JP3252928B2 - Method for dyeing polyurethane elastic yarn / polyamide fiber mixed and woven fabric containing metal compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for dyeing a metal compound-containing polyurethane elastic yarn / polyamide fiber knitted and woven fabric. More specifically, the present invention relates to a dyeing method for obtaining a polyurethane elastic yarn / polyamide fiber cross-knitted fabric which has excellent resistance to chlorine deterioration and excellent color fastness even when used in chlorinated water such as a pool.

[0002]

2. Description of the Related Art Conventionally, a cross-knitted fabric of polyurethane elastic yarn and polyamide fiber is dyed with an acid dye at pH 3 to 5, and then an aqueous solution of tannic acid and tartar (pH 3 to 5).
5) A fix (Fix) treatment for immersion and fixation is performed. This fix treatment is performed to improve the color fastness of the polyamide fiber to chlorine generated in the chlorinated water. Japanese Patent Publication No. 60-44444 discloses a method of containing a metal oxide such as zinc oxide in a polyurethane elastic yarn in order to prevent deterioration of the polyurethane elastic yarn due to chlorine generated in chlorinated water.

However, in the above-mentioned method, when a cross-knitted woven fabric of polyurethane elastic yarn and polyamide fiber is dyed on an acidic side such as pH 3 to 5, or a fix treatment is performed to improve the color fastness of the polyamide fiber. When performing, since the metal compound elutes from the polyurethane elastic yarn, it was difficult to suppress the deterioration of the polyurethane elastic yarn due to chlorine.

[0004] In order to obtain a sufficient chlorine-deterioration inhibiting effect of the metal compound-containing polyurethane, a method in which a metal compound is hardly eluted, for example, a method of performing a dyeing treatment and a fixation treatment near neutrality such as pH 5 to 6, or pH 5 No. 6 to 6, a method is proposed in which only the dyeing process is performed and the fix process is not performed. However, although these methods improve the chlorine-deterioration resistance of the polyurethane elastic yarn, the dyeing fastness of the polyamide fiber to chlorine is insufficient.

Further, Japanese Patent Application Laid-Open No. 4-352844 has proposed a method of dyeing polyamide fibers with a vat dye. In this method, since it is dyed on the alkaline side,
Dropping during dyeing of metal compounds such as zinc oxide is prevented, but vat dyes have poor affinity for polyamide fibers,
In addition, since the dye is limited, there is a disadvantage that a free color cannot be obtained.

[0006]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and an object of the present invention is to provide a polyurethane elastomer containing a metal compound which is excellent in the resistance to deterioration of chlorine in polyurethane and the fastness to chlorine dyeing of polyamide fibers. It is an object of the present invention to provide a dyeing method for obtaining a yarn / polyamide fiber knitted and woven fabric.

[0007]

Means for Solving the Problems The present inventors suppressed the elution of the metal compound contained in the polyurethane elastic yarn by dyeing the knitted and woven fabric of the metal compound-containing polyurethane elastic yarn and the polyamide fiber on the alkali side. In addition, the inventors have found that the contamination of the polyurethane elastic yarn by the monosulfonic acid type anionic dye is reduced, and have completed the present invention.

[0008] The method of dyeing a polyurethane elastic yarn / polyamide fiber knitted and woven fabric containing a metal compound according to the present invention comprises the steps of:
To 7.5 to 11 and dyeing with a monosulfonic acid type anionic dye.

The polyurethane elastic yarn used in the present invention has, for example, hydroxyl groups at both ends and a molecular weight of 6
A substantially linear polymer having a molecular weight of from 0.00 to 5000; an organic diisocyanate; a chain extender having a polyfunctional active hydrogen atom; and a terminating agent having a monofunctional active hydrogen atom in one or more steps. Obtained by
It is obtained by spinning an elastic high molecular polymer having a urethane group in the molecule by dry spinning, wet spinning, melt spinning, or the like. The polyurethane elastic yarn used in the present invention can also be obtained by spinning the above prepolymer comprising a polymer having hydroxyl groups at both ends and an organic diisocyanate, while reacting the above chain extender and terminal terminator. Can be

Examples of the linear polymer having a hydroxyl group at both terminals include polyester diol, polylactone diol, polyether diol, polyester amide diol, polythioether diol, polyhydrocarbon diol, polycarbonate diol, polysiloxane diol, and the like. Polyurethane diol and the like.

As the organic diisocyanate, m-
And p-phenylene diisocyanate, 2,4- and 2,6-toluylene diisocyanate, p-xylylene diisocyanate, 4,4'-dimethyl-1,3-xylylene diisocyanate, 1-alkylphenylene-
2,4- and 2,6-diisocyanates, 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. Preferred is diphenylmethane-4,4'-diisocyanate.

Examples of the chain extender include ethylenediamine, 1,2-propylenediamine, hexamethylenediamine, xylylenediamine, 4,4'-diphenylmethanediamine, hydrazine, 1,4-diaminopiperazine, ethylene glycol, 1,4 -Butanediol,
Examples thereof include 1,8-hexanediol and water. These are used alone or as a mixture of two or more. Particularly preferred are diamines.

As the terminal terminator, for example, various dialkylamines are used. These may be used alone or in combination of two or more.

The polyurethane elastic yarn containing a metal compound used in the present invention can be obtained by adding a metal compound during the production process of the polyurethane elastic yarn. As the metal compound, a compound containing zinc, iron, magnesium, tin, nickel, aluminum, barium, calcium, or the like is used, and preferably, a white metal compound such as zinc oxide, magnesium oxide, or hydrotalcite is used. For example, the metal compound-containing polyurethane elastic yarn may be prepared by preparing a slurry containing the metal compound, adding it to a solution or dispersion of the additive, and mixing with the polymer spinning solution upstream of the fiber spinning orifice, or It can be obtained by injecting into a combined spinning solution. Alternatively, it can be obtained by separately adding a dry powder of the metal compound or a slurry of the metal compound in a suitable medium to the polymer spinning solution. The addition amount is preferably 0.5 to 5% by weight based on the polyurethane elastic yarn. If the amount is less than 0.5% by weight, the effect of the polyurethane elastic yarn on the resistance to chlorine deterioration is poor, which is not preferred. When the amount added is 5
If the amount exceeds 10% by weight, the mechanical strength of the polyurethane elastic yarn is remarkably reduced, which is not preferable.

In preparing the polyurethane elastic yarn, an organic or inorganic compound such as a gas yellowing inhibitor, an ultraviolet absorber, an antioxidant, a fungicide, and sulfuric acid may be added to the polymer spinning solution, if desired. Inorganic fine particles such as barium, aluminum silicate, magnesium silicate, calcium silicate, and zinc oxide; and antiadhesives such as calcium stearate, magnesium stearate, polytetrafluoroethylene, and organopolysiloxane can also be appropriately blended.

The polyamide fiber used in the present invention is, for example, a homopolymer containing 95% by weight or more of polyhexamethylene adipamide obtained by polymerization of hexamethylenediamine and adipic acid, and a polycapramide obtained by polymerization of ε-caprolactam. Is obtained by spinning a homopolymer or the like by a known method. The polymerization of the homopolymer is performed by a known method, and the degree of polymerization is not particularly limited as long as it is within a range of ordinary fiber formation. The polyamide fiber used in the present invention may also contain components other than those described above as components of the copolymer as long as the object of the present invention is not impaired. Further, the polyamide fiber may contain additives usually added, such as a matting agent, a stabilizer, and an antistatic agent. Examples of the method for producing the polyamide fiber include a method of drawing after spinning at a winding speed of 1000 to 1500 m / min or a method of spinning and winding at a high speed of 3500 m / min or more (so-called high-speed spinning).

Various cloth knitting methods are used for producing the cloth comprising the above-mentioned metal compound-containing polyurethane elastic yarn and polyamide fiber used in the present invention. For example, warping and knitting are carried out in a usual warp knitting step. The knitting can be performed by a warp knitting method or a normal weaving method.

In the present invention, the cloth obtained as described above is dyed with a monosulfonic acid type anionic dye at pH 7.5 to 11.

The anionic dye used in the present invention is not particularly limited, but is preferably a dye which does not decompose and discolor in alkali (pH 7.5 to 11) and has excellent dyeing properties.

Specifically, the dyes are classified into acid dyes and direct dyes in the Color Index classification, and dyes having a monosulfone group are preferred. Examples of the dye which does not decompose and discolor on the alkali side and has good dyeing properties include the following dyes.

C1 Acid Orange 7 Sola
r Orange (Sumitomo Chemical)

[0022]

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C1 Acid Red 88 Rocc
elline NS (Sumitomo Chemical)

[0024]

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C1 Direct Black 51 Dire
ct Fast Black (Sumitomo Chemical)

[0026]

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C1 Direct Black 19 Sumi
light Black G (Sumitomo Chemical)

[0028]

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Other anionic dyes include the following dyes, but are not limited thereto.

C1 Acid Yellow 25 C1 Acid Violet 9 C1 Acid Red 116 C1 Acid Orange 30 C1 Direct Yellow 8 C1 Direct Orange 37 C1 Direct Brown 173 C1 Direct Black 91 and the like.

In the present invention, in order to adjust the pH to 7.5 to 11, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate and the like can be mentioned. Preferably, it is a hydroxide of sodium or potassium. In the case of hydroxides of alkali metals or alkaline earth metals other than sodium or potassium, the dyeing bath becomes alkali, but it is not preferable because it causes a reaction such as a chelate reaction with a dye.

The dyeing temperature and time are not particularly limited.
In order to obtain a high dyeing rate, the dyeing temperature should be 60 to 110.
C. is preferred. More preferably, 80 to 9
5 ° C. When the dyeing temperature is higher than 110 ° C., the dyeing rate is high, but the dye is easily decomposed and discolored. When the dyeing temperature is lower than 60 ° C., the stability of the dye is improved, but the dyeing rate is undesirably low. The dyeing time is preferably from 15 to 60 minutes. If the dyeing time is longer than 60 minutes, the dyeing rate increases, but the dye is easily decomposed. If the dyeing time is less than 15 minutes, the dyeing rate is not sufficient, which is not preferable.

It is also possible to add leveling or suspending agents to the dyebath. The pH of the dye bath is preferably from 7.5 to 11, but from the viewpoint of the dyeing rate, the stability of the dye and the elution of the metal compound in the polyurethane, the pH is more preferably from 8 to 10. On the other hand, the contamination of the polyurethane elastic yarn by the anionic dye decreases as the alkali becomes higher,
pH 9-11 is preferred.

When dyeing with an anionic dye with an alkali, the ionic bond between the polyamide fiber and the anionic dye becomes insufficient, and the color fastness may be poor. In order to prevent this, after the above staining, pH
The treatment may be performed with an acid of 3 to 5. However, since the metal compound in the polyurethane is eluted with acetic acid or formic acid, which is usually used, it is preferable to use an acidic substance which does not easily react with the metal compound or an acid substance which does not easily elute into the dyeing bath even when reacted. For example, oxalic acid, tartaric acid, and citric acid are preferably used. When acid treatment is performed after dyeing, the treatment is preferably performed at 60 to 100 ° C. within 20 minutes.

In the present invention, the knitted fabric of the polyurethane elastic yarn containing the metal compound and the polyamide fiber is dyed on the alkaline side at pH 7.5 to 11 using an anionic dye. Elution can be prevented, and therefore, a decrease in the chlorine deterioration resistance of the polyurethane elastic yarn contained in the cross-knitted fabric can be prevented, and the obtained cross-knitted fabric has a color fastness to chlorine. Are better. Furthermore, in the present invention, since the dye is dyed with the monosulfone-type anionic dye, the polyurethane elastic yarn contained in the obtained knitted woven fabric can reduce the stain by the dye and produce a desired color.

[0036]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition,% in the following examples means weight% (owf) with respect to the total weight of the fiber unless otherwise specified. The measuring method used in the examples is as follows.

(1) Magnesium oxide content measurement A fiber sample whose weight was measured is ashed in a platinum dish in a muffle furnace at 800 ° C. for 10 minutes. The resulting residue is dissolved in a 50% by weight aqueous HCl solution. Perkin Elmer Model 370 equipped with a magnesium lamp and calibrated with a known amount of magnesium oxide-containing sample according to atomic absorption spectrometry (described in Perkin Elmer Corporation (1937), Norwalk, Conn.) By filtration to remove insolubles. Analyze with an atomic absorption spectrophotometer (or equivalent). The magnesium oxide content is then calculated as a percentage of the total weight of the fiber.

(2) Measurement of resistance to chlorine deterioration (deterioration of polyurethane elastic yarn by chlorine) <Stress retention of knitted fabric> Stress at the time of the third 80% elongation when warp knitted fabric is repeatedly stretched by 80% Is measured with a Tensilon tensile tester manufactured by Orientec. Specifically, a sample cut at 25 mm in width (direction orthogonal to the warp direction) is marked at 100 mm intervals in the warp direction of the knitted fabric, and the portion marked at the above 100 mm interval is gripped by a tensile tester. At a pulling rate of 100% / min.
The stress at the time of the third 80% elongation when the elongation to 0 mm is repeated is read. The sample became longer than the initial length as the polyurethane elastic yarn deteriorated, and the portion longer than the initial length (that is, the interval of 100 mm marked above) was recorded as permanent strain. Next, after performing the chlorinated water exposure test described below, the stress is measured in the same manner, and the ratio of the stress after the chlorinated water exposure test to the stress before performing the chlorinated water exposure test (stress retention) is calculated. I do.

<Exposure test of chlorinated water> The above sample was stretched by 50% using an elongating machine, and kept at an active chlorine concentration of 3 ppm at about 25 ° C. by adding a sodium hypochlorite solution. After being immersed for 10 hours in a 20-liter water bath adjusted to 0 while stirring, the sample was dried and measured for physical properties. The condition of the warp knitted fabric in the chlorinated water exposure test correlates with the condition of the swimsuit exposed in the chlorinated pool.

<Measurement of chlorine concentration in chlorinated water> In the above test, the concentration of chlorine in the chlorinated water is defined as the concentration of chlorine that can oxidize iodine ions to iodine. This concentration is determined by titration with potassium iodide or sodium thiosulfate, and the amount of active chlorine (Cl ₂ ) is 100
Record as copies per million. The titration method is as follows: 20 ml of an aqueous potassium iodide solution, 10 ml of glacial acetic acid and 5 ml of a 0.5% starch solution are added to the chlorinated water to be analyzed and the mixture is treated with 0.01 N sodium thiosulphate for a starch / iodine end point. Titrate to.

(3) Measurement of dyeing rate: 10 c from the parent material after pre-setting (190 ° C. × 40 seconds)
A test piece of mx 10 cm was cut out, and the room temperature was 20 ° C and the humidity was 6
The weight after standing for 24 hours in a 5% RH constant temperature and humidity chamber is measured to the nearest 1 / 10,000 g, and this is defined as the cloth weight A before dyeing. This is sewn on the parent fabric again, and dyeing and sorving (described later) are performed. After the dough is finally set (180 ° C. × 30 seconds), the test piece is removed from the parent dough, left in the above-mentioned constant temperature and humidity chamber for 24 hours, and the weight is measured. The same weight measurement is carried out after pre-setting and final setting under the same conditions as above but without any dye.
These are referred to as the fabric weight a before blank dyeing and the fabric weight b after blank dyeing, respectively. From the obtained weight,
The dyeing rate is calculated by the following equation. When no dye remains in the residual bath (Comparative Examples 1 and 2), the dyeing rate of the acid dye is as follows:
The amount of the dye charged was directly used as the dyeing rate.

[0042]

(Equation 1)

(4) Contamination of polyurethane elastic yarn The polyurethane elastic yarn was taken out from the dyed fabric, and judged as gray scale contamination of 1 to 5 class.

(5) Washing Fastness The washing fastness was evaluated according to the A-2 method of JIS L-0844.

Example 1 1000 g of polytetramethylene glycol having an average molecular weight of 1200 and 312 g of 4,4'-diphenylmethane diisocyanate were reacted while stirring at 95 ° C. for 90 minutes in a stream of nitrogen gas to obtain a prepolymer having a residual isocyanate group. A polymer was obtained. Then, after cooling to room temperature, dry dimethylformamide 2360
g was added and dissolved to obtain a prepolymer solution. On the other hand, 23.4 g of ethylenediamine and 3.7 of diethylamine
was dissolved in 1570 g of dry dimethylformamide, and the prepolymer solution was added thereto at room temperature.
A polyurethane solution of 00 poise (30 ° C.) was obtained.

To this viscous polymer solution, 3.0% by weight of magnesium oxide, 2% by weight of 4,4′-butylidene-bis (3-methyl-6-t-butylphenol),
0.7% by weight of (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-benzotriazole was added. The polymer solution was dry-spun to obtain a 4-filament, 40 denier magnesium oxide-containing polyurethane elastic yarn. Using the magnesium oxide-containing polyurethane elastic yarn 40 denier obtained by the above-mentioned production method and the polyamide fiber 50 denier and 17 filament obtained by melt-spinning polyhexamethylene adipamide, using a tricot machine under the following conditions: The knitted fabric was dyed and finished to produce a warp-knitted 2-way cloth for watering. <Construction conditions> Warping and knitting were performed in a normal warp knitting process. Magnesium oxide-containing polyurethane elastic yarn was prepared using an elastic yarn warping machine manufactured by Riva (Germany) using a 21 ″ beam.
00 pieces were stretched twice and wound up. Using a 21 "beam, 600 polyamide fibers were wound at a winding tension of 0.1 g / denier using a warping machine manufactured by KARL MAYER (Germany).

KARL MAYER (Germany): 28 gauges / inch Number of beams: 6 Yarn supply: polyamide fiber 160 cm / rack Magnesium oxide-containing polyurethane elastic yarn 80 cm /
Rack Number of courses on the knitting machine: 80 courses / inch Woven fiber: half Threading: front polyamide fiber back Polyurethane elastic yarn containing magnesium oxide Fabric amount: 330 g / m in weight, 120 cm width Number of courses: 114 courses / inch Number of wells: 75 Well / inch The above warp knitted fabric is subjected to a nonionic activator (Neugen HC: Daiichi Kogyo Seiyaku Co., Ltd.) using a circular dyeing machine CUT-FM-1.
(2 g / l) at 70 ° C. for 10 minutes. Using this fabric, monosulfonic acid type anionic dye Acid Red 88 (1% owf) and Direct Black
Using 19 (6% owf), alkalinize with sodium carbonate (pH 8-11) and stain, then monogen (Daiichi Kogyo Seiyaku Co., Ltd.) 1 g / l and Na ₂ CO ₃ 0.3 g / l
(Bath ratio 1:20) was subjected to a sorbing treatment at 60 ° C. for 10 minutes, and thereafter, tests of magnesium oxide content, chlorine deterioration resistance, dyeing rate, contamination to polyurethane, and washing fastness were performed. Table 1 shows the results.

[0048]

[Table 1]

(Comparative Example 1) Magnesium oxide was prepared in the same manner as in Example 1 except that the same fabric was used as in Example 1 and acidified (pH 3 and 5) with acetic acid and dyed. Tests were performed for the content, chlorine deterioration resistance, dyeing rate, and contamination to polyurethane. Table 2 shows the results.

[0050]

[Table 2]

(Comparative Example 2) Using the same fabric as in Example 1, using Direct Red 173 (disulfonic acid type) as a dye,
Staining with acetic acid at pH 3 and pH 5,
And in the same manner as in Example 1 except that the solution was dyed at pH 9 and pH 10 using sodium carbonate.
Tests were conducted on magnesium oxide content, chlorine deterioration resistance, dyeing rate, and contamination to polyurethane. Table 3 shows the results.

[0052]

[Table 3]

In Example 1, Comparative Example 1 and Comparative Example 2, dyeing was started at 40 ° C. at a temperature increase of 2 ° C./min and performed at 90 ° C. for 30 minutes. From Tables 1 and 2, it was found that the dyeing with alkali resulted in a small amount of eluted magnesium oxide and little deterioration of the polyurethane elastic yarn. Furthermore, it was also found that the polyurethane elastic yarn was less contaminated by an anionic dye, so that the fastness was improved. As shown in Tables 1 to 3, the monosulfonic acid type acid dye is superior to the disulfone type acid dye in dyeing rate on polyamide fibers.

[0054]

The polyurethane elastic yarn / polyamide fiber knitted fabric containing a metal compound dyed by the method of the present invention has excellent resistance to deterioration of chlorine in polyurethane elastic yarn and dyeing fastness of polyamide fiber to chlorine.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) D06P 3/24 D04B 21/00 D06P 3/82

Claims (1)

(57) [Claims] 1. A method comprising adjusting the pH of a dye bath to 7.5 to 11 and dyeing with a monosulfonic acid type anionic dye.
A method for dyeing a metal compound-containing polyurethane elastic yarn / polyamide fiber interwoven fabric.