Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
  • B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
  • B29C45/14811—Multilayered articles
• • 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
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • 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
  • B60—VEHICLES IN GENERAL
  • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
  • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
  • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
  • B60R13/04—External Ornamental or guard strips; Ornamental inscriptive devices thereon
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
  • C09J123/28—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C2791/00—Shaping characteristics in general
  • B29C2791/001—Shaping in several steps
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C2791/00—Shaping characteristics in general
  • B29C2791/004—Shaping under special conditions
  • B29C2791/006—Using vacuum
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
  • B29C51/08—Deep drawing or matched-mould forming, i.e. using mechanical means only
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
  • B29C51/14—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor using multilayered preforms or sheets
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2715/00—Condition, form or state of preformed parts, e.g. inserts
  • B29K2715/006—Glues or adhesives, e.g. hot melts or thermofusible adhesives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
  • B29K2995/002—Coloured
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
  • B29K2995/0026—Transparent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
  • B29L2031/3044—Bumpers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
  • B29L2031/3055—Cars
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/51—Elastic
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/712—Weather resistant
• • 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
  • B32B2323/00—Polyalkenes
  • B32B2323/10—Polypropylene
• • 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
• • 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
  • B32B2605/00—Vehicles
  • B32B2605/08—Cars
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof

Definitions

• the present invention relates to sheet materials generally and more particularly relates to a sheet material suitable for use as a flexible, weatherable paint film.
• Automotive manufacturers require that automotive parts have an exterior paint appearance which meets demanding performance and appearance specifications, such as weatherability, resistance to ultraviolet light degradation, high gloss, and high distinctness-of-image (DOI).
• the adhesive layer used to bond the paint film to a substrate must withstand the effects of changes in temperature over a wide range of temperatures without losing adhesion or cohesive strength. For instance, some industry tests involve subjecting the paint film to an abrupt change in temperature from approximately 0°C to approximately 100°C. The adhesive must be capable of withstanding such a temperature change without delamination of the paint film from the substrate occurring. Further, since the paint film may be used to surface parts having complex three-dimensional configurations, the adhesive must exhibit good elongation properties at thermoforming temperatures. There remains a need for an adhesive material that possesses the characteristics listed above.
• the adhesive composition of the present invention comprises a mixture or blend of a chlorinated polypropylene and a higher molecular weight chlorinated polyolefin that provides both good adhesion to adjacent film layers and good elongation and cohesive strength over a wide range of temperatures.
• the chlorinated polypropylene has a higher softening point than the chlorinated polyolefin, which enhances the cohesive strength of the adhesive composition, while the chlorinated polyolefin component provides good adhesion at room temperature.
• the two chlorinated components have comparable chlorine content in order to ensure chemical compatibility.
• the adhesive composition of the present invention includes a chlorinated polypropylene component having a peel strength of at least about 0.8 lbs./in. at 100°C and a chlorinated polyolefin component having a peel strength of at least about 5 lbs./in. at room temperature. Room temperature is defined as about 15°C to about 30°C.
• the chlorinated polypropylene component has a peel strength of at least about 1.0 lbs./in. at 100°C
• the chlorinated polyolefin component has a peel strength of at least about 7 lbs./in. at room temperature.
• the chlorinated polyolefin is present in the composition at a concentration of about 1 to about 10 weight percent and the chlorinated polypropylene is present in an amount of about 5 to about 20 weight percent.
• the adhesive composition may further comprise any compatible solvent known in the art.
• the chlorinated polypropylene component has a peel strength of at least about 0.8 lbs./in. at room temperature, and the chlorinated polyolefin component has a peel strength of at least about 0.2 lbs./in. at 100°C.
• the chlorinated polypropylene component has a peel strength of at least about 1.0 lbs./in. at room temperature, and the chlorinated polyolefin has a peel strength of at least about 0.4 lbs./in. at 100°C.
• the two chlorinated components have similar chlorine contents.
• both components have a chlorine content of about 20 to about 40 weight percent.
• the chlorinated polypropylene has a softening point of at least about
• the adhesive composition may also comprise an epoxy component, preferably in an amount of about 0.1 to about 2.0 weight percent on a dry solids basis.
• the adhesive composition may contain a pigment component, such as carbon black, titanium oxide, and mixtures thereof.
• the adhesive composition may also contain further additives such as UN screeners, heat stabilizers, antioxidants, and mixtures thereof.
• the adhesive composition is in the form of a film layer.
• the adhesive layer comprises about 30 to about 70 weight percent chlorinated polyolefin component and about 30 to about 70 weight percent chlorinated polypropylene component.
• the adhesive layer comprises about 30 weight percent chlorinated polyolefin and about 70 weight percent chlorinated polypropylene.
• the present invention provides a flexible, weatherable decorative sheet material comprising a decorative paint film and an adhesive layer overlying the inner surface of the decorative paint film, wherein the adhesive layer comprises the chlorinated polypropylene and chlorinated polyolefin components described above.
• the decorative paint film has a 60 degree gloss value of at least 60.
• the decorative sheet material may include a primer layer adhering the inner surface of the decorative paint film to the adhesive layer.
• the primer layer comprises an acrylic polymer composition.
• the decorative sheet material may further include a thermoformable backing layer adhered to the opposing surface of the adhesive layer.
• the decorative sheet material may include an extensible mask layer releasibly adhered to the outer surface of the paint film to form a protective film overlying the paint film.
• a mask layer comprising a polymer selected from the group consisting of polyurethane, polyolefin, polyester, and polyamide may be used.
• the present invention also includes a method of making a flexible weatherable decorative sheet material.
• the method includes the steps of forming a thermoformable decorative paint film and applying a coating of an adhesive composition to the inner surface of the paint film to form an adhesive layer, wherein the adhesive composition comprises the chlorinated components described above.
• the method may also include the steps of applying a primer layer to the inner surface of the decorative paint film prior to application of the adhesive layer.
• the method may include the step of applying a thermoformable backing layer to the exposed surface of the adhesive layer, such that the adhesive layer bonds the backing layer to the paint film.
• the decorative paint film may be formed by applying at least one coating layer to a smooth flexible casting surface and drying the coating layer on the casting surface to produce a paint film so that the outer surface of the paint film is releasably bonded to the casting surface.
• the decorative paint film may comprise a single layer of a pigmented polymer or may comprise both a clear coat layer and a pigmented color coat layer.
• the decorative sheet material constructed using the method outlined above may be thermo formed into a three-dimensional shape and the exposed surface of the thermoformable backing layer may be bonded to a substrate to form a composite shaped part.
• the decorative sheet material of the present invention may be inserted into a mold, such as a compression mold or an injection mold, and bonded to the substrate to form the composite shaped part.
• the decorative sheet material may be inserted into the mold in the form of a substantially flat sheet or after thermoforming the sheet material into a preform.
• Figure 1 is a perspective view of an automobile illustrating the front fascia of the automobile having a decorative paint film applied thereto;
• Figure 2 is a front view of an automobile front fascia having a decorative paint film applied thereto;
• Figure 3 is a cross-sectional view of the fascia shown in Figure 2 taken along line 3-3 of Figure 2;
• Figure 4 is a cross-sectional view of the decorative sheet material of the present invention adhered to a substrate
• Figure 5 is a cross-sectional view of the decorative sheet material of the present invention including a clear coat and a color coat layer;
• Figure 6 is a cross-sectional view of the decorative sheet material of the present invention having a single paint film layer
• Figure 7 is a schematic illustration of a process for construction of the decorative sheet material of the present invention
• Figure 8 is a schematic illustration of a process for applying the mask layer to the outer surface of a decorative paint film
• Figures 9A-9D are schematic illustrations of the steps in a thermoforming process used to construct a preform.
• Figures 10A-10C are schematic illustrations of steps in an injection molding process for forming a composite shaped part.
• Figure 1 illustrates an automobile 10 having a composite shaped part 12.
• the composite shaped part 12 is a complex, contoured three-dimensional front fascia of the automobile 10.
• the composite shaped part 12 has a decorative sheet material 14 applied thereto.
• the decorative sheet material 14 of the present invention is particularly advantageous for providing a decorative surface on a composite shaped part 12 of an automobile 10.
• the present invention could be used in a variety of applications requiring a weatherable, decorative surface.
• Figure 2 is a front view of the composite shaped part 12 having the decorative sheet material 14 applied thereto.
• Figure 3 is a cross-sectional side view of the composite shaped part 12 comprising a substrate 16 having a decorative sheet material 14 applied thereto.
• the decorative sheet material 14 undergoes different amounts of elongation at different points along the contoured surface of the composite shaped part 12.
• the decorative sheet material 14 of the present invention has a three-dimensional configuration in which certain areas of the sheet material have been subjected to elongation in excess of about 300%, and other areas of the sheet material are substantially non-elongated.
• the difference in gloss value between the elongated areas and the non-elongated areas should be no more than 10 gloss units with a minimum 60 degree gloss value of at least 60.
• the decorative sheet material 14 of the present invention is capable of maintaining a high level of gloss regardless of the amount of elongation experienced by the decorative sheet material during a thermoforming or molding process.
• Figure 4 shows a greatly expanded cross-sectional view of a composite shaped part 12 comprising a decorative sheet material 14 of the present invention adhered to a substrate 16.
• the decorative sheet material includes a mask layer 20, a clear coat layer 22, a color coat layer 24, a primer layer 26, an adhesive layer 28, and a thermoformable backing layer 30.
• the extensible mask layer 20 is designed to maintain gloss and DOI during forming processes and molding processes.
• Forming processes include, but are not limited to, thermoforming, cold stretching, and vacuum forming. Molding processes include, but are not limited to, injection molding, compression molding, and blow molding.
• the mask layer 20 also adds strength to the decorative sheet material 14 and improves process uniformity during the thermoforming process. Additionally, the extensible mask layer 20 protects the underlying layers of the decorative sheet material 14 from scratching or marring until the part is ready for display.
• the mask layer 20 is capable of stretching up to about 600 percent during thermoforming and has a room temperature elongation at break of at least about 200 percent. The mask layer 20 may be retained as the outer layer of the decorative sheet material 14 during construction of the final product, such as an automobile.
• the mask layer 20 may be removed to reveal the underlying decorative paint film 18.
• the extensible mask layer 20 can be maintained as a protective layer and removed only after the vehicle has completed shipment and is ready for delivery to a customer.
• the extensible mask layer 20 is releasably bonded to the underlying decorative paint film 18 and may be stripped away from the underlying layers in a single piece.
• the mask layer 20 is transparent or substantially transparent to permit visual inspection of the part for surface defects without removal of the mask layer.
• the extensible mask layer 20 maintains high gloss and DOI during injection or compression molding, such as thermoplastic or thermoset compression molding, where the mold is roughened or deglossed.
• Roughened molds are less expensive than highly polished molds and are also functionally superior to highly polished molds because the rough mold surface enhances air removal from the mold as the mold closes.
• the extensible mask layer 20 protects the paint film 18 from loss of gloss or other damage caused by the mold without resorting to the use of highly polished molds.
• the extensible mask layer 20 is about 0.3 mils to about 3.0 mils in thickness.
• the extensible mask layer 20 comprises polyurethane, polyolefin, such as polyethylene and polypropylene, polyester, such as polyethylene terephthalate, or polyamide.
• the mask layer 20 comprises a dried film of an aliphatic or aromatic polyester or polyether polyurethane in the form of a dispersion or a solution.
• polyurethane polymers QA 5218 and QA 5026 manufactured by Mace Adhesives and Coatings of Dudley, Massachusetts, may be used to form the mask layer 20.
• the mask layer 20 comprises about 85 to about 99.5 weight percent polyurethane water-borne dispersion.
• a small amount of surfactant (about 0.05 to about 0.2 weight percent), such as SURFYNOL 104H manufactured by Air Products of Allentown, PA, is added to lower surface tension.
• the mask layer 20 composition may include additional additives designed to migrate into the clear coat layer 22 to enhance weatherability or other desirable properties of the clear coat layer or to prevent migration of additives from the clear coat into the mask layer.
• Migratory additives suitable for use with the present invention include, but are not limited to, hardness enhancers, release agents, ultraviolet light stabilizers, antioxidants, dyes, lubricants, surfactants, catalysts, and slip additives.
• the migratory additives useful in the present invention include benzophenone, silicones, waxes, triazoles, and triazines.
• the migratory additives are encouraged to migrate into the outer surface of the clear coat layer 22 by the heat and/or pressure present during thermoforming processes and in-mold processes. Additionally, the presence of these additives in the mask layer 20 prevents migration of additive components from the clear coat layer 22 into the mask layer.
• Ultraviolet light stabilizers such as TINUVIN 1130 and TINUVIN 292, both manufactured by Ciba Geigy of Hawthorne, NY, can be added as migratory additives in the mask layer 20 composition.
• Silicone additives such as BYK333 manufactured by BYK Chemie of Wallingford, CT, can be added to lower the coefficient of friction of the clear coat layer 22.
• the migratory additives are generally added in amounts ranging from about 0.01 to about 2.0 weight percent, with all additives accounting for no more than about 5.0 weight percent of the mask layer 20 composition.
• Figures 5 and 6 are greatly expanded cross-sectional views of two embodiments of the decorative sheet material 14 of the present invention.
• the decorative paint film 18 may comprise a single layer 25 of a pigmented polymer, as shown in Figure 6, or may comprise multiple layers, as shown in Figures 4 and 5. If a single layer 25 of pigmented polymer is used, the polymer may be selected from the group consisting of urethane polymers, acrylic polymers, fiuoropolymers, and alloys of a fluoropolymer and an acrylic polymer. FLUOREX® films manufactured by Rexam are examples of alloys of a fluoropolymer and an acrylic polymer.
• the single layer 25 of pigmented polymer may also include UV screeners to enhance weatherability, antioxidants, heat stabilizers, and other conventional additives.
• the pigmented polymer layer 25 may further include pigments, dyes, and/or flakes to enhance visual appearance.
• the decorative paint film 18 may also comprise both a clear coat layer 22 and a color coat layer 24.
• the clear coat layer 22 is formed from a substantially transparent weatherable polymer composition 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 part 12. Additionally, the clear coat layer 22 must be formable from a two-dimensional surface to a three-dimensional surface without objectionable loss of appearance or performance properties.
• the clear coat layer 22 is selected from the group consisting of urethane polymers, acrylic polymers, fluoropolymers, and alloys or a fluoropolymer and an acrylic polymer (such as FLUOREX® films).
• the clear coat layer 22 may include UV screeners, antioxidants, heat stabilizers, and other conventional additives.
• the clearcoat layer 22 is about 0.3 to about 3 mils in thickness.
• the color coat layer 24 is formed of a polymer composition containing a uniformly dispersed pigment to provide the appearance necessary for exterior automobile use.
• the color coat layer 24 is selected from the group consisting of urethane polymers, acrylic polymers, fluoropolymers, and alloys of a fluoropolymer and acrylic polymer (such as FLUOREX® films).
• the color coat layer 24 may include pigments, dyes, and/or flakes to enhance visual appearance and improve weatherability.
• the color coat layer 24 is about 0.3 to about 3 mils in thickness.
• a color adjustment layer 27 may be added between the clear coat layer 22 and the color coat layer 24 to enhance visual appearance.
• the color adjustment layer 27 can be applied in coating form and include pigments, dyes and/or flakes or applied as a graphic design using printing methods such as gravure, rotary screen, flat bed step-and-repeat screen, ink jet, flexographic or other printing techniques.
• the primer layer 26 improves adhesion between the color coat layer 24 and the adhesive layer 28.
• the primer layer 26 preferably comprises an acrylic polymer prepared in solution using any compatible solvent known in the art, such as toluene. In one embodiment, the primer layer 26 is prepared from a solution comprising about 65 to about 85 weight percent acrylic composition and about 5 to about 10 weight percent solvent.
• An acrylic polymer suitable for use in the primer layer 26 is acrylic adhesive 68070 manufactured by DuPont.
• the primer layer 26 may be opaque, colored or clear.
• Opaque is defined as less than 1 percent transmission at a wavelength of less than 400 ran.
• the primer layer 26 is preferably about 0.2 to about 2 mils in thickness.
• the primer layer 26 may be colored or opaque to protect the underlying thermoformable backing layer 30 from damage caused by UV exposure. Pigments such as carbon black, titanium oxide, and mixtures thereof may be added to impart color to the acrylic polymer composition used in the primer layer 26. Additionally, additives such as UV screeners, antioxidants, and heat stabilizers may be added to the primer layer 26.
• the adhesive layer 28 adheres the decorative paint film 18 to a thermoformable backing layer 30.
• the adhesive layer 28 comprises a mixture or blend of a chlorinated polypropylene and a higher molecular weight chlorinated polyolefin.
• the adhesive layer 28 is formed from a mixture of about 5 to about 20 weight percent chlorinated polypropylene and about 1 to about 10 weight percent of a higher molecular weight chlorinated polyolefin formed in solution.
• a compatible solvent known in the art, such as toluene is present in an amount of about 60 to about 80 weight percent. After evaporation of the solvent, the dried adhesive layer 28 comprises about 30 to about 70 weight percent chlorinated polyolefin and about 30 to about 70 weight percent chlorinated polypropylene.
• the adhesive layer 28 comprises about 30 weight percent chlorinated polyolefin and about 70 weight percent chlorinated polypropylene.
• a chlorinated polypropylene suitable for use with the present invention is HARDLEN 13-LP manufactured by Advanced Polymer.
• a higher molecular weight chlorinated polyolefin suitable for use with the present invention is SUPERCHLON 822S manufactured by CP/Phibrochem of Fort Lee, NJ.
• the adhesive layer 28 should be capable of stretching about 300 to about 600 percent. Due to the substantial elongation capability of the adhesive layer 28, the adhesive layer maintains the necessary adhesive strength to prevent delamination of the decorative paint film 18 from the thermoformable backing layer 30 over a wide temperature range.
• the adhesive layer 28 must have good adhesion to the backing layer 30 and the primer layer 26. Additionally, the adhesive layer 28 must exhibit good cohesive strength at 100°C and good elongation properties at thermoforming temperature (about 190° to about 200°C).
• the blend of chlorinated polypropylene and higher molecular weight chlorinated polyolefin provides both good adhesion to adjacent film layers and good elongation and cohesive strength over a wide range of temperatures.
• the chlorinated polypropylene component such as HARDLEN 13-LP, has a higher softening point than the chlorinated polyolefin component, which enhances the cohesive strength of the adhesive layer 28, particularly at elevated temperatures.
• the higher molecular weight chlorinated polyolefin component such as SUPERCHLON 822S, provides good adhesion at room temperature.
• the two chlorinated components should have comparable chlorine content in order to ensure chemical compatibility.
• the two chlorinated components preferably have a chlorine content of about 20 to about 40 weight percent, and most preferably, a chlorine content of about 20 to about 30 weight percent.
• the higher molecular chlorinated polyolefin should have a peel strength at room temperature of at least about 5 lbs./in., and preferably about 7 lbs./in. Additionally, the chlorinated polyolefin should have a peel strength at 100°C of at least about 0.2 lbs./in., and preferably at least about 0.4 lbs./in.
• the chlorinated polypropylene should have a peel strength of at least about 0.8 lbs./in at room temperature, and preferably at least about 1.0 lbs./in. Further, the chlorinated polypropylene should have a peel strength at 100°C of at least about 0.8 lbs./in., and preferably at least about 1.0 lbs./in.
• the softening point of the chlorinated polypropylene component should be at least about 85°C, and preferably at least about 100°C.
• Peel strength at room temperature was measured using Sintech System I manufactured by Sintech, Inc. Peel strength at elevated temperature was measured using an INSTRON machine, model 4467, coupled with a heating unit that allows temperature control of the sample. Using either machine, peel strength was measured using a 180 degree peel with a cross head speed of 4 inches/minute.
• An epoxy component such as EPON 828RS manufactured by Shell Chemical, may be added in small amounts (approximately about 0.1 to about 2.0 weight percent on a dry solids basis) as an acid scavenger.
• the adhesive layer 28 may be colored or opaque to protect the underlying thermoformable backing layer 30 from damage caused by UV exposure. Pigments such as carbon black, titanium oxide, and mixtures thereof may be added to impart color to the polymer composition used in the adhesive layer 28. Additives such as UN screeners, antioxidants, and heat stabilizers may be added to the adhesive layer 28.
• the adhesive layer 28 is about 0.2 to about 2 mils in thickness.
• the thermoformable backing layer 30 bonds the decorative paint film 18 of the decorative sheet material 14 to the substrate 16.
• the backing layer 30 provides bulk and/or rigidity for handling the decorative sheet material 14 as a thermoformed preform.
• the backing layer 30 also provides thickness to prevent glass fibers, fillers or other sources of visual roughening or "orange peel" from the substrate 16 from affecting the visual appearance of the decorative sheet material 14.
• the backing layer 30 must bond well with both the substrate 16 and the adhesive layer 28.
• the backing layer 30 may be selected from the group consisting of thermoplastic olefin, acrylonitrile-butadiene-styrene terpolymer, polypropylene, thermoplastic polyimide, polyethylene oxide, polycarbonate, polyvinyl chloride, polystyrene, styrene/polyphenylene oxide ( ⁇ ORYEL), polybutylene terephthalate, nylon, PETG copolyester, and mixtures, laminates and copolymers thereof, depending on the material used as the substrate 16.
• Figure 7 illustrates a process for constructing the decorative sheet material 14 of the present invention.
• a film carrier 33 is advanced from a supply roll 38 through a series of process steps.
• the film carrier 33 preferably comprises a polyester casting film having a high gloss surface.
• the film carrier 33 is important for high gloss applications because it imparts high gloss and DOI to the decorative sheet material 14.
• the film carrier 33 comprises polyethylene terephthalate (PET) in a grade without slip additives.
• PET polyethylene terephthalate
• the film carrier 33 is about 1 to about 3 mils in thickness, preferably about 2 mils in thickness.
• the film carrier 33 passes through a first coating station 40. If a single pigmented layer 25 is used as the decorative paint film 18, the pigmented layer is deposited onto the film carrier 33 using coating station 40 and the resulting film is dried by dryer 46. If a decorative paint film 18 having multiple coatings is desired, the first coating station 40 may deposit the clear coat layer 22. The clear coat layer 22 then passes through a dryer 42. Thereafter, a color coat layer 24 is deposited on the dried clear coat layer 22 using coating station 44. The color coat layer 24 is then dried using dryer 46. Optionally, the dried color coat layer 24 can be subjected to a corona treatment (not shown).
• the coating stations 40 and 44 may utilize any conventional coating or casting techniques, such as reverse roll coating or slot die coating techniques. Slot die coating methods are preferred.
• the dryers 42 and 46 may utilize any conventional drying technique.
• the dryers 42 and 46 are ovens having multiple heating zones wherein each successive heating zone operates at a progressively higher temperature.
• an oven having four to six heating zones ranging in temperature from about 200 F to about 400 F may be used.
• dryer 42 may be eliminated from the process such that the color coat 24 is applied to the clear coat 22 while the clear coat is still wet.
• the film carrier advances to a primer coating station 48, where the primer layer 26 is deposited onto the exposed layer of the decorative paint film 18.
• the primer layer 26 is then dried using dryer 49.
• the film carrier advances to an adhesive coating station 50, where the adhesive layer 28 is deposited onto the primer layer 26.
• the adhesive layer 28 is dried using dryer 51.
• the primer coating station 48 and adhesive coating station 50 may utilize any conventional coating or casting technique, such as reverse roll coating or slot die coating techniques.
• the dryers 49 and 51 may utilize any conventional drying technique.
• a thermoformable backing layer 30 is advanced from a supply roll 52 and laminated to the adhesive-coated surface of the film carrier 33.
• FIG. 8 illustrates a process for preparing a decorative sheet material 14 having a mask layer 20.
• a non-extensible carrier 34 is advanced from a supply roll 58.
• the carrier 34 may be constructed of the same material used for the film carrier 33.
• the carrier 34 comprises a polyethylene terephthalate film.
• the carrier 34 advances through a coating station 60, where the mask layer 20 is deposited onto a surface of the carrier.
• the coating station 60 may utilize any coating or casting technique known in the art, such as reverse roll coating or slot die coating techniques.
• the coated carrier 34 passes through a dryer 62 to form a dried mask layer 20.
• the dryer 62 used to dry the mask layer 20 may utilize any conventional drying technique.
• the dryer 62 comprises an oven with multiple heating stages. The dryer 62 evaporates the solvents present in the mask layer 20 composition.
• the layers of the decorative sheet material 14 formed in the process illustrated in Figure 7 are advanced from a supply roll 56.
• the film carrier 33 is stripped away from the remaining layers to expose either the single pigmented layer 25 or the clear coat layer 22 of the decorative paint film 18, depending on the construction of the paint film used.
• the exposed outer layer of the decorative paint film 18 is laminated and releasably bonded to the mask layer 20 by nipping the two films between two rollers, 64 and 65, with or without applying heat to the layers.
• the resulting decorative sheet material 14 is collected by product roll 67.
• the non-extensible carrier 34 may be stripped away to expose the mask layer 20 before or after collection of the sheet material 14 by product roll 67.
• the decorative paint film 18, primer layer 26, and adhesive layer 28 are coated directly onto the dried mask layer 20 rather than laminating the coated films together.
• the mask layer is coated onto the clear coat layer 22.
• a decorative sheet material 14 prepared according to Figure 7 could be stripped from carrier 33 so that the mask layer 20 can be coated directly onto the clear coat layer 22.
• the decorative sheet material 14 of the present invention can be adhered to a supporting substrate 16 in accordance with known laminating or bonding techniques.
• a supporting substrate 16 include metal, wood, and molded polymer substrates.
• exterior automobile parts are particularly suitable as the substrate 16.
• Suitable polymers for use as the substrate 16 include, for example, thermoplastic olefin, acrylonitrile-butadiene-styrene terpolymer, polypropylene, thermoplastic polyimide, polyethylene oxide, polycarbonate, polyvinyl chloride, polystyrene, styrene/polyphenylene oxide (NORYEL), polybutylene terephthalate, nylon, PETG copolyester, Sheet Molding Compounds (SMC), RIM urethanes, and mixtures, laminates and copolymers thereof.
• the decorative sheet material 14 may be applied to the substrate 16 by a variety of methods. These methods include, but are not limited to, compression molding, such as thermoplastic or thermoset compression molding, injection molding and the like. In an injection molding process, the decorative sheet material 14 may be preformed as described below or placed in the mold as a substantially flat sheet. If the sheet material 14 is placed in the mold without performing, the heat and/or pressure of the molding process conforms the sheet material to the desired shape.
• Figures 9A-9D illustrate the steps in a thermoforming process.
• FIG 9A shows heating of the decorative sheet material 14 of the present invention by heating elements 70.
• the heating step softens and increases the extensibility of the decorative sheet material 14 so that the sheet material will readily conform to the contoured outer surface of the mold 74.
• the mold 74 is brought into contact with the heated decorative sheet material 14 and a vacuum is drawn to encourage conformity of the sheet material 14 to the contours of the mold 74. Thereafter, the mold 74 is removed from the decorative sheet material 14 and the sheet material is allowed to cool and harden into the three- dimensional configuration.
• FIGs 10A-10C illustrate steps in an in-mold surfacing process.
• the thermoformed decorative sheet material 14 is placed in the mold cavity 78 of an injection mold 76.
• the decorative sheet material is placed in the mold cavity 78 with the mask layer 20 facing the inner surface of the injection mold 76.
• the decorative sheet material 14 may be placed in the mold cavity 78 as a flat, two-dimensional insert rather than as a preform.
• the mold 76 may have a roughened inner surface.
• the injection mold 76 is shut and a moldable polymer 82 is introduced into the mold 76 through the injection mold barrel 80.
• the polymer 82 bonds to the backing layer 30 and conforms to the contoured shape of the mold cavity 78.
• the moldable polymer 82 is allowed to cool and harden into a composite shaped part 12 comprising a substrate 16 bonded to a decorative sheet material 14, as shown in Figure IOC.
• the mask layer 20 of the decorative sheet material may be stripped from the composite shaped part 12 to expose the paint film finish when desired.
• EXAMPLE 1 The peel strength data shown in Table 1 illustrates the good balance of adhesion and cohesive strength provided by a blend of chlorinated polypropylene (HARDLEN 13-LP) and a higher molecular weight chlorinated polyolefin (SUPERCHLON 822S).
• HARDLEN 13-LP chlorinated polypropylene
• SUPPERCHLON 822S a higher molecular weight chlorinated polyolefin
• the HARDLEN 13-LP component exhibits good peel strength at 100°C
• the SUPERCHLON 822S component adds good peel strength at room temperature (about 15 to about 30°C).
• the two chlorinated components have similar chlorine contents: 24.5 weight percent for SUPERCHLON 822S and 26 weight percent for HARDLEN 13-LP.
• EXAMPLE 2 An adhesive layer of the present invention was compared to two available adhesives: Eastman 343-1 and Novacote 222. Adhesive layers were formed as described above and subjected to peel strength testing using the peel strength equipment described above.
• the adhesive layer of the present invention comprised about 30 weight percent SUPERCHLON 822s and about 70 weight percent HARDLEN 13-LP. As shown by the data, the adhesive of the present invention provides a better combination of room temperature and elevated temperature peel strength than the comparative examples.

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• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Manufacturing & Machinery (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Laminated Bodies (AREA)
• Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)

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• 2000
  • 2000-02-16 WO PCT/US2000/003919 patent/WO2000051829A2/en not_active Application Discontinuation
  • 2000-02-16 CA CA002360504A patent/CA2360504A1/en not_active Abandoned
  • 2000-02-16 EP EP00919306A patent/EP1144205A3/de not_active Withdrawn
  • 2000-02-16 AU AU40014/00A patent/AU4001400A/en not_active Abandoned

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