IE920053A1 - A method for the production of a shaped cellulose article - Google Patents
A method for the production of a shaped cellulose articleInfo
- Publication number
- IE920053A1 IE920053A1 IE005392A IE920053A IE920053A1 IE 920053 A1 IE920053 A1 IE 920053A1 IE 005392 A IE005392 A IE 005392A IE 920053 A IE920053 A IE 920053A IE 920053 A1 IE920053 A1 IE 920053A1
- Authority
- IE
- Ireland
- Prior art keywords
- cellulose
- stretched
- article
- fibre
- speed
- Prior art date
Links
- 229920002678 cellulose Polymers 0.000 title claims abstract description 22
- 239000001913 cellulose Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 230000015271 coagulation Effects 0.000 claims description 9
- 238000005345 coagulation Methods 0.000 claims description 9
- 230000001112 coagulating effect Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 15
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 14
- 238000009987 spinning Methods 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 5
- 230000001143 conditioned effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000578 dry spinning Methods 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- 241000157282 Aesculus Species 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000010181 horse chestnut Nutrition 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B25—HAND TOOLS; PORTABLE POWER-DRIVEN TOOLS; MANIPULATORS
- B25J—MANIPULATORS; CHAMBERS PROVIDED WITH MANIPULATION DEVICES
- B25J5/00—Manipulators mounted on wheels or on carriages
- B25J5/007—Manipulators mounted on wheels or on carriages mounted on wheels
-
- 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
- D01D5/06—Wet 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
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Robotics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
To produce a cellulosic article, a cellulosic amine oxide solution is pressed through a nozzle or through a slit, then passed through an air slit and finally coagulated in a precipitation bath. According to the invention, it is not stretched in the air gap, i.e. the ratio of discharge rate to hole emergence rate is at most 1; only the coagulated cellulose is stretched or deep-drawn.
Description
LENZING AKTIENGESELLSCHAFT, an Austrian Company, of Werkstrasse, A-4860 Lenzing, Austria 5015 The present invention relates to a method for the production of a shaped cellulose article, in which a cellulose amine oxide solution is forced through a nozzle or a gap, is then conducted through an air gap and is finally coagulated in a coagulating bath.
It is known that fibres with good performance characteristics can only be obtained from high polymers, when a fibre-structure is achieved (Ullmann, 5th edition, Vol. A10, 456). To this end, it is inter alia necessary to align in the fibre microoriented regions in the polymer, for instance fibrids. This orientation is defined by the production method and is based upon physical or physicochemical processes. In many cases, this orientation is effected by stretching.
Both the process step in which this stretching occurs and the conditions under which it is carried out determine the fibre characteristics obtained. In melt spinning, the fibres are stretched when in a warm plastic state, while the molecules are still mobile. Dissolved polymers may be dry spun or wet spun. In dry spinning, stretching occurs as the solvent escapes or evaporates; the filaments extruded into a coagulating bath are stretched during the - 1 IE 920053 coagulation. Methods of this type are known and are amply described. However, in all of these cases, it is important for the transition from the liquid state (regardless of whether it is a melt or a solution) to the solid state to occur in such a manner that an orientation of the polymer chains or polymer chain packets (in other words fibrids, fibrils etc.) may also be achieved during the formation of the filaments.
There are several possibilities available for preventing the sudden evaporation of a solvent from a filament during dry spinning.
The problem of extremely rapid coagulation of the polymers during wet spinning (as for instance in the case of cellulose amine oxide solutions) until now could only be resolved by a combination of dry spinning and wet spinning.
It is therefore known to introduce polymer solutions into the coagulant through an air gap. In EP-A-295 672, there is described the production of aramid fibres, which are introduced into a non-coagulating medium through an air gap, are stretched, and are subsequently coagulated.
East German Patent 218 121 is directed to the spinning of cellulose in amine oxides by way of an air gap, arrangements being provided for preventing adhering.
According to US Patent 4 501 886, a cellulose triacetate solution is spun by means of an air gap.
In US Patent 3 415 645, the production of aromatic polyamides from solutions in a dry-wet spinning method is also described.
A degree of orientation is achieved in the air gap in all of these methods, because even the mere fact of a viscous solution being allowed to flow downwards out through a small opening causes an orientation to occur, due to gravitational force on the particles of the solution. This orientation by means of gravitational force can even be increased, if the speed of extrusion of the polymer solution - 2 IE 920053 and the marching-off velocity of the filament are adjusted so that stretching occurs.
A method of this type is described in Austrian Patent 387 792 (or its equivalents US 4 246 221 and US 4 416 698). A solution of cellulose in NMMO (NMMO = N-Methylmorpholine-N-Oxide) and water is formed, is stretched in the air gap and is subsequently precipitated. The stretching takes place at a stretching ratio of at least 3.
A disadvantage of this method is the lack of flexibility in regard to the ability to change the characteristics of the shaped article. A minimum spin to stretch ratio is required in order to obtain corresponding textile properties. Only extremely modest textile fibre characteristics are achievable in the case of very low draw ratio, which means that extremely poor average toughness (i.e. the product of fibre tenacity and fibre elongation) is achieved for example in fibre production. A further disadvantage is that the effect of the so-called marching-off/exit speed resonance (see Navard, Haudin Spinning of a Cellulose N-Methylmorpholine-N-Oxide Solution, Polymer Process Engineering 3(3), 291 (1985)), which leads to irregular fibre diameters, is greater, the greater the spin to stretch ratio. Finally, it is also disadvantageous that formation occurs for all practical purposes only in the air gap. Later formation is only possible with extreme difficulty. The bandwidth of possible products is obviously restricted by this. Subsequent influencing of the product characteristics would be desirable, by virtue of which this method would gain considerable flexibility.
It is an object of the present invention to overcome these disadvantages.
This object is achieved according to the invention by a method of the type initially described, in that the ratio of marching-off speed to hole exit velocity is at most 1, and that the shaped article is stretched or deep drawn after coagulation.
According to the invention, the marching-off speed is - 3 IE 920053 therefore less than (or at most equal to) the hole exit velocity (spinning speed) of the spinning mass, so that no stretching can occur. The cellulose thus remains in a relatively unoriented condition until coagulation in the coagulating bath. This is advantageous, because the less the orientation before or at coagulation, the greater the possibility of influencing the characteristics afterwards. Because of the low orientation, the coagulated (precipitated) cellulose has an elasticity, which is almost like rubber. In accordance with the invention, this cellulose may then be stretched or deep drawn in order to obtain the desired characteristics; the flexibility sought is thus assured.
A further advantage exists in that as a result of the stretching no longer being present, the air gap may be made almost as short as wished, so that even if the spinning nozzles have a very high hole density, there is nonetheless no danger of adjacent fibres adhering. As productivity can be considerably increased in large-scale production by raising the hole density, this is also a considerable advantage of the present invention.
The invention is described in more detail with reference to the following examples: Example 1 : Production of a fibre with a marching-off speed to hole exit velocity ratio less than 1 (comparative test) A 13% cellulose NMMO solution (cellulose of the Viskokraft type made by ICP, 10% water, 77% NMMO, 0.1% oxalic acid as stabiliser) was forced through a nozzle having 100 holes (hole diameter in each case 130 /im). The rate of ejection was 16.5 g/min; the resulting speed of ejection was thus 10.35 m/min. The 100 filaments were conducted through an 8 mm long air gap and then through a 15 cm long spinning bath (temperature : 2°C, NMMO concentration : 5%) at a rate of 6 m/min. The ratio of marching-off speed to exit velocity was thus 0.58.
The resulting fibre had a tenacity of 11.8 cN/tex at an elongation of 77.5%. The value for elongation is extremely high; - 4 IE 920053 this proves that the cellulose is present in a relatively unordered state.
Example 2 : Stretch of the fibre after coagulation in air The same procedure was employed in this test as in Example 1. In this case however, after the spinning bath, i.e. after coagulation, the fibre was wound onto a godet roll at 6 m/min and the filament bundle was conducted over a second godet roll at a rate of 13 m/min. The stretch thus amounted to 117%. (Stretch of a fibre in percentage terms in the sense of this application means (final length less initial length) divided by initial length, all multiplied by 100). The fibres thereby obtained bad a tenacity of 22.4 cN/tex at an elongation of 15.3%.
Example 3 : Stretch of the fibre after coagulation in water Here, again as in Example 1, the fibre was conducted through a spinning bath at 6 m/min (marching-off speed to exit velocity : 0.58) and subsequently conducted through an 80 cm long stretching bath with water (temperature : 77°C). The second godet roll was driven at two different speeds v. The fibres obtained had the following properties : V Stretch Titre Conditioned Conditioned tenacity elongation m/min 'o dtex cN/tex % 14 133 32.4 19.7 17.5 21 250 10.3 22.3 9.2 Example 4 : Production of a fibre with a marching-off speed to hole exit velocity ratio greater than 1 (comparative test) A 13% cellulose NMMO solution (cellulose of the Visokraft type made by ICP, 10% water, 77% NMMO, 0.1% oxalic acid as stabiliser) was forced through a nozzle having 100 holes (hole diameter in each case 70 pm). The delivery was 5.1 g/min, which - 5 IE 920053 corresponds to an exit velocity of 11.1 m/min. The marching-off velocity of the first godet roll was 33.3 m/min, which means that the ratio of marching-off speed to exit velocity was 3.0. At the speed of the godet roll 1, the filaments were conducted through a spinning bath, the temperature of which was 33°C and the NMMO concentration of which was 10%. The subsequent stretching bath had a temperature of 79°C and an NMMO concentration of 9%. The second godet roll after the stretching bath had a draw-off velocity of 46.9 m/min, which means that the stretching amounted to 41%.
The textile characteristics of the fibre obtained were : Titre : 3.5 dtex Conditioned tenacity : 25 cN/tex Conditioned elongation : 8.8% At a ratio of marching-off speed to hole exit velocity greater than 1, the fibres are still capable in principle of being stretched, but not however to the extent recorded for Examples 2 to 4 Example 5 : Manufacture of a foil A 9% cellulose NMMO solution (cellulose of the Buckeye V5 type made by Proctor & Gamble, 12% water, 79% NMMO, 0.1% oxalic acid as stabiliser) was forced through a slit nozzle (gap 50 pm, length mm). The ejection rate was 21.3 g/min which corresponds to an exit velocity of 11.7 m/min. The extruded solution was then drawn through a 7 mm long air gap and subsequently through a 15 cm long spinning bath (temperature : 24°C, NMMO concentration : 20%) by means of a first godet roll at a rate of 6 m/min. The ratio of marching-off speed to exit velocity was thus 0.51. In the same operation, the foil was conducted through an 80 cm long stretching bath (temperature : 90°C; concentration : 20%) and was stretched by a second godet roll (speed : 11 m/min). The stretch thus amounted to 83%. The characteristics of the washed and dried foil 2 were : Thickness : 10 pm; Strength : 200 N/mm ; Elongation : 6.5%. - 6 IE 920053 Example 6 : Manufacture of a shaped article A foil similar to that of Example 5 was manufactured, but not stretched, i.e. the foil was removed after the first godet roll. It was deep drawn 3 mm in an unstretched state with a glass rod, and washed and dried, whereby a dimensionally stable shaped article resulted. - 7 IE 920053
Claims (4)
1. A method for producing a cellulose shaped article, in which a cellulose amine oxide solution is forced through a nozzle or a gap, is subsequently conducted through an air gap and is finally coagulated in a coagulating bath, characterised in that the ratio of marching-off speed to hole exit velocity is at most 1 and that the shaped article is stretched or deep drawn after coagulation.
2. A method for producing a shaped cellulose article, substantially as described herein by way of example.
3. A shaped cellulose article produced by the method of Claim 1 or Claim 2. Dated this 8th day of January, 1992. TOMCINS & CO., Applicant's Agents, App (Signed)
4. 5, Dartmouth Road, DUBLIN 6.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0003191A AT395862B (en) | 1991-01-09 | 1991-01-09 | METHOD FOR PRODUCING A CELLULOSIC MOLDED BODY |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| IE920053A1 true IE920053A1 (en) | 1992-07-15 |
Family
ID=3479697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE005392A IE920053A1 (en) | 1991-01-09 | 1992-01-08 | A method for the production of a shaped cellulose article |
Country Status (28)
| Country | Link |
|---|---|
| EP (1) | EP0494851B1 (en) |
| JP (1) | JP3072442B2 (en) |
| KR (1) | KR100210294B1 (en) |
| AT (1) | AT395862B (en) |
| AU (1) | AU648618B2 (en) |
| BG (1) | BG60110B2 (en) |
| BR (1) | BR9200035A (en) |
| CA (1) | CA2059042C (en) |
| CZ (1) | CZ282935B6 (en) |
| DE (1) | DE59208903D1 (en) |
| ES (1) | ES2109333T3 (en) |
| FI (1) | FI102391B (en) |
| GR (1) | GR3025632T3 (en) |
| HU (1) | HU212701B (en) |
| IE (1) | IE920053A1 (en) |
| IL (1) | IL100619A0 (en) |
| MA (1) | MA22373A1 (en) |
| MX (1) | MX9200098A (en) |
| NO (1) | NO303738B1 (en) |
| PL (1) | PL169424B1 (en) |
| PT (1) | PT99990A (en) |
| RO (1) | RO107703B1 (en) |
| RU (1) | RU2061115C1 (en) |
| SK (1) | SK280035B6 (en) |
| TR (1) | TR25874A (en) |
| YU (1) | YU47786B (en) |
| ZA (1) | ZA9110159B (en) |
| ZW (1) | ZW192A1 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USH1592H (en) * | 1992-01-17 | 1996-09-03 | Viskase Corporation | Cellulosic food casing |
| US5451364A (en) * | 1992-01-17 | 1995-09-19 | Viskase Corporation | Cellulose food casing manufacturing method |
| ATA53792A (en) * | 1992-03-17 | 1995-02-15 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC MOLDED BODIES, DEVICE FOR IMPLEMENTING THE METHOD AND USE OF A SPINNING DEVICE |
| DE4308524C1 (en) * | 1992-06-16 | 1994-09-22 | Thueringisches Inst Textil | Process for the production of cellulose fibers and filaments by the dry-wet extrusion process |
| AT401271B (en) * | 1993-07-08 | 1996-07-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSE FIBERS |
| DE4421482C2 (en) * | 1994-06-20 | 1997-04-03 | Fraunhofer Ges Forschung | Process for producing oriented cellulose films and the films produced by this process and their use |
| US5603884A (en) * | 1994-11-18 | 1997-02-18 | Viskase Corporation | Reinforced cellulosic film |
| EP0795052B2 (en) * | 1994-12-02 | 2006-04-26 | Akzo Nobel N.V. | Method of producing shaped cellulose bodies, and yarn made of cellulose filaments |
| US5658525A (en) * | 1995-08-04 | 1997-08-19 | Viskase Corporation | Cellulose food casing manufacturing method |
| TW389799B (en) * | 1995-08-29 | 2000-05-11 | Asahi Chemical Ind | Cellulose multifilament yarn and fabric made thereof |
| DE19541824A1 (en) * | 1995-11-10 | 1997-05-15 | Thueringisches Inst Textil | Reliable, cellulose filament yarn spinning from morpholine oxide soln. |
| AT404032B (en) * | 1996-03-04 | 1998-07-27 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC FIBERS |
| GB9605504D0 (en) * | 1996-03-15 | 1996-05-15 | Courtaulds Plc | Manufacture of elongate members |
| US6165401A (en) * | 1997-04-25 | 2000-12-26 | Lenzing Aktiengesellschaft | Process for the production of cellulosic moulded bodies |
| AT404731B (en) | 1997-04-25 | 1999-02-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC FLAT FILMS AND THEIR USE |
| DE59812212D1 (en) * | 1997-04-25 | 2004-12-09 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC MOLDED BODIES |
| DE10200405A1 (en) | 2002-01-08 | 2002-08-01 | Zimmer Ag | Cooling blowing spinning apparatus and process |
| DE10204381A1 (en) | 2002-01-28 | 2003-08-07 | Zimmer Ag | Ergonomic spinning system |
| DE10206089A1 (en) | 2002-02-13 | 2002-08-14 | Zimmer Ag | bursting |
| DE10314878A1 (en) * | 2003-04-01 | 2004-10-28 | Zimmer Ag | Method and device for producing post-stretched cellulose filaments |
| AT6807U1 (en) * | 2004-01-13 | 2004-04-26 | Chemiefaser Lenzing Ag | CELLULOSIC FIBER OF THE LYOCELL GENERATION |
| DE102004024030A1 (en) | 2004-05-13 | 2005-12-08 | Zimmer Ag | Lyocell process with polymerization-degree-dependent adjustment of the processing time |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB796544A (en) * | 1954-10-13 | 1958-06-11 | British Celanese | Improvements in the manufacture of artificial filaments and like products |
| US3767756A (en) * | 1972-06-30 | 1973-10-23 | Du Pont | Dry jet wet spinning process |
| US4416698A (en) * | 1977-07-26 | 1983-11-22 | Akzona Incorporated | Shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent and a process for making the article |
| US4464323A (en) * | 1982-08-09 | 1984-08-07 | E. I. Du Pont De Nemours And Company | Process for preparing high strength cellulosic fibers |
| FR2617511B1 (en) * | 1987-07-01 | 1989-12-15 | Inst Textile De France | PROCESS FOR THE PREPARATION OF A CELLULOSE SPINNING SOLUTION IN THE PRESENCE OF TERTIARY AMINE OXIDE AND ADDITIVE |
-
1991
- 1991-01-09 AT AT0003191A patent/AT395862B/en not_active IP Right Cessation
- 1991-12-17 AU AU89798/91A patent/AU648618B2/en not_active Ceased
- 1991-12-19 MA MA22657A patent/MA22373A1/en unknown
- 1991-12-23 YU YU197691A patent/YU47786B/en unknown
- 1991-12-27 ZA ZA9110159A patent/ZA9110159B/en unknown
-
1992
- 1992-01-06 ZW ZW1/92A patent/ZW192A1/en unknown
- 1992-01-06 KR KR1019920000040A patent/KR100210294B1/en not_active IP Right Cessation
- 1992-01-06 BG BG95726A patent/BG60110B2/en unknown
- 1992-01-06 RO RO149066A patent/RO107703B1/en unknown
- 1992-01-08 NO NO920105A patent/NO303738B1/en not_active IP Right Cessation
- 1992-01-08 JP JP4001348A patent/JP3072442B2/en not_active Expired - Lifetime
- 1992-01-08 PT PT99990A patent/PT99990A/en not_active Application Discontinuation
- 1992-01-08 IE IE005392A patent/IE920053A1/en not_active IP Right Cessation
- 1992-01-08 RU SU925010549A patent/RU2061115C1/en not_active IP Right Cessation
- 1992-01-08 CZ CS9245A patent/CZ282935B6/en unknown
- 1992-01-08 BR BR929200035A patent/BR9200035A/en not_active IP Right Cessation
- 1992-01-08 SK SK45-92A patent/SK280035B6/en unknown
- 1992-01-08 HU HU9200066A patent/HU212701B/en not_active IP Right Cessation
- 1992-01-08 FI FI920071A patent/FI102391B/en not_active IP Right Cessation
- 1992-01-08 CA CA002059042A patent/CA2059042C/en not_active Expired - Fee Related
- 1992-01-08 PL PL92293116A patent/PL169424B1/en unknown
- 1992-01-09 DE DE59208903T patent/DE59208903D1/en not_active Expired - Lifetime
- 1992-01-09 TR TR92/0017A patent/TR25874A/en unknown
- 1992-01-09 ES ES92890003T patent/ES2109333T3/en not_active Expired - Lifetime
- 1992-01-09 IL IL100619A patent/IL100619A0/en unknown
- 1992-01-09 MX MX9200098A patent/MX9200098A/en not_active IP Right Cessation
- 1992-01-09 EP EP92890003A patent/EP0494851B1/en not_active Expired - Lifetime
-
1997
- 1997-12-10 GR GR970403284T patent/GR3025632T3/en unknown
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