KR930011340B1 - Process for the preparation of elastic fiber - Google Patents

Abstract

adding the ester-forming three functional compd. of formula (I) (where R1,R2,R3=-OH, -CO2H, or -R5OH (R5; alkyl group above C1)) with the amount of 0.1-0.5 mol% against the added aromatic carboxylic acid compn., and the nucleating agent of formula (II) (where M; alkali earth metal of valence 1, R1,R2; alkyl group above C12) with amount of 0.16-1.0 mol% against added aromatic carboxylic acid compn. to each polyetherester block copolymer composed of 10/90 - 30/70 of hard segment of aromatic polyester and soft segment of polyether to obtain elastic material; melt spinning and cooling-solidifying; and drawing with the range of 0.40X <= Y <= 0.70X (where X; breaking multiplying rate, Y; range of drawing ratio).

Description

Method of Making Elastic Fiber

The present invention relates to a method for producing elastic fibers by melt spinning using a polyether ester block copolymer system.

In general, rubber fibers and spandex fibers containing polyurethane as the main component are generally used as elastic fibers, but rubber fibers have limited physical properties, mechanical properties, and chemical stability.

On the other hand, spandex fibers have high mechanical properties and are capable of producing cetastic fibers (20 to 40d), and are thus widely used in knitted fabrics because they can impart high elastic properties without damaging the feel of the surface.

Among these spandex fibers, the fiber produced by dry spinning or wet spinning is particularly excellent in physical and mechanical properties, and thus requires complicated equipment at high cost, and is produced by dry spinning and wet spinning in spite of poor productivity. It is common.

On the other hand, it is known to manufacture spandex by melt spinning method which is relatively low in manufacturing cost and high productivity in simple equipment, but in general, polyurethane is obtained by melting polyurethane at relatively low temperature by using polyurethane with softening point due to its extremely poor thermal stability. It is also known that thermal and physical properties are inferior because of loss.

In general, the composition of the polyether ester block copolymer is composed of a hard segment and a soft segment, and the main component of the hard segment is an aromatic polyester, among which polybutylene terephthalate is generally used. It is also known that the main component of aliphatic polyether is polytetramethylene glycol or the like.

In the polyetherester block copolymer, the elastic properties of the crystallized hard segment portion are small crystals and are widely and thinly distributed in the non-crystalline soft segment, and the hard segment portion catches the amorphous portion, thus acting as an intersection point of the rubber-like network structure. Will be

In practice, such copolymers cannot be broadly classified into three regions: the crystallized hard segment portion, the soft segment portion which is crystallized when the stress occurs, and the amorphous soft segment portion. It is also known that it is greatly influenced by the intersect point size of the network structure.

It is also well known to increase the content of soft segments in order to improve the elastic properties in the production of elastic fibers. However, when the content of the soft segment is increased (more than 70% of all polymers), the fraction of the hard segment is relatively small, thereby reducing the role of the entanglement point of the rubbery network structure, which not only weakens the elasticity but also decreases the crystallinity. Due to the difficulty of solidification, fusion between yarns and fusion with the spinning device occurs from the spinneret to the winding, which leads to inability to wind up.

In order to solve this problem, it may be considered to lower the content of the soft segment or to lengthen the cold zone after the extrusion of the oil. When the content of the soft segment is lowered, the elastic properties of the elastic yarn obtained are greatly weakened and the cooling zone after the melt extrusion is extended. The longer the resistance, the greater the resistance of the air, the greater the tension on the ejection yarn, so that single yarns are generated and the windingability is deteriorated.

Therefore, the present invention is prepared by melt spinning using a polyether ester block copolymer having excellent elastic fibers, that is, excellent thermal stability, light resistance and high elastic properties without defects of the conventional spandex fibers described above, and interlocking polyester fibers It is an object of the present invention to provide a method for producing an elastomeric fiber having high stretch and recovery properties on a surface after carrying out teaching, teaching, or training.

The present inventors reached the present invention as follows while devising means to solve the following problems.

In other words, by adding a small amount of chemical crosslinking in the fiber while increasing the content of the soft segment, the nucleus agent improves the role of the entanglement point of the rubbery network structure, and in this case, a nucleating agent is added to compensate for the decrease in crystallinity due to the introduction of the crosslinking. When preparing an elastomeric fiber by preparing a polyether ester block copolymer and melt spinning by the method of through-hole, the elastic fiber is elongated at a certain range of breaking magnification in order to remove the permanent deformation portion remaining unrecovered upon extension and recovery. And relaxed heat treatment have been developed.

In general, when the crystallinity is low, time fusion from the spinneret to the coiling or welding between the spinnerets occurs as described above, which leads to an unwinding state. By adding a nucleating agent, the crystallization of the hard segment is promoted to improve the crystallinity. In addition to solving the problems of the physical properties of the entanglement point by the crystal phase was further increased to produce an elastic fiber having excellent elastic properties, wherein the elastic fibers do not recover slightly when stretched, recovered, the permanent In order to remove the deformed portion, the surface of the polyester fiber can be stretched between 0.4 times and 0.7 times the breaking ratio of the melt-spun elastomeric fiber, and then subjected to relaxation heat treatment. Could.

Accordingly, the present invention provides a block copolymer in the production of a polyether ester block copolymer having an aromatic polyester as a hard segment and a polyether as a soft segment in which the weight fraction of the hard segment / soft segment is 10/90 to 30/70. An elastomer obtained by adding the ester-forming trifunctional compound represented by the following general formula (I) and the crystal nucleating agent represented by the following general formula (II) to the copolymer by the amount represented by the following formula (III) was melt-spun and cooled and solidified. The present invention relates to a method for producing an elastomeric fiber which is subsequently stretched in the range represented by the following formula (IV) and subsequently subjected to a relaxation heat treatment.

Where R ₁ , R ₂ , R ₃ = -OH or -CO ₂ H or -R ₅ OH (R ₅ = C ₁ or more alkyl group)

M = 1-valent alkaline earth metal R ₁ , R ₂ = C ₁₂ or more alkyl group

(III) a. The amount of the crosslinking agent added is 0.1 to 0.5 mol% based on the added aromatic carboxylic acid component.

b. The amount of the nucleating agent added is 0.16 to 1.0 mol% based on the added aromatic carboxylic acid component.

(IV) 0.40 X ≤ Y ≤ 0.70 X where X is the breaking ratio of the unstretched elastic fiber and Y is the stretching range

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

As the hard segment, aromatic dicarboxylic acids and ester-forming derivatives thereof and ethylene glycol, tetramethylene glycol, hexamethylene glycol and ester-forming derivatives thereof are generally used. In the present invention, aromatic dicarboxylic acids and ester-forming derivatives thereof are used. Dimethyl terephthalate was used as the sex derivative and tetramethylene glycol was used as the glycol component.

In addition, polyoxytetramethylene glycol having an average molecular weight of 500 to 5000 and ester-forming derivatives thereof are generally used as the soft segment. In the present invention, polytetramethylene glycol having an average molecular weight of 2000 is used, and the soft segment weight ratio is 70 for all polymers. It was made to be -90%.

In addition, ester-forming trifunctional compounds were those represented by general formula (I). Specifically, trimethyl-1, 3, 5-benzenetricarboxylate, trimeric acid, 2, 3-bis (acetyloxy ) Benzoic acid, resatophenone, 1, 3, 5-triethylolbenzene and the like were used, and 0.1 to 0.5 mol% was added to the added aromatic dicarboxylic acid component.

In this case, when the addition amount is less than 0.1 mol%, the elastic properties were lowered when the elastomeric fiber was prepared. When the addition amount was less than 0.5 mol%, the crosslinking density was too high. It was not a satisfactory level.

In addition, the addition time during the polymerization process of the ester-forming trifunctional compound can be added at any stage before the polycondensation is completed, but when the high polymerization time of the high polymerization polyether ester block copolymer having an intrinsic viscosity of 1.2 or more is slow, Since the stability of the intermediate pressure is significantly reduced and the elastic properties are halved, it is preferable to add the intrinsic viscosity at 0.5 or less.

As the nucleating agent, one represented by General Formula (II) was used. Specifically, Mark N-10 (MARK NA-10, ADEK A ARGUS Chem. Japan) having a molecular weight of 384 and Mark N-11 (molecular weight of 508) were used. MARK NA-11) was used.

In this case, it is determined that the amount of the added amount is sufficient to promote the crystallization of the hard segment. In the present invention, 0.16 to 1 mol% is suitable for the aromatic dicarboxylic acid and the ester-forming derivative thereof.

When the added amount was less than 0.16 mol%, it did not contribute significantly to the crystallization promoting effect of the hard segment, and up to about 1 mol% was judged to be sufficient for the crystallization promoting effect of the hard segment.

In addition, the addition time of the nucleating agent could be added at any stage of the polymerization process. In addition, titanium oxide (TiO ₂ ) generally used as an additive, a hindered phenol compound as an antioxidant, and a benzotriazole compound as an ultraviolet absorber were used.

Obtained by drying in a rotary vacuum dryer using the polyetherester block copolymer polymer described above and melt spinning at a spinning speed of 500 to 1000 m / min with a 0.5 mm diameter general nozzle using a screw extrusion type spinner The elastomeric fiber could easily be spun even with a high soft segment content of the polymer.

The elastic fibers obtained by stretching in the range of 0.4 to 0.7 times at the elastic fiber breaking ratio thus prepared are the surfaces having elasticity and good elastic properties after crosslinking with polyester fibers and heat treatment in dyeing and processing. Preparation was possible.

In addition, the elastic fibers obtained by stretching as described above have many potentials in terms of elasticity, so that knitting and weaving can be easily performed even when using a knitting machine and a twisting machine that do not have separate stretch steepness.

At this time, the stretching ratio requires 0.4 times or more of the breaking ratio of the elastic fibers in the melt-stretched and unstretched state after solidification. The elastic properties of the elastic fibers obtained by insufficient orientation crystallization of the molecular chains of the hard segment at low magnifications of less than 0.4 times If it is not sufficiently improved, the stretching process becomes a problem if it is more than 0.7 times.

In addition, when the fiber is partially relaxed by using a loosening roller during stretching, and then subjected to a continuous heat treatment while winding, the elastic fiber obtained by the present invention is particularly improved in elasticity and recovery of elastic fibers, and it is possible to give more excellent elasticity and recovery characteristics to the knitted fabric obtained after knitting. have.

The present invention is described in detail with reference to the following Examples.

However, the present invention is not limited to the examples.

The physical property measurement method used in the Example and the comparative example is as follows.

* Intrinsic Viscosity: Polymer was calculated from solution viscosity using a mixture of phenol and T.C.E (tetrachloroethane) at a concentration of 1.2% at 35 ° C.

* Crystallinity: The crystallization of the aromatic polyester portion of the elastomer composition is calculated by X-ray.

* Strength, elongation: After using an Instron tensile tester, the sample was elongated at a rate of 1000% per minute, and the strength was shown as strength per denier when judged, and elongation was expressed as elongation at break (%).

* Breaking Ratio: (Exposure / 100) +1

* Instant stretch recovery rate: Apply the load of 50% elongation to 10cm of sample, stop for 5 seconds after 100% elongation, remove the load and immediately read the length ℓ of the sample and calculate it by the following equation.

Preparation of catalyst slurries used during polymerization; Magnesium diacetate 4 whiskers were dried at 150 ° C. for 24 hours, 11.2 g of the mixture was mixed with 200 ml of methanol, refluxed for 2 hours, cooled and cooled, and then 44.4 ml of tetrabutyl titanate and 150 ml of tetramethylene glycol were added. Stirred for time to prepare a slurry.

Example 1

194.18 parts by weight of dimethyltetraphthalate, 135.18 parts by weight of tetramethylene glycol, 403.98 parts of polytetramethylene glycol having a number average molecular weight of 2000, 0.756 parts by weight of pyrogar trireacetate, and 3 parts of catalyst slurry in a reactor equipped with a stirrer, a distillation machine, and a nitrogen introduction pipe. The part was put into a reactor, the reaction temperature was increased to 200 ° C. over 2 hours while the ester exchange reaction was performed at 160 ° C., and 85% or more of theoretical amount of methanol was distilled off, and 0.05 parts by weight of Irganox 1010 and 0.1 weight of Iganox 1222 were used. After adding parts and raising internal temperature to 240 degreeC, Mark N-1-1. 92 parts by weight was added, and the reaction was carried out for 30 minutes under weak vacuum and 4 hours under high vacuum of 0.1 mmHg or less.

Then 0.21 parts of tinuvin-327 (tinuvin-327) was added and the reaction was terminated after 15 minutes stirring.

As for the obtained polymer, the soft segment component was 71 weight% with respect to the whole polymer, the intrinsic viscosity was 1.2 dl / g, and the crystallinity was 34%. An elastic fiber of 160 deniers of fineness was produced using the obtained polymer using a nozzle having a diameter of 0.5 mm and a 5-hole nozzle in a screw extrusion type spinning machine at a discharge rate of 12 g / min and a winding speed of 700 m / min.

At this time, the elastic fiber obtained was 1.65 g / d, elongation was 520%, 10% t elongation recovery was 85%.

Example 2

The elastic fiber obtained in Example 1 was cold drawn using a loosening roller at a magnification of 6.2 times 0.45 times (= 2.79), and a loose heat treatment at 100 ° C. resulted in 104 fine deniers and a strength of 1.75 g / d, elongation at 540%, 100% elongation showed 94% of instantaneous elongation recovery.

Comparative Example 1

116.51 parts by weight of dimethyl terephthalate, 81.12 parts by weight of tetramethylene glycol, 402.49 parts of polytetramethylene glycol with a number average molecular weight of 2000, and 1.8 parts by weight of crushed slurry were placed in a reactor equipped with a stirrer, a type group, and a nitrogen introduction pipe at 160 ° C. After transesterification, the mixture was heated to 200 ° C. over 2 hours, and then 90% or more of theoretical amount of methanol was distilled off. Then, 0.03 parts of Iganox 1010 and 0.06 parts by weight of Iganox were added, and the inner temperature was raised to 240 ° C., followed by weak vacuum. The reaction was carried out for 30 minutes under a high vacuum of 0.1 mmHg or less for 4 hours.

Then 0.13 parts of Tinuvin-327 was added and the reaction was terminated after 15 minutes stirring. The obtained polymer had 83 weight% of the soft segment component with respect to the whole polymer, and the intrinsic viscosity was 1.08.

The polymer was wound in a screw extrusion type spinning machine using a nozzle having a diameter of 0.5 mm and a 5-hole nozzle at a discharge rate of 12 g / min and a spinning speed of 700 m / min, and the overall physical properties of the elastic fiber obtained at this time are shown in Table 1.

Comparative Example 2

The reaction was carried out in the same manner as in Example 1 except that Mark N-A-10 was not used.

Comparative Example 3

The same reaction was carried out in Example 1, except that 0.756 parts by weight of pyrogar triacetate was not used.

[Comparative Example 4]

The reaction was carried out in the same manner as in Example 1 except that the addition amount was reduced to 0.126 parts by weight instead of 0.756 parts by weight of pyrogar triacetate.

[Comparative Example 5]

The reaction was carried out in the same manner as in Example 1 except that the addition amount was reduced to 0.384 parts by weight instead of 1.92 parts by weight of Mark N A-10.

Comparative Example 6

In Example 1, it reacted similarly to Example 1 except having increased the addition amount to 1.512 weight part instead of 0.756 weight part of pyro gar triacetate.

The physical properties of the elastic fibers produced by the Examples and Comparative Examples are shown in Table 1 below.

TABLE 1

Claims (1)

In producing a polyether ester block copolymer having a hard segment / soft segment having a weight fraction of 10/90 to 30/70 using an aromatic polyester as a hard segment and a polyether as a soft segment, Elastomer formed by adding the amount represented by the following formula (III) to the ester-forming trifunctional compound represented by the general formula (I) and the crystal nucleating agent represented by the following general formula (II) is melt-spun and cooled to solidify the following formula After stretching in the range shown by (IV), the relaxation heat processing is performed continuously, The manufacturing method of the elastic fiber characterized by the above-mentioned. Wherein R ₁ , R ₂ , R ₃ = -OH or -CO ₂ H or -R ₅ OH (R ₅ = C ₁ or more alkyl group) Wherein M = 1 valent alkaline earth metal R ₁ , R ₂ = C ₁₂ or more alkyl group. (III) a. The amount of the crosslinking agent added is 0.1 to 0.5 mol% based on the added aromatic carboxylic acid component. b. The amount of the nucleating agent added is 0.16 to 1.0 mol% based on the added aromatic carboxylic acid component. (IV) 0.40 X ≤ Y ≤ 0.70 X where X is the breaking ratio of the unstretched elastic fibers and Y is the stretching range.