DE1213954B - Composite fibers or threads made from acrylonitrile polymers - Google Patents

Composite fibers or threads made from acrylonitrile polymers

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Publication number
DE1213954B
DE1213954B DEP19615A DEP0019615A DE1213954B DE 1213954 B DE1213954 B DE 1213954B DE P19615 A DEP19615 A DE P19615A DE P0019615 A DEP0019615 A DE P0019615A DE 1213954 B DE1213954 B DE 1213954B
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DE
Germany
Prior art keywords
threads
thread
polymers
fibers
composite fibers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
DEP19615A
Other languages
German (de)
Other versions
DE1213954C2 (en
Inventor
Alvin Leonard Breen
Robert Burns Taylor Jun
Lothar Helmut Belck
Karl Glenn Siedschlag Jun
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of DE1213954B publication Critical patent/DE1213954B/en
Application granted granted Critical
Publication of DE1213954C2 publication Critical patent/DE1213954C2/en
Expired legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/32—Side-by-side structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/26—Composite fibers made of two or more materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S425/00—Plastic article or earthenware shaping or treating: apparatus
    • Y10S425/217—Spinnerette forming conjugate, composite or hollow filaments
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/04—Polyester fibers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/09—Polyolefin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/10—Polyvinyl halide esters or alcohol fiber modification
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/21—Nylon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2922—Nonlinear [e.g., crimped, coiled, etc.]
    • Y10T428/2924—Composite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2922—Nonlinear [e.g., crimped, coiled, etc.]
    • Y10T428/2925—Helical or coiled
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer
    • Y10T428/2969—Polyamide, polyimide or polyester
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2973—Particular cross section
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3146—Strand material is composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
    • Y10T442/3154—Sheath-core multicomponent strand material

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Multicomponent Fibers (AREA)

Description

BUNDESREPUBLIK DEUTSCHLAND DEUTSCHES MTTWl· PATENTAMT Int. Cl.: FEDERAL REPUBLIC OF GERMANY GERMAN MTTWl · PATENT OFFICE Int. Cl .:

DOIfDOIf

AUSLEGESCHRIFTEDITORIAL

Deutsche Kl.: 29 b - 3/65 German class: 29 b - 3/65

Nummer:
Aktenzeichen:
Anmeldetag:
Auslegetag:Number:
File number:
Registration date:
Display day:

1213 954
P19615IV c/29 b
8. November 1957
7. April 19661213 954
P19615IV c / 29 b
November 8, 1957
April 7, 1966

Es ist bekannt, Kräuselgarn aus Verbundfäden aus synthetischen Polymeren herzustellen, deren exzentrisch angeordnete Komponenten sich in ihrem Schrumpfungsvermögen unterscheiden. Durch eine Schrumpfungsbehandlung entsteht dann die Krauselung (USA.-Patentschrift 2443 711). Nachteilig ist dabei die geringe Kräuselbeständigkeit.It is known to make crimped yarn from composite threads to produce synthetic polymers whose eccentrically arranged components are in their Differentiate shrinkage capacity. The puckering is then created by a shrinking treatment (U.S. Patent 2,443,711). The disadvantage here is the low resistance to curling.

Aus der französischen Patentschrift 1124 921 ist es bekannt, die Kräuselbeständigkeit solcher Verbundfäden zu erhöhen, indem man den Faden vor der Schrumpfung längenstabilisiert. Dadurch kommt die Komponente hoher elastischer Erholung auf die Innenseite der Wendel, wird also zur lastaufnehmenden Komponente.From French patent specification 1124 921 it is known the crimp resistance of such composite threads by stabilizing the length of the thread before it shrinks. This comes about the component of high elastic recovery on the inside of the helix becomes the load-bearing one Component.

Diese letztgenannte Lösung ist zwar bereits infolge der erheblichen Erhöhung der Kräuselbeständigkeit sehr vorteilhaft, läßt aber noch Wünsche offen.This last-mentioned solution is already due to the considerable increase in the crimp resistance very advantageous, but leaves something to be desired.

Erfindungsgegenstand sind Verbundfasern oder -fäden, bestehend aus mindestens zwei Komponenten aus synthetischen Acrylnitrilpolymerisaten von unterschiedlichem Schrumpfvermögen, die im Querschnitt gesehen exzentrisch zueinander angeordnet sind. Die Fasern oder Fäden sind dadurch gekennzeichnet, daß eines der Polymeren ionisierbare Gruppen enthält, und zwar in einer um mindestens 30 Milliäquivalente je Kilogramm Polymeres größeren Menge als die anderen.The subject of the invention are composite fibers or threads, consisting of at least two components made of synthetic acrylonitrile polymers with different shrinkage capacities, which in cross section viewed eccentrically to each other. The fibers or threads are characterized in that one of the polymers contains ionizable groups by at least 30 milliequivalents more per kilogram of polymer than the others.

Bevorzugt sind Fasern oder Fäden, die dadurch gekennzeichnet sind, daß diejenige Komponente, die die überschüssigen ionisierbaren Gruppen enthält, außerdem ein übliches nichtionogenes Modifizierungsmittel enthält, wie es zum Färben von Polyacrylnitril mit Dispersionsfarbstoffen verwendet wird.Fibers or threads are preferred which are characterized in that the component which which contains excess ionizable groups, also a conventional nonionic modifying agent contains how it is used for coloring polyacrylonitrile with disperse dyes will.

Unter Acrylnitrilpolymerisaten sind Homopolymere des Acrylnitril und Mischpolymere mit einem Acrylnitrilgehalt von mehr als 85% zu verstehen.Acrylonitrile polymers include homopolymers of acrylonitrile and copolymers with one To understand acrylonitrile content of more than 85%.

Die Verbundfasern oder -fäden gemäß der Erfindung weisen eine reversible Kräuselung auf, worunter zu verstehen ist, daß bei der Einwirkung von Quellmitteln auf den zerdrückten und verdichteten Faden der ursprüngliche Kräuselzustand wiederhergestellt wird und auch nach erfolgtem Trocknen so bleibt.The composite fibers or filaments according to the invention have a reversible crimp, among which it is to be understood that when swelling agents act on the crushed and compressed thread the original curled state is restored and remains so even after drying.

Den Wert dieser Kräuselreversibilität zeigen die Fasern, besonders wenn sie in ein Gewebe eingearbeitet werden. Unter dem Einfluß eines Quellmittels, wie Wasser (und ebenso bei Entfernung desselben), winden sie sich im Gewebe oder drehen sich, aber nach Entfernen des Quellmittels, z. B. nach dem Trocknen, nehmen sie die Kräuselung wieder an, die sie ursprünglich hatten, Gewebe, welche die erfindungsgemäßen Fasern enthalten, erlangen durch die Verbundfasern oder -fäden aus Acrylnitrilpolymerisaten The fibers show the value of this curl reversibility, especially when they are incorporated into a fabric will. Under the influence of a swelling agent such as water (and also when it is removed), they twist or twist in the tissue, but after removing the swelling agent, e.g. B. after the When dry, they reassume the curl they originally had, fabrics made with the present invention Containing fibers obtained through the composite fibers or threads made of acrylonitrile polymers

Anmelder:Applicant:

E. I. du Pont de Nemours and Company,E. I. du Pont de Nemours and Company,

Wilmington, Del. (V. St. A.)Wilmington, Del. (V. St. A.)

Vertreter:Representative:

Dr.-Ing. W. Abitz, Patentanwalt,Dr.-Ing. W. Abitz, patent attorney,

München 27, Pienzenauer Str. 28Munich 27, Pienzenauer Str. 28

Als Erfinder benannt:
Alvin Leonard Breen, West Chester, Pa.;
Robert Burns Taylor jun., Wilmington, Del.;
Lothar Helmut Belck, Waynesboro, Va.;
Karl Glenn Siedschlag jun.,
Wilmington, Del. (V. St, A>)Named as inventor:
Alvin Leonard Breen, West Chester, Pa .;
Robert Burns Taylor, Jr., Wilmington, Del .;
Lothar Helmut Belck, Waynesboro, Va .;
Karl Glenn Siedschlag jun.,
Wilmington, Del. (V. St, A>)

Beanspruchte Priorität:Claimed priority:

V. St. v. Amerika vom 9. November 1956
(621443),V. St. v. America 9 November 1956
(621443),

vom 18. Februar 1957
(640 722, 640723)dated February 18, 1957
(640 722, 640723)

QueHbehandlung eine größere Fülligkeit und behalten dieselbe bei oder erlangen sie sogar in verstärktem Maß, nachdem sie wiederholt solchen Behandlungen unterworfen sind. Aus diesen Fasern bestehende Gewebe können mit Vorteil auch einer physikalischen Bearbeitung unterworfen werden, um Fülligkeit in dem größtmöglichen Ausmaß zu entwickeln. Da die Schrumpfung bei der Endbehandlung gering ist, besitzen die Garne von Geweben, die solche Fäden enthalten, eine verhältnismäßig offene Struktur der Art, daß die Gewebe ungewöhnliche Elastizitätseigenschaften aufweisen. Die reversible Windungskräuselung bietet auch besondere Vorteile bei Geweben mit samtartiger Oberfläche, wie sie für Teppiche und Polsterbezüge verwendet werden, bei denen der im Einsatz erfolgenden Verdichtung der Fasern begegnet werden muß; wenn man die Fasern mit Wasser oder anderen Quellmitteln behandelt oder einfach -der Einwirkung feuchter Luft aussetzt, winden bzw. lösen sie sich aus dem verdichteten Zustand heraus, winden sich aber beim Trocknen erneut undTreating them with a greater fullness and maintaining it or even acquiring it to a greater extent Measure after repeatedly subjected to such treatments. From these fibers Existing tissues can advantageously also be subjected to physical processing in order to To develop fullness to the greatest possible extent. As the shrinkage in the final treatment is low, the yarns of fabrics containing such threads have a relatively open one Structure such that the fabrics have unusual elastic properties. The reversible Winding pucker also offers particular advantages in fabrics with a velvety surface, such as those used for Carpets and upholstery covers are used in which the compaction takes place in use Fibers must be encountered; if the fibers are treated with water or other swelling agents or simply-exposed to the action of moist air, they twist or loosen themselves from the compressed state out, but twist again as they dry and

609 557/296·609 557/296

kehren dabei in den hochgekräuselten und voluminö- Schrumpfung eine um zumindest 0,4%, vorzugsweise sen Zustand zurück, in dem sie sich vor der Verdich- zumindest 0,6%, größere reversible Längenänderung rung befanden. als die andere Komponente ergeben.In the process, the highly curled and voluminous return shrinkage by at least 0.4%, preferably sen state in which they are before the compression at least 0.6%, greater reversible change in length were found. than the other component.

Daß ein Unterschied in dem Gehalt an ionisier- Zur Ermittlung der Kräuselreversibilität wird ausThat there is a difference in the content of ionizing material is used to determine the curl reversibility

baren Gruppen der Komponenten die in dem ur- 5 den versteckten, nicht entspannten Fäden bzw. dem sprünglichen Zustand vorhandene Kräuselung eines Fadenbündel ein einzelner Faden genommen. Ein durch längeren Einsatz zusammengedrückten Ver- 7,6 cm langes Stück des Fadens wird bei einem bundfadens wiederherstellt, war nicht zu erwarten. 30%igen Durchhang zwischen seinen Enden mit den Denn eine Quellung führt zu einer Vergrößerung des gegenüberliegenden Seiten eines rechteckigen Kupfer-Abstandes der Hauptvalenzketten voneinander, nicht io drahtrahmens verbunden. Rahmen und Faden werdes Abstandes der Atome innerhalb der Kette, so daß den dann 15 Minuten abgekocht, um die Kräuselung eine Längenänderung überhaupt nicht zu erwarten zu entwickeln. Der gekräuselte Faden wird dann in war. Noch ferner lag es, daß der Unterschied von nur einen Spezialbetrachtungshalter eingebracht, indem 30 Milliäquivalenten ionisierbarer Gruppen je Kilo- man seine Enden mittels Band oder Klebstoff so gramm Polymeres in den beiden Komponenten eine 15 befestigt, daß der Durchhang etwa 10% und die solch starke unterschiedliche Längsquellung ergibt, Fadenlänge zwischen den festgelegten Enden etwa daß dieser Unterschied als Triebkraft zur Wieder- 6,4 cm beträgt. Faden und Betrachtungshalter werden herstellung der ursprünglichen Kräuselung wirkt. dann vertikal in einem verstöpselten Prüfrohr ange-groups of the components that are hidden in the original, non-relaxed threads or the a single thread is taken from the initial state of crimping of a bundle of threads. A by using a compressed length of 7.6 cm long piece of thread with a bundle thread was restored was not to be expected. 30% slack between its ends with the This is because swelling leads to an enlargement of the opposite sides of a rectangular copper gap of the main valence chains from one another, not connected to the wire frame. Frame and thread become Spacing of the atoms within the chain, so that the then boiled for 15 minutes to get the crimp a change in length is not expected to develop at all. The crimped thread is then turned into was. It was still further that the difference was brought in by just one special viewing holder 30 milliequivalents of ionizable groups per kilo of its ends using tape or glue like this grams of polymer in the two components attached a 15 that the sag is about 10% and the such strong different longitudinal swelling results, thread length between the fixed ends about that this difference as the driving force to the return is 6.4 cm. Thread and viewer will be production of the original crimp works. then placed vertically in a plugged test tube

Zur Ermittlung der reversiblen Längenänderung ordnet, das ein Entwässerungsmittel enthält. Das werden Strähnen der versteckten, nicht entspannten ao Rohr wird in senkrechter Lage über Nacht (18 bis Fäden 15 Minuten in Wasser gekocht. Dann werden 24 Stunden) auf 70° C gehalten. Nach dieser Kondi-Strähnen von einem Gesamttiter von etwa 300 den tionierung, bei welcher die Trocknung des Fadens und einer Länge von 15 cm in einer mit Gummi- erfolgt, bringt man das Rohr auf Raumtemperatur backen versehenen Klemme eingeklemmt, senkrecht (etwa 25° C). Man läßt 30 Minuten lang abkühlen von dieser herabhängen gelassen und mit einer 1,2-g- 25 und zählt dann die Gesamtzahl an Kräuselungen, die Klemme belastet. Die Probe wird in senkrechter Lage sich im Faden zwischen den festgelegten Enden befinin einem verstöpselten Glasrohr angeordnet, das am den, wobei alle Umkehrstellen der Kräuselung außer Boden ein Entwässerungsmittel enthält. Das Rohr acht gelassen werden. Dann wird das Entwässerungswird in senkrechter Lage über Nacht (18 bis 24 Stun- mittel aus dem Glasrohr entfernt, das Rohr mit den) auf 70° C gehalten. Nach dieser 70° C-Kondi- 30 Wasser gefüllt und in vertikaler Lage 6 Stunden auf tionierung, bei welcher die Probe trocknet, wird die 70° C gehalten. Hierauf zählt man wie oben die Zahl Trockenlänge bei 70° C, d. h. der Abstand zwischen der in dem nassen Faden befindlichen Kräuselungen, den beiden Klemmen, mit einem Kathetometer ge- Dieser Prüfzyklus wird in der zur Erzielung repromessen. Hierauf entfernt man das Entwässerungs- duzierbarer Ergebnisse erforderlichen Weise wiedermittel aus dem Rohr, füllt dasselbe mit Wasser und 35 holt. Die Kräuselreversiblität unter Gleichgewichtshält es in senkrechter Lage 6 Stunden auf 70° C. Die bedingungen bzw. Veränderung in der Zahl der Länge der nassen Probe wird bei 70° C bestimmt. Die Kräuselungen je Zentimeter gekräuselte Fadenlänge Zyklen werden in der zur Erzielung reproduzierbarer zwischen 25° C im trocknen .und 70° C im nassen Ergebnisse erforderlichen Weise wiederholt. Zustand, ausgedrückt als AK/cm, wird nach der fol-To determine the reversible change in length assigns that contains a dehydrating agent. The strands of the hidden, non-relaxed ao tube are kept in a vertical position overnight (18 to threads 15 minutes in water. Then 24 hours) are kept at 70 ° C. After these conditioning strands of a total titer of about 300 deniering, in which the drying of the thread and a length of 15 cm takes place in a clamp provided with rubber bake, the tube is brought to room temperature bake clamped, vertically (about 25 ° C ). Allow to cool for 30 minutes and hang from this with a 1.2 g-25 and then count the total number of crimps placed on the clamp. The sample is placed in a vertical position in the thread between the fixed ends in a plugged glass tube which contains a dehydrating agent at the point where the crimp is reversed except for the bottom. The pipe eight be left. Then the drainage is kept in a vertical position overnight (18 to 24 hours a day from the glass tube, the tube with the) at 70 ° C. After this 70 ° C conditioning, water is filled and in a vertical position for 6 hours, during which the sample dries, the 70 ° C is maintained. Then count as above the number of dry length at 70 ° C., ie the distance between the crimps in the wet thread, the two clamps, using a cathetometer. The drainage-reducing results are then removed from the pipe again, as required, filled with water and taken out. The curl reversibility under equilibrium holds it in a vertical position for 6 hours at 70 ° C. The conditions or change in the number of the length of the wet sample is determined at 70 ° C. The crimps per centimeter of crimped thread length cycles are repeated in the manner necessary to achieve reproducible results between 25 ° C in the dry and 70 ° C in the wet. Condition, expressed as AK / cm, is determined according to the following

Eine Komponente des gekräuselten Fadens soll, 40 genden Gleichung erhalten, in welcher das Vorzeidamit eine Kräuselreversibilität entwickelt wird, nach chen des AK/cm nicht berücksichtigt ist:A component of the crimped thread should be given the following equation, in which the sign is thus developed with a crimp reversibility, after calculating the AK / cm, this is not taken into account:

■ _ Zahl der Kräuselungen (bei 25° C/trocken) — Zahl der Kräuselungen (bei 70 °C/naß)■ _ number of crimps (at 25 ° C / dry) - number of crimps (at 70 ° C / wet)

δ λ./ cm — ■ ^ δ λ. / cm - ■ ^

Gekräuselte Gesamtlänge des Fadens (bei 25° C/trocken)Total crimped length of the thread (at 25 ° C / dry)

Beim Verspinnen werden die Polymeren einer be- Unterbrechung der Polymerisation an dem gewünsch-During spinning, the polymers are subject to an interruption of the polymerization at the desired

sonders geformten Düse zugeführt. Die Düse ist so ten Punkt dient. Die Monomeren werden dem Reak-specially shaped nozzle supplied. The nozzle is used so th point. The monomers are

ausgebildet, daß die Komponenten gesondert aus- 50 tionsgefäß mit relativen Geschwindigkeiten vondesigned that the components separately aus- 50 tion vessel with relative speeds of

gepreßt werden, die eine Komponente sich aber 93, 63, 6,00 bzw. 0,37 % zugeführt. Das Polymere hatare pressed, but one component is added to 93, 63, 6.00 or 0.37%. The polymer has

exzentrisch über die andere Komponente legt. Solche eine grundmolare Viskosität von 1,5 und enthält aufeccentrically over the other component. Such an intrinsic viscosity of 1.5 and contains

Düsen sind üblich. 1 kg (trocken) 54 Milliäquivalente Säuregruppen. EsNozzles are common. 1 kg (dry) 54 milliequivalent acid groups. It

Die Verbundfäden werden, soweit durchführbar, enthält 6 % Methylacrylat.The composite threads, as far as practicable, contain 6% methyl acrylate.

versteckt und dann (um die Kräuselung zu entwik- 55 Ein Mischpolymeres (b) wird in entsprechenderhidden and then (in order to develop the crimp)

kehl) in im wesentüchen spannungsfreien Zustand Weise aus Acrylnitril und Natriumstyrolsulfonat beikehl) in a substantially stress-free state from acrylonitrile and sodium styrene sulfonate

einer Schrumpfungsbehandlung unterworfen. relativen Beschickungsgeschwindigkeiten der Monomeren von 97,0 bzw. 3,0 hergestellt. Das Polymeresubjected to a shrinkage treatment. relative feed rates of the monomers of 97.0 and 3.0, respectively. The polymer

_ . . besitzt eine grundmolare Viskosität von 1,5 und ent-_. . has an intrinsic viscosity of 1.5 and

üeispiel 1 6o hält au£ lkg ^^^ 204 Milliäquivalente Säure-Example 1 6o holds up to £ lkg ^^^ 2 04 milliequivalents of acid

a) Hier nicht geschützte Herstellung gruppen.a) Manufacture groups that are not protected here.

der Ausgangsstoffe Ein Mischpolymeres (c) wird in entsprechenderof the starting materials A copolymer (c) is used in the corresponding

Weise durch stetige Polymerisation einer Monomeren-Way through continuous polymerization of a monomer

Ein Mischpolymeres (a) wird aus Acrylnitril, beschickung hergestellt, die aus 94% Acrylnitril und Methylacrylat und Natriumstyrolsulfonat durch 65 6% Methylacrylat besteht. Das Polymere hat eine stetige Polymerisation in Wasser mit einem K2S2O8- grundmolare Viskosität von 2,1 und enthält auf Katalysator, Natrium-meta-bisulfit als Aktivator und 1 kg (trocken) 26 Milliäquivalente Säuregruppen, die mit Na2CO3 hergestellt, welch letztgenanntes zur: in Form von Säureendgruppen des bei der Polymeri-A mixed polymer (a) is made from acrylonitrile, feed, which consists of 94% acrylonitrile and methyl acrylate and sodium styrene sulfonate by 65 6% methyl acrylate. The polymer has a steady polymerization in water with a K 2 S 2 O 8 - intrinsic viscosity of 2.1 and contains on catalyst, sodium meta-bisulfite as an activator and 1 kg (dry) 26 milliequivalents of acid groups, which with Na 2 CO 3 produced, the latter for: in the form of acid end groups of the polymer

sation verwendeten Natrium-meta-bisulfit-Aktivators und K2S2O8 vorliegen dürften. Das Polymere enthält ^O'VoMethylacrylat.Sation used sodium meta-bisulfite activator and K 2 S 2 O 8 should be present. The polymer contains ^ O'Vo methyl acrylate.

b) Herstellen eines erfindungsgemäßen Verbundfadensb) producing a composite thread according to the invention

Eine 25°/oige Lösung des Mischpolymeren (a) in Dimethylformamid und eine 25°/oige Lösung des Mischpolymeren (b) in Dimethylformamid werden gleichzeitig bei gleichen Zuführungsgeschwindigkeiten xo als die beiden Komponenten eines Verbundfadens Seite an Seite versponnen, wobei man mit einer entsprechenden Spinndüse, die achtzehn Düsenöffnungen von 0,152 mm Durchmesser besitzt, so arbeitet, daß für jeden Faden jede Komponente in gleicher Raummenge ausgepreßt wird. Die Lösungen werden bei 125° C in ein Inertgas von 180° C ausgepreßt und nach Aufbringung einer Spinnausrüstung mit einer Geschwindigkeit von 183 m/Min, aufgewickelt. Die gesponnenen Fäden werden in Wasser von 95° C um 300% (also vierfach, d.h. um das Vierfache ihrer Länge vor der Verstreckung) verstreckt und getrocknet. Die Kräuselreversibilität beträgt 1,77.A 25% solution of the copolymer (a) in dimethylformamide and a 25% solution of the Copolymers (b) in dimethylformamide are simultaneously at the same feed rates xo as the two components of a composite thread spun side by side, one with a corresponding Spinneret having eighteen orifices 0.152 mm in diameter works so that for each thread each component is squeezed out in the same amount of space. The solutions will be at 125 ° C in an inert gas of 180 ° C and after applying a spinning finish with a Speed of 183 m / min, wound up. The spun threads are placed in water at 95 ° C 300% (i.e. four times, i.e. four times its length before stretching) stretched and dried. The curl reversibility is 1.77.

Einkomponentige Fäden aus den Polymeren der beiden Komponenten, die in der gleichen Weise erspönnen und gestreckt werden, ergeben nach Schrumpfung und Einwirkung von Wasser bei 25° C reversible Längenänderungen von 3,67 bzw. 6,51 %.One-component threads made from the polymers of the two components, which spon the same way and stretched result after shrinkage and exposure to water at 25 ° C reversible changes in length of 3.67 and 6.51%, respectively.

30 Beispiel 230 Example 2

Aus 22%igen Lösungen von Polyacrylnitril (Homopolymeres), dessen grundmolare Viskosität 2,0 beträgt und das 26 Milliäquivalente Säuregruppen je Kilogramm enthält, und des Mischpolymeren (c) gemäß Beispiel 1 in Dimethylformamid werden Verbundfäden ersponnen. Man verwendet eine entsprechende Spinndüse, die hundertvierzig Düsenöffnungen von 0,119 mm Durchmesser aufweist. Das gesponnene Fadenbündel wird in Dampf um 300% (d. h. auf das Vierfache seiner ursprünglichen Länge vor der Verstreckung) verstreckt. Einkomponentige Fäden aus den Polymeren der Komponenten, die in der gleichen Weise ersponnen und verstreckt sind, ergeben reversible Längenänderungen von 1,0 bzw. 1,3%. Die Kräuselreversibilität beträgt 0,16.From 22% solutions of polyacrylonitrile (homopolymer) with an intrinsic viscosity of 2.0 and which contains 26 milliequivalents of acid groups per kilogram, and the copolymer (c) In accordance with Example 1 in dimethylformamide, composite threads are spun. One uses a corresponding one Spinneret having one hundred and forty orifices 0.119 mm in diameter. That The spun thread bundle is steamed by 300% (i.e. four times its original length before stretching) stretched. One-component threads made from the polymers of the components included in are spun and drawn in the same way, result in reversible changes in length of 1.0 and 1.3%. The curl reversibility is 0.16.

Beispiel 3Example 3

Ein Mischpolymeres von einer grundmolaren Viskosität von 2,0, das Acrylnitril und Vinylacetat im Gewichtsverhältnis von 95:5 enthält, wird mit einem Mischpolymeren von einer grundmolaren Viskosität von 2,0, das Acrylnitril und 2-Methyl-5-vinyl-pyridin im Gewichtsverhältnis von 50:50 enthält, im Verhältnis von 90:10 Teilen miteinander vermischt. Die Endzusammensetzung dieses Gemisches beträgt also 90,5 Teile Acrylnitril, 4,5 Teile Vinylacetat und 5,0 Teile 2-Methyl-5-vinyl-pyridin; das Gemisch enthält auf 1 kg (trocken) 380 Milliäquivalente basischer Gruppen. Man verspinnt eine 22%ige Lösung dieses Polymeren und eine Lösung von Polyacrylnitril, das auf 1 kg 26 Milliäquivalente saurer Gruppen enthält und eine grundmolare Viskosität von 2,0 aufweist, in Dimethylformamid trocken und verstreckt den Verbundfaden in Wasser von 95° C auf das Vierfache. Durch Kochen des Fadenmaterials in spannungsfreiem Zustand erhält man ein ganz ausgezeichnet gekräuseltes Produkt, das 7,9 Kräuselungen je Zentimeter (gestreckt) aufweist. Die Kräuselreversiblität beträgt 4,0.A mixed polymer with an intrinsic molar viscosity of 2.0, the acrylonitrile and vinyl acetate in the Contains weight ratio of 95: 5, is with a copolymer of an intrinsic molecular viscosity of 2.0, which contains acrylonitrile and 2-methyl-5-vinyl-pyridine in a weight ratio of 50:50, in the ratio of 90:10 parts mixed together. The final composition of this mixture is therefore 90.5 parts of acrylonitrile, 4.5 parts of vinyl acetate and 5.0 parts of 2-methyl-5-vinyl-pyridine; the mixture contains to 1 kg (dry) 380 milliequivalents of basic groups. A 22% solution of this is spun Polymers and a solution of polyacrylonitrile, which contains 26 milliequivalents of acidic groups per 1 kg and has an intrinsic viscosity of 2.0, dry in dimethylformamide and draws the composite thread four times as much in water at 95 ° C. By boiling the thread material in a tension-free State you get a very excellently crimped product with 7.9 crimps per centimeter (stretched). The curl reversibility is 4.0.

Claims (2)

Patentansprüche:Patent claims: 1. Verbundfasern oder -fäden, bestehend aus mindestens zwei Komponenten aus synthetischen Acrylnitrilpolymerisaten von unterschiedlichem Schrumpfvermögen, die im Querschnitt gesehen exzentrisch zueinander angeordnet sind, dadurch gekennzeichnet, daß eines der Polymeren ionisierbare Gruppen enthält, und zwar in einer um mindestens 30 Milliäquivalente je Kilogramm Polymeres größeren Menge als die anderen.1. Composite fibers or threads, consisting of at least two synthetic components Acrylonitrile polymers of different shrinkage capacity, seen in cross section are arranged eccentrically to one another, characterized in that one of the polymers contains ionizable groups, and although in an amount greater than that by at least 30 milliequivalents per kilogram of polymer others. 2. Fasern oder Fäden nach Anspruch 1, dadurch gekennzeichnet, daß diejenige Komponente, die die überschüssigen ionisierbaren Gruppen enthält, außerdem ein übliches nichtionogenes Modifizierungsmittel enthält, wie es zum Färben von Polyacrylnitril mit Dispersionsfarbstoffen verwendet wird.2. fibers or threads according to claim 1, characterized in that that component which contains the excess ionizable groups, also a common non-ionic Contains modifying agents such as those used for coloring polyacrylonitrile with disperse dyes will. In Betracht gezogene Druckschriften:
Deutsche Patentschrift Nr. 744111;
USA.-Patentschriften Nr. 2 443 711, 2 428 046,
2 517694.Considered publications:
German Patent No. 744111;
U.S. Patents Nos. 2,443,711, 2,428,046,
2 517694.
DE1957P0019615 1954-02-26 1957-11-08 Composite fibers or threads made from acrylonitrile polymers Expired DE1213954C2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US41278154 US2931091A (en) 1954-02-26 1954-02-26 Crimped textile filament
US62144356A 1956-11-09 1956-11-09
US64072257A 1957-02-18 1957-02-18
US64072357A 1957-02-18 1957-02-18

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DE1213954B true DE1213954B (en) 1966-04-07
DE1213954C2 DE1213954C2 (en) 1973-07-19

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DEP13646A Pending DE1202932B (en) 1954-02-26 1955-02-24 Process for producing curled composite threads
DE1957P0019615 Expired DE1213954C2 (en) 1954-02-26 1957-11-08 Composite fibers or threads made from acrylonitrile polymers

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DE1213954C2 (en) 1973-07-19
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NZ119936A (en) 1900-01-01
DE1202932B (en) 1965-10-14
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US3038236A (en) 1962-06-12
BE562290A (en) 1960-06-03
CA612603A (en) 1961-01-17
FR1205162A (en) 1960-02-01
CA612156A (en) 1961-01-10
GB869301A (en) 1961-05-31
IL10853A (en) 1900-01-01
CH388527A (en) 1965-02-28
IE23508B1 (en) 1962-08-29
IT586979A (en) 1900-01-01
AT227367B (en) 1963-05-10
NL113165C (en) 1966-08-15
US2931091A (en) 1960-04-05
IT535256A (en) 1900-01-01
SE206010C1 (en) 1966-07-12
IE23508L (en) 1958-05-09
FI35507A (en) 1965-12-10
NL109099C (en) 1964-08-17
FR1124921A (en) 1956-10-22

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