JPH0533264A - Union fabric made of chlorine-resistant polyurethane elastic yarn - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a polyurethane elastic yarn interwoven fabric excellent in chlorine fastness to dye and chlorine embrittlement resistance. [Structure] Zinc ion and / or magnesium ion is contained in the surface layer of polyurethane elastic yarn in a polyurethane elastic yarn interlaced fabric subjected to dyeing treatment in an amount of 0.1 to 1.0% by weight based on the weight of the elastic yarn. Chlorine resistant polyurethane elastic yarn interwoven fabric. [Effect] By preferentially impregnating the surface of the fiber, which is easily deteriorated by chlorine, with metal ions, a polyurethane elastic yarn interwoven fabric excellent in chlorine embrittlement resistance can be obtained. In addition, since there is no limitation on dyeing and fixing treatment, color development,
It also has excellent dyeing fastness to chlorine.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chlorine-resistant polyurethane elastic yarn interwoven fabric, and more particularly to a chlorine-resistant polyurethane elastic fabric excellent in dyeing fastness and chlorine embrittlement resistance in a chlorine-treated water environment such as a swimming pool. It relates to a yarn-knitted fabric.

[0002]

2. Description of the Related Art Conventionally, polyurethane elastic yarn interwoven fabrics have been used for foundations, swimwear, leotards and the like. Of these, swimwear especially 0.5 is used in a swimming pool.
Since it is used in an environment of chlorinated water of ˜3 ppm or more, there are problems such as discoloration by chlorine (chlorine fastness) and brittleness of polyurethane elastic yarn. As a measure for improving the chlorine fastness, fixing treatment with tannic acid and tartar has been conventionally performed. Regarding the brittleness of polyurethane elastic yarn, a method has recently been proposed to prevent the embrittlement by adding a metal salt such as zinc oxide, magnesium oxide or hydrotalcite during spinning (Japanese Patent Publication No. 60-4344).
4 and JP-A-59-133248).

However, when the dyeing treatment under acidic conditions or the fixing treatment with tannic acid / tartar is carried out, the metal salt on the fiber surface, which is particularly useful for preventing chlorine embrittlement, elutes and the chlorine embrittlement resistance is sufficiently retained. There was a problem that was not done. Therefore, in order to maintain chlorine embrittlement resistance, neutral dyeing and fixing treatment using synthetic tannin have been carried out, but a sufficiently satisfactory coloring property and chlorine fastness have been obtained. The current situation is that there is none.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems of the prior art, and to improve the coloring property and chlorine fastness imparted by dyeing treatment under acidic conditions or fixing treatment with tannic acid / tartar. It is an object of the present invention to provide a chlorine-resistant polyurethane elastic yarn interlaced fabric that can impart chlorine embrittlement resistance without damaging it.

[0005]

According to the present invention, zinc ion and / or magnesium ion is added to the surface layer of polyurethane elastic yarn in a polyurethane elastic yarn interwoven fabric which has been subjected to a dyeing treatment, based on the weight of the elastic yarn. 1 to 1.0% by weight
The chlorine-resistant polyurethane elastic yarn interwoven fabric is characterized by being contained.

In the present invention, after the dyeing treatment and the fixing treatment are completed, zinc ion and / or magnesium ion are contained in the range of 0.1 to 1.0% by weight on the surface of the polyurethane elastic yarn which is easily subjected to chlorine embrittlement. Since it is adsorbed by, it is possible to impart chlorine embrittlement resistance while maintaining color development and chlorine fastness. The polyurethane elastic yarn in the knitted fabric in the present invention has zinc ions and / or magnesium ions localized on the yarn surface, and the same ions are added to the central part obtained by adding these metal ions during spinning. Is completely different from the localized one.

The polyurethane elastic yarn interwoven fabric used in the present invention is an interwoven fabric of polyamide fiber and polyurethane elastic yarn. Examples of the polyamide fibers include polyamide fibers such as nylon 6, nylon 66, nylon 6/10, nylon 4, nylon 8 and the like. Polyamide stretched yarn obtained by stretching unstretched yarn obtained by melt spinning of these, initial Young's modulus of 200 to 300 kg / mm ² , elongation at break of 5
0-70% high speed spinning (spinning speed 4000-6000m
/ Min) polyamide yarn and the like are also preferably used. The polyamide fiber is wool in a broad sense,
Contains natural fibers such as silk.

The polyurethane elastic yarn includes, for example, a substantially linear polymer having hydroxyl groups at both ends and having a molecular weight of 600 to 5000, an organic diisocyanate, a chain extender having a polyfunctional active hydrogen atom, and a monofunctional active hydrogen. An elastic high molecular polymer having a urethane group in the molecule, which is obtained by reacting an end-capping agent having an atom in one step or multiple steps,
It is obtained by dry spinning or wet spinning. It can also be obtained by spinning the above prepolymer consisting of a polymer having hydroxyl groups at both ends and an organic diisocyanate while reacting the above chain extender and terminal blocking agent.

Examples of the linear polymer having hydroxyl groups at both terminals include polyester diol, polylactone diol, polyether diol, polyester amide diol, polythioether diol, polyhydrocarbon diol, polycarbonate diol, polysiloxane diol, Polyurethane diol or the like is used.

As the organic diisocyanate, for example, m
-Or p-phenylene diisocyanate, 2,4- or 2,6-toluylene diisocyanate, p-xylylene diisocyanate, 4,4'-dimethyl-1,3-
Xylylene diisocyanate, 1-alkylphenylene-2,4 or 2,6-diisocyanate, 3- (α-
Isocyanatoethyl) phenyl isocyanate, 2,
6-diethylphenylene-1,4-diisocyanate,
Diphenylmethane-4,4'-diisocyanate, diphenyl-dimethylmethane-4,4'-diisocyanate, diphenylether-4,4'-diisocyanate, naphthylene-1,5-diisocyanate, 1,6-
Hexamethylene diisocyanate, cyclohexylene-
4,4'-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and the like are used. Preferred is diphenylmethane-4,4'-diisocyanate.

Examples of the chain extender include hydrazine, polyhydrazide, polysemicarbazide, polyol, polyamine, hydroxylamine and water. As the terminal stopper, for example, dialkylamine or the like is used. You may use these individually by 1 type or in mixture of 2 or more types.

When the polyurethane elastic yarn is spun, a known compounding agent of an organic or inorganic substance in the polyurethane polymer composition, such as a gas yellowing inhibitor, an ultraviolet absorber, an antioxidant, an antifungal agent, is desired. Inorganic fine particles such as barium sulfate, aluminum silicate, magnesium silicate, calcium silicate, and zinc oxide, and an anti-adhesive agent such as calcium stearate, magnesium stearate, polytetrafluoroethylene, and organopolysiloxane can be appropriately mixed.

The zinc ion and magnesium ion used in the present invention may be used as salts having appropriate solubility, for example, salts with sulfate ion, acetate ion and the like. The content of these metal ions is 0.1 to 1.0% by weight based on the weight of the fiber. If the content of the metal ions is less than 0.1% by weight, the chlorine embrittlement resistance is insufficient, and if it exceeds 1.0% by weight, the chlorine resistance effect is not improved and the cost increases. A suitable penetrant may be used to effectively adsorb zinc ions and magnesium ions to the polyurethane elastic yarn. As the penetrant, for example, Meisserin H-100X (manufactured by Meisei Chemical Co., Ltd.)
Ethylene oxide adducts of alkylphenols such as are used.

Chlorine embrittlement resistant yarn containing metal salts such as zinc oxide, magnesium oxide and hydrotalcite was subjected to dyeing treatment under acidic conditions and fixing treatment with tannic acid / tartar stone, resulting in inclusion from the fiber surface. The present invention is also applied to a polyurethane elastic yarn interwoven fabric having a chlorine embrittlement resistance reduced by elution of a metal salt, and by applying zinc ions and / or magnesium ions to the fiber surface, the chlorine embrittlement resistance is improved. Can be supplemented.

[0015]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. In addition,
Unless otherwise specified,% in the following examples means% by weight (owf) based on the total weight of the fiber. Moreover, each measured value in the examples was measured as follows.

(1) Determination of zinc ion or magnesium ion concentration 80 weighted fiber samples (polyurethane elastic yarn)
Ashed in a platinum dish in a 0 ° C. muffle furnace for 10 minutes. The resulting residue was dissolved in 50 wt% HCl solution. Insoluble matter was removed by filtration and calibrated with a sample containing a zinc or magnesium lamp according to the method of atomic absorption spectrometry [described in Perkin Elmer Corporation (1973), Norwalk, Conn.] And containing a known amount of zinc oxide or magnesium oxide. Perkin Elmer Model 370 Atomic Absorption Spectrophotometer (or equivalent device). The zinc ion or magnesium ion concentration was then calculated as a percentage of the total fiber weight.

(2) Distribution measurement of zinc ion or magnesium ion The distribution of zinc and magnesium in the cross section of the polyurethane elastic yarn was measured as follows. First, fix the sample thread with the adhesive in the stretched state, and
uetol-812, manufactured by Nissin EM). This is trimmed with a microtome to expose the cross section of the sample, and then about 30 is applied to the surface of the sample to impart conductivity.
Carbon was vapor-deposited at 0 angstrom, and a carbon paste was applied between the sample and the sample stand to obtain an EPMA measurement sample. For the measurement of EPMA, JCXA-733 (manufactured by JEOL Ltd.) was used, and the accelerating voltage was 1 in the electron beam irradiation system.
5 KV, irradiation current: 8 × 10 ⁻⁸ A, X-ray measurement system dispersive crystal: LiF, analysis mode: line analysis, RENGE: 50
0cps full scale, SCAN SPEE
D: Slow 3 was used.

(3) Chlorine Embrittlement Measurement of Polyurethane Elastic Yarn Interwoven Fabric In the case of a tubular knitted fabric, after denitting the knitted fabric, the polyurethane elastic yarn is taken out and the breaking strength is measured with a Tensilon tensile tester manufactured by Orientec. It was measured. That is, the breaking strength of the polyurethane elastic yarn was measured at a sample gripping width of 50 mm and a pulling speed of 500 mm / min. When the knitted fabric was a 2WEY tricot, the third stress when the fabric was repeatedly stretched 80% in the machine direction was measured with a Tensilon tensile tester manufactured by Orientec. That is, the sample was marked in the longitudinal direction of the knitted fabric at intervals of 100 mm, and the sample cut into a width of 25 mm was repeatedly stretched to 80 mm at a sample gripping width of 100 mm and a pulling speed of 300 mm / min. .. The above operation was performed every 10 hours of the exposure test for chlorinated water. However, although the sample becomes longer than the initial length as the polyurethane elastic yarn becomes brittle, the portions marked at 100 mm intervals in the initial stage are grasped by a tensile tester with a grip width of 1
The part which became longer than the initial length was recorded as a permanent set after being gripped according to 00 mm.

(4) Chlorinated water exposure test The sample was extended by 50% and immersed in an immersion bath. Immersion bath is about 2
5ppm, 3ppm by addition of sodium hypochlorite solution
The active chlorine concentration was maintained and the pH was adjusted to 7.0 with acetic acid.
The sample was immersed in a stirred water bath having a volume of 0 liter for 10 hours and then dried to measure the physical properties. The chlorinated water was replaced every 5 hours. The performance of polyurethane elastic yarn interwoven fabrics in chlorinated water exposure tests correlates with the performance of swimwear exposed in chlorinated pools.

(5) Measurement of Chlorine Concentration in Chlorinated Water In this specification, it is defined as the concentration of chlorine capable of oxidizing iodine ions to iodine. This concentration was determined by titration with potassium iodide and sodium thiosulfate and recorded as the number of active chlorine (Cl ₂ ) per million copies. Titration method is 20 ml for chlorinated water to be analyzed
Aqueous potassium iodide solution, 10 ml of glacial acetic acid and 5 ml of 0.5% by weight starch solution were added, and the mixture was added to 0.01N.
Titrated with sodium thiosulfate to the starch / iodine end point.

(6) Color Difference Measurement The fastness of the dyed knitted fabric is represented by the color difference using the CIE _Lab color system. The dyed knitted fabric is color-measured with a Macbeth spectrophotometer MS-2020 type before the exposure to the chlorine-treated water exposure test,
The color was measured again each time the chlorine-treated water exposure test was completed, and the color difference ΔE ^* _ab between the two was determined by the following formula.

[Equation 1] ΔE ^* _ab = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2 where ΔL ^* is the difference in psychological brightness between the two, Δa ^{* And} Δb ^* are the differences in the chromaticness index in the CIE _ab color system of both. The larger the ΔE ^* _ab value, the larger the color difference between the two.

Example 1 Polytetramethylene glycol 1 having an average molecular weight of 1200
000 g and 312 g of 4,4'-diphenylmethane diisocyanate were added at 90 ° C. in a nitrogen gas stream at 90 ° C.
The reaction was carried out with stirring for a minute to obtain a prepolymer having an isocyanate group remaining. Then after cooling it to room temperature,
2360 g of dry dimethylformamide was added and dissolved to obtain a prepolymer solution. On the other hand, ethylenediamine 2
3.4 g and diethylamine 3.7 g were dissolved in dry dimethylformamide 1570 g, to which the prepolymer solution was added at room temperature to give a viscosity of 1200 poise (30
C.) to obtain a polyurethane solution.

To this viscous polymer solution, 2% by weight of 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), 2- (2'-hydroxy-3'-t-butyl-) was added. 0.7% by weight of 5'-methylphenyl) -5-chloro-benzotriazole was added. This polymer solution was dry-spun to obtain a 4-filament, 40-denier yarn. Polyurethane elastic yarn 40d obtained by the above method
And polyamide filaments 50d and 17 filaments obtained by melt-spinning polyhexamethylene adipamide are aligned and knitted into a tubular knitted fabric with a tubular knitting machine, and dyeing processing (dyeing treatment and fixing treatment is performed under the following conditions. ) Was given.

Dyeing conditions Scouring Score roll FC-250 (manufactured by Kao Corporation) 2 g / l, 60 ° C. × 20 minutes Dyeing Lany Brill. Blue G 5% owf Ammonium sulfate 3% owf acetic acid 1% owf 90 ° C. × 60 minutes Bath ratio 1:40 Fixing tannic acid 3% owf acetic acid 1.8% owf 80 ° C. × 30 minutes Bath ratio 1:40 Tartar 1. 5% owf acetic acid 0.9% owf 80 ° C. × 30 minutes Bath ratio 1:40

The obtained polyurethane elastic yarn interwoven fabric is
Zinc acetate 10% owf, 80 ° C x 30 minutes, bath ratio 1:20
The fabric was subjected to a chlorine-treated water exposure test to measure the breaking strength and discoloration degree of the drawn polyurethane elastic yarn. The results are shown in Table 1. At this time, the zinc ion concentration of the polyurethane elastic yarn was 0.25% by weight.

Example 2 In Example 1, after the dyeing process, zinc acetate 10
% Owf, Meisserin H-100X, 1.0% owf,
A chlorine-treated water exposure test was conducted in the same manner as in Example 1 except that the treatment was carried out at 80 ° C. for 30 minutes at a bath ratio of 1:20, the breaking strength and the degree of discoloration were measured, and the results are shown in Table 1. At this time, the zinc ion concentration of the polyurethane elastic yarn is 0.35% by weight.
Met. The distribution state of the contained metal in the cross section of the obtained polyurethane elastic yarn was subjected to line analysis, and the result is shown in FIG. It can be seen from FIG. 1 that zinc ions are distributed in the surface layer of the polyurethane elastic yarn.

Example 3 In Example 1, after the dyeing process, magnesium acetate 10% owf, Meisserin H-100X, 1.0%
chlorinated water exposure test was conducted in the same manner as in Example 1 except that the treatment was carried out at owf, 80 ° C. × 30 minutes, and a bath ratio of 1:20, the breaking strength and the degree of discoloration were measured, and the results are shown in Table 1. .. At this time, the magnesium ion concentration of the polyurethane elastic yarn was 0.35% by weight.

Example 4 A chlorine-treated water exposure test was conducted in the same manner as in Example 2 except that the bath ratio was changed to 1: 7, and the breaking strength and the degree of discoloration were measured. Is shown in Table 1. At this time, the zinc ion concentration of the polyurethane elastic yarn is 0.9.
It was 1% by weight.

Comparative Example 1 Example 1 is the same as Example 1 except that after the dyeing step, the chlorine-treated water exposure test was carried out without zinc acetate treatment.
The breaking strength and the degree of fading were measured in the same manner as in, and the results are shown in Table 1.

Comparative Example 2 In Example 1, after the dyeing process, zinc acetate 1.
0% owf, Meisserin H-100X, 1.0% owf
A chlorine-treated water exposure test was conducted in the same manner as in Example 1 except that the treatment was carried out at 80 ° C. for 30 minutes at a bath ratio of 1:20, the breaking strength and the degree of discoloration were measured, and the results are shown in Table 1. The zinc ion concentration was 0.05% by weight.

Comparative Example 3 In Example 1, 2.5% by weight of zinc oxide and 4,4'-butylidene-bis (3-methyl-6-t) were added to the polymer solution.
-Butylphenol) 2% by weight, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-
Example 1 except that 4-filament, 40 denier zinc oxide-containing polyurethane elastic yarn obtained by dry spinning with the addition of 0.7% by weight of chloro-benzotriazole was used.
A chlorinated water exposure test was conducted in the same manner as above, the breaking strength and the degree of fading were measured, and the results are shown in Table 1. The distribution state of the metal contained in the zinc oxide-containing polyurethane elastic yarn was subjected to a line analysis, and the result is shown in FIG. It can be seen from FIG. 2 that zinc ions have fallen off from the surface layer of the polyurethane elastic yarn.

[0032]

[Table 1]

Example 5 2.5% by weight of hydrotalcite, 2% by weight of 4,4'-butylidene-bis (3-methyl-6-t-butylphenol) were added to the polymer solution obtained in Example 1. 2- (2 '
-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-benzotriazole (0.7% by weight) was added, and this was dry-spun to form a 4-filament, 40-denier hydrotalcite-containing polyurethane elastomer. I got a thread. This polyurethane elastic yarn containing hydrotalcite 4
0d and polyamide fiber 50d 17 filaments were knitted on a tricot machine under the following conditions, and warped 2WA
A Y tricot polyurethane elastic yarn interwoven fabric was prepared.

Knitting conditions: Warping and knitting were performed in a normal warp knitting process. Polyurethane elastic yarn was wound on a warp machine for elastic yarn manufactured by Riba Co., Ltd. using a 21 ″ beam to stretch 600 filaments twice and wound. Polyamide fiber was wound using a 21 ″ beam on a warp machine manufactured by KARL MAYER. 600 pieces, winding tension 0.1
It was wound up at g / d. Made by KARL MAYER: 28 gauges / inch Beam number: 6 Supply yarn: Polyamide fiber 160cm / rack Hydrotalcite-containing polyurethane elastic yarn 80cm /
Rack Number of courses on the machine: 80 courses / in set Fiber: Half yarn Usage: Front polyamide fiber Back Polyurethane elastic yarn containing hydrotalcite Raw material Quantities: 330 g / m basis weight, 120 cm width 114 courses / inch courses, number of wells 75 wells /
The obtained 2WAY tricot polyurethane elastic yarn interwoven fabric was subjected to the same treatment as in Example 1 and then subjected to a chlorinated water exposure test to measure the stress and the degree of fading at the third cycle of 80% elongation. The results are shown in Table 2.

Example 6 The polyurethane elastic yarn interwoven fabric obtained in Example 5 was subjected to the same treatment as in Example 2 and then subjected to a chlorinated water exposure test to obtain the third stress at 80% elongation. Measure the degree of fading,
The results are shown in Table 2.

Example 7 The polyurethane elastic yarn interwoven fabric obtained in Example 5 was subjected to the same treatment as in Example 3 and then subjected to a chlorinated water exposure test to obtain the third stress at 80% elongation. Measure the degree of fading,
The results are shown in Table 2.

Comparative Example 4 The polyurethane elastic yarn interwoven fabric obtained in Example 5 was subjected to the same treatment as in Comparative Example 1 and then subjected to a chlorinated water exposure test, and the stress of the third time was repeated at 80% elongation repetition. The degree of fading was measured and the results are shown in Table 2.

Comparative Example 5 Comparative Example 1 was applied to the polyurethane elastic yarn interwoven fabric obtained in Example 5.
After the same treatment as described above, synthetic tannin (NY Sti
Cker, manufactured by Shichifuku Kagaku Co., Ltd.), and subjected to a chlorine-treated water exposure test on the obtained fabric, and at the time of 80% elongation, 3
The second stress and the degree of fading were measured, and the results are shown in Table 2.

[0039]

[Table 2]

[0040]

The chlorine-resistant polyurethane elastic yarn interwoven fabric of the present invention is subjected to a dyeing treatment and a fixing treatment, and then a certain amount of a metal salt useful for preventing chlorine embrittlement is adsorbed on the surface of the polyurethane elastic yarn. As a result, chlorine embrittlement resistance can be imparted while maintaining color development and chlorine fastness, and it is possible to effectively protect the fiber surface that is easily embrittled by chlorine-treated water.

[Brief description of drawings]

FIG. 1 is a zinc ion distribution diagram by line analysis of a cross section of a polyurethane elastic yarn obtained in Example 2.

FIG. 2 is a zinc ion distribution diagram by line analysis of a cross section of a polyurethane elastic yarn obtained in Comparative Example 3.

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Claims (1)

Claim: What is claimed is: 1. A zinc ion and / or a magnesium ion is added to the surface layer of the polyurethane elastic yarn in the polyurethane elastic yarn interwoven fabric subjected to a dyeing treatment in an amount of 0.1 to the weight of the elastic yarn. A chlorine-resistant polyurethane elastic yarn interwoven fabric characterized by containing up to 1.0% by weight.