JP6134012B2 - Nylon latent crimped yarn with excellent stretch and cool feeling - Google Patents

Description

  The present invention relates to a nylon latent crimped yarn excellent in stretchability and cooling feeling. More specifically, on the cross section of the raw yarn, (i) nylon 64 random copolymer and (ii) nylon 6 polymer or nylon 66 Stretch nylon that exhibits excellent cool feeling due to excellent dyeability, fastness to dyeing and stretchability, and high official moisture content, as the polymer is composite-spun in a side-by-side shape. It relates to latent crimped yarn.

  Nylon stretch yarns have production techniques similar to polyester stretch yarns. However, polyester-based stretch yarns are widely used in applications such as tee shirts, jackets and trousers, and recently used in composite yarns with other materials. However, nylon stretch yarn is mainly used for outdoor wear, inner wear, and socks, and has a difference in usage.

  However, when polyester high-stretch yarn is used as a fabric material used with stretchable moisture-permeable and waterproof polyurethane film, there is a problem in dyeing fastness and there is a problem that dyeability, friction resistance, cool feeling, etc. are lowered. .

  As a result, recently, the use of nylon stretch yarns is increasing greatly for outdoor wear materials.

  As a first conventional technique used for producing nylon stretch yarns, there is a method of producing nylon 66 stretch yarns by drawing and twisting nylon 66 at a high temperature in the false twisting step.

  In the conventional method described above, nylon 66 semi-drawn yarn (POY) having a high melting point is subjected to low-speed false twisting at a high temperature by a pin false twist method or a disk false twist method, and crimped to an unoriented raw yarn by a physical method. The nylon 66 stretch yarn produced has a high crimp rate and exhibits stretchability on the fabric.

  However, in the case of the first conventional method described above, South Korea does not produce nylon 66 for clothing, but uses hexamethylenediamine, which is an expensive raw material, and imports it at a relatively high price compared to nylon 6. . For this reason, the manufacturing cost is increased, and the productivity is lowered because low-speed false twisting is performed at a high temperature. Moreover, since it has to have a high crimp rate at high temperature, there exists a problem that the probability that unevenness will generate | occur | produce will become high.

  The second conventional technology used to manufacture nylon stretch yarns is a composite of nylon 66 polymer and nylon 6 polymer, which have a difference of 4-5% in shrinkage, in a side-by-side shape on the cross section of the raw yarn. There is a method for producing a nylon latent crimped yarn by spinning.

  However, in the second conventional method described above, since the difference in shrinkage between the nylon 66 polymer and the nylon 6 polymer is as low as 4 to 5%, it is difficult for the crimp to appear naturally, and the crimp in the original yarn state is generated. There is a problem that the occurrence of crimping on the fabric is significantly reduced.

  Another conventional technique used for producing nylon stretch yarns is to produce nylon latent crimped yarns by composite spinning of nylon polymers having different relative viscosities (RV) in a side-by-side shape on the cross section of the original yarn. There is also a method. However, nylon spins at a high speed at a spinning speed of 3,000 m / min or more. For this reason, there is a problem that it is difficult to produce on a commercial scale due to the occurrence of a bending phenomenon of the yarn at the lower part of the spinneret due to the difference in relative viscosity, or the spinning speed is lowered to greatly reduce the spinnability and the yarn-making property.

  The purpose of the present invention is to produce a nylon latently crimped yarn with excellent dyeability, fastness to dyeing and stretchability, high official moisture content, good cold feeling, and excellent uniformity of raw yarn. An object of the present invention is to provide a nylon latent crimped yarn excellent in stretchability and cooling feeling, which can be produced at low cost and high productivity.

  In order to achieve the object as described above, in the present invention, nylon 64 random copolymer (A) and one polymer (B) selected from nylon 6 and nylon 66 are formed side by side on the cross section of the raw yarn. Nylon latent crimped yarn is produced by composite spinning.

  The nylon 64 random copolymer (A) is composed of 10 to 30 mol% of pyrrolidone which is a nylon 4 monomer and 70 to 90 mol% of caprolactam which is a nylon 6 monomer.

  The nylon latent crimped yarn according to the present invention is excellent in dyeability, dyeing fastness and stretchability, and has a high official moisture content, and thus exhibits a good cooling feeling.

  Further, the nylon latent crimped yarn according to the present invention is low in production cost, high in productivity, and excellent in yarn uniformity.

  Therefore, the nylon latent crimped yarn according to the present invention is particularly useful as a fabric material for outdoor wear used with a stretchable moisture-permeable waterproof polyurethane film.

  Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

  As shown in FIGS. 1 and 2, the nylon latent crimped yarn according to the present invention is made of a nylon 64 random copolymer (A) and a polymer (B) selected from nylon 6 and nylon 66 as a raw yarn. It is characterized in that it is compound-spun in a side-by-side shape on the cross section.

  1 and 2 are schematic views showing a cross section of a nylon latent crimped yarn according to the present invention.

  The nylon 64 random copolymer (A) is composed of 10 to 30 mol% of pyrrolidone as a nylon 4 monomer and 70 to 90 mol% of caprolactam as a nylon 6 monomer, and has a molecular weight of 70,000 to 120,000 g. The polydispersity index is 1-2.

  Nylon 64 random copolymer (A) is produced by caprolactam and 2-pyrrolidone anion addition polymerization, has a low degree of determinism of 50% or less, a low melting point, and a high moisture content. Therefore, it is difficult to use as engineering plastic. However, it is suitable for use in clothing with appropriate strength and elongation.

  On the other hand, nylon 46 polymer is produced by polycondensation of 1,4-diaminobutane and adipic acid, and has the highest deterministic degree, high melting point, and frictional resistance among nylons pressed at room temperature. Mainly used in engineering plastics because of its excellent deformation resistance, low deformation coefficient, and excellent resistance to oil and grease.

  In the present invention, the weight ratio of one polymer (B) selected from nylon 6 and nylon 66 to nylon 64 random copolymer (A) composite-spun in a side-by-side shape on the cross section of the raw yarn is 25 It is preferably ~ 50: 75-50.

  The nylon latent crimped yarn according to the present invention has a boiling water shrinkage of 30 to 50%, a crimp rate of 20 to 50%, and an official moisture content of 5 to 8%.

The nylon 64 random polymer (A) has a relative viscosity (RV) measured by the sulfuric acid viscosity method of 2.4 to 3.0, a melting point of 150 to 190 ° C., and a specific gravity of 1.11 to 1.13 g / cm. ³ .

  One polymer (B) selected from nylon 6 and nylon 66 has a relative viscosity (RV) measured by the sulfuric acid viscosity method of 2.4 to 2.7.

  Nylon 64 random copolymer (A) is an anionic or bulk content of caprolactam, a nylon 6 polymer monomer, and pyrrolidone, a nylon 4 polymer monomer, in a ratio of 70-90 mol% to 10-30 mol%. Obtained by polymerization. As the molar ratio of caprolactam increases, the properties of nylon 6 become stronger and the melting point is increased. However, the official moisture content is reduced and has the disadvantage of being equal to general nylon 6 and nylon 66 in the aforementioned properties. ing. Pyrrolidone can be obtained from cellulose by enzymatic degradation and is also widely known as a bio-based material. Nylon 4 is known as a butyrolactam polymer (also called 2-pyrrolidone or α-pyrrolidone) that forms a polymer while a 2-pyrrolidone ring is opened under specific conditions. ing. The high shrinkage polymer thus produced has a boiling water shrinkage of 30% to 60%, a melting point of 0 to 190 ° C., and a sulfuric acid viscosity when spinning with a general raw yarn. The relative viscosity (RV) measured using the method has a range of 2.4-3.0. Such partner viscosity is similar to that of nylon 6 and nylon 66. Therefore, when producing latent crimped yarn, it is possible to improve spinnability and use existing composite spinning equipment. It is possible to produce the yarn without major modification.

  Pyrrolidone, a nylon 4 monomer, is a bio-based raw material and can be used as an environmentally friendly material. Recently, in the high oil price era due to the depletion of fossil fuel, consumers interested in environmentally friendly materials are increasing rapidly. In addition, it is a substance that has the image of not destroying the natural environment when used for clothing, and is suitable as a future fiber to be used in the future, where resource depletion is expected.

  However, since pure nylon 4 has a high melting point, the processing temperature for processing and the range of decomposition temperature are very similar when melt spinning, and the processing is impossible. In addition, because of its high moisture content, it is not suitable for engineering plastics.

  When nylon 4 is used for clothing, it has a strong hydrophilic property because it contains more amide groups than general nylon. Therefore, the present invention uses nylon 64 random copolymer obtained by copolymerizing nylon 4 and nylon 6 at a certain ratio, lowers the melting point, secures the processing temperature, and controls the determinism to achieve high shrinkage performance. It was allowed to express. When a high shrinkage polymer that is a copolymer of nylon 4 and nylon 6 is used and side-by-side composite spinning is used, the moisture content increases due to the high shrinkage polymer that appears on the surface. Therefore, when the clothes touch the human skin, the touch can be softened and the comfort can be felt by the high moisture content. Also, by absorbing and maintaining the moisture of human skin, not only can you always feel comfort, but it is also possible to develop a cool sensation in the summer due to the higher moisture content compared to general nylon. It is the same context that cellulose-based fibers generally exhibit a better cooling sensation.

  Nylon 64 random copolymer is stable in spinnability and has a low spinning temperature. In the case of composite spinning with nylon 6, since spinning is possible even at a spinning temperature lower than that of nylon 66, an energy saving effect can also be provided.

  In the case of nylon 64 and nylon 610 in which the same molar amount of nylon 6 and nylon 4 are copolymerized, such a high shrinkage characteristic does not appear, but rather the water content decreases. However, in the case of nylon 64 random copolymer, the formation of molecular chains in the polymer is changed to a lander and high shrinkage appears. As a result, when performing side-by-side composite spinning, the nylon 4 copolymer undergoes more shrinkage in the form of a bimetal, and an effect like a latent winding axis can be exhibited. If there is a difference in shrinkage ratio due to processing, a spring-like structure will be formed using the yarn of spiral structure. Manufacturing is possible. Also, since the two polymers are nylon series, they can be dyed with acid dyes, and since they contain a large amount of amine groups that are dyeing sites, it is possible to produce latent crimped yarns with excellent dyeability and fastness. It is.

  Hereinafter, the present invention will be described in detail through examples and comparative examples.

  However, the scope of protection of the present invention is not construed as being limited to the following examples.

[Example 1]
Nylon 64 random copolymer (random co-polymer) obtained by anion polymerization of 30 mol% of pyrrolidone and 70 mol% of caprolactam and having a melting point of 170 ° C. and a relative viscosity (RV) of 2.6. Nylon 6 having a (RV) of 2.6 was discharged at a spinning temperature of 260 ° C. using a side-by-side composite spinning system and using each press machine. After spinning into a 50:50 weight ratio in a spin pack, it was cooled / solidified using a cooling chamber. An 85 denier / 24 filament semi-drawn yarn was manufactured by winding through a first godet roll and a second godet roll at a speed of 3000 m / min.

  The semi-drawn yarn wound in this way is drawn at a spinning speed of 500 m / min and a draw ratio of 1.26 by using a drawing winder, and a drawn yarn of 70 denier / 24 filament specifications is wound up to be a nylon latent crimp. Yarn was produced.

[Comparative Example 1]
Nylon 66 was manufactured using a general nylon first heater semi-drawn yarn (POY) production facility, and a half-drawn yarn of 85 denier / 24 filament was produced at a spinning speed of 3000 m / min. Set the temperature of the first heater to 220 ° C or higher, pass through a pin false twist type false twister at a draw ratio of 1.3 and a spinning speed of 300m / min. Manufactured.

[Comparative Example 2]
Nylon 6 and nylon 66 were discharged using the respective extruding machines and spun so as to be compounded in an area ratio of 50:50 in the spinning pack. Thereafter, the film was cooled / solidified using a cooling chamber and wound through a first godet roll and a second godet roll at a speed of 3000 m / min to produce a semi-drawn yarn.

  The semi-drawn yarn wound up in this way was drawn using a drawing winder at a spinning speed of 700 m / min and a draw ratio of 1.23 and wound up to produce a highly stretchable yarn.

  The physical properties in Table 1 were evaluated by the following methods.

(Boiling water shrinkage measurement method (in-house method))
1) After winding the sample to be measured on the frame 20 times, prepare the sample with the clip sandwiched between both. Create 3 samples per sample.
2) Tie both ends so that the length is 50 cm, apply a certain initial load, and measure the length.
The initial load is 1/10 g of the test yarn thickness (denier).
-For example, if the test yarn is 50 denier, suspend a 5 g weight.
-Measurement length: L ₀
3) Leave in a constant temperature and humidity atmosphere for 24 hours.
-About 25 ° C, 65%
-The initial load is maintained as it is.
4) Measure the length of the test yarn after standing.
- Measurement length: _{L 1}
-The initial load is maintained as it is.
5) Delay calculation formula-delay (L ₂ ) = (L ₀ −L ₁ ) / L ₀ × 100 (%)
6) The delay test yarn (L ₂ ) is immersed in boiling water (90 to 95 ° C.) for 30 minutes.
-Immerse the entire test yarn in boiling water.
-Keep the initial load as it is (make sure the weight under the initial load does not touch the bottom).
7) Take out the test yarn, wipe off the moisture, and leave it under a constant temperature and humidity atmosphere for 24 hours.
-About 25 ° C, 65%
-The initial load is maintained as it is.
8) Measure the length of the test yarn after standing.
-Measurement length: L3
-The initial load is maintained as it is.
9) Boiling water calculation formula Boiling water shrinkage ratio (L ₄ ) = (L ₂ −L ₃ ) / L ₂ × 100 (%)

(Crimp rate measurement method)
1. Sample preparation-After winding the sample to be measured on the frame 10 times, prepare the sample with the clip between both sides. Create 3 samples per sample.
2. When the temperature of the steam bath reaches a predetermined temperature, a sample is put in a glass guide that is fitted into a clip so that it can be put into the steam bath, and is carefully lifted into the steam bath.
3. Treat with boiling water for 20 minutes, then remove the sample to remove moisture and leave for 12 hours.
4). The initial load-displayed den / 25 g and the static load-displayed den * 2 g are calculated and measured by the following formula.
5. Apply static load + initial load and measure length after 2 minutes -L
6). Remove the static load and measure the length after 3 minutes with only the initial load -L ₁
7). Calculation formula Crimp rate = (L−L ₁ ) / L × 100

(Cool feeling measurement method)
1. Experimental environment: 20 ° C., 65% RH
2. Experimental equipment: KES-F7 Thermo Labo II (Kalto Tech)
3. Qmax value: A value obtained by measuring the amount of instantaneous electric power supplied for temperature correction when the fabric contacts the unit sensor.
4). Sample preparation: Using a circular knitting machine, the test fabric is knitted, smelted and dyed in the same manner, and then width-adjusted to prepare a test piece.

  The nylon latent crimped yarn of the present invention is useful as a garment yarn, particularly as a fabric material for outdoor wear.

It is the schematic which shows the cross section of the nylon latent crimped yarn which concerns on this invention. It is the schematic which shows the cross section of the nylon latent crimped yarn which concerns on this invention. It is an electron micrograph of the nylon latent crimped yarn of the present invention before weaving and processing. It is an electron micrograph of the nylon latent crimped yarn of the present invention that has been woven and processed.

A Nylon 64 random polymer B Nylon 6 polymer or nylon 66 polymer

Claims (6)

Nylon 64 random copolymer (A), which is a random copolymer of nylon 6 and nylon 4, and one polymer (B) selected from nylon 6 and nylon 66 are compound-spun in a side-by-side shape on the cross section of the raw yarn. Nylon latent crimped yarn excellent in stretch and cooling feeling, characterized by   The nylon 64 random copolymer (A) is composed of 10 to 30 mol% of pyrrolidone as a nylon 4 monomer and 70 to 90 mol% of caprolactam as a nylon 6 monomer, and has a molecular weight of 70,000 to 120,000 g. The nylon latent crimped yarn excellent in stretchability and cooling feeling according to claim 1, wherein the polydispersity index is 1-2.   The weight ratio of one polymer (B) selected from nylon 6 and nylon 66 to the nylon 64 random copolymer (A) composite-spun in a side-by-side shape on the cross section of the raw yarn is 25 to 50:75. The nylon latent crimped yarn excellent in stretchability and cooling feeling according to claim 1, wherein the nylon latent crimp yarn is.   The nylon latent crimped yarn has a boiling water shrinkage rate of 30 to 50%, a crimp rate of 20 to 50%, and an official moisture content of 5 to 8%. Nylon latent crimped yarn with excellent stretch and cool feeling. Nylon 64 random polymer (A) has a relative viscosity (RV) measured by the sulfuric acid viscosity method of 2.4 to 3.0, a melting point of 150 to 190 ° C., and a specific gravity of 1.11 to 1.13 g. The nylon latent crimped yarn excellent in stretchability and cooling feeling according to claim 1, which is / cm ³ . The polymer (B) selected from nylon 6 and nylon 66 has a relative viscosity (RV) measured by a sulfuric acid viscosity method of 2.4 to 2.7. Nylon latent crimped yarn excellent in stretchability and cooling feeling as described.

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