Patent Description:
Polymers are used in a wide variety of molded articles for use in the automotive, industrial, and appliance markets, among others. Vehicles, for example, include many interior and exterior parts and attachments that are constructed from polymers, such as mirror casings, fenders, bumper covers, spoilers, dashboards, interior trim, and the like. Such articles generally are prepared by molding an article from a polyolefin or other resin and applying to the molded article one or more film-forming coating layers to protect and/or color the article. One of the difficulties associated with the use of polymeric substrates is that typical film-forming compositions used for protective and/or decorative coatings may not adhere. In refinishing molded articles constructed from polymers, for example, addition of an adhesion promoting layer can make the refinishing process complex, time-consuming, and expensive. Coatings and methods to reduce this time and complexity are therefore desired. <CIT> relates to single component storage stable, waterborne coating compositions. <CIT> relates to polyurethane or polyurethane polymer hybrid dispersions with reduced hydrophilicity, methods for producing the same and the use thereof. <CIT> relates to block copolymers comprising at least two blocks, a first block containing residues of a first radically polymerizable monomer and, optionally, a minor amount of a hydroxy functional radically polymerizable monomer, and a second block containing residues of a second radically polymerizable monomer and, optionally, a minor amount of a hydroxy functional radically polymerizable monomer. <CIT> relates to methods and systems for coating articles having a plastic substrate, such as certain interior and exterior parts on automobiles. <CIT> relates to a process for obtaining an aqueous coating composition comprising a block copolymer and polymer where the composition is preferably suitable for application to a plastic substrate more preferably a hydrophobic plastic substrate. <CIT> relates to thermosetting coating compositions containing flow control agents. <CIT> relates to primer compositions that are useful in the refinishing of motor vehicles. <CIT> relates to stable aqueous polymer dispersions for use in coatings for untreated polyolefinic substrates. <CIT> relates to waterborne or solventborne coatings in two or more than two layers, wherein the primer or adhesion promoter layer is color matched to the basecoat or color coat layer, and to coating methods of making the same. <CIT> relates to a coating composition suitable for use with a variety of plastic components, including thermoplastic polyolefin (TPO).

The present invention relates to a method of treating a plastic substrate comprising applying a coating composition directly onto at least a portion of a plastic substrate, wherein the coating composition comprises: (i) a film-forming polymer, (ii) an adhesion promoter, and (iii) a triblock copolymer, wherein the (ii) adhesion promoter is a (non)chlorinated polyolefin, wherein one block of the copolymer comprises cycloalkyl(meth)acrylate or aryl(meth)acrylate units, wherein another block of the copolymer comprises hydroxy functional and/or non-hydroxy functional (meth)acrylic acid alkyl esters and a third block of the copolymer comprises (meth)acrylic acid units.

The invention also relates to a method of treating a plastic substrate comprising (<NUM>) cleaning at least a portion of a plastic substrate, (<NUM>) treating the cleaned portion with an adhesion promoter comprising a (non)chlorinated polyolefin and (<NUM>) applying a coating composition directly onto the treated portion, wherein steps (<NUM>) and (<NUM>) directly follow step (<NUM>) with no steps in between steps (<NUM>) and (<NUM>) or steps (<NUM>) and (<NUM>), wherein the coating composition comprises a film-forming polymer and where at least one of (i) the adhesion promoter and (ii) the coating composition comprises an adhesion promoting additive, the adhesion promoting additive comprising a triblock copolymer comprising (a) a first block and (b) a second block comprising units having functional groups that promote adhesion to the plastic substrate, wherein the first block comprises hydroxy functional and/or non-hydroxy functional (meth)acrylic acid alkyl esters and a third block of the copolymer comprises (meth)acrylic acid units.

The invention also relates to a a coating composition comprising (i) a film-forming polymer, (ii) an adhesion promoter, and (iii) a triblock copolymer, wherein the (ii) adhesion promoter is a (non)chlorinated polyolefin, wherein one block of the copolymer comprises cycloalkyl(meth)acrylate or aryl(meth)acrylate units, wherein another block of the copolymer comprises hydroxy functional and/or non-hydroxy functional (meth)acrylic acid alkyl esters and a third block of the copolymer comprises (meth)acrylic acid units. Additionally, the present invention also relates to a plastic substrate comprising a coating deposited from the coating composition of any of claims <NUM>-<NUM>. The invention also relates to a use of a coating composition of any one of claims <NUM>-<NUM> to improve the adhesion of coating layers to a plastic substrate.

For the purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. It is also to be understood that the specific compositions and methods described in the following specification are simply exemplary embodiments of the invention. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

The present invention is generally directed to coating compositions having adhesion to polymeric substrates. Phrases such as "having adhesion", "promote adhesion" or "adhesion promoter" or the like in reference to a composition refer to a feature of that composition that reduces, if not avoids, delamination of a film-forming composition from a substrate. The present coating compositions generally comprise a block copolymer as an adhesion promoter, wherein one of the blocks of the copolymer comprises units having functional groups that promote adhesion to a polymeric substrate. Methods of treating and/or coating polymeric substrates using these coating compositions are also within the scope of the present invention.

Although reference is made herein to a block copolymer, the block copolymer can have any number of blocks and any number of monomer units. For example, the copolymer can be a diblock copolymer or a triblock copolymer. In the present invention, a triblock copolymer is present. The block copolymers described herein are described in reference to blocks [A], [B], [C] and the like, each having at least <NUM> monomeric units, where each of blocks [A], [B] and [C] are different from each other. For example, a diblock copolymer according to the present invention may be referenced as [A]-b-[B], where the symbols [A] and [B] refer to two distinct blocks of the copolymer and the symbol "b" denotes the block structure of block [A] and block [B]. Similarly a triblock copolymer according to the present invention may be referenced as [A]-b-[B]-b-[C] or [A]-b-[C]-b-[B], where the symbols [A], [B] and [C] refer to three distinct blocks and the symbol "b" denotes the block structure of blocks [A], [B] and [C].

A coating composition according to the present invention comprises (i) a film-forming polymer, (ii) an adhesion promoter, and (iii) a triblock copolymer, wherein the (ii) adhesion promoter is a (non)chlorinated polyolefin, wherein one block of the copolymer comprises cycloalkyl(meth)acrylate or aryl(meth)acrylate units, wherein another block of the copolymer comprises hydroxy functional and/or non-hydroxy functional (meth)acrylic acid alkyl esters and a third block of the copolymer comprises (meth)acrylic acid units. The block copolymer may comprise up to <NUM> weight percent (wt. %) of the total weight of the first, second and third components, such as up to <NUM> wt. % or up to <NUM> wt. % or up to <NUM> wt.

At least one of the blocks in the block copolymer comprises monomeric units that promote adhesion to a polymeric substrate. The other block or blocks of the block copolymer may be selected for suitable reaction with the first and/or second components to produce a resinous binder and/or to provide desired properties to the resinous binder and/or a coating composition produced therefrom.

A first block (an [A] block) of the block copolymer may be produced from monomers reactive with groups present in the first or second component. For example, the first block of the block copolymer may be produced from hydroxyl functional monomers that are reactive with groups present in the second component, such as isocyanate groups. Suitable hydroxyl functional monomers of the first block of the block copolymer that are reactive with isocyanate groups of the second component include hydroxyl functional (meth)acrylic acid alkyl esters such as <NUM>-hydroxyethyl(meth)acrylate, <NUM>-hydroxypropyl(meth)acrylate, <NUM>-hydroxypropyl(meth)acrylate, <NUM>-hydroxybutyl(meth)acrylate, and corresponding acrylates, or an adduct of (meth)acrylic acid/glycidyl neodecanoate. In addition, other suitable hydroxyl containing monomers that may be used include ethylene glycol allyl ether, propylene glycol allyl ether, butylene glycol allyl ether, diethylene glycol allyl ether, cyclomethylol propene allyl ether and hydroxymethylnorbornene, allyl alcohol, methyl allyl alcohol, propyl alcohol and unsaturated fatty alcohols. The first block may comprise hydroxyl functional methacrylic acid alkyl esters. Alternatively, the first block of the block copolymer may be produced from amine functional monomers that are reactive with groups present in the second component, such as isocyanate groups. Suitable amine functional monomers of the first block of the block copolymer that are reactive with isocyanate groups of the second component include polyamines having at least two functional groups such as di-, tri-, or higher functional polyamines, which may be aromatic and/or aliphatic.

A second block (a [B] block) of the block copolymer includes units having functional groups that promote adhesion to a polymeric substrate, such units including but not limited to cycloalkyl(meth)acrylate or aryl(meth)acrylate units, such as isobornyl(meth)acrylate, isodecyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, tetradecyl(meth)acrylate, hexadecyl(meth)acrylate, octadecyl(meth)acrylate, stearyl (meth)acrylate, dicyclopentenyloxymethyl(meth)acrylate, benzyl(meth)acrylate, <NUM>-phenoxyethyl(meth)acrylate, <NUM>,<NUM>,<NUM>-trimethyl-cyclohexyl(meth)acrylate, <NUM>-methylphenyl(meth)acrylate, <NUM>-naphtyl(meth)acrylate, <NUM>-phenyl-n-propyl(meth)acrylate and <NUM> phenyl-aminoethyl(meth)acrylate, C6 to C20 optionally substituted alkyl(meth)acrylamide monomers such as t-octyl(meth)acrylamide and n-decyl(meth)acrylamide, vinylic monomers such as vinyl toluene, vinyl esters of versatic acid such as VEOVA® <NUM> or VEOVA® <NUM>, vinyl chloride and vinylidene chloride, and mixtures thereof.

The block copolymer of the present invention further includes a third block, a [C] block, which may be comprised of monomers similar to those in [A] block or [B] block and/or include (meth)acrylic acid units. For triblock copolymers having a [C] block, the blocks may be arranged as [A]-b-[B]-b-[C] or [A]-b-[C]-b-[B].

The block copolymer (e.g. diblock or triblock) may be produced via controlled radical polymerization of at least one ethylenically unsaturated monomer via a reverse addition-fragmentation chain transfer (RAFT) mechanism, atom transfer radical polymerization (ATRP) or nitroxide mediated polymerization (NMP) technique. It is to be understood that the first, second, and, if used, third blocks of the block copolymer may be produced in any order (sequence), and that one of the blocks may be reactive with the first and/or second component, while another of the blocks has functional groups that promote adhesion to a polymeric substrate.

A coating composition according to the present invention comprises the above-described block copolymer of the present invention that is a triblock copolymer as an additive in a coating composition. As used herein, an "additive" is a component to a composition that is not intended to function as a reactant. As such, the present invention also includes a coating composition comprising a film-forming polymer and the block copolymer of the present invention, wherein the block copolymer is not intended to react with the film-forming polymer, meaning that some deminimus reaction between the block copolymer additive and film-forming polymer may or may not occur. One block of the block copolymer additive includes the second block (the [B] block) described above having units with functional groups that promote adhesion to a polymeric substrate such as those described above. One or more blocks of the block copolymer additive may include the first block (the [A] block) and /or the third block (the [C] block) described above.

By "film-forming polymer" it is meant a polymer that can form a self-supporting continuous film on at least a horizontal surface of a substrate upon removal of any diluents or carriers in the composition or upon curing at ambient or elevated temperatures. The coating composition of the present invention including the block copolymer as an additive exhibits enhanced adhesion to a polymeric substrate compared to a coating composition not including an additive of the block copolymer.

The film-forming polymer may be a thermoplastic and/or thermosetting polymer and may be waterborne or solvent-based.

As used herein, the term "thermosetting" refers to polymeric compositions that "set" irreversibly upon curing or crosslinking, wherein the polymer chains of the polymeric components are joined together by covalent bonds. This property is usually associated with a crosslinking reaction of the composition constituents often induced, for example, by heat or radiation. Curing or crosslinking reactions also may be carried out under ambient conditions. Once cured or crosslinked, a thermosetting resin will not melt upon the application of heat and is insoluble in solvents. Suitable thermosetting film-forming polymers include, for example, acrylic polymers, polyvinyl polymers, phenolics, polyester polymers, polyurethane polymers, polyamide polymers, polyether polymers, polysiloxane polymers, copolymers thereof, and mixtures thereof.

As used herein, the term "thermoplastic" refers to polymeric compositions that comprise polymeric components that are not joined by covalent bonds and thereby can undergo liquid flow upon heating and are soluble in solvents. Suitable thermoplastic film-forming polymers include, but are not limited to, acrylic polymers, thermoplastic polyolefins, such as polyethylene, polypropylene, polyamides, such as nylon, thermoplastic polyurethanes, thermoplastic polyesters, vinyl polymers, polycarbonates, acrylonitrile-butadiene-styrene ("ABS") copolymers, ethylene propylene diene terpolymer ("EPDM") rubber, copolymers, and mixtures of any of the foregoing. Generally these polymers can be any polymers of these types made by any method known to those skilled in the art. Such polymers may be solvent borne or water dispersible, emulsifiable, or of limited water solubility.

The film-forming polymer may be a primer composition and/or a basecoat composition. By "primer composition" (also referred to as a "sealer") it is meant a coating composition designed to adhere to substrates and function as a binding layer between the substrate and an overlying coating composition, such as a basecoat composition. By "basecoat composition" it is meant a coating composition that typically is applied over a primer composition and may include components (such as pigments and/or flake material) that impact the color and/or visual effects of the basecoat composition.

The coating composition including the block copolymer as an additive further includes an adhesion promoter, particularly a polyolefin additive, where the polyolefin additive enhances adhesion of the coating composition to a substrate. The polyolefin additive may or may not be chlorinated. Suitable chlorinated polyolefins (CPOs) are those available commercially from Nippon Paper Chemicals under the trade designations SUPERCHLON E-<NUM>, E-<NUM>, and/or E-<NUM>, and suitable non-chlorinated polyolefins are commercially available from Eastman under the trade name ADVANTIS 510W and/or those available commercially from Nippon Paper Chemicals under the trade names AUROREN AE <NUM> and/or AE-<NUM>.

The block copolymer additive and the adhesion promoter additive, may be provided as separate additions to the coating composition or together as a premixture or as a composite material. By "composite material", it is meant to include a structure wherein the block copolymer of the present invention at least partially encapsulates the adhesion promoter additive.

As used herein, the term "encapsulated" refers to a feature of particles of the adhesion promoter additive that are at least partially enclosed by (i.e. covered by) the block copolymer to an extent sufficient to physically separate particles of the adhesion promoter additive from each other within a dispersion, which may be aqueous or solvent based, thereby preventing agglomeration of the adhesion promoter additive. It will be appreciated that dispersions of the composite material of the present invention may also include adhesion promoter additive that is not encapsulated within the block copolymer. Encapsulation, or at least partial encapsulation, of the adhesion promoter additive in the block copolymer of the present invention may be accomplished by adding the adhesion promoter additive into a block copolymer solution with solvent(s) in which the adhesion promoter additive may not be dissolved in at room temperature.

The concentration of block copolymer additive in a coating composition of the present invention may be up to <NUM> wt. % or up to <NUM> wt. % or up to <NUM> wt. The block copolymer as described herein above may be used as an additive in a concentration of at least <NUM> wt. % or at least <NUM> wt. % or at least <NUM> wt. % or at least <NUM> wt. % or at least <NUM> wt. % or at least <NUM> wt. % or at least <NUM> wt. The block copolymer as described herein above may be used as an additive in a concentration of <NUM> to <NUM> wt. % or <NUM> to <NUM> wt. % based on the total solids in the coating composition.

The concentration of adhesion promoter additive in a coating composition of the present invention block copolymer may be as described herein above may be used as an additive in a concentration of up to <NUM> wt. % or up to <NUM> wt. % or up to <NUM> wt. The adhesion promoter additive may be used as an additive in a concentration of at least <NUM> wt. % or at least <NUM> wt. % or at least <NUM> wt. The block copolymer as described herein above may be used as an additive in a concentration of <NUM> to <NUM> wt. % or <NUM> to <NUM> wt. % based on the total solids in the coating composition.

The present invention is further directed to treating a polymeric substrate comprising applying to at least a portion of the substrate a coating composition as described above. Particularly suitable polymeric substrates for use with the coating compositions of the present invention include plastic substrates. As used herein, the term "plastic" includes any thermoplastic or thermosetting synthetic nonconductive material used in injection or reaction molding, sheet molding, or other similar processes whereby parts are formed, such as, for example, acrylonitrile butadiene styrene ("ABS"), thermoplastic polyolefin ("TPO"), polycarbonate, thermoplastic elastomer, polyester thermoset, polyurethane, thermoplastic polyurethane, sheet molded compound, and fiberglass reinforced polyester, among others. Common examples of polyolefins are polypropylene, polyethylene, and polybutylene and include the class of thermoplastic polyolefin. TPO generally refers to polymer/filler blends usually including some fraction of PP (polypropylene), PE (polyethylene), BCPP (block copolymer polypropylene), rubber, and a reinforcing filler. Common fillers include, though are not restricted to talc, fiberglass, carbon fiber, wollastonite, and MOS (metal oxy sulfate). Common rubbers include EPR (ethylene propylene rubber), EPDM (EP-diene rubber), EO (ethylene-octene), EB (ethylbenzene), and SEBS (styrene-ethylene-butadiene-styrene).

In treating a polymeric substrate, the coating composition of the present invention having the block copolymer as a reactant of the resinous binder therein is suitable for use as a primer composition applied directly to a polymeric substrate and promoting adhesion thereto. In use, the first, second and third components are blended together. The blended reactants (which may include a non-reactive adhesion promoter additive, such as a polyolefin, e.g. CPO) are deposited onto the polymeric substrate by any conventional method including brushing, dipping, flow coating, spraying and allowed to cure at ambient conditions or at elevated temperature, as needed for curing the coating composition. The substrate may be pre-cleaned prior to deposition of the coating composition. The cleaning step refers to the removal of unwanted foreign matter from the surface, such as soil, dirt, cutting oils, waxes, finger oils, and sanding dust, among other things. The substrate may be cleaned by, for example, mechanically separating the unwanted matter from the substrate, dissolving the unwanted foreign matter, contacting the substrate with a detergent, or a combination of two or more of these methods. As used herein, the term "detergent" refers to a substance that reduces the surface tension of water, i.e., a surface-active agent or a surfactant, which concentrates at oil-water interfaces, exerts emulsifying action, and aids in removing contaminants from a surface. Examples of detergents that might be used in the practice of the present invention include, without limitation, the anionic, nonionic, and cationic surfactants described earlier, as well as soaps. For example, the detergent may include d-Limonene, an oil extracted from citrus rind. The detergent may be provided in a cleaning composition, in which the detergent may, for example, comprise <NUM> to <NUM> percent by weight, or <NUM> to <NUM> percent by weight, or <NUM> to <NUM> percent by weight of the cleaning composition based on the total weight thereof. The amount of detergent present in the cleaning composition can range between any combination of the recited values, inclusive of the recited values.

Cleaning of the substrate may include contacting the substrate with an object, such as a pad or sponge, having a cleaning composition comprising a detergent in contact with or absorbed therein. The step of cleaning the substrate may include contacting the substrate with an abrasive material having a cleaning composition comprising a detergent contained therein. Abrasive materials suitable for use in the methods and systems of the present invention are commercially available and include, for example, SCOTCH-BRITE™ Scuff Sponges, commercially available from <NUM> Company, St. Paul, Minnesota, and BEAR-TEX® Scuff Pads and Sponges, commercially available from Norton Abrasives.

In contrast to conventional practice, the coating composition of the present invention having the block copolymer as a reactant of the resinous binder therein is applied directly to the cleaned substrate, with no other treatment of the substrate, other than optional cleaning thereof. In this manner, conventional pre-treatment steps of wiping the substrate one or more times with a solvent and/or treatment of the substrate with a composition containing CPO are avoided. According to the present invention, a polymeric substrate may be treated by cleaning at least a portion of the substrate and applying the composition of the present invention having the block copolymer as a reactant of the resinous binder therein directly on to the cleaned portion of the substrate.

The coating composition including the triblock copolymer as an additive is also suitable for use as a primer composition applied directly to a substrate (which may or may not be pre-cleaned) and promoting adhesion thereto. A polymeric substrate may be treated by first cleaning at least a portion of the polymeric substrate as described above. Directly thereafter, the cleaned portion is treated with an adhesion promoter that is a (non)chlorinated polyolefin (e.g. CPO) which is dried, such as by flashing. The coating composition including the triblock copolymer as an additive is applied directly onto the treated portion of the substrate. The treating step and applying step directly follow the cleaning step with no steps in between the cleaning and treating steps and or between the treating and applying steps. Alternatively, the coating composition including the triblock copolymer as an additive and further comprising an adhesion promoter additive, that is a (non)chlorinated polyolefin (e.g. CPO), may be applied directly to a cleaned polymeric substrate or an untreated polymeric substrate. By "untreated", it is meant that the substrate has not been pre-cleaned with a detergent, solvent, or CPO or the like. In this manner, the conventional steps of multiple CPO wipes may be avoided.

In another aspect of the invention, the triblock copolymer may be included as an adhesion promoter. For example, a polymeric substrate may be treated by first cleaning at least a portion of the polymeric substrate as described above. Directly thereafter, the cleaned portion is treated with an adhesion promoter comprising the triblock copolymer alone or in combination with a material such as a polyolefin (e.g. CPO), which is dried. A coating composition applied thereover may or may not include the triblock copolymer as an additive (non-reactive) or as a reactive component of the coating composition.

The coating compositions of the present invention may be used as a primer composition and/or a basecoat composition in a multi-layered coating system. As such, further coating compositions may be applied to the coating compositions of the present invention. Examples of such further coating compositions include protective and/or decorative coating systems, such as basecoat compositions and/or clearcoat compositions and/or colored coating compositions, as described below.

Protective and/or decorative coating systems that may be used in the present invention include, for example, those protective and/or decorative coating systems that are conventionally used in automotive refinish coating applications and automotive OEM applications, among others. Examples of suitable protective and/or decorative coating systems include single-layer coating systems, such as pigmented direct gloss coating systems, and multi-layered systems, such as systems that include a pigmented basecoat layer and a clear top coating layer. One or more layers of the protective and/or decorative coating system may be deposited from a coating composition that includes a polymeric composition that includes, without limitation, hydroxyl or carboxylic acid-containing acrylic copolymers, hydroxyl or carboxylic acid-containing polyester polymers and oligomers, isocyanate or hydroxyl-containing polyurethane polymers, and/or amine or isocyanate-containing polyureas. The one or more layers of the protective and/or decorative coating system may be deposited from a coating composition that includes one or more other additive ingredients, including those which are well known in the art of formulating surface coatings, such as dyes, pigments, surfactants, flow control agents, thixotropic agents, fillers, anti-gassing agents, organic co-solvents, catalysts, and other customary auxiliaries.

The coating compositions of the present invention may be used in refinishing of plastic articles. As used herein, the term "refinishing" refers to the act of restoring or repairing the surface or finish of an article or, in the case of automobile repairs, for example, the preparation of the surface or finish of an uncoated replacement article in connection with such a repair.

Illustrating the invention are the following examples that are not to be considered as limiting the invention to their details. All parts and percentages in the examples, as well as throughout the specification, are by weight unless otherwise indicated.

The coatings produced in the Examples herein were tested for adhesion in a cross hatch adhesion test and/or a jet wash test.

The cross hatch adhesion test was performed using a template to cut at least <NUM> parallel lines <NUM> apart that is placed upon the applied cured coating layers. With the retractable knife perpendicular to the panel surface, <NUM> parallel lines were cut through to the substrate surface using the <NUM> spacing template. The template was repositioned to make additional cuts at <NUM> degrees to the first set and cut as described above to create a grid of <NUM> squares. The film was lightly brushed with a soft brush or tissue to remove any detached flakes or ribbons of coatings. A <NUM> (<NUM> inch) long piece of tape (<NUM>#<NUM> or equivalent) was placed over the scribed lines in the same direction as one set of the lines. The taped was smoothed firmly over the substrate with an eraser or the backside of the blade-holder handle. The tape was then pulled off in one rapid, continuous motion while keeping the tape as close as possible to <NUM>°. The result was reported as the percentage adhesion of the test panel, e.g. no failure would be recorded as <NUM> percent adhesion or pass.

The jet wash test was performed to measure the resistance of coatings to the action of high pressure/hot water jet washer. A paint film was incised with a General #<NUM> scriber to form a cross. The incisions were deep enough to cut into the substrate and be approximately <NUM> (<NUM> inches) in length and were at least <NUM> (<NUM>/<NUM> inch) from all edges of the panel. Any paint or plastic shards caused by the cutting were wiped away or gently scraped. A panel was fastened into the jet wash chamber and the nozzle of the jet wash machine was positioned in the center of the cross, with the jet parallel to one of the branches. The jet washer was started and position maintained. The following test conditions were used:.

The result is recorded. A "Pass" indicates no peeling of the coating on the cross. A "Fail" indicates partial or total delamination.

A triblock copolymer was prepared having a first block comprising acrylic acid, a second block comprising isobornyl acrylate, and a third comprising hydroxyethyl acrylate and butyl acrylate.

The first block (Block [A]) was prepared using the materials listed in Table <NUM>. Charge #<NUM> was added into a <NUM> four-necked glass flask equipped with a condenser, temperature measuring probe, mechanical stirring device, and monomer/initiator feeding inlet. The mixture was degassed by purging with nitrogen at room temperature for <NUM> minutes while stirring. Then the mixture was heated to <NUM>, and, at <NUM>, <NUM>% (by weight) of Charge #<NUM> was charged into the reactor and then followed by Charge #<NUM>. The reaction mixture was held at <NUM> for <NUM> minutes. After holding, the rest of Charge #<NUM> was fed over <NUM> hours at <NUM>, and then the reaction mixture was held at <NUM> until the solids stalled. The final solids were experimentally measured at <NUM>%, and the weight averaged molecular weight (Mw) was <NUM>/mol and polydispersity was <NUM> (measured by gel permeation chromatography using polystyrene standards).

The second block (Block [B]) was prepared with the materials listed in Table <NUM>. Charge #<NUM> was added into a <NUM> four-necked glass flask equipped with a condenser, temperature measuring probe, mechanical stirring device, and monomer/initiator feeding inlet. The mixture was degassed by purging with nitrogen at room temperature for <NUM> minutes while stirring. Then the mixture was heated to <NUM>, and, at <NUM>, <NUM>% (by weight) of Charge #<NUM> was charged into the reactor and then followed by Charge #<NUM>. The reaction mixture was held at <NUM> for <NUM> minutes. After holding, the rest of Charge #<NUM> was fed over <NUM> hours at <NUM>, and then the reaction mixture was held at <NUM> until the solids stalled. The final solids of the resulting diblock copolymer [A]-b-[B] were experimentally measured at <NUM>%, and the weight averaged molecular weight (Mw) was <NUM>/mol and polydispersity was <NUM> (measured by gel permeation chromatography using polystyrene standards).

The third block was prepared using the materials listed in Table <NUM>. Charge #<NUM> was added into a <NUM> four-necked glass flask equipped with a condenser, temperature measuring probe, mechanical stirring device and monomer/initiator feeding inlet. The mixture was degassed by purging with nitrogen at room temperature for <NUM> minutes while stirring. Then the mixture was heated to <NUM>, and, at <NUM>, <NUM>% (by weight) of Charge #<NUM> was charged into the reactor and then followed by Charge #<NUM>. The reaction mixture was held at <NUM> for <NUM> minutes. After holding, the rest of Charge #<NUM> was fed over <NUM> hours at <NUM>, and then the reaction mixture was held at <NUM> until the solids stalled. The final solids of the triblock copolymer were experimentally measured at <NUM>%, and the weight averaged molecular weight (Mw) was <NUM>/mol and polydispersity was <NUM> (measured by gel permeation chromatography using polystyrene standards).

A sheet of thermoplastic polyolefin was cleaned with an aliphatic hydrocarbon solvent mixture and coated with a two-component isocyanate based primer composition (commercially available from PPG Industries, Inc. in Europe as product D8505/DP4000) including as a reactant <NUM> wt. % Triblock Copolymer <NUM> of Example <NUM>. The coating was post cured at room temperature for <NUM> hours and then subjected to a cross hatch adhesion test as reported in Table <NUM>.

The results reported in Table <NUM> show that the coating composition of the present invention having the block copolymer as a reactant of the resinous binder passed the cross hatch adhesion testing, while a control coating composition (without the triblock copolymer) failed.

A triblock copolymer was prepared having a first block comprising acrylic acid, a second block comprising isobornyl acrylate, and a third block comprising butyl acrylate.

Parts A and B of Example <NUM> were repeated to produce a diblock copolymer. The third block was prepared with the materials listed in Table <NUM>. Charge #<NUM> was added into a <NUM> four-necked glass flask equipped with condenser, temperature measuring probe, mechanical stirring device, and monomer/initiator feeding inlet. The mixture was degassed by purging with nitrogen at room temperature for <NUM> minutes while stirring. Then the mixture was heated to <NUM>, and, at <NUM>, <NUM>% (by weight) of Charge #<NUM> was charged into the reactor and then followed by Charge #<NUM>. The reaction mixture was held at <NUM> for <NUM> minutes. After holding, the rest of Charge #<NUM> was fed over <NUM> hours at <NUM>, and then the reaction mixture was held at <NUM> until the solids stalled. The final solids were experimentally measured at <NUM>%, and the weight averaged molecular weight (Mw) was <NUM>/mol and polydispersity was <NUM> (measured by gel permeation chromatography using polystyrene standards).

A dispersion of the Triblock Copolymer <NUM> of Example <NUM> in deionized water was prepared with the materials listed in Table <NUM>. Charge #<NUM> was added into a <NUM> four-necked glass flask equipped with condenser, temperature measuring probe, mechanical stirring device, and monomer/initiator feeding inlet. Charge #<NUM> was added into the flask slowly with mixing. After Charge #<NUM> was finished, Charge #<NUM> was fed into the flask slowly with mixing. After a stable dispersion was formed, the mixture was heated to <NUM>, and vacuumed off the solvent which came with block copolymer <NUM>. After stripping off all of the solvent, a stable dispersion at <NUM>% solids with translucent color was obtained.

Thermoplastic polyolefin ("TPO") substrates were pre-cleaned with an aliphatic hydrocarbon mixture, and then were wiped with a chlorinated polyolefin solution and the solvent was allowed to flash off. The Triblock Copolymer <NUM> Dispersion of Example <NUM> was included as an additive at <NUM> wt. % in a waterborne basecoat Envirobase HP Chrysler PS2, commercially available from PPG Industries, Inc. The mixture was then applied with a SATA jet <NUM> WSB nozzle to achieve complete opacity. After ambient dehydration, two coats of DS4000 clearcoat (commercially available from PPG Industries, Inc. ) were applied. After <NUM> minutes of ambient solvent flash, the final coat was baked at <NUM> for <NUM> minutes.

Cross hatch adhesion and jet wash test were performed after <NUM> days ambient cure as reported in Table <NUM>. The coating composition of the present invention including the block copolymer as an additive exhibited superior performance compared to a control coating composition without the additive.

A first block (Block [A]) was prepared using the materials listed in Table <NUM>. Charge #<NUM> was added into a <NUM> four-necked glass flask equipped with condenser, temperature measuring probe, mechanical stirring device, and monomer/initiator feeding inlet. The mixture was degassed by purging with nitrogen at room temperature for <NUM> minutes while stirring. Then, the mixture was heated to <NUM>, and at <NUM>, Charge #<NUM> and Charge #<NUM> were co-fed over <NUM> hours. After the feeds were complete, the reaction mixture was held at <NUM> until the solids stalled. The final solids were experimentally measured at <NUM>%, and the weight averaged molecular weight (Mw) was <NUM>/mol and polydispersity was <NUM> (measured by gel permeation chromatography using polystyrene standards).

The second block (Block [B]) was prepared with the materials listed in Table <NUM>. Charge #<NUM> was added into a <NUM> four-necked glass flask equipped with condenser, temperature measuring probe, mechanical stirring device, and monomer/initiator feeding inlet. The mixture was degassed by purging with nitrogen at room temperature for <NUM> minutes while stirring. Then the mixture was heated to <NUM>, and, at <NUM>, <NUM>% (by weight) of Charge #<NUM> was charged into the reactor and then followed by Charge #<NUM>. The reaction mixture was held at <NUM> for <NUM> minutes. After holding, the rest of Charge #<NUM> was fed over <NUM> hours at <NUM>, and then the reaction mixture was held at <NUM> until the solids stalled. The final solids of the diblock copolymer [A]-b-[B] were experimentally measured at <NUM>%, and the weight averaged molecular weight (Mw) was <NUM>/mol and polydispersity was <NUM> (measured by gel permeation chromatography using polystyrene standards).

The third block (Block [C]) was prepared with the materials listed in Table <NUM>. Charge #<NUM> was added into a <NUM> four-necked glass flask equipped with condenser, temperature measuring probe, mechanical stirring device, and monomer/initiator feeding inlet. The mixture was degassed by purging with nitrogen at room temperature for <NUM> minutes while stirring. Then the mixture was heated to <NUM>, and, at <NUM>, Charge #<NUM> and #<NUM> were fed over <NUM> hours, and then held at <NUM> for <NUM> hour. After holding, Charge #<NUM> was added into the flask over <NUM> minutes, and then the reaction mixture was held at <NUM> until solids production stalled. The final solids was experimentally measured at <NUM>%, and the weight averaged molecular weight (Mw) was <NUM>/mol and polydispersity was <NUM> (measured by gel permeation chromatography using polystyrene standards).

A mixture of Triblock Copolymer <NUM> with chlorinated polyolefin was prepared with the materials listed in Table <NUM>. Charge #<NUM> was added into a <NUM> four-necked glass flask equipped with condenser, temperature measuring probe, mechanical stirring device, and monomer/initiator feeding inlet. The mixture was heated to <NUM>, and, at <NUM>, Charge #<NUM> was added into the flask. The mixture was held at <NUM> until the SUPERCHLON® <NUM> was totally dissolved. Charge #<NUM> was added into the flask, and then the mixture was cooled to <NUM>, and <NUM> grams solvent was stripped out at lower pressure. The solids content of the final resin solution was <NUM>%.

Thermoplastic polyolefin substrates were pre-cleaned with an aliphatic hydrocarbon mixture. A two-component isocyanate based primer composition, ECS25, commercially available from PPG Industries, was prepared using the material of Example <NUM> (<NUM> wt. % Triblock Copolymer <NUM> as a reactant), and the primer was applied to the pre-cleaned substrates. The primer was cured at ambient temperature for <NUM> minutes and then coated with a basecoat, Envirobase HP Chrysler PS2, commercially available from PPG Industries, and a clearcoat, DC4010, commercially available from PPG Industries, applied as "wet on wet" layers, which were then were baked in a single curing step at <NUM> for <NUM> minutes.

After <NUM> days' ambient cure, cross hatch adhesion testing and jet wash test were performed as reported in Table <NUM>. The primer with triblock copolymer and chlorinated polyolefin additive passed both the cross hatch adhesion and jet wash tests, while a primer control (without the triblock copolymer and chlorinated polyolefin additive) failed on both tests.

A dispersion was produced from the materials listed in Table <NUM> by placing Charge #<NUM> into a <NUM> flask, and then vacuuming off methyl ethyl ketone and ethanol brought by the block copolymer from Part B of Example <NUM>. After over <NUM>% of the methyl ethyl ketone and ethanol were stripped off, Charge #<NUM> was added into the flask and then the mixture was heated to <NUM> until totally dissolved. After totally dissolved, Charge #<NUM> was added into the mixture, and then followed by Charge #<NUM>. Charge #<NUM> was added into the mixture with mixing. The solvents were vacuumed off, and a stable dispersion at <NUM>% solids content was obtained.

Thermoplastic polyolefin substrates were cleaned with aliphatic hydrocarbon substrates, and then BYK-<NUM> (an adhesion promoter available from BYK USA Inc. ) was wiped onto the substrates to increase the surface energy. The material of Example <NUM> was added into a waterborne basecoat, Envirobase HP Chrysler PS2, commercially available from PPG Industries, at <NUM>% based on total weight, and applied to the pre-cleaned substrates to full opacity. The final coatings were baked at <NUM> for <NUM> minutes after clearcoat, DC4010, commercially available from PPG Industries, was applied. Cross hatch adhesion testing was done at <NUM> hours and <NUM> days post cure as reported in Table <NUM>. With the Block Copolymer/CPO Dispersion of Example <NUM> added into the basecoat, cross hatch adhesion passed, while a basecoat without the additive (control) failed.

A dispersion was produced from the materials listed in Table <NUM> by placing Charge #<NUM> into a <NUM> flask, and then vacuuming off methyl ethyl ketone and ethanol brought by Triblock Copolymer <NUM> from Example <NUM>. After over <NUM>% of the methyl ethyl ketone and ethanol were stripped off, Charge #<NUM> was added into the flask and then the mixture was heated to <NUM> until totally dissolved. After totally dissolved, Charge #<NUM> was added into the mixture, and then followed by Charge #<NUM>. Charge #<NUM> was added into the mixture with mixing. And then all of the solvents were vacuumed off, and a stable dispersion at <NUM>% solids content was obtained.

Thermoplastic polyolefin substrates were cleaned with aliphatic hydrocarbon substrates, and then BYK-<NUM> was wiped onto the substrates to increase the surface energy. The material of Example <NUM> was added into a waterborne basecoat, Envirobase HP T472 fine lenticular metallic, commercially available from PPG Industries, at <NUM>% based on total weight, and applied to the pre-cleaned substrates to full opacity. The final coatings were baked at <NUM> for <NUM> minutes after a clearcoat composition, DC4010, commercially available from PPG Industries, was applied. Cross hatch adhesion testing was done at <NUM> hours and <NUM> days post cure, as reported in Table <NUM>, with the basecoat having the additive of Example <NUM> passing and failure by a basecoat without additive (control).

A triblock copolymer was prepared using the materials listed in Table <NUM>. Charge #<NUM> was added into a <NUM> four-neck glass flask equipped with a condenser, temperature measuring probe, mechanical stirring device, and monomer/initiator feeding inlet. The mixture was degassed by purging with nitrogen at room temperature for <NUM> minutes while stirring. Then the mixture was heated to <NUM>, and at <NUM>, and charges #<NUM> and #<NUM> were fed into the reactor over <NUM> hour with a <NUM> minute hold half way through feed. The reaction mixture was held for <NUM> hour after the feed, and then charge #<NUM> was charged into the reactor over <NUM> and the reaction mixture was held for <NUM> hour. Charges #<NUM> and #<NUM> were then fed into the reactor over <NUM> minutes, and the reaction mixture was held for <NUM> hour before feeding #<NUM> and #<NUM> over <NUM> hours. The reaction mixture was held for <NUM> hours before charging #<NUM> and #<NUM> into the reactor over <NUM> hour. The reaction mixture was held for <NUM> hours before cooling down. The final solids was <NUM>% by weight.

A dispersion was produced from the materials listed in Table <NUM> by placing Charge #<NUM> into a <NUM> flask, and then vacuuming off methyl ethyl ketone, DOWANOL PM and xylene brought by the Triblock Copolymer <NUM> of Example <NUM> and a non-chlorinated polyolefin (Eastman Adhesion Promoter <NUM>-<NUM>). After over <NUM>% of the solvents were stripped off, Charge #<NUM> was added into the flask and then the mixture was heated to <NUM> until totally dissolved. After totally dissolved, Charge #<NUM> was added into the mixture, and then followed by Charge #<NUM>. Charge #<NUM> was added into the mixture with mixing. The solvents were vacuumed off, and a stable dispersion at <NUM>% solids content was obtained.

Thermoplastic polyolefin substrates were cleaned with aliphatic hydrocarbon substrates, and then BYK-<NUM> was wiped onto the substrates to increase the surface energy. The material of Example <NUM> was added into a waterborne basecoat, Envirobase HP T472 fine lenticular metallic, commercially available from PPG Industries, at <NUM>% based on total weight, and applied to the pre-cleaned substrates to full opacity. The final coatings were baked at <NUM> for <NUM> minutes after clearcoat, DC4010, commercially available from PPG Industries, was applied. Cross hatch adhesion testing was done of the coatings and a control coating (without the copolymer/CPO additive) at <NUM> hours and <NUM> days post cure as reported in Table <NUM>.

Material was prepared using the components listed in Table <NUM>. Charge #<NUM> was added into a <NUM> four-necked glass flask equipped with a condenser, temperature measuring probe, mechanical stirring device, and monomer/initiator feeding inlet. The mixture was heated to <NUM> and then charge #<NUM> was slowly added into the flask over <NUM> minutes. The non-CPO dispersion with triblock copolymer was formed after mixing for <NUM> minutes.

Thermoplastic polyolefin substrates were pre-cleaned with an aliphatic hydrocarbon mixture. A two-component isocyanate based primer composition, D8505/DP4000, commercially available from PPG Industries, Inc. in Europe, was prepared using the material of Example <NUM> (<NUM> wt. % Triblock Copolymer <NUM> as a reactant) and the primer was applied to the pre-cleaned substrates. The primer was cured for <NUM> minutes at <NUM>.

After <NUM> days' ambient cure, cross hatch adhesion testing was performed as reported in Table <NUM>. The primer with triblock copolymer and non-chlorinated polyolefin passed the cross hatch adhesion test, while the control primer (without copolymer and non-chlorinated polyolefin) failed.

Claim 1:
A method of treating a plastic substrate comprising applying a coating composition directly onto at least a portion of a plastic substrate, wherein the coating composition comprises:
(i) a film-forming polymer,
(ii) an adhesion promoter, and
(iii) a triblock copolymer,
wherein the (ii) adhesion promoter is a (non)chlorinated polyolefin, wherein one block of the copolymer comprises cycloalkyl(meth)acrylate or aryl(meth)acrylate units, wherein another block of the copolymer comprises hydroxy functional and/or non-hydroxy functional (meth)acrylic acid alkyl esters and a third block of the copolymer comprises (meth)acrylic acid units.