Coated substrates prepared with waterborne sealer and primer compositions

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MULTI-LAYER COATED SUBSTRATE

Field of invention

[0001] The present invention relates to multilayer coated substrates prepared with water-based primer and/or sealing compositions.

History of the invention

[0002] In the automotive refinish industry, a typical multi-layer coating stack applied to a substrate includes a solvent-borne primer, a solvent-borne sealer, and one or more aesthetic topcoats. The substrate and each applied coating layer are generally sanded between applications for aesthetic and adhesion purposes. For convenience, it is desirable that each coating dry and/or cure to a sandable point within fifteen minutes of application. Each coating is also designed to provide high film build with a minimum of coating layers, producing smoothness and levelness without cracking or microporosity. As new regulations continue to force coatings manufacturers to reduce emissions, challenges arise in designing environmentally friendly refinish coatings with properties comparable to their solvent-based predecessors.

[0003] It would be desirable to provide water-based primer and sealer compositions that can be used to prepare multi-layer coated substrates with properties similar to their solvent-based counterparts.

Summary of the invention

[0004] The present invention relates to a multilayer coated substrate comprising:

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2/60 (A) a substrate;

(B) a primer composition applied directly to a substrate surface, forming a first coating;

(C) a sealing composition applied over the first coating; and (D) at least one top coating applied over the sealing composition.

[00 05] The present invention also relates to a substrate coated with multiple layers comprising:

(A) a substrate;

(B) a first composition comprising a primer or sealer composition applied directly to a surface of the substrate, forming a first coating; and (C) at least one topcoat applied over the first coating. The primer and/or sealer compositions comprise a water-based curable film-forming composition, which in turn comprises:

(a) a first component comprising an aqueous dispersion of a pigment and (i) polymeric urethane film particles having a core-film morphology and having hydroxyl functional groups, wherein the core of the particles with a polymeric urethane film is prepared from a mixture of monomers comprising ethylenically unsaturated hydrophobic monomers and wherein the core of the particles with a polymeric urethane film comprises a polyurethane or polyurethane-urea polymer; or (ii) particles with a polymeric acrylic film having a core-film morphology and having hydroxyl functional groups, wherein the core of the particles is prepared with

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3/60 polymeric acrylic film from a mixture of monomers comprising ethylenically unsaturated hydrophobic monomers and the film of particles is prepared with polymeric acrylic film from a mixture of monomers comprising ethylenically unsaturated hydrophilic monomers;

(b) a second component comprising a polyisocyanate crosslinking agent; and, optionally, (c) a water-dispersible acrylic polymer with hydroxyl functionality.

Detailed description of the invention

[0006] Other than the operating examples, or unless expressly specified otherwise, all numerical ranges, quantities, values and percentages such as those for amounts of materials, reaction times and temperatures, ratios of quantities, values for molecular weight (either number average molecular weight (M_n) or weight average molecular weight (M_w)) and others in the following portion of the specification may be read as if prefaced by the term about although the term about may not expressly appear with the value, quantity or range. Accordingly, unless otherwise indicated, all numerical parameters presented in the following specification and in the appended claims are approximations that may vary depending on the desired properties to be obtained by the present invention. At a minimum, 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 interpreted in light of the number of significant figures reported and applying techniques

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4/60 usual rounding.

[0007] Likewise for molecular weights, either number average molecular weight (M_n) or weight average molecular weight (M_w), these quantities are determined by gel permeation chromatography using polystyrene as standards as is well known to those skilled in the art and as discussed in U.S. Pat.^s 4,739,019, in column 4, lines 2-45.

[0008] Although the numerical ranges and parameters showing the broad scope of the invention are approximations, the numerical values presented in the specific examples are reported as accurately as possible. However, any numerical value inherently contains certain errors resulting from the standard variation found in its respective test measurements. Furthermore, when numerical ranges of varying scope are shown here, it will be assumed that any combination of these values including the values mentioned may be used.

[0009] Plural referents, when used herein, encompass the singular and vice versa. For example, although the invention has been described in terms of a cationic acrylic resin derived from an epoxy-functional acrylic resin, a plurality, including a mixture of such resins, may be used.

[0010] Any numerical references to quantities, unless otherwise specified, are by weight. The term equivalent weight is a calculated value based on the relative quantities of the various ingredients used in the preparation of the specified material and is based on the solids of the specified material. Relative quantities are those which

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5/60 gives the theoretical weight in grams of the material, such as a polymer, produced from the ingredients and gives a theoretical number of the particular functional group that is present in the resulting polymer. The theoretical polymer weight is divided by the theoretical number of functional group equivalents to give the equivalent weight. For example, the equivalent weight of urethane is based on the equivalents of urethane groups in the polyurethane material.

[0011] When used in the following description and claims, the following terms have the meanings set forth below:

[0012] When used herein, the term polymer refers to prepolymers, oligomers, homopolymers, and copolymers; the prefix poly refers to two or more. Composite material means a combination of two or more different materials.

[0013] When used herein, based on total weight of resin solids or based on total weight of organic binder solids (used interchangeably) of the composition means that the amount of the component added during formation of the composition is based on the total weight of resin solids (non-volatile) of the film-forming materials, including crosslinkers and polymers present during formation of the composition, but not including water, solvent or any solid additives such as hindered amine stabilizers, photoinitiators, pigments including fillers and extender pigments, flow modifiers, catalysts and UV light absorbers.

[0014] When used herein, the terms thermoset and curable may be used interchangeably and if

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6/60 refer to resins that solidify irreversibly in response to curing or crosslinking, with the polymer chains of the polymer components being joined by covalent bonds. This property is usually associated with a crosslinking reaction of the constituents of the composition, often induced, for example, by heat or radiation. See, Hawley, Gessner G., The Condensed Chemical Dictionary, ninth edition, page 856; Surface Coatings, vol. 2, Oil and Colour Chemists' Association, Australia, TAFE Educational Books (1974). Curing or crosslinking reactions can also be carried out under ambient conditions. Ambient conditions means that the coating undergoes a heat-setting reaction without the aid of heat or other energy, e.g. without baking in an oven, using forced air, or the like. Typically, the ambient temperature ranges from 60°F to 90°F (15.6°C to 32.2°C), with a typical room temperature being 72°F (22.2°C). Once cured or crosslinked, a thermoset resin will not melt upon application of heat and is insoluble in solvents. When used in this specification and the appended claims, the articles a, an, the, and the include plural referents, and are used interchangeably with the terms at least one, at least one, one or more, and one or more, unless expressly and unambiguously limited to one referent.

[0015] The various examples of the present invention presented herein will be understood as non-limiting with respect to the scope of the invention.

[0016] The term reactive refers to a functional group capable of undergoing a reaction with itself and/or other functional groups spontaneously or upon application of heat.

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7/60 or in the presence of a catalyst or by any other means known to those skilled in the art.

[0017] Essentially free of a material means that the composition has only trace or incidental amounts of a given material, and that the material is not present in an amount sufficient to affect any properties of the composition. These materials are not essential to the composition and therefore the composition is free of these materials in any appreciable or essential amount.

[0018] The multilayer coated substrates of the present invention may comprise:

(A) a substrate;

(B) a primer composition applied directly to a surface of the substrate, forming a first coating; (C) a sealing composition applied over the first coating; and (D) at least one top coat applied over the sealing composition.

[00 19] Alternatively, multilayer coated substrates may comprise:

(A) a substrate;

(B) a first composition comprising a primer or sealer composition applied directly to a surface of the substrate, forming a first coating; and (C) at least one topcoat applied over the first coating. In this scenario there is only one primer or sealer present in the stack of coatings, but not both.

[0020] Non-metallic substrates (A) include polymeric, plastic, polyester, polyolefin, polyamide, cellulosic, polystyrene, polyacrylic,

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8/60 poly(ethylene naphthalate), polypropylene, polyethylene, nylon, EVOH, poly(lactic acid), other green polymeric substrates, poly(ethylene terephthalate) (PET), polycarbonate, polycarbonate acrylonitrile butadiene styrene (PC/ABS), polymer composites, and the like. Automotive parts typically formed from thermoplastic and thermoset materials include bumpers and trim.

[0021] Metal substrates used in the present invention include ferrous metals, non-ferrous metals, and combinations thereof. Suitable ferrous metals include iron, steel, and alloys thereof. Non-limiting examples of useful steel materials include cold rolled steel, pickled steel, steel surface treated with any of metallic zinc, zinc compounds and zinc alloys (including electrogalvanized steel, hot dip galvanized steel, GALVANNEAL steel, and zinc alloy coated steel) and/or zinc-iron alloys. Likewise, substrates of aluminum, aluminum alloys, zinc-aluminum alloys such as GALFAN, GALVALUME, aluminum-coated steel and aluminum alloy-coated steel substrates, as well as metallic magnesium, metallic titanium, and alloys thereof, may be used. Steel substrates (such as cold-rolled steel or iron phosphide-rich organic coating) are also suitable for use in the present invention. Such weldable coating compositions are disclosed in U.S. Pat. n^ss 4,157,924 and 4,186,036. Cold-rolled steel is also suitable when pretreated with a suitable solution known in the art, such as a metal phosphate solution, an aqueous solution containing at least one Group IIIB or IVB metal, a

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9/60 organic phosphate solution, an organic phosphonate solution, and combinations thereof, as discussed below.

[0022] Alternatively, the substrate may comprise more than one metal or metal alloy wherein the substrate may be a combination of two or more metal substrates assembled together such as hot-dip galvanized steel assembled with aluminum substrates. Alternatively the substrate may comprise a composite material such as fiberglass composite. It is desirable to have a coating system that can be applied to both metal and non-metallic parts. The substrate may comprise a part of a vehicle. Vehicle is used herein in its broadest sense and includes all types of vehicles, such as, but not limited to, airplanes, helicopters, cars, trucks, buses, vans, golf carts, motorcycles, bicycles, railroad cars, and the like. It will be appreciated that the portion of the vehicle that is coated in accordance with the present invention may vary depending on the purpose for which the coating is being used.

[0023] The form of the substrate may be in the form of a sheet, plate, bar, rod or any desired shape, but is usually in the form of an automobile part such as a body, door, fender, hood or bumper. When desired, the thickness of the substrate may be varied.

[0024] The substrates to be used may be bare substrates. By bare we mean a virgin substrate that has not been treated with (or has been devoid of) any pre-treatment compositions such as phosphating baths, heavy metal rinses, etc. Additionally, the

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10/60 substrates may undergo one or more treatment steps known in the art prior to application of the curable film-forming composition.

[0025] Prior to depositing any coating compositions onto the surface of the substrate, it is common practice, although not necessary, to remove foreign matter or previously applied paints such as OEM coatings from the surface by thoroughly stripping, cleaning and degreasing the surface. When the substrate is not an existing vehicle part, such cleaning typically occurs after the substrate has been formed (stamping, welding, etc.) into an end-use shape. The substrate surface may be cleaned by physical or chemical means, or both, such as by mechanically scraping the surface (e.g., sanding) or by cleaning/degreasing with commercially available acidic or alkaline cleaning agents that are well known to those skilled in the art, such as sodium metasilicate and sodium hydroxide. A non-limiting example of a cleaning agent is CHEMKLEEN 163, an alkaline cleaner commercially available from PPG Industries, Inc.

[0026] In an OEM configuration, a metal substrate may optionally be pretreated with any suitable solution known in the art, such as a metal phosphate solution, an aqueous solution containing at least one Group IIIB or IVB metal, an organic phosphate solution, an organic phosphonate solution, and combinations thereof. The pretreatment solutions may be essentially free of environmentally harmful heavy metals such as chromium and nickel. Suitable phosphate conversion coating compositions may be any of those

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11/60 known in the art that are free of heavy metals. Examples include zinc phosphate, which is most commonly used, iron phosphate, manganese phosphate, calcium phosphate, magnesium phosphate, cobalt phosphate, zinc-iron phosphate, zinc-manganese phosphate, zinc-calcium phosphate, and other types of layers, which may contain one or more multivalent cations. Phosphating compositions are known to those skilled in the art and are described in U.S. Pat.^ss 4,941,930, 5,238,506 and 5,653,790.

[0027] Group IIIB or IVB transition metals and rare earth metals referred to herein are those elements included in such groups in the CAS Periodic Table of the Elements as shown, for example, in the Handbook of Chemistry and Physics, 63^the edition (1983).

[0028] Typical Group IIIB and IV transition metal compounds and rare earth metal compounds are zirconium, titanium, hafnium, yttrium and cerium compounds and mixtures thereof. Typical zirconium compounds can be selected from hexafluorozirconic acid, alkali and alkaline earth metal salts thereof, zirconium ammonium carbonate, zirconyl nitrate, zirconium carboxylates and zirconium hydroxy carboxylates such as hydrofluorozirconic acid, zirconium acetate, zirconium oxalate, zirconium ammonium glycolate, zirconium ammonium lactate, zirconium ammonium citrate, and mixtures thereof. Hexafluorozirconic acid is very commonly used. An example of a titanium compound is fluorotitanic acid and its salts. An example of a hafnium compound is hafnium nitrate. An example of a yttrium compound is yttrium nitrate. An example of a cerium compound is cerium nitrate.

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12/60 cerium.

[0029] Typical compositions to be used in the pretreatment step include non-conductive organic phosphate and organic phosphonate pretreatment compositions such as those disclosed in U.S. Pat.^ss 5,294,265 and 5,306,526. Such organic phosphate and organic phosphonate pretreatments are commercially available from PPG Industries, Inc., under the trade name NUPAL®. A repair primer coating is conventionally applied to a substrate in several application layers to a total dry film thickness of about 100 to 150 microns. The purpose of the primer coat is to even out small variations in the thickness of the underlying layer that are created when the original Class A surface is partially sanded, creating a gradient of film thicknesses on top of which the repair layer system is applied. To provide this uniform surface, a significant portion of the primer thickness may be removed during the sanding step (approximately 50%). Therefore, significantly more importance is placed on the ability to achieve 50 micron dry film thickness per application and the sanding properties of the primer, rather than the smoothness of the primer itself.

[0030] In contrast, the purpose of applying a sealer over the repair area is to provide a smooth, consistent surface over which the repair topcoat layers can be applied. The sealer is expected to provide this smoothness without any sanding, and the sealer is conventionally applied in a coating to a dry film thickness of around 25 microns. The sealer

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13/60 can be applied over a previously applied primer to hide the sanding scratch marks produced when sanding the primer. Often, in the absence of a sealer, these sanding marks can be transmitted through the base coat and are visible as an optical defect on the repair part. A sealer (or sealant) may also be applied to a partial sand repair spot to negate the often varying surface energies created by the multiple exposed surfaces. These varying surface energies sometimes lead to visible optical defects in the base coat layer (known as tint). In this case the sealer provides a consistent surface energy layer across the surface, over which the top coat is applied. Since the sealant is applied prior to the repair topcoat and is generally not sanded, the halo area across the edge of the repair where the adjoining sealant film blends into the original unsanded area should be smooth enough to be coated without further processing. It is also desirable for the sealant to dry and be processable within 10 to 15 minutes after application.

[0031] The multilayer coated substrates of the present invention may further comprise (B) a primer composition applied directly to a surface of the substrate, forming a first coating; and (C) a sealer composition applied over the first coating. A topcoat may then be applied over the sealer composition. Alternatively, the multilayer coated substrates of the present invention may further comprise (B) a first composition comprising

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14/60 a primer composition or a sealer composition applied directly to a substrate surface, forming a first coating. A topcoat may then be applied over the first coating. At least one of the primer and sealer compositions comprises a water-based curable film-forming composition which in turn comprises:

(a) a first component comprising an aqueous dispersion of a pigment and (i) polymeric urethane film particles having a core-film morphology and having hydroxyl functional groups, wherein the core of the particles with a polymeric urethane film is prepared from a mixture of monomers comprising ethylenically unsaturated hydrophobic monomers and wherein the core of the particles with a polymeric urethane film comprises a polyurethane or polyurethane-urea polymer; or (ii) polymeric acrylic film particles having a core-film morphology and having hydroxyl functional groups, the core of the polymeric acrylic film particles being prepared from a monomer mixture comprising ethylenically unsaturated hydrophobic monomers and the film of the polymeric acrylic film particles being prepared from a monomer mixture comprising ethylenically unsaturated hydrophilic monomers;

(b) a second component comprising a polyisocyanate crosslinking agent; and, optionally, (c) a water-dispersible acrylic polymer with hydroxyl functionality.

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15/60

[0032] Pigments suitable for use in the aqueous dispersion of the first component (a) include any organic and/or inorganic pigments typically used in primer or sealer compositions. Examples of pigments and/or pigment compositions include, but are not limited to, crude pigment of dioxazine carbazole, azo, monoazo, diazo, naphthol AS, salt type (flakes), benzimidazolone, condensation, metal complex, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrole pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavantrone, pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments, diketopyrrole pyrrole red (DPPBO red), titanium dioxide, carbon black and mixtures thereof. The terms pigment and color filler may be used interchangeably.

[0033] The polymeric particles used in the first component (a) of the water-based curable film-forming composition may comprise (I) polymeric urethane film particles having a core-film morphology and having hydroxyl functional groups, wherein the core of the particles with a polymeric urethane film is prepared from a mixture of monomers comprising ethylenically unsaturated hydrophobic monomers and wherein the core of the particles with a polymeric urethane film comprises a polyurethane or polyurethane-urea polymer.

[0034] The core (inner domain) and skin (surface domain) polymers can be covalently bonded, and the polymer particles are typically formed by emulsion polymerization in an aqueous medium. Exemplary polymerization methods are demonstrated in

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16/60 examples below. Typically, the core constitutes 30 to 70 weight percent of the polymer particle, while the film usually constitutes 70 to 30 weight percent of the polymer particle. Often, the weight ratio of core to film is greater than 1:1. Also, the core may be internally crosslinked through the use of monomers having multiple ethylenically unsaturated groups, such as ethylene glycol dimethacrylate. These internally crosslinked monomers are typically used in amounts up to 10 weight percent, such as 3 to 10 weight percent, based on the total weight of resin solids in the particles. The film polymer is designed to be more polar than the core by including functional groups such as hydroxyl and acid groups. The film polymer is typically formed from polyisocyanates and polyols including acid-functional polyols, in an amount sufficient to allow dispersion of the polymer particles in an aqueous medium.

[0035] Ethylenically unsaturated monomers used to prepare the core of the urethane film particles may include hydrophobic monomers such as n-butyl (meth)acrylate, isobutyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, and t-butyl (meth)acrylate, usually together with one or more other polymerizable ethylenically unsaturated monomers, including monomers having multiple ethylenically unsaturated groups such as ethylene glycol dimethacrylate and hexanediol diacrylate. By hydrophobic is meant that the monomers have nonpolar properties and have a tendency to interact with, be miscible with, or be

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17/60 dissolved in nonpolar solvents such as alkanes and oils. By definition, a molecule can be nonpolar either when there is an equal sharing of electrons between the two atoms of a diatomic molecule or because of the symmetrical arrangement of polar bonds in a more complex molecule such that there is no overall dipole in the molecule.

[0036] Other useful alkyl esters of acrylic acid or methacrylic acid include aliphatic alkyl esters containing from 1 to 30, and usually from 4 to 18, carbon atoms in the alkyl group. Non-limiting examples include methyl (meth)acrylate, ethyl (meth)acrylate, and n-butyl (meth)acrylate. Other suitable copolymerizable ethylenically unsaturated monomers include vinyl aromatic compounds such as styrene and vinyl toluene. Ethylenically unsaturated monomers with hydroxyl functionality such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate may also be used in amounts that do not significantly adversely affect the hydrophobicity of the core.

[0037] Urethane film polymer particles often contain primary hydroxyl functional groups. Usually, more than 50 percent of the hydroxyl functional groups in the particles are primary; often more than 75 percent, and more often more than 90 percent. It is also possible for 100 percent of the hydroxyl functional groups in the particles to be primary. An exemplary mixture of monomers used to prepare the core of the polymer particles comprises at least one of n-butyl (meth)acrylate, isobutyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate,

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18/60 stearyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and styrene, and, optionally, at least one of hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate .

[0038] The film of urethane film polymer particles comprises a polyurethane or polyurethane-urea polymer containing acid functional groups. Polyurethane polymers are prepared by reacting polyols with a polyisocyanate; often the ratio of OH/NCO equivalents is less than 1:1 so that free isocyanate groups are present in the intermediate isocyanate prepolymer. Suitable polyols include ethylene glycol, propylene glycol, butylene glycol, 1,6-hexylene glycol, neopentyl glycol, diethylene glycol, glycerol, trimethylolpropane and pentaerythritol. Polyols having dual functionality, such as dimethylolpropionic acid, are also suitable, as they incorporate acid functional groups into the resulting polyurethane. Additionally, such polymeric polyols may have acid functional groups. The organic polyisocyanate used to prepare polyurethane may be an aliphatic or aromatic polyisocyanate or a mixture of the two. Diisocyanates are most commonly used, although higher polyisocyanates may be used in place of or in combination with diisocyanates. Examples of suitable aromatic diisocyanates are 4,4'-diphenylmethane diisocyanate and toluene diisocyanate. Examples of suitable aliphatic diisocyanates include straight-chain aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate. Cycloaliphatic diisocyanates may also be used. Examples include

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19/60 isophorone diisocyanate and 4,4'-methylene-bis-(cyclohexyl isocyanate). Examples of higher polyisocyanates are: 1,2,4-triisocyanatobenzene polyphenyl polymethylene isocyanate. The free isocyanate end groups are then reacted with polyols, such as trimethylolpropane and pentaerythritol, to produce a urethane film with a plurality of curable hydroxyl end groups. This molecular architecture is particularly advantageous for ambient cure applications.

[0039] As noted above, polyurethanes can be prepared with unreacted carboxylic acid groups, which after neutralization with bases such as amines allow dispersion in aqueous media. Neutralization of acid groups of the polymer can be done using, for example, inorganic bases such as ammonium hydroxide or amines such as dimethylethanolamine, diisopropanolamine, triethylamine and the like. Effective dispersion techniques may include high shear mixing such as by homogenization, emulsification by use of an emulsifier, use of rotor/stator mixers, Cowles dispersers, or mixing a small volume of material with a conventional agitator at a high agitation rate.

[0040] Where the film of polymer particles comprises a polyurethane-urea polymer, a polyurethane polymer may be prepared using reagents described above, but with an OH/NCO equivalent ratio of less than 1:1 so that free isocyanate groups are present in the product. During production of the particles in the aqueous medium, the free isocyanate groups of the polyurethane polymer film may react with (poly)amines present in the aqueous medium to

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20/60 form urea bonds in the particles.

[0041] A polyamine is an amine with at least two amino groups. For example, the polyamine may be a diamine, and the amine nitrogens in the diamine are equally reactive; that is, all of the amine nitrogens are equally likely to react with another functional group. Alternatively, the amine nitrogens of the diamine may be unequal in reactivity due to spherical hindrance. Examples of suitable diamines include ethylenediamine, 1,2-diaminopropane, 1,5-diamino-2-methyl-pentane, 1,3-diaminopentane, 1,2-diamino-cyclohexane, 1,6-diaminohexane, 1,11-diamino-undecane, 1,12-diamino-dodecane, 3-(cyclohexylamino)propylamine, l-amino-3,3,5-trimethyl-5-amino-methylcyclohexane, (isophorone diamine (IPDA)), 4,4'-diaminodicyclohexyl-methane, 3,3'-dimethyl-4,4'-diamino-dicyclohexyl-methane, 3,3'-[1,4-butanediyl-bis-(oxy)bis]-lpropanamine, methanediamine, and diamino-functional polyamine polyethers having aliphatically linked primary amino groups, examples of which include JEFFAMINE D-230, JEFFAMINE D-400, JEFFAMINE D-2000, and JEFFAMINE D-4000, available from Huntsman Corporation.

[0042] Suitable higher polyamines include primary and secondary triamines and/or tetramines. Examples of suitable triamines include, but are not limited to, diethylenetriamine, dipropylenetriamine, bis(hexamethylene)triamine, and triamino-functional polyether polyamines having aliphatically linked primary amino groups (examples include JEFFAMINE T-403, T-3000, T5000, obtainable from Huntsman Corporation). For example, the amine may be poly(ethylene glycol) or poly(ethylene glycol)

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21/60 propylene) terminated with amine (i.e., an amine at each end, thus making the amine bifunctional), such as a polypropylene having an average molecular weight of 4000 or a polyethylene having an average molecular weight of 600. One skilled in the art will understand that these types of products are sold with a blend of polymers having a relatively wide range of molecular weights, such as 4000 +/- 500 or 600+/200, but that the average molecular weight is 4000 or 600. Monoamines can also be used to react with isocyanate to generate urea linkages. Suitable monoamines include ethanolamine and diethanolamine.

[0043] The polymeric particles used in the first component (a) of the water-based curable film-forming composition may alternatively comprise (II) polymeric acrylic film particles having a core-film morphology and having hydroxyl functional groups, wherein the core of the particles with polymeric acrylic film is prepared from a mixture of monomers comprising ethylenically unsaturated hydrophobic monomers and wherein the film of the polymeric particles with acrylic film is prepared from a mixture of monomers comprising ethylenically unsaturated hydrophilic monomers.

[0044] The core of the acrylic film polymer particles can be prepared in a manner similar to that of the urethane film polymer particles, using similar monomers and techniques. The film of the acrylic film polymer particles is prepared from a monomer mixture comprising ethylenically unsaturated hydrophilic monomers, or from monomers that can be rendered hydrophilic. The term hydrophilic, as

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22/60 As understood in the art, it means that the monomers or repeating units in the resulting polymer have a tendency to interact with, be miscible with, or be dissolved by water and/or other polar substances. The monomers themselves may be polar. By definition, a polar molecule has a net dipole as a result of the opposite charges (i.e., having partial positive charges and partial negative charges) of the asymmetrically arranged polar bonds within its structure. When acid-functional monomers are used, the hydrophilic monomers may be selected to provide the resulting polymer with an acid number of at least 45 mg KOH/g resin, such as at least 60 mg KOH/g resin, or at least 125 mg KOH/g resin, based on the total weight of the resin solids of the polymer. Suitable hydrophilic monomers include one or more of methoxy-poly(ethylene glycol) (meth)acrylate, (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. Ethylenically unsaturated monomers with hydroxyl functionality, such as hydroxyalkyl acrylates and methacrylates, may be used; that is, hydroxyalkyl (meth)acrylates typically having 2 to 4 carbon atoms in the hydroxyalkyl group, such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxy-functional caprolactone adducts, as well as other monomers with beta-hydroxy ester functionality.

Methyl (meth)acrylate, (meth)acrylonitrile, dimethylaminoethyl (meth)acrylate and hydrophilic (meth)acrylamides such as isopropyl-(meth)acrylamide are suitable hydrophilic monomers.

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23/60

[0045] Other suitable hydrophilic monomers include ethylenically unsaturated monomers with amine functionality such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and the like. Protonated (cationic) derivatives of these monomers may also be used. As noted above, monomers containing groups that can become hydrophilic upon polymerization may also be used to form the particle film. For example, ethylenically unsaturated monomers with epoxy functionality such as glycidyl methacrylate and the like can be used to form the polymer, and then the epoxy functionality groups in the resulting polymer can be post-reacted with a compound such as an amino alcohol using known methods to make the polymer more hydrophilic.

[0046] In an exemplary particle, the acrylic film polymer particles have primary hydroxyl functional groups; the core of the acrylic film polymer particles is prepared from a mixture of monomers comprising at least one of n-butyl (meth)acrylate, isobutyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and styrene, and optionally hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; and the film of the polymer particles with acrylic film is prepared from a mixture of monomers comprising at least one of methoxy polyethylene glycol (meth)acrylate, (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-(meth)acrylate

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24/60 hydroxybutyl, hydroxy-functional caprolactone adducts, methyl (meth)acrylate, (meth)acrylonitrile, dimethylaminoethyl (meth)acrylate, isopropyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and ethylene glycol dimethacrylate. These particles are particularly useful in sealant compositions.

[0047] The polymeric particles (I) and (II) have a core/skin structure as noted above. While not intending to be bound by any theory, it is believed that the core/skin structures of the particles contribute to superior film builds achievable with the water-based curable film-forming compositions used as primers and/or sealers on the multilayer coated substrates of the present invention, when compared to those of conventional primer and sealer compositions.

[0048] The particles used in the compositions of the present invention typically have an average particle size of 10 to 300 nm, such that they would be considered nanoparticles. Particle size can be determined by numerous methods known in the art, such as the method described below. Particle size is measured with a Malvern Zetasizer, which is a high-performance two-angle particle size analyzer for improved detection of aggregates and the measurement of small or dilute samples, and very low or high concentration samples using dynamic light scattering. Typical applications of dynamic light scattering are the characterization of particles, emulsions or molecules, which have been dispersed or dissolved in a liquid. The Brownian motion of particles

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25/60 or suspended molecules causes the laser light to be scattered at different intensities. Analysis of these intensity fluctuations yields the speed of Brownian motion and hence the particle size using the Stokes-Einstein relation. The particle sizes reported for all examples are the mean value of the Z mean.

[0049] The first component (a) is present in the water-based curable film-forming composition in amounts of at least 25 weight percent, such as at least 40 weight percent or at least 50 weight percent, and in amounts of at most 95 weight percent, such as at most 90 weight percent or at most 85 weight percent, based on the total weight of the resin solids in the curable film-forming composition.

[0050] The second component (b) in the water-based curable film-forming composition comprises a polyisocyanate crosslinking agent. When used herein, the term polyisocyanate is intended to include blocked (or capped) polyisocyanates as well as unblocked polyisocyanates. Although higher polyisocyanates such as diisocyanate isocyanurates are often used, diisocyanates may also be used. Mixtures of polyisocyanate crosslinking agents may be used.

[0051] Polyisocyanates that can be used as crosslinking agents can be prepared from a variety of isocyanate-containing materials. Examples of suitable polyisocyanates include the following diisocyanates and trimers prepared therefrom: toluene diisocyanate, 4,4'-methylene-bis(toluene)isocyanate, 4,4'-methylene-bis(toluene)isocyanate, and 4,4'-methylene-bis(toluene)isocyanate.

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26/60 cyclohexyl), isophorone diisocyanate, an isomeric mixture of 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, tetramethylxylylene diisocyanate and 4,4'-diphenylmethylene diisocyanate. Isocyanate prepolymers, e.g. reaction products of polyisocyanates with polyols, can also be used. The polyisocyanate crosslinking agent is usually emulsifiable or dispensable in water for use in the water-based curable film-forming compositions of the present invention.

[0052] If the polyisocyanate is to be blocked or capped, any aliphatic, cycloaliphatic or aromatic alkyl phenolic or monoalcohol compound known in the art may be used as a capping agent for the polyisocyanate. Examples of suitable blocking agents include those materials that would block at elevated temperatures such as lower aliphatic alcohols including methanol, ethanol and n-butanol; cycloaliphatic alcohols such as cyclohexanol; aromatic alkyl alcohols such as phenylcarbinol and methylphenylcarbinol; and phenolic compounds such as phenol itself and substituted phenols in which the substituents do not affect coating operations, such as cresol and nitrophenol. Glycol ethers can also be used as capping agents. Suitable glycol ethers include ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether, and propylene glycol methyl ether. Other suitable capping agents include oximes such as methyl ethyl ketoxime, acetone oxime, and cyclohexanone oxime, lactams such as epsilon-caprolactam, pyrazoles such as dimethyl pyrazole, and amines such as

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27/60 dibutylamine.

[0053] The amount of crosslinking agent in the curable film-forming composition generally ranges from 5 to 75 weight percent, based on the total weight of resin solids in the curable film-forming composition. For example, the minimum amount of crosslinking agent may be at least 5 weight percent, often at least 10 weight percent, and more often at least 15 weight percent. The maximum amount of crosslinking agent may be 75 weight percent, more often 60 weight percent, or 50 weight percent. Ranges of crosslinking agent may include, for example, 5 to 50 weight percent, 5 to 60 weight percent, 10 to 50 weight percent, 10 to 60 weight percent, 10 to 75 weight percent, 15 to 50 weight percent, 15 to 60 weight percent, and 15 to 75 weight percent.

[0054] The water-based curable film-forming composition may further comprise (c) a water-dispersible acrylic polymer with hydroxyl functionality. Suitable acrylic compounds include copolymers of one or more alkyl esters of acrylic acid or methacrylic acid, optionally together with one or more other polymerizable ethylenically unsaturated monomers. Suitable alkyl esters of acrylic acid or methacrylic acid include aliphatic alkyl esters containing from 1 to 30, and often from 4 to 18, carbon atoms in the alkyl group. Non-limiting examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Other monomers

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Suitable copolymerizable ethylenically unsaturated 28/60 compounds include vinyl aromatic compounds such as styrene and vinyl toluene; nitriles such as acrylonitrile and methacrylonitrile; vinyl and vinylidene halides such as vinyl chloride and vinylidene fluoride; and vinyl esters such as vinyl acetate.

[0055] The water-dispersible acrylic polymer (c) may include hydroxyl-functional groups, which are often incorporated into the polymer by including one or more hydroxyl-functional monomers in the reactants used to produce the copolymer. The ratio of primary hydroxyl functional groups to secondary hydroxyl functional groups in the acrylic copolymer is usually at least 2.5:1. Useful hydroxyl-functional monomers include hydroxyalkyl acrylates and methacrylates, typically having 2 to 4 carbon atoms in the hydroxyalkyl group, such as hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, hydroxy-functional adducts of caprolactone and hydroxyalkyl acrylates, and corresponding methacrylates, as well as beta-hydroxy ester-functional monomers described below. Acrylic polymer can also be prepared with N-(alkoxymethyl)acrylamides and N-(alkoxymethyl)methacrylamide.

[0056] Beta-hydroxy ester functional monomers can be prepared from ethylenically unsaturated epoxy functional monomers and carboxylic acids having from about 13 to about 20 carbon atoms, or from ethylenically unsaturated acid functional monomers and epoxies containing at least 5 carbon atoms that are not polymerizable with the ester functional monomer.

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29/60 ethylenically unsaturated acid functionality.

[0057] Useful ethylenically unsaturated epoxy-functional monomers used to prepare the beta-hydroxy ester-functional monomers include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methallyl glycidyl ether, 1:1 (molar) adduct of ethylenically unsaturated monoisocyanates with hydroxy-functional monoepoxides such as glycidol, and glycidyl esters of polymerizable polycarboxylic acids such as maleic acid. (Note: These epoxy-functional monomers can also be used to prepare epoxy-functional acrylic polymers.) Examples of carboxylic acids include saturated monocarboxylic acids such as isostearic acid and unsaturated aromatic carboxylic acids.

[0058] Useful ethylenically unsaturated acid-functional monomers used to prepare the beta-hydroxy ester-functional monomers include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid; and monoesters of dicarboxylic acids such as monobutyl maleate and monobutyl itaconate. Typically, the ethylenically unsaturated acid-functional monomer and the epoxy compound react in a 1:1 equivalent ratio. The epoxy compound does not contain ethylenic unsaturation that would participate in free radical-initiated polymerization with the unsaturated acid-functional monomer. Useful epoxy compounds include 1,2-pentene oxide, styrene oxide, and glycidyl ethers or esters, often containing 8 to 30

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30/60 carbon atoms, such as butyl glycidyl ether, octyl glycidyl ether, phenyl glycidyl ether and para-(t-butyl) phenyl glycidyl ether. Particular glycidyl esters include those of the structure:

The II CH₂ — CH—CI-12 —o—C — R o

where R is a hydrocarbon radical containing from about 4 to about 26 carbon atoms. Typically, R is a branched hydrocarbon group having from about 8 to about 10 carbon atoms, such as neopentanoate, neoheptanoate, or neodecanoate. Suitable glycidyl esters of carboxylic acids include VERSATIC ACID 11 (versatic acid 11) and CARDURA E, each of which is commercially available from Shell Chemical Co.

[0059] Acrylic polymers can be prepared via aqueous emulsion polymerization techniques and used directly in the preparation of aqueous coating compositions. Most commonly, acrylic polymers are prepared via organic solution polymerization with salt-forming groups such as acid or amine groups, and after neutralization of these groups with a base or acid, the polymers can be dispersed in an aqueous medium. In general, any method for producing such polymers that is known to those skilled in the art using art-recognized amounts of monomers may be used. Typically, the acrylic polymer has a glass transition temperature (T_g) calculated greater than 10°C, often around 29°C.

[0060] Acrylic polymer is often added

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31/60 water-dispersible (c) in the water-based curable film-forming composition in the form of an aqueous emulsion of the acrylic polymer, and typically the acrylic polymer is prepared from a reactant mixture comprising butyl acrylate, methyl methacrylate, styrene, hydroxyethyl methacrylate, acrylic acid, and a reaction product of acrylic acid and a glycidyl ester.

[0061] When used, the water-dispersible acrylic polymer (c) is usually present in the first component of the water-based curable film-forming composition in an amount of up to 30 weight percent, based on the total weight of resin solids in the first component of the curable film-forming composition. The water-dispersible acrylic polymer may be used as a grinding vehicle for the pigment in the first component. At least a portion (less than 100 percent) of the aqueous acrylic polymer emulsion may be used as a grinding vehicle, or up to 100 percent (i.e., all of it).

[0062] The water-based curable film-forming compositions used in the present invention may contain adjunct ingredients conventionally used in coating compositions. Optional ingredients such as, for example, plasticizers, surfactants, thixotropic agents, anti-gassing agents, organic co-solvents, flow controllers, antioxidants, UV light absorbers, and similar additives conventional in the art may be included in the composition. Typically, these ingredients are present at up to about 40% by weight, based on the total weight of resin solids.

[0063] The curable film-forming compositions based on

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32/60 water of the present invention usually have a total solids content of at least 50 weight percent, and a VOC of up to 2.1.

[0064] It is often not practical to store ambient cure coatings as a one-component composition, but instead they must be stored as multi-component coatings to prevent the components from curing prior to use. The term multi-component coatings refers to coatings in which several components are kept separately until shortly before application. The compositions of the present invention are usually multi-component coatings, such as a two-component coating, wherein the first component (a) is a first component and the second component (b) is a second component. When the hydroxyl-functional water-dispersible acrylic polymer (c) is present, it may be a separate third component and/or combined with one or both of the other two components. It is usually present in at least the first component since it is often used as a grinding vehicle for the pigment in the first component.

[0065] In the multilayer coated substrates of the present invention comprising both a primer composition and a sealer composition, either or both of them comprise any of the water-based curable film-forming compositions described above. If both comprise a water-based curable film-forming composition described above, they may be the same or different. If the primer composition does not comprise

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33/60 any of the water-based curable film-forming compositions described above, it may be any conventional primer composition known in the art. Likewise, if the sealer composition does not comprise any of the water-based curable film-forming compositions described above, it may be any conventional sealer composition known in the art. In any case, at least one of them comprises a water-based curable film-forming composition described above.

[0066] After application of the sealant composition, light sanding of the sealant may be carried out, although this is often not necessary, and at least one additional coating composition may be applied. Usually this comprises one or more top coats. A topcoat provides, among other things, aesthetic properties such as color to the substrate, and may be a monocoat or a composite coating system comprising a colored basecoat followed by a clearcoat. Multicoat coated substrates of the present invention, prepared using waterborne primer and/or sealer compositions of the present invention, demonstrate minimal to any defects in the form of cracking and/or microporosity.

[0067] Each coating composition (primer, sealer, tech.) can be applied by known application techniques, such as dipping or immersion, spraying, intermittent spraying, dipping followed by spraying, spraying followed by dipping, brushing or rolling. Usual spraying techniques and equipment for aerial spraying and electrostatic spraying, manual or automatic methods can be used.

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34/60

[0068] After application of a composition, a film is formed by removing the solvent, i.e., organic solvent and water, from the film by heating or by a period of air drying. Appropriate drying conditions will depend on the particular composition and/or application, but in some cases a drying time of about 5 to 30 minutes at a temperature of about room temperature to 60°C will be sufficient. If desired, more than one coating layer of each composition may be applied. Usually between coatings, the previously applied coating is dried quickly, i.e., exposed to ambient conditions for the desired period of time.

[0069] The primer composition of the present invention can be applied in no more than two coats and further demonstrates a dry film thickness of at least 50 microns or at least 60 microns, or at least 100 microns to a maximum of 125 microns. This is not usually possible with waterborne primer compositions, which typically require three or more coats to achieve comparable film build, resulting in film defects such as cracking and/or microcracking. Dry film thicknesses can be measured 24 hours after application of the coating when cured at ambient temperatures, using a DUALSCOPE FMP40C with an FD13H probe, available from Fischer Technologies, Inc., according to the manufacturer's instructions.

[0070] The primer composition of the present invention is typically curable at a temperature below 60°C, often below 30°C. It is also sandable within fifteen minutes of application. The primer composition of the present invention can be cured overnight in

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35/60 ambient temperatures or by forced curing for 30 minutes at 60°C.

[0071] When both a primer and a sealer are used, the sealer composition may be applied over the primer composition, usually after the primer has been sanded. The sealer composition of the present invention may be applied in no more than two coats and further demonstrates a dry film thickness of 20 to 50 microns. Typically, the sealer composition of the present invention is curable at a temperature below 60°C, often below 30°C. Light sanding or removal of surface imperfections is possible within fifteen minutes of drying.

[0072] Each of the features and examples described above, and combinations thereof, are encompassed by the present invention. Thus, the present invention is designed for the following non-limiting aspects: in a first aspect, the present invention provides a multilayer coated substrate comprising: (A) a substrate; (B) a primer composition applied directly to a surface of the substrate, forming a first coating; (C) a sealing composition applied over the first coating; and (D) at least one topcoat applied over the sealing composition; wherein the sealing composition comprises a water-based curable film-forming composition, the water-based curable film-forming composition comprising: (a) a first component comprising an aqueous dispersion of a pigment and (i) urethane film polymer particles having a core-film morphology and having hydroxyl functional groups, wherein the core of the urethane film polymer particles is prepared

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36/60 from a mixture of monomers comprising ethylenically unsaturated hydrophobic monomers and the core of the particles with a urethane polymer film comprising a polyurethane or polyurethane-urea polymer; or (II) acrylic film polymer particles having a core-film morphology and having hydroxyl functional groups, the core of the acrylic film polymer particles being prepared from a monomer mixture comprising ethylenically unsaturated hydrophobic monomers and the film of the acrylic film polymer particles being prepared from a monomer mixture comprising ethylenically unsaturated hydrophilic monomers; (b) a second component comprising a polyisocyanate crosslinking agent; and, optionally, (c) a water-dispersible acrylic polymer with hydroxyl functionality.

[0073] In a second aspect, there is provided a multilayer coated substrate according to the first aspect above, the primer composition comprising a water-based curable film-forming composition, the water-based curable film-forming composition comprising: (a) a first component comprising an aqueous dispersion of a pigment and (I) urethane film polymer particles having a core-film morphology and having hydroxyl functional groups, wherein the core of the urethane film polymer particles is prepared from a monomer mixture comprising ethylenically unsaturated hydrophobic monomers and wherein the core of the urethane film polymer particles comprises a polyurethane or polyurethane-urea polymer; or (II)

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37/60 polymeric particles with acrylic film having a core-film morphology and having hydroxyl functional groups, the core of the polymeric particles with acrylic film being prepared from a mixture of monomers comprising ethylenically unsaturated hydrophobic monomers and the film of the polymeric particles with acrylic film being prepared from a mixture of monomers comprising ethylenically unsaturated hydrophilic monomers; (b) a second component comprising a polyisocyanate crosslinking agent; and, optionally, (c) a water-dispersible acrylic polymer with hydroxyl functionality.

[0074] In a third aspect, on a multi-layer coated substrate according to the second aspect above, the primer composition is applied in no more than two coats and demonstrates a dry film thickness of 50 to 150 microns.

[0075] In a fourth aspect, in a multilayer coated substrate according to any of the above aspects, the first component in the water-based curable film-forming composition comprises an aqueous dispersion of a pigment and the urethane film-forming polymer particles of (I), wherein the core of the urethane film-forming polymer particles is prepared from a monomer mixture comprising: (1) at least one of n-butyl (meth)acrylate, isobutyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and styrene, and optionally further comprising: (2) at least one of styrene (meth)acrylate, ...

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38/60 hydroxyethyl and hydroxypropyl (meth)acrylate.

[0076] In a fifth aspect, in a multilayer coated substrate according to any one of the first to third aspects above, the first component in the sealant composition comprises an aqueous dispersion of a pigment and the acrylic film polymer particles of (II), the core of the acrylic film polymer particles being prepared from a mixture of monomers comprising: (1) at least one of n-butyl (meth)acrylate, isobutyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and styrene, and optionally further comprising: (2) at least one of hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; and wherein the film of the polymeric particles with acrylic film is prepared from a mixture of monomers comprising at least one of methoxy-polyethylene glycol (meth)acrylate, (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxy-functional caprolactone adducts, methyl (meth)acrylate, (meth)acrylonitrile, dimethylaminoethyl (meth)acrylate, isopropyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and ethylene glycol dimethacrylate.

[0077] In a sixth aspect, on a multi-layer coated substrate according to any of the above aspects, the sealant composition is applied in no more than two layers.

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39/60 coatings and demonstrates a dry film thickness of 20 to 50 microns.

[0078] In a seventh aspect, in a substrate coated with multiple layers according to any of the above aspects, the sealant composition is curable at a temperature below 60°C.

[0079] In an eighth aspect, in a multilayer coated substrate according to any of the above aspects, the sealant composition further comprises the water-dispersible acrylic polymer (c) in the form of an aqueous emulsion of an acrylic polymer, the acrylic polymer being prepared from a reactant mixture comprising butyl acrylate, methyl methacrylate, styrene, hydroxyethyl methacrylate, acrylic acid, and a reaction product of acrylic acid and a glycidyl ester.

[0080] In a ninth aspect, in a multilayer coated substrate according to the eighth aspect above, at least a portion of the aqueous emulsion of the acrylic polymer is used as a grinding vehicle for the pigment.

[0081] In a tenth aspect, the present invention provides a multilayer coated substrate, comprising: (A) a substrate; (B) a primer composition applied directly to a surface of the substrate, forming a first coating; (C) a sealer composition applied over the first coating; and (D) at least one topcoat applied over the sealer composition; wherein the primer composition comprises a water-based curable film-forming composition, the water-based curable film-forming composition comprising: (a) a first component comprising an aqueous dispersion of a

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40/60 pigment and (I) urethane film polymer particles having a core-film morphology and having hydroxyl functional groups, the core of the urethane film polymer particles being prepared from a monomer mixture comprising ethylenically unsaturated hydrophobic monomers and the core of the urethane film polymer particles comprising a polyurethane or polyurethane-urea polymer; or (II) acrylic film polymer particles having a core-film morphology and having hydroxyl functional groups, the core of the acrylic film polymer particles being prepared from a monomer mixture comprising ethylenically unsaturated hydrophobic monomers and the film of the acrylic film polymer particles being prepared from a monomer mixture comprising ethylenically unsaturated hydrophilic monomers; (b) a second component comprising a polyisocyanate crosslinking agent; and, optionally, (c) a water-dispersible acrylic polymer with hydroxyl functionality.

[0082] In an eleventh aspect, there is provided a multilayer coated substrate according to the above tenth aspect, the sealing composition comprising a water-based curable film-forming composition, the water-based curable film-forming composition comprising: (a) a first component comprising an aqueous dispersion of a pigment and (I) urethane film polymer particles having a core-film morphology and having hydroxyl functional groups, the core of the urethane film polymer particles being prepared

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41/60 from a mixture of monomers comprising ethylenically unsaturated hydrophobic monomers and the core of the urethane film polymer particles comprising a polyurethane or polyurethane-urea polymer; or (II) acrylic film polymer particles having a core-film morphology and having hydroxyl functional groups, the core of the acrylic film polymer particles being prepared from a monomer mixture comprising ethylenically unsaturated hydrophobic monomers and the film of the acrylic film polymer particles being prepared from a monomer mixture comprising ethylenically unsaturated hydrophilic monomers; (b) a second component comprising a polyisocyanate crosslinking agent; and, optionally, (c) a water-dispersible acrylic polymer with hydroxyl functionality.

[0083] In a twelfth aspect, on a multi-layer coated substrate according to the above eleventh aspect, the sealant composition is applied in no more than two coats and demonstrates a dry film thickness of 20 to 50 microns.

[0084] In a thirteenth aspect, on a multi-layer coated substrate according to any one of the tenth to twelfth aspects above, the primer composition is applied in no more than two coats and demonstrates a dry film thickness of 50 to 150 microns.

[0085] In a fourteenth aspect, in a multilayer coated substrate according to any one of the tenth to thirteenth aspects above, the first component in the primer composition comprises an aqueous dispersion of a

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42/60 pigment and the urethane film polymer particles of (I), wherein the core of the urethane film polymer particles is prepared from a mixture of monomers comprising: (1) at least one of n-butyl (meth)acrylate, isobutyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and styrene, and optionally further comprising: (2) at least one of hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate.

[0086] In a fifteenth aspect, in a multilayer coated substrate according to any one of the tenth to fourteenth aspects above, the primer composition is curable at a temperature below 60°C.

[0087] In a sixteenth aspect, in a multilayer coated substrate according to any one of the tenth to fifteenth aspects above, the primer composition further comprises the water-dispersible acrylic polymer (c) in the form of an aqueous emulsion of an acrylic polymer, the acrylic polymer being prepared from a reactant mixture comprising butyl acrylate, methyl methacrylate, styrene, hydroxyethyl methacrylate, acrylic acid, and a reaction product of acrylic acid and a glycidyl ester.

[0088] In a seventeenth aspect, in a multilayer coated substrate according to the above sixteenth aspect, at least a portion of the aqueous emulsion of the acrylic polymer is used as a grinding vehicle for the pigment.

[0089] In an eighteenth aspect, the present invention provides a multilayer coated substrate comprising:

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43/60 (A) a substrate; (B) a first composition comprising a primer or sealer composition applied directly to a surface of the substrate, forming a first coating; and (C) at least one topcoat applied over the first coating; wherein the first composition comprises a water-based curable film-forming composition, the water-based curable film-forming composition comprising: (a) a first component comprising an aqueous dispersion of a pigment and (I) urethane film polymer particles having a core-film morphology and having hydroxyl functional groups, wherein the core of the urethane film polymer particles is prepared from a mixture of monomers comprising ethylenically unsaturated hydrophobic monomers and wherein the core of the urethane film polymer particles comprises a polyurethane or polyurethane-urea polymer; or (II) acrylic film polymer particles having a core-film morphology and having hydroxyl functional groups, the core of the acrylic film polymer particles being prepared from a monomer mixture comprising ethylenically unsaturated hydrophobic monomers and the film of the acrylic film polymer particles being prepared from a monomer mixture comprising ethylenically unsaturated hydrophilic monomers; (b) a second component comprising a polyisocyanate crosslinking agent; and, optionally, (c) a water-dispersible acrylic polymer with hydroxyl functionality; wherein when the first composition comprises a primer composition, the first

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44/60 coating will be applied in not more than two coats and demonstrate a dry film thickness of 50 to 150 microns, and when the first composition comprises a sealant composition, the first coating composition will be applied in not more than two coats and demonstrate a dry film thickness of 20 to 50 microns.

[0090] The following examples are intended to illustrate variations of the invention, and are not to be construed as limiting the invention in any way. Unless otherwise indicated, all parts are given by weight.

Examples

Example A

[0091] A polyester diol for use in preparing a urethane dispersion was prepared as follows: Into a 4-necked round bottom flask equipped with a stirrer, gas inlet, packed column, thermometer, and condenser were added 2478 g of 1,6-hexanediol, 1456 g of neopentyl glycol, 1533 g of adipic acid, 2324 g of isophthalic acid, 343 g of maleic anhydride, 7.2 g of butylstannoic acid, and 7.2 g of triphenyl phosphite. The reaction mixture was heated in stages in an atmosphere of N₂ inert to a maximum temperature of 230 °C while ensuring that the head temperature did not exceed 100 °C. When the acid number reached 10, a Dean Stark siphon was attached to the flask and 100 g of toluene was added to facilitate removal of the final amounts of water. The reaction was continued until the residual acid number was less than 2, after which the reaction was cooled to 180 °C and a vacuum was applied for 30 minutes. The resulting viscous resin had 99% solids, a viscosity of 80% solids in butyl glycol of Z1

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45/60 (Gardner-Holdt), and a theoretical OH index of 110. Example B

[0092] A urethane dispersion for use in preparing urethane film particles was prepared as follows: Into a 4-necked round bottom flask equipped with a stirrer, gas inlet tube, addition funnel, thermometer, and condenser were added 120.6 g of dimethylolpropionic acid, 616.2 g of the polyester diol of Example A, 1.5 g of triphenyl phosphite, 1.9 g of Ionol, 1.5 g of dibutyltin dilaurate. The mixture was heated at 80°C for 30 min to dissolve the dimethylolpropionic acid. Then, 613.5 g of butyl methacrylate was added and the mixture was cooled to 50°C and kept in an air atmosphere. Then, 466.2 g of isophorone diisocyanate was added via the addition funnel over 20 min while ensuring that the temperature did not exceed 70°C. Then, the addition funnel was rinsed with 30 g of butyl methacrylate, and the mixture was heated to 100°C. The reaction was maintained at 100°C for 2-3 hours until the NCO index stabilized. Then, 160.8 g of trimethylolpropane and 81.6 g of pentaerythritol were added, and the reaction was maintained for 1 hour. After this time, infrared analysis showed complete consumption of isocyanate. The solution was cooled to 90°C, 145 g of butyl glycol and 48.1 g of dimethylethanolamine were added, and stirred for 10 minutes. Then, 1923 g of the above solution was dispersed in 217.6 g of deionized water that was preheated to 30 °C in a 4-necked round-bottom flask in an air atmosphere. The resulting small particle size water-based dispersion had a solids content of 31.5%, a viscosity of 228 cps, a pH value of d 6.7, and a particle size of

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46/60 particle of approximately 50 nm.

Example C

[0093] A dispersion of urethane film particles was prepared as follows: in a 4-necked round bottom flask equipped with a stirrer, a gas inlet for spraying N₂, thermometer and condenser, were added 2750 g of the urethane dispersion of Example B, 410 g of deionized water, 74.3 g of 2-ethylhexyl acrylate, 11 g of butyl methacrylate, 222.8 g of styrene and 165 g of hydroxyethyl methacrylate. The solution was heated to 35°C and sparged with N₂ for 30 minutes to remove dissolved oxygen. Then, a solution of 0.0033 g of ferrous ammonium sulfate in 25 g of deionized water was added followed by the addition of a solution of 3.18 g of isoascorbic acid, 3.21 g of dimethylethanolamine in 75 g of deionized water. The solution was stirred for 5 minutes and approximately 80% of a solution of 14.5 g of a 35% hydrogen peroxide solution diluted in 120 g of deionized water was added over approximately 5 minutes. This resulted in a heat evolution with a maximum temperature of 68 °C. The reaction was then held at 65 °C for 30 min, then cooled to 30 °C. The remainder of the hydrogen peroxide solution was then added over 2-3 min. A solution of 17.8 g of dimethylethanolamine in 35 g of deionized water was added. The nearly clear solution had a solids content of 43%, a viscosity of 290 cps, a pH value of 7.5, and a particle size of approximately 60 nm.

Example D

[0094] A dispersion of film-like particles was prepared

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47/60 urethane as follows: in a 4-necked round bottom flask equipped with a stirrer, a gas inlet for spraying N₂, thermometer and condenser, 500 g of the urethane dispersion of Example B, 95 g of deionized water, 22.5 g of butyl acrylate, 7.5 g of butyl methacrylate, 56.2 g of styrene and 75 g of hydroxypropyl methacrylate were added. Then, a solution of 0.7 g of mercaptopropionic acid, 0.6 g of dimethylethanolamine in 20 g of deionized water was added. The solution was heated to 35°C and sparged with N₂ for 30 minutes to remove dissolved oxygen. Then, a solution of 0.43 g of LUPEROX TBH70x (t-butyl hydroperoxide) in 15 g of deionized water was added. Then, a solution of 0.0069 g of ferrous ammonium sulfate, 0.43 g of sodium metabisulfite, and 0.21 g of dimethylethanolamine in 50 g of deionized water was added for approximately 5 minutes to initiate polymerization. This resulted in a rapid release of heat with a maximum temperature of 70°C. The reaction was then maintained at 65°C for 30 min, then cooled to 30°C. Then, a solution of 2.5 g of dimethylethanolamine in 5 g of deionized water was added. The nearly clear solution had a solids content of 44%, a viscosity of 224 cps, and a pH value of 8.2.

Example E

[0095] An acrylic dispersion for use as component (c) in the water-based curable film-forming composition was prepared as follows: In a 4-necked round bottom flask equipped with a stirrer, gas inlet to spray N₂, thermometer and condenser, 289 g of CARDURA E, 190 g of DOWANOL PM were added and the mixture was heated in

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48/60 reflux (approximately 135°C). To an adding funnel were added 80 g of t-butyl peracetate (LUPEROX 7M50) and 40 g of DOWANOL PM, to a second adding funnel were added 238 g of butyl acrylate, 190.4 g of methyl methacrylate, 428.4 g of styrene, 375.7 g of hydroxyethyl methacrylate and 86.7 g of acrylic acid. The initiator solution is added over a total of 4 hours, the monomer addition occurs over a total of 3 hours (not including shutdowns - see below). The initiator and monomer additions are started. After 40 minutes the monomer addition is stopped, an additional 30.6 g of acrylic acid and 5 g of DOWANOL PM are added and the mixture is stirred for 10 minutes. The monomer addition is restarted (50 minutes). After another 30 minutes (total of 80 minutes), the monomer addition is stopped and 30.6 g of acrylic acid and 5 g of DOWANOL PM are added and the mixture is stirred for 10 minutes. The monomer addition is restarted (90 minutes). After another 40 minutes, the monomer addition is stopped and 30.6 g of acrylic acid and 5 g of DOWANOL PM are added and the mixture is stirred for 10 minutes. The monomer addition is restarted (140 minutes), and the monomer addition is complete after 40 minutes. After the additions are complete, the reaction is held for 1.5 hours. The resin is then cooled to 90°C, followed by the addition of 90.8 g of DMEA. A fine particle size dispersion is produced by dispersing 1845 g of deionized water that has been preheated to 70°C. The final dispersion had a solids content of 40%, a viscosity of 700 cps, a pH value of 7.5, and a particle size of approximately 90 nm.

Example F

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[0096] A hyperbranched acrylic polymer for use in the preparation of acrylic film particles was prepared as follows: A 300 cm electrically heated continuous stirred tank reactor was filled with³ with an internal cooling coil with butyl glycol and the temperature was adjusted to 210°C. The following load was fed into the reactor at a rate of 100 mL/min - 1600 g of methyl methacrylate, 1460 g of butyl acrylate, 400 g of hydroxyethyl methacrylate, 400 g of acrylic acid and 140 g of allyl methacrylate, 320 g of butyl glycol and 160 g of t-butyl peroxide at a rate of 100 mL/min. The residence time in the reactor was approximately 3 minutes. The reactor was kept volumetrically filled at a pressure of 400-600 psi, and the temperature was maintained constant at approximately 210 °C. The reactor production was drained to a 3000 cm continuous stirred tank reactor.³ equipped with a pressure relief valve and set at 170°C. Then, an initiator solution was added to the contents of the tank reactor at a rate of 3 mL/min. The composition of this solution was 80 g of butyl glycol and 40 g of t-butyl peroxide. When approximately 1500 g had been collected in the second reactor, the outlet valve was opened and the material was fed into a collection vessel at a rate that maintained a constant fill level, resulting in a residence time of 20 minutes. The resulting hyperbranched acrylic polymer had a solids content of 87.5%, an acid number of 65, a number average molecular weight of 1870, and a weight average molecular weight of 18000.

Example G

[0097] A dispersion of

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50/60 particle with acrylic film: In a 4-necked round bottom flask equipped with a stirrer, a gas inlet for spraying N₂, thermometer and condenser, 527 g of Example F, 47 g of dimethylethanolamine and 1914 g of deionized water that was preheated to 50°C were added. The solution was maintained at 50°C and sparged with N₂ for 30 min to remove dissolved oxygen. A solution of 3.46 g of ascorbic acid and 5.2 g of dimethylethanolamine in 20 g of deionized water was added, followed by a solution of 0.027 g of ferrous ammonium sulfate in 4 g of deionized water. In an addition funnel, 6 g of t-butyl hydroperoxide (LUPEROX TBH70X) in 114 g of deionized water was added. In a separate addition funnel, 316.8 g of butyl acrylate, 316.8 g of butyl methacrylate, 316.8 g of styrene, and 158.3 g of hydroxyethyl methacrylate were added. The monomer and initiator solutions were then added simultaneously over 2.5 h. After the additions were complete, the polymer was kept for 1 h at 50 °C. Then, a solution of 11.7 g of dimethylethanolamine in 10 g of deionized water was added. The final dispersion had a solids content of 42.5%, a viscosity of 170 cps, a pH value of 7.8, and a particle size of 75 nm.

Sealer:

[0098] Urethane acrylate sealant coatings were prepared by first producing an abrasive paste (Examples H and I) prepared with the following ingredients. The binder portion of the abrasive paste may consist of the urethane film particles of Example C or the acrylic dispersion of Example E.

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Table 1. Abrasive pastes for polyurethane acrylate sealing coating

<td></td><td></td><td>Example H</td><td>Example I</td>

<td>Load</td><td>Name</td><td>Weight (g)</td><td>Weight (g)</td>

<td>1 (a)</td><td>Urethane film particles from Example C</td><td> 833</td><td> —</td>

<td>1 (b)</td><td>Acrylic dispersion of Example E</td><td> —</td><td> 527</td>

<td> 2</td><td>DISPERBYK 024¹</td><td> 16</td><td> 10</td>

<td> 3</td><td>DISPEX® Ultra PA 4550²</td><td> 21</td><td> 13</td>

<td> 4</td><td>SURFYNOL 104E³</td><td> 25</td><td> 16</td>

<td> 5</td><td>Carbon black</td><td> 25</td><td> 15</td>

<td> 6</td><td>Titanium dioxide</td><td> 546</td><td> 343</td>

<td> 7</td><td>Barium sulfate</td><td> 614</td><td> 390</td>

<td> 8</td><td>Talc</td><td> 437</td><td> 277</td>

<td> 9</td><td>Calcium carbonate</td><td> 240</td><td> 152</td>

<td> 10</td><td>Water DL</td><td> 94</td><td> 142</td>

<td> 11</td><td>10 DMEA/90 DI water</td><td> 53</td><td> 30</td>

<td> 12</td><td>Water DL</td><td> 287</td><td> 121</td>

¹Obtainable from BYK²Obtainable from BASF³Obtainable from Air Products

[0099] The ingredients of charges 1 through 10 were first dispersed with a high speed Cowles mixer for 30 minutes. Charge 11 was added and agitation continued for 30 minutes. Charge 12 was added and the mixture was milled in a Hockmeyer micro mill until a Hegman of 7 was achieved.

[0100] The sealing coating compositions of the present invention were prepared as shown below:

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Table 2. Acrylate polyurethane sealant coating compositions

<td></td><td></td><td>Example J</td><td>Example K</td>

<td>Load</td><td>Name</td><td>Weight (g)</td><td>Weight (g)</td>

<td>1 (a)</td><td>Abrasive paste from Example H</td><td> 375</td><td> —</td>

<td>1 (b)</td><td>Abrasive paste from Example I</td><td> —</td><td> 367</td>

<td> 2</td><td>Urethane film particles from Example C</td><td> 254</td><td> 244</td>

<td> 4</td><td>Hardener EHW8224¹</td><td> 97</td><td> 103</td>

<td> 5</td><td>T494 Reducer²</td><td> 73</td><td> 88</td>

¹Water-reducible isocyanate available from PPG Industries Water-based reducer available from PPG Industries

[0101] The final paints had a solids content of 53% at room temperature viscosity and a 20 second application time in a DIN #4 cup.

[0102] The sealer coating compositions of Example J and Example K were spray applied under ambient conditions to 24 x 34 x 0.04 aluminum door skin panels over a gray coil coating. The substrate panels were obtained from Q-Lab of Westlake, Ohio. The gray coil coating was first scuffed using a Scotch-Brite scouring pad. The coating compositions were applied to a coating and then dried. The dry film thickness was 25-33 microns. The control coat was a solventborne refinish sealer commercially available from PPG Industries, Inc., as ECS25. This was applied in one coat and dried rapidly under ambient conditions from glossy to matte. The dry film thickness was approximately 25-28 microns. Film thicknesses of all coatings were measured using a DUALSCOPE FMP40C with an FD13H probe, obtainable from Fischer Technologies, Inc., according to the manufacturer's instructions.

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53/60

[0103] Sealer coatings were tested for their air drying ability by a procedure called very fine particle removal. Removal in a sealer is done prior to the application of the base coat if there is dust or other very fine particles to be removed. It is a very light hand sanding. Removal in the sealers was accomplished with 800 grit sandpaper obtainable from 3M within 10 minutes after the coatings were finished matte. Removal is considered a pass if the coating is not tacky, the sandpaper does not drag, and a powder forms under the sandpaper. The hardness of sealer coatings can also be measured via a Konig pendulum hardness analyzer using ASTM D4366.

[0104] After approximately 30 minutes, the sealer coats were top coated. The first top coat was a base coat available from PPG Industries, T409, applied to the door skin panels in two coats and dried in forced air after each coat. The total dry film thickness was 4-6 microns. A commercially available 2K clear coat refinish coat from PPG Industries, Inc., as DC2000, was then applied over the coated panel in two coats with a quick dry between coats. The clear coated panels were allowed to dry overnight. The dry film thickness was approximately 50 microns.

[0105] The appearance of the coating stack was measured with a WAVESCAN Byk and the results are reported as DOI/du/Wa/Wb/Wc/Wd. The measurement Wa is for short wavelength structure (0.01-0.3 mm). Wc for long wavelengths

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54/60 intermediate wavelengths (1-3 mm) and Wd for longer wavelength structures (10-30 mm). Smoothness is a particularly important property for an automotive coating and can depend on the relative roughness of all layers in the coating stack. Smaller du and W values and larger DOI values indicate a smoother film.

Table 3. Particle removal rating (denib) and appearance values

<td></td><td>Denib</td><td>DOI</td><td>of</td><td>Wa</td><td>Wb</td><td>WC</td><td>Wd</td>

<td>Example J</td><td>Raisin</td><td> 87, 9</td><td> 6,4</td><td> 25,2</td><td> 39,5</td><td> 28</td><td> 35,2</td>

<td>Example K</td><td>Raisin</td><td> 88, 9</td><td> 6, 8</td><td> 25, 1</td><td> 35, 6</td><td> 24,2</td><td> 26, 8</td>

<td>ECS25 Control</td><td>Raisin</td><td> 85</td><td> 3, 1</td><td> 19,1</td><td> 49,9</td><td> 40, 6</td><td> 34,4</td>

Acrylic sealant coatings were prepared by first producing an abrasive paste (Example L) prepared from the following ingredients. The binder portion of the abrasive paste may consist of the acrylic dispersion of Example E.

Table 4. Abrasive paste for acrylic sealer coating

<td></td><td></td><td>Example L</td>

<td>Load</td><td>Name</td><td>Weight (g)</td>

<td> 1</td><td>Acrylic dispersion of Example E</td><td> 490</td>

<td> 2</td><td>DISPERBYK 024¹</td><td> 9</td>

<td> 3</td><td>DISPEX® Ultra PA 4550²</td><td> 12</td>

<td> 4</td><td>SURFYNOL 104E³</td><td> 15</td>

<td> 5</td><td>Carbon black</td><td> 5</td>

<td> 6</td><td>Titanium dioxide</td><td> 321</td>

<td> 7</td><td>Barium sulfate</td><td> 361</td>

<td> 8</td><td>Talc</td><td> 257</td>

<td> 9</td><td>Calcium carbonate</td><td> 141</td>

<td> 10</td><td>Water DL</td><td> 131</td>

<td>11 (a) 11 (b)</td><td>10 DMEA/90 DI water 5 DMEA/95 of water Dl</td><td> 57</td>

<td> 12</td><td>Water DL</td><td> 131</td>

¹Obtainable from BYK²Obtainable from BASF

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55/60 ³Obtainable from Air Products

[0106] The ingredients of charges 1 through 10 were first dispersed with a high speed Cowles mixer for 30 minutes. Charge 11(a) and/or 11(b) was added and agitation continued for 30 minutes. Charge 12 was added and the mixture was ground in a Hockmeyer micro mill until a Hegman of 7 was achieved.

[0107] Sealant coating compositions of the present invention were prepared as shown below:

Table 5. Acrylic sealant coating composition

<td></td><td></td><td>Example M</td>

<td>Load</td><td>Name</td><td>Weight (g)</td>

<td> 1</td><td>Abrasive paste from Example L</td><td> 63</td>

<td> 2</td><td>Acrylic film particles from Example G</td><td> 47</td>

<td> 3</td><td>Hardener EHW8224¹</td><td> 13</td>

<td> 4</td><td>T494 Reducer²</td><td> 8</td>

¹Water-reducible isocyanate obtainable from PPG Industries

Water-based reducer available from PPG Industries

[0108] The final paint had a solids content of 53% and an application viscosity of 34 cPs on a Brookfield CAP 2000 #1 spindle at 900 rpm. The sealer coating composition of Example M was applied under ambient conditions to 12 x 4 x 0.032 steel panels with a gray electroplating coating. The substrate panels were obtained from ACT Laboratories Inc., LLC of Hillsdale, Michigan. The coating composition was applied in one coat and then dried with forced air. Dry film thickness was 28-38 microns. The control coating was a solvent-borne refinish sealer, ECS25, commercially available from PPG Industries, Inc. This was applied by spraying in two coats and dried rapidly under ambient conditions from glossy to matte. Film thickness was approximately 40-45 microns.

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56/60 microns.

[0109] After approximately 30 minutes, the sealer coats were top coated. The first top coat was a base coat available from PPG Industries, Inc., T409, applied to the panels in two coats using forced air after each coat. The film thickness was 4-6 microns. A commercially available 2K clear coat refinish coat from PPG Industries, Inc., as DC4010, was then applied over the coated panel in two coats with a quick dry between coats. The clear coated panels were allowed to dry overnight. The clear coat film thickness was approximately 57-60 microns.

[0110] Table 6 lists the hardness and appearance test results.

Table 6. Appearance and hardness of Konig acrylic stack sealer coatings

<td></td><td>King (s)</td><td>of</td><td>Wa</td><td>Wb</td><td>WC</td><td>Wd</td><td>We</td>

<td>Example M</td><td> 94</td><td> 3,5</td><td> 12,2</td><td> 30,1</td><td> 18,4</td><td> 30,3</td><td> 13,5</td>

<td>ECS25 Control</td><td> 64</td><td> 1,5</td><td> 11, 1</td><td> 26, 0</td><td> 14,3</td><td> 20,5</td><td> 13, 1</td>

[0111] It can be concluded from the data shown in Tables 3 and 6 that sealer formulas of the present invention have the drying speed, as well as appearance, required to meet or exceed solvent-based control in the refinish repair process.

First:

[0112] Primer coatings were prepared by first producing an abrasive paste (Example N) prepared with the following ingredients. The binder portion of the abrasive paste may consist of a dispersion of film-coated particles

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57/60 urethane from Example D.

Table 7. Abrasive paste for polyurethane acrylate primer coating

<td></td><td></td><td>Example N</td>

<td>Load</td><td>Name</td><td>Weight (g)</td>

<td> 1</td><td>Urethane-filmed particles of Example D</td><td> 741</td>

<td> 2</td><td>DISPERBYK 024¹</td><td> 16</td>

<td> 3</td><td>DISPEX® Ultra PA 4550²</td><td> 21</td>

<td> 4</td><td>SURFYNOL 104E³</td><td> 25</td>

<td> 5</td><td>Carbon black</td><td> 23</td>

<td> 6</td><td>Titanium dioxide</td><td> 524</td>

<td> 7</td><td>Barium sulfate</td><td> 607</td>

<td> 8</td><td>Talc</td><td> 432</td>

<td> 9</td><td>Calcium carbonate</td><td> 238</td>

<td> 10</td><td>Water DL</td><td> 323</td>

<td> 11</td><td>10 DMEA/90 water</td><td> 53</td>

<td> 12</td><td>Water DL</td><td> 323</td>

¹Obtainable from BYK²Obtainable from EFKA³Obtainable from Air Products

[0113] The ingredients of charges 1 through 10 were first dispersed with a high speed Cowles mixer for 30 minutes. Charge 11 was added and agitation continued for 30 minutes. Charge 12 was added and the mixture was milled in a Hockmeyer micro mill until a Hegman of 7 was achieved.

[0114] The primer coating compositions of the present invention were prepared as shown below:

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Table 8. Primer coating compositions

<td></td><td></td><td>Example 0</td><td>Example P</td><td>Example Q</td>

<td>Load</td><td>Name</td><td>Weight (g)</td><td>Weight (g)</td><td>Weight (g)</td>

<td> 1</td><td>Abrasive paste from Example N</td><td> 122</td><td> 122</td><td> 122</td>

<td> 2</td><td>Urethane-filmed particles of Example D</td><td> 77</td><td> 77</td><td> 77</td>

<td> 4</td><td>Hardener EHW8224¹</td><td> 28</td><td> 28</td><td> 28</td>

<td> 5</td><td>T494 Reducer²</td><td> 9</td><td> 17</td><td> 28</td>

<td colspan="5"></td>

<td colspan="2">% solids</td><td> 52</td><td> 55</td><td> 57</td>

<td>Viscosity</td><td>(cPs)</td><td> 32</td><td> 40</td><td> 55</td>

¹Water-reducible isocyanate available from PPG Industries.

Water-based reducer available from PPG Industries.

Wedge panel

[0115] Flexural strength properties as a function of weathering conditions were tested against a one-component water-based primer. The control was EPW115, a commercially available primer from PPG Industries, Inc. It was reduced by 5, 10, and 15 weight percent using the same T494 reducer shown in Table 8. The primer coating compositions of the present invention and the control were spray applied under two atmospheric conditions onto 4 x 18 x 0.026 steel panels having a zinc phosphate pretreatment with 17 evenly spaced holes (concave panels). The concave panels were obtained from ACT Laboratories Inc., LLC of Hillsdale, Michigan. These concave panels were used to measure the ability of coatings to resist flexure by spraying a coating wedge. The wedge is created by moving more slowly starting at the bottom of the panel and more quickly as the application continues toward the top. This results in the greatest area of film thickness at the bottom.

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59/60 bottom and thinner film thickness at the top. The coatings were flash dried vertically for 5 minutes at ambient conditions and then baked for 30 minutes at 60°C. The coating around the holes is evaluated for bending. The dry film thickness is measured near the slope area around the hole. By this method, the minimum dry film thickness at which bending occurs is recorded.

Table 9. DFT in bending (Um)

<td>Application conditions</td><td>Viscosity</td><td>Experimental (Examples 0, P, Q)</td><td>EPW 115</td>

<td></td><td>Low</td><td> 13</td><td> 10</td>

<td>18°C (65^SF)</td><td>Average</td><td> 22</td><td> 11</td>

<td>80% HR</td><td>High</td><td> 39</td><td> 15</td>

<td>25°C (77^SF)</td><td>Low</td><td> 41</td><td> 24</td>

<td>24% HR</td><td>Average</td><td> 69</td><td> 23</td>

<td></td><td>High</td><td> 74</td><td> 33</td>

Primer application

[0116] The composition of primer coating composition of Example P was spray applied under ambient conditions to 12 x 4 x 0.032 steel panels with a gray electroplating coating. The substrate panels were obtained from ACT Laboratories Inc., LLC of Hillsdale, Michigan. The control coat was a solvent-based refinish primer commercially available from PPG Industries, Inc., as D839. The coating compositions were applied in two coats with a 5-minute ambient flash dry between each coat followed by a 30-minute bake at 60°C.

[0117] Primer coatings were tested for Konig hardness via ASTM D4366 and by evaluating the response to sanding. Typically a garage will sand a primer to remove surface imperfections as well as to

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60/60 creates a physical bond for adhesion of subsequent coats. It is important for garage production to be able to sand a primer very quickly after the baking process. The primers of the present invention were sanded with 320 grit sandpaper obtainable from 3M using a pneumatic disc sander obtainable from Hutchings Mfg. Co., 5 minutes after removing the coatings from the oven. Sanding ability is considered approved if the coating is not sticky, the sandpaper is not clogged, and dust forms under the sandpaper.

Table 10. Sandability and Konig rating of primer coating

<td></td><td>King (s)</td><td>Sanding capacity</td>

<td>Example P</td><td> 36</td><td>Good</td>

<td>D839 Control</td><td> 47</td><td>Good</td>

[0118] From Tables 9 and 10 it can be seen that the two-component primer of the present invention demonstrates improved flexural strength over the current one-component water-based primer over a very wide range of relative humidity. The primer of the present invention is very similar in hardness to the solvent-based control. It sands comparatively well to the solvent-based control when freshly baked and cooled.

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