EP0031078B1 - Fibres et filaments synthétiques de titre très fin et procédé de filage à sec pour leur fabrication - Google Patents
Fibres et filaments synthétiques de titre très fin et procédé de filage à sec pour leur fabrication Download PDFInfo
- Publication number
- EP0031078B1 EP0031078B1 EP80107777A EP80107777A EP0031078B1 EP 0031078 B1 EP0031078 B1 EP 0031078B1 EP 80107777 A EP80107777 A EP 80107777A EP 80107777 A EP80107777 A EP 80107777A EP 0031078 B1 EP0031078 B1 EP 0031078B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- spinning
- filaments
- dtex
- 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
Links
- 238000000578 dry spinning Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229920002994 synthetic fiber Polymers 0.000 title abstract description 6
- 238000009987 spinning Methods 0.000 claims abstract description 139
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 141
- 239000000835 fiber Substances 0.000 claims description 53
- 239000002904 solvent Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 14
- 229920002972 Acrylic fiber Polymers 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003495 polar organic solvent Substances 0.000 claims description 3
- 206010040925 Skin striae Diseases 0.000 claims 1
- 239000012209 synthetic fiber Substances 0.000 abstract description 5
- 238000001704 evaporation Methods 0.000 description 22
- 230000008020 evaporation Effects 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 9
- 239000013557 residual solvent Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004744 fabric Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 230000001934 delay Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 238000009997 thermal pre-treatment Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 241001295925 Gegenes Species 0.000 description 1
- 238000007200 Mander carbonylation reaction Methods 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 241000170793 Phalaris canariensis Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 210000001520 comb Anatomy 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012821 model calculation Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 210000002023 somite Anatomy 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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 spinning solution in the spinning shaft must be subjected to a high degree of warpage.
- the warping (V) during spinning is defined as the ratio of the take-off speed to the ejection speed
- the present invention therefore relates to a process for the production of synthetic fibers and threads from spinning solutions with a solids content of 25 to 35% of thread-forming acrylonitrile polymers with at least 85% by weight of acrylonitrile units in polar organic solvents after a dry spinning process at a spinning shaft temperature of preferably between 30 ° C.
- 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 can for example, with the usual spinnerets with hole diameters of about 0.15 to 0.8 mm, preferably 0.2 to 0.4 mm, and in usual spinning shafts. 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.
- 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 above 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 the work is carried out with high delays.
- the spinning solution for example, 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, e.g. a bean or kidney shape.
- the spinning solution had a viscosity of 30 ball falling seconds 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 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 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 withdrawal 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 delay was 107.
- the threads were again wetted with oil-containing preparation, wound on spools, 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 shaft temperature was 150 ° C, the air temperature 200 ° C and the air volume 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 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.
Landscapes
- 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)
Claims (5)
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 (fr) | 1981-07-01 |
EP0031078A3 EP0031078A3 (en) | 1983-05-25 |
EP0031078B1 true EP0031078B1 (fr) | 1986-07-23 |
EP0031078B2 EP0031078B2 (fr) | 1992-06-03 |
Family
ID=6089296
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80107777A Expired - Lifetime EP0031078B2 (fr) | 1979-12-21 | 1980-12-10 | Fibres et filaments synthétiques de titre très fin et procédé de filage à sec pour leur fabrication |
Country Status (6)
Country | Link |
---|---|
US (2) | US4400339A (fr) |
EP (1) | EP0031078B2 (fr) |
JP (1) | JPS56101909A (fr) |
AT (1) | ATE20909T1 (fr) |
DE (2) | DE2951803A1 (fr) |
IE (1) | IE52101B1 (fr) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3225266A1 (de) * | 1982-07-06 | 1984-01-12 | Bayer Ag, 5090 Leverkusen | Kontinuierliches trockenspinnverfahren fuer acrylnitrilfaeden und - fasern |
DE3225267A1 (de) * | 1982-07-06 | 1984-01-12 | Bayer Ag, 5090 Leverkusen | Herstellung loesungsmittelarmer polyacrylnitril-spinnfaeden |
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 |
BR9006842A (pt) * | 1989-06-28 | 1991-08-06 | Michelin Rech Tech | Monofilamento aramida,processo para se obter pelo menos um monofilamento aramida,montagem e artigo |
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 (fr) | 1995-11-30 | 1997-06-19 | Kimberly-Clark Worldwide, Inc. | Voile en non-tisse a microfibres extra-fines |
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)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE364509A (fr) * | 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 (fr) * | 1951-10-09 | |||
NL248550A (fr) * | 1959-02-20 | |||
NL253933A (fr) * | 1959-07-18 | |||
US3531368A (en) * | 1966-01-07 | 1970-09-29 | Toray Industries | Synthetic filaments and the like |
JPS4711254U (fr) * | 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 |
-
1979
- 1979-12-21 DE DE19792951803 patent/DE2951803A1/de active Granted
-
1980
- 1980-12-04 US US06/213,531 patent/US4400339A/en not_active Expired - Lifetime
- 1980-12-10 DE DE8080107777T patent/DE3071670D1/de not_active Expired
- 1980-12-10 EP EP80107777A patent/EP0031078B2/fr not_active Expired - Lifetime
- 1980-12-10 AT AT80107777T patent/ATE20909T1/de not_active IP Right Cessation
- 1980-12-19 IE IE2680/80A patent/IE52101B1/en unknown
- 1980-12-22 JP JP18057680A patent/JPS56101909A/ja active Granted
-
1983
- 1983-02-22 US US06/468,620 patent/US4497868A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0031078A3 (en) | 1983-05-25 |
IE52101B1 (en) | 1987-06-24 |
DE2951803C2 (fr) | 1989-03-16 |
IE802680L (en) | 1981-06-21 |
DE3071670D1 (en) | 1986-08-28 |
US4400339A (en) | 1983-08-23 |
DE2951803A1 (de) | 1981-07-02 |
EP0031078A2 (fr) | 1981-07-01 |
JPH0128125B2 (fr) | 1989-06-01 |
ATE20909T1 (de) | 1986-08-15 |
EP0031078B2 (fr) | 1992-06-03 |
JPS56101909A (en) | 1981-08-14 |
US4497868A (en) | 1985-02-05 |
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