IMPROVED MELT EXTRUSION PROCESSES AND FILMS PRODUCED THEREBY

Abstract: The invention relates to a process for melt extruding a film layer of a thermoplastic olefin which comprises extruding the film having physical characteristics under process conditions selected by reference to the Draw ratio Dr and the Aspect ratio A such that draw resonance is avoided in which in addition the process conditions are defined by reference to the Deborah number such that the molten polymer is extruded at a Draw ratio of at least 30 in a high elasticity region at a DOLLAR (g)lc value of characteristic time as defined herein of from 0.001 to 0.6 s, a Deborah number as defined herein in excess of 0.005 and an A value as defined herein lower than 0.8. Narrower ranges of these parameters may be defined for application of the invention to different polymer types.

Description: TITLE Improved Melt Extrusion Processes and Films Produced Thereby FTELD OF THE INVENTION The invention relates to improved melt extrusion processes and the films produced thereby .The invention relates especially but not exclusively to melt extrusion processes designed to provide improved operating conditions and/or improved film properties. BACKGROUND OF THE INVENTION Melt processing conditions are conventionally thought to be constrained by phenomena such as draw resonance which leads to a variation in the draw ratio; sharkskin or surface melt fracture; or breaking of the molten portion of the film connecting the solidified film portion and the die gap. These phenomena have generally led to a limitation of the melt processing speed, of the thickness and of the degree of orientation which could be achieved in the resulting films. The industry has tried to alleviate these problems in a variety of ways including the inclusion of additives to improve surface melt fracture, the blending with a branched polymer such as LDPE and other polymeric or oligomeric components, as well as by modification ofthe extrusion apparatus using additional draw off rollers. One route to improve draw resonance behaviour is to provide the polymer itself with more elastic behaviour by branching or modification of the polymer as decsribed for example in Dow US5272236-A .US5278272-A, and EP-608369-A1. Low draw ratios are however used. Ways of avoiding the various adverse processing phenomena are described in our co-pending patent application WO93/31348.The disclosure addresses ways of avoiding unstable draw resonance zones by appropriate control of the Draw or stretch ratio, Dr, and of the Aspect ratio, A. WO93/31348 did not disclose how additional control can be exercised to place basically non- or low elasticity molten polymer fluids into regions where they exhibit more elastic behaviour. All the art disclosed in the above prior published applications and patents appears to be of lesser relevance, and is incorporated herein by cross reference and will not be discussed in detail herein. The invention provides means of reaching and operating in an process envelope where the polymer melt acts elastically, even when the polymer is initially of a non- or low-elasticity type. The novel operating envelope which can be reached enables polymer films to be made which have suφrising physical properties and can be made at high line speeds. SUMMARY OF THE INVENTION-EXTRUSION PROCESS According to a broad aspect of the invention there is provided a process for melt extruding a film layer of a thermoplastic oiefin which comprises extruding the film having physical characteristics under process conditions selected by reference to the Draw ratio Dr and the Aspect ratio A such that draw resonance is avoided characterised in that in addition the process conditions are defined by reference to the Deborah number such that the molten polymer is extruded at a Draw ratio of at least 30 in a high elasticity region at a λ . value of characteristic time as defined herein of from 0.001 to 0.6 s, a Deborah number as defined herein in excess of 0.005 and an A value as defined herein lower than 0.8. According to a first detailed aspect of ,the invention there is also provided a process for melt extruding a film layer of a polyolefin comprising at least 50 wt%, preferably at least 80wt% of ethylene derived units which process comprises extruding the film having physical characteristics under process conditions selected by reference to the Draw ratio, Dr, and the Aspect ratio, A, such that draw resonance is avoided characterised in that in addition the process conditions are defined by reference to the Deborah number, De, such that the molten polymer is extruded at a Draw ratio of at least 30 in a high elasticity region at a λ c value of characteristic time as defined herein of from 0.005 to 0.2 seconds at 260°C, a Deborah number as defined herein in excess of 0.005 and an A value as defined herein lower than 0.8, preferably less than 0.2. According to a second detailed aspect of the invention there is further provided a process for melt extruding a film layer of a polyolefin comprising at least 50 wt %, preferably at least 80wt% of propylene derived units which process comprises extruding the film having physical characteristics under process conditions selected by reference to the Draw ratio, Dr, and the Aspect ratio, A, such that draw resonance is avoided characterised in that in addition the process conditions are defined by reference to the Deborah number, De, such that the molten polymer is extruded at a Draw ratio of at least 30 in a high elasticity region at a λ, value of characteristic time as defined herein of from 0.001 to 0.6 and especially 0.002 to 0.4 seconds at 260°C, a Deborah number as defined herein in excess of 0.005 and an A value as defined herein lower than 0.8, preferably less than 0.2. The parameters De, Dr and A used to define and select the extrusion conditions are defined herein in detail by reference to the drawings, see Figure 3. They are dimensionless. λ c is expressed in seconds and changes with temperature. The draw ratio essentially describes the intensity of the extrusion or drawing process and thereby the extent to which the cross-section of the extrudate is reduced below that of the extrusion die orifice. The invention permits operation at very high draw ratios and hence also at high line speeds. The invention gives a relatively thin cross-section product after extrusion is completed. As to the spatial arrangement or geometry of the extrusion machinery, the high draw ratio at high extrusion speeds is associated with a small airgap (the distance between the extrusion orifice and the location where the extrudate is solidified, such as the cooling drum surface in the cast film process). The airgap is represented in the defining formulae which follow by "X". For a cast extrusion process the Draw ratio is defined to be the ratio ofthe film velocity at the chill roll to the film velocity at the die exit, i.e. Uf/Uo. The Draw ratio approximates the ratio of the initial film thickness at the die orifice to the thickness of the extruded film. The Aspect ratio represents in more defined form the geometry of the extrusion process. Apart from the airgap X, the Aspect ratio is inversely proportional to the width of the die represented by half the die width "Lo" in the formulae. The Aspect ratio is the ratio of X and Lo. For cast extrusion the airgap height is taken from the die exit to the contact point between the polymer web and the chill roll. It may be measured with a caliper. The invention is preferably at low aspects ratios and is associated with small airgaps X. The consequence of the practice of the invention is that an extruded film becomes considerably thinner upon extrusion by the high draw ratio but that its width is not reduced (the phenomenon referred to often as neck-in ) by anywhere near the same amount because of the small airgap. In other words the high draw ratio leads primarily to a desirable reduction in the thickness ofthe extruded layer. The Deborah number De includes as a parameterλ c and so is proportional with the elasticity displayed by the extruded material under the prevailing extrusion conditions. The Deborah number also includes as a parameter the extrusion speed Uo. The λ c and extrusion speed parameters combine in the invention to give a high line speed for extrusion in a more elastic area of rheological polymer behaviour. The λ c value can be determined by the methodology described in the prior published WO96/31348 and is then referred to as the old λ c value. However, the invention can be better defined to achieve its purpose of stable operation at high speed by defining the λ c parameter differently; it is then referred to as the new χ c value. The new λ c value is determined by fitting the curve of the dynamic viscosity, η ' , vs. frequency of oscillation, ω , with a modified Cross equation (Cross, 1966), such that: η (ω ) = \+(λ c ω)™ where η 0 is the zero-shear rate viscosity and m a power law index. The Cross equation is applied to the results of the dynamic measurements described in WO 96/31348, p5. The resulting characteristic time, is the reciprocal of the frequency that corresponds to the transition from Newtonian to power-law regimes. For the purpose of material characterization the frequency span over which the fit is carried out must be of about the same length for the set of polymers to be compared and is typically from 0.01 to 250rad/s. The fitting is done using the Innovative Rheological Interface software (IRIS registered Trade mark) version 5.0 developed at the University of Massachussets Amherst, USA by Winter and co-workers. For the purposes of this invention, λ c is a direct output of "general data regression module" in the IRIS software. Preferably De is from De mm < De < De mm , where De min and De^ are lower and upper bounds for the Deborah number. These are defined as: b - ylb 2 - 4(0.5 + 3 x lQ- 2 Dr - 3.6 x \0 ~ *Dr 2 - A)a De„ and -De„„ = 2a Dr - l with b = 3 \Dr - 596 - 0.37Dr 2 , a = 5020Dr - 1.1 x 10 5 - 57,5Dr 2 for 40 < /> ≤ 100 and A < \ . The modified definition of λ t helps to better define the stable operating envelope for the invention. For a given Draw ratio, the stretching force increases while the Deborah number increases. The extrusion can be that of a self supporting film or of a layer in a multilayer film, the other layers of which may or may not be extruded under the conditions arising out ofthe invention. Suitably if the polymer comprises predominantly ethylene derived units, has a Melt Index, as measured by ASTM 1238, condition E, ("MI") of 30g/10min or less, preferably 20g/10min or less, even more preferably 8g/10min or less, even more preferably 4g/10min or less. Preferably the MI is at least 0.2, especially at least 0.5. The characteristic time, χ c , of 0.005 seconds at 260C, more preferably 0.01 and drawing said polyolefin at a draw ratio Dr of 30 or more , preferably 35 or more and using an aspect ratio A of 0.8 or less, preferably 0.2 or less. Preferably the polyolefin is a polyethylene copolymer having a density of from 0.90 to 0.94, especially 0.910 to 0.935, a melt index of from 0.2 to 20, especially from 0.5 to 15 and a molecular weight distribution as defined herein of from 1.5 to 6, especially from 2 to 5. Advantageously the polyethylene copolymer has an Melt Index Ratio (MIR) determined by the ratio of I 21 over I 2 as per ASTM test of less than 35, preferably less than 30 and has a low internal energy of activation. That implies that the polymer is one which will basically be quite low-elastic in behaviour under conventional extrusion conditions and which will lack modification, such as long chain branching, to enhance its elasticity during extrusion. The polymer may also be a polypropopylene homo or copolymer having a melt flow rate determined by an ASTM test of from 1 to 30 especially from 4 to 20. The relexation time or the characteristic time which is synonymous at 260°C is from 0.001 to 0.6 seconds especially from 0.02 to 0.4 seconds. - 1 - Preferred ethylene based polymers that may be processed according to the invention preferably have a characteristic time of 0.005 seconds at 260C or less. Examples include all polymers that are drawn during formation into a product. Further examples include but are not limited to polyolefins which are homopolymers or copolymers of C2 to C30 a-olefins (for the purpose of this invention ethylene is defined to be an a-olefin). Likewise polyolefins such as linear low density poly ethylenes, high density polyethylene, very low density polyethylene, narrow molecular weights distribution (Mw/Mn) polymers such as those available under the trade name EXACT TM from Exxon Chemical Company in Houston Texas may be used. Additional preferred polymers that may be processed according to the invention include polymers of polar monomers. Preferred examples include polyesters and copolymers of ethylene or propylene with a polar monomer. Specific preferred examples include nylon polymers, polyethylene terephtalate polymers, ethylene vinyl acetate polymers, polyvinyl chloride polymers, ethylene acrylate polymers and the like. Particularly preferred examples include Escorenc LL-3003 a linear low density polyethylene available from Exxon Chemical Company in Houston, Texas that has a melt index of 3.2g/10min and a density of 0.9175 and Exceed ECD350D60 a polyethylene also available from Exxon Chemical Company that has a melt index of l .Og/lOmin and a density of 0.917. The invention is adapted for use at and is preferably used at high draw ratios such as a draw ratio as defined herein varies from 40 to 150.The process is especially useful in a cast extrusion process in which the airgap X as herein defined is from 1 to 20 inches, especially from 1.5 to 6 inches. SUMMARY OF INVENTION-START UP FOR EXTRUSION PROCESS Conventionally when extrusion lines are to be operated at high line speeds, the desired geometry is established and then slowly the output (amount of film extruded per unit time) and line speed are increased until the target is reached. A considerable part of the operating envelope provided by the invention is best reached by a different method so as to avoid draw resonance instability or other fatal disturbances which would prevent the high line speeds from being reached. Thus preferably the invention also provides a process for starting up a process for melt extruding a polyolefin into a film at a high draw ratio while avoiding instability which comprises the steps of: a) commencing at a low output of less than 50% of the final target output and a low line speed at less than 60% ofthe final target line speed; b) increasing the output towards the target output such that De is increased to between 0.0015 and 0.0028 while changing the line speed by less than 5% towards the final line speed; c) increasing the line speed without substantially reducing the output to obtain a draw ratio of up to 40; and d) reducing the output to obtain a draw ratio in excess of 40 while De is maintained between De min and De max as herein defined. By operating in this way the unstable operating zone and rupture zone in Figure 2A and 2B as descrribed in the Examples can be avoided while high line speeds and Draw ratios can be reached. SUMMARY OF INVENTION-FILM OR FILM LAYER The process of the invention also leads to a film or film layer which has a high degree of orientation in its machine ( drawing ) direction but has by comparison a low degree of stretch in the transverse direction. This leads in turn to surprisingly high transverse tensile and tear strengths which can be used to obtain a balance of properties not otherwise achievable. The invention thus thirdly provides a film layer prepared by a melt extrusion process which has a thickness of from 3 to 75 microns, a molecular weight distribution of from 2 to 4, and a CDBI as defined herein of from 50 to 90%, which has a machine direction tensile strength as defined herein of from 50psi to 120psi and a transverse direction tensile strenth higher than 45psi. Preferably the transverse direction Elmendorf tear strength is higher than 500g/mil. DRAWINGS Figure 1 illustrates the definition of the Draw ratio, Dr, the Aspect ratio, A, and the Deborah number, De, and their consituent terms. Figure 2A and 2B shows plots of the variables referred to above in the cast extrusion of certain materials LL-3003 and ECD-350D60 as described in the Examples which follow. Figure 3 is a 3-dimensional plot of the above variables to illustrate the extended operating envelope employed in the invention. EXAMPLES The following polymers were melt extruded into film: a) Escorene LL-3003 a polyethylene derived of ethylene and 1-hexene sold by Exxon Chemical Company having an MI of 3.2 and a density of 0.9175 The grade is made in a gas phase reactor using a titanium chloride catalyst with an aluminum alkyl activator b) EXCEED ECD-350D60 a polyethylene grade sold by Exxon Chemical Company, having an MI of 1.0, a density of 0.917 and made using a metallocene catalyst with methyl alumixane as activator in a gas phase process using hexene- 1 as comonomer. The polymers were extruded on a Black Clawson cast extruder line in which the extruded film is deposited on a cooled drum under the following conditions: The die width is 107cm and the airgap between die orifice and drum surface is 8.1 cm. The extrusion temperature measured in the melt at the extruder exit is 440 and 470°F for Examples A and B respectively. The air-knife pressure was adjusted to a low 0.1 psi and 0.5psi for Examples A and B respectively. The chill roll temperature was set and controlled to about 81 °F. The stable region can be reached by the method best explained by reference to Figure 2A. At (a) in the Figure extrusion is started at a low output of less than 50% of the final target output, actually at lOOlbs/h with the line speed being actually 460 ft/min i.e. less than 60% of the final target line speed. At (b) the output is increased towards the target output increasing the Deborah number to about 0.025 while the line speed is kept at an actual speeed of 460ft/min, less than a 5% change towards the final line speed. At (c) line speed is increased to 938 ft/min, increasing the Draw ratio Dr in the process, without substantially reducing the output so keeping the Deborah number constant to obtain a draw ratio of up to 40. Finally at (d) the output is reduced so decreasing the Deborah number and increasing the Draw ratio to obtain a Draw ratio of 100 well in excess of 40. Overall the result of the operation is that the the polymer is taken past the region in which draw resonance occurs and then the output speed is increased in a manner to avoid the rupture region in which the melt-strenth becomes insufficient to maintain the molten portion ofthe extrudate in the airgap (see Figure 2B for the rupture region which also exists for Figure 2A but which is not shown). The films prepared in the stable operating region had the following characteristics: Table LL-3003 ECD350 ECD350 Figure 2 A Figure 2B Figure 2B Draw ratio 80 46 61 Output (lbs/h) 293 408 408 line speed ( ft/min) 938 500 700 Melt temp (°F/°C) 440/227 470/243 470/243 Shrinkage %MD 84 78 82 Shrinkage %TD -41 -27 -34 Gauge ( average ) 0.41 0.86 0.65 Elmendorf tear MD 359 254 214 Elmendorf tear TD 737 800 1350 Oxygen vapour transmission ratio 894 650 640 Dart Impact (g/mil) 148 112 Ultimate tensile strength MD(psi) 14390 8204 Ultimate tensile strength TD (psi) 7157 31300 Birefringence 16.5 The films show a stress strain behaviour which indicates that the plateau region can be controlled at the higher line speeds employed as shown in the figures. Films of the invention may be less prone to transverse tear failure when placed under longitudinal stretch when used a stretch film layer. The stress strain curve for the film may show a plateau region which is either lowered relative to conventioanlly extruded films of similar materials or extended so to permit a higher level overall of stretch. The films may also be pre-stretched to a greaterr extent than hitherto with attendant benefits in pallet stretch film. High pre-strecth levels reduce materials cost while maintaining the holding force for the pallet. The invention can also be used to make primary film which is subsequently post-oriented below the crystalline melting point. Such film would have superior tensile strength and thickness compared to conventionally extruded films.

Claims: CLAIMS We Claim: 1. A process for melt extruding a film layer of a thermoplastic oiefin which comprises extruding the film having physical characteristics under process conditions selected by reference to the Draw ratio Dr and the Aspect ratio A such that draw resonance is avoided characterised in that in addition the process conditions are defined by reference to the Deborah number such that the molten polymer is extruded at a Draw ratio of at least 30 in a high elasticity region at a λ t value of characteristic time as defined herein of from 0.001 to 0.6 s, a Deborah number as defined herein in excess of 0.005 and an A value as defined herein lower than 0.8. 2. A process according to claim 1 or claim 2 in which the polyolefin is a polyethylene copolymer having a density of from .0.90 to 0.94, especially 0.910 to 0.935, a melt index of from 0.2 to 20, especially from 0.5 to 15 and a molecular weight distribution as defined herein of from 1.5 to 6, especially from 2 to 4 and the process is performed at χ c of 0.005 to 0.2. 3. A process acccording to claim 1 or claim 2 any of the proceeding claims in which the polymer has an Melt Index Ratio ( I 21/12 ) of less than 35. 4. A process acccording to any of the proceeding claims in which the draw ratio as defined herein varies from 40 to 150. 5. A process according to any of the preceding claims in which theprocess is a cast extrusion process in which the airgap X as herein defined is from 1 to 20 inches, especially from 2 to 10 inches. 6. A process for starting up a process for melt extruding a polyolefin into a film at a high draw ratio while avoiding instability .which comprises the steps of: a) commencing at a low output of less than 50% of the final target output and a low line speed at less than 60% ofthe final target line speed; b) increasing the output towards the target output such that De is increased to between 0.0015 and 0.0028 while changing the line speed by less than 5% towards the final line speed; c) increasing the line speed without substantially reducing the output to obtain a draw ratio of up to 40; and d) reducing the output to obtain a draw ratio in excess of 40 while De is maintained between De min and De max as herein defined. 7. A film layer prepared by a melt extrusion process which has a thickness of from 3 to 75 microns, a molecular weight distribution of from 2 to 4, which has a machine direction tensile strength as defined herein of from 50psi to 120psi and a transverse direction tensile strenth higher than 45psi.

Inventors: AGASSANT JEAN-FRANCOIS, CHAMBON FRANCOIS H, DEMAY YVES, OHLSSON STEFAN B, SILAGY DAVID, AGASSANT, JEAN-FRANCOIS, CHAMBON, FRANCOIS, H., DEMAY, YVES, OHLSSON, STEFAN, B., SILAGY, DAVID
Applicants: EXXON CHEMICAL PATENTS INC, EXXON CHEMICAL PATENTS INC.
Application year: 1997
Main classification: B29C47
IPC codes: B29C47, B29C55