CA2391261A1 - Films with improved blocking resistance and surface properties - Google Patents
Films with improved blocking resistance and surface properties Download PDFInfo
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- CA2391261A1 CA2391261A1 CA 2391261 CA2391261A CA2391261A1 CA 2391261 A1 CA2391261 A1 CA 2391261A1 CA 2391261 CA2391261 CA 2391261 CA 2391261 A CA2391261 A CA 2391261A CA 2391261 A1 CA2391261 A1 CA 2391261A1
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- layer
- ethylene
- copolymer
- density polyethylene
- skin
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
- B32B2255/205—Metallic coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/746—Slipping, anti-blocking, low friction
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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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/91—Product with molecular orientation
-
- 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
- Y10T428/31—Surface property or characteristic of web, sheet or block
-
- 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]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
-
- 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
-
- 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
-
- 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
- Y10T428/31928—Ester, halide or nitrile of addition polymer
Abstract
The invention discloses methods of improving blocking resistant properties a nd reducing the coefficient of friction of a multilayer film comprising providi ng at least one layer of an ethylene-propylene impact copolymer having from abo ut 3 % to about 30 % by weight ethylene, wherein said copolymer has no more tha n two peaks in the melting curve within the range from about 110 ~C to about 1 65 ~C, and wherein said layer is non-heat sealable, to a multilayer film having a core layer comprising polypropylene, high density polyethylene (HDPE) or linear low density polyethylene (LLDPE), whereby anti-blocking and coefficie nt of friction characteristics of said film is improved without necessity of adding an antiblock or slip agent.
Description
FILMS WITH IMPROVED BLOCKING RESISTANCE
AND SURFACE PROPERTIES
BACKGROUND OF INVENTION
The invention relates to methods for preparing polymer films. In particular, the invention relates to methods of preparing polymer films with improved blocking resistance and reduced coefficient of friction (COF) without the necessity of adding an antiblock or slip agent.
Two side processable films (i.e. two side treated) allow for diverse functionality. For example, the outside of the film may be metallized, printed or laminated and the inside of the film may have cold seal coating and promotional print. Films which are treated on both sides, either with corona or flame treatment, have been used in the past; however, such films have the tendency to become blocked. This is especially a problem for cavitated films or when one of the surfaces is subsequently metallized since blocking leads to metal pick off and loss of functionality. Blocking manifests itself as, among other things, undesirable adhesion between layers of polymer films. Therefore, such films need to be highly loaded with antiblocks or slip agents to reduce blocking and/or reduce COF.
Antiblocking agents (AB) are additives which are incorporated into the skin layers of films to prevent the surfaces of films from sticking to one another or other surfaces. AB usually are finely divided, solid, infusible materials, such as silica, but can be minerals or waxes. They function by forming minute protruding asperities which maintain separating air spaces so as to interfere with adhesion.
Slip agents are modifiers which act as internal lubricants by exuding to the surface of a polymer film during and after processing; whereby, they lubricate the surface to reduce the COF, and thereby, improve slip characteristics.
It has been standard practice for many years to use AB or slip agents to reduce the COF of the surface of polypropylene films. Thus, blocking of adjacent layers of film on mill rolls is prevented and film can readily be unwound for use or WO 01/36195 PCT/iJS00/30108 for further processing. In the absence of the slip agent, the layer-to-layer COF is so great that smooth unwinding of the film is virtually impossible. Typical slip or antiblock agents are high molecular weight fatty acid amides such as stearamide or oleamide. It has become standard practice in the art to incorporate about 0.1 to 1%, preferably 0.2 to 0.5% by weight of such compounds into polyolefin films as slip agents.
However, there are many disadvantages with using antiblocking and slip agents in films. Plate-out, for example, is an objectionable coating of these agents which forms on converting or end-use equipment. Additionally, these agents may scratch the opposite metal layer in a metallized film which could damage the barrier properties of the film. Moreover, these agents may interfere or destroy the adhesion of metal coatings to films.
Accordingly, it is one of the purposes of this invention, among others, to produce polymer films with improved blocking resistance and surface properties, by providing an economical and relatively uncomplicated method of making polymer films that imparts superior characteristics to the films, without requirement for additives such as antiblock or slip agents.
SUMMARY OF THE INVENTION
The present invention is a method providing a layer of an ethylene-propylene (EP) impact copolymer to multilayer films having a core layer of polypropylene, high density polyethylene (HDPE) or linear low density polyethylene (LLDPE), and a product resulting therefrom. The layer of the EP
impact copolymer has from about 3% to about 30% by weight ethylene, and is non-heat sealable. The EP impact copolymer has no more than two peaks in the melting curve within the range from about 110°C to about 165°C.
The films may be surface treated on one or both skin Layers with flame or Corona treatment. The core layer of these films may be cavitated with a cavitating agent such as polybutylene terephthalate (PBT).
The EP impact copolymer layer can be a skin layer or an intermediate layer of a multilayer film. An intermediate layer can be a tie layer. The EP impact copolymer layer can fiuther include ethylene propylene butylene (EPB) terpolymer or polypropylene or ethylene-propylene random copolymer or propylene butylene propylene copolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE) or high density polyethylene (HDPE) or blends of the aforementioned polymers.
The film can also include a second skin layer which can include high density polyethylene (HDPE) or ethylene propylene butylene (EPB) terpolymer or ethylene-propylene random copolymer or EP impact copolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE) or propylene butene copolymer or polypropylene homopolymer or ethylene-vinyl acetate copolymer (EVA) or ethylene-methyacrylic acid copolymer (EMA) or ethylene-vinyl alcohol copolymer (EVOH) or blends of the aforementioned polymers. An intermediate layer can be interposed between the core layer and the second skin layer. Such an intermediate layer can include polypropylene and from about 1%
to about 15% by weight titanium dioxide. A second intermediate layer can be interposed between the core layer and the EP block copolymer skin layer, and can include polypropylene.
In the embodiment in which the EP impact copolymer layer is an intermediate layer, it is placed adjacent to a skin layer, e.g., interposed between the core layer and a first skin layer. A second intermediate layer can also be interposed between the core layer and a second skin layer, and can include polypropylene or ethylene-propylene impact copolymer. An intermediate layer can be a tie layer.
The skin layers can also include high density polyethylene (HDPE) or ethylene propylene butylene (EPB) terpolymer or ethylene-propylene random copolymer or propylene butylene (PB) copolymer or polypropylene homopolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE) or blends of the aforementioned polymers.
The present invention provides multilayer films with improved anti-blocking and COF characteristics without the necessity of adding an antiblock or slip agent.
This gives the ability to produce sealable clear and cavitated films structures, which are processable on both sides, with outstanding surface properties without the use of additives.
These and other advantages of the present invention will be appreciated from the detailed description and examples which are set forth herein. The detailed description and examples enhance the understanding of the invention, but are not intended to limit the scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the invention have been chosen for purposes of illustration and description, but are not intended in any way to restrict the scope of the invention. The preferred embodiments of certain aspects of the invention are shown in the accompanying drawings, wherein:
FIG. 1 is a graph showing the effect impact copolymer skin layers have on blocking forces of films. The blocking conditions are 140° F, 750 psi for one hour.
1 S FIG. 2 is a graph showing the effect impact copolymer skin layers have on blocking forces of films. The blocking conditions are 125° F, 125 psi for 24 hours.
FIG. 3 is a graph showing the effect of blending the impact copolymer of skin layers with terpolymer or homopolymer polypropylene.
FIG. 4 is a graph showing the effect of blending the impact copolymer of skin layers with terpolymer or homopolymer polypropylene.
FIG. 5 is a graph showing the effect of impact copolymer which is blended into the treated skin resin.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention provides is a method providing a layer of an ethylene-propylene (EP) impact copolymer to multilayer films having a core layer including polypropylene (PP), high density polyethylene (HDPE) or linear low density polyethylene (LLDPE), and a product resulting therefrom. The multilayer films of the present invention can be monoaxially or biaxially oriented. The copolymer layer is non-heat sealable.
AND SURFACE PROPERTIES
BACKGROUND OF INVENTION
The invention relates to methods for preparing polymer films. In particular, the invention relates to methods of preparing polymer films with improved blocking resistance and reduced coefficient of friction (COF) without the necessity of adding an antiblock or slip agent.
Two side processable films (i.e. two side treated) allow for diverse functionality. For example, the outside of the film may be metallized, printed or laminated and the inside of the film may have cold seal coating and promotional print. Films which are treated on both sides, either with corona or flame treatment, have been used in the past; however, such films have the tendency to become blocked. This is especially a problem for cavitated films or when one of the surfaces is subsequently metallized since blocking leads to metal pick off and loss of functionality. Blocking manifests itself as, among other things, undesirable adhesion between layers of polymer films. Therefore, such films need to be highly loaded with antiblocks or slip agents to reduce blocking and/or reduce COF.
Antiblocking agents (AB) are additives which are incorporated into the skin layers of films to prevent the surfaces of films from sticking to one another or other surfaces. AB usually are finely divided, solid, infusible materials, such as silica, but can be minerals or waxes. They function by forming minute protruding asperities which maintain separating air spaces so as to interfere with adhesion.
Slip agents are modifiers which act as internal lubricants by exuding to the surface of a polymer film during and after processing; whereby, they lubricate the surface to reduce the COF, and thereby, improve slip characteristics.
It has been standard practice for many years to use AB or slip agents to reduce the COF of the surface of polypropylene films. Thus, blocking of adjacent layers of film on mill rolls is prevented and film can readily be unwound for use or WO 01/36195 PCT/iJS00/30108 for further processing. In the absence of the slip agent, the layer-to-layer COF is so great that smooth unwinding of the film is virtually impossible. Typical slip or antiblock agents are high molecular weight fatty acid amides such as stearamide or oleamide. It has become standard practice in the art to incorporate about 0.1 to 1%, preferably 0.2 to 0.5% by weight of such compounds into polyolefin films as slip agents.
However, there are many disadvantages with using antiblocking and slip agents in films. Plate-out, for example, is an objectionable coating of these agents which forms on converting or end-use equipment. Additionally, these agents may scratch the opposite metal layer in a metallized film which could damage the barrier properties of the film. Moreover, these agents may interfere or destroy the adhesion of metal coatings to films.
Accordingly, it is one of the purposes of this invention, among others, to produce polymer films with improved blocking resistance and surface properties, by providing an economical and relatively uncomplicated method of making polymer films that imparts superior characteristics to the films, without requirement for additives such as antiblock or slip agents.
SUMMARY OF THE INVENTION
The present invention is a method providing a layer of an ethylene-propylene (EP) impact copolymer to multilayer films having a core layer of polypropylene, high density polyethylene (HDPE) or linear low density polyethylene (LLDPE), and a product resulting therefrom. The layer of the EP
impact copolymer has from about 3% to about 30% by weight ethylene, and is non-heat sealable. The EP impact copolymer has no more than two peaks in the melting curve within the range from about 110°C to about 165°C.
The films may be surface treated on one or both skin Layers with flame or Corona treatment. The core layer of these films may be cavitated with a cavitating agent such as polybutylene terephthalate (PBT).
The EP impact copolymer layer can be a skin layer or an intermediate layer of a multilayer film. An intermediate layer can be a tie layer. The EP impact copolymer layer can fiuther include ethylene propylene butylene (EPB) terpolymer or polypropylene or ethylene-propylene random copolymer or propylene butylene propylene copolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE) or high density polyethylene (HDPE) or blends of the aforementioned polymers.
The film can also include a second skin layer which can include high density polyethylene (HDPE) or ethylene propylene butylene (EPB) terpolymer or ethylene-propylene random copolymer or EP impact copolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE) or propylene butene copolymer or polypropylene homopolymer or ethylene-vinyl acetate copolymer (EVA) or ethylene-methyacrylic acid copolymer (EMA) or ethylene-vinyl alcohol copolymer (EVOH) or blends of the aforementioned polymers. An intermediate layer can be interposed between the core layer and the second skin layer. Such an intermediate layer can include polypropylene and from about 1%
to about 15% by weight titanium dioxide. A second intermediate layer can be interposed between the core layer and the EP block copolymer skin layer, and can include polypropylene.
In the embodiment in which the EP impact copolymer layer is an intermediate layer, it is placed adjacent to a skin layer, e.g., interposed between the core layer and a first skin layer. A second intermediate layer can also be interposed between the core layer and a second skin layer, and can include polypropylene or ethylene-propylene impact copolymer. An intermediate layer can be a tie layer.
The skin layers can also include high density polyethylene (HDPE) or ethylene propylene butylene (EPB) terpolymer or ethylene-propylene random copolymer or propylene butylene (PB) copolymer or polypropylene homopolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE) or blends of the aforementioned polymers.
The present invention provides multilayer films with improved anti-blocking and COF characteristics without the necessity of adding an antiblock or slip agent.
This gives the ability to produce sealable clear and cavitated films structures, which are processable on both sides, with outstanding surface properties without the use of additives.
These and other advantages of the present invention will be appreciated from the detailed description and examples which are set forth herein. The detailed description and examples enhance the understanding of the invention, but are not intended to limit the scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the invention have been chosen for purposes of illustration and description, but are not intended in any way to restrict the scope of the invention. The preferred embodiments of certain aspects of the invention are shown in the accompanying drawings, wherein:
FIG. 1 is a graph showing the effect impact copolymer skin layers have on blocking forces of films. The blocking conditions are 140° F, 750 psi for one hour.
1 S FIG. 2 is a graph showing the effect impact copolymer skin layers have on blocking forces of films. The blocking conditions are 125° F, 125 psi for 24 hours.
FIG. 3 is a graph showing the effect of blending the impact copolymer of skin layers with terpolymer or homopolymer polypropylene.
FIG. 4 is a graph showing the effect of blending the impact copolymer of skin layers with terpolymer or homopolymer polypropylene.
FIG. 5 is a graph showing the effect of impact copolymer which is blended into the treated skin resin.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention provides is a method providing a layer of an ethylene-propylene (EP) impact copolymer to multilayer films having a core layer including polypropylene (PP), high density polyethylene (HDPE) or linear low density polyethylene (LLDPE), and a product resulting therefrom. The multilayer films of the present invention can be monoaxially or biaxially oriented. The copolymer layer is non-heat sealable.
5 PCT/i1S00/30108 EP impact copolymer includes blocks of propylene and EP copolymer.
These copolymers are made by incorporating the rubbery material, ethylene-propylene rubber (EPR), in the reactor with polypropylene. EPR is an elastomer, made by the copolymerization of ethylene and propylene, which typically contains 5 40-90% ethylene.
The EP impact copolymers utilized in the present invention contain 3-30%
ethylene, preferably 7-20%. These impact copolymers have no more than two peaks in the melting curve within the range of from about 110°C to about 165°C as measured by a differential scanning calorimeter. Impact copolymer ( 1 ) of the present invention has one small peak around 119°C and a second large peak around 163°C. An example of such an impact copolymer is Montell 8523 EP
impact copolymer. This impact copolymer includes blocks of propylene and EP
copolymer wherein the total ethylene concentration is 15-20%. Impact copolymer (2) of the present invention has one small peak around 11 S°C and a second large peak around 162°C. An example of such an impact copolymer is Fina 4520.
The ethylene concentration of this impact copolymer is approximately 10%.
Homopolymer PP is preferred as the PP used as the core layer in the methods of the present invention. One particularly suitable homopolymer PP is the resin sold as Fina 3371. Another suitable homopolymer PP is sold as Amoco 6371.
One particularly suitable HDPE for use as a core layer with the methods of the present invention is the resin sold as M6211 by Equistar. Another particularly suitable HDPE is the resin sold as HDZ 128 by Exxon. Other suitable HDPE
resins include, for example, BDM 94-25 available from Fina Oil and Chemical Co., Dallas, TX, and 19C and 19F available from Nova Corporation, Sarnia, Ontario, Canada.
The core layer of the multilayer film can be cavitated. Any suitable organic or inorganic cavitating agent can be used. A preferred organic cavitant is PBT. An example of an inorganic cavitant is calcium carbonate (CaC03).
By the methods of the present invention, the antiblocking and COF
characteristics of such multilayer films are improved without necessity of adding an antiblock or slip agents; but, these agents can be added if desired.
These copolymers are made by incorporating the rubbery material, ethylene-propylene rubber (EPR), in the reactor with polypropylene. EPR is an elastomer, made by the copolymerization of ethylene and propylene, which typically contains 5 40-90% ethylene.
The EP impact copolymers utilized in the present invention contain 3-30%
ethylene, preferably 7-20%. These impact copolymers have no more than two peaks in the melting curve within the range of from about 110°C to about 165°C as measured by a differential scanning calorimeter. Impact copolymer ( 1 ) of the present invention has one small peak around 119°C and a second large peak around 163°C. An example of such an impact copolymer is Montell 8523 EP
impact copolymer. This impact copolymer includes blocks of propylene and EP
copolymer wherein the total ethylene concentration is 15-20%. Impact copolymer (2) of the present invention has one small peak around 11 S°C and a second large peak around 162°C. An example of such an impact copolymer is Fina 4520.
The ethylene concentration of this impact copolymer is approximately 10%.
Homopolymer PP is preferred as the PP used as the core layer in the methods of the present invention. One particularly suitable homopolymer PP is the resin sold as Fina 3371. Another suitable homopolymer PP is sold as Amoco 6371.
One particularly suitable HDPE for use as a core layer with the methods of the present invention is the resin sold as M6211 by Equistar. Another particularly suitable HDPE is the resin sold as HDZ 128 by Exxon. Other suitable HDPE
resins include, for example, BDM 94-25 available from Fina Oil and Chemical Co., Dallas, TX, and 19C and 19F available from Nova Corporation, Sarnia, Ontario, Canada.
The core layer of the multilayer film can be cavitated. Any suitable organic or inorganic cavitating agent can be used. A preferred organic cavitant is PBT. An example of an inorganic cavitant is calcium carbonate (CaC03).
By the methods of the present invention, the antiblocking and COF
characteristics of such multilayer films are improved without necessity of adding an antiblock or slip agents; but, these agents can be added if desired.
The multilayer film of the present invention can be surface treated on one or both outermost layers, which are referred to herein as skin layers, with flame or Corona treatment. The usefulness of two-side treated films is that they allow for future processing capability on both sides. Examples of processing includes metallization, printing, lamination and cold seal. Thus, a film can be metallized, printed or laminated on one surface and have cold seal and/or inside print applied to its opposite treated side.
The multilayer film of the present invention can be metallized with the following metals: aluminum, copper, silver, chromium, gold, and mixtures thereof.
Aluminum is the substrate that is typically preferred for metallizing.
Suitable coatings for the multilayer film of the present invention can be solvent based, water based or 100% solids based. Examples of suitable coatings are polyvinylidene chloride (PVdC), acrylic, ethylene acrylic acid, polyvinyl alcohol (PVOH), ethylene methyl acrylate (EMA) and acrylonitrile. Blends of these polymers are also suitable as coatings. Examples of acrylic coatings which are particularly suitable are composed of a terpolymer of methyl acrylate, methyl methacrylate, and methyacrylic acid.
Examples of coating application methods that are particularly suitable for applying the above coatings and coating combinations are rod, direct gravure (forward and reverse), offset gravure, slot die, and air knife coating.
Coating curing/drying methods can consist of hot air convection, electron beam, ultraviolet, and microwave. The range of acceptable coating weights are 0.1-10.0 g/msi with 3.0 and below g/msi preferred.
Some of the aforementioned coatings can be crosslinked. A primer coating can be used with the aforementioned coatings to enhance adhesion of a coating to a skin layer. Typical primer coating layers are acrylic, styrene acrylic, EAA
(ethylene-acrylic acid copolymer), EMA, urethane, epoxy, PEI
(polyethyleneimine), polyester, and vinyl amine.
Additives well known in the art such as amorphous silica, wax and talc can be added to the above coatings to improve COF and other surface properties.
The multilayer film of the present invention can be metallized with the following metals: aluminum, copper, silver, chromium, gold, and mixtures thereof.
Aluminum is the substrate that is typically preferred for metallizing.
Suitable coatings for the multilayer film of the present invention can be solvent based, water based or 100% solids based. Examples of suitable coatings are polyvinylidene chloride (PVdC), acrylic, ethylene acrylic acid, polyvinyl alcohol (PVOH), ethylene methyl acrylate (EMA) and acrylonitrile. Blends of these polymers are also suitable as coatings. Examples of acrylic coatings which are particularly suitable are composed of a terpolymer of methyl acrylate, methyl methacrylate, and methyacrylic acid.
Examples of coating application methods that are particularly suitable for applying the above coatings and coating combinations are rod, direct gravure (forward and reverse), offset gravure, slot die, and air knife coating.
Coating curing/drying methods can consist of hot air convection, electron beam, ultraviolet, and microwave. The range of acceptable coating weights are 0.1-10.0 g/msi with 3.0 and below g/msi preferred.
Some of the aforementioned coatings can be crosslinked. A primer coating can be used with the aforementioned coatings to enhance adhesion of a coating to a skin layer. Typical primer coating layers are acrylic, styrene acrylic, EAA
(ethylene-acrylic acid copolymer), EMA, urethane, epoxy, PEI
(polyethyleneimine), polyester, and vinyl amine.
Additives well known in the art such as amorphous silica, wax and talc can be added to the above coatings to improve COF and other surface properties.
The multilayer film of the present invention can also be treated opposite the metallized or coated side to further enhance film functionality with minimal risk of film blocking.
In one embodiment of the present invention the layer of an EP impact copolymer can be a skin layer of a multilayer film. "Skin layer" as used herein means outermost layer of a composite film. When used as a skin layer, the impact copolymer creates a naturally rough surface, even with two-side treated films.
The resulting film has a matte surface finish appearance.
In another embodiment of the present invention the layer of EP impact copolymer can be an intermediate layer of a multilayer film. This intermediate layer is placed adjacent to a skin layer. This intermediate layer can be a tie layer. The use of EP impact copolymers as an intermediate layer alters the outer skin layer morphology. The rough texture of the impact copolymer is "transferred" to the skin layer.
The layer of EP impact copolymer can further include ethylene propylene butylene (EPB) terpolymer or polypropylene or ethylene-propylene random copolymer or propylene butylene copolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE) or high density polyethylene (HDPE) or blends of the aforementioned polymers.
In the embodiment in which the EP impact copolymer layer is a skin layer, the film can further include a second skin layer. Preferably, this second skin layer can include high density polyethylene (HDPE) or ethylene propylene butylene (EPB) terpolymer or ethylene-propylene random copolymer or ethylene-propylene impact copolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE) or propylene butene copolymer or polypropylene homopolymer or ethylene-vinyl acetate copolymer (EVA) or ethylene-methyacrylic acid copolymer (EMA) or ethylene-vinyl alcohol copolymer (EVOH) or blends of the aforementioned polymers.
A suitable HDPE for use as a skin layer is readily available, e.g., Equistar XM6030A or Eon HD6704.67. A suitable LLDPE for use as a skin layer is readily available, e.g., DowlexTM 2038 or DowlexTM 2027A (The Dow Chemical Company).
In this embodiment an intermediate layer can be preferably interposed between the core layer and the second skin layer. The intermediate layer can include polypropylene and from about 1% to about 15% by weight titanium dioxide. Additionally, a second intermediate layer can be interposed between the core layer and the first skin layer. This second intermediate layer can be interposed between the core layer and the EP impact copolymer skin layer. This second intermediate layer can preferably include polypropylene.
In the embodiment in which the EP impact copolymer layer is an intermediate layer, placed adjacent to a first skin layer, the film can further include a second intermediate layer on the side of the core layer opposite the first intermediate layer. The second intermediate layer can be interposed between the core layer and a second skin layer, and can include polypropylene or ethylene-propylene impact copolymer. The intermediate layers can be tie layers. The skin layers in this embodiment can include high density polyethylene (I~PE) or ethylene propylene butylene (EPB) terpolymer or ethylene-propylene random copolymer or propylene butylene (PB) copolymer or polypropylene homopolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE) or ethylene-vinyl acetate copolymer (EVA) or ethylene-methyacrylic acid copolymer (EMA) or ethylene-vinyl alcohol copolymer (EVOH) or blends of the aforementioned polymers.
As can be seen from the Examples below, these EP impact copolymer resins outperform (in the context of blocking) traditional EP random copolymers and EPB terpolymer, both containing antiblocking additives. In general, the blocking forces are dramatically reduced when impact copolymer is used either as a skin or intermediate layers. When impact copolymers are used as skin layers, in addition to significantly reducing blocking forces, they provide improved adhesion over homopolymer skins (in terms of cold seal adhesion). V~Jhen used as intermediate layers, they reduce blocking forces and lower COF. This allows for use of desirable resins (co- or terpolymers) without concerns about blocking and/or high loadings of antiblocks. Therefore, the benefits of random copolymers or terpolymers in terms of sealability can be achieved without the negatives in terms of COF and blocking by using an intermediate layer of impact copolymer under the sealant layer.
EXAMPLE OF A MOST PREFERRED EMBODIMENT
A preferred embodiment of the methods of the instant invention is a biaxially oriented three-layer film structure having two processable sides and an overall thickness of 50 gauge. The film includes the following components: i) a 44.2 gauge homopolymer polypropylene core layer made of Amoco 6371 resin; ii) a 2.3 gauge high density polyethylene (HDPE) skin layer made of Equistar XM6030A resin on one side of the core layer; and iii) a 3.5 gauge EP block copolymer skin layer made of Montell 8523 resin on the other side of the core layer.
The HDPE skin layer is flame treated during orientation and subsequently vacuum metallized to form a metallized layer on the HDPE skin layer. The film utilizes 70 BSMII metallization technology involving vacuum deposition of a 99.88% pure aluminum wire source to form the metallized layer. The metallized layer is formed solely from the wire source. Thus, a resulting metallized layer containing 99.88% by weight aluminum is deposited upon the )=APE layer. The EP
block copolymer skin layer is corona treated during orientation to form an unmetallized cold seal (CS) layer opposite the metallized layer. No additives are incorporated into any of the layers aside from a stabilizer and a fluoropoIymer which is added to the HDPE layer.
i. Clear Structures Using Impact Copolymer as a Skin Layer The film structure used in the following example includes a homopolymer polypropylene or copolymer core layer (B), with a treated EP impact copolymer skin layer (A), and the opposite treated skin layer of HDPE or EPB terpolymer or EP random copolymer (C). The layer (C) opposite the EP impact copolymer can be metallized. Treatment can be flame or corona on both sides.
Data demonstrating the superior blocking resistance of the EP impact copolymer skin layer was generated with a sample roll that was metallized later.
The blocking performance as compared to a sample with an EP random copolymer skin layer, produced at the same time, is shown in the Table I. It is clear that the 5 EP impact copolymer provides lower blocking forces when compared to EP
random copolymer.
Table I
Treated Skin OppositeBlocking Test (grn)Actual Blocking Performance the Metal @ 1 hr, 140F, 750 When Unwinding Roll psi EP Impact Copolymer2.4 No Blocking EP Random Copolymer13.2 Occasional blocking and metat + Antiblock Particles pick-off Additional blocking data of multiple two-side treated films is shown in Table II. The data compares several different skin layers (A) and (C) which were placed in blocking jigs and evaluated at different temperatures, pressures and time.
The blocking results for each skin resin type and condition are shown. Once I 5 again, the blocking data demonstrates the ability of the EP impact copolymer to release from the opposite treated surface or metallized layer without the use of any antiblocking particulates.
Table II
Skin Layer Skin Layer Blocking Test (glin)Blocking Test A C @ (g/in) @
1 hr, 140F, 750 24 hr, 125F, 125 psi psi EP Impact Aluminum 4.1 0.1 Copolymer Layer EP Impact HDPE 23.2 2.6 Copolymer Terpolymer HDPE 55.1 13.6 with Antiblock ii. Cavitated Structures The structure of the film used in the example from which the data is generated is shown below. The thickness of the layer is expressed in gauge (ga) which is 0.00001 inch.
Treated Print Surface - I~PE 2 ga PP + 4% Ti02 10 ga PP + pBT 51 ga PP 10 ga Non-print Surface - Variable 2 ga Treated As shown in Table III, different resin types and different additive packages were used to vary the non-print surface. The structure with the impact copolymer skin consistently had the lowest blocking force.
Table III
i '~ Variable Blocking Conditions -1 I Print SurfaceNon-print Surface24 hrs/24 hrs/ 72 hrs/72 hrs/
125 125 psi 50 psi i psi 50 psi HDPE EPB Terpolymer 168.0 51.5 20.9 88.8 HDPE + siliconEPB Terpolymer 129.5 58.6 28.0 77.6 spheres HDPE PP + AB 52.3 8.5 2.8 7.8 ~
HDPE PP + CaC03 ' 12.0 3.7 ' 2.3 3.8 'I
HDPE Impact Copolymerj 3.6 1.5 0.5 1.1 The basic film structure from which the data of Table IV is generated is shown below:
Treated A Variable Skin 4 ga B PP + Cavitating Agent 78 ga C Variable Skin 4 ga Table IV shows the effect the use of impact copolymer as a skin layer has on blocking forces and COF in multilayer films. In each instance, substituting an impact copolymer skin layer for a homopolymer PP or a EPB terpolymer or a HDPE skin layer lowered the blocking force. The effect was greater at the lower pressure.
Table IV
Variable ', Blocking TMI Kinetic gr sled/no delay Surface A Surface 24 hrs/ 125 1 hr/ 140F/
C F/
125 psi 750 psi A/C ClC
Homopolymer Homopolymeri 2.4 BTD 0.512 pp + 4% Ti02PP + 4% j Ti02 EPB TerpolymerEPB 63.3 84.1 0.813 +2300 ppm Terpolymer AB +
2300 ppm AB
HDPE + 1000 EPB ~ 32.0 70.5 0.279 0.941 ppm AB Terpolymer I
+
2300 ppm AB
HDPE + 1000 ~ Homopolymer. 2.2 79.7 0.239 0.318 ppm AB PP + 5400 i ppm AB ;
Homopolymer Impact i 0.2 14.9 0.573 pp + 4% Ti02Copolymer (1) EPB TerpolymerImpact ~ 0.7 34.8 0.544 + 2300 ppm Copolymer AB (1) HDPE + 1000 Impact ~ 0.3 15.1 0.254 I
ppm AB Copolymer j (1) Impact ! 0.0 7.7 0.551 Homopolymer Copolymer (2) pp + 4% Ti02 EPB TerpolymerImpact ~ 1.7 58.4 0.618 + 2300 ppm Copolymer AB (2) HDPE + 1000 Impact ~ 0.2 10.2 0.233 ppm AB Copolymer (2) HDPE + 1000 70% EPB j 11. I 18.6 0.390 0.329 ppm AB Terpolymer ~
+
2300 ppm ~
ABl 30% Impact Copolymer ( 1 ) HDPE + 1000 30% EPB 2.9 13.6 ' 0.308 0.563 ~
ppm AB Terpolymer i +
2300 ppm AB/
70% Impact I
Copolymer ( 1 ) HDPE + 1000 70% f 0.8 25.4 0.237 0.423 Variable Blocking TMI Kinetic COF 200 gr sled/no delay Surface A Surface C 24 hrs/ 125F/1 hr/140F/
~
125 psi 750 psi A/C I C/C
ppm AB Homopolymer pp + 5400 ppm AB/ 30%
Impact Copolymer ( 1 ) HDPE + 1000 30% 0.2 12.4 0.239 ' 0.424 ppm AB Homopolymer PP + 5400 ppm AB/ 70%
Impact Copolymer ( 1 ) Figures 1 and 2 show the effect that the using impact copolymer as a skin layer in contrast with using homopolymer polypropylene or terpolyrner as a skin layer. The blocking conditions are set at 140° F, 750 psi for one hour and at I25° F, 125 psi for 24 hours. Under both blocking conditions using an impact copolymer skin layer lowered the blocking force. The effect was greater at the lower pressure blocking conditions. [Note: BTD=blocked to destruction.]
Figures 3 and 4 show the effect of blending the impact copolymer of the skin layer with terpolymer or homopolymer polypropylene. The second skin layer of these samples is composed of HDPE with 1000 ppm antiblock. All films are two side treated. As the percentage of impact copolymer is increased, the blocking force is decreased. This is especially seen when blending with a terpolymer.
The blocking conditions are set at 140° F, 750 psi for one hour.
IS
The structure of the film from which the data in Fig. 5 was generated is shown below:
Treated A Variable Skin 4 ga B PP + Cavitating Agent 78 ga C EPB Terpolymer + AB 4 ga In this example, the impact copolymer is blended into the treated skin resin.
The treated surface was tested against itself. The COF of the samples with impact 5 copolymer layers was lowered without the use of antiblock. The COF at a 50%
loading was not always better than the 20% loading, so there may be a point at which the effectiveness diminishes or reverses. Figure 5 is a graph showing this effect.
In one embodiment of the present invention the layer of an EP impact copolymer can be a skin layer of a multilayer film. "Skin layer" as used herein means outermost layer of a composite film. When used as a skin layer, the impact copolymer creates a naturally rough surface, even with two-side treated films.
The resulting film has a matte surface finish appearance.
In another embodiment of the present invention the layer of EP impact copolymer can be an intermediate layer of a multilayer film. This intermediate layer is placed adjacent to a skin layer. This intermediate layer can be a tie layer. The use of EP impact copolymers as an intermediate layer alters the outer skin layer morphology. The rough texture of the impact copolymer is "transferred" to the skin layer.
The layer of EP impact copolymer can further include ethylene propylene butylene (EPB) terpolymer or polypropylene or ethylene-propylene random copolymer or propylene butylene copolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE) or high density polyethylene (HDPE) or blends of the aforementioned polymers.
In the embodiment in which the EP impact copolymer layer is a skin layer, the film can further include a second skin layer. Preferably, this second skin layer can include high density polyethylene (HDPE) or ethylene propylene butylene (EPB) terpolymer or ethylene-propylene random copolymer or ethylene-propylene impact copolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE) or propylene butene copolymer or polypropylene homopolymer or ethylene-vinyl acetate copolymer (EVA) or ethylene-methyacrylic acid copolymer (EMA) or ethylene-vinyl alcohol copolymer (EVOH) or blends of the aforementioned polymers.
A suitable HDPE for use as a skin layer is readily available, e.g., Equistar XM6030A or Eon HD6704.67. A suitable LLDPE for use as a skin layer is readily available, e.g., DowlexTM 2038 or DowlexTM 2027A (The Dow Chemical Company).
In this embodiment an intermediate layer can be preferably interposed between the core layer and the second skin layer. The intermediate layer can include polypropylene and from about 1% to about 15% by weight titanium dioxide. Additionally, a second intermediate layer can be interposed between the core layer and the first skin layer. This second intermediate layer can be interposed between the core layer and the EP impact copolymer skin layer. This second intermediate layer can preferably include polypropylene.
In the embodiment in which the EP impact copolymer layer is an intermediate layer, placed adjacent to a first skin layer, the film can further include a second intermediate layer on the side of the core layer opposite the first intermediate layer. The second intermediate layer can be interposed between the core layer and a second skin layer, and can include polypropylene or ethylene-propylene impact copolymer. The intermediate layers can be tie layers. The skin layers in this embodiment can include high density polyethylene (I~PE) or ethylene propylene butylene (EPB) terpolymer or ethylene-propylene random copolymer or propylene butylene (PB) copolymer or polypropylene homopolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE) or ethylene-vinyl acetate copolymer (EVA) or ethylene-methyacrylic acid copolymer (EMA) or ethylene-vinyl alcohol copolymer (EVOH) or blends of the aforementioned polymers.
As can be seen from the Examples below, these EP impact copolymer resins outperform (in the context of blocking) traditional EP random copolymers and EPB terpolymer, both containing antiblocking additives. In general, the blocking forces are dramatically reduced when impact copolymer is used either as a skin or intermediate layers. When impact copolymers are used as skin layers, in addition to significantly reducing blocking forces, they provide improved adhesion over homopolymer skins (in terms of cold seal adhesion). V~Jhen used as intermediate layers, they reduce blocking forces and lower COF. This allows for use of desirable resins (co- or terpolymers) without concerns about blocking and/or high loadings of antiblocks. Therefore, the benefits of random copolymers or terpolymers in terms of sealability can be achieved without the negatives in terms of COF and blocking by using an intermediate layer of impact copolymer under the sealant layer.
EXAMPLE OF A MOST PREFERRED EMBODIMENT
A preferred embodiment of the methods of the instant invention is a biaxially oriented three-layer film structure having two processable sides and an overall thickness of 50 gauge. The film includes the following components: i) a 44.2 gauge homopolymer polypropylene core layer made of Amoco 6371 resin; ii) a 2.3 gauge high density polyethylene (HDPE) skin layer made of Equistar XM6030A resin on one side of the core layer; and iii) a 3.5 gauge EP block copolymer skin layer made of Montell 8523 resin on the other side of the core layer.
The HDPE skin layer is flame treated during orientation and subsequently vacuum metallized to form a metallized layer on the HDPE skin layer. The film utilizes 70 BSMII metallization technology involving vacuum deposition of a 99.88% pure aluminum wire source to form the metallized layer. The metallized layer is formed solely from the wire source. Thus, a resulting metallized layer containing 99.88% by weight aluminum is deposited upon the )=APE layer. The EP
block copolymer skin layer is corona treated during orientation to form an unmetallized cold seal (CS) layer opposite the metallized layer. No additives are incorporated into any of the layers aside from a stabilizer and a fluoropoIymer which is added to the HDPE layer.
i. Clear Structures Using Impact Copolymer as a Skin Layer The film structure used in the following example includes a homopolymer polypropylene or copolymer core layer (B), with a treated EP impact copolymer skin layer (A), and the opposite treated skin layer of HDPE or EPB terpolymer or EP random copolymer (C). The layer (C) opposite the EP impact copolymer can be metallized. Treatment can be flame or corona on both sides.
Data demonstrating the superior blocking resistance of the EP impact copolymer skin layer was generated with a sample roll that was metallized later.
The blocking performance as compared to a sample with an EP random copolymer skin layer, produced at the same time, is shown in the Table I. It is clear that the 5 EP impact copolymer provides lower blocking forces when compared to EP
random copolymer.
Table I
Treated Skin OppositeBlocking Test (grn)Actual Blocking Performance the Metal @ 1 hr, 140F, 750 When Unwinding Roll psi EP Impact Copolymer2.4 No Blocking EP Random Copolymer13.2 Occasional blocking and metat + Antiblock Particles pick-off Additional blocking data of multiple two-side treated films is shown in Table II. The data compares several different skin layers (A) and (C) which were placed in blocking jigs and evaluated at different temperatures, pressures and time.
The blocking results for each skin resin type and condition are shown. Once I 5 again, the blocking data demonstrates the ability of the EP impact copolymer to release from the opposite treated surface or metallized layer without the use of any antiblocking particulates.
Table II
Skin Layer Skin Layer Blocking Test (glin)Blocking Test A C @ (g/in) @
1 hr, 140F, 750 24 hr, 125F, 125 psi psi EP Impact Aluminum 4.1 0.1 Copolymer Layer EP Impact HDPE 23.2 2.6 Copolymer Terpolymer HDPE 55.1 13.6 with Antiblock ii. Cavitated Structures The structure of the film used in the example from which the data is generated is shown below. The thickness of the layer is expressed in gauge (ga) which is 0.00001 inch.
Treated Print Surface - I~PE 2 ga PP + 4% Ti02 10 ga PP + pBT 51 ga PP 10 ga Non-print Surface - Variable 2 ga Treated As shown in Table III, different resin types and different additive packages were used to vary the non-print surface. The structure with the impact copolymer skin consistently had the lowest blocking force.
Table III
i '~ Variable Blocking Conditions -1 I Print SurfaceNon-print Surface24 hrs/24 hrs/ 72 hrs/72 hrs/
125 125 psi 50 psi i psi 50 psi HDPE EPB Terpolymer 168.0 51.5 20.9 88.8 HDPE + siliconEPB Terpolymer 129.5 58.6 28.0 77.6 spheres HDPE PP + AB 52.3 8.5 2.8 7.8 ~
HDPE PP + CaC03 ' 12.0 3.7 ' 2.3 3.8 'I
HDPE Impact Copolymerj 3.6 1.5 0.5 1.1 The basic film structure from which the data of Table IV is generated is shown below:
Treated A Variable Skin 4 ga B PP + Cavitating Agent 78 ga C Variable Skin 4 ga Table IV shows the effect the use of impact copolymer as a skin layer has on blocking forces and COF in multilayer films. In each instance, substituting an impact copolymer skin layer for a homopolymer PP or a EPB terpolymer or a HDPE skin layer lowered the blocking force. The effect was greater at the lower pressure.
Table IV
Variable ', Blocking TMI Kinetic gr sled/no delay Surface A Surface 24 hrs/ 125 1 hr/ 140F/
C F/
125 psi 750 psi A/C ClC
Homopolymer Homopolymeri 2.4 BTD 0.512 pp + 4% Ti02PP + 4% j Ti02 EPB TerpolymerEPB 63.3 84.1 0.813 +2300 ppm Terpolymer AB +
2300 ppm AB
HDPE + 1000 EPB ~ 32.0 70.5 0.279 0.941 ppm AB Terpolymer I
+
2300 ppm AB
HDPE + 1000 ~ Homopolymer. 2.2 79.7 0.239 0.318 ppm AB PP + 5400 i ppm AB ;
Homopolymer Impact i 0.2 14.9 0.573 pp + 4% Ti02Copolymer (1) EPB TerpolymerImpact ~ 0.7 34.8 0.544 + 2300 ppm Copolymer AB (1) HDPE + 1000 Impact ~ 0.3 15.1 0.254 I
ppm AB Copolymer j (1) Impact ! 0.0 7.7 0.551 Homopolymer Copolymer (2) pp + 4% Ti02 EPB TerpolymerImpact ~ 1.7 58.4 0.618 + 2300 ppm Copolymer AB (2) HDPE + 1000 Impact ~ 0.2 10.2 0.233 ppm AB Copolymer (2) HDPE + 1000 70% EPB j 11. I 18.6 0.390 0.329 ppm AB Terpolymer ~
+
2300 ppm ~
ABl 30% Impact Copolymer ( 1 ) HDPE + 1000 30% EPB 2.9 13.6 ' 0.308 0.563 ~
ppm AB Terpolymer i +
2300 ppm AB/
70% Impact I
Copolymer ( 1 ) HDPE + 1000 70% f 0.8 25.4 0.237 0.423 Variable Blocking TMI Kinetic COF 200 gr sled/no delay Surface A Surface C 24 hrs/ 125F/1 hr/140F/
~
125 psi 750 psi A/C I C/C
ppm AB Homopolymer pp + 5400 ppm AB/ 30%
Impact Copolymer ( 1 ) HDPE + 1000 30% 0.2 12.4 0.239 ' 0.424 ppm AB Homopolymer PP + 5400 ppm AB/ 70%
Impact Copolymer ( 1 ) Figures 1 and 2 show the effect that the using impact copolymer as a skin layer in contrast with using homopolymer polypropylene or terpolyrner as a skin layer. The blocking conditions are set at 140° F, 750 psi for one hour and at I25° F, 125 psi for 24 hours. Under both blocking conditions using an impact copolymer skin layer lowered the blocking force. The effect was greater at the lower pressure blocking conditions. [Note: BTD=blocked to destruction.]
Figures 3 and 4 show the effect of blending the impact copolymer of the skin layer with terpolymer or homopolymer polypropylene. The second skin layer of these samples is composed of HDPE with 1000 ppm antiblock. All films are two side treated. As the percentage of impact copolymer is increased, the blocking force is decreased. This is especially seen when blending with a terpolymer.
The blocking conditions are set at 140° F, 750 psi for one hour.
IS
The structure of the film from which the data in Fig. 5 was generated is shown below:
Treated A Variable Skin 4 ga B PP + Cavitating Agent 78 ga C EPB Terpolymer + AB 4 ga In this example, the impact copolymer is blended into the treated skin resin.
The treated surface was tested against itself. The COF of the samples with impact 5 copolymer layers was lowered without the use of antiblock. The COF at a 50%
loading was not always better than the 20% loading, so there may be a point at which the effectiveness diminishes or reverses. Figure 5 is a graph showing this effect.
Impact Copol~,~mer Used as a Tie Layer The structure of the film used to generate the data in Table V is shown below:
Treated A Variable Skin 4 ga B Variable Tie 8-12 ga C PP + Cavitating Agent 58 ga B Variable Tie 8-12 ga A Variable Skin 4 ga In these samples, the impact copolymer was used as tie layers. Because the samples were made one side treated only, the treated surface was tested against itself. Both blocking conditions showed reduced blocking force when the tie layers were impact copolymer. The COF of the samples with impact copolymer layers was significantly reduced without the use of antiblock. This effect was particularly dramatic when the skin layer had no antiblock formulated into it. See Table V.
Table V
Variable Blocking Skin Tie 24 hrs/ 125F/
1 hr/ 140F/
I TMI Kinetic I25 psi 750 psi 1 COF
200 gr 1 sled/no delay HDPE Homopolymer 46.5 147.4 ' 0.476 PP
EPB TerpolymerHomopolymer 103.3 106. I i 0.724 PP
+ AB
i i EPB TerpolymerImpact 5.5 84.7 0.501 '~ + AB Copolymer j II EP Random Homopolymer 133.7 89.3 ~ 2.367 PP
~ Copolymer i EP Random Impact 8. I 109.1 I 0.559 Copolymer Copolymer PB Copolymer Homopolymer 93.8 81.7 1.856 PP
PB Copolymer Impact 7.6 76.7 0.640 Copolymer The data in Table VI is generated using the film structure shown below:
Treated D Variable Skin 4 ga C Variable Tie + Ti02 16 ga A PP + Cavitating Agent 46 ga B Variable Tie 16 ga E EPB Terpolymer with AB 4 ga In these samples, the impact copolymer is used as the tie layer. One tie layer includes titanium dioxide. Because the sample was made with only one side treated, the treated surface was tested against itself. When the tie layer was impact copolymer, reduced blocking forces were seen under conditions of 125°F/125 psi.
The COF of the samples with impact copolymer layers was lowered without the use of antiblock. Again, this effect was particularly dramatic when the skin layer had no antiblock formulated into it. (See Table VL) Table VI
Variable Blocking Skin Tie 24 hrs/ 125F/ TMI Kinetic COF
125 psi gr sled/no delay HDPE I Homopolymer PP 36.6 0.471 t +
Ti02 EPB TerpolyrnerHomopolymer PP 64.8 0.865 +
+ AB Ti02 EPB TerpolymerImpact Copolymer 55.4 0.815 +
+ AB Ti02 EP Random Homopolymer PP 87.1 1.463 +
Copolymer Ti02 EP Random Impact Copolymer 29.1 0.685 +
Copolymer Ti02 PB Copolymer Homopolymer PP 83.7 1.621 +
Ti02 PB Copolymer Impact Copolymer 63.5 0.952 +
Ti02 This invention provides the use of films containing EP impact copolymer for improved performance after vacuum metallization with aluminum and/or after coating with various solvent based, water based, and solventless coatings.
Two base film designs suitable for vacuum metallizing and coating utilizing an EP impact copolymer are as follows:
Design A - EP Impact Copolymer as a Skin Layer in a 3 to 5 Layer Structure Treated Coating or Metallizing Layer Resins: HDPE, PP homopolymer, EVOH copolymer, EP random copolymer, PB
copolymer, EPB terpolyrner, MDPE, LLDPE, EVA, EMA or blends of above.
Additives: Optional use of antiblock er Thickness: 2-16 a thickness.
O tional Tie La er - Pol olefin based w/o tional Ti02 4-28 a thickness Isotactic PP homopolymer, HDPE, or LLDPE (20-100 ga thickness) w/o tional addition of cavitatin a ent O tional Tie La er - Pol olefin based w/o tional Ti02 -(4-28 a thickness Block Resistant Layer -Resins: EP impact copolymer or blends thereof w/other polyolefins Additives: None er Thickness: 2-16 a thickness Untreated or Treated Design B - EP Impact Copolymer as a Tie Layer in a 4 or 5 Layer Structure Treated Coating or Metallizing Layer Resins: HDPE, PP homopolymer, EVOH copolymer, EP random copolymer, PB
copolymer, EPB terpolymer, MDPE, LLDPE, EVA, EMA or blends of above Additives: Optional use of antiblock er Thickness: 2-16 a thickness Optional Tie Layer Resins: Polyolefin based Additives: Optional Use of Ti02 L er Thickness: 4-28 a thickness Isotactic PP homopolymer, HDPE or LLDPE (20-100 ga thickness) W/o tional addition of cavitatin a ent Tie Layer Resins: EP impact copolymer or blends thereof w/other polyolefins Additives: Optional use of Ti02 L er Thickness: 4-28 a thickness Block Resistant Side Resins: HDPE, PP homopolymer, EP random copolymer, PB copolymer, EPB
terpolymer, MDPE, LLDPE or blends of above Additives: Optional use of antiblock L er Thickness: 2-16 a thickness Untreated or Treated The film described in the Example of a Most Preferred Embodiment (see above) was vacuum metallized with aluminum to obtain an optical density of 2.4 on the non-EP impact copolymer side of the film. The resulting average barrier properties after metallization are as follows: Water Vapor Transmission Rate (WVTR)=0.015 g/100 in.2 /24 hr, Oxygen Transmission Rate (OTR~2.0 cc/100 in.2 /24 hr. This metallized barner film is particularly suitable for use in triplex laminations and also for use as an inner layer in a duplex lamination. In a duplex lamination, cold seal would be applied to the treated EP impact copolymer surface yielding excellent adhesion.
Data demonstrating the superior blocking resistance of this film was generated with a sample roll that was produced on an experimental line. The blocking performance as compared to another sample with an EP random copolymer skin layer containing antiblock produced at the same time is shown in the Table VII. The benefits of the EP impact copolymer in terms of film blocking are evident.
TABLE VB
Treated Skin OppositeBlocking Test (g/in)Actual Blocking the @
Metal lhr, 140F, 7~0 psi Performance When Unwindin Roll EP lm act Co of er 2.4 No Blockin EP Random Copolymer 13.2 Occasional blocking + and Antiblock Particles metal ick-off The base film described in the Example of a Most Preferred Embodiment (see above) was coated with a high barrier saran (Daran 8500 PVdC at 2.6 g/msi ) on the non-EP impact copolymer side of the film (HDPE skin), instead of being metallized. An epoxy primer was applied prior to the saran coating to achieve adequate saran adhesion. The resulting film had an OTR of 0.445 cc/100 in.2/24 hr and a WVTR of 0.18 g/100 in.z/24 hr. This clear barrier film is particularly suitable also for use in triplex laminations and also for use as an inner layer in a duplex lamination. In a duplex lamination, cold seal would be applied to the treated EP
impact copolymer surface yielding excellent adhesion. Similarly, the film in this example can be coated on the side opposite the EP impact copolymer with other 5 coatings including acrylic, ethylene acrylic acid, PVOH, EMA and acrylonitrile.
Data displaying the improvement in blocking resistance when using the treated EP impact copolymer opposite the coated side of this film is shown in Table VIII. The control is a treated EP random copolymer surface. Similar to the metallized film, it can be seen that the one side coated films also have improved 10 blocking resistance when the side opposite the coating contains EP impact copolymer.
TABLE VIII
Treated Skin OppositeCoating Type Blocking Test (g/in) Coated Surface @ 24 hr, 125F, 125 si EP Im act Co of mer PVdC 1.5 EP Random Co of er PVdC 6.5 EP Im act Co of mer PVOH 0.4 EP Random Co of er PVOH 15.5 EP Im act Co of er Ac lic 4.3 EP Random Copolymer Acrylic ~ 68.7
Treated A Variable Skin 4 ga B Variable Tie 8-12 ga C PP + Cavitating Agent 58 ga B Variable Tie 8-12 ga A Variable Skin 4 ga In these samples, the impact copolymer was used as tie layers. Because the samples were made one side treated only, the treated surface was tested against itself. Both blocking conditions showed reduced blocking force when the tie layers were impact copolymer. The COF of the samples with impact copolymer layers was significantly reduced without the use of antiblock. This effect was particularly dramatic when the skin layer had no antiblock formulated into it. See Table V.
Table V
Variable Blocking Skin Tie 24 hrs/ 125F/
1 hr/ 140F/
I TMI Kinetic I25 psi 750 psi 1 COF
200 gr 1 sled/no delay HDPE Homopolymer 46.5 147.4 ' 0.476 PP
EPB TerpolymerHomopolymer 103.3 106. I i 0.724 PP
+ AB
i i EPB TerpolymerImpact 5.5 84.7 0.501 '~ + AB Copolymer j II EP Random Homopolymer 133.7 89.3 ~ 2.367 PP
~ Copolymer i EP Random Impact 8. I 109.1 I 0.559 Copolymer Copolymer PB Copolymer Homopolymer 93.8 81.7 1.856 PP
PB Copolymer Impact 7.6 76.7 0.640 Copolymer The data in Table VI is generated using the film structure shown below:
Treated D Variable Skin 4 ga C Variable Tie + Ti02 16 ga A PP + Cavitating Agent 46 ga B Variable Tie 16 ga E EPB Terpolymer with AB 4 ga In these samples, the impact copolymer is used as the tie layer. One tie layer includes titanium dioxide. Because the sample was made with only one side treated, the treated surface was tested against itself. When the tie layer was impact copolymer, reduced blocking forces were seen under conditions of 125°F/125 psi.
The COF of the samples with impact copolymer layers was lowered without the use of antiblock. Again, this effect was particularly dramatic when the skin layer had no antiblock formulated into it. (See Table VL) Table VI
Variable Blocking Skin Tie 24 hrs/ 125F/ TMI Kinetic COF
125 psi gr sled/no delay HDPE I Homopolymer PP 36.6 0.471 t +
Ti02 EPB TerpolyrnerHomopolymer PP 64.8 0.865 +
+ AB Ti02 EPB TerpolymerImpact Copolymer 55.4 0.815 +
+ AB Ti02 EP Random Homopolymer PP 87.1 1.463 +
Copolymer Ti02 EP Random Impact Copolymer 29.1 0.685 +
Copolymer Ti02 PB Copolymer Homopolymer PP 83.7 1.621 +
Ti02 PB Copolymer Impact Copolymer 63.5 0.952 +
Ti02 This invention provides the use of films containing EP impact copolymer for improved performance after vacuum metallization with aluminum and/or after coating with various solvent based, water based, and solventless coatings.
Two base film designs suitable for vacuum metallizing and coating utilizing an EP impact copolymer are as follows:
Design A - EP Impact Copolymer as a Skin Layer in a 3 to 5 Layer Structure Treated Coating or Metallizing Layer Resins: HDPE, PP homopolymer, EVOH copolymer, EP random copolymer, PB
copolymer, EPB terpolyrner, MDPE, LLDPE, EVA, EMA or blends of above.
Additives: Optional use of antiblock er Thickness: 2-16 a thickness.
O tional Tie La er - Pol olefin based w/o tional Ti02 4-28 a thickness Isotactic PP homopolymer, HDPE, or LLDPE (20-100 ga thickness) w/o tional addition of cavitatin a ent O tional Tie La er - Pol olefin based w/o tional Ti02 -(4-28 a thickness Block Resistant Layer -Resins: EP impact copolymer or blends thereof w/other polyolefins Additives: None er Thickness: 2-16 a thickness Untreated or Treated Design B - EP Impact Copolymer as a Tie Layer in a 4 or 5 Layer Structure Treated Coating or Metallizing Layer Resins: HDPE, PP homopolymer, EVOH copolymer, EP random copolymer, PB
copolymer, EPB terpolymer, MDPE, LLDPE, EVA, EMA or blends of above Additives: Optional use of antiblock er Thickness: 2-16 a thickness Optional Tie Layer Resins: Polyolefin based Additives: Optional Use of Ti02 L er Thickness: 4-28 a thickness Isotactic PP homopolymer, HDPE or LLDPE (20-100 ga thickness) W/o tional addition of cavitatin a ent Tie Layer Resins: EP impact copolymer or blends thereof w/other polyolefins Additives: Optional use of Ti02 L er Thickness: 4-28 a thickness Block Resistant Side Resins: HDPE, PP homopolymer, EP random copolymer, PB copolymer, EPB
terpolymer, MDPE, LLDPE or blends of above Additives: Optional use of antiblock L er Thickness: 2-16 a thickness Untreated or Treated The film described in the Example of a Most Preferred Embodiment (see above) was vacuum metallized with aluminum to obtain an optical density of 2.4 on the non-EP impact copolymer side of the film. The resulting average barrier properties after metallization are as follows: Water Vapor Transmission Rate (WVTR)=0.015 g/100 in.2 /24 hr, Oxygen Transmission Rate (OTR~2.0 cc/100 in.2 /24 hr. This metallized barner film is particularly suitable for use in triplex laminations and also for use as an inner layer in a duplex lamination. In a duplex lamination, cold seal would be applied to the treated EP impact copolymer surface yielding excellent adhesion.
Data demonstrating the superior blocking resistance of this film was generated with a sample roll that was produced on an experimental line. The blocking performance as compared to another sample with an EP random copolymer skin layer containing antiblock produced at the same time is shown in the Table VII. The benefits of the EP impact copolymer in terms of film blocking are evident.
TABLE VB
Treated Skin OppositeBlocking Test (g/in)Actual Blocking the @
Metal lhr, 140F, 7~0 psi Performance When Unwindin Roll EP lm act Co of er 2.4 No Blockin EP Random Copolymer 13.2 Occasional blocking + and Antiblock Particles metal ick-off The base film described in the Example of a Most Preferred Embodiment (see above) was coated with a high barrier saran (Daran 8500 PVdC at 2.6 g/msi ) on the non-EP impact copolymer side of the film (HDPE skin), instead of being metallized. An epoxy primer was applied prior to the saran coating to achieve adequate saran adhesion. The resulting film had an OTR of 0.445 cc/100 in.2/24 hr and a WVTR of 0.18 g/100 in.z/24 hr. This clear barrier film is particularly suitable also for use in triplex laminations and also for use as an inner layer in a duplex lamination. In a duplex lamination, cold seal would be applied to the treated EP
impact copolymer surface yielding excellent adhesion. Similarly, the film in this example can be coated on the side opposite the EP impact copolymer with other 5 coatings including acrylic, ethylene acrylic acid, PVOH, EMA and acrylonitrile.
Data displaying the improvement in blocking resistance when using the treated EP impact copolymer opposite the coated side of this film is shown in Table VIII. The control is a treated EP random copolymer surface. Similar to the metallized film, it can be seen that the one side coated films also have improved 10 blocking resistance when the side opposite the coating contains EP impact copolymer.
TABLE VIII
Treated Skin OppositeCoating Type Blocking Test (g/in) Coated Surface @ 24 hr, 125F, 125 si EP Im act Co of mer PVdC 1.5 EP Random Co of er PVdC 6.5 EP Im act Co of mer PVOH 0.4 EP Random Co of er PVOH 15.5 EP Im act Co of er Ac lic 4.3 EP Random Copolymer Acrylic ~ 68.7
Claims (28)
1. A method of improving blocking resistant properties and reducing the coefficient of friction of a multi layer film comprising:
providing at least one layer of an ethylene-propylene impact copolymer having from 7% to 20% by weight ethylene, wherein said copolymer has no more than two peaks in the melting curve within the range from about 110°C
to about 165°C, and wherein said layer is non-heat scalable, to a multi-layer film having a core layer comprising polypropylene, high density polyethylene (HDPE) or linear low density polyethylene (LLDPE), whereby anti-blocking and coefficient of friction characteristics of said filth is improved without necessity of adding an antiblock or slip agent.
providing at least one layer of an ethylene-propylene impact copolymer having from 7% to 20% by weight ethylene, wherein said copolymer has no more than two peaks in the melting curve within the range from about 110°C
to about 165°C, and wherein said layer is non-heat scalable, to a multi-layer film having a core layer comprising polypropylene, high density polyethylene (HDPE) or linear low density polyethylene (LLDPE), whereby anti-blocking and coefficient of friction characteristics of said filth is improved without necessity of adding an antiblock or slip agent.
2. A method according to Claim 1 wherein said at least one layer is a skin layer.
3. A method according to Claim 1 wherein said film is surface treated on at least one skin layer with flame or Corona treatment.
4. A method cording to Claim 2 wherein said film comprises a second skin layer comprising high density polyethylene (HDPE) or ethylene propylene butylene (EPB) terpolymer or ethylene-propylene random copolymer or ethylene-propylene impact copolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE) or propylene butene copolymer or polypropylene homopolymer or ethylene-vinyl alcohol copolymer (EVOH) or ethylene-vinyl acetate copolymer (EVA) or ethylene-methyacrylic acid copolymer (EMA).
5. A method according to Claim 1 wherein said at least one layer is placed adjacent to a skin layer as a tie layer.
6. A method according to Claim 1 wherein said core layer is cavitated.
7. A method according to Claim 4 which further comprises adding a cavitating agent to said core layer; and interposing art intermediate layer, which comprises polypropylene and from about 1% to about 15% by weight titanium dioxide, between said core layer and said second skin layer; and interposing a second intermediate layer, which comprises polypropylene, between said core layer and said first skin layer.
8. A method according to Claim 5 which further comprises:
interposing said do layer between said core layer and a first skin layer which comprises high density polyethylene (HDPE) or ethylene propylene butylene (EPB) terpolymer or ethylene-propylene random copolymer or propylene butylene copolymer or polypropylene homopolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE), interposing a second tie layer, which comprises polypropylene or ethylene-propylene impact copolymer, between said core layer and, a second skin layer which comprises high density polyethylene (HDPE) or ethylene propylene butylene (EPB) terpolymer or ethylene-propylene random copolymer or propylene butylene copolymer or polypropylene homopolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE) or ethylene-vinyl alcohol copolymer (EVOH) or ethylene-vinyl acetate copolymer (EVA) or ethylene-methyacrylic acid copolymer (EMA).
interposing said do layer between said core layer and a first skin layer which comprises high density polyethylene (HDPE) or ethylene propylene butylene (EPB) terpolymer or ethylene-propylene random copolymer or propylene butylene copolymer or polypropylene homopolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE), interposing a second tie layer, which comprises polypropylene or ethylene-propylene impact copolymer, between said core layer and, a second skin layer which comprises high density polyethylene (HDPE) or ethylene propylene butylene (EPB) terpolymer or ethylene-propylene random copolymer or propylene butylene copolymer or polypropylene homopolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE) or ethylene-vinyl alcohol copolymer (EVOH) or ethylene-vinyl acetate copolymer (EVA) or ethylene-methyacrylic acid copolymer (EMA).
9. A method according to Claim 1 which further comprises adding ethylene propylene butylene (EPB) terpolymer or polypropylene or ethylene-propylene random copolymer or propylene butylene copolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE) or high density polyethylene (HDPE) to said at least one layer.
10. A multi-layer film with improved blocking resistance and reduced coefficient of friction comprising:
a) a core layer comprising one of polypropylene, high density polyethylene (HDPE) or linear low density polyethylene (LLDPE), and b) at least one additional layer comprising an ethylene-propylene (EP) impact copolymer having from 7% to 20% by weight ethylene and which has no greater than two peaks in the melting curve within a range of from about 120°C to about 165°C, said layer being non-heat sealable, and c) no required slip or antiblock agent in either said core layer or said at least one additional layer.
a) a core layer comprising one of polypropylene, high density polyethylene (HDPE) or linear low density polyethylene (LLDPE), and b) at least one additional layer comprising an ethylene-propylene (EP) impact copolymer having from 7% to 20% by weight ethylene and which has no greater than two peaks in the melting curve within a range of from about 120°C to about 165°C, said layer being non-heat sealable, and c) no required slip or antiblock agent in either said core layer or said at least one additional layer.
11. A multi-layer film according to Claim 10 wherein said at least one additional layer is a first skin layer.
12. A multi-layer film according to Claim 11 wherein said film further comprises a second skin layer comprising a polymer selected from the group consisting of ethylene propylene butylene (EPB) terpolymer, ethylene-propylene random copolymer, medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), propylene butene copolymer, polypropylene homopolymer, ethylene-vinyl alcohol copolymer (EVOH), ethylene-vinyl acetate copolymer (EVA) and ethylene-methyacrylic acid copolymer (EMA).
13. A multi-layer film according to Claim 12 which further comprises at least one intermediate layer wherein said at least one intermediate layer is interposed between a skin layer and said core layer.
14. A multi-layer film according to Claim 13 wherein said at least one intermediate layer comprises a polyolefin.
15. A multi-layer film according to Claim 14 wherein said at least one intermediate layer further comprises titanium dioxide.
16. A multi-layer film according to Claim 12 wherein the said second skin layer is metallized or coated.
17. A multi-layer film according to Claim 16 wherein the said second skin layer is metallized with a metal selected from the group consisting of aluminum, copper, silver, chromium and gold.
18. A multi-layer film according to Claim 16 wherein said second skin layer is coated with a polymer selected from the group consisting of polyvinylidene chloride (PVdC), acrylic, ethylene acrylic acid, polyvinyl alcohol (PVOH), ethylene methyl acrylate (EMA) and acrylonitrile.
19. A multi-layer film according to Claim 10 wherein said at least one additional layer is an intermediate layer and wherein said at least one additional layer is interposed between said core layer and a first skin layer wherein said first skin layer comprises a polymer selected from the group consisting of high density polyethylene (HDPE), ethylene propylene butylene (EPB) terpolymer, ethylene-propylene random copolymer, medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), propylene butene copolymer and polypropylene homopolymer.
20. A multi-layer film according to Claim 19 wherein said film further comprises a second skin layer which comprises a polymer selected from the group consisting of ethylene propylene butylene (EPB) terpolymer, ethylene-propylene random copolymer, medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), propylene butene copolymer, polypropylene homopolymer, ethylene-vinyl alcohol copolymer (EVOH), ethylene-vinyl acetate copolymer (EVA), ethylene-methyacrylic acid copolymer (EMA) and high density polyethylene (HDPE).
21. A multi-layer film according to Claim 20 which further comprises a second intermediate layer comprising a polyolefin interposed between said core layer and said second skin layer.
22. A multi-layer film according to Claim 21 wherein the said second skin layer is metallized or coated.
23. A multi-layer film according to Claim 22 wherein the said second skin layer is metallized with a metal selected from the group consisting of aluminum, copper, silver, chromium and gold.
24. A multi-layer film according to Claim 22 wherein said second skin layer is coated with a polymer selected from the group consisting of polyvinylidene chloride (PVdC), acrylic, ethylene acrylic acid, polyvinyl alcohol (PVOH), ethylene methyl acrylate (EMA) and acrylonitrile.
25. A multi-layer film according to Claim 10 wherein said at least one additional layer is a first skin layer, and wherein said film further comprises a second skin layer comprising high density polyethylene (HDPE), and wherein said second skin layer is coated.
26. A multi-layer film according to Claim 25 which further comprises at least one intermediate layer wherein said at least one intermediate layer is interposed between a skin layer and said core layer.
27. A multi-layer film according to Claim 10 wherein said at least one additional layer is a first skin layer, and wherein said film further comprises a second skin layer comprising high density polyethylene (HDPE), wherein said second skin layer is metallized.
28. A multi-layer film according to Claim 27 which further comprises at least one intermediate layer wherein said at least one intermediate layer is interposed between a skin layer and said core layer.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US43902399A | 1999-11-12 | 1999-11-12 | |
| US09/439,023 | 1999-11-12 | ||
| US09/471,959 | 1999-12-23 | ||
| US09/471,959 US6495266B1 (en) | 1999-11-12 | 1999-12-23 | Films with improved blocking resistance and surface properties |
| PCT/US2000/030108 WO2001036195A1 (en) | 1999-11-12 | 2000-11-01 | Films with improved blocking resistance and surface properties |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2391261A1 true CA2391261A1 (en) | 2001-05-25 |
Family
ID=27031890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2391261 Abandoned CA2391261A1 (en) | 1999-11-12 | 2000-11-01 | Films with improved blocking resistance and surface properties |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US6495266B1 (en) |
| EP (1) | EP1250223B1 (en) |
| JP (1) | JP2003514687A (en) |
| AT (1) | ATE247560T1 (en) |
| AU (1) | AU781112B2 (en) |
| BR (1) | BR0015184A (en) |
| CA (1) | CA2391261A1 (en) |
| DE (1) | DE60004708T2 (en) |
| ES (1) | ES2204720T3 (en) |
| WO (1) | WO2001036195A1 (en) |
Families Citing this family (44)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7393592B2 (en) * | 2000-11-16 | 2008-07-01 | Exxonmobil Oil Corporation | Lamination grade coextruded heat-sealable film |
| AU2002239587A1 (en) * | 2000-12-22 | 2002-07-08 | Exxonmobil Chemical Patents Inc. | Composites comprising semicrystalline random ethylene / propylenecopolymers |
| US7179506B2 (en) * | 2001-08-24 | 2007-02-20 | Mount Holyoke College | Surface modification of solid phase objects by poly(vinyl alcohol) |
| ES2305371T3 (en) | 2002-06-26 | 2008-11-01 | Avery Dennison Corporation | POLYMERIC FILMS ORIENTED IN THE DIRECTION OF MACHINING. |
| US6844077B2 (en) * | 2003-03-26 | 2005-01-18 | Exxonmobil Oil Corporation | High barrier metallized film with mirror-like appearance |
| EP1518867B1 (en) * | 2003-08-11 | 2007-01-10 | ExxonMobil Chemical Patents Inc. | Polymers of ethylene and optionally, copolymerizable esters, films using such polymers and stretch hood packaging processesusing such films |
| US20050186414A1 (en) * | 2003-10-01 | 2005-08-25 | Toray Plastics (America), Inc. | Polypropylene multi-layer barrier films |
| DE502005004155D1 (en) * | 2004-12-23 | 2008-06-26 | Florian Felix | SLIP COVER FOR WINTER SPORTS |
| US7833208B2 (en) | 2004-12-29 | 2010-11-16 | Kimberly-Clark Worldwide, Inc. | Multilayer absorbent article |
| US20060233988A1 (en) * | 2005-04-18 | 2006-10-19 | Toray Plastics (America), Inc. | Multi-layer barrier film structure |
| US7695822B2 (en) * | 2005-05-10 | 2010-04-13 | Toray Plastics (America), Inc. | Tie-layer for polyolefin films |
| KR101302727B1 (en) * | 2005-05-12 | 2013-09-03 | 클로페이 플라스틱 프로덕츠 캄파니, 인코포레이티드 | Elastomeric films with brittle nonblocking skins |
| US20070031653A1 (en) * | 2005-08-02 | 2007-02-08 | Toray Plastics (America), Inc. | Multi-layer barrier film structure |
| US20070082185A1 (en) * | 2005-10-12 | 2007-04-12 | Japan Polypropylene Corporation | Multi-layered film |
| US20070224376A1 (en) * | 2006-03-23 | 2007-09-27 | Benoit Ambroise | Metallized multi-layer films, methods of manufacture and articles made therefrom |
| BRPI0711963B1 (en) | 2006-06-14 | 2019-09-17 | Avery Dennison Corporation | COMFORTABLE AND HIGHLESS MACHINE DIRECTED ORIENTATION LABELS AND LABELS, AND PREPARATION PROCESSES |
| BRPI0713492A2 (en) | 2006-06-20 | 2012-01-24 | Avery Dennison Corp | multi-layer polymeric film for labeling hot melt adhesives and label and label thereof |
| US7666518B2 (en) * | 2006-07-12 | 2010-02-23 | Toray Plastics (America), Inc. | Reprocessed polyhydroxy amino ether coated polypropylene film |
| CN101489787B (en) | 2006-07-17 | 2012-12-12 | 艾利丹尼森公司 | Asymmetric multilayered polymeric film and label stock and label thereof |
| KR20090093981A (en) * | 2006-12-15 | 2009-09-02 | 피나 테크놀러지, 인코포레이티드 | Polypropylene blown film |
| US20080205800A1 (en) * | 2007-02-28 | 2008-08-28 | Toray Plastics (America), Inc. | Transparent biaxially oriented polypropylene film with low moisture vapor and oxygen transmission rate |
| DE102008015965A1 (en) * | 2008-03-20 | 2009-09-24 | Varta Microbattery Gmbh | Galvanic element with foil seal |
| CA2733574C (en) * | 2008-08-15 | 2017-04-11 | Toray Plastics (America), Inc. | Heat sealable monoaxially-oriented propylene-based film with directional tear |
| EP2172510A1 (en) * | 2008-10-01 | 2010-04-07 | Dow Global Technologies Inc. | Barrier films and method for making and using the same |
| CA2743215A1 (en) * | 2008-11-21 | 2010-05-27 | Berry Plastics Corporation | Multi-layer stretch film |
| EP2382650B1 (en) * | 2008-12-31 | 2019-04-10 | 3M Innovative Properties Company | Roll of a flexible web and method of producing a component comprising the roll of the flexible web |
| CA2803285C (en) * | 2010-07-29 | 2015-12-08 | Toray Plastics (America), Inc. | Heat sealable film with linear tear properties |
| US9669591B2 (en) | 2010-07-29 | 2017-06-06 | Toray Plastics (America), Inc. | Heat sealable film with linear tear properties |
| WO2012016248A2 (en) | 2010-07-29 | 2012-02-02 | Toray Plastics (America), Inc. | High barrier heat sealable film with linear tear properties |
| WO2012039856A1 (en) * | 2010-09-20 | 2012-03-29 | Exxonmobil Oil Corporation | Multi-layer films having improved sealing properties |
| UA110567C2 (en) * | 2012-03-28 | 2016-01-12 | Tarkett Gdl Sa | Multilayer surface covering |
| MX2014014612A (en) * | 2012-05-30 | 2015-07-06 | Toray Plastics America Inc | Heat sealable monoaxially oriented propylene-based film with directional tear. |
| US9676532B2 (en) | 2012-08-15 | 2017-06-13 | Avery Dennison Corporation | Packaging reclosure label for high alcohol content products |
| US10308776B2 (en) * | 2012-12-18 | 2019-06-04 | Exxonmobil Chemical Patents Inc. | Polyethylene films and method of making same |
| US20140271754A1 (en) * | 2013-03-15 | 2014-09-18 | Clopay Plastic Products Company, Inc. | Polymeric materials providing improved infrared emissivity |
| JP6205205B2 (en) * | 2013-08-09 | 2017-09-27 | 昭和電工パッケージング株式会社 | Molding packaging material |
| US20150104628A1 (en) * | 2013-10-11 | 2015-04-16 | The Procter & Gamble Company | Multi-Layer Polymeric Films Containing Energy Dissipating Layers |
| US20150104627A1 (en) * | 2013-10-11 | 2015-04-16 | The Procter & Gamble Company | Multi-Layer Polymeric Films |
| EP3149097A1 (en) | 2014-06-02 | 2017-04-05 | Avery Dennison Corporation | Films with enhanced scuff resistance, clarity, and conformability |
| WO2016138155A1 (en) * | 2015-02-24 | 2016-09-01 | Jindal Films Americas Llc | Monoweb barrier films for cold-seal applications |
| EP3072686B1 (en) * | 2015-03-26 | 2019-01-09 | The Procter and Gamble Company | Multi-layer polymeric films |
| US10899113B2 (en) * | 2016-12-21 | 2021-01-26 | Chevron Phillips Chemical Company Lp | Multilayer cast films with reduced blocking and methods of making same |
| US20200156358A1 (en) * | 2017-04-12 | 2020-05-21 | Dow Global Technologies Llc | Multilayer Films Containing a Slip Agent |
| WO2018217673A1 (en) * | 2017-05-23 | 2018-11-29 | Jindal Films Americas Llc | Metallized, oriented and thin lldpe films |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4345005A (en) | 1979-06-28 | 1982-08-17 | Mobil Oil Corporation | Oriented polypropylene film substrate and method of manufacture |
| DE3069631D1 (en) | 1979-07-27 | 1984-12-20 | Ici Plc | Metallized films and method of producing them |
| US4522887A (en) | 1983-04-18 | 1985-06-11 | Toray Industries, Inc. | Laminated film of biaxially oriented polypropylene and an olefin polymer film |
| US4604322A (en) | 1985-08-06 | 1986-08-05 | Hercules Incorporated | Metallizable polypropylene film |
| US4692380A (en) | 1985-08-06 | 1987-09-08 | Hercules Incorporated | Metallizable polypropylene film |
| DE3701307A1 (en) | 1987-01-17 | 1988-07-28 | Hoechst Ag | MULTILAYER FILM WITH A BIAXIAL STRETCHED POLYPROPYLENE FILM |
| DE3940197A1 (en) | 1989-12-05 | 1991-06-06 | Hoechst Ag | DOUBLE-SIDED SEALABLE, BIAXIAL-ORIENTED POLYOLEFIN MULTILAYER FILM, THEIR PRODUCTION AND THEIR USE |
| CA2047148C (en) | 1990-07-25 | 2000-07-04 | Walter B. Mueller | High melt flow polypropylene medical film |
| DE4035343A1 (en) | 1990-11-07 | 1992-05-14 | Hoechst Ag | HEAT-SEALED PACKAGING FOIL |
| EP0515969B1 (en) | 1991-05-28 | 1996-09-04 | Hoechst Aktiengesellschaft | Biaxially oriented opaque multilayer sealable polypropylene film, process of preparation and use thereof |
| CA2071254A1 (en) | 1991-06-17 | 1992-12-18 | Masatsugi Murakami | Metallized wrapping film |
| US5209884A (en) | 1991-10-11 | 1993-05-11 | Mobil Oil Corporation | Process for producing a multi-layer high opacity film structure of improved whiteness and machinability |
| DE4135097A1 (en) | 1991-10-24 | 1993-04-29 | Hoechst Ag | NON-SEALABLE, MATTE, TRUE, BIAXIAL-ORIENTED POLYOLEFIN MULTILAYER FILM, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| AU662202B2 (en) * | 1992-02-24 | 1995-08-24 | Montell North America Inc. | Polyolefin compositions having good transparency and impact resistance |
| DE4222740A1 (en) | 1992-07-10 | 1994-01-13 | Hoechst Ag | Low-sealing, biaxially oriented polyolefin multilayer film with high shrinkage |
| IT1271420B (en) * | 1993-08-30 | 1997-05-28 | Himont Inc | POLYOLEFINIC COMPOSITIONS WITH A HIGH BALANCE OF RIGIDITY AND RESILIENCE |
| US5491019A (en) | 1994-03-28 | 1996-02-13 | W. R. Grace & Co.-Conn. | Oxygen-permeable multilayer film |
| US5425996A (en) | 1994-04-05 | 1995-06-20 | Borden, Inc. | Biaxially oriented polypropylene metallized white film |
| TW394731B (en) | 1995-03-29 | 2000-06-21 | Toray Industries | Polyolefin-based laminate film |
| JPH1086297A (en) * | 1996-09-12 | 1998-04-07 | Idemitsu Petrochem Co Ltd | Polypropylene multilayered film and laminated film using the same |
-
1999
- 1999-12-23 US US09/471,959 patent/US6495266B1/en not_active Expired - Fee Related
-
2000
- 2000-11-01 BR BR0015184A patent/BR0015184A/en not_active Application Discontinuation
- 2000-11-01 AU AU14525/01A patent/AU781112B2/en not_active Ceased
- 2000-11-01 AT AT00976794T patent/ATE247560T1/en not_active IP Right Cessation
- 2000-11-01 EP EP00976794A patent/EP1250223B1/en not_active Expired - Lifetime
- 2000-11-01 JP JP2001538169A patent/JP2003514687A/en not_active Withdrawn
- 2000-11-01 WO PCT/US2000/030108 patent/WO2001036195A1/en active IP Right Grant
- 2000-11-01 DE DE2000604708 patent/DE60004708T2/en not_active Expired - Lifetime
- 2000-11-01 ES ES00976794T patent/ES2204720T3/en not_active Expired - Lifetime
- 2000-11-01 CA CA 2391261 patent/CA2391261A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| ES2204720T3 (en) | 2004-05-01 |
| US6495266B1 (en) | 2002-12-17 |
| AU781112B2 (en) | 2005-05-05 |
| DE60004708D1 (en) | 2003-09-25 |
| EP1250223B1 (en) | 2003-08-20 |
| DE60004708T2 (en) | 2004-06-17 |
| BR0015184A (en) | 2002-07-23 |
| EP1250223A1 (en) | 2002-10-23 |
| ATE247560T1 (en) | 2003-09-15 |
| WO2001036195A1 (en) | 2001-05-25 |
| JP2003514687A (en) | 2003-04-22 |
| AU1452501A (en) | 2001-05-30 |
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