KR910004470B1 - Manufacturing process of nylon - 6 fiber - Google Patents

Abstract

copolymerized monomer as shown following, R-(COOH)2 [where R is (a) or (b); M is Li, Na, K and small amount of water is added to caprolactam 0.3-10mol%, then make the mixture react at 230-280 deg.C for 5-12 hours. Diamine is added to the above reacted mixture with the amount of 1±0.3 times as the copolymerized moromer, then letting it react at 250-280 deg.C for 20-30 hours, he it chipped, extracted and dried. The dried material is solid polymerized at 160-195 deg.C for 15-25 hours, so that the viscosity (R.V) becomes 2.40-2.70 and concentration of -NH2 15-30 meq/kg. Then it is melt spun in a conventional way to make basic dye dyeable nylon 6 fiber.

Description

Method for preparing nylon 6 fibers that are soluble in basic dyes

The present invention relates to a process for preparing nylon 6 fibers that are soluble in basic dyes.

In general, nylon 6 fiber has excellent dyeability by acid dyes, but dyeability by basic dyes is poor, and pattern carpets, which require various colors, have been restricted in color expression.

Therefore, the present invention is to avoid the conventional dyeing method in the production of pattern carpet with nylon 6 fibers and after the tufting (dying) in the dyeing mixture of acid dyes and basic dyes in the dyeing process of the manufacturing process It is an object of the present invention to provide functional nylon 6 fibers capable of expressing shortening and more various colors. As a method for imparting affinity to basic dyes of conventional nylon 6 fibers, a method of introducing sulfonic acid or salts thereof into 6 nylon molecules (US Pat. Nos. 3,184, 436, 3,389, 549, 3,898, 200, Japanese Patent Publication) 44-1236), or a method of blending a modifier to a polymer in a spinning step (Japanese Patent Publication No. 47-22465, Japanese Patent Application Publication No. 48-88195), but there is a basic reactive group ( Dicarboxylic acid containing -SO₃M ⁺ ) should be used as copolymerization monomer, and diamines are used to increase the degree of polymerization of the polymer. However, in case of nylon 66, a salt of adipic acid and hexamethylene diamine is used as a reactant. Thus, the degree of polymerization can be enhanced with a sulfometal salt dicarboxylic acid and a diamine salt together with a reactant which is a main raw material. When added simultaneously with the initial reaction, the diamine salt does not melt in the caprolactam and thus does not participate in the polymerization reaction. In other words, when the sulfometal salt dicarboxylic acid and diamine are added to the caprolactam in the initial stage of the reaction, salts are formed and thus they do not participate in the copolymerization.

In order to solve the above problems, US Pat. No. 3,451,535 discloses copolymerization monomers to improve the hydrophilicity of additives when polymerizing nylon 6.

It is transformed into a form to participate in the reaction, but by this method there is a problem that must be synthesized separately copolymerized monomer.

Meanwhile, or

Using a triazine derivative as a modifier and spinning the nylon 6 polymer simply by blending it, the modifier is decomposed due to the high temperature spinning temperature, and byproducts such as phenol are generated to impair the human body and work. There is a problem that becomes difficult to manage.

Therefore, the present inventors have completed the present invention as a result of intensive studies to develop nylon 6 fibers that are soluble in basic dyes that can solve all the problems of the prior art.

That is, the present invention is to prepare a modified nylon 6 fiber having a dye resistance to the basic dye effectively using a sulfometal salt carboxylic acid and diamine without synthesizing the monomer separately as follows.

That is, in the present invention, 0.3 to 10 mol% of the copolymerized monomer of the following structural formula (I) together with a small amount of water is added to caprolactam and reacted at 230 to 280 ° C. for 5 to 12 hours. Diamine was added in an amount of 1 ± 0.3 times the amount of Structural Formula (I), followed by reaction for 20-30 hours at 250 to 280 ° C, followed by chipping, followed by extraction and drying for solid phase polymerization at 160 to 195 ° C for 15-25 hours. (RV) is 2.40 to 2.70 and the concentration of the -NH 2 group is 15 to 30 meq / kg and then melt spinning in a conventional manner to a method for producing a nylon 6 fiber soluble in basic dyes.

Below

R- (COOH) ₂ ... … … … … … … … … … … … … … … … (Ⅰ)

With the proviso that R is

M is Li, Na, K

R '-(NH ₂ ) ₂ . … … … … … … … … … … … … … … … (Ⅱ)

Provided that R ′ is a hydrocarbon of 2 to 8 carbon atoms,

At least one selected from the group.

In the present invention, in order to prevent the formation of a salt of the copolymerized monomer of formula (I) and the diamine of formula (II), water (H 2 O) or more is added to caprolactam. It was possible to obtain a copolymer by participating, but in the case of conventional nylon 6 polymerization, when the water content is more than 7wt%, process trouble occurs, and thus it cannot be a suitable method.

In the present invention, the copolymerization monomer of Structural Formula (I) is mixed with caprolactam, and the reaction is performed by adding water under conventional nylon 6 polymerization conditions, and then diamine is added to complete the reaction. It was possible to obtain a nylon 6 polymer which is soluble in basic dyes. In addition, in the present invention, when 0.3 mol% or less of the copolymerized monomer of Structural Formula (I) is added, the affinity for basic dyes is lowered. There is.

On the other hand, if the amount of diamine is less than the above-mentioned range, the viscosity of the polymer does not increase sufficiently. If the above-mentioned range is exceeded, the concentration of the -NH 2 group is increased, resulting in contamination of the basic dye by the acid dye in the final dyeing process. There is a problem.

After obtaining a nylon 6 polymer by the present invention to prepare a filament yarn using a conventional method, the overall physical properties of the yarn showed the level of the existing regular filament yarn, it can be seen that the dyeing to the basic dye is very good. . That is, as a result of dyeing in the same bath as the conventional regular nylon 6 yarn, the color effect (Color Effect) of a different color was expressed.

Looking at the present invention through the following examples in more detail.

Example 1

A mixture of 100 parts of caprolactam, 1.2 parts of water, 0.09 parts of acetic acid and 2.0 parts of 5-sodium sulfoisophthalic acid was reacted at 250 ° C for 6 hours, and then 0.8 parts of hexamethylenediamine was dissolved in 0.8 parts of caprolactam. It was added to the reaction product, reacted for 20 hours at 265 ° C, chipped, extracted for 25 hours in an aqueous 80 ppm Na₂CO ₃ solution, dried for 7 hours at 110 ° C, and then subjected to solid phase polymerization at 170 ° C × 16 hours under vacuum (0.5 Torr) to RV 2.52, A polymer of -NH 2 concentration 22 meq / kg was obtained.

The polymer was melt spun by a conventional method to prepare 1300 _D / 69 fil BCF yarn, and then dyed. (See Table 1).

Example 2

A mixture of 100 parts of caprolactam, 1.5 parts of water, 0.09 parts of acetic acid and 4.0 parts of 2-sodium sulfoterephthalic acid was reacted at 245 ° C. for 8 hours, and then 1.2 parts of tetramethylenediamine were dissolved in 1.2 parts of caprolactam. It was added to the reaction product, reacted for 20 hours at 265 ° C, chipped, and then subjected to solid phase polymerization in the same manner as in Example 1 to obtain a polymer having a RV 2.48, -NH 2 concentration of 24 meq / kg, followed by melt spinning and dyeing in the same manner as in Example 1. (See Table 1)

TABLE 1

Claims (1)

0.3 to 10 mol% of the copolymerized monomer of Structural Formula (I) was added to the caprolactam with a small amount of water and reacted at 230 to 280 ° C for 5 to 12 hours, and then the diamine of Structural Formula (II) was added to the reactant. 1 ± 0.3 times the amount of I) added, reacted for 20-30 hours at 250-280 ° C, extracted and dried by chipping, and then solid phase polymerization at 160-195 ° C for 15-25 hours to obtain a viscosity (RV) of 2.40-2.70. And a concentration of -NH 2 groups of 15 to 30 meq / kg and then melt spinning in a conventional manner, a method for producing nylon 6 fibers soluble in basic dyes. Below R-(COOH) ₂ ································ (I) Where R is

M is Li, Na, K R '-(NH ₂ ) ₂ (II) Provided that R 'is a hydrocarbon having 2 to 8 carbon atoms,

At least one selected from the group.