JPS61289125A - Conjugate fiber having self-crimping property - Google Patents

Abstract

PURPOSE:To obtain the titled conjugate 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 high-shrinkage polymer consisting of a polyether ester amide polymer and/or polyether amide polymer derived from (A) a 6-20C aliphatic diamine, (B) a 6-15C aliphatic dicarboxylic acid (essentially equimolar amount to the aliphatic diamine 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 low-shrinkage polymer consisting of a crystalline polyamide. A conjugate fiber having sufficiently high tenacity even at fine denier can be produced without causing the thermal decomposition, foaming, gelatinization, etc., of the elastomer.

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 poor dyeing properties against acid dyes and metal-containing dyes that are generally used for dyeing nylon fibers, and are difficult to dye 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 purpose of this invention 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 W4 fiber that can be stably melt-spun without causing problems such as thermal decomposition, foaming, or gelation of the elastomer during melt-spinning.

The second purpose 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 at 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, and low friction properties compared to conventionally known polyamide composite fibers (Japanese Patent Laid-Open No. 58-104220, etc.).
It has patty knitting properties, heat resistance, and light resistance, and is also suitable for socks, etc.
Another object of the present invention is to provide an excellent composite fiber having excellent stretch back, J-peel resistance, texture, and touch as a knitted or woven product.
L.

[Means for solving the problems and effects] These objects of the present invention are to
1, a low shrinkage polymer and (A) having 6 to 20 carbon atoms;
an aliphatic diamine, (B) an aliphatic dicarboxylic acid having 6 to 15 carbon atoms in a substantially equimolar amount to the aliphatic diamine, (
C) Poly(alkylene oxide) glycol and/or having a number average molecular weight of 300 to 2000
'□・/or poly(alkylene oxide) diamine, and (D) a polyether ester amide polymer derived from a dicarboxylic acid having 4 to 20 carbon atoms. High.

Self-rolling made by melt-spinning a shrinkable polymer
This is achieved by using composite fibers with amazing shrinkage properties.
1. do.
, 11.: The low shrinkage polymer of the composite fiber according to the present invention is manufactured by
(□(゛It is necessary to use crystalline polyamide in order to improve abrasion resistance, durability, feel and texture when hanging, and to obtain normal pressure dyeability and high color development.
Among them, nylon 6 or nylon 66 is preferred. In particular, in relation to the melting properties of high-shrinkage polymers, nylon 6, which has a lower melting point and higher melt viscosity than nylon 66,
Most preferred for composite spinning.

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).

Examples of the component (A) include hexamethylene diamine, heptamethylene diamine, octamethylene diamine, decamethylene diamine, nonamethylene diamine, dodecamethylene diamine, hexadecamethylene diamine, and the like. In addition, the other component (B) is:
Adipic acid, pimelic acid, speric acid, azelaic acid,
Examples include sebacic acid, undecanedioic acid, dodecanedioic acid, and brassylic 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.

Polyamide units derived from the above components (A) and (B) include nylon 6.6, nylon 6.9, nylon 6.10, nylon 6.12, nylon 8.6,
Nylon 8/10. Nylon 10.6, Nylon 10.
10. Nylon 11/6, Nylon 11/10. Nylon 11/12, Nylon 12/6, Nylon 12/10
．． Nylon 12.12 or the like is preferably selected.

The reason why m and n of the nylon m-n used in this way is limited to the above range is mainly due to the relationship between the physical and chemical properties of the polymer and the polymerization properties, but especially the elastomer properties and chemical properties at high temperatures. From the viewpoint of characteristics, it is generally preferable for m+n to be larger.

For example, if m+n is too small, such as m<5 or n<6, the affinity with the component (C) decreases, and a homogeneous high-performance elastomer cannot be obtained. Among them, preferred polyamide units are nylon 6.10. They are nylon 6.12, nylon 11.6, and nylon 12.6. Furthermore, depending on the purpose and application, these amide-forming components can be used in combination, and other amide-forming components can be copolymerized and used for purposes such as controlling the melting point of polyether ester amide. This is also permissible in a small amount range.

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 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 in the range of 300 to 2000, but in reality, it is preferable to use a number within this range that does not cause coarse phase separation during polymerization and has 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.

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 acids such as diphenoxyethane dicarboxylic acid and sodium 5-sulfoisophthalate; alicyclic dicarboxylic acids such as 1,4-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, and dicyclohexyl-4,4'-dicarboxylic acid. Acids: Mention may also be made of aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedioic acid (decanedicarboxylic acid). Among them, terephthalic acid, isophthalic acid,
Dicarboxylic acids such as 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, whereas if it exceeds 70% by weight, the high temperature properties, mechanical properties, and peeling resistance from the low shrinkage polymer will be insufficient. Not.

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. 'OX 10' mol/(] or more is better.Roughly, 3.OXlo-3mo I/
g or more, particularly 3.5X10'
It is preferable that the mo is 110 or more in order to obtain extremely high peeling resistance.

From the above ingredients, polyether ester amide poly
, 47 is not particularly limited, and any conventional method may be used. For example, after preparing a nylon salt from components (A) and (B), it is reacted with component (D) to create a polyamide prepolymer with 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. There is a method of producing a polyamide prepolymer and then proceeding with polymerization under normal pressure or reduced pressure. Alternatively, there is a method in which the above-mentioned nylon salt, components (C) and ([)) are simultaneously charged into a reaction tank, melt-polymerized, and then polymerized all at once under high vacuum. It is preferable in that there is little coloring.

Alternatively, the (A) ci and the (8) component may be directly subjected to the reaction without preparing the nylon salt from the (8) component and the CB) component 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 are prepared in advance so that there is no deviation between the charged amount of polymerization raw materials and the polymer composition, and also in the molar balance with poly(alkylene oxide) glycol and/or adipic acid. It is preferable to charge a large amount for polymerization.

Heat resistance of polymer obtained by polymerization by the above method
5. .

In order to further improve light resistance and
1゛)' No. 60-15455, Japanese Patent Application Laid-open No. 60-1545
,, r:・1゛1 No. 6, JP-A-60-49060, JP-A-60-49060, JP-A-60-49060
(; 5 Sho 60-49061, Japanese Unexamined Patent Publication Sho 6
0-535'') Publication No. 57, Japanese Patent Application Laid-open No. 60-53558, etc.
1 ((, Stabilizers (antioxidants, light stabilizers, etc.) known by
・11!・,・ and) are preferably used alone or in combination of two or more.
□゛Pa; Yes.
1;・)1. As this antioxidant, for example, N, N'-□“
”5
,,1' dirt phenolic compound; 4,4'-bis(4);
- Aromatic amine compounds such as α, α-dimethylbenzyl) diphenylamine; Phosphite compounds such as tris-2,4-di-tert-butylphenyl phosphite;
Examples include sulfide compounds such as dilauryl thiodipropionate; 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.

66.6 parts by weight of undecamethylenediamine adipate aqueous solution with a concentration of 67.4 wt%, terephthalic acid 13.
1 part by weight, number average molecule! 49.8 parts by weight of poly(tetramethylene oxide) glycol 1632, 0.5 parts by weight of "Irganox" 1098 (antioxidant) and 0.05 parts by weight of antimony trioxide catalyst were placed in a reaction vessel equipped with a helical ribbon stirring blade. After purging with nitrogen and heating and stirring at 265°C for 1 hour to obtain a homogeneous and transparent solution, the solution was reduced to lmmHg or less in 1.5 hours at 265°C according to the vacuum program.
The polymerization conditions were brought to ℃. 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 had a relative viscosity (ηr) of 1.67 measured in orthochlorophenol at 25°C at a concentration of 0.5 wt%, and a melting point of 21 by DSC.
It was 0°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%, “for MAR” PEP-4Q
, 2wt%, “Tinuvin” 326 0.1wt
%, and "5anol" 13770 Q, 1vt
% 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 mixed at a Merck temperature of 270'C1 and a gold pack temperature of 270°C, so that the weight ratio of the high shrinkage polymer (@joint core part) and 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,
Stockings were knitted using a KT-34 knitting machine manufactured by Hyozan Seiki at 650 rDIll. 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, and has better dyeing properties and light resistance.
The problem of yellowing was also improved.

[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.

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) an aliphatic diamine having 6 to 20 carbon atoms; (B) an aliphatic dicarboxylic acid having 6 to 15 carbon atoms in a substantially equimolar amount to the aliphatic diamine; (C) an aliphatic dicarboxylic acid having a number average molecular weight of 300 to 2,000. , poly(alkylene oxide) glycol and/or poly(alkylene oxide) diamine, and (D) a polyether ester amide polymer and/or polyether amide polymer derived from a dicarboxylic acid having 4 to 20 carbon atoms. Composite fibers with self-crimping properties made by melt-spinning a shrinkable polymer into composite fibers. (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 conjugate fiber having self-crimping properties as set forth in claim 1. (3) The low shrinkage polymer contains 95 wt% nylon 6.
A conjugate fiber having self-crimping properties 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 self-crimping properties according to claim 1. (5) The component (A) that induces the highly contractile polymer is hexamethylene diamine, and/or the component (B) is sebacic acid and/or dodecanedioic acid, and/or the component (C 2. The self-crimping composite fiber according to claim 1, wherein the component is poly(tetramethylene oxide) glycol having a number average molecular weight of 500 to 3,000.