JPS61289121A - Fiber having elasticity and production thereof - Google Patents

Abstract

PURPOSE:To obtain an elastic fiber having excellent heat-stability, light resistance and flexural fatigue resistance, by melt-spinning a polymer composed of undecamethylenediamine, etc., terephthalic acid, etc., and poly(alkylene oxide) glycol, etc., and drawing the fiber at a specific draw ratio. CONSTITUTION:The objective fiber can be produced by melt-spinning a polyether ester amide polymer and/or polyether amide polymer derived from (A) un decamethylenediamine and/or dodecamethylenediamine, (B) terephthalic acid and/or cyclohexane-1,4-dicarboxylic acid (equimolar amount to the component A), (C) a poly(alkylene oxide) glycol and/or poly(alkylene oxide) diamine having a number-average molecular weight of 300-6,000 and (D) a 4-20C dicarboxylic acid, cooling and solidifying the spun fiber and drawing the fiber successively or continuously at a draw ratio larger than 0.5 times the breaking elongation of the elastic fiber.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to melt-spun elastic fibers that are effective for imparting stretchability to fabrics by cross-knitting, inter-weaving, inter-twisting, etc. It relates to its manufacturing method.

[Prior Art] Conventionally, rubber latex fibers and spandex fibers containing polyurethane as a main component have been used as elastic fibers.

Rubber latex fibers have the disadvantage of poor physical properties, mechanical properties, and chemical stability, which limits their uses.

On the other hand, spandex fibers can be made into thin elastic fibers (e.g. 20 to 40 deniers) with high mechanical properties, so they can impart high elastic properties without impairing the feel of the fabric. It is expected to be widely used in knitting and fabrics. Among these spandex fibers, fibers produced by dry spinning or wet spinning have particularly excellent physical and mechanical properties. Many spandex fibers are manufactured using the wet spinning method.

On the other hand, it is known that spandex fibers can be produced by the melt spinning method, which is low in spinning cost, uses simple equipment, and has high productivity, but polyurethane has extremely poor thermal stability, so polyurethane with a lower softening point is used. Melt spinning must be carried out at relatively low temperatures, and therefore only elastic fibers with poor thermal and physical properties and inferior quality can be obtained.

[Problems to be Solved by the Invention] Therefore, the present invention provides an excellent elastic fiber that does not have the drawbacks of the conventional spandex fibers described above, that is, it is manufactured by melt spinning, and has good thermal stability, cold resistance, and bending fatigue resistance. Our main purpose is to provide high quality elastic fibers with excellent light resistance.

Another object of the present invention is to provide elastic fibers that are excellent in dyeability with acid dyes and metal-containing dyes, in order to improve color development when used in interweaving or interweaving with polyamide fibers.

In general, the present invention utilizes conventionally known polyester amide ether elastic fibers (Japanese Patent Publication No. 45-9193).
Another object is to provide a method by which elastic fibers can be obtained which have better mechanical and elastic properties than those of the present invention.

[Means for Solving the Problems and Effects] These objects of the present invention are as follows: (A) undecamethylene diamine and/or dodecamethylene diamine; acid and/or
or cyclohexane-1,4-dicarboxylic acid, (C
) Poly(alkylene oxide) L, glycol and/or poly(alkylene oxide) diamine having a number average molecular weight of 300 to 6000, and (D) having 4 carbon atoms.
~20〉.

Polyester ester derived from dicarboxylic acid
, - Steramide polymer and/or polyether;
1′): 1 fiber; and the polyether ester a
・、・□、) Midopolymer and/or polyether amide polymer
()°゛) (゛After melt-spinning Lima and solidifying it by cooling, this elastic range
)■1□ At a magnification of 0.5 times or more than the fiber rupture magnification, sequential
Elastic fibers are produced by stretching 1゜'1゛ or continuously.
; or, after the above-mentioned stretching, by successively or continuously relaxing heat treatment.
) 1; A method for producing elastic fibers.

The polyetheresteramide polymer and/or polyetheramide polymer used in the present invention is a copolymer derived from the components (A), (B), (C) and (D) described above.

The polyamide hard segment of the polyether ester amide in the present invention is a polyamide unit mainly composed of the above-mentioned components (A) and (B). Aliphatic diamines such as octamethylene diamine, decamethylene diamine, adipic acid,
Aromatic dicarboxylic acid units such as azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and isophthalic acid may be included.

The above components (A) and (B) are used in substantially equimolar amounts, and may be prepared in advance in the form of a salt, or may be provided in a substantially equimolar mixture during the polymerization step. . In particular, in the case of a reaction system that does not cause phenomena such as sublimation or distillation out of the system under the polymerization reaction conditions of diamines and dicarboxylic acids, it is not necessary to use the salt as a salt in advance, but in general,
Use in salt form gives good results.

Poly(alkylene oxide) glycols having a number average molecular weight of 300 to 6,000 include polyethylene glycol, poly(1,2- and 1,3-propylene oxide)
Glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, block or random copolymers of ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, among others, Poly(tetramethylene oxide) glycol is preferably used because of the physical properties of polyether esteramide, which is excellent in heat resistance, water resistance, mechanical strength, elastic recovery, and the like.

The number average molecular weight of this poly(alkylene oxide) glycol can be used within the range of 300 to 6,000, but in reality, it is preferable to use poly(alkylene oxide) glycol within this range to avoid coarse phase separation during polymerization and to have excellent low-temperature properties and mechanical properties. It is sufficient to select and use a molecular weight range. This optimum molecular weight range differs depending on the type of poly(alkylene oxide) glycol. For example, in the case of polyethylene glycol, the molecular weight range is 300~
6000, particularly preferably 1000 to 4000, and
In the case of poly(propylene oxide) glycol, a molecular weight range of 300 to 5000, particularly preferably 500 to 3000 is preferable, and in the case of poly(tetramethylene oxide) glycol, a molecular weight range of 500 to 3000, particularly 500 to 2500 is preferable. .

In addition, as a poly(alkylene oxide) diamine having a number average molecular weight of 300 to 6,000, the hydrogen of the hydroxyl group (-〇H>) at both ends of the above-mentioned poly(alkylene oxide) glycol compound is replaced with an aminoalkyl group (-RNH2
) can be mentioned. Note that R above means an alkylene group having 2 or more carbon atoms.

The dicarboxylic acids having 4 to 20 carbon atoms used as the component (D) include terephthalic acid, isophthalic acid, naphthalene-2,6-dica-levonic acid, naphthalene-2,
Aromatic dicarboxylic acid such as 7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, sodium 5-sulfoisophthalate M: 1,
Alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid; and succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedioic acid ( Mention may be made of aliphatic dicarboxylic acids such as decanedicarboxylic acid). Among them, dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, and dodecadiic acid,
It is preferably used in terms of the color tone and physical properties of the resulting elastic fibers.

Polyether ester amide polymer and/or polyether amide polymer formed by copolymerizing these components are
It is obtained that the amount of copolymerization of polyetherester units and polyetheramide units derived from poly(alkylene oxide) glycol and/or poly(alkylene oxide) diamine and dicarboxylic acid is 40 to 90% by weight. Preferred for enhancing the properties of elastic fibers.

If the copolymerization amount is less than 40% by weight, the flexibility and elastic recovery properties will be insufficient, and if it exceeds 90% by weight, the high temperature properties and mechanical properties will be insufficient.

The polymerization method for producing the polyether ester amide polymer from the above components is not particularly limited, and any conventional method may be used. For example, after preparing a nylon salt from component (8) and component (B), it is reacted with component (D) to produce a polyamide prepolymer with carboxylic acid groups at both ends, and this prepolymer is mixed with poly(alkylene oxide) glycol. A method of reacting under vacuum, or the nylon salt,
Each component (C) and (D) is charged into a reaction tank, and a carboxylic acid-terminated polyamide prepolymer is produced by heating and reacting at high temperature in the presence or absence of water, and then under normal pressure or reduced pressure. There is a way to proceed with polymerization. Alternatively, there is a method in which the nylon salt, components (C) and ([)) are simultaneously charged into a reaction tower, melt polymerized, and then polymerized all at once under high vacuum. It is preferable in that there is little coloring.

Alternatively, components (A) and (B) may be directly subjected to the reaction without preparing a nylon salt from components (^) and (B) in advance.

The method for polymerizing this polyether ester amide is as follows:
Since this is a polyester type vacuum polymerization method, some sublimable components such as adipic acid are distilled off outside the reaction system during polymerization. For this reason, the above-mentioned sublimable components should be added in large amounts in advance to avoid deviations between the amount of polymerization raw materials charged and the polymer composition, as well as the molar balance with poly(alkylene oxide) glycol and/or adipic acid. It is preferable to charge and polymerize.

In order to roughly improve the heat resistance and light resistance of the polymer obtained by polymerization by the above-mentioned method, Japanese Patent Application Laid-Open No. 60-15455
Publication No. 15456/1983, Japanese Patent Application Laid-Open No. 1988-15456
49060, JP 60-49061, JP 60-53557@, JP f) B2O5355
It is preferable to use stabilizers (antioxidants, light stabilizers, etc.) known from No. 8 Publication M etc. alone or in combination of two or more.

Examples of the antioxidant include hindered phenol compounds such as N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid amide): 4,4'-bis Aromatic amine compounds such as (4-α,α-dimethylbenzyl)diphenylamine; phosphite compounds such as nidris-2,4-di-tert-butylphenyl phosphite; sulfide compounds such as dilaurylthiodipropionate ; Examples include copper salts such as copper iodide.

Examples of light stabilizers include hindered amine compounds such as bis(2,2,6゜6-tetramethyl-4-piperidinyl) sebacate, and examples of ultraviolet absorbers include 2(2'-hydroxy Examples include -3'-tert-butyl-5'methylphenyl)-5-chlorobenzotriazole.

The polymer thus obtained is melt-spun in a conventional manner, and the spun fibers are cooled and solidified.

After melt-spinning and cooling and solidifying to obtain elastic fibers, the elastic fibers are stretched at a ratio of 0.5 times or more than the rupture ratio of the elastic fibers, and the resulting elastic fibers are wound and knitted with other fibers. Elasticity is developed by heat treatment during dyeing and finishing of interlacing, weaving, and finishing, and it is possible to obtain a fabric with good stretchability.

In addition, since the elastic fiber obtained by drawing in this way has a large part of its elasticity latent, it cannot be used even if a knitting machine or a twisting machine without an active elongating yarn feeding device is used. It can be easily inter-knitted, inter-woven or inter-twisted. Moreover, since the elasticity is partially hidden, the apparent modulus is high, so there is no unevenness during inter-knitting, inter-weaving, and inter-twisting, and it is easy to manufacture uniform products. You can do it with

The magnification during this stretching must be at least 0.5' times the breaking magnification of the unstretched elastic fiber after melt-spinning assimilation. Since the chains cannot be sufficiently oriented and crystallized, the elastic properties of the resulting elastic fibers cannot be sufficiently improved. Note that this stretching ratio may be such that fiber breakage during stretching does not pose a problem, and for example, the upper limit thereof may be about 0.8 times.

The above-mentioned breaking ratio refers to a value measured by the following method.

The melt-spun, cooled and solidified elastic fibers are taken up by a roller, then wound up at substantially the same speed as this take-up speed to obtain unstretched elastic fibers, and the elastic fibers are tested in a tensile tester. , the section length is 10 cm, and the tensile speed is 500%/min, and the magnification at break is measured, and this value is taken as the rupture magnification.

When winding is performed subsequent to the above-mentioned stretching, the fibers may be wound in a partially relaxed state using a relaxation roller that rotates at a lower speed than the stretching roller.

If elastic fibers are manufactured by sequentially or continuously performing relaxation heat treatment and winding after the above-mentioned stretching, the elasticity, recovery properties, and fatigue resistance of the obtained elastic fibers will further improve. Particularly good stretchability and recovery properties can be imparted to the knitted fabrics obtained by such methods.

The above-mentioned stretching and heat treatments may be performed either sequentially or continuously, but it is preferable to perform them continuously in order to improve the uniformity of the resulting product.

[Example] Undecamethylene diamine and cyclohexane-1,4-
Nylon salt aqueous solution with dicarboxylic acid (a degree 63.6wt
%) 43. i parts by weight, 11.9 parts by weight of adipic acid, 64.8 parts by weight of poly(tetramethylene oxide) glycol having a number average molecular weight of 810, "Irganox" 109
8 (Antioxidant) 0.5 parts by weight and antimony trioxide catalyst 0.1 parts by weight were placed in a reaction vessel equipped with a helical ribbon stirring blade, and the mixture was replaced with nitrogen and heated and stirred at 265°C for 1 hour to form a homogeneous transparent material. After forming a solution, the polymerization conditions were brought to 1 mmHg or less and 265° C. in 1 hour according to a vacuum program. When the reaction was carried out under these conditions for 4.0 hours, a viscous colorless and transparent molten polymer was obtained, and this polymer was made into a gut and discharged into water to form a chip. The resulting polyether ester amide was heated at 25°C in orthochlorophenol.
, the relative viscosity (ηr) measured at 0.5% concentration is 1.94
The melting point determined by DSC was 208°C.

This polyether ester amide was dried in a rotary vacuum dryer, and "Irganox" was used as a heat stabilizer and light stabilizer.
-1010Q-, 2wt%, “MARK” PEP-4
0.2wt%, "Tinuvin" 326 0.1w
t%, and "5anol" 13770 Q, '1
wt% was added and mixed.

The obtained polyether ester amide chips were melt-spun at Merck temperature of 240°C and die pack temperature of 235°C, cooled and solidified, then filled with silicone oil and rolled at a winding speed of 5.
At 00m/min, fineness is 38. It was wound up as an O denier elastic fiber. The strength of the obtained elastic fiber is 1.000/
(1. The elongation was 375%, indicating good elasticity.

[Effects of the Invention] Since the elastic fiber according to the present invention is produced by a melt spinning method, it is possible to easily obtain elastic fibers with high productivity and fine fineness, thereby providing high-quality and practical elastic fibers. be able to. Moreover, since the elastic fiber according to the present invention has excellent thermal stability, it can be stably spun even when melt-spun at high temperatures (for example, about 250°C), and has excellent elasticity with high elastic properties. It can be a fiber.

In general, the elastic fiber according to the present invention has less deterioration in elastic properties at low temperatures and also has excellent bending fatigue resistance. Moreover, since this elastic fiber has good dyeability with acid dyes and metal-containing dyes, it can be dyed well even when used together with polyamide fiber.

Since this elastic fiber also has excellent light resistance, it is possible to obtain an elastic fiber that does not yellow due to light and has excellent retention of mechanical properties and elastic properties.

Moreover, according to the method of the present invention, elastic fibers with better properties than conventional polyesteramide ether elastic fibers can be easily produced.

Further, according to the method of the present invention, after melt spinning and cooling solidification, the elastic fibers obtained by stretching at a magnification of 0.5 times or more than the breaking magnification of the elastic fibers and winding the elastic fibers can be interwoven with other fibers. In this case, elasticity is developed by heat treatment during dyeing and finishing after cross-knitting, and a fabric having good stretchability can be obtained. The elastic fibers obtained by stretching in this way have a large part of their elasticity latent, so they can be easily stretched even when using a knitting machine or a twisting machine that is not equipped with an active stretching yarn feeding device. It can be inter-knitted, inter-woven or inter-twisted. Moreover, because the elasticity is partially hidden,
Since the apparent modulus is high, unevenness does not occur during cross-knitting, cross-weaving, and cross-twisting, making it possible to easily produce a well-balanced product. Furthermore, after the above stretching,
When elastic fibers are produced by performing relaxation heat treatment and winding, the elasticity, recovery properties, and fatigue resistance of the resulting elastic fibers are greatly improved, so it is particularly suitable for knitted fabrics obtained by inter-knitting, inter-weaving, etc. It can provide elasticity and recovery properties.

Claims (5)

[Claims] (1) (A) undecamethylene diamine and/or dodecamethylene diamine, (B) terephthalic acid and/or cyclohexane-1,4-dicarboxylic acid in a substantially equimolar amount as the diamine component, (C) number Poly(alkylene oxide) glycol and/or poly(alkylene oxide) diamine having an average molecular weight of 300 to 6,000, and (D) having 4 to 2 carbon atoms.
1. An elastic fiber obtained by melt-spinning a polyether ester amide polymer and/or a polyether amide polymer derived from 0 dicarboxylic acid. (2) (A) undecamethylene diamine and/or dodecamethylene diamine, (B) terephthalic acid and/or cyclohexane-1,4-dicarboxylic acid in a substantially equimolar amount as the diamine component, (C) number Poly(alkylene oxide) glycol and/or poly(alkylene oxide) diamine having an average molecular weight of 300 to 6,000, and (D) having 4 to 2 carbon atoms.
Polyether ester amide polymer and/or polyether amide polymer derived from 0 dicarboxylic acid is melt-spun, cooled and solidified, and then sequentially or A method for producing elastic fibers characterized by continuous stretching. (3) (A) undecamethylene diamine and/or dodecamethylene diamine, (B) terephthalic acid and/or cyclohexane-1,4-dicarboxylic acid in a substantially equimolar amount as the diamine component, (C) number Poly(alkylene oxide) glycol and/or poly(alkylene oxide) diamine having an average molecular weight of 300 to 6,000, and (D) having 4 to 2 carbon atoms.
Polyether ester amide polymer and/or polyether amide polymer derived from 0 dicarboxylic acid is melt-spun, cooled and solidified, and then sequentially or continuously at a magnification of 0.5 times or more of the breaking magnification of the elastic fiber. 1. A method for producing elastic fibers, which comprises stretching the fibers and then sequentially or continuously subjecting them to relaxation heat treatment. (4) Component (C) has a number average molecular weight of 500 to 3000
The elastic fiber according to claim 1, which is poly(tetramethylene oxide) glycol. (5) Component (C) has a number average molecular weight of 500 to 3000
The method for producing an elastic fiber according to claim 2 or 3, characterized in that the fiber is poly(tetramethylene oxide) glycol.