Patent Publication Number: US-2013237638-A1

Title: Low temperature, moisture curable coating compositions and related methods

Description:
FIELD 
     The present invention relates to coating compositions, such as low temperature, moisture curable coating compositions, related coated substrates, and methods for depositing a coating on a substrate. 
     BACKGROUND INFORMATION 
     Low temperature, moisture-curable coating compositions are desirable in many applications. For example, such coating compositions are, in at least some cases, preferable over, for example, thermally-cured or radiation cured coating compositions because (i) little or no energy is required to cure the composition, (ii) the materials from which some substrates are constructed cannot withstand elevated temperature cure conditions, and/or (iii) large or complex articles to be coated may not be convenient for processing through thermal or radiation cure equipment. 
     Some coating compositions are based on the hydrolysis and condensation of silane based materials that form a crosslinked Si—O—Si matrix. These compositions often form hard, highly crosslinked films, which are limited in flexibility. Therefore, the resultant coatings are often susceptible to chipping or thermal cracking due to embrittlement of the coating film. Moreover, such films can be especially unsuitable for use in coating substrates that can bend or flex, such as elastomeric automotive parts and accessories, for example, elastomeric bumpers and body side moldings, as well as consumer electronics equipment, among other things. The coating compositions applied to such elastomeric substrates typically must be very flexible so the coating can bend or flex with the substrate without cracking. 
     As a result, it would be desirable to provide low temperature, moisture curable coating compositions that are capable of producing a flexible, crack resistant coating when applied to a substrate and cured. In addition, it would be desirable to provide such coating compositions that can produce hard coatings within a relatively short period of time after application and cure under ambient conditions, without significantly detrimentally impacting other coating properties, such as appearance. 
     SUMMARY OF THE INVENTION 
     In certain respects, the present invention is directed to coating compositions. These coating compositions comprise: (a) an ungelled, secondary amine-containing, Michael addition reaction product of reactants comprising: (i) a compound comprising more than one site of ethylenic unsaturation, and (ii) an aminofunctional silane; (b) a primary amine functional polysiloxane; and (c) a compound comprising functional groups reactive with amine groups. 
     In some respects, the present invention is directed to coating compositions that comprise: (a) an ungelled, secondary amine-containing, Michael addition reaction product of reactants comprising: (i) a compound comprising more than one site of ethylenic unsaturation, and (ii) an aminofunctional silane; (b) a primary amine functional polysiloxane; (c) a polyepoxide; and (d) an alkoxy- and/or silanol-functional polysiloxane. 
     The present invention is also related to, inter alia, substrates at least partially coated with such compositions and methods for coating substrates with such compositions. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term “about”. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. 
     Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements. 
     Also, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of “1 to 10” is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10. 
     In this application, the use of the singular includes the plural and plural encompasses singular, unless specifically stated otherwise. In addition, in this application, the use of “or” means “and/or” unless specifically stated otherwise, even though “and/or” may be explicitly used in certain instances. 
     As previously mentioned, certain embodiments of the present invention are directed to coating compositions, such as low temperature, moisture curable coating compositions. As used herein, the term “low temperature, moisture curable” refers to coating compositions that, following application to a substrate, are capable of curing in the presence of ambient air, the air having a relative humidity of 10 to 100 percent, such as 25 to 80 percent, and a temperature in the range of −10 to 120° C., such as 5 to 80° C., in some cases 10 to 60° C. and, in yet other cases, 15 to 40° C. As used herein, the term “cure” refers to a coating wherein any crosslinkable components of the composition are at least partially crosslinked. In certain embodiments, the crosslink density of the crosslinkable components, i.e., the degree of crosslinking, ranges from 5% to 100%, such as 35% to 85%, or, in some cases, 50% to 85% of complete crosslinking. One skilled in the art will understand that the presence and degree of crosslinking, i.e., the crosslink density, can be determined by a variety of methods, such as dynamic mechanical thermal analysis (DMTA) using a Polymer Laboratories MK III DMTA analyzer conducted under nitrogen. 
     As will also be appreciated by those skilled in the art, the degree of cure can be determined by testing the solvent resistance of a coating to double rubs of methyl ethyl ketone. The higher the number of double rubs with no damage to the coating, the greater the degree of cure. In this test, an index finger holding a double thickness of cheesecloth saturated with methyl ethyl ketone is held at a 45° angle to the coating surface. The rub is made with moderate pressure at a rate of 1 double rub per second. As used herein, when it is stated that a coating is “completely cured” it means that the coating is resistant to 100, in some cases 200, double rubs of methyl ethyl ketone according to the foregoing procedure, with no damage to the coating. 
     The coating compositions of the present invention comprise an ungelled, secondary amine-containing, Michael addition reaction product of reactants comprising a compound comprising more than one site of ethylenic unsaturation, i.e., a polyethylenically unsaturated compound, such as a poly (meth)acrylate, and an aminofunctional silane. As used herein, the term “(meth)acrylate” is intended to include both methacrylates and acrylates. As used herein, the term “secondary amine-containing” refers to compounds comprising a secondary amine, which is a functional group wherein two organic substituents are bound to a nitrogen together with one hydrogen. As used herein, the term “ungelled” refers to resins that are substantially free of crosslinking and have an intrinsic viscosity when dissolved in a suitable solvent, as determined, for example, in accordance with ASTM-D1795 or ASTM-D4243. The intrinsic viscosity of the resin is an indication of its molecular weight. A gelled resin, on the other hand, since it is of essentially infinitely high molecular weight, will have an intrinsic viscosity too high to measure. As used herein, a resin (or polymer) that is “substantially free of crosslinking” refers to a reaction product that has a weight average molecular weight (Mw), as determined by gel permeation chromatography, of less than 1,000,000. 
     In certain embodiments, the compound comprising more than one site of ethylenic unsaturation comprises a polyethylenically unsaturated monomer, such as di- and higher acrylates. Specific examples of suitable polyethylenically unsaturated monomers are diacrylates, such as 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, 1,4-butanediol dimethacrylate, poly(butanediol) diacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, triethylene glycol diacrylate, triisopropylene glycol diacrylate, polyethylene glycol diacrylate, and/or bisphenol A dimethacrylate; triacrylates, such as trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol monohydroxy triacrylate, and/or trimethylolpropane triethoxy triacrylate; tetraacrylates, such as pentaerythritol tetraacrylate, and/or di-trimethylolpropane tetraacrylate; and/or pentaacrylates, such as dipentaerythritol (monohydroxy) pentaacrylate. 
     In addition to or in lieu of the aforementioned polyethylenically unsaturated monomers, the compositions of the present invention may comprise the Michael addition reaction product of reactants comprising a polyethylenically unsaturated oligomer. As will be appreciated, the term “oligomer” and “polymer” are frequently used interchangeably. Although the term “oligomer” is generally used to describe a relatively short polymer, the term has no generally accepted definition with respect to the number of repeating monomer units. As used herein, therefore, in describing compounds comprising more than one site of ethylenic unsaturation, the terms “oligomer” and “polymer” are meant to be interchangeable. 
     Examples of some specific polyethylenically unsaturated oligomers suitable for use in the present invention include, for example, urethane acrylates, polyester acrylates and mixtures thereof, particularly those that are free of hydroxyl functional groups. Specific examples of such materials include urethane acrylates, such as Ebecryl 220 and Ebecryl 264 available from Cytec Surface Specialties Inc. and polyester acrylates, such as Ebecryl 80 available from UCB Chemicals. 
     As previously indicated, in certain embodiments of the coating compositions of the present invention, the compound(s) comprising more than one site of ethylenic unsaturation identified above is reacted with an aminofunctional silane. As used herein, the term “aminofunctional silane” refers to a compound having a molecular structure that includes an amine group and a silicon atom. 
     In certain embodiments, the aminofunctional silane utilized in the foregoing reaction comprises a compound having the formula: 
     
       
         
         
             
             
         
       
     
     wherein R′ is an alkylene group having from 2 to 10 carbon atoms, R″ is an alkyl, aryl, alkoxy, or aryloxy group having from 1 to 8 carbon atoms, R′″ is an alkyl group having from 1 to 8 carbon atoms, and p has a value of from 0 to 2. In certain embodiments of the present invention, R′ is an alkylene group having from 2 to 5 carbon atoms and p is 0, the use of which the inventors have discovered is, in at least some embodiments, best for obtaining dust free films in 10 minutes or less and completely cured films within 24 hours, under the low temperature, moisture cure conditions described earlier. 
     Specific examples of aminofunctional silanes which are suitable for use in the present invention include aminoethyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylphenyldiethoxysilane, γ-aminopropyltrimethoxysilane, δ-aminobutyltriethoxysilane, δ-aminobutylethyldiethoxysilane. In certain embodiments, the aminofunctional silane comprises a γ-aminopropyltrialkoxysilane. 
     In certain embodiments of the present invention, little or no other reactant, such as a polyamine, is added to the reactant mixture for the Michael addition reaction. As a result, in certain embodiments, the reactants taking part in the Michael addition reaction are substantially free, or, in some cases, completely free of any polyamine. As used herein, the term “polyamine” refers to compounds comprising two or more primary or secondary amino groups. As used herein, unless specifically stated otherwise, the term “substantially free” means that the material being discussed is present in a composition, if at all, as an incidental impurity. In other words, the material does not affect the properties of the composition. As used herein, the term “completely free” means that the material being discussed is not present in a composition at all. The inventors have discovered that the presence of any significant quantity of polyamine can, in at least some cases, result in increased yellowing, the generation of additional unwanted byproducts, and/or an undesirable accelerated building of viscosity in the Michael addition reaction product. 
     In certain embodiments, the ungelled Michael addition reaction product is formed by simply blending the reactants at room temperature or at a slightly elevated temperature, for example, up to 100° C. The reaction of an amine group with an ethylenically unsaturated group which occurs in this invention is often referred to as a Michael addition reaction. As a result, as used herein, the term “Michael addition reaction product” is meant to refer to the product of such a reaction. Such products can be more heat and light stable than greater acrylyl content-containing products. It should be recognized that slowly adding the aminofunctional silane to the compound comprising more than one site of ethylenic unsaturation results in there being a large excess of acrylate groups to aminofunctional silane. Unless the temperature of the reaction mixture is kept sufficiently low, a gelled product can be the result. It is sometimes better, therefore, to add the unsaturated material to a reaction vessel already containing an aminofunctional silane to obtain an ungelled reaction product. The reaction can be carried out in the absence of a solvent or in the presence of an inert solvent. Examples of suitable inert solvents are toluene, butyl acetate, methyl isobutyl ketone, and ethylene glycol monoethyl ether acetate. It is often desirable that the reaction be conducted in the absence of moisture or in a controlled amount of moisture to avoid unwanted side reactions and possibly gelation. 
     In certain embodiments, Michael addition reaction is conducted such that the equivalent ratio of the ethylenically unsaturated groups to the amine groups is at least 1:1, in some cases, at least 1.05:1. 
     In certain embodiments, the Michael addition reaction product identified above is present in the coating compositions of the present invention in an amount of at least 20 percent by weight, such as at least 30 percent by weight, such as at least 40 percent by weight, based on the total weight of the composition. In certain embodiments, the Michael addition reaction product identified above is present in the coating compositions of the present invention in an amount of no more than 80 percent by weight, such as no more than 60 percent by weight, with the weight percents being based on the total weight of the composition. 
     In certain embodiments, the coating compositions of the present invention further comprise a Michael addition reaction product of reactants comprising, or, in some cases, consisting essentially of: (a) a compound comprising one site of ethylenic unsaturation, and (b) an aminofunctional silane. 
     In certain embodiments, the compound comprising one site of ethylenic unsaturation comprises a (meth)acrylate, including, for example, any C 1 -C 30  aliphatic alkyl ester of (meth)acrylic acid, non-limiting examples of which include methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, N-butyl(meth)acrylate, t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, N-butoxy methyl (meth)acrylamide, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate. 
     As previously indicated, in accordance with certain embodiments of the present invention, the compound(s) comprising one site of ethylenic unsaturation identified above is reacted with an aminofunctional silane. Suitable aminofunctional silanes for this purpose include any of the aminofunctional silanes previously identified herein. 
     In certain embodiments of the present invention, little or no other reactant, such as a polyamine, is added to the reactant mixture for the Michael addition reaction. As a result, in certain embodiments, the reactants taking part in the Michael addition reaction are substantially free, or, in some cases, completely free of any polyamine. 
     In certain embodiments, the Michael addition reaction is performed by simply blending the reactants at room temperature or at a slightly elevated temperature, for example, up to 100° C. The reaction can be carried out in the absence of a solvent or in the presence of an inert solvent. Examples of suitable inert solvents include any of the solvents previously identified herein. 
     In certain embodiments, Michael addition reaction is conducted such that the equivalent ratio of the ethylenically unsaturated groups to the amine groups is at least 1:1, in some cases, at least 1.05:1. 
     In certain embodiments, the Michael addition reaction product of the reaction between an aminofunctional silane and a compound comprising one site of ethylenic unsaturation identified above is present in the coating compositions of the present invention in an amount of up to 30 percent by weight, such as up to 25 percent by weight, based on the total weight of the composition. In certain embodiments, the Michael addition reaction product of the reaction between an aminofunctional silane and a compound comprising one site of ethylenic unsaturation identified above is present in the coating compositions of the present invention in an amount of at least 10 percent by weight, such as at least 15 percent by weight, based on the total weight of the composition. 
     The coating compositions of the present invention also comprise a primary amine functional polysiloxane, such as those having a general structure (I): 
     
       
         
         
             
             
         
       
     
     in which each R 1  may be a difunctional organic radical independently selected from the group consisting of aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl, and cycloalkyl radicals, each R 2  may independently selected from the group consisting of aryl, phenyl, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, and —OSi(R 2 ) 2 R 1 NH 2 . The polysiloxane may have a structure where x is 1 to 30, such as 10 to 20. In some cases, x is selected so that the polysiloxane has an amine equivalent weight ranging from about 100 to about 1,000, such as 200 to 500. In some embodiments, R 2  may be selected from phenyl, methyl, methoxy, —OSi(R 2 ) 2 R 1 NH 2  and mixtures of any thereof. In specific embodiments, the primary amine functional polysiloxane may comprise methyl and phenyl substitution at R 2 . In some embodiments, for example, at least one R 2  is methyl, at least one R 2  is methoxy, at least one R 2  is phenyl, and at least one R 2  is —OSi(R 2 ) 2 R 1 NH 2 , For example, according to one embodiment, the primary amine functional polysiloxane may be SILRES® HP2000 an amino functional, methyl phenyl silicone resin, having an amine equivalent weight of 230-255, commercially available from Wacker Chemical Corporation, Adrian, Mich. 
     In certain embodiments, the primary amine functional polysiloxane is present in the coating compositions of the present invention in an amount of up to 20 percent by weight, such as up to 10 percent by weight, based on the total weight of the composition. In certain embodiments, the primary amine functional polysiloxane is present in the coating compositions of the present invention in an amount of at least 0.1 percent by weight, such as at least 1 percent by weight, based on the total weight of the composition. 
     In certain embodiments, the coating compositions of the present invention also comprise one or more cyclic diamines having the structure (II): 
     
       
         
         
             
             
         
       
     
     wherein R 1  and each R 2 , which may be the same or different, represents H or a C 1  to C 6  alkyl group. In certain embodiments, R 1  is H or methyl. In certain embodiments, each R 2  is H or methyl. Specific examples of such compounds, which are suitable for use in the present invention, include 4-amino-2,2,6,6-tetramethylpiperidine, 4-amino-1,2,2,6,6-pentamethylpiperidine, and 4-aminopiperidine, as well as mixtures thereof. 
     In certain embodiments, the cyclic diamine is present in the coating compositions of the present invention in an amount of up to 20 percent by weight, such as up to 10 percent by weight, based on the total weight of the composition. In certain embodiments, the cyclic diamine is present in the coating compositions of the present invention in an amount of at least 0.1 percent by weight, such as at least 1 percent by weight, based on the total weight of the composition. 
     In certain embodiments, the amine functional components are present in the composition in amounts such that ratio of primary amine groups to secondary amine groups ranges from 1:5 to 5:1, such as 1:2 to 2:1, or, in some cases, 1:1. 
     In certain embodiments, particularly where the coating compositions is intended for use as a primer, the coating compositions of the present invention may further comprise a phenalkamine. As will be appreciated, phenalkamines are a class of Mannich bases obtained by reacting a cardinol-containing extract derived from cashew nutshell liquid, an aldehyde compound, such as formaldehyde, and an amine. Commercially available phenalkamines often use ethylenediamine and diethyltriamine as the amine. 
     In certain embodiments, the phenalkamine is present in the coating compositions of the present invention in an amount of up to 20 percent by weight, such as up to 10 percent by weight, based on the total weight of the composition. In certain embodiments, the phenalkamine is present in the coating compositions of the present invention in an amount of at least 0.1 percent by weight, such as at least 1 percent by weight, based on the total weight of the composition. 
     The coating compositions of the present invention further comprise a compound comprising functional groups reactive with amine groups. As will be appreciated by those skilled in the art, such functional groups include, but are not limited to, isocyanates, epoxies, and ethylenically unsaturated groups. In certain embodiments, such a compound is selected from a polyepoxide, a compound having two or more ethylenically unsaturated groups, or a mixture thereof. 
     As used herein, the term “polyepoxide” refers to an epoxy resin having at least two 1,2-epoxide groups per molecule. In certain embodiments, the epoxy equivalent weight ranges from 100 to 4000 based on solids of the polyepoxide, such as between 100 and 1000. The polyepoxides may be, for example, saturated or unsaturated, and may be, for example, aliphatic, alicyclic, aromatic, or heterocyclic. They may contain substituents such as, for example, halogens, hydroxyl groups, and ether groups. 
     Suitable classes of polyepoxides include epoxy ethers obtained by reacting an epihalohydrin, such as epichlorohydrin, with a polyphenol in the presence of an alkali. Suitable polyphenols include, for example, resorcinol, catechol, hydroquinone, bis(4-hydroxyphenyl)-2,2-propane (Bisphenol A), bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-hydroxyphenyl)-1,1-ethane, bis(2-hydroxyphenyl)-methane, 4,4-dihydroxybenzophenone, and 1,5-dihydroxynaphthalene. In some cases, the diglycidyl ether of Bisphenol A is especially suitable. 
     Other suitable polyepoxides include polyglycidyl ethers of polyhydric alcohols and/or polyhydric silicones. Suitable polyhydric alcohols include, without limitation, ethylene glycol, propylene glycol, butylene glycol, 1,6-hexylene glycol, neopentyl glycol, diethylene glycol, glycerol, trimethylol propane, and pentaerythritol. These compounds may also be derived from polymeric polyols, such as polypropylene glycol. 
     Examples of other suitable polyepoxides include polyglycidyl esters of polycarboxylic acids. These compounds may be formed by reacting epichlorohydrin or another epoxy material with an aliphatic or aromatic polycarboxylic acid, such as succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, 2,6-naphthalene dicarboxylic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, or trimellitic acid. Dimerized unsaturated fatty acids containing about 36 carbon atoms (Dimer Acid) and polymeric polycarboxylic acids, such as carboxyl terminated acrylonitrile-butadiene rubber, may also be used in the formation of these polyglycidyl esters of polycarboxylic acids. 
     Polyepoxides derived from the epoxidation of an olefinically unsaturated alicyclic compound are also suitable for use in the coating compositions of the present invention. These polyepoxides are nonphenolic and are obtained by epoxidation of alicyclic olefins with, for example, oxygen, perbenzoic acid, acid-aldehyde monoperacetate, or peracetic acid. Such polyepoxides include the epoxy alicyclic ethers and esters well known in the art. 
     Other suitable polyepoxides include epoxy novolac resins. These resins are obtained by reacting an epihalohydrin with the condensation product of aldehyde and monohydric or polyhydric phenols. A typical example is the reaction product of epichlorohydrin with a phenol-formaldehyde condensate. 
     Suitable polyepoxides also include epoxy-functional organopolysiloxanes, such as the resins described in U.S. Pat. No. 6,344,520 at col. 3, line 46 to col. 6, line 41, the cited portion of which being incorporated herein by reference. 
     The coating compositions of the present invention may contain one polyepoxide or a mixture of two or more polyepoxides. 
     In certain embodiments of the present invention, the amine functional components (referred to herein as component 1) and the compound(s) comprising functional groups reactive with amine groups (referred to herein as component 2) are present in the composition in amounts such that the molar ratio of amine groups in the composition to the reactive groups reactive therewith is 0.7 to 1.3, in some cases, 0.9 to 1.1, and, in yet other cases 1:1. 
     In certain embodiments, the coating compositions of the present invention also comprise an alkoxy- and/or silanol-functional polysiloxane, such as those of the formula: 
     
       
         
         
             
             
         
       
     
     wherein each R 1  is independently selected from the group comprising alkyl and aryl radicals, R 2  and R 9  which may be identical or different, are selected each independently from the group comprising hydrogen, alkyl and aryl radicals, n is selected so that the molecular weight for the polysiloxane is in the range of from 400 to 10,000. 
     Suitable polysiloxanes include, but are not necessarily limited to, those having a molecular weight ranging from 500 to 6000 and an alkoxy content ranging from 10 to 50%. 
     Examples of suitable alkoxy-functional polysiloxanes include: Silres SY-550 and SY-231 from Wacker Silicone; Rhodorsil Resin 10369 A, Rhodorsil 48V750, 48V3500 from Rhodia Silicones; and SF1147 from General Electrics. Suitable silanol-functional polysiloxanes include, but are not limited to, Silres SY 300, Silres SY 440, Silres MK and REN 168 from Wacker Silicone, Dow Corning&#39;s DC-840, DC-3074, DC3037, DC233 and DC-431 HS silicone resins and DC-Z-6018 intermediate and Rhodia Silicones&#39; Rhodorsil Resin 6407 and 6482×. 
     In certain embodiments, the previously described alkoxy- and/or silanol-functional polysiloxane is present in the coating compositions of the present invention in an amount of up to 40 percent by weight, such as up to 30 percent by weight, based on the total weight of the composition. In certain embodiments, the previously described alkoxy- and/or silanol-functional polysiloxane is present in the coating compositions of the present invention in an amount of at least 5 percent by weight, such as at least 10 percent by weight, based on the total weight of the composition. 
     The coating compositions of the present invention may also include a cure promoting catalyst, such as a tin catalyst and/or a base catalyst. Suitable base catalysts include triphenylphosphine, ethyltriphenyl phosphonium iodide, tetrabutyl phosphonium iodide and tertiary amines, such as benzyldimethylamine, dimethylaminocyclohexane, triethylamine, and the like, N-methylimidazole, and tetrabutyl ammonium hydroxide. When used, such catalysts are, in certain embodiments, present in an amount of 0.1 to 1 percent by weight, based on the total weight of the coating composition. 
     In certain embodiments, the coating compositions of the present invention also comprise a colorant. As used herein, the term “colorant” means any substance that imparts color and/or other opacity and/or other visual effect to the composition. The colorant can be added to the coating in any suitable form, such as discrete particles, dispersions, solutions and/or flakes. A single colorant or a mixture of two or more colorants can be used in the coating compositions of the present invention. 
     Example colorants include pigments, dyes and tints, such as those used in the paint industry and/or listed in the Dry Color Manufacturers Association (DCMA), as well as special effect compositions. A colorant may include, for example, a finely divided solid powder that is insoluble but wettable under the conditions of use. A colorant can be organic or inorganic and can be agglomerated or non-agglomerated. Colorants can be incorporated into the coatings by use of a grind vehicle, such as an acrylic grind vehicle, the use of which will be familiar to one skilled in the art. 
     Example pigments and/or pigment compositions include, but are not limited to, carbazole dioxazine crude pigment, azo, monoazo, disazo, naphthol AS, salt type (lakes), benzimidazolone, condensation, metal complex, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments, diketo pyrrolo pyrrole red (“DPPBO red”), titanium dioxide, carbon black and mixtures thereof. The terms “pigment” and “colored filler” can be used interchangeably. 
     Example dyes include, but are not limited to, those that are solvent and/or aqueous based such as phthalo green or blue, iron oxide, bismuth vanadate, anthraquinone, perylene, aluminum and quinacridone. 
     Example tints include, but are not limited to, pigments dispersed in water-based or water miscible carriers such as AQUA-CHEM 896 commercially available from Degussa, Inc., CHARISMA COLORANTS and MAXITONER INDUSTRIAL COLORANTS commercially available from Accurate Dispersions division of Eastman Chemical, Inc. 
     As noted above, the colorant can be in the form of a dispersion including, but not limited to, a nanoparticle dispersion. Nanoparticle dispersions can include one or more highly dispersed nanoparticle colorants and/or colorant particles that produce a desired visible color and/or opacity and/or visual effect. Nanoparticle dispersions can include colorants such as pigments or dyes having a particle size of less than 150 nm, such as less than 70 nm, or less than 30 nm. Nanoparticles can be produced by milling stock organic or inorganic pigments with grinding media having a particle size of less than 0.5 mm. Example nanoparticle dispersions and methods for making them are identified in U.S. Pat. No. 6,875,800 B2, which is incorporated herein by reference. Nanoparticle dispersions can also be produced by crystallization, precipitation, gas phase condensation, and chemical attrition (i.e., partial dissolution). In order to minimize re-agglomeration of nanoparticles within the coating, a dispersion of resin-coated nanoparticles can be used. As used herein, a “dispersion of resin-coated nanoparticles” refers to a continuous phase in which is dispersed discreet “composite microparticles” that comprise a nanoparticle and a resin coating on the nanoparticle. Example dispersions of resin-coated nanoparticles and methods for making them are described, for example, in U.S. Pat. No. 7,605,194 at col. 3, line 56 to col. 16, line 25, the cited portion of which being incorporated herein by reference. 
     Example special effect compositions that may be used in the coating compositions of the present invention include pigments and/or compositions that produce one or more appearance effects such as reflectance, pearlescence, metallic sheen, phosphorescence, fluorescence, photochromism, photosensitivity, thermochromism, goniochromism and/or color-change. Additional special effect compositions can provide other perceptible properties, such as opacity or texture. In certain embodiments, special effect compositions can produce a color shift, such that the color of the coating changes when the coating is viewed at different angles. Example color effect compositions are identified in U.S. Pat. No. 6,894,086, which is incorporated herein by reference. Additional color effect compositions can include transparent coated mica and/or synthetic mica, coated silica, coated alumina, a transparent liquid crystal pigment, a liquid crystal coating, and/or any composition wherein interference results from a refractive index differential within the material and not because of the refractive index differential between the surface of the material and the air. 
     In certain embodiments, a photosensitive composition and/or photochromic composition, which reversibly alters its color when exposed to one or more light sources, can be used in the coating compositions of the present invention. Photochromic and/or photosensitive compositions can be activated by exposure to radiation of a specified wavelength. When the composition becomes excited, the molecular structure is changed and the altered structure exhibits a new color that is different from the original color of the composition. When the exposure to radiation is removed, the photochromic and/or photosensitive composition can return to a state of rest, in which the original color of the composition returns. In certain embodiments, the photochromic and/or photosensitive composition can be colorless in a non-excited state and exhibit a color in an excited state. Full color-change can appear within milliseconds to several minutes, such as from 20 seconds to 60 seconds. Example photochromic and/or photosensitive compositions include photochromic dyes. 
     In certain embodiments, the photosensitive composition and/or photochromic composition can be associated with and/or at least partially bound to, such as by covalent bonding, a polymer and/or polymeric materials of a polymerizable component. In contrast to some coatings in which the photosensitive composition may migrate out of the coating and crystallize into the substrate, the photosensitive composition and/or photochromic composition associated with and/or at least partially bound to a polymer and/or polymerizable component in accordance with certain embodiments of the present invention, have minimal migration out of the coating. Example photosensitive compositions and/or photochromic compositions and methods for making them are identified in United States Published Patent Application No. 2006-0014099 A1, which is incorporated herein by reference. 
     In general, the colorant can be present in the coating composition in any amount sufficient to impart the desired visual and/or color effect. The colorant may comprise from 1 to 65 weight percent of the present compositions, such as from 3 to 40 weight percent or 5 to 35 weight percent, with weight percent based on the total weight of the compositions. 
     The coating compositions of the present invention can, if desired, be formulated with a variety of organic solvents, such as ketones, including methyl ethyl ketone, hydrocarbons, such as toluene and xylene, and mixtures thereof. 
     In certain embodiments, however, the coating compositions of the present invention are substantially free, or, in some cases, completely free of any solvent, such as an organic solvent or an aqueous solvent, i.e., water. Stated differently, in certain embodiments, the coating compositions of the present invention are substantially 100% active. 
     The coating compositions of the present invention can be utilized as one package compositions or as two package compositions. As two packs, one package comprises component 1 described above and the second pack comprises component 2 described above. The previously described additives and other materials can be added to either package as desired or necessary. The two packages are simply mixed together at or near the time of use. 
     In certain embodiments of the present invention, such as the previously described two package composition, the package comprising the component 1 also includes a moisture scavenger. Suitable moisture scavenging ingredients include calcium compounds, such as CaSO 4 -½H 2 O, metal alkoxides, such as tetraisopropyltitanate, tetra n butyl titanate-silanes, QP-53 14, vinylsilane (A171), and organic alkoxy compounds, such as triethyl orthoformate, trimethyl orthoformate, tetramethyl orthosilicate, and methylorthoformate. 
     In certain embodiments, the moisture scavenger is present in the package comprising component 1 in an amount of up to 10 percent by weight, such as 0.25 to 9.75 percent by weight, or, in some cases 5 percent by weight, based on the total weight of component 1. 
     The present invention is also directed to multi-pack coating compositions, wherein (A) a first pack comprises an amine functional component comprising: (1) an ungelled, secondary amine-containing, Michael addition reaction product of reactants comprising: (a) a compound comprising more than one site of ethylenic unsaturation, and (b) an aminofunctional silane; and (2) a primary amine functional polysiloxane; and (B) a second pack comprises a compound comprising functional groups reactive with amine groups. 
     The coating compositions of the present invention are suitable for application to any of a variety of substrates, including human and/or animal substrates, such as keratin, fur, skin, teeth, nails, and the like, as well as plants, trees, seeds, agricultural lands, such as grazing lands, crop lands and the like; turf-covered land areas, e.g., lawns, golf courses, athletic fields, etc., and other land areas, such as forests and the like. 
     Suitable substrates include cellulosic-containing materials, including paper, paperboard, cardboard, plywood and pressed fiber boards, hardwood, softwood, wood veneer, particleboard, chipboard, oriented strand board, and fiberboard. Such materials may be made entirely of wood, such as pine, oak, maple, mahogany, cherry, and the like. In some cases, however, the materials may comprise wood in combination with another material, such as a resinous material, i.e., wood/resin composites, such as phenolic composites, composites of wood fibers and thermoplastic polymers, and wood composites reinforced with cement, fibers, or plastic cladding. 
     Suitable metallic substrates include, but are not limited to, foils, sheets, or workpieces constructed of cold rolled steel, stainless steel and steel surface-treated with any of zinc metal, zinc compounds and zinc alloys (including electrogalvanized steel, hot-dipped galvanized steel, GALVANNEAL steel, and steel plated with zinc alloy), copper, magnesium, and alloys thereof, aluminum alloys, zinc-aluminum alloys such as GALFAN, GALVALUME, aluminum plated steel and aluminum alloy plated steel substrates may also be used. Steel substrates (such as cold rolled steel or any of the steel substrates listed above) coated with a weldable, zinc-rich or iron phosphide-rich organic coating are also suitable for use in the process of the present invention. Such weldable coating compositions are disclosed in, for example, U.S. Pat. Nos. 4,157,924 and 4,186,036. Cold rolled steel is also suitable when pretreated with, for example, a solution selected from the group consisting of a metal phosphate solution, an aqueous solution containing at least one Group IIIB or IVB metal, an organophosphate solution, an organophosphonate solution, and combinations thereof. Also, suitable metallic substrates include silver, gold, and alloys thereof. 
     Examples of suitable silicatic substrates are glass, porcelain and ceramics. 
     Examples of suitable polymeric substrates are polystyrene, polyamides, polyesters, polyethylene, polypropylene, melamine resins, polyacrylates, polyacrylonitrile, polyurethanes, polycarbonates, polyvinyl chloride, polyvinyl alcohols, polyvinyl acetates, polyvinylpyrrolidones and corresponding copolymers and block copolymers, biodegradable polymers and natural polymers—such as gelatin. 
     Examples of suitable textile substrates are fibers, yarns, threads, knits, wovens, nonwovens and garments composed of polyester, modified polyester, polyester blend fabrics, nylon, cotton, cotton blend fabrics, jute, flax, hemp and ramie, viscose, wool, silk, polyamide, polyamide blend fabrics, polyacrylonitrile, triacetate, acetate, polycarbonate, polypropylene, polyvinyl chloride, polyester microfibers, glass fiber fabric and carbon fibers. 
     Examples of suitable leather substrates are grain leather (e.g. nappa from sheep, goat or cow and box-leather from calf or cow), suede leather (e.g. velours from sheep, goat or calf and hunting leather), split velours (e.g. from cow or calf skin), buckskin and nubuk leather; further also woolen skins and furs (e.g. fur-bearing suede leather). The leather may have been tanned by any conventional tanning method, in particular vegetable, mineral, synthetic or combined tanned (e.g. chrome tanned, zirconyl tanned, aluminium tanned or semi-chrome tanned). If desired, the leather may also be re-tanned; for re-tanning there may be used any tanning agent conventionally employed for re-tanning, e.g. mineral, vegetable or synthetic tanning agents, e.g., chromium, zirconyl or aluminium derivatives, quebracho, chestnut or mimosa extracts, aromatic syntans, polyurethanes, (co) polymers of (meth)acrylic acid compounds or melamine, dicyanodiamide and/or urea/formaldehyde resins. 
     Examples of suitable compressible substrates include foam substrates, polymeric bladders filled with liquid, polymeric bladders filled with air and/or gas, and/or polymeric bladders filled with plasma. As used herein the term “foam substrate” means a polymeric or natural material that comprises a open cell foam and/or closed cell foam. As used herein, the term “open cell foam” means that the foam comprises a plurality of interconnected air chambers. As used herein, the term “closed cell foam” means that the foam comprises a series of discrete closed pores. Example foam substrates include polystyrene foams, polymethacrylimide foams, polyvinylchloride foams, polyurethane foams, polypropylene foams, polyethylene foams, and polyolefinic foams. Example polyolefinic foams include polypropylene foams, polyethylene foams and/or ethylene vinyl acetate (EVA) foam. EVA foam can include flat sheets or slabs or molded EVA forms, such as shoe midsoles. Different types of EVA foam can have different types of surface porosity. Molded EVA can comprise a dense surface or “skin”, whereas flat sheets or slabs can exhibit a porous surface 
     The coating compositions of the present invention can be applied to such substrates by any of a variety of methods including spraying, brushing, dipping, and roll coating, among other methods. In certain embodiments, however, the coating compositions of the present invention are applied by spraying and, accordingly, such compositions often have a viscosity that is suitable for application by spraying at ambient conditions. 
     After application of the coating composition of the present invention to the substrate, the composition is allowed to coalesce to form a substantially continuous film on the substrate. Typically, the film thickness will be 0.01 to 20 mils (about 0.25 to 508 microns), such as 0.01 to 5 mils (0.25 to 127 microns), or, in some cases, 0.1 to 2 mils (2.54 to 50.8 microns) in thickness. The coating compositions of the present invention may be pigmented or clear, and may be used alone or in combination as primers, basecoats, or topcoats. 
     The coating compositions of the present invention can be cured in a relatively short period of time to provide films that have good early properties which allow for handling of the coated objects without detrimentally affecting the film appearance and which ultimately cure to films which exhibit excellent hardness, solvent resistance and impact resistance. For example, the coating compositions of the present invention can dry in air at low temperatures to a dust free or tack free state in about 30 minutes, in some case 10 minutes or less. Thereafter, they will continue to cure in air at low temperatures so that a completely cured coating is formed in from, for example, 12 hours to 24 hours. 
     As a result, as previously indicated, the present invention is also directed to methods for coating a substrate. These methods comprise: (A) combining the contents of a first package and a second package, wherein (1) the first package comprises: (a) an ungelled, secondary amine-containing, Michael addition reaction product of reactants comprising: (i) a compound comprising more than one site of ethylenic unsaturation, and (ii) an aminofunctional silane; and (b) a primary amine functional polysiloxane, (2) the second package comprises a compound comprising functional groups reactive with amine groups, and (3) the contents of the first package and the second package are combined such that molar ratio of amine groups to the functional groups reactive with amine groups in the resulting combination is 0.7 to 1.3; (B) applying the combination to at least a portion of the substrate; (C) allowing the combination to coalesce form a substantially continuous film; and (D) allowing the combination to cure within 24 hours in the presence of air having a relative humidity of 10 to 100 percent and a temperature −10 to 120° C. 
     Illustrating the invention are the following examples that are not to be considered as limiting the invention to their details. All parts and percentages in the examples, as well as throughout the specification, are by weight unless otherwise indicated. 
     Example 1 
     A Michael addition product was prepared using the ingredients and amounts in Table 1. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                 Ingredients 
                 Parts By Weight 
               
               
                   
                   
               
             
            
               
                   
                 Charge 1 
                   
               
               
                   
                 γ-aminopropyltrimethoxysilane 1   
                 64.2% 
               
               
                   
                 Charge 2 
               
               
                   
                 Ethyl acrylate 
                 35.8% 
               
               
                   
                   
               
               
                   
                   1 γ-aminopropyltrimethoxysilane: Silquest A1110 available from Momentive Performance Materials 
               
            
           
         
       
     
     Charge #1 was added to an appropriate sized, 4-necked flask equipped with a motor driven stainless steel stir blade, water-cooled condenser, and a heating mantle with a thermometer connected through a temperature feedback control device. The contents were stirred under a nitrogen blanket. Charge #2 was added at an appropriate rate to keep the temperature &lt;60° C. Upon completion of Charge #2, the reaction temperature was set to 60° C. The reaction was held at temperature until the disappearance of the acrylate double bond was demonstrated by IR (peak at ˜1621 cm −1 ) and/or NMR (peaks at ˜5.7-6.4 ppm) analysis. 
     Example 2 
     The Michael addition product of Example 1 was mixed with Aromatic 100 in the amount listed in Table 2. Materials were mixed at &lt;40° C. and the final solution was stored under a nitrogen blanket. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 2 
               
               
                   
                   
               
               
                   
                 Ingredients 
                 Parts By Weight 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 Michael addition product of Example 1 
                 95.0% 
               
               
                   
                 Aromatic 100 
                 5.0% 
               
               
                   
                   
               
            
           
         
       
     
     Example 3 
     A Michael addition product was prepared using the ingredients and amount in Table 3. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 3 
               
               
                   
                   
               
               
                   
                 Ingredients 
                 Parts By Weight 
               
               
                   
                   
               
             
            
               
                   
                 Charge 1 
                   
               
               
                   
                 γ-aminopropyltrimethoxysilane 1   
                 60.0% 
               
               
                   
                 Charge 2 
               
               
                   
                 1,6-hexanediol diacrylate 
                 40.0% 
               
               
                   
                   
               
               
                   
                   1 γ-aminopropyltrimethoxysilane: Silquest A1110 available from Momentive Performance Materials 
               
            
           
         
       
     
     Charge #1 was added to an appropriate sized, 4-necked flask equipped with a motor driven stainless steel stir blade, water-cooled condenser, and a heating mantle with a thermometer connected through a temperature feedback control device. The contents were stirred under a nitrogen blanket. Charge #2 was added at an appropriate rate to keep the temperature &lt;60° C. Upon completion of Charge #2, the reaction temperature was set to 60° C. The reaction was held at temperature until the disappearance of the acrylate double bond was demonstrated by IR (peak at ˜1621 cm −1 ) and/or NMR (peaks at ˜5.7-6.4 ppm) analysis. 
     Example 4 
     The Michael addition product of Example 3 was mixed with Aromatic 100 in the amount listed in Table 4. The materials were mixed at &lt;40° C. and the final solution was stored under a nitrogen blanket. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 4 
               
               
                   
                   
               
               
                   
                 Ingredients 
                 Parts By Weight 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 Michael addition product of Example 3 
                 95.0% 
               
               
                   
                 Aromatic 100 Solvent 
                 5.0% 
               
               
                   
                   
               
            
           
         
       
     
     Example 5 
     A pigmented composition was prepared using the ingredients and amounts listed in Table 5. Amounts are in parts by weight. 
     
       
         
           
               
               
               
             
               
                 TABLE 5 
               
               
                   
               
               
                   
                   
                 Formula 
               
               
                 Ingredient 
                 Material Name 
                 Weight 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                 Eponex 1510 1   
                 Epoxy Resin 
                 8502.66 
               
               
                 K-Sperse XD-A504 2   
                 Dispersant 
                 115.57 
               
               
                 EFKA-2720 3   
                 De-aeration additive 
                 42.00 
               
               
                 1970A Naphthol Red 170 4   
                 Naphthol Red #170 
                 948.60 
               
               
                   
                 pigment 
               
               
                 1070 Naphthol Red 170 4   
                 Naphthol Red 
                 716.78 
               
               
                   
                 pigment 
               
               
                 R-1599D Easy Disp Red Iron 
                 Red Iron Oxide 
                 1987.14 
               
               
                 Oxide 5   
               
               
                 RV-6911 Quindo Violet 6   
                 Quinacridone 
                 224.06 
               
               
                   
                 CI: 46500 
               
               
                 Bentone SD-1 7   
                 Organophilic Clay 
                 38.40 
               
               
                 Tinuvin 144 8   
                 Butylpropanedioate 
                 357.60 
               
               
                 Tinuvin 328 9   
                 Benzotriazole 
                 357.60 
               
               
                 BYK-088 10   
                 Polysiloxane 
                 399.60 
               
               
                 Letdown 
               
               
                 BYK-333 10   
                 Polyether Modified 
                 120.00 
               
               
                   
                 Dimethylpolysiloxane 
                   
               
               
                   
                 Totals 
                 13810.02 
               
               
                   
               
               
                   1 Commercially available from Hexion 
               
               
                   2 Commercially available from King Industries 
               
               
                   3 Commercially available from BASF 
               
               
                   4 Commercially available from Lansco Colors 
               
               
                   5 Commercially available from Rockwood Pigments NA 
               
               
                   6 Commercially available from Sun Chemical 
               
               
                   7 Commercially available from Elementis Specialties 
               
               
                   8 Commercially available from Fine Grinding Corp 
               
               
                   9 Commercially available from BASF 
               
               
                   10 Commercially available from BYK Chemie 
               
            
           
         
       
     
     The pigmented composition was pre-dispersed with a high speed cowles blade. Eponex 1510, K-Sperse XD-A504, and EFKA-2720 were added to the batch container. The Cowles blade mixer was then turned on with enough speed to produce a vortex. Each subsequently listed material was added until incorporated by the mixing. After the final ingredient was added, the total batch was pre-mixed until reaching a temperature of 124F. BYK-333 was held out of the batch until after processing. The cowles blade was removed and the batch was moved to a Premier HM-1.5 “C” mill using a 75% charge of 1.2-1.7 mm Zirconox media. Once the mill was turned on the batch settings were 2400 feet per minute speed and 8.0 pounds per square inch pressure. The batch was processed for 120 minutes at 127° F., and a flow rate of 15 gallons per hour. A hegman grind of 8.0 was reached. At the end of the batch BYK-333 was added. 
     Example 6 
     Coating compositions were prepared by combining the ingredients listed in Table 6 in a suitable container equipped with a paddle blade mixer. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 6 
               
               
                   
                   
               
               
                   
                 Example 
                 Example 
                 Example 
                 Example 
               
               
                   
                 6A 
                 6B 
                 6C 
                 6D 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Product of Example 5 
                 37.3 
                 g 
                 37.3 
                 g 
                 37.3 
                 g 
                 37.3 
                 g 
               
               
                 Dibutyltin dilaurate 
                 0.5 
                 g 
                 0.5 
                 g 
                 0.5 
                 g 
                 0.5 
                 g 
               
               
                 4-amino-2,2,6,6- 
                 2.0 
                 g 
                 2.0 
                 g 
                 2.0 
                 g 
                 2.0 
                 g 
               
               
                 tetramethylpiperidine 11   
               
               
                 Product of Example 4 
                 24.8 
                 g 
                 24.8 
                 g 
                 24.8 
                 g 
                 24.8 
                 g 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Product of Example 2 
                 6.9 
                 g 
                 6.9 
                 g 
                 — 
                 — 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 DC-3074 12   
                 21.7 
                 g 
                 21.7 
                 g 
                 21.7 
                 g 
                 21.7 
                 g 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Eponex 1510 13   
                 6.0 
                 g 
                 6.0 
                 g 
                 6.0 
                 g 
                 — 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Butyl Acetate 
                 9.0 
                 g 
                 9.0 
                 g 
                 9.0 
                 g 
                 9.0 
                 g 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 SILRES HP2000 14   
                 — 
                 7.0 
                 g 
                 7.0 
                 g 
                 7.0 
                 g 
               
               
                   
               
               
                   11 Commercially available from Sigma-Aldrich 
               
               
                   12 Commercially available from Dow Corning 
               
               
                   13 Commercially available from Hexion 
               
               
                   14 Commercially available from Wacker Chemie AG 
               
            
           
         
       
     
     The coating compositions were spray applied onto 4 inch by 12 inch steel panels that were coated with commercially available and cured PPG ELECTROCOAT (ED 6060C) and PRIMER (HP 77224ER). The substrate panels were obtained from ACT Test Panels, Inc. of Hillsdale, Mich. The coatings were applied in two coats. A one minute room temperature flash was allowed between coats. Where appropriate the composite coating was allowed to flash for ten minutes at room temperature before baking for fifteen minutes. Results are set forth in Table 7. 
     
       
         
           
               
               
               
               
               
               
             
               
                   
                 TABLE 7 
               
               
                   
                   
               
               
                   
                   
                 Fischer 
                 Fischer 
                 Cross 
                 Cross 
               
               
                   
                   
                 Micro- 
                 Micro- 
                 hatch tape 
                 hatch tape 
               
               
                   
                   
                 Hardness 2   
                 Hardness 2   
                 adhesion - 
                 adhesion - 
               
               
                   
                 20° 
                 after 
                 after 
                 baked @ 
                 baked @ 
               
               
                   
                 gloss 1   
                 1 day 3   
                 4 days 3   
                 15′/140° F. 4   
                 15′/200° F. 4   
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 Example 
                 74 
                 5 
                 70 
                 1B 
                 2B 
               
               
                 6A 
               
               
                 Example 
                 78 
                 12 
                 120 
                 5B 
                 5B 
               
               
                 6B 
               
               
                 Example 
                 78 
                 12 
                 121 
                 5B 
                 5B 
               
               
                 6C 
               
               
                 Example 
                 79 
                 16 
                 127 
                 5B 
                 5B 
               
               
                 6D 
               
               
                   
               
               
                   1 NOVO GLOSS statistical 20° Glossmeter available from Paul N. Gardner Company, Inc. of Pompano Beach, Florida. 
               
               
                   2 Fischer MicroHardness testing recorded on a Fischer HM 2000 unit available from Fischer Technology USA of Windsor, Ct. 
               
               
                   3 25° C. 50% relative humidity 
               
               
                   4 Adhesion follows the procedure as outlined by ASTM D3002 and D3359. 5B adhesion is excellent adhesion and 0B denotes no adhesion 
               
            
           
         
       
     
     In each of Examples 6A-6D the amine and epoxy stoichiometry was kept constant at 1:1, where possible. Immediately apparent is the significant improvement in adhesion and hardness with the compositions of the present invention (Examples 6B-6D) relative to Example 6A. Moreover, in all cases the appearance of the coating, as reflected by 20° gloss, was maintained. 
     It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications which are within the spirit and scope of the invention, as defined by the appended claims.