EP0031078B2 - Feinsttitrige Synthesefasern und -fäden und Trockenspinnverfahren zu ihrer Herstellung - Google Patents

Feinsttitrige Synthesefasern und -fäden und Trockenspinnverfahren zu ihrer Herstellung Download PDF

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Publication number
EP0031078B2
EP0031078B2 EP80107777A EP80107777A EP0031078B2 EP 0031078 B2 EP0031078 B2 EP 0031078B2 EP 80107777 A EP80107777 A EP 80107777A EP 80107777 A EP80107777 A EP 80107777A EP 0031078 B2 EP0031078 B2 EP 0031078B2
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EP
European Patent Office
Prior art keywords
spinning
dtex
filaments
dmf
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.)
Expired - Lifetime
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EP80107777A
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German (de)
English (en)
French (fr)
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EP0031078B1 (de
EP0031078A3 (en
EP0031078A2 (de
Inventor
Ulrich Dr. Reinehr
Toni Herbertz
Hermann Josef Jungverdorben
Joachim Dross
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Bayer AG
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Bayer AG
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Application filed by Bayer AG filed Critical Bayer AG
Priority to AT80107777T priority Critical patent/ATE20909T1/de
Publication of EP0031078A2 publication Critical patent/EP0031078A2/de
Publication of EP0031078A3 publication Critical patent/EP0031078A3/de
Publication of EP0031078B1 publication Critical patent/EP0031078B1/de
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Classifications

    • 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
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • 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
    • D01D5/04—Dry spinning methods
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • 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
    • 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
    • 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
    • Y10T428/2978—Surface characteristic

Definitions

  • Such fine-titer fibers which generally have a final fiber titer between 0.4-0.8 dtex, have compared to conventional synthetic fibers, e.g. Acrylic fibers, which are in the titre range from 1.3 dtex, have a number of advantages such as: high gloss, appealing chandelier, elegance in the fabric, soft feel, high flexibility and pliability as well as high fiber strength, due to the high number of fine fibers in the yarn cross-section.
  • the object of the present invention was to produce fine-titer acrylic fibers by a dry spinning process.
  • the present invention therefore relates to a process for the production of synthetic fibers and filaments from spinning solutions with a solids content of 25 to 35% of thread-forming acrylonitrile polymers with at least 85 wt Below the boiling point of the spinning solvent used and a spinning air temperature of at most 300 ° C and with further treatment of the spinning material in a manner known per se to produce fibers or threads, thermally pretreated spinning solutions are used, the viscosity of which changes during the spinning time by a maximum of 5%, that the Spinning solution with a delay of at least 20 is spun and that the spinning produces threads with individual spinning titers of 3 dtex and below.
  • the process according to the invention is in principle a dry spinning process which can be carried out with the same equipment as a process by which coarser titers are spun.
  • So z. B. with the usual spinnerets with hole diameters of about 0, 15 to 0.8 mm, preferably 0.2 to 0.4 mm, and in conventional spinning shafts.
  • the spinning solutions With average K values of the polymers of about 80, the spinning solutions thus have viscosities of about 20 to 100 falling ball seconds at 80 ° C. (for the falling ball method, see K. Jost, Rheologica Acta (1958) Vol. 1, No. 2-3, page 303).
  • the viscosity stability of the spinning solution is important so that the high warpage, which is preferably 30 to 500 but can also be higher, can be exerted by the process according to the invention.
  • Spinning solutions are preferred whose viscosity (measured in ball falling seconds) changes during the spinning time, i.e. usually less than 1% over hours, but ideally not at all. Such solutions have proven to be particularly highly warpable, while spinning solutions, the viscosity of which is not constant, are more prone to thread breaks at high warpage (see Example 2).
  • a viscosity-stable spinning solution can be prepared by keeping the solution at a certain minimum temperature for a certain time before spinning.
  • the spinning solution should not have a temperature of more than 150 ° C, the spinning shaft temperature should not exceed 200 ° C and the spinning air temperature at most about 400 ° C should be.
  • a non-dumbbell-shaped cross-sectional shape of the fine-titer fibers is always obtained by the process according to the invention if the spinning conditions are chosen to be as mild as possible and work is carried out with high delays.
  • the spinning solution is cooled to temperatures of about 20 ° C. to about 100 ° C. after the viscosity-stabilizing thermal treatment and before spinning, at the same time the spinning shaft temperature is set to a value between about 30 ° C. and preferably below the boiling point of the solvent used and with spinning air worked up to about 300 ° C.
  • the fiber cross section also has an intermediate shape, for example a bean or kidney shape.
  • the DMF evaporation rate per capillary in (mg / sec) in connection with the dwell time of the threads in the spinning shaft have proven to be suitable variables for describing the cross-sectional shape formed.
  • the DMF evaporation rate with a residence time of one second in the spinning shaft may be the value of do not exceed if non-dumbbell-shaped cross-sectional shapes are to be obtained.
  • the evaporation rate must be lower and with shorter dwell times correspondingly higher.
  • Fig. 1 shows the curve obtained when the DMF evaporation rate in plots as ordinate against the dwell time (in seconds) in the spinning shaft as the abscissa. It is approximately a hyperbola, which divides the area into dumbbell and non-dumbbell-shaped fiber cross-sectional structures.
  • Non-dumbbell-shaped fiber cross-sectional profiles are understood to mean both bean-shaped as well as kidney-shaped and round cross-sectional shapes and transitions between the individual profiles. As can be seen in Fig.
  • the values of the ordinate in the form of the DMF evaporation rate represent a measure of the thermal spinning conditions such as shaft, air and spinning solution temperature
  • the values of the abscissa in the form of the residence time of the threads in the spinning shaft are a measure of the mechanical spinning conditions, such as take-off speed and shaft length, mean.
  • Each point on the curve of Fig. 1 represents a certain amount of DMF, the DMF content in the thread may vary depending on the titer. In other words, the course of the curve is independent of the spin titer.
  • the curve also shows that a certain amount of DMF must be evaporated in order to change the cross-sectional structure. In the case of low dwell times, this is significantly greater than with longer dwell times in the spinning shaft.
  • dumbbell-shaped cross sections are never reached below a certain evaporation rate, regardless of the residence time.
  • the DMF evaporation rate per capillary in (mg / sec) can be determined from the difference between the amount of spinning solvent per capillary (mg / sec) and the residual solvent amount per capillary (mg / sec). This should be shown on a model calculation for example 1. The following applies:
  • the DMF evaporation rate R 1 for a spinning solution concentration other than 70.5% by weight DMF, at which the cross-sectional shape changes is calculated as follows: at 1.16 seconds dwell time in the spinning shaft.
  • the fine-titer fibers according to the invention in contrast to conventionally dry-spun acrylic fibers, have no barky, fibrillated surface with grooves of limited length at changing angles to the fiber axis.
  • the fine-titer fibers have smooth surfaces in the longitudinal direction and grooves and striations that run parallel to the fiber axis and are not interrupted, so that the light is reflected in a directed manner.
  • Such acrylic fibers and threads with a single spinning titre of at most 3 dtex td individual end titers of 0.07 - 1.04 dtex are a further subject of the invention, preferably with round to bean-shaped cross sections.
  • fine-titer fibers e.g. Interlockware made of 3-cylinder yarns has a very soft feel compared to conventional acrylic goods made of 1.6 dtex fibers. This is particularly useful for articles that are worn close to the skin and are very useful.
  • fine-tinned spinning material In the case of the aftertreatment of fine-tinned spinning material, it has proven to be extremely advantageous to warm the spinning material to about 79-80 ° C. prior to the stretching process by passing it through troughs with warm washing liquid, preferably water, in order to achieve a more uniform stretching.
  • the fine titre spun material can be post-treated in the usual way by washing-stretching-preparing-drying-crimping-cutting to produce finished acrylic fibers. Because of the large titer fineness of the threads, especially in the case of spinning titer less than 1 dtex, it is also advantageous to draw in stages.
  • the titer determination according to the gravimetric method is very imprecise for fine titers ( ⁇ 0.5 dtex).
  • the titer was therefore determined by the microscopic method by determining the thread diameter "d" with the eyepiece micrometer according to DIN 53 811 according to the formula:
  • the spinning solution had a viscosity of 30 falling seconds when measured at 80 ° C. This value remained unchanged after 1, 3 and 5 hours.
  • the spinning solution was then cooled to 35 ° C. and dry spun from a 720 hole nozzle with nozzle hole diameters of 0.2 mm.
  • the shaft temperature was 50 ° C, the air temperature 200 ° C and the air volume 40 m 3 / h.
  • the take-off speed was 400 m / min.
  • the dwell time of the threads in the spinning shaft was 0.87 seconds. 19.8 ccm / min were conveyed from the spinning pump.
  • the total spin titer was 144 dtex and the residual solvent content of DMF in the spun material was 9.9% by weight, based on polymer solids.
  • the DMF evaporation rate is then calculated to be 0.305
  • the single spin titer was 0.2 dtex.
  • the warpage V was 457.
  • the threads were wetted with oil-containing preparation at the shaft exit, wound onto spools, wound into a cable compartment, stretched 1: 3.6 times in boiling water and aftertreated in the usual way to give fibers with a final titre of 0.07 dtex.
  • the fiber capillaries were embedded in methyl methacrylate and cross-cut.
  • the light microscopic images produced in the differential interference contrast method showed that the sample cross sections are completely uniform and round.
  • the mean thread diameter was determined with the fiber measuring eyepiece.
  • the fibers had an extremely high gloss. When examined in a scanning electron microscope, the fibers showed smooth surfaces with longitudinal stripes. The striations were completely parallel to the fiber axis and, unlike those with conventional acrylic fibers, were not interrupted.
  • An acrylonitrile copolymer with the chemical composition of Example 1 was, as described there, dissolved in DMF, filtered and the spinning solution was cooled to 40 ° C. in front of the nozzle. Then, dry spinning was carried out from a 720-hole nozzle with a nozzle hole diameter of 0.2 mm.
  • the shaft temperature was 50 ° C
  • the take-off speed was 250 m / min and the dwell time of the threads in the spinning shaft was 1.39 seconds. 52.8 ccm / min were conveyed from the spinning pump.
  • the total spin titer was 648 dtex.
  • the residual solvent content in the spun material was 10.8%.
  • the DMF evaporation rate was 0.856
  • the single spin titer was 0.9 dtex.
  • the warpage was 107.
  • the threads were again wetted with oil-containing preparation, wound on bobbins, folded into a cable, stretched 1: 3.6 times in boiling water and aftertreated in the usual way to give fibers with a final titer of 0.3 dtex.
  • the fiber cross sections were again completely uniform and circular.
  • the fibers also had a very high gloss again and showed a smooth surface in the scanning electron microscope with striations that were longitudinally striped parallel to the fiber axis.
  • An acrylonitrile copolymer with the chemical composition from Example 1 was dissolved in DMF as described there.
  • the spinning solution was then filtered, cooled to 90 ° C. and dry-spun from a 720-hole nozzle with a nozzle hole diameter of 0.2 mm.
  • the cell temperature was 150 0 C, the air temperature 200 ° C and the air amount 40 m 3 / h.
  • the take-off speed was 180 m / min. It was spun on a shorter-sized spinning shaft, so that a residence time of 1.66 sec. revealed.
  • the spinning pump became 82.8 ccm / min. promoted.
  • the total spin titer was 1304 dtex.
  • the residual solvent content in the spinning material was 13.5%.
  • the DMF evaporation rate was 1.225
  • the single spin titer was 1.8 dtex.
  • the warpage was 48.
  • the threads were post-treated with 1: 4, 0-fold stretching to fibers with a final titer of 0.6 dtex.
  • the fibers had a round to slightly bean-shaped cross-sectional profile. Her shine was again extraordinarily high. In the scanning electron microscope, striations and striations running on the surface parallel to the fiber axis were again observed, which showed no interruptions.
  • the following table shows the dependence of the cross-sectional shape on the DMF evaporation rate in demonstrated.
  • the spinning material was stretched 1: 3.6 times in boiling water and post-treated as usual.
  • the single-spin and single-end titers were again determined using the light microscopic method and the cross-sectional shapes were determined using light microscopic images using the differential interference contrast method.
  • the different dwell times in the spinning shaft were achieved in addition to different take-off speeds by other shaft lengths.
  • cross-sectional shapes deviating from the dumbbell shape arise primarily with spin titers less than 3 dtex.
  • the single spin titer was 1.81 dtex.
  • the warping was 80.
  • the threads were again wetted with oil-containing preparation, collected on bobbins, folded into a cable, stretched 1: 4.0 times in boiling water and post-treated into fibers in the usual way.
  • the final fiber titer was 0.56 dtex.
  • the fibers show the typical dumbbell shape.
  • part of the batch from Example 5a was cooled to 40 ° C. in front of the nozzle and dry-spun from a 1050-hole nozzle with a nozzle hole diameter of 0.25 mm.
  • the shaft temperature was 190 ° C, the air temperature 380 ° C and the air volume 40 m 3 / h.
  • the Take-off speed was 250 m / min and the dwell time of the threads in the spinning shaft was 2.11 seconds. 161 ccm / min were conveyed from the spinning pump.
  • the total spin titer was 1891 dtex.
  • the residual solvent content in the spinning material was 8.8%.
  • the DMF evaporation rate was 1.727
  • the single spin titer was 1.80 dtex. The warpage was 80.
  • the threads were post-treated as described in Example 5a.
  • the final fiber titer was 0.58 dtex.
  • the fibers in turn show the typical dumbbell shape.
  • Part of the batch from Example 5 was in the heating device on at 80 ° C rather than dissolved, filtered, and the spinning solution upstream of the nozzle again held to 112 ° C at 135 0 C. Then spinning was carried out as described in Example 5a. The threads could not be put on. There were constant tears below the nozzle.
  • the single spin titer was 3.86 dtex.
  • the warpage was 60.
  • the threads were post-treated with 1: 4.0 times stretching to fibers with a final titer of 1.2 dtex.
  • the fibers have a dumbbell-shaped cross-sectional profile.
  • the transition of the cross-sectional shape from round to dumbbell shape with a dwell time of 1.16 seconds in the spinning shaft according to Fig. 1 only at an evaporation rate of 3.05 is expected, the cross-sectional shape changes from round to dumbbell-shaped at a 65% concentration of spinning solution much earlier.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
EP80107777A 1979-12-21 1980-12-10 Feinsttitrige Synthesefasern und -fäden und Trockenspinnverfahren zu ihrer Herstellung Expired - Lifetime EP0031078B2 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80107777T ATE20909T1 (de) 1979-12-21 1980-12-10 Feinsttitrige synthesefasern und -faeden und trockenspinnverfahren zu ihrer herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2951803 1979-12-21
DE19792951803 DE2951803A1 (de) 1979-12-21 1979-12-21 Feinsttitrige synthesefasern und -faeden und trockenspinnverfahren zu ihrer herstellung

Publications (4)

Publication Number Publication Date
EP0031078A2 EP0031078A2 (de) 1981-07-01
EP0031078A3 EP0031078A3 (en) 1983-05-25
EP0031078B1 EP0031078B1 (de) 1986-07-23
EP0031078B2 true EP0031078B2 (de) 1992-06-03

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ID=6089296

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EP80107777A Expired - Lifetime EP0031078B2 (de) 1979-12-21 1980-12-10 Feinsttitrige Synthesefasern und -fäden und Trockenspinnverfahren zu ihrer Herstellung

Country Status (6)

Country Link
US (2) US4400339A (it)
EP (1) EP0031078B2 (it)
JP (1) JPS56101909A (it)
AT (1) ATE20909T1 (it)
DE (2) DE2951803A1 (it)
IE (1) IE52101B1 (it)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3225267A1 (de) * 1982-07-06 1984-01-12 Bayer Ag, 5090 Leverkusen Herstellung loesungsmittelarmer polyacrylnitril-spinnfaeden
DE3225266A1 (de) * 1982-07-06 1984-01-12 Bayer Ag, 5090 Leverkusen Kontinuierliches trockenspinnverfahren fuer acrylnitrilfaeden und - fasern
JPS616160A (ja) * 1984-06-19 1986-01-11 東レ株式会社 繊維補強水硬性物質
DE3424343A1 (de) * 1984-07-03 1986-01-16 Bayer Ag, 5090 Leverkusen Verfahren und vorrichtung zum trockenspinnen
AU634554B2 (en) * 1989-06-28 1993-02-25 Michelin Recherche Et Technique S.A. Aramid monofilament and method for obtaining same
US5715804A (en) * 1994-07-29 1998-02-10 Yamaha Corporation Hybrid bow string formed from strands of polyethylene resin and polyparabenzamide/polybenzobisoxazole resin
JPH0842995A (ja) * 1994-07-29 1996-02-16 Yamaha Corp 洋弓用弦
WO1997021862A2 (en) * 1995-11-30 1997-06-19 Kimberly-Clark Worldwide, Inc. Superfine microfiber nonwoven web
DE19829164A1 (de) 1998-06-30 2000-03-30 Bayer Faser Gmbh Elastanfäden und Verfahren zu ihrer Herstellung
US7175903B1 (en) * 2000-11-17 2007-02-13 Pliant Corporation Heat sealable polyvinyl chloride films
CN109629027B (zh) * 2017-10-09 2021-10-22 中国石油化工股份有限公司 一种干法腈纶1.33dtex短纤维的生产方法
US11180867B2 (en) 2019-03-20 2021-11-23 University Of Kentucky Research Foundation Continuous wet-spinning process for the fabrication of PEDOT:PSS fibers with high electrical conductivity, thermal conductivity and Young's modulus

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE364509A (it) * 1928-10-29
US1950026A (en) * 1929-07-02 1934-03-06 Celanese Corp Manufacture of artificial filaments or threads
US2072100A (en) * 1929-11-27 1937-03-02 Celanese Corp Spinning of artificial filaments
BE514101A (it) * 1951-10-09
US3097415A (en) * 1959-02-20 1963-07-16 Acrylonitrile fiber and process for
NL253933A (it) * 1959-07-18
US3531368A (en) * 1966-01-07 1970-09-29 Toray Industries Synthetic filaments and the like
JPS4711254U (it) * 1971-03-03 1972-10-11
SE403141B (sv) * 1973-02-05 1978-07-31 American Cyanamid Co Smeltspinningsforfarande for framstellning av en akrylnitrilpolymerfiber
JPS539301A (en) * 1976-07-12 1978-01-27 Mitsubishi Rayon Co Production of leather like sheet structre
DE2657144C2 (de) * 1976-12-16 1982-12-02 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung hydrophiler Fasern
DE2658916A1 (de) * 1976-12-24 1978-07-06 Bayer Ag Polyacrylnitril-filamentgarne
JPS5394625A (en) * 1977-01-20 1978-08-18 Asahi Chem Ind Co Ltd Production of acrylic fiber
JPS53147818A (en) * 1977-05-26 1978-12-22 Asahi Chem Ind Co Ltd Production of acrylic fiber
JPS602405B2 (ja) * 1977-09-22 1985-01-21 三菱レイヨン株式会社 アクリロニトリル系異繊度単糸混合連続フイラメント糸の製造法
US4205039A (en) * 1977-11-17 1980-05-27 American Cyanamid Company Process for melt-spinning acrylonitrile polymer fiber
US4219523A (en) * 1978-08-30 1980-08-26 American Cyanamid Company Melt-spinning acrylonitrile polymer fiber from low molecular weight polymers
JPS56377A (en) * 1979-06-15 1981-01-06 Teijin Ltd Production of suede like raised fabric

Also Published As

Publication number Publication date
DE3071670D1 (en) 1986-08-28
JPS56101909A (en) 1981-08-14
IE52101B1 (en) 1987-06-24
US4497868A (en) 1985-02-05
IE802680L (en) 1981-06-21
ATE20909T1 (de) 1986-08-15
US4400339A (en) 1983-08-23
EP0031078B1 (de) 1986-07-23
JPH0128125B2 (it) 1989-06-01
EP0031078A3 (en) 1983-05-25
DE2951803A1 (de) 1981-07-02
EP0031078A2 (de) 1981-07-01
DE2951803C2 (it) 1989-03-16

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