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WO2025061584A1 - Solution à base de pvdf résistant aux produits chimiques et film de revêtement transparent acrylique et procédé de fabrication - Google Patents

Solution à base de pvdf résistant aux produits chimiques et film de revêtement transparent acrylique et procédé de fabrication Download PDF

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Publication number
WO2025061584A1
WO2025061584A1 PCT/EP2024/075617 EP2024075617W WO2025061584A1 WO 2025061584 A1 WO2025061584 A1 WO 2025061584A1 EP 2024075617 W EP2024075617 W EP 2024075617W WO 2025061584 A1 WO2025061584 A1 WO 2025061584A1
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Prior art keywords
film
clear coat
acrylic
coat film
pvdf
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PCT/EP2024/075617
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English (en)
Inventor
Cheng Yang
Quan Song
Grady Wayne ALTMAN
Angus William Geddes FINDLAY
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Akzo Nobel Coatings International BV
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Akzo Nobel Coatings International BV
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Publication of WO2025061584A1 publication Critical patent/WO2025061584A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/14—Homopolymers or copolymers of vinyl fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2433/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters

Definitions

  • the present disclosure relates to a solution based polyvinylidene fluoride (PVDF) and acrylic clear coat film, method of making such film, and its application as a topcoat with improved chemical resistance, weatherability, formability and good adhesion to fluoropolymers, polyurethanes and other polymers.
  • PVDF polyvinylidene fluoride
  • the present disclosure also describes methods of applying the clear coat on bright and paint films to satisfy chemical resistance requirements of, e.g., automotive interior parts.
  • Background of the invention Decorative polymeric components have become standard in the automobile industry, primarily because polymers are relatively flexible, corrosion-resistant, and inexpensive.
  • Polymeric parts also reduce vehicle weight, which enhances performance, especially fuel economy.
  • Polymeric structures having metallized finishes are now commonly used as substitutes for articles that are expected to have a chrome-plated appearance, such as automobile grilles, door frames, dash boards, instrument consoles, badges, logos, signages, and other exterior and interior decorations.
  • decorative film and film laminates have been replacing conventional in situ methods of coating automotive body or interior parts to provide decorative surface finishes. For example, instead of spraying decorative paint onto a part, decorative film can be thermoformed onto a part through a three-dimensional overlay method (“TOM”) or form over part (“FOP”) process.
  • TOM three-dimensional overlay method
  • FOP form over part
  • Decorative paint film laminates can be thermoformed and/or injection molded into a part to provide gloss, color, and weatherability to the surface of the part.
  • metallized film laminates can be formed onto a part to provide a metallized polymeric finish and can complement and even replace bright, reflective metal surface treatments, particularly chrome plating.
  • a clear coat film oftentimes forms part of the film laminate as a topcoat, or outwardly facing layer, of the laminate. It is desirable that the clear coat film be substantially transparent while imparting weathering and chemical resistance.
  • the clear coat film may need to be formed from a 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. It may also need to fulfill other desired characteristics such as UV resistance, toughness, scratch resistance, and mar resistance. Additionally, the clear coat film is desirably formable from a two-dimensional surface to a three-dimensional surface without objectionable loss of appearance or performance properties.
  • Certain applications for film and film laminates require, among other things, resistance to chemicals present in sunscreen lotions, such as octyl methoxycinnamate, octocrylene, avobenzone, para aminobenzoic acid, homosalate, titanium dioxide, zinc oxide, benzophenones, benzylidenes, salicylates, oxybenzone, phenylbenzimidazole sulfonic acid, oxybenzone, and/or other known UV filters, and chemicals present in insect repellents, such as N, N diethyl-meta- toluamide (DEET).
  • sunscreen lotions such as octyl methoxycinnamate, octocrylene, avobenzone, para aminobenzoic acid, homosalate, titanium dioxide, zinc oxide, benzophenones, benzylidenes, salicylates, oxybenzone, phenylbenzimidazole sulfonic acid, oxybenzone, and/or other
  • Commonly used clear coats are formed from alloys of a fluoropolymer, such as polyvinylidene fluoride (PVDF), and an acrylic polymer.
  • PVDF polyvinylidene fluoride
  • Such clear coat films are typically cast from dispersions of PVDF and (meth)acrylic mixtures. Higher amounts of PVDF typically increase the chemical resistance of a PVDF/acrylic coating.
  • coatings containing high concentrations of dispersion-based PVDF have increased haze and reduced clarity and transparency.
  • Clear coat films for high reflective surface finishes such as chrome finishes require low haze, high clarity, and transparency. While these properties may be achievable in clear coat films made with dispersions having a low PVDF content, e.g., 50 wt% or lower, such levels compromise the chemical resistance of the coating.
  • Such clear coat films have poor resistance to chemicals such as sunscreen lotion and insect repellents, particularly those containing N,N-diethyl-meta-toluamide (DEET).
  • Clear coats cast from solutions are also known.
  • EP 0 285 071 A2 is for example disclosed a thermofoldable laminate for use on an exterior car body panel comprising an exterior clear coat above a color coat.
  • the clear coat comprises a thermoplastic paint system containing 50-70 wt% PVDF and 30-50 wt% acrylic resin.
  • the PVDF and acrylic resin are dissolved in a mixture of ketones and then applied by reverse roll coater on a carrier.
  • WO 00/78538 A1 is disclosed a multilayer decorative sheet useful in vehicles comprising a clear coat with appearance properties for exterior automotive use.
  • the clear coat comprises a blend of preferably 50 to 75 wt% PVDF and 25 to 50 wt% acrylic resin.
  • the PVDF and acrylic- based clear coat can be prepared as a solution or as a dispersion of PVDF in a solution of acrylic resin.
  • a mixture of ketones and an acetate ester as co-solvent are used as solvent for the PVDF and acrylic resin.
  • a disadvantage of solutions of PVDF/acrylic with a relatively high PVDF content in ketone solvents is that such solutions must be heated to obtain a substantially clear solution. This may give rise to storage and shelf-life issues.
  • US 2010/310880 is disclosed the use of lactam solvent for PVDF/acrylic systems in order to obtain a clear solution at room temperature.
  • Lactam solvent however, has toxicological risks and other disadvantages. Therefore, there is a need for a clear coat film having substantial clarity while demonstrating excellent chemical resistance, weatherability, formability and good adhesion to polymers such as fluoropolymers and polyurethanes, that is formed from a composition that can be stored at room temperature. Summary The present inventors have found a solution based PVDF/acrylic clear coat film which has the desired clarity and transparency, formability and weatherability while demonstrating improved chemical resistance.
  • the present disclosure provides a chemical resistant clear coat film wherein the film is formed from a solution of polyvinylidene fluoride (PVDF) homopolymer and (meth)acrylic (co)polymer in a solvent system comprising dimethyl sulfoxide and ketone, wherein the weight ratio of PVDF homopolymer to (meth)acrylic (co)polymer in the clear coat film is 58:42 or greater. In certain embodiments, the weight ratio of PVDF homopolymer to (meth)acrylic (co)polymer in the clear coat film is 58:42 to 75:25. In some embodiments, the solution further comprises a crosslinker capable of crosslinking the (meth)acrylic (co)polymer.
  • PVDF polyvinylidene fluoride
  • the solution further comprises a crosslinker capable of crosslinking the (meth)acrylic (co)polymer.
  • the ketone is selected from a group consisting of dimethyl ketone (acetone), diethyl ketone, methyl ethyl ketone (MEK), methyl isobutyl ketone, optionally substituted or unsubstituted cyclohexanone, such as trimethylcyclohexanone (TMCHONE), cyclopentanone, and mixtures thereof.
  • the clear coat film may comprise UV absorbers and/or hindered amine light absorbers (HALS).
  • HALS hindered amine light absorbers
  • the clear coat film may have a total haze value of 1 or less as measured by ASTM D1003, and a chemical resistance rating of 2 or less as measured by GM standard test method GMW14445.
  • the one or more film layers may comprise a pigmented paint film layer.
  • the present disclosure provides a method of making a chemical resistant clear coat film. Said method comprises the steps of dissolving a polyvinylidene fluoride (PVDF) homopolymer and (meth)acrylic (co)polymer in a solvent system comprising dimethyl sulfoxide and ketone to form a solution, wherein the weight ratio of PVDF homopolymer to (meth)acrylic (co)polymer in the solution is 58:42 or greater; casting the solution onto a base layer; and drying the solution to form the clear coat film.
  • the base layer is a carrier. In certain embodiments, the base layer is a paint film layer.
  • the base layer may be a metallized film layer.
  • the clear coat film has a total haze value of 1 or less as measured by ASTM D1003, and a chemical resistance rating of 2 or less as measured by GM standard test method GMW14445. In another exemplary embodiment, the clear coat film has a total haze value of 1 or less as measured by ASTM D1003, and a chemical resistance rating of 2 or less as measured by Ford standard test method BI 113-08.
  • FIG.1 is a cross-sectional view of a bright metallized laminate having the chemical resistant clear coat film of the present disclosure as a topcoat.
  • FIG.2 is a cross-sectional view of a paint film laminate having the chemical resistant clear coat film of the present disclosure as a topcoat.
  • FIG.3 is a schematic illustration of a process for manufacturing a paint film laminate as described in the present disclosure.
  • the following description of the preferred embodiment(s) is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
  • a range of “1 to 10” is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
  • concentrations, dimensions and other parameters are expressed in the form of a range, a preferable range, an upper limit value, a lower limit value or preferable upper and limit values, it should be understood that any ranges obtainable by combining any upper limit or preferable value with any lower limit or preferable value are also specifically disclosed, irrespective of whether the obtained ranges are clearly mentioned in the context.
  • acrylate and “acrylic” are used broadly (and interchangeably) herein and encompass materials prepared from, for example, one or more of acrylic acid, methacrylic acid, or any acrylate or methacrylate compound. Thus, for example, a homopolymer consisting entirely of polymerized (meth)acrylic acid would still be an “acrylate” polymer even though no (meth)acrylate monomer was employed.
  • carrier refers to a base plastic film onto which a coating is cast.
  • the carrier can comprise a polyester casting film, such as polyethylene terephthalate (PET) film, or a biaxially oriented polypropylene (BOPP) film, etc.
  • curing and like terms as used herein, refers to a process of setting or drying of a material to form a coating on a carrier, film, base layer, or substrate.
  • dispersion refers to a finely divided solid or liquid in a continuous liquid medium.
  • An aqueous dispersion is a dispersion in which the continuous liquid medium is water.
  • formable with respect to a layer, means that the layer can be formed, shaped or molded from a two-dimensional surface to a three-dimensional surface without objectionable loss of appearance or performance properties.
  • homopolymer refers to a polymer formed from a single type of monomer.
  • insect repellent refers to a composition that repels insects that can be applied to the skin.
  • Such composition can be in lotion, gel or liquid form and can be applied manually or via spray or aerosol.
  • Such composition can comprise N, N diethyl-meta-toluamide (DEET) in amounts of 20-30%.
  • DEET N, N diethyl-meta-toluamide
  • (meth) as used in “(meth)acrylate”, “(meth)acrylic acid”, and the like is intended to indicate that either a hydrogen or methyl group may be attached to the pertinent carbon atom of the monomer.
  • (meth)acrylic encompasses both acrylics and methacrylics, as well as mixtures thereof.
  • polymer includes both homopolymers and copolymers (e.g., polymers of two or more different monomers) and oligomers. Resin is used simultaneously with polymer.
  • solution refers to a homogenous mixture of two or more substances in relative amounts that can be varied continuously up to the limit of solubility.
  • substrate refers to the base material onto which a film (single or multi-layered) is laminated.
  • a substrate can comprise, for example, acrylonitrile butadiene styrene copolymer (ABS), polycarbonate (PC), thermoplastic polyolefin (TPO), thermoplastic polyurethane (TPU), formable polyester, glass fiber-thermoset composites, polyvinyl Chloride (PVC), stainless steel and aluminum.
  • ABS acrylonitrile butadiene styrene copolymer
  • PC polycarbonate
  • TPO thermoplastic polyolefin
  • TPU thermoplastic polyurethane
  • formable polyester glass fiber-thermoset composites
  • glass fiber-thermoset composites glass fiber-thermoset composites
  • PVC polyvinyl Chloride
  • stainless steel stainless steel and aluminum.
  • silk lotion refers to a composition that contains a compound that absorbs, reflects, or scatters radiation in the UV range and that can be applied to the skin.
  • the sunscreen lotion can be in the form of a lotion, a gel, a liquid, and can be applied manually or via spray or aerosol.
  • the sunscreen lotion may contain octyl methoxycinnamate, octocrylene, avobenzone, para aminobenzoic acid, homosalate, titanium dioxide, zinc oxide, benzophenones, benzylidenes, salicylates, oxybenzone, phenylbenzimidazole sulfonic acid, oxybenzone, and/or other known UV filters.
  • the sunscreen lotion can be waterproof.
  • the sunscreen lotion may have an SPF of 15, or 30, or 45, 50 or as commercially available. Unless otherwise specified, the term “UV” is intended to mean ultraviolet.
  • total haze value refers to the sum of the internal haze and the surface haze. All percentages, ratios and proportions used herein are given on a weight basis unless otherwise specified.
  • the present disclosure relates to a solution based clear coat film having improved chemical resistance. It has been surprisingly found that this clear coat film can be achieved by using a solution of polyvinylidene fluoride (PVDF) homopolymer rather than a dispersion of PVDF.
  • PVDF polyvinylidene fluoride
  • PVDF polyvinylidene fluoride
  • solvent system comprising dimethyl sulfoxide and a ketone
  • PVDF/acrylic clear coat has chemical resistance to chemicals such as sunscreen lotion and insect repellant while maintaining desired clarity.
  • the clear coat can be used as a topcoat on a film laminate, such as paint film laminate or a metalized formable laminate.
  • a chemical resistant clear coat film wherein the film is based on a solution of polyvinylidene fluoride (PVDF) homopolymer and a (meth)acrylic (co)polymer in a solvent system comprising dimethyl sulfoxide and ketone, wherein the weight ratio of PVDF homopolymer to (meth)acrylic (co)polymer in the clear coat film is 58:42 or greater.
  • PVDF polyvinylidene fluoride
  • PVDF copolymers such as Solef® 21510/1001 PVDF copolymer, available from Solvay, and Kynar® SL PVDF copolymer, available from Arkema
  • Solef® 21510/1001 PVDF copolymer available from Solvay
  • Kynar® SL PVDF copolymer available from Arkema
  • PVDF homopolymers in dispersion may form clear coat films with good chemical resistance, these clear coat films have a total haze value greater than 1, which is unacceptable for certain automotive applications.
  • the visual quality of high reflective chrome finishes suffers if the clear coat has any haze.
  • PVDF homopolymer used to make the clear coat film of the present disclosure can be selected from PVDF homopolymers known to those skilled in the art, such as those sold by Arkema as Kynar® 500 Plus and Kynar® 500 FSF PVDF, those sold by Solvay as Hylar® 5000S PVDF, or those sold by Bengal Fluorochemicals as INOFLAR 5125.
  • the PVDF homopolymer can have a melting point of 155°C or higher, or 155-178°C.
  • the PVDF homopolymer can be present in the solution in amounts of up to 15 wt%.
  • the (meth)acrylic (co)polymer used in the clear coat film can be a homopolymer or a copolymer, or mixtures thereof.
  • the (meth)acrylic (co)polymer can be a resin that has properties that may improve certain properties of the solution or clear coat film formed therefrom, for example, adhesion promotion, viscosity control, hardness, scratch resistance, abrasion resistance, blocking resistance, outstanding clarity, and crosslinking functionalities.
  • the (meth)acrylic (co)polymer can also be in solution.
  • the (meth)acrylic (co)polymer can be at 30-40 wt% in a solvent mixture, such as DuPont 68070 and 68080 acrylic adhesives.
  • the (meth)acrylic (co)polymer can be present in the solution in amounts of up to 10 wt%, such as 4 wt% to 7 wt% based on the weight of the solution.
  • the ratio of PVDF homopolymer to (meth)acrylic polymer in the chemical resistant clear coat film of the present disclosure is 58:42 or greater. In some embodiments, the ratio can be 58:42 to 75:25. At ratios lower than 58:42, the film’s chemical resistance starts to deteriorate. Higher ratios may reduce other preferable properties, such as, gloss, hardness, and scratch resistance.
  • the ketone in the clear coat composition of the present disclosure can be aliphatic, cycloaliphatic, aromatic, or mixtures of two or more of these types of ketones.
  • the ketones can be linear or branched aliphatic and/or cycloaliphatic ketones and can be chosen from dimethyl ketone (acetone), diethyl ketone, methyl ethyl ketone (MEK), methyl isobutyl ketone, optionally substituted or unsubstituted cyclohexanone, such as trimethylcyclohexanone (TMCHONE), cyclopentanone, and others, and mixtures thereof.
  • TMCHONE trimethylcyclohexanone
  • the weight ratio of DMSO to ketone in the clear coat solution can be, for example, 10:90 to 90:10, or 70:30 to 30:70.
  • the total amount of solvent in the clear coat solution can be 80-90wt%.
  • the total amount of DMSO and ketone in the clear coat solution can range from 70 to 90 wt%, or 73 to 85wt%.
  • the solvent system used for the solution of PVDF homopolymer and (meth)acrylic (co)polymer described in the present disclosure can be binary, i.e., consisting of DMSO and ketone. In another embodiment, the solvent system can be tertiary, comprising a third solvent.
  • the solvent system can have more than three solvents. These additional solvents can comprise 1-methoxy-2-propanol, diethylene glycol monobutyl ether acetate, 1-methoxy-2-propanol acetate, other glycol ethers, ethyl acetate, dimethyl glutarate, dimethyl adipate, dimethyl succinate, toluene, isopropyl alcohol, and propyl acetate.
  • the total amount of DMSO plus ketone in the solvent system can range from 85 to 100 wt%, depending on whether there are other solvents present.
  • the clear coat film of the present disclosure can comprise other optional components.
  • the (meth)acrylic (co)polymer comprises crosslinkable functional groups such as OH-groups, carboxylic groups, or NH-groups.
  • the solution preferably comprises a crosslinker with crosslinkable functionalities, such as melamine, isocyanate, blocked isocyanate, and carbodiimide functionalities capable of crosslinking the (meth)acrylic (co)polymer(s) with hydroxyl, carboxylic, or NH- functionalities.
  • Crosslinking the (meth)acrylic (co)polymers may further improve chemical, scratch and abrasion resistance of the clear coat film.
  • the (meth)acrylic (co)polymer is an OH-functional (meth)acrylic (co)polymer and the solution comprises a crosslinker reactive with the OH-functionality of the (meth)acrylic (co)polymer.
  • the solution may also include other optional ingredients or additives that do not adversely affect the solution or the clear coat film formed therefrom. Such optional ingredients are typically included in a clear coat film to enhance film aesthetics, to facilitate manufacturing, processing, handling, and application of the solution or film, and to further improve a particular functional property of the solution or the film resulting therefrom.
  • Such optional ingredients include, for example, UV absorbers, hindered amine light stabilizers, catalysts, lubricants, surfactants, anticorrosion agents, flow control agents, thixotropic agents, antioxidants, adhesion promoters, and mixtures thereof.
  • ultraviolet light absorbers such as Tinuvin® 928, manufactured by BASF
  • these optional ingredients can be present in amounts up to 10 wt%, or up to 5 wt% of the dry film. It will be understood by those skilled in the art that clear coat films may be available in different colors.
  • the formable metallized laminates described herein may be made in various colors by incorporating appropriately tinted (i.e., colored) clear coat films.
  • clear coat films may be tinted, for example, using pigments, inks, or mica, and such can be added as desired without undue experimentation. If tinted, clear coats are preferably transparent rather than opaque.
  • a method of making a chemical resistant clear coat film comprises the following steps: (a) dissolving a polyvinylidene fluoride (PVDF) homopolymer and (meth)acrylic (co)polymer in a solvent system comprising dimethyl sulfoxide and ketone to form a solution, wherein the weight ratio of PVDF homopolymer to (meth)acrylic (co)polymer in the solution is 58:42 or greater; (b) casting the solution onto a base layer; and (c) drying the solution to form the clear coat film.
  • the solution can be made by first dissolving PVDF in DMSO and ketone under heating and agitation.
  • This dissolution step can be done at a temperature sufficient to dissolve the PVDF, such as 30 to 60°C.
  • (meth)acrylic (co)polymer and other desired optional ingredients, such as crosslinkers or UV absorbers, can be added while maintaining the heating and agitation, until all ingredients are fully dissolved.
  • the solution can be made by first dissolving (meth)acrylic (co)polymer and desired additives, such as UV absorbers, in DMSO and ketone. This dissolution step can be done at a temperature of 30 to 60°C.
  • PVDF can then be dissolved in the DMSO/ketone/acrylic solution under agitation at the same or a slightly higher temperature in the range of, for example, 40 to 65°C, to fully dissolve the PVDF.
  • the order of addition of the crosslinker will depend on the type of crosslinker. For example, melamine and blocked isocyanate crosslinkers can be added in any addition sequence even though they are oftentimes added last. If unblocked isocyanate or carbodiimide is used as a crosslinker, it is added just before casting.
  • the clear coat solution of the present disclosure can be cast onto a base layer and then dried by conventional methods.
  • the base layer can be a carrier, such as a PET film.
  • the clear coat solution can be cast directly onto a carrier.
  • the base layer can be another film that has already been cast on a carrier.
  • This already cast film can comprise one or multiple layers.
  • Such film layers can be, e.g., a clear PVF base film, a metallized film layer, a paint film color base layer or other film layers on which a clear coat is typically applied as a topcoat.
  • U.S. Pat. Nos. 6,287,672, 6,565,955, 6,858,287 and 7,854,985 include examples of the different layers of film that can be disposed under a clear coat film. These previously cast layers may be already fully cured, or partially cured, or they may be uncured.
  • a film layer can be cast wet-on-wet (meaning that the underlying layer is not dry), or wet-on-dry (meaning the underlying layer is dry), depending on the application.
  • an adhesive layer may be present between the clear coat layer and the base layer to help the chemical resistant clear coat film adhere to the base layer.
  • clear coat film may be formed by casting the clear coat solution onto the base layer via knife-over roll coating process, a reverse roll coating process, or a slot die coating process. Slot die coating methods are preferred. These techniques are well known in the art and will not be further discussed herein.
  • the solution can be cast at a wet thickness of, for example, from 1 to 500 ⁇ m. Once it dries, the thickness would be 2.5 – 75 micrometers.
  • the casting process can be adjusted to achieve the desired dry film thickness.
  • the dry film thickness may depend on the solids content of the wet solution and the density of solvent. If slot die casting is used, one of skill in the art can vary the pump speed to adjust the volume of solution delivered. The line speed can also be adjusted. If a different casting process is used, the adjustment process in order to achieve the desired dry thickness may be different. The desired thickness will depend on the application.
  • the clear coat film has a thickness of from 0.1 mil (2.5 micrometers) to 3.0 mils (75 micrometers), and more typically from 0.2 mils (5 micrometers) to 0.6 mils (15 micrometers).
  • the clear coat film of the present disclosure may be coextensive in boundaries with the base layer, or it may be disposed on only a portion or separate portions of the base layer.
  • the clear coat film can be formable from a two-dimensional surface to a three-dimensional surface without objectionable loss of appearance or performance properties.
  • the solvent can be optionally flashed off, for example, for 1 to 5 minutes at room temperature, and the film is then dried using any conventional drying technique.
  • the solvents can be evaporated, whereby the clear coat solution becomes drier but still uncured or a fully crosslinked coating film is not formed yet.
  • the clear coat solution can then be cured with the base layer. Curing is preferably carried out thermally at a temperature of 60 to 200°C.
  • the thermally curable solution is preferably one which comprises the crosslinkers described above.
  • the dryers are ovens having multiple heating zones wherein each successive heating zone operates at a progressively higher temperature. For example, an oven having four to six heating zones ranging in temperature from 200°F to 400°F may be used.
  • the carrier is stable when exposed to heat while the clear coat film and underlying layers (if present) are dried/cured.
  • a film laminate is provided, wherein a film comprising the chemical resistant clear coat film described above is heat pressed onto a substrate to form the film laminate.
  • the clear coat film is the outward facing layer, or topcoat of the laminate.
  • the substrate can comprise polycarbonate, poly(methyl methacrylate) (PMMA), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), cyclic olefin copolymers (COC), polyetherimides (PEI), polystyrenes, polyimides, polypropylenes (PP) and polyethylenes (PE), polyvinyl fluorides (PVF), polyvinylidene fluorides (PVDF), acrylonitrile butadiene styrene copolymer (ABS), or a combination of one or more of the foregoing.
  • the film can comprise the chemical resistant clear coat film described above as the only layer.
  • the film can comprise a multi-layer structure as described above, comprising the chemical resistant clear coat film of the present disclosure on one or more film layers.
  • the one or more other film layers can comprise, e.g., a clear PVF base film, acrylic, polyurethane, or polyester resins, a metallized layer, a paint film color base, or other film layers on which a clear coat can be typically applied as a topcoat.
  • U.S. Pat. Nos. 6,287,672, 6,565,955, 6,858,287 and 7,854,985 include examples of the different layers of film that can be disposed under a clear coat film.
  • the clear coat film is outwardly facing, opposite the substrate, and the one or more other film layers are disposed between the clear coat film and the substrate.
  • the film laminate may further comprise a release liner releasably adhered to the outwardly facing clear coat film side of the laminate.
  • a release liner is a removable carrier sheet – it can be removed from the clear coat film without damage to the film.
  • the release liner may be of materials known to one skilled in the art. Suitable release liners include polyester films, e.g., polyethylene-terephthalate (PET), or polyolefin films, e.g., polypropylene (PP), or other polymer known films.
  • PET is particularly preferred as a release carrier since PET films are very heat stable and stay flat during film casting and curing even at higher temperatures.
  • An example of a suitable release carrier is REL 8752, which is a silicon-coated release PET film from St. Gobain.
  • the liner can optionally be coated with an adhesive or a low surface energy coating. Suitable low surface energy coatings may include, for example, those formed from polyacrylics, silicones, and/or fluorochemicals.
  • an additional layer such as a tacky polyester, may be applied on the chemical resistant clear coat film on the surface opposite the one or more film layers that have already been cast. After further processing, such additional layer may function as a release liner that can later be removed to expose the clear coat film as a topcoat.
  • the chemical resistant clear coat film of the present disclosure can be incorporated into film laminates similar to how conventional clear coats are incorporated into film laminates, provided that the chemical resistant clear coat film is the topcoat of the film laminate.
  • the film can be a metallized film or formable bright film such as described in U.S. Patent Nos. 6,287,672, 6,565,955 and 6,858,287, incorporated by reference herein, wherein the chemical resistant clear coat film of the present disclosure is the clear topcoat.
  • a bright metallized formable film laminate can include a formable, weatherable chemical resistant clear coat film as described in the present disclosure, a formable clear coat leveling layer on the weatherable clear coat film, and a discontinuous layer of indium islands deposited on the formable leveling layer, opposite the chemical resistant clear coat film.
  • a discontinuous layer of metal islands may be deposited upon the formable base layer and then a second discontinuous layer of metal islands can be deposited onto the first discontinuous layer of metal islands. The presence of multiple metallic layers facilitates the retention of optical and reflective properties as the formable laminate is stretched.
  • FIG. 1 is a cross-sectional view of a bright film laminate with a chemical resistant clear coat film in accordance with one aspect of the present disclosure.
  • the chemical resistant clear coat film 10 is the outer, topcoat layer and is opposite to the substrate 14.
  • Leveling layer 11 can comprise PVF, polyurethane or polyester resins.
  • Metal layer 12 is vacuum deposited on the leveling layer 11.
  • Adhesive layer 13 can comprise polyurethane, polyester or acrylic resins.
  • the chemical resistant clear coat film 10, leveling layer 11, metal layer 12, and adhesive layer 13 together form multi-layered film 15. In FIG.1, the multi-layered film 15 has been laminated (e.g., via heat) to a substrate 14 to form bright film laminate 16.
  • Substrate 14 can comprise acrylonitrile butadiene styrene copolymer (ABS), polycarbonate (PC), thermoplastic polyolefin (TPO), polypropylene (PP) or polyethylene terephthalate (PET), etc.
  • the film can be a paint film which itself can comprise one or more layers, such as described in U.S. Patent No.7,854,985, incorporated by reference herein, wherein the chemical resistant clear coat film of the present disclosure is the clear topcoat. Paint film laminates, methods of forming them, and ways of applying them to substrates may be found in U.S. Pat. No.7,854,985.
  • the chemical resistant clear coat film 10 is the outer, topcoat layer.
  • Base coat layer 21 can comprise a PVDF acrylic alloy, polyurethane or polyester or acrylic resins.
  • Optional adhesive layer 22 can comprise polyurethane, polyester or acrylic resins.
  • the chemical resistant clear coat film 10, Base coat layer 21, and optional adhesive layer 22 together form multi-layered film 18.
  • Substrate 14 has been laminated (e.g., via heat) to the multi-layered film 18 to form paint film laminate 17.
  • Substrate 14 can comprise acrylonitrile butadiene styrene copolymer (ABS), polycarbonate (PC), thermoplastic polyolefin (TPO), polypropylene (PP) or polyethylene terephthalate (PET), etc.
  • FIG.3 is a schematic illustration of a generic process for manufacturing a paint film laminate comprising the chemical resistant clear coat film of the present disclosure. As shown, a carrier 33 is advanced from a supply roll 38 through a series of process steps.
  • the carrier 33 preferably comprises an extruded polyester film having a high gloss surface which can impart high gloss to the surface of the clear coat on which other layers, such as base coat or adhesives, are deposited.
  • the carrier 33 comprises polyethylene terephthalate (PET).
  • the carrier 33 can be 2 to 4 mils in thickness, preferably 2 mils in thickness.
  • the carrier 33 passes through a first coating station 40 that may deposit a first coating, such as the chemical resistant clear coat film of the present disclosure.
  • the carrier 33 coated with the first coating then passes through a dryer 41.
  • a second coating is deposited in coating station 42 and dried by dryer 43.
  • the coating stations 40 and 42 may utilize any conventional coating or casting techniques, such as reverse roll coating or slot die coating techniques. Slot die coating methods are preferred.
  • a third coating can be deposited in coating station 44 and dried by dryer 46.
  • a primer coating can then be deposited over the third coating in coating station 48 and optionally dried by dryer 49.
  • an adhesive coating can be deposited in coating station 50 and 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 substrate or backing sheet 30 is advanced from a supply roll 52 and laminated to the adhesive-coated surface of the film on carrier 33.
  • the resulting paint film laminate is collected by product roll 54.
  • Dryers 41, 43, 46 and 49 may utilize any conventional drying technique.
  • these dryers are ovens having multiple heating zones wherein each successive heating zone operates at a progressively higher temperature.
  • dryer 41 may be eliminated from the process such that the second coating 42, such as base coat or adhesive is applied to the clear coat while the clear coat is still wet using a “wet on wet” coating technique.
  • the carrier 33 can then be removed from the multiple layer film laminate structure, exposing the chemical resistant clear coat topcoat layer before the film laminate is thermoformed and injection molded.
  • the following examples are illustrative of the present invention and are not intended to limit the scope of the invention in any way. Those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments that are disclosed and still obtain a like or similar result without departing from the scope of the invention. Examples Materials The following list indicates some of the raw materials and ingredients used in the following examples. Alternative materials or suppliers may be substituted as is appreciated by one skilled in the art.
  • Acrylic Black Dispersion – jet black pigment dispersion custom made for AkzoNobel Acrylic Resin A – 40 wt% solution of OH-functional methacrylic copolymer in solvent mixture of glycol ether acetate and other esters Bayhydur 302 – isocyanate crosslinker available from Covestro BYK-346 – silicone surfactant available from BYK Chemie CYCAT® 600 - strong acid catalyst based on dodecylbenzene sulfonic acid from Allnex Cymel® 303LF – methylated, monomeric melamine crosslinker available from Allnex Cymel® 385 – methylated high imino melamine crosslinker available from Allnex Cymel® XW 3106 - alkylated, high solids melamine crosslinker available from Allnex Desmodur® 2802 – polyfunctional carbodiimide crosslinker available from Covestro Diethylene Glycol Monobutyl Ether Acetate (DB Acetate) are solvents commercial
  • Total haze is measured by a BYK Hazegard unit in accordance with standard method ASTM D1003.
  • Adhesion Initial cross hatch adhesion test was tested in accordance with ASTM D3359 cross cut tape test method B. This method provides for cutting through the film in a crosshatch pattern of specified spacing, taping the cut area with 3M 989 Scotch tape, and then rapidly removing the tape. The area with cuts is inspected to determine if paint has been loosened or removed, and the area is given a rating. Test results were reported according to the test method from 0B - 5B.
  • Heat and Humidity Aging The procedures for testing heat and humidity aging are described in Tables 11 and 12. Heat aging was performed following the GMW16717 method. Heat and humidity aging was performed following the GMW14729 method. Water Bath Water bath testing involved submerging the sample piece in a water bath of 80°C ⁇ 2°C for 3 hours. The requirements for the water bath testing are described in Tables 11 and 12. Color Fastness The conditions and procedures for testing color fastness are described in Tables 11 and 12. In the automotive industry, weathering tests of films and laminates used in automobiles are generally carried out in Florida and Arizona, as color fastness must be guaranteed upon exposure to both high temperatures and sunlight. Such conditions are generally simulated in the laboratory.
  • Color fastness after exposure to light is carefully evaluated by means of various analytical methods which include the exposure of test samples to artificial light sources under controlled irradiation and humidity conditions.
  • Color fastness has a small color change, ⁇ E measured according to automotive standard SAE J2412 for interior testing (such as for automotive interior trim components) and SAE J2527 for exterior testing. These test standards involve exposing samples to Xenon Arc light, accelerating the simulation of the outdoor or indoor environmental conditions, depending on which test is used. The smaller the ⁇ E, the better the color fastness. A ⁇ E of 3 or less is commonly considered acceptable for most automotive applications.
  • Chemical Resistance Various samples of PVDF/acrylic films were tested to evaluate their chemical resistance.
  • Step 8) None 2 (Slight Change) Cloth Impression Very Slight Cloth Color Transfer None Discoloration/Spotting AATCC (Proc.1) Min.4 Sur Slight surface defect - can only be seen at certain 3 (Moderate face Defect (Step 8) angles Change) Cloth Impression No more than 50% of tests area Cloth Color Transfer AATCC (Proc.2) Min.4.5 Discoloration/Spotting AATCC (Proc.1) Min.3.5 4 (Significant Surface Defect (Step 8) Moderate surface defect - can be seen at all Change) angles Cloth Impression Significant cloth impression on more than 50% of tested area Cloth Color Transfer AATCC (Proc.2) Min.4 Discoloration/Spotting AATCC (Proc.1) Rating ⁇ 3.5 Surface Defect (Step 8) Severe 5 (Severe Change) Cloth Impression Severe Cloth Color Transfer AATCC (Proc.2) Rating ⁇ 3.5 *AATCC refers to the American Association of Textile Chemists
  • Examples 14-18 Solution-based PVDF/Acrylic Clear Coat Film
  • the PVDF/acrylic films of Examples 14-18 having the compositions shown in Table 5 were prepared as follows. DMSO and MEK were charged into a lined paint can, and agitation and heating commenced. Kynar 500 was slowly added during the heating and agitation. The agitation speed was increased during the course of addition and dissolution in order to maintain a vortex.
  • Tinuvin 928, Acrylic Resin A and Permutex 9116 were added in that order. Agitation and heating were maintained until 54°C, to ensure full dissolution of all ingredients.
  • the formulations were filtered through a 100 micron bag and allowed to stand overnight to allow air bubbles to rise. Each formulation was cast on a 2 mil PET release carrier to form a clear coat with a 0.2 -0.5 mil dry film thickness. The coatings were dried at 200°F for 2 minutes, followed by 350°F for 5 minutes in vented static ovens.
  • Example 19-23 Solution-based PVDF/Acrylic Clear Coat Film
  • the PVDF/acrylic films of Examples 19-23 having the compositions shown in Table 7 were prepared as follows. DMSO and MEK were charged into a lined paint can, and agitation and heating were started. Elvacite 2041 and Tinuvin 928 were slowly added under heating and agitation. When Elvacite 2041 was mostly dissolved at ⁇ 40°C, Kynar 500 was slowly added.
  • Examples 22 and 23 were deemed acceptable. No change in appearance was observed for Example 23 after the GM and Ford tests.
  • Examples 26 and 27 Laminates Comprising Metallized Films with Chemical Resistant Clear Coats as Topcoat on Tedlar® PVF Base Layer DMSO and MEK were charged into a 2.5 gallon stainless steel vessel, and agitation and heating were commenced. Under heating and adequate agitation, slowly add Hylar 5000S. Increase agitation speed during the course of addition and dissolution to maintain a vortex. After dissolution of Hylar 5000S around 35-40°C, add Tinuvin 928, DuPont 68080 (for Ex.26) or Acrylic Resin A (for Ex.27), and Cymel 303 in order. Keep agitating and heating to 50°C, to ensure full dissolution of all ingredients.
  • the resulting film was then metallized with indium and tin on the Tedlar side to an optical density of 1.1- 1.3.
  • the metallized side was then coated with an adhesive coating and laminated to a piece of acrylonitrile butadiene styrene (ABS) or polycarbonate (PC).
  • ABS acrylonitrile butadiene styrene
  • PC polycarbonate
  • the clear topcoat side was then subjected to sunscreen lotion and insect repellent testing, following GM’s GMW14445 and Ford’s BI 113-08, Method A testing procedures. Both samples showed good resistance to both GM and Ford testing liquids, with a rating of 1 for all tests.
  • Examples 28-29 Laminates Comprising Metallized Films with Chemical Resistant Clear Coats as Topcoat and Polyurethane Base Layer To make the base coats for Examples 28 and 29, Tinuvin 1130 with DPM were premixed. Then the premix was slowly added into HD-2125 under adequate agitation sufficient to maintain a good vortex. The mixture was left to soak for at least 48 hours prior to use. The Bayhydur 302 was then added under adequate agitation just before casting the coatings.
  • a 0.6-0.7 mil dry thickness film of the clear base coat was then cast over the respective clear topcoat specified in Table 14.
  • the coating was then dried in a vented oven at 250°F for 3 min, followed by 350°F for 3 min.
  • the resulting two-layer clear film was then metallized with indium and tin to an optical density of 1.1-1.3 on the base coat side.
  • the resulting metallized side was then coated with an adhesive coating and laminated to pieces of acrylonitrile butadiene styrene (ABS) or polycarbonate (PC).
  • ABS acrylonitrile butadiene styrene
  • PC polycarbonate
  • the release liner was then removed and the chemical resistant clear topcoat side was subjected to sunscreen lotion and insect repellent testing, following GM’s GMW14445 and Ford’s BI 113-08, Method A test procedures.
  • Examples 30-31 Paint Films with Chemical Resistant Clear Coat as Topcoat and a Color Base Coat Table 15
  • Example Ex.30 Ex.31 Chemical Resistant Ex.26 Ex.27 Clear Coat Base Coat Kynar 500 22.25% 22.25% Elvacite 2042 7.42% 7.42% Acrylic Black Dispersion 19.91% 19.91% Tinuvin 900 0.74% 0.74% DB Acetate 41.74% 41.74% Dimethyl Phthalate 7.94% 7.94%
  • DB acetate and DMP were charged into a container and agitation was started. Tinuvin 900 was added under adequate agitation.
  • the coating was then dried in a vented oven at 250°F for 3 min, followed by 350°F for 3 min, to form a chemical resistant clear coat film having a dry film thickness of 0.2-0.5 mil.
  • a 1.5 mil dry thickness film of the color base coat was cast over the respective clear topcoat specified in Table 15.
  • the coating was then dried in a vented oven at 380°F for 4 min.
  • the release liner was then removed, and the chemical resistant clear topcoat side was subjected to sunscreen lotion and insect repellent tests, following GM’s GMW14445 and Ford’s BI 113-08, Method A testing procedures. The two examples passed all tests with a rating of 1.
  • Examples 32-33 Dissolution of PVDF/acrylic in different solvents Kynar 500® FSF® and Elvacite 2041 were dissolved in two different solvent mixtures as follows. The wt.% used and solvents used summarized in Table 16. The solvents were charged into a lined paint container equipped with an air mixer and a digital thermometer. Under agitation and heating, Kynar 500® FSF® was slowly added. The agitation speed was increased during addition and dissolution to maintain a vortex. After the Kynar 500® FSF® fully dissolved/dispersed, Elvacite 2041 was added. The mixture was heated to 60°C and maintained at 60 °C for 15 minutes under agitation, to ensure full dissolution of Kynar 500® FSF® and Elvacite 2041.
  • Example Ex.32 Ex.33 Kynar 500® FSF®- PVDF 14.4 % 14.3 % Elvacite 2041 – acrylic resin 6.3 % 6.2 % gamma-Butyrolactone (BLO) - solvent 39.7% 0 Dimethyl Sulfoxide (DMSO) - solvent 0 39.7% Methyl Ethyl Ketone (MEK) - solvent 39.7% 39.8%
  • clear solutions of PVDF/acrylic were formed at 60 °C.
  • the solution of Example 32 started gelling upon cooling and was completely gelled when cooled down to 28 °C.
  • the solution of Example 33 remained clear and after 72 hours under ambient conditions all components remained in solution.
  • Examples 34-36 Film with crosslinked clearcoat A clearcoat was prepared as follows. DMSO and MEK were charged into a 2.5 gallon stainless steel vessel, and agitation and heating were commenced. Under heating and adequate agitation, Kynar 500 was slowly added. Agitation speed was increased during the course of addition and dissolution to maintain a vortex. After dissolution of Kynar 500 around 35-40°C, Tinuvin 900, and Elvacite 4412 were added. Agitation and heating to 50°C were kept, to ensure full dissolution of all ingredients. The formulations were then filtered through a 100 micron bag and left standing overnight to allow air bubbles to rise.
  • the clearcoat was cast as a 0.5 mil (DFT) topcoat film onto a 2 mil (50 microns) PET carrier film on a pilot coater equipped with a slot die coating head and a 3-zone oven. Line speed was maintained at 3 ft/min and the oven temperatures were set at 250°F/320°F/380°F for the first, second and third zones, respectively.
  • a base coat was coated on top of the clear coat at a dry film thickness of 1 mil and dried in the 3-zone oven wherein the line speed was maintained at 3 ft/min and the oven temperatures were set at 250°F/320°F/320°F for the first, second and third zones, respectively. The thus-formed film was then laminated to ABS.
  • the thus-formed laminate was thermofolded to a flat mold at 320 °F before it was cut for making test plaques.
  • the plaques were tested for pencil hardness (according to ISO 15184), scratch resistance (Chrysler Scratch Resistance LP-463DD-18-02 Method A), gloss retention (the percent of 20 ° gloss retained after the samples go through the abrasion resistance test using a BYK Micro Tri-gloss meter), abrasion resistance (Chrysler Crock Mar Resistance LP-463PB-51-01; CS-10; 500 g weight, 1000 cycles), and chemical resistance to brake fluid (exposure to brake fluid for 30 minutes at 158 °F; GMW147014.3.1.3 Method 3). The results are shown in Table 18.
  • Example Ex.35 Ex.36 Clearcoat Ex.35 clearcoat Fluorex Clear Test results Pencil hardness 3H HB Scratch resistance 5N* 3N* Gloss retention > 60% ⁇ 30% Abrasion resistance pass pass Chemical resistance to brake fluid 9 (pass)** 6 (fail)** * The maximum load that did not result in scratching. ** The rating scale is from 1 (total structure destruction) to 10 (no change at all). Rating 8 (only slight surface change) or above is considered acceptable. The results show that a film with a clear PVDF/acrylic topcoat comprising OH-functional acrylic resin and a crosslinker has improved chemical, scratch, and abrasion resistance (Ex. 35) over a film with a commercially available PVDF/acrylic clearcoat film with nonreactive acrylic resin (Ex.36).

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Abstract

La présente divulgation concerne une solution à base de polyfluorure de vinylidène (PVDF) et un film de revêtement transparent acrylique et son application en tant que couche de finition résistante aux intempéries présentant une résistance chimique améliorée qui peut, par exemple, satisfaire aux exigences de résistance chimique de parties intérieures d'automobile. La présente divulgation concerne également des procédés de fabrication du film de revêtement transparent résistant aux produits chimiques et des stratifiés comprenant le film de revêtement transparent.
PCT/EP2024/075617 2023-09-21 2024-09-13 Solution à base de pvdf résistant aux produits chimiques et film de revêtement transparent acrylique et procédé de fabrication Pending WO2025061584A1 (fr)

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EP0285071A2 (fr) 1987-03-27 1988-10-05 Avery International Corporation Procédé de peinture par transfert à sec et produit obtenu
WO2000078538A1 (fr) 1999-06-22 2000-12-28 Maurer Scott D Moulage architectural
WO2000078539A1 (fr) * 1999-06-21 2000-12-28 Avery Dennison Corporation Feuilles decoratives imprimees de decoloration, procedes et appareil correspondants
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