Decorative sheet material simulating the appearance of a base coat/clear coat paint finish

Abstract

A flexible decorative sheet material for use in surfacing automobile body panels and the like is disclosed. The sheet material is characterized by having the appearance of a glossy base coat/clear coat automotive paint finish. The material comprises a substantially transparent outer layer, and a pigmented coating on the undersurface of the outer layer which is visible therethrough. The pigmented coating preferably has reflective flakes uniformly distributed therein to impart to the sheet material the appearance of a base coat/clear coat paint finish. Also disclosed are shaped articles which have such sheet materials adhered to one side thereof, and a method for making such sheet materials.

Claims

That which we claim is: 1. A flexible decorative sheet material suitable for use in surfacing panels, such as automobile body panels, said sheet material being characterized by having the appearance of a glossy, base coat/clear coat automotive paint finish, and comprising a flexible outer layer having a smooth, glossy outer surface with a distinctness of image value of 65 percent or greater and formed of a flexible, optically clear weatherable polymer, and a pigmented coating adhered to the opposite surface of said outer layer and visible through the clear outer layer. 2. A decorative sheet material as claimed in claim 1 wherein said flexible outer layer has a distinctness of image value of 75 percent or greater. 3. A decorative sheet material as claimed in claim 1, wherein said outer layer has a 2° haze value of 1 percent or less. 4. A decorative sheet material as claimed in claim 1, further comprising a bonding layer carried by said pigmented coating. 5. A decorative sheet material as claimed in claim 1, wherein said pigmented coating includes reflective flakes oriented generally parallel to said outer layer. 6. A decorative sheet material as claimed in claim 1, wherein said pigmented coating comprises a first pigmented coating on certain portions of the undersurface of the outer layer and visible therethrough, and a second pigmented coating of a different color on certain other portions of the undersurface of the outer layer, which second pigmented coating is also visible therethrough. 7. A decorative sheet material as claimed in claim 1, wherein said pigmented coating is of a thickness less than said outer layer. 8. A decorative sheet material as claimed in claim 1, wherein said outer layer has a thickness of about 0.5 to 300 mils. 9. A decorative sheet material as claimed in claim 1, wherein said weatherable polymer is selected from the group consisting of fluoropolymers, acrylate polymers, urethane polymers, vinyl polymers, and blends thereof. 10. A decorative sheet material as claimed in claim 1, wherein said substantially clear layer comprises a cast, substantially molecularly unoriented film. 11. A flexible decorative sheet material suitable for use in surfacing panels, such as automobile body panels, said sheet material being characterized by having the appearance of a glossy, base coat/clear coat automotive paint finish, and comprising a flexible optically clear outer layer having a smooth outer surface with a distinctness of image value of 65 percent or greater and formed of a cast, substantially molecularly unoriented flexible weatherable polymer selected from the group consisting of fluoropolymers, acrylate polymers, urethane polymers, vinyl polymers, and blends thereof, and a pigmented coating adhered to the opposite surface of said outer layer formed of a flexible polymer with pigments distributed therein. 12. A decorative sheet material as claimed in claim 11, wherein said pigmented coating has reflective flakes uniformly distributed therein in generally parallel alignment to said film to impart to the sheet material the appearance of a base coat/clear coat paint finish. 13. A decorative sheet material as claimed in claim 11, wherein the mean angle of inclination of said flakes to said film is less than about 6.5 degrees. 14. A shaped article having a contoured decorative outer surface, comprising a supporting substrate and a decorative sheet material adhered to one side of said substrate and conforming to said contoured surface, said decorative sheet material being characterized by having the appearance of a glossy, base coat/clear coat automotive paint finish, and comprising a flexible outer layer having a smooth outer surface with a distinctness of image value of 65 percent or greater and formed of a flexible, optically clear weatherable polymer, and a pigmented coating adhered to the opposite surface of said outer layer formed of a flexible polymer with pigments distributed therein. 15. A shaped article as claimed in claim 14, wherein said substantially clear outer layer comprises a substantially molecularly unoriented cast film. 16. A shaped article as claimed in claim 14, wherein said pigmented coating has reflective flakes uniformly distributed therein. 17. A shaped article as claimed in claim 14, wherein said supporting substrate is a rigid metal substrate. 18. A shaped article as claimed in claim 14, wherein said supporting substrate is a molded polymer substrate. 19. A shaped article as claimed in claim 14, further comprising a bonding layer carried by said pigmented coating and adhered to said supporting substrate.
CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of application Ser. No. 924,299 filed Oct. 28, 1986, now U.S. Pat. No. 4,810,540. FILED OF THE INVENTION The present invention relates to sheet materials generally, and particularly relates to a sheet material which can be used to provide a decorative surface on automobile body panels and the like. BACKGROUND OF THE INVENTION Among the most important selling features of automobiles is the quality of their painted finish. For this reason, nearly half of automobile assembly costs are devoted to coating operations. See generally, "Automobile Coatings: Helping Detroit Woo Consumers", Chemical Week, 30 (July 4, 1984). As aerodynamic body styles become more prevalent, and sharp edges and other decorative detail features continue to be removed from automobile bodies, paint finish will exert an increasingly important influence on the overall decorative appearance of automobiles. For these reasons, about 70% of the cars sold in the U.S. market are coated with a metallic finish. The difference in brightness and hue obtained when such a finish is observed emphasizes the styling lines of the car, highlighting small curvatures. This effect is known as "flop." The new base coat/clear coat paint finishes, which provide "wet look" paint finishes with or without a metallic appearance, can be used to produce a very high quality metallic finish with excellent flop, and are emerging as the finish of choice in the automobile industry. See, e.g., J. Schrantz, "Painting the Corvette", Industrial Finishing, 18 (March, 1984). In addition, because the clear coat protects the base coat, greater quantities of pigments can be incorporated into the base coat without the weatherability of the finish being unacceptably decreased. Base coat/clear coat finishes, however, and particularly metallic finishes, pose significant (and expensive) pollution problems arising from the evaporation of harmful paint solvents. Moreover, they are difficult to provide on plastic automobile body panels, which are becoming a popular mode of construction in the industry. Finally, base coat/clear coat paint finishes in general involve multiple painting steps which are very expensive to perform when high quality standards are maintained. Accordingly, objects of the present invention are to provide a way to produce automobiles and the like with high quality decorative finishes like a base coat/clear coat finish, which can be used on molded plastic body panels, which does not require expensive painting steps, and which serves to reduce the emission control problems previously faced by manufacturers who wished to produce automobiles with base coat/clear coat finishes. SUMMARY OF THE INVENTION The foregoing objects are achieved by a flexible decorative sheet material, disclosed herein, for use in surfacing automobile body panels and the like. This sheet material is characterized by having the appearance of a base coat/clear coat paint finish when viewing the outer surface thereof. The sheet material comprises a glossy, substantially transparent outer layer and a pigmented coating on the undersurface of the outer layer and visible therethrough. The glossy "wet look" is achieved by a combination of layered coatings, with the outer or top layer being of good optical clarity and exceptionally good surface smoothness. The outer layer must be of high gloss and should possess a high distinctness-of-image value, preferably of 65 percent or higher, and most desirably of 75 percent or higher. The outer layer should also have low surface haze, preferably a 2 degree haze value of 1 percent or less. Additionally, the outer layer must be weatherable, so as to withstand exposure to sunlight and temperature extremes without hazing, color change, cracking, crazing or embrittlement. These properties are achieved in accordance with the present invention by casting the clear outer layer on a smooth high gloss carrier, and thereafter coating the pigmented coating layer onto the outer layer by suitable coating application methods such as spraying or roll coating. The advantage of spraying is the resulting similarity in appearance with spray-applied paint, although this application method is not essential. The outer layer is formed from a substantially clear weatherable polymer, preferably a polymer selected from the group consisting of fluoropolymers, acrylate polymers, urethane polymers, vinyl polymers and blends thereof. The transparent outer layer is preferably of a thickness greater than that of the pigmented coating layer. The precise thickness of the pigmented coating is, however, selected to impart the specific predetermined appearance to the sheet material which is desired. The pigmented coating optionally has reflective flakes uniformly distributed therein to impart to the sheet material the appearance of a metallic base coat/clear coat paint finish. The reflective flakes in the pigmented coating are preferably oriented generally parallel to the outer layer. Sheet materials of the present invention include dual-color sheet materials which comprise a substantially transparent outer layer and a pigmented coating on the undersurface thereof, wherein the pigmented coating comprises a first pigmented coating on certain portions of the undersurface of the outer layer and visible therethrough, and a second pigmented coating of a different color on certain other portions of the undersurface of the outer layer, which second pigmented coating is also visible therethrough. Also disclosed herein are shaped articles having a contoured decorative outer surface suitable for use as automobile body panels and the like. The articles comprise a supporting substrate and a decorative sheet material adhered to one side of the substrate, conforming to the contoured surface to impart to the outer surface the appearance of a base coat/clear coat paint finish. The decorative sheet material is as described above. The supporting substrate, which may be formed of a number of materials, is preferably a rigid metal substrate or a molded polymer substrate. The present invention allows paint and finish handling steps involving solvents to be performed in a central plant, and the "finish" to be shipped, in sheet form, to a number of automobile assembly plants and the like. This allows solvent emission control problems attendant to such procedures to be handled in a centralized location, reduces the emission control expenses at numerous assembly plants, and serves to reduce the cost and complexity of solvent emissions control in general. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view of a decorative sheet material of the present invention. FIG. 2 is a schematic diagram which illustrates the properties of sheet materials of the present invention. FIG. 3 is a schematic illustration of a method for making decorative sheet materials of the present invention. FIG. 4 is an article of the present invention with a portion broken away to show the decorative sheet material on the outer surface thereof. DETAILED DESCRIPTION OF THE INVENTION A decorative sheet material 10 of the present invention is illustrated in FIG. 1. The sheet material comprises a substantially clear outer film 11, a pigmented coating 12 on the undersurface of the film 11, and a bonding layer 13 carried by the inner surface of the pigmented coating. Films 11 for practicing the present invention should be selected so they are transparent, thermoformable and weatherable. The film 11 is about 0.5 to about 300 thousandths of an inch thick, and is preferably from about one to about two thousandths of an inch thick. Such films are preferably substantially molecularly unoriented cast films, as opposed to films which have been oriented or biaxially oriented, and are preferably substantially colorless. The cast film is formed before the pigmented coating is applied thereto. Such films are prepared by a number of known liquid casting methods, such as by spreading a solvent solution having a polymer dissolved therein onto a carrier with a casting die, doctor bar, or reverse roll coater, then evaporating the solvent, and then stripping the polymer film from the carrier. The reverse roll coating method is the preferred method of making liquid cast films for the present invention. Other liquid casting methods are also known and useful for practicing the present invention. In appropriate cases, a plastisol, organosol, or dispersion of the polymer can be cast onto the carrier instead of a solvent solution. For example, polytetrafluoroethylene, which is virtually insoluble, can be liquified and cast as a dispersion. Such liquid cast film processes, and some current uses of cast films, are discussed in Plastics Engineering, at pages 29-33 (May, 1983). Thus, for purposes of the present invention, "substantially molecularly unoriented cast films" are liquid cast films, and not melt cast films or films formed by extrusion. Polymers suitable for forming such cast films are preferably weatherable polymers selected to provide a film which will not significantly fade, peel, crack, or chalk when exposed to the environment, for the intended life of the product for which the decorative sheet material is made. A number of known testing procedures, in which objects are exposed to either the natural environment over an extended time or a harsh artificial environment for a short time, are used to determine the weatherability of polymers. Such weatherable polymers include fluoropolymers, acrylate polymers, urethane polymers, vinyl polymers, and blends thereof. Acrylate polymers useful for practicing the present invention are obtained from a variety of acrylic monomers, such as acrylic and methacrylic acids, and their amides, esters, salts, and corresponding nitriles. Particularly suitable monomers for such polymers are methyl methacrylate, ethyl acrylate, and acrylonitrile. The polymers may each be used in the form of homopolymers, or with various other monomers which can be copolymerized therewith. Additional illustrative examples of acrylate polymers useful for the present invention are polyacrylates and polymethacrylates which are homopolymers and copolymers of acrylic acid ester and methacrylic acid ester, such as, for example, polyacrylic acid isobutyl ester, polymethacrylic acid methyl ester, polymethacrylic acid ethylhexyl ester, polyacrylic acid ethyl ester; copolymers of various acrylic acid esters and/or methacrylic acid esters, such as, for example, methacrylic acid methyl ester/acrylic acid cyclohexyl ester copolymers; and copolymers of acrylic acid esters and/or methacrylic acid esters with styrene and/or alphamethylstyrene, as well as the graft polymers and copolymers and polymer mixtures composed of acrylic esters, methacrylic acid esters, styrene and butadiene. A group of transparent, weatherable blends of acrylate polymers and polyvinylidene fluoride polymers useful for practicing the present invention are disclosed in U.S. Pat. No. 3,524,906. The disclosures of this patent, and all other patent references cited herein, are specifically intended to be incorporated herein by reference. Fluoropolymers useful for practicing the present invention include polymers and copolymers formed from trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, monochlorotrifluoroethylene and dichlorodifluoroethylene. Copolymers of these monomers formed from fluoroolefins such as vinylidene fluoride are also useful. Further illustrative examples of fluoropolymers useful for practicing the present invention include polyvinyl fluoride and polyvinylidene fluoride. The fluoropolymer may be a fluorinated ethylene/propylene copolymer (the easily fabricated "FEP" resins), or a copolymer of ethylene/chlorotrifluoroethylene such as "HALAR." Vinylidene fluoride/hexafluoropropene and vinylidene fluoride/perfluoro (alkyl vinyl ether) dipolymers and terpolymers with tetrafluoroethylene are additional illustrative fluoropolymers useful for practicing the present invention. A preferred weatherable polymer for use in the present invention is an alloy of an acrylic polymer and polyvinylidene fluoride, such as "FLUOREX" (a trademark of Rexham Corporation). Urethane polymers useful for practicing the present invention are prepared by reacting a polyisocyanate with a compound containing at least two active hydrogen atoms, such as a polyol, a polyamine, or a polyisocyanate. Polyurethane resins for use in the present invention should be selected from resins in which the reactants have been chosen to provide weatherable, thermoformable polymers. Numerous suitable polyurethane resins useful for practicing the present invention are available. Generally, aromatic polyisocyanates tend to yellow, and aliphatic polyisocyanates are more preferred. Particularly noteworthy recent developments in this area are disclosed in U.S. Pat. No. 4,578,426 (disclosing resins which give coatings resistant to gasoline and having high flexibility, scratch resistance and weather resistance) and U.S. Pat. No. 4,501,852 (disclosing chemical resistant, abrasion resistant, elastic and durable polyurethanes). In addition, films formed of vinyl polymers, such as polyvinylchloride films and films formed from copolymers thereof, may also be used to practice the present invention, though such films are generally not as weatherable as films formed from the previously discussed polymers. The pigmented coating 12 is preferably formed of the same polymer as the outer film 11, or may optionally be formed of a different polymer which will bond to the outer film 11 during the manufacture of the decorative sheet material, as explained below. Pigments are dispersed in the polymer at a suitable concentration to form a substantially opaque coating of the desired color. The specific pigments are selected as desired depending upon the desired color. When the decorative sheet material 10 of the invention is used in automobile body applications, the pigments are selected so that the coating will match the automotive paint standard, and the pigments employed may include conventional nonmetallic pigments as well as metallic pigments. In the embodiment illustrated in FIG. 1 the pigmented coating 12 is a metallic finish, and to this end, the coating has reflective flakes 14 uniformly distributed therein. The reflective flakes 14 may, for example, comprise aluminum flakes or mica flakes. Mica flakes used in the present invention may be untreated, or tinted or otherwise surface treated, as known in the art. The reflective flakes 14 are oriented generally parallel to the outer film 11, with the flakes preferably being oriented so the mean angle of inclination of the flakes to the outer film 11 is less than about 6.5 degrees. The precise limits of the angle of inclination depends on a number of conditions, including the particular type of reflective flake used, the composition of the pigmented coating 12, and the composition of the outer preformed film 11. The flakes contribute to the "flop" effect described previously. Flop is due to the orientation of the reflective flakes generally parallel to the surface of the finish. As illustrated in FIG. 2, the observer at A' sees the light A reflected by the flakes. A similar situation exists for the observer at B' with light B. Because of the phenomenon of flop, light intensity is lower at B' than A'; i.e., the finish appears darker at B' than A'. The bonding layer 13 carried by the inner surface of the pigmented coating 12 may comprise a coating or preferably a film laminated to the pigmented coating. Bonding of the pigmented coating 12 to a film bonding layer can be achieved in accordance with known laminating procedures, and with known adhesives. The bonding layer 13 is selected to bond to the substrate for which the decorative sheet material is intended. For example, a decorative sheet material having a fusible olefin bonding layer can be placed in a mold during injection of an olefin resin. Another approach is to bond a PVC film to a fluoropolymer pigment layer with an acrylic adhesive and, in turn, bond the PVC film to an olefin film with a polyester isocyanate adhesive. The pigmented coating 12 may also be laminated to an olefin film with a permanent type acrylic pressure-sensitive adhesive. Still another approach is to coat the pigmented layer 12 with a soluble olefin resin which adheres thereto and bonds to the injected resin without having or requiring an olefin film layer. Such a resin is chlorinated polyolefin 343-1 from Eastman Kodak. This resin may be used in conjunction with an acrylic primer or ingredient to bond to desired fluorocarbon films. Corona treatment of the olefin surface to be bonded to the cast film may optionally be used to achieve an optimum bond. Bonding may also be improved by surface treating the cast film, as by corona treatment. The preferred method for making the decorative sheet material 10 of the present invention is by reverse-roll coating, as illustrated in FIG. 3. Reverse-roll coating involves providing a puddle 20 of polymer solution between an applicator roll 21 and a metering roll 22. The rolls (21,22), which rotate in the same direction, are spaced apart a predetermined distance to meter a film 23a of the solution onto the applicator roll. The film on the applicator roll is then applied to a suitable smooth surfaced, high gloss carrier 24. A preferred carrier material for use in the invention is a polyethylene terephthalate (PET) film. PET films useful as a carrier for casting are manufactured in a number of grades depending on end use requirements. Most grades contain particulate material such as clay to slightly roughen the surface for improved slip. While this roughening improves film winding and handling, it increases surface haze and reduces distinctness-of-image (DOI) of films cast on such surfaces. For low haze and high DOI, the preferred PET film for use in the present invention has no slip additive. Such films are commercially available with one side treatment or knurled edges to facilitate winding. Table 1 below illustrates the effect of surface roughness on haze and DOI of a nonmetallic Fluorex™ lab-made black base coat/clear coat liquid cast film. TABLE 1______________________________________Film Grade Ra.sup.1 (μm) DOI.sup.2 (%) 2° Haze.sup.2 (%)______________________________________4300 0.006 70 0.23000 0.010 68 0.42000 0.028 34 1.7______________________________________ .sup.1 Ra Average roughness was measured on the Surtronic 3P surface roughness measurement instrument. Ra is affected by the length of the sample surface measured and the cutoff wavelength of the measurement. Ra values in this test were taken at a sample length of 4.8 mm and a cutoff wavelength of 0.25 mm. .sup.2 DOI distinctnessof-image measurements and 2° Haze measurements were made on the Hunterlab Dorigon Model D47R6 instrument from Hunter Associates Laboratory, Inc of Reston, VA. The Dorigon D47R6 measures, in percent, the amount of incident light reflected from materials relative to a standard. For nonmetallic surfaces, the standard is the amount of light reflected by a piece of polished black glass with an index of refraction of 1.567. DOI and 2° Haze are each expresse as a percentage of the specular reflectance of the specimen being measured. DOI is the sharpness of the reflected image, as measured by the ratio of the reflectance at 0.3° from specular to the reflectance at the specular angle. DOI is zero for a perfect diffuser and 100 for a perfect mirror. The 2° Haze value is the amount of spreading of specular reflectance as measured by the ratio of specular reflectance at 2° from specular to reflectance at the specular angle. Haze is zer for a perfect mirror and 100 for a perfect diffuser. The values reported in the above table were taken from hand made lab samples to illustrate the relative effect of casting surface on the finished product. Several different grades of Hostaphan® PET film from American Hoechst were employed. Film type 4300 does not contain slip additive and is coated on one side to improve adhesion. The lab sample was made by casting the Fluorex onto the uncoated side. Film types 3000 and 2000 contain different slip additives in different amounts. The critical concern is the surface roughness. Type 300 is acceptable, type 2000 is unacceptable, and type 4300 is preferred. In general, PET films with surface roughness of about 0.018 μm or less are useful for this invention. The actual DOI measurements for commercial production would be higher than the hand prepared lab samples noted above. Again referring to FIG. 3, after coating the film 23a onto the carrier 24, the carrier is advanced past a spray apparatus and the film 23a is sprayed with a liquid pigmented polymer to form the pigment coating layer 12. An advantage of application by spraying is that the resulting appearance properties simulate that of spray-applied paint to a high degree. While other application methods may be employed, spray application is the preferred method when a metallic pigmented coating is employed. As the solvents and diluents dry from the coating, the pigments become oriented in a generally parallel orientation, similar to the orientation of metallic pigments in a spray-applied metallic automotive paint finish. In the preferred embodiment illustrated, the liquid pigmented polymer is sprayed on the film before the film has solidified. The coated film is then dried, removed from the carrier, and--if desired--provided with a bonding layer in accordance with known procedures. If flakes are present in the pigmented polymer, spraying the pigmented polymer onto the cast film before the cast film has solidified allows the flakes to settle into the cast layer somewhat, and gives a greater depth effect to the film. The foregoing procedure is preferably used to coat the entire undersurface of the cast film. If desired, a striking visual effect can be achieved by spraying portions of the undersurface of the cast film with a liquid pigmented polymer, after which the other portions of the undersurface of the cast film is sprayed with a liquid pigmented polymer pigmented a different color than the preceding pigmented polymer. This technique can be used to provide decorative sheet materials which have a two-tone colored appearance, and the coatings can overlap so that the colored regions provided by this technique feather into one another. In combination, these two polymer coatings provide an opaque and uninterrupted (in opacity) coating to the undersurface of the substantially clear film. The decorative sheet material of the present invention can be adhered to a supporting substrate in accordance with known laminating or bonding techniques. Illustrative examples of supporting substrates include metal, wood, and molded polymer substrates. As illustrated in FIG. 4, a shaped article 30 of the present invention comprises a supporting substrate 31 which has a contoured outer surface, and a decorative sheet material 10 adhered to one side of the substrate so as to conform to the contoured surface of the substrate. As explained above, particularly suitable shaped articles of the present invention are exterior automobile body parts such as body panels and bumpers. The decorative sheet material can be bonded to molded polymer substrates by placing the sheet material into a mold having a contoured, three-dimensional molding surface. A moldable polymer is then introduced into the mold on one side of the sheet material. The sheet material is then molded into a contoured three-dimensional configuration conforming to the molding surface of said mold, while molding said polymer to form a shaped article with the decorative sheet material adhered to the outer surface thereof. Preferably, the decorative sheet material includes a bonding layer, as described above, formed of a polymer different from the pigmented coating, wherein the decorative sheet material is placed into the mold with the bonding layer oriented inwardly away from the molding surface so as to become adhered to the moldable polymer. Suitable polymers for the molded polymer substrate include, for example, polyvinyl chloride, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene, polyethylene, polypropylene, polyethylene terephthalate glycol (PETG), nylon, and RIM urethanes. Polyolefin homopolymers and copolymers (ionomers, etc.) are inexpensive thermoplastic resins which have excellent molding properties and are particularly preferred for practicing the present invention. Polypropylene, for example, when glass filled and foamed with a blowing agent, has performance properties suitable for structural or engineering uses. Acid copolymers of polyethylene, such as Du Pont's "SURLYN" are similar in performance and in addition have exceptional toughness. Preferably, the tear strength of the preformed film is less than the bond strength of the preformed film to the supporting substrate. This will prevent tears from developing in the preformed film running across the surface of the article, and quickly destroying the article. In the drawings and specification, typical preferred embodiments of the invention have been disclosed. Although specific terms are employed, they are used in a generic and descriptive sense only and not for purposes of limitation, the scope of the invention being set forth in the following claims.

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Patent Citations (22)

    Publication numberPublication dateAssigneeTitle
    GB-2084513-AApril 15, 1982Nissan MotorSheet for ornamentation
    US-2880542-AApril 07, 1959Abraham S ButterweichDecorative sheeting with multi-color sparkle effect
    US-3524906-AAugust 18, 1970American Cyanamid CoTransparent and weatherable polymer blends of acrylate polymers and polyvinylidene fluoride
    US-3549405-ADecember 22, 1970Dow Chemical CoIridescent resinous film bodies and a substrate coated therewith
    US-3697070-AOctober 10, 1972Mobil Oil CorpMetallizing coating compositions
    US-3806397-AApril 23, 1974Kukoff JDecorative articles
    US-3988494-AOctober 26, 1976Mobil Oil CorporationMetallizing coating compositions
    US-4126727-ANovember 21, 1978Congoleum CorporationResinous polymer sheet materials having selective, decorative effects
    US-4215170-AJuly 29, 1980Eurographics Holding, N. V.Metallization process
    US-4248917-AFebruary 03, 1981Stauffer Chemical CompanyPressure sensitive products with decorative appearance
    US-4307149-ADecember 22, 1981Columbia Ribbon & Carbon Mfg. Co., Inc.Transfer elements and process for making same
    US-4311757-AJanuary 19, 1982Formica CorporationDecorative metallic laminates
    US-4359491-ANovember 16, 1982Jin An Industrial Co., Ltd.Process for the preparation of a thermal transferable twinkling pattern
    US-4409280-AOctober 11, 1983Mannington MillsDecorative surface coverings
    US-4501852-AFebruary 26, 1985Mobay Chemical CorporationStable, aqueous dispersions of polyurethane-ureas
    US-4533592-AAugust 06, 1985Minnesota Mining And Manufacturing CompanyThermally stable flame retardant reflective and retroreflective trim
    US-4578426-AMarch 25, 1986Basf AktiengesellschaftProduction of coatings
    US-4584231-AApril 22, 1986Vcf Packaging Films, Inc.Solvent cast acrylic film
    US-4664859-AMay 12, 1987Vcf Films Inc. Div. Of PmcProcess for solvent casting a film
    US-4678690-AJuly 07, 1987Rexham CorporationPremasked decal
    US-4769265-ASeptember 06, 1988Coburn Jr Joseph WLaminated decorative film and methods of making same
    US-4810540-AMarch 07, 1989Rexham CorporationDecorative sheet material simulating the appearance of a base coat/clear coat paint finish

NO-Patent Citations (2)

    Title
    Chemical Week, Jul. 4, 1984, p. 30, Automotive Coatings: Helping Detroit Woo Consumers.
    Polymers Paint Colour Journal, Oct. 29, 1980, pp. 796 and 798, The Orientation of Aluminum Pigments in Automotive Finishes, Contributed by Toyo Aluminum K. K.

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    US-RE35894-ESeptember 08, 1998Rexam Industries Corp.Injection molded plastic article with integral weatherable pigmented film surface
    US-2005129883-A1June 16, 2005Snow Larry G.Print receptive articles
    US-5215826-AJune 01, 1993Rexham Industries Corp.Surfacing film with thermoformable carrier layer
    US-5968657-AOctober 19, 19993M Innovative Properties CompanyPaint film assembly with masking film and method of making same
    US-2011086954-A1April 14, 2011E. I. Du Pont De Nemours And CompanyFluoropolymer liquid composition
    US-2005074622-A1April 07, 2005Vogel Randall Allen, Smillie Benjamin Andrew, Christian LeboeufMulti-layer sheet comprising an ionomer layer
    US-2008154004-A1June 26, 2008Ronald Earl Uschold, Jian Wang, Masahiro YamamotoCrosslinkable Vinyl Fluoride Copolymers
    US-6440546-B1August 27, 2002Ream Industries Corp.Gloss-adjusting mask layer with particulate filler
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    US-8025928-B2September 27, 2011E. I. Du Pont De Nemours And CompanyProcess for forming fluoropolymer coated film
    US-5518786-AMay 21, 1996Avery Dennison CorporationExterior automotive laminate with pressure sensitive adhesive
    US-2005084697-A1April 21, 2005Smillie Benjamin A.Multi-layer sheet having a weatherable surface layer
    US-7968199-B2June 28, 2011Basf Coatings AgMethod for producing films having a coating the films obtained in this way and their use for producing molded parts in particular for use in automobile construction
    US-2007138443-A1June 21, 2007Service Arnold L MElectrically conductive polymer films and process for making same
    US-RE35970-ENovember 24, 1998Rexam Industries Corp.Injection molded plastic article with integral weatherable pigmented film surface
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    US-5132148-AJuly 21, 1992Eastman Kodak CompanyFlexible and stretchable sheet material useful in forming protective and decorative coatings
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    US-5972472-AOctober 26, 1999E. I. Du Pont De Nemours And CompanyProcess of forming controlled gloss fluoropolymer films
    US-6284183-B1September 04, 2001Avery Dennison CorporationThick sheet laminating process for making exterior automotive body panels
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    US-5916643-AJune 29, 1999Avery Dennison CorporationDry paint transfer-laminated body panels having deep-draw high DOI automotive paint coat
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    US-6113838-ASeptember 05, 2000Avery Dennison CorporationControl of metallic appearance in automotive cast paint films
    US-5960527-AOctober 05, 1999Rexam Industries Corp.Method of injection molding plastic automobile body parts with integral weatherable pigmented film surface
    WO-2011018285-A1February 17, 2011Evonik Degussa GmbhAqueous silane systems for bare corrosion protection and corrosion protection of metals
    US-7144612-B2December 05, 2006Laminate Products, Inc.Decorative system composite and method
    US-2006057392-A1March 16, 2006Smillie Benjamin A, Lenges Geraldine MMulti-layer sheet having a weatherable surface layer
    EP-2468833-A1June 27, 2012E. I. du Pont de Nemours and CompanyFluorpolymer-Beschichtungszusammensetzungen mit Haftpolymeren und Substratbeschichtungsverfahren
    US-7853454-B2December 14, 2010Laminate Products, Inc.Method of producing a paint film part
    US-6254712-B1July 03, 2001Avery Dennison CorporationExtrusion coating process for making high transparency protective and decorative films
    WO-2013006616-A1January 10, 2013Dow Global Technologies LlcDispositifs optoélectroniques incorporant des compositions de polymères fluorés pour la protection
    US-6723427-B1April 20, 2004Avery Dennison CorporationFade printed decorative sheets and methods and apparatus for making the same
    US-2007166469-A1July 19, 2007Snow Larry G, Debergalis MichaelFluoropolymer coating compositions containing adhesive polymers and substrate coating process
    WO-0168337-A2September 20, 20013D Media Solutions NordicA surface decoration having a 3-dimensional effect and method for producing same
    US-6626530-B2September 30, 2003E. I. Du Pont De Nemours And CompanyProcess for making protected printed images
    WO-0238385-A2May 16, 2002E.I. Dupont De Nemours And CompanyProcede de formation d'images imprimees protegees
    US-5202180-AApril 13, 1993Avery Dennison CorporationDecorative web
    US-6932921-B2August 23, 2005E. I. Du Pont De Nemours And CompanyElectrically conductive polymer films
    US-RE36457-EDecember 21, 1999Rexam Industries, Corp.Injection molded plastic article with integrated weatherable pigmented film surface
    US-7005103-B2February 28, 2006Guardian Automotive Trim, Inc.Method of making a colored automotive trim product
    US-6733870-B2May 11, 2004Avery Dennison CorporationExtrusion coating process for making protective and decorative films
    US-2008156367-A1July 03, 2008Ronald Earl Uschold, Jian Wang, Masahiro YamamotoCrosslinkable Vinyl Fluoride Copolymer Coated Film and Process for Making Same
    US-6083335-AJuly 04, 20003M Innovative Properties CompanyPaint film assembly with masking film and method of making same
    US-5514427-AMay 07, 1996Rexam Industries Corp.Injection molded plastic article with integral weatherable pigmented film surface
    US-6348117-B1February 19, 2002E. I. Du Pont De Nemours And CompanyProcess of preparing textured fluoropolymer films
    EP-3178796-A1June 14, 2017Corning IncorporatedGlass article comprising anti-glare surface
    US-5194336-AMarch 16, 1993Sumitomo Electric Industries Ltd.Chromatically colored fluororesin-coated material
    US-6017989-AJanuary 25, 2000The Standard Products CompanyExterior automotive component of an elastomeric modified polyolefin material having pleasing appearance
    US-6565955-B2May 20, 2003Soliant LlcBright indium-metallized formable film laminate
    US-2004123942-A1July 01, 2004Spain Patrick L., Truog Keith L., Frank RohrbacherDry paint transfer process for making deep-draw high doi automotive body panels
    US-7833380-B2November 16, 2010Laminate Products, Inc.Decorative system composite and method
    US-8679619-B2March 25, 2014E I Du Pont De Nemours And CompanyMultilayer, co-extruded, ionomeric decorative surfacing
    US-6399193-B1June 04, 2002The University Of Massachusetts LowellSurfacing laminate with bonded with pigmented pressure sensitive adhesive
    US-2006286559-A1December 21, 2006Kraft Foods Holdings, Inc.Nucleic acids for detection of Listeria
    US-5037680-AAugust 06, 1991Decoma International Inc.Exterior automotive component with pigmented substrate and clear coating
    US-5870643-AFebruary 09, 1999Eastman Kodak CompanySingle-use flash cameras with reflector or siren
    US-5079084-AJanuary 07, 1992Toyota Jidosha Kabushiki KaishaReactive injection molding of a reinforced plastic product and method for manufacturing thereof
    WO-9409983-A1May 11, 1994Avery Dennison CorporationStratifie auto-adhesif pour l'exterieur d'automobiles
    US-6579397-B1June 17, 2003Avery Dennison CorporationDry paint transfer process for making deep draw high DOI automotive body panels
    WO-9815592-A1April 16, 1998E.I. Du Pont De Nemours And CompanyControlled gloss fluoropolymer films
    WO-2015160568-A1October 22, 2015E. I. Du Pont De Nemours And CompanyComposition liquide de revêtement de fluoropolymère et film revêtu de fluoropolymère
    US-6110547-AAugust 29, 2000Grand Polymer Co., Ltd., Toyota Shatai Kabushiki KaishaMethod of molding automobile outer trim part, laminated film or sheet for use therein and automobile outer trim part
    US-5707697-AJanuary 13, 1998Avery Dennison CorporationDry paint transfer product having high DOI automotive paint coat
    US-2011086172-A1April 14, 2011E. I. Du Pont De Nemours And CompanyProcess for forming fluoropolymer coated film
    US-6319438-B1November 20, 2001Guardian Automotive Trim, Inc.Extruded automotive trim and method of making same
    US-5618593-AApril 08, 1997The Standard Products CompanyWeatherstrip molding and method of making same
    US-7303793-B2December 04, 2007E. I. Du Pont De Nemours And CompanyMulti-layer sheet having a weatherable surface layer
    US-6336988-B1January 08, 2002Avery Dennison CorporationExtrusion coating process for making protective and decorative films
    US-6966962-B2November 22, 2005Avery Dennison CorporationDry paint transfer-lamination process for making high DOI automotive body panels
    US-2008261037-A1October 23, 2008E. I. Du Pont De Nemours And CompanyFluoropolymer Coated Film, Process for Forming the Same, and Fluoropolymer Liquid Composition
    US-7070675-B2July 04, 2006E. I. Du Pont De Nemours And CompanyFluoropolymer film structures and laminates produced therefrom
    EP-1236585-A2September 04, 2002E. I. du Pont de Nemours and CompanySurfaces décoratives pour panneaux architecturaux
    US-6835267-B1December 28, 2004Avery Dennison CorporationDry paint transfer process and product
    DE-102004010787-A1September 22, 2005Basf Coatings AgVerfahren zur Herstellung einer mehrschichtigen Folie F und ihre Verwendung
    US-2009047449-A1February 19, 2009E.I. Du Pont De Nemours And CompanyProcesses for Preparing Printable and Printed Articles
    US-2005142330-A1June 30, 2005Albert Richard C.Decorative surfaces for architectural panels
    US-6187233-B1February 13, 2001Guardian Automotive Trim, Inc.Automotive trim with clear top coat and method of making same
    US-8062744-B2November 22, 2011E. I. Du Pont De Nemours And CompanyFluoropolymer coated films useful for photovoltaic modules
    US-2014065406-A1March 06, 2014Kth Holding AbOxygen barrier for packaging applications
    US-8168297-B2May 01, 2012E. I. Du Pont De Nemours And CompanyFluoropolymer coated film, process for forming the same, and fluoropolymer liquid composition
    US-7399506-B2July 15, 2008Laminate Products, Inc.Decorative system composite and method
    US-2006257592-A1November 16, 2006Robert Lafave, Robert BowlingDecorative system composite and method
    US-5653927-AAugust 05, 1997Avery Dennison CorporationControl of metallic appearance in automotive cast paint films
    US-6197405-B1March 06, 2001Graphic Origins LimitedSurface decoration having a 3-dimensional effect, and method of producing a surface decoration having a 3-dimensional effect, as well as utilization of a decoration having a 3-dimensional effect
    US-8119235-B1February 21, 2012E. I. Du Pont De Nemours And CompanyMultilayer, co-extruded, ionomeric decorative surfacing
    US-2008026228-A1January 31, 2008E. I. Du Pont De Nemours And CompanyMulti-Layer Sheet Having a Weatherable Surface Layer
    WO-2015073364-A2May 21, 2015E. I. Du Pont De Nemours And CompanyDispersion de pigment
    US-6632518-B1October 14, 2003E. I. Du Pont De Nemours And CompanyFluoropolymer film structures and laminates produced therefrom
    US-2002160680-A1October 31, 2002Laurence Kenneth John, Drees Terry Paul, O'brien Kevin Francis, Fairbanks Robert P.Decorative laminate assembly and method of producing same
    WO-2015017616-A1February 05, 2015E. I. Du Pont De Nemours And CompanyLiquid fluoropolymer coating composition, fluoropolymer coated film, and process for forming the same
    US-9219182-B2December 22, 2015Dow Global Technologies LlcOptoelectronic devices incorporating fluoropolymer compositions for protection
    US-6803110-B2October 12, 2004Formica CorporationDecorative laminate assembly and method for producing same
    US-7608311-B2October 27, 2009E. I. Du Pont De Nemours And CompanyPrint receptive articles
    US-2004241420-A1December 02, 2004Hongyi Zhou, Hua Wang, Graf John FrederickMethods for manufacturing silver multilayered films and the articles obtained therefrom
    WO-2004108411-A1December 16, 2004General Electric CompanyProcedes pour fabriquer des films multicouches argentes et articles obtenus selon ce procede
    US-2006122860-A1June 08, 2006Lafave Robert JMethod of producing a paint film part
    US-6858287-B2February 22, 2005Soliant LlcFormable bright film having discontinuous metallic layers
    US-2003170460-A1September 11, 2003John Sienkiewicz, Randazzo Joseph J.Extruded automotive trim and method of making same
    US-2005106386-A1May 19, 2005Vogel Randall A., Paul John W., Karlheinz HausmannThermoformable multi-layer sheet
    US-5192611-AMarch 09, 1993Kansai Paint Co., Ltd.Patterned film forming laminated sheet
    US-6096396-AAugust 01, 2000Rexam Industries Corp.Decorative sheet material suitable for use as a flexible weatherable paint film or decal
    US-6838130-B1January 04, 2005Avery Dennison CorporationDry paint transfer process and product
    US-7195727-B2March 27, 2007Guardian Industries Corp.Extruded automotive trim and method of making same
    US-6984280-B2January 10, 2006Avery Dennison CoporationDry paint transfer process for making deep-draw high doi automotive body panels
    US-7553540-B2June 30, 2009E. I. Du Pont De Nemours And CompanyFluoropolymer coated films useful for photovoltaic modules
    US-2006068213-A1March 30, 2006O'brien Kevin, Bryce ColeDecorative laminate assembly with improved tie sheet and bridging agent
    US-6649003-B1November 18, 2003Avery Dennison CorporationDry paint transfer lamination process for making high DOI automotive body panels
    US-6709723-B2March 23, 2004Avery Dennison CorporationThick sheet lamination product for use in exterior automotive body panels
    US-6180195-B1January 30, 2001Rexam Industries Corp.Automobile body formed of interconnected molded plastic articles
    US-2009274922-A1November 05, 2009Roys John E, Coons Lindsay SHigh Gloss Laminates for Decorative Automotive Parts
    US-2010247789-A1September 30, 2010E. I. Du Pont De Nemours And CompanyFluoropolymer coating compositions containing adhesive polymers and substrate coating process
    CN-100450739-CJanuary 14, 2009Lg化学株式会社采用橡胶溶胶的pvc-橡胶地板及其生产方法
    US-2006105663-A1May 18, 2006Stefan Greulich, Vogel Randall APolymer assemblies with decorative surfaces
    EP-1034089-A4October 18, 2000Du PontStructures lustrees en film stratifie
    US-7488399-B2February 10, 2009E. I. Du Pont De Nemours And CompanyMulti-layer sheet having a weatherable surface layer
    WO-0168337-A3January 17, 20023D Media Solutions Nordic, Harald JohnsenA surface decoration having a 3-dimensional effect and method for producing same
    US-7842765-B2November 30, 2010E. I. Du Pont De Nemours And Company, Dupont-Mitsui Fluorochemicals Co LtdCrosslinkable vinyl fluoride copolymers
    US-2005074623-A1April 07, 2005Vogel Randall AllenMulti-layer lonomer sheet having improved weathering
    US-7192536-B2March 20, 2007E. I. Du Pont De Nemours And CompanyElectrically conductive polymer films and process for making same
    WO-02058944-A1August 01, 2002Formica CorporationElement laminaire decoratif et procede de fabrication
    US-6773804-B2August 10, 2004Avery Dennison CorporationExtruded polymeric high transparency films
    US-5536539-AJuly 16, 1996Rexam Industries Corp.Injection molded plastic article with integral weatherable pigmented film surface
    US-9637657-B2May 02, 2017E I Du Pont De Nemours And CompanyLiquid fluoropolymer coating composition and fluoropolymer coated film
    US-2003190434-A1October 09, 2003Byers Alicia D., Burgman John W., Derouin Lana L., Humbert Erik J., Letzring Hans F., Millero Edward R.Process for applying automotive quality effect coatings to metal substrates
    US-9707746-B2July 18, 2017Entrotech, Inc.Protected graphics and related methods
    US-8124221-B2February 28, 2012E. I. Du Pont De Nemours And Company, Dupont-Mitsui Flourochemicals Co LtdCrosslinkable vinyl fluoride copolymer coated film and process for making same
    US-2008110564-A1May 15, 2008Robert Lafave, Robert BowlingDecorative System Composite and Method
    US-2008213600-A1September 04, 2008Basf Coatings AktiengesellschaftProcess for Producing Sheets (F) Bearing a Coating (B), the Resultant Sheets (F), and Their Use for Producing Moldings, Especially for Use in the Autombile Construction
    US-2007154704-A1July 05, 2007Debergalis Michael, Larry Glen SnowFluoropolymer coated films useful for photovoltaic modules
    US-2003039809-A1February 27, 2003Harald JohnsenSurface decoration having a 3-dimesional effect and method for producing same
    US-2005129882-A1June 16, 2005Snow Larry G.Processes for preparing printable and printed articles
    US-2009293944-A1December 03, 2009E. I. Du Pont De Nemours And CompanyFluoropolymer Coated Films Useful for Photovoltaic Modules
    US-7081300-B2July 25, 2006Formica CorporationDecorative laminate assembly and method of producing same
    US-2004209057-A1October 21, 2004Enlow Howard H., Markey John J., Roys John E., Truog Keith L., Frederick YoungExtruded polymeric high transparency films
    US-2009260677-A1October 22, 2009E. I. Du Pont De Nemours And CompanyFluoropolymer Coated Films Useful for Photovoltaic Modules
    EP-1034089-A1September 13, 2000E.I. Du Pont De Nemours And CompanyStructures lustrees en film stratifie
    US-2004175572-A1September 09, 2004Horst Hintze-Bruning, Frank Strickmann, Walter LassmannColor-and/or effect producing films, method for production and use thereof
    US-7682666-B2March 23, 2010Basf Coatings AgMethod of producing a color and/or effect film exhibiting an isotropic flop behavior and an isotropic color locus
    WO-2016097825-A1June 23, 2016Ferro EmilianoRevêtement de pièces ou d'objets et son procédé d'obtention
    EP-0900681-A1March 10, 1999Commercial Body Fittings LtdImproved door seal
    EP-2468829-A1June 27, 2012E. I. du Pont de Nemours and CompanyFluoropolymer coated film
    US-2004123941-A1July 01, 2004Spain Patrick L., Truog Keith L., Frank RohrbacherDry paint transfer-lamination process for making high doi automotive body panels
    US-2004247876-A1December 09, 2004Robert Lafave, Robert BowlingDecorative system composite and method
    US-6602591-B1August 05, 2003Guardian Automotive Trim, Inc.Automotive trim with clear top coat and method of making same
    US-8048518-B2November 01, 2011E.I. Du Pont De Nemours And CompanyFluoropolymer coated films useful for photovoltaic modules
    US-6060135-AMay 09, 2000E. I. Du Pont De Nemours And CompanyLustrous laminate film structures