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WO2002000448A2 - Film de masquage de protection extensible, et pieces fabriquees avec ce film - Google Patents

Film de masquage de protection extensible, et pieces fabriquees avec ce film Download PDF

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Publication number
WO2002000448A2
WO2002000448A2 PCT/US2001/041090 US0141090W WO0200448A2 WO 2002000448 A2 WO2002000448 A2 WO 2002000448A2 US 0141090 W US0141090 W US 0141090W WO 0200448 A2 WO0200448 A2 WO 0200448A2
Authority
WO
WIPO (PCT)
Prior art keywords
sheet material
paint film
mask
layer
urethane polymer
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US2001/041090
Other languages
English (en)
Other versions
WO2002000448A3 (fr
Inventor
Mark O'neil Outlaw
Mark Alan Beard
Neil Allen Rollins
Guerry Wayne Taylor
Thomas Randall Fields
Scott William Huffer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Image Products Group LLC
Original Assignee
Rexam Image Products Inc
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 Rexam Image Products Inc filed Critical Rexam Image Products Inc
Priority to AU2001273619A priority Critical patent/AU2001273619A1/en
Publication of WO2002000448A2 publication Critical patent/WO2002000448A2/fr
Anticipated expiration legal-status Critical
Publication of WO2002000448A3 publication Critical patent/WO2002000448A3/fr
Ceased legal-status Critical Current

Links

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
    • 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
    • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0025—Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
    • B29C37/0028—In-mould coating, e.g. by introducing the coating material into the mould after forming the article
    • B29C37/0032—In-mould coating, e.g. by introducing the coating material into the mould after forming the article the coating being applied upon the mould surface before introducing the moulding compound, e.g. applying a gelcoat
    • 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
    • B29C45/14827—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 using a transfer foil detachable from the insert
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
    • 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
    • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0025—Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
    • B29C37/0028—In-mould coating, e.g. by introducing the coating material into the mould after forming the article
    • B29C2037/0042—In-mould coating, e.g. by introducing the coating material into the mould after forming the article the coating being applied in solid sheet form, e.g. as meltable sheet
    • 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
    • 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
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers

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).
  • Many of the automotive parts have a complex shape which requires high degrees of elongation of the paint film. Due to differences in the amount of elongation experienced by different areas of the part during the thermoforming and/or molding process, uniformity of appearance has been difficult to achieve with paint films applied prior to molding.
  • U.S. Patent No. 5, 968,657 discloses a masking film comprising a urethane layer, wherein the masking film is removably bonded to a paint film.
  • the masking film remains in place while the paint film is thermoformed and/or molded in order to substantially retain the high gloss and DOI of the paint film during such processes.
  • the use of urethane-containing mask layers can result in yellowing of the underlying clear coat layer of the paint film, leading to reduced aesthetic quality.
  • the present invention provides a decorative paint film that includes a formable protective mask that remains in place on the film during forming or molding operations.
  • the presence of the formable protective mask prevents loss of gloss and DOI during a forming or molding process.
  • the protective mask may be kept in place during construction of the final product, such as an automobile, in order to protect the visual appearance of the paint film finish.
  • the mask may be subsequently stripped off to reveal a high quality, high gloss paint film finish.
  • NMP N-methyl-2-pyrrolidone
  • the present invention provides a mask having a reduced concentration of NMP, such that yellowing of the clear coat is avoided.
  • the low level of NMP is attained by using a blend or mixture of a polyester urethane polymer and a polyether urethane polymer, wherein the polyether urethane polymer has a lower concentration of NMP than the polyester urethane polymer, such that the mask has a lower overall NMP concentration than a mask made solely of the polyester urethane polymer.
  • the mask may comprise at least two layers, a first layer adjacent to the outer surface of the paint film and comprising a blend or mixture of a polyester urethane polymer and a polyether urethane polymer and a second layer overlying the first layer of the mask and comprising a polyester urethane polymer.
  • the present invention provides a flexible, weatherable, decorative heat material useful in lieu of painting for providing a decorative finish.
  • the sheet material comprises a decorative paint film, the paint film having an inner surface and a weatherable outer surface suitable for forming an exterior finish for a part, such as an automobile body part.
  • the sheet material further comprises an extensible mask releasably adhered to the outer surface of the paint film to form a protective film overlying the paint film, the mask comprising no more than about 50 mg/m 2 of N-methyl-2-pyrrolidone.
  • the mask comprises about 6 to about 50 mg/m 2 of N-methyl-2-pyrrolidone.
  • the mask comprises about 6 to about 20 mg/m 2 of N-methyl-2-pyrrolidone.
  • the mask comprises a mixture of about 30 to about 50 weight percent of a polyether urethane polymer and about 50 to about 70 weight percent of a polyester urethane polymer, the polyether urethane polymer having a lower concentration of NMP than the polyester urethane polymer.
  • the mask comprises at least two layers, a first layer comprising a mixture of a polyester urethane polymer and a polyether urethane polymer, such as the mixture described above, adjacent to the outer surface of the paint film and a second layer comprising a polyester urethane layer overlying the first layer.
  • the decorative paint film may comprise a single layer of a polymer composition containing pigments, dyes, flakes, or mixtures thereof.
  • the paint film comprises a clear coat layer of a transparent weatherable polymer forming the outer surface and an underlying color coat layer of a polymer composition containing at least one of pigments, dyes, flakes or mixtures thereof, the color coat layer forming the inner surface of the paint film.
  • the sheet material may further include a thermoformable backing layer bonded to the inner surface of the paint film.
  • the thermoformable backing layer may be selected from the group consisting of thermoplastic olefm, polyethylene, acrylonitrile-butadiene-styrene terpolymer, polypropylene, thermoplastic polyimide, polyethylene oxide, polycarbonate, polyvinyl chloride, polystyrene, styrene/polyphenylene oxide (NORYEL), polybutylene terephthalate, nylon, PETG copolyester, and mixtures, laminates and copolymers thereof.
  • the sheet material may also include an adhesive layer affixing the paint film to the thermoformable backing layer.
  • the adhesive layer comprises one or more layers selected from the group consisting of urethane adhesives, acrylic adhesives, acrylic adhesives with crosslinkers, chlorinated polyolefins and mixtures thereof.
  • the above-described decorative sheet material may be used to form a preform for in-mold surfacing of a part by thermoforming the decorative sheet material into a three-dimensional configuration.
  • a composite shaped part may also be constructed by adhering the preform to a substrate of a thermoplastic polymer, which conforms to the three-dimensional configuration of the preform and is adhered thereto.
  • the decorative sheet material of the composite shaped part 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 and wherein the elongated areas and the non- elongated areas have a 60 degree gloss value within 10 gloss units from one another and in excess of 60.
  • a motor vehicle comprising a plurality of composite shaped parts wherein the extensible mask remains in place on the parts to protect the paint finish of the vehicle from damage during manufacture and shipment of the vehicle and is subsequently removed upon delivery of the vehicle to a customer.
  • a method of making a flexible, weatherable decorative sheet material includes applying a coating comprising a urethane polymer composition onto a casting surface and drying the polymer coating to form a continuous extensible polymer mask releasably adhered to the casting surface and comprising no more than about 50 mg/m 2 of NMP.
  • the coating application step comprises applying a coating of a mixture of a polyester urethane polymer and a polyether urethane polymer onto the casting surface.
  • the coating application step may comprise applying a first coating overlying the casting surface and comprising a polyester urethane polymer, and a second coating overlying the first coating and comprising a mixture or blend of a polyether urethane polymer and a polyester urethane polymer.
  • a decorative paint film is formed having an inner surface and a weatherable outer surface suitable for forming an exterior finish for a part. The weatherable outer surface of the paint film is releasably bonded to the exposed surface of the mask.
  • the decorative paint film may be formed by applying at least one coating layer to a smooth flexible casting surface, drying the coating layer on the casting surface to produce a paint film with an outer surface releasably bonded to the casting surface and with the inner surface exposed, and bonding the exposed inner surface of the paint film to a thermoformable backing layer.
  • the step of releasably bonding the outer surface of the paint film may include stripping the casting surface from the paint film to expose the weatherable outer surface of the paint film, bringing the exposed weatherable outer surface of the paint film into contact with the mask, and bonding the mask and the paint film together.
  • the bonding may be accomplished by applying pressure and/or heat to the layers.
  • the decorative sheet material constructed as described above may be thermoformed into a three-dimensional shape while the mask remains in place. Additionally, the thermoformed decorative sheet material may be inserted into an injection mold with the mask facing the mold surface. Thereafter, molten thermoplastic polymer is injected into the mold and hardening of the injected thermoplastic polymer is effected in order to bond the polymer to the decorative sheet material to form a composite shaped part. The mask may be thereafter stripped from the composite shaped part to expose the decorative surface of the sheet material.
  • 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 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 10 A- IOC are schematic illustrations of steps in an injection molding process for forming a composite shaped part
  • Figure 11 is a cross-sectional view of a multiple layer embodiment of the mask of the present invention.
  • Figure 12 is a schematic illustration of a process for construction of another embodiment of the decorative sheet material of the present invention.
  • FIG. 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.
  • composite parts of automobiles include, but are not limited to, hoods, bumpers, roofs, trunk lids, door panels and A, B and C pillars.
  • 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, even after experiencing a high level of elongation, such as in excess of about 300% or even as high as about 600%, 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 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 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 20 also adds strength to the decorative sheet material 14 and improves process uniformity during the thermoforming process. Additionally, the extensible mask 20 protects the underlying layers of the decorative sheet material 14 from scratching or marring until the part is ready for display.
  • the mask 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 20 may be retained as the outer layer of the decorative sheet material 14 during construction of the final product, such as an automobile. Thereafter, the mask 20 may be removed to reveal the underlying decorative paint film 18.
  • the extensible mask 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 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 20 is transparent or substantially transparent to permit visual inspection of the part for surface defects without removal of the mask.
  • the mask 20 contains pigments or dyes such that the mask exhibits a slight tint so that the presence of the mask can be discerned, but inspection of the underlying paint film 18 is still possible.
  • the extensible mask 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 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 paint film 18 exhibits a 60 degree gloss value of at least 60, and more preferably at least 65.
  • the extensible mask 20 is about 0.3 mils to about 3.0 mils in thickness.
  • the extensible mask 20 comprises no more than about 50 mg/m 2 of N- methyl-2-pyrrolidone (NMP).
  • NMP N- methyl-2-pyrrolidone
  • the mask comprises about 6 to about 50 mg/m 2 of NMP, most preferably about 6 to about 20 mg/m 2 of NMP.
  • These NMP concentrations refer to the final concentrations in the mask 20 after drying of the mask.
  • the extensible mask 20 comprises a urethane polymer composition.
  • the mask 20 comprises a dried film of an aliphatic or aromatic polyester and/or polyether polyurethane in the form of an dispersion or a solution.
  • a preferred mask 20 embodiment comprises a polyester urethane polymer and a polyether urethane polymer, wherein the polyether urethane polymer has a lower concentration of NMP than the polyester urethane polymer, thereby lowering the overall concentration of NMP as compared to a mask made solely using the polyester urethane polymer.
  • the mask 20 may comprise a blend or mixture of the polyester urethane polymer and the polyether urethane polymer, such as a mixture comprising about 50 to about 70 weight percent of the polyester urethane polymer and about 30 to about 50 weight percent of the polyether urethane polymer.
  • the mask 20 may comprise at least two layers, a first layer 20A adjacent to the outer surface of the paint film and comprising a mixture of a polyester urethane polymer and a polyether urethane polymer, such as the mixture described above, and a second layer 20B overlying the first layer of the mask and comprising a polyester urethane polymer.
  • the polyester urethane polymer component generally provides better adhesiveness to the underlying paint film and the polyether urethane polymer component provides greater elongation properties, as well as the lower concentration of NMP.
  • a commercially available example of a polyester urethane polymer suitable for use in the present invention is QA 5218 polymer manufactured by Mace Adhesives and Coatings of Dudley, MA.
  • a commercially available embodiment of the polyether urethane polymer suitable for use in the present invention is QA 5545 polymer, also manufactured by Mace Adhesives and Coatings.
  • the mask 20 preferably comprises about 85 to about 99.5 weight percent polyurethane water-borne dispersion.
  • a small amount of surfactant about 0.05 to about 2.0 weight percent
  • SURFYNOL 104H manufactured by Air Products of Allentown, PA
  • Isopropyl alcohol may also be added in small amounts, such as up to about 5% by weight, in order to reduce surface tension.
  • the mask 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.
  • 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, triazines and combinations thereof.
  • the migratory additives are encouraged to migrate into the outer surface of the clear coat layer 22 by the heat present during thermoforming or molding processes.
  • the presence of these additives in the mask 20 prevents migration of additive components from the clear coat layer 22 into the mask.
  • 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 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 20 composition.
  • FIGS 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 polymer, as shown in Figure 6, or may comprise multiple layers, as shown in Figures 4 and 5. If a single layer 25 of polymer is used, the polymer may be selected from the group consisting of urethane polymers, acrylic polymers, fluoropolymers, 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 polymer may also include UV screeners to enhance weatherability, antioxidants, heat stabilizers, and other conventional additives.
  • the polymer layer 25 preferably includes pigments, dyes, flakes, or mixtures thereof 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 pigments, dyes, flakes, or mixtures thereof to provide the appearance necessary for exterior automobile use and improve weatherability.
  • the color coat layer 24 is selected from the group consisting of urethane polymers, acrylic polymers, fluoropolymers, and alloys or a fluoropolymer and acrylic polymer (such as FLUOREX® films).
  • 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 is an optional layer that 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.
  • 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 wavelengths less than 400 nm.
  • 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 one or more layers selected from the group consisting of urethane adhesives, acrylic adhesives, acrylic adhesives with cross linkers, chlorinated polyolefins and mixtures thereof.
  • a mixture of a chlorinated polypropylene and a higher molecular weight chlorinated polyolefin is used.
  • the adhesive layer 28 is prepared 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 chlorinated polypropylene suitable for use with the present invention is HARDLEN 13LP 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.
  • 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 UV 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, polyethylene, acrylonitrile-butadiene-styrene terpolymer, polypropylene, thermoplastic polyimide, polyethylene oxide, polycarbonate, polyvinyl chloride, polystyrene, styrene/polyphenylene oxide (NORYEL), 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 using a "wet on wet" coating technique.
  • 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. Alternatively, dryer 49 may be eliminated from the process such that the adhesive layer 28 is applied to the primer layer 26 while the primer layer is still wet using a "wet on wet" coating technique.
  • thermoformable backing layer 30 is advanced from a supply roll 52 and laminated to the adhesive-coated surface of the film carrier 33.
  • the backing layer 30 can be subjected to a corona treatment (not shown) prior to lamination.
  • the resulting laminate is collected by product roll 54.
  • Figure 8 illustrates a process for preparing a decorative sheet material 14 having a mask 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 20 is deposited onto a surface of the carrier.
  • the mask 20 may comprise more than one layer.
  • the coating station 60 may deposit two layers, a first coating overlying the carrier 34 and comprising a polyester urethane polymer, and a second coating overlying the first coating and comprising a mixture or blend of a polyether urethane polymer and a polyester urethane polymer.
  • 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 20.
  • the dryer 62 used to dry the mask 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 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 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 20 before or after collection of the sheet material 14 by product roll 67.
  • a single or multiple layer decorative paint film 18, primer layer 26, and adhesive layer 28 are coated directly onto the dried mask 20 rather than laminating the coated films together.
  • the resulting multi-layer film is laminated to a backing layer 30 as described above.
  • the mask 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 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, polyethylene, 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.
  • 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 preforming, 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.
  • Thermoforming is often used to create a preform in a three-dimensional configuration that roughly approximates the three-dimensional configuration of the final product.
  • the preform is then placed in a mold for in-mold surfacing of a desired substrate 16 to form the final product.
  • Figure 9 A 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 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 20 of the decorative sheet material may be stripped from the composite shaped part 12 to expose the paint film finish when desired.
  • Figure 12 illustrates a process for forming one preferred embodiment of the decorative paint film of the present invention.
  • a layer of acrylonitrile-butadiene-styrene terpolymer (ABS) is extruded from extruder 84 onto roller 86.
  • the layer of ABS material passes through a nip created by roller 86 and roller 88 in order to adjust the thickness of the ABS layer.
  • the ABS layer is about 60 to about 100 mils in thickness after passing through the nip.
  • the ABS layer then enters a second nip created by rollers 88 and 90.
  • a paint film supplied by supply roll 92 also enters the nip created by rollers 88 and 90.
  • the surface 94 of the paint film is an exposed adhesive layer capable of adhering to a hot layer of ABS.
  • the adhesive layer may comprise a heat-activatable adhesive, such as ELVACITE 2009, or a thin layer of ABS terpolymer.
  • the decorative paint film is nipped to the sheet of ABS and collected on collection roll 96.
  • One or more of the rollers, 86, 88 and 90, may be chilled in order to cool the ABS layer.
  • a paint film may be cost-effectively adhered to an ABS backing layer.
  • the resulting material may then be thermoformed into any desired shape as described in connection with Figures 9A-9D.
  • the decorative paint film used in the process illustrated in Figure 12 may be constructed according to the process described in connection with Figure 7, with the exception of the addition of the thermoformable backing layer.
  • the extruded ABS layer acts as the backing layer.
  • the sheet material of this embodiment can be used as a composite shaped part without the need for a further substrate layer.
  • EXAMPLE 1 A mask composition according to the present invention, shown in Table 1, was prepared. As shown, the composition comprised about 56% polyester urethane polymer (QA 5218) and about 36% polyether urethane polymer (QA 5545).
  • Blending should only take about 5 minutes of mixing time.
  • a clear coat and color coat were prepared according to the formulations in Tables 2-4.
  • the mask composition was coated onto 2 mil PET and dried.
  • the dried mask was laminated to a paint film comprising a 1.9 mil clear coat layer prepared according to Table 4, a 1.9 mil color coat prepared according to Tables 2-3, a 1 mil acrylic primer layer, a .5 mil layer of a urethane adhesive (NC222 made by Novacote Flex Pack), and a 30 mil thermoplastic olefin backing layer.
  • the resulting laminate was thermoformed into a three dimensional preform and the mask was removed.
  • the preform was then submerged in a water bath at a temperature of 40°C for a period of 10 days.
  • the laminate was also subjected to 10 days of heat aging at a temperature of 80°C and 10 days of humidity exposure at 50°C and 95-100% RH. No yellowing of the clear coat was visible after any of these tests.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention se rapporte à un matériau en feuille décoratif souple et résistant aux intempéries, qui comporte un film de peinture décorative thermoformable présentant une surface interne, et une surface externe résistante aux intempéries et pouvant former une couche de finition extérieure sur une pièce, telle qu'une pièce de carrosserie automobile. Ce matériau en feuille comprend une couche de masquage extensible collée de façon libérable à la surface externe du film de peinture de manière à former un film protecteur recouvrant le film de peinture. La couche de masquage comprend au plus environ 50 mg/m2 de N-méthyl-2-pyrrolidone, de préférence environ 6 à 50 mg/m2 de N-méthyl-2-pyrrolidone. La couche de masquage peut comprendre un polymère de polyester-uréthane et un polymère de polyéther-uréthane, la teneur en N-méthyl-2-pyrrolidone du polymère de polyéther-uréthane étant plus faible que celle du polymère de polyester-uréthane. L'invention se rapporte également à une méthode de fabrication du matériau en feuille décoratif de l'invention et d'une pièce composite façonnée recouverte dudit matériau.
PCT/US2001/041090 2000-06-26 2001-06-21 Film de masquage de protection extensible, et pieces fabriquees avec ce film Ceased WO2002000448A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001273619A AU2001273619A1 (en) 2000-06-26 2001-06-21 Paint film with protective extensible mask and parts made therefrom

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US60323500A 2000-06-26 2000-06-26
US09/603,235 2000-06-26

Publications (2)

Publication Number Publication Date
WO2002000448A2 true WO2002000448A2 (fr) 2002-01-03
WO2002000448A3 WO2002000448A3 (fr) 2003-03-13

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AU (1) AU2001273619A1 (fr)
WO (1) WO2002000448A2 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1859932A1 (fr) * 2006-05-22 2007-11-28 Yamaha Hatsudoki Kabushiki Kaisha Feuille décorative, produit formé et appareil de transport
US7968199B2 (en) 2005-05-03 2011-06-28 Basf Coatings Ag Method for producing films having a coating the films obtained in this way and their use for producing molded parts in particular for use in automobile construction
US8551279B2 (en) 2008-03-25 2013-10-08 3M Innovative Properties Company Multilayer articles and methods of making and using the same
US8932424B2 (en) 2008-03-25 2015-01-13 3M Innovative Properties Company Paint film composites and methods of making and using the same
JP2018159584A (ja) * 2017-03-22 2018-10-11 株式会社ファルテック レーダカバーの製造方法及びレーダカバー
CN109070570A (zh) * 2016-04-08 2018-12-21 沙特基础工业全球技术有限公司 可热成型的掩膜及其使用方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6835267B1 (en) * 1987-03-27 2004-12-28 Avery Dennison Corporation Dry paint transfer process and product
US5026448A (en) * 1989-04-03 1991-06-25 Reafler Gerald G Method of forming a glossy basecoat-clearcoat surface on a substrate
TW224443B (fr) * 1992-07-31 1994-06-01 Minnesota Mining & Mfg
US5968657A (en) * 1997-08-18 1999-10-19 3M Innovative Properties Company Paint film assembly with masking film and method of making same
AU2881900A (en) * 1999-03-01 2000-09-21 Rexam Industries Corp. Decorative sheet material including mask layer

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7968199B2 (en) 2005-05-03 2011-06-28 Basf Coatings Ag Method for producing films having a coating the films obtained in this way and their use for producing molded parts in particular for use in automobile construction
EP1859932A1 (fr) * 2006-05-22 2007-11-28 Yamaha Hatsudoki Kabushiki Kaisha Feuille décorative, produit formé et appareil de transport
US7678469B2 (en) 2006-05-22 2010-03-16 Yamaha Hatsudoki Kabushiki Kaisha Decorative sheet, formed product and transportation apparatus
US8551279B2 (en) 2008-03-25 2013-10-08 3M Innovative Properties Company Multilayer articles and methods of making and using the same
US8932424B2 (en) 2008-03-25 2015-01-13 3M Innovative Properties Company Paint film composites and methods of making and using the same
US8992718B2 (en) 2008-03-25 2015-03-31 3M Innovative Properties Company Multilayer articles and methods of making and using the same
US9656442B2 (en) 2008-03-25 2017-05-23 3M Innovative Properties Company Paint film composites and methods of making and using the same
CN109070570A (zh) * 2016-04-08 2018-12-21 沙特基础工业全球技术有限公司 可热成型的掩膜及其使用方法
CN109070570B (zh) * 2016-04-08 2021-02-19 沙特基础工业全球技术有限公司 可热成型的掩膜及其使用方法
JP2018159584A (ja) * 2017-03-22 2018-10-11 株式会社ファルテック レーダカバーの製造方法及びレーダカバー

Also Published As

Publication number Publication date
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WO2002000448A3 (fr) 2003-03-13

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