KR100669646B1 - Process of making a polyamide polymer having good dyeing property and nylon 6 fiber produced by the same - Google Patents

Abstract

A method for preparing a polyamide polymer is provided to obtain a polyamide(nylon 6) polymer having excellent dyeing property and fastness and capable of dark color dyeing while avoiding a need for tin or heavy metals. The method for preparing a polyamide polymer via polymerization of epsilon-caprolactam comprises adding 0.2-0.8 parts by weight of an aromatic diamine compound as a dyeing property modifier based on 100 parts by weight of epsilon-caprolactam during the polymerization, and further adding a magnesium compound and an organic copper compound each in an amount of 50ppm or less on the metal element basis. The mixed material are extracted and dried to obtain a viscosity relative to sulfuric acid of 2.5-3.0 and a terminal amine content of 60-90 meq/kg.

Description

Process of making a polyamide polymer having good dyeing property and nylon 6 fiber produced by the same}

The present invention relates to a method for preparing a polyamide (nylon 6) polymer having excellent dyeing resistance to acid dyes and capable of deep dyeing, and to nylon 6 fibers made from the polymer.

That is, the present invention can be dyed in dark colors without using tin or heavy metals that adversely affect the environment or the human body, and at the same time, a method of producing a polyamide polymer having excellent washing fastness and contamination fastness, which is not easily changed and discolored. It relates to nylon 6 fibers produced by.

Conventionally, polyamide fibers have been very useful in many fields because they have superior strength, abrasion resistance, and dyeability compared to other synthetic fibers. However, in recent years, the required characteristics in each field are gradually diversified and require outstanding functional characteristics. Increasingly, the demand for improvement in the characteristics, that is, productivity and dyeability, has been gradually increased in general medical use.

In particular, since the dyeing, operation, and color fastness are very important factors for general-purpose medical fibers, polyamide 6 fibers having more differentiated and specialized characteristics, ie, easy to dye with acid dyes, have excellent operation and improved dyeing uniformity. The demand is increasing.

Various methods have been studied to improve the dyeability, and the most typical method is to increase the number of amine end groups of the polyamide. US Pat. No. 2274831 adds a polyvalent amine containing tertiary nitrogen. Japanese Patent Application Laid-Open No. 62-41313 discloses a method for producing ultrafine filaments, and the polyamine is added in the polymerization step to increase the amine end content to 90 to 160 meq / kg. In addition, Japanese Patent Application Laid-Open No. 52-124927 discloses a method of increasing the amine end by adding a polyvalent amine to a melt spinning melter after polymerization. So 48-28974 discloses a method of copolymerizing adipic acid with N-β-aminoethylpiperazine and blending it with polyamide 6 to improve dyeability. It is introduced.

In addition, a method of introducing a strongly basic amino group of N-alkylpiperazines into the main chain or terminal (US Patent No. 3300448), blending N-pyrrolidone polymer, polyalkylenepolyamine, polyamino triazole and the like in a spinning step (Japanese Patent Publication Nos. 37-8972, 43-15587, 42-20851), and the like.

Among the above methods, polyvalent amines such as US Pat. No. 2274831 and Japanese Patent Application Laid-open No. 62-41313 have a low affinity for acidic dyes of tertiary nitrogen, and the tertiary nitrogen in the polymerization step is not affected. There is a possibility that the branch reaction occurs to degrade the quality of the polymer.

In addition, when employing a method of blending N-pyrrolidone polymer, polyalkylene polyamine, polyamino triazole and the like, there is a problem that the process management is complicated and difficult to obtain uniform quality.

The present inventors have solved the conventional problems, and as a method for providing a polyamide (nylon 6) fibers having better dyeability to acid dyes in the polymerization step in Korea Patent No. 0138171 (registration date: February 17, 1998) As a stabilizer of the release polymer, a method of producing a polyamide fiber having excellent radioactivity and dye resistance by adding an aliphatic diamine compound and a magnesium compound together has been proposed.

The method of the inventors of the present invention has the advantage that it is possible to improve the overall productivity by improving the dyeing resistance to the diamine compound and at the same time to prevent the extension and disconnection of the nozzle wiping cycle by the addition of magnesium compound, but somewhat weak in terms of heat treatment and color fastness There was a downside.

The present invention supplements the problems of the method of the Korean Patent No. 0138171, the inventors of the present invention to provide a nylon 6 fiber made of the polymer and a method for producing a polyamide polymer having high fastness and high fastness as well as excellent dyeing resistance. It is to put.

In the present invention, in preparing a polyamide fiber by polymerization of ε-caprolactam, 0.2 to 0.8 parts by weight relative to 100 parts by weight of ε-caprolactam is added as a dye-improving modifier in the polymerization step, and magnesium is used as the second component. It is characterized in that the completion of the polymerization by adding a compound and the same compound to less than 50ppm each based on the metal element, and a method for producing a polyamide polymer having excellent dye-adhesion to extract and dry it chipping and to nylon 6 fibers made of the polymer It is about. In the present invention, the polyamide chip prepared through the extraction and drying process is characterized in that the sulfuric acid relative viscosity of 2.5 to 3.0 and the amine terminal content of 60 to 90 meq / kg.

In the present invention, the aromatic diamine compound used is one selected from paraphenylenediamine, metaphenylenediamine, paraxylenediamine, and metaxylenediamine, and the amount is 0.2 to 0.8 parts by weight based on 100 parts by weight of ε-caprolactam. It is preferable to use. If the added amount is less than 0.2 part by weight, there is no effect of improving the dyeing property, and if it exceeds 0.8 part by weight, the polymerization viscosity is significantly lowered, which is not preferable.

In addition, in the present invention, the amine end group content of the polymer is preferably 60 ~ 90 meq / kg, less than 60 meq / kg is less deep color effect, more than 90 meq / kg is poor saengseongsa and likely to cause disproportionate Not desirable

In addition, in this invention, the magnesium compound added as a 2nd component uses 1 type chosen from magnesium oxide, magnesium acetate, and magnesium chloride, and the compound uses 1 type selected from copper chloride, copper acetate, and copper iodide.

If the added amount of magnesium compound exceeds 50ppm on the basis of the metal element, there is a problem that the viscosity decreases due to the polymerization rate. Also, if the added amount of the copper compound exceeds 50ppm on the basis of the metal element, the thermal stability is excellent but the color of the chip is discolored. This adversely affects the appearance of yarn and knitwear.

When preparing fibers using the polyamide 6 of the present invention, addition of conventional additives and processing aids is possible. For example, heat stabilizers such as copper iodide and copper acetate and light stabilizers using manganese compounds, matting agents such as titanium dioxide, and the like can be added, and antistatic agents include conventional materials such as polyalkylene oxides and It is possible to add derivatives thereof.

In the present invention, the relative viscosity of sulfuric acid of the polyamide polymer is preferably 2.5 to 3.0 or less, but if the viscosity is less than 2.5, the strength is insufficient when the fiber is used, and if the viscosity exceeds 3.0, there is a problem of detergency.

According to the present invention, by adding an aromatic diamine compound, which is a rigid component, the dyeing resistance can be improved by controlling the concentration of the amine terminal group, and by adding a magnesium compound and the copper compound together as a second component, a polyamide polymer having excellent heat resistance and fastness can be obtained. It can be prepared, and when melt-spun using it has the advantage of improving workability and weedability, dyeing uniformity, color fastness.

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]

Example  One

100 parts by weight of ε-caprolactam, 1.5 parts by weight of water, and 0.4 parts by weight of a metaxylenediamine component as a dye modifier, and as a second component, a magnesium compound and a copper compound were added at 20 ppm based on metal elements, respectively, to prepare a mixture. After the first ring-opening reaction under atmospheric pressure, and then the second condensation reaction at a vacuum degree of 250torr. After chipping, extraction and drying were performed to obtain a polyamide 6 chip having a physical property of sulfuric acid relative viscosity of 2.67 and an amine terminal of 85 meq / kg.

After maintaining the polyamide 6 chip at a moisture content of 0.05 parts by weight or less, through a spinning nozzle made of SUS-316 material having an odd number of 68 holes of 0.25 mm diameter, cooling air at a spinning temperature of 270 ° C. and 20 ° C. at a wind speed of 0.5 m / min. Cooling while blowing to give an emulsion, and then adjusted the draw ratio at the spinning speed 4500m / min to obtain 70d / 68f nylon 6 fiber having a yarn property of 5.2g / d, 45% elongation.

Comparative example  One

100 parts by weight of ε-caprolactam, 1.5 parts by weight of water, 0.34 part by weight of a hexamethylenediamine component as a dye modifier, and a magnesium compound at 30 ppm as a second component to prepare a mixture, which was then primary ring-opened under atmospheric pressure. The reaction was followed by a second condensation reaction at a vacuum degree of 250 torr. After chipping, extraction and drying process steps to obtain the physical properties of the relative viscosity of sulfuric acid 2.68, amine terminal 84 meq / kg. Thereafter, the yarns were spun in the same manner as in Example 1 to obtain yarns of 70 d / 68f having a strength of 5.0 g / d and elongation of 46%.

Comparative example  2

100 parts by weight of ε-caprolactam, 1.5 parts by weight of water and 0.1 parts by weight of acetic acid were added, and a magnesium compound was added at 30 ppm as a second component to prepare a mixture, which was then subjected to primary ring-opening reaction under atmospheric pressure. The second condensation reaction was carried out at a vacuum degree of 500 torr. After chipping, extraction and drying process steps to obtain the physical properties of the relative viscosity of sulfuric acid 2.71, amine end 46meq / kg. Thereafter, the yarn was spun in the same manner as in Example 1 to obtain a yarn of 70 d / 68f having a strength of 4.8 g / d and elongation of 46%.

As a result of dyeing the nylon 6 yarn of the present invention and the conventional regular type nylon yarn prepared by the above method under the conditions of Table 1, the yarn of the present invention has a very good dyeing speed compared to the regular type (Comparative Example 2). Indicated.

Table 1

Then, in order to comparatively evaluate the fastness in the knitted fabric, the circular knitted fabric made of polyamide yarn of 1de grade single yarn fineness prepared in the above Examples and Comparative Examples and spandex having a total fineness of 20 denier was knitted in the size of 28 gauge and 30 in. The center weight of the circular knitted fabric was opened with a basis weight of 200 gr / m2, and then it was immersed in a 3% solution of aqueous polyurethane, and then squeezed at a pickup rate of 50%, and then at a temperature of 180 ° C. The circular knit dough was pretreated by heat setting the aqueous polyurethane for 40 seconds.

Refining the circular knitted fabric treated with water-based polyurethane, using a metal dye 4% owf, pH adjuster 2g / l, anionic surfactant 1g / l, the temperature was raised to 100 ℃ at a temperature increase rate of 1 ℃ / min and 40 minutes Were dyed, cooled to 50 ° C. at 1 ° C./min, and washed three times with 50 ° C. warm water. The polyamide / spandex circular knitted fabric was finally prepared and evaluated for washing fastness, sweat fastness and dyeing quality before and after dry heat setting at 170 ° C. for 60 seconds in Table 2.

[Table 2]

5: very good, 4: always pass, 3-4: sometimes pass, 2-3: fail

◎: very good, ○: excellent, △: normal

Appearance dyeing quality; Visually compare the uniformity of dyes after dyeing.

Color fastness evaluation: Assessed by classifying into 5 grades.

As can be seen through the results of Table 1 and Table 2, the yarn made of the polyamide polymer prepared by the present invention not only has excellent dyeing and fastness, but also excellent dyeing quality in polyamide / spandex circular knitted fabrics. The dyeing quality is good even after dry heat setting.

Claims (6)

In preparing a polyamide polymer by polymerization of ε-caprolactam, an aromatic diamine compound is added by 0.2 to 0.8 parts by weight relative to 100 parts by weight of ε-caprolactam as a dye-improving modifier in the polymerization step, and a magnesium compound as a second component. And the organic copper compound is added to less than 50ppm based on the metal element, respectively, and polymerized, extracted and dried to produce a sulfuric acid relative viscosity of 2.5 to 3.0 and an amine terminal content of 60 to 90 meq / kg. Process for preparing polyamide polymer. The method according to claim 1, wherein the aromatic diamine compound is selected from paraphenylenediamine, metaphenylenediamine, paraxylenediamine, and metaxylenediamine. The method for producing a polyamide polymer having excellent dyeing property according to claim 1, wherein the magnesiumated compound is one selected from magnesium oxide, magnesium acetate, and magnesium chloride. The method of claim 1, wherein the copper compound is one selected from copper chloride, copper acetate, and copper iodide. Nylon 6 fiber prepared by melting and spinning using the polymer prepared by the method of claim 1. Woven fabrics prepared using the nylon 6 fibers of claim 5.