WO2013103767A1 - Stratifié décoratif ou transparent - Google Patents

Stratifié décoratif ou transparent Download PDF

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Publication number
WO2013103767A1
WO2013103767A1 PCT/US2013/020222 US2013020222W WO2013103767A1 WO 2013103767 A1 WO2013103767 A1 WO 2013103767A1 US 2013020222 W US2013020222 W US 2013020222W WO 2013103767 A1 WO2013103767 A1 WO 2013103767A1
Authority
WO
WIPO (PCT)
Prior art keywords
top coat
laminate
face
carrier
ink
Prior art date
Application number
PCT/US2013/020222
Other languages
English (en)
Inventor
John J. Markey
Original Assignee
Avery Dennison Corporation
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 Avery Dennison Corporation filed Critical Avery Dennison Corporation
Publication of WO2013103767A1 publication Critical patent/WO2013103767A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00—Processes for producing special ornamental bodies
    • B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44F—SPECIAL DESIGNS OR PICTURES
    • B44F1/00—Designs or pictures characterised by special or unusual light effects
    • B44F1/06—Designs or pictures characterised by special or unusual light effects produced by transmitted light, e.g. transparencies, imitations of glass paintings
    • B44F1/066—Designs or pictures characterised by special or unusual light effects produced by transmitted light, e.g. transparencies, imitations of glass paintings comprising at least two transparent elements, e.g. sheets, layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00—Decorative or ornamental articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised 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 at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised 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 at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised 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 at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/16—Homopolymers or copolymers of vinylidene fluoride

Definitions

  • the present su bject matter relates to various laminate assembles that can be readily formed to produce aesthetically attractive trim components, plaques, or other articles.
  • the su bject matter relates to laminates having an outer transparent layer and one or more designs or indicia embedded within the laminate and viewa ble through the outer layer.
  • the su bject matter also relates to methods of forming the laminates a nd various intermediate assemblies.
  • Decorative and/or informational display articles such as plaques or trim components typically include an outer clear layer that covers a design or indicia. Such items are frequently exposed to harsh environments yet must remain clear, not yellow or otherwise d iscolor, and not be so thick as to cause optical distortion of the underlying design or indicia. Providing an article that effectively addresses all of these competing demands is difficult, particularly for providing such article in a cost- effective manner. Thus, a need exists for a decorative and/or informational article and related methods of producing such which satisfies the noted demands.
  • the subject matter provides an intermediate layered assembly adapted for forming a transparent or decorative laminate.
  • the layered assembly comprises a polymeric carrier defining a first face and an oppositely directed second face.
  • the layered assembly also comprises a generally transparent top coat disposed on the first face of the carrier.
  • the top coat defines an exposed face directed away from the carrier.
  • the layered assembly also comprises a layer of one or more inks on the exposed face of the top coat.
  • the subject matter provides a decorative laminate comprising an acrylic substrate defining an outer face.
  • the decorative laminate also comprises a layer of one or more inks on the outer face of the substrate.
  • the decorative laminate additionally comprises a generally transparent top coat disposed on the ink layer.
  • the subject matter provides a method for producing an intermediate layered assembly that is adapted for forming a transparent or decorative laminate.
  • the method comprises providing a polymeric carrier defining a first face and an oppositely directed second face.
  • the method also comprises depositing a generally transparent top coat material on the first face of the carrier, wherein an exposed outer face is defined which is directed away from the carrier.
  • the method additionally comprises applying at least one region of ink on the exposed face of the top coat, to thereby produce the intermediate layered assembly.
  • the subject matter provides a method for producing a decorative laminate.
  • the method comprises providing a polymeric carrier defining a first face and an oppositely directed second face.
  • the method also comprises depositing a generally transparent top coat material on the first face of the carrier, wherein an exposed outer face is defined which is directed away from the carrier, me metnoa also comprises applying at least one region or ink on tne exposed race or tne top coat, to thereby form an intermediate assembly.
  • the method further comprises providing an acrylic substrate defining an outer face.
  • the method also comprises positioning the intermediate assembly and the substrate such that the ink and the exposed face of the intermediate assembly are directed toward the outer face of the substrate.
  • the method comprises laminating the positioned intermediate assembly and the substrate together to thereby form the decorative laminate.
  • Figure 1 is a schematic illustration showing a preferred process for forming a preferred embodiment intermediate assembly and a preferred embodiment laminate in accordance with the present subject matter.
  • the present subject matter relates to a laminated assembly that can be used to provide a three dimensional appearance for print or other designs "suspended" or embedded in the laminate.
  • An example of such a laminated assembly is an automotive applique, ornament, or interior trim component.
  • the laminate uses an intermediate assembly including a top coat of one or more acrylates and polyvinyldifluoride (PVDF) which is disposed upon print or other designs which reside upon a polyethylene terephthalate (PET) film carrier.
  • PVDF polyvinyldifluoride
  • PET polyethylene terephthalate
  • the print or designs can be formed from any conventional ink or printing material.
  • This intermediate assembly is then laminated to a clear acrylic or otner suitame suostrate. me resulting laminate can oe rurtner processed to rorm a wide array or articles and the like.
  • the intermediate assembly is formed, then laminated to a suitable substrate as follows.
  • a carrier film 10 is provided.
  • the carrier film 10 is polyethylene terephthalate (PET).
  • a top coat 20 such as the previously described blend of acrylate(s) and PVDF is applied to the carrier film 10.
  • the top coat material is solvent cast onto the carrier film 10.
  • one or more regions of a primer material 30 are optionally applied to an exposed face or region of the top coat 20.
  • the region(s) of primer 30 correspond to the region(s) of one or more printing inks to be applied in phase (IV). It is also contemplated that depending upon the optical characteristics of the primer, a continuous or su bstantially continuous layer of primer 30 could be deposited upon the face of the top coat 20.
  • ink or other like materials are deposited on the region(s) of primer to form designs or indicia 40. Upon deposition of ink to form the designs or indicia 40, an intermediate assembly A is thus formed.
  • a suitable substrate 50 is provided.
  • the substrate as previously noted is preferably formed from acrylic.
  • the intermediate assembly A is then laminated to the substrate 50 in phase (VI).
  • the designs or indicia 40 are "sandwiched" or disposed between the top coat 20 and the substrate 50.
  • heat and pressure are applied to the intermediate assembly and the substrate to secure the components together.
  • the carrier 10 can be removed in phase (VII).
  • the resulting laminate B produced in phase (VIII) can then be formed as desired, stored, distributed, or used in subsequent processes to form one or more products.
  • the carrier such as carrier 10 illustrated in Figure 1, is preferably a polymer film or web, and most preferably a sacrificial carrier since the carrier is removed in phase (VII).
  • the carrier is preferably a film formed from PET.
  • the thermal and strength properties of PET films make PET a preferred material for the carrier, particularly when used in conjunction with the preferred top coat material described in greater detail herein.
  • the subject matter includes the use of other materials besides or in addition to PET.
  • the carrier defines a first face and an oppositely directed second face. Typical thicknesses for the carrier are from about 0.1 mil to about 10 mil, with about 1 mil being preferred.
  • top coat such as top coat 20 depicted in Figure 1, is clear or generally transparent. This means that the top coat when used in the laminates described herein and at the thicknesses described herein, exhibits a light transmittance in the visible light range of at least 85%, preferably at least 90%, more prefera bly at least 95%, and most preferably at least 98%.
  • the top coat material is a blend of one or more acrylates and polyvinyldifluoride (PVDF).
  • the acrylate component is preferably polyethyl methacrylate (PEMA) however other similar materials exhibiting comparable properties could be used. Additional preferred acrylates include but are not limited to poly(methyl methacrylate) (PM MA), polymers of butyl methacrylate (BMA) and methyl methacrylate (MMA), and combinations thereof. It is also contemplated that other acrylates could be used.
  • PEMA is generally preferred.
  • the preferred PEMA material is commercially available such as for example from Lucite International under the designation ELVACITE 2042-ICI.
  • the polyvinyldifluoride component is also available from one or more commercial sources such as for example from Elf Atocnem under tne designation KYNAK SUU. it is also contemplated tnat otner grades or KYNAK could be used such as for example KYNA 720 and 301F.
  • the top coat material preferably utilizes particular proportions of the one or more acrylates and the PVDF.
  • the top coat material includes from about 25% to about 50% and more preferably from about 34% to about 42% of acrylates, and from about 50% to about 75% and more preferably from about 58% to about 63% by weight of PVDF. These percentages are by weight of total resin solids in the dry top coat.
  • the top coat material comprises about 37% acrylic(s) and about 63% PVDF.
  • the top coat material comprises about 40% acrylic(s) and about 60% PVDF.
  • the top coat material may also comprise effective amounts of dispersing agents from Lubrizol Corporation such as SOLSPERSE 17000, and UV absorbers such as TINUVIN 900 from BASF.
  • the top coat material is formed from AVLOY available from Avery Dennison Corp.
  • AVLOY is a blend of approximately 60% polyvinyldifluoride and about 40% acrylic.
  • TROGAMID is a family of generally clear polyamide or nylon resins having good adhesion, thermal stability, high strength, abrasion resistance, and clarity.
  • top coats could be used such as those available from Dainippon Plastics of Osaka, JP, and Shin-Etsu Chemical of Tokyo, JP.
  • top coat material is disposed on a face of the carrier such as on the first face of the carrier.
  • the top coat material is prereraoiy disposed immediately on and in intimate contact witn tne carrier. I ne top coat defines a nrst face directed toward the carrier and an oppositely directed second face.
  • a typical thickness for the top coat layer is from about 0.1 to about 10 mil, and preferably from about 1 to about 2 mils.
  • primer 30 depicted in Figure 1 The use of a primer such as primer 30 depicted in Figure 1, between the top coat and the ink or material forming the design or indicia is optional. However, as will be appreciated, if a primer is used, the selection of the primer largely depends upon the materials of the top coat and the material forming the design or indicia. Primer materials suitable for use with GV-series inks have been found to be useful in this regard.
  • the primer if used, is disposed on the exposed face, i.e., the second face, of the top coat.
  • the materials used for forming designs and/or indicia such as 40 shown in Figure 1 on the top coat include, but are not limited to GV-series inks.
  • GV-series inks are known in the printing industry and are typically formulated for printing on vinyl surfaces where a high gloss is required.
  • Another non-limiting example of a preferred ink is UVIFORM 3D HTX ink available from Fuji Film Sericol of Kansas City, Kansas.
  • the ink comprises one or more pigments which may be organic pigments or nonorganic pigments.
  • the ink may further comprise one or more stabilizers, flow agents, viscosity adjusting agents, UV blockers or absorbers, and other components.
  • the inks or like materials can be applied in a variety of manners.
  • the inks are applied onto the primer if primer is used.
  • the one or more ink materials are deposited on the exposed, i.e., the second face, of the top coat.
  • the inks are applied by printing ana most prereraoiy Dy electronic or digital printing tecnniques sucn as Dy ink jet printing.
  • Other suitable processes include, but are not limited to rotogravure printing techniques since that technique is typically the most suitable and economical. A variety of other techniques could potentially be used such as offset printing or flexo printing techniques, especially for short length printing runs.
  • the ink may be dried or cured as desired.
  • the layer or region of ink is preferably deposited in a desirable design, arrangement, pattern or the like, to produce a desired appearance or indicia.
  • the layer can be continuous and substantially cover the exposed face of the top coat. However, in forming designs or indicia, it is expected that the ink layer will be discontinuous and thus, not cover or overlie all portions of the top coat.
  • the su bstrate such as substrate 50 in Figure 1 is preferably formed from an impact modified acrylic.
  • the selected acrylic material preferably also exhibits excellent UV stability, clarity and extremely low gel defect count per area.
  • a preferred material for the substrate is AC YLITE 400 available from Rowland Technologies of Wallingford, CT.
  • the acrylic is preferably ACRYLITE, an impact modified acrylic resin from Degussa may also be used.
  • Other suitable su bstrate materials include, but are not limited to high clarity, low gel optical grade acrylics which preferably are suitably modified for impact applications.
  • the substrate may include one or more polycarbonate materials.
  • the thickness of the substrate typically ranges from about 5 mils to about 30 mils, and preferably from about 10 mils to about 20 mils. For certain embodiments, a thickness of about 17 mils has been found to be useful.
  • the substrate defines an outer face for contacting the ink layer(s), designs, and/or indicia. LUU3UJ it may also oe preferred to utilize one or more layers or a laminating aanesive in tne layered assembly and/or the laminate.
  • the present subject matter also provides various preferred embodiment methods for preparing the intermediate layered assemblies and decorative laminates.
  • the methods comprise providing a polymeric carrier as described herein.
  • a generally transparent top coat material is deposited on the carrier. Deposition of the top coat material can be performed in a variety of fashions, however solvent casting of an initially flowable top coat material is preferred. After formation of an exposed outer face of the top coat, one or more primer materials and/or ink materials are applied.
  • the subject matter is not limited to any particular application technique, however printing is generally preferred.
  • the ink is dried to thereby form the intermediate assembly.
  • the intermediate assembly can be stored or transported for use in subsequent processing. Or, the intermediate assembly can be immediately or substantially immediately used in a process for forming a decorative laminate.
  • a substrate is provided and appropriately positioned relative to the intermediate assembly.
  • the intermediate assembly and the substrate are positioned such that the ink and the exposed face of the intermediate assembly are directed toward an outer face of the substrate.
  • the components are then laminated to one another.
  • laminating includes the application of heat and pressure to the components.
  • the heat and pressure applied to the intermediate assembly and the substrate are sufficient to securely bond those components together.
  • the ink layer e.g., the design and/or indicia
  • the ink layer is then embedded or "suspended" between the generally transparent top coat layer and the substrate.
  • tne carrier is tnen removed rrom tne laminated assemoiy.
  • the carrier could be removed or partially removed prior to or during lamination.
  • a wide array of articles, products, and feedstock can be produced by subjecting the laminated assembly to additional processing.
  • various articles such as trim components can be produced by cutting or patterning the laminated assembly and thermoforming portions of the assembly into desired shapes and configurations.
  • two substrates are used to "sandwich" a layer of an ink or other like material.
  • the ink can be applied to one face of one of the substrates, or to a face of each of the substrates.
  • a decorative laminate comprises a first acrylic substrate, a layer of ink, an optional layer of a laminating adhesive, and a second acrylic substrate.
  • both acrylic substrates comprise AC YLITE 400.
  • Laminates such as the preferred embodiment laminate B depicted in Figure 1 can be used in a wide array of forming operations such as thermoforming to produce articles such as trim components, plaques, logos, decorative or informational items, and the like.
  • the laminates can be stored, shipped, and/or sold in sheet form or wound in roll form.
  • a prime application of the preferred embodiment laminates is for interior trim parts in automobiles, trucks, boats, and other vehicles.
  • another prime application is for trim components for appliances such as refrigerators, washers, dryers and the like.
  • LUU38J me various articles rormea as aescrmea nerem exniDit excellent resistance to weatner ana other exterior elements.
  • the articles also are resistant to a wide array of chemical agents.
  • Articles produced by the methods described herein provide for a see-through outer layer which is light transmissive. It is contemplated that the articles could also be used for lighting elements with one or more coloring agents to impart a desired color in one or more regions of the article or lighting element. Additional applications include but are not limited to automotive radio bezels, shifter plates, center consoles, door switch clusters, door trim, and passenger side dash trim strips.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un ensemble stratifié qui comprend un ou plusieurs dessins ou éléments visuels disposés entre une couche de revêtement supérieure et une couche de substrat acrylique. Le stratifié peut être soumis à une ou plusieurs opérations de formage afin de produire un large éventail d'articles tels que des pièces d'automobile.
PCT/US2013/020222 2012-01-05 2013-01-04 Stratifié décoratif ou transparent WO2013103767A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261583285P 2012-01-05 2012-01-05
US61/583,285 2012-01-05

Publications (1)

Publication Number Publication Date
WO2013103767A1 true WO2013103767A1 (fr) 2013-07-11

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ID=47563637

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2013/020222 WO2013103767A1 (fr) 2012-01-05 2013-01-04 Stratifié décoratif ou transparent

Country Status (1)

Country Link
WO (1) WO2013103767A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994009983A1 (fr) * 1992-11-05 1994-05-11 Avery Dennison Corporation Stratifie auto-adhesif pour l'exterieur d'automobiles
US6723427B1 (en) * 1999-06-21 2004-04-20 Avery Dennison Corporation Fade printed decorative sheets and methods and apparatus for making the same
US20070116903A1 (en) * 2005-11-18 2007-05-24 Solaint Llc Decorative Paint film laminate
US20090250164A1 (en) * 2006-10-03 2009-10-08 The Procter & Gamble Company Methods of Making Articles for Applying Color on Surfaces

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994009983A1 (fr) * 1992-11-05 1994-05-11 Avery Dennison Corporation Stratifie auto-adhesif pour l'exterieur d'automobiles
US6723427B1 (en) * 1999-06-21 2004-04-20 Avery Dennison Corporation Fade printed decorative sheets and methods and apparatus for making the same
US20070116903A1 (en) * 2005-11-18 2007-05-24 Solaint Llc Decorative Paint film laminate
US20090250164A1 (en) * 2006-10-03 2009-10-08 The Procter & Gamble Company Methods of Making Articles for Applying Color on Surfaces

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