JP3087857B2 - Dyeing treatment method for knitted knitted fabric - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of dyeing a knitted and knitted fabric containing at least a polyurethane-based elastic fiber and a polyamide-based fiber, and more particularly, to a polyurethane-based elastic fiber provided with anti-deterioration properties in various chlorine water environments. The present invention relates to a dyeing method for a knitted fabric containing the same, which does not lower the deterioration prevention property.

[0002]

2. Description of the Related Art Polyurethane elastic fibers obtained from 4,4'-diphenylmethane diisocyanate, a polyhydroxy polymer having a relatively low degree of polymerization and a polyfunctional active hydrogen compound have a high degree of rubber elasticity. It has excellent mechanical properties, such as tensile strength and recoverability, and also has excellent thermal behavior. For this reason, it has been widely noticed and used as a functional material for clothing such as foundations, socks and sportswear.

[0003] However, when a product using such elastic fibers mainly composed of a long-chain synthetic elastic segmented polyurethane is exposed to a chlorine water environment such as a detergent using chlorine bleaching, the physical properties of the segmented polyurethane become poor. It is known that significant degradation occurs. Also, swimwear made of polyurethane fiber and polyamide fiber is known to deteriorate the physical properties of the fiber when exposed to water containing an active chlorine concentration of 0.5 to 3 ppm for a long time in a swimming pool. I have.

[0004] Improvements have been made to provide such degradation-inhibiting properties against chlorine-induced degradation or to impart resistance to such degradation. For example, zinc oxide (JP-B-60-43444), magnesium oxide, and aluminum oxide (JP-B-61-35283) are described as chlorine deterioration inhibitors.

[0005]

However, when a product such as a knitted or knitted fabric using a polyurethane-based elastic fiber containing a chlorine-deterioration inhibitor is subjected to dyeing, finishing, processing, etc., the dyeing and dyeing are particularly important. Acetic acid as the acid during the fixing process,
When an acid such as formic acid is used, the pH of the treatment solution is low, and the chlorine-deterioration inhibitor contained is eluted, and although the raw fiber has chlorine resistance,
There is a problem that resistance is almost lost in products via dyeing or the like.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and provides a textile product containing at least a dyed and dye-fixed polyurethane elastic fiber with resistance to chlorine water. It provides a manufacturing method.

[0007] That is, the present invention relates to a method for preparing 0.5 to 5.
0 wt% of the following compound groups: one [magnesium oxide, zinc oxide, aluminum oxide, magnesium hydroxide, zinc hydroxide, aluminum hydroxide, hydrotalcite compound _{MgxAly (OH) zCO 3 · IH} 2 0 ] or Dyeing a knitted knitted fabric containing at least a polyurethane-based elastic fiber containing at least two kinds and a polyamide-based fiber, and fixing the dye with an anionic phenol compound which does not take a quinone structure in contact with an alkali. In this method, a cross-knitted fabric is dyed using 0.01 to 10% by weight of orthoformate based on the weight of the fabric.

[0008] The polyurethane-based elastic fiber in the present invention is an elastic fiber obtained by spinning the following polymer composition mainly composed of polyurethane. As the polyurethane in the present invention, a polymer diol having a number average molecular weight of 600 or more, preferably 1000 to 5000 and a melting point of 60 ° C. or less, an isocyanate mainly composed of an organic diisocyanate, and a molecular weight of 400 or less And a polymer obtained by reacting the polyfunctional active hydrogen compound.

Examples of the polymer diols include polyether glycols such as polytetramethylene ether glycol and polyethylene propylene ether glycol, ethylene glycol, 1.6-hexanediol. ,
At least one of glycols such as 1,4-butanediol and neopentyl glycol and at least one of dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, β-methyladipic acid and isophthalic acid Polyester glycols, polycaprolactone glycols, polyhexamethylene dicales obtained by reacting with one kind
Examples thereof include one kind of polymer diol such as bone glycol, or a mixture or copolymer of two or more kinds thereof.

The organic diisocyanate includes 4
.4'-diphenylmethane diisocyanate, 1.5-
Naphthalene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4. Examples thereof include one or a mixture of two or more organic diisocyanates such as 4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate. Further, a small amount of triisocyanate may be used in combination.

Examples of the polyfunctional active hydrogen compound include ethylenediamine, 1.2-propylenediamine, hexamethylenediamine, xylylenediamine, 4.4'-diphenylmethanediamine, hydrazine, 1.4-diaminopiperazine, and ethylene glycol. 1,4-butanegio-
Or a mixture of two or more of these. If desired, a small amount of a terminator such as monoamine or monoalcohol may be used in combination with these compounds. However, preference is given to diamines alone or those based on diamines.

The method of spinning the polyurethane-based composition into elastic fibers is not particularly limited, but it is preferable to dissolve the polyurethane-based composition in a solvent and dry spin. NN-dimethylformamide as a solvent,
Examples include NN-dimethylacetamide, tetramethylurea, and hexamethylphosphonamide, but are not limited thereto. Components other than polyurethane constituting the polyurethane-based composition are metal oxides,
There are chlorine water deterioration inhibitors such as metal hydroxides.
Examples thereof include magnesium oxide, zinc oxide, aluminum oxide, magnesium hydroxide, zinc hydroxide, aluminum hydroxide, and hydrotalcite compounds, which may be used alone or as a mixture of two or more. Particularly preferred is magnesium oxide or zinc oxide. The addition to these polyurethane solutions is not particularly limited,
It is preferable to add as particles having an average particle diameter of 0.05 to 3 μm. The amount of the chlorine water deterioration inhibitor such as a metal oxide to be added is suitably 0.5 to 5.0% by weight, preferably 1.0 to 3.0% by weight, based on the polyurethane.

The polyurethane elastic fiber used in the present invention has an appropriate denier in the range of 20 to 100, preferably 40 to 80. These elastic fibers are used in the form of a covering yarn or a bare yarn. The polyamide fiber cross-knitted with the polyurethane elastic fiber of the present invention is not particularly limited, but is typified by 6 nylon and 6.6 nylon. The knitted knitted fabric may be a horizontal knitted fabric or a warp knitted fabric, and may be a tricot knitted fabric or a raschel knitted fabric, and is not limited. Examples of the knitting structure include a half knitting, a reverse half knitting, a double atlas knitting, a double denbitch knitting and the like, but are not particularly limited. In addition, it is preferable that the surface of the knitted fabric is made of polyamide fiber from the viewpoint of hand.

[0014] The knitted fabric is subjected to refining, relaxation and drying under ordinary conditions. Heat set temperature is 150 ° C ~
The temperature is 190 ° C, preferably 160 ° C to 180 ° C. The dyeing conditions are in a dyeing bath for 20 to 120 minutes, preferably 40 to 90 minutes. The dyeing machine may be a commonly used one such as a win dyeing machine or a jet dyeing machine. Dyes may be any of acid dyes, gold-containing dyes, fluorescent dyes, disperse dyes, reactive dyes, and direct dyes as long as they are ordinary dyes selected by dye manufacturers for dyeing polyamide fibers. Good.

The dye fixing agent used in the present invention includes:
An anionic phenol compound which does not form a quinone structure upon contact with an alkali, such as a phenolsulfonic acid formaldehyde resin, a novolak type resin sulfone compound, a novolak type resin methanesulfonic acid, and benzylation. Examples thereof include phenolsulfonic acid, thiophenol compounds, dihydroxydiphenylsulfone compounds, ligand compounds, and metal chelate compounds thereof. The amount of the anionic phenol compound used is in the range of 1 to 20% owf, preferably 3 to 10% owf, based on the polyamide fiber. When the amount of the anionic phenol compound is less than 1% owf, a durable dye fixing effect is not achieved. When the amount is more than 20% owf, the fixing effect is good but the texture becomes hard, which is not preferable.

As a method of applying the anionic phenol compound to the fabric, a method of immersing the knitted fabric after dyeing in an anionic phenol compound solution, or a method of applying the anionic phenol compound solution to the fabric A method of padding or a method of spraying on a knitted fabric is mentioned, but from the point that the dye fixing agent can be efficiently applied to the knitted fabric with as few steps as possible, including the dyeing process, and the dispersion of performance can be reduced. In view of this, the method of applying by immersion is preferable.
The temperature for fixing the dye is 40 ° C to 100 ° C, preferably 60 ° C to 90 ° C. In addition, according to the method of the present invention, a resin processing agent, a softening agent, an antistatic agent, a water repellent and the like can be added to the treatment liquid used for immersion, padding or spraying.

In the present invention, orthoformate is used in place of acetic acid, formic acid or the like as the acid. Examples of orthoformate include trimethyl orthoformate and triethyl orthoformate, and trimethyl orthoformate is particularly preferred. The amount of orthoformate used is preferably from 0.01 to 10% by weight, particularly preferably from 0.5 to 5% by weight, based on the weight of the dough. If the amount of orthoformate used is less than 0.01% by weight, there is no dye fixing effect, and if it is more than 10% by weight, the chlorinated water deterioration inhibitor is eluted and the performance of the product is remarkably deteriorated. Also, the orthoformate and an alkali agent such as soda ash may be used in combination.
When the dye fixing method of the present invention is not used, the amount of the chlorinated water deterioration inhibitor is extremely reduced after the treatment, and even if the fiber is spun and included in the fiber, the chlorinated water deterioration inhibitor in the dyed final product is used. Becomes small and loses its effect. Hereinafter, the present invention will be described with reference to examples. The percentages in the examples are weight percentages unless otherwise specified.

[0018]

Examples-Examples 1-2, Comparative Examples 1-4 Polytetramethylene ether glycol having a hydroxyl group at both ends and having a number average molecular weight of 2,000 was mixed with 4.4'-diphenylmethane diisocyanate in moles. The reaction was carried out at a ratio of 1: 2 to produce a prepolymer, followed by chain extension with 1.2 propylene diamine, and a polymer concentration of 30% (solvent was dimethylformamide) and 2000 poise (30 ° C.).
A polyurethane solution having a viscosity of. To this solution, 3% of magnesium oxide (average particle size: 0.1 to 2 μm) dispersed in dimethylformamide by an attritor was added to polyurethane, and an antioxidant, an ultraviolet absorber, and a gas yellowing inhibitor were added. The mixture was added, mixed and stirred to obtain a spinning dope.

After defoaming, the spinning stock solution is spun from a die having a hole diameter of 0.2 mm and 5 holes, extruded into a spinning tower in which heated air at 180 ° C. is flown, and false twisted at a rotation speed of 10,000 rpm. The yarn was wound at a spinning speed of 500 m / min while applying an oil agent to the yarn at a rate of 6% to obtain a polyurethane elastic fiber (A) having 40 deniers and 5 filaments. As a comparison,
A polyurethane elastic fiber (B) was obtained in the same manner as in (A) except that no magnesium oxide was added. In addition to (A) and (B), a 50-denier, 12-filament fiber (C) of 6 nylon fibers was prepared. The greige machine was knitted using a 28 gauge tricot machine manufactured by Kalmeier Knitting Machine. (A), (B) The draft of the fiber is 1
The knitting conditions are as follows: (A), (B) 70 cm / 480 course of fiber knitting length, (C) 160 cm / 480 course of fiber knitting length, (55 knitting on-machine course)
S), the knitting structure is half knitting.

The greige fabric containing each of the components (A) and (B) thus obtained was refined, relaxed, dried and heat-set, and each knitted fabric was dyed. Dyeing is a dye;
Color Rhodamine B, 1.5% owf
(Acid dye), trimethyl orthoformate 1 g /
1, soda ash 0.1 g / l 45 from 40 ° C to 95 ° C
And 95 ° C. for 30 minutes (bath ratio 1:13). After washing with hot water at 50 ° C. for 10 minutes, a dye fixing treatment was subsequently performed. In the dye fixing treatment, 5% owf of a formalin condensate of bisphenol sulfone and aromatic sulfonic acid (Nylon Super-N manufactured by Nissei Kasei) is used as a dye fixing agent.
(Bath ratio 1:15), from 40 ° C to 70 ° C for 10 minutes,
Treated at 70 ° C. for 20 minutes. The obtained knitted fabric is stretched and dehydrated,
After dewatering with a mangle, it was dried and set with a pin tenter at 160 ° C. for 30 seconds.

Comparative Example 5 A processing method similar to that of Example 1 was used except that natural tannin was used as a dye fixing agent.

Example 3, Comparative Example 6 For printing, after dyeing with a fluorescent dye under the above conditions, printing,
Steaming was performed at 100 ° C. for 40 minutes, and washing with water, alkaline soaping, washing with hot water, and washing with water were repeated. In the dye fixing treatment, a formaldehyde condensate of sulfonated dihydroxydiphenyl sulfone (FK707, manufactured by Fuji Chemical) is used as a dye fixing agent in an amount of 5% o.
wf (bath ratio 1:15), 10 from 40 ° C to 70 ° C
After treatment at 70 ° C for 20 minutes, dehydration and spreading, 160
It dried at 30 degreeC for 30 second, and set.

Each of the knitted fabrics obtained by the above-described method was measured for deterioration by chlorine water. The conditions for this degradation test are:
Each knitted fabric is stretched 40% in the warp direction and 30 pp at 30 ° C.
m of chlorine water (pH = 7.5) for 6 hours, the stress before and after the immersion was measured, and its deterioration (brittleness) was determined. Table 1 shows the results.

[0024]

[Table 1]

The fixing formulas A to G in Table 1 were obtained by adding the following orthoformate to the dye fixing dye solution described above. H and I are chemicals used in the dye fixing step in printing. A: Trimethyl orthoformate 0.5 g / l B: Trimethyl orthoformate 1 g / l C: Trimethyl orthoformate 10 g / l D: Trimethyl orthoformate 0.005 g / l E: Acetic acid 0.4 g / l F: G: trimethyl orthoformate 0.5 g / l H: trimethyl orthoformate 0.5 g / l I: acetic acid 0.4 g / l

[0026]

According to the present invention, the effect of imparting chlorine-resistant water resistance to a cross-knitted fabric made of a polyurethane-based elastic fiber and a polyamide-based fiber to which a metal oxide or the like, particularly magnesium oxide or zinc oxide has been added, is obtained by dyeing. This will be sufficient for the final product to be provided, and an excellent product can be provided.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-57-29609 (JP, A) JP-A-59-59912 (JP, A) JP-A-3-279472 (JP, A) JP-A-4-1992 209875 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D06P 3/82 D04B 21/18 D06P 1/651 D06P 3/02

Claims (1)

(57) [Claims] 1. A cross-knitted fabric containing at least 0.5 to 5.0% by weight of a polyurethane elastic fiber containing one or more of the following compounds in a fiber and a polyamide fiber: A cross-knitting process wherein, when dyeing and fixing the dye with an anionic phenol compound which does not form a quinone structure in contact with an alkali, 0.01 to 10% by weight of an orthoformate is used based on the weight of the fabric. Knitted fabric dyeing method. * Compounds: magnesium oxide, zinc oxide, aluminum oxide, magnesium hydroxide, zinc hydroxide, aluminum hydroxide, hydrotalcite compounds.