CA2208232C - High molecular weight high density polyethylene with improved tear resistance - Google Patents
High molecular weight high density polyethylene with improved tear resistance Download PDFInfo
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- CA2208232C CA2208232C CA 2208232 CA2208232A CA2208232C CA 2208232 C CA2208232 C CA 2208232C CA 2208232 CA2208232 CA 2208232 CA 2208232 A CA2208232 A CA 2208232A CA 2208232 C CA2208232 C CA 2208232C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/02—Ziegler natta catalyst
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/06—Metallocene or single site catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1397—Single layer [continuous layer]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/24992—Density or compression of components
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Abstract
Articles fabricated from certain high molecular weight high density polyethy lenes (HMW-HDPE) combined with a second component, exhibit superior puncture propagation tear resistance and puncture propagati on tear length. The second component may be an elastomer such as styrene-butadiene-styrene, styrene-isoprene-styrene, EPR, EPDM, butyl rub ber, metallocene-calatyzed polyethylene, and combination s thereof. The second component or components will be present in a fabricated article from 1 to 15 weight percent. Articles include fi lms, bags made from films, and extrusion blow-molded articles.
Description
HIGH MOLECULAR WEIGHT HIGH DENSITY POLYETHYLENE
WITH IMPROVED TEAR RESISTANCE
S
TECHNICAL FIELD
This invention relates generally to high molecular weight high density polyethylene compositions with improved physical properties. More specifically this invention relates to high molecular weight (Hr;IW) high density polyethylene (HDPE) that when combined with a second component and made into a film or a container will exhibit improved puncture propagation tear resistance improved puncture propagation tear length. Such can result in improved impact strength and improved tensile strength.
BACKGROUND
Linear polyethylenes in general, and high density polyethylenes in particular, and high molecular weight high density polyethylenes more particularly, have gained wide use, for instance, as grocery (shoppers) retail sacks (also known as tee-shirt bags) and extrusion blow molded bottles or containers. However one of the problems that has continued to be bothersome in most of these applications is the linear high density polyethylene material's tendency to be "splitty".
This splittiness is generally thought to be due to the fact that a linear high density polyethylene has very few branches, certainly few, if any, long chain branches off of the polymer back bone. Such branching might permit entanglement which could, in certain instances, prevent a tear from being propagated once initiated, and/or retard the growth of a tear. Accordingly, once a tear or puncture is initiated in such substantially linear polyethylenes, if there is a load on the polyethylene film, a bag made from the film, or a container it will tend to "zipper" or split at a rapid rate causing failure of the bag and possible evacuation and damage of the contents.
Many approaches to solving this zippering or splittiness problem have been attempted. Usually the inclusion of an amount, for instance 5 to 10 weight percent of linear low density polyethylene (density in the range of from 0.915 to 0.930 g/cm3) has been moderately successful perhaps due to the branching provided by the LLDPE(more branching in general is observed for LLDPE than HDPE). The linear low density polyethylene (LLDPE) while providing some improvement in dart drop impact and puncture propagation tear also causes unacceptable stretching or elongation at or near the heat seal under an applied load. Such stretching can cause a bag, for instance a heavily laden grocery bag, to deform generally rendering the bag unacceptable, or at least less functional for its intended purpose.
Conventional low density polyethylene (LDPE) has been blended with HMW HDPE and also gives some relief from the splitting or zippering problem, but again, bags made from films based on such a blend are generally unacceptably stretchy as well.
However, while both of these solutions to the splitting problem are used in the industry, both of these solutions present an inherent difficulty. That difficulty is that the HMW-HDPE is relatively high in melt viscosity while in general, both LDPE and LLDPE are relatively much lower in melt viscosity. This leads to inhomogeneity in the melt and in the resulting film, leading to areas of good performance and areas of poor performance, which is a similarly unacceptable 1 S solution to the zippering problem. Attempts to homogenize such a mixture to improve the dispersion, thereby improving the overall physical properties have generally met with poor success as well, because while getting the lower viscosity materials more uniformly dispersed, the higher molecular weight or higher viscosity materials (HIVIW-HDPE) tend to be subjected to heat and sheer causing some cross-linking and thereby a generally unacceptable diminution of bulk film properties.
Ways to gauge the improvement or lack of improvement in tear properties include standard tests in the film industry such as tear or Elmendorf tear, where generally a nick or cut is placed in the film to be tested. While these tests are of value in HDPE film testing, a more realistic commercial indicator of film properties, especially for HMW-HDPE, is the puncture propagation tear (PPT) and the puncture propagation tear length (PPTL). These two tests are indicative of a tear that would be similar to one initiated in an everyday situation by the puncture of a film, or a bag based on the film, and the subsequent length of the tear for a specific puncture.
Another way to improve the tear and puncture propagation tear properties of an HMW-HDPE material might be to extrude, adjacent to the HDPE, for instance in a coextrusion, a more highly branched polymer material. This, however, is a more expensive method of solving this problem and is therefore generally commercially unacceptable.
WITH IMPROVED TEAR RESISTANCE
S
TECHNICAL FIELD
This invention relates generally to high molecular weight high density polyethylene compositions with improved physical properties. More specifically this invention relates to high molecular weight (Hr;IW) high density polyethylene (HDPE) that when combined with a second component and made into a film or a container will exhibit improved puncture propagation tear resistance improved puncture propagation tear length. Such can result in improved impact strength and improved tensile strength.
BACKGROUND
Linear polyethylenes in general, and high density polyethylenes in particular, and high molecular weight high density polyethylenes more particularly, have gained wide use, for instance, as grocery (shoppers) retail sacks (also known as tee-shirt bags) and extrusion blow molded bottles or containers. However one of the problems that has continued to be bothersome in most of these applications is the linear high density polyethylene material's tendency to be "splitty".
This splittiness is generally thought to be due to the fact that a linear high density polyethylene has very few branches, certainly few, if any, long chain branches off of the polymer back bone. Such branching might permit entanglement which could, in certain instances, prevent a tear from being propagated once initiated, and/or retard the growth of a tear. Accordingly, once a tear or puncture is initiated in such substantially linear polyethylenes, if there is a load on the polyethylene film, a bag made from the film, or a container it will tend to "zipper" or split at a rapid rate causing failure of the bag and possible evacuation and damage of the contents.
Many approaches to solving this zippering or splittiness problem have been attempted. Usually the inclusion of an amount, for instance 5 to 10 weight percent of linear low density polyethylene (density in the range of from 0.915 to 0.930 g/cm3) has been moderately successful perhaps due to the branching provided by the LLDPE(more branching in general is observed for LLDPE than HDPE). The linear low density polyethylene (LLDPE) while providing some improvement in dart drop impact and puncture propagation tear also causes unacceptable stretching or elongation at or near the heat seal under an applied load. Such stretching can cause a bag, for instance a heavily laden grocery bag, to deform generally rendering the bag unacceptable, or at least less functional for its intended purpose.
Conventional low density polyethylene (LDPE) has been blended with HMW HDPE and also gives some relief from the splitting or zippering problem, but again, bags made from films based on such a blend are generally unacceptably stretchy as well.
However, while both of these solutions to the splitting problem are used in the industry, both of these solutions present an inherent difficulty. That difficulty is that the HMW-HDPE is relatively high in melt viscosity while in general, both LDPE and LLDPE are relatively much lower in melt viscosity. This leads to inhomogeneity in the melt and in the resulting film, leading to areas of good performance and areas of poor performance, which is a similarly unacceptable 1 S solution to the zippering problem. Attempts to homogenize such a mixture to improve the dispersion, thereby improving the overall physical properties have generally met with poor success as well, because while getting the lower viscosity materials more uniformly dispersed, the higher molecular weight or higher viscosity materials (HIVIW-HDPE) tend to be subjected to heat and sheer causing some cross-linking and thereby a generally unacceptable diminution of bulk film properties.
Ways to gauge the improvement or lack of improvement in tear properties include standard tests in the film industry such as tear or Elmendorf tear, where generally a nick or cut is placed in the film to be tested. While these tests are of value in HDPE film testing, a more realistic commercial indicator of film properties, especially for HMW-HDPE, is the puncture propagation tear (PPT) and the puncture propagation tear length (PPTL). These two tests are indicative of a tear that would be similar to one initiated in an everyday situation by the puncture of a film, or a bag based on the film, and the subsequent length of the tear for a specific puncture.
Another way to improve the tear and puncture propagation tear properties of an HMW-HDPE material might be to extrude, adjacent to the HDPE, for instance in a coextrusion, a more highly branched polymer material. This, however, is a more expensive method of solving this problem and is therefore generally commercially unacceptable.
Also, in the category of solutions to the tear problem, are certain machine or extruder manipulations that can improve the tear strength. Because of the very high melt strength of HMW-HDPE, the film is generally fabricated using a high stalk configuration. This configuration allows for the melt to relax prior to blowing up to the full lay-flat width desired for the finished product. To achieve more relaxation which in turn improves tear and impact properties, film fabricators attempt to maximize the stalk height and the blow-up ratio. Typically the stalk height is six to eight times the die diameter and the blow-up ratio ranges from three to five times the die diameter. These parameters are limited by the stability of the bubble at reasonable production rates.
U.S. Patent 5,110,685 discloses blends of high density polyethylene with elastomers to produce low friction, abrasion resistant coatings. Specifically this document discloses a mufti part blend:
a) a high density PE blend of i) high molecular weight HDPE present from 10 to 80 percent by weight;
ii) medium molecular weight HI)PE present from 20 to 70 percent by weight; and iii) low molecular weight HDPE making up the balance of the HDPE
blend;
b) an EPDM elastomer.
Various blends of a) and b) with carbon black and optionally talc, are tested to determine their abrasion resistance and, as a measure of low friction, the coefficient of friction. Such a blend of different MW I~PEs would yield a film that would generally be unsuitable for consumer bags because of dilution of the MW of HMW-HDPE products generally leads to reduced impact properties. This phenomenon is well known to those of ordinary skill in the art regarding performance of medium MW products relative to performance of HMW products.
Dart impact (another important physical property of films) of medium MW
properties are typically 50 % less than those achieved from HMW based products.
There is therefore a need to produce a high molecular weight high density polyethylene film that can be fabricated into, for instance, tee-shirt bags, that have superior resistance to puncture propagation tear and improved puncture propagation tear length and are generally commercially practicable from an economic and fabrication standpoint.
_,-~;=1-~,:--,:~. _ -3-94B064.PCT ' 4 -SUMMARY
With the present invention, and in particular with a preferred embodiment, the above mentioned problems are substantially overcome resulting in an article fabricated from a HMW-HDPE composition that has superior puncture propagation tear resistance, superior puncture propagation tear length, and improved J-tear. The HMW-HDPE
composition will include a majority component (PR~iW-I-~PE) and a minority component (a material to improve tear properties). When well dispersed, such a minority component will generally be useful in improving these test results.
In accordance with an embodiment of the present invention, we provide a film (and/or an extrusion blow molded article) comprising (a) in the range of from 85 to 99 weight percent of a HMW-HDPE (first component) having a density in the range of from 0.940 to 0.970 g/cc, the HMW-HDPE will be either a homopolymer or a copolymer. If it is a copolymer, generally it will be a copolymer of ethylene and an alpha-olefin.
The alpha-olefin content will be present up to 2 mole percent based on the total moles of the HMW-HDPE, said HMW-HDPE having a melt index in the range of from 0.02 to 1.0 dg/min.;
and (b) in the range of from 1 to 15 weight percent of a second component selected from the group consisting of styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), ethylene-propylene rubber (EPR) ethylene-propylene-diene-monomer rubber (EPDM), butyl rubber, a metallocene-catalyzed LLDPE and combinations thereof; where said film has a PPT (MD) above 2.0 KgF, a PPT KgF (TD) above 2.2, a PPTL (TD) below 92 mm and a PPTL
(l~) up to 100 mm.
Preferably the film will have in the range of from 90 to 99 weight percent of an HMW-HDPE and in the range of from 10 to 1 weight percent of the second component.
More preferably, the film will have in the range of from 93 to 99 weight percent of HMW-HDPE, and in the range of from 1 to 7 weight percent of the second component, all weight percentages based on the total weight of the composition.
These and other features, aspects, and advantages of the present invention will become better understood with reference to the following description and appended claims.
9ao6..Rwo AMENDED SHEET
IPEA/EP
94B064.PCT - 5 -DESCRIPTION OF TFiE PREFERRED EMBODIMENTS
In an embodiment of our invention, certain HMW-HDPE compositions and applications based on these compositions are disclosed. These polyethylene compositions have unique properties which make them particularly well suited for use in applications that require resistance to puncture propagation tear and improvement of puncture propagation tear length in films and impact strength and tensile strength in extrusion blow molded articles.
These compositions have combinations of properties that render them superior to compositions previously available for many uses such as tee-shirt shoppers bags, retail bags, produce bags, extrusion blow molded articles and other uses known to those of skill in the art.
Following is a detailed description of certain preferred HMW-HDPE compositions within the scope of an embodiment of the present invention, preferred methods of producing these compositions and preferred applications of these compositions. Values given in the text and claims are determined as follows;
using ASTM test methods of common use to measure film performance;
Dart Drop Impact: ASTM D-1709 Tensile Strength: ASTM D-882 Elmendorf Tear (MD and TD): ASTM D 1922 Elongation: ASTM D 882 Puncture Propagation Tear : ASTM D 2582-93 PP Tear Length (mm) MD and TD: ASTM D-2582-93 9asosa.xwo I~~lIiE~DE~ S~-iEET
tPEA/EP ~~
94B064.PCT - 6 -HMW-HDPE Resin The polyethylene composition of an embodiment of the present invention for use in film or extrusion blow molded articles may be made from an ethylene homopolymer or ethylene copolymer or a blend of an ethylene copolymer with an ethylene homopolymer. The density of the preferred materials are generally in the range of from 0.940 to 0.970 g/cc. In a preferred embodiment the density ranges from 0.948 to 0.965 g/cc. More preferred density in the range of from 0.950 g/cc to 0.960 g/cc. The HMW-HDPE will have a melt index as measured according to the ASTM D-1238 in the range of from 0.02 to 5 dg/min.
Preferably the melt index will be in the range of from 0.02 to 1 dg/min., most preferred 0.03 to 0.1 dg/min. If the ethylene polymer is a copolymer it will be generally an ethylene alpha-olefin copolymer, the alpha-olefin utilized to make the copolymer will be selected from the group consisting of butene-1, pentene-1, 4-methyl-1-pentene, hexene-1, and octene-1.
The alpha-olefin will be present in the copolymer in the range of up to 2 moles/mole of copolymer.
The HMW-HI7PE may be made by a number processes including but not limited to gas phase, fluidized bed, slurry or solution processes. Catalysts used for polymerization are generally selected from the traditional Ziegler-Natta type, zirconium-type or metallocene-type catalyst systems. Such catalysts and their products are well known.
Second Comaonents The second component may be chosen from the group consisting of SBS, SIS, EPR, EPDM, butyl rubber, metallocene-catalyzed LLDPEs, and combinations thereof.
Preferred are the SBS elastomers or the metallocene-catalyzed LLDPEs. SBS and SIS
materials are available, for instance, from Dexco Corporation under the trade name Vector.
The approximate physical properties of these SBS elastomers are as follows:
- Melt flow rate (ASTM D-1238) @ 200 °C, 15 Kg =20 to above 0.1, preferred 12 to above 0.1 dg/mln., more preferred 8 to above 0.1 dg/min.
- Molecular weight (weight average molecular weight) 20,000 to 100,000 preferred 40,000 to 100,000, more preferred 80,000 to 100;000. Styrene content in the range of from to 50 percent, preferably, in the range of from 20 to 40 percent, more preferably in the range of from 25 to 35 percent. EPR, EPDM and butyl rubber are well known polymers and are widely available from a number of commercial sources.
9.wo a4MENDED S!-fECT
IPEAlEP
w0 96!18678 PCT/US95/15960 Where the second component is a metallocene-catalyzed LLDPE the specific resin chosen optionally will have a melt index below 2 dg/min., and a density in the range of from 0.915 to 0.925 g/cc. In any case, the choice of a second component, as recognized by those of ordinary skill in the art, will be controlled in that substantially no diminution of the end product properties occur.
The Polyethylene Film Composition The composition of the film in a preferred embodiment of the present invention, has in the range of from 85 to 99 weight percent of an HMW-HDPE
polyethylene and in the range of from 1 to 15 weight percent of a second component selected from the group consisting of SBS, SIS, EPR EPDM, butyl rubber, metallocene-catalyzed LLDPE, and combinations thereof. Preferably the HMW-HDPE will be present in the range of from 90 to 99 weight percent and the second component will be present in the range of from 10 to 1 weight percent.
More preferably, the HMW-HDPE will be present in the range of from 93 to 97 weight percent and elastomer will be present in the range of from 7 to 3 weight percent. All weight percents based on the total weight of the film composition. If the second component is employed in the blend excess of 15% by weight, the film will still have usefi~l properties, but the expense of such a quantity of second component in the blend will likely make the resulting fabricated product too expensive to be commercially viable, or the properties of the film would make it generally unsuitable for shopper's bags and the like. At less than 1 percent by weight, the positive effect of the second component on the properties of the bulk film will diminish below a generally beneficial point.
In certain embodiments of the present invention, additives of the type normally used to inhibit oxidation, U-V inhibitors, acid scavengers, U-V
absorbers, anti-static materials, colorants, slip agents, and the like may be included in the bulk film composition without substantially changing the desirable properties described in the present application.
Uses of the Film There are many uses for films made from compositions representing certain embodiments of our invention. Various kinds of bags are one such use. Among bags there are many types as well such as grocery bags, often called "tee-shirt bags", general merchandise bags, bags used to line refuse containers (industrial, commercial and residential) (commonly known as "can liners"), and the like.
Those of ordinary skill in the art will recognize that the nominal thickness of a film, bag or other article will have an effect on some gross mechanical properties of the article. Grocery sacks generally are made in nominal 0.5 mil (12.7 p,m) thickness.
Thicker cross sections would likely result in higher puncture force even without the teachings of our invention. Application of the teachings of our invention to such thicker cross section will generally filrther improve puncture force, PPT and PPTL.
Evaluation of Film Materials In the evaluation of polymer films in general, many parameters are of importance. However, in the evaluation of linear polyethylene, more specifically high molecular weight high density polyethylene films, the measurements of importance to manufactures of shoppers' bags, retail bags and can liners will be;
dart drop impact, which is generally a measure of the amount of force taken to burst a specific thickness of film, in grams; the Elmendorf tear which is an indication of the materials' ability to resist tear; and the TD/MD tear ratio is useful as an indicator of orientation balance. Generally, films with a lower TD/IVID
ratio, indicative of improved tear with better balance, tend to be less splitty than those with higher ratios.
However, in high molecular weight high density polyethylene films, a test that approximates real world performance where sharp and/or heavy objects may be contained in a film or a bag made from a film, the puncture propagation tear in kilograms of force in both the machine and transverse directions (MD and TD) is an important measurement. Films which require greater force to tear tend to be less splitty and have more of a J-tear character. J-tear refers to that type of tear which results in the film not tearing in a straight line, but one in which the tears make a sharp turn and changes direction and resembles the letter "J". This is particularly critical in shopper's bags since straight line tears often lead to catastrophic failure. These results compliment tear properties measured by the Elmendorf tear test. A further refinement of the puncture propagation tear test is the puncture propagation tear length under a given set of conditions. This will be an indication of whether or not a specific film not only has a resistance to puncture propagation tear, but under given conditions how far such a tear will propagate.
Examples _g_ °'O 96/18678 PGT/US95/1s9G0 Examples 1-5 This set of examples demonstrates that in the e:~trusion of HMW-I~PE
into film, certain second components (minority components) blended into the HMW-I~PE will yield a film with a dramatic improvement in PPT and PPTL
over an HMW-HI~PE without any additives (except for stabilizers, anti-oxidants, and the like). The minority component blends also show an improvement over blends of HMW-HLPE with more traditional blend partners, such as LLDPEs.
All runs were made on an AlpineT"" extruder with a 160 mm (coextrusion die) equipped with internal bubble cooling (IBC) having a die gap of 1.5 mm. Blowup ratio was 4.7, stalk height ratio 6. F~Im gauge averaged a nominal 0.5 mils (I3~tm).
Example parameters and film physical properties are shown in Table 1., _ Example 1 was performed using an HMW-I~PE Grade 7000 FT"" (available from Exxon Chemical Co.) which is a bimodal HIvIW-HI~PE with a den~ty of 0.952 g/cc, and a MI of 0.04 dg/m.
In Example 2, 5 weight percent of the HMW-HI7PE was replaced with a 1.0 MIr 0.918 g/cc density LLDPE (traditional Ziegler-Natta catalyzed) (Grade LL-1001T"" available from Exxon Chemical Co.) In Examples 3 and 4, 5, and 10 weight percent respectively of the HMW-I~PE was replaced with a 1.0 MI, 0.918 g/cc density metallocene-catalyzed LLDPE available from Exxon Chemical Co.
In example 5, 5 weight percent of the HMW-I~PE was replaced with Vector~ 8508 (available from Dexco Polymers).
In comparing the substantially 100 percent HMW-I~PE (Example 1 ) and the 95 percent HMW-I~PE, 5 percent Ziegler-Natta catalyzed LLDPE (ExatDple 2) with Examples 3 and 5 (5 weight percent metallocene-catalyzed LLDPE and 5 .
weight percent Vector SBS respectively), the following observations on specisc physical properties are made:
Iv>D/TD ratio; while an improvement of 60+% is observed from Example 1 to Example 2, a X00 improvement is observed from Example 1 to Examples 3 or 5;
PPT 11~; substantially no difference is observed between Examples l and 2, but a 20 percent improvement is observed between Example l and Examples 3 or 5;
PPTL MD; a slight decrease is noted from Example 1 to Example 2 while a substantial reduction (~25 percent) comparing Example 1 to Examples 3 or 5;
PPTL TD; a less than 10 percent reduction is seen Example 2 to Example 1, while a 20+ percent reduction is seen Examples 3 or 5 to Example 1.
Although the present invention has been described in considerable detail with reference to certain preferred versions thereof, other versions are possible.
For example, while films and bags have been exemplified, other uses such as for instance extrusion blow molding, are contemplated. Therefore, the spirit and scope of the appended claims should not be limited to the description of the preferred versions contained therein.
Table 1 c EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE
Die diameter (mm) 160 160 160 160 160 Die GAP (mm) 1.5 1.5 1.5 1.5 1.5 Blow Up Ratio 4.7 4.7 4.7 4.7 4.7 Stalk Height Ratio 6 6 6 6 6 Output Rate (lb/hr) (kg/hr) 280 (127)280 (127)280 (127)280 (127)280 (127) Filin Gauge, ave. (mil) (microns)0.51 (13)0.51 0.52 0.502 0.53 (13) (13) (12) (14) Filin Gauge, low (mil) (microns)0.42 (11)0.42 0.38 0.37 0.31 . (11) (10) (10) (8) Filin Gauge, high (mil) (microns)0.63 (16)0.64 0.65 0.73 0.68 (16) (16) (18) (17) Gauge Variation, % 20.6 21.6 26 35 35 Dart Drop (g) 160 160 160 116 158 Dart Drop (g/mil) (g/microns) 314 (12.3)314 (12.3)309 (12.3)231 (9.7)300 (11.3) Elinendorf Tear (g), MD 7.2 7.4 5.2 4.6 4.6 Elinendorf Tear (glmil) 13.6 (0.55)14.8 9.7 (0.40)9.4 (0.38)9 (0.33) (0.57) (g/microns), MD
Elmendorf Tear (g), TD 35.8 64 86.8 132.2 67.6 Elmendorf Tear (g/mil) 71.4 (2.75)121.5 162.9 254.6 127.5 (4.92) (6.68) (11.02) (4.83) (g/microns), TD
TD/MD Ratio 5 8.6 16.7 28.7 14.7 Tensile @ Yield (psi) (MPa), 5720 (39.8)5542 6166 5206 6133 MD (38.6) (42.9) (36.2) (42.7) Tensile @ Yield (psi) (MPa), 4686 (32.6)4968 4797 4644 4816 TD (34.6) (33.4) (32.3) (33.5) Elongation @ Yield (%), MD 4.8 4.99 5.1 5.1 5.3 Elongation @ Yield (%), TD 4.38 4.4 4.4 4.6 4.4 Ultimate Tensile (psi) (MPa), 13552 13174 14324 14416 15941 MD (94.4) (91.7) (99.7) (100.4) (111.0) Ultimate Tensile (psi) (MPa), 9178 (63.9)10145 7690 7029 7451 TD (70.6) (53.6) (48.9) (51.9) Ultimate Elongation (%), MD 316 297 226 262 246 Ultimate Elongation (%), TD 383 416 402 472 327 PPTear (kgF), MD 1.82 1.89 2.22 2.25 2.32 ' PPTear (kgF), TD 2.12 2.22 2.49 2.56 2.5 PPTear Length (mm), MD 126.4 121.4 89.6 88 83.4 PPTear Length (mm), TD 97.2 90 74.2 71 73.6 st:,.K ~ -11-.Wf~. E k i-z ~ ~~~~~t;t'-~.
U.S. Patent 5,110,685 discloses blends of high density polyethylene with elastomers to produce low friction, abrasion resistant coatings. Specifically this document discloses a mufti part blend:
a) a high density PE blend of i) high molecular weight HDPE present from 10 to 80 percent by weight;
ii) medium molecular weight HI)PE present from 20 to 70 percent by weight; and iii) low molecular weight HDPE making up the balance of the HDPE
blend;
b) an EPDM elastomer.
Various blends of a) and b) with carbon black and optionally talc, are tested to determine their abrasion resistance and, as a measure of low friction, the coefficient of friction. Such a blend of different MW I~PEs would yield a film that would generally be unsuitable for consumer bags because of dilution of the MW of HMW-HDPE products generally leads to reduced impact properties. This phenomenon is well known to those of ordinary skill in the art regarding performance of medium MW products relative to performance of HMW products.
Dart impact (another important physical property of films) of medium MW
properties are typically 50 % less than those achieved from HMW based products.
There is therefore a need to produce a high molecular weight high density polyethylene film that can be fabricated into, for instance, tee-shirt bags, that have superior resistance to puncture propagation tear and improved puncture propagation tear length and are generally commercially practicable from an economic and fabrication standpoint.
_,-~;=1-~,:--,:~. _ -3-94B064.PCT ' 4 -SUMMARY
With the present invention, and in particular with a preferred embodiment, the above mentioned problems are substantially overcome resulting in an article fabricated from a HMW-HDPE composition that has superior puncture propagation tear resistance, superior puncture propagation tear length, and improved J-tear. The HMW-HDPE
composition will include a majority component (PR~iW-I-~PE) and a minority component (a material to improve tear properties). When well dispersed, such a minority component will generally be useful in improving these test results.
In accordance with an embodiment of the present invention, we provide a film (and/or an extrusion blow molded article) comprising (a) in the range of from 85 to 99 weight percent of a HMW-HDPE (first component) having a density in the range of from 0.940 to 0.970 g/cc, the HMW-HDPE will be either a homopolymer or a copolymer. If it is a copolymer, generally it will be a copolymer of ethylene and an alpha-olefin.
The alpha-olefin content will be present up to 2 mole percent based on the total moles of the HMW-HDPE, said HMW-HDPE having a melt index in the range of from 0.02 to 1.0 dg/min.;
and (b) in the range of from 1 to 15 weight percent of a second component selected from the group consisting of styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), ethylene-propylene rubber (EPR) ethylene-propylene-diene-monomer rubber (EPDM), butyl rubber, a metallocene-catalyzed LLDPE and combinations thereof; where said film has a PPT (MD) above 2.0 KgF, a PPT KgF (TD) above 2.2, a PPTL (TD) below 92 mm and a PPTL
(l~) up to 100 mm.
Preferably the film will have in the range of from 90 to 99 weight percent of an HMW-HDPE and in the range of from 10 to 1 weight percent of the second component.
More preferably, the film will have in the range of from 93 to 99 weight percent of HMW-HDPE, and in the range of from 1 to 7 weight percent of the second component, all weight percentages based on the total weight of the composition.
These and other features, aspects, and advantages of the present invention will become better understood with reference to the following description and appended claims.
9ao6..Rwo AMENDED SHEET
IPEA/EP
94B064.PCT - 5 -DESCRIPTION OF TFiE PREFERRED EMBODIMENTS
In an embodiment of our invention, certain HMW-HDPE compositions and applications based on these compositions are disclosed. These polyethylene compositions have unique properties which make them particularly well suited for use in applications that require resistance to puncture propagation tear and improvement of puncture propagation tear length in films and impact strength and tensile strength in extrusion blow molded articles.
These compositions have combinations of properties that render them superior to compositions previously available for many uses such as tee-shirt shoppers bags, retail bags, produce bags, extrusion blow molded articles and other uses known to those of skill in the art.
Following is a detailed description of certain preferred HMW-HDPE compositions within the scope of an embodiment of the present invention, preferred methods of producing these compositions and preferred applications of these compositions. Values given in the text and claims are determined as follows;
using ASTM test methods of common use to measure film performance;
Dart Drop Impact: ASTM D-1709 Tensile Strength: ASTM D-882 Elmendorf Tear (MD and TD): ASTM D 1922 Elongation: ASTM D 882 Puncture Propagation Tear : ASTM D 2582-93 PP Tear Length (mm) MD and TD: ASTM D-2582-93 9asosa.xwo I~~lIiE~DE~ S~-iEET
tPEA/EP ~~
94B064.PCT - 6 -HMW-HDPE Resin The polyethylene composition of an embodiment of the present invention for use in film or extrusion blow molded articles may be made from an ethylene homopolymer or ethylene copolymer or a blend of an ethylene copolymer with an ethylene homopolymer. The density of the preferred materials are generally in the range of from 0.940 to 0.970 g/cc. In a preferred embodiment the density ranges from 0.948 to 0.965 g/cc. More preferred density in the range of from 0.950 g/cc to 0.960 g/cc. The HMW-HDPE will have a melt index as measured according to the ASTM D-1238 in the range of from 0.02 to 5 dg/min.
Preferably the melt index will be in the range of from 0.02 to 1 dg/min., most preferred 0.03 to 0.1 dg/min. If the ethylene polymer is a copolymer it will be generally an ethylene alpha-olefin copolymer, the alpha-olefin utilized to make the copolymer will be selected from the group consisting of butene-1, pentene-1, 4-methyl-1-pentene, hexene-1, and octene-1.
The alpha-olefin will be present in the copolymer in the range of up to 2 moles/mole of copolymer.
The HMW-HI7PE may be made by a number processes including but not limited to gas phase, fluidized bed, slurry or solution processes. Catalysts used for polymerization are generally selected from the traditional Ziegler-Natta type, zirconium-type or metallocene-type catalyst systems. Such catalysts and their products are well known.
Second Comaonents The second component may be chosen from the group consisting of SBS, SIS, EPR, EPDM, butyl rubber, metallocene-catalyzed LLDPEs, and combinations thereof.
Preferred are the SBS elastomers or the metallocene-catalyzed LLDPEs. SBS and SIS
materials are available, for instance, from Dexco Corporation under the trade name Vector.
The approximate physical properties of these SBS elastomers are as follows:
- Melt flow rate (ASTM D-1238) @ 200 °C, 15 Kg =20 to above 0.1, preferred 12 to above 0.1 dg/mln., more preferred 8 to above 0.1 dg/min.
- Molecular weight (weight average molecular weight) 20,000 to 100,000 preferred 40,000 to 100,000, more preferred 80,000 to 100;000. Styrene content in the range of from to 50 percent, preferably, in the range of from 20 to 40 percent, more preferably in the range of from 25 to 35 percent. EPR, EPDM and butyl rubber are well known polymers and are widely available from a number of commercial sources.
9.wo a4MENDED S!-fECT
IPEAlEP
w0 96!18678 PCT/US95/15960 Where the second component is a metallocene-catalyzed LLDPE the specific resin chosen optionally will have a melt index below 2 dg/min., and a density in the range of from 0.915 to 0.925 g/cc. In any case, the choice of a second component, as recognized by those of ordinary skill in the art, will be controlled in that substantially no diminution of the end product properties occur.
The Polyethylene Film Composition The composition of the film in a preferred embodiment of the present invention, has in the range of from 85 to 99 weight percent of an HMW-HDPE
polyethylene and in the range of from 1 to 15 weight percent of a second component selected from the group consisting of SBS, SIS, EPR EPDM, butyl rubber, metallocene-catalyzed LLDPE, and combinations thereof. Preferably the HMW-HDPE will be present in the range of from 90 to 99 weight percent and the second component will be present in the range of from 10 to 1 weight percent.
More preferably, the HMW-HDPE will be present in the range of from 93 to 97 weight percent and elastomer will be present in the range of from 7 to 3 weight percent. All weight percents based on the total weight of the film composition. If the second component is employed in the blend excess of 15% by weight, the film will still have usefi~l properties, but the expense of such a quantity of second component in the blend will likely make the resulting fabricated product too expensive to be commercially viable, or the properties of the film would make it generally unsuitable for shopper's bags and the like. At less than 1 percent by weight, the positive effect of the second component on the properties of the bulk film will diminish below a generally beneficial point.
In certain embodiments of the present invention, additives of the type normally used to inhibit oxidation, U-V inhibitors, acid scavengers, U-V
absorbers, anti-static materials, colorants, slip agents, and the like may be included in the bulk film composition without substantially changing the desirable properties described in the present application.
Uses of the Film There are many uses for films made from compositions representing certain embodiments of our invention. Various kinds of bags are one such use. Among bags there are many types as well such as grocery bags, often called "tee-shirt bags", general merchandise bags, bags used to line refuse containers (industrial, commercial and residential) (commonly known as "can liners"), and the like.
Those of ordinary skill in the art will recognize that the nominal thickness of a film, bag or other article will have an effect on some gross mechanical properties of the article. Grocery sacks generally are made in nominal 0.5 mil (12.7 p,m) thickness.
Thicker cross sections would likely result in higher puncture force even without the teachings of our invention. Application of the teachings of our invention to such thicker cross section will generally filrther improve puncture force, PPT and PPTL.
Evaluation of Film Materials In the evaluation of polymer films in general, many parameters are of importance. However, in the evaluation of linear polyethylene, more specifically high molecular weight high density polyethylene films, the measurements of importance to manufactures of shoppers' bags, retail bags and can liners will be;
dart drop impact, which is generally a measure of the amount of force taken to burst a specific thickness of film, in grams; the Elmendorf tear which is an indication of the materials' ability to resist tear; and the TD/MD tear ratio is useful as an indicator of orientation balance. Generally, films with a lower TD/IVID
ratio, indicative of improved tear with better balance, tend to be less splitty than those with higher ratios.
However, in high molecular weight high density polyethylene films, a test that approximates real world performance where sharp and/or heavy objects may be contained in a film or a bag made from a film, the puncture propagation tear in kilograms of force in both the machine and transverse directions (MD and TD) is an important measurement. Films which require greater force to tear tend to be less splitty and have more of a J-tear character. J-tear refers to that type of tear which results in the film not tearing in a straight line, but one in which the tears make a sharp turn and changes direction and resembles the letter "J". This is particularly critical in shopper's bags since straight line tears often lead to catastrophic failure. These results compliment tear properties measured by the Elmendorf tear test. A further refinement of the puncture propagation tear test is the puncture propagation tear length under a given set of conditions. This will be an indication of whether or not a specific film not only has a resistance to puncture propagation tear, but under given conditions how far such a tear will propagate.
Examples _g_ °'O 96/18678 PGT/US95/1s9G0 Examples 1-5 This set of examples demonstrates that in the e:~trusion of HMW-I~PE
into film, certain second components (minority components) blended into the HMW-I~PE will yield a film with a dramatic improvement in PPT and PPTL
over an HMW-HI~PE without any additives (except for stabilizers, anti-oxidants, and the like). The minority component blends also show an improvement over blends of HMW-HLPE with more traditional blend partners, such as LLDPEs.
All runs were made on an AlpineT"" extruder with a 160 mm (coextrusion die) equipped with internal bubble cooling (IBC) having a die gap of 1.5 mm. Blowup ratio was 4.7, stalk height ratio 6. F~Im gauge averaged a nominal 0.5 mils (I3~tm).
Example parameters and film physical properties are shown in Table 1., _ Example 1 was performed using an HMW-I~PE Grade 7000 FT"" (available from Exxon Chemical Co.) which is a bimodal HIvIW-HI~PE with a den~ty of 0.952 g/cc, and a MI of 0.04 dg/m.
In Example 2, 5 weight percent of the HMW-HI7PE was replaced with a 1.0 MIr 0.918 g/cc density LLDPE (traditional Ziegler-Natta catalyzed) (Grade LL-1001T"" available from Exxon Chemical Co.) In Examples 3 and 4, 5, and 10 weight percent respectively of the HMW-I~PE was replaced with a 1.0 MI, 0.918 g/cc density metallocene-catalyzed LLDPE available from Exxon Chemical Co.
In example 5, 5 weight percent of the HMW-I~PE was replaced with Vector~ 8508 (available from Dexco Polymers).
In comparing the substantially 100 percent HMW-I~PE (Example 1 ) and the 95 percent HMW-I~PE, 5 percent Ziegler-Natta catalyzed LLDPE (ExatDple 2) with Examples 3 and 5 (5 weight percent metallocene-catalyzed LLDPE and 5 .
weight percent Vector SBS respectively), the following observations on specisc physical properties are made:
Iv>D/TD ratio; while an improvement of 60+% is observed from Example 1 to Example 2, a X00 improvement is observed from Example 1 to Examples 3 or 5;
PPT 11~; substantially no difference is observed between Examples l and 2, but a 20 percent improvement is observed between Example l and Examples 3 or 5;
PPTL MD; a slight decrease is noted from Example 1 to Example 2 while a substantial reduction (~25 percent) comparing Example 1 to Examples 3 or 5;
PPTL TD; a less than 10 percent reduction is seen Example 2 to Example 1, while a 20+ percent reduction is seen Examples 3 or 5 to Example 1.
Although the present invention has been described in considerable detail with reference to certain preferred versions thereof, other versions are possible.
For example, while films and bags have been exemplified, other uses such as for instance extrusion blow molding, are contemplated. Therefore, the spirit and scope of the appended claims should not be limited to the description of the preferred versions contained therein.
Table 1 c EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE
Die diameter (mm) 160 160 160 160 160 Die GAP (mm) 1.5 1.5 1.5 1.5 1.5 Blow Up Ratio 4.7 4.7 4.7 4.7 4.7 Stalk Height Ratio 6 6 6 6 6 Output Rate (lb/hr) (kg/hr) 280 (127)280 (127)280 (127)280 (127)280 (127) Filin Gauge, ave. (mil) (microns)0.51 (13)0.51 0.52 0.502 0.53 (13) (13) (12) (14) Filin Gauge, low (mil) (microns)0.42 (11)0.42 0.38 0.37 0.31 . (11) (10) (10) (8) Filin Gauge, high (mil) (microns)0.63 (16)0.64 0.65 0.73 0.68 (16) (16) (18) (17) Gauge Variation, % 20.6 21.6 26 35 35 Dart Drop (g) 160 160 160 116 158 Dart Drop (g/mil) (g/microns) 314 (12.3)314 (12.3)309 (12.3)231 (9.7)300 (11.3) Elinendorf Tear (g), MD 7.2 7.4 5.2 4.6 4.6 Elinendorf Tear (glmil) 13.6 (0.55)14.8 9.7 (0.40)9.4 (0.38)9 (0.33) (0.57) (g/microns), MD
Elmendorf Tear (g), TD 35.8 64 86.8 132.2 67.6 Elmendorf Tear (g/mil) 71.4 (2.75)121.5 162.9 254.6 127.5 (4.92) (6.68) (11.02) (4.83) (g/microns), TD
TD/MD Ratio 5 8.6 16.7 28.7 14.7 Tensile @ Yield (psi) (MPa), 5720 (39.8)5542 6166 5206 6133 MD (38.6) (42.9) (36.2) (42.7) Tensile @ Yield (psi) (MPa), 4686 (32.6)4968 4797 4644 4816 TD (34.6) (33.4) (32.3) (33.5) Elongation @ Yield (%), MD 4.8 4.99 5.1 5.1 5.3 Elongation @ Yield (%), TD 4.38 4.4 4.4 4.6 4.4 Ultimate Tensile (psi) (MPa), 13552 13174 14324 14416 15941 MD (94.4) (91.7) (99.7) (100.4) (111.0) Ultimate Tensile (psi) (MPa), 9178 (63.9)10145 7690 7029 7451 TD (70.6) (53.6) (48.9) (51.9) Ultimate Elongation (%), MD 316 297 226 262 246 Ultimate Elongation (%), TD 383 416 402 472 327 PPTear (kgF), MD 1.82 1.89 2.22 2.25 2.32 ' PPTear (kgF), TD 2.12 2.22 2.49 2.56 2.5 PPTear Length (mm), MD 126.4 121.4 89.6 88 83.4 PPTear Length (mm), TD 97.2 90 74.2 71 73.6 st:,.K ~ -11-.Wf~. E k i-z ~ ~~~~~t;t'-~.
Claims (7)
1. A high molecular weight-high density polyethylene (HMW-HDPE) composition comprising:
a) a first component present in the range of from 85 to 99 weight percent, said first component is an HMW-HDPE, said HMW-HDPE having;
i) a density in the range of from 0.940 to 0.970 g/cc;
ii)an alpha-olefin comonomer content up to 2 mole percent based on the total moles of the HMW-HDPE;
iii) melt index in the range of from 0.02 to 2.0 dg/min. .; and b) in the range of from 1 to 15 weight percent, of metallocene-catalyzed linear low density polyethylene (LLDPE).
a) a first component present in the range of from 85 to 99 weight percent, said first component is an HMW-HDPE, said HMW-HDPE having;
i) a density in the range of from 0.940 to 0.970 g/cc;
ii)an alpha-olefin comonomer content up to 2 mole percent based on the total moles of the HMW-HDPE;
iii) melt index in the range of from 0.02 to 2.0 dg/min. .; and b) in the range of from 1 to 15 weight percent, of metallocene-catalyzed linear low density polyethylene (LLDPE).
2 The composition of claim 1 wherein said first component is present in the range of from 90 to 99 weight percent and said first component has a density in the range of from 0.950 to 0.960 g/cc and a melt index in the range of from 0.3 to 0.1 dg/min.
3.The use of the composition of either claim 1 or 2 in a film wherein said film has a puncture propagation tear (MD) above 2.0 KgF, and a puncture propagation tear length (MD) up to 100 mm.
4. The use, of claim 3 wherein said film has a puncture propagation tear (MD) above 2.1 KgF, and a puncture propagation tear length (MD) up to 95 mm.
5. The use of claim 3 wherein said film has a puncture propagation tear (MD) above 2.2 KgF, and a puncture propagation tear length (MD) up to 90 mm.
6. Use of any one of claims 3, 4, or 5 wherein the film is used in a tee-shirt bag or a can liner.
7. Use of the composition of either claim 1 or 2 as an extrusion blow-molded article.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/354,393 US5635262A (en) | 1994-12-12 | 1994-12-12 | High molecular weight high density polyethylene with improved tear resistance |
| US08/354,393 | 1994-12-12 | ||
| PCT/US1995/015960 WO1996018678A1 (en) | 1994-12-12 | 1995-12-12 | High molecular weight high density polyethylene with improved tear resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2208232A1 CA2208232A1 (en) | 1996-06-20 |
| CA2208232C true CA2208232C (en) | 2001-04-24 |
Family
ID=23393140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2208232 Expired - Fee Related CA2208232C (en) | 1994-12-12 | 1995-12-12 | High molecular weight high density polyethylene with improved tear resistance |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5635262A (en) |
| EP (1) | EP0797622B1 (en) |
| AT (1) | ATE177460T1 (en) |
| CA (1) | CA2208232C (en) |
| DE (1) | DE69508278T2 (en) |
| WO (1) | WO1996018678A1 (en) |
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| US8202001B1 (en) * | 2006-01-26 | 2012-06-19 | Chunhua Zhang | Self-opening bag pack and method thereof |
| EP1878764B2 (en) | 2006-07-14 | 2015-04-22 | Borealis Technology Oy | High density polyethylene |
| US8263198B2 (en) | 2007-09-26 | 2012-09-11 | Chevron Phillips Chemical Company Lp | System and method for creating high gloss plastic items via the use of styrenic copolymers as a coextruded layer |
| US8215803B2 (en) | 2009-08-19 | 2012-07-10 | Gregg Singer | Cover sleeve for CFL bulb |
| US8993681B2 (en) | 2011-07-14 | 2015-03-31 | Exxonmobil Research And Engineering Company | Dendritic ethylene polymers and processes for making |
| US8915623B1 (en) * | 2012-02-01 | 2014-12-23 | St. Albert Innovations, LLC | Cover for a light bulb |
| GB2580929B (en) | 2019-01-30 | 2021-11-17 | Innovia Films Ltd | Film |
| US20230037446A1 (en) * | 2021-07-14 | 2023-02-09 | Colormasters, LLC | Recyclable multilayer films and methods of making same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3024211A (en) * | 1956-09-06 | 1962-03-06 | Us Rubber Co | Plastic composition of isotactic monoolefin polymer and cyclized natural rubber |
| US3919358A (en) * | 1974-08-02 | 1975-11-11 | Goodrich Co B F | Thermoplastic polymer blends of (1) EPDM having a high degree of unstretched crystallinity with (2) polyethylene |
| GB2007685B (en) * | 1977-10-11 | 1982-05-12 | Asahi Dow Ltd | Composition for drawn film cold drawn film made of said composition and process for manufacture of said film |
| US4493923A (en) * | 1984-03-27 | 1985-01-15 | Shell Oil Company | High notched impact toughness propylene polymer compositions |
| US5071686A (en) * | 1985-11-29 | 1991-12-10 | Genske Roger P | Films of polypropylene blends and polyethylene blends and articles made therewith |
| US4770912A (en) * | 1987-07-23 | 1988-09-13 | Union Camp Corporation | Polyethylene resin blend |
| DE3733342A1 (en) * | 1987-10-02 | 1989-04-13 | Basf Ag | THERMOPLASTIC MOLDS, THEIR PRODUCTION AND THEIR USE |
| JP2660047B2 (en) * | 1988-04-29 | 1997-10-08 | 三井石油化学工業株式会社 | Films and sheets that can be heat sterilized to form easily openable packages |
| US4911985A (en) * | 1989-02-21 | 1990-03-27 | Allied-Signal Inc. | High density polyethylene compositions containing polyisobutylene rubber and filler |
| US5254617A (en) * | 1989-11-16 | 1993-10-19 | Mitsui Petrochemical Industries, Ltd. | Resin composition for producing a film and method for producing a film by using the same |
| US5153039A (en) * | 1990-03-20 | 1992-10-06 | Paxon Polymer Company, L.P. | High density polyethylene article with oxygen barrier properties |
| US5110685A (en) * | 1990-05-18 | 1992-05-05 | Exxon Chemical Patents, Inc. | Low friction, abrasion resistant polymer coating |
| WO1991019763A1 (en) * | 1990-06-18 | 1991-12-26 | Exxon Chemical Patents Inc. | New hdpe resins and products with improved properties |
| US5338589A (en) * | 1991-06-05 | 1994-08-16 | Hoechst Aktiengesellschaft | Polyethylene molding composition |
| DE4139827A1 (en) * | 1991-12-03 | 1993-06-09 | Basf Ag, 6700 Ludwigshafen, De | THERMOPLASTIC MOLDING |
-
1994
- 1994-12-12 US US08/354,393 patent/US5635262A/en not_active Expired - Fee Related
-
1995
- 1995-12-12 AT AT95943038T patent/ATE177460T1/en not_active IP Right Cessation
- 1995-12-12 CA CA 2208232 patent/CA2208232C/en not_active Expired - Fee Related
- 1995-12-12 DE DE1995608278 patent/DE69508278T2/en not_active Expired - Fee Related
- 1995-12-12 EP EP19950943038 patent/EP0797622B1/en not_active Expired - Lifetime
- 1995-12-12 WO PCT/US1995/015960 patent/WO1996018678A1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| EP0797622B1 (en) | 1999-03-10 |
| ATE177460T1 (en) | 1999-03-15 |
| DE69508278D1 (en) | 1999-04-15 |
| WO1996018678A1 (en) | 1996-06-20 |
| DE69508278T2 (en) | 1999-09-30 |
| CA2208232A1 (en) | 1996-06-20 |
| EP0797622A1 (en) | 1997-10-01 |
| US5635262A (en) | 1997-06-03 |
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| EEER | Examination request | ||
| MKLA | Lapsed |