CA1191315A - Linear low density polyethylene film and method of making - Google Patents
Linear low density polyethylene film and method of makingInfo
- Publication number
- CA1191315A CA1191315A CA000432639A CA432639A CA1191315A CA 1191315 A CA1191315 A CA 1191315A CA 000432639 A CA000432639 A CA 000432639A CA 432639 A CA432639 A CA 432639A CA 1191315 A CA1191315 A CA 1191315A
- Authority
- CA
- Canada
- Prior art keywords
- draw
- film
- low density
- density polyethylene
- linear low
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- 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
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
- B29C43/222—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length characterised by the shape of the surface
-
- 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
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of 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
- 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
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- 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
- B29C48/911—Cooling
-
- 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
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
- B29C48/9155—Pressure rollers
-
- 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
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
- B29C48/917—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means by applying pressurised gas to the surface of the flat article
-
- 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
-
- 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
-
- 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
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/04—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
-
- 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
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
- B29K2023/0608—PE, i.e. polyethylene characterised by its density
- B29K2023/0625—LLDPE, i.e. linear low density polyethylene
Abstract
LINEAR LOW DENSITY POLYETHYLENE FILM
AND METHOD OF MAKING
ABSTRACT OF THE DISCLOSURE
A method for producing a linear low density poly-ethylene (LLDPE) film by slot-die extrusion from an extrudate having an inherent draw resonance tendency whereby draw resonance is eliminated in the production of film at high speeds. Film of commercially uniform gauge thickness is obtained having significantly improved strength over films formed by conventional slot-die extrusion of LLDPE.
AND METHOD OF MAKING
ABSTRACT OF THE DISCLOSURE
A method for producing a linear low density poly-ethylene (LLDPE) film by slot-die extrusion from an extrudate having an inherent draw resonance tendency whereby draw resonance is eliminated in the production of film at high speeds. Film of commercially uniform gauge thickness is obtained having significantly improved strength over films formed by conventional slot-die extrusion of LLDPE.
Description
1~13~5 sack~ound of the Invention Thermoplastic film or sheet material hAs achieved widespread use in the ~abrication of many useful article~.
Particular utility for thexmoplastic film has been found in the area of covering materials, such as diaper film and operating room table covers, due to the moisture barrier character of the plastic film, among other properties. Thin film of this type is typically produced by extrusion, the two general methods of extruding film being blown tubing and slot-die extrusion.
In the slot~die method of producing thermoplastic film, the heated plastic extrudate or melt, typically composed of polyethylene, polypropylene, and copolymers thereof, is extruded out of a narrow slot in an elongated die. Flat film is generally made in considerable widths on relatively large machi.nes which run at high production rates on the order of 300 to 1000 or more feet-per-m.inute. The hot extrudate extxuded in the form of a web from the slot-die is drawn and stretched through an air-gap to the desired gauge thickness and width by stretching rollers which form a nip or this purpose. The nipping rollers ma~ also serve as an embossing or calendering means for the film if particular textures or surface charac-teristics and properties are desired for the film. The film then typically passes from the nipping rollers to a chill roller where it is cooled and set, and then to a take-up roller.
It has been known to use linear low density poly-ethylene as the polymer composition in the slot-die extrusion of film. The densities of this polymer have varied usually between about 0.915 - 0.940 g/cm . Linear low density polyethylene ~herein simply sometimes LLDP~) as the term is used in this descxiption is polyethylene haviny little or no long chain :~ , : ' ~, ~' .
~ r~
branching, with short chain branching in an amowlt necessary to obtain the deslred density, currently for instance less than about 0.940 g/cm3. For example, a common density for LLDPE used in diaper film is 0.926 g/cm3, and for operating room table covers is 0.918 g/cm3. Linear low density polyethylene has been considered desirable in that it exhibits a good balance of mechanical properties in film form, particularly ultimate tensile strength, impact resistance, burst strength and tear strength characteristics.
A serious drawback to the use of LLDPE is its suscep tibility to draw resonance at a relatively low draw or take-up rate, typically at a take-up rate of about 40 feet per minute or more. Draw resonance is a phenomenon associated with stretching motions and it is manifested in the occurrence of periodic fluctuations in the thickness of the extrudate as it is drawn.
Draw resonance is primarily a function of the take-up rate as well as the draw ratio, the draw ratio being the ratio of the die-slot width to the film thickness. In regard to the latter, for a given linear low density polyethylene extrudate, draw resonance is expected to be more severe in drawing a thinner gauge of the film, and its onset at a lower draw speed, than in a thicker gauge film.
Film exhibiting draw resonance can have gauge thick-ness variations on the order of ~5~, or morej which is considered to be commercially unsatisfactory. Such gauge variations deteriorate product uniformity and reduce the reliability and saleability of the film~ As a consequence, LLDPE which has been produced by conventional slot-die extrusion techniques has been drawn at take-up rates less than the critical point at which draw resonance sets in which i5 usuall~
about a production speed of 30 to 40 feet~per-minute. This i9 a factor which seriously limits productivity.
There is conseguently a need in the industry for a method for producing LLDPE film by slot-die extrusion techniques at relatively high draw rates with substantial elimination of draw resonance in the extrudate to thereby yield a thermoplastic film which is uniform in gauge thickness within the range of commercial acceptability.
Summary of the Invention It is a principal object of this invention to produce a uniform thermoplastic film using linear low density poly-ethylene drawn at take-up rates greater than 40 feet~per-minute, the point at which draw resonance typically occurs with conven-tional slot-die extrusion machinery. Particularly, it i~ an object o~ this inv~ntion to produce such a film at very high take up speeds on the order of several hundred feet~per-minute, or more, without the onset of draw resonance in the drawn extrudate.
To these ends, it has been discovered that substantial elimination of draw resonance in LLDPE extrudate can be achieved through reduction of the draw-gap between the die-slot and the drawing roller or rollers. In particular, it has been found -that a draw-gap of about zero to not more than about six inches between the slot of the extrusion die and the draw roller enables LLDP~ film to be drawn at speeds of several hundred feet-per-minute with gauge variations well within commercial tolerances for uniformity.
~ urthermore, surprisingly it has been discovered that the LLDP~ film produced by the method of this invention is stronger by significant orders of magnitude in both the machin~
! :
3~LS
diraction and cross direction. These findings and other advan-tages of this invention will be further understood in view of the following description.
In preferred form embodying the principles of this invention, a conventional slot-die extrusion apparatlls for production of diaper film is adapted to provide a draw-gap between about zero and about six inches, for example, one inch.
A first roller in cooperation with an air-knife, serves to draw the ex~rudate into the desired gauye thickness and width. The LLDPE extrudate is extruded at a temperature above its crytal-lization temperature. The distance between the slot of the die (herein simply sometimes die-slot) and the ~irst roller is the critical draw-gap. In the preferred form with an air-knife, the gap is the distance between the slot and the nip formed by the roller and the air-knife acting on the LLDPE web. The draw roller is either operated without the application of heat or at an elevated temperature, particularly for purposes of subsequent embossing. The draw roller is preferably coated with a poLy~
tetrafluoroethylene for better film release characteristicsO At the draw roller, the LLDPE crystallizes and it has been found that the short draw-gap provides the benefits of this invention~
After the draw roller, the film may be introduced into a nip formed by an embossing roller which cooperates with a rubber roller to form an embossing system for embossing the surface of the film to a desired texture. A chill roll is thereafter employed to cool and set the film after it has passed through the embossing roller system, with the film ultimately being wound on a take-up rollO Thus, according to this inven-tion, LLDPE extrudate is heated to a temperature above its crystallization temperature and extruded through the slot-dic.:.
3;~L3~
Immediately upon introduction into the short gap maintained between the slot-die and the draw nip, the LLDPE i5 caused to be drawn to the desired gauge thickness and width film. ~sing this short-draw technique, 100~ LLDPE film of 32 inches in width and a gauge thickness of 1 mil has been drawn as fast as S70 f.p.m.
with only nominal variation on gauge thickness. For commercial applications, any take-up rate of about 300 f.p.m., or more, is considered very acceptable.
Although the instant invention solves the problem of draw resonance in slot-die extrusion of LLDPE films drawn at high take-up rates, a precise understanding of why the short-draw technique is so effective is not yet available. The elimination of draw resonance by a short-draw zone is quite unexpected. One would logically expect that a longer draw ~one, which allows the deformation (strain) to be applied over a longer time interval, to be better and less ~r- n~;ng for the molecular network to ad~ust. The improvement in physical properties is also quite unexpected. One would expect the longer residence time available in a longer draw process to allow the molecular network to relax -the strains imposed by the extrusion process and lead to a more randomi~ed (isotropic) orientation typical of stronger films. In both cases the reverse was found, the short-draw led to a complete elimination of draw resonance and to a remarkably strong film.
As mentioned above, another unexpected by-product and advantage of this short~draw technique is that the LI.DPE film has tensile properties significantly better than film made by a conventional process. This phenomenon is again not yet under-stood completely, but greater tensile properties in both the machine direction and cross direc~ion are obtained which far o~
3~
exceed any tensile properties obtained by conventional slot-dic extrusion film production proces~es.
These and other advantages of this invention will be further understood with reference to the drawings, in which:
BRIEF DESCRJPTION OF THE DRAWINGS
Fig. 1 is a perspective diagrammatic view of an apparatus illustrating a technique for drawing a LLDPE film according to this invention, including embossing rolls and a take-up roll.
Fig. 2 is an elevational diagrammatic view illus-trating the relative positioning of the slot-die, draw roller and air-knife of the apparatus of Fig. 1.
Fig. 3 is a graph relating tensile strength to linear low density polyethylene content by weight of the extrudate for 1 mil gauge film of 0.935 g/cm3 density where the balance of the film content is low density polyethylene.
Fig. 4 is an elevational dlagrammatic view illus-trating another technique for drawing and embossing a thermo-plastic film according to thls invention.
DETAILED DESCRIPTION OE THE INVENTION
It is a primary objective of this invention to sub-stantially eliminate the draw resonance which typically occurs when an extrudate containing linear low density polyethylene, or blends of LLDPE with polyethylene, polypropylene, or copolymers thereof, is drawn to make thermoplastic film at take-up speeds greater than about 40 feet-per-minute. It is a collateral objective of this invention to thereby produce a thermoplastic film which is substantially uniform in gauge thickness within commercial tolerances, and which also exhibits improved tensile properties that are not obtainable through any con~entional ~, _ 7 slot-dle extrusion or perhaps even conventional blown tubing fllm productlon pro~ess. The ~ollowing detailed description, which is taken in conjunction with the accompanying drawings, is illustrative of the features and advantages of the process a~d product produced by that process of the present invention.
It wlll be understood that certain values for the extrudate, conditions o~ operation of the film producing appa-ratus, and actual film parameters used herein ln the compilation of the described data are each representative of a range over which the instant invention is expected to be effective. For instance, the density of the extrudate containing linear low density polyethylene is not limited to the specific density utilized in the cornpilation of the following data, since the short-draw techniqua for eliminatior~ of draw resonance is anticipa-ted to be advantageo~s over the whole range of densities of commercially employed linear low density poLyethylene.
Likewise, the actual percentage of linear low densi.ty poly-ethylene making up the e~trudate is also variable. So too, the gauge thickness of the film produced in accordance with thi3 invention is not limi-ted to any specific value,i.e., the one mil gauge used herein merely is representative of a comrnon gauge of diaper film.
~ ith this in mind, reference is now made to Figs. 1 and ~ which show in diagrammatic form a system for drawing and embossing thermoplastic film in accordance with the principles of this inventionO The drawing and embossing apparatus, are generally indicated at 9. ~ heated extrudate, or melt, to be described more fully hereafter, is supplied to a slot-die extruder 10 from a suitable source (not shown) and is extruded through an elongate die-slot 11 in the form of a web 120 The :~
. . .
I
web 12 i9 drawrl horizont~lly khroucJh a shortened draw-gap 13 by draw roller D. The draw roller D cooperates with an air-knife 14 to thereby define, in effect, a "draw nip" through which the web 12 is caused to pass. The nip thus formed serves to dr~w the extruded web 12 into a film 15 of the desired gauge thick-ness and width. The draw-gap 13 has a substantially constant length X as measured perpendicularly from the die-slot 11 to the draw nip.
The film 15 subsequently passes from the draw roller D
to a system of embossing rolls. One of the rolls is a steel roll S having a surface which is embossed, as by conventional engraving methods, with a desired pattern that is to be imparted to the film 15. The other roll in the embossing roll system is a resilient or rubber roll R which presents a resilient surface for co-action with the non-resilient steel roll S when impres-sing the steel roll pattern into the film lS. The peri.pheral speed of the rubber and steel rolls is maintained at a speed at or slightly greater than that of the draw roller D in order to effect good release of the film ~rom the draw roller D.
The embossed film proceeds fro'm the embossing roll system to a take-up or wind~up roll T. The take-up roll T can likewise be operated at a peripheral speed c~ ~nsurate with that of the eMbossing system and draw roller to prevent any additional stretching of the now embossed film; alternatively, 'the take-up roller T can be run at a peripheral speed in excess of that of the embossing rolls to thereby stretch the film lS.
A chill roller (not shown) may be employed intermediate the embossing roll system and the take-up roll T if it is necessary to cool and set the film after it has passed through the embos-sing roller system. :.
3;~i In accordance with the discovery of this inventlon,the draw-gap length X is maintained at not more than about 9iX
inches. With the draw-gap 13, thus shortened, an extrudate containing linear low density polyethylene can be drawn into film at take-up speeds well in excess of 40 feet-per-minute, the latter rate representing the approximate rate at which conven-tional slot-die draw extrusion techniques experience draw resonance ln the extrudate. Draw resonance in the LLDPE extru-date is thus eliminated for all practical purposes through the shortening of the draw-gap.
In a preferred technique for producing the film 15 according to this invention, LLDPE forming part of a melt is heated to a temperature in excess of its crystalli~ation temper-ature which is approximately 230 F, as well as the melting temperature of the extrudate which is typically around 2S2 F.
A melt temperature of about 375 to 450F has been advanta-geously employed. The die 10 and die-slot 11 are maintained at an elevated temperature, generally approaching around 500 F.
The particular linear low density polyethylene resin used herein is commerically sold under the name Dowlex 2037, /nd has a melt index of 2.5 gms/10 minutes and a density of 0.935 g/cm3. As stated above, the melt may comprise a blend of thermoplastic materials with the linear low density poly-ethylene, such as a polymer selected from the group of poly-ethylene, polypropylene and the copolymers thereof. With Dowlex 2037, it has been found advantageous to provide a draw-gap distance X of about 1 inch, with the extrudate being drawn through this distance into a film of approximately 1 mil gauge thickness, which is a typical thickness for diaper-type films.
For purposes of subsequent embossing of the film, such as by the , .. 11 .......... .. .
I
embossing rolls R and S, the draw roller D has a surface temper-ature maintained in the range of about 230-260F. ~he draw roller D is preferably coated with a polytetrafluoroethylene for a better film releasing characteristic. The e~oossing roll system employs a water cooled rubber roll R, and an embossing steel roll S which has a surface temperature maintained in the range of about 80-110F if no stretching is desired and about 160F with stretching.
By using the short-draw extrusion method with the foregoing apparatus set up as described for subsequent embossing of the film, the extrusion data reflective of the draw take-up speed of the draw roller D and the width of the film 15 thus produced were obtained using a melt of 100% linear low density polyethylene drawn into a film of one mil gauge without draw resonance occurring. Draw speeds on the order of about 250 f.p.m. to about 570 f.p.m. were employed and film widths oE
about 32 to about ~0 inches were drawn. A draw rate o~ several hundred f.p.m. with nominal gauge varia~ions i9 considered to be a commercially acceptable rate for production of film incorpor ating linear low density polyethyleneO
An unusual and unexpected advantage of the short-draw technique is that the film produced has significantly better tensile properties than equivalent film obtained through pro-cesses such as a conventional or longer draw slot-die extrusion.
Referring to the graph of Fig. 3, the mechanical properties of one mil gauge diaper-type film made of melts having varying linear low density polyethylene CQntent by weight and produced from the short-draw technique are shown. The graph shown here was compiled using blends of LLDPE and LDPE. The ultimate tensile strengths for the films produced, measured in :.
3~
pounds/square inch, are shown for the machine direction ~MD, dotted line), the cross direction (CD, dashed and dotted line) and at 25~ elongation in the machine direction, (25~ MD, solid line). These ultimate tensile strengths reflect the point at which the film will rupture or break. As shown in this graph, 100~ linear low density polyethylene film formed by this tech-nique and having a mean density of 0.935 and 1 mil gauge has an ultimate tensile strength in the machine direction of about 6#/in width in the ~achine direction, 4.4#/in width in the cross direction, and 2.4#/in width at 25~ elongation in the machine direction. These tensile measurements as shown in the graph and in the following table were obtained with a 1 inch width of a strip of film. In general, the advantageous results achieved by this process are particularly evident in extrudate blends containing at least 30% LLDPE by weight.
Referring to the following table, the tensile proper-ties for the short-drawn film of this invention formed at high take-up speeds are compared to conventional slot-die extruded film made from an identical l,LDPE extrudate of 1 mil gauge where a low take-up speqd of 30 feet/min and a conven-tional gap of about 9 inches were employed.
Ultimate Tensile ConventionalInvention Strengths Slot-Die Extrusion (~/in width) (~/in width) MD 3.9 6 As shown, tensile strengths in the slot-die short-drawn film of the invention are significantly and unexpectedly better in both machine direction (MD) and cross direction (CD) than those obtainable with the conventional slot-die technique.
_ .
. ~
s Fur-thermore, whereas the strength in the ~D for the conventional is 11~ greater than the Cr), there is a 36~ greater strength in the MD of the LLDPE film of the invention.
It will be furthex noted that film produced by the short-draw technique of this invention also exhibits improved tensile proper-ties over blown film made from an identical extrudate. The film produced by the short-draw technique is thus superior in tensile qualities over conventionally cast film and blown film formed from an identical extrudate.
The above description of the short-draw technique for production of a thermoplastic film embodying the principles of this inventicn is by way of illustration and not limitation. It will be obvious tha-t there are other equivalent forms of the invention which employ the advantageous properties and results achieved by this invention without departing from the spirit and scope thereof. For example, with reference to Fig, 4, an alternative embodiment is shown for forming a thermoplastic filrn according to this invention with subsequent embossing. In this second embodiment, the draw roller D described in relation to the previously discussed embodiment has been removed fxom the apparatus. The steel embossing roller S here functions to both draw the extrudate from the slot-die 10 through a nip made with the air-knife 14, and to thereupon emboss the film 15 thereby formed by impressing a pattern thereon in cooperation with rubber roll R. Take-up roll T subsequently winds up the embossed film 15. Other variations will be also understood to a ¦
person of skill in this art~
What is claimed iso ~13-
Particular utility for thexmoplastic film has been found in the area of covering materials, such as diaper film and operating room table covers, due to the moisture barrier character of the plastic film, among other properties. Thin film of this type is typically produced by extrusion, the two general methods of extruding film being blown tubing and slot-die extrusion.
In the slot~die method of producing thermoplastic film, the heated plastic extrudate or melt, typically composed of polyethylene, polypropylene, and copolymers thereof, is extruded out of a narrow slot in an elongated die. Flat film is generally made in considerable widths on relatively large machi.nes which run at high production rates on the order of 300 to 1000 or more feet-per-m.inute. The hot extrudate extxuded in the form of a web from the slot-die is drawn and stretched through an air-gap to the desired gauge thickness and width by stretching rollers which form a nip or this purpose. The nipping rollers ma~ also serve as an embossing or calendering means for the film if particular textures or surface charac-teristics and properties are desired for the film. The film then typically passes from the nipping rollers to a chill roller where it is cooled and set, and then to a take-up roller.
It has been known to use linear low density poly-ethylene as the polymer composition in the slot-die extrusion of film. The densities of this polymer have varied usually between about 0.915 - 0.940 g/cm . Linear low density polyethylene ~herein simply sometimes LLDP~) as the term is used in this descxiption is polyethylene haviny little or no long chain :~ , : ' ~, ~' .
~ r~
branching, with short chain branching in an amowlt necessary to obtain the deslred density, currently for instance less than about 0.940 g/cm3. For example, a common density for LLDPE used in diaper film is 0.926 g/cm3, and for operating room table covers is 0.918 g/cm3. Linear low density polyethylene has been considered desirable in that it exhibits a good balance of mechanical properties in film form, particularly ultimate tensile strength, impact resistance, burst strength and tear strength characteristics.
A serious drawback to the use of LLDPE is its suscep tibility to draw resonance at a relatively low draw or take-up rate, typically at a take-up rate of about 40 feet per minute or more. Draw resonance is a phenomenon associated with stretching motions and it is manifested in the occurrence of periodic fluctuations in the thickness of the extrudate as it is drawn.
Draw resonance is primarily a function of the take-up rate as well as the draw ratio, the draw ratio being the ratio of the die-slot width to the film thickness. In regard to the latter, for a given linear low density polyethylene extrudate, draw resonance is expected to be more severe in drawing a thinner gauge of the film, and its onset at a lower draw speed, than in a thicker gauge film.
Film exhibiting draw resonance can have gauge thick-ness variations on the order of ~5~, or morej which is considered to be commercially unsatisfactory. Such gauge variations deteriorate product uniformity and reduce the reliability and saleability of the film~ As a consequence, LLDPE which has been produced by conventional slot-die extrusion techniques has been drawn at take-up rates less than the critical point at which draw resonance sets in which i5 usuall~
about a production speed of 30 to 40 feet~per-minute. This i9 a factor which seriously limits productivity.
There is conseguently a need in the industry for a method for producing LLDPE film by slot-die extrusion techniques at relatively high draw rates with substantial elimination of draw resonance in the extrudate to thereby yield a thermoplastic film which is uniform in gauge thickness within the range of commercial acceptability.
Summary of the Invention It is a principal object of this invention to produce a uniform thermoplastic film using linear low density poly-ethylene drawn at take-up rates greater than 40 feet~per-minute, the point at which draw resonance typically occurs with conven-tional slot-die extrusion machinery. Particularly, it i~ an object o~ this inv~ntion to produce such a film at very high take up speeds on the order of several hundred feet~per-minute, or more, without the onset of draw resonance in the drawn extrudate.
To these ends, it has been discovered that substantial elimination of draw resonance in LLDPE extrudate can be achieved through reduction of the draw-gap between the die-slot and the drawing roller or rollers. In particular, it has been found -that a draw-gap of about zero to not more than about six inches between the slot of the extrusion die and the draw roller enables LLDP~ film to be drawn at speeds of several hundred feet-per-minute with gauge variations well within commercial tolerances for uniformity.
~ urthermore, surprisingly it has been discovered that the LLDP~ film produced by the method of this invention is stronger by significant orders of magnitude in both the machin~
! :
3~LS
diraction and cross direction. These findings and other advan-tages of this invention will be further understood in view of the following description.
In preferred form embodying the principles of this invention, a conventional slot-die extrusion apparatlls for production of diaper film is adapted to provide a draw-gap between about zero and about six inches, for example, one inch.
A first roller in cooperation with an air-knife, serves to draw the ex~rudate into the desired gauye thickness and width. The LLDPE extrudate is extruded at a temperature above its crytal-lization temperature. The distance between the slot of the die (herein simply sometimes die-slot) and the ~irst roller is the critical draw-gap. In the preferred form with an air-knife, the gap is the distance between the slot and the nip formed by the roller and the air-knife acting on the LLDPE web. The draw roller is either operated without the application of heat or at an elevated temperature, particularly for purposes of subsequent embossing. The draw roller is preferably coated with a poLy~
tetrafluoroethylene for better film release characteristicsO At the draw roller, the LLDPE crystallizes and it has been found that the short draw-gap provides the benefits of this invention~
After the draw roller, the film may be introduced into a nip formed by an embossing roller which cooperates with a rubber roller to form an embossing system for embossing the surface of the film to a desired texture. A chill roll is thereafter employed to cool and set the film after it has passed through the embossing roller system, with the film ultimately being wound on a take-up rollO Thus, according to this inven-tion, LLDPE extrudate is heated to a temperature above its crystallization temperature and extruded through the slot-dic.:.
3;~L3~
Immediately upon introduction into the short gap maintained between the slot-die and the draw nip, the LLDPE i5 caused to be drawn to the desired gauge thickness and width film. ~sing this short-draw technique, 100~ LLDPE film of 32 inches in width and a gauge thickness of 1 mil has been drawn as fast as S70 f.p.m.
with only nominal variation on gauge thickness. For commercial applications, any take-up rate of about 300 f.p.m., or more, is considered very acceptable.
Although the instant invention solves the problem of draw resonance in slot-die extrusion of LLDPE films drawn at high take-up rates, a precise understanding of why the short-draw technique is so effective is not yet available. The elimination of draw resonance by a short-draw zone is quite unexpected. One would logically expect that a longer draw ~one, which allows the deformation (strain) to be applied over a longer time interval, to be better and less ~r- n~;ng for the molecular network to ad~ust. The improvement in physical properties is also quite unexpected. One would expect the longer residence time available in a longer draw process to allow the molecular network to relax -the strains imposed by the extrusion process and lead to a more randomi~ed (isotropic) orientation typical of stronger films. In both cases the reverse was found, the short-draw led to a complete elimination of draw resonance and to a remarkably strong film.
As mentioned above, another unexpected by-product and advantage of this short~draw technique is that the LI.DPE film has tensile properties significantly better than film made by a conventional process. This phenomenon is again not yet under-stood completely, but greater tensile properties in both the machine direction and cross direc~ion are obtained which far o~
3~
exceed any tensile properties obtained by conventional slot-dic extrusion film production proces~es.
These and other advantages of this invention will be further understood with reference to the drawings, in which:
BRIEF DESCRJPTION OF THE DRAWINGS
Fig. 1 is a perspective diagrammatic view of an apparatus illustrating a technique for drawing a LLDPE film according to this invention, including embossing rolls and a take-up roll.
Fig. 2 is an elevational diagrammatic view illus-trating the relative positioning of the slot-die, draw roller and air-knife of the apparatus of Fig. 1.
Fig. 3 is a graph relating tensile strength to linear low density polyethylene content by weight of the extrudate for 1 mil gauge film of 0.935 g/cm3 density where the balance of the film content is low density polyethylene.
Fig. 4 is an elevational dlagrammatic view illus-trating another technique for drawing and embossing a thermo-plastic film according to thls invention.
DETAILED DESCRIPTION OE THE INVENTION
It is a primary objective of this invention to sub-stantially eliminate the draw resonance which typically occurs when an extrudate containing linear low density polyethylene, or blends of LLDPE with polyethylene, polypropylene, or copolymers thereof, is drawn to make thermoplastic film at take-up speeds greater than about 40 feet-per-minute. It is a collateral objective of this invention to thereby produce a thermoplastic film which is substantially uniform in gauge thickness within commercial tolerances, and which also exhibits improved tensile properties that are not obtainable through any con~entional ~, _ 7 slot-dle extrusion or perhaps even conventional blown tubing fllm productlon pro~ess. The ~ollowing detailed description, which is taken in conjunction with the accompanying drawings, is illustrative of the features and advantages of the process a~d product produced by that process of the present invention.
It wlll be understood that certain values for the extrudate, conditions o~ operation of the film producing appa-ratus, and actual film parameters used herein ln the compilation of the described data are each representative of a range over which the instant invention is expected to be effective. For instance, the density of the extrudate containing linear low density polyethylene is not limited to the specific density utilized in the cornpilation of the following data, since the short-draw techniqua for eliminatior~ of draw resonance is anticipa-ted to be advantageo~s over the whole range of densities of commercially employed linear low density poLyethylene.
Likewise, the actual percentage of linear low densi.ty poly-ethylene making up the e~trudate is also variable. So too, the gauge thickness of the film produced in accordance with thi3 invention is not limi-ted to any specific value,i.e., the one mil gauge used herein merely is representative of a comrnon gauge of diaper film.
~ ith this in mind, reference is now made to Figs. 1 and ~ which show in diagrammatic form a system for drawing and embossing thermoplastic film in accordance with the principles of this inventionO The drawing and embossing apparatus, are generally indicated at 9. ~ heated extrudate, or melt, to be described more fully hereafter, is supplied to a slot-die extruder 10 from a suitable source (not shown) and is extruded through an elongate die-slot 11 in the form of a web 120 The :~
. . .
I
web 12 i9 drawrl horizont~lly khroucJh a shortened draw-gap 13 by draw roller D. The draw roller D cooperates with an air-knife 14 to thereby define, in effect, a "draw nip" through which the web 12 is caused to pass. The nip thus formed serves to dr~w the extruded web 12 into a film 15 of the desired gauge thick-ness and width. The draw-gap 13 has a substantially constant length X as measured perpendicularly from the die-slot 11 to the draw nip.
The film 15 subsequently passes from the draw roller D
to a system of embossing rolls. One of the rolls is a steel roll S having a surface which is embossed, as by conventional engraving methods, with a desired pattern that is to be imparted to the film 15. The other roll in the embossing roll system is a resilient or rubber roll R which presents a resilient surface for co-action with the non-resilient steel roll S when impres-sing the steel roll pattern into the film lS. The peri.pheral speed of the rubber and steel rolls is maintained at a speed at or slightly greater than that of the draw roller D in order to effect good release of the film ~rom the draw roller D.
The embossed film proceeds fro'm the embossing roll system to a take-up or wind~up roll T. The take-up roll T can likewise be operated at a peripheral speed c~ ~nsurate with that of the eMbossing system and draw roller to prevent any additional stretching of the now embossed film; alternatively, 'the take-up roller T can be run at a peripheral speed in excess of that of the embossing rolls to thereby stretch the film lS.
A chill roller (not shown) may be employed intermediate the embossing roll system and the take-up roll T if it is necessary to cool and set the film after it has passed through the embos-sing roller system. :.
3;~i In accordance with the discovery of this inventlon,the draw-gap length X is maintained at not more than about 9iX
inches. With the draw-gap 13, thus shortened, an extrudate containing linear low density polyethylene can be drawn into film at take-up speeds well in excess of 40 feet-per-minute, the latter rate representing the approximate rate at which conven-tional slot-die draw extrusion techniques experience draw resonance ln the extrudate. Draw resonance in the LLDPE extru-date is thus eliminated for all practical purposes through the shortening of the draw-gap.
In a preferred technique for producing the film 15 according to this invention, LLDPE forming part of a melt is heated to a temperature in excess of its crystalli~ation temper-ature which is approximately 230 F, as well as the melting temperature of the extrudate which is typically around 2S2 F.
A melt temperature of about 375 to 450F has been advanta-geously employed. The die 10 and die-slot 11 are maintained at an elevated temperature, generally approaching around 500 F.
The particular linear low density polyethylene resin used herein is commerically sold under the name Dowlex 2037, /nd has a melt index of 2.5 gms/10 minutes and a density of 0.935 g/cm3. As stated above, the melt may comprise a blend of thermoplastic materials with the linear low density poly-ethylene, such as a polymer selected from the group of poly-ethylene, polypropylene and the copolymers thereof. With Dowlex 2037, it has been found advantageous to provide a draw-gap distance X of about 1 inch, with the extrudate being drawn through this distance into a film of approximately 1 mil gauge thickness, which is a typical thickness for diaper-type films.
For purposes of subsequent embossing of the film, such as by the , .. 11 .......... .. .
I
embossing rolls R and S, the draw roller D has a surface temper-ature maintained in the range of about 230-260F. ~he draw roller D is preferably coated with a polytetrafluoroethylene for a better film releasing characteristic. The e~oossing roll system employs a water cooled rubber roll R, and an embossing steel roll S which has a surface temperature maintained in the range of about 80-110F if no stretching is desired and about 160F with stretching.
By using the short-draw extrusion method with the foregoing apparatus set up as described for subsequent embossing of the film, the extrusion data reflective of the draw take-up speed of the draw roller D and the width of the film 15 thus produced were obtained using a melt of 100% linear low density polyethylene drawn into a film of one mil gauge without draw resonance occurring. Draw speeds on the order of about 250 f.p.m. to about 570 f.p.m. were employed and film widths oE
about 32 to about ~0 inches were drawn. A draw rate o~ several hundred f.p.m. with nominal gauge varia~ions i9 considered to be a commercially acceptable rate for production of film incorpor ating linear low density polyethyleneO
An unusual and unexpected advantage of the short-draw technique is that the film produced has significantly better tensile properties than equivalent film obtained through pro-cesses such as a conventional or longer draw slot-die extrusion.
Referring to the graph of Fig. 3, the mechanical properties of one mil gauge diaper-type film made of melts having varying linear low density polyethylene CQntent by weight and produced from the short-draw technique are shown. The graph shown here was compiled using blends of LLDPE and LDPE. The ultimate tensile strengths for the films produced, measured in :.
3~
pounds/square inch, are shown for the machine direction ~MD, dotted line), the cross direction (CD, dashed and dotted line) and at 25~ elongation in the machine direction, (25~ MD, solid line). These ultimate tensile strengths reflect the point at which the film will rupture or break. As shown in this graph, 100~ linear low density polyethylene film formed by this tech-nique and having a mean density of 0.935 and 1 mil gauge has an ultimate tensile strength in the machine direction of about 6#/in width in the ~achine direction, 4.4#/in width in the cross direction, and 2.4#/in width at 25~ elongation in the machine direction. These tensile measurements as shown in the graph and in the following table were obtained with a 1 inch width of a strip of film. In general, the advantageous results achieved by this process are particularly evident in extrudate blends containing at least 30% LLDPE by weight.
Referring to the following table, the tensile proper-ties for the short-drawn film of this invention formed at high take-up speeds are compared to conventional slot-die extruded film made from an identical l,LDPE extrudate of 1 mil gauge where a low take-up speqd of 30 feet/min and a conven-tional gap of about 9 inches were employed.
Ultimate Tensile ConventionalInvention Strengths Slot-Die Extrusion (~/in width) (~/in width) MD 3.9 6 As shown, tensile strengths in the slot-die short-drawn film of the invention are significantly and unexpectedly better in both machine direction (MD) and cross direction (CD) than those obtainable with the conventional slot-die technique.
_ .
. ~
s Fur-thermore, whereas the strength in the ~D for the conventional is 11~ greater than the Cr), there is a 36~ greater strength in the MD of the LLDPE film of the invention.
It will be furthex noted that film produced by the short-draw technique of this invention also exhibits improved tensile proper-ties over blown film made from an identical extrudate. The film produced by the short-draw technique is thus superior in tensile qualities over conventionally cast film and blown film formed from an identical extrudate.
The above description of the short-draw technique for production of a thermoplastic film embodying the principles of this inventicn is by way of illustration and not limitation. It will be obvious tha-t there are other equivalent forms of the invention which employ the advantageous properties and results achieved by this invention without departing from the spirit and scope thereof. For example, with reference to Fig, 4, an alternative embodiment is shown for forming a thermoplastic filrn according to this invention with subsequent embossing. In this second embodiment, the draw roller D described in relation to the previously discussed embodiment has been removed fxom the apparatus. The steel embossing roller S here functions to both draw the extrudate from the slot-die 10 through a nip made with the air-knife 14, and to thereupon emboss the film 15 thereby formed by impressing a pattern thereon in cooperation with rubber roll R. Take-up roll T subsequently winds up the embossed film 15. Other variations will be also understood to a ¦
person of skill in this art~
What is claimed iso ~13-
Claims (18)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of continuously producing a length of thermoplastic film, comprising the steps of:
continuously extruding an extrudate comprising linear low density polyethylene having a propensity for draw resonance at high draw speeds when passed through a slot-die in the form of a web, with the extrudate at a temperature above its crystallization temperature;
locating a draw roller for the web adjacent the slot of the die to thereby produce a short draw-gap of not more than about six inches;
drawing the web into a film having commercially uniform gauge thickness with the draw roller at take-up speeds of at least about several hundred f.p.m.; and maintaining the short draw-gap at said speeds whereby said film is continuously formed and draw resonance is substantially eliminated in the web.
continuously extruding an extrudate comprising linear low density polyethylene having a propensity for draw resonance at high draw speeds when passed through a slot-die in the form of a web, with the extrudate at a temperature above its crystallization temperature;
locating a draw roller for the web adjacent the slot of the die to thereby produce a short draw-gap of not more than about six inches;
drawing the web into a film having commercially uniform gauge thickness with the draw roller at take-up speeds of at least about several hundred f.p.m.; and maintaining the short draw-gap at said speeds whereby said film is continuously formed and draw resonance is substantially eliminated in the web.
2. The method of claim 1 further including an air-knife used in conjunction with the draw roller to form the draw-gap into which the web is introduced to be formed into said film.
3. The method of claim 2 further including the step of embossing the film with an embossing roller and a rubber roller which cooperate to thereby emboss the surface of the film with a desired texture.
4. The method of claim 3 wherein the surface of the draw roller is maintained at a temperature that will cause crystallization of the film on the draw roller.
5. The method of claim 4 wherein the tempera-ture of the draw roller is maintained in the range of from about 230°F to about 260°F.
6. The method of claim 3 wherein the draw roller is coated with a polytetrafluoroethylene.
7. The method of claim 1 wherein the draw-gap is about one inch.
8. The method of claim 1 wherein the extrudate comprises a blend of linear low density polyethylene and low density polyethylene.
9. The method of claim 1 wherein the extrudate further comprises a polymer selected from the group of polyethylene, polypropylene and the copolymers thereof.
10. The method of claim 9 wherein the extrudate is comprised of at least about 30% linear low density polyethylene by weight.
11. The method of claim 1 wherein the extrudate is 100% linear low density polyethylene.
12. A length of thermoplastic film produced by the method of claim 1.
13. The thermoplastic film of claim 12 where-in the extrudate is comprised of at least about 30%
linear low density polyethylene by weight.
linear low density polyethylene by weight.
14. The thermoplastic film of claim 12 wherein the extrudate further comprises a polymer selected from the group of polyethylene polypropylene and the copolymers thereof.
15. A method for continuously producing a length of thermoplastic film, the thermoplastic film comprised of linear low density polyethylene having a tendency for draw resonance when drawn from a slot-die into a film at high speed, comprising the steps of:
heating a melt containing linear low density polyethylene to a temperature greater than the crystal-lization temperature of the linear low density polyethylene;
continuously extruding the melt through a slot-die in the form of a web;
drawing the web from the slot-die through a nip defined in part by a draw roller whereby the web is drawn into a film, a short draw-gap over which the web is drawn between the nip and the slot of the die being not more than about six inches; and continuously driving the draw roller so as to produce film of a commercially uniform gauge thickness at a rate of at least about several hundred f.p.m.;
whereby the short draw-gap between the slot-die and the nip substantially eliminates draw resonance in the web.
heating a melt containing linear low density polyethylene to a temperature greater than the crystal-lization temperature of the linear low density polyethylene;
continuously extruding the melt through a slot-die in the form of a web;
drawing the web from the slot-die through a nip defined in part by a draw roller whereby the web is drawn into a film, a short draw-gap over which the web is drawn between the nip and the slot of the die being not more than about six inches; and continuously driving the draw roller so as to produce film of a commercially uniform gauge thickness at a rate of at least about several hundred f.p.m.;
whereby the short draw-gap between the slot-die and the nip substantially eliminates draw resonance in the web.
16. The method of claim 15 wherein linear low density polyethylene comprises at least about 30% by weight of the extrudate.
17. The method of claim 16 wherein the film produced has a gauge thickness of approximately 1 mil.
18. A length of thermoplastic film produced by the method of claim 15, 16 or 17.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US06/400,416 US4668463A (en) | 1982-07-21 | 1982-07-21 | Method of making linear low density polyethylene film |
US400,416 | 1982-07-21 |
Publications (1)
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CA1191315A true CA1191315A (en) | 1985-08-06 |
Family
ID=23583523
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA000432639A Expired CA1191315A (en) | 1982-07-21 | 1983-07-18 | Linear low density polyethylene film and method of making |
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US (1) | US4668463A (en) |
JP (1) | JPS5967016A (en) |
AR (1) | AR231615A1 (en) |
AU (1) | AU553258B2 (en) |
BE (1) | BE897338A (en) |
BR (1) | BR8303887A (en) |
CA (1) | CA1191315A (en) |
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DE (1) | DE3326056A1 (en) |
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IT (1) | IT1163825B (en) |
NL (1) | NL189654C (en) |
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CA1054763A (en) * | 1974-10-31 | 1979-05-22 | William J. Bonner | Method and apparatus for embossing sheets |
JPS5835131B2 (en) * | 1975-04-01 | 1983-08-01 | 帝人株式会社 | Thermoplastic resin film manufacturing equipment |
US4115499A (en) * | 1975-04-04 | 1978-09-19 | Monsanto Research Corporation | Large void-free polyethylene castings |
US4182606A (en) * | 1975-11-20 | 1980-01-08 | Fiber Industries, Inc. | Slit extrusion die |
US4336212A (en) * | 1977-10-11 | 1982-06-22 | Asahi-Dow Limited | Composition for drawn film, cold drawn film made of said composition and process for manufacture of said film |
US4243619A (en) * | 1978-03-31 | 1981-01-06 | Union Carbide Corporation | Process for making film from low density ethylene hydrocarbon copolymer |
US4193961A (en) * | 1978-04-04 | 1980-03-18 | Kling-Tecs, Inc. | Method of extruding polypropylene yarn |
US4211743A (en) * | 1978-05-24 | 1980-07-08 | Nauta Roll Corporation | Apparatus and method for embossing web material |
US4294791A (en) * | 1979-01-05 | 1981-10-13 | Teijin Limited | Process for producing thermoplastic resin film of markedly reduced thickness unevenness |
US4255365A (en) * | 1979-01-23 | 1981-03-10 | E. I. Du Pont De Nemours And Company | Pneumatic gauge adjustment of edge-pinned cast web |
JPS5846212B2 (en) * | 1979-05-18 | 1983-10-14 | 旭化成株式会社 | polyethylene composition |
US4339507A (en) * | 1980-11-26 | 1982-07-13 | Union Carbide Corporation | Linear low density ethylene hydrocarbon copolymer containing composition for extrusion coating |
US4310295A (en) * | 1981-01-28 | 1982-01-12 | E. I. Du Pont De Nemours And Company | Device for uniform web pinning |
US4394474A (en) * | 1981-04-21 | 1983-07-19 | The Dow Chemical Company | Product and process for reducing block and increasing slip of linear low density ethylene copolymer films |
US4486377A (en) * | 1982-09-27 | 1984-12-04 | Union Carbide Corporation | Process for reducing draw resonance in polymeric film |
-
1982
- 1982-07-21 US US06/400,416 patent/US4668463A/en not_active Expired - Lifetime
-
1983
- 1983-07-18 CA CA000432639A patent/CA1191315A/en not_active Expired
- 1983-07-19 SE SE8304038A patent/SE461713B/en not_active IP Right Cessation
- 1983-07-20 FR FR8311968A patent/FR2530530B1/en not_active Expired
- 1983-07-20 AR AR293662A patent/AR231615A1/en active
- 1983-07-20 DE DE19833326056 patent/DE3326056A1/en active Granted
- 1983-07-20 BR BR8303887A patent/BR8303887A/en not_active IP Right Cessation
- 1983-07-20 BE BE0/211212A patent/BE897338A/en not_active IP Right Cessation
- 1983-07-20 IT IT22158/83A patent/IT1163825B/en active
- 1983-07-21 CH CH4007/83A patent/CH653952A5/en not_active IP Right Cessation
- 1983-07-21 GB GB08319664A patent/GB2124139B/en not_active Expired
- 1983-07-21 JP JP58133555A patent/JPS5967016A/en active Granted
- 1983-07-21 NL NLAANVRAGE8302606,A patent/NL189654C/en not_active IP Right Cessation
- 1983-07-21 AU AU17160/83A patent/AU553258B2/en not_active Ceased
Also Published As
Publication number | Publication date |
---|---|
IT8322158A1 (en) | 1985-01-20 |
AU1716083A (en) | 1984-01-26 |
FR2530530A1 (en) | 1984-01-27 |
NL8302606A (en) | 1984-02-16 |
DE3326056C2 (en) | 1993-01-28 |
BE897338A (en) | 1984-01-20 |
US4668463A (en) | 1987-05-26 |
SE461713B (en) | 1990-03-19 |
GB2124139A (en) | 1984-02-15 |
NL189654C (en) | 1993-06-16 |
JPH0359823B2 (en) | 1991-09-11 |
AR231615A1 (en) | 1985-01-31 |
BR8303887A (en) | 1984-02-28 |
IT8322158A0 (en) | 1983-07-20 |
SE8304038L (en) | 1984-01-22 |
SE8304038D0 (en) | 1983-07-19 |
AU553258B2 (en) | 1986-07-10 |
DE3326056A1 (en) | 1984-01-26 |
JPS5967016A (en) | 1984-04-16 |
CH653952A5 (en) | 1986-01-31 |
NL189654B (en) | 1993-01-18 |
GB8319664D0 (en) | 1983-08-24 |
GB2124139B (en) | 1986-03-12 |
IT1163825B (en) | 1987-04-08 |
FR2530530B1 (en) | 1987-08-28 |
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