KR940007751B1 - Process for preparing nylon-6-fiber having good dyeing and antistatic property - Google Patents

Abstract

The nylon 6 fiber having excellent dyeing property and antistatic property is prepd. by add-mixing and reacting caprolactum, water and 0.3-10 mole% of the copolymonomer of formula R-(COOH)2 (I) and 2-15 wt.% of polyethylene glycol diamine at 230-280 deg.C for 5-12 hrs.; inputting and reacting a diamine of formula R'-(NH2)2 (II) of 1±3 times amt. w.r.t. amt. of the copolymonomer (I) at 250-280 deg.C for 20-30 hrs. and making a chip and extracting, drying; then solid-phase polymerizing that at 160-195 deg.C for 15-25 hrs. to form 2.40-2.70 viscosity (R.V) and 15-30 meq/kg of NH2 concentration of the solid-phase polymer; then melt-spinning that. In formulas, R is gp. of formula (1) or (2); R' is C2-C8 hydrocarbon gp. of formula (3), (4) or (5); M is Li, Na or K.

Description

Manufacturing method of nylon 6 fiber with excellent dyeing and antistatic properties

The present invention relates to a method for producing a nylon 6 fiber which is soluble in basic dyes and has excellent antistatic properties.

In general, nylon 6 fibers have excellent dyeability with acid dyes but poor dyeability with basic dyes, and have been constrained by the color development of pattern carpets, which require various colors. There were many problems in use because of the occurrence.

Therefore, the present invention is to avoid the conventional dyeing method of the dyeing method for producing a pattern carpet of nylon 6 fibers and to be dyed in a salt bath mixed with an acid dye and a basic dye after tufting, and at the same time to exhibit antistatic properties It is an object of the present invention to provide a method for producing functional nylon 6 fibers that can shorten the manufacturing process and reduce manufacturing costs and express various colors.

In the conventional case, there is a method of introducing sulfonic acid or a salt thereof into nylon 6 molecules in order to give affinity to basic dyes for nylon 6 fibers, or blending triazine derivatives with a modifier in the spinning step to the polymer in a spinning step. However, in order to introduce sulfonic acid groups into 6 molecules of nylon, dicarboxylic acids containing basic reactive groups should be used as copolymerization monomers. In this case, diamines are used to increase the polymerization degree of the polymer.

However, in case of nylon 66, since adipic acid and hexamethylene diamine salt are used as reactants, the degree of polymerization can be increased even by reacting sulfometal salt dicarboxylic acid and diamine salt with the reactant which is the main raw material, but in case of nylon 6, sulfogue salt dicarboxylic acid and When diamine is added at the beginning of the reaction, the diamine salt does not melt in the caprolactam, thereby preventing participation in the polymerization reaction.

That is, when the sulfometal salt dicarboxylic acid and diamine are added to the caprolactam in the initial stage of the reaction, salts are formed to prevent participation in the copolymerization.

In order to improve such a problem, U.S. Patent No. 3,451,535, in order to improve the hydrophilicity of the additive during nylon 6 polymerization, is involved in the reaction by modifying the copolymerized monomer, but in this way, the copolymerized monomer must be separately synthesized. There is a problem.

In addition, the method of spinning by simply blending to the nylon 6 polymer by using triazine derivatives as a modifier is not only decomposes the modifier due to the high temperature of spinning temperature, but also by-products such as phenol are generated, which impedes the human body and work. There is a problem that process control becomes difficult.

Fibers obtained from polyamides have excellent mechanical properties, but have various obstacles due to poor antistatic properties, and improvements have been required. Many proposals have been made so far to improve the antistatic properties of such polyamide fibers, but permanent antistatic properties cannot be expected.

Therefore, the present invention has been made in order to solve the above problems, and the purpose of the present invention is to provide a nylon 6 fiber having excellent dyeing resistance to basic dyes and at the same time improved antistatic properties.

That is, the present invention is a reaction of 5 to 12 hours at 230 to 280 ℃ by adding 0.3 to 10 mol% of copolymerized monomer of the formula (I) and 2 to 15% by weight of polyethylene glycol diamine with a small amount of water with respect to caprolactam After the reaction, the reaction mixture was added to the reactant of Structural Formula (II) by 1 ± 0.3 in multiples of the amount of Structural Formula (I), reacted for 20 to 30 hours at 250 to 280 ° C, chipped and extracted and dried at 160 to 195 ° C. Solid phase polymerization for 15 to 25 hours so that the viscosity (R. V) of the solid phase polymer is 2.40 to 2.70 and the concentration of -NH ₂ group is 15 to 30 meq / kg, and then melt spinning by a conventional method It relates to a method for producing nylon 6 fibers with excellent antistatic properties.

Below

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 copolymer monomer and the diamine, 7 wt% or more of water (H ₂ O) is added to the caprolactam, and the salt is dissolved in water to participate in the polymerization reaction. However, in the conventional nylon 6 polymerization, if the water content is more than 7% by weight, process trouble only occurs, and thus it cannot be a suitable method.

In the present invention, the copolymerized monomer of formula (I) and polyethylene glycol diamine are mixed with caprolactam and reacted by adding water under conventional nylon 6 polymerization conditions, followed by the completion of the reaction by adding diamine of formula (II). Interfering with the reaction due to formation was prevented, and a nylon 6 polymer that was saltable to the basic dye and excellent in antistatic properties was obtained. In the present invention, when the amount of polyethylene glycol diamine added to impart antistatic property is less than 2% by weight, desired antistatic properties cannot be obtained. When the content exceeds 15% by weight, the antistatic property is good but the physical properties are deteriorated. There is this.

In addition, the average molecular weight of the polyethylene glycol diamine used in the present invention is 1000 to 8000 is good, the case of 2000 to 6000 can provide excellent antistatic properties and physical properties.

And in order to prevent the oxidation of polyethylene glycol diamine in the present invention, it is preferable to add 0.5 to 1.5% by weight of the antioxidant.

In addition, in the present invention, when less than 0.3 mol% of copolymerized monomer of Structural Formula (I) is added, the affinity for basic dye is lowered. have.

On the other hand, when the amount of diamine added is less than the above-mentioned range, the viscosity of the composite does not increase sufficiently. If the above-mentioned range is exceeded, the concentration of -NH ₂ groups is increased to contaminate basic dyes by acid dyes in the final dyeing process. There is a problem that occurs.

After obtaining a nylon 6 polymer by the present invention to produce a filament yarn by a conventional method using the same, the overall physical properties of the yarn showed the level of the conventional regular filament yarn, the dyeing and antistatic properties of the basic dye is very good Could see.

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

Example 1

In a polyamide reactor, a mixture of 100 parts of carolactam, 1.2 parts of water, 0.09 parts of acetic acid, 2.5 parts of 5-sodium sulfoisophthalic acid, and 6.5 parts of polyethylene glycoldiamine having an average molecular weight of 4,000, 1.0 parts of Irganox 1010 as an antioxidant After the reaction was carried out at 260 ° C. for 6 hours, the solution of 0.82 parts of hexamethylenediamine dissolved in 0.82 parts of caprolactam was added to the reactor for 20 hours at 270 ° C., followed by chipping, followed by extraction for 25 hours in an aqueous 80 ppm Na ₂ CO ₃ solution. Drying at 110 ° C. for 7 hours and solid phase polymerization at 170 ° C. for 16 hours under vacuum (10.5torr) yielded a polymer of R. V = 2.53, terminal group (-NH ₂ ) = 20meq / kg.

This composite product was prepared by BCF yarn of 1300D / 69fil and dyed with basic dye, showing good affinity (Table-1) and excellent antistatic properties (Table-2).

TABLE 1

Example 2

To the polyamide reactor, 1.0 part of Irganox was added as an antioxidant to a mixture of 100 parts of carolactam, 1.2 parts of water, 0.09 parts of acetic acid, 2.5 parts of 5-sodium sulfoisophthalic acid, and 4.5 parts of polyethylene glycol diamine having an average molecular weight of 2,000 parts. After reacting at 260 ° C. for 6 hours, a solution obtained by dissolving 0.76 parts of 1,4-phenylenediamine in 0.76 parts of caprolactam was added to the reactor and reacted at 270 ° C. for 22 hours, followed by extraction and solid state polymerization in the same manner as in Example 1. After obtaining a polymer of V = 2.50 and terminal group (-NH ₂ ) = 23.0 meq / kg, BCF yarn of 1300D / 69fil was prepared and showed good affinity to basic dyes and excellent antistatic properties (Table-2). ).

Comparative Example 1

A mixture of 100 parts of carolactam, 1.2 parts of water, 0.09 parts of acetic acid and 2.5 parts of 5-sodium sulfoisophthalic acid was reacted in a polyamide reactor at 260 ° C. for 6 hours, followed by 0.82 parts of hexamethylenediamine and 0.82 parts of caprolactam. The dissolved solution was added to the reactor and reacted at 270 ° C. for 20 hours, followed by extraction, drying and solid state polymerization in the same manner as in Example 1 to prepare 1300D / 69fil BCF, which showed good affinity for basic dyes. The malleability was poor (Table-2).

Comparative Example 2

1.0 parts of antioxidant Irganox 1010 was added to a mixture of 100 parts of carolactam, 1.0 part of water, 0.09 part of acetic acid, and 6.5 parts of polyethylenegulicoldiamine having an average molecular weight of 4,000 to a polyamide reactor. Extraction and drying yielded a polymer having a level of R. V = 2.65 and terminal group (-NH ₂ ) = 42 meq / kg, followed by spinning to prepare B300 yarn of 1300D / 69fil. The antistatic property was relatively good (Table 2). The affinity for basic dyes was poor.

TABLE 2

Claims (1)

To the reactant reacted by adding a small amount of water and 0.3-10 mol% of the copolymerized monomer of the following structural formula (I) to the caprolactam, the diamine of the following structural formula (II) was added in a 1 ± 0.3 multiple of the amount of the structural formula (I). In the preparation of nylon 6 fibers by melt spinning the reacted and chipped solid phase polymerized product, when reacting the reactants, 2 to 15% by weight of polyethylene glycol diamine other than the caprolactam, water, and the copolymerized monomer of formula (I) Process for producing nylon 6 fibers excellent in dyeing and antistatic properties, characterized in that the addition. Below

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

Selection of at least one or more from the group.