JP3035893B2 - Dyed knitted knitted fabric and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dyed knitted knitted fabric and a method for producing the same. More specifically, the present invention relates to the improvement of chlorine-resistant discoloration resistance of a dyed knitted fabric containing a polyurethane-based elastic fiber and a polyamide-based fiber and / or a polyester-based fiber. The substance having an amount of 50 meq / g or more contains at least one kind in an amount of 0.1 to 20% based on the weight of the fiber, so that the color of the fabric after dyeing is not impaired. The present invention relates to a dyed knitted knitted fabric which significantly improves the chlorine fading resistance of a fabric and a method for producing the same. (Method of measuring the reaction amount of chlorine) The substance is mixed with an aqueous solution of sodium hypochlorite and dilute acetic acid,
React with chlorine for a predetermined time. After a predetermined time has passed, an aqueous solution of potassium iodide and acetic acid are added, and chlorine that has not reacted with the sample is reacted with potassium iodide. By titrating the reaction product with an aqueous solution of sodium thiosulfate,
The chlorine consumption of the sample at a predetermined time is determined. From the chlorine consumption of the sample at a predetermined time, the consumption at the reaction time 0 is extrapolated to obtain the chlorine reaction amount of the substance.

[0002]

2. Description of the Related Art Conventionally, dyed products dyed using compound dyes such as acid dyes, disperse dyes, metal-containing dyes, reactive dyes, and direct dyes are discolored and faded in a chlorine-containing environment such as chlorine bleaching. It is known to Particularly, a knitted knitted fabric composed of a polyurethane-based elastic fiber and a polyamide-based synthetic fiber dyed with an acid dye, a disperse dye, a metal-containing dye, a reactive dye, or the like is used to form an active chlorine concentration of 0.5 to 0.5% for swimming pools.
Exposure to chlorine water containing 3 ppm for a long time causes discoloration, yellowing, dullness, and the like of the dyed product, particularly in a fluorescent color and a vivid color, which greatly impairs its value.
Conventionally, as a method of improving such chlorine discoloration resistance, a method of using a dye having good chlorine discoloration resistance, a method of imparting water repellency to a fiber or a fabric by some method, and a post-treatment of a dyed product Methods to improve the chlorine discoloration resistance have been proposed and studied, but up to now, without impairing the color of the fabric immediately after dyeing by applying,
Further, a method satisfying the chlorine discoloration resistance has not been developed.

[0003]

As a method for improving the chlorine discoloration resistance, tannic acid, which is usually used as a dye fastness improver as disclosed in JP-A-57-14358, is prepared by using a polyamide-based synthetic fiber. There is proposed a method of giving the knitted fabric including the knitted fabric. However, natural tannic acid itself is a yellow-brown colored compound, so that when used for clear or light-colored, particularly vivid blue dyeings, the color and vividness of the original dye are greatly impaired. In addition, since tannic acid is a polyhydroxybenzene derivative containing a large number of galloyl groups in its molecule, it contains a basic additive (for example, an oxidizing agent added to polyurethane elastic fiber to suppress deterioration of the elastic polyurethane fiber by chlorine water). When a strong basic substance such as magnesium or zinc oxide is present, two adjacent hydroxyl groups contained in the galloyl group are oxidized to an irreversibly quinone structure, which is further colored in a dark color such as brown and the color of the dyed material. May be changed.

[0004]

Means for Solving the Problems In view of such a current situation, the present inventor has made intensive studies based on a new idea, and as a result, has arrived at an epoch-making invention which has solved the above-mentioned problems. That is, the present invention relates to a knitting method comprising at least a polyurethane-based elastic fiber and a polyamide-based fiber and / or a polyester-based fiber dyed with a compound dye such as an acid dye, a disperse dye, a metal-containing dye, a reactive dye, and a direct dye. A knitted fabric, wherein the reaction amount of chlorine measured by the method described below is 50
By impregnating at least one kind of substance having a milliequivalent / g in a high-temperature bath by 0.1% to 20% with respect to the weight of the knitted fabric by impregnating the fabric, the original color of the dyed product is impaired. An object of the present invention is to provide a dyed product which has significantly improved resistance to chlorine discoloration and fading in various chlorine-containing environments without any problems, and a method for producing the same. The present invention improves the chlorine discoloration and discoloration resistance by incorporating the substance at the time of dyeing and / or before and after dyeing, and contributes to the improvement of the durability of the product.

[0005] (Method for measuring the reaction amount of chlorine) A method for measuring the reaction amount of chlorine (hereinafter referred to as C) is shown below. In the measurement methods,% indicates% by weight. (1) Reagent and its preparation method Sodium hypochlorite solution Nacalai Tesque's sodium hypochlorite (special grade reagent)
Dilute 30 g to 1 L with pure water. Dilute acetic acid aqueous solution (10%) 5 g of acetic acid is diluted with pure water to make the total amount 50 g. Starch indicator (5%) 1 g of soluble starch manufactured by Nacalai Tesque, Ltd. is dissolved in pure water to make the total amount 20 g. Acetate acetate Nacalai Tesque's special grade reagent is used as it is. Potassium iodide aqueous solution (20%) Potassium iodide manufactured by Nakarai Tesque (special grade reagent) 100
g in pure water to make the total amount 500 g. N / 10 sodium thiosulfate normal solution The normal solution manufactured by Nacalai Tesque, Inc. is used as it is. (Titer of specified solution; f) Solvent Select an appropriate solvent according to the properties of the substance (hereinafter referred to as a sample) for which the reaction amount of chlorine is measured.

[0006] In the present case, chloroform, methanol, ethanol, isopropyl alcohol, methyl isopropyl ketone (all of which are special grade reagents manufactured by Nacalai Tesque) and pure water were used as they were and / or as a mixture. (2) Preparation of sample solution A predetermined amount of the sample (Sg, preferably around 0.1 g) is precisely weighed with an analytical balance and dissolved in a solvent (selected in (1)-) in a 100 ml volumetric flask. 100 total
ml. (3) Apparatus used (the number in parentheses indicates the number) 25 ml burette (1) Whole pipette 25 ml (1), 10 ml (2), 5 ml
(1) 2 ml (1) Female pipette 10 ml (1) Erlenmeyer flask with stopper 100 ml (measurement number + 2 for blank test) Magnetic stirrer, stirrer (same number as Erlenmeyer flask) Clock (1)

(4) Operation for quantifying the reaction amount of chlorine A 25 ml burette is charged with a normal solution of N / 10 sodium thiosulfate. The sodium hypochlorite solution is dispensed to each of the 100 ml Erlenmeyer flasks containing the number of stirrers using a 25 ml hole pipette. Prepare two blank tests. The sample solution is dispensed into a Erlenmeyer flask using a 10 ml whole pipette. 10ml solvent for blank test
Dispense. While stirring, add 10 ml of a 10% diluted aqueous solution of acetic acid to each Erlenmeyer flask using a 10 ml pipette. The time point when the dilute acetic acid aqueous solution is first added is set to 0 minute, and the timing is started. After reaching the predetermined time, take out one Erlenmeyer flask,
5 ml of a 20% aqueous potassium iodide solution and 2 ml of acetic acid
Add. The reaction time is set at 5, 10, 20, 30, or 40 minutes as a standard. While stirring, a normal solution of sodium thiosulfate is added dropwise until almost no color is obtained. Add a few drops of starch indicator,
Continue dripping until the purple color has completely disappeared. The point at which the purple color has completely disappeared is the titration end point. Hereinafter, the titration amount is measured by the same operation at each predetermined time. (Titration required; Vm
l) For the blank test, perform titration in the same manner as immediately after adding dilute acetic acid and after completing the titration of the sample containing the sample. The average value of these two times is defined as the required titration amount (V ₀ ml) for the blank test.

(5) Calculation of chlorine reaction amount (C) Reaction time is x, (V ₀ -V) of each reaction time is y,
The correlation between x and y was determined by the least squares method in the form of the following equation (1). y = a + bx (correlation coefficient: r) Equation (1) The correlation coefficient of the straight line is preferably 0.98 or more from the viewpoint of measurement accuracy. C was calculated by the following equation (2) from the extrapolated value (ie, a) of the obtained reaction time (y) of the straight line to 0. C = a × f ÷ S Formula (2) (unit of C; milliequivalent / g, f; titer of N / 10 sodium thiosulfate normal solution, S; sample amount (g))

In the present invention, the substance having a chlorine reaction amount of 50 meq / g or more (hereinafter referred to as a chlorine discoloration inhibitor) is 4,4'-methylenebisphenol,
4 ′-(1-methylethylidene) bisphenol (bisphenol A), 4,4′-ethylidenebisphenol, 4,4 ′-(1-α-methylbenzylidene) bisphenol, 4,4′-cyclohexylidenebisphenol, 4, 4 '-[1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylidene] bisphenol, 4,4'-[(4-hydroxyphenyl)
Methylene] bis (methylphenol), 4,4'-
[(4-hydroxyphenyl) methylene] bis (2,6
-Dimethylphenol), 4,4'-methylenebis (2,6-dimethylphenol), 4,4 '-(1-methylethylidene) bis (2-methylphenol), 4,
4 ', 4 "-ethylidene trisphenol, 4,4',
4 "-methylidine trisphenol, 2,2'-methylenebis (4-methylphenol), 4,4 '-(1-methylethylidene) bis (2,6-dimethylphenol), phenolphthalein, 1,4- Phenylene
4,4'-bisphenol, 1,4-bis (4-hydroxyphenyl) cyclohexane, bis (3,5-dihydroxyphenyl) methane, 2,2'-bis (4-hydroxynaphthyl) methane, 2,2'- Bis (5-hydroxynaphthyl) methane, 2,2′-bis (6-hydroxynaphthyl) methane, 2,2′-bis (7-hydroxynaphthyl) methane, 2,2′-bis (8-hydroxynaphthyl) methane , 2,2'-bis (4,7-dihydroxynaphthyl) methane, 2,2'-bis (3,6-dihydroxynaphthyl) methane, etc., and a diphenylmethane derivative having a hydroxyl group introduced therein, and a polymer using these as a monomer .

Diphenylsulfone derivatives having a hydroxyl group introduced therein, such as bis (4-hydroxyphenyl) sulfone and bis (3,5-dihydroxyphenyl) sulfone, and multimers containing these as monomers, 4,4'-dihydroxydiphenylsulfide A diphenyl sulfide derivative having a hydroxyl group introduced therein, such as bis (3,5-dihydroxyphenyl) sulfide,
Diphenyl ether derivatives into which hydroxyl groups have been introduced, such as 4,4'-dihydroxydiphenyl ether and bis (3,5-dihydroxyphenyl) ether, and polymers having these as monomers, 4,4'-dihydroxyazobenzene, bis (3,5 Azobenzene derivatives having a hydroxyl group introduced therein, such as -dihydroxy) azobenzene, and a polymer having these as a monomer, 3,3'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 3,5-dihydroxybiphenyl, 2,4- Dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 2,3'-dihydroxybiphenyl, 3,5,4'-trihydroxybiphenyl, 2,4,4'-trihydroxybiphenyl, 2,6,4'-trihydroxy Biphenyl, 3,3
Biphenyl derivatives having a hydroxyl group introduced, such as', 5,5'-tetrahydroxybiphenyl, and multimers using these as monomers.

2,2'-bis (4-hydroxynaphthyl), 2,2'-bis (5-hydroxynaphthyl),
2,2′-bis (6-hydroxynaphthyl), 3,3 ′
-Bis (6-hydroxynaphthyl), 2,2'-bis (8-hydroxynaphthyl), 1,1'-bis (3-hydroxynaphthyl), 1,1'-bis (4-hydroxynaphthyl), 1′-bis (5-hydroxynaphthyl), 1,1′-bis (6-hydroxynaphthyl),
1,1′-bis (7-hydroxynaphthyl), 1,1 ′
-Binaphthyl derivatives having a hydroxyl group introduced therein, such as bis (8-hydroxynaphthyl), multimers using these as monomers, 3-hydroxybenzoic acid and / or methyl, ethyl, isopropyl, and t-butyl containing this as an acid component ,
Amyl and stearyl esters and their multimers as monomers, 4-hydroxybenzoic acid and / or methyl, ethyl, isopropyl and t
-Butyl, amyl and stearyl esters and their multimers as monomers, 3,5-dihydroxybenzoic acid and / or methyl, ethyl as an acid component thereof,
Isopropyl, t-butyl, amyl and stearyl esters and their multimers as monomers.

2,4-dihydroxybenzoic acid and / or methyl, ethyl, isopropyl, t-butyl, amyl and stearyl esters containing the same as an acid component and multimers containing these as monomers, 3-hydroxyacetophenone, -Dihydroxyacetophenone, 3,5-
Hydroxyacetophenones such as dihydroxyacetophenone and 2,4-dihydroxyacetophenone and multimers containing these as monomers, 3-hydroxybenzylethylketone, 4-hydroxybenzylethylketone,
3-hydroxybenzyl-isopropyl ketone, 4-hydroxybenzyl-isopropyl ketone, 3-hydroxybenzyl butyl ketone, 4-hydroxybenzyl butyl ketone, 3-hydroxybenzyl amyl ketone, 4-hydroxybenzyl amyl ketone, 4-hydroxybenzyl stearyl ketone, 3 Examples thereof include hydroxybenzyl ketones such as -hydroxybenzyl stearyl ketone and the like, and multimers using these as monomers, alkylphenols such as isopropyl phenol, butyl phenol, and amyl phenol, and multimers using these as monomers.

[0013] A multimer containing as a monomer a substance having a chlorine reaction amount of 50 meq / g or more as measured by the above-mentioned method is an aromatic compound produced by oxidatively coupling these monomers. Nucleo-aromatic direct conjugates are more preferred.
The multimer is produced by a known method, for example, Horse-ra.
It is carried out by oxidative coupling of phenolic compounds by a dish peroxidase enzyme. Also,
Formalin condensates using the above-mentioned phenols as raw materials, such as conventional novolak resins, may be used.

When a substance having a chlorine reaction amount of at least 50 meq / g as measured by the method of the present invention is used, it may be used alone or in combination of two or more. In the present invention, the substance used as a chlorine discoloration inhibitor is more preferably 60 meq / g or more, more preferably 70 meq / g, in which the amount of the substance reacting with chlorine measured by the above method is 60 meq / g or more. It is desirable to include a substance having an equivalent weight / g or more in the dyed product. The substance used as a chlorine discoloration inhibitor in the present invention is preferably such that the substance itself has a high whiteness or is colorless from the viewpoint of affecting the color of the dyed material, and particularly preferable is 4,4.
4'-biphenol, bisphenol A, 4,4'-dihydroxydiphenylsulfone, and 4,4'-methylenebisphenol. As the polyhydroxybezen derivative in the present invention, a polyhydroxybenzene derivative (phenol, resorcin, phloroglucin, etc.) which does not take a quinone structure when oxidized is preferable. The amount of the chlorine discoloration inhibitor contained in the knitted fabric is 0.1 to 20% by weight.
However, it is preferably 0.5 to 10% by weight. If it is less than the above range, the effect is hard to be recognized, and if it exceeds this range, the texture of the knitted fabric is not preferable.

The polyamide fiber in the present invention is not particularly limited, but is represented by nylon 6 and nylon 6.6. The normal pressure cationic dyeable polyester fiber in the present invention is not particularly limited, but for imparting normal pressure cationic dyeability, for example, sodium 5-sulfoisophthalate or a long-chain alkylene glycol is used in combination. It is represented by a polyester-based fiber produced by melt-spinning a polymerized polyester.

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 1,000 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 are used. Polymers obtained by the reaction are exemplified.

As the polymer diol, at least one of polyether glycols such as polytetramethylene glycol and polyethylene propylene glycol, ethylene glycol, 1,6-hexanediol, 1,4-butanediol and neopentyl glycol is used. Adipic acid, suberic acid, azelaic acid, sebacic acid, β-
One or more polymer diols such as polyester glycols, polycaprolactone glycol, and polyhexamethylene dicarbonate glycol obtained by reacting at least one of dicarboxylic acids such as methyladipic acid and isophthalic acid. A mixture or a copolymer can be exemplified.

As the organic diisocyanate, 4,4
'-Diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 4,4
Examples thereof include one or a mixture of two or more organic diisocyanates such as' -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, ethylene glycol, , 4-butanediol, 1,6-hexanediol, water and the like, or a mixture of two or more thereof. If desired, a small amount of a terminator such as a monoamine or monoalcohol may be used in combination with these compounds. However, preference is given to diamines alone or those mainly composed of 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. Examples of the solvent include, but are not limited to, N, N-dimethylformamide, N, N-dimethylacetamide, tetramethylurea, hexamethylphosphonamide and the like. Non-polyurethane constituents of the polyurethane-based composition include stabilizers such as lubricants, ultraviolet absorbers, anti-yellowing agents, pigments, antistatic agents, surface treatment agents, flame retardants, fungicides, reinforcing agents and chlorine. Water degradation inhibitors are exemplified. In particular, chlorine water deterioration inhibitors include magnesium oxide, zinc oxide, aluminum oxide,
Examples thereof include metal oxides and metal hydroxides such as magnesium hydroxide, zinc hydroxide, aluminum hydroxide, and hydrotalcite compounds, and these 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, but the average particle size is 0.0
It is preferable to add as 5 to 3 μm particles.

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 knitted knitted fabric which is the object of the present invention is a knitted knitted fabric formed by using the polyurethane-based elastic fiber and the above-mentioned polyamide-based fiber. The fabric may be a tricot knitted fabric or a raschel knitted fabric, but is not limited thereto. Examples of the knitting structure include half knitting, reverse half knitting, double atlas knitting, and double Denby knitting, but are not particularly limited. In addition, it is preferable that the surface of the knitted fabric is made of a polyamide-based fiber from the viewpoint of hand.

The knitted fabric is subjected to refining, relaxation and drying under ordinary conditions. Heat set temperature is 150 ~ 1
The temperature is 90 ° C, preferably 160 to 180 ° C. The dyeing conditions are 20 to 120 minutes in a dye bath, preferably 40 to 60 minutes.
Minutes. The dyeing machine may be a commonly used one such as a Wins dyeing machine or a jet dyeing machine. The dye may be any of an acidic dye, a metal-containing dye, a fluorescent dye, and a disperse dye as long as it is a normal dye selected by a dye maker for dyeing polyamide fibers. When dyeing using a strong acid bath at the time of dyeing, strong basic substances such as magnesium oxide added to polyurethane fibers for the purpose of suppressing deterioration due to chlorine water may fall off, and the desired performance may not be exhibited. . In order to minimize such degradation, formate, acetate, butyrate and the like are added to the dye bath so that the pH of the dye bath from the start to the end of dyeing is not lowered to 4.5 or less. Is preferable. By adding the organic acid ester to the dye bath, it is possible to minimize the falling off of the fiber due to the dyeing of the basic additive.

As a method for causing the dyed cross-knitted fabric to contain a substance having a chlorine reaction amount of 50 meq / g or more as measured by the above method, a method of mixing at the time of fiber production,
There is a method of dissolving it in an organic solvent and incorporating it by immersion, padding and spraying, etc., but generally, it may be carried out by the same method as when dyeing with a disperse dye. The method is exemplified below, but the production method is not limited to this. A predetermined amount of at least one compound is dispersed using a commercially available anionic dispersant such as a naphthalenesulfonic acid formalin condensate using a disperser such as a ball mill, a dyno mill or an attritor. A knitted knitted fabric containing a polyamide-based fiber and a polyurethane-based elastic fiber is immersed in the compound dispersion that has been heated in advance, and is immersed in a bath for 20 to 120 minutes, preferably 40 to 60 minutes, at a bath temperature of 40 to 95. C., preferably at 60-85 C.
The compound is incorporated on the fiber surface. In order to further increase the content yield, a carrier agent such as orthophenylphenol may be simultaneously added to the treatment bath for treatment. Further, the application of the compound to the knitted or knitted fabric may be performed before dyeing, may be performed simultaneously with the dyeing, and is usually performed after dyeing for the purpose of improving the color fastness of various dyes. It may be performed simultaneously with or after the dye fixing treatment with a compound or the like.

[0024]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. In the following examples, the reaction amount of chlorine measured by the above method on a cross-knitted fabric containing at least dyed polyurethane elastic fiber and polyamide fiber and / or polyester fiber is 50 meq / g or more. The improvement in the chlorine discoloration resistance of a dyed product in chlorine water by including a certain substance will be described. Parts in the examples mean parts by weight. Example 1 Polytetramethylene ether glycol having a hydroxyl group at both terminals and having a number average molecular weight of 2,000 was reacted with 4,4'-diphenylmethane diisocyanate at a molar ratio of 1: 2 to produce a prepolymer. , 2-propylenediamine, and a polymer concentration of 30% (solvent is N, N-dimethylformamide) at 200 poise (3
(0 ° C.). To this solution, 3% of magnesium oxide (average particle size: 0.1 to 2.0 μm) based on polyurethane is dispersed and added in dimethylformamide with an attritor, and further, a whiteness improver, an antioxidant, and an ultraviolet absorber The agent and the gas yellowing inhibitor were added, and mixed and stirred to obtain a spinning dope.

After the defoaming, the spinning stock solution was spun out from a spinneret having a hole diameter of 0.2 mm and 5 holes, extruded into a spinning tube in which heated air at 180 ° C. was flown, and subjected to false twist at a rotation speed of 10,000 rpm. The yarn was wound at a spinning speed of 500 m / min while applying 6% of the oil agent to the yarn to obtain a 40-denier 5-filament polyurethane-based elastic fiber (A). As a polyamide fiber, a 6.6 nylon fiber (B) of 50 denier and 12 filaments produced by melt spinning was prepared. As the polyester fiber, a 50-denier, 10-filament, normal-pressure cationic dyeable polyester fiber (C) produced by melt spinning was prepared. The greige machine was knitted using a 28 gauge tricot machine manufactured by KARL MAYER Knitting Machine. (A) The draft of the fiber is 100%, the knitting conditions are (A) the fiber braided length of 70 cm / 480 course, and (B) and (C) the fiber braided length of 160 cm / 4.
80 courses (55 courses on the machine), the knitting structure is half knitting.

The greige fabric containing (A) and (B) thus obtained was refined, relaxed, dried and heat-set to dye each knitted fabric. For dyeing, acetic acid 0.4 was added to the dye bath.
g / L, ammonium sulfate 2 g / L, anionic leveling agent 1.2 g / L
Is dissolved in a bath ratio of 1:13 and the dye: Kayacyl Bl
ue BR, 5% owf (acid dye), 40 ° C to 95%
The test was performed at 60 ° C. for 60 minutes. After washing with hot water at 50 ° C. for 10 minutes, subsequently, as a chlorine discoloration inhibitor, bisphenol A having a reaction amount of chlorine of 79.5 meq / g and 5% owf measured by the above method was dyed, and the knitted fabric was dyed. It was contained by immersing in a dispersion and treating at 40 ° C. to 80 ° C. for 50 minutes. Further, a dye fixing treatment was performed using an anionic polyphenol other than tannic acid. The obtained dyed knitted fabric is stretched and dewatered, drained with a mangle,
It was dried at 60 ° C. with a pin tenter and set.

The dyed knitted fabric obtained by the above-described method was measured for its hue discoloration with chlorine water. The condition of the chlorine discoloration test was that one part of the knitted fabric was made to have an effective chlorine concentration of 100%.
The sample is immersed in 400 parts of chlorine water having a pH of 7.0 and a chlorine water treatment at a bath temperature of 40 ° C. for 30 minutes so that the chlorine water flow hits the surface of the knitted fabric at right angles to the surface of the knitted fabric. The discoloration was measured by measuring the hue of the dyed and knitted fabric, and the difference in hue before and after the treatment with chlorinated water was determined. From the result, the chlorine fastness (discoloration grade) was determined. The results are shown in Table 1 below.

Example 2 Using a knitted knitted fabric containing (A) and (C), 0.4 g / L of acetic acid and 0.5 g / L of an anionic leveling agent are dissolved in a dye bath. Dye: Diacryl Brill at a bath ratio of 1:18
ant Blue AC-E, 1% owf (basic dye), a cross-knitted fabric dyed according to the same formulation as in Example 1 except that dyeing was performed at 40 ° C. to 100 ° C. for 60 minutes, and chlorine was prepared. Water treatment was performed. The results are shown in Table 1.

Example 3 Example 4 was repeated except that 4,4'-biphenol having a reaction amount of chlorine of 98.7 meq / g and 5% owf was used as a chlorine discoloration inhibitor. A knitted knitted fabric dyed in the same manner as in No. 1 was produced and treated with chlorine water. Table 1 shows the results.

Example 4 Example 4 was repeated except that 4,4'-methylenebisphenol having a reaction amount of chlorine of 94.4 meq / g and 5% owf was used as a chlorine discoloration inhibitor. A knitted knitted fabric dyed in the same manner as in No. 1 was produced and treated with chlorine water. Table 1 shows the results.

Example 5 Other than using 3,5-dihydroxybenzyl ethyl ketone, 5% owf, which has a chlorine reaction amount of 76.1 meq / g as measured by the above method, as a chlorine discoloration inhibitor. Prepared a knitted knitted fabric dyed in the same manner as in Example 1, and treated with chlorine water. Table 1 shows the results.

Example 6 As a chlorine discoloration inhibitor, bisphenol A having a chlorine reaction amount of 56.3 meq / g as measured by the above method.
As a monomer, Horsera-dish perox
bisphenol A polymer (average molecular weight 100
A knitted knitted fabric dyed in the same manner as in Example 1 except that 0) and 5% owf were used was prepared and treated with chlorine water. Table 1 shows the results.

-Example 7- As a chlorine discoloration inhibitor, 4,4'-biphenol having a reaction amount of chlorine of 98.7 meq / g as measured by the above method was used except that 2% owf was used. A cross-knitted fabric dyed in the same manner as in Example 1 was produced, and treated with chlorine water.
Table 1 shows the results.

-Example 8- As a chlorine discoloration inhibitor, 4,4'-biphenol having a reaction amount of chlorine of 98.7 meq / g as measured by the above method was used, except that 10% owf was used. A cross-knitted fabric dyed in the same manner as in Example 1 was produced, and treated with chlorine water. Table 1 shows the results.

Comparative Example 1 A knitted knitted fabric dyed in the same manner as in Example 1 was prepared without using any chlorine discoloration inhibitor, and treated with chlorine water. Table 1 shows the results.

Comparative Example 2 A knitted knitted fabric dyed with the same formulation as in Example 2 was prepared without using any chlorine discoloration inhibitor, and treated with chlorine water. The results are shown in Table 1.

Comparative Example 3 Dyeing was carried out in the same manner as in Example 2, except that no chlorinated discoloration inhibitor was used and tannic acid / tartar treatment was used as the chlorine discoloration inhibitor and the dye fixing agent. The knitted knitted fabric was prepared and treated with chlorine water. Table 1 shows the results.

Comparative Example 4 Dyeing was carried out in the same manner as in Example 1 except that no chlorinated discoloration inhibitor was used and tannic acid / tartar treatment was used as the chlorine discoloration inhibitor and the dye fixing agent. The knitted knitted fabric was prepared and treated with chlorine water. Table 1 shows the results.

[0039]

According to the present invention, the resistance to chlorine discoloration and discoloration of a cross-knitted fabric containing at least a dyed polyurethane elastic fiber, a polyamide fiber and / or a normal pressure cationic dyeable polyester fiber is dyed. The color can be improved without impairing the color of the product, and a product having excellent chlorine resistance can be provided.

[0040]

[Table 1] In Table 1, (A) is a polyurethane elastic fiber,
(B) shows a polyamide-based fiber, (C) shows a polyester fiber dyeable with a normal pressure cationic dye, and the content indicates the weight% based on the knitted fabric.

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI // D06M 101: 32 101: 34 101: 38 (56) References JP-A-49-14798 (JP, A) JP-A-57 -176259 (JP, A) JP-A-3-287873 (JP, A) JP-A-5-33264 (JP, A) JP-A-5-25783 (JP, A) (58) Fields investigated (Int. . ^7, DB name) D06P 5/04 D06P 3/82 D06M 11/00 - 15/72

Claims (2)

(57) [Claims] 1. A polyurethane-based elastic fiber and a polyamide-based fiber and / or a normal-pressure cationic dyeable polyester-based fiber dyed with a compound dye such as an acid dye, a disperse dye, a metal-containing dye, a reactive dye, and a direct dye. A knitted fabric containing at least one or more substances having a chlorine reaction rate of 50 meq / g or more, as determined by the following method, in the knitted fabric; A dyed knitted knitted fabric characterized in that the knitted fabric is contained in an amount of up to 20%. (Method of measuring the reaction amount of chlorine) The substance is mixed with an aqueous solution of sodium hypochlorite and dilute acetic acid,
React with chlorine for a predetermined time. After a lapse of a predetermined time, an aqueous solution of potassium iodide and acetic acid are added, and chlorine not reacted with the sample is reacted with potassium iodide. The reaction product is titrated with an aqueous solution of sodium thiosulfate to determine the chlorine consumption of the sample over a predetermined period of time. From the chlorine consumption of the sample at a predetermined time, the consumption at the reaction time 0 is extrapolated to obtain the chlorine reaction amount of the substance. 2. The method according to claim 1, wherein the reaction amount of chlorine measured by the following method is 50 milliequivalent /
2. A method for producing a dyed knitted knitted fabric according to claim 1, wherein a substance having a weight of at least g is contained by subjecting said knitted fabric to a high-temperature immersion treatment. (Method of measuring the reaction amount of chlorine) The substance is mixed with an aqueous solution of sodium hypochlorite and dilute acetic acid,
React with chlorine for a predetermined time. After a predetermined time has passed, an aqueous solution of potassium iodide and acetic acid are added, and chlorine that has not reacted with the sample is reacted with potassium iodide. By titrating the reaction product with an aqueous solution of sodium thiosulfate,
The chlorine consumption of the sample at a predetermined time is determined. From the chlorine consumption of the sample at a predetermined time, the consumption at the reaction time 0 is extrapolated to obtain the chlorine reaction amount of the substance.