CA2172980C - Dispersible film - Google Patents
Dispersible film Download PDFInfo
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- CA2172980C CA2172980C CA002172980A CA2172980A CA2172980C CA 2172980 C CA2172980 C CA 2172980C CA 002172980 A CA002172980 A CA 002172980A CA 2172980 A CA2172980 A CA 2172980A CA 2172980 C CA2172980 C CA 2172980C
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- Prior art keywords
- ethylene copolymer
- range
- polymer blend
- ethylene
- weight percent
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Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- 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]
-
- 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
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
Abstract
Bales of unvulcanized rubber, or compounding ingredients for unvulcanized rubber are packaged in film or bags made from an ethylene .alpha.-olefin copolymer having a Vicat softening point below 90 °C and a melting point below 100 °C, and optionally a second ethylene copolymer is added to improve processability of the first ethylene copolymer. The second ethylene copolymer will contain more long-chain branches than the first ethylene copolymer. Such films may be included in a rubber compounding operation.
Description
W~ 95/09199 PCT/US94111126 2~~29~
DISPERSIBLE FILM
' This invention relates to compositions, films, bags, packages, and compounded materials derived from cahylene ba sed polymer blends .
BACKGROUND
In the manufacture of c:lastomeric mechanical goods and in some polymerization processes, elastomers a.nd/or numerous additives are combined in a plasticized, and/or a blended mix prior to molding, curing or reaction/polymerization of the mix. In certain applications materials may be contained in bags, where the bags with the materials inside have been processed substantially in their totality and incorporated into the end product without removal of the bag or wrap..
For example, in the manufacture of synthetic rubber, such as butyl, chlorobutyl, 2o EPDM, and EPR, raw rubber pieces (referred to as "crumbs") are passed from a reactor through a drying oven, and collected in a compression mold where they are =
compressed into bales gf:nerally in the range of 14" x 28" x 8". The bales are then placed in large containers ("bins") sized to receive 30-45 of the bales for storage and transport. The bales are placed in the bin at elevated temperatures ( 120°-210°
F, 48°C-98°C) which can cause bale to bale sticking if the bales are in direct contact with each other. This is done while the bales are still as warm as practical.
Substantially, the sticking; and cold /low of the rubber makes it difficult to remove individual bales from the: bin. Further, exposure to elevated temperatures during storage and transit would cause further sticking and cold flow. This sticking led to the development of thermoplastic film bale wrap to separate the bales. Bale wrap film is applied, by conventional in-line equipment, to completely encapsulate or wrap the rubber bale after the drying and molding steps, prior to being placed in the bin. The film prevents rubber-to-rubber contact, and also resists the cold flow of the rubber.
On arrival at a fabricating location (for example, a tire manufacturing location), the bales are removed from the box and the rubber or elastomer is compounded with to other ingredients. The other ingredients may be placed with the elastomer in a mixing device. The ingredients may be placed in the mixing device "loose" or preferably in so called '°remote" weighing or compound ingredient bags.
In particular, film of the present invention is well suited to form remote weighing bags for materials such as sulfur, peroxide, primary and secondary accelerators, stearic acid, zinc oxide, plasticizers and oils, and other materials added to internal mixers (or blenders, compounding devices and reaction vessels) in small quantities.
Such compounding bags also find use for carrying ingredients in many chemical operations such as mixing, blending, compounding, reaction blending and polymerization.
A remote weighing system using compounding bags can consist of a simple manual set-up where a worker pre-weighs batches of specific components, or it could be as elaborate as an automatic form, fill and seal operation. In either case, the result is preweighed, packaged components, increases safety and minimizes health WO 95/09199 PCT/US94i11126 concerns by which can be introduced to the mixing/compounding process. Such pre-weighing substantially eliminating the need for in-line weighing of ingredients.
Remote weighing with bags has many advantages over the "scoop and shovel"
method of addition; i. ~e., ( 1 ) improved housekeeping; (2) improved industrial hygiene; (3) loss control; (4) accuracy and quality control; and (S) labor savings.
Polyethylene has been used for both bale wrap and compounding bags because of its plasticity and antibloc;k properties, and because it can be obtained at a relatively low cost. Bale wrap films now available include those made from low density 1o homopolymer polyethylene (LDPI=?), ethylene vinyl acetate (EVA) copolymers, blends of these two o:r blends of each, with other additives. Poiyethylenes previously used for these films have been made from free radical polymerizations, or traditional Ziegler-Natta catalyzed polymerizations. Although LDPE and EVA
films were successful in preventing sticking and cold flow of the rubber bales they present other problems. The first of these problems in a stack of rubber bales, is the splitting of film due t:o insuffcie:nt film strength and poor environmental stress crack resistance which occurs due to stress put on the film by the cold flow of the rubber and the nature of v.he container where the bales are placed.
2o The second problem is a processing problem after compounding and/or mixing of the elastomer and other ingredients. Many end use applications cannot tolerate the presence of LDPE and E'VA in an unmelted, or partially unmeited, state in a rubber or plastic compound. Two solutions to this problem are known. The first solution is to make the bale wrap easily peelable, facilitating its removal prior to placing the elastomer into compounding mixers. See for example U. S. Patent number 4, 848, S 64.
The second solution is to change the melting and softening point behavior of the bulk film. This second solution allows the bale wrap film and/or the compounding bag to be placed in a mechanical mixer still covering the bale or compound ingredients. As the mechanical mixer begins to mix, imparting energy to all components, the heat generated or heat imparted, substantially softens or plasticizes all ingredients to permit formation of a substantially homogeneous rubber or plastic compound which may then be fabricated in to useful articles.
In order to achieve this substantially homogeneous mix, the bale wrap or compounding bag must be melted, or at least softened, and then mixed during the io mixing cycle. U. S. Patent 5,145,747 approaches this solution by extruding or coextruding an EVA with up to 30% of a compatible wax to depress the Vicat softening point and the melting point of the bulk film. U. S. 5,145,747, adds a wax to a 6-12 wt% VA ethylene copolymer to reduce the Vicat softening point of the EVA. However such EVA materials exhibit a tendency to split and stress-crack during shipment and handling of elastomer bales, negatively effecting the film's ability to protect the elastomer bales. The EVA may have sufficient VA to lower the Vicat softening point to for instance 82°C. However such a VA level will make film formation difftcult, and if a film can be formed, the high VA
content will make the films very tacky, making the handling of bales wrapped in such a film, 2o very difficult.
The present invention provides an extrudable film forming composition which has a Vicat softening point and melting point low enough to permit its inclusion in a rubber compound while improving the film strength and environmental stress crack resistance.
~ 1 ~98Q
Snmmarv of the Invention With the present invention, it has been found that the above-mentioned disadvantages associated with prior art solutions can be minimized or eliminated by 5 the use of a film made from at least one low density polyethylene resin, where the resin has a Vicat softening point up. to 100°C and a density up to 0.915 g/cm3. A
film having a melt point: temperature to achieve such compatibility will generally also allow shorter mixing times for the rubber being compounded, therefore providing for greater productivity. One aspect of our invention, a polyethylene l0 film, formed from an ethylene-a-olefin copolymer or terpolymer, is provided wherein such film has:
a) a density in the range of from about 0.85 to about 0.915 g/cm3;
b) a melt index in the range of from about 0.1 to about 10 grams per 10 minutes;
c) a Vicat softening point not exceeding 100°C;
d) a melting point not exceeding 120°C;
e) a CDBI exceeding 50'%; and fj a Mw/Mn not exceeding 3Ø
Such films provide sufficiE.nt sealability at sealing temperatures, as well as splitting and creep resistance, while packaging the rubber bale, and also provide a Vicat softening point and melting point low enough to enable the wrapped bale or compound ingredient bag to be placed in a mechanical mixer along with other ingredients, and then mixed into a substantially homoeeneous rubber compound.
In a preferred embodiment, .a second ethylene polymer is added to improve the melt processability for instance neck-in, of the first ethylene copolymer. The second ethylene polymer may be a polyethylene homopolvmer or a copolymer of ethylene and an ethylenically unsaturated ester of a carboxylic acid. The second ethylene polymer is preferably any polymer with sufficient long chain branching to to contribute to the melt processability of the first ethylene copolymer. The second ethylene copolymer may have: a melt index in the range of from 0.1 dg/min. to 2.0 dg/min., preferably in the range of from 0.1 dg/min. to 1 dg/min.
In a more preferred embodiment, the first ethylene copolymer is present in the range of from about 75 to abnut 99 weight percent of the total blend weight.
The second ethylene copolymer or ethylene homopolymer is present in the range of from about 2S to about I weight percent based on the total blend weight.
In the preferred embodiments, it is preferred that a film made from one or more of 2o these ethylene polymers has a Vicat softening point not exceeding 90°C and the melting point does not exceed 110°C. More preferably the Vicat softening point does not exceed 82°C and the melting point does not exceed 100°C.
6a In a further aspect of the invention, there is provided a package comprising:
a) an article selected from the group consisting of an unvulcanized rubber, a vulcanized rubber, compounding ingredients for unvulcanized rubber, and combinations thereof wherein said article is covered with and in contact with a film;
b) said film made from a polymer blend, said polymer blend having:
i) a first ethylene: copolymer present in the range of from about 75 to about 99 weight percent, said percentage based on the total polymer blend weight, said first ethylene copolymer being an ethylene-a-olefin copolymer, wherein said first ethylene copolymer has a density in the range of from about 0.85 to about 0.915 g/cm.3, said first ethylene copolymer having a Vicat softening point less than about 100°C., said first ethylene copolymer having a melting point not exceeding about 120°C., said a-olefin being selected from the group consisting of propylene-1, butene-1, pentene-1, hexene-1, octene-1 and decene-1; and ii) a second ethylene copolymer, containing long chain branching, present in the range of from about 1 to about 25 weight percent based on the total weight of the polymer blend, said ethylene copolymer having in the range of from about 65 to about 99 weight percent of ethylene and in the range of from about 1 to about 35 weight percent of an ethylenically unsaturated acrylic acid ester based on the total weight of the second ethylene copolymer, wherein said polymer blend has a Vicat softening point in the range of from about 10°C. to about 90°C.
and a melting point in the range of from about 30 ° C . to about 110 ° C.
Preferably, the ethylenically unsaturated acrylic acid ester is selected from the group consisting of methyl acrylate, butyl acrylate, and ethyl acrylate.
In yet a further aspect of the invention, there is provided a package comprising:
a) an article selected from the group consisting of an unvulcanized rubber, a vulcanized rubber, compounding ingredients for unvulcanized rubber, and combinations thereof wherein said article is covered with and in contact with a film; and said film being made from a polymer blend having:
i) a first ethylene copolymer present in the range of from about 75 to 6b about 99 weight percent, said percentage based on the total polymer blend weight, said first ethylene copolymer being an. ethylene-a-olefin copolymer, wherein said first ethylene copolymer has a density in the range of from about 0.85 to about 0.915 g/cm.3, said first ethylene copolymer having a Vicat softening point less than about 100°C., said first ethylene copolymer having a melting point not exceeding about 120°C., said alpha-olefin being selected from the group consisting of propylene-1, butene-l, pentene-1, hexene-1, octene-1 and decene-1; and ii) a second ethylene copolymer, containing long chain branching, present in the range of from about 1 to about 25 weight percent based on the total weight of the polymer blend, said'. ethylene copolymer having in the range of from about 65 to about 99 weight percent of ethylene and in the range of from about 1 to about 35 weight percent of vinyl acetate based on the total weight of the second ethylene copolymer, wherein said polymer blend has a Vicat softening point in the range of from about 10°C. to about 90°C. and a melting point in the range of from about 30°C. to about 110 ° C .
Description of the Preferred Embodiments Our invention concerns certain films, their production and applications. These films have unique properties which make them particularly well suited for use in certain compounding or manufacturing operations. These films have combinations of properties rendering them superior to films previously available for many such compounding or manufacturing operations. Following is a detailed description of certain preferred film vvithin the scope of our invention, preferred methods of producing these films and preferred applications of these films. Those skilled in the art will appreciate that numerous modifications to these preferred embodiments can be made without departing from the scope of the invention. For example, though the properties of the film are exemplified in elastomer compounding applications, they have numerous other uses. To the extent our description is to specific, this is solely for the purpose of illustrating preferred embodiments of our invention and should not be taken as limiting our invention to these specific embodiments.
Various values given in the text and claims are determined as follows:
Melt index (MI): ASTN1 D 1238 C'.ondition E 190°C, 2.16 kg mass;
expressed in g/10 min Vicat softening point: A;STM-1525 with a 1000 g weight Melting point: Di~'erential Scanning Calorimeter (DSC) second melting curve melting peak in degrees centigrade.
The film of the present invention fc>r use as a rubber bale wrap or compounding bag, has the following properties: good seal strength, a low melting point, good sealability, a low Vicat softening point, resistance to splitting and resistance to stress cracking. The low Vicat softening point and the low melting point improves 11~9~
DISPERSIBLE FILM
' This invention relates to compositions, films, bags, packages, and compounded materials derived from cahylene ba sed polymer blends .
BACKGROUND
In the manufacture of c:lastomeric mechanical goods and in some polymerization processes, elastomers a.nd/or numerous additives are combined in a plasticized, and/or a blended mix prior to molding, curing or reaction/polymerization of the mix. In certain applications materials may be contained in bags, where the bags with the materials inside have been processed substantially in their totality and incorporated into the end product without removal of the bag or wrap..
For example, in the manufacture of synthetic rubber, such as butyl, chlorobutyl, 2o EPDM, and EPR, raw rubber pieces (referred to as "crumbs") are passed from a reactor through a drying oven, and collected in a compression mold where they are =
compressed into bales gf:nerally in the range of 14" x 28" x 8". The bales are then placed in large containers ("bins") sized to receive 30-45 of the bales for storage and transport. The bales are placed in the bin at elevated temperatures ( 120°-210°
F, 48°C-98°C) which can cause bale to bale sticking if the bales are in direct contact with each other. This is done while the bales are still as warm as practical.
Substantially, the sticking; and cold /low of the rubber makes it difficult to remove individual bales from the: bin. Further, exposure to elevated temperatures during storage and transit would cause further sticking and cold flow. This sticking led to the development of thermoplastic film bale wrap to separate the bales. Bale wrap film is applied, by conventional in-line equipment, to completely encapsulate or wrap the rubber bale after the drying and molding steps, prior to being placed in the bin. The film prevents rubber-to-rubber contact, and also resists the cold flow of the rubber.
On arrival at a fabricating location (for example, a tire manufacturing location), the bales are removed from the box and the rubber or elastomer is compounded with to other ingredients. The other ingredients may be placed with the elastomer in a mixing device. The ingredients may be placed in the mixing device "loose" or preferably in so called '°remote" weighing or compound ingredient bags.
In particular, film of the present invention is well suited to form remote weighing bags for materials such as sulfur, peroxide, primary and secondary accelerators, stearic acid, zinc oxide, plasticizers and oils, and other materials added to internal mixers (or blenders, compounding devices and reaction vessels) in small quantities.
Such compounding bags also find use for carrying ingredients in many chemical operations such as mixing, blending, compounding, reaction blending and polymerization.
A remote weighing system using compounding bags can consist of a simple manual set-up where a worker pre-weighs batches of specific components, or it could be as elaborate as an automatic form, fill and seal operation. In either case, the result is preweighed, packaged components, increases safety and minimizes health WO 95/09199 PCT/US94i11126 concerns by which can be introduced to the mixing/compounding process. Such pre-weighing substantially eliminating the need for in-line weighing of ingredients.
Remote weighing with bags has many advantages over the "scoop and shovel"
method of addition; i. ~e., ( 1 ) improved housekeeping; (2) improved industrial hygiene; (3) loss control; (4) accuracy and quality control; and (S) labor savings.
Polyethylene has been used for both bale wrap and compounding bags because of its plasticity and antibloc;k properties, and because it can be obtained at a relatively low cost. Bale wrap films now available include those made from low density 1o homopolymer polyethylene (LDPI=?), ethylene vinyl acetate (EVA) copolymers, blends of these two o:r blends of each, with other additives. Poiyethylenes previously used for these films have been made from free radical polymerizations, or traditional Ziegler-Natta catalyzed polymerizations. Although LDPE and EVA
films were successful in preventing sticking and cold flow of the rubber bales they present other problems. The first of these problems in a stack of rubber bales, is the splitting of film due t:o insuffcie:nt film strength and poor environmental stress crack resistance which occurs due to stress put on the film by the cold flow of the rubber and the nature of v.he container where the bales are placed.
2o The second problem is a processing problem after compounding and/or mixing of the elastomer and other ingredients. Many end use applications cannot tolerate the presence of LDPE and E'VA in an unmelted, or partially unmeited, state in a rubber or plastic compound. Two solutions to this problem are known. The first solution is to make the bale wrap easily peelable, facilitating its removal prior to placing the elastomer into compounding mixers. See for example U. S. Patent number 4, 848, S 64.
The second solution is to change the melting and softening point behavior of the bulk film. This second solution allows the bale wrap film and/or the compounding bag to be placed in a mechanical mixer still covering the bale or compound ingredients. As the mechanical mixer begins to mix, imparting energy to all components, the heat generated or heat imparted, substantially softens or plasticizes all ingredients to permit formation of a substantially homogeneous rubber or plastic compound which may then be fabricated in to useful articles.
In order to achieve this substantially homogeneous mix, the bale wrap or compounding bag must be melted, or at least softened, and then mixed during the io mixing cycle. U. S. Patent 5,145,747 approaches this solution by extruding or coextruding an EVA with up to 30% of a compatible wax to depress the Vicat softening point and the melting point of the bulk film. U. S. 5,145,747, adds a wax to a 6-12 wt% VA ethylene copolymer to reduce the Vicat softening point of the EVA. However such EVA materials exhibit a tendency to split and stress-crack during shipment and handling of elastomer bales, negatively effecting the film's ability to protect the elastomer bales. The EVA may have sufficient VA to lower the Vicat softening point to for instance 82°C. However such a VA level will make film formation difftcult, and if a film can be formed, the high VA
content will make the films very tacky, making the handling of bales wrapped in such a film, 2o very difficult.
The present invention provides an extrudable film forming composition which has a Vicat softening point and melting point low enough to permit its inclusion in a rubber compound while improving the film strength and environmental stress crack resistance.
~ 1 ~98Q
Snmmarv of the Invention With the present invention, it has been found that the above-mentioned disadvantages associated with prior art solutions can be minimized or eliminated by 5 the use of a film made from at least one low density polyethylene resin, where the resin has a Vicat softening point up. to 100°C and a density up to 0.915 g/cm3. A
film having a melt point: temperature to achieve such compatibility will generally also allow shorter mixing times for the rubber being compounded, therefore providing for greater productivity. One aspect of our invention, a polyethylene l0 film, formed from an ethylene-a-olefin copolymer or terpolymer, is provided wherein such film has:
a) a density in the range of from about 0.85 to about 0.915 g/cm3;
b) a melt index in the range of from about 0.1 to about 10 grams per 10 minutes;
c) a Vicat softening point not exceeding 100°C;
d) a melting point not exceeding 120°C;
e) a CDBI exceeding 50'%; and fj a Mw/Mn not exceeding 3Ø
Such films provide sufficiE.nt sealability at sealing temperatures, as well as splitting and creep resistance, while packaging the rubber bale, and also provide a Vicat softening point and melting point low enough to enable the wrapped bale or compound ingredient bag to be placed in a mechanical mixer along with other ingredients, and then mixed into a substantially homoeeneous rubber compound.
In a preferred embodiment, .a second ethylene polymer is added to improve the melt processability for instance neck-in, of the first ethylene copolymer. The second ethylene polymer may be a polyethylene homopolvmer or a copolymer of ethylene and an ethylenically unsaturated ester of a carboxylic acid. The second ethylene polymer is preferably any polymer with sufficient long chain branching to to contribute to the melt processability of the first ethylene copolymer. The second ethylene copolymer may have: a melt index in the range of from 0.1 dg/min. to 2.0 dg/min., preferably in the range of from 0.1 dg/min. to 1 dg/min.
In a more preferred embodiment, the first ethylene copolymer is present in the range of from about 75 to abnut 99 weight percent of the total blend weight.
The second ethylene copolymer or ethylene homopolymer is present in the range of from about 2S to about I weight percent based on the total blend weight.
In the preferred embodiments, it is preferred that a film made from one or more of 2o these ethylene polymers has a Vicat softening point not exceeding 90°C and the melting point does not exceed 110°C. More preferably the Vicat softening point does not exceed 82°C and the melting point does not exceed 100°C.
6a In a further aspect of the invention, there is provided a package comprising:
a) an article selected from the group consisting of an unvulcanized rubber, a vulcanized rubber, compounding ingredients for unvulcanized rubber, and combinations thereof wherein said article is covered with and in contact with a film;
b) said film made from a polymer blend, said polymer blend having:
i) a first ethylene: copolymer present in the range of from about 75 to about 99 weight percent, said percentage based on the total polymer blend weight, said first ethylene copolymer being an ethylene-a-olefin copolymer, wherein said first ethylene copolymer has a density in the range of from about 0.85 to about 0.915 g/cm.3, said first ethylene copolymer having a Vicat softening point less than about 100°C., said first ethylene copolymer having a melting point not exceeding about 120°C., said a-olefin being selected from the group consisting of propylene-1, butene-1, pentene-1, hexene-1, octene-1 and decene-1; and ii) a second ethylene copolymer, containing long chain branching, present in the range of from about 1 to about 25 weight percent based on the total weight of the polymer blend, said ethylene copolymer having in the range of from about 65 to about 99 weight percent of ethylene and in the range of from about 1 to about 35 weight percent of an ethylenically unsaturated acrylic acid ester based on the total weight of the second ethylene copolymer, wherein said polymer blend has a Vicat softening point in the range of from about 10°C. to about 90°C.
and a melting point in the range of from about 30 ° C . to about 110 ° C.
Preferably, the ethylenically unsaturated acrylic acid ester is selected from the group consisting of methyl acrylate, butyl acrylate, and ethyl acrylate.
In yet a further aspect of the invention, there is provided a package comprising:
a) an article selected from the group consisting of an unvulcanized rubber, a vulcanized rubber, compounding ingredients for unvulcanized rubber, and combinations thereof wherein said article is covered with and in contact with a film; and said film being made from a polymer blend having:
i) a first ethylene copolymer present in the range of from about 75 to 6b about 99 weight percent, said percentage based on the total polymer blend weight, said first ethylene copolymer being an. ethylene-a-olefin copolymer, wherein said first ethylene copolymer has a density in the range of from about 0.85 to about 0.915 g/cm.3, said first ethylene copolymer having a Vicat softening point less than about 100°C., said first ethylene copolymer having a melting point not exceeding about 120°C., said alpha-olefin being selected from the group consisting of propylene-1, butene-l, pentene-1, hexene-1, octene-1 and decene-1; and ii) a second ethylene copolymer, containing long chain branching, present in the range of from about 1 to about 25 weight percent based on the total weight of the polymer blend, said'. ethylene copolymer having in the range of from about 65 to about 99 weight percent of ethylene and in the range of from about 1 to about 35 weight percent of vinyl acetate based on the total weight of the second ethylene copolymer, wherein said polymer blend has a Vicat softening point in the range of from about 10°C. to about 90°C. and a melting point in the range of from about 30°C. to about 110 ° C .
Description of the Preferred Embodiments Our invention concerns certain films, their production and applications. These films have unique properties which make them particularly well suited for use in certain compounding or manufacturing operations. These films have combinations of properties rendering them superior to films previously available for many such compounding or manufacturing operations. Following is a detailed description of certain preferred film vvithin the scope of our invention, preferred methods of producing these films and preferred applications of these films. Those skilled in the art will appreciate that numerous modifications to these preferred embodiments can be made without departing from the scope of the invention. For example, though the properties of the film are exemplified in elastomer compounding applications, they have numerous other uses. To the extent our description is to specific, this is solely for the purpose of illustrating preferred embodiments of our invention and should not be taken as limiting our invention to these specific embodiments.
Various values given in the text and claims are determined as follows:
Melt index (MI): ASTN1 D 1238 C'.ondition E 190°C, 2.16 kg mass;
expressed in g/10 min Vicat softening point: A;STM-1525 with a 1000 g weight Melting point: Di~'erential Scanning Calorimeter (DSC) second melting curve melting peak in degrees centigrade.
The film of the present invention fc>r use as a rubber bale wrap or compounding bag, has the following properties: good seal strength, a low melting point, good sealability, a low Vicat softening point, resistance to splitting and resistance to stress cracking. The low Vicat softening point and the low melting point improves 11~9~
the ability of the film to be incorporated into a homogeneous mixture of rubber and rubber compounding ingredients to form homogeneous rubber compounds.
The film of the present invention for use as rubber bale wrap and compounding bags may be made from a single ethylene copolymer or terpolymer, or a blend of such ethylene copolymer with other ethylene copolymers, or with ethylene homopoiymers.
In an embodiment of the present invention, a film is made for either bale wrapping to or for making compounding bags. 1(n either case, the film must have softening and melting characteristics that permit its inclusion into the rubber compounding process, and such inclusion wilt result in a substantially homogeneous compounded eiastomer blend.
The film may be made from an ethylene a-olefin copolymer or terpoIymer (first ethylene polymer). This first ethylene polymer has a density in the range of from about 0.85 to about 0.915 g/cm~, a Vicat softening point. less than about 100°C
and a differential scanninc; calorimeter (DSC) second melting point (melting point) not exceeding about I20°C. The a.-olefin utilized to make first ethylene polymer is 2o selected from propylene-:L, butene-1, pentene-1, hexene-l, octene-1 and decene-1.
The a-olefin or a-olefins incorporation will be in the range of from about 0.2 to about 20 mole percent, based on the i:otal moles of the copolymer or terpolymer. The first ethylene copolymer has a CDBI exceeding 50 % , preferably exceeding 65 %
. The first ethylene copolymer has a molecular weight distribution as determined by weight average molecular weight divided by number l~~y~0 average molecular wei;;ht (Mw/Nln) not exceeding 3.0, preferably not exceeding 2.5, more preferably not exceeding 2.8.
Preferably, the film made from the first ethylene polymer has a Vicat softening point in the range of from about 10°C to about 90°C and a melting point of from about 30°C to about 110°C. More preferably, the film made from the first ethylene polymer has a Vicat softening point in the range of from about 25°C to about 82°C
and a DSC melting point in the range of from about 50°C to about 100°C.
The first ethylene polymer may be made by a number of processes, including high pressure, low pressure. gas phase, fluidized bed, slurry or solution processes.
Where free radical polymerization is not used, the catalysts used for the polymerization are generally of the metallocene-alumoxane, or metallocene-ionic activator types, although metallocene-alumoxane catalysts are preferred. Such catalysts are well known. Thus, useful catalysts are those disclosed in EP
129368, U. S. Patents numbers 5,026,798 and 5,198,401.
Optionally, a second e~:hylene polymer may be blended into the first ethylene polymer. The second ethylene polymer is preferably not used for depressing either 2o the Vicat softening point or the melting point of the first ethylene polymer, although such depression is not precluded. The main purpose of the second ethylene polymer is to improve melt processability (reduced neck-in and higher melt strength) of the blend over the processability of the first ethylene polymer alone. The second ethylene polymer is generally a molecule containing long chain branching. Long chain branching is defined herein as a chain length of at least 6 carbon atoms, above 6 carbon atones the length cannot be determined using 13C
nuclear magnetic resonance spectroscopy (NMIg). The long chain branch can ' W O 95!09199 PCT/US9dl1 I 126 ~ I~ ~~~~~
contain as many carbon atoms as the polymer back-bone. Long chain branching is determined using 13C ~~SR and is quantified using the method of Randall (Rev.
Macromol. Chem. Phi, C29 (2 and 3), pages 285-297. fVhereas the first ethylene . polymer contains less lc>ng chain branches. Generally, the fewer the long chain 5 branches, the more difficult the resin is to melt process. Difficulty in processing can be manifested by bubble instability in blown film and draw resonance, surging andlor neck-in in cast films.
to In another embodiment of the presem invention, the second ethylene polymer is a polyethylene homopolymer or preferably an ethylene copolymer of ethylene and an ethylenicaliy unsaturated carboxylic acid ester. Preferred ethylenically unsaturated acrylic acid esters include, for example, vinyl acetate, methyl acrylate, butyl acrylate, and ethyl acryl<ite. A most preferred ester monomer is vinyl acetate.
These comonomers are present in the second ethylene polymer within a range of from 1 to 35 weight percent, preferably from I to I S weight percent of the unsaturated acrylic acid ester, based on the total weight of the second ethylene polymer.
The second ethylene pohrmers are chosen , in general, primarily based on their ability to enhance proces,sability of the first ethylene polymer and their melting points and/or Vicat softening points. That is, the melting points and/or Vicat softening points of such polymers should not have a substantial deleterious effect on these same parameters of the first ethylene polymer, and the film made therefrom at the level of inclusion in the blends, but will mitigate processing debits of the first ethylene polymer. In general, a 10% improvement in bubble stability or neck-in would be desirable:.
WO 95!09199 PCT/US94111126 11 21129~~
When the second ethylene polymer is included in the manufacture of film, it is present in the range of from about 25 to about 1 weight percent based on the total weight of the blend. 'The first ethylene polymer is present in the range of from about 75 to about 99 weight percent, based on the total weight of the blend.
In the preferred embodiment, the first ethylene polymer is present in the range of from about 85 weight percent to about 95 weight percent based on the total weight of the blend. The second ethylene polymer is present in the range of from 1o about 15 to about 5 weight percent based on the total weight of the blend.
More preferably the second ethylene copolymer is present in the blend at less than 10%, preferably less than 8 weight percent. Also the second copolymer may be present above 10 weight percent, preferably more than 12 weight percent.
It should be understood that the first ethylene polymer may be used for film manufacture without the use of the second ethylene polymer. However, in either the case where the first ethylene polymer is used alone, or in the case where it is blended with the second ethylene polymer, it is understood that the Vicat softening point of the resulting fiIrn does not exceed I 00°C, and the melting point of the film 2o does not exceed 120°C. Preferably, the film made from the blend has a Vicat softening point in the rzmge of from about IO,aC to about 100r~C, and a melting point of from about 30°C to about 110°C. More preferably, the film has a Vicat softening point in the range of from about 25°C to about 82°C, and a melting point in the range of from about 50°C to about 100°C.
It should be further understood: that additives often found in films are contemplated by our invE:ntion as well. Such additives will be understood by those WO 95!09199 PCTIUS94111126 ~17~.980 skilled in the art to include those that will have an effect on surface characteristics of films, processability of resins being made into films, and thermal stability of resins or film. These, and other types of additives, are normally carried in polyolefins, but may be added without such polyolefin earners. The additive types mentioned are not meant to be a cornpiete list, but merely illustrative.
In the practice of this invention, the rubber is compounded utilizing a mechanical mixer. The compounded rubber ca.n include mixed unvulcanized rubber with the bale wrap and/or a compounding ingredient bag film of this invention. The to compounded rubber can also include accelerators, promoters, curing or crosslinking agents, filter:>, colorants, anti-oxidants, and other adjuvants.
Both the rubbers and additives are well known. See for instance, U. S. Patents 4,394,473; 5,145,747; and 4,848,564.
Example 1:
A film was made using a~ siip and anti-block master batch (AMPACET
50568), manufactured by Ampacet Corporation containing 5 weight percent slip and 20 weight percent anti-block, and the remaining 75 weight percent is a 0.3 MI
2o ethylene vinyl acetate copolymer film grade polyethylene resin containing 6 weight percent vinyl acetate. The master batch was added to Exactj~" 3027 (a 3.5 melt index, 0.900 density, et:hyiene butene copolymer polyethylene available from Exxon Chemical Company having a nominal Mw/Mn of 2 and nominal CDBI of 90%} at a 2 weight percent level based on the total weight of the blend. This resulted in a total slip and anti-block Levels of 1,000 parts per million (ppm) and 4,000 ppm, respectively.
*trade-mark WO 95/09199 PCTIUS94l11I26 ~ 1 T~98~
The film was prepared on a Black Clawson~cast film extrusion line run in an embossed mode. The oF~eratin~ rate was 22.8 meters per minute of film. The resin showed a tendency to neck-in, in the range of 35 to 40 cm out of a fatal die length of 91 cm. While the neck-in was significant, a commercial film could be made.
The film would have a Vicat softening point of 76°C and a melting point of 92°C.
Example 2:
A second run was accomplished as disclosed in Example 1. The second run was made using 88 weight percent E~s:ACTT"" 3027 low density polyethylene from 1o Exxon Chemical Company, 2 weight percent Ampacet 50568 and 10 weight percent of a 0.31 MI, 6 weight percent vinyl acetate EVA copolymer Escorene LD-317.09 (available from Exxon Chemical Company). The neck-in for this blend was ~ - 10 cm. Three. different film thicknesses were produced nominal 50 microns, 44 microns, and 38 microns. The Vicat softening point of the film was °C, the melting point was 9I °C.
Table I shows the physical properties of the three films thicknesses produced in Example 2.
2o Table II shows various resins that either were made into films or might have been candidates for film makins;, based solely on the Vicat softening point.
;However, as experience was gained, the resin's eactrudability, its melting point and the splitting or stress crack resistance of a film became of critical concern. Within these parameters, only a few of the films produced met all the requirements, specifically the film of Example 1 and the film of Example 2, EMB-5~ I . The EMB-540 film was marginal due to elevated melting point. Several resins are identified in Table II
that were not made into film. However, films made from these polymers would be *trade-mark expected to have similar, if not equal properties to the bulk resin, such as Vicat softening point and melting point. The results shown on this table would indicate that based in Vicat softening point alone, all of the polymers or films made therefrom would .be of interest for bale wrap or compound ingredient bags.
However, experience itas shown that the Attane~ product (XU61 S 12.13, Dow Chemical Company) would be only marginally acceptable in film form (without any additives to lower the melting point), due to the relatively high melting point.
Even as mentioned above, the EMB-540 has marginal performance again, due to a higher than desirable malting point.
to *trade-mark TABLE I
XE:MB-551 FILM
(Example 2) PHYSICAL PROPERTIES
TARGET GAUGE (microns) 38 44 SO
ACTUAL GAUGE (microns) 37 45 51 COF 0.090 0.115 0.130 MD ULTIMATE TENSILE (grams) 3287 4006 4445 TD ULTIMATE TENSI1:.E {grams)2768 3022 4072 MD ELONGATION (%) 541 56'7 558 TD ELONGATION (%) 623 592 651 MD TENSILE at 10% (grams) 375 461 472 TD TENSILE at 10% (grams) 321 416 472 d o ~ a~
z z w c o z z ~.
z z z v a r I a a :.
b a E.a., p°, U
o~'ooooorr~ rr C .~
G
a>
C~
G
O ~ r. w r. ~n w ~n ~l ~ V~' v p ~ C'~', ~' ~C.
8 ~ ~ ~ w ~ ~ ~ w c x.6'0 w c~c'~aa ~~, ~~ ~~ o > .-.
U V U
o ~ N ~' 0 0 orb a ~a ~~ ~
>
> ~ N ~'L~'' ~ O O t0'7 O °n ° M O W O ~O
o ~ ~ y O ~' O N v ~ t~
p, W A ~' ap ~ vi v .C O .a ~e~
M a ~ ~ 0~0 C o ~ cV ~ O ~~ ~ > O rR
w v + ~ ~ ~ ~ N ~ v n.~ a a d z v 1F + ~ .~ N
~B~TITUTE SHEET (RULE 26~
TABLE III
SP NG PERFORMANCE
Film of Example 2 used to Wrap Butyl Rubber Bales:
Film Thickness (microns) v8 44 50 to Days A~in~ 8 12 8 12 8 12 Bale Packout Temperature 62.5°C no ____ ____ ____ 68°C no ____ ___ no no - ____ 64.5°C ____ ____ ____ ____ no ____ 70.5°C ____ ____ ____ ____ ____ no ---- not tested All bales shown in Table III were loaded at the temperatures shown at a commercial facility at commercial conditions. Nearly 40% of all bags at all 2o temperatures had no tears. The remaining 60% had minor tears attributable to impact or abrasion, but none due to cold flow splitting.
As shown in Table II, films were nnade from a 0.3 MI, 6% VA (EMB-540) had occasional splitting and stress cracks after storage. However, due to a slightly high Vicat and melting point, an improvement was sought. An EVA with a higher MI and a higher VA content would have lower Vicat softening point and lower the melting point properties.
PCTlUS94t11126 The XEMB-547 and the EMB-547-E were made from resins with 2MI, 9% VA
and 2.5 MI and 8.5% VA respectively, but both exhibited unacceptable splits and stress cracking. Another attempt to achieve the correct balance of properties was EMB-549 (0.4 MI, 13.3% VA). This film provided the proper Vicat and melting point, but again showed poor split and stress crack resistance and poor extrudability. The film of the present invention showed the best combination of properties.
Table III contains further data on whether splits or stress cracking in the film were observed during storage under conditions (number of days and temperature) such shown in Table III for 3 different film thicknesses of the film of Example 2.
Table III shows the film as produced in Example 2, in three thicknesses, where the film was used to package bales of butyl rubber, stored for from 8 to I2 days.
Bale temperatures at loading, ranging from about 62.5°C to 70.5°C, were noted as the loading temperature will have an effect on the creep and cold flow of the rubber, the creep and cold flow are contributing elements to splitting and stress cracking.
The film of the present invention for use as rubber bale wrap and compounding bags may be made from a single ethylene copolymer or terpolymer, or a blend of such ethylene copolymer with other ethylene copolymers, or with ethylene homopoiymers.
In an embodiment of the present invention, a film is made for either bale wrapping to or for making compounding bags. 1(n either case, the film must have softening and melting characteristics that permit its inclusion into the rubber compounding process, and such inclusion wilt result in a substantially homogeneous compounded eiastomer blend.
The film may be made from an ethylene a-olefin copolymer or terpoIymer (first ethylene polymer). This first ethylene polymer has a density in the range of from about 0.85 to about 0.915 g/cm~, a Vicat softening point. less than about 100°C
and a differential scanninc; calorimeter (DSC) second melting point (melting point) not exceeding about I20°C. The a.-olefin utilized to make first ethylene polymer is 2o selected from propylene-:L, butene-1, pentene-1, hexene-l, octene-1 and decene-1.
The a-olefin or a-olefins incorporation will be in the range of from about 0.2 to about 20 mole percent, based on the i:otal moles of the copolymer or terpolymer. The first ethylene copolymer has a CDBI exceeding 50 % , preferably exceeding 65 %
. The first ethylene copolymer has a molecular weight distribution as determined by weight average molecular weight divided by number l~~y~0 average molecular wei;;ht (Mw/Nln) not exceeding 3.0, preferably not exceeding 2.5, more preferably not exceeding 2.8.
Preferably, the film made from the first ethylene polymer has a Vicat softening point in the range of from about 10°C to about 90°C and a melting point of from about 30°C to about 110°C. More preferably, the film made from the first ethylene polymer has a Vicat softening point in the range of from about 25°C to about 82°C
and a DSC melting point in the range of from about 50°C to about 100°C.
The first ethylene polymer may be made by a number of processes, including high pressure, low pressure. gas phase, fluidized bed, slurry or solution processes.
Where free radical polymerization is not used, the catalysts used for the polymerization are generally of the metallocene-alumoxane, or metallocene-ionic activator types, although metallocene-alumoxane catalysts are preferred. Such catalysts are well known. Thus, useful catalysts are those disclosed in EP
129368, U. S. Patents numbers 5,026,798 and 5,198,401.
Optionally, a second e~:hylene polymer may be blended into the first ethylene polymer. The second ethylene polymer is preferably not used for depressing either 2o the Vicat softening point or the melting point of the first ethylene polymer, although such depression is not precluded. The main purpose of the second ethylene polymer is to improve melt processability (reduced neck-in and higher melt strength) of the blend over the processability of the first ethylene polymer alone. The second ethylene polymer is generally a molecule containing long chain branching. Long chain branching is defined herein as a chain length of at least 6 carbon atoms, above 6 carbon atones the length cannot be determined using 13C
nuclear magnetic resonance spectroscopy (NMIg). The long chain branch can ' W O 95!09199 PCT/US9dl1 I 126 ~ I~ ~~~~~
contain as many carbon atoms as the polymer back-bone. Long chain branching is determined using 13C ~~SR and is quantified using the method of Randall (Rev.
Macromol. Chem. Phi, C29 (2 and 3), pages 285-297. fVhereas the first ethylene . polymer contains less lc>ng chain branches. Generally, the fewer the long chain 5 branches, the more difficult the resin is to melt process. Difficulty in processing can be manifested by bubble instability in blown film and draw resonance, surging andlor neck-in in cast films.
to In another embodiment of the presem invention, the second ethylene polymer is a polyethylene homopolymer or preferably an ethylene copolymer of ethylene and an ethylenicaliy unsaturated carboxylic acid ester. Preferred ethylenically unsaturated acrylic acid esters include, for example, vinyl acetate, methyl acrylate, butyl acrylate, and ethyl acryl<ite. A most preferred ester monomer is vinyl acetate.
These comonomers are present in the second ethylene polymer within a range of from 1 to 35 weight percent, preferably from I to I S weight percent of the unsaturated acrylic acid ester, based on the total weight of the second ethylene polymer.
The second ethylene pohrmers are chosen , in general, primarily based on their ability to enhance proces,sability of the first ethylene polymer and their melting points and/or Vicat softening points. That is, the melting points and/or Vicat softening points of such polymers should not have a substantial deleterious effect on these same parameters of the first ethylene polymer, and the film made therefrom at the level of inclusion in the blends, but will mitigate processing debits of the first ethylene polymer. In general, a 10% improvement in bubble stability or neck-in would be desirable:.
WO 95!09199 PCT/US94111126 11 21129~~
When the second ethylene polymer is included in the manufacture of film, it is present in the range of from about 25 to about 1 weight percent based on the total weight of the blend. 'The first ethylene polymer is present in the range of from about 75 to about 99 weight percent, based on the total weight of the blend.
In the preferred embodiment, the first ethylene polymer is present in the range of from about 85 weight percent to about 95 weight percent based on the total weight of the blend. The second ethylene polymer is present in the range of from 1o about 15 to about 5 weight percent based on the total weight of the blend.
More preferably the second ethylene copolymer is present in the blend at less than 10%, preferably less than 8 weight percent. Also the second copolymer may be present above 10 weight percent, preferably more than 12 weight percent.
It should be understood that the first ethylene polymer may be used for film manufacture without the use of the second ethylene polymer. However, in either the case where the first ethylene polymer is used alone, or in the case where it is blended with the second ethylene polymer, it is understood that the Vicat softening point of the resulting fiIrn does not exceed I 00°C, and the melting point of the film 2o does not exceed 120°C. Preferably, the film made from the blend has a Vicat softening point in the rzmge of from about IO,aC to about 100r~C, and a melting point of from about 30°C to about 110°C. More preferably, the film has a Vicat softening point in the range of from about 25°C to about 82°C, and a melting point in the range of from about 50°C to about 100°C.
It should be further understood: that additives often found in films are contemplated by our invE:ntion as well. Such additives will be understood by those WO 95!09199 PCTIUS94111126 ~17~.980 skilled in the art to include those that will have an effect on surface characteristics of films, processability of resins being made into films, and thermal stability of resins or film. These, and other types of additives, are normally carried in polyolefins, but may be added without such polyolefin earners. The additive types mentioned are not meant to be a cornpiete list, but merely illustrative.
In the practice of this invention, the rubber is compounded utilizing a mechanical mixer. The compounded rubber ca.n include mixed unvulcanized rubber with the bale wrap and/or a compounding ingredient bag film of this invention. The to compounded rubber can also include accelerators, promoters, curing or crosslinking agents, filter:>, colorants, anti-oxidants, and other adjuvants.
Both the rubbers and additives are well known. See for instance, U. S. Patents 4,394,473; 5,145,747; and 4,848,564.
Example 1:
A film was made using a~ siip and anti-block master batch (AMPACET
50568), manufactured by Ampacet Corporation containing 5 weight percent slip and 20 weight percent anti-block, and the remaining 75 weight percent is a 0.3 MI
2o ethylene vinyl acetate copolymer film grade polyethylene resin containing 6 weight percent vinyl acetate. The master batch was added to Exactj~" 3027 (a 3.5 melt index, 0.900 density, et:hyiene butene copolymer polyethylene available from Exxon Chemical Company having a nominal Mw/Mn of 2 and nominal CDBI of 90%} at a 2 weight percent level based on the total weight of the blend. This resulted in a total slip and anti-block Levels of 1,000 parts per million (ppm) and 4,000 ppm, respectively.
*trade-mark WO 95/09199 PCTIUS94l11I26 ~ 1 T~98~
The film was prepared on a Black Clawson~cast film extrusion line run in an embossed mode. The oF~eratin~ rate was 22.8 meters per minute of film. The resin showed a tendency to neck-in, in the range of 35 to 40 cm out of a fatal die length of 91 cm. While the neck-in was significant, a commercial film could be made.
The film would have a Vicat softening point of 76°C and a melting point of 92°C.
Example 2:
A second run was accomplished as disclosed in Example 1. The second run was made using 88 weight percent E~s:ACTT"" 3027 low density polyethylene from 1o Exxon Chemical Company, 2 weight percent Ampacet 50568 and 10 weight percent of a 0.31 MI, 6 weight percent vinyl acetate EVA copolymer Escorene LD-317.09 (available from Exxon Chemical Company). The neck-in for this blend was ~ - 10 cm. Three. different film thicknesses were produced nominal 50 microns, 44 microns, and 38 microns. The Vicat softening point of the film was °C, the melting point was 9I °C.
Table I shows the physical properties of the three films thicknesses produced in Example 2.
2o Table II shows various resins that either were made into films or might have been candidates for film makins;, based solely on the Vicat softening point.
;However, as experience was gained, the resin's eactrudability, its melting point and the splitting or stress crack resistance of a film became of critical concern. Within these parameters, only a few of the films produced met all the requirements, specifically the film of Example 1 and the film of Example 2, EMB-5~ I . The EMB-540 film was marginal due to elevated melting point. Several resins are identified in Table II
that were not made into film. However, films made from these polymers would be *trade-mark expected to have similar, if not equal properties to the bulk resin, such as Vicat softening point and melting point. The results shown on this table would indicate that based in Vicat softening point alone, all of the polymers or films made therefrom would .be of interest for bale wrap or compound ingredient bags.
However, experience itas shown that the Attane~ product (XU61 S 12.13, Dow Chemical Company) would be only marginally acceptable in film form (without any additives to lower the melting point), due to the relatively high melting point.
Even as mentioned above, the EMB-540 has marginal performance again, due to a higher than desirable malting point.
to *trade-mark TABLE I
XE:MB-551 FILM
(Example 2) PHYSICAL PROPERTIES
TARGET GAUGE (microns) 38 44 SO
ACTUAL GAUGE (microns) 37 45 51 COF 0.090 0.115 0.130 MD ULTIMATE TENSILE (grams) 3287 4006 4445 TD ULTIMATE TENSI1:.E {grams)2768 3022 4072 MD ELONGATION (%) 541 56'7 558 TD ELONGATION (%) 623 592 651 MD TENSILE at 10% (grams) 375 461 472 TD TENSILE at 10% (grams) 321 416 472 d o ~ a~
z z w c o z z ~.
z z z v a r I a a :.
b a E.a., p°, U
o~'ooooorr~ rr C .~
G
a>
C~
G
O ~ r. w r. ~n w ~n ~l ~ V~' v p ~ C'~', ~' ~C.
8 ~ ~ ~ w ~ ~ ~ w c x.6'0 w c~c'~aa ~~, ~~ ~~ o > .-.
U V U
o ~ N ~' 0 0 orb a ~a ~~ ~
>
> ~ N ~'L~'' ~ O O t0'7 O °n ° M O W O ~O
o ~ ~ y O ~' O N v ~ t~
p, W A ~' ap ~ vi v .C O .a ~e~
M a ~ ~ 0~0 C o ~ cV ~ O ~~ ~ > O rR
w v + ~ ~ ~ ~ N ~ v n.~ a a d z v 1F + ~ .~ N
~B~TITUTE SHEET (RULE 26~
TABLE III
SP NG PERFORMANCE
Film of Example 2 used to Wrap Butyl Rubber Bales:
Film Thickness (microns) v8 44 50 to Days A~in~ 8 12 8 12 8 12 Bale Packout Temperature 62.5°C no ____ ____ ____ 68°C no ____ ___ no no - ____ 64.5°C ____ ____ ____ ____ no ____ 70.5°C ____ ____ ____ ____ ____ no ---- not tested All bales shown in Table III were loaded at the temperatures shown at a commercial facility at commercial conditions. Nearly 40% of all bags at all 2o temperatures had no tears. The remaining 60% had minor tears attributable to impact or abrasion, but none due to cold flow splitting.
As shown in Table II, films were nnade from a 0.3 MI, 6% VA (EMB-540) had occasional splitting and stress cracks after storage. However, due to a slightly high Vicat and melting point, an improvement was sought. An EVA with a higher MI and a higher VA content would have lower Vicat softening point and lower the melting point properties.
PCTlUS94t11126 The XEMB-547 and the EMB-547-E were made from resins with 2MI, 9% VA
and 2.5 MI and 8.5% VA respectively, but both exhibited unacceptable splits and stress cracking. Another attempt to achieve the correct balance of properties was EMB-549 (0.4 MI, 13.3% VA). This film provided the proper Vicat and melting point, but again showed poor split and stress crack resistance and poor extrudability. The film of the present invention showed the best combination of properties.
Table III contains further data on whether splits or stress cracking in the film were observed during storage under conditions (number of days and temperature) such shown in Table III for 3 different film thicknesses of the film of Example 2.
Table III shows the film as produced in Example 2, in three thicknesses, where the film was used to package bales of butyl rubber, stored for from 8 to I2 days.
Bale temperatures at loading, ranging from about 62.5°C to 70.5°C, were noted as the loading temperature will have an effect on the creep and cold flow of the rubber, the creep and cold flow are contributing elements to splitting and stress cracking.
Claims (11)
1. A rubber bale wrap film having at least one layer comprising a polymer blend, said polymer blend having:
a) a first ethylene copolymer present in the range of from about 75 to about 99 weight percent, said percentage based on the total polymer blend weight wherein said first ethylene copolymer is formed in the presence of a metallocene-alumoxane catalyst, said first ethylene copolymer being an ethylene-.alpha.-olefin copolymer, wherein said first ethylene copolymer has a density in the range of from about 0.85 to about 0.915 g/cm.3, said first ethylene copolymer having a Vicat softening point less than about 100°C., said first ethylene copolymer having a melting point not exceeding about 120°C, said .alpha.-olefin being selected from the group consisting of propylene-1, butene-1, pentene-1, hexene-1, octene-1 and decene-1; and b) a second ethylene copolymer, containing long chain branching, present in the range of from about 1 to about 25 weight percent based on the total weight of the polymer blend, said second ethylene copolymer having in the range of from about 65 to about 99 weight percent of ethylene and in the range of from about 1 to about 35 weight percent of an ethylenically unsaturated acrylic acid ester based on the total weight of the second ethylene copolymer, wherein said polymer blend has a Vicat softening point in the range of from about 10°C. to about 90°C. and a melting point in the range of from about 30°C. to about 110°C.
a) a first ethylene copolymer present in the range of from about 75 to about 99 weight percent, said percentage based on the total polymer blend weight wherein said first ethylene copolymer is formed in the presence of a metallocene-alumoxane catalyst, said first ethylene copolymer being an ethylene-.alpha.-olefin copolymer, wherein said first ethylene copolymer has a density in the range of from about 0.85 to about 0.915 g/cm.3, said first ethylene copolymer having a Vicat softening point less than about 100°C., said first ethylene copolymer having a melting point not exceeding about 120°C, said .alpha.-olefin being selected from the group consisting of propylene-1, butene-1, pentene-1, hexene-1, octene-1 and decene-1; and b) a second ethylene copolymer, containing long chain branching, present in the range of from about 1 to about 25 weight percent based on the total weight of the polymer blend, said second ethylene copolymer having in the range of from about 65 to about 99 weight percent of ethylene and in the range of from about 1 to about 35 weight percent of an ethylenically unsaturated acrylic acid ester based on the total weight of the second ethylene copolymer, wherein said polymer blend has a Vicat softening point in the range of from about 10°C. to about 90°C. and a melting point in the range of from about 30°C. to about 110°C.
2. The rubber bale wrap film as recited in claim 1 wherein said ethylenically unsaturated acrylic acid ester is selected from the group consisting of methyl acrylate, butyl acrylate, and ethyl acrylate.
3. The rubber bale wrap film as recited in claim 1, wherein said polymer blend has a Vicat softening point in the range of from about 25°C. to about 82°C, and a DSC second melting peak in the range of from about 50°C. to about 100°C.
4. A rubber bale wrapped with the rubber bale wrap film of claim 1.
5. A rubber bale wrap film having at least one layer comprising a polymer blend, said polymer blend having:
a) a first ethylene copolymer present in the range of from about 75 to about 99 weight percent, said percentage based on the total polymer blend weight, wherein said first ethylene copolymer is formed in the presence of a metallocene-alumoxane catalyst, said first ethylene copolymer being an ethylene-.alpha.-olefin copolymer, wherein said first ethylene copolymer has a density in the range of from about 0.85 to about 0.915 g/cm.3, said first ethylene copolymer having a Vicat softening point less than about 100°C., said first ethylene copolymer having a melting point not exceeding about 120°C., said .alpha.-olefin being selected from the group consisting of propylene-1, butene-1, pentene-1, hexene-1, octene-1 and decene-1; and b) a second ethylene copolymer, containing long chain branching, present in the range of from about 1 to about 25 percent by weight based on the total weight of the polymer blend, said second ethylene copolymer having in the range of from about 65 to about 99 weight percent of ethylene and in the range of from about 1 to about 35 weight percent of vinyl acetate based on the total weight of the second ethylene copolymer, wherein said polymer blend has a Vicat softening point in the range of from about 10°C. to about 90°C. and a melting point in the range of from about 30°C. to about 110°C.
a) a first ethylene copolymer present in the range of from about 75 to about 99 weight percent, said percentage based on the total polymer blend weight, wherein said first ethylene copolymer is formed in the presence of a metallocene-alumoxane catalyst, said first ethylene copolymer being an ethylene-.alpha.-olefin copolymer, wherein said first ethylene copolymer has a density in the range of from about 0.85 to about 0.915 g/cm.3, said first ethylene copolymer having a Vicat softening point less than about 100°C., said first ethylene copolymer having a melting point not exceeding about 120°C., said .alpha.-olefin being selected from the group consisting of propylene-1, butene-1, pentene-1, hexene-1, octene-1 and decene-1; and b) a second ethylene copolymer, containing long chain branching, present in the range of from about 1 to about 25 percent by weight based on the total weight of the polymer blend, said second ethylene copolymer having in the range of from about 65 to about 99 weight percent of ethylene and in the range of from about 1 to about 35 weight percent of vinyl acetate based on the total weight of the second ethylene copolymer, wherein said polymer blend has a Vicat softening point in the range of from about 10°C. to about 90°C. and a melting point in the range of from about 30°C. to about 110°C.
6. A compounding bag comprising a film made from a polymer blend, said polymer blend having:
a) a first ethylene copolymer present in the range of from about 75 to about 99 weight percent, said percentage based on the total polymer blend weight, wherein said first ethylene copolymer is formed in the presence of a metallocene-alumoxane catalyst, said first ethylene copolymer being an ethylene-.alpha.-olefin copolymer, wherein said first ethylene copolymer has a density in the range of from about 0.85 to about 0.915 g/cm.3, said first ethylene copolymer having a Vicat softening point less than about 100°C., said first ethylene copolymer having a melting point not exceeding about 120°C., said .alpha.-olefin being selected from the group consisting of propylene-1, butene-1, pentene-1, hexene-1, octene-1 and decene-1; and b) a second ethylene copolymer, containing long chain branching, present in the range of from about 1 to about 25 weight percent based on the total weight of the polymer blend, said second ethylene copolymer having in the range of from about 65 to about 99 weight percent of ethylene and in the range of from about 1 to about 35 weight percent of an ethylenically unsaturated acrylic acid ester based on the total weight of the second ethylene copolymer, wherein said polymer blend has a Vicat softening point in the range of from about 10°C. to about 90°C. and a melting point in the range of from about 30°C. to about 110°C.
a) a first ethylene copolymer present in the range of from about 75 to about 99 weight percent, said percentage based on the total polymer blend weight, wherein said first ethylene copolymer is formed in the presence of a metallocene-alumoxane catalyst, said first ethylene copolymer being an ethylene-.alpha.-olefin copolymer, wherein said first ethylene copolymer has a density in the range of from about 0.85 to about 0.915 g/cm.3, said first ethylene copolymer having a Vicat softening point less than about 100°C., said first ethylene copolymer having a melting point not exceeding about 120°C., said .alpha.-olefin being selected from the group consisting of propylene-1, butene-1, pentene-1, hexene-1, octene-1 and decene-1; and b) a second ethylene copolymer, containing long chain branching, present in the range of from about 1 to about 25 weight percent based on the total weight of the polymer blend, said second ethylene copolymer having in the range of from about 65 to about 99 weight percent of ethylene and in the range of from about 1 to about 35 weight percent of an ethylenically unsaturated acrylic acid ester based on the total weight of the second ethylene copolymer, wherein said polymer blend has a Vicat softening point in the range of from about 10°C. to about 90°C. and a melting point in the range of from about 30°C. to about 110°C.
7. A compounding bag as recited in claim 6, wherein said ethylenically unsaturated acrylic acid ester is selected from the group consisting of methyl acrylate, butyl acrylate, and ethyl acrylate.
8. A compounding bag comprising a film made from a polymer blend, said polymer blend having:
a) a first ethylene copolymer present in the range of from about 75 to about 99 weight percent, said percentage based on the total polymer blend weight, wherein said first ethylene copolymer is formed in the presence of a metallocene-alumoxane catalyst, said first ethylene copolymer being an ethylene-.alpha.-olefin copolymer, wherein said first ethylene copolymer has a density in the range of from about 0.85 to about 0.91 g/cm.3, said first ethylene copolymer having a Vicat softening point less than about 100°C., said first ethylene copolymer having a melting point not exceeding about 120°C., said .alpha.-olefin being selected from the group consisting of propylene-1, butene-1, pentene-1, hexene-1, octene-1 and decene-1; and b) a second ethylene copolymer, containing long chain branching, present in the range of from about 1 to about 25 weight percent based on the total weight of the polymer blend, said second ethylene copolymer having in the range of from about 65 to about 99 weight percent of ethylene and in the range of from about 1 to about 35 weight percent of vinyl acetate based on the total weight of the second ethylene copolymer, wherein said polymer blend has a Vicat softening point in the range of from about 10°C. to about 90°C. and a melting point in the range of from about 30°C. to about 110°C.
a) a first ethylene copolymer present in the range of from about 75 to about 99 weight percent, said percentage based on the total polymer blend weight, wherein said first ethylene copolymer is formed in the presence of a metallocene-alumoxane catalyst, said first ethylene copolymer being an ethylene-.alpha.-olefin copolymer, wherein said first ethylene copolymer has a density in the range of from about 0.85 to about 0.91 g/cm.3, said first ethylene copolymer having a Vicat softening point less than about 100°C., said first ethylene copolymer having a melting point not exceeding about 120°C., said .alpha.-olefin being selected from the group consisting of propylene-1, butene-1, pentene-1, hexene-1, octene-1 and decene-1; and b) a second ethylene copolymer, containing long chain branching, present in the range of from about 1 to about 25 weight percent based on the total weight of the polymer blend, said second ethylene copolymer having in the range of from about 65 to about 99 weight percent of ethylene and in the range of from about 1 to about 35 weight percent of vinyl acetate based on the total weight of the second ethylene copolymer, wherein said polymer blend has a Vicat softening point in the range of from about 10°C. to about 90°C. and a melting point in the range of from about 30°C. to about 110°C.
9. A package comprising:
a) an article selected from the group consisting of an unvulcanized rubber, a vulcanized rubber, compounding ingredients for unvulcanized rubber, and combinations thereof wherein said article is covered with and in contact with a film;
b) said film made from a polymer blend, said polymer blend having:
i) a first ethylene copolymer present in the range of from about 75 to about weight percent, said percentage based on the total polymer blend weight, said first ethylene copolymer being an ethylene-.alpha.-olefin copolymer, wherein said first ethylene copolymer has a density in the range of from about 0.85 to about 0.915 g/cm.3, said first ethylene copolymer having a Vicat softening point less than about 100°C., said first ethylene copolymer having a melting point not exceeding about 120°C., said .alpha.-olefin being selected from the group consisting of propylene-1, butene-1, pentene-1, hexene-1, octene-1 and decene-1; and ii) a second ethylene copolymer, containing long chain branching, present in the range of from about 1 to about 25 weight percent based on the total weight of the polymer blend, said ethylene copolymer having in the range of from about 65 to about 99 weight percent of ethylene and in the range of from about 1 to about 35 weight percent of an ethylenically unsaturated acrylic acid ester based on the total weight of the second ethylene copolymer, wherein said polymer blend has a Vicat softening point in the range of from about 10°C. to about 90°C. and a melting point in the range of from about 30°C. to about 110°C.
a) an article selected from the group consisting of an unvulcanized rubber, a vulcanized rubber, compounding ingredients for unvulcanized rubber, and combinations thereof wherein said article is covered with and in contact with a film;
b) said film made from a polymer blend, said polymer blend having:
i) a first ethylene copolymer present in the range of from about 75 to about weight percent, said percentage based on the total polymer blend weight, said first ethylene copolymer being an ethylene-.alpha.-olefin copolymer, wherein said first ethylene copolymer has a density in the range of from about 0.85 to about 0.915 g/cm.3, said first ethylene copolymer having a Vicat softening point less than about 100°C., said first ethylene copolymer having a melting point not exceeding about 120°C., said .alpha.-olefin being selected from the group consisting of propylene-1, butene-1, pentene-1, hexene-1, octene-1 and decene-1; and ii) a second ethylene copolymer, containing long chain branching, present in the range of from about 1 to about 25 weight percent based on the total weight of the polymer blend, said ethylene copolymer having in the range of from about 65 to about 99 weight percent of ethylene and in the range of from about 1 to about 35 weight percent of an ethylenically unsaturated acrylic acid ester based on the total weight of the second ethylene copolymer, wherein said polymer blend has a Vicat softening point in the range of from about 10°C. to about 90°C. and a melting point in the range of from about 30°C. to about 110°C.
10. The package as recited in claim 9, wherein said ethylenically unsaturated acrylic acid ester is selected from the group consisting of methyl acrylate, butyl acrylate, and ethyl acrylate.
11. A package comprising:
a) an article selected from the group consisting of an unvulcanized rubber, a vulcanized rubber, compounding ingredients for unvulcanized rubber, and combinations thereof wherein said article is covered with and in contact with a film; and said film being made from a polymer blend having:
i) a first ethylene copolymer present in the range of from about 75 to about weight percent, said percentage based on the total polymer blend weight, said first ethylene copolymer being an ethylene-.alpha.-olefin copolymer, wherein said first ethylene copolymer has a density in the range of from about 0.85 to about 0.915 g/cm.3, said first ethylene copolymer having a Vicat softening point less than about 100°C., said first ethylene copolymer having a melting point not exceeding about 120°C., said alpha-olefin being selected from the group consisting of propylene-1, butene-1, pentene-1, hexene-1, octene-1 and decene-1; and ii) a second ethylene copolymer, containing long chain branching, present in the range of from about 1 to about 25 weight percent based on the total weight of the polymer blend, said ethylene copolymer having in the range of from about 65 to about 99 weight percent of ethylene and in the range of from about 1 to about 35 weight percent of vinyl acetate based on the total weight of the second ethylene copolymer, wherein said polymer blend has a Vicat softening point in the range of from about 10°C. to about 90°C. and a melting point in the range of from about 30°C. to about 110°C.
a) an article selected from the group consisting of an unvulcanized rubber, a vulcanized rubber, compounding ingredients for unvulcanized rubber, and combinations thereof wherein said article is covered with and in contact with a film; and said film being made from a polymer blend having:
i) a first ethylene copolymer present in the range of from about 75 to about weight percent, said percentage based on the total polymer blend weight, said first ethylene copolymer being an ethylene-.alpha.-olefin copolymer, wherein said first ethylene copolymer has a density in the range of from about 0.85 to about 0.915 g/cm.3, said first ethylene copolymer having a Vicat softening point less than about 100°C., said first ethylene copolymer having a melting point not exceeding about 120°C., said alpha-olefin being selected from the group consisting of propylene-1, butene-1, pentene-1, hexene-1, octene-1 and decene-1; and ii) a second ethylene copolymer, containing long chain branching, present in the range of from about 1 to about 25 weight percent based on the total weight of the polymer blend, said ethylene copolymer having in the range of from about 65 to about 99 weight percent of ethylene and in the range of from about 1 to about 35 weight percent of vinyl acetate based on the total weight of the second ethylene copolymer, wherein said polymer blend has a Vicat softening point in the range of from about 10°C. to about 90°C. and a melting point in the range of from about 30°C. to about 110°C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/128,927 US5415905A (en) | 1993-09-29 | 1993-09-29 | Dispersible film |
| US128,927 | 1993-09-29 | ||
| PCT/US1994/011126 WO1995009199A1 (en) | 1993-09-29 | 1994-09-29 | Dispersible film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2172980A1 CA2172980A1 (en) | 1995-04-06 |
| CA2172980C true CA2172980C (en) | 2002-03-26 |
Family
ID=22437658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002172980A Expired - Fee Related CA2172980C (en) | 1993-09-29 | 1994-09-29 | Dispersible film |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US5415905A (en) |
| EP (1) | EP0721481B1 (en) |
| AU (1) | AU7925294A (en) |
| BR (1) | BR9407684A (en) |
| CA (1) | CA2172980C (en) |
| DE (1) | DE69429273T2 (en) |
| WO (1) | WO1995009199A1 (en) |
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| JP3372130B2 (en) * | 1995-05-12 | 2003-01-27 | 三井化学株式会社 | Rubber wrapping film and rubber veil |
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| CA2208690A1 (en) * | 1996-09-06 | 1998-03-06 | James Robert Mccandless | Package for compounding rubber, compounded rubber and tire having tread thereof |
| US6297326B1 (en) | 1996-10-18 | 2001-10-02 | Kimberly-Clark Corporation | Grafted polyolefin compositions |
| US6107405A (en) * | 1996-10-18 | 2000-08-22 | Kimberly Clark Corporation | Method of making grafted polyolefin compositions |
| US5916969A (en) * | 1996-11-22 | 1999-06-29 | Kimberly-Clark Corporation | Article and composition of matter made from polyolefins and PEO blend and method of making the same |
| CN1239973A (en) * | 1996-12-05 | 1999-12-29 | 埃克森化学专利公司 | Dispersible film |
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| US5912076A (en) | 1996-12-31 | 1999-06-15 | Kimberly-Clark Worldwide, Inc. | Blends of polyethylene and peo having inverse phase morphology and method of making the blends |
| US6153700A (en) * | 1996-12-31 | 2000-11-28 | Kimberly-Clark Worldwide, Inc. | Water-degradable flushable film of polyolefin and poly(ethylene oxide) and personal care article therewith |
| US6063866A (en) * | 1996-12-31 | 2000-05-16 | Kimberly-Clark Worldwide, Inc. | Blends of polyolefin and poly(ethylene oxide) and process for making the blends |
| US5700872A (en) * | 1996-12-31 | 1997-12-23 | Kimberly Clark Worlwide, Inc. | Process for making blends of polyolefin and poly(ethylene oxide) |
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| US6111014A (en) | 1996-12-31 | 2000-08-29 | Kimberly-Clark Worldwide, Inc. | Film of monomer-grafted polyolefin and poly(ethylene oxide) |
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| US6117947A (en) * | 1997-12-31 | 2000-09-12 | Kimberly-Clark Worldwide, Inc. | Method of modifying poly(ethylene oxide) |
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| US6777046B1 (en) | 1998-07-07 | 2004-08-17 | Curwood, Inc. | Puncture resistant, high shrink films, blends, and process |
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| AU2377700A (en) * | 1998-12-29 | 2000-07-31 | Kimberly-Clark Worldwide, Inc. | Heat-activated adhesives |
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| US6576576B1 (en) | 1999-12-29 | 2003-06-10 | Kimberly-Clark Worldwide, Inc. | Multicomponent fibers |
| AU2001243509A1 (en) * | 2000-03-17 | 2001-10-03 | Tredegar Film Products Corporation | Co-extruded bale wrap |
| US6610793B1 (en) | 2000-05-26 | 2003-08-26 | Kimberly-Clark Worldwide, Inc. | Modified poly(ethylene oxide), method of making same and articles using same |
| US6790519B1 (en) | 2000-05-26 | 2004-09-14 | Kimberly-Clark Worldwide, Inc. | Moisture-induced poly(ethylene oxide) gel, method of making same and articles using same |
| US6607819B2 (en) | 2000-12-28 | 2003-08-19 | Kimberly-Clark Worldwide, Inc. | Polymer/dispersed modifier compositions |
| US6403706B1 (en) | 2000-12-28 | 2002-06-11 | Kimberly-Clark Worldwide, Inc. | Methods of making polymer/dispersed modifier compositions |
| US6515075B1 (en) | 2001-07-12 | 2003-02-04 | Kimberly-Clark Worldwide, Inc. | Films, fibers and articles of chemically modified polyethylene oxide compositions with improved environmental stability and method of making same |
| US7341142B2 (en) * | 2001-11-09 | 2008-03-11 | Cabot Corporation | Elastomer composite materials in low density forms and methods |
| WO2005012604A2 (en) * | 2003-07-31 | 2005-02-10 | Mitsubishi Rayon Co., Ltd. | Carbon fiber bundle, process for producing the same, and thermoplastic resin composition and molded article thereof |
| US20060086455A1 (en) * | 2004-10-27 | 2006-04-27 | Larry Laurenzi | Method of labeling rubber component bags |
| US7439306B2 (en) * | 2004-11-23 | 2008-10-21 | Exxonmobil Chemical Patents Inc. | Polyethylene blends with improved Vicat softening point |
| AR107047A1 (en) | 2015-12-22 | 2018-03-14 | Dow Global Technologies Llc | PACKAGING FILM |
| WO2017221041A1 (en) * | 2016-06-19 | 2017-12-28 | Laskus Przemyslaw Marcin | Knurled multilayer polyolefin films for use as antiadhesive interleaves, as well as process and technological line for manufacturing the same |
| US20230022818A1 (en) * | 2019-12-16 | 2023-01-26 | Sabic Global Technologies B.V. | Multilayer films for packaging rubber bales |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4378067A (en) * | 1981-02-26 | 1983-03-29 | The Goodyear Tire & Rubber Company | Packaged reclaim rubber and compounded rubber prepared therefrom |
| US4394473A (en) * | 1981-10-06 | 1983-07-19 | The Coca-Cola Company | Rubber compounding bags and film made from syndiotactic 1,2-polybutadiene |
| US4430457A (en) * | 1982-05-10 | 1984-02-07 | Cities Service Company | Cling/stretch wrap compositions |
| FR2528055B1 (en) * | 1982-06-03 | 1986-01-24 | Charbonnages Ste Chimique | COMPOSITIONS OF RADICAL POLYETHYLENE AND ETHYLENE / A-OLEFIN COPOLYMERS AND THEIR APPLICATION TO THE MANUFACTURE OF FILMS |
| US4722959A (en) * | 1985-06-25 | 1988-02-02 | Nippon Petrochemicals Co., Ltd. | Flame-retardant olefin polymer composition |
| US5051297A (en) * | 1986-04-25 | 1991-09-24 | Rexene Products Company | Novel film compositions |
| EP0342822A3 (en) * | 1988-05-17 | 1991-11-13 | Exxon Chemical Patents Inc. | Synthetic rubber bale wrap |
| US4848564A (en) * | 1988-06-07 | 1989-07-18 | Exxon Chemical Patents Inc. | Synthetic rubber bale wrap |
| US5032463A (en) * | 1988-07-18 | 1991-07-16 | Viskase Corporation | Very low density polyethylene film from blends |
| EP0385599A3 (en) * | 1989-02-13 | 1992-08-05 | Exxon Chemical Patents Inc. | Film and polymer composition for film |
| US5112696A (en) * | 1989-07-20 | 1992-05-12 | E. I. Du Pont De Nemours And Company | Tough monolayer shrink film for products containing moisture |
| IL92868A0 (en) * | 1989-12-25 | 1990-09-17 | Syfan | Shrink films |
| JPH04142351A (en) * | 1990-10-02 | 1992-05-15 | Mitsui Petrochem Ind Ltd | Ethylene/pentene-1 copolymer composition |
| US5525659A (en) * | 1993-09-08 | 1996-06-11 | The Dow Chemical Company | Batch inclusion packages |
-
1993
- 1993-09-29 US US08/128,927 patent/US5415905A/en not_active Expired - Fee Related
-
1994
- 1994-06-17 US US08/261,550 patent/US5500260A/en not_active Expired - Fee Related
- 1994-09-29 DE DE69429273T patent/DE69429273T2/en not_active Expired - Fee Related
- 1994-09-29 BR BR9407684A patent/BR9407684A/en not_active IP Right Cessation
- 1994-09-29 EP EP94929979A patent/EP0721481B1/en not_active Expired - Lifetime
- 1994-09-29 CA CA002172980A patent/CA2172980C/en not_active Expired - Fee Related
- 1994-09-29 AU AU79252/94A patent/AU7925294A/en not_active Abandoned
- 1994-09-29 WO PCT/US1994/011126 patent/WO1995009199A1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| US5415905A (en) | 1995-05-16 |
| DE69429273D1 (en) | 2002-01-10 |
| EP0721481B1 (en) | 2001-11-28 |
| CA2172980A1 (en) | 1995-04-06 |
| AU7925294A (en) | 1995-04-18 |
| DE69429273T2 (en) | 2002-07-18 |
| US5500260A (en) | 1996-03-19 |
| BR9407684A (en) | 1997-02-04 |
| EP0721481A1 (en) | 1996-07-17 |
| WO1995009199A1 (en) | 1995-04-06 |
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| EEER | Examination request | ||
| MKLA | Lapsed |