JPH0748785A - Method for dyeing and processing polyamide fiber - Google Patents

Abstract

(57) [Summary] [Objective] To provide a processing method for imparting high hygroscopicity and excellent wet fastness to an acid dye dyeing product of a polyamide fiber modified by graft polymerization of a vinyl monomer having an acid group. . [Structure] A polyamide-based fiber is graft-polymerized with a vinyl-based monomer having an acidic group, then dyed with an acid dye, and then fixed with a polyamine dye-fixing agent under alkaline conditions.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dyeing method for imparting high hygroscopicity and excellent wet fastness to a polyamide fiber dyeing material modified by graft polymerization.

[0002]

2. Description of the Related Art It is known that high hygroscopicity, excellent antistatic property, and antifouling property can be obtained by graft-polymerizing a vinyl-based monomer having an acidic group onto a polyamide-based fiber and substituting hydrogen for carboxylic acid with sodium. well known.

However, this graft-polymerized polyamide fiber is dyed with an acid dye in a medium and dark color, fixed with a dye fixing agent for an ordinary acid dye, and then subjected to sodium displacement treatment to be dyed. Since the wet fastness of the fiber is remarkably reduced, a dyed product having high hygroscopicity and excellent wet fastness at the same time has not yet been obtained.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is an acid dye dyeing product of a polyamide fiber modified by graft polymerization of a vinyl monomer having an acid group. It is an object of the present invention to obtain a dyeing method which improves wet fastness without lowering hygroscopicity.

[0005]

SUMMARY OF THE INVENTION The present invention achieves the above object and has the following configuration. That is, the present invention 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 a fixing treatment is performed with a polyamine-based dye-fixing agent under alkaline conditions. The subject is a method of dyeing and processing a polyamide fiber. Hereinafter, the present invention will be described in detail.

In the present invention, a polyamide fiber is used as a processing object. Polyamide fiber here means nylon 4, nylon 6, nylon 12, nylon 46,
Although polyamide fibers represented by nylon 66 are mainly mentioned, the polyamide fibers are not necessarily limited to these, and other polyamide fibers may be used. 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. The above vinyl-based monomers 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 can be 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 an 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, the dyed polyamide fiber is fixed with a polyamine dye fixing agent under alkaline conditions. Normally, tannic acid-based adhesives and aromatic sulfonic acid condensates are used as fixing agents for acidic dyes, but these fixing agents have no fixing effect under alkaline conditions, and perform fixing treatment under acidic conditions. And the hygroscopicity of the modified polyamide fiber decreases, and if alkali treatment is applied to restore this hygroscopicity, the coating film due to the adhesive is destroyed by the alkali, resulting in a significant decrease in wet fastness. . When a polyamine dye fixing agent is used as in the method of the present invention, the polyamine dye fixing agent has a dye fixing action even under alkaline conditions. Therefore, an alkali for imparting hygroscopicity at the same time as the dye fixing treatment is used. Since the treatment can be done in one bath, it is very advantageous from the viewpoint of processing cost.

Examples of the polyamine-based dye fixing agent used herein include tertiary amine-based resins, cationic resins thereof, and quaternary amine-based resins. Generally, when a direct dye or a reactive dye is used. Any dye fixing agent applied to can be used.

The conditions for the fixing treatment are as follows: the fixing agent is 2 to 7% owf under alkaline conditions and the temperature is 50 to 80 ° C.
By performing the treatment for about 0 minutes, an excellent fixing effect can be obtained. The alkaline condition for the fixing treatment is usually in the range of pH 11 to 12, but it suffices if the graft-treated product contains an alkali metal capable of imparting hygroscopicity, and depending on the type of alkali metal, Usually 1-3
It can be carried out at a concentration of 0 g / l.

Examples of the alkaline agent to be used include carbonates such as sodium, potassium and lithium, hydrogencarbonates, acetates, hydroxides, etc., but are not limited to these, but generally sodium carbonate and sodium acetate Can be preferably used.

[0015]

[Working] After dyeing fibers made by graft-polymerizing vinyl monomers with acidic groups onto polyamide fibers with an acid dye,
When the fixing treatment is carried out by the conventional method with a conventional fixing agent for acid dyes such as tannin-tartarite and an aromatic sulfonic acid condensate,
A film is formed on the surface of the fiber, and the wet fastness of the dyed fiber is improved, but the hygroscopicity is not improved. Therefore, in order to improve the hygroscopicity, if an alkaline group is used to replace the acidic groups in the graft fiber with an alkali agent, the hygroscopicity is improved, but the coating of the adhesive is destroyed by the alkali agent used, and the dyed fiber The wet fastness of is markedly reduced.

As in the present invention, when a fiber obtained by graft-polymerizing a vinyl-based monomer having an acidic group on a polyamide-based fiber is dyed with an acid dye and then fixed with a polyamine-based dye-fixing agent under alkaline conditions, a polyamine is obtained. Dye fixing agents have relatively high alkali resistance and can react with free unreacted dyes to prevent dye elution, resulting in dyeing fibers with good wet fastness, and at the time of fixing treatment. Since the alkaline group simultaneously replaces the acidic groups in the graft fiber with the alkaline agent, the hygroscopicity of the fiber is significantly improved.

[0017]

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 (%) = (humidified weight of sample-absolute dry weight of sample) /
Absolute dry weight of sample x 100 (2) Dyeing fastness Washing fastness: JIS L-0844 (C
Evaluation of discoloration and fading and cotton cloth contamination was performed by the method). Sweat alkali fastness: JIS L-0848 (A
Method) was evaluated with an alkaline artificial sweat. Rubbing fastness: Evaluation was performed with a friction tester type II (Gakushin type) of JIS L-0849.

Example 1 Nylon 6 woven fabric (Basis weight: 63 g / m ² ) was irradiated with an electron beam of 200 KV and 10 megarad, and then immersed in a 5% aqueous solution of acrylic acid at a liquid temperature of 50 ° C. for 5 minutes to obtain a graft ratio of about 12 % Grafted fabric was obtained. This was dyed with a dyeing bath shown in the following formulation 1 at a bath ratio of 1:50 at 95 ° C. for 30 minutes,
The fixing bath shown in the following prescription 2 at a bath ratio of 1:50, 80 ° C, 30
The dyeing cloth of the present invention was obtained by carrying out fixing treatment for a minute.

Prescription 1 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 Adjust to pH 4.5 Prescription 2 Kayafix M 3% owf (Nippon Kayaku Co., Ltd., polyamine dye fixing agent) Sodium carbonate 20 g / liter (pH 11.
3)

For comparison with the present invention, a dyeing cloth for comparison (comparative example) was prepared by the same method and conditions as in this example except that the fixing bath shown in the following prescription 3 was used in place of prescription 2 in this example. 1) was obtained. Prescription 3 Kayafix M 3% owf Acetic acid pH adjusted to 4.5

The performances of the present invention and the comparative work cloth were measured and evaluated, and the results are shown in Table 1.

[Table 1]

As is clear from Table 1, the dyed cloth obtained by the method of the present invention had high hygroscopicity and exhibited excellent dyeing fastness. On the other hand, in Comparative Example 1 in which the fixing treatment was performed in an acidic bath instead of in an alkaline bath, excellent dyeing fastness was obtained, but the basic property of hygroscopicity was not imparted at all.

Example 2 Nylon 6 woven fabric which had been subjected to the graft treatment in the above Example 1 was prepared, and a dyeing bath shown in the following prescription 4 was added thereto to obtain a bath ratio of 1:50.
After dyeing at 100 ° C for 30 minutes at
Fixing treatment was carried out at 70 ° C. for 30 minutes in the fixing bath shown in 1) at a bath ratio of 1:50 to obtain a dyed fabric of the present invention. Prescription 4 Mitsui Nylon Black 10% owf (Mitsui Toatsu Chemical Co., Ltd., acid dye) Leveler NKD 2% owf Formic acid pH adjusted to 4.2 Prescription 5 Kayafix UR 3% owf (Nippon Kayaku Co., polyamine cation Dye fixing agent) Sodium carbonate 20 g / liter (pH 11.
3)

For comparison with the present invention, the fixing bath shown in the following Formulation 6 was used instead of Formulation 5 in this Example, and the fixing treatment was carried out at 80 ° C. for 20 minutes at a bath ratio of 1:50. A dyed fabric for comparison (Comparative Example 2) was obtained by the same method as in this example. Prescription 6 Sun Life E-27 3% owf (Nikaka Chemical Co., Ltd., dye fixing agent for aromatic sulfonic acid condensate) Sodium carbonate 30 g / liter (p
H11.1)

For comparison with the present invention, a fixing bath shown in the following formulation 7 was used in place of the formulation 5 in this example.
A dyeing cloth was obtained in the same manner as in this example except that the fixing treatment was carried out at 80 ° C. for 20 minutes at a bath ratio of 1:50, and then 80% in an aqueous solution of 30 g / liter of sodium carbonate.
Dyeing cloth for comparison (Comparative Example 3) was obtained by performing sodium substitution treatment at 30 ° C. for 30 minutes. Prescription 7 Sunlife E-27 3% owf Formic acid pH adjusted to 4.5

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

[Table 2]

As is apparent from Table 2, the dyed cloth obtained by the method of the present invention had high hygroscopicity and exhibited excellent dyeing fastness. On the other hand, Comparative Example 2 in which fixing treatment was performed under alkaline conditions using a conventional fixing agent for acidic dyes and Comparative Example 3 in which sodium substitution treatment was performed under alkaline conditions after fixing treatment under acidic conditions All of them showed high hygroscopicity, but their dyeing fastness was extremely low.

[0028]

EFFECTS OF THE INVENTION According to the method of the present invention, it is possible to impart excellent wet fastness and high hygroscopicity to an acid dye dyeing product of a polyamide fiber graft-polymerized with a vinyl monomer having an acid group.

Claims (1)

[Claims] 1. A method of graft-polymerizing a vinyl-based monomer having an acidic group onto a polyamide-based fiber, followed by dyeing with an acid dye, and then fixing treatment with a polyamine-based dye-fixing agent under alkaline conditions. A method for dyeing and processing a polyamide fiber.