DE2338286A1 - CURLABLE COMPOSITE FIBERS - Google Patents

Description

Priority: July 27, 1972, No. 74664/1972, Japan

The invention relates to a crimpable composite fiber, one component of which is a homopolyamide and the other component of which represents a random copolyamide. The fiber of the present invention is superior in curl developability and a knitted fabric made from this fiber is particularly suitable for stretch hosiery, among other things.

A composite thread has hitherto been described as a crimpable composite fiber which, in the cross section of the fiber, is side-by-side or inner-shaped arrangement showed *

However, these known crimpable composite fibers show only insufficient crimp and, due to the restoring force, when they are entangled, they fail to maintain satisfactory bulk and curl.

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Furthermore, the shrinkage of this well-known fesure in undulating water is slight. Preferred shrinkage seamers cattle specifically required for pantyhose yarn, which is one of the predominant uses for this species. Represents fibers. Filaments that shrink more than 1! -j. in boiling water and the crimp shrinkage that occurs when the knitted product is relaxed in the heat must be taken into consideration. For these known fibers know. As a result, conventional knitting machines are not used and a modification of the machine is required, i.e. the modification of the hose. In addition, the large extent of the knitted structure causes disadvantages in later processes such as the process of forming the crimp, and there is a tendency for imperfections to be introduced into the knitted fabric.

In order to meet the above requirements, various improvements in the production of composite yarns with less shrinkage and large Schrumpi ^were: ungf; force desired by certain types of copolymers selected or improved post-treatment methods and the like have been applied. These improvements satisfy the stated requirements to some extent, but these improvements have failed to meet the two requirements discussed above.

One of these improvements is the subject of Japanese Patent Application 25507/1967. For this published Japanese patent application it was essential that

(1) to use as a component a material that is im

consisted essentially of crystallizable homopolyamide and to use a material consisting essentially of statistical nichtisomorphem copolyamide containing at least 20 * jC each of the two Polymereinheiteri contained therein umfeßte (preferably was a polymer of units equal to the Poly / Ser

409867/1039 bad original

units of homopolyamide),

(2) both components at the same time to form a composite fiber to spin with an eccentric arrangement,

(5) to draw the thread thus obtained under such conditions, that only the homopoly components crystallize can,

(4) to crystallize the copolyir.erisate component to create crimp to cause by keeping the fiber in a relaxed state has been heat treated, and then

(5) stretch the fiber to remove the crimp.

This method enables the production of a collapsible composite fiber having latentex crimp which satisfies the above requirements Fulfills. However, there is a stretching stage in this process (5) is required, improvement in productivity becomes extremely difficult. Likewise in Stufo (4), NutoniTien with a special copolyir, eren, for crystallization treatment under severe conditions is required, and therefore the physical properties of the fiber become noticeable worsened.

These difficulties are alleviated by the crimpable of the present invention Composite fiber avoided.

The invention therefore relates to a crimpable composite fiber which has been obtained by the following process steps:

(a) Deformation of homopolyamide and random copolyamide in an eccentric arrangement to form a fiber,

(b) drawing the fiber thus obtained,

(c) thermal relaxation of the fiber obtained, so that the component consisting of random copolyamide according to shows no crystalline structure upon examination by X-ray diffraction, and developing part of the Ripple of latent curl ability.

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The preferred percentage shrinkage of the fibers produced in this way in boiling water is less than 15 1 - >> preferably about 10 %. The number of crimps of the crimpable fiber thus produced is less than 25, preferably less than 20/25 mm.

A knitted fabric obtained from the composite fiber produced in this way develops with sufficient thermal relaxation treatment with the aid of boiling water or steam, crimping and crystallization of the copolymer occurs. the obtained fiber is therefore a very advantageous product with high curl developability.

The invention is described below with reference to the accompanying Drawings explained in more detail.

In the drawings, Figure 1 shows the spinneret arrangement for the composite spinning, which is used according to the invention. FIG. 2 shows the schematic process of processing the yarn according to the invention.

FIG. 3 shows a triangular coordinate diagram for copolyamide 6/66 / 6T.

FIG. 4 shows a triangular coordinate diagram for copolyamide 6/66/610.

FIG. 5 shows a triangular coordinate diagram for copolyamide 6/66 / G12.

FIG. 6 shows a triangular coordinate diagram for copolyamide 66 / 6T / 61O.

FIG. 7 shows a triangular coordinate diagram for copolyamide 66 / 6T / 612.

The homopolyamides used according to the invention include polycapronamide (Nylon 6), polyhexamethylene adipamide (nylon 66), polyundecamide (nylon 11), polydodecamide (nylon 12), polyhexamethylene

AQ98Ö7 / 1039

deoamide (nylon 610) and polyhexamethylene dodecamide (nylon 612).

Random copolyamides suitable according to the invention include:

(1) Bicomponent copolymer from 6/66, made from £ -Caprolactam (hereinafter referred to as 6M) and hexa-

methylenediammonium adipate (hereinafter referred to as the 66 salt), the proportion of 6M being in the range of 30 to 60 wt .- #;

(2) a three-component copolymer made from 6/66 / 6T from 6M, 66 salt and hexamethylene diammonium

terephthalate (hereinafter referred to as 6T salt), its composition is represented by the area bounded by a, b, c, d, e, f and g in Figure 3, the proportions of 6M, 66 salt and 6T in each point a, b, c, d, e, f and g by the weight ratios 85: 0: 15, 65:20:15, 60: 40: 0, 30: 70: 0, 10:70: 20, 5:55:40 and 35: 0:65, respectively, are shown;

(3) a three-component copolymer of 6/66/610, made from 6M, 66 salt and hexamethylene diammonium seba-

cat (610 salt), the composition of which is represented by the area which is defined in Figure 4 by a, b and c, the proportions of 6M, 66 salt and 610 salt in each point a, b and c are represented by the weight ratios 60: 40: 0, 30: 70: 0 and 30:40: 30, respectively;

(4) a three-component copolymer of 6M, 66-salt and the salt of hexamethylenediamine and dodecanedicarboxylic acid

(612 salt), the composition of which is determined by the a, b and c in Figure 5 is shown, the proportions of 6M, 66-salt and 612-salt in each point a, b and c show the weight ratios 50: 50: 0, 30: 70: 0 and 25:45:30, respectively;

(5) a three-component copolymer made from 66 / 6T / 610 from 66 salt, 6T salt and 610 salt, its composition is represented by the area defined by a, b, c, d, e and f in Figure 6, the proportions of 66 salt, 6T salt and 610 salt in each point a, b, c, d, β and f the weight ratios 62.5: 22.5: 15, 55s3Oi15 »45:35:20, 0: 35:65, 0:20:80 and 17.5: 22.5: 60 show}

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(6) a three-component copolymer made from 66 / 6T / 612 from 66 salt, 6T salt and 612 salt, the same composition is represented by the area defined by o, b, c, d and e in FIG. 7, with the proportions on 66 salt, 6T salt and 612 salt in each point a, b, c, d and e the weight ratios 65: 25: 10, 40:40:20, 0:45:55, 0: 52.5: 67.5 and 27.5: 32.5: 5.40, respectively.

Those outside the composition specified above Copolymers can meet the requirements of the invention for the copolyamide do not meet and are therefore erfindungsgeirilß locked out.

For example, the three-component copolymer can be made from 6/66 / 6T in a copolymerization ratio of 5/70/25 or 5/60/35 (Weight ratio), the three-component copolymer is 66 / 6T / 610 in a copolymerization weight ratio of 60/30/10, 40/40/20, 20/40/40 and 10/40/50, and the three-component copolymer from 66 / 6T / 612 in the copolymerization weight ratio 70/25/5, 60/30/10, 35/45/20, 20/50/30 or 10/50/40 meet the crystallization conditions required according to the invention, form however, insufficient crimp for crimped yarn due to its low boiling water shrinkage, which may cause it only less than 10 # difference in boiling water shrinkage versus that of homopolyamide is achieved.

On the other hand, the three-component copolymer of 6/66 / 6T with a copolymerization weight ratio of 25 / 72.5 / 2.5 or 80/10/10, the three-component copolymer of 6/66/610 im Copolymerization weight ratio of 20/70/10, 20/60/20, 20/50/30 or 15/45/40, the three-component copolymer of 6/66 / 612 with a copolymerization weight ratio of 20/50/30, 20/60/20 or 20/70/10, the three-component copolymer of 66/61/610 with a copolymerization weight ratio of 20/20 60, 30/20/50, 40/20/40, 50/20/30, 70/10/20, 50/10/40, 30/10/60

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or 20/10/70, the three-component copolymer of 66 / 6T / 612 with a copolymerization weight ratio of 20/30/50, 35 / 30/35, 65/20/15, 40/20/40, 10/20/70 or 30/10/60 and the like al G according to the invention Copolyiuerißat the requirements im In terms of shrinkage in boiling water, meet them however, do not meet the conditions with regard to crystallization that are required according to the invention.

In addition, the three-component copolymer made from 6/66 / 6T with one; Copoljuierization weight ratio of 10/85/5 »10 / 80/10, 5 / Ö5 / 1O, 5/90/5, 90/5/5, 85/10/5 or 85/5/10 neither the Crystallization conditions, nor the conditions in terms of on the shrinkage in boiling water, which is essential for an inventive 3 Copolymer are required.

Also the three-component copolymer of 6/66 / 6T with a copolymerization ratio 20/20/60 or 25/10/65, which meets the crystallization conditions and the required shrinkage shows in boiling water, has extremely reduced spinnability and stretchability and is therefore in accordance with the invention locked out.

A random copolymer suitable for the purpose of the invention is a copolymer from which a fiber is obtained which shows no more than 10 f> difference in thermal shrinkage from the fiber obtained from the homopolyamide, and as in the published Japanese patent application described 25507/1967, can not be converted into the crystalline structure upon treatment with steam of 100 to 200 ⁰ C for 10 ~ ⁴ to 0.5 second in the relaxed state, which does not in testing using a densitometer X-ray reflection along shows the equatorial direction in the plane (100) and (010, 110) and accordingly shows only one peak instead of two separate intrinsic peaks and which forms a crystalline or pseudocrystalline structure in the relaxation treatment with boiling water or steam.

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SAD ORIGfNAL

23382S6

The drawing of the random copolymer filament selected in accordance with the invention under the usual conditions of thermal drawing for polyamide fibers does not lead to crystallization of the polymer.

became

Previously / as a typical copolymer component for crimpable composite fibers, copolyamide made from 66/610 with a copolymerization ratio of $ 30 to 70, copolyamide made from 66/61 (hexamethylene diammonium isophthalate) with a copolymerization ratio of 60 to 9? f and copolyamide of 66/6 with a copolymerization ratio of 5 to 20 # are proposed, and these copolyamides have satisfactory thermal shrinkage.

With these copolyamides, however, crystallization occurs thermal relaxation treatment after stretching and around the thermal shrinkability for the effective formation of the To take advantage of crimp, it was necessary to develop sufficient crimp at this stage. / Is result was a removal the crimp by drawing is required after the thermal relaxation treatment. It also occurs when diminishing the curling in the step of the thermal relaxation treatment for the purpose of eliminating the stretching stage (5), noticeable crystallization of the copolymer in this Stage one and the thermal shrinkage of the copolymer can therefore not be used for effective crimping. One therefore, sufficient shirring cannot be ensured by shirring treatment in knitted fabrics. In other words, with these known typical copolyamides, the most effective method of curling was thermal Take advantage of the shrinkage of the copolymer in order to develop as much curling as possible in the step of the thermal relaxation treatment, and removing the crimp in the drawing step (5) was therefore essential.

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In contrast, according to the invention, during the step of the thermal relaxation treatment occurs through partial development of the Crimp does not induce crystallization and therefore residual crimp ability can be retained at this stage. According to the invention therefore, there is no difference in crimp achieved through the entire crimp formation at this stage is observed, and therefore it is not necessary to develop excessive curl, thereby meeting the requirements pucker developability, boiling water shrinkage and suitability for knitted fabrics or hosiery to be fulfilled.

In the thermal relaxation treatment , it is most effective in terms of curl developability, boiling water shrinkage percentage, productivity for yarn and suitability for knitting to make 5 "to 30 # of the curl.

Composite yarns with these properties can be obtained by introducing the yarn under steam or a heated gaseous fluid medium into a heat-relaxation treatment zone provided after the drawing step. The drawn thread is passed under steam or a fluid medium heated to 100 to 200 ^° C. through a chamber or a tube for less than 0.5 second. In this step, the yarn is fed to the chamber, wherein a percent relaxation of the yarn of more than 15 ^, preferably is obtained from 20 to 25 f>. By applying this relaxation heat conditions, the shrinkage percentage of the filament can be reduced to about 10 f> in boiling water, while the crystallization of the present as a fiber component statistical Gopolymerisats is virtually avoided. In this way, a technically suitable high production speed of more than 800 m / inch, preferably 800 to 1000 m / inch, can be achieved; FIG. 2 shows a preferred example of the heat relaxation treatment zone. Undrawn threads are drawn through the

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zone (which includes the conveyor belt 3) of the heat treatment chamber 5 supplied. This chamber has an access opening for the Provided thread. Steam or another heated fluid medium is blown in from a nozzle element in the direction of the arrow. Lie Thermal relaxation conditions for the thread can be excellent at Values are held by the medium at the same time through both the inlet opening and the outlet opening is blown in. The through this V.'armebe.Virälur ^ r.-zone guided threads are with the help of a spindle on one Cpu-Ie wound up.

As already stated, in the method according to the invention the copolymer component during the heat recovery treatment does not crystallize and it is not necessary to fully develop the curl at this stage. One Therefore, the step of drawing to remove the crimp is not required and the treatment speed becomes essential increases up to 1200 m / min due to the mild heat relaxation treatment.

The invention is illustrated in more detail by the following examples.

In the examples, the percentage shrinkage is calculated using the following equation:

percentage shrinkage in boiling- L - L- |

the water (Ji) = x 100 (#)

in which I represents the length of the strand made by winding 50 turns and then hanging it up under a load of 0.1 g / d is obtained and

L _{1 means} the length of the strand obtained by removing the attached weight described for 5 minutes, allowing it to dry in the air for 24 hours and loading with a weight νοη "Ό-, 1 g / d.

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The curl developing ability is given by the following equation calculated:

Curling development capability = ^ra "" ^m ^ _χ ^ ₀ / m \

in which In _{1 represents} the length of the strand obtained by winding the composite filament yarn in 50 loops, treating with the aid of a water vapor atmosphere at normal pressure for one minute under load with an attached weight of 0.0012 g / d, allowing it to dry in air for 60 Minutes under this load was obtained and

m means the length of the strand made by removing the weight of 0.0012 g / d, left to stand for one minute and then loaded with an attached weight of 0.33 g / d is achieved during one minute.

The number of crimps means the number of crimps over a length of 25 mm, the crimping thread weighing mg / d is loaded. The route from one curve apex to the next curve apex is called a ripple or from one Minimum to other minimumum viewed as a ripple.

The percentage relaxation is calculated using the following equation:

V - Vi

. Relaxation {%) = ' _x iqo

where V is the speed of the draw roller and V _{1 is} the speed of the Fcröer roller.

The relative viscosity (η, _Γβ1 ) of the polymer is the viscosity of the solution, 1 g of the polymer being dissolved in 100 ml of a 95.5 # strength sulfur acid.

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In the examples below, the measurement of the stretch-back was carried out as in Example 1.

example 1

In a 400 l autoclave, 120 kg of a 50 Jf aqueous solution of hexamethylene diammonium adipate (hereinafter referred to as 66 salt) 40 kg £ -caprolactam (hereinafter referred to as 6M) added and dissolved therein so that a weight ratio of 66 salt to 6M of 60/40 was obtained. Then became the interior of the autoclave was purged with nitrogen for polymerization. The autoclave was heated to 230 ° C for one hour while steam was gradually withdrawn and the internal pressure was kept at 17.5 kg / cm. Then the internal pressure was during a Relaxed duration of 1 hour from 17.5 kg / cm to atmospheric pressure and heating was continued for 1 hour while nitrogen was bubbled through at atmospheric pressure. From the thus obtained statistical copolyamide 66/6 (copolyamide of polyhexamethylene adipamide and polycapramide) with a relative viscosity of 2.43 ale of a component and homopolyamide 66 (polyhexamethylene adipamide, hereinafter referred to as nylon 66) with a relative viscosity of 2.47 as the second component became the Composite spinning in the same volume ratio of the components with the aid of a spinneret with five openings for kidney-shaped ones Composite core carried out, the openings of which each have a diameter of 0.3 mm.

According to FIG. 1, the ^L is made from the statistical copolyamide 66/6. standing component fed through the channel a and the homopolyamide through the channels b and c. As shown in FIG. 2, the undrawn filaments obtained in this way are drawn 3.5 times by feed roller 1 and draw roller 3 and then thermally relaxed by introducing the filament yarn into a 30 cm long heating chamber 5 which, under steam of 155 ° C was kept and in which steam from the nozzle 4 at the top of the

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Heating chamber 5 was initiated. The feed speed of the yarn was 800 m / min and the yarn was thermally relaxed at a rate of 21 f> relaxation in the heating chamber 5 by adjusting the speed of the draw roller 3 and the removal roller 6. Here, the composite fibers were obtained of 21 d / 5 f, the $ 20 developed latent crimp (Number of crimps 11/25 mm).

For comparison purposes, undrawn yarn made from composite fibers II, which had been produced in the manner described above, was drawn 3 »5 times, with yarns of 20d / 5f being obtained. The crimp developability and boiling water shrinkage percentage of these filaments I and II were measured. The threads were also tested in the following manner. The thread was knitted with the aid of a circular knitting machine with a diameter of 9.5 cm and 400 needles under a knitting tension of 1 g to form a smooth knitted fabric with 62 courses per 2.54 cm and 32 wales per 2.54 cm. The knitted fabric was subjected to 5 minutes in boiling water at 100 ⁰ C of a thermal Entspannungsbeharidlung what he air at by increasing the heating temperature from normal temperature to 100 ⁰ C for 40 minutes allowed to dry, the heating treatment at 100 ⁰ C for 30 minutes was continued the temperature was lowered to 60 ° C over 15 minutes and the fabric was then air dried for 24 hours. The stretch-back was measured as the tension (g) on stretching to 50,56.
The results are shown in Table 1.

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Tabel

3> robe properties of the yarn

Curl percentage- Percentage shrinkage capacity fung .in boiling

water

Ripple

capability

Evaluation of the knit fabric

irregular default ripple

CO OO O

I II

23 * 7 JC

9 18 good no 97

bad numerous streak-like impurities 54
regularities

O UJ (O ro

CO CO OO

OD O)

As is clear from the results, the invention increases Treating the ability to pucker noticeably limits the percent shrinkage in boiling water and leads to extremely good knitting properties. On the other hand, it became only from the copolyamide component the composite fiber I produced one-component fiber among the the same conditions as described above, stretched and subjected to the thermal relaxation treatment and thereafter the X-ray examination was carried out in accordance with Japanese Patent Application Laid-Open No. 25507/1967. All Teot results after drawing the thread, performing the Thermal relaxation treatment and treatment with boiling water are summarized in Table 2. The results show the crystallization of this copolyamide during the thermal relaxation treatment process.

After stretching

table 2

incomplete crystalline structure. With the aid of the densitometer there was no peak splitting observed (one peak).

After the thermal relaxation treatment

Incomplete crystalline structure. No peak splitting was observed in the densitometer (a peak).

After treatment with boiling water

Crystalline structure was observed. Splitting in two peaks at 100 and 010, 110 was clearly observed in densitometer.

Example 2 From a copolyamide prepared as in Example 1 with a

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Copolymerization ratio of hexamethylenediammonium adipate to ε-caprolactam of 70/30 (weight ratio) and a relative viscosity of 2.43 as one component and nylon 66 as the second component were composite spinning in the manner shown in Example 1 in the same volume ratio of the components using an in Figure 1 shown composite spinning nozzle of the kidney type with 5 openings each having a diameter of 0.3 mm composite threads produced. The thus obtained undrawn Fädei were stretched to 3.5 times and thermally relaxed by subjecting the stretched yarn was introduced at a percentage relaxation of 21 56 in a 30 cm long heating chamber under a water vapor atmosphere of 160 ⁰ C, with the yarn in the Heizkainmer 5 was thermally relaxed at a speed of 800 m / min. With a thermal relaxation percentage of 2296, a composite fiber III of 22d / 5f was obtained, which developed 20 Jb latent crimp (number of crimps 11/25 mm).

On the other hand, the same procedure was repeated except that copolyamide having a copolymerization ratio was used of hexamethylene diammonium adipate to ε-caprolactam of 30/70 (weight ratio) and a relative viscosity of 2.41 was used. A composite fiber IV of 22d / 5f with a curl number of 12/25 mm was obtained. The ripple developability and testing of fibers III and IV after knitting and after boiling water treatment are in Table 3 shown.

In addition, one-component threads were made from the copolyamide components of fibers III and IV examined with the aid of X-rays. The results are summarized in Table 4.

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Table 3

Sample properties of the yarn

Ripple development Percentage shrinkage Krause1 development capacity in boiling capacity

water

valuation of Knitted fabric

irregular default ripple

III
IV

(O OO O

24
15th

9 *

9 Ji

Table 4

Well no

bad some streak-like irregularities

101 53

sample

After this
Stretch

After
thermal
Relaxation treatment

After treatment in .seenSem water

III

Incomplete crystalline structure. There was no peak splitting in the densitometer observed (one peak).

Incomplete crystalline structure, no peak splitting was observed in the densitometer observed (one peak).

Has a crystalline structure. Splitting into two peaks at levels 100 and 010, 110 was made in the densitometer clearly observed.

IV

Incomplete crystalline structure. There was no peak splitting in the densitometer observed (one peak).

Has a crystalline structure. Splitting into two peaks in the levels 100 and 010, 110 was clearly observed using the densitometer.

Has a crystalline structure. Split into two peaks at level 100 and 010, 110 was measured using the densitometer clearly observed.

For comparison, a yarn of the same composition as IV was thermally relaxed-drawn in the manner described in Example 1 of published Japanese patent application 25507/1967. A composite fiber of 22d / 5f was obtained. A knitted fabric made of the composite fiber thus obtained was treated as described above. It showed good curling ability and good retraction (default). The curling developability and shrinkage percent in boiling water were $ 22 and $ 8, respectively .

From the above results, it can be seen that with regard to on the crimp development ability, the retraction or the resilience of the knitted fabric and the crimp condition of the yarns, which are crystallized in the thermal expansion stage, do not show good results after the treatment according to the invention, however, good results by the thermal relaxation stretching treatment according to Japanese Patent Application 25507/1967. The copolymers according to the invention therefore only lead to good results if the crystallization conditions required according to the invention are fulfilled.

Example 3

The same procedure was followed to make composite yarn as used in Example 1, with the modification that a copolyamide of nylon 66/6 with a copolymerization ratio of 40/60 and a relative viscosity of 2.48 was used. From the non-drawn composite thread obtained in this way pilament yarn of 21d / 5f was obtained according to the procedure given for sample I in example 1, with the exception that the thermal relaxation treatment in a hot air atmosphere of 175 ° C was carried out. The test of the thread gave a value of 22 £ for the crimp developability and 11 jG for percent shrinkage in boiling water. Check of a knitted fabric and measurement with the help of X-rays gave essentially the same results.

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Same as for sample I from example 1.

Example 4

To 135 kg of 40% aqueous solution of hexamethylene diammonium adipate (66 salt) in a 400-1 autoclave, 16 kg of hexamethylene diammonium terephthalate (6T salt) was added and dissolved therein, and then 30 kg of ε-caprolactam (6M) was added and dissolved , a weight ratio of 6M to 66 salt to 6T salt of 30:54:16 was achieved. Then the inside of the autoclave was purged with nitrogen for polymerization. The autoclave was heated for 1 hour at 23O ⁰ C while gradually steam was removed and the internal pressure at 17 "5 kg / cm was maintained. Then, the internal pressure was brought to atmospheric pressure from 17.5 kg / cm 2 over a period of 1 hour, and heating was continued for 1 hour while bubbling nitrogen at atmospheric pressure. The thus obtained three-component copolyamide of 6/66 / 6T having a relative viscosity of 2.51 as a component and nylon 66 having a relative viscosity of 2.47 as the other component was made into a thread by composite spinning in the same volume ratio of the components with the aid a composite spinning nozzle of the kidney type shown in FIG. 1 with 5 openings each having a diameter of 0.3 mm.

According to Figure 1, the copolyamide component is fed through channel a and nylon 66 through channels b and c. As shown in FIG. 2, the undrawn filaments obtained in this way are drawn 3.3 times by the feed roller 1 and the draw roller 3 and then thermally relaxed by introducing the drawn yarn into a 30 cm long heating chamber 5, which is below Water vapor is kept at 160 ⁰ C, which is supplied from the nozzle 4 at the upper end of the heating chamber 5. The yarn was fed at a speed of 700 m / min and thermally relaxed in the heating chamber 5 at a rate of 23 $, the process

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The speeds of the drawing roller 3 and the take-out roller 6 were adjusted so that composite yarns of 22d / 5f which developed 25 ^ latent crimps were obtained (number of crimps Π / 25 mm). '

The pucker developability and boiling water shrinkage percentage of the pasers were $ 25 and 8 ° C, respectively. The evaluation of the crimpability and the resilience of knitted fabrics made from the yarn gave good values. The results of the measurement with the aid of X-rays are summarized in Table 5.

Table 5

After the incomplete crystalline structure, no long peak splitting was observed in the densitometer (a peak).

According to the ther- incomplete crystalline structure, it

mixing no peak splitting was found in the densitome

Observed with tension (one peak), action

After Behänd- _m There crystalline structure was observed in lung seven 'split into two peaks at 100 and 010, 110 dendem water was observed in the densitometer.

Example 5

From the statistical three-component gopolyamide 6/66 / 6T prepared as in Example 4 with a copolymerization weight ratio of ^ -caprolactam, hexamethylenediammonium adipate and hexamethylenedlammonium terephthalate of 20/50/30 and a relative viscosity of 2.47 as a component and nylon 66 with having a relative viscosity of 2.47 as the other component, composite fibers were prepared by composite spinning in the manner described in Example 4. The undrawn filaments obtained ^{in this way were drawn 3.4 times on a draw} pin (2 in FIG. 2) heated to 110 ° C. and then the drawn yarn was subjected to a thermal relaxation treatment by

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it τοη at a percentage of 21% -Relaxation a 30 cm long heating chamber 5 under water vapor 173 ⁰ C was fed into which steam was blown from the Dampfeinblasdüse the upper end of Heizkamaer. 5 The yarn was fed under steam at 173 ⁰ C at a rate of 1100 m / min of the heating chamber 5, wherein a composite fiber of 21 d / 5 f 15 9 ^ latent crimp (Number of crimps 9/25 mm) was obtained. The crimp developability and boiling water shrinkage percentage of the pilament yarn were 24 % and $ 11, respectively. The examination of the knitted fabric and the examination with the aid of X-rays led to essentially the same result as in the example

Example 6

From the three-component random copolyamide 6/66 / 6T, made as in Example 4- with a copolymerization weight ratio of ε-caprolactam, hexamethylene diammonium adipate and hexamethylene diammonium terephthalate of 30/65/5 and a relative viscosity of 2.48 as a component, and Nylon 66 with a relative viscosity of 2.47 as the other component was incorporated in the manner described in Example 4 Compound thread III of 22d / 5f with a number of crimps of 15/25 mm was obtained.

On the other hand, using random copolyamide with a copolymerization ratio of & -caprolactam, hexamethylene diammonium adipate and hexamethylene diammonium terephthalate of 80/10/10 and a relative viscosity of 2.46 a composite fiber of 22d / 5f (IV) with a number of crimps of 14/25 mm was obtained by treating in the manner described above.

The crimp developability of the threads and the test of the knitted fabric obtained and after the treatment in boiling Filaments III and IV waters performed as in Example 1 are shown in Table 6.

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In addition, the measurement with the aid of X-rays on the threads III and IV was carried out in the manner described in Example 1 carried out. The results obtained are shown in the table.

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Tabel

sample Properties of the Yarn Well
bad
and rough
Ripple
Ie 7 Evaluation of the Knitted fabric Ripple t
ability to develop improper
Ripple Provision III
IV $ 24
17 * no
some streak
fen-like un
regularity
th 113
56 sample Percentage shrinkage frizz
able to function in boiling
Water ability IV 8th *
8th *
T a b e 1 III

CO OD O

^ After the - * stretching

Incomplete crystalline structure. No peak splitting was observed in the densitometer observed (one peak).

Incomplete crystalline structure. No peak split was made observed in the densitometer (one peak).

After the thermal relaxation treatment

Incomplete crystalline structure. No peak splitting was observed in the densitometer observed (one peak).

Has a crystalline structure. Splitting into two peaks at levels 100 and 010, 110 was using of the densitometer clearly observed.

After handling it has a crystalline structure. The collection the splitting into two peaks in the planes of the water and 010, 110 became clear in the densitometer observed.

Has a crystalline structure. Splitting into two peaks in levels 100 and 010, 110 were clearly observed in the densitometer.

2338236

For comparison purposes, a yarn of the same composition was used like IV in the same way as in example 1 of the known Japanese patent application 25507/1967 thermally relaxed-stretched, whereby composite fibers of 22d / 5f were obtained. The knitted fabric made from the composite filament yarns thus obtained was treated in the manner described above. The knitted fabric showed good puckerability and good resilience (stretching-back ability). The ripple developability and the boiling water shrinkage percentages of the yarn were 23 # and 8 #, respectively.

From the above results, it can be seen that in terms of curl developability, retraction ability of the knitted fabric and the crinkle state of the crystallizable Copolymers existing yarns in the thermal relaxation stage do not show good results by the thermal relaxation treatment according to the invention, but they do good results due to the thermal relaxation-stretching treatment as described in Japanese Patent Application 25507/1967. The material according to the invention therefore leads to good results only by using a specific random copolymer which the invention, described crystallization conditions met.

Example 7

The same procedure was used to produce composite yarn as in Example 4, except that a copolyamide having a copolymerization weight ratio of £. -Caprolactam, hexamethylene diammonium adipate and hexamethylene diammonium terephthalate of 40/10/50 and a relative viscosity of 2.50 was used. The non-drawn composite thread obtained in this way was drawn 3.3 times with the aid of a drawing pin (2 in FIG. 2) which was ^{heated to 110 ° C.,}

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in a 30 cm long under steam at 16O ⁰ C held heating chamber 5 introduced was supplied to the water vapor from the nozzle 4 at the upper end of the heating chamber 5, and then thermally relaxed. The yarn was fed to the heating chamber 5 at a speed of 800 m / min and thermally relaxed at a relaxation of 21 <fc , resulting in composite threads of 23 d / 5f which developed 20 ^ crimps (number of crimps 14/25 mm ). The crimp developability and the boiling water shrinkage percentage of the filament yarns were 25 # and 10 #, respectively. The examination of the knitted fabric and the measurement with the aid of X-rays led to essentially the same results as in Example 4.

Example 8

A composite fiber of 21d / 5f was prepared in the same manner as in Example 4, except that according to Example 4 were obtained undrawn filaments thermally expanded in a Eeißluftatmosphäre of 180 ⁰ C. The Kräuselungsentwicklungsfähigkeit and percent shrinkage of the filaments in boiling water were 23 f> VIC. 8th #. The examination of the knitted fabric and the examination by means of X-rays gave essentially the same results as in Example 4.

Example 9

Undrawn composite fibers were made in the same manner as in Example 4, with the modification that nylon 6 was used as the homopolyamide. The thermal relaxation took place in same way as in example 41 with composite filaments of 22d / 5f with a number of crimps of 15/25 mm.

The fiber showed a curl developability of 23 % and a boiling water shrinkage percentage of 9 #. The examination of the knitted fabric and the examination by X-ray

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development led to essentially the same result as in Example 4.

Example 10

To 150 kg of a 40 $ aqueous solution of hexamethylenediammonium adipate (66 salt) in a 400-1 autoclave was 5 kg Hexamethylene diammonium sebacate was added and dissolved therein, and then 35 kg of ε-caprolactam (6M) was added and dissolved, a weight ratio of 6M: 66 salt: 610 salt of 35: 60: 5 was obtained. Then the inside of the autoclave purged with nitrogen for polymerization. The autoclave was heated to 230 ° C. for 1 hour while steam was gradually removed and the internal pressure was kept at 17.5 kg / cm. Then the internal pressure was reduced over a period of 1 hour from

17.5 kg / cm2 was brought to atmospheric pressure and heating was continued for 1 hour while keeping nitrogen at atmospheric pressure was passed through. With the thus obtained statistical three-component copolyamide 6/66/610 of a relative viscosity of 2.50 as a component and nylon-66 with a relative A viscosity of 2.47 as the other component was obtained using composite spinning with the same volume ratio of the components a composite spinning nozzle of the kidney type (according to Figure 1) carried out, which had 5 openings with a diameter of 0.3 mm each.

According to Figure 1, the copolyamide component is fed through channel a and nylon 66 through channels b and c. As shown in Figure 2, the thus obtained unstretched filaments are stretched by the feed roller 1 and the tension roller 3 to the 315-fold and then thermally relaxed by inserting it in a held under steam of 155 ⁰ C, 25 cm long heating chamber 5 will. Steam is introduced into this chamber from the nozzle 4 at the upper end of the heating chamber 5. The yarn was fed to the heating chamber at a speed of 800 m / min and was fed into the heating chamber 5 by adjusting the speed of the drawing roller

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and the take-out roller 6 relaxed at a rate of 22 Jt, wherein a composite fiber IV of 22d / 5f with a number of crimps of 15/25 mm was obtained.

For comparison, undrawn yarn was made from the composite filaments VI obtained in the same manner as before, drawn 3.5 times to obtain a yarn of 20d / 5f. Table 8 shows curling developability and percentages Shrinkage in boiling water for these threads V and VI, as well as the testing of a knitted fabric made from yarn of these filaments, which was carried out under the same conditions as in Example 1.

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Table 8

Properties of the yarn Evaluation of the knit fabric

Sample Curl Development Percentage Shrinkage Ability

Pucker ability Irregular curling recovery

ßelung ability

CO GO CO

VI

23 % 7 %

11

18 good
bad

no 102

numerous streak-like irregularities 57

ro

OJ CO

CO

ro co

As is clear from the results, the treatment of the present invention remarkably improves the curl developability, reduces the percentage shrinkage in boiling water and leads to extremely good properties of the knitted fabric.

On the other hand, the one-component filament that was merely from the random copolyamide present as a component of the composite fiber V was made, among the same Stretched conditions as above and subjected to the thermal relaxation treatment. Then the exam carried out by X-ray radiation according to Japanese Patent Application No. 25507/1967. The test results that follow the drawing of the thread, carrying out the thermal relaxation treatment and treating with boiling water are summarized in Table 9. The results show that no crystallization of the copolyamide occurs during the thermal relaxation treatment.

Table 9

After completion, incomplete crystalline structure. No stretching test with the densitometer was found

Peak splitting observed (one peak).

According to the ther- Incomplete crystalline structure. By

mixing de- testing with the densitometer was no

voltage-splitting of the peak observed (one peak), plot

After loading ^ ⁸ ^ ¹¹ ^ crystalline structure observed o · irTaia * ^m densitometer was split into two water ^ IOCs 100 and 010, significantly beobacHbet 110

Example 11

With the random three-component copolyamide prepared as in Example 10 6/66/610 with a copolymerization weight ratio of ε-caprolactam, hexamethylene diammonium

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adipate and hexamethylene diammonium sebacate of 50/45/5 and a relative viscosity of 2.53 as one component and nylon 66 with a relative viscosity of 2.47 as the other component, the composite spinning was carried out as in Example 10. The undrawn loads thus obtained were stretched 3.3 times by the feed roller 1 and draw roller 3 shown in FIG 4 was fed at the upper end of the heating chamber 5. The yarn was fed to the heating chamber 5 at a speed of 1000 m / min and thermally relaxed by adjusting the speed of the draw roller 3 and the removal roller 6 with a relaxation of 20 <fc. Compound yarns of 21d / 5f were obtained, which formed 10 $ crimps (number of crimps 7/25 mm).

The crimp developability and the boiling water shrinkage percentage of these threads were 23 % and 11 fC, respectively. The evaluation of the knitted fabric and the X-ray examination led to essentially the same result as in Example 10.

Example 12

From the random three-component copolyamide prepared as in Example 10 6/66/610 with a copolymerization weight ratio of 6-caprolactam to hexamethylene diammonium adipate Hexamethylene diammonium sebacate of 35/50/15 and a relative viscosity of 2.45 as one component and nylon 66 with one relative viscosity of 2.47 as the other component became a composite thread in the manner described in Example 10 for Sample 5 VII of 22d / 5f with a number of crimps of 14/25 mm manufactured.

On the other hand, it was made using a random copolyamide with a copolymerization ratio of ^ -caprolactam

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to hexamethylene diammonium adipate to hexamethylene diammonium sebacate of 20/50/30 and a relative viscosity of 2.47 by treating in the same manner as described above, a composite thread VIII of 22d / 5f with a number of crimps of 14/25 now received.

The curling development ability of the threads and the evaluation of the knitted fabric produced as in Example 1 and with boiling Water treated from threads VII and VIII are shown in Table 10. In addition, threads VII and VIII the X-ray test was carried out. The The result is shown in Table 11.

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Tabel

Properties of the sample Yarn Evaluation of the knit fabric Irregular herb
selung Reset
capital sample Ripple development
ability Percentage
shrinkage Crimp ability no
some stripes
like irregularity
moderation 96
55 YII
VIII $ 25>
16 Ji £ 10
9 #
tab Well
insufficiently large
be crimp
hurry 11 VIII VII

After stretching

After the thermal relaxation
plot

Incomplete crystalline structure. There was no peak splitting in the densitometer observed (one peak).

Incomplete crystalline structure. There was no peak splitting in the densitometer observed (one peak).

Incomplete crystalline structure. No peak splitting was observed in the densitometer (a Peak).

Has a crystalline structure. ■ In the densitometer, the splitting clearly observed in two peaks at levels 100 and 010, 110.

After treatment in
boiling
water

Has a crystalline structure. In the densitometer the splitting was observed clearly observed in two peaks at levels 100 and 010, 110.

Has a crystalline structure. In the densitometer the splitting was observed clearly observed in two peaks at levels 100 and 010, 110.

ro

OJ

cc

NJ

CQ

σ »

For comparison, a yarn of the same composition as VIII in the same way as in Example 1 of Japanese Patent Application 25507/1967 thermally relaxed-stretched, with a Composite fiber of 22d / 5f was obtained. The one obtained from the Knitted fabric made of composite fibers was treated in the manner described above. The knitted fabric showed good puckerability and stretching-back ability. The curl developability was 25 # ■ and the shrinkage in boiling water was 8 #.

From the above results, in view of pucker developability, recoverability of the knitted fabric and Kruselungszuotand can be seen that in the thermal relaxation stage Crystallizable yarns do not show good results in the treatment according to the invention, but they do show good results show when they undergo thermal relaxation-stretching treatment according to Japanese Patent Application 25507/1967. Good results can only be achieved when the material according to the invention is used which fulfills the conditions specified according to the invention.

Example 13

The procedure described in Example 10 for the production of composite yarn was used, with the modification that a three-component random copolyamide 6/66/610 with a copolymerization weight ratio of 30/50/20 and a relative viscosity of 2.49 was used and that nylon 6 with a relative viscosity of 2.45 was used as the homopolyamide to make the undrawn thread. From the undrawn thread thus obtained, composite threads of 22d / 5f with a crimp number of 14/25 mm were produced according to the method described in Example 10 for sample V, with the modification that the undrawn yarn was drawn and the thermal relaxation treatment in hot air atmosphere of 175 ^{Subject to 0} C.

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2333286

became. The curl developability of the fiber was 23 # and the percent shrinkage in boiling water was 12 #. Evaluation of the knitted fabric and the test by X-rays led to practically the same Ex * result as for sample V of example 10.

Example 14

To 150 kg of a 40 aqueous solution of hexamethylenediammonium acetate (66 salt) in a 400-1 autoclave, 10 kg of the salt of hexamethylenediamine and dodecanedicarboxylic acid (612 salt) were added and dissolved therein, and then 30 kg of 8- Caprolactam (6M) was added and dissolved so that a weight ratio of 6M: 66 salt: 612 salt of 30:60:10 was achieved. Then the inside of the autoclave was purged with nitrogen for polymerization. The autoclave was heated for 1 hour at 23O ⁰ C, and gradually steam was removed and the internal pressure at

17.5 kg / cm was maintained. Then the internal pressure was during

was brought to atmospheric pressure from 17.5 kg / cm 2 over a period of 1 hour and heating was continued for 1 hour while

approximately
Nitrogen was bubbled through at atmospheric pressure / 1 hour.

From the thus obtained three-component random copolyamide having a relative viscosity of 2.45 as a component and nylon 66 having the relative viscosity of 2.47 as the other component, composite spinning in the same volume ratio of the components was carried out using a spinneret shown in FIG kidney-shaped composite threads carried out, which had five openings each with a diameter of O ₁ 3 mm.

In Figure 1, the copolyamide component is fed through channel a and nylon 66 through channels b and c. As shown in Figure 2, the thus obtained unstretched filaments were stretched by the feed roller 1 and the tension roller 3 to 3.5 times, and then by introducing into a 30 cm long heating chamber 5, kept under steam at 160 ⁰ C and in which the water

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water vapor was introduced from the nozzle 4 at the upper end of the heating chamber 5 ', thermally relaxed. The yarn was fed to the heating chamber at a speed of 800 m / min and thermally relaxed in the heating chamber 5 at a rate of 23 pounds by adjusting the speeds of the draw roller 3 and the take-off roller 6. Thereby, composite yarns of 22d / 5f developing 25 f crimps with a number of crimps of 17/25 mm were produced.

The curl developability and the percentage shrinkage in boiling water the fibers were 25 # and 9 $, respectively. the The rating of the knitted fabric, the gathering property and the resilience were good. The measurement with the help of X-rays led to essentially the same result as for sample V according to example 10.

Example 15

From the random three-component copolyamide prepared as in Example 14 having a copolymerization weight ratio of 8-caprolactam, hexamethylene diammonium adipate and salt of hexamethylene diamine and dodecanedicarboxylic acid of 35/60/5 and a relative viscosity of 2.46 as one component and nylon 66 one relative viscosity of 2.47 as the other component, composite spinning was carried out as in Example 14. The so obtained undrawn threads were drawn 3 »5 times and then introduced into a 30 cm long heating chamber 5 under a steam atmosphere of 168 C, in which the yarn with a Speed of 1100 m / min was introduced. Thermal relaxation was done with $ 21 relaxation being Composite yarns of 21 d / 5f were obtained, the 10 ° C crimp developed with a number of curls of 7/25 mm.

The curl developability of the fiber was 24 j £ that percent shrinkage in boiling water 11 pounds. The review of the knitted fabric and the X-ray test gave essentially the same results as in Example

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Example 16

From a random three-component copolyamide prepared as in Example 14 6/66/612 with a copolymerization weight ratio of δ-caprolactam, hexamethylene diammonium adipate and the salt of hexamethylenediamine and dodecanedicarboxylic acid of 30/55/15 and a relative viscosity of 2.48 as one component and nylon 66 having a relative viscosity of 2.47 as the other component were used in that described in Example 14 Wise composite threads K of 22d / 5f with a number of crimps of 17/25 are now obtained.

On the other hand, using three-component random copolyamide with a copolymerization weight ratio of 20/50/30 and a relative viscosity of 2.46 composite filaments X of 22d / 5f with a number of crimps of 16/25 mm produced by treatment in the manner described above. The curl developability and evaluation of the prepared and treated with boiling water as in Example 1 The knitted fabrics from IX and X are shown in Table 12. In addition, the X-ray test was carried out on monocomponent filaments from the copolyamide components of the fibers IX and X. The results obtained are shown in Table 13.

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Tabel Properties of the yarn Evaluation of the knit fabric

Sample Curl Development Percentage Curl Ability Irregular Curl Resilience Shrinkage

CO
OO
O

IX • 26 pounds 11 # T away Well no 103 I. X 17 # 10 # bad some stripes
term irregular
opportunities 51 Hurry

IX

After stretching

Incomplete crystalline structure. There was no peak splitting in the densitometer observed (one peak).

Incomplete crystalline structure. No peak splitting was observed in the densitometer (a Peak),

After the thermal relaxation
plot

After treatment in boiling water

Incomplete crystalline structure. There was no peak splitting in the Densitometec observed (one peak).

Has a crystalline structure. Splitting into two peaks at levels 100 and 010, 110 was made in the densitometer clearly observed.

Has a crystalline structure. Splitting into two peaks at levels 100 and 010, 110 was made in the densitometer clearly observed.

Has a crystalline structure. Splitting into two peaks in planes qq 100 and 010, 110 was clearly observed in the meter.

For comparison, filament yarns of the same composition as X were subjected to thermal relaxation-drawing treatment according to Example 1 of Japanese Patent Application Laid-Open No. 25507/1967 to obtain composite fibers of 22d / 5f. The knitted fabric made from the composite fibers thus obtained was treated in the manner described above. This knitted fabric exhibited good puckering properties and good resilience. The crimp developability of the filaments was 24 % and the percentage shrinkage in boiling water was 7 %.

From the above results, it is in view of the curl developability and the resilience of the knitted fabric as well as the crimp condition can be seen that yarns which Crystallize in the thermal expansion stage, do not show good results after the treatment according to the invention that however, with them, good results by the thermal relaxation-stretching treatment described in Japanese Patent Application 25507/1967. Good results can can only be achieved if the material according to the invention is used which fulfills the conditions defined according to the invention.

Example 17

The same procedure was followed for making composite thread as used in Example 14, with the modification that the three-component random copolyamide used is 6/66/612 Copolymerization ratio of 40/55/5 (weight ratio) and a relative viscosity of 2.43. From the thus obtained Undrawn threads became a composite fiber of 22d / 5f with a number of crimps in the manner described in Example 14 of 18/25 mm, with the modification that the undrawn Threads were subjected to a thermal relaxation treatment in a hot air atmosphere of 175 ° C. The ripple development

capacity and the percentage shrinkage in the boiling V / as-

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Ber of the yarn were 24 % and 10 #, respectively. The evaluation of the knitted fabric and the test with the aid of X-rays led to essentially the same result as in Example 14.

Example 18

To 240 kg of a 7% aqueous solution of hexamethylenediaramonium nebacate (610 salt) in a 400-1 autoclave, 30 kg of hexamethylenediammonium terephthalate (6T salt) were added and dissolved, and then 25 kg of a 40% aqueous solution of Hexamethylene diammonium adipate (66 salt) was added and dissolved so that a weight ratio of 66 salt: 6T salt: 610 salt of 10:30:60 was obtained. Then, the inside of the autoclave was purged with nitrogen for polymerization. The autoclave was heated for 1 hour at 23O ⁰ C while gradually vapor was removed and the internal pressure at 17.5 kg / cm was maintained. Then, the internal pressure was brought to atmospheric pressure from 17.5 kg / cm 2 over a period of 1 hour, and heating was continued for 1 hour while nitrogen was bubbled through at atmospheric pressure. With the thus obtained three-component random copolyamide of 66 / 6T / 61O having a relative viscosity of 2.45 as a component and nylon 66 having a relative viscosity of 2.47 as the other component, composite spinning was carried out in the manner shown in Example 1 . The undrawn threads obtained ^{in this way were drawn 3.3 times on a draw} pin (2 in FIG. 2) heated to 110 ° C. and then drawn into a 30 cm long heating chamber 5 under steam at 165 ° C. from the superheated steam nozzle was introduced at the upper end of the heating chamber 5, up to a relaxation of 22 $> thermally relaxed, while the yarn was fed to the heating chamber 5 at a speed of 800 m / min. As a result, composite yarns of 21d / 5f which developed 15 % crimp (number of crimps 12/25 mm) were obtained. The crimp developability and the shrinkage percentage of the filament yarns in boiling water were 23 pounds

A09807 / 1039

or 11 ^. Evaluation of knitted fabric and testing with Using X-rays gave essentially the same results as Sample I in Example 1.

Example 19

From the random three-component copolyamide prepared as in Example 18 66 / 6T / 61O with a copolymerization weight ratio of hexamethylene diammonium adipate, hexamethylene diammonium terephthalate and hexamethylene diammonium sebacate of 15/25/60 and a relative viscosity of 2.43 as one component and nylon 66 having a relative viscosity of 2.47 as the other component was specified in Example 18 Way of a composite fiber of 22d / 5f with a number of crimps of 14/25 mm (IX).

On the other hand, using random copolyamide 66 / 6T / 610 having a copolymerization weight ratio of 20/20/60 and a relative viscosity of 2.45 a composite thread of 22d / 5f (XII) by treatment in the above obtained which had a number of crimps of 14/25 mm.

The crimp developability of pilament yarns and the Evaluation of the knitted fabric produced and treated with boiling water, which was carried out as in Example 1, are shown for XI and XII in Table 14. In addition, the measurement was carried out with the aid of X-rays on threads XI and XII carried out. The results are shown in Table 15.

4 & 98Q7 / 1Q39

Tabel Properties of the yarn

O
CO
OO

Sample Curl Development Percentage Shrinkage Ability

XI

XII

25th

16

sample

9 8

Evaluation of the knit fabric

Pucker Ability Irregular Curling Recovery

ability

Well

Well

Tabel

no

some streak-like irregularities

111

60

XII

After stretching

Incomplete crystalline structure, no peak splitting was observed in the densitometer observed (one peak).

Incomplete crystalline structure. No peak splitting was observed in the densitometer (a Peak).

After the thermal relaxation
plot

After treatment in
boiling water

Incomplete crystalline structure. There was no peak splitting in the densitometer observed (one peak).

Has a crystalline structure. In the densitometer the splitting was observed clearly observed in two peaks at levels 100 and 010, 110.

Has a crystalline structure. In the densitometer the splitting was observed clearly observed in two peaks at levels 100 and 010, 110.

Has a crystalline structure. In the co densitometer the splitting OO tion clearly observed in two peaks at levels 100 ^ O and 010, 110. "

2338235

For comparison purposes, a yarn of the same composition was used as XII in the same manner as in Example 1 of Japanese Patent Application 25507/1967 to form a composite fiber from 22d / 5f thermally relaxed-stretched. The one from the knitted fabric made of composite yarn thus obtained was treated in the above-mentioned manner. The curling ability and the knit reset were good. The ripple developability was $ 24 and the percent shrinkage in boiling water was 9 ^.

The above results show that in terms of curl developability and recovery of the knitted fabric and condition of the crimp yarns that are in the thermal Crystallize relaxation stage, show no good results in the treatment according to the invention, but they do good results due to the thermal relaxation-stretching treatment which is described in well-known Japanese Patent Application 25507/1967. Good results can only be obtained using the material of the present invention which is that described herein Conditions met.

Example 20

The same procedure was used to produce composite yarn as in Example 18, except that a two-component copolyamide 6T / 61O having a copolymerization ratio of 20/80 (weight ratio) and a relative viscosity of 2.51 was used. From the thus obtained unstretched composite filaments of composite fibers were mixed with 2oD / 5f having a crimp of 13/25 mm as prepared in Example 18 in the same manner, except that the undrawn yarn is stretched and subjected to thermal relaxation treatment in a hot air atmosphere at 180 ⁰ C became. The Kräuselungsentwicklungsfähigkeit and shrinkage percentage in boiling water of the filament yarn were 25% and 10 f ..

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^"43 ~ 2338236

The evaluation of the knitted fabric and the X-ray examination produced essentially the same results as for Sample XI in Example 19.

Example 21

To 220 kg of a 25% aqueous solution of the salt of hexamethylenediamine and dodecanedicarboxylic acid (612 salt) in a 400-1 autoclave, 35 kg of hexamethylenediammonium terephthalate (6T salt) were added and dissolved, and then 25 kg of a 40 # - igen aqueous solution of hexamethylenediammonium adipate (66 salt) was added and dissolved so that a weight ratio of 66 salt: 6T salt: 612 salt / 10: 35:55 was achieved. The thus obtained three-component copolyamide 66 / 6T / 612, which was prepared as in Example 18 and had a relative viscosity of 2.43 as one component and nylon 66 having a relative viscosity of 2.47 as the other component, were spun together in the manner indicated in Example 1 composite threads produced. The undrawn threads thus obtained were ^{drawn 3.3 times on a draw} pin (2 in FIG. 2) heated to 110 ° C. and then thermally relaxed as in Example 18, a composite fiber of 22d / 5f with a number of crimps of 13/25 mm was obtained. The Kräuselungsentwicklungsfähigkeit and the shrinkage percentage in boiling v / ater of the fibers were 25 i "or $ 9. A knitted fabric made from the fibers had good puckering properties and good resilience. The evaluation of the knitted fabric and the examination with the aid of X-rays led to essentially the same results as in Example 1.

Example 22

From the random three-component copolyamide prepared as in Example 21 66 / 6T / 612 with a copolymerization weight ratio of 25/35/40 and a relative viscosity of 2.46 as a component and nylon 66 of a relative viscosity of 2.47 as the other component were used in the example

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18 described way composite threads XIII of 2Od / 5f with a Number of crimps of 13/25 mm preserved. On the other hand was using copolyamide 66 / 6T / 612 with a copolymerization ratio of 35/25/40 (wt.) and a relative viscosity of 2.47 a composite fiber (XIV) of 2Od / 5f with a Number of crimps of 14/25 mm produced by treatment in the manner described above.

The ripple development ability and the rating of the manufactured and knitted fabric made from fibers XIII and XIV treated with boiling water as in Example 1 are shown in Table 16 shown. In addition, the X-ray examination of the fibers XIII and XIV was carried out. The Results are shown in Table 17.

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Table 16

Properties of the Yarn Valuation; of the knitted fabric 17th Irregular herb
selung Reset
capital robe Ripple lung development
ability Percentage
shrinkage Crimp ability no 110 XIII 23 % $ 10 Well some stripes
term irregular
opportunities 61 XIV 17 % 9 * · tab insufficient Hurry

sample

<s * After the -* stretch ο

XIII

Incomplete crystalline structure. The observation in the densitometer showed no peak splitting (one peak). XIV

Incomplete crystalline structure. The observation in the densitometer showed no peak splitting (C a peak).

After the thermal incomplete crystalline structure, see relaxation The observation in the densitometer demonstration treatment te no peak splitting (one peak). Has a crystalline structure. The observation in the densitometer clearly showed a split into two peaks in levels 100 and 010, 110.

After treatment in boiling water

Has a crystalline structure. The observation in the densitometer clearly showed a split into two peaks in levels 100 and 010, 110. Has a crystalline structure. The observation in the densitometer clearly showed a split into two peaks in levels 100 and 010, 110. "

For comparison purposes, a yarn of the same composition as XIV was thermally relaxed-stretched in the manner indicated in Example 1 of Japanese patent application 25507/1967, a composite fiber of 20d / 5f being obtained. The knitted fabric made from the composite fibers thus obtained was treated in the above-mentioned manner. The puckerability and the resilience were good. The curl developability was 24 % and the percent shrinkage in boiling water was 8%.

From the above results, it can be seen that in terms of curl developability and resilience of the knitted fabric as well as the condition of the crimp Yarns that crystallize in the thermal tension stage, show no good results in the treatment according to the invention, but rather good results in the thermal Show relaxation-stretching treatment described in known Japanese Patent Application No. 25507/1967 is. Good results can only be achieved if the material according to the invention is used, which is the one described Conditions met.

Example 23

The same procedure was used for the production of composite yarn as in Example 1, with the modification that a three-component copolyamide 66 / 6T / 612 was used with a copolymerization weight ratio of 5/35/60, which had a relative viscosity of 2, 48 had. From the undrawn threads obtained in this way, composite fibers of 22d / 5f with a number of crimps of 13 / 25mm were produced according to the manner described in Example 18, with the modification that the undrawn yarn was drawn and a thermal relaxation treatment in a hot air atmosphere of 180 ^° C. was subjected.

409807/1038

The crimp developability of the filajnent yarn was 24 % and the percentage shrinkage in boiling water was 11 #. The puckering ability and the resilience of the knitted fabric were good. The evaluation of the knitted fabric and the X-ray examination gave essentially the same results as for Sample I in Example 1.

Belapiel 24

With three-component random copolyamide 6/66 / 6T having a copolymerization ratio of 30/30/40 (weight ratio) and a relative viscosity of 2.53 as one component and nylon 6 having a relative viscosity of 2.45 as prepared as in Example 4 as the other component, composite spinning was carried out as in Example 4. The resulting undrawn filaments were stretched on a heated at 110 ⁰ C draw pin (2 in Figure 2) to 3.3 times, and then by introducing into a 30 cm long heating chamber with steam at 173 ⁰ O, which consists of a Heißdampfdüse on The yarn was introduced into the heating chamber at a speed of 800 m / min and composite threads of 23d / 5f were obtained, the 30 f. crimp with a Number of crimps of 21/25 mm developed. The crimp developability of the filament yarns was 27 f> and their boiling water shrinkage was 10 #. The evaluation of the knitted fabric in terms of puckering ability and resilience was good. The X-ray examination gave essentially the same results as in Example 4.

Example 25

The procedure described in Example 4 was followed with the modification that a statistical component was used as a component Three component copolyamide 6/66 / 6T with a copolymerization weight ratio of 50/4/45 and a relative viscosity of 2.45 was used, with a composite fiber of 21d / 5f with a number of crimps of 17/25 mm was obtained.

409807/1039

The crimp developability of the yarn was 27% and its shrinkage in boiling water 10 #. The evaluation of the The knitted fabric was good in terms of gatherability and resilience. The X-ray examination resulted in the essentially to the same results as in example 4

Example 26

From the random three-component copolyamide prepared as in Example 4 6/66 / 6T with a copolymerization weight ratio of 15/65/20 and a relative viscosity of 2.53 as one component and nylon 66 of relative viscosity 2.47 as all other components became composite filaments by composite spinning through a composite spinning pin for kidney-shaped threads shown in Figure 1 is shown, with 15 openings with a diameter of 0.5 each now made.

According to Figure 1, the copolyamide component is fed through channel a and nylon 66 through channels b and c. As shown in Figure 2, the thus obtained unstretched filaments were stretched by a Zufuhrungswalze 1 and a tension roller 3 to the 313-fold and then kept under steam at 165 ⁰ C by introducing it into a 30 cm long heating chamber 5 »and in which the steam was blown in from the nozzle 4 at the upper end of the heating chamber 5, thermally relaxed. The threads were fed in at a speed of 900 m / min and thermally relaxed at a relaxation of 19 ° , whereby composite threads of 1600 d / 60f with a number of crimps of 5 / 25mm were obtained.

The Kräuselungsentwicklungsfähigkeit the fiber was $ 15 and its boiling water shrinkage was 8 $>

The filament yarn thus obtained was twisted to 40T / m and closed processed a pile carpet with sufficient bulk, whose pile length was 8 mm and whose weight was 750 g / m. It was

4Θ9807 / Ί029

de observed that the carpet obtained in this way is extremely advantageous Plore properties showed. The number of crimps after the coloring was 17/25 mm.

Example 27

The procedure described in Example 26 was used with the modification that a random three-component copolyamide 6/66/61 with a copolymerization weight ratio of 10/50/40 and a relative viscosity of 2.51 was used as a component for the production of the undrawn thread was used. After stretching ^{3.3 times on a draw} pin (2 in FIG. 2) heated to 120 ° C., the yarn was then thermally relaxed, with composite fibers of 16OOd / 60f with a number of crimps of 3/25 mm being formed. The Kräuselungsentwicklungsfähigkeit of the fibers was 13 $> and the shrinkage percentage in boiling water 7 #. A carpet produced from the composite yarns thus obtained as in Example 26 showed high bulk with very good quality. It was confirmed that the yarn was extremely good in terms of pile properties.

Example 28

From the three component random copolyamide 66 / 6T / 610 prepared as in Example 18 having a copolymerization weight ratio of 50/30/20 and a relative viscosity of 2.54 as a component and nylon-66 having a relative viscosity of 2.47 as Another component was made a composite fiber by composite spinning as in Example 26. The resulting undrawn filaments were stretched on a heated at 120 ⁰ C draw pin (2 in Figure 2) to 3.3 times and then in a 30 cm long heating chamber, which was maintained under steam at 17O ⁰ C and in which steam was blown from the nozzle 4 at the upper end of the heating chamber 5 is introduced. The yarn was

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speed of 900 m / min supplied and thermally relaxed with 18 fi relaxation, a composite fiber of 16OOd / 60f with a number of crimps of 3/25 mm was obtained. The crimp developability and the boiling water shrinkage percentage of the filament yarn were 14% and 8 %, respectively. A carpet made from the composite yarns thus obtained as in Example 26 exhibited high bulk and superior quality. It was confirmed that the yarn also exhibited extremely good pile properties.

Example 29

The procedure described in Example 28 was followed, with the modification that a statistical three-component copolyamide 66 / 6T / 61O with a copolymerization weight ratio of 40/30/30 and a relative viscosity of 2.45 could be used as an option was used to obtain a composite filament yarn of 160Od / 6Of with a number of crimps of 4/25 ma . The curl developability and the boiling water shrinkage percentage of the fibers were 14 # and 9 #, respectively. A carpet made from the obtained yarns as in Example 26 had high bulk and was highly resilient and exhibited excellent quality. The yarns were also extremely good in terms of pile properties,

Example 30

The same procedure was followed as in Example 28, except that a three-component random copolyamide 66 / 6T / 61O having a copolymerization weight ratio of 25/30/45 and a relative viscosity of 2.51 was used as one component , whereby composite yarns of 16OOd / 6Of with a number of crimps of 6/25 mm were obtained. The obtained yarn showed a crimp developability of 16 ^ and a boiling water shrinkage of 7 #. A carpet made from the yarns obtained as in Example $ 2 had high bulk and good elasticity and was of high quality.

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The yarn had extremely good pile properties.

Example 31

The procedure described in Example 26 was used, with the modification that a statistical three-component copolyainide 66 / 6T / 612 with a copolymerization ratio of 50/30/20 (weight ratio) and a relative viscosity of 2.42 as a component for preparing the undrawn Composite yarn was used. Then the yarn was drawn and as in Example 28 subjected to a thermal relaxation treatment, where composite filament yarn of 16OOd / 6Of with a number the crimp of 5/25 mm was obtained. The ripple developability of the yarn was £ 14, and its boiling water shrinkage was £ 8. One as in example 26 from the Carpet made of yarns thus obtained had high bulk and high elasticity and excellent quality. The yarn also showed excellent pile properties.

Example 32

The same procedure as used in Example 31, except that was used as a component of a Dreikomponen copolyamide 66 / 6T / 612 having a copolymerization weight ratio of 35/35/30 and a relative viscosity of 2.52. A composite fiber of 16OOd / 60f with a number of crimps of 8/25 mm was obtained. The crimp developability and the boiling water shrinkage percentage of this fiber were 15 % and 9 #, respectively. A carpet produced from the yarns thus obtained as in Example 26 had high bulk and was highly elastic with excellent quality. It was confirmed that the yarn also had extremely good pile properties.

Example 33

Undrawn yarn was, as in Example 4, from a statistical! Three-component copolyamide 6/66 / 6T with a copolymerization

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weight ratio of 20/30/50 and a relative viscosity of 2.55 as one component and nylon 66 of relative viscosity 2.47 as the other component. The thus obtained undrawn composite yarn were stretched using a draw pin (2 in Figure 2), which was heated to 110 ⁰ C at 3.3 times, introduced into a kept under a steam atmosphere of 165 C 30 cm long heating chamber 5 and thermally relaxed. The steam was introduced through nozzle 4 at the top of the heating chamber 5. The yarn was fed to the heating chamber 5 at a speed of 800 m / min and thermally relaxed with a relaxation of 23% to obtain composite yarns of 21d / 5f which developed 20 latent crimp with the number of crimps of 13/25 mm . The curl developability and boiling water shrinkage percentage of the fibers were 25 # and 11 #, respectively. The evaluation of the knitted fabric and the X-ray test led to essentially the same results as in Example 4.

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Claims (12)

PATENT CLAIMS f 1, yCrinkleable composite fiber, which consists of components of a homopolyamide and a random copolyamide arranged eccentrically in the fiber and which has been drawn after its formation, characterized in that it has been subjected to a thermal relaxation treatment in which part of the latent crimp has been developed, but no crystal structure recognizable by X-ray diffraction was formed in the copolyamide random component. 2. Crimpable composite fiber according to claim 1, characterized in that it contains a random copolyamide as a fiber component, which in the form of a one-component thread after treatment with water vapor from 100 ⁰ C to 200 ⁰ C for 10 "" * to 0.5 seconds none by X-ray diffraction shows recognizable crystal structure. 3. Crimpable composite fiber according to claim 1 or 2, characterized characterized in that they are as homopolyamide polycapronamide, polyhexamethylene adepamide, polyundecamide, polydodecamide, Contains polyhexamethylene bebacamide or polyhexamethylene dodecamide. 4. Crimpable composite fiber according to claims 1 to 3 »thereby characterized in that it is a statistical copoly- 4098Θ7 / 1039 2333288 amide is a copolymer of ε-caprolactam and hexamethylene diammonium adipate , a copolymer of 5-caprolactam, hexamethylene diammonium adipate and hexamethylene diammonium terephthalate, a copolymer of E-caprolactam, hexamethylene diammonium adipate and the salt of hexamethylenediamine and dodecanediearboxylic acid, a copolymer of hexamethylenediamonium adipate, hexamethylenediamraonium terephthalate and hexamethylene diammonium sebacate or a copolymer of hexamethylene diammonium adipate, hexamethylene diammonium terephthalate and the salt of hexamethylenediamine and dodecanediearboxylic acid. 5. Crimpable composite fiber according to claim 4, characterized in that it is a random copolymer contains, which is formed from 30 to 60 wt. Ji 6-caprolactam is. 6. Crimpable composite fiber according to claim 4, characterized in that it is a random copolymer 6/66 / 6T of a composition which lies in the triangular coordinate system in the area bounded by a line which is the -points of the weight ratios of ^ -caprolactam to hexamethylene diammonium adipate to hexamethylene diammonium terephthalate from 85: 0:15, 65:20:15, 60: 40: 0, 30: 70: 0, 10:70:20, 5:55:40 and 35: 0:65 connects. 409897/1039 7. Composite fiber capable of crinkling according to claim 41, characterized in that ßie is a random copolymer 6/66/610 contains, the composition of which lies in the area bounded by the line which marks the points of the Gewi The ratio of k-caprolactam to hexamethylene diammonium adipate to hexamethylene diammonium sebacate of 60: 40: 0, 30: 70: 0 and 30:40:30 in the triangular coordinate system, B. Krause1baren composite fiber according to claim 4, daaarch characterized in that it is a random copolymer 6/66/612 contains its composition in the triangular coordinate system lies inside the area bounded by the line which marks the points of the weight ratios from £ - Caprolactam to hexamethylene diammonium adipate to the salt of hexamethylene diamine and dodecanedicarboxylic acid of 50: 50: 0, 30: 70: 0 and 24:45:30. 9. Crimpable composite fiber according to claim 4, characterized in that it is a random copolymer 66 / 6T / 61O contains its composition in the triangular coordinate system is within the range bounded by the line showing the points of the weight ratios of hexamethylene diammonium adipate to hexamethylene diammonium terephthalate to hexamethylene diammonium sebacate from 62.5: 22.5: 15, 55:30:15, 45:35:20, 0:35:65, 0:20:80 and 17.5: 22.5: 60 connects. 409807/1039 " ⁵⁶ " 2338236 10. Crimpable composite fiber according to claim 4, characterized in that it is a random copolymer 66 / 6T / 612 contains its composition in the triangular coordinate system is within the range bounded by the line showing the points of the weight ratios of hexamethylene diammonium adipate to hexamethylene diammonium terephthalate Salt from
dem / hexamethylenediamine and dodecanedicarboxylic acid of 65 * 25: 10, 40: 40:20, 0:45:55, 0: 32.5: 67.5 and 27.5: 32.5: 40 connects. 11. Crimpable composite fiber according to claims 1 to 10, characterized in that after the thermal relaxation treatment the statistical copolyamide present as a thread component in the test by X-ray diffraction did not Shows crystal structure and that the fiber has a crimpability of 5 to 30 #. 12. Crimpable composite fiber according to claims 1 to 11, characterized in that the difference in the percentage shrinkage in boiling water between the homopolyamide and the statistical copolyamide is at least 10 % . 13- crimpable composite fiber according to claims 1 to 12, characterized in that it has been subjected to a thermal relaxation treatment at a temperature between 130 ^° C and the melting point of the lowest melting component. 409807/1039 23382S6 ί4. Process for making a crimpable composite fiber according to claims 1 to 13 by composite spinning of a homopolyamide and a random copolyamide into a composite fiber with eccentric Arrangement, stretching and subsequent thermal relaxation of the composite fiber obtained, characterized in that the composition of the statistical Copolyamides and the relaxation conditions are chosen so that the random copolyamide passes through the test X-ray diffraction has no crystal structure and that part of the curl develops latent curling ability will. 409807/1039