DE1669436B2 - Composite thread made from two polymers that shrink at different rates - Google Patents

Description

H ₂ N- (CH ₂ J ₃ -R- (CH ₂ J ₃ -NH ₂

where R denotes the groups -O- or -0- (CH ₂ ) "- O- and) i can be 2 to 4, and 25 to 80 mol percent of hexamethylenediamine has been prepared.

2. composite thread according to claim 1, characterized in that that the shell made of polyhexamethylene adipamide or polycaprolactam and the core made of the copolyether amide, which is produced by polycondensation of adipic acid with 40 mole percent ether diamine of the formula

H ₂ N- (CH ₂ ), - O- (CH ₂ I ₂ -O- (CH ₂ ) ₃ - NH ₂

and 60 mole percent hexamethylenediamine was made

3. composite thread according to claims 1 and 2, characterized in that the weight ratio from shell to core is between 30:70 and 70:30.

40

Composite threads in the context of the invention are understood to mean mono- and multifilament threads which are in an produced in a known manner by spinning two different spinning masses using special nozzles will. Devices in such nozzles allow two polymer solutions or melts so squeezed out of a nozzle hole that core-sheath threads or threads in which the the two polymers each form part of the thread surface and the thread cross-section.

Composite threads are of particular importance immediately after spinning and drawing without special treatment or under the action of water, steam or the like Form ripple. For the production of such composite threads one uses polymers with different physical and / or chemical properties, especially those with different strengths Tendency to shrink. A crimp always occurs when both polymers have at least part of the Form a surface or with an eccentric formation of a core-shell structure.

A known method relates to the production of composite threads from two polymers with different strong shrinkage capacity. The more rapidly shrinking thread component is intended to unite Have a shrinkage of at least 7% and the difference in the shrinkage capacity of the two components at least 10%, preferably 20%. As examples of useful polymer combinations polyamides are made from dicarboxylic acids and diamines or from caprolactam on the one hand and polyethyleneterephthalate on the other hand called. In addition, one of the thread components can also be a Be copolyamide or copolyester.

Composite thread made according to the known method using various polymer combinations show depending on the type and amount of the composition after heat treatment a more or less strong ripple. For example, a core-sheath thread has an eccentric Formation of core and sheath, which consists of polyamide and polyethylene terephthalate, after treatment with water at 95 ° C., a number of crimped arcs of J15 per JO cm of thread length.

From FR-PS 14 50 006 there are already composite threads made of homopolyamides on the one hand and copolyamides on the other hand became known, the copolyamide being a copolyetheramide. for its production in addition to ether diamines AH-SaIz and or caprolactam and preferably a cyclic dicarboxylic acid be used. Experiments have shown that threads that have a copolyether amide component contain, for the manufacture of which caprolactam was used, unfavorable properties unless a cyclic dicarboxylic acid was also used. Such However, products that contain terephthalic acid, for example, are not only much more expensive, but also also more difficult to manufacture that you can only get from very high due to the poor solubility of terephthalic acid can run out of dilute aqueous solutions.

It has now been found that composite threads are made from two polymers which shrink to different degrees with an eccentric design of the core and jacket, very much better properties, especially with regard to the number of crimped arcs when the sheath of these threads is made of a homopolyamide and the Core made of a copolyether amide, which by polycondensation of adipic acid with 75 to 20 mol percent, preferably 50 to 40% by volume ether diamine, of the formula

H ₂ N- (CH ₂ ), - R - ICH ₂ I ₃ - NH ₂

wherein R is the groups -O- or O - (CH ₂ ) ,, O and η can be 2 to 4, and 25 to 80 mol percent, preferably 50 to 60 mol percent. Hexamethylenediamine is made.

The parts by weight of shell and core of the invention The composite thread should be 30:70 to 70:30, preferably 50:50.

The known homopolyamides are suitable as sheath components of the composite thread, for example from those from caprolactam, hexamethylenediamine and adipic acid, Aininoundecansüure and other.

Preferred properties have composite threads whose sheath is made of polyhexamethylene adipainide or polycaprolactam and its core from the copolyether amide by polycondensation of adipic acid with 40 mole percent ether diamine of the formula

H ₂ N - (CH ₂ )., - O - (CH ₂ J ₂ - O - (CH ₂ )., - NH,

and 60 mole percent hexamethylenediamine was produced.

Copolyether amides of the composition mentioned are made in accordance with the German patent (Registration Aktz. G 47 579 IV d / 39c) produced. The procedure described there works es, copolyether amides in any ratio of ether diamine to hexamethylene diamine with a sufficiently high molecular weight and good thread-forming properties. These copolyetheramides have a surprisingly high shrinkage capacity.

Table I shows the shrinkage values of some copolyether amide and other polymer threads in Water of 95 and 20'C put together.

Table I.

Thread material

Shrink at

95 C 20 C

Copolyether amide from adipic acid and hexamethylenediamine
and ether diamine *)

50 mole percent 50 mole percent
40 mole percent 60 mole percent
30 mole percent 70 mole percent
Polyamide made from caprolactam
Polyamide made from adipic acid-hexamethylenediamine

80 mole percent copolyamide
Caprolactam and 20 mole percent
Adipic acid hexamethylenediamine

*) Ether diimine of the formula

H ₂ N- (CHj) ₁ -O- (CH ₂ ), -0- (CH ₂ I ₃ -NH ,.

60% 8th% 35% 50% 40% 20% 38% 14% 11% 6.2% 7 to 5.4% 35 to 9 8%

Composite thread mainly the difference in the shrinkage capacity of the two polymer components of Is important, it becomes clear what advantages the invention offers.

The composite threads according to the invention are produced by known melt spinning processes, wherein as the spinning temperature for the melt spinning of the homopolyamide used as a sheath component Usual temperature is chosen. Neither in the spinning process nor in drawing are changes in the normal process conditions required.

A particular advantage of the composite thread according to the invention is to be seen in the fact that they are already at Immersion in water at normal temperature can ripple.

Compared to composite threads of a known type, in which the core is made, for example, of polyethylene terephthalate and the sheath consists of a polyamide, the threads according to the invention have the advantage that they have a core and sheath firmly bonded together because of the greater chemical similarity of the components stay.

The production of composite threads according to the invention is explained using the example:

By means of a spinneret, which is used for the production of core-sheath composite thread with eccentric Training of core and jacket is suitable. the melt of a homopoiyamide is spun (as a coat) and the copolyetheramide from adipic acid. Hexamethylene diamine and ether diamine der formula

35

The table shows that the shrinkage capacity of the relatively shrinking least Copolyätheramid yarns in water at 95 ⁰ C is still in the order of said copolyamide, while the Copolyätheramid having the highest tendency to shrink undergoes almost an equally strong shrinkage already in water at 2OC. Since, as was said above, for the tendency of the

Table II

H ₂ N- (CH ₂ )., - O - (CH ₂ ), -Q- (CHj) ₃ - NH ₂

(as the core). The temperature of the spinning device is about 280 C. The thread is at a speed withdrawn from the nozzle of 750 m min, then cold-stretched in a ratio of 1: 3.5 and wound up. Table II shows the textile data of composite threads according to the invention with various Composition of the copolyether amide as well as different amounts of core and shell components compiled. Corresponding data from known composite threads are used for comparison specified.

Composite thread material
Sheath core

Polyamide ¹ ) A
Polyamide ¹ ) B
Polyamide ¹ ) C
Polyamide ¹ ) A
Polyamide ¹ ) A
Polyamide ² ) A
Polyamide ¹ ) copolyamide ³ )
Polyamide ¹ ) polyethylene terephthalate

') Polyamide from caprolactam.

² ) polyamide made from adipic acid and hexamethylenediamine.

') Copolyamide from caprolactam and adipic acid-hexamethylenediamine in a ratio of 80:20.
A = copolyether amide from adipic acid-hexamc.hylenediamine and ether diamine in a ratio of 60:40. B = copolyether amide from adipic acid-hexamethylenediamine and ether diamine in a ratio of 30:70. C = copolyether amide from adipic acid-hexamethylenediamine and ether diamine in a ratio of 80:20.

Weight
percent
Coat too
core ! "here
(the / a
filaments) strain
(%) Firm
speed
(g / den) Shrinkage
(95 C)
in water Shrinkage
(20 C)
in water Ripple
arc number
per 10 cm Ripple
strain Krauset
con-
traklion 50:50 40/10 37.5 3.9 18% 7.4% J37 175% 70% 50:50 40/10 28.0 2.7 10% 5.7% 79.5 9% 43% 50:50 40/10 35.4 2.9 13% 5.6% 134 22% 16% 70:30 40/10 40.0 4.0 16% 7.0% not 63% 62% 30:70 40/10 34.4 3.2 26% 11.4% certainly 110% 79% 50:50 40/10 33.5 2.9 16% 6.8% 934 197% 75% 50:50 40/10 30.6 3.5 15% 5.2% 569 78% 48% 50:50 40/10 36.8 4.6 17% 1.7% 115 72% 53%

To measure properties that are not known per se, the following methods were used, after the curling was triggered by treatment with water at 95 ° C for 2 minutes became.

1. Crimp elongation

A piece of thread about 1 m long that has been treated in this way is now loaded with 50 mg / den, in such a way that the crimp is largely pulled out. The stretched thread is on the top Attached to the edge of a slightly sloping wall. Then you wedge just above the weight smaller weight of 0.5 mg / den and then carefully remove the larger weight. Under this The thread is left under normal climatic conditions for 12 hours. After this time you tighten it Insert the thread with the attached weight into an electronic tensile strength tester and determine the Elongation under load of 0.05 p / den.

2. Curl contraction

Strands of thread (8 m in length) are whipped and hung for 30 seconds without tension in distilled water at 70 ° C. The wet strands are then loaded with weights of 0.2 g / den for 1 minute. The length determined under this load is b. After removing the weights, the strands are dried hanging freely without load for 30 minutes at 50 to 60 ° C. and then conditioned for 1 hour. Then they are loaded for 1 minute with a weight of 0.002 g / den. The length determined here is a. The calculation of the crimp contraction is based on the equation related shrinkage possibility (sheet 1) and given load (sheet 2). The curves show the course of the crimp elongation for composite threads of the following composition:

Curve α or o, =
Curve h or b _t =

Curve c- or r, =

Curl contraction (%) = - -, -

100.

The diagrams also show the crimp elongations of various composite threads under defi-polycaprolactam and copolyether amide A (for an explanation, see Table II below).
Polycaprolactam and copolyamide (made from 80% caprolactam and 20% hexamethylenediamine adipic acid).

Polycaprolactam and polyethylene terephthalate.

The sheath consists of the first-mentioned polymer and the core of the thread consists of the the second mentioned. The ratio of the sheath to the core is in all cases 50:50 and the thread denier 40 denier (10 single threads).

To determine the crimp elongation values for sheet 1, the threads were placed in a frame with a Clamp spacing of 30 cm in each case clamped in such a way that various shrinkage options were possible. With 10% shrinkage possibility, the clamped thread length was z. B. 33 cm, with 80% shrinkage possibility 54 cm. The threads clamped in this way were first boiled in water for 60 minutes and then dried in hot air (60 ° C.) for 60 minutes finally fixed in saturated steam at 115 ° C. for 3 minutes. The crimp elongation was determined as described in connection with Table II, with the difference that the length of the measured pieces of thread was only 30 cm.

The crimp elongation values evident from sheet 2 were determined after the threads were under the loads shown in the diagram were treated in water for 2 minutes at 95 ° C.

It can be seen from both diagrams that the composite thread according to the invention has the most favorable crimp having.

For this purpose 2 sheets of drawings

Claims (1)

Patent claims: 1. Composite thread made of two differently shrinking polymers with an eccentric design of core and shell, in which the shell consists of a homopolyamide and the core of a copolyether amide, thereby characterized in that the jacket is made of a homopolyamide and the core is made of a copolyether amide, that by polycondensation of adipic acid with 75 to 20 mol percent ether diamine of the formula