JPH11229235A - Polyurethane elastic yarn and its elastic cloth for swimming suit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyurethane elastic yarn having excellent dyeing fastness to chlorine and chlorine durability, useful as a yarn for an elastic cloth for swimming suit, by including a specific metal compound and a prescribed phosphoric ester compound. SOLUTION: A polymer diol having 500-5,000 number-average molecular weight and containing hydroxyl groups at both terminal groups is reacted with an organic diisocyanate and a polyfunctional active hydrogen-containing chain extender to give a polyurethane polymer. The polymer in an amount of 100 pts.wt. is mixed with 0.1-10 pts.wt. of at least one kind among an oxide, a compound oxide and a hydroxide of a metal selected from Mg, Zn and Al or a hydrotalcite compound and an effective amount of a phosphoric ester compound of the formula (R is a 1-30C straight-chain or branched-chain alkyl, a 5-6C cycloalkyl or the like; (n) is 1 or 2) to give the objective yarn capable of suppressing reduction in activity of a metal compound which is a chlorine deterioration inhibitor even by dye fixing treatment of a cross knitted and woven fabric with a polyamide-based yarn and/or a polyester-based yarn.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION Polyurethane elastic fibers of a polyurethane polymer obtained from an organic diisocyanate, a polymer diol and a chain extender having a polyfunctional active hydrogen atom are generally called spandex and have excellent rubber elasticity. . For this reason, cross-knitted fabrics that are mixed and knitted, mixed and woven with various fibers such as polyester and polyamide, and dyed are now being used more and more widely as various stretch material clothing and sports clothing. TECHNICAL FIELD The present invention relates to a polyurethane elastic fiber having excellent chlorine resistance. More specifically, a cross-knitted fabric of polyurethane elastic fiber and other natural or synthetic fibers, especially when used for swimwear, has a chlorine durability and chlorine resistance under an active chlorine water environment for disinfection in a swimming pool. The present invention relates to a polyurethane elastic fiber having good dyeing fastness and an elastic cloth for watering the same with a polyamide-based fiber or a polyester-based fiber.

[0002]

2. Description of the Related Art Swimwear using a fabric obtained by cross-knitting, weaving and dyeing polyurethane elastic fibers with other natural fibers, chemical fibers and synthetic fibers has an active chlorine concentration of 0.5 to 3 ppm in a pool.
When repeatedly exposed to chlorine water, the polyurethane elastic fiber is deteriorated by chlorine and its physical performance is deteriorated. As a result, there has been a problem that when the swimsuit wears, the pressure on the swimsuit decreases, and the swimsuit shifts or degrades due to the flow of water or the water pressure during swimming, and the polyurethane elastic fibers in the fabric break. As another problem, there has been a problem that dyes dyed on other natural fibers, chemical fibers, and synthetic fibers are deteriorated by chlorine and the dyes of swimwear are discolored.

[0003] In order to improve the chlorine durability of polyurethane elastic fibers, it has been proposed to add various chlorine deterioration inhibitors. For example, zinc oxide (JP-B-60-4344)
No. 4), magnesium oxide, aluminum oxide (JP-B-61-35283), hydrotalcite compounds (JP-A-59-133248), and a solid solution of magnesium oxide and zinc oxide (JP-A-6-81215). A method has been proposed for improving the chlorine durability by adding a metal compound such as that disclosed in U.S. Pat.

[0004] On the other hand, with respect to the prevention of discoloration and fading of dyes due to chlorine, at the time of dyeing a fabric, a process for stabilizing and fixing the dye of the fabric using a polyphenol compound in a post-process after dyeing is widely used. Is being done. In the fixing treatment, the phenolic compound fixing agent used is roughly classified into a natural tannin mainly composed of tannic acid and a formalin condensate of diphenylsulfone which is a synthetic tannin and 4,4′-methylenebisphenol and naphthalenesulfonic acid. Examples include compounds such as formalin condensates, polyhydric phenol derivatives, and aromatic polymer derivatives. The fixing treatment is excellent in the effect of improving the color fastness by chlorine.

However, when a polyurethane elastic fiber cloth containing the metal compound is subjected to a fixing treatment,
The metal compound contained in the polyurethane elastic fiber is easily eluted into the fixing bath, or the phenol compound is adsorbed on the surface of the metal compound,
As a chlorine deterioration inhibitor, there has been a problem that the activity with respect to chlorine is reduced and the chlorine durability of the polyurethane elastic fiber is greatly reduced. For this reason, fixing treatment with synthetic tannic acid was sometimes performed, but the chlorine dyeing fastness of the water-knitted knitted fabric was reduced, and the chlorine durability of the polyurethane elastic fiber was not at a satisfactory level.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to add a polyurethane knitted woven fabric of polyurethane elastic fiber to a polyurethane elastic fiber during a fixing process using a phenol compound in a dyeing process. Metal oxides are eluted into the dyeing bath or phenol fixation treatment bath and suppress the decrease in activity of the metal compound against chlorine, and provide excellent chlorine dyeing fastness and excellent chlorine durability polyurethane elastic fiber and its water-attaching elastic fabric. To provide.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve these problems, and as a result, they have specified amounts of a specific metal compound and a specific phosphate compound as a chlorine deterioration inhibitor. The polyurethane elastic fiber and a fabric using the elastic fiber have been found to simultaneously satisfy both color fastness to chlorine and chlorine durability, and have completed the present invention.

That is, the present invention relates to (a) a number average molecular weight of 5
Polyurethane polymer 1 obtained by reacting a polymer diol having hydroxyl groups at both terminal groups of 00 to 5000 with an organic diisocyanate and a chain extender having a polyfunctional active hydrogen atom
(B) one or two metal compounds selected from the group consisting of oxides, composite oxides, hydroxides and hydrotalcite compounds of metals selected from Mg, Zn and Al
0.1 to 10 parts by weight of the seed or more, and (c) the following formula (1)
Is a polyurethane elastic fiber containing an effective amount of a phosphate compound represented by the formula (1).

[0009]

Embedded image (Where R is a linear or branched alkyl group having 1 to 30 carbon atoms, an alkoxypolyoxyalkylene group, a cycloalkyl group having 5 to 6 carbon atoms, 1 to 10 carbon atoms)
A cycloalkyl group having 5 to 6 carbon atoms substituted by an alkyl group, and n represents an integer of 1 or 2. The addition amount of the phosphoric acid ester compounds is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the metal compound.

The metal compounds according to the present invention are Mg, Z
Oxides, composite oxides, hydroxides and hydrotalcite compounds of metals selected from n and Al are one or more metal compounds. As such a metal compound,
For example, magnesium oxide, magnesium hydroxide, zinc oxide, zinc hydroxide, aluminum oxide, aluminum hydroxide, a hydrotalcite compound (for example, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H
₂ O) a divalent metal M (where M represents at least one selected from zinc and magnesium) and aluminum, and the molar ratio of the divalent metal to aluminum is 1
To 5 are listed. Particularly preferred metal compounds are MgO, ZnO, composite oxides of MgO and ZnO, hydrotalcite compounds, and, for example, the following composite oxides represented by the following formula.

[0011]

Embedded image 2ZnO.ZnAl ₂ O ₄ 3ZnO.ZnAl ₂ O ₄ 4ZnO.ZnAl ₂ O ₄ 5ZnO.ZnAl ₂ O ₄ These complex oxides can be obtained by, for example, firing a hydrotalcite compound ( Japanese Patent Publication No. 51-376
No. 40 and Japanese Patent Publication No. 51-20997).
It is not limited to this. The metal compounds are preferably added before the spinning step of polyurethane elastic fibers in order to enhance the effect of preventing chlorine deterioration. The addition amount of the metal compound is 0.1 to 100 parts by weight of the polyurethane polymer.
It is in a range of 10.0 parts by weight, preferably 0.5 to 7.0 parts by weight. Excessive addition of these metal compounds in an amount of 10.0 parts by weight or more is not preferable because it adversely affects spinning stability during production and elastic recovery of polyurethane elastic fibers, and a sufficient effect is not more than 0.1 parts by weight. Can't expect.

In the present invention, these metal compounds are preferably fine powders having an average particle diameter of 1 μm or less from the viewpoint of spinning stability. The surface of the inorganic metal compound particles may or may not be surface-treated with a fatty acid, a fatty acid ester, a silane coupling agent, a titanate coupling agent, or a mixture thereof. The phosphate compound used in the present invention is a compound represented by the formula (1).

Preferred examples of the phosphoric acid ester include mono- or dimethyl acid phosphate, mono- or diethyl-acid phosphate, mono- or di-propyl acid phosphate, mono- or di-isopropyl acid phosphate, mono- or dibutyl acid phosphate, mono- or dibutyl acid phosphate. Dilauryl acid phosphate, mono or distearyl acid phosphate, mono or di (2-ethylhexyl) acid phosphate, mono or diisodecyl acid phosphate, mono or dibutoxyethyl acid phosphate, mono or dioleyl acid phosphate, Mono or ditetradecyl acid phosphate, mono or di (2-hydroxyethyl) methacrylate acid phosphate, polyoxyalkylene glycol alkylene Chromatography ether acid phosphate compound can be mentioned. These phosphoric esters may be used in a mono- or di-form, alone or in combination of different kinds.

The phosphate compound is a compound represented by the formula (1)
Of 1 to 30 carbon atoms, preferably 3 to 3 carbon atoms
25 are preferred. More preferably, it has 10 to 2 carbon atoms.
0. The phosphate compound may be contained in the polyurethane polymer before spinning the polyurethane elastic fiber. In order to effectively include the phosphate compound in the polyurethane elastic fiber, it is preferable to add the compound at a stage before the spinning from the time of polyurethane polymerization.

The amount of the phosphoric acid ester compound is 0.01 to 10 parts by weight based on 100 parts by weight of the metal oxide based on the metal compound added to the polyurethane polymer.
Parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight. The phosphate compound exhibits its effect even with a very small amount of about 10 ppm to 1 part by weight based on 100 parts by weight of the polyurethane elastic fiber. The step of adding the phosphate ester compound can be performed in a step from before the polymerization to before the spinning step as long as it does not adversely affect the polyurethane polymerization reaction. Preferably, it is added after the completion of the polyurethane polymerization.

The high molecular weight diol which is one of the raw materials of the polyurethane polymer of the present invention is a substantially linear polymer having a molecular weight of 500 to 5,000 having hydroxyl groups at both ends, for example, polyoxyethylene. Homopolyether diols such as glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxypentamethylene glycol, or 2 having 2 to 6 carbon atoms
Copolymerized polyether diols composed of at least one kind of oxyalkylene; one or more dibasic acids such as adipic acid, sebacic acid, maleic acid, itaconic acid, azelaic acid, malonic acid and ethylene glycol; -Propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propanediol,
1,4 butanediol, 1,3-butanediol, hexamethylene glycol, diethylene glycol, 1,
Polyester diol obtained from one or more glycols such as 10-decanediol, 1,3-dimethylolcyclohexane and 1,4-dimethylolcyclohexane; or polyesteramide diol; polyester ether diol; Polylactone diols such as caprolactone diol and polyvalerolactone diol; and polycarbonate diols. Preferably, polyoxytetramethylene glycol, copolymerized poly (tetramethylene neopentylene)
Ether diol, copolymerized poly (tetramethylene 2-
Methylbutylene) ether diol.

As the organic diisocyanate, for example,
Among the aliphatic, alicyclic and aromatic diisocyanates, any of those which are soluble or liquid under the reaction conditions can be applied. For example, methylene-bis (4-phenyl isocyanate), methylene-bis (3-methyl-4-phenyl isocyanate), 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, m- and p-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-xylylene diisocyanate, m- and p-phenylene diisocyanate, 4,4′-dimethyl-1 ,
3-xylylene diisocyanate, 1-alkylphenylene-2,4 and 2,6-diisocyanate, 3- (α
-Isocyanatoethyl) phenyl isocyanate,
2,6-diethylphenylene-1,4-diisocyanate, diphenyl-dimethylmethane-4,4-diisocyanate, diphenylether-4,4′-diisocyanate, naphthylene-1,5-diisocyanate, 1,6
-Hexamethylene diisocyanate, methylene-bis (4-cyclohexyl isocyanate), 1,3- and 1,4-cyclohexylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like. Can be Preferably, it is methylene-bis (4-phenyl isocyanate).

Examples of the chain extender having a polyfunctional active hydrogen atom include hydrazine, polyhydrazine, and linear or branched aliphatic, alicyclic and aromatic active hydrogen having 2 to 10 carbon atoms. Examples of the compound having an amino group include ethylenediamine, 1,2-propylenediamine, diamines such as diamines having a urea group described in JP-A-5-155841, hydroxylamine, and water, and low-molecular-weight glycols. For example, ethylene glycol, 1,2-propylene glycol, 1,3-
Propylene glycol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, hexamethylene glycol, diethylene glycol, 1,10-decanediol, 1,3-dimethylolcyclohexane , 1,4-dimethylolcyclohexane and the like can be used. Preferably, they are ethylenediamine and 1,2-propylenediamine.

As the terminal terminator having a monofunctional active hydrogen atom, for example, dialkylamine such as diethylamine is used. These chain extenders and terminal stoppers may be used alone or in combination of two or more. Regarding a method for producing a polyurethane polymer using a polyalkylene ether diol, a diisocyanate compound, and a diamine compound, a known polyurethane-forming reaction technique can be used. For example, a polyalkylene ether diol and an organic diisocyanate are used in a ratio of 1: 1.2 to
The reaction is carried out at a ratio of 2.0, preferably 1: 1.3 to 1.8 (molar ratio) to synthesize a urethane prepolymer having isocyanate groups at both ends to obtain a urethane moiety. Next, the urethane prepolymer is subjected to a chain elongation reaction with a diamine compound and a glycol compound to obtain a polyurethane polymer.

Regarding the operation of the polyurethane-forming reaction, a solvent such as dimethylformamide, dimethylsulfoxide and dimethylacetamide may be used at the time of synthesizing the urethane prepolymer or at the time of reacting the urethane prepolymer with an active hydrogen-containing compound. In addition, the stoichiometric ratio of the various compounds used in the present invention is such that the sum of the hydroxyl groups of the polyalkylene ether diol and the active hydrogens of the diamine compound and the like is 1.00 to 1.07 with respect to the isocyanate group of the isocyanate compound. Desirably, it is an amount.

In the polyurethane polymer composition, in addition to the above-mentioned inorganic metal compound, additives of known organic or inorganic compounds used for polyurethane elastic fibers, for example, heat stabilizers, antioxidants, ultraviolet absorbers, yellowing An inhibitor, a thermal discoloration inhibitor, an antiblock agent, a pigment, an antistatic agent, a fungicide, a colorant, a filler, and the like may be added in combination. The polyurethane polymer composition thus obtained is spun by a known dry spinning method, wet spinning method or the like.

Polyurethane-modified silicone, polyether-modified silicone, polyorganosiloxane, amino-modified silicone,
Mineral oil particles such as mineral oil, talc, silica, and colloidal alumina; powders of higher fatty acid metal salts such as magnesium stearate and calcium stearate; solid waxes at room temperature such as higher aliphatic carboxylic acids, higher aliphatic alcohols, paraffin, and polyethylene And the like.

The polyurethane elastic fiber used in the present invention is not knitted or woven alone, but is knitted and woven with other natural fibers, chemical fibers and synthetic fibers to form a fabric. Become. The polyurethane elastic fiber in the present invention does not select other fibers to be a knitted fabric. However, synthetic fibers are widely used at present because of their durability against wear and stretching fatigue when wearing swimwear products, the texture felt by the human body during wearing, and the form stability of the products.

As synthetic fibers, polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, copolymerized polyterephthalate containing polytetramethylene glycol and ethylene glycol as diol components as main components, and cationic dyeable polyester fibers thereof, Nylon 6, Nylon 66
Synthetic fibers such as polyamide, polyacrylic, polypropylene, polyvinyl chloride, polyvinyl alcohol, etc .; regenerated cellulose fibers such as copper ammonia rayon, viscose rayon, purified cellulose fibers, regenerated protein fibers, semi-synthetic fibers, and cotton. , Silk, wool, and other natural fiber materials, as well as covering, core spun yarn, air covering, ply twist, twist twist, interlaced conjugate fibers and their respective fibers as they are, circular knit fabric, flat knit fabric, It is processed into a cross-knitted / cross-woven fabric which is cross-knitted or cross-woven such as warp knitting and dyed and used for various purposes.

Various knitting methods are used to produce a knitted fabric composed of polyurethane elastic fibers and other natural fibers, chemical fibers and synthetic fibers. The knitted knitted fabric may be warp knit or weft knit, and examples thereof include tricot, Russell, and circular knit. The knitting organization is half knitting, reverse half knitting,
Any knitting structure such as double atlas knitting and double denby knitting may be used. In addition, from the viewpoint of texture, it is preferable that the surface of the knitted fabric is made of other natural fibers, chemical fibers, and synthetic fibers. A woven fabric composed of polyurethane elastic fibers and other natural fibers, synthetic fibers, and synthetic fibers is woven by a usual method. The fabric may be either one-way stretch using polyurethane elastic fiber only for warp or weft, or two-way stretch using both for warp and weft.

The fabric using the polyurethane elastic fiber of the present invention can be used for girdle, brassiere, intimate product,
Various stretch foundations such as underwear, socks mouth rubber, tights, pantyhose, waistband,
Applications include body suits, spats, swimwear, stretch sportswear, stretch fabrics, stretch outerwear, bandages, supporters, medical wear, stretch lining, disposable diapers, and the like. The fabric of the present invention is particularly suitable for swimwear used in pools. In particular, polyamide fibers are generally subjected to a fixing treatment using natural or synthetic tannin after dyeing to improve chlorine dyeing fastness, and the utility of polyurethane elastic fibers in the present invention is very high. .

In the case of a cross-knitted fabric of polyamide fibers and polyurethane elastic fibers, in order to fix the dye after dyeing, a fixing treatment is carried out using natural tannin containing a natural product as a polyphenol compound and synthetic tannin as a synthetic polyphenol compound. Do. In a cross-knitted fabric of polyester fibers and polyurethane elastic fibers, a dye fixing treatment may be performed with a natural or synthetic tannin before and / or simultaneously with the dyeing of the polyurethane elastic fibers. In any of the fixing treatments, the pH of the treatment bath is adjusted to 3 to 7, and the treatment is carried out at 80 ° C. to 130 ° C. after a normal temperature raising process. The longer the processing time, the better, but preferably 20 to 60 minutes. If necessary, a scum inhibitor and a softening agent in the bath may be mixed in the treatment bath.

[0028]

Next, the present invention will be described more specifically with reference to examples and the like, but the present invention is not limited to these examples and the like. In addition, the measuring method described in an Example is as follows. (1) Method of evaluating the repellency of elastic fiber After winding up 400 g of 40 denier / 5 filament elastic fiber into a paper tube, it was dried at 25 ° C. and 65% RH in an atmosphere of 30%.
After standing for a day, the paper tube is placed on a satin finish roller, and the elastic fiber is sent out at a roller surface speed of 40 m / min while rotating the roller. The sent out elastic fiber is wound up on a satin roller having the same diameter, which is set at a distance of 50 cm. The surface speed on the take-up roller is gradually decreased from 80 m / min, and the elastic fiber is entangled with the paper tube on the paper roller on the sending-out roller and reversely wound, and the speed Sm / at the time when the elastic fiber is cut and no longer sent out. Measure minutes. The smaller the value of Sm / min, the better the separation of the elastic yarn from the paper tube, and it is judged that the removability is good. In general, polyurethane elastic yarns tend to stick to each other since the polymer itself has properties similar to rubber, and thus have poor disintegration properties. However, if the yarn separation is too good, the outer layer of the elastic fiber wound on the paper tube is liable to drop when transporting the polyurethane elastic fiber wound on the paper tube, causing a handling problem. In this measurement, S (hereinafter, referred to as SI) of the elastic fiber of the inner layer of the cheese is SI = 50 to 65 m / min. S
When the value of I is out of this range, if the value is small, the yarn is liable to drop during transportation or in the warping process, and if the value is large, reverse winding or breakage of the cheese frequently occurs, which is a problem.

(2) Effective chlorine concentration A 25 ml chlorine water sample is weighed in a 100 ml Erlenmeyer flask, and 2 g of dried potassium iodide is added and shaken. Titration with a 1 / 100N sodium thiosulfate solution,
When the solution changes from orange to light yellow, the starch solution is added. 1/100 until blue color disappears due to iodine starch reaction
Titrate with N sodium thiosulfate solution. Separately, 25 ml of ion-exchanged water is sampled and titrated by the same operation as above to obtain a Planck titer. The effective chlorine concentration H is given by the following equation (1).

[0030]

(Equation 1) Here, H is the effective chlorine concentration (ppm), Vs is the titration amount (ml) of 1 / 100N sodium thiosulfate solution when titrated with chlorine water, and Vb is 1/100 when titrated ion-exchanged water.
The titer (ml) of 100N sodium thiosulfate, f is the titer of 1 / 100N sodium thiosulfate, and Ws is the weight (g) of chlorine water.

(3) Measuring method of breaking strength and elongation Tensile tester (UTM-3 manufactured by Orientec Co., Ltd.)
-100) under an atmosphere of 20 ° C. and 65% RH. It is measured at a strain rate of 1000% for 1 minute with a yarn sample length of 5 cm width. (4) Evaluation of raw yarn (evaluation of chlorine durability) Chlorine resistance of yarn after boiling water treatment (strong retention rate)
After treatment in boiling water of No. 7 for 60 minutes, the mixture was cooled at room temperature for 2 hours. Then, it is immersed in a chlorine water tank having a length of 1 m, a width of 1 m and a depth of 30 cm. The effective chlorine average concentration of this chlorine water tank was adjusted to 7.0 ppm, pH 7, and water temperature to 30 ° C.

Chlorine resistance of the yarn after the synthetic tannin treatment (strong retention rate)
7. Treat in boiling water of No. 7 for 60 minutes. Next, a cylindrical knitted fabric obtained by knitting using a pantyhose knitting machine a metal frame in which polyurethane elastic fibers were stretched and fixed and a polyamide fiber 50 denier / 17 filament obtained by melt-spinning polyhexamethylene adipamide was used as a synthetic tannin. Sun Life: TN-8
5% by weight of the sample
After adding the concentration, the mixture is further treated with an aqueous solution adjusted to pH 4 with acetic acid at 80 ° C. for 30 minutes. After the treatment, the substrate is washed with ion-exchanged water, cooled at room temperature for 2 hours, and then immersed in the above-mentioned chlorine water tank.

Chlorine resistance of yarn after natural tannin treatment (strong retention rate)
7. Treat in boiling water of No. 7 for 60 minutes. Subsequently, a metal frame having polyurethane elastic fibers stretched and fixed, and a tubular knitted fabric obtained by knitting a polyamide fiber 50 denier / 17 filament obtained by melt-spinning polyhexamethylene adipamide using a pantyhose knitting machine, using tannic acid (Dainippon Pharmaceutical Co., Ltd.) was added to the sample at a concentration of 5% by weight, and further treated with an aqueous solution adjusted to pH 4 with acetic acid at 80 ° C. for 30 minutes. After the treatment, it is washed with ion-exchanged water and cooled at room temperature for 2 hours.
Immerse in the chlorine water tank described above. The strength retention after the above and after immersion for 24 hours and air drying for 18 hours is shown by the following formula. The longer the retention rate, the higher the chlorine durability. Strength retention (%) = (Strength of elastic fiber after immersion in chlorine water /
Strength of elastic fiber before immersion in chlorine water) x 100

(5) Evaluation of fabric chlorine durability Polyurethane elastic fiber and polyamide fiber 50 denier / 17 filament obtained by melt-spinning polyhexamethylene adipamide are knitted using a tricot machine and warp knitted. A two-way tricot was made. Knitting structure is half, knitting is polyamide fiber on the front, polyurethane elastic fiber on the bag, 28 gauge, front runner 160 cm / 480 course, back runner 80
cm / 480 courses. 20 in this step
The number of thread breaks of the polyurethane elastic fiber when anti-knitting was evaluated.

Further, the obtained two-way tricot greige was scoured, relaxed, dried and heat-set for dyeing. Dyeing was performed using Irgalan Black as a dye.
BGL 2.7% owf, ammonium sulfate 3% owf, acetic acid 0.
Treatment was performed at 95 ° C. for 30 minutes in a 2% owf bath (pH 5.5). The stained 2-way tricot was fixed with natural tannin containing tannic acid. The fixation treatment is performed using HiFix SLA (containing 30% tannic acid,
Dainippon Pharmaceutical Co., Ltd .; trade name) in a 6% owf bath (pH
In 3.7), treatment was performed at 90 ° C. for 30 minutes.

A knitted fabric made of polyurethane elastic fiber and nylon 6 is stretched 50% in the weft direction to form one
The immersion for 2 hours and the air drying for 12 hours are repeated. The average effective chlorine concentration during the immersion for 12 hours is constantly adjusted to 2.0 ppm, pH 7 and water temperature of 35 ° C., and air drying for 12 hours is performed after rinsing with tap water. When the fabric is taken out from the 12-hour immersion, the presence or absence of a defect in the knitted fabric is confirmed, and the number of days until the occurrence of the defect is defined as the chlorine durability days of the knitted fabric. The longer the chlorine durability days, the higher the chlorine durability.

(6) Color fastness Polyurethane elastic fiber and nylon 6 knitted fabric are placed in an aqueous solution of sodium hypochlorite adjusted to an effective chlorine concentration of 100 ppm, pH 7, and 25 ° C. for 30 minutes, and discoloration and discoloration from the original fabric are performed. Was determined by a gray scale for discoloration according to JIS.

[0038]

Example 1 500 g of polytetramethylene ether glycol having a number average molecular weight of 1800 was reacted with 118 g of 4,4'-diphenylmethane diisocyanate under stirring in a dry nitrogen atmosphere at 80 ° C. for 3 hours, and the terminal was isocyanate. A capped polyurethane prepolymer was obtained. After cooling to room temperature, 956 g of dimethylacetamide was added and dissolved to prepare a polyurethane prepolymer solution. Separately, 10.84 g of ethylenediamine and 1.98 g of diethylamine were dissolved in 515 g of dimethylacetamide, and this was added to the prepolymer solution at room temperature to obtain a polyurethane solution having a viscosity of 3250 poise (30 ° C.).

In this polyurethane solution, 1 part by weight of 4,4'-butylidenebis- (3-methyl-6-t-butylphenol) and 2- (2'-hydroxy-3) were added to 100 parts by weight of the solid content of polyurethane. '-T-butyl-5'
-Methylphenyl) -5-chloro-benzotriazole (0.5 part by weight) and 4.0 parts by weight of a composite oxide 3ZnO.ZnAl ₂ O ₄ having an average particle diameter of 1 μm or less as a metal compound, and further a phosphoric ester compound Mono and di (1: 1) stearyl acid phosphate (trade name Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) as a composite oxide 3ZnO.ZnAl ₂ O ₄
0.2 parts by weight was added to 100 parts by weight to produce a spinning stock solution. This was dry-spun to obtain a polyurethane elastic fiber (A) having 40 denier / 5 filaments. The results of evaluating various properties of the elastic fiber are shown in Table 1 together with Examples 2 and Comparative Examples.

[0040]

Example 2 A method similar to that of Example 1 was repeated, except that the metal oxide and the phosphate compound shown in Table 1 were used instead of the metal oxide and the phosphate compound used in the spinning solution of Example 1. Thus, polyurethane elastic fibers (B) to (E) of 40 denier / 5 filaments were obtained.

[0041]

Comparative Example 1 A method similar to that of Example 1 was repeated except that the metal oxide and the phosphate compound described in Table 1 were used instead of the metal oxide and the phosphate compound used in the spinning solution of Example 1. Thus, polyurethane elastic fibers (a) to (f) of 40 denier / 5 filaments were obtained. However, the polyurethane elastic fiber (a) does not contain a metal oxide, the polyurethane elastic fibers (c) to (e) do not contain a phosphate compound, and the polyurethane elastic fiber (f) does not contain a metal oxide. No compound is added.

[0042]

[Table 1]

From the above Table 1, the polyurethane elastic fibers obtained in Examples 1 and 2 have lower inner layer SI values than the polyurethane elastic fibers obtained in Comparative Example 1,
It can be seen that the yarn separation from the paper tube is good. In addition, it has high strength retention after treatment with boiling water, synthetic tannin and natural tannin, and is excellent in chlorine resistance. In particular, the synthetic tannins and natural tannins have considerably superior chlorine resistance.

[0044]

Embodiment 3 Polyurethane elastic fibers (A) and (B)
A polyamide fiber of 50 denier / 17 filament of nylon 6 obtained by melt-spinning polyhexamethylene adipamide is knitted by using a tricot machine, and a warp knitting 2 wa
A y tricot was made. The knitting structure is half, the knitting is polyamide fiber on the front, polyurethane elastic fiber on the bag, 28 gauge, front runner 160
cm / 480 course, back runner 80cm / 480
The course was conducted under the conditions.

The resulting two-way tricot greige was scoured,
Relaxing, drying, heat setting and staining were performed.
Dyeing was performed using Irgalan Black BG as a dye.
L2.7% owf, ammonium sulfate 3% owf, acetic acid 0.2% ow
The treatment was performed at 95 ° C. for 30 minutes in the bath f (pH 5.5). The stained 2-way tricot was fixed with natural tannin containing tannic acid. The fixing treatment is performed in a 6% owf bath (pH 3.7) containing HiFix SLA (containing 30% of tannic acid, manufactured by Dainippon Pharmaceutical Co., Ltd.).
At 90 ° C. for 30 minutes. Using this dough,
Table 2 shows the results of the chlorine durability test and the color fastness test of the fabric.

[0046]

Comparative Example 2 Fabrics were prepared in the same manner as in Example 3 using polyurethane elastic fibers (a) to (f). Table 2 shows the results of a chlorine durability test and a dyeing fastness test of the dough using this dough.

[0047]

Example 4 Nylon 6 polyamide fiber 5 of Example 3
Instead of 0 denier / 17 filaments, a 2-way tricot greige of polyurethane elastic fiber and cationic dyeable polyester fiber using 50 denier / 17 filament cationic dyeable polyester fiber is prepared, and scouring, relaxing, drying, heat setting and dyeing. did. Dyeing is performed using, as a dye, Diacryl Brilliant Bl.
ue AC-E In a bath of 2.0% owf, ammonium sulfate 3% owf, acetic acid 0.2% owf, pH 5.5, the mixture was treated at 105 ° C. for 30 minutes. As a synthetic tannin-fixing treatment, a 5% ow of a synthetic fixing agent containing a sulfonated product of a formalin condensate of diphenyl sulfone as a main component (trade name: Hifix GM manufactured by Dainippon Pharmaceutical Co., Ltd.) is applied to the dyed 2-way fabric.
In a bath containing f, treatment was performed at 90 ° C. for 30 minutes to prepare a dyed 2-way tricot. Table 2 shows the results of a chlorine durability test and a dyeing fastness test of the dough using this dough.

[0048]

Comparative Example 3 Fabrics were produced in the same manner as in Example 4 using polyurethane elastic fibers (a) to (f). Table 2 shows the results of a chlorine durability test and a dyeing fastness test of the dough using this dough.

[0049]

[Table 2] From the above Table 2, the knitted knitted fabric obtained from Example 3 has the same or higher dyeing fastness to chlorine water as compared with the knitted knitted fabric obtained from Comparative Example 2, but the chlorine durability test evaluation. It can be seen that the durability days are high and that it has excellent chlorine resistance.

[0050]

The polyurethane elastic fiber of the present invention is obtained by using natural tannin or synthetic tannin in the dye fixing treatment for improving the dyeing fastness of a cross-knitted fabric made of synthetic fiber such as polyamide fiber or polyester fiber. Even if the treatment used is performed, a decrease in the activity of the chlorine deterioration inhibitor in the polyurethane elastic fiber is suppressed. For this reason, the elastic cloth manufactured according to the present invention is suitable for use in, for example, a swimsuit for swimming, which has a strong demand for chlorine resistance and fastness to dyeing which are frequently used in a chlorine water environment such as in a swimming pool. ing.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI D01F 1/10 D01F 1/10 D03D 15/08 D03D 15/08 // D01F 6/70 D01F 6/70 Z

Claims (4)

[Claims] 1. A polyurethane polymer obtained by reacting (a) a polymer diol having hydroxyl groups at both terminal groups with a number average molecular weight of 500 to 5,000, an organic diisocyanate, and a chain extender having a polyfunctional active hydrogen atom, by 100 weight (B) one or more metal compounds selected from the group consisting of oxides, composite oxides, hydroxides, and hydrotalcite compounds of metals selected from Mg, Zn, and Al. 1 to
An elastic polyurethane fiber comprising 10 parts by weight and (c) an effective amount of a phosphate compound represented by the following formula (1). Embedded image (Where R is a linear or branched alkyl group having 1 to 30 carbon atoms, an alkoxypolyoxyalkylene group, a cycloalkyl group having 5 to 6 carbon atoms, 1 to 10 carbon atoms)
A cycloalkyl group having 5 to 6 carbon atoms substituted by an alkyl group, and n represents an integer of 1 or 2. ) 2. The method according to claim 1, wherein the metal compound is ZnO, MgO, ZnO.
O and MgO composite oxide, divalent metal M (where M is Z
represents at least one selected from n and Mg. )
And the molar ratio of the divalent metal to Al is from 1 to 5
The polyurethane elastic fiber according to claim 1, wherein the polyurethane elastic fiber is one or more selected from the group consisting of a composite oxide and a hydrotalcite compound. 3. The polyurethane elastic fiber according to claim 1, wherein the phosphate compound is added in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the metal compound. 4. An elastic cloth for water use, comprising the polyurethane elastic fiber of claim 1 and a polyamide-based fiber or a polyester-based fiber.