JP6386561B2 - Nylon blend composition with improved moisture absorption rate and shrinkage rate, nylon fiber produced therefrom and method for producing the same - Google Patents

Description

  The present invention relates to a nylon blend composition having improved moisture absorption and shrinkage, a nylon fiber produced therefrom, and a method for producing the same.

  Nylon 6 usually has properties such as excellent strength, elastic recovery rate, and dyeability, but most synthetic fibers including nylon 6 have a drawback of low moisture absorption. Cotton, which is a natural fiber, has a high moisture absorption rate and feels better than conventional synthetic fibers, but it cannot be processed into microfibers, cannot produce an excellent feel, and has an extremely poor UV blocking property. In addition, since the price is expensive, the emergence of innovative nylon synthetic fibers has been demanded.

  Synthetic fiber researchers have long been researching new synthetic fibers that can take advantage of the advantages of cotton, such as high moisture absorption and excellent fit, while maintaining the advantages of conventional synthetic fibers. It can be said that nylon 4 (a resin in which a 2-pyrrolidone monomer is homopolymerized) has attracted the most attention as a result of such efforts.

  Nylon 4 like this appeared as a dream synthetic fiber to replace cotton in 1973 due to its strength of high moisture absorption and strength due to its low lipophilic carbon number per repeating unit in the structure, While the melting point is 265 ° C., the thermal decomposition temperature is 260 ° C., and there is a technical problem that the heat resistance of the spinning process is very poor.

  In fact, there is a demand for production of a nylon blend composition capable of complementing the physical properties of nylon 4 and nylon 6.

  The present invention has improved moisture absorption and shrinkage, including 70% to 95% by weight resin polymerized with 2-pyrrolidone and 5 to 7 carbon lactams; and 5% to 30% by weight nylon 6 resin. The object is to provide a nylon blend composition or the like for fiber production.

  However, the technical problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

  The present invention has improved moisture absorption and shrinkage, including 70% to 95% by weight resin polymerized with 2-pyrrolidone and 5 to 7 carbon lactams; and 5% to 30% by weight nylon 6 resin. A nylon blend composition for fiber manufacture is provided.

  The resin obtained by polymerizing 2-pyrrolidone and a lactam having 5 to 7 carbon atoms may be a nylon 4,6 resin.

  The 2-pyrrolidone or the lactam having 5 to 7 carbon atoms can be obtained from biomass.

  The resin obtained by polymerizing the 2-pyrrolidone and the lactam having 5 to 7 carbon atoms may have a weight average molecular weight of 50 kg / mol to 200 kg / mol.

  As an embodiment of the present invention, there is provided a nylon-based fiber with improved moisture absorption and shrinkage, which is produced from the nylon blend composition.

  The nylon fiber may have a moisture absorption rate of 5% to 10%.

  The shrinkage ratio of the nylon fiber may be 10% to 40%.

  The nylon fiber may have a strength of 3 g / d to 5 g / d.

  In one embodiment of the present invention, 70 wt.% To 95 wt.% Of a resin polymerized with 2-pyrrolidone and 5 to 7 carbon lactam, and 5 wt. And a method for producing a nylon blend composition with improved moisture absorption and shrinkage.

  The resin obtained by polymerizing 2-pyrrolidone and a lactam having 5 to 7 carbon atoms may be a nylon 4,6 resin.

  The melt blending can be performed at 230 ° C to 270 ° C.

  The spinning step may be performed through a heat setting process at 140 ° C to 180 ° C.

  The nylon blend composition according to the present invention comprises 70% to 95% by weight of a resin polymerized with 2-pyrrolidone and a lactam having 5 to 7 carbon atoms; and 5% to 30% by weight of a nylon 6 resin. Produces industrial and apparel products with excellent spinning processability, high moisture absorption, low shrinkage and high strength, and uniform fiber cross-section. Therefore, it was confirmed that there was no shrinkage non-uniformity phenomenon during post-processing, excellent shape stability, and very useful as a fiber material for industrial and clothing.

FIG. 1 is a cross-sectional view of a fiber manufactured according to an embodiment of the present invention, measured with an optical microscope.

  While the inventors of the present invention have been studying a nylon blend composition, spinning is performed by melt-blending a resin obtained by polymerizing 2-pyrrolidone and a lactam having 5 to 7 carbon atoms and a nylon 6 resin at a constant weight ratio. It was confirmed that a nylon blend composition excellent in fiber properties such as processability, moisture absorption and shrinkage, and strength could be produced, and the present invention was completed.

  The present invention is described in detail below.

  The present invention has improved moisture absorption and shrinkage, including 70% to 95% by weight resin polymerized with 2-pyrrolidone and 5 to 7 carbon lactams; and 5% to 30% by weight nylon 6 resin. A nylon blend composition is provided.

  In the resin obtained by polymerizing 2-pyrrolidone and a lactam having 5 to 7 carbon atoms, examples of the lactam having 5 to 7 carbon atoms include piperidone, caprolactam, enantholactam and the like. However, it is not limited thereto, and preferably ε-caprolactam can be used.

  The resin obtained by polymerizing 2-pyrrolidone and a lactam having 5 to 7 carbon atoms may be a nylon 4,6 resin, and the nylon 4,6 resin uses ε-caprolactam as a lactam having 5 to 7 carbon atoms. Nylon 4 (resin in which 2-pyrrolidone monomer is homopolymerized) is manufactured with improved poor spinning processability and heat resistance.

  For example, a resin in which 2-pyrrolidone and a lactam having 5 to 7 carbon atoms according to the present invention are polymerized is obtained by anionic polymerization of a monomer containing 2-pyrrolidone and a lactam having 5 to 7 carbon atoms to co-polymerize nylon 4 and 6. After producing the polymer, the unreacted monomer and catalyst in the nylon 4,6 copolymer are purified with water, the pH is controlled through ion exchange of the purified water, and the pH-controlled water is removed. It can manufacture by concentrating and collect | recovering the said unreacted monomers.

The nylon 6 resin is a resin in which ε-caprolactam having 6 carbon atoms is polymerized, and has a chemical structure of (C ₅ H ₁₀ CONH) _n .

  The resin in which 2-pyrrolidone and a lactam having 5 to 7 carbon atoms according to the present invention are polymerized (for example, nylon 4,6 resin) and nylon 6 resin are not required to have a separate reactive compatibilizing agent. , It has a characteristic of excellent kneadability between each other. That is, the resin blended with 2-pyrrolidone and a lactam having 5 to 7 carbon atoms and the nylon blend composition including the nylon 6 resin have a single melting temperature (Tm) and a single crystallization temperature (Tc). Have.

  That is, the nylon blend composition according to the present invention includes 70% to 95% by weight of resin obtained by polymerizing 2-pyrrolidone and a lactam having 5 to 7 carbon atoms; and 5% to 30% by weight of nylon 6 resin. However, it is not limited to this. At this time, if the weight ratio of the resin in which pyrrolidone and a lactam having 5 to 7 carbon atoms are polymerized is less than the above range, there is a problem that the moisture absorption rate is lowered, and the pyrrolidone and the lactam having 5 to 7 carbon atoms are polymerized. When the weight ratio of the resin is more than the above range, there is a problem that spinning stability is lowered and it is difficult to set spinning conditions, the shrinkage ratio is increased, and the strength is lowered.

  The 2-pyrrolidone or the lactam having 5 to 7 carbon atoms can be obtained from biomass.

  Specifically, the 2-pyrrolidone is produced by producing 4-aminobutyric acid using glutamic acid or sodium glutamate produced by microbial fermentation as a starting material and using glutamic acid decarboxylase (GAD) as a catalyst, and then catalyst or dehydration therefrom. 2-pyrrolidone can be obtained using an agent.

  The resin obtained by polymerizing the 2-pyrrolidone and the lactam having 5 to 7 carbon atoms may have a weight average molecular weight of 50 kg / mol to 200 kg / mol. At this time, when the weight average molecular weight of the resin in which 2-pyrrolidone and a lactam having 5 to 7 carbon atoms are polymerized is less than 50 kg / mol, there is a problem that the mechanical properties of the fiber product are deteriorated. When the weight average molecular weight exceeds 200 kg / mol, there is a problem that the viscosity during fiber spinning is high and the fluidity is poor.

  The nylon blend composition includes various stabilizers, lubricants, mold release agents, pigments, dyes, flame retardants, reinforcing agents, antioxidants, antistatic agents, conductive additives, EMI shielding agents, as required. One or more selected from the group consisting of crystal nucleating agents, antibacterial agents, deodorants, lubricants, and the like can be further included within a range that does not affect physical properties, appearance, and moldability.

  The present invention also provides a nylon fiber with improved moisture absorption and shrinkage produced from the nylon blend composition.

  The nylon fiber may have a moisture absorption rate of 5% to 10%.

  The shrinkage ratio of the nylon fiber may be 10% to 40%.

  The nylon fiber may have a strength of 3 g / d to 5 g / d.

  That is, the nylon fiber produced from the nylon blend composition according to the present invention is excellent in spinning processability, maintains a high moisture absorption rate, and has a low shrinkage rate and a high strength property, and the fiber cross section is low. It exhibits uniform characteristics, has no unevenness during post-processing to produce industrial and garment products, has excellent form stability, and is very useful as a textile material for industrial and garment applications. is there.

  In the present invention, 70 wt% to 95 wt% of a resin in which 2-pyrrolidone and a lactam having 5 to 7 carbon atoms are polymerized; and 5 wt% to 30 wt% of nylon 6 resin are melt-blended and then spun. Provided is a method for producing a nylon fiber having an improved shrinkage rate while being excellent in hygroscopicity and spinning processability. Examples of the resin obtained by polymerizing 2-pyrrolidone and a lactam having 5 to 7 carbon atoms include nylon 4,6 resin using ε-caprolactam as a lactam having 5 to 7 carbon atoms.

  The melt blending may be performed at 230 ° C to 270 ° C. At this time, the melt blending is performed at 230 ° C. to 270 ° C., so that the nylon 4, 6 resin and the nylon 6 resin are stable and effectively blended so as to be excellent in kneadability.

  In the spinning step, it is preferable to go through a heat setting process at 140 ° C. to 180 ° C. in order to improve the shrinkage rate of the manufactured nylon fiber, but is not limited thereto.

  Hereinafter, preferred examples will be presented to help understanding of the present invention. However, the following examples are provided only for easier understanding of the present invention, and the contents of the present invention are not limited by the following examples.

[Example]
Example 1

  (1) Production of resin (nylon 4, 6 resin) in which 2-pyrrolidone and ε-caprolactam are polymerized

25.5 g 2-pyrrolidone and 79.1 g ε-caprolactam as monomers, 8.4 g potassium hydroxide (KOH) as an alkaline catalyst, 1.76 g CO ₂ initiator and 1,6-hexamethylene diisocyanate as an isocyanate compound Nylon 4,6 copolymer was manufactured by adding 0.32 g of (1,6-hexaethylene diisocynate) and anionic polymerization. 2-Pyrrolidone and ε-caprolactam as unreacted monomers in the nylon 4,6 copolymer and potassium hydroxide (KOH) as an alkaline catalyst were purified with water. The pH was controlled by removing K ⁺ through ion exchange of purified water. Nylon 4,6 resin (Mw = 140 kg / mol) was finally produced by concentrating the pH-controlled water by reverse osmosis membrane and distillation to recover 2-pyrrolidone and ε-caprolactam as unreacted monomers. .

  (2) Production of nylon blend composition

  4.75 kg of nylon 4,6 resin produced in the above (1) and 0.25 kg of nylon 6 resin (KN-138 / Kolon) were mixed and melt blended at 235 ° C. to produce a nylon blend composition. The nylon blend composition was spun with a 36-hole spinning machine under the conditions of a spinning pressure of 100 kgf, a draw ratio of 1.15, and a heat setting temperature of 175 ° C. to finally produce a fiber yarn.

  The result of measuring the cross section of the produced fiber with an optical microscope is shown in FIG. As a result, it was confirmed that the cross section of the fiber was formed uniformly.

  Example 2

  Example 1 was repeated except that 4 kg of nylon 4,6 resin and 1 kg of nylon 6 resin were mixed.

  Example 3

  The same procedure as in Example 1 was performed except that 3.5 kg of nylon 4,6 resin and 1.5 kg of nylon 6 resin were mixed.

  Example 4

  The same procedure as in Example 1 was conducted except that 4 kg of nylon 4,6 resin and 1 kg of nylon 6 resin were mixed and the test was carried out at a heat setting temperature of 160 ° C.

  Comparative Example 1

  5 kg of the nylon 4,6 resin produced in (1) of Example 1 was used alone, and was carried out under the condition of a heat setting temperature of 160 ° C.

  Comparative Example 2

    The same operation as in Example 1 was conducted except that 5 kg of nylon 6 resin (KN-138 / Kolon) was used alone.

  Experimental example

  1. Moisture absorption measurement

  In order to measure the moisture absorption rate of the fibers obtained by spinning the nylon blend compositions of Examples 1 to 4 and Comparative Examples 1 and 2, 10 g of each fiber was prepared and placed in an oven at 105 ° C. for 35 minutes. deep. After removal from the oven, the dried fibers were weighed and the moisture absorption was calculated using the following formula:

  Moisture Retention (%) = (weight of fiber−weight of dried fiber) / weight of dried fiber × 100

  2. Boiling water shrinkage measurement

  In order to measure the boiling water shrinkage of the nylon blend composition of Examples 1 to 4 and the nylon resin spun by Comparative Examples 1 and 2, about 1 m of each raw yarn was sampled, and both ends were tied to a length of 50 cm. Then, after applying a certain initial load (0.1% of the thickness of the raw yarn), it was stored at constant temperature and humidity for 24 hours. The length of the raw yarn at this time is defined as the length of the original yarn before shrinkage. After maintaining the initial load, soaked in boiling water (90-95 ° C) for 30 minutes, wiped off moisture and stored at constant temperature and humidity for 24 hours. Then, the length of the raw yarn was measured and defined as the length of the original yarn after shrinkage.

  The boiling water shrinkage was calculated using the following formula:

  Boiling water shrinkage rate (%) = (length of raw yarn before shrinkage−length of raw yarn after shrinkage) / length of raw yarn before shrinkage × 100

  3. Strength measurement

  In order to measure the strength of the fibers obtained by spinning the nylon blend compositions of Examples 1 to 4 and the nylon resins according to Comparative Examples 1 and 2, the fibers were collected so that the number of twists and other original changes did not occur (100 mm ), The fiber was fixed to a clamp of a tensile strength tester (Universal tensile test machine (Instron)), and the tensile strength was measured by applying a sufficient force at a tensile speed of 200 mm / min.

  The measurement results of the moisture absorption rate, shrinkage rate, and strength as described above are summarized in Table 1 below.

  As shown in Table 1 above, the fibers produced from the nylon blend compositions according to Examples 1 to 4 have a moisture absorption rate of 5.0% to 7.4%, and thus maintain a high moisture absorption rate. I was able to confirm. In addition, as shown in Table 1 above, the fibers manufactured from the nylon blend compositions according to Examples 1 to 4 have a shrinkage ratio of 14% to 35%, and thus have low shrinkage characteristics. did it. In addition, as shown in Table 1 above, the fibers manufactured from the nylon blend compositions according to Examples 1 to 4 have a strength of 3.5 g / d to 4.11 g / d, and thus have high strength characteristics. It was confirmed that it had.

  On the other hand, since the fiber manufactured from the nylon 4,6 resin according to Comparative Example 1 has a high shrinkage rate of 45%, it can be confirmed that the characteristic of the low shrinkage rate is lowered. Since the fiber manufactured from the resin has a low moisture absorption of 4.5%, it was confirmed that the high moisture absorption was not maintained.

  Therefore, the fiber manufactured from the nylon blend composition according to the present invention has excellent spinning processability, maintains a high moisture absorption rate, has a low shrinkage rate and a high strength property, and has a uniform cross section of the fiber. In other words, there is no shrinkage non-uniformity phenomenon during post-processing for the production of industrial and clothing products, it is excellent in form stability, and is very useful as a fiber material for industrial and clothing.

  The above description of the present invention is given for illustrative purposes only, and for those who have ordinary knowledge in the technical field to which the present invention pertains, other specific details can be used without departing from the technical idea and essential features of the present invention. It will be appreciated that the form can be easily transformed. Therefore, it should be understood that the above-described embodiments are illustrative in all aspects and are not limited.

Claims (12)

2-pyrrolidone and 5- to 7-carbon lactam anionically polymerized by adding a CO ₂ initiator and an isocyanate compound under an alkali catalyst ; and 70% to 95% by weight of nylon 6 resin; A nylon blend composition for producing fibers having improved moisture absorption and shrinkage, comprising 30% by weight. The resin obtained by anionic polymerization of the 2-pyrrolidone and the lactam having 5 to 7 carbon atoms by adding a CO ₂ initiator and an isocyanate compound under an alkali catalyst is a nylon 4,6 resin. A nylon blend composition for producing fibers with improved moisture absorption and shrinkage. The nylon blend composition for fiber production with improved moisture absorption rate and shrinkage rate according to claim 1 or 2, wherein the 2-pyrrolidone or the lactam having 5 to 7 carbon atoms is obtained from biomass. When the 2-pyrrolidone and the lactam having 5 to 7 carbon atoms are anionically polymerized by adding a CO ₂ initiator and an isocyanate compound under an alkali catalyst, the weight average molecular weight is 50 kg / mol to 200 kg / mol. The nylon blend composition for fiber manufacture with improved moisture absorption rate and shrinkage rate according to any one of claims 1 to 3 . A nylon-based fiber with improved moisture absorption and shrinkage produced from the nylon blend composition according to any one of claims 1 to 4 . Nylon fiber moisture absorption and shrinkage is improved according to claim 5 moisture absorption of the nylon fibers is 5% to 10%. The nylon fiber having improved moisture absorption and shrinkage rate according to claim 5, wherein the shrinkage rate of the nylon fiber is 10% to 40%. 6. The nylon fiber with improved moisture absorption and shrinkage rate according to claim 5, wherein the nylon fiber has a strength of 3 g / d to 5 g / d. 2-pyrrolidone and a lactam having 5 to 7 carbon atoms are anionically polymerized by adding a CO ₂ initiator and an isocyanate compound under an alkali catalyst , and 70% to 95% by weight of a nylon 6 resin and 5% by weight of a nylon 6 resin A method for producing a nylon-based fiber with improved moisture absorption and shrinkage, wherein 30% by weight is melt blended and then spun. The resin obtained by anionic polymerization of the 2-pyrrolidone and the lactam having 5 to 7 carbon atoms by adding a CO ₂ initiator and an isocyanate compound under an alkali catalyst is a nylon 4 or 6 resin. Item 10. A method for producing a nylon fiber with improved moisture absorption rate and shrinkage rate according to Item 9. The method for producing a nylon fiber with improved moisture absorption and shrinkage rate according to claim 9 or 10, wherein the melt blending is performed at 230 ° C to 270 ° C. The method for producing a nylon fiber with improved moisture absorption rate and shrinkage rate according to any one of claims 9 to 11, wherein the spinning step undergoes a heat setting process at 140 ° C to 180 ° C. .