WO2001036195A1 - Films with improved blocking resistance and surface properties - Google Patents
Films with improved blocking resistance and surface properties Download PDFInfo
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- WO2001036195A1 WO2001036195A1 PCT/US2000/030108 US0030108W WO0136195A1 WO 2001036195 A1 WO2001036195 A1 WO 2001036195A1 US 0030108 W US0030108 W US 0030108W WO 0136195 A1 WO0136195 A1 WO 0136195A1
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- Prior art keywords
- layer
- ethylene
- copolymer
- density polyethylene
- propylene
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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
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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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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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
- 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
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
- B32B2255/205—Metallic coating
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31—Surface property or characteristic of web, sheet or block
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—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
Definitions
- the invention relates to methods for preparing polymer films.
- 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 allow for diverse functionality.
- 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 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.
- 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.
- 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).
- PBT polybutylene terephthalate
- 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 further 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.
- EPB ethylene propylene butylene
- MDPE medium density polyethylene
- LLDPE linear low density polyethylene
- HDPE high density polyethylene
- 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.
- 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.
- HDPE high density polyethylene
- EPB ethylene propylene butylene
- PB propylene butylene copolymer or polypropylene homopolymer or medium density polyethylene (MDPE) or linear low density polyethylene (LLDPE) or blends of the aforementioned polymers.
- MDPE medium density polyethylene
- LLDPE linear low density polyethylene
- 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.
- 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.
- 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.
- 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.
- 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 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 115°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 HDZ128 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 (CaCO 3 ).
- 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.
- 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.
- 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.
- acrylic coatings which are particularly suitable are composed of a terpolymer of methyl acrylate, methyl methacrylate, and methyacrylic acid.
- 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.
- 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.
- 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.
- 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.
- EPB ethylene propylene butylene
- MDPE medium density polyethylene
- LLDPE linear low density polyethylene
- HDPE high density polyethylene
- the film can further include a second skin layer.
- 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 (E VOH) or blends of the aforementioned polymers.
- HDPE high density polyethylene
- EPB ethylene propylene butylene
- MDPE medium density polyethylene
- LLDPE linear low density polyethylene
- EVA ethylene-vinyl acetate copolymer
- EMA ethylene-methyacrylic acid copolymer
- E VOH ethylene-viny
- a suitable HDPE for use as a skin layer is readily available, e.g., Equistar XM6030A or Exxon 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).
- 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.
- 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.
- the film 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 (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 ethylene-vinyl acetate copolymer (EVA) or ethylene-methyacrylic acid copolymer (EMA) or ethylene-vinyl alcohol copolymer (EVOH) or blends of the aforementioned polymers.
- HDPE high density polyethylene
- EPB ethylene propylene butylene
- PB ethylene-propylene random copolymer or propylene butylene
- PB medium density polyethylene
- EVA ethylene-vinyl acetate copolymer
- EMA ethylene-methyacrylic acid copolymer
- EVOH ethylene-vin
- these EP impact copolymer resins outperform (in the context of blocking) traditional EP random copolymers and EPB terpolymer, both containing antiblocking additives.
- the blocking forces are dramatically reduced when impact copolymer is used either as a skin or intermediate layers.
- 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).
- When 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.
- 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.
- a resulting metallized layer containing 99.88% by weight aluminum is deposited upon the HDPE 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 fluoropolymer which is added to the HDPE layer.
- CS unmetallized cold seal
- EXAMPLE 1 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 EP impact copolymer provides lower blocking forces when compared to EP random copolymer.
- 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 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.
- 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.
- Table IV shows the effect the use of impact copolymer as a skin layer has on blocking forces and COF in multilayer films.
- 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.
- Figures 1 and 2 show the effect that the using impact copolymer as a skin layer in contrast with using homopolymer polypropylene or terpolymer as a skin layer.
- 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 te ⁇ olymer.
- the blocking conditions are set at 140°F, 750 psi for one hour.
- the impact copolymer is blended into the treated skin resin.
- the treated surface was tested against itself.
- the COF of the samples with impact 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.
- 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 VI.)
- 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
- Resins HDPE, PP homopolymer, EVOH copolymer, EP random copolymer, PB copolymer, EPB te ⁇ olymer, MDPE, LLDPE, EVA, EMA or blends of above.
- Additives Optional use of antiblock Layer Thickness: 2-16 ga thickness.
- Isotactic PP homopolymer HDPE, or LLDPE (20-100 ga thickness) w/optional addition of cavitating agent
- Resins Polyolefin based Additives: Optional Use of TiO 2 Layer Thickness: 4-28 ga thickness
- Resins HDPE, PP homopolymer, EP random copolymer, PB copolymer, EPB te ⁇ olymer, MDPE, LLDPE or blends of above
- 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.
- WVTR Water Vapor Transmission Rate
- OTR Oxygen Transmission Rate
- This metallized barrier 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.
- 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. 2 /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.
- the film in this example can be coated on the side opposite the EP impact copolymer with other coatings including acrylic, ethylene acrylic acid, PVOH, EMA and acrylonitrile.
- Table VHI 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 VHI.
- 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 blocking resistance when the side opposite the coating contains EP impact copolymer.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00976794A EP1250223B1 (en) | 1999-11-12 | 2000-11-01 | Films with improved blocking resistance and surface properties |
BR0015184A BR0015184A (en) | 1999-11-12 | 2000-11-01 | Films with blocking resistance and improved surface properties |
CA 2391261 CA2391261A1 (en) | 1999-11-12 | 2000-11-01 | Films with improved blocking resistance and surface properties |
DE2000604708 DE60004708T2 (en) | 1999-11-12 | 2000-11-01 | FILMS WITH IMPROVED BLOCKING RESISTANCE AND SURFACE PROPERTIES |
AU14525/01A AU781112B2 (en) | 1999-11-12 | 2000-11-01 | Films with improved blocking resistance and surface properties |
JP2001538169A JP2003514687A (en) | 1999-11-12 | 2000-11-01 | Film with improved blocking resistance and surface properties |
AT00976794T ATE247560T1 (en) | 1999-11-12 | 2000-11-01 | FILMS WITH IMPROVED BLOCKING RESISTANCE AND SURFACE PROPERTIES |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US43902399A | 1999-11-12 | 1999-11-12 | |
US09/439,023 | 1999-11-12 | ||
US09/471,959 US6495266B1 (en) | 1999-11-12 | 1999-12-23 | Films with improved blocking resistance and surface properties |
US09/471,959 | 1999-12-23 |
Publications (1)
Publication Number | Publication Date |
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WO2001036195A1 true WO2001036195A1 (en) | 2001-05-25 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US2000/030108 WO2001036195A1 (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) |
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Citations (4)
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 |
EP0536917A1 (en) * | 1991-10-11 | 1993-04-14 | Mobil Oil Corporation | Multi-layer high opacity film structure of improved whiteness and machinability |
JPH1086297A (en) * | 1996-09-12 | 1998-04-07 | Idemitsu Petrochem Co Ltd | Polypropylene multilayered film and laminated film using the same |
US5789046A (en) * | 1990-07-25 | 1998-08-04 | W. R. Grace & Co.-Conn. | High melt flow polypropylene medical film |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0023389B1 (en) | 1979-07-27 | 1984-11-14 | Imperial Chemical Industries 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 |
US4692380A (en) | 1985-08-06 | 1987-09-08 | Hercules Incorporated | Metallizable polypropylene film |
US4604322A (en) | 1985-08-06 | 1986-08-05 | 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 |
DE4035343A1 (en) | 1990-11-07 | 1992-05-14 | Hoechst Ag | HEAT-SEALED PACKAGING FOIL |
DE59207030D1 (en) | 1991-05-28 | 1996-10-10 | Hoechst Ag | Sealable, opaque, biaxially oriented polypropylene multilayer film, process for its production and its use |
CA2071254A1 (en) | 1991-06-17 | 1992-12-18 | Masatsugi Murakami | Metallized wrapping film |
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 |
-
1999
- 1999-12-23 US US09/471,959 patent/US6495266B1/en not_active Expired - Fee Related
-
2000
- 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 ES ES00976794T patent/ES2204720T3/en not_active Expired - Lifetime
- 2000-11-01 AT AT00976794T patent/ATE247560T1/en not_active IP Right Cessation
- 2000-11-01 BR BR0015184A patent/BR0015184A/en not_active Application Discontinuation
- 2000-11-01 WO PCT/US2000/030108 patent/WO2001036195A1/en active IP Right Grant
- 2000-11-01 AU AU14525/01A patent/AU781112B2/en not_active Ceased
- 2000-11-01 CA CA 2391261 patent/CA2391261A1/en not_active Abandoned
- 2000-11-01 DE DE2000604708 patent/DE60004708T2/en not_active Expired - Lifetime
Patent Citations (4)
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 |
US5789046A (en) * | 1990-07-25 | 1998-08-04 | W. R. Grace & Co.-Conn. | High melt flow polypropylene medical film |
EP0536917A1 (en) * | 1991-10-11 | 1993-04-14 | Mobil Oil Corporation | Multi-layer high opacity film structure of improved whiteness and machinability |
JPH1086297A (en) * | 1996-09-12 | 1998-04-07 | Idemitsu Petrochem Co Ltd | Polypropylene multilayered film and laminated film using the same |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 1998, no. 09 31 July 1998 (1998-07-31) * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7833208B2 (en) | 2004-12-29 | 2010-11-16 | Kimberly-Clark Worldwide, Inc. | Multilayer absorbent article |
US8353888B2 (en) | 2004-12-29 | 2013-01-15 | Kimberly-Clark Worldwide, Inc. | Multilayer absorbent article |
CN110709241A (en) * | 2017-04-12 | 2020-01-17 | 陶氏环球技术有限责任公司 | Multilayer films containing slip agents |
Also Published As
Publication number | Publication date |
---|---|
EP1250223B1 (en) | 2003-08-20 |
DE60004708D1 (en) | 2003-09-25 |
CA2391261A1 (en) | 2001-05-25 |
ATE247560T1 (en) | 2003-09-15 |
US6495266B1 (en) | 2002-12-17 |
AU781112B2 (en) | 2005-05-05 |
DE60004708T2 (en) | 2004-06-17 |
BR0015184A (en) | 2002-07-23 |
EP1250223A1 (en) | 2002-10-23 |
JP2003514687A (en) | 2003-04-22 |
ES2204720T3 (en) | 2004-05-01 |
AU1452501A (en) | 2001-05-30 |
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