WO1979000103A1 - Metallized decorative film laminate and process - Google Patents

Metallized decorative film laminate and process Download PDF

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Publication number
WO1979000103A1
WO1979000103A1 PCT/US1978/000040 US7800040W WO7900103A1 WO 1979000103 A1 WO1979000103 A1 WO 1979000103A1 US 7800040 W US7800040 W US 7800040W WO 7900103 A1 WO7900103 A1 WO 7900103A1
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WO
WIPO (PCT)
Prior art keywords
laminate
film
pressure sensitive
layer
sensitive adhesive
Prior art date
Application number
PCT/US1978/000040
Other languages
French (fr)
Inventor
W Grimes
Original Assignee
Stauffer Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Stauffer Chemical Co filed Critical Stauffer Chemical Co
Priority to DE19782856983 priority Critical patent/DE2856983A1/en
Publication of WO1979000103A1 publication Critical patent/WO1979000103A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal 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
    • B32B15/082Layered products comprising a layer of metal comprising metal 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 comprising vinyl resins; comprising acrylic resins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal 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
    • B32B15/09Layered products comprising a layer of metal comprising metal 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 comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/042Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B44DECORATIVE ARTS
    • B44CPRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/10Applying flat materials, e.g. leaflets, pieces of fabrics
    • B44C1/105Applying flat materials, e.g. leaflets, pieces of fabrics comprising an adhesive layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B44DECORATIVE ARTS
    • B44CPRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/10Applying flat materials, e.g. leaflets, pieces of fabrics
    • B44C1/14Metallic leaves or foils, e.g. gold leaf
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/412Transparent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08Dimensions, e.g. volume
    • B32B2309/10Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105Thickness
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2317/00Animal or vegetable based
    • B32B2317/18Cellulose, modified cellulose or cellulose derivatives, e.g. viscose
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2327/00Polyvinylhalogenides
    • B32B2327/06PVC, i.e. polyvinylchloride
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00Decorative or ornamental articles

Definitions

  • the present invention relates to a metallized decorative film and a process for making it by applying the metallic film by transfer lamination.
  • the decorative film can be used to apply decoration to a desired substrate, e.g., a motor vehicle..
  • Metallized decorative films which are suitable for exterior use and which contain a substantially transparent, plasticized film have been formed in the past by laminating the transparent film to a vacuum metallized film, e.g., a vacuum metallized polyester film, which is then overlaminated with a clear polyvinyl fluoride film which aids in protecting the polyester film from ultraviolet degradation.
  • a vacuum metallized film e.g., a vacuum metallized polyester film
  • a clear polyvinyl fluoride film which aids in protecting the polyester film from ultraviolet degradation.
  • Such complex laminates are rather stiff and difficult to form into complex shapes and are subject to moisture degradation at the exposed edge of the lamination between the polyvinyl fluoride film and the polyester film.
  • the present invention is a metallized decorative film laminate and the process for making it.
  • the laminate comprises: (a) a substantially transparent plastic film; (b) a thin metallic layer having one side attached to one side of the plastic film by means of an adhesive layer; and (c) a pressure sensitive adhesive layer attached to the other side of the metallic layer, said adhesive layer being optionally covered on its exposed surface by a release liner.
  • the film laminate is formed by applying the metallic layer to one side of the plastic film by transfer lamination followed by attachment of the pressure sensitive adhesive layer and, if desired, release liner to the other side of the metallic layer.
  • Figure 1 shows the substantially transparent plastic film to which the metallized layer is to be attached
  • Figure 2 shows the plastic film/metallic layer combination after the latter has been adhesively attached to the plastic film by transfer lamination and as the carrier film in the transfer laminate responsible for the transfer lamination step is being removed;
  • Figure 3 shows the laminate from Figure 2 after application of a tie coat to the protective or release coating remaining from the transfer laminate used in the previous step
  • Figure 4 shows a desired end product after a release liner and pressure sensitive adhesive have been attached to the tie coat in the laminate of Figure 3.
  • Figure 1 shows the substantially transparent plastic film 1 which may be any conventional, substantially transparent and flexible film known to persons of ordinary skill in the art of fabricating decorative pressure sensitive products.
  • the term "substantially transparent” as used herein is intended to encompass those plastic films which are transparent enough to allow a viewer to perceive the decorative effect generated by the metallic layer in the laminate of the present invention.
  • the thickness of the film 1 can range from about 0.05 mm. to about 0.5 mm., and the film can be a homo- or copolymer of vinyl chloride (the preferred film material), a polyester resin, a cellulose resin, or the like. Films of this type are well known in the art and have been used heretofore in forming decorative laminates which differ in construction from the present laminate.
  • Figure 2 shows the laminate subcombination that results when a thin metallic layer 2 is adhesively attached to the plastic film 1. This is accomplished by transfer laminating this layer 2 to the film 1 by means of a "metallized transfer laminate" which is indicated generally by the reference numeral 10 in Figure 2.
  • metallized transfer laminate Such laminates are well known but have not hitherto been used to laminate thin metallic layers to the type of substantially transparent plastic film used herein to form decorative metallized laminates useful as decorative trim, for example, on such substrates as motor vehicles, and the like.
  • Preferred metallized transfer laminates of this type are available under the trademark "Chromtex" from Kurz-Hastings, Inc., Philadelphia, Pa.
  • the metallized transfer laminate comprises an adhesive layer 3 attached to a thin metallic layer 2 which is bonded to a carrier film 4, preferably by means of a protective or release coating 5.
  • the metallized transfer laminate 10 is applied to the substantially transparent film 1 in such a way so as to adhesively bond metallic layer 2 to film 1.
  • the carrier film 4 in the metallized transfer laminate 10 is then stripped off as shown in Figure 2.
  • the carrier film 4 may be formed of a suitable flexible material capable of being coated, if desired, by the resinous solution which constitutes the protective or release coating 5.
  • suitable carrier films 4 are formed from polyethylene terephthalate, crystallized copolymers of polyethylene terephthalate and isophthalate, oriented polystyrene, polyvinyl flouroide, acetate coated paper, and polyolefins, such as polyethylene and polypropylene.
  • the carrier film 4 can have a thickness of from about 0.013 mm. to about 0.125 mm.
  • the protective or release coating 5 is preferably included in the metallized transfer laminate 10 since it aids ⁇ n stripping the carrier film 4 from the laminate construction after the metallic layer 2 has been adhesively bonded to transparent film 1.
  • the release coating 5 may be formed by coating the carrier film 4 and is preferably a resinous solution comprising solvents which do not adversely affect the film 4 and an organic solute not normally compatible therewith.
  • Some representative release coatings include the polyurethanes, silicones, phenol formaldehyde solutions, solvent systems of polyesters and combinations such as methyl methacrylate, ethylene terephthalate, and ethylene isophthalate and water and organic solvent systems of polyvinyl acetate and polyvinyl chloride.
  • the coating used to form release layer 5 may be uniformly applied by conventional coating techniques, such as, direct roller coating, reverse roller coating or by flexographic or rotogravure coating.
  • the release coating 6, when dried, constitutes a layer which, while not bonded to the carrier film 4 in any chemical sense, superficially adheres to it.
  • the metallic layer 2 which is attached, preferably to the surface of release coating 5, may be formed of any metal such as gold; silver, aluminum, magnesium, titanium, nickel, zinc, copper, chromium, cobalt, selenium or the like.
  • Metallic compounds as well as alloy s can also constitute the layer.
  • Aluminum or an aluminum alloy are often preferred for reasons of economy and durability.
  • the thickness of this layer will generally range from about 500 to about 750 Angstroms to about 12,500 Angstroms.
  • the films may be deposited on the release coating 5 by the known thermal evaporation or cathodic sputtering techniques as described in U.S. Patent No. 2,993,806.
  • adhesive layer 3 in the metallized transfer laminate 10 will depend upon the character of the plastic film 1 to which it will be attached.
  • Heat activatable adhesives that are compatible with plastic film 1 can be used and include rubber-phenolic and polyester-isocyanate systems, polyurethane, and solutions of vinyl chloride/ vinyl acetate, vinyl acetate/acrylate and vinyl acetate/ maleate copolymers.
  • the selected adhesive will dry to a water-white clear film and remain clear even upon outdoor exposure.
  • Figure 4 in the Drawings shows a preferred and finished laminate of the present invention wherein a layer of pressure sensitive adhesive 7 and a release liner 8 have been applied to the exposed surface of the tie coat 6.
  • the pressure sensitive adhesive 7 which is used in the present laminate may also be any of the pressure sensitive adhesives which are known and conventionally used in the art.
  • pressure sensitive adhesives which may be utilized in the product of this invention, they may be based upon any elastomeric material such as: (1) natural rubber; (2) synthetic rubbers including, for example, styrene-butadiene copolymers, polyisobutylene, butadiene-acrylonitrile copolymers, polychloroprene, and polyisoprene; (3) acrylic copolymers containing at least 50 percent, by weight, of a C 4 -C 12 alkyl acrylate ester, i.e., an alkyl acrylate ester wherein the alkyl group contains from 4 to 12 carbon atoms, together with a hardening comonomer, for example, vinyl acetate, styrene, methyl methacrylate, methyl acrylate, ethyl acrylate, e
  • a release liner 8 is preferably affixed to the side of the pressure sensitive layer 7 which is furthest removed from film 1.
  • the release liner 8 may be any of the release liners known to persons of ordinary skill in the art of making pressure sensitive products including removable, water soluble protective coatings, and the like.
  • One preferred liner material is silicone coated release paper having a thickness of from about 0.05 mm. to about 0.3 mm.
  • a release liner may not be needed.
  • a preferred process for affixing the combination containing the film 1 and the pressure sensitive adhesive 7 and release liner 8 comprises transfer coating.
  • a fluid solution of the adhesive 7 is applied to the release liner 8, and the resulting composite is heated to dry the adhesive layer 7.
  • the adhesive side of this adhesive/liner laminate is then laminated to the exposed surface of the protective layer 6 at a conventional lamination nip to form the product shown in Figure 4.
  • the adhesive layer 7 is brought into contact with a desired substrate and, when properly positioned, pressure is applied to securely affix it to a desired substrate, e.g., a motor vehicle.
  • This Example illustrates how one product of the present invention was made under laboratory conditions.
  • a transparent polyvinyl chloride (PVC) exterior grade film having a thickness of about 0.07 mm. was laminated to a release coated polyester film which had been metallized followed by coating of the metallized surface with a clear, light stable, heat activatable adhesive ("No. 9353 Chromtex Smooth Gold 78 with 840 adhesive", available from Kurz-Hastings. Inc., Philadelphia, Pa.).
  • This metallized transfer laminate was 0.02 mm. in thickness and had its adhesive side laminated to the matte or dull side of the PVC film by passing both films over a series of heated drums. This raised the temperature of the heat activatable adhesive to about 135°C. for proper activation and formation of a satisfactory bond of the metallized transfer laminate to the PVC film.
  • the polyester film was then removed from the transfer laminate leaving a PVC film/adhesive/metal layer/release coated intermediate structure.
  • a polyurethane polymer tie coat was applied to the release coating.
  • the polyurethane polymer that was used was a fully reacted polyurethane polymer supplied as a solution in toluene and isopropanol (available as "Milloxane LS-516" from Millmaster Onyx).
  • a layer of about 0.025 mm. of pressure sensitive adhesive was applied to the tie coat layer by means of a conventional transfer technique.
  • the adhesive that was used herein was a high molecular weight thermoplastic acrylic terpolymer, which is available as "Durotak 801053" from National Starch and Chemical Corp.
  • the wet adhesive is coated directly onto release paper at a thickness of about 0.076 mm. followed by evaporation of the solvent by heating at 100°C. for 2 minutes. This is followed by lamination of the dried adhesive to the tie coat layer by passing the adhesive/release liner laminate and the PVC containing laminate through a laminating nip.

Abstract

A decorative film laminate is disclosed comprising: (a) a substantially transparent plastic film (1); (b) a thin metallic layer (2) having one side attached to one side of the film (1) by an adhesive layer (3); and (c) a pressure sensitive adhesive layer (7) attached to the other side of the metallic layer (2), the adhesive layer (7) being optionally covered on its exposed surface by a release liner (8). The film laminate is formed by applying the metallic layer (2) to one side of the plastic film (1) by transfer lamination followed by attachment of the pressure sensitive adhesive layer (7), and, if desired release liner (8) to the other side of the metallic layer (2).

Description

METALLIZED DECORATIVE FILM LAMINATE AND PROCESS
Background of the Invention
Field of the Invention
The present invention relates to a metallized decorative film and a process for making it by applying the metallic film by transfer lamination. The decorative film can be used to apply decoration to a desired substrate, e.g., a motor vehicle..
Description of the Prior Art
Metallized decorative films which are suitable for exterior use and which contain a substantially transparent, plasticized film have been formed in the past by laminating the transparent film to a vacuum metallized film, e.g., a vacuum metallized polyester film, which is then overlaminated with a clear polyvinyl fluoride film which aids in protecting the polyester film from ultraviolet degradation. Such complex laminates are rather stiff and difficult to form into complex shapes and are subject to moisture degradation at the exposed edge of the lamination between the polyvinyl fluoride film and the polyester film.
Direct vacuum metallization of a flexible plastic film is difficult to accomplish since various ingredients in the film tend to "gas off" during the metallization process interfering with both the maintenance of the vacuum and the uniformity of the metal deposit. One solution to this problem has been the suggestion that a barrier layer of a long chain thermoplastic polyvinyl resin containing a large number of highly polar groups be placed over the plasticized resin and that this layer be metallized and then coated with a transparent film, U.S. Patent No. 2,993,806 to E. M. Fisher et al. Another solution which has been proposed in U.S. Patent No. 3,107,198 to L. E. Amborski et al. is to treat the metallized layer with a complex compound of the Werner type.
Summary of the invention
The present invention is a metallized decorative film laminate and the process for making it. The laminate comprises: (a) a substantially transparent plastic film; (b) a thin metallic layer having one side attached to one side of the plastic film by means of an adhesive layer; and (c) a pressure sensitive adhesive layer attached to the other side of the metallic layer, said adhesive layer being optionally covered on its exposed surface by a release liner. The film laminate is formed by applying the metallic layer to one side of the plastic film by transfer lamination followed by attachment of the pressure sensitive adhesive layer and, if desired, release liner to the other side of the metallic layer.
Brief Description of the Drawings
Certain preferred embodiments of the present invention are shown in greater enlarged cross-sectional view in the Drawings which accompany and form a portion of this specification wherein:
Figure 1 shows the substantially transparent plastic film to which the metallized layer is to be attached;
Figure 2 shows the plastic film/metallic layer combination after the latter has been adhesively attached to the plastic film by transfer lamination and as the carrier film in the transfer laminate responsible for the transfer lamination step is being removed;
Figure 3 shows the laminate from Figure 2 after application of a tie coat to the protective or release coating remaining from the transfer laminate used in the previous step; and
Figure 4 shows a desired end product after a release liner and pressure sensitive adhesive have been attached to the tie coat in the laminate of Figure 3.
Description of the Preferred Embodiments
Figure 1 shows the substantially transparent plastic film 1 which may be any conventional, substantially transparent and flexible film known to persons of ordinary skill in the art of fabricating decorative pressure sensitive products. The term "substantially transparent" as used herein is intended to encompass those plastic films which are transparent enough to allow a viewer to perceive the decorative effect generated by the metallic layer in the laminate of the present invention. The thickness of the film 1 can range from about 0.05 mm. to about 0.5 mm., and the film can be a homo- or copolymer of vinyl chloride (the preferred film material), a polyester resin, a cellulose resin, or the like. Films of this type are well known in the art and have been used heretofore in forming decorative laminates which differ in construction from the present laminate.
Figure 2 shows the laminate subcombination that results when a thin metallic layer 2 is adhesively attached to the plastic film 1. This is accomplished by transfer laminating this layer 2 to the film 1 by means of a "metallized transfer laminate" which is indicated generally by the reference numeral 10 in Figure 2. Such laminates are well known but have not hitherto been used to laminate thin metallic layers to the type of substantially transparent plastic film used herein to form decorative metallized laminates useful as decorative trim, for example, on such substrates as motor vehicles, and the like. Preferred metallized transfer laminates of this type are available under the trademark "Chromtex" from Kurz-Hastings, Inc., Philadelphia, Pa.
The metallized transfer laminate comprises an adhesive layer 3 attached to a thin metallic layer 2 which is bonded to a carrier film 4, preferably by means of a protective or release coating 5. The metallized transfer laminate 10 is applied to the substantially transparent film 1 in such a way so as to adhesively bond metallic layer 2 to film 1. The carrier film 4 in the metallized transfer laminate 10 is then stripped off as shown in Figure 2.
The carrier film 4 may be formed of a suitable flexible material capable of being coated, if desired, by the resinous solution which constitutes the protective or release coating 5. Examples of suitable carrier films 4 are formed from polyethylene terephthalate, crystallized copolymers of polyethylene terephthalate and isophthalate, oriented polystyrene, polyvinyl flouroide, acetate coated paper, and polyolefins, such as polyethylene and polypropylene. The carrier film 4 can have a thickness of from about 0.013 mm. to about 0.125 mm.
The protective or release coating 5 is preferably included in the metallized transfer laminate 10 since it aids άn stripping the carrier film 4 from the laminate construction after the metallic layer 2 has been adhesively bonded to transparent film 1. The release coating 5 may be formed by coating the carrier film 4 and is preferably a resinous solution comprising solvents which do not adversely affect the film 4 and an organic solute not normally compatible therewith. Some representative release coatings include the polyurethanes, silicones, phenol formaldehyde solutions, solvent systems of polyesters and combinations such as methyl methacrylate, ethylene terephthalate, and ethylene isophthalate and water and organic solvent systems of polyvinyl acetate and polyvinyl chloride. The coating used to form release layer 5 may be uniformly applied by conventional coating techniques, such as, direct roller coating, reverse roller coating or by flexographic or rotogravure coating. The release coating 6, when dried, constitutes a layer which, while not bonded to the carrier film 4 in any chemical sense, superficially adheres to it.
The metallic layer 2 , which is attached, preferably to the surface of release coating 5, may be formed of any metal such as gold; silver, aluminum, magnesium, titanium, nickel, zinc, copper, chromium, cobalt, selenium or the like. Metallic compounds as well as alloy s can also constitute the layer. Aluminum or an aluminum alloy are often preferred for reasons of economy and durability. The thickness of this layer will generally range from about 500 to about 750 Angstroms to about 12,500 Angstroms. The films may be deposited on the release coating 5 by the known thermal evaporation or cathodic sputtering techniques as described in U.S. Patent No. 2,993,806.
The nature of adhesive layer 3 in the metallized transfer laminate 10 will depend upon the character of the plastic film 1 to which it will be attached. Heat activatable adhesives that are compatible with plastic film 1 can be used and include rubber-phenolic and polyester-isocyanate systems, polyurethane, and solutions of vinyl chloride/ vinyl acetate, vinyl acetate/acrylate and vinyl acetate/ maleate copolymers. Preferably, the selected adhesive will dry to a water-white clear film and remain clear even upon outdoor exposure.
Removal of the carrier film 4 from the metallized transfer laminate 10/plastic film 1 combination will leave release coating 5 exposed, if such a coating is present. When such a coating is in the transfer laminate 10 for its release properties, it may be necessary to apply a resinous tie coat 6 (as shown in Figure 3) to the exposed surface of release coating 5 in order to provide a site for later secure attachment of a layer of pressure sensitive adhesive 7 and, if desired, a release liner 8 (as shown in Figure 4). Tie coats which are compatible with and thus have good anchorage to both release coating 5 and the desired pressure sensitive adhesive 7 will adequately serve the intended purpose. The tie coat should also possess good cohesive, strength so that it will not be a site of internal failure in the final laminate. Polyurethane tie coats having the above-described compatibilities and cohesive strength are one representative class of tie coats that may be used.
Figure 4 in the Drawings shows a preferred and finished laminate of the present invention wherein a layer of pressure sensitive adhesive 7 and a release liner 8 have been applied to the exposed surface of the tie coat 6.
The pressure sensitive adhesive 7 which is used in the present laminate may also be any of the pressure sensitive adhesives which are known and conventionally used in the art. As for the applicable tacky, pressure sensitive adhesives which may be utilized in the product of this invention, they may be based upon any elastomeric material such as: (1) natural rubber; (2) synthetic rubbers including, for example, styrene-butadiene copolymers, polyisobutylene, butadiene-acrylonitrile copolymers, polychloroprene, and polyisoprene; (3) acrylic copolymers containing at least 50 percent, by weight, of a C4-C12 alkyl acrylate ester, i.e., an alkyl acrylate ester wherein the alkyl group contains from 4 to 12 carbon atoms, together with a hardening comonomer, for example, vinyl acetate, styrene, methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate and vinyl chloride; and (4) polymers of alkyl vinyl ethers such, for example, as polymethyl vinyl ether and polyethyl vinyl ether. Acrylic pressure sensitive adhesives are most preferred since they have the best balance of adhesive and cohesive properties for the present laminate. The thickness of the adhesive layer 7 will generally be in the range of from about 0.013 mm. to about 0.05 mm.
If the laminate of the present invention is to be manufactured at one location and used at another location, a release liner 8 is preferably affixed to the side of the pressure sensitive layer 7 which is furthest removed from film 1. The release liner 8 may be any of the release liners known to persons of ordinary skill in the art of making pressure sensitive products including removable, water soluble protective coatings, and the like. One preferred liner material is silicone coated release paper having a thickness of from about 0.05 mm. to about 0.3 mm. Of course, if the film/adhesive composite is to be manufactured and applied to a desired substrate at the same manufacturing location, a release liner may not be needed.
A preferred process for affixing the combination containing the film 1 and the pressure sensitive adhesive 7 and release liner 8 comprises transfer coating. In such a process, a fluid solution of the adhesive 7 is applied to the release liner 8, and the resulting composite is heated to dry the adhesive layer 7. The adhesive side of this adhesive/liner laminate is then laminated to the exposed surface of the protective layer 6 at a conventional lamination nip to form the product shown in Figure 4.
When the laminate of the present invention is to be used, the adhesive layer 7 is brought into contact with a desired substrate and, when properly positioned, pressure is applied to securely affix it to a desired substrate, e.g., a motor vehicle.
The Example which follows illustrates certain preferred embodiments of the present invention.
EXAMPLE
This Example illustrates how one product of the present invention was made under laboratory conditions.
A transparent polyvinyl chloride (PVC) exterior grade film having a thickness of about 0.07 mm. was laminated to a release coated polyester film which had been metallized followed by coating of the metallized surface with a clear, light stable, heat activatable adhesive ("No. 9353 Chromtex Smooth Gold 78 with 840 adhesive", available from Kurz-Hastings. Inc., Philadelphia, Pa.). This metallized transfer laminate was 0.02 mm. in thickness and had its adhesive side laminated to the matte or dull side of the PVC film by passing both films over a series of heated drums. This raised the temperature of the heat activatable adhesive to about 135°C. for proper activation and formation of a satisfactory bond of the metallized transfer laminate to the PVC film. The polyester film was then removed from the transfer laminate leaving a PVC film/adhesive/metal layer/release coated intermediate structure.
In order to satisfactorily bond pressure sensitive adhesive and release paper to the release coated side of the structure resulting from the previous steps, approximately 0.005 mm. of a polyurethane polymer tie coat was applied to the release coating. The polyurethane polymer that was used was a fully reacted polyurethane polymer supplied as a solution in toluene and isopropanol (available as "Milloxane LS-516" from Millmaster Onyx). After the tie coat layer was allowed to dry by being heated at 70°C. for 30 sec, a layer of about 0.025 mm. of pressure sensitive adhesive was applied to the tie coat layer by means of a conventional transfer technique. The adhesive that was used herein was a high molecular weight thermoplastic acrylic terpolymer, which is available as "Durotak 801053" from National Starch and Chemical Corp. In such a technique, the wet adhesive is coated directly onto release paper at a thickness of about 0.076 mm. followed by evaporation of the solvent by heating at 100°C. for 2 minutes. This is followed by lamination of the dried adhesive to the tie coat layer by passing the adhesive/release liner laminate and the PVC containing laminate through a laminating nip.
After lamination, a high level of adhesion was exhibited between the layer of pressure sensitive adhesive and tie coat. The resulting laminate is useful as a metallized film for such end uses as automobile trim.
The above Example shows a preferred embodiment of the present invention and should not be construed in a limiting sense. The scope of protection that is sought is given in the claims which follow.

Claims

What is Claimed:
1. A decorative film laminate which comprises:
(a) a substantially transparent plastic film;
(b) a thin metallic layer adhesively attached to one side of the plastic film; and
(c) a layer of pressure sensitive adhesive attached to the thin metallic layer on the side of said metallic layer that is remote, from the side attached to the plastic film.
2. A laminate as claimed in Claim 1 wherein the transparent plastic film is selected from the group consisting of a homopolymer of vinyl chloride, a copolymer of vinyl chloride, a polyester resin, and a cellulosic resin.
3. A laminate as claimed in Claim 1 wherein the transparent plastic film is from about 0.05 mm. to about 0.5 mm. in thickness.
4. A laminate as claimed in Claim 1 wherein the substantially transparent film and the metallic layer are attached to one another by means of an adhesive.
5. A laminate as claimed in Claim 4 wherein the adhesive is a heat activatable adhesive.
6. A laminate as claimed in Claim 1 wherein the metallic layer has a thickness of from about 500 to about 12,500 Angstroms.
7. A laminate as claimed in Claim 1 wherein a release coat layer and tie coat layer lie between the metallic layer and the pressure sensitive adhesive.
8. A laminate as claimed in Claim 1 wherein the pressure sensitive adhesive is an acrylic pressure sensitive adhesive.
9. A laminate as claimed in Claim 1 wherein a rlease liner is also present and is joined to the surface of the pressure sensitive adhesive.
10. A laminate as claimed in Claim 1 wherein the plastic film is polyvinyl chloride , the pressure sensitive adhesive is an acrylic adhesive and a release liner is also present and is attached to the surface of the pressure sensitive adhesive.
11. A method of forming the laminate of Claim 1 which comprises:
(a) adhesively attaching a metallized transfer laminate to one side of the substantially transparent plastic film, said transfer laminate having the thin metallic layer attached to a carrier film;
(b) stripping the carrier film from the product resulting from Step (a); and
(c) attaching a layer of pressure sensitive adhesive to the side of the metallic layer which is remote from the side attached to the substantially transparent film.
12. A method as claimed in Claim 11 which further comprises applying a tie coat to the product resulting from Step (b) prior to application of the layer of pressure sensitive adhesive.
13. A method as claimed in Claim 11 wherein the pressure sensitive adhesive is attached to a release liner when attached to the metallic layer.
PCT/US1978/000040 1977-08-19 1978-07-10 Metallized decorative film laminate and process WO1979000103A1 (en)

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US82621977A 1977-08-19 1977-08-19
US826219 1977-08-19

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AU (1) AU517725B2 (en)
BE (1) BE869779A (en)
CA (1) CA1125156A (en)
CH (1) CH627967A5 (en)
FR (1) FR2400431A1 (en)
GB (1) GB2021295B (en)
IL (1) IL54970A (en)
IT (1) IT7850753A0 (en)
NL (1) NL7807262A (en)
NO (1) NO782804L (en)
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WO (1) WO1979000103A1 (en)

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EP0039729A1 (en) * 1979-11-05 1981-11-18 Dunmore Corp Metalized polyester resin laminate.
FR2491832A1 (en) * 1980-10-09 1982-04-16 Swarovski Co D DECORATIVE PADS FOR ORNAMENTAL USE, IN PARTICULAR FOR DECORATING TEXTILES
US4353766A (en) * 1980-05-19 1982-10-12 Dunmore Corporation Light and heat reflecting surface
EP0133821A2 (en) * 1983-08-10 1985-03-06 Minnesota Mining And Manufacturing Company Layered composite for applying graphics having areas of both mirror-like metal and patterned appearance
GB2167241A (en) * 1984-09-17 1986-05-21 Simmonds Precision Products Hermetic sealing of instrument housing assemblies
US4687680A (en) * 1983-12-28 1987-08-18 Oike Industrial Co., Ltd. Stamping foil
EP0320225A2 (en) * 1987-12-07 1989-06-14 The D.L.Auld Company Decorative article and process for making the same
US4902546A (en) * 1986-04-16 1990-02-20 Dennison Manufacturing Company Transfer metallization laminate
US5030513A (en) * 1989-04-27 1991-07-09 Ppg Industries, Inc. Paint composites
US5030514A (en) * 1989-04-27 1991-07-09 Ppg Industries, Inc. Paint composites
US5242751A (en) * 1989-04-27 1993-09-07 Ppg Industries, Inc. Paint composites
US5262242A (en) * 1990-01-31 1993-11-16 Kansai Paint Co., Ltd. Colored films for use in vacuum forming
WO1994006624A1 (en) 1992-09-17 1994-03-31 Signgold Corporation Gold film for computer-aided sign making system
EP0619180A2 (en) * 1993-04-05 1994-10-12 Fritz Borsi Kg Process for coating a support plate, and support plate thus produced
US5580604A (en) * 1995-03-06 1996-12-03 Chang; Chih C. Method of manufacturing a hot-stamped decal
GB2308332A (en) * 1995-12-21 1997-06-25 Shih Ting Jone Manufacturing vacuum-deposited gold foil
US20130078413A1 (en) * 2011-09-22 2013-03-28 High Voltage Graphics, Inc. Hybrid Mixed Media Decorative Articles and Methods for Making the Same
CN103282213A (en) * 2010-12-28 2013-09-04 3M创新有限公司 Decorative article
US9849652B2 (en) 2012-10-12 2017-12-26 High Voltage Graphics, Inc. Flexible heat sealable decorative articles and method for making the same

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US4241129A (en) * 1978-12-15 1980-12-23 The Dow Chemical Company Delamination resistant multilayer metal/polymer composites
US4407871A (en) 1980-03-25 1983-10-04 Ex-Cell-O Corporation Vacuum metallized dielectric substrates and method of making same
US4431711A (en) 1980-03-25 1984-02-14 Ex-Cell-O Corporation Vacuum metallizing a dielectric substrate with indium and products thereof
JPS57147870U (en) * 1981-03-13 1982-09-17
FR2584021B1 (en) * 1985-06-27 1988-05-13 Radulescu Tudor PROCESS FOR THE MANUFACTURE OF ARTICLES WITH ARTISTIC EFFECTS CREATED BY TRUE GOLD LEAVES, APPLIED INSIDE THE MASS OF POLYMETACRYLIC ESTERS (P.M.M.A.)

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US3014828A (en) * 1957-04-19 1961-12-26 Noc Chemical Arts Inc Di Decoration of plastic film materials
US3235395A (en) * 1962-03-27 1966-02-15 Walter G Scharf Transfers for metallic coatings
DE1569922B2 (en) * 1962-04-09 1973-08-09 Les Ets Marechal S.A., Paris PROCESS FOR THE PRODUCTION OF ADHESIVE FILMS
US3276933A (en) * 1962-09-17 1966-10-04 Radiant Color Company Transfer sheet and method
US3340121A (en) * 1963-12-20 1967-09-05 Carl F Lawrenz Method of applying decorative coatings to metal parts
US3480500A (en) * 1965-05-24 1969-11-25 American Greetings Corp Processes for making debossed decorative metal foil
US3516842A (en) * 1966-04-07 1970-06-23 Diamond Int Corp Heat transfer label
US3516904A (en) * 1966-04-07 1970-06-23 Diamond Int Corp Heat transfer decalcomania for application to plastic bottles made from a laminate of a polyamide adhesive,a printed layer,and a wax like heat release layer
US3660190A (en) * 1967-12-30 1972-05-02 Kalle Ag Process for the manufacture of a composite material having a metal layer
US3615992A (en) * 1968-04-12 1971-10-26 Ppg Industries Inc Method of producing adhesive products
US3837956A (en) * 1970-05-28 1974-09-24 Austral Erwin Eng Co Preparation of plastic-metal products including laminates,composite tubes and the like
US3949139A (en) * 1972-02-10 1976-04-06 Avery Corporation Laminar reflective platelets and compositions and articles comprising them
US3985602A (en) * 1974-10-11 1976-10-12 Sangray Corporation Transfer process and composite sheet therefor
US4012552A (en) * 1975-03-10 1977-03-15 Dennison Manufacturing Company Decorative metal film heat transfer decalcomania
US4041200A (en) * 1975-12-11 1977-08-09 Gaf Corporation Stack of tiles which have a release layer on one major face and an adhesive layer on the opposed major face does not require disposable release interlayers

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0039729A1 (en) * 1979-11-05 1981-11-18 Dunmore Corp Metalized polyester resin laminate.
EP0039729A4 (en) * 1979-11-05 1982-03-29 Dunmore Corp Metalized polyester resin laminate.
US4353766A (en) * 1980-05-19 1982-10-12 Dunmore Corporation Light and heat reflecting surface
FR2491832A1 (en) * 1980-10-09 1982-04-16 Swarovski Co D DECORATIVE PADS FOR ORNAMENTAL USE, IN PARTICULAR FOR DECORATING TEXTILES
EP0133821A2 (en) * 1983-08-10 1985-03-06 Minnesota Mining And Manufacturing Company Layered composite for applying graphics having areas of both mirror-like metal and patterned appearance
EP0133821A3 (en) * 1983-08-10 1986-06-25 Minnesota Mining And Manufacturing Company Layered composite for applying graphics having areas of both mirror-like metal and patterned appearance
US4687680A (en) * 1983-12-28 1987-08-18 Oike Industrial Co., Ltd. Stamping foil
GB2167241A (en) * 1984-09-17 1986-05-21 Simmonds Precision Products Hermetic sealing of instrument housing assemblies
US4902546A (en) * 1986-04-16 1990-02-20 Dennison Manufacturing Company Transfer metallization laminate
EP0320225A2 (en) * 1987-12-07 1989-06-14 The D.L.Auld Company Decorative article and process for making the same
EP0320225A3 (en) * 1987-12-07 1990-01-10 The D.L.Auld Company Decorative article and process for making the same
US5030514A (en) * 1989-04-27 1991-07-09 Ppg Industries, Inc. Paint composites
US5030513A (en) * 1989-04-27 1991-07-09 Ppg Industries, Inc. Paint composites
US5242751A (en) * 1989-04-27 1993-09-07 Ppg Industries, Inc. Paint composites
US5262242A (en) * 1990-01-31 1993-11-16 Kansai Paint Co., Ltd. Colored films for use in vacuum forming
EP0660773A1 (en) * 1992-09-17 1995-07-05 Signgold Corporation Gold film for computer-aided sign making system
WO1994006624A1 (en) 1992-09-17 1994-03-31 Signgold Corporation Gold film for computer-aided sign making system
EP0660773B1 (en) * 1992-09-17 2001-08-01 Signgold Corporation Gold film for computer-aided sign making system
EP0619180A2 (en) * 1993-04-05 1994-10-12 Fritz Borsi Kg Process for coating a support plate, and support plate thus produced
EP0619180A3 (en) * 1993-04-06 1994-12-21 Borsi Kg F Process for coating a support plate, and support plate thus produced.
US5580604A (en) * 1995-03-06 1996-12-03 Chang; Chih C. Method of manufacturing a hot-stamped decal
GB2308332A (en) * 1995-12-21 1997-06-25 Shih Ting Jone Manufacturing vacuum-deposited gold foil
CN103282213A (en) * 2010-12-28 2013-09-04 3M创新有限公司 Decorative article
US20130078413A1 (en) * 2011-09-22 2013-03-28 High Voltage Graphics, Inc. Hybrid Mixed Media Decorative Articles and Methods for Making the Same
US9849652B2 (en) 2012-10-12 2017-12-26 High Voltage Graphics, Inc. Flexible heat sealable decorative articles and method for making the same

Also Published As

Publication number Publication date
GB2021295A (en) 1979-11-28
SE436477B (en) 1984-12-17
FR2400431A1 (en) 1979-03-16
JPS5434386A (en) 1979-03-13
AU517725B2 (en) 1981-08-20
CH627967A5 (en) 1982-02-15
SE7903051L (en) 1979-04-05
GB2021295B (en) 1982-04-28
NL7807262A (en) 1979-02-21
IL54970A0 (en) 1978-08-31
IT7850753A0 (en) 1978-08-17
CA1125156A (en) 1982-06-08
NO782804L (en) 1979-02-20
BE869779A (en) 1979-02-19
IL54970A (en) 1981-03-31
AU3749778A (en) 1980-01-03

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