IE920053A1 - A method for the production of a shaped cellulose article - Google Patents

A method for the production of a shaped cellulose article

Info

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
Application number
IE005392A
Original Assignee
Chemiefaser Lenzing Ag
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Chemiefaser Lenzing Ag filed Critical Chemiefaser Lenzing Ag
Publication of IE920053A1 publication Critical patent/IE920053A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00Preparation of cellulose ethers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B25HAND TOOLS; PORTABLE POWER-DRIVEN TOOLS; MANIPULATORS
    • B25JMANIPULATORS; CHAMBERS PROVIDED WITH MANIPULATION DEVICES
    • B25J5/00Manipulators mounted on wheels or on carriages
    • B25J5/007Manipulators mounted on wheels or on carriages mounted on wheels
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/06Wet spinning methods
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02Cellulose; 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)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (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.
IE005392A 1991-01-09 1992-01-08 A method for the production of a shaped cellulose article IE920053A1 (en)

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

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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)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5451364A (en) * 1992-01-17 1995-09-19 Viskase Corporation Cellulose food casing manufacturing method
USH1592H (en) * 1992-01-17 1996-09-03 Viskase Corporation Cellulosic food casing
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
US5902532A (en) * 1994-12-02 1999-05-11 Akzo Nobel Nv Process for manufacturing cellulose objects
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
AT404731B (en) 1997-04-25 1999-02-25 Chemiefaser Lenzing Ag METHOD FOR PRODUCING CELLULOSIC FLAT FILMS AND THEIR USE
US6165401A (en) * 1997-04-25 2000-12-26 Lenzing Aktiengesellschaft Process for the production of cellulosic moulded bodies
BR9804868A (en) * 1997-04-25 1999-08-24 Chemiefaser Lenzing Ag Process for the production of molded cellulose 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)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
AT395862B (en) 1993-03-25
HU9200066D0 (en) 1992-04-28
EP0494851A3 (en) 1993-03-17
IL100619A0 (en) 1992-09-06
PL169424B1 (en) 1996-07-31
JPH04308219A (en) 1992-10-30
ZW192A1 (en) 1992-04-01
FI920071A (en) 1992-07-10
EP0494851B1 (en) 1997-09-17
MX9200098A (en) 1992-07-31
ES2109333T3 (en) 1998-01-16
SK280035B6 (en) 1999-07-12
NO303738B1 (en) 1998-08-24
FI920071A0 (en) 1992-01-08
DE59208903D1 (en) 1997-10-23
HU212701B (en) 1996-10-28
GR3025632T3 (en) 1998-03-31
AU648618B2 (en) 1994-04-28
KR100210294B1 (en) 1999-07-15
PL293116A1 (en) 1992-11-02
CZ282935B6 (en) 1997-11-12
TR25874A (en) 1993-09-01
EP0494851A2 (en) 1992-07-15
YU197691A (en) 1994-06-10
MA22373A1 (en) 1992-07-01
ATA3191A (en) 1992-08-15
CA2059042C (en) 2002-05-14
CA2059042A1 (en) 1992-07-10
JP3072442B2 (en) 2000-07-31
PT99990A (en) 1994-02-28
HUT64111A (en) 1993-11-29
YU47786B (en) 1996-01-09
ZA9110159B (en) 1992-09-30
RO107703B1 (en) 1993-12-30
FI102391B1 (en) 1998-11-30
CS4592A3 (en) 1992-08-12
BG60110B2 (en) 1993-10-29
AU8979891A (en) 1992-07-16
KR920014831A (en) 1992-08-25
FI102391B (en) 1998-11-30
BR9200035A (en) 1992-09-08
RU2061115C1 (en) 1996-05-27
NO920105L (en) 1992-07-10
NO920105D0 (en) 1992-01-08

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