JPH06212543A - Knit fabric for swimming suit and its production - Google Patents

Abstract

PURPOSE:To obtain knit fabric suitable for swimming suit having chlorine resistance and excellent handle and dyeability by interknitting urethane-based elastic yarn containing a specific compound and polyester yarn dyeable with cationic dye under normal pressure. CONSTITUTION:Urethane-based elastic yarn containing 0.5-4.5wt.% one or more compounds selected from the group consisting of magnesium oxide, zinc oxide, aluminum oxide, magnesium hydroxide, zinc hydroxide, aluminum hydroxide and a hydrotalcite compound and polyester yarn dyeable with cationic dye under normal pressure obtained by copolymerization of >=2mol% of a monomer containing a metal sulfonate group based on a dicarboxylic acid compound constituting the polyester are interknitted and then dyed at 80-100 deg.C to give knit fabric for swimming suit having >=4.0g/de strength (DT) at break of yarn, 25-35% elongation (DE) at break, satisfying DTX(DE)<1/2>>=22.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a knitted fabric for water wear, which is knitted with a polyurethane elastic fiber (A) and a polyester fiber (B) dyeable with a cationic dye of atmospheric pressure. The present invention relates to a knitted fabric for water wearing, which comprises knitting a polyurethane-based elastic fiber having deterioration preventive properties under a chlorine hydrogen environment and a cationic dye-dyeable polyester fiber having high fiber strength.

[0002]

2. Description of the Related Art Conventionally, a swimsuit has been made of a knitted knitted fabric of ether-type urethane elastic fibers and polyamide fibers. Since the knitted fabric is dyed with an acid dye, the wetness most needed for the swimsuit is obtained. The fastness was inferior, and it was easy to discolor by transferring to another object when taking it home after wearing it, or the dye was decomposed by the chlorine water in the pool. In addition, when metal-containing dyes were used to improve fastness, viscous lines were generated and a clear color could not be obtained, and when a one-bath type fixing agent or tannin fixing agent was used, these were adsorbed on polyurethane fibers. It is easy to be damaged and deteriorated by light and chlorine.

A swimsuit made of a knitted knitted fabric of polyester-based urethane elastic fibers and polyester fiber yarns was also made, but the knitted fabric requires high-pressure dyeing at 130 ° C. in order to produce a clear color. In this case, the polyurethane fiber was hydrolyzed so much that it could not be produced. Further, in the case of dark color dyeing, at least 120 ° C is necessary, and even in this case, the deterioration is large, and even if the production is possible, the tension is small,
The durability was poor and no vivid color was obtained.

As a method for avoiding such a drawback, as a method for improving the durability of the polyurethane fiber against chlorine, Japanese Patent Publication Nos. 60-43444 and 61-3.
Japanese Patent No. 5283 discloses a chlorine deterioration inhibitor. Further, as a method which does not use dyeing conditions of high temperature and high pressure, it is possible to use a polyester fiber obtained by copolymerizing a compound having an acidic group, which is known from Japanese Patent Publication No. 34-10497.

[0005]

However, when a product such as a mixed knitted fabric using the polyurethane elastic fiber containing the above-mentioned chlorine deterioration inhibitor is exposed to dyeing, finishing, processing, etc., the durability of the final product is improved. However, since it is not possible to increase the degree of polymerization by using the copolyester fiber as it is, the denier of the single fiber cannot be made thin, and the texture becomes hard and the process passability is low. It had the drawback of being bad. The present invention eliminates the drawbacks of these conventional knitted fabrics for water, and because it has excellent chlorine resistance, it does not cause discoloration of dyed fabrics due to chlorine water used in pools, etc., and has an aesthetic color. In addition, it is intended to provide a knitted fabric for water wear, which has excellent dyeing fastness, does not reduce the tightening force, and has excellent durability.

[0006]

That is, the present invention provides a knitted fabric which is knitted with a polyurethane elastic fiber (A) and an atmospheric pressure cationic dye dyeable polyester fiber (B),
(A) in the knitted fabric contains 0.5 to 4.5% by weight of one or more of the following compound groups in the fiber, and (B) in the knitted fabric contains a metal sulfonate group. 2 mol% of the monomer having with respect to the dicarboxylic acid component constituting the polyester
A fiber composed of the above-described copolyester, wherein the physical properties of the fiber after atmospheric pressure cation dyeing satisfy the following formula, and a knitted fabric for water wearing,
It is a method for producing a knitted fabric for swimming, which comprises dyeing in a dyeing bath at 100 ° C. * Compound group: magnesium oxide, zinc oxide, aluminum oxide, magnesium hydroxide, zinc hydroxide, aluminum hydroxide, hydrodalcite compound. DT × (DE) ^1/2 ≧ 22 DT: shows the breaking strength of the fiber and is 4.0 g / d or more. DE: The breaking elongation of the fiber is 25 to 35%.

The polyurethane elastic fiber in the present invention is an elastic fiber obtained by spinning a polymer composition mainly composed of the following polyurethane. The polyurethane in the present invention has a number average molecular weight of 600 or more, preferably 1
A polymer obtained by reacting a polymer diol having a melting point of 000 to 5,000 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 can be mentioned.

As the polymer diol, polyether glycols such as polytetramethylene glycol and polyethylene propylene ether glycol, glycols such as ethylene glycol, 1.6-hexanediol, 1.4-butanediol and neopentyl glycol are used. Of at least one of adipic acid, suberic acid, azelaic acid, sebacic acid, β-methyladipic acid, and isophthalic acid and other organic dicarboxylic acids, and the like. Examples thereof include one type of polymer diol such as methylene dicarbonate glycol, or a mixture or copolymer of two or more types thereof.

As the organic diisocyanate, 4
* 4'-diphenylmethane diisocyanate, 1.5-
One or two of organic diisocyanates such as naphthalene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and isophorone diisocyanate. A mixture of two or more species can be exemplified. Further, 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 4-butanediol, 1-6-hexanediol, water and the like, or a mixture of two or more thereof. If desired, these compounds may be used in a small amount in combination with a terminating agent such as monoamine or monoalcohol. However, preferred are diamines alone or those based on diamines.

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. N.N-dimethylformamide as a solvent,
Examples include N · N-dimethylacetamide, tetramethylurea, hexamethylphosphonamide, and the like, but the invention is not limited thereto. Compositions other than polyurethane that make up the polyurethane-based composition, there are chlorine water deterioration inhibitors such as metal oxides, metal hydroxides, these are magnesium oxide, zinc oxide, aluminum oxide,
Examples thereof include magnesium hydroxide, zinc hydroxide, aluminum hydroxide, and hydrotalcite-type compounds, which may be used alone or as a mixture of two or more kinds. Particularly preferred is magnesium oxide or zinc oxide. The addition to these polyurethane solutions is not particularly limited, but it is preferable to add them as particles having an average particle size of 0.05 to 3 μm. The amount of the chlorine water deterioration inhibitor such as the metal oxide added is preferably 1.0 to 3.0% by weight.

The polyurethane elastic fiber used in the present invention preferably has a denier in the range of 20 to 100, preferably 40 to 70 denier. Further, these elastic fibers are used in the state of covering yarn or bare yarn.

The normal pressure cationic dye-dyeable polyester fiber interwoven with the polyurethane elastic fiber of the present invention is a polyester fiber dyeable with a cationic dye at 100 ° C. or lower. In order for the fiber to exhibit excellent easy dyeability and high fiber strength, 5-metal sulfoisophthalic acid or its ester-forming derivative is added to the dicarboxylic acid component in an amount of 0.5 to 0.5%.
5.0 mol% is preferably present, and the sulfonate compound represented by Chemical formula 1 is preferably present in an amount of 0.1 to 3.0 mol% with respect to the dicarboxylic acid component, and the glycol component represented by Chemical formula 2 is a glycol component. 1.
It is desirable that 0 to 6.0 mol% be present. When the content of 5-metal sulfoisophthalic acid or its ester-forming derivative is less than 0.5 mol% of the dicarboxylic acid component, the dyeability of the cationic dye becomes low, and conversely, when it is more than 5.0 mol% of the dicarboxylic acid component, With the polymerization degree of melt viscosity that can be spun by the method described above, not only the desired physical properties of the fiber cannot be obtained, but also the operability during molding such as spinning is deteriorated and the melting point of the polyester is lowered, resulting in light resistance and hydrolysis resistance. It is not preferable because it deteriorates the property.

[0014]

[Chemical 1]

[0015]

[Chemical 2]

In the present invention, if the amount of the sulfonate compound represented by Chemical formula 1 is less than 0.1 mol% with respect to the carboxylic acid component, the effect of improving the drawability becomes small, and the fiber having the desired physical properties cannot be obtained, which is not preferable. On the contrary, if it is more than 3.0 mol% with respect to the dicarboxylic acid component, the degree of polymerization of the polyester will reach a level at a too low level in the polycondensation reaction step, which is not preferable. Further, if the amount of glycol represented by Chemical Formula 2 is less than 1.0 mol% of the glycol component, the dyeing effect becomes small and the desired dyeability of the fiber cannot be obtained. On the other hand, when the content of the glycol component is more than 6.0 mol%, the melting point, light resistance and hydrolysis resistance of the polyester are lowered, which is not preferable. In the present invention, the amount of each component is
When it is in the above preferred range, it is possible to satisfy the practical balance between the physical properties of fibers and the dyeability of atmospheric pressure cations for the first time. More preferable amounts of these components are 5-metal sulfoisophthalic acid or its ester-forming derivative in an amount of 1.0 to 2.0 mol% of the dicarboxylic acid component, and the sulfonate compound represented by the above chemical formula 1 as the dicarboxylic acid component. On the other hand, 0.5 to 2.0 mol%, and the glycol represented by Chemical Formula 2 is 2.0 to 4.5 mol% of the glycol component.

The normal pressure cationic dye-dyeable polyester fibers may be filament yarns or spun yarns, but filament yarns are preferred in view of the appearance of the swimsuit. The denier number of filament yarns does not have to be specifically considered, but considering the thickness and texture of the swimsuit, the total denier is 30 to 70 denier, and the single fiber denier is 0.5 to denier.
5 denier is preferred.

A knitted fabric is knitted by interlacing the above-mentioned urethane type elastic fiber and the polyester fiber dyeable with the atmospheric pressure cationic dye. The knitted fabric may be a horizontal knitted fabric or a warp knitted fabric, but a warp knitted fabric is preferable from the viewpoint of the function of a swimsuit. Further, it may be knitted by a tricot knitting machine or a Russell knitting machine. Further, the knitting structure may be any knitting structure such as half knitting, reverse half knitting, double atlas knitting, double denby knitting, etc., but the elongation rate of the warp of the knitted fabric is 50% or more, preferably 100% or more and 80% horizontal. The above is preferable. In addition, it is preferable that the surface of the knitted fabric is made of polyester fiber in terms of texture. The polyester filament yarn may be only the polyester fiber dyeable with the above-mentioned atmospheric pressure cationic dye, or may be a regular regular polyester fiber as a part thereof. In this case, the regular polyester filament yarn that is not dyed with the cationic dye remains undyed, and a white pattern pattern is obtained.

The knitted fabric is scoured and relaxed under normal conditions,
Drying is performed. Heat set temperature is 150-190 ℃
Is suitable, and preferably 160 to 180 ° C. The dyeing conditions are 20 to 120 minutes, preferably 40 to 60 minutes in a dyeing bath at 80 to 100 ° C. If it is less than 80 ° C, the dyeing effect is significantly reduced. Further, in the case of printing, it is for preventing the brittleness of the polyurethane elastic fiber. A dye that develops color under normal pressure saturated steam may be used. The dyeing machine may be a normal machine such as a Wins dyeing machine or a jet dyeing machine, and may be a normal pressure machine or a high pressure machine. Dyes are those selected by dye makers as general cationic dyes, as long as they are ordinary ones selected by dye makers for cationic dye-dyeable polyesters and those whose fastness and other properties can be used. It may be.

Since the knitted fabric for water wearing as described above uses the urethane type elastic fiber having improved chlorine resistance, it is less deteriorated by the chlorine water in the pool and the like, the durability is improved, and the strength is increased. Since the normal pressure cationic dyeable polyester fiber yarn of No. 1 is used, it can be dyed at 90 to 100 ° C., and the texture of the knitted fabric is remarkably improved by thinning the single fiber, and the urethane type elastic fiber Since it is less deteriorated and is dyed with a cationic dye, the wet fastness is excellent, and the bright color fastness to light is also excellent. In particular, the DT × (DE) of the atmospheric pressure cationic dye-dyeable polyester fiber (B) after dyeing under the dyeing conditions described in Examples described later.
^1/2 is 22 or more, preferably 30 or less, DT is 4.0 g
/ D or more, preferably 6.0 g / d or less, DE is 25 to
A knitted fabric having 35% and high physical properties that can be practically used as a knitted fabric for swimming is obtained.

The present invention will be specifically described with reference to the following examples.

Example 1 Number average molecular weight 200 having hydroxyl groups at both ends
Polytetramethylene ether glycol of 0 and 4.4 '
-Diphenylmethane diisocyanate in a molar ratio of 1:
A prepolymer is produced by reacting in a ratio of 2 and then 1
-Chain extension was carried out with 2 propylenediamine to obtain a polyurethane solution having a polymer concentration of 30% (solvent: dimethylformamide) and a viscosity of 2000 poise (30 ° C). To this solution, 3% of magnesium oxide (average particle size: 0.1 to 2 μm) dispersed in dimethylformamide with an attritor was added to polyurethane, and an antioxidant, an ultraviolet absorber and a gas yellowing inhibitor were further added. The mixture was added, mixed and stirred to obtain a spinning dope.

After defoaming the spinning solution, it was discharged from a die having a hole diameter of 0.2 mm and a number of holes of 5 holes, and the solvent was removed in a spinning cylinder in which heated air of 180 ° C. was passed, and the spinning was carried out at 10,000 rpm. Then, while applying 6% of the oil agent to the yarn, it was wound at a spinning speed of 500 m / min to obtain 40 denier and 5 filaments of polyurethane elastic fiber (a).

Dimethyl terephthalate (DMT) 100
0 part, 5-sodium sulfoisophthalic acid dimethyl ester (DSN) 1.3 mol%, ethylene glycol 70
0 part, and R in the glycol shown in Chemical Formula 2 above.
Is a 2.2-dimethylpropylene group, and 4.2 mol% of glycol having a value of m + n of 4 is taken in a transesterification reactor, and 0.33 parts of zinc acetate dihydrate (DMT + DS is added thereto.
0.030 mol% relative to N), antimony trioxide 0.
39 parts (0.025 mol% with respect to DMT + DSN) and 5 mol% of sodium acetate as a diethylene glycol production inhibitor with respect to the monomer containing a metal sulfonate group
After the addition, the transesterification reaction was carried out while elevating the temperature from 140 ° C. to 230 ° C. over 3 hours in a nitrogen gas atmosphere while distilling off by-product methanol out of the system. Trimethyl phosphate 0.026 parts (0.036 mol% with respect to DMT + DSN) was added to this reaction system, and stirred for 15 minutes. The obtained product is transferred to a polycondensation can which has been heated to 230 ° C. in advance,
m-Sodium sulfobenzoic acid (SBA) 1.3 mol%
Was added as a 20% by weight solution of ethylene glycol and stirred at normal pressure under a nitrogen gas atmosphere for 20 minutes, and then the internal temperature was gradually raised to 230 to 275 ° C. for 60 minutes while the system was gradually adjusted to 0.1%.
Reduce the pressure to mmHg, then 275 ° C, 0.1 mmHg
The polycondensation reaction was carried out until the viscosity of the produced polymer reached 3400 poise to obtain a copolyester having a predetermined composition.

Each of the obtained polymers was dried by a conventional method and melt-spun at a spinning temperature of 285 ° C. and a winding speed of 600 m / min using a Y-shaped nozzle of an extrusion type spinning machine. The unstretched yarn thus obtained was mixed with a heating roller at 85 ° C. at a draw ratio of 1 at which the elongation of the finally obtained stretched yarn would be 35%.
Stretching heat treatment was performed using a hot plate at 50 ° C. to obtain deformed bright fibers (b) of normal pressure cationic dyeable polyester fiber yarn 50 denier 36 filaments.

[0025]

[Comparative Examples 1 to 3] As a comparison, the same method as in Example 1 was used, except that magnesium oxide was not added at all (a)
Polyurethane elastic fiber (a ′) was obtained in the same manner as for obtaining. The atmospheric pressure cationic dye-dyeable polyester fiber was produced in the same manner as in (b) shown in Example 1 except that the DSN was 2.6 mol% and SBA was not added. (B ')

A knitted fabric was formed from the obtained fibers in the combinations shown in Table 1. The composition conditions are shown below. -(A), (a ') warp draft: 100% -Knitting machine: Karlmayer 28 gauge tricot machine-Knitting stand: (a), (a') weaving length 70 cm
/ 480 course (b), (b ') weaving length 160 cm / 480 course On-machine course 55 course Scouring, relaxing and drying the four types of raw fabric thus obtained
Each knitted fabric was heat-set and dyed. The dyeing conditions are shown below. Machine: Atmospheric pressure roco-type jet dyeing machine Dye: Aizen Cathilon Red, FB-DP 1.8% owf (Cation dye manufactured by Hodogaya Chemical Co., Ltd.) Auxiliary agent: Bogoshi 3 dl / l Acetic acid 0.3 cc / l Sodium acetate 0.3 g / l Dyeing temperature × time: The temperature was raised from 40 ° C. to 95 ° C. in 50 minutes, and dyeing was carried out at 95 ° C. for 40 minutes. After dyeing, 1 g / l of nonionic activator was added at 80 ° C., and soaping was carried out for 20 minutes. Drying set: After centrifugal dehydration, a bath of 5 g / l of Emalox OEP-1 (antistatic agent manufactured by Yoshimura Yuka Kagaku Co., Ltd.) was passed through, deliquoring was performed with a mangle, and then dry setting was performed with a pin tenter at 160 ° C. for 30 seconds. When examining the deterioration, it was as shown in Table 1.

Here, seawater fastness: JIS L 0847'75 Tensile force when stretching the fabric: 80% in Instron type tester
Draw an S-S curve during elongation and compare the return curve with the stress at 50% elongation. Deterioration of polyurethane elastic yarn due to chlorine water: pool immersion 2
00 hours later

[0028]

[Table 1]

In the examples, the hue was clear, almost all the dye had been exhausted, the elastic properties of the polyurethane elastic yarn were not impaired, and the chlorine resistance was also strong. On the other hand, Comparative Example 1 had many unexhausted dyes in dyeing, and the concentration was difficult to obtain.
The stretchability of the polyurethane elastic yarn was deteriorated by the high temperature treatment, and in Comparative Example 2, the fastness to light and the fastness to water / seawater were poor, and the deterioration of the polyurethane elastic yarn due to chlorine water was large.

Since Comparative Example 3 has a low dyeing temperature, the dye is scarcely exhausted, the density is remarkably thin as compared with Comparative Example 4, the light fastness is poor, and it is not practical. Further, in Comparative Example 4, the tension force when the fabric was stretched was weak, and the deterioration of the polyurethane elastic yarn due to chlorine water was also large.

[0031]

According to the present invention, a polyurethane-based elastic fiber to which a metal oxide or the like, particularly magnesium oxide or zinc oxide is added, and an atmospheric pressure cationic dye dyeable polyester fiber having excellent mechanical properties are used. By the knitted knitted fabric, a knitted fabric with excellent chlorine resistance and excellent texture and practical dyeability can be obtained.

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Claims (2)

[Claims] 1. A knitted fabric interwoven with a polyurethane-based elastic fiber (A) and a polyester fiber (B) dyeable with an atmospheric pressure cationic dye, wherein (A) in the knitted fabric is In the knitted fabric containing (B) a metal sulfonate group-containing monomer of 0.5 to 4.5% by weight of one or more of the following compound groups, a dicarboxylic acid constituting a polyester: A knitted fabric for water use, characterized in that the fiber is composed of a copolymerized polyester containing 2 mol% or more with respect to the components, and the physical properties of the fiber after cationic dyeing at atmospheric pressure satisfy the following formula. * Compound group: magnesium oxide, zinc oxide, aluminum oxide, magnesium hydroxide, zinc hydroxide, aluminum hydroxide, hydrotalcite compound. DT × (DE) ^1/2 ≧ 22 DT: shows the breaking strength of the fiber and is 4.0 g / d or more. DE: The breaking elongation of the fiber is 25 to 35%. 2. A method for producing a knitted fabric for water wearing, which comprises dyeing the knitted fabric according to claim 1 in a dyeing bath at 80 to 100 ° C.