WO2008064112A1

WO2008064112A1 - Polyethylene useful for producing film and molded articles in a process which uses solid state stretching

Info

Publication number: WO2008064112A1
Application number: PCT/US2007/084942
Authority: WO
Inventors: Michael Mcleod; Gerhard Guenther; Shannon B. Hoesing
Original assignee: Fina Technology, Inc.
Priority date: 2006-11-21
Filing date: 2007-11-16
Publication date: 2008-05-29
Also published as: US20080118692A1; CA2663929A1; KR20090091705A; US10040261B2; EP2083990A4; EP2083990A1; JP2010510094A; US20140138870A1; MX2009005315A

Abstract

Applicants have discovered that certain polyethylene (PE) homopolymers or copolymers of ethylene and C3 to C-f o alpha-olefin monomers are more suitable for oriented processes than other polyethylene resins. In an aspect, the PE has a MFI of 0.3 g/10 min. to 5.0 g/10 min,, a melting point of from 11O0C to 140°C, a density of from 0.912 g/cm3 to 0.965 g/cm3(%), a haze of 10% or less, a clarity of at least 90, and a gloss of at (east 60. The polyethylene is heated and formed into an article, cooled, and then the article is stretch oriented. In an embodiment, the film, tape, the melt extruded, injection blow molded, injection stretch blow molded, cast, and thermoformed articles that can be produced with this polyethylene has a thickness of 0.1 miI to 100 mils. The polyethylene exhibits excellent elasticity, toughness, stretch and optical properties for such applications.

Description

POLYETHYLENE USEFUL FOR PRODUCING FILM AND MOLDED ARTICLES IN A PROCESS WHICH USES SOLID STATE STRETCHING

RELATED APPLICATIONS

This Application claims the benefit of U.S. Provisional Patent Application No. 60/860,285, filed November 21 , 2006.

FIELD

This invention relates to using certain single site catalyzed polyethylene resins in processes where an article is formed, such as through melt extrusion, injection molding, injection b!ow molding, or casting, then cooled, and then orienting or stretching the article. The articles have good optical properties, gauge distribution, stretching properties, and toughness. BACKGROUND OF THE INVENTION

The present invention pertains to tape, film, fibers, packaging and containers made from certain types of polyethylene resins. A variety of applications in which films, sheets, tape and other articles are extruded, molded, blown or cast, cooled, and then later heated and stretched or orientated are known in the art and for example also include a double bubble method for biaxially orienting thermoplastic films such as that disclosed in U.S. Pat. Nos. 3,456,044 and 3,555,604 to Pahlke. This method including the steps of producing a primary tubing by melt extrusion from a die, inflating the tubing by introducing air into the interior thereof, then cooling and collapsing the tubing, reinflating the tubing to form a secondary bubble, then reheating the film to its draw temperature. In the draw or expansion zone, the tubing is oriented in the transverse direction through radial expansion of the bubble and oriented in the machine direction by drawing down the bubble. When machine and/or transverse stretching occurs, the bubble expansion is accompanied by a reduction of the thickness.

Applicants have discovered that certain polyolefins, and more preferably a polyethylene (PE) homopoiymer or copolymer resin, are more suitable for the oriented processes. The polyethylene resins exhibit excellent elasticity, toughness, stretch and optical properties for such applications,

Brief Description of the Drawings

Figure 1 is the Molecular Weight Distribution Traces for M3410 and D350;

Figure 2 shows the Sheet Optics and Gauge Consistency for D350;

Figure 3 shows the Sheet Optics and Gauge Consistency for M3410; Figure 4 shows the Thickness Across the Sheet Width for M3410 and D350; Figure 5 shows the Crystallization Exotherms for M3410 and D350;

Figure 6 shows the Melting Endotherms for M341G and D350;

Figure 7 shows the Stretching Temperature Range for M3410 and D350;

Figure 8 shows the Drawing Force Versus Time at Various Temperatures for M3410;

Figure 9 shows the Drawing Force Versus Time at Various Temperatures for D350;

Figure 10 shows the Maximum Stretching Stress Versus Lower Temperature Stretching for M3410 and D350;

Figure 11 shows the Apparent Toughness Versus Lower Temperature Stretching for M3410 and D350;

Figure 12 shows M3410 Film Under Crossed Polarizers; Figure 13 shows D350 Film Under Crossed Polarizers;

Figure 14 shows a hole in the D350 Film; and Figure 15 shows the Gloss Versus Stretching Temperature for M3410 and D350. DETAILED DESCRIPTION

This invention relates to using certain single site catalyzed polyethylene resins, such as metaliocene catalysts, in processes where an article is formed, such as through melt extrusion, injection molding, injection blow molding, or casting, then cooled, and then orienting or stretching the article. The articles have good optical properties, gauge distribution, stretching properties, and toughness.

Such suitable polyethylene resins may be polyethylene homopolymers or copolymers of ethylene and C3 to C-^o alpha-olefin monomers. When copolymers are used, the ethylene content will typically range from about 90 to about 100 mol %, with the balance, if any, being made up of the polyethylene resins may be polyethylene homopolymers or copolymers of ethylene and C3 to C^ 0 alpha olefins. The polyethylene resin disclosed herein may be virgin resin, or used in blend or coex formulations with reprocessed film, regrind, post consumer recycle or other virgin polyolefin resins.

In an embodiment, such suitable polyethylene resins have a Melt Flow Index (MFI), (g/10 min.) of from 0.3 g/10 min. to 5.0 g/10 min., a density of from

0.912 g/cm³ to 0.965 g/cm³, in another embodiment 0.912 g/cm³ to 0.950 g/cm3, and yet in another embodiment 0.915 g/cm³ to 0.940 g/cm³. Density was measured under ASTM D 792 guidelines. The Melt Flow Index was measured under ASTM D 1238 guidelines.

In an additional embodiment, suitable polyethylene resins have a melting point of from 11O⁰C to 14O⁰C (248⁰F to 284°F), and in yet another embodiment a melting point of from 125⁰C to 135°C (257°F to 275°F). In an embodiment, the suitable polyethylene resins have a haze (%) of 10% or less, and in another embodiment of 5% or less, clarity of at least 90, and in alternative embodiment at least 95, and in a further embodiment a clarity of at least 98 or greater, and a gloss of at ieast 60%, or alternatively a gloss of 75% or greater. Haze testing was performed under ASTM D 1003 guidelines. Clarity testing was performed under ASTM D 1746 guidelines, and 45° gloss was tested under ASTM D 2457 guidelines.

The new applications where this type of resin is useful includes two step processes, where the article is formed, such as through melt extrusion, injection molding, injection blow molding, or casting, is cooled, and is then oriented or stretched in applications such as thermoforming (where a sheet is extruded quenched and reheated and formed in a mold in a subsequent step), tape (where the resin is extruded and quenched and then subsequently reheated and drawn or stretched in one or more directions), injection stretch blow molding (ISBM) (where a preform is injection molded and then reheated to a softened state where it is deformabfe (below melting temperature) and blown into a mold in a subsequent step), and a "double bubble" process (where film is blown and quenched or cooled to a solid state, and then reheated to a softened state where it is deformable (below melting temperature) and stretched in one or more directions.

There are a vast number of end use applications for the articles produced with the disclosed polyethylene. For example, the films and sheets of the present invention can be used for: food packaging, fragrance and fragrance-impregnated products packaging (e.g. detergents), photographic film packaging, medical applications, geomembranes, agricultural products (e.g., fertilizers, insecticides), converting operations where printing solvents and other surface treatments must not migrate through the film, and packaging where sorption of flavor, aroma, or colorant compounds must be minimized. The films may be used in monolayer and multilayer applications. The films of the present invention can also be used for other applications, where good barrier properties are an advantage, as well as any other uses known to those of ordinary skill in the art for polyethylene films.

In an embodiment, the thickness of the film, tape, injection blow molded, injection stretch blow molded, and thermoformed articles that can be produced with this type of polyethylene is from 0.1 mil to 100 mils, in other embodiments, films and tapes may have a thickness of 0.1 mils to 5 mils, injection stretch blow molded articles may have a thickness of 5 mils to 50 mils and thermoformed articles may have a thickness of 5 mils to 100 mils.

The packaging also includes monolayer and multilayer packaging such as stretch wrap applications and methods (e.g., pulling a film over a container, tray, backing, or other item or packaging, with or without heat sealing), shrink wrap

(shrink in both the machine and transverse directions), skin wraps, vacuum wraps, and molded/shaped packaging, for example.

The articles produced with these methods and the disclosed polyethylene resin also includes garbage bags, shopping bags, food bags, bags for consumer items, containers, drums, jars, and bottles, for example.

The fibers may also be used in a broad spectrum of products and components used, for example, in artificial turf and woven tape used for carpet, An example of an embodiment of the polyethylene (PE) of this invention is grade M3410 produced by a metallocene catalyst, commercially available from Total Petrochemicals, USA, Inc. PE resins like M3410 have improved gauge distribution in cast sheeting used in tape production, thermoforming, and uniaxially and biaxially oriented polyethylene films. Through its higher shear response and melt strength, it improves gauge distribution in double bubble and machine direction orientation blown film processes to produce end articles with a more uniform gauge. Providing more consistent gauge in the forming step is critical for the subsequent orienting step or steps. Such usages for the polyethylene (PE) resin known as M3410EP were previousϊy unknown as was the suitability of such resin for these applications and articles. M3410 is a polyethylene-hexene copolymer resin that has better performance than other metallocene resins in machine direction orientation (MDO) or biaxiaily oriented processes relative to other metallocene resins at the same or similar melt flow index (Ml) and density (g/cc), including for example, CPC D350 a medium density metaliocene polyethylene (mMDPE) polymer sold by Chevron Philips Chemical Company (CPC). Another polyethylene resin sold by Total Petrochemicals USA, inc. and known as M2710 has also been found to be suitable for such applications. The resin properties of an embodiment of Total M3410 polyethylene resin are set forth in Table 1A. in an embodiment, the recommended processing extrusion melt temperature for M3410 is from 38O⁰F to 41 OT (193⁰C to 210⁰C). The resin properties of an embodiment of Total M2710 polyethylene resin are set forth in Table 1 B. The resin and mechanical properties of the CPC D350 polyethylene resin are set forth in Table 2,

Table 1A. M3410 Resin Properties

Resin Properties Typical Value ASTM Method

Melt Flow Index, g/10 min D1238

190° C/2.16 kg 0.9

190° C/21.6 kg (HLMI) 30

Density, g/cm³ 0.934 D792

Melting Point, ⁰F 255 D3417

Table 1 B. M2710 Resin Properties

Resin Properties Typical Value ASTM Method

Melt Flow Index, g/10 min D1238

190°C/2.16 kg 0.9

190° C/21.6 kg (HLMI) 30

Density, g/cm³ 0.927 D792

Melting Point, ⁰F 250 D3417

In contrast, a metallocene medium density polyethylene D350 resin, for example, was found to be unsuitable for such applications. The physical properties of that resin are set forth in Table 2.

Table 2. D350 Resin and Physical Properties

Physical Properties Metric English Comments

Density 0.933 g/cc 0.0337 Ib/in ASTM D1505

Melt Flow 0.7 g/10 min 0.7 g/10 min Condition 190/2.16; A

Mechanical Properties

Secant Modulus, MD 0.42 GPa 60.9 ksi at 1 %; ASTM D882

Secant Modulus, TD 0.46 GPa 66.7 ksi at 1%; ASTM D882

Coefficient of Friction 0,6 0.6 Kinetic; ASTM D 1894

Coefficient of Friction, Static 0.7 0.7 ASTM D 1894

Elmendorf Tear Strength MD 45 Q 45 g ASTM D1922

Elmendorf Tear Strength TD 280 g 28O g ASTM D 1922

Dart Drop Test 120 g 0.265 Ib 26 in; ASTM D 1709

Optical Properties

Haze 7 % 7 % ASTM D 1003

Gloss 66 % 66 % 45; ASTM D2457 The M3410 polymer is characterized by a high shear response. Additionally, the molecular architecture of M3410 differs from other metailocene catalyzed PE resins, such as D350.

Other polyethylene homopolymers or copolymers that have similar resin and mechanical properties may also be suitable for such uses, including but not limited to Total Petrochemical M2710.

Another advantage this type of PE resin, such as M3410, has over other metailocene catalyzed PE resins, such as D350, is in its thermal behavior. The M3410 resin provides a wider processing window. Another way these advantages of using PE resins like M3410 can be quantified is the change in stress at lower stretching temperatures; this temperature range is where solid- state stretching is preferred, since it is where more crystalline deformation takes place. When film produced by PE resins are stretched at a hotter temperature, there is a tendency to achieve less orientation and in the extreme case, films are drawn too thinly and holes form, EXAMPLES Example 1

A polyethylene copolymer known as M3410 was prepared by polymerizing ethylene and hexene in a slurry reactor in the presence of a metaliocene catalyst. The resin was cast molded into a sheet and cooled. The sheet was then heated to between 115°C to 119°C (239⁰F to 246°F) and bilaterally oriented/transversely stretched using a Bruckner™ Karo IV stretching frame. This polymer was compared against a commercial resin D350 sold by Conoco-Philips Corporation. Table 3 is a comparison of the rheology of the D350 PE resin and the M3410 resin.

Table 3. Rheology - Carreau-Yasuda Parameters and Melt Indices

D350, Lot M3410, Lot

8100811 D51222401

Zero Shear Vise. (Pa^sec) 1.027E+04 2.822E+05

Relax. Time (sec.) 6.666E-03 6.071 E-04

Rheo. Breadth 0.478 0.112

Power Law Index 0 0

Activation Energy to Fiow (kJ/moi) 28.97 30.41

MI2 (dg/min) 0.79 0.91

HLMI (dg/min) 12.7 28.5

Shear Response (HLM/MI2) 16.08 31.32

M3410 is characterized by a high shear response, almost twice that of the D350 resin. The low "a" parameter in the Carreau-Yasuda fit of the viscosity data also quantifies this difference.

Molecular weight traces show that resins like M3410 have a broader distribution than D350 (Figure 1). This advantage is quantified by a larger value for D¹ {M_z/M_w), as well as a less skewed and less peaked distribution. See Table 4.

Tabϊe 4. Molecular Weights and Dimensionless Molecular Parameters

D350, Lot M3410, Lot

8100811 D51222401

Mn 38350 30291

Mw 108327 85933

Mz 205382 173192

Mp 88739 71772

D 2.82 2.84

D¹ 1.90 2.02

Skewness -0.751 -0,446

Kurtosis 1.290 0.224 These differences in molecular architecture appear to provide a critical advantage of better gauge distribution. This advantage can be realized in numerous processes.

A comparison of cast sheets made from D350 and M3410 in Figure 2 and Figure 3, respectively provides a visual example of this difference in properties and performance. By visually examining a sheet made from each type of PE resin, it is apparent that M3410 (see Figure 3) has a more consistent sheet thickness than D350 (see Figure 2). When quantified through gauge consistency, see Figure A, the differences in thickness across and extruded sheet made with the same extruder at the same temperature and processing conditions, M3410 has a much lower standard deviation in thickness than D350.

See Table 5, showing the thickness profile across the surface of the sheet.

Resin M3410 has a better stretching behavior as a result of its more consistent gauge.

Table 5. Gauge Consistency

D350, Lot M3410, Lot 8100811 D51222401

Average (mils) 16.82 16.20 Std Dev. (mils) 0.73 0.25

M3410 also has a broader crystallization range and melting range than D350. See Figure 5 and Figure 6. This increased breadth, particularly in

melting behavior, provides a broader temperature range for heating the formed article and stretching it into its final oriented shape. All solid-state stretching processes benefit, including for example, oriented tape, monofilament, fully oriented yarn, fibers, injection stretch blow molding, thermoforming, melt extrusion, injection molding, and machine direction or uniaxially and biaxiaily oriented films.

The advantages can be quantified in several ways. For example, one is in the temperatures at which a sheet can be stretched to a 4x4 areal draw ratio into oriented film. M3410 has a slightly lower melting temperature than D350. See Table 6.

Table 6 DSC - Thermal Properties

D350, Lot M3410. Lot

8100811 D51222401

Crystallization Peak (⁰C) 112.1 111.9

Crystallization Enthalpy (J/g) -149.7 -149.2

Melt Temp. (⁰C) 124.5 123.2

Melting Enthalpy (J/g) 161.7 151.6

As a result, M3410 can first be successfully drawn at 115⁰C versus 118⁰C for D350. See Figure 7, showing stretching temperature range. However, M3410 can be drawn with 100% success over a 5⁰C range, versus only a range of 4°C for the D350 resin. M3410 has a broader temperature range for solid- state stretching.

Force data collected during stretching also helps illustrate the behavior of both resins. Stretching data was collected for both M3410 and D350 over a 6⁰C temperature range. See Figure 8 (M3410 drawing force vs. time) and Figure 9 (D350 drawing force vs. time). However, D350 regularly broke before reaching a fuli 4x4 areal draw at 117⁰C, as illustrated by the sudden drop in force. See Figure 9. At 122°C the film made from D350 consistently tore open and no oriented films could be drawn without holes forming therein. The maximum stretching stress at the lower stretching temperatures are shown in Figure 10. The slope of stress versus temperature is -0.535 for M3410, versus -0.770 for D350, This shallower slope is a processing advantage. It illustrates that M3410 is less sensitive to changes in temperature than D350. Another method to illustrate this effect is apparent toughness, which is the area under the stress-strain curve. The slope of apparent toughness versus temperature is -1.018 for M3410, versus -1.518 for D350. See Figure 11. The significance of this test is that the smaller the slope, the broader the temperature range, and the easier it is to process. This result reinforces that M3410 is less sensitive to changes in temperature than D350.

The importance of uniform gauge can also be readily seen in oriented film placed under crossed polarizers. The isochromes in the film are lines of constant stress. M3410 film produces a symmetric, uniform pattern. See Figure 12. The M3410 film center has a uniform halo without it being bisected by thicker, less drawn lanes of material. In contract, the film made from D350 consistently produced an asymmetric pattern with thicker lanes extending in the direction of stretching, here the machine direction. See Figure 13. These thicker lanes are due to propagation of sheet gauge variation, which produces unequal stretching during the stretching step. At 122°C, this variation was sufficient to produce holes in the film adjacent to thick lanes of lightly drawn D350. See Figure 14,

Film optical properties are also superior with M3410. M3410 consistently produced films with a higher gloss, greater clarity, and a iower haze at its lowest stretching temperature relative to D350 at its lowest stretching temperature. See Figure 15 (gloss vs. stretching temperature) and Table 7, Table 7 shows the optical properties of the two film types, using the ASTM D1003 and D 2457 tests.

Table 7. Oriented Film Optical Properties

Material Temp. Time Transmittance Haze (%) Clarity Gloss (45°)

(⁰C) (sec)

M3410, Lot D51222401 115 30 92.6 ± 0.08 2.42 ± 0.22 99.2 ± 0.07 86.3 ± 3.2

M3410, Lot D51222401 116 30 92.6 ± 0.08 3.96 ± 1.24 98.4 ± 1.28 80.7 ± 3

M3410, Lot D51222401 117 30 92.6 ± 0.11 6.88 ± 3.63 98.5 ± 0.5 75.1 ± 4.8

M 3410, Lot D51222401 118 30 92.6 ± 0.08 10.3 ± 2.8 97.7 ± 0.7 52.1 ± 9.6

M3410, Lot D51222401 119 30 92.4 ± 0.41 15.4 ± 3.12 96.9 ± 0.62 41.7 ± 3.4

D350, Lot 8100811 117 30 92.6 ± 0.1 4.47 ± 0.99 97.7 ± 0.45 56 ± 16.4

D350, Lot 8100811 118 30 92.5 ± 0.24 9.21 ± 1.84 95.7 ± 0.96 47 ± 18.2

D350, Lot 8100811 119 30 92.7 ± 0.39 26.8 ± 7.22 91.2 ± 2.88 22.9 ± 7.6

D350, Lot 8100811 120 30 92.7 ± 0.36 34.7 ± 8.65 89.9 ± 2.29 18.6 ± 2.2

D350, Lot 8100811 121 30 92.5 ± 0.97 41.8 ± 3.57 83.2 ± 1.95 9.5 ± 3.8

This superiority is maintained for each incremental increase in temperature. For example, M3410 stretched at 117⁰C has a gloss of 75,1 versus 22.9 for D350 stretched at 119⁰C. M3410's optical properties are due to its molecular architecture and how it improves casting and stretching behavior. in the foregoing specification, the invention has been described with reference to specific embodiments thereof, and has been demonstrated as effective in providing methods for preparing polymers using peroxide initiators and other additives. However, it will be evident that various modifications and changes can be made thereto without departing from the scope of the invention as set forth in the appended claims. Accordingly, the specification is to be regarded in an illustrative rather than a restrictive sense. For example, specific combinations or amounts of vinyl monomers, diene copolymers, multifunctional peroxide initiators, chain transfer agents, cross-linking agents, and other components falling within the claimed parameters, but not specifically identified or tried in a particular polymer system, are anticipated and expected to be within the scope of this invention. Further, the methods of the invention are expected to work at other conditions, particularly temperature, pressure and proportion conditions, than

those exemplified herein.

Claims

CLAIMSWhat is claimed is:

1. An article comprised of: polyethylene having a melt flow index of from 0.3 g/10 min to 5.0 g/10 min, a density of from 0.912 g/cm³ to 0.965 g/cm³, and a melting point of from 110⁰C to 140°C, wherein said polyethylene is formed into an article by melt extrusion, injection molding, blow molding, or casting; wherein said formed article is cooled and then oriented uniaxially or biaxially into an oriented article; and wherein the oriented article has a thickness of 0.1 mil to 100 mils, a haze of 10% or less, a clarity of at least 90, and a gloss of at least 60%.

2. The article of claim 1 , wherein the polyethylene is further comprised of a copolymer.

3. The article of claim 1 , wherein the polyethylene is produced using a single site catalyst, such as a metallocene catalyst.

4. The article of claim 1 , wherein the article is cast.

5. The article of claim 1 , wherein the article is extruded blown film.

6. The article of claim 1 , wherein the article is in a form of a seamless tube.

7. The article of claim 1 , wherein the article is a bag.

8. The article of claim 1 , wherein the article is a packaging or a container.

9. The article of claim 1 _τ wherein the article is injection blow molded.

10. The article of claim 1 , wherein the article is injection stretch blow molded.

11. The article of claim 1 , wherein the article is thermoformed.

12. A method of making an article, comprising the steps of: providing an extrusion grade polyethylene homopolymer or copolymer having a melt flow index of from 0.3 g/10 min to 5.0 g/10 min, a density of from

0.912 g/cm³ to 0.965 g/cm³, and a melting point of from 11O⁰C to 14O⁰C; heating said polyethylene and forming an extruded, molded, or cast article; allowing the formed article to cool to a solid state; reheating the formed article; and orienting the article uniaxially or biaxially, thereby forming an oriented article.

13. The method of claim 12, wherein the article is uniaxialiy oriented by stretching said article in a machine direction.

14. The method of claim 12, wherein the article is biaxially oriented by stretching said article in a machine direction and then separately stretching said article in a transverse direction to produce a biaxially-oriented article.

15. The method of claim 12, wherein the article is biaxially oriented by simultaneously stretching said article in a machine direction and stretching said article in a transverse direction to produce a biaxially-oriented article.

16. The method of claim 12, wherein the article is a seamless tube.

17. The method of claim 12, wherein the article is a bag.

18. The method of claim 12, wherein the article is packaging or a container.

19. The method of claim 12, wherein the article is tape.

0. The method of claim 12, wherein the article is a fiber or a monofilament,