below.

Example 8 A polyurethane elastic fiber and a dyed polyurethane elastic fiber having the same formulation as in Example 1 except that 4,4'-dihydroxybiphenyl, 0.2% was used as a chlorine deterioration inhibitor. It was prepared and evaluated for its resistance to deterioration by chlorine water.
The results are shown in Table 2 below.

-Example 9-A polyurethane-based elastic fiber was produced in the same manner as in Example 1, except that 5% owf of tannic acid and 2.5% owf of tartar were used as a dye fixing agent during dyeing. Polyurethane elastic fibers dyed with the same formulation as 1 were produced, and the deterioration resistance of these elastic fibers to chlorine water was evaluated. The results are shown in Table 2 below. -Comparative Example 1-A polyurethane elastic fiber and a dyed polyurethane elastic fiber having the same formulation as in Example 1 were produced without adding any chlorine deterioration inhibitor, and the deterioration resistance to chlorine water was evaluated. The results are shown in Table 2 below.

Comparative Example 2 A polyurethane type elastic fiber and a dyed polyurethane type elastic fiber were prepared by the same formulation as in Example 1 except that 3% of magnesium oxide was used as a chlorine deterioration inhibitor, and it was resistant to chlorine water. The deterioration property was evaluated. The results are shown in Table 2 below.

Comparative Example 3 A polyurethane elastic fiber having the same formulation as in Example 1 except that 3% of magnesium oxide was used as a chlorine deterioration inhibitor, and 5% of tannic acid was used as a dye fixing agent during dyeing.
Example 1 except using wf and tartarite 2.5% owf
Polyurethane elastic fibers dyed with the same formulation as above were prepared, and the deterioration resistance of these elastic fibers to chlorine water was evaluated. The results are shown in Table 2 below.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a product having excellent chlorine resistance, which is capable of improving the deterioration of chlorine in polyurethane elastic fibers used in a chlorine-containing environment due to chlorine.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shoji Ido 2-1-1 Katata, Otsu City, Shiga Toyobo Co., Ltd. Research Institute (72) Inventor Hajime 2-1-1 Katata, Otsu City, Shiga Prefecture No. Toyobo Co., Ltd.

Claims (1)

[Claims] 1. At least one substance having a reaction amount of chlorine of 50 meq / g or more measured by the method shown in the present text is contained in an amount of 0.1 to 20% by weight based on the weight of fiber. Polyurethane elastic fiber.