JPS61289127A - Conjugate fiber having crimping property - Google Patents

Abstract

PURPOSE:To obtain the titled fiber having high stretchability and useful for stockings, etc., by carrying out the composite melt spinning using a crystalline polyamide as the low-shrinkage component and a specific polyether ester amide polymer, etc., as the high-shrinkage component. CONSTITUTION:The objective fiber can be produced by the composite melt spinning of a polyether ester amide polymer and/or polyether amide polymer (a high-shrinkage polymer) derive from (A) the diamine of formula (R is 1-4C alkylene or alkylidene; R1 and R2 are H or CH3), (B) a 6-15C aliphatic or alicyclic carboxylic acid (essentially equimolar amount to the diamine component A), (C) a polyalkylene oxide glycol and/or polyalkylene oxide diamine having a number-average molecular weight of 300-2,000 and (D) a 4-20C dicarboxylic acid, and a crystalline polyamide (a low-shrinkage polymer). No thermal decomposition, foaming or gelatinization of the elastomer occurs during spinning.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a composite fiber having self-crimping properties. In particular, the present invention relates to self-crimping composite fibers made by melt-spinning polyamide and elastomer, which have high elasticity and are useful for socks and the like.

[Prior Art] Conventionally, self-crimpable polyamide composite fibers include fibers made by laminating nylon 6 or nylon 66 with copolymerized nylon, and fibers made by laminating nylon 6 and polyurethane into an eccentric core. Sheath-shaped composite fibers have been used. In particular, the latter is an extremely stretchable fiber that takes advantage of polyurethane's excellent elastic recovery properties, and is produced as a material for high-quality socks.

However, composite spinning of polyurethane and nylon 6 is prone to thermal decomposition foaming and gelation due to the thermal instability of polyurethane.In order to avoid this, melt composite spinning is carried out at a relatively low temperature, but this is still extremely difficult for polyurethane. The temperature is high, and advanced silk spinning technology is required for stable production.

In addition, composite fibers of nylon 6 and polyurethane have high elasticity and high recovery properties, but at the cost of low strength due to polyurethane's poor heat resistance, they are difficult to make into fabric products. There is a problem in that strength and elastic properties are significantly reduced by intermediate setting and finishing setting.

Further, composite fibers of nylon 6 and polyurethane have a problem in that they have poor dyeing properties against acid dyes and metal-containing dyes that are generally used for dyeing nylon fibers, making it difficult to dye them in deep colors.

[Problems to be Solved by the Invention] Therefore, the present invention eliminates the drawbacks of the above-mentioned conventional self-crimping composite fibers of polyamide and elastomer.
The main objective is to provide an excellent self-crimping conjugate fiber useful for making knitted fabric products with excellent stretchability and recovery properties.

The first objective is to provide a composite fiber that can be stably melt-spun without causing problems such as thermal decomposition, foaming, or gelling of the elastomer during melt-spinning.

The second objective is to provide a highly elastic conjugate fiber that has sufficiently high strength even when the fineness is reduced.

The third objective is to provide a composite fiber that does not cause interfacial delamination between the polyamide and elastomer even if it is made into a knitted or woven product and is worn for a long period of time, and does not cause functional deterioration or appearance deterioration during use.

The fourth object is to provide a composite fiber that has excellent color development even when dyed with acidic dyes or metal-containing dyes under normal pressure.

The fifth object is to provide a conjugate fiber that does not cause a decrease in strength or elastic properties due to the thermal properties of the elastomer even when it is made into a fabric product and is subjected to intermediate setting or finishing setting.

The sixth objective is to provide a composite fiber that has improved the problem of reduced light resistance of product fabrics, such as photo-yellowing of elastomers.

Furthermore, the present invention utilizes conventionally known polyamides.
It has superior elasticity, crimp development, low friction, knitting properties, heat resistance, and light resistance compared to composite fibers (Japanese Unexamined Patent Publication No. 58-104220), and is also suitable for use in socks, etc. Another object of the present invention is to provide an excellent composite fiber having excellent stretch back, peeling resistance, texture, and touch as a textile product.

[Means and effects for solving the problems] These objects of the present invention are to provide a low shrinkage polymer made of crystalline polyamide, and (A) the following formula (1) % formula % (wherein R is carbon (B) aliphatic or alicyclic having 6 to 15 carbon atoms in a substantially equimolar amount to the diamine component; R1 and R2 represent H or CH3; Group dicarboxylic acid, (C) number average molecular weight 300-2000
of poly(alkylene oxide) glycol and/or poly(alkylene oxide) diamine, and (
D) Composite fibers having crimpability obtained by melt-composite spinning a high shrinkage polymer consisting of a polyether ester amide polymer and/or a polyether amide polymer derived from a dicarboxylic acid having 4 to 20 carbon atoms; This is achieved by

The low-shrinkage polymer of the composite fiber according to the present invention is made of crystalline polyamide in order to improve the abrasion resistance, durability, feel and feel of the product when worn, and to obtain high color development due to its ability to be dyed under normal pressure. Among them, nylon 6 or nylon 66 is preferable. In particular, nylon 6, which has a lower melting point and higher melt viscosity than nylon 66, is generally preferable for composite spinning in view of the relationship with the melting characteristics of the high shrinkage polymer.

The polyether ester amide polymer and/or polyether amide polymer used as the high shrinkage polymer in the composite fiber according to the present invention is the above-mentioned (A), (B),
It is a copolymer derived from components (C) and (D).

This polyether ester amide is composed of an amorphous high-To polyamide hard segment and a low-Tg polyether soft segment, and the former segment provides an elastomer that not only provides transparency but also has excellent high-temperature properties.

R in the diamine component represented by formula (I>) is alkylene or alkylidene having 1 to 4 carbon atoms, typically methylene, isopropylene, etc. Such diamines include trans and/or cis-4 ，
4'-diaminodicyclohexylmethane can be cited as a representative example. Examples of aliphatic or alicyclic dicarboxylic acids having 6 to 15 carbon atoms include aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid, and 1,4-cyclohexanedicarboxylic acid and 1,2-cyclohexane dicarboxylic acid. There are alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-dicarboxylic acid, but azelaic acid, sebacic acid, and dodecanedioic acid are preferred from the viewpoint of polymerizability.

Component (A) and component (8) 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.

One of the components (C), with a number average molecular weight of 300 to
2000 poly(alkylene oxide) glycols include polyethylene glycol, poly(1,2- and 1,3-propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, ethylene oxide and propylene Examples include block or random copolymers with oxide, block or random copolymers with ethylene oxide and tetrahydrofuran, and among others, heat resistance,
Poly(tetramethylene oxide) glycol is preferably used because of the physical properties of polyether ester amide, which is excellent in water resistance, mechanical strength, elastic recovery, and the like.

In addition, as a poly(alkylene oxide) diamine having a number average molecular weight of 300 to 2,000, the hydrogen of the hydroxyl group (-OH) 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.

Examples of dicarboxylic acids having 4 to 20 carbon atoms used as the component (D) include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, and naphthalene-2,7-dicarboxylic acid.
dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid,
Aromatic dicarboxylic a such as diphenoxyethanedicarboxylic acid, sodium 5-sulfoisophthalate; alicyclic dicarboxylic such as 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid acids; and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedic acid (decanedicarboxylic acid). Among them, terephthalic acid, inphthalic acid, 1
, 4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, and dodecadiic acid are preferably used from the viewpoint of the color tone and physical properties of the resulting fibers.

The polyether ester amide polymer and/or polyether amide polymer formed by copolymerizing these components is
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 30 to 70% by weight. Preferable for enhancing the properties of composite fibers.

If the copolymerization amount is less than 30% by weight, the stretchability and elastic recovery properties will be insufficient; conversely, if it exceeds 70% by weight, the high temperature properties, mechanical properties, and peeling resistance from the low-shrinkage polymer will be insufficient. .

In order to improve the peeling resistance from the low shrinkage polymer, which is polyamide, the concentration of amide bonds in the high shrinkage polymer should be 2. It is preferable that it is OXl 0-3 mol/g or more. In general, it is preferable that the ratio is 3.0×10 to 3 mol/17 or more in order to obtain high peeling resistance.

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, component (A), component (B), and ((
)) component to produce a polyamide prepolymer having carboxylic acid groups at both ends, and reacting this prepolymer with poly(alkylene oxide) glycol under vacuum, or (A).
I (B), (C) and ([)) components are simultaneously charged into a reaction tank, melt polymerized, and then polymerized all at once under high vacuum, or (A) component and (B) component Examples include a method of preparing a salt from and then proceeding with polymerization of this salt together with components (C) and (D).
l The latter two methods are especially recommended because of the first point that high-quality polyetheresteramide can be obtained.6 Note that this method of polymerizing polyetheresteramide is a polyester type vacuum polymerization method, so there are no During polymerization, sublimable components such as adipic acid are partially distilled off. 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 further improve the heat resistance and light resistance of the polymer obtained by polymerization by the above 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 60-53558
It is preferable to use stabilizers (M-forming inhibitors, light stabilizers, etc.) known from Japanese Patent Publication No. 2003-100003 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); Aromatic amine compounds such as (4-α,α-dimethylbenzyl)diphenylamine, phosphite compounds such as nidris-2,4-di-tert-butylphenyl phosphite, and sulfide compounds such as nidilaurylthiodipropionate. copper chloride etc.
Examples include copper salts.
1 In addition, as a light stabilizer,
Examples include hindered amine compounds such as bis(2,2,6゜6-tetramethyl-4-piperidinyl) sebacate, and ultraviolet absorbers such as 2(2'-hydroxy-3'-tert-butyl-5 'methylphenyl)-5
-chlorobenzotriazole and the like.
- The high-shrinkage polymer thus obtained is melt-composite-spun with a low-shrinkage polymer in a conventional manner, and the spun fibers are cooled and solidified, and then drawn sequentially or continuously. The problem of unwinding problems due to elastomer welding of the wound yarn during the spinning process,
Problems caused by the high friction properties of elastomers in the spinning and knitting processes, as well as problems in product texture, can be improved by applying an oil agent such as silicone to the cooled and solidified yarn. However, in order to essentially solve these problems, the composite form of the fiber should be an eccentric core-sheath composite with an elastomer as the eccentric core, and the outer surface of the elastomer should be completely covered with crystalline polyamide, a low-shrinkage polymer. Coating is preferred.

When the composite fibers obtained in this way are woven alone or with other fibers, the crimp is completely developed by heat treatment during dyeing and finishing after the weaving, and good elasticity is achieved. It can be a fabric having

[Example] A polyether ester amide used as a highly shrinkable polymer was produced by polymerizing in the following method.

4.4'-diaminodicyclohexylmethane 20.8
Parts by weight, Dodeca 29839.4 parts by weight, number average molecular weight 6
40 poly(tetramethylene oxide) glycol 4
6.0 parts by weight, 0.5 parts by weight of ``Irganox'' 1098 (!! antioxidant), and 0.5 parts by weight of antimony trioxide catalyst.
05 parts by weight was charged into a reaction vessel equipped with a helical ribbon stirring blade, the atmosphere was replaced with nitrogen, and the mixture was heated and stirred at 270°C for 1 hour to obtain a homogeneous and transparent solution. polymerization conditions. When the reaction was carried out under these conditions for 2.5 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 obtained polyether ester amide was dissolved in orthochlorophenol at 25°C and 0.05°C.
The relative viscosity (ηr) measured at a concentration of 5 wt% is 1. d8, and the glass transition point measured by TMA was 125°C.

This polyether ester amide is dried in a rotary vacuum dryer, and "IrganOX" is used as a heat stabilizer and light stabilizer.
-1010Q, 2wt%, “)IARK” PEP-
40.2wt%, "Tinuvin" 326 0.1
wt%, and '5anol'13770 0.1v
t% was added and mixed.

On the other hand, as a low shrinkage polymer, titanium oxide is used at 0.03
A nylon 6 polymer containing sulfuric acid with a relative viscosity of 2.70 was used.

Both of the above-mentioned polymers were heated at a Merck temperature of 270'C and a silver bag temperature of 270°C, so that the weight ratio of the high-shrinkage polymer (eccentric core part) to the low-shrinkage polymer (eccentric sheath part) was 52:48. Then, melt composite spinning was performed, followed by drawing and winding to obtain a 20 denier, 2 filament eccentric core/sheath composite yarn.

The spinning and drawing state at this time was stable, and there was no yarn breakage during spinning and drawing.

This composite yarn and the conventional nylon 6/elastomer composite yarn using polyurethane as the elastomer,
It was knitted into stockings using a KT-341ii machine manufactured by Hyozan Seiki at 650 rl)m. The knitting properties were extremely good.

The stockings after dyeing and finishing showed extremely good elasticity and recovery. In addition, the composite yarn obtained here has higher strength than conventional polyamide/elastomer composite yarn, has better dyeing properties and light resistance, and has improved the problem of yellowing.

[Effects of the Invention] The self-crimping conjugate fiber according to the present invention is an excellent self-crimping conjugate fiber useful for making knitted fabric products with fine crimping, excellent elasticity and recovery properties, It has the following excellent properties.

Firstly, it can be stably melt-spun without causing problems such as thermal decomposition, foaming, or gelling of the elastomer during melt composite spinning.Secondly, it has high elasticity, which has sufficient strength even at fine fineness. Thirdly, even if the product is knitted and woven and worn for a long period of time, there will be no interfacial delamination between the polyamide and elastomer, and there will be no loss of functionality or deterioration of appearance during use. ,Fourthly, it has excellent color development even when dyed with acidic dyes or metal-containing dyes under normal pressure.
Fifthly, even when intermediate setting or finishing setting is performed on a fabric product, there is no decrease in strength or elasticity due to the thermal properties of the elastomer.Sixthly, the product does not suffer from light yellowing of the elastomer. The problem of decreased light resistance of fabrics has been improved.

Roughly, the composite fiber according to the present invention has superior stretchability, crimp development, low friction, knitting performance, heat resistance, and light resistance to conventionally known polyamide composite fibers, and furthermore, It has excellent stretch back, peeling resistance, texture, and feel for knitted and woven products such as socks.

Claims (5)

[Claims] (1) A low-shrinkage polymer made of crystalline polyamide, (A) The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (However, in the formula, R is a carbon number of 1 to 4 (B) an aliphatic or alicyclic dicarboxylic acid having 6 to 15 carbon atoms in a substantially equimolar amount to the diamine component; (C) poly(alkylene oxide) glycol and/or poly(alkylene oxide) diamine having a number average molecular weight of 300 to 2000, and (D) a polyether ester amide polymer derived from a dicarboxylic acid having 4 to 20 carbon atoms. A composite fiber having crimpability obtained by melt-composite spinning a highly shrinkable polymer consisting of a polyetheramide polymer and/or a polyetheramide polymer. (2) The high-shrinkage polymer and the low-shrinkage polymer are combined into an eccentric core-sheath shape, and the high-shrinkage polymer forms an eccentric core and the low-shrinkage polymer forms an eccentric sheath. A composite fiber having crimpability according to claim 1, characterized in that: (3) The low shrinkage polymer contains 95 wt% nylon 6.
A composite fiber having crimpability according to claim 1, which is a polyamide containing the above. (4) The low shrinkage polymer is 90wt of nylon 66.
% or more of polyamide, having crimpability according to claim 1. (5) The component (A) that induces the highly contractile polymer is 4,4'-diaminodicyclohexylmethane, and/or the component (B) and the component (D) are dodecanedioic acid, and 2. The crimpable composite fiber according to claim 1, wherein the component (C) is poly(tetramethylene oxide) glycol having a number average molecular weight of 500 to 1,000.