US20120088054A1 - Non-PVC Film and Non-PVC Film Laminate - Google Patents

Non-PVC Film and Non-PVC Film Laminate Download PDF

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Publication number
US20120088054A1
US20120088054A1 US13/040,642 US201113040642A US2012088054A1 US 20120088054 A1 US20120088054 A1 US 20120088054A1 US 201113040642 A US201113040642 A US 201113040642A US 2012088054 A1 US2012088054 A1 US 2012088054A1
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Prior art keywords
film
layer
recited
advertising
graphic
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Abandoned
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US13/040,642
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English (en)
Inventor
Sujith CHACKO
Frank Y. Shih
Chad Cummings
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Avery Dennison Corp
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Avery Dennison Corp
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Application filed by Avery Dennison Corp filed Critical Avery Dennison Corp
Priority to US13/040,642 priority Critical patent/US20120088054A1/en
Assigned to AVERY DENNISON CORPORATION reassignment AVERY DENNISON CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CUMMINGS, CHAD, CHACKO, SUJITH, SHIH, FRANK Y.
Publication of US20120088054A1 publication Critical patent/US20120088054A1/en
Priority to US14/028,492 priority patent/US10703131B2/en
Priority to US15/801,294 priority patent/US20180050522A1/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • 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
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44F—SPECIAL DESIGNS OR PICTURES
    • B44F1/00—Designs or pictures characterised by special or unusual light effects
    • B44F1/06—Designs or pictures characterised by special or unusual light effects produced by transmitted light, e.g. transparencies, imitations of glass paintings
    • B44F1/066—Designs or pictures characterised by special or unusual light effects produced by transmitted light, e.g. transparencies, imitations of glass paintings comprising at least two transparent elements, e.g. sheets, layers
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/08—Fastening or securing by means not forming part of the material of the label itself
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    • B32B2307/40—Properties of the layers or laminate having particular optical properties
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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    • B32B2307/00—Properties of the layers or laminate
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    • B32B2307/71—Resistive to light or to UV
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    • B32B2307/00—Properties of the layers or laminate
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    • B32B2413/00—Belts
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2605/00—Vehicles
    • 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
    • Y10T428/14—Layer or component removable to expose adhesive
    • Y10T428/1476—Release layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • 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
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2848—Three or more layers
    • 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]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

  • the present invention is in the field of non-PVC films and non-PVC film laminates for use with small format, and large format graphic films and presentations, advertising media, promotional media, static visual communications, vehicle and product wraps and other commercial applications.
  • the film may be clear, transparent, translucent or have other desirable optical properties.
  • PVC films have been used widely in a number of promotional and advertising campaigns, such as outdoor graphics applications in the past. Such applications include signs, banners, fleet marketing graphics, architectural and wall covering, consumer product labeling and other pressure sensitive products.
  • PVC based products There is an increasing awareness on the environmental and health impacts and effects of using PVC based products, which has increased significantly in recent years.
  • PVC-based products there is a movement to reduce or even eliminate PVC-based products from the consumer marketing, promotional and advertising product streams.
  • Films for outdoor marketing and graphics applications ideally should have at least some of the following properties: printability, durability, color retention, and scratch resistance. Conformability and proper mechanical properties such as tensile elongation and tensile strength are also preferable for the application process.
  • a non-conformable film i.e. a film which does not have sufficient elongation or flexibility may not follow the contour of the subject or surface to which it is applied, creating bubbles or gaps between the surface and the film.
  • Insufficient elongation properties may make the film hard to apply over a surface, e.g. those surfaces that have curves, angles, ridges and other non-planar configurations, but too much elongation may deform the film and potentially causing a distortion of the printed indicia.
  • Films with a low tensile strength may cause the film to break easily when being stretched such as when the film is being applied to a non-planar surface.
  • the invention is directed to a non-PVC based film product having similar properties to those of conventional PVC offerings that is suitable for use in connection with marketing promotions, graphics, branding campaigns and other printed or imaged communication based initiatives.
  • a non-PVC film which may be clear, transparent, translucent or have other desirable optical properties, is made of polyurethane, polyurethane-acrylic copolymer, polyurethane-acrylic blend, or urethane-acrylic hybrid polymer.
  • a non-PVC transparent film in another exemplary embodiment of the presently described invention, includes a top layer and a bottom layer.
  • the top layer includes a polyurethane, polyurethane-acrylic copolymer, polyurethane-acrylic blend, or urethane-acrylic hybrid polymer.
  • the bottom layer includes an emulsion based, solvent-based, or extruded non-PVC based polymer.
  • a non-PVC film laminate in another exemplary embodiment of the presently described invention, includes a top layer, a bottom layer, an adhesive layer and a substrate.
  • the top layer includes a urethane-acrylic hybrid polymer.
  • the bottom layer has a non-PVC emulsion based polymer.
  • the substrate layer bears printed or imaged indicia or graphics.
  • an advertising graphic includes a surface having promotional indicia provided thereon, a transparent film having front and back faces, with the back face in contact with the surface and the front face exposed to an atmosphere (e.g. air) or non-atmosphere (e.g. ice).
  • the film includes a first layer and a second layer substantially beneath the first layer, and an adhesive layer beneath the second layer opposite the first layer.
  • the first layer of the film includes a urethane-acrylic hybrid polymer and the second layer includes non-PVC emulsion based polymer.
  • FIG. 2 is a block diagram illustrating an exemplary manufacturing process for making one embodiment of the film according to the present invention
  • FIG. 3 is a flow chart illustrating another manufacturing process for making one embodiment of the film according to the present invention.
  • FIG. 4 is a sectional illustration of one exemplary embodiment of a film according to the present invention.
  • FIG. 5 is a sectional illustration of a further exemplary embodiment of a film laminate according to the present invention.
  • FIG. 6 illustrates the top view of an exemplary embodiment of an advertising graphic applied on a surface according to the present invention.
  • FIG. 7 illustrates an exemplary embodiment of a roll of an advertising graphic according to the present invention.
  • the present invention relates to a film and a film laminate used for outdoor graphics applications, advertising, promotions and other marketing campaigns. More particularly, the present invention relates to a non-PVC transparent film and non-PVC film laminate for use in such applications.
  • the film and film laminate provide suitable outdoor durability, scratch resistance, gloss, conformability, tensile elongation and tensile strength.
  • a single layer transparent film with properties suitable for use in the outdoor graphics applications is made of polyurethane, polyurethane-acrylic copolymer, polyurethane-acrylic blend or polyurethane-acrylic hybrid polymer.
  • a multi-layer transparent film provides properties suitable for use in the outdoor graphics applications.
  • the multi-layer film has at least two layers.
  • the first layer is made of polyurethane, polyurethane-acrylic copolymer, polyurethane-acrylic blend or urethane-acrylic hybrid polymer.
  • the thickness of this first layer can be from about 0.3 mil (7.6 microns) to about 2 mils (50.8 microns).
  • the other layers provide additional mechanical strength, improved adhesion, improved conformability and reduced cost to the overall construction.
  • the number of layers can be determined based on the final requirement on the product, the cost restriction and availability of processing equipments.
  • Such other layers can be made from emulsion polymers, solvent polymers or extruded polymers.
  • Suitable polymers include, without limitation, acrylic polymers, styrene acrylic polymers, vinyl acetate ethylene copolymers, and polyolefins. The thickness of such other layer can vary from about 0 mil to about 2 mils.
  • emulsion polymers include, without limitation, JONCRYL 617A JONCRYL 1987, JONCRYL 98, JONCRYL FLX5000, ACRONAL NX4612X and ACRONAL OPTIVE 410 available from BASF, Ludwigshafen, Germany; and VINNAPAS EF 811 from Wacker Chemicals, Kunststoff, Germany or combinations thereof.
  • a non-PVC transparent film includes a top layer and a bottom layer.
  • the top layer is made of polyurethane, polyurethane-acrylic copolymer, polyurethane-acrylic blend or polyurethane-acrylic hybrid polymer.
  • the bottom layer includes a non-PVC emulsion based polymer.
  • the non-PVC based polymer can be an emulsion based polymer, a solvent based polymer, and/or an extruded polymer.
  • the non-PVC based polymer is an acrylic polymer.
  • graphics refers to a visually perceptible presentation on some surface that is intended to brand, illustrate, entertain, inform, advertise, announce and market a product, service, event or the like.
  • FIG. 1 provides a sectional view of an exemplary film prepared in accordance with the presently described invention.
  • the film 100 has two layers.
  • the film may be transparent, translucent, clear or have other desirable optical properties.
  • the top layer 102 is, in one exemplary embodiment, a urethane-acrylic hybrid polymer.
  • Bottom layer 104 is in the presently described embodiment a strengthening polymer layer.
  • the film layers may have at least one additive added to either one or both, or two additives added to one or both of the layers. If an intermediate layer is included (see FIG. 4 ) the additive may also be present in the intermediate layer.
  • the additives are selected from a group including UV stabilizing agents, free-radical scavengers, cross-linking agents, thickeners, flow and leveling agents, rheology modifiers, surfactants, defoamers, dispersants, wetting agents, dyes, pigments, co-solvents or combinations thereof.
  • the urethane-acrylic hybrid polymer of the top layer 102 is a combination of urethane polymer and acrylic polymer mixed at the molecular level.
  • the top layer 102 is preferred to be created from waterborne dispersions, although other methods for producing the urethane-acrylic hybrid polymer may also be used.
  • the urethane-acrylic hybrid polymer dispersions prepared according to the above described methods have been found to show better mechanical properties when compared to a simple blend of the two polymers due to the molecular level mixing which occurs through use of the foregoing processes.
  • the urethane-acrylic hybrid polymer dispersions can be further improved to be free of N-methylpyrrolidone (NMP), a component typically used as a processing solvent in other applications.
  • NMP N-methylpyrrolidone
  • Suitable urethane-acrylic hybrid polymer dispersions for use in the compositions of the present invention are those with aliphatic acrylic monomers and aliphatic polyurethane components.
  • moisture such as dew, rain or snow; temperature deviations; light and other conditions which may impact the film performance.
  • moisture may cause components of the film or images thereon to bleach out or fade, and the film itself to whiten. Therefore, maintaining a proper balance of hydrophilic monomers and other components is required in order for this film to achieve the required resistance when exposed to such conditions.
  • the monomers and other components should also be selected so as to be balanced to achieve the required tensile properties, block resistance, scratch resistance, transparency, and gloss.
  • the amount of acrylic present in the urethane-acrylic hybrid polymer controls the tensile properties of this top layer.
  • Suitable urethane-acrylic hybrid dispersions for use in the present invention are available under the trade name HYBRIDUR from Air Products, Allentown, Pa., including HYBRIDUR 870; HYBRIDUR 570; HYBRIDUR 580; HYBRIDUR 878; and NEOPAC R9000 from DSM NeoResins, of Waalwijk, The Netherlands.
  • UV blocking agents and free radical scavengers can be added to the top layer to improve the outdoor durability.
  • UV blocking agents suitable for this application are typically benzotrizole based compounds, or other compounds capable of absorbing UV energy in the required region.
  • Commercially available UV absorbing agents include, without limitation, TINUVIN 400 DW, TINUVIN 292 from BASF, Ludwigshafen, Germany; and HOSTAVIN 3310 from Clariant; Muttenz, Switzerland.
  • the amount of UV blocking agent can range from about 0% to about 5%.
  • Free radical scavengers may also be added to the top layer of the film to improve the weather durability of the top layer.
  • Suitable free radical scavengers include but are not limited to TINUVIN 1130, TINUVIN 123 DW from BASF, Ludwigshafen, Germany; and HOSTAVIN 3065 from Clariant, Muttenz, Switzerland.
  • the amount of free radical scavengers can range from about 0% to about 5%.
  • UV blocking systems can also be used for improving weathering durability of this film.
  • These include nano sized zinc oxide and cerium oxide or combinations thereof which may be used to achieve the UV resistance required for the film.
  • Suitable nano metal oxides include but are not limited to NANOBYK 3840, NANOBYK 3810 from BYK Additives, of Altana, Wesel, Germany. The total amount of additives may range from about 0% to about 10%.
  • the bottom layer 104 has a polymer layer that improves tensile properties of the overall film 100 which may also reduce the cost of the overall film.
  • strengthening polymer layer include, without limitation, emulsion based polymers, solvent based polymers, and extruded polymers.
  • Suitable polymers include, without limitation, acrylic polymers, styrene acrylic polymers, vinyl acetate ethylene copolymers, and polyolefins.
  • UV stabilizers and free radical scavengers can also be added to the bottom layer. The additives together can range from about 0% to about 5% of the total formulation.
  • acrylic polymers When acrylic polymers are used in the bottom layer 104 , the acrylic polymers can be the same or different from those used in the top layer 102 . Both aliphatic and aromatic acrylics can be suitable for inclusion in the bottom layer. Suitable acrylic polymers include acrylic emulsions that have superior block resistance, tensile properties and clarity, such as JONCRYL 617A available from BASF, Ludwigshafen, Germany.
  • the thickness of the top layer 102 can range from about 0.5 mil to about 5 mils.
  • the thickness of the bottom layer 104 can range from about 0.5 mil (12.7 microns) to about 5 mils (127 microns).
  • the thickness of the top layer 102 is too thin, the chemical resistance, scratch resistance and outdoor durability of the film may suffer.
  • the thickness of the bottom layer 104 is too thin, the tensile properties of the whole film may not be sufficient. Contrary to the above, when the top and bottom layers 102 , 104 respectively, are too thick, the thickness of the construction may also impact the conformability of the film.
  • the film 100 can be generated using any process suitable for such purpose.
  • the film compositions were first deposited onto a removable support or carrier layer by techniques well known to those skilled in the art. Examples of such techniques include die coating, knife coating, curtain coating and reverse roll coating.
  • the removable support can be separated after the compositions have been dried.
  • An exemplary removable support can be selected from a group including a siliconized belt, a release paper, and a release film such as PET or other suitable materials.
  • FIG. 2 An exemplary method of making a film according to the present invention is illustrated in the block diagram 200 of FIG. 2 .
  • the next step 210 is to provide the top layer components and a removable support.
  • the top layer components are blended to form a top layer composition.
  • the top layer composition includes polyurethane, polyurethane-acrylic copolymer, polyurethane-acrylic blend, or urethane-acrylic hybrid dispersions and at least one of free radical scavenger and UV blocking agent.
  • the removable support is coated with the top layer composition, such as by slot die coating, curtain coating or other acceptable methods.
  • the top layer composition is dried.
  • Drying may occur by using a heated or ambient air environment, curing or by other suitable methods.
  • the bottom layer components are provided.
  • the bottom layer components are blended to form a bottom layer composition.
  • the bottom layer composition includes emulsion polymer or solvent polymer and at least one of a free radical scavenger and a UV blocking agent.
  • the bottom layer composition is coated over the top layer at step 240 , such as by slot die coating.
  • the bottom layer composition is dried.
  • the film is further laminated with a pressure sensitive adhesive (PSA) coated release liner before proceeding to the next step.
  • PSA pressure sensitive adhesive
  • the separation or removal can be accomplished by using a peel blade or knife which serves to separate the film from the carrier or support layer.
  • the film can be separated by the carrier at a sharp angle so that the film can be easily picked up from the carrier or support.
  • the film is rolled up and ready for use.
  • the film can be cut and separated into sheets or sections of equivalent sizes or of varying lengths. The method ends at step 255 .
  • top layer and the bottom layer are substantially coextensive with one another, that is the edges and/or sides are aligned and in juxtaposition. It is of course possible, that the top layer could be applied in a pattern over the bottom layer so that the layers are not completely juxtaposed on one another.
  • the compositions of the top layer and the bottom layer can be coated onto a removable support simultaneously.
  • Flowchart 300 in FIG. 3 illustrates such an exemplary process.
  • the next step 310 is to provide the top layer components, the bottom layer components and a removable support.
  • the top layer components are blended to form a top layer composition.
  • the bottom layer components are blended to form a bottom layer composition.
  • the top layer composition and the bottom layer composition are coated simultaneously using a dual die with the top layer composition contacting the removable support and the bottom layer composition contacting the top layer composition.
  • the top layer and bottom layer can be formed separately and then extruded or coated on to the support or carrier through a common apparatus.
  • the coated compositions are dried.
  • the film is further laminated with a PSA coated release liner before proceeding to the next step.
  • the removable support or carrier layer can be removed from the dried two layer film in step 330 .
  • the film can be rolled up and ready for use or sheeted depending on the requirements of the particular application.
  • the film may then be printed or imaged by conventional methods such as by ink jet and electrostatic printing technologies or alternatively, the film can be applied over another substrate which may have been printed or imaged previously.
  • the method ends at step 335 .
  • the film can be further overcoated with a varnish or other material to provide a glossy appearance. This step may occur during the film forming process, after printing or after collection of the material after the production process has been completed.
  • the film of the present invention can be used in operative association with a graphic or other message.
  • operative association includes applying the film over the graphic or message, including the graphic or message as part of the film either as an additional layer, such as a printing layer or previously printed layer, or applying a graphic or message over the film.
  • the film can be used as a printable media for outdoor applications, architectural and transportation type advertising campaigns and the like.
  • the film can also be used as a protective film to be laminated over a subject, such as a protective laminate for electronic appliances, architectural, artistic or aesthetic elements, a retro-reflective license plate, a retro-reflective signage film, a name plate, a label, automotive exterior and interior parts, and the like. Additional exemplary uses may include safety signs, a graphic display, governmental mandated displays, military applications or a surface that needs protection in the outdoor environment.
  • the film can also include an adhesive layer.
  • the adhesive can be a pressure sensitive adhesive, glue, and any other type of adhesives that are optically transparent, and when used to contact the printed indicia, would not affect the printed indicia.
  • the adhesive may be pattern coated, and may be selected for particular properties such as permanent, removable or repositionable and the like.
  • the adhesive can be random copolymer adhesives or block copolymer adhesives. Random copolymer adhesives include those based upon acrylic and/or methacrylic copolymers, a-olefin copolymers, silicone copolymers, chloroprene/acrylonitrile copolymers, and the like.
  • Block copolymer adhesives including those based upon linear block copolymers (i.e., A-B and A-B-A type), branched block copolymers, star block copolymers, grafted or radial block copolymers, and the like, and natural and synthetic rubber adhesives.
  • a description of useful pressure sensitive adhesives can be found in Encyclopedia of Polymer Science and Engineering, Vol. 13. Wiley-Interscience Publishers (New York, 1988). Additional descriptions of useful pressure sensitive adhesives can be found in Encyclopedia of Polymer Science and Technology, Vol. 1, Interscience Publishers (New York, 1964).
  • release liner When pressure sensitive adhesives are used, a release liner can be used to protect the adhesive from inadvertent contact with unintended surfaces. Any release liner suitable for the chosen adhesive can be used.
  • release liners can be coated papers or films, and super calendared paper, for example. Coating materials suitable for release liners include, for example, silicone-based and fluorine-based materials, or any other material that has the desired releasing properties, for example, waxes and carbamates.
  • FIG. 4 illustrates one embodiment of the current invention.
  • the film 400 has a top layer 402 , a bottom layer 404 , an intermediate layer 406 and a release liner 408 .
  • the release liner can be peeled off to expose the adhesive surface.
  • the film can be attached to the surface to be protected through the adhesive layer.
  • the intermediate layer may include an adhesive layer, a tie coating layer or an adhesion promoting layer.
  • FIG. 5 illustrates a cross-sectional view of one embodiment of a film laminate.
  • the film laminate 500 is comprised of a top layer 502 , a bottom layer 504 , an adhesive layer 506 , an ink layer 510 , and an underlying substrate layer 512 . Though referred to as an ink layer, the ink may not necessarily form a continuous layer.
  • Various printable materials can be used as the underlying substrate layer.
  • a non-PVC based printable material is preferred to make the whole film laminate non-PVC based.
  • International patent application PCT/US08/84812 describes various films created using non-PVC compositions and is incorporated herein by reference in its entirety.
  • Ink or toner anchor coatings such as polyvinyl alcohol can be added to increase the anchorage of the printing to the laminate.
  • FIG. 6 illustrates a top view of an exemplary embodiment of an advertising graphic film applied to a surface according to the present invention.
  • the film laminate bearing advertising graphic 614 is posted on a surface 616 through the use of an adhesive.
  • FIG. 7 illustrates an exemplary embodiment of a roll of the film laminate 700 according to the present invention.
  • thickeners such as thickeners, flow and leveling agents, and rheology modifiers can be added to each of the top and bottom formulations to achieve desired coating quality.
  • suitable thickeners include, without limitation, ACRYSOL RM-2020 NPR, TM8W, and UCAR POLYPHOBE 115 TR from Dow Chemicals, Midland, Mich.
  • suitable flow and leveling agents include without limitation, ZONYL FS300 from Dupont; Polyfox PF-156A from Omnova Solutions; and Masurf from Mason Chemical Company and others with similar chemistry. The percent incorporation can vary from 0% to 10% in both layers.
  • Additional viscosity modifiers can be included in the formulation to modify the viscosity to a desired level and/or to impart desirable flow characteristics.
  • urethane based alkali swellable associative thickeners can be urethane based alkali swellable associative thickeners.
  • Products like UCAR polyphobe 102 from Arkema Emulsion Systems or Rheolate 350 from Element is typical examples that can be used in the formulations.
  • the percent incorporation can vary from between 0% to 10% in both layers.
  • Other components, such as water or isopropyl alcohol (IPA) can also be added to the formulation at about 0% to about 10%.
  • Cross-linking agents can be added to the top layer formulations to improve the mechanical properties of that film layer.
  • suitable cross-linking agents include, without limitation, polyaziridine based CX-100 from DSM Neo Resins, Waalwijk, The Netherlands; UCARLINK XL-255E, ERL-4221, ERL-4234 from Dow Chemicals, Midland, Mich.; and COATOSIL 1770, SILQUEST A-187 from Momentive Performance Materials Inc., Waterford, N.Y.
  • additives for example, surfactants, defoamers, dispersants, wetting agents, dyes, pigments and co-solvents known to those skilled in the art can be added to the composition of each of the top layer and bottom layer.
  • Film thickness is measured using TMI Model 49-70 Precision Micrometer available from Testing Machines Inc. in Ronkonkoma, N.Y.
  • the specimen is placed between an upper and a lower anvil.
  • the upper anvil rests on top of the specimen and the thickness is measured and displayed on the digital readout.
  • This test is used to describe the color of a sample.
  • This 3-dimensional color space system was developed by the International Commission on Illumination (CIE), and defines L* as representing the lightness of the color, ranging from 0 (black) to 100 (white).
  • CIE International Commission on Illumination
  • a* represents the color's position along the red (magenta)/green axis, in which negative values represent green and positive values represent red or magenta
  • b* represents the color's position along the blue/yellow axis, in which negative values represent blue and positive values represent yellow.
  • the test is conducted using a COLOR I 5 Benchtop Spectrophotometer available from X-Rite, Inc., Grand Rapids, Mich.
  • the test method is TAPPI T524 om-94.
  • Accelerated weathering test simulates the damaging effects of long term outdoor exposure of materials by exposing test samples to light, moisture and temperature extremes. Sample is tested and observed for light fastness (fading of colors), and weatherability (cracking, chalking, curling, shrinkage, etc. . . . ). An Atlas CI65A Xenon Arc Weather-Ometer from Atlas Material Testing Technology LLC in Chicago, Ill. is used for this test.
  • a printing pattern with white, yellow, magenta, cyan and black stripes is first printed on a printable substrate.
  • the film of the current invention which may be transparent, translucent, clear or have other desirable optical properties, is then laminated over the print layer to make a film laminate through the use of a pressure sensitive adhesive.
  • the sample is first tested for CIE L*a*b* Color Space before placed in the Weather-Ometer.
  • the sample is allowed to age in the Weather-Ometer for a designated amount of time.
  • the sample is taken out of the Weather-Ometer for CIE L*a*b* Color Space reading and observation for any changes in shrinkage, chalking, cracking etc. . . . If there is no visible change after 2000 hours, and the changes in L*, a* and b* together, represented by ⁇ E, is less than 10, the sample is given a pass grade.
  • ⁇ E value is calculated using the following formula:
  • ⁇ E ⁇ square root over (( ⁇ L 2 + ⁇ a 2 + ⁇ b 2 )) ⁇ .
  • Gloss is measured using a BYK Gardner Micro-TRI-Gloss Gloss Meter from BYK Gardner USA in Columbia, Md.
  • the universal measurement angle 60° is used for the measurement.
  • the acceptable gloss reading is 80 or higher.
  • the tensile elongation and tensile strength of the film is tested using Instron Model 5542 from Instron Co. in Canton, Mass.
  • a modified ASTM D882 was used to determine the tensile strength and percentage elongation of the films of the present invention. The procedure is as follows:
  • the standard requires a minimum ultimate elongation of 180% and a minimum tensile strength of 0.5 pound per square inch (“psi”) (6,895 N/m 2 ).
  • PSA pressure sensitive adhesive
  • Test samples approximately 2.5 inch (63.5 mm) ⁇ 2.5 inch (63.5 mm) are applied over painted 4 inch (101.6 mm) ⁇ 12 inch (304.8 mm) aluminum panels from Frontier Tank Center in Richfield, Ohio.
  • Brazier rivet heads which are 11.4 mm (diameter) ⁇ 3.3 mm (height) ⁇ 7.62 mm (shaft diameter) (0.45′′ (diameter) ⁇ 0.13′′ (height) ⁇ 0.3′′ (shaft diameter)) are uniformly distributed over the aluminum panel.
  • Application is done so as to minimize forming any wrinkles especially around these rivet heads. Entrapped air is released with the use of pin pricks while a brush with hard bristles and plastic squeegee is used to get the best conformation of the film around the rivet.
  • the sample is dwelled for 24 hours at ambient condition. The diameter of the lifted portion of the film around the rivet is measured and recorded. The sample is then placed in Atlas Ci5000 Xenon Arc Weather-Ometer from Atlas Electric Devices Co. in Chicago, Ill., using a UVB 313 bulb for 1000 hours. The sample is then taken out and the diameter of the film lifted around the rivets is measured again. When the change in diameter is less than 0.0625 inch (1.58 mm), the sample is given a pass grade.
  • Test sample is coated with a pressure sensitive adhesive under the trade name S8072 from Avery Dennison Corporation in Pasadena, Calif. at about 30 gram per square meter (gsm) coat weight.
  • the sample is then attached to a clean aluminum panel from 0-Lab Corporation of Cleveland, Ohio.
  • the sample is dwelled at ambient condition for 24 hours.
  • a 5 inch (127 mm) cross hatch in both machine direction (MD) and cross-machine direction (CD) are made on the film.
  • the sample is then aged at 160° F. (71° C.) for 48 hours. The dimension change in the MD and CD are measured. If the shrinkage is less than 0.33% in both directions, the sample is given a pass grade.
  • Table 2 lists five examples of formulations used to create the top layer.
  • Table 3 lists two examples of formulations used to create the bottom layer.
  • Table 4 lists five examples of the film created using Example 5 as the top layer, Example 7 as the bottom layer at various thickness of each layer.
  • HYBRIDUR 870 by itself was made into a film.
  • the film thickness is about 1.7 mils (43 microns)
  • the tensile elongation is 80%.
  • the film thickness is about 2.4 mils (61 microns)
  • the tensile elongation is around 150%.
  • the films show heavy shrinking.
  • Examples 8 to 12 have been tested for various properties.
  • the films have been tested for film thickness, gloss at 60 degrees, and tensile elongation.
  • each sample is coated with about 30 gsm of a pressure sensitive adhesive under the trade name 58072 from Avery Dennison Corporation in Pasadena, Calif.
  • the adhesive coated sample is further laminated onto a printable film.
  • the printable film is Example No. 29B in the PCT application PCT/US08/84812, which has been incorporated by reference herein in its entirety.
  • Table 5 lists the properties measured for each of the samples. All examples have passed the accelerated weathering test, have a gloss at 60 degree higher than 90, and tensile elongation higher than 200. All of the samples have passed the scratch resistance test, rivet testing, and shrinkage test.
  • a three-layer film was created using HYBRIDUR 870 as the top layer, JONCRYL 617 A as the middle layer, and VINNAPAAS EF 811 as the third layer.
  • Each layer can be from about 0.5 mil (12.7 microns) to about 2 mils (50.8 microns) thick.
  • Table 6 lists four additional examples of formulations used to create the top layer.
  • Table 7 lists five additional examples of formulations used to create the bottom layer.

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US20140017433A1 (en) 2014-01-16
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JP2017100455A (ja) 2017-06-08
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KR20130037670A (ko) 2013-04-16
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