KR930007821B1 - Method of producing polyamide fiber dyeable to basic dyes - Google Patents

Abstract

adding the polymer material which is selected from the polymers whose molecular weights are above 50,000 and are shown in formula (I) (where R is chosen among Na, K, Ca, Li, Mg, Zn, Al and n is 250-700) with the amount of 0.5-10 wt.% per carprolactam, and the monomer shown in formula (II) (where R' is a hydrocarbon having 2-8 carbon number) with the amount of 0.1-5 wt.% per carprolactam, into the carprolactam so that the weight ratio of the monomer of the formula (II) and the polymer of the formula (I) is 1:1 - 1:10; and melt-spinning the mixture.

Description

Method for producing polyamide fibers that are saltable to basic dyes

The present invention relates to a method for producing polyamide fibers that are saltable to basic dyes.

More specifically, the present invention relates to a method for producing a polyamide fiber that is basic dye salt-free, which is free from viscosity, weakening by light, and contamination by acid dyes.

In general, polyamide fibers have excellent dyeing properties for acid dyes, but because they have poor dyeing properties for basic dyes, there are many limitations in expressing colors that can meet consumer's preference for products requiring various colors such as pattern carpets. Have been received. When the present invention is applied to the pattern carpet, etc., the conventional method can be removed from the conventional dyeing method (YARN DYEING) and after the tufting (TUFTING) can be dyed in a dye bath mixed with an acid dye and a basic dye, as a result of the pattern carpet It is an object of the present invention to provide a method for producing a functional polyamide fiber which can shorten the manufacturing process and express various colors.

Conventional methods for imparting affinity for basic dyes to polyamide fibers include sulfonic acids, or salts thereof introduced into polyamide molecules (US Pat. No. 3,184,436, 3,389,549, 3,898,200, Japanese Patent Publication No. 44-1236), Alternatively, a method of blending a modifier to a polymer in a spinning step (Japanese Patent Publication No. 47-22465, Japanese Patent Publication No. 48-88195) has been introduced.

Among these, triazine derivatives are used as modifiers to simply blend and spin polyamide polymers, which not only decompose the modifiers due to the high spinning temperature, but also cause byproducts such as phenol, which cause obstacles to the human body and the process. There is a problem that becomes difficult to manage.

The basic reactor (-SO ₃ ^- M ⁺⁾ In order to introduce a sulfonic acid group in the polyamide molecules dicarboxylic method of polymerizing by a dicarboxylic acid as a copolymerizable monomer containing a and, with hexamethylenediamine to increase the molecular weight in the case of this method, The method of adding the same diamines together had the following problems. In other words, when a dicarboxyl monomer containing a basic reactive group is used, the degree of polymerization decreases due to the amine end group blockage, and when the diamines are added together, there is a concern that contamination with acid dyes may occur.

In addition, when the dicarboxylic monomer is used, due to the low melting point and the characteristics of the molecular structure (OPEN MOLECULAT STRUCTURE), the dye is easily destroyed by daylight after dyeing the basic dye, causing a decrease in the light fastness.

In order to solve this problem, US Pat. No. 4,083,893 discloses a polyamide fiber which prevents a decrease in viscosity and a decrease in light fastness after excitation dyeing by adding a polymer material having a molecular weight of about 70,000 containing a basic reactive group instead of a dicarboxyl monomer to the polymerization. The preparation method of the present is presented.

However, this method also has a problem in that staining by acid dyes occurs due to the presence of terminal amino groups in the molecular backbone.

Accordingly, the present inventors have completed the present invention as a result of research to develop a basic dye saltable polyamide fiber that can simultaneously solve all the problems of the prior art. According to the present invention, the use of a characteristic dicarboxyl monomer containing a basic reactive group together with a high molecular material, particularly a basic reactive group, can be suitably used to prevent a decrease in polymerization degree, low light fastness, contamination by acid dyes, and excellent dyeing resistance to basic dyes. It will be described in detail as a method for producing a dye chlorinated polyamide fiber.

In carrying out the polyamide polymerization, the polymer material of the structural formula [I] is 0.5 to 10% by weight with respect to the caprolactam, and the material of the structural formula [II] is 0.1 to the caprolactam with a small amount of water and other additives. The present invention relates to a method for producing a basic dye saltable polyamide fiber, which is polymerized by adding 5% by weight.

Provided that R is selected from Na, K, Ca, Li, Mg, Zn, Al, and n is from 250 to 700

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

In the present invention, two compounds of formulas (I) and (II) are added together with a small amount of water and other known additives, and then reacted and chipped at 230 to 280 ° C for 10 to 20 hours to give a viscosity (RV) of the polymer. It is characterized by obtaining a basic dye saltable polyamide fiber by obtaining a neutralized product having a concentration of 2.5 to 2.8 and a terminal amino group of 15 to 30 (equivalent to 10 ⁶ g), washing with water, drying and melt spinning in a conventional manner. .

In the present invention, the structural formula [I] has a molecular weight of 50,000 to 150,000, and is excellent in thermal stability (stable without chemical change up to 460 ° C), and is stable even at high temperatures as in a polymerization process, without chemical bonding with polyamide. Dispersed in the polyamide backbone in the molecular state. Since the substance is dispersed without causing a chemical bond with the polyamide, when the molecular weight is less than 50,000, there is a risk of escaping during the extraction process.

In particular, in the structural formula [I], R has good compatibility with caprolactam in the case of Li, Mg, and Ca, and Na and K have good compatibility but are prone to aggregation, and Al and Zn are insoluble in caprolactam, and thus difficult to use. Do.

When the polymer material of the structural formula [I] is added in an amount less than 0.5% by weight with respect to caprolactam, the affinity for the basic dye is lowered, and thus the object of the present invention cannot be achieved. Since the manufacturing cost is too high and the basic physical properties of the filament may be lowered, the preferred amount is 0.5 to 10% by weight.

On the other hand, it is preferable that the addition amount of a structural formula [II] substance shall be 0.1-5 weight% with respect to caprolactam. If the added amount is less than 0.1% by weight, it is difficult to achieve the purpose of preventing staining by acid dyes, and when the amount is more than 5% by weight, the degree of polyamide polymerization is lowered. In the present invention, the material of the structural formula [II] and the polymer material of the structural formula [I] are preferably used in a weight ratio of 1: 1 to 1:10, more preferably 1: 1 to 1: 6.

If the above range is less than 1: 1, the problem of lowering the daylight fastness occurs, and if the ratio exceeds 1:10, the manufacturing cost rises, there is a fear that the spinning process occurs and the basic physical properties of the filament may decrease.

Example 1

3 1,000 g of caprolactam, 20 g of water, 1 g of acetic acid, tetrabutyl phosphonium 3, and 5 g of dicarboxylic benzenesulfonate (TPBS) were added together with polystyrene sulfonate lithium salt (LPS) as shown in Table 1. After that, the mixture was reacted at 260 ° C for 24 hours to prepare polyamide.

The polymer thus obtained was extracted with distilled water for 24 hours in the same manner as a conventional polyamide chip manufacturing method to remove monomers and oligomers and then dried at 100 ° C. in a vacuum oven for 15 hours to obtain final polyamide. The polymer was melt-spun in a conventional manner to prepare 1,300D / 69fil BCF (Bulked Continuous Yarn), and then acidic dye NAVY BLUE-BN and basic dye CATIONIC-RED 0.5% owf, bath ratio 1: It was dyed at 40.

This was measured by the weatherfastness and the results are shown in Table 1.

Example 2

Experimented in the same manner as in Example 1, except that 40 grams of polystyrene sulfonate lithium salt (LPS) and tetrabutyl phosphonium 3,5-dicarboxyl benzenesulfonate (TPBS) were added as shown in Table 2 to the polyamide obtained. The physical properties were measured and shown in Table 2.

Comparative Example 1

3 40 g of polystyrene sulfonate lithium salt (LPS) together with caprolactam, 1,000 g, 20 g of water, and 1 g of acetic acid were added to the reactor, followed by reacting at 260 ° C. for 24 hours to prepare a polyamide. Experimental results are shown in Table 3.

Comparative Example 2

3 1,000 g of caprolactam, 20 g of water, and 1 g of acetic acid were added together with 10 g of tetrabutyl phosphonium 3 and 5-dicarboxyl benzenesulfonate (TPBS), followed by reaction at 260 ° C for 24 hours to prepare polyamide. Experiments were carried out in the same manner as in Example 1, and the results are shown in Table 3.

TABLE 1

TABLE 2

TABLE 3

* Among the above results, dye absorption rate means that dyes of basic dye chlorinated polyamide are mixed in acid dyes and basic dyes in a mixed salt bath.

Claims (3)

A method for producing a polyamide fiber chlorinated to a basic dye, characterized in that the polyamide polymer melted and spun together by adding a polymer of formula [I] and a monomer of formula [II] together. Provided that R is selected from Na, K, Ca, Li, Mg, Zn and Al, and n is from 250 to 700 Provided that R 'is a hydrocarbon having 2 to 8 carbon atoms According to claim 1, wherein the polymer material of formula [I] is selected to have a molecular weight of 50,000 or more to add 0.5 to 10% by weight based on the caprolactam and 0.1 to 5% by weight of the monomer of the formula [II] A method for producing a polyamide fiber that is salty to a basic dye, characterized by polymerizing. The method for producing a polyamide fiber soluble in a basic dye according to claim 1, wherein the weight ratio of the monomer of the formula [II] and the polymer material of the formula [I] is 1: 1 to 1:10.