AU7012598A - Method for producing cellulosed formed parts - Google Patents
Method for producing cellulosed formed parts Download PDFInfo
- Publication number
- AU7012598A AU7012598A AU70125/98A AU7012598A AU7012598A AU 7012598 A AU7012598 A AU 7012598A AU 70125/98 A AU70125/98 A AU 70125/98A AU 7012598 A AU7012598 A AU 7012598A AU 7012598 A AU7012598 A AU 7012598A
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- Australia
- Prior art keywords
- film
- cellulosic
- transverse direction
- stretched
- flat film
- 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.)
- Abandoned
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- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 238000000034 method Methods 0.000 claims description 51
- 239000012528 membrane Substances 0.000 claims description 41
- 229920002678 cellulose Polymers 0.000 claims description 36
- 239000001913 cellulose Substances 0.000 claims description 36
- 238000001556 precipitation Methods 0.000 claims description 33
- 238000001125 extrusion Methods 0.000 claims description 24
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 15
- 230000035699 permeability Effects 0.000 claims description 10
- 150000003512 tertiary amines Chemical class 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000005022 packaging material Substances 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 95
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000001035 drying Methods 0.000 description 12
- 239000011780 sodium chloride Substances 0.000 description 12
- 229920000297 Rayon Polymers 0.000 description 6
- 238000000502 dialysis Methods 0.000 description 5
- 229920000298 Cellophane Polymers 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/08—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique transverse to the direction of feed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
- B29K2001/08—Cellulose derivatives
- B29K2001/12—Cellulose acetate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/008—Wide strips, e.g. films, webs
-
- 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)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Thermal Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Cell Separators (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Description
1 Process for the production of cellulosic moulded bodies The present invention deals with a process for the manufacture of cellulosic moulded bodies, in particular cellulosic flat films and cellulosic membranes in the form of flat membranes whereby a solution of cellulose in an aqueous tertiary amine oxide is moulded in film form by means of an extrusion die, which has an oblong extrusion gap, and led through an air gap into a precipitation bath whereby the cellulosic flat film is formed in the precipitation bath. From US-A-2 179 181 it is known that tertiary amine oxides have the ability to dissolve cellulose and that cellulosic moulded bodies such as fibres can be won from these solutions as a result of precipitation/regeneration. A process for the production of solutions of this kind is for example known from EP-A-0 356 419. According to this publication first of all a suspension of cellulose is prepared in an aqueous tertiary amine oxide. The amine oxide contains up to 40 weight % water. The aqueous cellulose suspension is transferred into the solution in a thin film treatment apparatus. From DE-A-28 44 163 it is known for the production of cellulose fibres that an air gap is provided between the spinning nozzle and the precipitation bath to achieve drawing at the nozzle. This nozzle drawing is necessary since the stretching of the filaments is made more difficult after the contact of the moulded spinning solution with the aqueous precipitation bath. In the precipitation bath the fibre structure set in the air gap is fixed. A process for the production of cellulosic threads is, furthermore, known from DE-A-28 30 685 whereby a solution of cellulose is formed to filaments in a tertiary amine oxide in a warm condition, the filaments are cooled down with air and finally introduced to a precipitation bath to precipitate the dissolved cellulose. The surface of the spun filaments is, furthermore, moistened with water to reduce their tendency to stick to neighbouring filaments.
2 From DE-A-195 15 137 a process is known for the production of flat films whereby first of all a tubular film is formed using a ring nozzle, said film being cut to flat films following washing and drying. When manufacturing the tubular films, the extruded tube is extended in the air gap both in the drafting direction and in the transverse direction. This happens as a result of gas pressure effective in the inside of the tube. The disadvantages of this process lie in the complicated design of the device to be used and in the washing and drying process which is more complex with tubular films than with flat films. Processes for the manufacture of cellulosic tubular films are, moreover, well know from US-A-5 277 857 and EP-A-0 662 283. According to these know processes a cellulose solution is formed to a tube via an extrusion nozzle with a ring-shaped extrusion gap, said tube being drawn over a cylindrical mandrel and introduced to a precipitation bath. In order that the extruded tube does not stick to the surface of the mandrel its surface is covered with a water film so that the inner side of the tube coagulates and slides over the cylindrical mandrel. According to EP-A-0 662 283 the tubular film is extended after washing by blowing in a gas. DE-C-44 21 482 describes a blowing process for the manufacture of oriented cellulosic films whereby the cellulose solution is extruded via a film blowing nozzle and an air gap downwards into a precipitation bath. It is mentioned that stretching can be performed transverse to the transport direction of the blown film via the gas pressure in the inside of the blown film and that the relation of mechanical longitudinal and transverse properties can be set. A process and a device for the manufacture of cellulosic films, particularly of tubular films, is also known from WO-A-95/07811 of the applicant. In this respect the dissolved cellulose is cooled before it is brought into the precipitation bath by subjecting the heated solution to a stream of gas immediately after extruding. From WO-A-97/24215 there is known a process for the production of an oriented cellulosic film in which a cellulosic solution is applied to a stretchable surface to which the solution sticks, the solution is then stretched by stretching the extendable surface and finally it is precipitated.
3 From EP-B-0 494 851 of the patent applicant there is known a process for the production of a cellulosic flat film in which a cellulosic solution is pressed through a nozzle or gap, it is then led through an air gap and then coagulated in a precipitation bath and the coagulated flat film is stretched in the longitudinal direction. With cellulosic membranes particularly in the form of flat membranes, i.e. membranes from a flat film, the permeability of the membranes is an important property. To solve certain separation tasks it is important to select membranes with the optimum permeability, pore size and pore structure for the respective separation task. Dialysis membranes made of regenerated cellulose in the form of flat films, tubular films or hollow threads have been known for some time whereby the regeneration of the cellulose carr take place by means of the cuoxam-process, the viscose process or by means of the hydrolysis of cellulose acetate. Depending upon the process used and the process conditions one obtains membrances with different dialysis properties. US- 4,354,938 describes for example a process for the production of dialysis membranes according to the viscose process, in which a tubular moulded membrane is stretched in the transverse direction by between 40 and 120 % by blowing up with air before drying , which leads to a membrane with a regular orientation in the longitudinal and transverse direction. When transferring the dried membranes in the wet state the membranes thus produced undergo a shrinkage in the longitudinal and transverse direction of 0.5 - 10 %. The ultrafiltration values lie in the range of between 2.5 ml/m 2 .h.mm Hg and 5,2 ml/m 2 .h.mm Hg at a wet thickness of 184 gm to 45 pm. In "membranes and membrane processes" by E. Staude, 1992, VCH Verlagsges.m.b.H. on page 19 it is described that the biaxial stretching of finished cellophane membranes lead to the enlargement of the pores, monoaxial stretching on the other hand leads to a reduction in the effective pore diameter.
4 However, the viscose process only offers limited possibilities to set membrane properties in a well aimed manner. Moreover, the recovery of the chemicals which accumulate in this process such as sodium sulphate and carbon bisulphide etc. is very expensive. The present invention has as an object to provide a process for the production of cellulosic flat films with improved mechanical properties. Moreover, it is the object of the invention to provide a process for the production of cellulosic membranes in the form of flat membranes by means of which membranes with a permeability which is optimised for the individual separation task to be accomplished can be achieved. This object is achieved by a process for the production of cellulosic flat films and cellulosic membranes in the form of flat membranes whereby a solution of cellulose in an aqueous tertiary amine oxide is moulded in the form of a film using an extrusion-nozzle which has an oblong extrusion gap , said solution being led through an air gap into a precipitation bath whereby the cellulosic flat film is formed in the precipitation bath, and in which according to the invention the cellulosic flat film is stretched in the transverse direction after entering the precipitation bath. The transverse stretching can thereby take place in the precipitation bath or at a later time. Under transverse stretching is understood a stretching in the direction of the width of the cellulosic flat film. It is known that cellulose films made according to the viscose process can hardly be shaped at all after regenerating and can only be stretched in the transverse direction to a limited extent. Surprisingly in accordance with the invention it was shown that in the case of films manufactured according to the amine oxide process according to the generic term of claim 1, transverse stretching is also possible after the precipitation of the film-like moulded solution of cellulose. In this way cellulosic flat films are obtained with improved mechancial properties. The costly blowing up of a tubular moulded cellulosic solution in the air gap is thereby not necessary. The transverse stretching of the films can be performed according to well known methods such as for example those used with thermoplastic films (as is for example described in the Handbook of Plastics Extrusion II, extrusion plants, Hanser-Verlag, 1986, 261-269), for example by 5 conveyor belts or by clamping devices which are attached to endless belts respectively chains by the fact that the belts are led in divergent directions. Preferably the cellulose solution is extruded using an extrusion die, which has an extrusion gap with a length of at least 40 cm. The cellulose solution can, however, also be extruded from an extrusion gap with a length of less than 40 cm which results in films with a lower width. According to one preferred embodiment of the process in accordance with the invention, the cellulosic flat fim is stretched in the longitudinal direction in the air gap, preferably in a range of 0.2 to 5 times. One further advantageous embodiment of the process according to the invention is characterised in that the cellulosic flat film is first washed after precipitation and stretched after washing. Surprisingly it has been shown that cellulosic flat films made using the process according to the invention can be stretched in the transverse direction in a washed state by up to 3.5 times their original width. In accordance with one further preferred embodiment of the process in accordance with the invention the cellulosic flat film is first of all washed after precipitation and dried and after that the dry cellulosic flat film is moistened and stretched preferably by spraying with water. Surprisingly it was shown that cellulosic flat films treated in this way can be stretched by up to 3.5 times their original width in the transverse direction. The process according to the invention has the advantage that by stretching the cellulosic flat film up to 3.5 times the original width in the transverse direction the mechanical properties of the film can be set in a wide range in the longitudinal and transverse direction. Preferably N-Methylmorpholine-N-oxide (NMMO) is used as the tertiary amine oxide.
6 The advantages described above of the process in accordance with the invention apply in particular to a production in accordance with the invention of cellulosic membranes in the form of flat membranes. In this respect the permeability of the membrane and thus also its ultrafiltration rate (UFR) can be influenced in particular by the selection of the speed at which the film-like moulded solution is drawn off in the air gap. In this respect it is shown that a lower draw-off speed increases the permeability and thus also the ultrafiltration rate of the membrane. By contrast the transverse stretching of the film after entering the precipitation bath increases the permeability of the membrane. Thus basic membrane properties can be controlled by the selection of draw-off speed and the transverse stretching of the film. The invention also relates to the use of a cellulosic flat film made by the process in accordance with the invention as a packaging material, in particular for foodstuff, as a material for waste and carrier bags, as film for agricultural applications, as a film for diapers, as asubstrate for compounds, as an office film, as a household film or as a membrane to separate substance mixtures. With the following examples the invention is described in greater detail. The cellulose solutions used were manufacturwd in accordance with the process described in EP-A-0 356 419. In all the examples the films were washed following precipitation of the cellulose and treated with glycerine (glycerine content of the dried film about 15 wt.%) and finally dried on a tenter frame, in which the films were fixed in the longitudinal and transverse direction. The properties listed in the examples were determined with the dried films, whereby the tenacity (longitudinal and transverse) and the longitudinal and transverse elongation were determined according to DIN 53457. The ultrafiltration rate given in the examples is defined as the per time unit of the volume of the permeate passing through the membrane wall relative to the membrane area and the test pressure.
7 UFR= V ml t.A.p h.m 2 .mmHg V = volume of liquid (permeate) [ml] t = time [h] A = membrane area [M 2 ] p = test pressure [mm Hg] The values for diffuse permeabilities are determined by the increase of the straight line arrived at by plotting ln(c/c) against time. InL' -A.Pdif.t CO c, = starting concentration c= concentration at time t A = membrane area [cm 2 ] V = dialysis volume [cm 3 ] Pdiff. = diffuse permeability [cm/min] t = time [min] To directly compare the different membranes all the permeabilities were converted to a wet thickness of 75 pm, i.e. the corresponding times for reaching the balanced state were standardised to this thickness . For example if with a membrane with a thickness of 200 gm, the balanced state of NaCl-dialysis was reached after 100 hours, then this corresponds to a time of 100 x 75 / 200 = 37,5 hours for a membrane with a thickness of 75 gm. Example 1 (comparison) A cellulose solution with a temperature of 85* C, containing 15.5 wt. % cellulose, 74.5 wt.% NMMO and 10.0 wt.% water, was extruded with a throughput of 37.8 kg/h by means of an 8 oblong extrusion nozzle, which had an extrusion gap with a length of 40 cm and a width of 300 gim, through an air gap of 20 mm into a precipitation bath, comprising 80 wt.% NMMO and 20 wt.% water. The film-like moulded cellulose solution emerged from the nozzle at a speed of 4.2 m/min and was drawn off with three times the emerging speed. The flat film obtained had the following properties: Thickness: 32 gm Tenacity (longitudinal direction): 177,1 N/mm 2 Tenacity (transverse direction): 62,3 N/mm 2 Elongation in longitudinal direction: 15,6 % Elongation in transverse direction: 114,0 % UFR: 3,5 ml/mm 2 .h.mm Hg PdiffNaOH: 2,5. 10- cm/min PdiffNaCl: 1,7. 10- cm/min Example 2 The procedure was the same as in example 1 except that the flat film was stretched by 50 % in the transverse direction on the tenter frame prior to drying. The flat film obtained had the following properties: Thickness: 21 pm 9 Tenacity (longitudinal direction): 194,0 N/mm 2 Tenacity (transverse direction): 78,8 N/mm 2 Longitudinal elongation: 17,5 % Transverse elongation: 70,3 % UFR: 4,5 ml/mm 2 .h.mm Hg Pdiff NaOH: 2,6. 10- cm/min Pdiff NaCl: 2,3.10-3 cm/min Example 3 The procedure was the same as in example 1 except that the flat film was stretched by 75% in the transverse direction on the tenter frame prior to drying. The flat film obtained had the following properties: Thickness: 18 ptm Tenacity (in longitudinal direction): 177,3 N/mm 2 Tenacity (transverse direction): 88,1 N/mm 2 Elongation in longitudinal direction: 17,5 % Elongation in transverse direction: 52,6 % UFR: 4,5 ml/mm 2 .h.mm Hg PdiffNaOH: 2,8.10-' cm/min Pdiff NaCl: 2,5. 10- cm/min Example 4 10 The procedure was the same as in example 1 except that the flat film was stretched by 100% in the transverse direction on the tenter frame prior to drying. The flat film obtained had the following properties: Thickness: 16 gm Tenacity (longitudinal direction): 181,5 N/mm 2 Tenacity (transverse direction): 114,7 N/mm 2 Elongation in longitudinal direction: 17,1 % Elongation in transverse direction: 37,2 % UFR: 5,1 ml/mm 2 .h.mm Hg PdiffNaOH: 3,2. 10- cm/min PdiffNaCl: 2,9.10-3 cm/min Example 5 The procedure was the same as in example 1 except that the flat film was stretched by 125% in the transverse direction on the tenter frame before drying. The flat film obtained had the following properties: Thickness: 14 pm Tenacity (longitudinal direction): 182,8 N/mm 2 Tenacity (transverse direction ): 122,7 N/mm 2 Elongation in longitudinal direction: 20,0 % Elongation in transverse direction: 36,8 % 11 UFR: 5,3 ml/mm 2 .h.mm Hg Pdiff NaOH: 3,1.10-3 cm/min Pdff NaCl: 2,8. 10-3 cm/min Example 6 The procedure was the same as in example 1 except that the flat film was stretched by 175 % in the transverse direction before drying on the tenter frame. The flat film obtained had the following properties: Thickness: 12 gm Tenacity (longitudinal direction): 138,0 N/mm 2 Tenacity (transverse direction): 131,5 N/mm 2 Elongation in longitudinal direction: 13,9 % Elongation in transverse direction: 27,9 % UFR: 5,5 ml/mm 2 .h.mm Hg Piff NaOH: 3,1. 10-3 cm/min PdiffNaCl: 3,1.10- cm/min Example 7 (comparison) A cellulose solution with a temperature of 1100 C, containing 15.0 wt. % cellulose, 74.5 wt. % NMMO and 10.5 wt.% water, was extruded with a throughput of 37.8 kg/h using an oblong extrusion nozzle, which had an extrusion gap with a length of 40 cm and a width of 300 pm, 12 through an air gap of 20 mm into a precipitation bath comprising 80 wt.% NMMO and 20 wt.% water. The film-like moulded cellulose solution emerged from the nozzle at a speed of 4.2 m/min and was drawn off at the same speed. This means that the flat film was not stretched in the longitudinal direction in the air gap. The flat film obtained had the following properties: Thickness: 71 gm Tenacity (longitudinal direction): 190,6 N/mm 2 Tenacity (transverse direction): 107,2 N/mm 2 Elongation in longitudinal direction: 19,9 % Elongation in transverse direction: 70,3 % UFR: 5,6 ml/mm 2 .h.mm Hg Pdiff NaOH: 5,2. 10-3 cm/min PdiffNaCl: 4,3.10-3 cm/min 13 Example 8 The procedure was the same as in example 7 except that the flat film was stretched on the tenter frame by 100% in the transverse direction prior to drying. The flat film obtained had the following properties: Thickness: 36 gm Tenacity (longitudinal direction): 185,0 N/mm 2 Tenacity (transverse direction): 169,1 N/mm 2 Elongation in the longitudinal direction: 26,6 % Elongation in the transverse direction: 29,2 % UFR: 5,9 ml/mm 2 .h.mm Hg Pdiff NaOH: 5,7.10' cm/min Pdiff NaCl: 4,6.10' cm/min Example 9 The procedure was the same as in example 7, except that the flat film was stretched 200% in the transverse direction prior to drying on the tenter frame. The flat film obtained had the following properties: Thickness: 24 ptm Tenacity (longitudinal direction): 13 9,6 N/mm 2 Tenacity (transverse direction): 179,3 N/mm 2 Elongation in the longitudinal direction: 36,2 % 14 Elongation in the transverse direction: 20,0 % UFR: 6,2 ml/mm 2 .h.mm Hg PdiffNaOH: 5,9.10-3 cm/min Pdiff NaCl: 5,0.i10' cm/min Example 10 (comparison) A cellulose solution with a temperature of 85 C, containing 15.5 wt. % cellulose, 74.5 wt. % NMMO and 10.0 wt. % water, was extruded with a throughput of 37.8 kg/h by means of an oblong extrusion nozzle, which had an extrusion gap with a length of 40 cm and a width of 300 gm, through an air gap of 20 mm into a precipitation bath, comprising a 80 wt.% NMMO and 20 wt.% water. The film-like moulded cellulose solution emerged from the nozzle at a speed of 4.2 m/min and was drawn off at the same speed. This means that the flat film was not stretched in the air gap in the longitudinal direction. The flat film obtained had the following properties: Thickness: 67 gm Tenacity (longitudinal direction): 224,1 N/mm 2 Tenacity (transverse direction): 165,1 N/mm 2 Elongation in the longitudinal direction: 25,6 % Elongation in the transverse direction: 54,3 % UFR: 5,5 ml/mm 2 .h.mm Hg Pdiff NaOH: 5,2.10- cm/min PdiT NaCl: 4,2.10 cm/mmin 15 Example 11 The procedure was the same as in example 10 except that the flat film was moistened again after drying on the tenter frame and was stretched on the tenter frame by 100 % in the transverse direction. The flat film obtained had the following properties in the dry state: Thickness: 34 tm Tenacity (longitudinal direction): 171,1 N/mm 2 Tenacity (transverse direction): 171,9 N/mm 2 Elongation in the longitudinal direction: 36,6 % Elongation in the transverse direction: 40,1 % UFR: 5,8 ml/mm 2 .h.mm Hg Pdiff NaOH: 5,9.10- cm/min PdiffNaCl: 4,4.10- cm/min Example 12 The procedure was the same as in example 10 except that the flat film was moistened again after drying on the tenter frame and was stretched by 200% in the transverse direction on the tenter frame. The flat film obtained had the following properties in the dry state: Thickness: 22 pm 16 Tenacity (longitudinal direction): 132,2 N/mm 2 Tenacity (transverse direction): 190,5 N/mm 2 Elongation in the longitudinal direction: 34,4 % Elongation in the transverse direction: 31,8 % UFR: 6,0 ml/mm 2 .h.mm Hg Pdiff NaOH: 5,6.10-3 cm/min Pdiff NaCl: 4,9.10- cm/min Example 13 A cellulose solution with a temperature of 85*C, containing 15.0 wt.% cellulose, 74.5 wt.% NMMO and 10.5 wt.% water, was extruded with a throughput of 37.8 kg/h using an oblong extrusion nozzle, which displayed an extrusion gap with a length of 40 cm and a width of 300 gim, through an air gap of 20 mm into a precipitation bath, comprising 80 wt. % NMMO and 20 wt.% water. The film-like moulded cellulose solution emerged from the nozzle with a speed of 4.2 m/min and was drawn off at the same speed. This means that the flat film was not stretched in the longitudinal direction in the air gap. The dry flat film was immersed in water for 2 minutes and afterwards was stretched on the tenter frame by 25 % in the transverse direction. The film obtained had the following properties in the dry state: Thickness: 49 jim Tenacity (longitudinal direction): 266,6 N/mm 2 17 Tenacity (transverse direction): 163,1 N/mm 2 Elongation in the longitudinal direction: 20,2 % Elongation in the transverse direction: 61,3 % UFR: 5,5 ml/mm 2 .h.mm Hg Pdiff NaOH: 5,3.10-3 cm/min Pdiff NaCl: 4,2.10-3 cm/min Example 14 The procedure was the same as in example 13 except that the film immersed in the water was stretched on the tenter frame by 75 % in the transverse direction. The flat film obtained had the-following properties in the dry state: Thickness: 37 pm Tenacity (longitudinal direction): 244,4 N/mm 2 Tenacity (transverse direction): 195,5 N/mm 2 Elongation in the longitudinal direction: 24,9 % Elongation in the transverse direction: 37,5 % UFR: 5,6 ml/mm 2 .h.mm Hg Pdiff NaOH: 5,3. 103 cm/min Pdiff NaCl: 4,3.10-3 cm/min 18 Example 15 The procedure was the same as in example 13 except that the flat film immersed in the water was stretched on the tenter frame by 100 % in the transverse direction. The film obtained had the following properties in the dry state: Thickness: 32 gm Tenacity (longitudinal direction): 235,8 N/mm 2 Tenacity (transverse direction): 232,9 N/mm 2 Elongation in the longitudinal direction: 26,9 % Elongation in the transverse direction: 35,1 % UFR: 5,8 ml/mm 2 .h.mm Hg -PifNaOH: 5,7. 10 cm/min PdiffNaCl: 4,5. 10- cm/min Example 16 The procedure was the same as in example 13 except that the flat film immersed in the water was stretched by 250% in the transverse direction. The flat film obtained had the following properties in the dry state: Thickness: 18 Am Tenacity (longitudinal direction): 187,6 N/mm 2 Tenacity (transverse direction): 265,2 N/mm 2 Elongation in the longitudinal direction: 38,0 % 19 Elongation in the transverse direction: 31,1 % UFR: 6,3 ml/mm 2 .h.mm Hg PdiffNaOH: 6. 10 cm/min Pdiff NaCl: 5,2. 10 3 cm/min Example 17 (comparison) A cellophane film manufactured according to the viscose process was moistened and dried on the tenter frame without stretching. The film obtained had the following properties in the dry state: Thickness: 30 pm Tenacity (longitudinal direction): 176,1 N/mm 2 Tenacity (transverse direction): 81,9 N/mm 2 Elongation in the longitudinal direction: 13,8 % Elongation in the transverse direction: 31,8 % Example 18 (comparison) A cellophane film produced according to the viscose process was moistened and stretched in the transverse direction on the tenter frame by 50 %. It was not possible to achieve a higher transverse stretching than 50% with the cellophane film without the film being torn.
20 The film obtained had the following properties in the dry state: Thickness: 21 pm Tenacity (longitudinal direction): 159,0 N/mm 2 Tenacity (transverse direction): 113,1 N/mm 2 Elongation in the longitudinal direction: 12,8 % Elongation in the transverse direction: 19,7 % Example 19 A cellulose solution with a temperature of 1100 C, containing 14.2 wt. % Cellulose, 76.2 wt. % NMMO and 9.6 wt.% water, was extruded by means of a longitudinal extrusion nozzle, which displayed an extrusion gap with a length of 40 cm and a width of 500 pm, with a throughput of 75.6 kg/h through an air gap of 3 cm vertically downwards into a regnerating bath, comprising a 98 wt. % water and 2 wt. % NMMO. The film-like moulded cellulose solution emerged from the nozzle at a speed of 5.0 m/min and was drawn off at three times that speed and stretched in the precipitation bath in the transverse direction by 50%. The flat film obtained displayed the following properties: Width: 55,0 cm Thickness: 33,0 jim Tenacity (longitudinal direction): 151,3 N/mm 2 Tenacity (transverse direction): 135,6 N/mm 2 Elongation in longitudinal direction: 16,4 % 21 Elongation in transverse direction: 37,3 % UFR: 4,7 ml/mm 2 .h.mm Hg PdiffNaOH: 2,6. 10- cm/min Pdiff NaCl: 2,4.l10'cm/min Example 20 A cellulose solution with a temperature of 85 C, containing 14.2 wt. % cellulose, 76.3 wt. % NMMO and 9.5 wt. % water, was extruded by means of a longitudinal extrusion nozzle, which had an extrusion gap with a length of 40 cm and a width of 500 pm, with a throughput of 75.6 kg/h through an air gap of 1 cm vertically downwards into a precipitation bath, comprising a 98 wt. % water and 2 wt. % NMMO. The film-like moulded cellulose solution emerged from the nozzle with a speed of 5.0 m/min and was drawn off with the same speed. After the precipitation bath the flat film was stretched in the transverse direction by 100%. The flat film obtained displayed the following properties: Width: 74,0 cm Thickness: 45,0 pm Tenacity (longitudinal direction): 119,1 N/mm 2 Tenacity (crosswise direction): 184,6 N/mm 2 Elongation in longitudinal direction: 42,0 % Elongation in crosswise direction: 32,0 % UFR: 6,1 ml/mm 2 .h.mm Hg Pdff NaOH: 5,7.10- cm/min Pdiff NaCl: 4,8. 10- cm/min
Claims (8)
1. Process for the manufacture of cellulosic flat films and cellulosic membranes in the form of flat membranes whereby a solution of cellulose in an aqueous tertiary amine oxide is moulded in the form of a film using an extrusion nozzle which has an oblong extrusion gap, said solution being led through an air gap into a precipitation bath whereby the cellulosic flat film is formed in the precipitation bath, characterised in that the cellulosic flat film is stretched in transverse direction after entering the precipitation bath.
2. Process according to claim 1, characterised in that the cellulosic flat film is stretched in the longitudinal direction in the air gap, preferably in a range of 0.2 to 5 times.
3. Process according to claim 1 or 2, characterised in that the cellulosic flat film is washed after precipitation and stretched after washing.
4. Process according to claims 1 or 2 characterised in that the cellulosic flat film is washed and dried after precipitation and that the dry cellulosic flat film is moistened and stretched.
5. Process according to one of claims 1 to 4, characterised in that the cellulosic flat film is stretched in the transverse direction by up to 3.5 times.
6. Process according to one of claims 1 to 5, characterised in that N-Methylmorpholine-N oxide is used as the tertiary amine oxide.
7. Process according to one of claims 1 to 6 for the manufacture of a cellulosic membrane characterised in that the permeability of the membrane is controlled by the transverse stretching of the film after it enters the precipitation bath. 23
8. Use of a cellulosic flat film made by the process according to claims 1 to 6 as a packaging material, in particular for foodstuffs, as a material for waste and carrier bags, as a film for agricultural applications, as a film for diapers, as a substrate for compounds, as an office film, as a household film or as a membrane to separate substance mixtures.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT705/97 | 1997-04-25 | ||
AT0070597A AT404731B (en) | 1997-04-25 | 1997-04-25 | METHOD FOR PRODUCING CELLULOSIC FLAT FILMS AND THEIR USE |
AT179797A AT405407B (en) | 1997-10-23 | 1997-10-23 | Process for producing cellulosic mouldings |
AT1797/97 | 1997-10-23 | ||
PCT/AT1998/000109 WO1998049224A1 (en) | 1997-04-25 | 1998-04-24 | Method for producing cellulosed formed parts |
Publications (1)
Publication Number | Publication Date |
---|---|
AU7012598A true AU7012598A (en) | 1998-11-24 |
Family
ID=25593666
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU70125/98A Abandoned AU7012598A (en) | 1997-04-25 | 1998-04-24 | Method for producing cellulosed formed parts |
Country Status (12)
Country | Link |
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US (1) | USRE38583E1 (en) |
EP (1) | EP0912628B1 (en) |
JP (1) | JP4375816B2 (en) |
CN (1) | CN1142967C (en) |
AU (1) | AU7012598A (en) |
BR (1) | BR9804868A (en) |
CA (1) | CA2258122A1 (en) |
DE (1) | DE59812212D1 (en) |
ES (1) | ES2232942T3 (en) |
ID (1) | ID21037A (en) |
NO (1) | NO321195B1 (en) |
WO (1) | WO1998049224A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US6235392B1 (en) | 1996-08-23 | 2001-05-22 | Weyerhaeuser Company | Lyocell fibers and process for their preparation |
US6221487B1 (en) | 1996-08-23 | 2001-04-24 | The Weyerhauser Company | Lyocell fibers having enhanced CV properties |
JP4547115B2 (en) * | 2001-08-29 | 2010-09-22 | 富士フイルム株式会社 | Method for producing optical compensation film |
CN104610557B (en) * | 2013-11-01 | 2018-03-02 | 中国科学院化学研究所 | A kind of regenerated cellulose film, functional membrane and preparation method thereof |
CN108790160B (en) * | 2018-06-12 | 2020-06-16 | 四川农业大学 | 3D prints-electrostatic spinning packagine machine and control system thereof |
DE102020109417A1 (en) | 2020-04-03 | 2021-10-07 | Ing. A. Maurer S.A. | Process for the production of tracing paper |
CN114539186A (en) | 2021-07-02 | 2022-05-27 | 华茂伟业绿色科技股份有限公司 | NMMO purification method and system and obtained NMMO hydrate crystal |
Family Cites Families (25)
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US2179181A (en) * | 1936-04-21 | 1939-11-07 | Soc Of Chemical Ind | Cellulose solutions and process of making same |
GB689395A (en) | 1950-02-28 | 1953-03-25 | Wingfoot Corp | Lateral stretching of thermoelastic films |
US2698967A (en) | 1951-01-19 | 1955-01-11 | American Viscose Corp | Production of regenerated cellulose films and sheets |
US3657115A (en) * | 1971-01-27 | 1972-04-18 | Us Interior | Semipermeable membranes their use and method for preparation wherein the membranes are stretched during the initial gelation period |
US4144080A (en) * | 1977-07-26 | 1979-03-13 | Akzona Incorporated | Process for making amine oxide solution of cellulose |
US4246221A (en) * | 1979-03-02 | 1981-01-20 | Akzona Incorporated | Process for shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent |
DE2736569B2 (en) * | 1977-08-13 | 1979-07-19 | Hoechst Ag, 6000 Frankfurt | Viscous membrane for hemodialysis and process for their manufacture |
ZA785535B (en) * | 1977-10-31 | 1979-09-26 | Akzona Inc | Process for surface treating cellulose products |
US4748186A (en) | 1986-06-30 | 1988-05-31 | Fmc Corporation | S-trifluorobutenyl derivatives and pesticidal uses thereof |
US5330567A (en) * | 1988-08-16 | 1994-07-19 | Lenzing Aktiengesellschaft | Process and arrangement for preparing a solution of cellulose |
AT392972B (en) * | 1988-08-16 | 1991-07-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING SOLUTIONS OF CELLULOSE AND DEVICE FOR IMPLEMENTING THE METHOD |
AT395862B (en) * | 1991-01-09 | 1993-03-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING A CELLULOSIC MOLDED BODY |
US5451364A (en) * | 1992-01-17 | 1995-09-19 | Viskase Corporation | Cellulose food casing manufacturing method |
US5658524A (en) | 1992-01-17 | 1997-08-19 | Viskase Corporation | Cellulose article manufacturing method |
US5277857A (en) * | 1992-01-17 | 1994-01-11 | Viskase Corporation | Method of making a cellulose food casing |
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 |
AT403584B (en) * | 1993-09-13 | 1998-03-25 | Chemiefaser Lenzing Ag | METHOD AND DEVICE FOR PRODUCING CELLULOSIC FLAT OR TUBE FILMS |
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 |
DE19515137A1 (en) * | 1995-04-25 | 1996-10-31 | Thueringisches Inst Textil | Process for the production of flat cellulose films |
GB9600006D0 (en) * | 1996-01-02 | 1996-03-06 | Courtaulds Fibres Holdings Ltd | Polymeric films |
GB9606914D0 (en) * | 1996-04-02 | 1996-06-05 | Courtaulds Fibres Holdings Ltd | Battery separators |
EP0807460A1 (en) * | 1996-05-15 | 1997-11-19 | Akzo Nobel N.V. | Cellulosic dialysis membrane |
AT405407B (en) | 1997-10-23 | 1999-08-25 | Chemiefaser Lenzing Ag | Process for producing cellulosic mouldings |
AT404731B (en) | 1997-04-25 | 1999-02-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC FLAT FILMS AND THEIR USE |
AT405405B (en) | 1997-10-23 | 1999-08-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC MOLDED BODIES |
-
1998
- 1998-04-24 ES ES98916620T patent/ES2232942T3/en not_active Expired - Lifetime
- 1998-04-24 AU AU70125/98A patent/AU7012598A/en not_active Abandoned
- 1998-04-24 CA CA002258122A patent/CA2258122A1/en not_active Abandoned
- 1998-04-24 WO PCT/AT1998/000109 patent/WO1998049224A1/en active IP Right Grant
- 1998-04-24 CN CNB988005409A patent/CN1142967C/en not_active Expired - Fee Related
- 1998-04-24 ID IDW980144D patent/ID21037A/en unknown
- 1998-04-24 DE DE59812212T patent/DE59812212D1/en not_active Expired - Lifetime
- 1998-04-24 BR BR9804868A patent/BR9804868A/en not_active IP Right Cessation
- 1998-04-24 JP JP54640298A patent/JP4375816B2/en not_active Expired - Lifetime
- 1998-04-24 EP EP98916620A patent/EP0912628B1/en not_active Expired - Lifetime
- 1998-12-22 NO NO19986044A patent/NO321195B1/en unknown
-
2001
- 2001-05-23 US US09/907,561 patent/USRE38583E1/en not_active Expired - Lifetime
Also Published As
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NO986044D0 (en) | 1998-12-22 |
JP4375816B2 (en) | 2009-12-02 |
BR9804868A (en) | 1999-08-24 |
ID21037A (en) | 1999-04-08 |
DE59812212D1 (en) | 2004-12-09 |
JP2000517262A (en) | 2000-12-26 |
ES2232942T3 (en) | 2005-06-01 |
CA2258122A1 (en) | 1998-11-05 |
EP0912628B1 (en) | 2004-11-03 |
CN1142967C (en) | 2004-03-24 |
CN1224435A (en) | 1999-07-28 |
WO1998049224A1 (en) | 1998-11-05 |
NO321195B1 (en) | 2006-04-03 |
USRE38583E1 (en) | 2004-09-14 |
EP0912628A1 (en) | 1999-05-06 |
NO986044L (en) | 1999-02-22 |
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