JPH06280173A - Dyeing of polyamide fiber - Google Patents

Abstract

PURPOSE:To provide a dyeing process for a polyamide fiber modified by graft- polymerization treatment without deteriorating the excellent moisture- absorptivity of the fiber. CONSTITUTION:A polyamide fiber is graft-polymerized with a vinyl monomer having acidic group. The modified polyamide fiber is dyed with an acid dye and then subjected to the substitution treatment with an alkali metal.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for dyeing a polyamide fiber by modifying the polyamide fiber by graft polymerization to dye the same.

[0002]

2. Description of the Related Art Synthetic fibers have excellent physical properties and processability, but on the other hand, because of their hydrophobicity, they also have problems such as discomfort caused by stuffiness when worn and static electricity. Therefore, many methods have been proposed to solve the above problems by graft-polymerizing various vinyl monomers onto synthetic fibers.

Among them, a vinyl monomer having an acidic group is graft-polymerized on a synthetic fiber, and then hydrogen of the acidic group is replaced with an alkali metal such as sodium or potassium. A processing method for imparting hygroscopicity has attracted particular attention. However, when the polyamide fiber modified by this method is dyed with an acid dye, it has a drawback that the improved hygroscopicity is significantly reduced. Further, when the above modified polyamide fiber is dyed in a light color, it can be dyed without any problem, but when it is dyed in a medium color or a dark color, there is a problem in dyeing property and it is difficult to dye in a medium dark color. there were.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and reduces the hygroscopicity of a polyamide fiber modified by graft-polymerizing a vinyl monomer having an acidic group. A first object is to obtain a processing method for dyeing without modification, and a second object is to provide a processing method for dyeing without lowering the dyeing property of the modified polyamide fiber. It is what

[0005]

The present invention achieves the above object and has the following structure. That is, the first invention of the present application is characterized in that a polyamide-based fiber is graft-polymerized with a vinyl-based monomer having an acidic group, then dyed with an acid dye, and then subjected to a substitution treatment with an alkali metal. The second invention of the present application is to graft-polymerize a vinyl-based monomer having an acidic group on a polyamide-based fiber, then dye it with an acid dye, perform a fixing treatment, and then carry out an alkali treatment. The present invention is directed to a method for dyeing and processing a polyamide fiber, which is characterized by performing a substitution treatment with a metal.

The present invention will be described in detail below.

In the present invention, the polyamide fiber is used as a dyeing object. The polyamide-based fiber here mainly refers to a polyamide fiber represented by nylon 4, nylon 6, nylon 12, nylon 46, and nylon 66, but is not necessarily limited to these and may be any other polyamide fiber. May be. Generally, nylon 6 and nylon 66 can be preferably used.

The fiber used may be in the form of a thread, a non-woven fabric, a woven fabric, a knitted fabric, or the like, and fibers other than polyamide fibers such as polyester fiber, acrylic fiber, rayon, cotton and wool. It does not matter even if the fibers are mixed or knitted.

In the present invention, first, the above-mentioned polyamide fiber is graft-polymerized with a vinyl monomer having an acidic group, and then dyed with an acid dye.

Examples of the vinyl-based monomer having an acidic group used here include, but are not limited to, compounds such as acrylic acid, methacrylic acid, itaconic acid, allyl sulfonic acid, methacryl sulfonic acid, and styrene sulfonic acid. is not. The vinyl monomer is
They may be used alone or in combination of two or more.
Generally, acrylic acid or methacrylic acid can be preferably used.

As a method for graft-polymerizing a vinyl-based monomer having an acidic group onto a polyamide-based fiber, either a thermal grafting method using a radical polymerization initiator or a radiation graft polymerization method not using a radical polymerization initiator is adopted. Good. When the thermal graft polymerization method is used, it is necessary to allow the solution to stay for a long time in a solution of a vinyl-based monomer having an acidic group. On the other hand, when the radiation graft polymerization method is used, particularly when the pre-irradiation method is used, radicals can be easily generated and the polymerization can be performed in a short time, which is industrially very advantageous.

After the above graft polymerization, dyeing with an acid dye is carried out in the method of the present invention. Here, as the acid dye, an azo dye, an anthraquinone dye, a carbonium dye, a metal complex salt dye or the like can be used. When dyeing, perform the dyeing according to the usual acid dyeing method.

In the present invention, after the above-mentioned dyeing, a substitution treatment with an alkali metal is performed. Examples of the alkali metal used here include lithium, sodium and potassium, but it is generally preferable to use sodium or potassium. As a method of replacement processing, for example,
The dyed polyamide fiber is put into a 0.1 to 10% by weight aqueous solution of sodium carbonate or potassium carbonate, and the temperature is 50 ° C or higher, preferably 60 to 100 ° C, for 10 minutes or longer,
Stirring treatment is preferably performed for 15 to 60 minutes. Thus,
A polyamide fiber dyed with an acid dye and having excellent hygroscopicity can be obtained.

As described above, in order to maintain high hygroscopicity even after dyeing, it is necessary to graft-polymerize a vinyl monomer having an acidic group, dye it with an acidic dye, and then perform a substitution treatment with an alkali metal. Dyeing with acidic dyes is usually done on the acidic side of pH 4 to pH 6. Therefore, if dyeing is performed after the substitution treatment with alkali metal, the substituted alkali metal returns to hydrogen again and the graft-polymerized fiber absorbs moisture. It is not preferable because it may cause deterioration of sex.

The first invention of the present application has the above configuration.

A second object of the present invention is to prevent the above-mentioned modified polyamide fiber from lowering its hygroscopicity and to dye it without lowering the dyeing property when it is dyed in a medium dark color. When dyeing in medium to dark colors, it is necessary to graft-polymerize a vinyl-based monomer having an acidic group onto a polyamide fiber, dye it with an acid dye, and then carry out a fixing treatment, and then carry out a substitution treatment with an alkali metal. is there. In other words, in the method of the first invention, after the dyeing with the acid dye, the fixing process of the acid dye is performed before the substitution process with the alkali metal.

Since the fixing treatment carried out here is carried out in an acidic bath, if the fixing treatment is carried out after the substitution treatment with an alkali metal, not only the hygroscopicity is deteriorated but also the dye is removed and the color tone is changed. It is not desirable because it will end up. In addition, if the dyeing and fixing treatment is performed after the substitution treatment with the alkali metal, the treatment in the acidic bath is performed twice, and the hygroscopicity decreases greatly and the pH during dyeing is increased.
However, care should be taken because the dyeing property will be extremely deteriorated by the shift from the acidic side to the alkaline side.

As the fixing treatment, tannic acid 2 to 4% ow
After treating f at 80-95 ° C for 20-30 minutes,
Treat with ~ 2% owf at 80-95 ° C for 20-30 minutes 2
Treatment method by bath process or 1-bath fixing agent such as Sun Life E-27 (Nikaka Chemical Co., Ltd., aromatic sulfonic acid condensate), Nylon Fix TH (Nippon Senka Kogyo Co., Ltd., polyphenol derivative) 80% at 2-8% owf
A one-bath treatment method in which treatment is performed at 90 ° C. for 20 to 30 minutes can be mentioned.

The second invention of the present application has the above configuration.

[0020]

[Operation] As in the method of the present invention, a polyamide-based fiber is graft-polymerized with a vinyl-based monomer having an acidic group, and then dyed with an acid dye, followed by substitution treatment with an alkali metal. Since the acidic groups are not affected by the acidic bath during dyeing, it is possible to obtain a polyamide fiber dyeing product having high hygroscopicity. Further, in the case of medium-deep color dyeing, when the graft fiber is dyed as in the present invention and then the fixing treatment and the alkali metal substitution treatment are performed in this order, high hygroscopicity is obtained as described above, and the alkali metal substitution Due to the dyeing and fixing treatment before the treatment, it is possible to obtain excellent dyeability without being affected by alkali during dyeing, and most of the dye drops off during the alkali metal substitution treatment. Since it disappears, you can obtain a product that does not affect the color tone.

[0021]

EXAMPLES Next, the present invention will be described in more detail by way of examples. The measurement and evaluation of the performance of the fibers in the examples were carried out by the following methods. (1) Hygroscopicity After the sample was completely dried at 105 ° C for 1 hour, 20 ° C x 65% R
The humidity was adjusted for 24 hours under the condition of H, and the moisture absorption rate was calculated by the following formula. Moisture absorption rate (%) = (humidity control sample weight-sample absolute dry weight) /
Absolute dry weight of the sample × 100 (2) Dyeing property L ^* of the sample was measured by a Macbeth measuring instrument MS-2020 ^.
The value was measured and evaluated. The smaller the L ^* value, the better the dyeing property, and the deeper the dyeing.

Example 1 Nylon 6 100% taffeta fabric (vertical 70d / 24f,
110 lines / inch, weft 70d / 24f, 80 lines / inch) are prepared, irradiated with an electron beam of 200 KV, 10 megarads, and immersed in a 10% aqueous solution of acrylic acid at 60 ° C. for 15 seconds, Graft polymerization treatment was performed. next,
In the dyeing bath shown in the following prescription 1, at a bath ratio of 1:50, 90 ° C,
After dyeing for 30 minutes, it was immersed in a 2% by weight aqueous solution of sodium carbonate at a liquid temperature of 80 ° C. for 20 minutes and subjected to a displacement treatment with sodium to obtain a dyed cloth according to the method of the present invention. Prescription 1 Kayanol Red NBR 0.2% owf (Nippon Kayaku Co., Ltd. acid dye) Rebelan NKD 1% owf (Maruhishi Yuka Kogyo Co., Ltd. leveling agent) Acetic acid 0.2 cc / liter

For comparison with the method of the present invention, a dyeing cloth for comparison (Comparative Example 1) was prepared in the same manner as in this Example except that the order of the dyeing step and the sodium substitution treatment step was changed. ) Got.

Further, as Reference Example 1, a processed cloth having no influence during dyeing was obtained by the same method as that of this example except that the dyeing step was omitted in this example.

The performances of the work cloths of the present invention, Comparative Example 1 and Reference Example 1 were measured and evaluated, and the results are shown in Table 1.

[Table 1]

As is clear from Table 1, the dyed cloth subjected to the dyeing process by the method of the present invention does not lower the moisture absorption rate like the dyed cloth of Comparative Example 1 by the conventional method, and the dyeing step is omitted. The moisture absorption rate which was almost the same as that of the processed cloth of Reference Example 1, which had no influence over time, was maintained.

Example 2 Nylon woven fabric which had been subjected to the same treatment up to the graft polymerization treatment in the above-mentioned Example 1 was prepared, and this was dyed in the dyeing bath shown in the following formulation 2 at a bath ratio of 1:50 at 90 ° C. for 30 minutes. After dyeing, as a fixing treatment, Sunlife E-27 (manufactured by Nika Kagaku Co., Ltd., 1-bath fixing agent) was applied at 3% owf at 80 ° C. for 30 days.
The dyed fabric of the present invention was obtained by treating for a minute and finally performing the displacement treatment with sodium as in Example 1. Prescription 2 Suminol Milling Red RS125 1% owf (Sumitomo Chemical Co., Ltd., acid dye) Levelan NKD 2% owf (Maruhishi Yuka Kogyo Co., Ltd., leveling agent) Acetic acid 0.2 cc / liter

For comparison with the present invention, a dyeing cloth for comparison (Comparative Example 2) was prepared in exactly the same manner as in this Example except that the order of the dyeing step and the sodium substitution treatment step was changed in this Example. Obtained. Further, for comparison with the present invention, a dyed fabric for comparison (Comparative Example 3) was obtained in exactly the same manner as in the present Example, except that the order of the fixing treatment and the sodium substitution treatment was changed in this Example. It was

Separately, as Reference Example 2, a nylon 6 taffeta woven fabric not subjected to a graft polymerization treatment was prepared and subjected to the same dyeing and fixing treatment as in the present embodiment.
Further, as Reference Example 3, a processed cloth having no influence during dyeing was obtained by the same method as in this Example except that the dyeing step was omitted in this Example.

The performances of the present invention and the dyed fabrics and comparative fabrics for comparison and reference were measured and evaluated, and the results are shown in Table 2 together.

[Table 2]

As is clear from Table 2, the dyed cloth dyed by the method of the present invention has an excellent hygroscopic property as in the case of the processed cloth which is subjected only to the graft polymerization treatment and the substitution treatment as shown in Reference Example 3, and has a medium moisture content. Even in the dyeing property when dyed in a dark color,
The same excellent dyeing property as that obtained by dyeing the woven fabric not subjected to the graft polymerization treatment shown in Reference Example 2 was obtained. on the other hand,
In each of the methods of Comparative Examples 2 and 3, the hygroscopicity was decreased, and when dyed in a medium dark color, the dyeing property was deteriorated due to poor dyeing or the dye dropped off, and the color tone was changed. .

[0032]

According to the method of the present invention, the polyamide fiber modified by graft polymerization can be dyed without impairing its hygroscopicity. Further, even in the case of dyeing with a medium dark color, dyeing can be performed without the dyeing property being deteriorated due to the falling of the dye, and the color tone is not changed.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display area // D06M 101: 34

Claims (2)

[Claims] 1. A method for dyeing a polyamide fiber, which comprises graft-polymerizing a vinyl monomer having an acidic group onto the polyamide fiber, then dyeing with an acid dye, and then subjecting the fiber to substitution treatment with an alkali metal. . 2. A polyamide system characterized by graft-polymerizing a vinyl-based monomer having an acidic group onto a polyamide fiber, then dyeing with an acid dye, fixing treatment, and then performing substitution treatment with an alkali metal. Textile dyeing method.