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US3857233A - Voluminous filament yarn and process to prepare same - Google Patents

Voluminous filament yarn and process to prepare same Download PDF

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Publication number
US3857233A
US3857233A US00378018A US37801873A US3857233A US 3857233 A US3857233 A US 3857233A US 00378018 A US00378018 A US 00378018A US 37801873 A US37801873 A US 37801873A US 3857233 A US3857233 A US 3857233A
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Prior art keywords
filament
filaments
abrasion resistance
yarn
false twist
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US00378018A
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J Cardinal
K Heinrich
G Bauer
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Hoechst AG
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Hoechst AG
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    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G1/00Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/02Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist
    • D02G1/0206Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist by false-twisting
    • D02G1/0246Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist by false-twisting at least some of the filaments being simultaneously broken or cut, e.g. by stretching or abrading
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G1/00Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/02Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist
    • D02G1/0286Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist characterised by the use of certain filaments, fibres or yarns
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S57/00Textiles: spinning, twisting, and twining
    • Y10S57/908Jet interlaced or intermingled

Definitions

  • ABSTRACT Object of the invention is a process for preparing a voluminous filament yarn with several loose filament ends sticking out by means of false twist texturization, optionally combined with a drawing process including the use of filaments having-at least partially-a flex abrasion resistance of less than abt. 1500 revolutions, said filament yarns being fed into known false twist texturizing devices and texturized therein, whereby the filaments having flex abrasion resistance values ofless than abt.
  • German Offenlegungsschrift l 660 606 describes a process for preparing such fluffy yarns, which me-- chanically rips and unravels the surface of a drawn filament yarn by rotatingbrushes. But this process is limited to foamed thermoplastic polymers and, obviously, it is applicable to coarse yarns only.
  • British Patent 971 573 claims a similar process, wherein two yarns of different elongation-at break are jointly submitted to a simultaneous stretching and texturizing treatment, and whereby the drawing proportion must be set in such a manner that the breaking filaments are those of the yarn having the lower elongation at break.
  • this process results in a fluffy yarn with several loose filament ends sticking out, it is, however, still ridden by a series of disadvantages. Since the effect looked for can be attained only by elongation, a portion of the filaments up to their breaking point, the yarn tension within the texturizing area cannot be chosen according to the optimal crimping properties. The yarn tension is predetermined already by the requirement of breaking one of the components.
  • an irregular adsorption of dyestuff is the unavoidable consequence of an irregular stretching treatment, so that the woven or knitted fabrics made of these yarns show an uneven coloration.
  • the filament yarns with several loose filament ends prepared as per British Patent 97] 573 show a strong tendency to pilling, such as itis known from spun fiber yarns made of synthetic highpolymers.
  • the object of the present invention to develop an operationally safe process for preparing voluminous filament yarns with several loose filament ends sticking out, whereby the filaments of the yarns display uniform characteristics all over their length and whereby the crimping properties may be freely set depending on the application field of the yarn.
  • the thus prepared fluffy yarns should also be usable for the formation of fabrics excelling in their extremely low tendencyto pilling.
  • the flex abrasion resistance influences the number of the loose filament ends sticking out which are produced in course of the process as per the invention, whereby the filament having the lower flex abrasion resistance does break easier while being exposed to the transversal stress of the texturizing area.
  • the number of the loose filament ends may also be influenced by setting the portion of filaments with a lower flex abrasion resistance used in the total filamentyarn.
  • the tendency to pilling of the woven and knitted fabrics is also decreasing substantially; however, as the term flex abrasion" already implies, it is not normally possible to produce or to use practically useful filament yarns having a flex abrasion resistance of e.g. Zero. But is is possible to use filaments having a flex abrasion resistance of eg as little at 5 revol. in cases, where especially strict requirements are set up concerning the lack of tendency to pilling of certain or knitted fabrics.
  • Threads of linear polymers which may partially be treated in a permanently cross-linked fashion can as well have a reduced flex abrasion resistance. Therefore, same are also well suitable for being processed according to the invention, within the said ranges of flex abrasion resistancevalues.
  • all of the filaments of the filament yarn may have the lower flex abrasion resistance of less than 1,500 revol. looked for, so that they may yield filament ends or only a portion of the filaments does possess these properties, while the rest shows a high flex abrasion resistance so that it does not break while being exposed to the transversal stress in the texturization area.
  • the filaments have to be interlaced slightly tighter for attaining a sufficient strength of the yarn, whilst in the latter case the continuous filaments guarantee anyway a sufficient strength of the yarn.
  • Filament yarns composed in the proportion of 7:3 to 3:7 of filaments having a lower flex abrasion resistance (less than 1,500 revol.) blended with filaments having a flex abrasion resistance of 1,500 and higher (e.g. 3,000 revol.), formed woven and knitted fabrics which excelled in a particularly attractive appearance and remarkable wear. It is also possible to choose freely depending on the specific application field the titer and the profile of the filaments, as well as the number of the filaments, which means the total titer of the filament yarn.
  • the titer will remain within the range of from 1 to 15 dtex per filament and below 300 dtex for the yarn, as it is usual for textile application purposes, but it may as well be set at a higher level for special purposes such as decorative fabrics.
  • the upper limit is, at most, given by the texturization process. ln case that different filaments are worked up into one yarn, their titers and cross sections may differ as well, of course.
  • the filaments are also made of different raw materials, their various characteristic may well be utilized for further effects, such as different shrinkage or bicomponeat-threads may result in additional bulk effects, different adsorption of dyestuffs may lead to mixture yarn or coloured twist yarn effects or the use of flame-proof or flame-retarding yarn components may produce filament yarns of ameliorated flame resistance.
  • a preferred embodiment of the invention are voluminous filament yarns of component blends. which show different individual titers and the loose filament ends of which are formed by the yarn component having the lowest individual titer.
  • both of the two kinds of filaments may be spun by means of one same spinning nozzle, or of two adjacent spinning nozzles, such as described by British Patent 1208 801. But it is also possible to ply the various types of filaments while passing the stretching area. A better blending may, in any case, be encouraged by interlacing or applying an electrostatic charge.
  • the usually preferred devices are false twist spindles, since the turning around on the spindle favors even better the formation of filament ends than the torsion stress alone occuring during the frictional texturization.
  • the number of the loose filament ends is also influenced, for instance, by the texturization parameters temperature, yarn tension upstream and downstream the spindle, coating product, number of spindle revolutions, travel speed of the yarn as well as by the shape and surface characteristics of the spindle. 1
  • a preferred embodiment of the invention for producing filament yarns consisting of polyester filaments is the simultaneously executed drawing and texturizing process of undrawn spinning materials (threads), whereby especially the use of undrawn, pre-orientated polyester filaments according to the U.S. Patent application Ser. No. 338,312 may give optimal texturization results.
  • the drawing proportion that is the proportion of the initial speed to the final speed of the yarns in the false twist texturization apparatus has to be chosen so as to draw all the filaments completely.
  • efforts have to be made by the choice of different pre-orientations to adapt, as far as possible, the drawing proportions of all filaments to each other. This is the only possibility that guarantees the all-over uniform drawing of all the filaments over 5. their total length, and thus to guarantee an even adsorptionof dyestuff.
  • the process according to the invention does not insist in imparting to the fed-in spinning yarns a flex abrasion resistance of less than e.g. 1,500 revol. already be fore the combined drawing and texturization, in case that undrawn or partially drawn filament yarns are utilized.
  • the reduction according tothe invention of the flex abrasion resistance of at least one titer of the filaments cannot be dispensed with at the moment of the yarn reaching the twister of the used false twist device.
  • the broken fil ament ends are partially still sticking out far of the filament yarn, so that they have to be interlaced at least temporarily before being submitted to further treatment.
  • a preferred method for ameliorating the filament bonding is to interlace the threads immediately after their having left the false twist texturization.
  • Theinterlacing by gas-blasting replaces generally more and more the twist process when preparing synthetic threads, since this gas-blasting may take place at high turnover speeds and continuously following other processing stages.
  • U.S. Pat. No. 2985 995 e.g. describes interlacing devices.
  • the open structure of the voluminous filament yarns may well be entirely preserved, if interlacing of the filament ends may be produced by application of a size which can be washed out again after weaving or knitting.
  • the voluminous filament yarns with loose filament ends sticking out according to the process of the invention show their superiority in course of their further treatment especially by the high degree of levelness of all their textile technological properties-all over the length of the yarn.
  • These yarns display a distinctly higher volume compared to the usual texturized filamentyarns having also a considerably higher covering power. Therefore, it is possible to produce the same individual impression of a specific material already at a noticeably reduced weight per square meter.
  • the most remarkable quality of the fabrics formed by the filament yarns of the invention is their extremely low tendency to pilling.
  • the flex abrasion resistance was determined, as said before, by means of a flex abrasion device, whereby the filaments to be examined are loaded with 0,45 g/dtex, the diameter of the wire being 0,02 mm up to 6,7 dtex 0,04 mm up to 13 dtex and 0,05 mm for even higer ti ters, flexing takes place at an angle of 1 10 at a speed of 126 revol/min.
  • EXAMPLE 1 a 67 f40 was prepared similar to example 1 of German Auslegeschrift l 720 647, whereby the 2,4 g of zinc acetate were replaced by 3,1 g of manganese acetate and whereby the quantity of the trimethoxysilanethanephosphonic acid-diethylester was increased from 48 g to 72 g.
  • the two polymer materials were spun in one spinning nozzle according to U.S. Pat. No. 2 398 729 at a temperature of 290C and the spinning threads'fed in and taken up at a speed of 1400 m/min.
  • the relative viscosity of the spinning threads amounted to 1,80 to 1,56.
  • the elongation at break of the filaments amounted to 310 percent for the coarse titers and 375 percent for the finetiter filaments at room temperature, the double refractions of the filaments amounted to 9,3 or 6,6- 10*.
  • the blended yarn obtained was submitted to a simultane ous draw-texturization in a false twist texturizing apparatus with false twist spindle having a'sapphire center pin.
  • the feed-in speed was 57 m/min the output speed was 166 m/min corresponding to a stretchproportion of 122,90.
  • the yarn was first directed in the texturization device over a contact heater 1 m long, having a surfacial temperature of 190C, the distance between the contact heater and the spindle was 15 cm.
  • a false twist was imparted to the filament yarn of 2,700 revol/m.
  • the filament yarn was interlaced in a gas jet after having left the texturizing device, and then rolled up.
  • the obtained voluminous filament yarn showed an average of two loose filament ends per cm of yarn length. This fact allows to estimate an average staple length of abt. 40 cm, considering the 40 individual filaments of the yarn component 67 f 40.
  • the broken filament ends showed a flex abrasion resistance of 350 revol., whilst the filaments of the other yarn component (67 f 12) showed a flex abrasion resistance of 3,630 revol (in each case is given the average out of 25 measurings).
  • EXAMPLE 2 A filament yarn of the total titer of dtex 135 f52 according to example 1 had been worked up to a fabric with linen weave in warp and weft, the weight per sq.m was 106 g. The fabric was finished as usual, i.e. washed, dried, dyed minutes at C) and set (156) and then submitted in this condition to a pilling test by the Random Tumble Pillinger Tester.
  • FIG. 1, line A represents the values measured.
  • comparative test C under the chosen test conditions shows a strong tendency to pilling, which climbs fast to value 7 (heavily pilled, shape of the pill mostly ripe) during the test and then remains on this level.
  • value 7 herein.
  • a fabric made of low-pilling polyethyleneterephthalate-fiber yarn shows after having passed an initial maximum stable values of the test grade 1,
  • Double-sided circular knit goods having a weight p/sq.m of abt. 173 g/sq.m each have also been produced of the filament yarns of example 1 as well as ofthe fiber yarn specified above, and submitted to corresponding pilling tests.
  • the pilling curves obtained for these knit goods were exactly of the same direction as the line of FIG. 1.
  • the fabrics produced of the voluminous filament yarns according to the invention showed remarkable differences concerning covering power, volume and purity of the appearance compared to those made of fiber yarns, at the same weight per square meter. All the criterions could be much better evaluated via the to the invention.
  • EXAMPLE 3 The undrawn blended filament yarn according to example l was submitted to a so-.called sequence texturization process.
  • the drawing of the yarn occurs between two feed-in devices at speeds of 48 and 166 m/min. over a pin heated to 90C..
  • the yarn, immediately after the drawingprocess still entirely free of loose or broken ends, was then directly fed into a continuously working false twist apparatus, the same embodiment as specified in expl. l.
  • the yarn was charged with a false twist of 2,700 r/m and after having left the texturization device the yarn is treated with a sizing product of acrylic acid ethylester, acrylic acid amide and acrylic acid sodium salt for amelioration of the filament bonding.
  • the size coating amounted to abt. 10wt/.
  • the obtained voluminous filament yarn having several loose filament ends sticking outshowed abt. 2 filament ends per cm of yarn length.
  • EXAMPLE 4 According to a further operational variation of the invention the filament yarn had been produced in such a way, that the two blended yarn components were spun separately, plyed in a draw'twister and then texturized.
  • the spun material was polyethyleneterephthalate, as described in example 1, at a temperature of 290C.
  • the yarn component for producing dtex 67f 12 was rolled up at a melt output of 35,5 g/min at a speed of 2 400 m/min., whilst the yarn component for dtex 67 f 40 was rolled up at a melt output of 32,5 g/min at a speed of 2,200 m/min.
  • the two spinning bobbins were fed into a known draw-twister and jointly drawn at a drawing proportion of 1:2,2 over a heated pin,'a surfacial temperature of C and an adjacent heater plate having a temperature of C.
  • the two yarn components were plyed on the draw-twister, the obtained blended yarn showed a twist of 20 r/m, loose ends of individual filaments could not be observed.
  • a separate measuring-of textile values showed for dtex 67f 12 a strength of 36,5 g/tex at a torsion of 27 percent and a flex abrasion resistance of 3,800 rev., whilst the yarn component 67 f40 had a strength of 27 g/tex at 32 percent of torsion and a flex abrasion resistance of 415 rev.
  • the blended yarn was fed into a known false twist texturizing device with a false twist spindle and texturized at a feed-in speed of 147,5 m/min, a contact heater temperature of C and a false twist of 2,300 twist per meter.
  • a thread tension of 25 g upstream the texturizing spindle with sapphire center pin and of 55 g downstream the spindle had been measured.
  • the obtained voluminous, highly elastic filament yarn showed not only a crimped, but also an excellent fiber-like character due to the numerous loose filament ends sticking out having an individual titer of dtex 1,7.
  • Process for preparing a voluminous filament yarn with several loose filament ends sticking out by means of false twist texturization including the use of filaments having at least partially-a flex abrasion resistance of less than about 1,500 cycles, said filament yarns being fed into known false twist texturizing devices and texturized therein, whereby the filaments having flex abrasion resistance values of less than about 1,500 cycles break in irregular intervals due to the transversal stress applied within the texturization area, interlacing the thus. obtained loose filament ends sticking out, at least temporarily.
  • filament yarns used consist at least partially of filaments made of thread-forming synthetic highpolymers.
  • filament yarns used consist of unstretched or partially stretched filament yarns, being composed of thread-forming synthetic high-polymers and wherein these filament yarns are simultaneously stretched and false twist texturized.
  • Process for preparing a voluminous filament yarn with several loose filament ends sticking out by means of a drawing process carried out prior to or simultaneously with false twist texturization including the use of filaments having at least partially a flex abrasion resistance of less than about 1,500 cycles, said filament yarns being fed into known false twist texturizing devices and texturized therein, whereby the filaments having flex abrasion resistance values of less than about 1,500 cycles break in irregular intervals due to the transversal stress applied within the texturization area, interlacing the thus obtained loose filament ends sticking out, at least temporarily.

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  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)

Abstract

Object of the invention is a process for preparing a voluminous filament yarn with several loose filament ends sticking out by means of false twist texturization, optionally combined with a drawing process including the use of filaments having-at least partially-a flex abrasion resistance of less than abt. 1500 revolutions, said filament yarns being fed into known false twist texturizing devices and texturized therein, whereby the filaments having flex abrasion resistance values of less than abt. 1500 revolutions break in irregular intervals due to the transversal stress applied within the texturization area, the thus obtained loose filament ends sticking out being interlaced, at least temporarily, by a process for ameliorating filament bonding as well as the voluminous filament yarns produced accordingly. The process allows of the trouble-free preparation of filament yarns being optionally texturized, having several loose filament ends sticking out, which excel in the uniformity of their characteristics all over the yarn length and which may be worked up to fabrics having an extremely low tendency to pilling.

Description

United States Patent 1191 Cardinalet al.-
[ VOLUMINOUS FILAMENT YARN AND PROCESS TO PREPARE SAME [75] Inventors: Jutta Cardinal, l-lofheim, Taunus,
Karl Heinrich; Gunther Bauer, both of Bobingen, all of Germany [22] Filed: July 10, 1973 21 Appl. No.: 378,018
[30] Foreign Application Priority Data Feb. 19, 1973 Germany 2308031 [52 US. Cl. 57/157 R, 57/140 R, 57/157 TS, 7 57/157 5 [51 Int. (:1 D02g 3/00, D02g 3/34 [58] Field of Search 57/140 BY, l57 TS, 157 R, 57/157 F, 157 S, 140 R, 2
1451 Dec. 31, 1974 8/1968 Port et al. 57/157 TS X l/l970 Asaka 57/157 TS Primary Examiner-John W. Huckert Assistant Examiner-Charles Gorenstein Attorney, Agent, or Firm-Connolly and Hutz [5 7 ABSTRACT Object of the invention is a process for preparing a voluminous filament yarn with several loose filament ends sticking out by means of false twist texturization, optionally combined with a drawing process including the use of filaments having-at least partially-a flex abrasion resistance of less than abt. 1500 revolutions, said filament yarns being fed into known false twist texturizing devices and texturized therein, whereby the filaments having flex abrasion resistance values ofless than abt. 1500 revolutions break in irregular intervalsrdue to the transversal stress applied within the texturization area, the thus obtained loose filament ends sticking out being interlaced, at least temporarily, by a process for ameliorating filament bonding as well as the voluminous filament yarns produced accordingly. The process allows of the trouble-free preparation of filament yarns being optimally texturized, having several loose filament ends sticking out, which excel in the uniformity of their characteristics all over the yarn length and which may be worked up to fabrics having an extremely low tendency to pilling.
8 Claims, 2 Drawing Figures VOLUMINOUS FILAMENT YARN AND PROCESS TO PREPARE SAME Therefore, processing methods have already been developed which are supposed to allow the preparation of filament yarns with loose filament ends out of ordinary filament yarns, while avoiding nevertheless the cutting of synthetic continuous threads (filaments) to staple fibers and their subsequent secondary spinning.
German Offenlegungsschrift" l 660 606 describes a process for preparing such fluffy yarns, which me-- chanically rips and unravels the surface of a drawn filament yarn by rotatingbrushes. But this process is limited to foamed thermoplastic polymers and, obviously, it is applicable to coarse yarns only.
According to British Patent 924 086 it is said to be possible to jointly draw filaments of different elongation in such a way that one of the components breaks and thus results in the loose ends looked for.
British Patent 971 573 claims a similar process, wherein two yarns of different elongation-at break are jointly submitted to a simultaneous stretching and texturizing treatment, and whereby the drawing proportion must be set in such a manner that the breaking filaments are those of the yarn having the lower elongation at break. Though this process results in a fluffy yarn with several loose filament ends sticking out, it is, however, still ridden by a series of disadvantages. Since the effect looked for can be attained only by elongation, a portion of the filaments up to their breaking point, the yarn tension within the texturizing area cannot be chosen according to the optimal crimping properties. The yarn tension is predetermined already by the requirement of breaking one of the components.
When practicing a simultaneous drawing and texturizing process, the elongation occurs at the beginning of the heater device of the used false twist texturizing apparatus. Due to the fact that this known process causes a portion of the filaments to break withinthe drawing zone, the loose ends jam the twister of the texturizing device again and again. Besides these processing difficulties, the treatment includes still further disadvantages according to the statements of British Patent 971 573: A filament does not break before being overstretched to an accordingly high extent, the area immediately adjacent to the break, however is not picked up right away by the pre-stretch godet, so that it remains unstretched or, at most, only partially stretched over'a certain length. As a matter of fact, an irregular adsorption of dyestuff is the unavoidable consequence of an irregular stretching treatment, so that the woven or knitted fabrics made of these yarns show an uneven coloration. Furthermore, the filament yarns with several loose filament ends prepared as per British Patent 97] 573 show a strong tendency to pilling, such as itis known from spun fiber yarns made of synthetic highpolymers.
Therefore, it is the object of the present invention to develop an operationally safe process for preparing voluminous filament yarns with several loose filament ends sticking out, whereby the filaments of the yarns display uniform characteristics all over their length and whereby the crimping properties may be freely set depending on the application field of the yarn. The thus prepared fluffy yarns should also be usable for the formation of fabrics excelling in their extremely low tendencyto pilling.
This problem could be solved by the application of a false twist texturation treatment, optionally combined with a drawing process, dealing withfilament yarns where at least a portion of the used filaments have a flex abrasion resistance of less than abt. 1500 revol.; The filament yarns to be treated are fed into known false twist texturizing apparatus and texturized, whereby the filaments having the lower flex abrasion resistance are breaking in irregular intervals due to the i the invention all continuous filaments may be used that consist, at least partially, of filaments either having initially a su'fficiently low flex abrasion resistance of less than 1,500 revol., or the flex abrasion resistance of which may be brought down to this level by known methods. Best suited are filaments which have a flex abrasion resistance of less than abt. 1000 revol. and especially those of less than 500 revol. The value of the flex abrasion resistance influences the number of the loose filament ends sticking out which are produced in course of the process as per the invention, whereby the filament having the lower flex abrasion resistance does break easier while being exposed to the transversal stress of the texturizing area. However, the number of the loose filament ends may also be influenced by setting the portion of filaments with a lower flex abrasion resistance used in the total filamentyarn. Depending on a reduction of the flex abrasion resistance, the tendency to pilling of the woven and knitted fabrics is also decreasing substantially; however, as the term flex abrasion" already implies, it is not normally possible to produce or to use practically useful filament yarns having a flex abrasion resistance of e.g. Zero. But is is possible to use filaments having a flex abrasion resistance of eg as little at 5 revol. in cases, where especially strict requirements are set up concerning the lack of tendency to pilling of certain or knitted fabrics.
Measuring the flex abrasion resistance is executed by means of the flex abrasion device as described, for instance, by Grunewald in Chemiefasern 12 (1962), pg. 853. By revol, i.e., revolutions, are used herein is meant cycles. This is clearly understood to one skilled in the art, and also from theproperfy of flex abrasion resistance in connection with which the term is used tained fro m synthetic highpolymers by using polymerizates with a sufficiently low molecular weight; as examples y,.l?99 .h9 aptqd st assp d nst ljeutsche Auslegeschrift 1278688. In the case of threads made of polyethyleneterephthalate, for instance, the following proportions between flex abrasion resistance and average molecular weight could be found: A flex abrasion resistance of 1,500 revol. is
linked to an average molecular weight abt. 12 500,-
whilst flex abrasion resistance values of less than revol. may be linked to average molecular weights of abt. 8,000. Polyethyleneterephthalate threads having so low a molecular weight cannot bemelt-spun any longer at an economically reasonable rate due to the low melt'viscosity of the polymers, but they may be prepared of polymers according to German Auslegeschrift 1237 727, Deutsche Auslegeschrift 1273 123 or Deutsche Auslegeschrift 1720 647.
Threads of linear polymers which may partially be treated in a permanently cross-linked fashion can as well have a reduced flex abrasion resistance. Therefore, same are also well suitable for being processed according to the invention, within the said ranges of flex abrasion resistancevalues.
Depending on the application, all of the filaments of the filament yarn may have the lower flex abrasion resistance of less than 1,500 revol. looked for, so that they may yield filament ends or only a portion of the filaments does possess these properties, while the rest shows a high flex abrasion resistance so that it does not break while being exposed to the transversal stress in the texturization area. In the first case, the filaments have to be interlaced slightly tighter for attaining a sufficient strength of the yarn, whilst in the latter case the continuous filaments guarantee anyway a sufficient strength of the yarn. Filament yarns composed in the proportion of 7:3 to 3:7 of filaments having a lower flex abrasion resistance (less than 1,500 revol.) blended with filaments having a flex abrasion resistance of 1,500 and higher (e.g. 3,000 revol.), formed woven and knitted fabrics which excelled in a particularly attractive appearance and remarkable wear. It is also possible to choose freely depending on the specific application field the titer and the profile of the filaments, as well as the number of the filaments, which means the total titer of the filament yarn. In most of the cases the titer will remain within the range of from 1 to 15 dtex per filament and below 300 dtex for the yarn, as it is usual for textile application purposes, but it may as well be set at a higher level for special purposes such as decorative fabrics. The upper limit is, at most, given by the texturization process. ln case that different filaments are worked up into one yarn, their titers and cross sections may differ as well, of course. In case that the filaments are also made of different raw materials, their various characteristic may well be utilized for further effects, such as different shrinkage or bicomponeat-threads may result in additional bulk effects, different adsorption of dyestuffs may lead to mixture yarn or coloured twist yarn effects or the use of flame-proof or flame-retarding yarn components may produce filament yarns of ameliorated flame resistance. On the other hand, it is alsopossible to modify the dyeing qualities of the filaments in an appropriate manner so that uniform coloration may take place. Since the process according to the invention draws the filaments evenly before breaking them, a uniform coloration all over their length including the loose filament ends is guaranteed, in contradiction to the known processing methods which provoke the breaking of the filaments by over stretching same in the stretching area.
A preferred embodiment of the invention are voluminous filament yarns of component blends. which show different individual titers and the loose filament ends of which are formed by the yarn component having the lowest individual titer.
Generally, it is useful to blend the individual components when processing filaments into one filament yarn. This blending may take place, depending on the specific conditions, in anyone of the different processing stages. For example, both of the two kinds of filaments may be spun by means of one same spinning nozzle, or of two adjacent spinning nozzles, such as described by British Patent 1208 801. But it is also possible to ply the various types of filaments while passing the stretching area. A better blending may, in any case, be encouraged by interlacing or applying an electrostatic charge.
When choosing the false twist texturization according to the process of the invention, the usually preferred devices are false twist spindles, since the turning around on the spindle favors even better the formation of filament ends than the torsion stress alone occuring during the frictional texturization. The number of the loose filament ends is also influenced, for instance, by the texturization parameters temperature, yarn tension upstream and downstream the spindle, coating product, number of spindle revolutions, travel speed of the yarn as well as by the shape and surface characteristics of the spindle. 1
Breaking of the filaments with reduced flex abrasion resistance takes place in irregular intervals under application of the usual texturization parameters, but the result is an even and not periodical distribution of the loose filament ends all over the total length of the filament yarn. In contradiction to the afore said, the hitherto known processing methods for the preparation of fluffy yarns, which induce the filaments to break by overstretching while being drawn, easily causes a plurality of filament ends to break simultaneously and thus leads at least to an irregular accumulation of the loose filament ends sticking out. All the filament yarns that may be submitted to a false twist process while being texturized are suitable for use in the process according to the invention. These yarns may be composed, i.e., of highmolecular polyamides, polyesters, polyolefins, polyacryl-nitriles, celluloses or threadforming copolymers or derivatives of these materials.
A preferred embodiment of the invention for producing filament yarns consisting of polyester filaments is the simultaneously executed drawing and texturizing process of undrawn spinning materials (threads), whereby especially the use of undrawn, pre-orientated polyester filaments according to the U.S. Patent application Ser. No. 338,312 may give optimal texturization results.
The drawing proportion, that is the proportion of the initial speed to the final speed of the yarns in the false twist texturization apparatus has to be chosen so as to draw all the filaments completely. When different filaments are utilized, efforts have to be made by the choice of different pre-orientations to adapt, as far as possible, the drawing proportions of all filaments to each other. This is the only possibility that guarantees the all-over uniform drawing of all the filaments over 5. their total length, and thus to guarantee an even adsorptionof dyestuff.
The process according to the invention does not insist in imparting to the fed-in spinning yarns a flex abrasion resistance of less than e.g. 1,500 revol. already be fore the combined drawing and texturization, in case that undrawn or partially drawn filament yarns are utilized. However, the reduction according tothe invention of the flex abrasion resistance of at least one titer of the filaments cannot be dispensed with at the moment of the yarn reaching the twister of the used false twist device. After being texturized the broken fil ament ends are partially still sticking out far of the filament yarn, so that they have to be interlaced at least temporarily before being submitted to further treatment. For this purpose are suitable all known process methods for amelioration of the filament bonding such as treatment by sizing or twisting of the yarn.v But in general the application of a twist onto the fluffy filament yarn is not so much preferred, since this high cost implying processing step is responsible for a loss of volume of the filament yarns. A preferred method for ameliorating the filament bonding is to interlace the threads immediately after their having left the false twist texturization. Theinterlacing by gas-blasting replaces generally more and more the twist process when preparing synthetic threads, since this gas-blasting may take place at high turnover speeds and continuously following other processing stages. U.S. Pat. No. 2985 995 e.g. describes interlacing devices. The open structure of the voluminous filament yarns may well be entirely preserved, if interlacing of the filament ends may be produced by application of a size which can be washed out again after weaving or knitting.
The voluminous filament yarns with loose filament ends sticking out according to the process of the invention show their superiority in course of their further treatment especially by the high degree of levelness of all their textile technological properties-all over the length of the yarn. These yarns display a distinctly higher volume compared to the usual texturized filamentyarns having also a considerably higher covering power. Therefore, it is possible to produce the same individual impression of a specific material already at a noticeably reduced weight per square meter. However, the most remarkable quality of the fabrics formed by the filament yarns of the invention is their extremely low tendency to pilling.
The known high tendency to pilling of spun fiber yarns made of synthetic fibers could be checked and brought down to an acceptable level by developing socalled low-pilling types of fibers (cf. to this subject e.g. P.Braun, Chemiefasern/Textilindustrie 1972, pg. 537 to 540"). It was found, surprisingly, that the yarns according to the invention despite their great volume and the general lack of yarn torsion could be worked up to fabri'cs, the tendency to pilling of which did not even reach that of the most pill-lacking spun fiber yarns known to the art.
The tendency to pilling of surfaces was tested by the Random Tumble Pilling Tester (cf. e.g. Baird, Legere, Standley in Textile Research Journal 26 (1956), pg. 731 and ASTM standards on textile materials 1961, pg: 552). The tendency to pilling was evaluated visually by application ofReutlinger Pillgrade" (synopsis of. e.g. Grunewald in Chemiefaser 12) 1968, pg. 936).
The flex abrasion resistance was determined, as said before, by means of a flex abrasion device, whereby the filaments to be examined are loaded with 0,45 g/dtex, the diameter of the wire being 0,02 mm up to 6,7 dtex 0,04 mm up to 13 dtex and 0,05 mm for even higer ti ters, flexing takes place at an angle of 1 10 at a speed of 126 revol/min.
The following examples illustrate the invention:
EXAMPLE 1 a 67 f40 was prepared similar to example 1 of German Auslegeschrift l 720 647, whereby the 2,4 g of zinc acetate were replaced by 3,1 g of manganese acetate and whereby the quantity of the trimethoxysilanethanephosphonic acid-diethylester was increased from 48 g to 72 g.
The two polymer materials were spun in one spinning nozzle according to U.S. Pat. No. 2 398 729 at a temperature of 290C and the spinning threads'fed in and taken up at a speed of 1400 m/min. The relative viscosity of the spinning threads amounted to 1,80 to 1,56. The elongation at break of the filaments amounted to 310 percent for the coarse titers and 375 percent for the finetiter filaments at room temperature, the double refractions of the filaments amounted to 9,3 or 6,6- 10*.
The blended yarn obtained was submitted to a simultane ous draw-texturization in a false twist texturizing apparatus with false twist spindle having a'sapphire center pin. The feed-in speed was 57 m/min the output speed was 166 m/min corresponding to a stretchproportion of 122,90. The yarn was first directed in the texturization device over a contact heater 1 m long, having a surfacial temperature of 190C, the distance between the contact heater and the spindle was 15 cm.
A false twist was imparted to the filament yarn of 2,700 revol/m. The filament yarn was interlaced in a gas jet after having left the texturizing device, and then rolled up.
The obtained voluminous filament yarn showed an average of two loose filament ends per cm of yarn length. This fact allows to estimate an average staple length of abt. 40 cm, considering the 40 individual filaments of the yarn component 67 f 40. The broken filament ends showed a flex abrasion resistance of 350 revol., whilst the filaments of the other yarn component (67 f 12) showed a flex abrasion resistance of 3,630 revol (in each case is given the average out of 25 measurings).
EXAMPLE 2 A filament yarn of the total titer of dtex 135 f52 according to example 1 had been worked up to a fabric with linen weave in warp and weft, the weight per sq.m was 106 g. The fabric was finished as usual, i.e. washed, dried, dyed minutes at C) and set (156) and then submitted in this condition to a pilling test by the Random Tumble Pillinger Tester. FIG. 1, line A represents the values measured.
For comparisons sake fabrics have been used made of fiber yarn, in one case a material made of a lowpilling polyester type, whereby the used polymer material was that ofv example 1, (of the yarn component 67 f40); The fiber yarn with N,,, 70/1 and a twist of 980 rev/m was composed of spun fibers having the individual titer dtex 1,7/40 mm, the flex abrasion resistance was that of the yarn component 67 f40 of example 1. This fiber yarn was worked up in the same manner to a fabric of'linen weave having the same weight per sq.m and being finished identically. The obtaining pilling line was shown with B in FIG. 1.
A further comparison was made on the basis of a fiber yarn made of normal polyester as per the yarn component 67f 12 of example 1. The material showed approximately the same flex abrasion resistance of abt. 3 800 revol., was however corresponding exactly to the aforedescribed spun fiber yarn of the low pilling type. Similar fabrics were also made of this material and their pilling properties tested (line C in FIG. 1).
As the lines of FIG. 1 demonstrate, comparative test C under the chosen test conditions (fiber yarn made of normal polyethylen-terephthalate) shows a strong tendency to pilling, which climbs fast to value 7 (heavily pilled, shape of the pill mostly ripe) during the test and then remains on this level. Contradictory to these results, a fabric made of low-pilling polyethyleneterephthalate-fiber yarn shows after having passed an initial maximum stable values of the test grade 1,
. i.e. only roughened, fluffy, fibrous (line B). Fabrics made of the voluminous filament yarn according to the invention having individual filament ends, at the begin-- ning of the-pilling test also shows first a climbing line, but already one hour of test time later it dropped back Zero, that means that the test fabric did not show any modifications later on.
Double-sided circular knit goods (lap Rodier) having a weight p/sq.m of abt. 173 g/sq.m each have also been produced of the filament yarns of example 1 as well as ofthe fiber yarn specified above, and submitted to corresponding pilling tests. The pilling curves obtained for these knit goods were exactly of the same direction as the line of FIG. 1.
The fabrics produced of the voluminous filament yarns according to the invention showed remarkable differences concerning covering power, volume and purity of the appearance compared to those made of fiber yarns, at the same weight per square meter. All the criterions could be much better evaluated via the to the invention.
EXAMPLE 3 The undrawn blended filament yarn according to example l was submitted to a so-.called sequence texturization process. The drawing of the yarn occurs between two feed-in devices at speeds of 48 and 166 m/min. over a pin heated to 90C.. The yarn, immediately after the drawingprocess still entirely free of loose or broken ends, was then directly fed into a continuously working false twist apparatus, the same embodiment as specified in expl. l. The yarn was charged with a false twist of 2,700 r/m and after having left the texturization device the yarn is treated with a sizing product of acrylic acid ethylester, acrylic acid amide and acrylic acid sodium salt for amelioration of the filament bonding. The size coating amounted to abt. 10wt/. The obtained voluminous filament yarn having several loose filament ends sticking outshowed abt. 2 filament ends per cm of yarn length.
EXAMPLE 4 According to a further operational variation of the invention the filament yarn had been produced in such a way, that the two blended yarn components were spun separately, plyed in a draw'twister and then texturized. The spun material was polyethyleneterephthalate, as described in example 1, at a temperature of 290C. The yarn component for producing dtex 67f 12 was rolled up at a melt output of 35,5 g/min at a speed of 2 400 m/min., whilst the yarn component for dtex 67 f 40 was rolled up at a melt output of 32,5 g/min at a speed of 2,200 m/min.
The two spinning bobbins were fed into a known draw-twister and jointly drawn at a drawing proportion of 1:2,2 over a heated pin,'a surfacial temperature of C and an adjacent heater plate having a temperature of C. The two yarn components were plyed on the draw-twister, the obtained blended yarn showed a twist of 20 r/m, loose ends of individual filaments could not be observed.
A separate measuring-of textile values showed for dtex 67f 12 a strength of 36,5 g/tex at a torsion of 27 percent and a flex abrasion resistance of 3,800 rev., whilst the yarn component 67 f40 had a strength of 27 g/tex at 32 percent of torsion and a flex abrasion resistance of 415 rev.
The blended yarn was fed into a known false twist texturizing device with a false twist spindle and texturized at a feed-in speed of 147,5 m/min, a contact heater temperature of C and a false twist of 2,300 twist per meter. At an output speed of the false twist device, being situated 1 percent below the input-speed, a thread tension of 25 g upstream the texturizing spindle with sapphire center pin and of 55 g downstream the spindle had been measured. The obtained voluminous, highly elastic filament yarn showed not only a crimped, but also an excellent fiber-like character due to the numerous loose filament ends sticking out having an individual titer of dtex 1,7.
We claim:
1. Process for preparing a voluminous filament yarn with several loose filament ends sticking out by means of false twist texturization including the use of filaments having at least partially-a flex abrasion resistance of less than about 1,500 cycles, said filament yarns being fed into known false twist texturizing devices and texturized therein, whereby the filaments having flex abrasion resistance values of less than about 1,500 cycles break in irregular intervals due to the transversal stress applied within the texturization area, interlacing the thus. obtained loose filament ends sticking out, at least temporarily.
2. process according to claim 1, wherein the filament yarns used consist at least partially of filaments made of thread-forming synthetic highpolymers.
3. Process according to claim 1, wherein at least part of the filaments used have a flex abrasion resistance of less than about 1,000 cycles.
4. Process according to claim 1, wherein at least part of the filaments used have a flex abrasion resistance of less than about 500 cycles.
5. Process according to claim 1, wherein the filament yarns used consist of thread-forming highmolecular polyesters.
6. Process according to claim 1, wherein the filament yarns used consist of unstretched or partially stretched filament yarns, being composed of thread-forming synthetic high-polymers and wherein these filament yarns are simultaneously stretched and false twist texturized.
7. Process according to claim 1 wherein the false twist texturization is performed by means of a false twist spindle.
8. Process for preparing a voluminous filament yarn with several loose filament ends sticking out by means of a drawing process carried out prior to or simultaneously with false twist texturization, including the use of filaments having at least partially a flex abrasion resistance of less than about 1,500 cycles, said filament yarns being fed into known false twist texturizing devices and texturized therein, whereby the filaments having flex abrasion resistance values of less than about 1,500 cycles break in irregular intervals due to the transversal stress applied within the texturization area, interlacing the thus obtained loose filament ends sticking out, at least temporarily.

Claims (8)

1. PROCESS FOR PREPARING A VOLUMINOUS FILAMENT YARN WITH SEVERAL LOOSE FILAMENT ENDS STICKING OUT BY MEANS OF FALSE TWIST TEXURIZATION INCLUDING THE USE OF FILAMENTS HAVING - AT LEAST PARTIALLY-A FLEX ABRASION RESISTANCE OF LESS THAN ABOUT 1,500 CYCLES, SAID FILAMENT YARNS BEING FED INTO KNOWN FALSE TWIST TEXTURIZING DEVICES AND TEXURIZED THEREIN, WHEREBY THE FILAMENTS HAVING FLEX ABRASION RESISTANCE VALUES OF LESS THAN ABOUT 1,500 CYCLES BREAK IN IRREGULAR INTERVALS DUE TO THE TRANSVERSAL STRESS APPLIED WITHIN THE TEXURIZATION AREA, INTERLACING THE THUS OBTAINED LOOSE FILAMENT ENDS STICKING OUT, AS LEAST TEMPORARILY.
2. process according to claim 1, wherein the filament yarns used consist - at least partially - of filaments made of thread-forming synthetic highpolymers.
3. Process according to claim 1, wherein at least part of the filaments used have a flex abrasion resistance of less than about 1,000 cycles.
4. Process according to claim 1, wherein at least part of the filaments used have a flex abrasion resistance of less than about 500 cycles.
5. Process according to claim 1, wherein the filament yarns used consist of thread-forming highmolecular polyesters.
6. Process according to claim 1, wherein the filament yarns used consist of unstretched or partially stretched filament yarns, being composed of thread-forming synthetic high-polymers and wherein these filament yarns are simultaneously stretched and false twist texturized.
7. Process according to claim 1, wherein the false twist texturization is performed by means of a false twist spindle.
8. Process for preparing a voluminous filament yarn with several loose filament ends sticking out by means of a drawing process carried out prior to or simultaneously with false twist texturization, including the use of filaments having - at least partially - a flex abrasion resistance of less than about 1,500 cycles, said filament yarns being fed into known false twist texturizing devices and texturized therein, whereby the filaments having flex abrasion resistance values of less than about 1,500 cycles break in irregular intervals due to the transversal stress applied withiN the texturization area, interlacing the thus obtained loose filament ends sticking out, at least temporarily.
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US3946548A (en) * 1973-03-02 1976-03-30 Teijin Limited Bulky multifilament yarn and process for manufacturing the same
US4019311A (en) * 1973-07-18 1977-04-26 Barmag Barmer Maschinenfabrik Aktiengesellschaft Process for the production of a multifilament texturized yarn
US4054025A (en) * 1975-07-23 1977-10-18 Bayer Aktiengesellschaft Process for the production of filament yarns with statistically distributed, broken individual filaments
DE2803401A1 (en) * 1977-01-26 1978-07-27 Eastman Kodak Co TEXTILE THREADS, PROCESS FOR THEIR MANUFACTURING AND YARNS MADE FROM THREADS
US4110965A (en) * 1976-12-20 1978-09-05 Monsanto Company Spun-like hand yarn process
US4115990A (en) * 1976-06-07 1978-09-26 Leesona Corporation Voluminous filamentary yarn and method of manufacture
WO1979000149A1 (en) * 1977-09-16 1979-03-22 Du Pont Polyester feed yarn for draw-texturing
US4262481A (en) * 1979-02-21 1981-04-21 Toray Industries, Inc. Spun yarn-like high bulky textured yarns and process for producing same
US4292799A (en) * 1978-10-26 1981-10-06 Toray Industries, Inc. Spun yarn-like textured yarns and process for producing same
US4297837A (en) * 1978-12-18 1981-11-03 Barmag Barmer Maschinenfabrik Aktiengesellschaft Method and apparatus for producing spun yarn characteristics in synthetic multifilament yarns
US4300344A (en) * 1978-11-24 1981-11-17 Hoechst Aktiengesellschaft Feed yarn and process for the manufacture of a voluminous false twist texturized hairy yarn
US4302929A (en) * 1978-11-24 1981-12-01 Hoechst Aktiengesellschaft Hairy monocomponent yarn
US4414801A (en) * 1978-07-10 1983-11-15 Fiber Industries, Inc. Process for making spun-like yarn with variable denier filaments
US4464894A (en) * 1978-02-27 1984-08-14 Phillips Petroleum Company Spun-like continuous multifilament yarn
US4513565A (en) * 1981-08-14 1985-04-30 Toray Industries, Inc. Sewing thread
US4519200A (en) * 1983-08-22 1985-05-28 Eastman Kodak Company Textile yarns with loops and free protruding ends
US4578940A (en) * 1981-08-14 1986-04-01 Toray Industries, Inc. Method for manufacturing sewing thread
US4590032A (en) * 1982-06-21 1986-05-20 Eastman Kodak Company Process for draw-fracturable yarn
US4656825A (en) * 1981-08-14 1987-04-14 Toray Industries, Inc. Sewing thread and method for manufacturing the same
US4829761A (en) * 1987-06-05 1989-05-16 Eastman Kodak Company Continuous filament yarn having spun-like or staple-like character
US5534334A (en) * 1992-09-10 1996-07-09 Toray Industries, Inc. Base fabric for ink ribbons
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US11161126B2 (en) 2017-04-19 2021-11-02 Kao Corporation Method for producing film
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US3946548A (en) * 1973-03-02 1976-03-30 Teijin Limited Bulky multifilament yarn and process for manufacturing the same
US4019311A (en) * 1973-07-18 1977-04-26 Barmag Barmer Maschinenfabrik Aktiengesellschaft Process for the production of a multifilament texturized yarn
US4054025A (en) * 1975-07-23 1977-10-18 Bayer Aktiengesellschaft Process for the production of filament yarns with statistically distributed, broken individual filaments
US4115990A (en) * 1976-06-07 1978-09-26 Leesona Corporation Voluminous filamentary yarn and method of manufacture
US4110965A (en) * 1976-12-20 1978-09-05 Monsanto Company Spun-like hand yarn process
DE2803401A1 (en) * 1977-01-26 1978-07-27 Eastman Kodak Co TEXTILE THREADS, PROCESS FOR THEIR MANUFACTURING AND YARNS MADE FROM THREADS
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WO1979000149A1 (en) * 1977-09-16 1979-03-22 Du Pont Polyester feed yarn for draw-texturing
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US4292799A (en) * 1978-10-26 1981-10-06 Toray Industries, Inc. Spun yarn-like textured yarns and process for producing same
US4300344A (en) * 1978-11-24 1981-11-17 Hoechst Aktiengesellschaft Feed yarn and process for the manufacture of a voluminous false twist texturized hairy yarn
US4302929A (en) * 1978-11-24 1981-12-01 Hoechst Aktiengesellschaft Hairy monocomponent yarn
US4297837A (en) * 1978-12-18 1981-11-03 Barmag Barmer Maschinenfabrik Aktiengesellschaft Method and apparatus for producing spun yarn characteristics in synthetic multifilament yarns
US4262481A (en) * 1979-02-21 1981-04-21 Toray Industries, Inc. Spun yarn-like high bulky textured yarns and process for producing same
US4656825A (en) * 1981-08-14 1987-04-14 Toray Industries, Inc. Sewing thread and method for manufacturing the same
US4513565A (en) * 1981-08-14 1985-04-30 Toray Industries, Inc. Sewing thread
US4578940A (en) * 1981-08-14 1986-04-01 Toray Industries, Inc. Method for manufacturing sewing thread
US4590032A (en) * 1982-06-21 1986-05-20 Eastman Kodak Company Process for draw-fracturable yarn
US4519200A (en) * 1983-08-22 1985-05-28 Eastman Kodak Company Textile yarns with loops and free protruding ends
US4829761A (en) * 1987-06-05 1989-05-16 Eastman Kodak Company Continuous filament yarn having spun-like or staple-like character
US5534334A (en) * 1992-09-10 1996-07-09 Toray Industries, Inc. Base fabric for ink ribbons
EP0826805A2 (en) * 1996-08-05 1998-03-04 Guilford Mills, Inc. Comingled composite yarn and method for forming same
EP0826805A3 (en) * 1996-08-05 2000-10-11 Guilford Mills, Inc. Comingled composite yarn and method for forming same
US11161126B2 (en) 2017-04-19 2021-11-02 Kao Corporation Method for producing film
US11351402B2 (en) 2017-04-19 2022-06-07 Kao Corporation Method for producing coating film
US20230081877A1 (en) * 2020-05-01 2023-03-16 Atex Technologies, Inc. Fray resistant structure

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