KR100748828B1 - Process for preparing a polyamide 6 fiber of excellent coloring property - Google Patents

Abstract

A manufacturing method of a polyamide 6 fiber with the excellent coloring property is provided to have the affinity for the basic dyestuffs and the contamination-proof property for the acidic dyestuffs. The polyamide 6 fiber is made from an epsilon-caprolactam. The 0.3 to 5.0 wt% of dicarboxy-benzene-sulfonate compound represented by a formula 1 to the epsilon-caprolactam is injected. The diamine compound represented by a formula 2 of H2N-R-NH2 is injected below the same mol % of the injected dicarboxy-benzene-sulfonate compound of 0.3 to 5.0 wt%. In the formula 1, Z is Na, K or Li, R is alkyl group of carbon number 1-3, m is 0 or 1, R' is hydrogen or alkyl group of carbon number 1-3. In the formula 2, R is alkyl or phenyl group of carbon number 2-12. The bis-caprolactam compound is added as the third component at the polymerization process or the spinning process. The added amount of the bis-carprolactam compound is 0.2 to 5.0 wt%. The bis-caprolactam compound is selected from terephthaloyl bis-caprolactam, isophthaloyl bis-caprolactam and carbonyl bis-caprolactam.

Description

Process for preparing a polyamide 6 fiber of excellent coloring property}

The present invention relates to a method for producing polyamide 6 fibers having affinity for basic dyes and little affinity for acidic dyes, and exhibiting excellent color development with respect to basic dyes.

Conventionally, polyamide fibers have been very useful in many fields because their strength, abrasion resistance, dyeability, etc. are superior to other synthetic fibers.

However, in recent years, the demand characteristics of each field are gradually diversified, and the demand for outstanding functional characteristics is becoming more frequent, and in the general medical field, more improved characteristics, that is, the demand for improvement in productivity and dyeability are gradually increased. have.

In general, polyamide fibers have excellent dyeing properties for acid dyes, but since they have poor dyeing properties for basic dyes, there are many limitations in expressing colors that can satisfy consumer's preference for products requiring various colors such as pattern carpet. Have been received. When the present invention is applied to the pattern carpet and pattern fabrics, etc., the conventional method can avoid dyeing (Yarn Dyeing) method and dyeing in a dye bath mixed with an acid dye and a basic dye, as a result of the pattern carpet or pattern fabric It is an object of the present invention to provide a method for producing functional polyamide 6 fibers which can shorten the manufacturing process and express various colors.

Many methods have been conventionally proposed for increasing the affinity for the basic dyes of polyamide 6 fibers.

For example, a method of introducing mono or dicarboxybenzene having a sulfonate group into a polyamide (Japanese Patent Publication Nos. 37-14646, 3737647) and di (sodium sulfonate) naphthalene-2-carboxylic acid compound A method of introducing into an amide (Japanese Patent Publication No. 44-1236), a method of introducing a poly (alkylene ether derivative) having a sulfonic acid group into a polyamide (Japanese Patent Publication Nos. 46-41016 to 41019), and a sulfonated polystyrene The method of introducing into polyamide (Japanese Patent Publication No. 43-24229), etc. are mentioned.

However, the methods proposed in Japanese Patent Publication No. 37-14646 and Japanese Patent Publication No. 44-1236 act as end-blockers during the polymerization reaction of ε-caprolactam, thereby inhibiting the increase in the degree of polymerization, thereby improving the physical and mechanical properties of the polymer. There is a problem of deterioration.

In addition, the method proposed in Japanese Patent Publication No. 46-41016 ~ 41019 can produce fibers having excellent affinity for basic dyes, but due to the fusion of yarn during the weaving process in spinning process, trimming and operationability are remarkably deteriorated. There is a problem of low washing fastness.

In addition, the sulfonated polystyrene proposed in Japanese Patent Publication No. 43-24229 has a poor compatibility with polyamide, which causes a lot of trimming in the spinning process, and has a drawback of eluting when immersed in warm hot water.

In addition, in order to obtain a desired molecular weight (i.e., sufficient degree of polymerization) together with an isophthalic acid component containing a metal sulfonic acid group, such as a 5-potassium sulfoisophthalic acid component, a method of adding and copolymerizing the same mole number of diamine is described in Japanese Patent. Publications 37-14645 and 37-14616, US Pat. No. 3,039,990.

However, since the polyamide copolymer obtained by this method has the same number of amino groups and carboxyl groups at the ends, it has sufficient affinity not only for basic dyes but also for acid dyes, and dyes them in an acid-base dye mixture bath together with general polyamides. In other words, there is a problem in that it does not exhibit vivid color development but shows color development contaminated by coloring each dye.

The present invention is to solve the problems of the prior art as described above, a compound that is added in the polymerization step of the polyamide 6 copolymer whose main material is an aromatic compound containing ε-caprolactam and sulfonic acid group, that is, dicarboxybenzenesulfo By controlling the molar ratio of the nate component to the diamine component appropriately to minimize the amine terminal concentration at an appropriate degree of polymerization, and by adding a biscaprolactam compound in the polycondensation step or spinning step to block the amine end group has a vivid color development for basic dye There is a technical problem to provide a method for producing polyamide 6 fibers.

The present invention is to solve the conventional problems as described above by adjusting the relative molar ratio of the specific compound added during the polymerization of the basic salt-type polyamide 6 copolymer to adjust the reactor at the polymer terminal to the dyeing seat to the acid dye By lowering the amine end as much as possible, and additionally blocking the amine end group by introducing a special third component in the polycondensation step or spinning step, it is not dyed in an acid dye, but only in a basic dye to express vivid color development. The present invention has been completed by finding out.

Normally, polyamide fibers are not dyed in basic dyes, but only in acid dyes, because the acid dyes are chemically bonded to the amine terminal groups.

Therefore, in order to dye only the basic dye, a method of replacing an amine terminal group with a sulfonic acid group having a basic dye salting type is required.

To this end, a method of copolymerizing by adding a compound containing sulfonic acid group in the polymerization step is common, but it is difficult to minimize the concentration of the amine terminal during polymerization because the appropriate amount of amine terminal group concentration is required to obtain an appropriate degree of polymerization. have.

Therefore, the present invention is designed to have a minimum amine end group at the desired degree of polymerization by appropriately adjusting the molar ratio of the compound added in the polymerization step, and to further lower the amine end group by adding a third component in the spinning step, this problem Solved.

Hereinafter, the present invention will be described in more detail.

The present invention uses at least one compound selected from the dicarboxybenzenesulfonate compounds represented by the following formula (1), and the diamine compound uses at least one compound selected from the compounds represented by the following formula (2) A method for producing a polyamide 6 copolymer for polyamide 6 fibers according to the present invention.

                     Below

(Wherein Z is Na or K or Li)

            R is an alkyl group having 1 to 3 carbon atoms

            m is 0 or 1

            R 'is hydrogen or an alkyl group having 1 to 3 carbon atoms)

       H2N-R-NH2 ----------------- (2)

(Wherein R is an alkyl group having 2 to 12 carbon atoms or a phenyl group)

In the present invention, in preparing a polyamide 6 copolymer containing an ε-caprolactam and an aromatic compound (dicarboxybenzenesulfonate) containing a sulfonic acid group as a main raw material, the amount of the aromatic compound containing a sulfonic acid group is ε-caprolactam It will be 0.3 to 5.0 parts by weight.

If the amount is less than 0.3 part by weight, the affinity for the basic dye may not be sufficient, and if it is more than 5.0 parts by weight, there is a problem that physical properties are greatly reduced, such as an increase in water absorption.

In addition, in the present invention, the diamine compound used to increase the degree of polymerization of the polyamide 6 copolymer is such that the amount added is equal to or less than the same mol% of the compound dose containing the sulfonic acid group.

If it is added to the polymerization in more than mol% sulfonate compound, there is a problem that the resistance to the acid dye is weakened and stained and stained in the acid dye as well as basic dye.

In the present invention, examples of the dicarboxybenzenesulfonate compound include 2,5- and 3,5-dicarboxybenzenesulphonic acid, 2,5- and 3,5-dicarboxyethylbenzenesulfonic acid, 2,5- and Sulfonate salts of sodium, potassium, and lithium, such as 3,5-dicarboxypropylbenzenesulfonic acid, or 2,5- and 3,5-dimethoxycarboxylic benzenesulfonates, 2,5- and 3,5-dimeth Sulfonate salt compounds of sodium, potassium, and lithium, such as oxycarboxylethylbenzenesulfonate, 2,5- and 3,5-dimethoxycarboxypropyl benzenesulfonate, 2,5- and 3,5-diethoxycar Sulfonate salt compounds of sodium, potassium, and lithium, such as carboxyethylbenzenesulfonate, 2,5- and 3,5-diethoxycarboxypropyl benzenesulfonate, 2,5- and 3,5-dihydroxycarboxyethyl Minimum selected from sulfonate salt compounds of sodium, potassium, and lithium, such as benzenesulfonate, 2,5- and 3,5-dihydroxycarboxypropylbenzenesulfonate Is one species.

Examples of the diamine compounds used for the purpose of increasing the degree of polymerization include ethylenediamine, tetramethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, paraphenylenediamine, and meta. At least one selected from phenylenediamine, paraxylenediamine, and metaxylenediamine.

At this time, the content of the amine terminal group of the copolymer polymer is preferably 30 meq / kg or less. If the concentration of the amine terminal group exceeds 30 meq / kg, the dye is not only high in affinity for basic dyes but also affinity for acid dyes. Unevenness and contamination are aggravated and undesirable.

In the present invention, the biscaprolactam compound, which is the third component added for the purpose of adjusting the amine terminal group concentration, is added in the polycondensation step or the spinning step, and the amine terminal group concentration can be arbitrarily adjusted by adjusting the addition amount. .

The amount of addition is preferably 0.2 to 5.0 parts by weight.

The biscaprolactam compound used is selected from terephthaloyl biscaprolactam, isophthaloyl biscaprolactam, carbonyl biscaprolactam.

In addition, in the present invention, it is possible to produce a fiber having various luster by adding titanium dioxide as a matting agent, and in addition, it is also possible to add a magnesium compound, a copper compound, a manganese compound, a zinc compound, etc. to impart functionality to impart functionality. Do.

The magnesium compound to be used uses one selected from magnesium oxide, magnesium acetate, and magnesium chloride, and the copper compound uses one selected from copper chloride, copper acetate, and copper iodide.

Manganese compounds introduced for the purpose of improving light resistance use one selected from manganese chloride, manganese oxide and manganese acetate.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the following Examples.

<Examples and Comparative Examples>

100 parts by weight of ε-caprolactam, 1.5 parts by weight of water, 1.6 parts by weight of 3.5-dicarboxybenzenesulfonic acid sodium, 0.4 parts by weight of methaxylenediamine, 0.015 parts by weight of manganese chloride, and 0.03 parts by weight of magnesium chloride The resulting mixture was stored in an intermediate storage tank, which was continuously fed to the atmospheric pressure continuous polymerization tower VK.

The polycondensation was carried out at a polymerization temperature of 260 ° C. for about 16 hours, and the second condensation reaction was carried out at a vacuum degree of 250 Torr in a polymerization tower VS equipped with a vacuum pump.

The race discharged by the gear pump was solidified in a water bath, and the polymer race was chipped, and then extracted and dried to obtain a final chip property of 2.7 and an amine terminal content of 28 meq / kg.

After maintaining the sulfonate-containing copolymerized polyamide chip at a moisture content of 0.05 parts by weight or less, a side feeder was installed in front of the extruder to obtain terephthaloylbiscaprolactam (TL), which is a terminal blocker, as shown in Table 1. Each mixture was added.

Spinning nozzles were made of SUS-316 nozzles with 68 odd-numbered 0.25 mm diameter nozzles, and cooled by blowing cooling air at 20 ° C at a wind speed of 0.5m / min at a spinning temperature of 265 ° C to give an emulsion, and then spinning speed. 70d / 68f polyamide 6 fibers having a yarn property of 5.2 g / d in strength and 45% elongation were prepared by adjusting the draw ratio at 4500 m / min.

After the preparation and refining using the yarn, the dye was immersed in a mixed salt of Navy Blue 0.5% owf and basic dye Catioinic-Red 0.5% owf with acid dyes.

In order to determine the contamination by acid dyes, the color difference (ΔE) was calculated and compared using the CIE L * a * b system.

<Table 1>

 Sulfonic acid group-containing polyamide (%)  TL (parts by weight)  Amine terminal (meq / kg)  Color difference (ΔE)  Basic dye coloring  Example 1  99.75  0.25  24  24  △  Example 2  99.50  0.50  22  23  ○  Example 3  99.25  0.75  19  21  ○  Example 4  99.00  1.0  14  21  ○  Example 5  98.00  2.0  8  20  ◎  Comparative Example 1  100  0  28  26  △ ~ ×

Note) Color development: The degree of color development by basic dye without contamination with acid dye

    ◎: very good, ○: good, △: normal, ×: contamination

    TL; Terephthaloyl biscaprolactam.

As shown in Table 1, the fibers prepared by the examples not only have excellent affinity for basic dyes, but also have a high staining resistance to acid dyes, and thus, less staining occurs during dyeing.

As can be seen from the above examples, the present invention provides a polyamide 6 copolymer fiber containing sulfonic acid groups that is resistant to acid dyes in a mixture of acid dyes and basic dyes and exhibits vivid color development for basic dyes. Can be.

In addition, the polyamide 6 fiber produced according to the present invention is not only for carpet, but also for general medical multifilament, which can be given a variety of colors by simultaneous bathing, dichroic effect, two-tone effect, pattern stripe, melange effect in knitted fabric, etc. It can be developed for the purpose of, and also has the advantage of showing a vivid color development to the basic dye.

Claims (3)

In preparing polyamide 6 fibers from ε-caprolactam, 0.3 to 5.0 parts by weight of the dicarboxybenzenesulfonate compound represented by the following formula (1) is added to ε-caprolactam, and the following formula (2) is used. A polyamide having excellent color development properties, wherein the diamine compound is added at the same mole% or less of the dicarboxybenzenesulfonate compound, and the biscaprolactam compound is added as a third component in a polycondensation step or a spinning step. Method of making fibers.                     Below

      (Wherein Z is Na or K or Li)                   R is an alkyl group having 1 to 3 carbon atoms                   m is 0 or 1                   R 'is hydrogen or an alkyl group having 1 to 3 carbon atoms)        H2N-R-NH2 ----------------- (2) (Wherein R is an alkyl group having 2 to 12 carbon atoms or a phenyl group) The method for producing a polyamide 6 fiber having excellent color development according to claim 1, wherein the amount of the biscaprolactam compound added is 0.2 to 5.0 parts by weight. The method of claim 1, wherein the biscaprolactam compound is selected from terephthaloyl biscaprolactam, isophthaloyl biscaprolactam, and carbonyl biscaprolactam.