JPS61289126A - Crimping conjugate fiber - 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) derived from (A) undecamethylenediamine and/or dodecamethylenediamine, (B) terephthalic acid and/or cyclohexane-1,4-dicar boxylic 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 300-6,000 and (D) a 4-20C dicarboxylic acid and a crystalline polyamide (a low-shrinkage polymer). No thermal decomposi tion, 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 characteristics, but at the cost of low strength due to polyurethane's poor heat resistance, they also have low strength when made into fabric products. There is a problem in that the strength and elastic properties are greatly reduced by 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 has superior elasticity, crimp development, low friction, knitting properties, heat resistance, and light resistance compared to conventionally known polyamide composite fibers (such as JP-A-58-104220@publication). Another object of the present invention is to provide an excellent conjugate fiber which has excellent stretch back, peeling resistance, texture, and feel that can be used in knitted and woven products such as socks.

[Means for Solving the Problems and Effects] These objects of the present invention are to provide a low shrinkage polymer made of crystalline polyamide, (A) undecamethylene diamine and/or dodecamethylene diamine, and (B) the above diamine. (C) poly(alkylene oxide) glycol and/or poly(alkylene oxide) diamine having a number average molecular weight of 300 to 6,000; , and (D) a high shrinkage polymer derived from a dicarboxylic acid having 4 to 20 carbon atoms and consisting of a polyether ester amide polymer and/or a polyether amide polymer. This is achieved by making it into fibers.

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 normal pressure dyeability and high color development. 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 CD), and the hard segment is a copolymer derived from components (A) and (B).
It is a polyamide unit mainly composed of components, but a small amount of copolymerized components include hexamethylene diamine,
It may contain aliphatic diamines such as heptamethylene diamine, octamethylene diamine, and decamethylene diamine, and aromatic dicarboxylic acid units such as adipic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and isophthalic acid. .

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.

One of the components (C), with a number average molecular weight of 300 to
6000 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 oxide Examples include block or random copolymers of ethylene oxide and tetrahydrofuran, and block or random copolymers of ethylene oxide and tetrahydrofuran.
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.

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~
6,000, particularly preferably 1,000 to 4,000.

In addition, in the case of poly(propylene oxide) glycol, the molecular weight range is 300 to 5000, especially 500 to 3000.
is preferable, and furthermore, in the case of poly(tetramethylene oxide) glycol, the molecular weight range is 500 to 3000.
, particularly preferably 500 to 2500.

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 (-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 acids such as diphenoxyethanedicarboxylic acid and sodium 5-sulfoiphthalate; Fats such as 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and dicyclohexyl-4,4'-dicarboxylic acid. Mention may be made of cyclic dicarboxylic acids; and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, and dodecanedioic acid (decanedicarboxylic acid). Among them, terephthalic acid, isophthalic 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, and 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 peel resistance with 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 OXIO-3mo+/a or more. Roughly, 3. OXlo-3mal/(preferably 11 or more, particularly 3.5X10'mol/
g or more is preferable in order to obtain extremely 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, after preparing a nylon salt from components (A) and (I3), it is reacted with component (D) to produce a polyamide prepolymer having carboxylic acid groups at both ends, and this prepolymer is added with poly(alkylene oxide) glycol. Alternatively, the nylon salt and each of the components (C) and (D) are placed in a reaction tank and reacted by heating at high temperature in the presence or absence of water to form a carboxylic acid terminal. producing a polyamide prepolymer;
There is a method in which the polymerization is then proceeded under normal pressure or reduced pressure.

Alternatively, there is a method in which the nylon salt, components (C), and (D) are simultaneously charged into a reaction tank, melt-polymerized, and then polymerized all at once under high vacuum. This is preferable in that there are few.

Alternatively, the components (A) and (B) may be directly subjected to the reaction without preparing a nylon salt from the components (A) 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 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, JP-A-60-15456, JP-A-60-
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-hydroxyhydrocinnamide); Aromatic amine compounds such as (4-α, α-dimethylbenzyl)diphenylamine,
; phosphite compounds such as tris-2,4-di-tert-butylphenyl phosphite; sulfide compounds such as nidilaurylthiodipropionate; and 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 ultraviolet absorbers include 2(2'-hydroxy- 3'-tertiary butyl-
Examples include 5'methylphenyl)-5-chlorobenzotriazole.

The high-shrinkage polymer thus obtained is melt-composite-spun with a low-shrinkage polymer in a conventional manner, and the spun fibers are solidified by cooling and then drawn sequentially or continuously. In the spinning process, the problem of unwinding due to elastomer welding of the wound yarn, troubles in the spinning and knitting processes due to the high friction of elastomer, and problems with product texture can be solved by cooling and solidifying. This can be improved by applying an oil agent such as silicone to the 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 fiber obtained in this way is mixed or woven alone or with other fibers, the crimp is completely developed by heat treatment during dyeing or finishing after the weaving, and it has good elasticity. It can be made of fabric.

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

Undecamethylene diamine and cyclohexane-1,4-
Nylon salt aqueous solution with dicarboxylic acid (m degree 63.6wt
%) 55.6 parts by weight, adipic acid 9.5 parts by weight, poly(tetramethylene oxide) glycol with a number average molecular weight of 640 41.7 parts by weight, "Irganox" 1098 (
0.5 parts by weight of antioxidant) and 0.1 parts by weight of antimony trioxide catalyst were placed in a reaction vessel equipped with a helical ribbon stirring blade, and the atmosphere was replaced with nitrogen and heated and stirred at 265°C for 1 hour to form a homogeneous transparent solution. After that, according to the decompression program, 1
The polymerization conditions were brought to 265° C. and less than 1 mmHg in hours. When the reaction was carried out under these conditions for 3.5 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, Q.
The relative viscosity (ηr) measured at a concentration of 5 wt% was 1.82, and the melting point by DSC was 239°C.

This polyether ester amide was dried in a rotary vacuum dryer, and "Irganox" was used as a heat stabilizer and light stabilizer.
-1010Q, 2*'t%, ") to JAR" PEP
-4Q, 2wt%, "Tinuvin" 326 0.
1wt%, and '5anol' LS770 Q,
1 wt% 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 2.62 was used.

Both of the above-mentioned polymers were melted at a melter temperature of 270°C and a cap pack temperature of 265°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. , 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,
Stockings were knitted at 65 Orpm using a KT-34 knitting machine manufactured by Hizan Seiki. 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 that has fine crimps, excellent stretchability, and recovery properties [useful for making li products]. , 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.

Furthermore, the composite fiber according to the present invention has superior stretchability, crimp development, low friction, knitability, heat resistance, and light resistance to conventionally known polyamide composite fibers, and also has superior properties in socks. It has excellent stretch back, peeling resistance, texture, and feel as a knitted or woven product.

Claims (5)

[Claims] (1) A low shrinkage polymer made of crystalline polyamide, (
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 average molecular weight 300 to 6000 poly(alkylene oxide) glycol and/or poly(alkylene oxide) diamine, and (D) 4 to 2 carbon atoms
1. A crimpable conjugate fiber obtained by melt-spinning a polyether ester amide polymer and/or a high shrinkage polymer made of a polyether amide polymer derived from a dicarboxylic acid of 0.0. (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. The crimpable composite fiber according to claim 1, characterized in that: (3) The low shrinkage polymer contains 95 wt% nylon 6.
The crimpable conjugate fiber according to claim 1, which is a polyamide containing the above. (4) The low shrinkage polymer is 90wt of nylon 66.
% or more of the crimpable conjugate fiber according to claim 1, wherein the crimpable conjugate fiber is a polyamide containing % or more. (5) Crimping properties according to claim 1, wherein the component (C) that induces the highly shrinkable polymer is poly(tetramethylene oxide) glycol having a number average molecular weight of 500 to 3,000. Composite fiber.