WO2008144193A2 - Special effect glazing - Google Patents

Special effect glazing Download PDF

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Publication number
WO2008144193A2
WO2008144193A2 PCT/US2008/062313 US2008062313W WO2008144193A2 WO 2008144193 A2 WO2008144193 A2 WO 2008144193A2 US 2008062313 W US2008062313 W US 2008062313W WO 2008144193 A2 WO2008144193 A2 WO 2008144193A2
Authority
WO
WIPO (PCT)
Prior art keywords
ink
panel
special effect
plastic
pigments
Prior art date
Application number
PCT/US2008/062313
Other languages
French (fr)
Other versions
WO2008144193A3 (en
WO2008144193A8 (en
Inventor
Eric F.J.M. Van Der Meulen
Sunitha Grandhee
Christophe Lefaux
Keith D. Weiss
Original Assignee
Exatec, Llc
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 Exatec, Llc filed Critical Exatec, Llc
Publication of WO2008144193A2 publication Critical patent/WO2008144193A2/en
Publication of WO2008144193A8 publication Critical patent/WO2008144193A8/en
Publication of WO2008144193A3 publication Critical patent/WO2008144193A3/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0027After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/009After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/043Improving the adhesiveness of the coatings per se, e.g. forming primers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/046Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/03Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • C09D11/32Inkjet printing inks characterised by colouring agents
    • C09D11/322Pigment inks
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/08Homopolymers or copolymers of acrylic acid esters

Definitions

  • a new trend in the automotive industry is to have a smooth transition between different parts of the car. For instance, not so long ago, almost all automobiles had chrome bumpers that were separate and distinct from the body of the vehicle. Today, bumpers are integrated with the body in the design of the car and exhibit the same color as the car body. To create more dynamic-looking automobiles, manufacturers are using ever-increasing amounts of special-effect pigments. Technology-based colors, such as those that create a liquid-metal effect or sparkle, and nature-based colors, such as calming neutrals, cool blues and warm browns, are driving automotive color trends worldwide.
  • the present invention provides for processes of printing an image on a plastic substrate using a special effects ink.
  • the processes of the present invention are particularly useful for imparting a distinctive aspect to plastic glazings such as windows, headlamps and tail lights, for use in automobiles.
  • the processes of the present invention may be used to provide smooth transition between different parts of the automobile body and the plastic glazings by printing images using special effect inks that match or complement the color used for the body of the car.
  • the processes of the present invention may also be used to print an image that appears continuous with an image on the body of the car.
  • One embodiment of the invention is a transparent plastic automotive panel comprising a plastic substrate, a non-black ink overlying a portion of the plastic substrate forming a printed substrate and a protective coating system overlying the ink.
  • In another embodiment of the invention comprises comprising a plastic film, the ink being printed on a portion of the film.
  • the plastic film is bonded to the substrate.
  • the ink is encapsulated between v ' the film and the substrate.
  • the ink includes a special effect ink.
  • the special effect ink is a color varying ink.
  • the special effect is a metallic ink.
  • special effect ink further comprises pigments selected from the group of pearlescent pigments, metallic pigments, or a combination of both.
  • the special effect ink is a thermal heat cure ink or a UV cure ink.
  • the plastic window assembly is incorporated into an automotive vehicle, the automotive vehicle having a body and the body of the automotive vehicle being of a color corresponding to the ink.
  • the ink includes a special effect ink.
  • the special effect ink is a color varying ink.
  • the special effect ink is a metallic ink.
  • the special effect ink further comprises pigments selected from the group of pearlescent pigments, metallic pigments, or a combination of both.
  • the protective coating system overlying the ink includes a weathering layer. wherein the protective coating system includes an abrasion resistant layer overlying the weathering layer. wherein the protective coating system includes an abrasion resistant layer overlying the weathering layer. wherein the protective coating system overlying the ink includes a weathering layer. wherein the protective coating system includes an abrasion resistant layer overlying the weathering layer. wherein the protective coating system includes an abrasion resistant layer overlying the weathering layer.
  • autonomous means any of a number of types of vehicles powered by a self contained or remote power plant which can be taken to include but are not limited to at least one of passenger cars, vans and motorcycles, light trucks, heavy duty trucks including off road vehicles, recreational vehicles such as mobile homes and campers, mass transit vehicles such as busses, locomotive vehicles such as trains and other light rail vehicles such as monorails and the like, as well as marine and aircraft.
  • the term "ink” means a composition comprising one or more pigments.
  • specialty effect pigment refers to a variety of pigments which impart optical effects including but not limited to sparkle, luster, glitter, color variation, color intensity variation, pearlescence, or any combination of these effects. These effects occur when the surface to which such a pigment is applied, is viewed from a different angle and/or with a different angle of illumination.
  • Special effect pigments include but are not limited to metallic pigments and pearlescent pigments.
  • Engelhard's Mearlite industrial-grade pearlescent pigments impart a range of optical effects, from a soft, satin luster to a sharp, metallic brilliance. These effects are due to plate-like crystals of bismuth oxychloride that have a silver-white transparent appearance.
  • special effect ink means an ink which comprises a one or more special effect pigments.
  • a special effect ink may additionally comprise one or more colored pigments.
  • the present invention provides for the printing of images onto the surface of plastic substrates with special effect ink.
  • the image is generally printed directly onto the surface of the plastic substrate.
  • Plastic substrates include plastic plaques, plastic sheets, molded plastic or plastic film, wherein film means a thin flexible plastic sheet.
  • the plastic may comprise any thermoplastic or thermoset polymeric resin.
  • the polymeric resins include, but are not limited to, polycarbonate, acrylic, polyarylate, polyester, and polysulfone, as well as copolymers and mixtures thereof.
  • the plastic substrates may be formed through the use of any technique known to those skilled in the art, such as molding, thermoforming, or extrusion.
  • the plastic substrate of the invention may be from about 0.05 m 2 to about 5 m 2 , or from about 025 m 2 to about 5 m 2 or from about 0.05 m 2 to about 2m 2 or from about 0.25 m 2 to about 2 m 2 , or from about 0.9 m 2 to about 2 m 2 .
  • the plastic substrate may be from about 3 to about 6 mm think or from about 2 to about 4, or from about 1 to about 3.
  • the plastic substrates may be planar or three dimensional (3-D), where three dimensional refers to any geometry that is not substantially planar. Processes of printing on three dimensional plastic surfaces are known by those of skill in the art, for example, US Patent Nos. 6,834,582, 6,698,345, 6,776,100, and 7,182,019. [0023] Colored inks and special effect inks can be can be applied by screen printing, inkjet printing, pad printing, mask & spray, spray coating, or other techniques known to those skilled in the art. These inks can also be curable by any appropriate processes such as by air drying, UV absorption, thermal absorption. [0024] The special effect ink, colored ink or combinations thereof is generally printed directly on the plastic substrate.
  • the substrate is then coated with a weathering layer followed by an abrasion resistance layer.
  • the plastic substrate is a film
  • the printed film is placed into the cavity of a mold and the plastic substrate is back molded onto the film, thereby encapsulating the ink.
  • This molding process is known to those skilled in the art as film insert molding (FIM).
  • FIM film insert molding
  • the molded plastic substrate is removed from the mold, inspected, and any preliminary processing is carried out such as cleaning, which includes the elimination of static electrical charges.
  • a protective coating system is then applied to the molded product.
  • the protective coating system may include a weathering layer followed by an abrasion resistance layer or either individually applied to the product.
  • the weathering layer may be applied by dipping the plastic substrate in the coating at room temperature and atmospheric pressure in a process known in the art as dip coating. Alternatively, the weathering layer may be applied by flow coating, curtain coating, spray coating, or other processes known to those skilled in the art. [0026]
  • the weathering layer may be comprised of but not limited to silicones, polyurethanes, acrylics, polyesters, polyurethane-acrylates, and epoxies, as well as mixtures or copolymers thereof.
  • the weathering layer preferably includes ultraviolet (UV) absorbing molecules, such as hydroxyphenyltriazine, hydroxybenzophenones, hydroxylphenylbenzotriazoles, hydroxyphenyltriazines, polyaroylresorcinols, and cyanoacrylates, among others.
  • UV ultraviolet
  • the weathering layer may be one homogenous layer or be comprised of multiple sub-layers, such as a primer and a topcoat.
  • a primer typically aids in adhering the topcoat to the plastic panel.
  • the primer for example may include, but not be limited to, acrylics, polyesters, epoxies, and copolymers and mixtures thereof.
  • the topcoat may include, but not be limited to, polymethylmethacrylate, polyvinylidene fluoride, polyvinylfluoride, polypropylene, polyethylene, polyurethane, silicone, polymethacrylate, polyacrylate, polyvinylidene fluoride, silicone hardcoat, and mixtures or copolymers thereof.
  • a weathering layer comprising multiple sub-layers is the combination of an acrylic primer (SHP401 or SHP470, Momentive Performance Materials, Waterford, NY) with a silicone hard- coat (AS4000 or AS4700, Momentive Performance Materials).
  • SHP401 or SHP470 Acrylic Primer
  • AS4000 or AS4700 Momentive Performance Materials
  • a variety of additives may be added to either or both the primer and the topcoat, such as colorants (tints), rheological control agents, mold release agents, antioxidants, and IR absorbing or reflecting pigments, among others.
  • the type of additive and the amount of each additive is determined by the performance required by the plastic panel to meet the specification and requirements for use in any selected application, such as an automobile window including but not limited to side windows, windscreens, backlites and panorama sunroofs.
  • the weathering layer may be over-coated via the deposition of an abrasion resistant layer.
  • This abrasion resistant film may be either comprised of one layer or a combination of multiple interlayers of variable composition.
  • the abrasion resistant layer is a substantially inorganic coating that adds additional or enhanced functionality to the automotive decorative glazing assembly by improving abrasion resistance.
  • inorganic coatings for the abrasion resistant layer include, but are not limited to, aluminum oxide, barium fluoride, boron nitride, hafnium oxide, lanthanum fluoride, magnesium fluoride, magnesium oxide, scandium oxide, silicon monoxide, silicon dioxide, silicon nitride, silicon oxy-nitride, silicon oxy- carbide, silicon carbide, hydrogenated silicon oxy-carbide, tantalum oxide, titanium oxide, tin oxide, indium tin oxide, yttrium oxide, zinc oxide, zinc selenide, zinc sulfide, zirconium oxide, zirconium titanate, or glass, and mixtures or blends thereof.
  • the abrasion resistant layer may be applied by any technique known to those skilled in the art. These techniques include deposition from reactive species, such as those employed in vacuum-assisted deposition processes, and atmospheric coating processes, such as those used to apply sol-gel coatings to substrates. Examples of vacuum-assisted deposition processes include, but not limited to, plasma enhanced chemical vapor deposition (PECVD), arc-PECVD, ion assisted plasma deposition, magnetron sputtering, electron beam evaporation, and ion beam sputtering. Examples of atmospheric coating processes include, but are not limited to, curtain coating, spray coating, spin coating, dip coating, and flow coating.
  • PECVD plasma enhanced chemical vapor deposition
  • arc-PECVD arc-PECVD
  • ion assisted plasma deposition magnetron sputtering
  • magnetron sputtering magnetron sputtering
  • electron beam evaporation electron beam evaporation
  • ion beam sputtering examples include, but
  • special effect ink means an ink which comprises a one or more special effect pigments.
  • a special effect ink may additionally comprise one or more colored pigments.
  • a wide variety of colored inks are known and one of skill in the art would know how to make a particular color. Briefly the full range of colors can be made with different combinations of three basics colors. Media that combines emitted light to create the sensation of a range of colors uses this type of additive color system. In an additive color system, the additive primary colors are red, green, and blue.
  • RGB red, green, blue
  • An example of a colored ink formulation suitable for use with a plastic film insert molding (FIM) process is NoriphanTM HTR with 50% Opaque White (code 945), 35% Blue transparent (code 566), and 22% Violet (code 472) offered by Proell, Inc., St. Charles, Illinois. It is noted that a retarder (e.g., slow evaporating solvent) has to be added prior printing on a film.
  • a retarder e.g., slow evaporating solvent
  • special effect pigment colors are doubled printed and backed with a highly opaque black print although other processes of printing known to those skilled in the art are acceptable.
  • special effect pigment refers to a variety of pigments which impart optical effects including but not limited to sparkle, luster, glitter, color variation, color intensity variation, pearlescence, or any combination of these effects. These effects occur when the surface to which such a pigment is applied, is viewed from a different angle and/or with a different angle of illumination.
  • Special effect pigments include but are not limited to metallic pigments and pearlescent pigments.
  • Mearlite® Engelhard-BASF
  • industrial-grade pearlescent pigments impart a range of optical effects, from a soft, satin luster to a sharp, metallic brilliance. These effects are due to plate-like crystals of bismuth oxychloride that have a silver-white transparent appearance.
  • special effect pigments are known including, but not limited to chameleon gold- green, chameleon green-blue, pearlescent blue, solar gold, pearlescent magenta- gold, chameleon copper-green, chameleon purple- green, chameleon green-purple, pearlescent green, and pearlescent lilac.
  • Special effects pigments also include metallic pigments, for example, silver, silver-gold, aluminum, bronze, and gold.
  • Metallic pigments are, by nature, completely different than other types of pigments used in printing. These pigments are flake-shaped, fully opaque and significantly larger. They consist of planar areas designed to reflect as much light as possible in order to create metallic sheen or luster. Metallic pigments are produced in a variety of particle sizes. The larger the flake size, the greater the degree of brilliance. Metallic flakes used in the graphic arts industry vary from 3 to 15 ⁇ m.
  • Aluminum pigments can be produced by a variety of means. The conventional process of producing aluminum pigments found in the graphic arts industry is by the wet grinding process (Hall process). The conventional process of producing bronze pigments in the graphic arts industry is by a dry grinding process (Hametag process). Other means of production, such as stamping and physical vapor deposition, can produce flatter and therefore more brilliant products.
  • Pearlescent finishes are also used in the glazing industry. These finishes are designed to create color through light interference effects. They are comprised of a thin layer of a metal oxide deposited on a supporting mica flake. The thickness of the metal oxide layer is such that a specific wavelength of light is reinforced, the lightness changes are accompanied by marked changes in hue and saturation that creates a pearlescent appearance. The metal oxide chosen may also provide color through light absorption.
  • Windows in the automotive industry typically exhibit a black-out area that encircles the edge of the window in order to mask the bonding system that glues the window to the car body.
  • this layer instead of printing this highly opaque black ink, one embodiment of the present invention provides for this layer as an ink that exhibits some type of special effect (e.g., color varying, metallic sparkle, etc.) due to the special pigments incorporated into the ink.
  • Another embodiment of the invention provides a process of printing which result in a shadow effect that gives the appearance of a 3-D image. In one embodiment this shadow effect is provided by printing part of the area of an image using one or more special effect inks and printing parts of the area of the image using standard colored inks.
  • this shadow effect is provided by printing a layer of halftones or shadings of colored ink over a layer of one or more special effect inks.
  • "Halftone” means the image that is produced through the use of equally spaced dot of varying size.
  • a plastic film is printed with one or more prints and then placed inside a mold cavity and over-molded.
  • the special effect inks are printed directly onto the plastic substrate.
  • the substate is coated with a weathering layer followed by the deposition of an abrasion resistant layer prior to the printing of the special effect ink.
  • the processes of the invention are suitable for use to print images over large areas including, but not limited to automotive windows.
  • the processes of the present invention can be used to add one or more images to a plastic substrate for example: borders, black-out layers, letters, symbols, numbers, logos, trademarks, regulatory designations, emblems, chrome strips, chrome accents, and reflectors.
  • the images may for example be printed on different areas of the plastic substrate and/or they may be printed with separate images layered on top of one and other.
  • a white background for the logo was screen printed on a 0.6 x 1.2 m polycarbonate film of 0.76 mm thickness using white ink.
  • a second image was printed with a chrome special effect ink on top of the background color.
  • a third image was a gold colored logo inside the chrome image.
  • a fourth image was printed using black ink to provide the 3-dimentional shadow effect.
  • FIG. 1 is a cross- section of a window with the film located on the exterior of the window according to one embodiment of the present invention.
  • the film was placed on the other side of the window (e.g., interior side of the substrate), the printed images would need to be printed or stacked in the opposite order so that the images viewed from the external side of the vehicle would be seen by an observer to be substantially similar.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • General Health & Medical Sciences (AREA)
  • Thermal Sciences (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Printing Methods (AREA)
  • Vehicle Waterproofing, Decoration, And Sanitation Devices (AREA)
  • Laminated Bodies (AREA)

Abstract

A transparent plastic automotive panel including a plastic substrate, a non- black ink overlying a portion of the plastic substrate forming a printed substrate and a protective coating system overlying the ink. Alternatively, the ink may be printed on a portion of a plastic film that overlies the substrate and is covered by the protective coating system.

Description

SPECIAL EFFECT GLAZING
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Application Serial No. 60/915,226 filed on May 1 , 2007.
BACKGROUND
[0002] A new trend in the automotive industry is to have a smooth transition between different parts of the car. For instance, not so long ago, almost all automobiles had chrome bumpers that were separate and distinct from the body of the vehicle. Today, bumpers are integrated with the body in the design of the car and exhibit the same color as the car body. To create more dynamic-looking automobiles, manufacturers are using ever-increasing amounts of special-effect pigments. Technology-based colors, such as those that create a liquid-metal effect or sparkle, and nature-based colors, such as calming neutrals, cool blues and warm browns, are driving automotive color trends worldwide.
[0003] Automotive designers understand that a keen awareness of future trends in a consumer's color preference is essential to developing a successful palette for their car and truck lines. The colors they select must not only give their vehicles identity and distinction on the road, but must also appeal to the broadest number of car buyers. Thus, further processes for enhancing customer appeal are needed.
SUMMARY
[0004] The present invention provides for processes of printing an image on a plastic substrate using a special effects ink. The processes of the present invention are particularly useful for imparting a distinctive aspect to plastic glazings such as windows, headlamps and tail lights, for use in automobiles. The processes of the present invention may be used to provide smooth transition between different parts of the automobile body and the plastic glazings by printing images using special effect inks that match or complement the color used for the body of the car. The processes of the present invention may also be used to print an image that appears continuous with an image on the body of the car.
[0005] One embodiment of the invention is a transparent plastic automotive panel comprising a plastic substrate, a non-black ink overlying a portion of the plastic substrate forming a printed substrate and a protective coating system overlying the ink.
[0006] In another embodiment of the invention comprises comprising a plastic film, the ink being printed on a portion of the film.
[0007] In another embodiment of the invention the plastic film is bonded to the substrate.
.. . . , , u -i - L x iu L- iu ■ II L -i u L - * Formatted: Bullets and Numbering |
:S£L™»™Jn another embodiment of the invention the ink is encapsulated between v ' the film and the substrate. [0008] In another embodiment of the invention the ink includes a special effect ink.
[0009] In another embodiment of the invention the special effect ink is a color varying ink. the special effect is a metallic ink.
[0010] 1. In another embodiment of the invention special effect ink further comprises pigments selected from the group of pearlescent pigments, metallic pigments, or a combination of both.
[0011] In another embodiment of the invention the special effect ink is a thermal heat cure ink or a UV cure ink.
1. In another embodiment of the invention the plastic window assembly is incorporated into an automotive vehicle, the automotive vehicle having a body and the body of the automotive vehicle being of a color corresponding to the ink.
wherein the ink includes a special effect ink.
wherein the special effect ink is a color varying ink.
wherein the special effect ink is a metallic ink.
wherein the special effect ink further comprises pigments selected from the group of pearlescent pigments, metallic pigments, or a combination of both. wherein the protective coating system overlying the ink includes a weathering layer. wherein the protective coating system includes an abrasion resistant layer overlying the weathering layer. wherein the protective coating system includes an abrasion resistant layer overlying the weathering layer. wherein the protective coating system overlying the ink includes a weathering layer. wherein the protective coating system includes an abrasion resistant layer overlying the weathering layer. wherein the protective coating system includes an abrasion resistant layer overlying the weathering layer. [0012] Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure. [0013] In one embodiment of the invention
BRIEF DESCRIPTION OF THE DRAWINGS.
DETAILED DESCRIPTION
[0014] As used herein, the term "automobile" means any of a number of types of vehicles powered by a self contained or remote power plant which can be taken to include but are not limited to at least one of passenger cars, vans and motorcycles, light trucks, heavy duty trucks including off road vehicles, recreational vehicles such as mobile homes and campers, mass transit vehicles such as busses, locomotive vehicles such as trains and other light rail vehicles such as monorails and the like, as well as marine and aircraft.
[0015] The term "ink" means a composition comprising one or more pigments.
[0016] The term "special effect pigment" refers to a variety of pigments which impart optical effects including but not limited to sparkle, luster, glitter, color variation, color intensity variation, pearlescence, or any combination of these effects. These effects occur when the surface to which such a pigment is applied, is viewed from a different angle and/or with a different angle of illumination. Special effect pigments include but are not limited to metallic pigments and pearlescent pigments. For example, Engelhard's Mearlite industrial-grade pearlescent pigments impart a range of optical effects, from a soft, satin luster to a sharp, metallic brilliance. These effects are due to plate-like crystals of bismuth oxychloride that have a silver-white transparent appearance.
[0017] As used herein "special effect ink" means an ink which comprises a one or more special effect pigments. A special effect ink may additionally comprise one or more colored pigments.
[0018] "Three dimensional" or "3D" mean not planar.
[0019] The present invention provides for the printing of images onto the surface of plastic substrates with special effect ink. The image is generally printed directly onto the surface of the plastic substrate. Plastic substrates include plastic plaques, plastic sheets, molded plastic or plastic film, wherein film means a thin flexible plastic sheet. The plastic may comprise any thermoplastic or thermoset polymeric resin.
The polymeric resins include, but are not limited to, polycarbonate, acrylic, polyarylate, polyester, and polysulfone, as well as copolymers and mixtures thereof.
The plastic substrates may be formed through the use of any technique known to those skilled in the art, such as molding, thermoforming, or extrusion.
[0020] The plastic substrate of the invention may be from about 0.05 m2 to about 5 m2, or from about 025 m2 to about 5 m2 or from about 0.05 m2 to about 2m2 or from about 0.25 m2 to about 2 m2, or from about 0.9 m2 to about 2 m2.
[0021] The plastic substrate may be from about 3 to about 6 mm think or from about 2 to about 4, or from about 1 to about 3.
[0022] The plastic substrates may be planar or three dimensional (3-D), where three dimensional refers to any geometry that is not substantially planar. Processes of printing on three dimensional plastic surfaces are known by those of skill in the art, for example, US Patent Nos. 6,834,582, 6,698,345, 6,776,100, and 7,182,019. [0023] Colored inks and special effect inks can be can be applied by screen printing, inkjet printing, pad printing, mask & spray, spray coating, or other techniques known to those skilled in the art. These inks can also be curable by any appropriate processes such as by air drying, UV absorption, thermal absorption. [0024] The special effect ink, colored ink or combinations thereof is generally printed directly on the plastic substrate. When the plastic substrate is molded plastic, a plastic plaque, or a plastic sheet, the substrate is then coated with a weathering layer followed by an abrasion resistance layer. When the plastic substrate is a film, the printed film is placed into the cavity of a mold and the plastic substrate is back molded onto the film, thereby encapsulating the ink. This molding process is known to those skilled in the art as film insert molding (FIM). The molded plastic substrate is removed from the mold, inspected, and any preliminary processing is carried out such as cleaning, which includes the elimination of static electrical charges. A protective coating system is then applied to the molded product. The protective coating system may include a weathering layer followed by an abrasion resistance layer or either individually applied to the product. [0025] The weathering layer may be applied by dipping the plastic substrate in the coating at room temperature and atmospheric pressure in a process known in the art as dip coating. Alternatively, the weathering layer may be applied by flow coating, curtain coating, spray coating, or other processes known to those skilled in the art. [0026] The weathering layer may be comprised of but not limited to silicones, polyurethanes, acrylics, polyesters, polyurethane-acrylates, and epoxies, as well as mixtures or copolymers thereof. The weathering layer preferably includes ultraviolet (UV) absorbing molecules, such as hydroxyphenyltriazine, hydroxybenzophenones, hydroxylphenylbenzotriazoles, hydroxyphenyltriazines, polyaroylresorcinols, and cyanoacrylates, among others.
[0027] The weathering layer may be one homogenous layer or be comprised of multiple sub-layers, such as a primer and a topcoat. A primer typically aids in adhering the topcoat to the plastic panel. The primer for example may include, but not be limited to, acrylics, polyesters, epoxies, and copolymers and mixtures thereof. The topcoat may include, but not be limited to, polymethylmethacrylate, polyvinylidene fluoride, polyvinylfluoride, polypropylene, polyethylene, polyurethane, silicone, polymethacrylate, polyacrylate, polyvinylidene fluoride, silicone hardcoat, and mixtures or copolymers thereof. One specific example of a weathering layer comprising multiple sub-layers is the combination of an acrylic primer (SHP401 or SHP470, Momentive Performance Materials, Waterford, NY) with a silicone hard- coat (AS4000 or AS4700, Momentive Performance Materials). [0028] A variety of additives may be added to either or both the primer and the topcoat, such as colorants (tints), rheological control agents, mold release agents, antioxidants, and IR absorbing or reflecting pigments, among others. The type of additive and the amount of each additive is determined by the performance required by the plastic panel to meet the specification and requirements for use in any selected application, such as an automobile window including but not limited to side windows, windscreens, backlites and panorama sunroofs.
[0029] The weathering layer may be over-coated via the deposition of an abrasion resistant layer. This abrasion resistant film may be either comprised of one layer or a combination of multiple interlayers of variable composition. The abrasion resistant layer is a substantially inorganic coating that adds additional or enhanced functionality to the automotive decorative glazing assembly by improving abrasion resistance.
[0030] Specific examples of possible inorganic coatings for the abrasion resistant layer include, but are not limited to, aluminum oxide, barium fluoride, boron nitride, hafnium oxide, lanthanum fluoride, magnesium fluoride, magnesium oxide, scandium oxide, silicon monoxide, silicon dioxide, silicon nitride, silicon oxy-nitride, silicon oxy- carbide, silicon carbide, hydrogenated silicon oxy-carbide, tantalum oxide, titanium oxide, tin oxide, indium tin oxide, yttrium oxide, zinc oxide, zinc selenide, zinc sulfide, zirconium oxide, zirconium titanate, or glass, and mixtures or blends thereof. [0031] The abrasion resistant layer may be applied by any technique known to those skilled in the art. These techniques include deposition from reactive species, such as those employed in vacuum-assisted deposition processes, and atmospheric coating processes, such as those used to apply sol-gel coatings to substrates. Examples of vacuum-assisted deposition processes include, but not limited to, plasma enhanced chemical vapor deposition (PECVD), arc-PECVD, ion assisted plasma deposition, magnetron sputtering, electron beam evaporation, and ion beam sputtering. Examples of atmospheric coating processes include, but are not limited to, curtain coating, spray coating, spin coating, dip coating, and flow coating. [0032] The processes of the present invention use special effect inks and/or various combinations of special effect inks and colored inks to create the special effect glazings which are part of present invention. As used herein "special effect ink" means an ink which comprises a one or more special effect pigments. A special effect ink may additionally comprise one or more colored pigments. [0033] A wide variety of colored inks are known and one of skill in the art would know how to make a particular color. Briefly the full range of colors can be made with different combinations of three basics colors. Media that combines emitted light to create the sensation of a range of colors uses this type of additive color system. In an additive color system, the additive primary colors are red, green, and blue. Additive mixing of red and green light produces shades of yellow or orange, mixing green and blue produces shades of cyan, and mixing red and blue produces shades of purple and magenta. Mixing equal proportions of the additive primary colors results in shades of grey. When all three colors are fully saturated, the resultant color is white. The color space that is generated is called the RGB ("red, green, blue") color space. Colored inks are compatible with the processes of the present invention and can be used to create a smooth visual transition from the car body to the glazing area.
[0034] An example of a colored ink formulation suitable for use with a plastic film insert molding (FIM) process) is Noriphan™ HTR with 50% Opaque White (code 945), 35% Blue transparent (code 566), and 22% Violet (code 472) offered by Proell, Inc., St. Charles, Illinois. It is noted that a retarder (e.g., slow evaporating solvent) has to be added prior printing on a film.
[0035] Usually, special effect pigment colors are doubled printed and backed with a highly opaque black print although other processes of printing known to those skilled in the art are acceptable. The term "special effect pigment" refers to a variety of pigments which impart optical effects including but not limited to sparkle, luster, glitter, color variation, color intensity variation, pearlescence, or any combination of these effects. These effects occur when the surface to which such a pigment is applied, is viewed from a different angle and/or with a different angle of illumination. [0036] Special effect pigments include but are not limited to metallic pigments and pearlescent pigments. For example, Mearlite® (Engelhard-BASF) industrial-grade pearlescent pigments impart a range of optical effects, from a soft, satin luster to a sharp, metallic brilliance. These effects are due to plate-like crystals of bismuth oxychloride that have a silver-white transparent appearance. A wide variety of special effect pigments are known including, but not limited to chameleon gold- green, chameleon green-blue, pearlescent blue, solar gold, pearlescent magenta- gold, chameleon copper-green, chameleon purple- green, chameleon green-purple, pearlescent green, and pearlescent lilac.
[0037] Special effects pigments also include metallic pigments, for example, silver, silver-gold, aluminum, bronze, and gold. Metallic pigments are, by nature, completely different than other types of pigments used in printing. These pigments are flake-shaped, fully opaque and significantly larger. They consist of planar areas designed to reflect as much light as possible in order to create metallic sheen or luster. Metallic pigments are produced in a variety of particle sizes. The larger the flake size, the greater the degree of brilliance. Metallic flakes used in the graphic arts industry vary from 3 to 15 μm. Aluminum pigments can be produced by a variety of means. The conventional process of producing aluminum pigments found in the graphic arts industry is by the wet grinding process (Hall process). The conventional process of producing bronze pigments in the graphic arts industry is by a dry grinding process (Hametag process). Other means of production, such as stamping and physical vapor deposition, can produce flatter and therefore more brilliant products.
[0038] Pearlescent finishes are also used in the glazing industry. These finishes are designed to create color through light interference effects. They are comprised of a thin layer of a metal oxide deposited on a supporting mica flake. The thickness of the metal oxide layer is such that a specific wavelength of light is reinforced, the lightness changes are accompanied by marked changes in hue and saturation that creates a pearlescent appearance. The metal oxide chosen may also provide color through light absorption.
[0039] Windows in the automotive industry typically exhibit a black-out area that encircles the edge of the window in order to mask the bonding system that glues the window to the car body. Instead of printing this highly opaque black ink, one embodiment of the present invention provides for this layer as an ink that exhibits some type of special effect (e.g., color varying, metallic sparkle, etc.) due to the special pigments incorporated into the ink. Another embodiment of the invention provides a process of printing which result in a shadow effect that gives the appearance of a 3-D image. In one embodiment this shadow effect is provided by printing part of the area of an image using one or more special effect inks and printing parts of the area of the image using standard colored inks. In another embodiment this shadow effect is provided by printing a layer of halftones or shadings of colored ink over a layer of one or more special effect inks. "Halftone" means the image that is produced through the use of equally spaced dot of varying size.
[0040] In another embodiment of the present invention, a plastic film is printed with one or more prints and then placed inside a mold cavity and over-molded. In yet another embodiment of the invention, the special effect inks are printed directly onto the plastic substrate. In another embodiment of the invention, the substate is coated with a weathering layer followed by the deposition of an abrasion resistant layer prior to the printing of the special effect ink. The processes of the invention are suitable for use to print images over large areas including, but not limited to automotive windows. [0041] The processes of the present invention can be used to add one or more images to a plastic substrate for example: borders, black-out layers, letters, symbols, numbers, logos, trademarks, regulatory designations, emblems, chrome strips, chrome accents, and reflectors. The images may for example be printed on different areas of the plastic substrate and/or they may be printed with separate images layered on top of one and other.
[0042] The following specific example is given to illustrate the invention and should not be construed to limit the scope of the invention. Example 1 -Logo with 3-dimentional effect
^ Formatted: Bullets and Numbering j
4ΦΦ3CTGG43Ϊ A white background for the logo was screen printed on a 0.6 x 1.2 m polycarbonate film of 0.76 mm thickness using white ink. A second image was printed with a chrome special effect ink on top of the background color. A third image was a gold colored logo inside the chrome image. A fourth image was printed using black ink to provide the 3-dimentional shadow effect.
KM53-7-M00441 All screens had 78 threads per centimeter mesh size. A 4 mm off- contact was used for printing. All inks were NORIPHAN® HTR inks (Proell.inc, St. Charles, Illinois). Between each print the film was run through a 3-zone tunnel dryer at 70-90-800C to flash off solvents. After all four prints, the film was post cured in an oven for 5 hours at 9O0C. After curing and cool down the film was trimmed to the size of the mold which was approximately 0.5 x 1.0 m, with a wall thickness of 4.8 mm. The film was placed in the mold and then the mold was injected with Lexan GLX143 polycarbonate resin (SABIC Innovative Plastics, Pittsfield, MA). The film can be positioned on either cavity of the mold. Thus the film with the printed images can end up on either the external or internal side of the window. Figure 1 is a cross- section of a window with the film located on the exterior of the window according to one embodiment of the present invention. One skilled in the art will recognize that if the film was placed on the other side of the window (e.g., interior side of the substrate), the printed images would need to be printed or stacked in the opposite order so that the images viewed from the external side of the vehicle would be seen by an observer to be substantially similar.
£0β38-M00451 The printed images and the plastic film become substantially bonded to the plastic substrate. After removal from the mold the resulting part was coated an acrylic primer (SHP-9X, Exatec LLC, Wixom, Michigan) and a weathering layer (SHX, Exatec LLC). An abrasion resistant layer was then deposited using an expanding arc PECVD technique. The resulting glazing system including the weathering layer and the abrasion resistant layer is known as the Exatec®900 coating system (Exatec L. L. C, Wixom, Ml).
!^Ci§l[004β? The preceding description is merely exemplary in nature and is in no way intended to limit the invention or its application or uses. A person skilled in the art will recognize from the previous description that modifications and changes can be made to the specifically described embodiments of the invention without departing from the scope of the invention as defined in the following claims.

Claims

CLAIMSWhat is claimed is
1. A transparent plastic automotive panel comprising: a plastic substrate, a non-black ink overlying a portion of the plastic substrate forming a printed substrate and a protective coating system overlying the ink.
2. The panel of Claim 1 wherein the ink comprises a multi-layer system including and ink selected from the group of opaque colored ink, translucent ink, special effect ink and any combination thereof.
3. The panel of Claim 1 further comprising a plastic film, the ink being printed on a portion of the film.
4. The panel of Claim 3 wherein the plastic film is bonded to the substrate.
5. The panel of Claim 4 wherein the ink is encapsulated between the film and the substrate.
6. The panel of Claim 3 wherein the ink includes a special effect ink.
7. The panel of Claim 6 wherein the special effect ink is a color varying ink.
8. The panel of Claim 6 wherein the special effect is a metallic ink.
9. The panel of Claim 6 wherein the special effect ink further comprises pigments selected from the group of pearlescent pigments, metallic pigments, or a combination of both.
10. The plastic window assembly of Claim 1 wherein the printed special effect ink is a thermal heat cure ink.
1 1. The plastic window assembly of Claim 1 wherein the ink is a UV cure ink.
12. The plastic window assembly of Claim 1 incorporated into an automotive vehicle, the automotive vehicle having a body and the body of the automotive vehicle being of a color corresponding to the ink.
13. The panel of Claim 1 wherein the ink includes a special effect ink.
14. The panel of Claim 13 wherein the special effect ink is a color varying ink.
15. The panel of Claim 13 wherein the special effect ink is a metallic ink.
16. The panel of Claim 13 wherein the special effect ink further comprises pigments selected from the group of pearlescent pigments, metallic pigments, or a combination of both.
17. The panel of Claim 1 wherein the protective coating system overlying the ink includes a weathering layer.
18. The panel of Claim 17 wherein the protective coating system includes an abrasion resistant layer overlying the weathering layer.
19. The panel of Claim 1 wherein the protective coating system includes an abrasion resistant layer overlying the weathering layer.
20. The panel of Claim 3 wherein the protective coating system overlying the ink includes a weathering layer.
21. The panel of Claim 20 wherein the protective coating system includes an abrasion resistant layer overlying the weathering layer.
22. The panel of Claim 3 wherein the protective coating system includes an abrasion resistant layer overlying the weathering layer.
PCT/US2008/062313 2007-05-01 2008-05-02 Special effect glazing WO2008144193A2 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2282849A2 (en) * 2008-05-02 2011-02-16 Exatec, LLC. Special effect glazing
CN103396015A (en) * 2013-08-07 2013-11-20 福建省万达汽车玻璃工业有限公司 Low-emissivity coated laminated skylight glass

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000053537A1 (en) * 1999-03-10 2000-09-14 Minnesota Mining And Manufacturing Company Decorative films for glass-paned window
US20040191521A1 (en) * 2003-03-31 2004-09-30 Exatec Llc Ink for a polycarbonate substrate
US20060025496A1 (en) * 2004-08-02 2006-02-02 Sunitha Grandhee Decorative ink for automotive plastic glazing

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000053537A1 (en) * 1999-03-10 2000-09-14 Minnesota Mining And Manufacturing Company Decorative films for glass-paned window
US20040191521A1 (en) * 2003-03-31 2004-09-30 Exatec Llc Ink for a polycarbonate substrate
US20060025496A1 (en) * 2004-08-02 2006-02-02 Sunitha Grandhee Decorative ink for automotive plastic glazing

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2282849A2 (en) * 2008-05-02 2011-02-16 Exatec, LLC. Special effect glazing
EP2282849A4 (en) * 2008-05-02 2013-04-24 Exatec Llc Special effect glazing
CN103396015A (en) * 2013-08-07 2013-11-20 福建省万达汽车玻璃工业有限公司 Low-emissivity coated laminated skylight glass

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WO2008144193A8 (en) 2009-02-26

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