Curable film-forming compositions exhibiting adhesion to various substrates and rapid sanding properties

Abstract

This invention relates to curable film-forming compositions and coating kits, each comprising: (a) a polyepoxide-functionalized polymer; (b) a polythiol-functionalized compound, wherein the polythiol-functionalized compound comprises at least two or at least three thiol functional groups, and wherein if the polythiol-functionalized compound contains hydroxyl functional groups, the ratio of thiol functional groups to hydroxyl functional groups in the polythiol-functionalized compound is not 1:1; (c) a reactive compound, different from the polythiol-functionalized compound (b), the reactive compound containing a plurality of side groups and / or terminal functional groups selected from carboxylic acids, anhydrides, amines, and phenols that are reactive with the epoxide functional groups; and (d) a pigment. The curable film-forming compositions exhibit a pigment-to-binder ratio greater than or equal to 2 and less than 3, adhesion to various substrates, and rapid sanding properties. The invention further relates to coated articles and methods for forming the same.

Description

Technical Field

[0001] This invention relates to curable film-forming compositions that exhibit adhesion to various substrates and rapid sanding properties. Background Technology

[0002] In the automotive repair industry, a typical multi-coat stack applied to a substrate includes a primer, optionally a sealer, and one or more aesthetic topcoats. For adhesion and appearance purposes, the substrate, primer, and any sealer are typically sanded between applications. For convenience, it is desirable that each coating dries and / or cures to a sandable degree, if necessary, within two hours of application. Each sandable coating is also designed to provide a high film structure with minimal coating thickness, resulting in smoothness and evenness for a superior appearance that replicates the OEM finish.

[0003] For ease of use, especially in the automotive repair and other environmentally friendly coatings markets, there is a particular need for primer compositions that can be applied directly to both metallic and other substrates with equal adhesion without altering the formulation. Current technologies typically offer only one of these properties within a single product. For example, epoxyamine primers offer good adhesion but require a long drying time before they can be sanded. Polyurethane primers are sandable shortly after application but exhibit poor adhesion to metals.

[0004] The desired outcome is to provide a curable film-forming composition that can be directly applied to a metal substrate as a primer, the curable film-forming composition having considerable adhesion and rapid sanding properties on various substrates. Summary of the Invention

[0005] This invention relates to a curable film-forming composition and a coating kit, wherein the curable film-forming composition and the coating kit each comprise:

[0006] (a) Polyepoxide-functionalized polymers;

[0007] (b) A polythiol functional compound, wherein the polythiol functional compound comprises at least two or at least three thiol functional groups, and wherein if the polythiol functional compound contains a hydroxyl functional group, the ratio of thiol functional groups to hydroxyl functional groups in the polythiol functional compound is not 1:1.

[0008] (c) A reactive compound, distinct from the polythiol functional compound (b), wherein the reactive compound contains a plurality of side groups and / or terminal functional groups selected from carboxylic acids, acid anhydrides, amines, and phenols that are reactive with epoxide functional groups; and

[0009] (d) Pigment. The curable film-forming composition exhibits a pigment-to-binder ratio greater than or equal to 2 and less than 3.

[0010] The present invention further relates to a method for forming a coated article, the method comprising:

[0011] (a) Applying the above-described curable film-forming composition directly to at least a portion of at least one substrate to form at least one coated substrate; and

[0012] (b) Exposing the at least one coated substrate to a temperature of at least 0°C, or at least 10°C, or at least 20°C and at most 60°C, or at most 40°C, or at most 30°C to cure the curable film-forming composition. Each coated substrate passes a sandability test (as defined below) less than two hours after the curable film-forming composition is applied to the substrate. Alternatively or additionally, when subjected to ISO 2409:2013(E) using a handheld single-blade cutting tool with 2mm pitch cuts, each coated substrate exhibits an adhesion rating of 0 to 2 within seven days after the curable film-forming composition is applied to each substrate.

[0013] The present invention further relates to coated articles comprising a substrate and the above-described curable film-forming composition applied to at least one surface of the substrate. The present invention also relates to coated articles prepared by the above-described method. Detailed Implementation

[0014] Except in operational examples, or unless otherwise explicitly stated, all numerical ranges, quantities, values, and percentages (such as those relating to the amount of material, reaction time and temperature, ratios of quantities, and molecular weight values ​​(whether number-average molecular weight (“M”)) shall be considered valid. n ") or weight-average molecular weight ("M") w The numerical ranges, quantities, values, and percentages of other values ​​in the following sections of the specification can be interpreted as if they begin with the word "about," even if the term "about" may not explicitly appear with a value, quantity, or range. Therefore, unless otherwise indicated, the numerical parameters set forth in the following specification and the appended claims are approximate values ​​that may vary depending on the desired properties sought to be obtained through the invention. At least, and without attempting to limit the application of the doctrine of equivalence to the scope of the claims, each numerical parameter should be interpreted at least based on the number of significant figures reported and by applying ordinary rounding techniques.

[0015] While the numerical ranges and parameters illustrating the broad scope of the invention are approximate, the values ​​described in specific examples are reported as accurately as possible. However, any numerical value inherently contains some error, which is necessarily caused by the standard deviation found in its corresponding test measurement. Furthermore, when describing numerical ranges of variation herein, any combination of these values, including those listed, is contemplated for use.

[0016] As used herein, plural indicators encompass singular, and vice versa. For example, while the invention has been described according to "one" polyepoxide-functionalized polymer, various mixtures comprising such polymers may be used.

[0017] Unless otherwise specified, any numerical reference to quantities is "by weight". The term "equivalent" is a calculated value based on the relative amounts of the various components used in the preparation of a given material and is based on the solidity of the given material. A relative quantity is the theoretical weight (in grams) of the material (such as a polymer) produced from the components and gives the theoretical number of a particular functional group present in the resulting polymer. The theoretical polymer weight is divided by the theoretical equivalent number of functional groups to obtain the equivalent. For example, the urethane equivalent is based on the equivalent number of urethane groups in a polyurethane material.

[0018] Each of the various examples of the invention presented herein is to be understood as non-limiting with respect to the scope of the invention.

[0019] The curable film-forming compositions and coating kits of the present invention comprise (a) a polyepoxide functional polymer (“polyepoxide”). As used herein, the terms “thermosetting” and “curable” are used interchangeably and refer to a resin that is irreversibly “cured” upon curing or crosslinking, wherein the polymer chains of the polymer components are linked together by covalent bonds. This property is generally associated with crosslinking reactions of the composition components, for example, caused by heat or radiation. See Hawley, Gessner G., The Condensed Chemical Dictionary, 9th edition, p. 856; Surface Coatings, Vol. 2; and Oil and Colour Chemists' Association, Australia, TAFE Education Books (1974). The curing or crosslinking reaction can also be carried out under ambient conditions. Ambient conditions refer to the coating undergoing a thermosetting reaction without the aid of heat or other energy, such as not being baked in an oven, using forced air, etc. Typically, the ambient temperature is in the range of 60 to 90°F (15.6 to 32.2°C), such as a typical room temperature of 72℉ (22.2°C). Once cured or crosslinked, the thermosetting resin will not melt and will not dissolve in solvents when heat is applied. For example, "cured composition" in some specific descriptions means that at least a portion of the polymerizable and / or crosslinkable components forming the curable composition undergoes polymerization and / or crosslinking via reactive functional groups, such that the cured film prepared from said composition exhibits at least 50% non-damaging rubbing against two methacrylates (MEK) according to ASTM D5402-19. The test method can be performed, for example, using a specified coarse cotton cloth or another suitable cloth such as a Wypall X80 towel available from Kimberly Clark Corporation. Furthermore, curing of the polymerizable composition refers to subjecting said composition to curing conditions (such as, but not limited to, heat curing) that cause the reactive functional groups of the composition to react and induce polymerization and the formation of polymeric products. When a polymerizable composition is subjected to curing conditions, the reaction rate of the remaining unreacted reactive groups gradually slows down after polymerization and after most of the reactive groups have reacted. The polymerizable composition can be subjected to curing conditions until it is at least partially cured. The term "at least partially cured" means that the polymerizable composition is subjected to curing conditions in which at least a portion (e.g., at least 5%) of the reactive groups of the composition react to form a polymeric product. The polymerizable composition can also be subjected to curing conditions such that complete curing is achieved (e.g., more than 50%, or more than 60%, or more than 80% of the reactive groups have reacted), and further curing does not result in further improvement of polymer properties (such as hardness).

[0020] As used herein and in the appended claims, the articles “a,” “an,” and “the” include plural indicators and are used interchangeably with the terms “at least one” and “one or more” unless explicitly and definitively limited to one indicator. As used herein, the term “polymer” means both oligomers, homopolymers, and copolymers as understood in the art.

[0021] Typically, polyepoxide-functionalized polymers (a) include non-acrylic polyepoxide-functionalized polymers. Suitable polyepoxide-functionalized polymers contain, for example, polyepoxides that are chain-extended by reacting them with polyepoxides and materials containing polyhydroxyl groups (such as materials containing alcohol hydroxyl groups and materials containing phenolic hydroxyl groups) (thus providing aromatic groups to the polyepoxide-functionalized polymer if desired), to extend the chain or construct the molecular weight of the polyepoxide.

[0022] Chain-extended polyepoxides are typically prepared by reacting the polyepoxide with a polyhydroxyl-containing material, either purifying it or in the presence of an inert organic solvent (such as ketones) (including methyl isobutyl ketone and methyl pentyl ketone), an aromatic compound (such as toluene and xylene), and a glycol ether (such as dimethyl ether of diethylene glycol). The reaction is usually carried out at a temperature of about 80°C to 160°C for about 30 to 180 minutes until a resinous reaction product containing epoxy groups is obtained.

[0023] The equivalence ratio of reactants (i.e., epoxy: a material containing multiple hydroxyl groups) is typically from about 1.00:0.75 to 1.00:2.00.

[0024] By definition, a polyepoxide has at least two 1,2-epoxy groups. Typically, the epoxide equivalent of a polyepoxide is between 100 and 2000, usually in the range of about 180 to 500. Epoxides can be saturated or unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic, or heterocyclic. The epoxide may contain substituents such as halogens, hydroxyl groups, and ether groups.

[0025] Examples of polyepoxides are polyepoxides with a 1,2-epoxide equivalent greater than 1 and typically about 2; that is, polyepoxides with an average of two epoxide groups per molecule. The most commonly used polyepoxides are polyglycidyl ethers of cyclic polyols, such as polyglycidyl ethers of polyphenols (e.g., bisphenol A, resorcinol, hydroquinone, benzyl alcohol, phloroglucinol, and catechol); or polyglycidyl ethers of polyols (e.g., alicyclic polyols, especially alicyclic polyols such as 1,2-cyclohexanediol, 1,4-cyclohexanediol, 2,2-bis(4-hydroxycyclohexyl)propane, 1,1-bis(4-hydroxycyclohexyl)ethane, 2-methyl-1,1-bis(4-hydroxycyclohexyl)propane, 2,2-bis(4-hydroxy-3-tert-butylcyclohexyl)propane, 1,3-bis(hydroxymethyl)cyclohexane, and 1,2-bis(hydroxymethyl)cyclohexane). Examples of aliphatic polyols include trimethylpentanediol and neopentanediol.

[0026] The polyhydroxyl-containing material used for chain extension or increasing the molecular weight of polyepoxides can be a polymeric polyol.

[0027] Polyesters, polyurethanes, or polyamides prepared with glycidol or glycidylamine, or reacted with epihaloalcohols, are also suitable epoxy functional resins.

[0028] Non-limiting examples of suitable polyepoxide functionalized polymers include EPON 828 and 1001, which are commercially available from Miller-Stephenson, Inc., and DEN431 (a polyepoxide resin based on phenolic varnish), which is available from OlinEpoxy, Olin Corporation.

[0029] Typically, based on the total weight of the polyepoxide-functionalized polymer (a) in the curable film-forming composition, the polyepoxide-functionalized polymer (a) comprises less than 25% by weight, or less than 20% by weight, or less than 15% by weight, or less than 10% by weight of an acrylic polyepoxide-functionalized polymer. In specific embodiments of the invention, the polyepoxide-functionalized polymer (a) may or may not include an acrylic polyepoxide-functionalized polymer.

[0030] Typically, the number-average molecular weight of polyepoxide-functionalized polymers (a) ranges from about 180 to 500, often in the range of about 186 to 350. Molecular weight (whether number-average or not) n ) or weight average (M) w The determination was made by gel permeation chromatography using polystyrene as a standard, as is well known to those skilled in the art and as discussed in U.S. Patent No. 4,739,019, column 4, lines 2-45.

[0031] Based on the total weight of the resin solids in the curable film-forming composition (i.e., the total weight of (a), (b), and (c), the polyepoxide functional polymer (a) is typically present in the curable film-forming composition of the present invention in an amount of at least 10% by weight, such as at least 20% by weight, or at least 35% by weight, or at least 40% by weight, or at least 45% by weight. Based on the total weight of the resin solids in the curable film-forming composition, the polyepoxide (a) may be present in the curable film-forming composition of the present invention in an amount of up to 90% by weight, such as up to 85% by weight, or at most 80% by weight. Therefore, polyepoxides may be present in the curable film-forming composition in amounts such as 10 to 90 wt%, or 10 to 85 wt%, or 10 to 80 wt%, or 20 to 90 wt%, or 20 to 85 wt%, or 20 to 80 wt%, or 35 to 90 wt%, or 35 to 85 wt%, or 35 to 80 wt%, or 40 to 90 wt%, or 40 to 85 wt%, or 40 to 80 wt%, or 45 to 90 wt%, or 45 to 85 wt%, or 45 to 80 wt%.

[0032] Unless otherwise specified, “total weight based on resin solids” as used herein refers to the amount of components added during composition formation based on the total weight of non-volatile resins of the film-forming material present during composition formation, including crosslinking agents, reactive diluents, and polymers, but excluding any water, volatile organic solvents, or any additive solids such as hindered amine stabilizers, photoinitiators, pigments including extender pigments and fillers, flow modifiers, catalysts, and UV light absorbers. Unless otherwise specified, the phrases “total weight based on composition solids” and “total weight based on composition solids” (used interchangeably) refer to the amount of components added during composition formation based on the total weight of solids (non-volatiles) of the film-forming material present during composition formation, including crosslinking agents, reactive diluents and polymers, pigments including extender pigments and fillers, and additive solids (such as hindered amine stabilizers, photoinitiators, flow modifiers, catalysts, and UV light absorbers), but excluding any water or volatile organic solvents.

[0033] The curable film-forming composition and coating kit of the present invention further include (b) a polythiol functional compound. The polythiol functional compound includes at least two, typically at least three thiol functional groups. If the polythiol functional compound contains a hydroxyl functional group, the ratio of thiol functional groups to hydroxyl functional groups in the polythiol functional compound is not 1:1. Typically, if the polythiol functional compound (b) contains a hydroxyl functional group, the ratio of thiol functional groups to hydroxyl functional groups in the polythiol functional compound (b) is greater than 1:1. More often, the polythiol functional compound (b) does not contain a hydroxyl functional group or any other reactive functional group, such as active hydrogen groups other than thiols.

[0034] The polythiol functional compound (b) suitable for curable compositions according to the invention comprises a polythiol having at least two, or more often at least three thiol groups per molecule, including monomeric compounds, oligomers, prepolymers, and polymers. Polythiools generally do not have ether bonds (-O-). Thioether bonds (-S-) and combinations thereof, including polysulfide bonds (-S-), are not recommended. x -), where x is at least 2, such as 2 to 4. Typically, curable film-forming compositions are substantially free of polysulfides and polysulfides. "Substantially free of" a material means that the composition contains only trace or incidental amounts of a given material, and the amount of said material present is insufficient to affect any property of the composition. These materials are not essential to the composition, and therefore, the composition does not contain any substantial or necessary amounts of these materials. If said material is present, it is only incidental based on the total weight of solids in the composition, typically less than 0.1% by weight.

[0035] The polythiol (b) used in this invention comprises a material of the following formula:

[0036] R 1 –(SH) n

[0037] Where R 1 It is an organic moiety, and n is an integer of at least 2, or at least 3, typically 3 to 6. This polythiol can, for example, include reaction products of thiol-functional organic acids and polyols. Therefore, the organic moiety R... 1 It may contain ester groups and / or be derived from polyols. Typically, the polythiol compound (b) contains ester groups. In a specific embodiment of the invention, the polythiol functional compound (b) has at least two ester functional groups and is tetrafunctional relative to the thiol functional group.

[0038] Examples of suitable polythiols that can be used in the curable compositions according to the invention may include formula HS-R. 2 The acid and structure of the thiol containing -COOH are R. 3 -(OH) n esters reacted with polyhydroxy compounds, wherein R 2 This includes divalent organic moieties that typically have 1 to 4 carbon atoms, where R 3 This includes an n-valent organic moiety typically having 4 to 13 carbon atoms, where n is at least 2, more often at least 3, and usually 3 to 6. The thiol-containing acid component and the polyhydroxy component can be reacted under suitable conditions to give a polythiol having the following general structure:

[0039] R 3 -(OC(=O)-R 2 -SH) n

[0040] Examples of such esters of thiol-containing acids include esters formed by the reaction of mercaptoacetic acid (HS-CH2COOH), α-mercaptopropionic acid (HS-CH(CH3)-COOH), or β-mercaptopropionic acid (HS-CH2CH2COOH) with polyhydroxy compounds (such as triols, tetraols, pentylols, hexaols, and mixtures thereof). Specific examples of suitable polythiol functional compounds (b) include, for example, trimethylolpropane tris (mercaptoacetic acid ester), trimethylolpropane tris (β-mercaptopropionate), pentaerythritol tetras (mercaptoacetic acid ester), and pentaerythritol tetras (β-mercaptopropionate), and mixtures thereof. Typically, such polythiol functional compounds (b) have a thiol equivalent of less than 330 g / equivalent, or less than 300 g / equivalent, or less than 200 g / equivalent, or less than 135 g / equivalent. A specific example of a polythiol suitable for the curable film-forming compositions of the present invention is THIOCURE PETMP (pentaerythritol tetra(3-mercaptopropionate)), commercially available from Bruno Bock ChemischeFabrik GmbH & Co. KG. When the polythiol (b) has two thiol functional groups, the thiol equivalent of the polythiol functional compound (b) is typically less than 300 g / equivalent, or less than 200 g / equivalent, or less than 135 g / equivalent.

[0041] Based on the total weight of the resin solids in the curable composition, polythiols (b) are typically present in the curable compositions of the present invention in an amount of 5 to 90% by weight. For example, based on the total weight of the resin solids in the curable composition, polythiols (b) may be present in the curable composition in an amount of at least 5% by weight, or at least 10% by weight, or at least 30% by weight, or at least 50% by weight, or even at least 60% by weight, as shown in the examples below. Furthermore, based on the total weight of the resin solids in the curable composition, polythiols (b) may be present in the curable composition in an amount of up to 75% by weight, and typically up to 60% by weight. Therefore, polythiols may be present in the curable film-forming composition in amounts such as 5 to 90 wt%, or 5 to 75 wt%, or 5 to 60 wt%, or 10 to 90 wt%, or 10 to 75 wt%, or 10 to 60 wt%, or 30 to 90 wt%, or 30 to 75 wt%, or 30 to 60 wt%, or 50 to 90 wt%, or 50 to 75 wt%, or 50 to 60 wt%, or 60 to 90 wt%, or 60 to 75 wt%.

[0042] The curable film-forming compositions and coating kits of the present invention further include (c) a reactive compound containing a functional group reactive with the epoxide functional group. The reactive compound (c) is different from the polythiol functional compound (b). The term "reactive" refers to a functional group that can spontaneously or upon heating or in the presence of a catalyst or by any other means known to those skilled in the art with itself and / or other functional groups. The reactive functional groups present on the reactive compound (c) may comprise carboxylic acids, acid anhydrides, amines, and / or phenols. Non-limiting examples of such compounds include acrylic, polyester, polyurethane, polyether, and / or polyamide polymers having multiple side groups and / or terminal reactive functional groups, such as any of the functional groups listed above. However, the reactive compound (c) need not be a polymer. Examples of suitable polycarboxylic acids include adipic acid, succinic acid, sebacic acid, azelaic acid, and dodecanoic acid. Acid anhydrides may in particular include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, chlorhexidine anhydride, etc. Mixtures of acids and / or acid anhydrides may also be used. It should be noted that the phrase "and / or" when used in a list means to cover alternative embodiments that include each individual component in the list as well as any combination of components. For example, the list "A, B and / or C" means to cover seven individual embodiments that include A, or B, or C, or A+B, or A+C, or B+C or A+B+C.

[0043] Non-limiting examples of suitable polyamines include primary or secondary diamines or polyamines, wherein the group attached to the nitrogen atom can be saturated or unsaturated, aliphatic, alicyclic, aromatic, aromatic-substituted-aliphatic, aliphatic-substituted-aromatic, and heterocyclic. Non-limiting examples of suitable aliphatic and alicyclic diamines include ethylenediamine, 1,2-diaminopropane, 1,5-diamino-2-methylpentane, 1,3-diaminopentane, 1,2-diaminocyclohexane, 1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, 3-(cyclohexylamino)propylamine, 3-aminomethyl-3,5,5-trimethylcyclohexyl-1-amine (isophorone diamine (“IPDA”)), 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-[1,4-butadiylbis-(oxy)bis]-1-propylamine, methyldiamine, and diamino-functionalized polyether polyamines having an aliphatic-linked primary amino group, examples of which include JEFFAMINE, available from Huntsman Corporation. D-230, JEFFAMINE D-400, JEFFAMINE D-2000, and JEFFAMINED-4000. Non-limiting examples of suitable aromatic diamines include phenylenediamine and toluenediamine, such as o-phenylenediamine and p-toluenediamine. Polynuclear aromatic diamines such as 4,4'-biphenylenediamine, methylenediphenylamine, and monochloromethylenediphenylamine are also suitable.

[0044] Alicyclic diamines are available from Huntsman Corporation (Houston, TX) under the name JEFFLINK. TM (such as JEFFLINK) TM 754) Commercially available. Other aliphatic cyclic polyamines, such as DESMOPEN NH 1520 from Bayer MaterialScience and / or CLEARLINK 1000 from Dorf Ketal, which are secondary aliphatic diamines, can also be used. POLYCLEAR 136 (available from BASF / Hansen Group LLC), a reaction product of isophorone diamine and acrylonitrile, is also suitable.

[0045] Suitable higher polyamines include primary and secondary triamines and / or tetraamines. Examples of suitable triamines include, but are not limited to, diethylenetriamine, dipropylenetriamine, bis(hexamethylene)triamine, and triaminofunctional polyether polyamines having an aliphatic-linked primary amino group (examples include JEFFAMINE T-403, T-3000, and T-5000, available from Huntsman Corporation). For example, the amine may be amine-terminated (i.e., each end has an amine, thus making the amine bifunctional) polyethylene glycol or polypropylene glycol.

[0046] Suitable compounds having phenolic functional groups include Phenodur PR 263 / 70B, which is available from Allnex USA, Inc.

[0047] Typically, reactive compounds (c) contain multiple reactive (e.g., primary or secondary) amine functional groups. Specific examples include polyamide amines, such as Delleet Evolution F3996 available from PPG Industries Automotive Refinish, and phenolic polyamines, such as Accelerator 2950CH, available from Huntsman.

[0048] In a specific embodiment of the present invention, the weight ratio of the polythiol functional compound (b) to the reactive compound (c) is less than or equal to 10, or less than or equal to 9.5, or less than or equal to 9, or less than or equal to 8.5, or less than or equal to 8.

[0049] In a specific example of the present invention, the equivalence ratio of the thiol (active hydrogen) group in the polythiol functional compound (b) to the reactive (active hydrogen) functional group in the reactive compound (c) is 4:1 to 1:4, or 3:1 to 1:3, or 2:1 to 1:2, such as 4:1, or 3.5:1, or 2.5:1, or 1.5:4, or 1.5:3 or 1.5:2.

[0050] Typically, based on the total weight of the resin solids in the curable film-forming composition, the reactive compound (c) is present in the curable film-forming composition in an amount of at least 1% by weight, or at least 2% by weight, or at least 5% by weight and at most 15% by weight, or at most 12% by weight, or at most 10% by weight. Therefore, the reactive compound (c) may be present in the curable film-forming composition in, for example, an amount of 1 to 15% by weight, or 1 to 12% by weight, or 1 to 10% by weight, or 2 to 15% by weight, or 2 to 12% by weight, or 2 to 10% by weight, or 5 to 15% by weight, or 5 to 12% by weight, or 5 to 10% by weight.

[0051] The curable film-forming compositions and coating kits of the present invention further include (d) pigments. “Pigment” means colorant, extender, filler particles, and / or corrosion-inhibiting pigment. Pigments can be added to the coating in any suitable form such as discrete particles, dispersions, solutions, and / or flakes. Colorants can be organic or inorganic and can be agglomerated or non-agglomerated. Colorants and other pigments can be incorporated into the coating by grinding or simple mixing. Colorants and other pigments can be incorporated into the coating by grinding with an abrasive medium (such as an acrylic abrasive medium), the use of which is well known to those skilled in the art. A single pigment or a mixture of two or more pigments can be used in the coatings of the present invention.

[0052] Suitable pigments include any pigments known in the field of surface coatings. Example pigments and / or pigment compositions include, but are not limited to, carbazole dioxazine crude pigments, azo, monoazo, diazo, naphthol AS, salt types (salt lakes), benzimidazolone, condensates, metal complexes, isoindolineone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, violet ketone, diketopyrrolopyrrole, thioindigo, anthraquinone, indigoanthraquinone, anthraquinone pyrimidine, flavinthrone, pinanthraquinone, anthraquinone, dioxazine, triarylcarbonium, quinophthalone pigments, diketopyrrolopyrrole red (“DPPBO Red”), titanium dioxide, carbon black and / or mixtures thereof.

[0053] Specific examples of pigments used in primer compositions include carbon black, titanium dioxide, barium sulfate, magnesium silicate, aluminum silicate, silica, corrosion-inhibiting pigments, etc. Pigments are generally non-thermal conductive. Typically, the curable film-forming compositions and coating kits of the present invention exhibit a pigment-to-binder ratio (P:B) greater than or equal to 2 and less than 3. "Pigment-to-binder ratio" refers to the solid weight ratio of pigment (d) (containing colorants, extenders, filler particles, and / or corrosion-inhibiting pigments) to components (a) + (b) + (c).

[0054] The curable film-forming compositions and coating kits of the present invention may contain auxiliary components conventionally used in coating compositions. Optional components, such as catalysts, plasticizers, surfactants, thixotropic agents and / or other rheology control agents, matting agents, organic cosolvents, flow control agents, antioxidants, UV light absorbers (as in topcoat compositions), corrosion inhibitors, and similar additives conventional in the art, may be included in the compositions. These components are typically present in up to about 40% by weight, based on the total weight of the resin solids.

[0055] Catalysts selected from the following may be particularly suitable: oxazolidinyl esters, alkylaminophenols, triethylamine, dimethylcyclohexylamine, dimethyloctylamine, dimethyldodecylamine, dimethylaminoethanol, tetramethylguanidine, diaza-bicyclo-octane, diaza-bicyclo-undecene, diaza-bicyclo-nonene, n-methyl-triaza-bicyclo-decene, and mixtures thereof.

[0056] It has been found that various zinc compounds (zinc phosphate, zinc carboxylate, zinc aluminum phosphate) commonly used in the art for corrosion inhibition lead to an undesirable increase in the viscosity of the composition, likely due to the complexation of thiols with zinc. However, zinc strontium phosphosilicate corrosion inhibitors can be combined with polythiols without increasing viscosity. In a specific embodiment of the invention, based on the total weight of resin solids in the curable film-forming composition, the composition further comprises at least 1% by weight, or at least 5% by weight, or at least 10% by weight and at most 30% by weight, or at most 27% by weight, or at most 25% by weight of zinc strontium phosphosilicate. Thus, zinc strontium phosphosilicate can be present in the curable film-forming composition in amounts, for example, 1 to 30% by weight, or 1 to 27% by weight, or 1 to 25% by weight, or 5 to 30% by weight, or 5 to 27% by weight, or 5 to 25% by weight, or 10 to 30% by weight, or 10 to 27% by weight, or 10 to 25% by weight.

[0057] The curable film-forming compositions and coating kits of the present invention are generally solvent-based. Suitable organic solvent media include ketones, such as methyl pentyl ketone and methyl isobutyl ketone; aromatic hydrocarbons, such as xylene; ethylene glycol ethers, such as propylene glycol methyl ether, propylene glycol monopropyl ether, ethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and ethylene glycol monohexyl ether; and / or esters, such as n-butyl acetate, 2-butoxyethyl acetate, and propylene glycol monomethyl ether acetate. Other solvents (including alcohols, such as butanol) may be suitable. Mixtures of any of the above solvents may also be used. Based on the total weight of the curable film-forming composition, the total solids content of the curable film-forming compositions of the present invention may be at least 20% by weight, or at least 30% by weight, or at least 40% by weight, or at least 50% by weight, and based on the total weight of the curable film-forming composition, the total solids content of the curable film-forming compositions of the present invention may be at most 90% by weight, or at most 80% by weight, or at most 75% by weight, or at most 70% by weight. Therefore, the total solids content of the curable film-forming composition of the present invention can be in the range of 20 to 90% by weight, or 20 to 80% by weight, or 20 to 75% by weight, or 20 to 70% by weight, or 30 to 90% by weight, or 30 to 80% by weight, or 30 to 75% by weight, or 30 to 70% by weight, or 40 to 90% by weight, or 40 to 80% by weight, or 40 to 75% by weight, or 40 to 70% by weight, or 50 to 90% by weight, or 50 to 80% by weight, or 50 to 75% by weight, or 50 to 70% by weight.

[0058] In specific examples of the invention, the composition is substantially free of chromate compounds, such as pigments containing chromates.

[0059] As described above, the present invention also relates to coating kits. Storing environmentally curing coatings as single-package compositions is generally impractical; instead, they must be stored as multi-package coatings to prevent the reactive components from curing before use. The term "multi-package coating" refers to a coating in which the various components are individually held until just before application. The coating kits of the present invention are typically multi-package coatings comprising multiple individual components, such as where a first component comprises a polyepoxide-functionalized polymer (a), a second component comprises a polythiol-functionalized compound (b), and a third component comprises a reactive compound (c). Pigment (d) may be present in one or more other components or as a separate fourth component; typically, pigment (d) is present in the first and / or third components. In another example, the first component comprises a polyepoxide-functionalized polymer (a), and the second component comprises a polythiol-functionalized compound (b) and a reactive compound (c). In this case, pigment (d) may be present in one or more other components (typically in the first component) or as a separate third component. In the example shown below, a polyepoxide-functionalized polymer (a) serves as an abrasive medium for pigment (d).

[0060] The present invention further relates to a coated article comprising a substrate and the above-described curable film-forming composition applied to at least one surface of the substrate. The curable film-forming composition can act as a primer, sealer, undercoat, and / or direct gloss topcoat, thereby imparting a decorative and / or protective finish to the substrate.

[0061] Non-metallic substrates A) include polymers, plastics, polyesters, polyolefins, polyamides, cellulose, polystyrene, polyacrylic acid, polyethylene naphthalate (PET), polypropylene, polyethylene, nylon, EVOH, polylactic acid (PLA), other “green” polymer substrates, polyethylene terephthalate (“PET”), polycarbonate, polycarbonate acrylonitrile butadiene styrene (“PC / ABS”), polyamides, polymer composites, etc. Automotive parts typically formed from thermoplastic and thermosetting materials include bumpers and trim pieces.

[0062] The metal substrates used in this 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 and / or zinc-iron alloys surface-treated with any of zinc metal, zinc compounds, and zinc alloys (including electro-galvanized steel, hot-dip galvanized steel, GALVANNEAL steel, and steels with zinc alloys). Additionally, aluminum, aluminum alloys, zinc-aluminum alloys (such as GALFAN, GALVALUME, aluminized steel, and aluminized alloy steel substrates), as well as magnesium metal, titanium metal, and alloys thereof, can be used. Steel substrates coated with a weldable zinc-rich or iron-phosphide-rich organic coating (such as cold-rolled steel or any of the steel substrates listed above) are also suitable for this invention. Such weldable coating compositions are disclosed in U.S. Patent Nos. 4,157,924 and 4,186,036. Cold-rolled steel is also suitable when pretreated with appropriate solutions known in the art, such as metal phosphate solutions, aqueous solutions containing at least one Group IIIB or Group IVB metal, organophosphate solutions, organophosphonate solutions, and combinations thereof, as discussed below.

[0063] The substrate may alternatively comprise more than one metal or metal alloy, as it may be a combination of two or more metal substrates assembled together, such as hot-dip galvanized steel assembled with an aluminum substrate. The substrate may alternatively comprise a composite material, such as a glass fiber composite. The coated article of the present invention may comprise at least two different substrates, which may include both metal and non-metal parts, and a curable film composition may be applied to each substrate with acceptable adhesion.

[0064] The coated articles may include vehicle parts made using one or more suitable substrates. The term "vehicle" is used herein in its broadest sense and includes all types of vehicles, such as, but not limited to, aircraft, helicopters, automobiles, trucks, buses, vans, golf carts, motorcycles, bicycles, railway vehicles, tanks, etc. It should be understood that the coated vehicle parts according to the invention may vary depending on the reason for the application of the coating.

[0065] The substrate can be in the form of a sheet, plate, rod, bar, or any desired shape, but it is typically in the form of automotive parts such as body panels, doors, fenders, hoods, or bumpers. The thickness of the substrate can be varied as needed.

[0066] Coated articles may alternatively include components of buildings, bridges, industrial protective structures, ships, railcars, railcar containers, water towers, power line towers, tunnels, oil or gas industry structures, marine structures, aerospace structures, bridge support structures, pipelines, oil rigs, storage tanks, or wind turbines that are prepared by reusing one or more suitable substrates.

[0067] The metal substrate to be used can be a bare substrate, allowing the curable film-forming composition to be applied directly to the metal (DTM) coating. "Bare" refers to a raw substrate that has not been treated (or has been stripped) with any pretreatment composition (such as conventional phosphating baths, heavy metal rinsing, etc.). Alternatively, the bare metal substrate used in this invention can be a cut edge of a substrate whose surface has been otherwise treated and / or coated. Alternatively, the substrate may undergo one or more treatment steps known in the art prior to applying the curable film-forming composition.

[0068] Before depositing any coating composition on a substrate surface, it is common practice, though not mandatory, to remove foreign matter or previously applied paint (such as OEM coatings) from the surface by thoroughly stripping, cleaning, and removing surface grease. When the substrate is not an existing vehicle part, this cleaning is usually performed after the substrate (stamped, welded, etc.) has been formed into its final use shape. The substrate surface can be cleaned by physical or chemical methods, or both, such as mechanically grinding (e.g., sanding) the surface or by using alkaline or acidic cleaners such as sodium metasilicate and sodium hydroxide, which are commercially available and well known to those skilled in the art. A non-limiting example of a cleaner is CHEMKLEEN 163, a commercially available alkaline-based cleaner, from PPG Industries, Inc.

[0069] The coated article of the present invention may further include at least one additional film-forming composition applied on top of the curable film-forming composition and / or as an intermediate layer between the curable film-forming composition and the substrate. This may include an electrodeposited layer, a primer, a sealing varnish, and / or one or more topcoats.

[0070] The purpose of applying a sealant to the repaired area is to provide a smooth and uniform surface on which a repair topcoat can be applied. The sealant is expected to provide this smoothness with minimal sanding, and is typically applied in one or two coats with a total dry film thickness of approximately 25 micrometers. The sealant can be applied over a previously applied primer to conceal sanding marks created during primer sanding. Typically, without the sealant, these sanding marks can be transmitted through the primer and are visible as optical defects in the repaired part. The sealant can also be applied to partially sanded repair points to counteract the typically variable surface energy resulting from multiple exposed surfaces. These variable surface energies can sometimes create optical defects (referred to as “ringing”) visible in the primer. In this case, the sealant provides a uniform surface energy layer across the surface, on which the topcoat is applied. Because the sealer is applied before the repair topcoat and is typically not sanded, the "feather-out" area toward the repair edge (i.e., where adjacent sealer films blend into the original, unsanded area) should be smooth enough to allow for topcoat application without additional treatment. It is further expected that the sealer will dry and be workable within 10 to 15 minutes after application. "Workable" means "set to touch" as defined in any of the methods disclosed in ASTM D-5895-13.

[0071] Topcoats, in particular, provide aesthetic properties (such as color) to the substrate and can be direct gloss topcoats or composite coating systems comprising a colored base coat followed by a clear coat. Such coatings can include any coating known in the field of surface coatings and can include curable compositions.

[0072] Each coating composition can be applied using known application techniques, such as dip or immersion, spraying, intermittent spraying, post-dip spraying, post-spray dipping, brushing, or roller coating. Conventional spraying techniques and equipment for air spraying and electrostatic spraying can be used, either manually or automatically.

[0073] After the composition is applied, a film is formed by expelling the solvent (i.e., organic solvents and water) from the film through heating or an air drying cycle. Suitable drying conditions will depend on the specific 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 of each composition can be applied. Typically, between coatings, the previously applied coating is flash-evaporated; that is, exposed to ambient conditions for the desired amount of time.

[0074] The curable film-forming compositions of the present invention, when applied to a substrate, typically exhibit a dry film thickness of at least 50 micrometers, or at least 60 micrometers, or at least 100 micrometers to at most 150 micrometers, or at most 125 micrometers. According to the manufacturer's instructions, the dry film thickness can be measured 24 hours after coating application using a DUALSCOPEFMP40C probe with an FD13H probe, available from Fischer Technologies, Inc., when cured at ambient temperature.

[0075] The curable film-forming composition of the present invention can be cured at a temperature of at least 0°C, or at least 10°C, or at least 20°C and at most 60°C, or at most 40°C, or at most 30°C. The curable film-forming composition is also sandable within two hours of application. For example, when cured at 20°C, the curable film-forming composition of the present invention is sandable within 60 to 120 minutes. Typically, each coated substrate passes a sandability test within two hours after the curable film-forming composition is applied to at least one substrate. The primer composition of the present invention can be cured overnight at ambient temperature or forcibly cured at 60°C for 30 minutes.

[0076] In the sanding test, a hand sanding block measuring 2.75 x 5 inches (7 x 12.7 cm), part number 05440, from 3M (3M), with gold P320 STICK-IT sandpaper (also available from 3M), is pressed against the coated substrate surface with a force of approximately 1 kg while held in proportion. The block is then moved across the surface 20 times, and the coating is deemed "sandable" when the block moves smoothly and leaves no coating on the paper that cannot be brushed off. A time of two hours or less is considered passing.

[0077] Typically, after the curable film-forming composition on the substrate has been cured, when subjected to ISO 2409:2013(E) using a handheld single-blade cutting tool with 2mm slits, the coated article exhibits an adhesion grade of 0 to 2 within seven days after the curable film-forming composition is applied to the substrate. When coated on at least two different substrates, when subjected to ISO 2409:2013(E) using a handheld single-blade cutting tool with 2mm slits, the coated article exhibits an adhesion grade of 0 to 2 on each of the substrates within seven days after the curable film-forming composition is applied to the substrate.

[0078] The coated article of the present invention can be prepared by a method comprising:

[0079] (a) Applying the above-described curable film-forming composition directly to at least a portion of at least one substrate (such as at least two different substrates) as described above to form at least one coated substrate; and

[0080] (b) Exposing the at least one coated substrate to a temperature of at least 0°C, or at least 10°C, or at least 20°C and at most 60°C, or at most 40°C, or at most 30°C to cure the curable film-forming composition. Each coated substrate passes the above-described abrasion test less than two hours after the curable film-forming composition is applied to the at least one substrate. Alternatively, when subjected to ISO 2409:2013(E) using a handheld single-blade cutting tool with 2mm kerf spacing, each coated substrate exhibits an adhesion rating of 0 to 2 within seven days after the curable film-forming composition is applied to each substrate.

[0081] At least one additional film-forming composition as described above can be applied on top of at least a portion of the curable film-forming composition of the present invention.

[0082] The following working examples are intended to further illustrate the invention. It should be understood that the invention described in this specification is not necessarily limited to the examples described in this section. Components mentioned elsewhere in this specification as suitable alternatives for use in the invention but not shown in the following working examples are intended to provide results equivalent to their shown counterparts. Unless otherwise specified, all parts are by weight.

[0083] Example

[0084] The mixture of polyepoxide functional polymers and pigments used to prepare curable film-forming compositions is prepared from the following series of components.

[0085] Table 1

[0086] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 <![CDATA[EPON 1001-T-75 a ]]> 0 0 24.2 95.0 31.7 50.4 43.4 <![CDATA[EPON 828 b ]]> 0 22.7 0 0 0 0 0 <![CDATA[DEN 431 c ]]> 21.8 0 0 0 0 0 0 n-Butyl acetate 67.8 67.8 67.8 67.8 67.8 67.8 67.8 Methylpentyl ketone 3.1 3.1 3.1 3.1 3.1 3.1 3.1 <![CDATA[Crayvallac A-72-260-A d ]]> 0.3 0.3 0.3 0.3 0.3 0.3 0.3 <![CDATA[Nuosperse 657na e ]]> 1.2 1.2 1.2 1.2 1.2 1.2 1.2 <![CDATA[Bentone SD-2 f ]]> 0.4 0.4 0.4 0.4 0.4 0.4 0.4 <![CDATA[Bentone 38 f ]]> 0.6 0.6 0.6 0.6 0.6 0.6 0.6 <![CDATA[Acematt ok 412 g ]]> 0.6 0.6 0.6 0.6 0.6 0.6 0.6 <![CDATA[Raven 410 carbon black powder h > 0.3 0.3 0.3 0.3 0.3 0.3 0.3 <![CDATA[Nicron 665 i ]]> 25.7 25.7 25.7 25.7 25.7 25.7 25.7 <![CDATA[ASP-200 j ]]> 15.4 15.4 15.4 15.4 15.4 15.4 15.4 <![CDATA[Tiona 595 k ]]> 25.7 25.7 25.7 25.7 25.7 25.7 25.7 <![CDATA[Bartex 10 l ]]> 27.1 27.1 27.1 27.1 27.1 27.1 27.1

[0087] a,b Polyepoxide functional polymers available from Hexion

[0088] c Polyepoxide functional polymers based on phenolic varnishes are available from Palmer Holland.

[0089] d Rheology modifiers available from Arkema Inc.

[0090] eDispersants available from Elementis Specialties

[0091] f Organic derivatives of bentonite clay available from Evonik

[0092] g Matting agents available from Palmer Holland

[0093] h Available from Birla Carbon

[0094] i Talc available from Imerys Performance Additives

[0095] j Kaolin available from BASF

[0096] k Titanium dioxide available from Cristal Global

[0097] l Barium sulfate is available from TOR Minerals International.

[0098] For each example, add the mass (in grams) of the material listed in Table 1 to a container containing 200 g of 1.2–1.6 mm ZIRCONOX grinding media and disperse on a LAU DAS200 disperser (LAU GmbH) for 2–4 hours. The grinding fineness of these dispersions is greater than 5, as described in ASTM D1210.

[0099] Table 2

[0100]

[0101] a Epoxy-functionalized silanes available from Momentive Performance Materials

[0102] b Pentaerythritol tetra(3-mercaptopropionate) is available from Bruno Bock GmbH.

[0103] c Polysulfides available from Akzo Nobel Chemicals

[0104] d A solution of 36% by weight polyamide amine and amine catalyst in solvent, available from PPG Industries Automotive Repair.

[0105] e Co-reaction mixture of catalyst and phenol polyamine available from Huntsman

[0106] A curable film-forming composition was prepared by mixing each component in the order listed in Table 2. Example 10 is comparative because it contains a polysulfide (see footnote c in Table 2) but no other polythiols. Example 11 is comparative because the pigment-to-binder ratio is less than 1. Example 12 is comparative because the pigment-to-binder ratio is equal to 3.

[0107] The composition was applied by spraying using a 1.4mm tip SATA HVLP applicator to produce a 3-5 mil dry film. The composition was applied to 4x12 inch cold-rolled steel, aluminum 6061T3, and electro-galvanized panels (available from ACT Corporation: part numbers 18661, 10288, 19081). These panels were prepared by grinding with a P180 abrasive disc using a double-acting pneumatic disc grinder and cleaned using a hydrocarbon degreaser.

[0108] Use the above abrasiveness test to determine the abrasiveness time. Two hours or less is considered acceptable.

[0109] Seven days after application, adhesion was tested using a handheld single-blade cutting tool with 2mm-pitch cuts, employing crosshatch and tape pull-off tests as described in ISO 2409:2013(E), and the adhesion was reported as described in the method described therein. Grades 0-2 were considered pass, while grades 3-5 were considered failure.

[0110]

[0111] Examples 8, 9 and 14 demonstrate that the curable film-forming compositions of the present invention containing aromatic epoxy resins exhibit adhesion to a variety of substrates and rapid sanding properties.

[0112] Examples 10 and 14 show that not all thiol resins produce acceptable adhesion and abrasion. In Example 14, polythiol functional compounds with three or more thiols per molecule produce acceptable adhesion and abrasion times. Comparative Example 10, which contains a polysulfide resin, does not exhibit acceptable abrasion or adhesion.

[0113] In Example 13, a small amount of phenolic polyamine produced an acceptable adhesion and sandable coating within 1 hour. Example 14 used a polyamide-amine resin to produce an acceptable adhesion and sandable coating within 2 hours.

[0114] Examples 11, 12, and 14 demonstrate that not all pigment-to-resin-solids weight ratios produce acceptable adhesion and sanding time. Comparative Example 11, with a P:B ratio of 1, does not exhibit acceptable adhesion or sanding time. Comparative Example 12, with a P:B ratio of 3, does not exhibit acceptable adhesion. Example 14, with a P:B ratio of 2.2, exhibits acceptable sanding and adhesion.

[0115] Although specific examples of the invention have been described above for illustrative purposes, it will be apparent to those skilled in the art that many detailed changes may be made to the invention without departing from the invention as defined in the appended claims.

[0116] Although various embodiments of the invention have been described by way of “including”, embodiments that are substantially composed of or consist of are also within the scope of the invention.

Claims

1. A curable film-forming composition comprising: (a) Polyepoxide functionalized polymers; (b) A polythiol functional compound, wherein the polythiol functional compound comprises at least two thiol functional groups, and wherein if the polythiol functional compound contains a hydroxyl functional group, the ratio of thiol functional groups to hydroxyl functional groups in the polythiol functional compound is not 1:

1. (c) A reactive compound, which is different from the polythiol functional compound (b), wherein the reactive compound contains a plurality of side groups and / or terminal functional groups that are reactive with epoxide functional groups, and the reactive compound includes polyamide amines and / or phenolic polyamines; as well as (d) Pigment, wherein the curable film-forming composition exhibits a pigment to binder ratio greater than or equal to 2 and less than 3.

2. The curable film-forming composition according to claim 1, wherein the weight ratio of the polythiol functional compound (b) to the reactive compound (c) is less than or equal to 10.

3. The curable film-forming composition according to claim 1 or 2, wherein the polyepoxide functional polymer (a) comprises a non-acrylic polyepoxide functional polymer.

4. The curable film-forming composition according to claim 1 or 2, wherein, based on the total weight of the polyepoxide functional polymer (a) in the curable film-forming composition, the polyepoxide functional polymer (a) comprises less than 25% by weight of an acrylic polyepoxide functional polymer.

5. The curable film-forming composition according to claim 1 or 2, wherein the polyepoxide functional polymer (a) contains aromatic groups.

6. The curable film-forming composition according to claim 1 or 2, wherein if the polythiol functional compound (b) contains a hydroxyl functional group, the ratio of thiol functional groups to hydroxyl functional groups in the polythiol functional compound (b) is greater than 1:

1.

7. The curable film-forming composition according to claim 1 or 2, wherein the polythiol functional compound (b) does not contain ether bonds or any reactive functional groups other than thiols.

8. The curable film-forming composition according to claim 1 or 2, wherein the thiol equivalent of the polythiol functional compound (b) is less than 330 g / equivalent.

9. The curable film-forming composition according to claim 1 or 2, wherein the polythiol functional compound (b) comprises the reaction product of a thiol functional organic acid and a polyol.

10. The curable film-forming composition according to claim 9, wherein the polythiol functional compound (b) has at least two ester functional groups and is tetrafunctional relative to the thiol functional group.

11. The curable film-forming composition according to claim 1 or 2, wherein the reactive compound (c) contains a plurality of reactive amine functional groups.

12. The curable film-forming composition according to claim 1 or 2, wherein if polysulfides and polysulfides are present, the total weight of solids in the composition is less than 0.1% by weight.

13. The curable film-forming composition according to claim 1 or 2, wherein the reactive compound (c) is present in the curable film-forming composition in an amount of at least 1% by weight and at most 15% by weight, based on the total weight of the resin solids in the curable film-forming composition.

14. The curable film-forming composition according to claim 1 or 2, wherein if a chromate compound is present, it is less than 0.1% by weight based on the total weight of solids in the composition.

15. The curable film-forming composition according to claim 1 or 2, wherein, based on the total weight of the resin solids in the curable film-forming composition, the composition further comprises at least 1% by weight and at most 30% by weight of strontium zinc phosphosilicate.

16. The curable film-forming composition according to claim 1 or 2, further comprising a catalyst selected from: oxazolidinyl alkane, alkylaminophenol, triethylamine, dimethylcyclohexylamine, dimethyloctylamine, dimethyldodecylamine, dimethylaminoethanol, tetramethylguanidine, diaza-bicyclo-octane, diaza-bicyclo-undecene, diaza-bicyclo-nonene, n-methyl-triaza-bicyclo-decene, and mixtures thereof.

17. The curable film-forming composition according to claim 1 or 2, wherein the pigment is non-thermal conductive.

18. A coated article comprising a substrate and a curable film-forming composition according to any one of claims 1 to 17 applied to at least one surface of said substrate.

19. The coated article of claim 18, wherein after the curable film-forming composition on the substrate is cured, when a cut is made at a 2 mm pitch using a handheld single-blade cutting tool according to ISO 2409:2013(E), the coated article exhibits an adhesion level of 0 to 2 within seven days after the curable film-forming composition is applied to the substrate.

20. A coated article comprising at least two different substrates and a curable film-forming composition according to any one of claims 1 to 17, applied to at least one surface of each of the substrates.

21. The coated article of claim 20, wherein, after the curable film-forming composition on the substrate is cured, when a cut is made at a 2 mm pitch using a handheld single-blade cutting tool according to ISO 2409:2013(E), the coated article exhibits an adhesion level of 0 to 2 on each of the substrates within seven days after the curable film-forming composition is applied to the substrate.

22. The coated article according to any one of claims 18 to 21, further comprising at least one additional film-forming composition applied on top of the curable film-forming composition and / or applied between the curable film-forming composition and the substrate.

23. The coated article according to any one of claims 18 to 21, wherein the coated article comprises components of vehicles, buildings, bridges, industrial protective structures, ships, railcar containers, water towers, power line towers, tunnels, oil or gas industry structures, marine structures, aerospace structures, bridge support structures, pipelines, oil rigs, storage tanks, or wind turbines.

24. A method for forming a coated article, the method comprising: (a) Applying the curable film-forming composition according to any one of claims 1 to 17 directly to at least a portion of at least one substrate to form at least one coated substrate; as well as (b) subjecting the at least one coated substrate to a temperature of at least 0°C and at most 60°C to cure the curable film-forming composition.

25. The method of claim 24, wherein each coated substrate passes a sandability test less than two hours after the curable film-forming composition is applied to the at least one substrate.

26. The method of claim 24, wherein when subjected to ISO 2409:2013(E) using a handheld single-blade cutting tool with 2 mm pitch cuts, each coated substrate exhibits an adhesion level of 0 to 2 within seven days after the curable film composition is applied to each substrate.

27. The method according to any one of claims 24 to 26, wherein the curable film-forming composition is directly applied to at least a portion of at least two different substrates.

28. The method according to any one of claims 24 to 26, wherein at least one of the substrates comprises a metal.

29. The method according to any one of claims 24 to 26, wherein the substrate comprises components of vehicles, buildings, bridges, industrial protective structures, ships, railcar containers, water towers, power line towers, tunnels, oil or gas industry structures, marine structures, aerospace structures, bridge support structures, pipelines, oil rigs, storage tanks, or wind turbines.

30. The method according to any one of claims 24 to 26, wherein the curable film-forming composition comprises a primer, a sealing varnish, a base coat, or a direct gloss topcoat, and imparts a decorative and / or protective finish to the substrate.

31. The method according to any one of claims 24 to 26, further comprising (c) applying at least one additional film-forming composition onto the top of at least a portion of the curable film-forming composition.

32. The method of claim 31, wherein the additional film-forming composition is a curable composition.

33. A coated article prepared by the method according to any one of claims 24 to 32.

34. A coating kit comprising: (a) Polyepoxide functionalized polymers; (b) A polythiol functional compound, wherein the polythiol functional compound comprises at least two thiol functional groups, and wherein if the polythiol functional compound contains a hydroxyl functional group, the ratio of thiol functional groups to hydroxyl functional groups in the polythiol functional compound is not 1:

1. (c) A reactive compound, which is different from the polythiol functional compound (b), wherein the reactive compound contains a plurality of side groups and / or terminal functional groups that are reactive with epoxide functional groups, and the reactive compound includes polyamide amines and / or phenolic polyamines; as well as (d) Pigment, wherein the curable film-forming composition exhibits a pigment to binder ratio greater than or equal to 2 and less than 3.

35. The coating kit of claim 34, comprising a plurality of separate components, wherein the first component comprises the polyepoxide functional polymer (a), the second component comprises the polythiol functional compound (b), and the third component comprises the reactive compound (c), and wherein the pigment (d) is present in the first component and / or the third component.

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