Title of Invention	A PROCESS FOR THE PREPARATION OF A COATING AND A METHOD OF COATING A SUBSTRATE WITH THE COATING
Abstract	(57) Abstract: The invention pertains to a process for the preparation of a coating, comprising the steps of preparing an organic solvent containing coating composition by combining (a) an organic solvent (b) a polyacetoacetate having acetoacetate groups and having a number average molecular weight in the range of 1000 to 5000 (c) a cross linker having at least two groups capable of crosslinking with the acetoacetate groups, and (d) at least one organosilane in which coating composition, the organosilane is present in an adhesion enhancing amount, and drying and/or curing the coating composition at a temperature between 5°C and 100°C. PRICE: THIRTY RUPEES

Title of Invention

A PROCESS FOR THE PREPARATION OF A COATING AND A METHOD OF COATING A SUBSTRATE WITH THE COATING

Abstract

(57) Abstract: The invention pertains to a process for the preparation of a coating, comprising the steps of preparing an organic solvent containing coating composition by combining (a) an organic solvent (b) a polyacetoacetate having acetoacetate groups and having a number average molecular weight in the range of 1000 to 5000 (c) a cross linker having at least two groups capable of crosslinking with the acetoacetate groups, and (d) at least one organosilane in which coating composition, the organosilane is present in an adhesion enhancing amount, and drying and/or curing the coating composition at a temperature between 5°C and 100°C. PRICE: THIRTY RUPEES

Full Text	The present invention relates to a process for the preparation of a coating and a method of coating a substrate with the coating. Coating compositions of this type are generally known from, for example, US-A-3668183, Polyenamine Coatings: I. Formulation of Coatings and Determination of Film Properties K.L. Hoy and C.H. Carder, ' Journal of Paint Technology, Vol. 46, No. 591, April 1974, pages 70-75, and "Polyenamine Coatings: II. Chemical Methods of Improving Film Properties", C.H. Carder and H.O. Colomb, Jr., Journal of Paint Technology, Vol. 46, No. 591, April 1974, pages 76-78. referred to respectively as "Polyenamine Coatings I" and "Polyenamine Coatings 11". Such coating compositions, when properly formulated and applied to a substrate, form a coating having highly desirable properties, such as hardness, flexibility and toughness. There is however, a continuing difficulty in that such coatings frequently do not adequately adhere to the substrate on which they are applied. US-A-3668183 generally discloses the production of polyenamine resins by the reaction of polyacetcacetates with blocked polyamines. Also disclosed there is the possible use of a silicone component in the polyacetoacetate end cap to improve acid resistance. WO-A-94/21738 discloses a crosslinkable liquid carrier-based coating composition comprising organic polymer(s) having acetoacetyl group functionality, a polyamine compound{s) having at least two acetoacetyl-reactive amino groups per molecule and a non-polymeric monoacetoacetyl compound(s) selected from a specific group of such compounds. The ratio of acetoacetyl groups of the acetoacetyl functional polymer(s) to the number of acetoacetyl-reactive amino wherein Z is an amino group, an amino-containing group, an epoxy group, an epoxy-containing group, a mercapto group, a mercapto-containing group, a vinyl group, a vinyl-containing group, an isocyanate group, an isocyanate-containing group, an ureido group, an ureido-containing group, an imidazole group or an imidazole-containing group, R is an aliphatic, alicylic or aromatic group, R' is an alkoxy group or alkoxyalkoxy groups, R" is an alkyl group having 1 to about 8 carbon atoms, X is 0 to about 20. a is 0 to 3, preferably 0 to 2, bis 1 to 4, 1 to 3, c is 0 to 3, and preferably 0 to 2, and the sum of a + b + c is 4. Preferred organosilanes are aminosilanes, epoxysilanes, mercaptosilanes, vinylsilanes, ureidosilanes, imidazolsilanes and isocyanatosilanes. Polyacetoacetates are acetoacetate-functionai compounds having at least two acetatoacetate groups. Polyacetoacetates are well known in the art, for example as demonstrated in the already mentioned US-A-3668183, US-A-5021537, "PoTyenamine Coatings I" and "Poiyenamine Coatings. 11". They can be described as the partial or complete acetoacetylation product of a monomeric polyalcohol having at least two free hydroxyl groups or an oligomeric or polymeric condensation derivative of such polyalcohols. The production of polyacetoacetates, "acetoacetylation", may be accomplished by various reaction schemes. Some examples are transesterification of alkyl acetoacetates, such as methyl, ethyl or t-butyl acetoacetate with polyols or the reaction of polyol or polythiol with diketene, or the diketene-acetone adduct 2,2,6-trimethyl-l,3-dioxin-4H-one. Such compounds and synthesis mechanisms are well known in the art (see for example US-A-3668183 and "The Acetoacetyl Functionality: A New Approach to Thermoset Coatings", R.J. Clemens, et al.. Proceedings: XVI^^ International Conference in Organic Coatings Science and Technology. 9-13 July 1990, Athens, Greece, page 127 et seq., and "Comparison of Methods for the Preparation of Acetoacetylated Coating Resins", J.5. Witzeman et al.. Journal of Coating Technology 62, No. 789, 101 (1990)) and need not be further detailed here. Preferably, polyacetoacetates used in the current invention are partial or couplet acetoacetylation products of (1) roonoroeric polyalcohols having 2 its 6 hydroxyl groups. (2) partial esters of polyalcohols with monocariioxyT 1 c acids (the carboxylic acids having 2 to 22 and preferably 5 to 18 carbon atoms), the partial esters having at least 2 unreacted hydroxyl groups, (3) polymeric condensates having at least 2 hydroxyl groups, suitable polymeric condensates being, for non-limiting example, polyesters, polyethers and/or polyurethanes (see, for example. The Chemistry of Organic Film Formers. D.H. Solomon, Robert E. Krieger Publishing Co., 1977) and (4) addition polymers containing at least two (2) hydroxyl groups. Some examples of monomeric polyalcohols having 2 to 6 hydroxyl groups which can be conveniently converted into polyacetoacetates include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol. 2-ethyl-2-butyl-propanediol, 2-methylpropanediol, 3-(nethyl-l,5-pentanediol, di-ethylene glycol, triethylene glycol, 1,4-cyclohexyldimethanol, dipropylene glycol, trimethylolethane, trimethylolpropane, glycerol, di-trimethylolpropane, pentaerythritol and the like. Suitable partial esters of polyalcohols with monocarboxylic acids containing 2 to 22, preferably 5 to 18 carbon atoms, the partial esters having at least 2 unreacted hydroxyl groups, include for example the reaction product of a triol, e.g. trimethylolpropane, with a monocarboxylic acid in a, for example, 1:1 molar ratio. Other suitable partial esters are the reaction products of a tetrol e.g. pentaerythritol, with a monocarboxylic acid in, for example, 1:1 or 1:2 molar ratio. Useful monocarboxylic acids are: acetic acid, hexanoic acid, 2-ethylhexanoic acid, nonaoic acid, 3,5,5-trimethylhexanoic acid, benzoic acid, oleic acid, linoleic acid, dehydrated castor oil fatty acid, and the like. It is well known that esterification of polyalcohols with monocarboxylic acids in a stoichiometric excess of the hydroxyl component generally yield a mixture of products with different degrees of esterification and having different hydroxyl functionalities. In addition to single alcohols and acids, mixtures of one or both reactants may also be used. Usually monomeric polyalcohols like trimethylolpropane, di-trimethylolpropane, pentaerythritol and other alcohols with 3 or more hydroxyl groups are partially esterified, however, if desired, polymeric preformed polyalcohols such as polyester-, polyether- and polyurethane polyols, and addition polymers, all containing 2 or more hydroxyl groups can be partially esterified with monocarboxylic acids and used as polyacetoacetate precursors. Partialmonocarboxylic acid esters of polyepoxy compounds represent a further group of suitable precursors for polyacetoacetate. Polyester polyols having at least 2 hydroxy!groups are suitable precursors for preparing polyacetoacetates. Usually the polyester polyols are made by the condensation of polyhydric alcohols and polycarboxylic acids or anhydrides, with or without the use of a monobasic acid, at temperatures at about 150°C to about 260°C and with a stoichiometric excess of the alcohol component. Suitable polyesters have a number average molecular weight of about 200 to about 5000, a hydroxyl number of about 50 to about 500 and a acid number of about 0 to about 50, preferably from 0 to about 20. Examples of polycarboxylic acids and anhydrides suitable for the preparation of polyester polyols include succinic acid, adipic acid, azaleic acid, terephthalic acid, l,4-cyc1ohexaned1carboxylic acid, fumaric acid, maleic acid, maleic anhydride, hexahydrophthalic anhydride, trimellitic anhydride and the like. Useful polyhydric alcohols (also sometimes referred to as "polyalcohols"), are ethylene glycol, diethylene glycol, 1.2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,5-hexanedlol, 1,4-cyclohexanediiDethanol, 2-methyl-l,3-propanediol, r.eopentyl glycol, 2-ethyl-2-butylpropanediol, glycerol, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, di-triraetnyiolpropane and other low molecular polyalcohols. Further classes of suitable polyalcohols for the production of polyesterpolyols are the reaction products of wjnoroeric polyalcohols with lactones, for example epsilon-caprolacton, alkoxylated polyalcohols such as the reaction products of glycerol, trimethylolpropane, neopentylglycol, water, ethylene glycol, Bisphenol A and the like with alkylene oxides, for example ethylene oxide, propylene oxide and mixtures thereof. The polyalcohols may be replaced partially or completely by mono- or polyepoxides e.g. the glycidyl ester of a C9-C11 branched aliphatic acid (available as Cardura® ElO from Shell) or diglycidyl ethers based on Bisphenol A- Polylactone polyesterpolyols are a next group of suitable precursors. These polyols are formed from the reaction of a lactone, e.g. epsilon caprolactone, and a polyalcohol, for example, those already mentioned above, such as ethylene glycol, trimethylolpropane, neopentyl glycol, and ethoxylated trimethyl ol propane. Polyurethanes with at least 2 hydroxyl groups are a further class of suitable polyacetoacetate precursors. Preparation of these polyurethanes usually involves the reaction of polyisocyanates with a stoichiometric excess of a monomeric or polymeric polyalcohols. The isocyanate component is selected from n-functional isocyanates wherein n is a number ranging from 2 to 5 preferably from 2 to 4 and especially from 3 to 4. The isocyanate component may include a single such n-functional isocyanate or combinations thereof. As specific examples of suitable n-functional isocyanates may be mentioned, for example, di isocyanates such as 1,6-hexane diisocyanate (commercially available, for example, under the trade designation HMDI from Bayer), isophorone di isocyanate (commercially available, for example, under the trade designation IPDI from Huels), tetrafflethylxylene di isocyanate (commercially available, for example, under the trade designation m-TMXDI from Cytec), 2-methyl-l,5-pentane di isocyanate, 2,2,4-tr1methyl-1,6-hexane diisocyanate, 1,12-dodecane di isocyanate and methylene b1s(4-cyclohexyl Isocyanate) (commercially available, for example, Desmodur® W from Bayer), and higher functional Isocyanates such as a biuret of 1,6-hexane diisocyanate (commercially available, for example, as Desmodur® N from Bayer), an isocyanurate of 1,6-hexane diisocyanate (commercially available, for example, as Desmodur® N-3390 from Bayer), an isocyanurate of isophorone diisocyanate (commercially available, for example, as Desmodur® Z-4370 from Bayer), a reaction product of tetramethylxylene diisocyanate and trimethylol propane (cormnercially available, for example, as Octane® 3160 from Cytec), and a reaction product of one mole of trimethylol propane and 3 moles of toluene diisocyante (commercially available, for example, as Desmodur® L from Bayer). Polyether polyois having at least 2 hydroxyl groups represent a further useful group of precursors for polyacetoacetates. Poly(oxyalkylene)diols, triols and tetrols are generally preferred. Usually this type of polyol is made from the reaction of alkylene oxides wherein the alkylene group contains 2-8 carbon atoms with monomeric poiyalcohols, for example, those already mentioned above, such as glycerol, trimethylolpropane, pentaerythritol, sorbitol and the like, or preformed polymeric poiyalcohols containing 2-6 hydroxyl groups such as polyester and polylactonepolyols. The reaction products of polyepoxides with monoalcohols and/or poiyalcohols, preferably having 2-6 hydroxyl groups can also be used as polyacetoacetate precursors. Suitable poiyalcohols for the preparation of polyurethane polyois are for example the monomeric types already mentioned above, such as ethylene glycol, neopentyl glycol, 6-hexanediol, 1,2-propanediol, diethyl ene glycol, 2-ethyl-2-butyl-l,3-propane did, triroethylol propane, glycerol, ditrimethylol propane, pentaerythritol and the like. Other suitable poiyalcohols are partial esters from poiyalcohols with monocarboxylic acids. Further usable poiyalcohols include for example polyesterpolyols and polyetherpolyols, preferably containing 2-6 hydroxylgroups. Addition polyois having 2-6 hydroxyl may also be employed. The preparation of polyurethane polyois is well-known in the art. Addition polymers having at least 2 hydroxyl groups are a very useful class of precursors for polyacetoacetates. Usually these hydroxyl-functional compounds are prepared by radical polymerization of ethylenically unsaturated monomers having one or more hydroxyl groups, generally in the presence of one or more comonomers which do not contain hydroxy! groups. A preferred group of hydroxy!-functional monomers are the hydroxyalkyl acrylates and hydroxyalkyl methacrylates. Representative monomers include: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydoxypropyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate and the like. Other useful hydroxy-functional monomers include the reaction product from methacrylic acid or acrylic acid with a monoepoxide, for example the glycidylether of a C9-C11 branched aliphatic acid, ethoxylated and propoxylated hydroxy-alkyl(meth)acrylates, ally! alcohol, and reaction products of hydroxyalkyl(meth)acrylates with lactones such as epsilon-caprolactone. Suitable non-hydroxyl-functional ethylenically unsaturated comonomers are, for example, the acrylic or methacrylic esters of monoalcohol having 1-18 carbon such as ethyl(meth)acrylate, butyl(meth)acrylate, methyl(raeth)acrylate, 2-ethyl-hexylacrylate and the like. Examples of other copolymerizable monomers include, for example, methacrylic acid, acrylic acid, glycidyl methacrylate, styrene, vinyl toluene, dibutyl maleate, vinyl acetate, vinyl versatate. allylglycfdyl ether, itaconlc acid, naleic acid and the like. A preferred number average molecular weight for addition polyols is about ECO to about 5000. An hydroxyl number of about 50 to 300 is preferred for the addition polyol. A preferred acid number is about 0 to 50. An alternative and very convenient method for the preparation of acetoacetate functional addition polymers consists of (co)polymering one or more acetoacetate functional ethylenically unsaturated monomers. Preferred acetoacetate functional monomers are the acetoacetic acid esters of hydroxyalkyl (meth)acrylates such as 2-{acetoacetoxy)ethyl methacrylate, 2-(acetoacetoxy)ethyl acrylate, 2-(acetoacetoxy)propyl methacrylate, 2-(acetoacetoxy)propyl acrylate, 4-(acetoacetoxy)butyl acrylate and the like, allyl acetoacetate and the acetoacetic acid ester of the reaction product of a hydroxyalkyl (meth)acrylate with a lactone, or the acetoacetic acid ester of the reaction product of (meth)acrylic acid or a hydroxyalkyl (meth)acrylate with an alkylene oxide. Usually the acetoacetate functional monomers are copolymerized with non-acetoacetate functional monomers such as alkyl (meth)acrylates, the alkyl group having 1 to 18 carbon atoms, hydroxyalkyl (meth)acrylates, styrene, acrylic acid, methacrylic acid, maleic anhydride, dibutyl fumarate, acrylonitrile, acrylamide, vinyl toluene or other ethylenically unsaturated monomers. "(Meth)acrylate" is a shorthand indication of both acrylate and methacrylate. All above-described polyalcohols are easily acetoacetylated by transesterification with alkyl acetoacetates of which the lower alkyl acetoacetates, having alkyl groups with 1 to 5 carbon atoms, are preferred such as methyl-, ethyl- or t-butyl acetoacetate. Another preferred method of acetoacetylation consists of reacting any of the nffintioned polyalcohols with diketene. Both methods are suitable for partial or complete conversion of the hydroxyl groups into acetoacetate groups. Preparation of polyacetoacetates are well known in the art and may be found, for example, in the above mentioned paper by Witzman et al. The polyacetoacetates of the current invention typically have a number average molecular weight (Mn) of about 200 to about 5000. More typically, they have a number average molecular weight less than 1000. Particularly for use in reduced VOC coating compositions, the polyacetoacetates used in the current invention preferably have a number average molecular weight of about 200 to about 3000 and more preferably, about 250 to about 1000. Even more preferably, the polyacetoacetates for such uses have a number average molecular weight of about 250 to about 750, most preferably about 250 to about 500. The pojyacetoacetates of this invention are acetoacetate-functional compounds which may be crosslinked via their acetoacetate groups. Cross! inkers for these acetoacetate-functional compounds of the current invention are well-known. Such crossllnkers are compounds having one or more groups capable of crosslinking with acetoacetate groups. For some examples, see US-A-3668183, EP-A-199087 and EP-A-240083, Depending on the ultimately desired coating characteristics, the ratio of acetoacetate groups in the polyacetoacetate group to groups in the crosslinker capable of crosslinking can be varied. The ratio is generally in the range of about 0.5 to about 2. The preferred ratio of acetoacetate groups in the polyacetoacetate to groups capable of crosslinking with acetoacetate is greater than 1, preferably between about 1.1 and about 2, more preferably between about 1.1 and about 1.5. As some examples of crossllnkers for polyacetoacetates herein described may be mentioned the following general classes of compounds and their derivatives and acidify cations: polyfunctional amines, ketimines, aldiraines, acryloyl and methacryloyl-functional polymers, copolymers and mixtures thereof. Preferred crossllnkers are blocked primary amino group-containing compounds comprising the condensation product of (i) an aldehyde or a ketone and (ii) a polyamine having 2 to 6 (preferably 2 to 4) primary amino groups and a molecular weight of about 60 to about 1500, most preferably about 60 to about 1000. Such blocked primary amino group-containing compounds are well known in the art from, for non-limiting example, EP-A-199087, EP-A-240083. US-A-5214086, US-A-4504630, US-A-4503174, US-A-4251597. WO-A-94/21738 and US-A-3975251. Preferred blocking agents are ketones and aldehydes having 3-10 carbon atoms and more preferably having 3-8 carbon atoms. Examples of suitable blocking agents include acetone, methylethylketone, methylisobutylketone, diethyl ketone, methylacrylketone, ethylamylketone, isobutyraldehyde, hexanaldehyde, heptanaldehyde, pentanone, cyclohexanone, isophorone, hydroxycitronellal and decanone. Blocked primary amino group-containing compounds preferred for use in the current invention include, for example, the ketimines and aldimines prepared from the reaction of a ketone or aldehyde with aliphatic, cycloaliphatic or arylaliphatic amines containing 2 or more, preferably 2 to 4, primary amine groups and from 2 to 200 carbon atoms. Examples of suitable amines Include: ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethy1enedi ami ne, decamethylenedi ami ne, 4,7-dioxadecane-l,10-diamine, dodecamethylenediamine, 4,9-dioxadodecane-l,12-d1aniine. 7-methyl-4,10-d1oxatridecane-l,13-diamine, 1,2-diaminodicyclohexane, 1,4-diaminocyclohexane, 4,i'-:-l2n1nodicyclohexy1 irethane, isophorone diamine, bis(3-methyl-4-aannccyclohexyl)raethane, 2,2-bis{4-aminocyclohexyl), nitrile tr1s{ethane) amine, bis(3-am1nopropy1) methylamine, 2-am1no-l-(methyl amino)propane, 3-amino-l-{cyclohexylamino)prapane, N-(2-hydroxyethyl)ethylene diamine, l,4-xyly1enediam1ne and 4-aminomethyl, l,8-octaned1am1ne. A particularly preferred group of polyamines that are useful in the practice of the present Invention can be represented by the following structural formula: H2N-(R'-NH)^-R-NH2 where the groups R and R' can be the same or different and represent an alkylene group containing from 2 to 6 and preferably from 2 to 4 carbon atoms and n is a number from 1 to 6 and preferably from 1 to 3. Included in the definition of alkylene group are cycloalkylene groups and alkylene groups containing an ether-oxygen atom. Examples of representative polyalkylene polyamines include diethylenetriamine, dipropylenetriamine and dibutylenetriamine. These polyamines have two primary amino groups and one secondary amino group. Also preferred as crosslinkers for polyacetoacetates are the ketimines and aldimines obtained from the adduct reaction of a partially ketone-or aldehyde-blocked polyamine with a mono- or polyfunctional epoxy, isocyanate, maleinate, fumarate, acryloyl or methacryloyl compound whereby the reacting components are chosen in such a way that the adduct contains at least 2 imine groups. Preferred polyamines are the above-mentioned amines of the structural formula H2N-{R'-NH)n-R-NH2 wherein n, R and R' are as described above. Other preferred polyamines for the formation of adducts have the structure R-NH-R'-NH2 wherein R is an alkyl or alkenyl group containing up to 20 carbon atoms and R' is an alkylene group containing 2-12 carbon atoms. As examples of preferred epoxy compounds may be mentioned the di- or polyglycldylethers of {cyclo)aliphatic or aromatic hydroxyl compounds such as ethylene glycol, butanediol, polypropyleneglycol, Bisphenol-A, Bisphenol-F; hydrogenated Bisphenol-A, hydrogenated Bisphenol-F, phenol formaldehyde novolaks, etc. Other suitable epoxy compounds are monofunctional glycidylethers and glycidylesters such a phenylglycidylether, 2-ethylhexylglycidylether, the glycidylester of a C9-C11 branched aliphatic acid (available under the tradename Cardura ElO from Shell) and the like. 01glycidylesters of dicarboxyllc acids containing for instance 6-24 carbon atoms can also be conveniently used. ,Further examples of suitable epoxy compounds are disclosed in EP 0 199 087, US 5,288,802, and EP 240 083. The epoxy resins are known to a skilled person and need no further description. Examples of suitable isocyanate compounds for the preparation of adducts with partially blocked polyamines include aliphatic, cycloaliphatic or aromatic mono-, di-, tri- or tetraisocyanates and polyisocyanate prepolymers thereof. Preferred isocyanates include 1,6-hexane diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, 2,2,4-trimethyl-1,6-hexane diisocyanate, 1,12-dodecane diisocyanate, methylene bis(4-cyclohexyl isocyanate), 2,4- and 2,6-toluene diisocyanate, 4,4-dlphenylmethane diisocyanate, xylene diisocyanate, the biuret of 1,6-hexane diisocyanate, the isocyanurate of 1,6-hexane diisocyanate, the isocyanurate of isophorone diisocyanate, the uretdione of 1,6-hexane diisocyanate, etc. Other preferred isocyanates are the reaction products of diols or triols with a stoichiometric excess of di- or tri isocyanate, for the reaction product of Isophorone diisocyanate or 1,6-hexane diisocyanate with a diol such as ethylene glycol, 1,2-propanediol and the Hke or with a triol such as triraethylol propane and the reaction product of tetramethylxylene dilsocyante with trimethylol propane. Additional suitable isocyanates are disclosed in EP-A- 199 087 and EP-A-139 513. Examples of suitable acryloyl or methacryloyl Include the {meth)acry1ic acid esters of mono-, di-, tri- or polyvalent hydroxyl compounds such as butanol, 2-ethylhexanol, ethylene glycol, neopentylglycol, 1,6-hexanediol, trimethylolpropane, ethoxylated trimethylolpropane, ditriraethylolpropane, pentaerythritol, diethylene glycol, polypropylene glycol, polyesterdiols and -triols, and polyurethanediols and -triols. The reaction products of {meth)arylic acid with epoxy compounds e.g. the glycidylether of Bisphenol A are also suitable for adduct formation with partially blocked polyamines. A further group of suitable reaction partners are maleate and fumarate compounds such as diethyl maleate, dibutyl fumarate and unsaturated polyesters containing one or more maleate or fumarate groups. Suitable unsaturated polyesters include, for example, the polycondensation product of maleic anhydride with neopentyl glycol. The unsaturated polyester resins are well-known in the art and need no further description for skilled persons. Particularly suitable ketimes are obtained by the reaction of a diisocyanate (such as hexamethylene diisocyanate) with a diketimine obtained from one mole dialkylene triamine (such as dipropylene triamine) and 2 moles ketone, as detailed in EP-A-199087 and EP-A-240083. In addition to the polyacetoacetate and crosslinker, the binder may comprise additional binder components such as Isocyanates, epoxides, and oxazolldlnes. The organosllanes useful in the current invention are of the following general Z is an anion group, an aim no-containing group, an epoxy group, an epoxy-containing group, a mercapto group, a mercapto-containing group, a vinyl group, a vinyl-containing group, an isocyanate group, an isocyanate-containing group, an ureido group, an ureldo-containing group, an imidazole group or an iraidazole-containing group. R isan aliphatic, alicyclic or aromatic group, R'is an alkoxy group or alkoxyalkoxy group, R" is an alkyl group having 1 to about 8 carbon atoms, X is 0 to about 20, a is 0 to 3, preferably 0 to 2, b is 1 to 4, preferably 1 to 3, c is 0 to 3, preferably 0 to 2, and the sum ofa + b + cis4. Typically, R is an alkylene group, e.g. methylene. Typically R' is a lower alkoxy or alkoxyalkoxy , e.g. ethoxy, propoxy, isopropoxy, ethoxyethoxy, etc. and, most commonly, aethoxy. As preferred organosilanes may be mentioned l«H2(CH2)3Si(0CH3)3, NH2CH2NH(CH2)3SI(OCH3)3. CH2(0)CH2CH2O(CH2)3Si(OCH3)3. SH{CH2)3Si{0CH3)3, and mixtures thereof. Some oreganos lanes useful in the current invention are listed below. Aminosilanes H2N(CH2)3Si{0C2H5)3 3-Aminopropyl-triethoxysilane H2N(CH2)3Si(CH3)(OC2H5)2 3-Ami nopropyl-methyl-diethoxysi1ane H2N(CH2)3Si(OCH3)3 3-Ami nopropyl-trimethoxysi1ane H2N(CH2)3Si C(0C2H4)20083)13 3-Aminopropyl-tris(2-methoxyethoxy- H3C-NHICH2)sSi(OCH3)3 N-Methyl-3-ami nopropyl-trimethoxy- silane H2N(CH2)2NH(CH2)3Si(OCH3)3 N-Aminoethyl-3-aminopropyl-tri- methoxy-silane ^ H2N(CH2)2NH(CH2)3Si(CH3)(0CH3)2 N-Ami noethyl-3-aminopropyl-methyl - dimethoxysilane (CH30)3-Si(CH2)3NH{CH2)3)Si(0CH3)3 N,N-Bis(trimethoxysilylpropyl)amine Mercaptosllanes HS(CH2)3Si(0C2H5)3 3-Mercaptopropyl-triethoxysilane HS(CH2)3Si(0CH3)3 3-Mercaptopropyl-trimethoxysilane HS(CH2)3Si(CH3)(OCH3)2 3-Mercaptopropyl-methyl-dimethoxy- silane Vinyl si lane H2C=C{CH3{C00(CH2)3Si(0CH3)3 3-Methacryloxypropyl-trimethoxysilane CH2=CHSi{0C2H5)3 Vinyltriethoxysilane CH2=CHSi(0CH3)3 Vinyltrirnethcxysilane CK2=CHS1(0C2H40CH3)3 Vinyl-tris(2-ia£thoxy-ethoxy)silane Epoxysilanes 0 /\ H2C-CH-CH2O(CH2)3Si{0CH3)3 3-Glycidyloxypropyl-trimethoxysilane {CH2)2S1(0CH3)3 2-(3.4-Epoxycyclohexyl)ethyltri- OI^^HJ methoxysilane Isocyanatosilane 0 = C = N{CH2)3Si(OC2H5)3 3-Isocyanatopropyltriethoxysilane A particularly effective "adhesion-enhancing amount" of organosilanes is about 1 to about 10 we1ght% based on binder solids, preferably about 1.5 to about 5 weight%. The coating compositions of the current Invention are typically, though not necessarily, formulated as well-known "two-pack" systems. Thus, in general the oreganos lane may be placed with either the crossllnker or with the polyacetoacetate. Further, the organosilane may be added as a "third component", that is, it may be added independently rather than with the crossllnker or polyacetoacetate. Independent addition of the organosilane is particularly desirable when the organosilane is capable of crosslinking with one of the binder components. Depending on the organosilane used, it may be present as either a "free" additive (that is, unreacted) or it may be present In the form of a reaction product with another component of the coating composition. The coating compositions of this invention may also contain a pigment component. The pigment component of this invention may be any of the generally well-known pigments or mixtures thereof used in coating formulations, as reported, e.g., in Pigment Handbook. T.C. Patton, Ed.. Wiley-Interscience. New York. 1973. The coating composition disclosed herein has been found to be particularly useful for pigment components which are substantially chromate-free. Non-limiting examples of such substantially chromate-free pigments are barium metaborate. zinc phosphate, aluminum triphosphate and mixtures thereof. Preferably, the pigment component, if employed, is present in a pigment volume concentration of about 10 to about 40. Coating compositions of the instant invention have been found to be particularly useful as primer coats, especially for aluminum substrates. Typically, when the current coating comopositions are formulated for use as such primer coats, the above-described substantially chromate-free pigments are employed. The coating composition generally contains an organic solvent which is commonly applied, for instance, in the Industrial preparation of paint, such as aliphatic or acrobatic hydrocarbons, esters, ethers, alcohols, ketones and ether acetates. However, the amount of solvent Is typically lower than what Is company required In that the current Invention may be formulated as a "high solids" (low solvent) coating composition. Such compositions are also referred to a "low VOC" coating compositions. Current "high solids" formulations have a VOC preferably below 420 g/1 and more preferably below 350 g/1. "VOC" refers to the "volatile organic content", which Is normally expressed as grams organic volatiles per liter organic component. The coating composition of the current invention may also contain other additives usual for such formulations. A particularly preferred additive is a water scavenger, such as a molecular sieve. Other typical .additives may be, for non-limiting example, dispersing agents, for instance, soya lecithin; fillers; reactive diluents; plasticizers; levelling agents, for instance, acrylate oligomers; anti-foaming agents, for instance, silicone oil; metal salts of organic acids, such as cobalt of ethyl hexanoate, dibutyl tin dilaurate; chelating agents; rheology control agents, for instance, bentonites, pyrolized silica, hydrogenated castor oil derivatives and adducts of a di- or triisocyanate and a monoamine; catalysts, such as phosphoric acid, phosphoric esters, and carboxylic acids; antioxidants, such as substituted phenols; and UV stabilizers, such as, benzophenones, triazoles, benzoates and hindered bipiridylamines. The coating composition may be applied to the substrate in any suitable manner, such as by roller coating, spraying, brushing, flow coating, or dipping. It is preferred that the composition Is applied by spraying. Suitable substrates include plastic in metals, such as Iron, steel, galvanized steel and, as earlier iner.rioned, the preferred aluminium. Prior to applying a coating of the current invention, the surface may be prepared In conventional ways, far example, cleaning (with, for example, solvent or a water based alkaline cleaner), mechanically treating For example, abrasion) and/or conversion coating (phosphorizing, chromating or anodizing). A temperature above ambient is not necessary to dry and cure the coating conq)os1t1ons disclosed herein; however, heat may be applied. Thus, the full range of temperatures, from, for example, about S'C to about lOO'C can be used to cure and/or dry the coating compositions of this invention. Accordingly, the present invention provides a process for the preparation of a coating, comprising the steps of preparing an organic solvent containing coating composition by combining (a) an organic solvent, (b) a polyacetoacetate having acetoacetate groups and having a number average molecular weight in the range of 1000 to 5000, (c) a crosslinker having at least two groups capable of crosslinking with the acetoacetate groups, and (d) at least one organosilane in which coating composition, the organosilane is present in an adhesion enhancing amount, and drying and/or curing the coating composition at a temperature between 5°C and 100°C. Accordingly, the present invention also provides a method of coating a substrate, wherein a substrate is coated with a coating as described above. The current invention is further disclosed and explained with reference to the following representative, though non-limiting, examples. EXAMPLES The adhesion and corrosion resistance of coating compositions according to the current invention were tested as detailed below. Preparation of polyacetoacetates The polyacetoacetates used in the following examples were prepared by transesterification of the polyols with ethyl acetoacetoacetate or t-butyl acetoacetate according to the methods described by Witzeman J.S. in Journal of Coating Technology 62, No. 789. 101 (1990). The acetoacetate of Test Nos. 1-20 and Comparative Tests I and II was prepared by acetoacetylation of a precondensate from ditn'methylolpropane (1 mole) and isononaoic acid (0.6 mole). Preparation of ketimfne resin The ketimine resin used in the following exam{5les is the adduct of 1,6-hexane diisocyanate (1 mole) with 2 moles-of the di retiming from dipropylene triamine and methyl isobutyl ketone. The ketimine resin was prepared according to the method described in EP-A-240083, and was used in the form of an 85% solution in a mixture of xylene and methyl isobutyl ketone. Adhesion Test To test adhesion, a "modified" DIN 53151 cross-hatch method was used to test initial adhesion, adhesion after water immersion and adhesion after immersion in hydraulic oil. In conventional cross-hatch adhesions tests, several grids are made wherein each grid has equal spacing in both the horizontal and vertical directions, for example, in one grid the spacing between the cuts is 0.1 mm in both the horizontal and vertical directions, in another grid the spacing is 0.2 mm, in another the spacing is 0.3 mm, etc. As a modification, the adhesion tests reported here were performed by using one grid wherein in both the horizontal and vertical directions the spacing between cuts was increased by 0.1 mm over the next previous cut; that is, the spacing between the first two cuts was 0.1 mm, between the second and third cuts was 0,2 mm, between the third and fourth cuts 0.3 mm, etc. until a spacing of 1.1 mm was acheived. Test Nos. 1-20 and Comparative Test Nos. I and II In Test Nos. 1-20, four (4) different si lanes were added, in separate tests, to the primer formulations described below. Various si lane concentration levels as well as the manner of adding the si lane to the coating composition (primer) were also tested. In Comparative Test Nos. I and II no si lanes were added. Otherwise, Comparative Test Nos. I and II were carried out in the same manner as Test Nos. 1-17. Results are reported in Tables 1 and 2. In Test Nos. 18-20 the ratio acetoacetate groups to crosslinking groups was varied. Experimental Method: Test Wos. 1-20 and Comparative Test Nos. I and II In Test Nos. 1-8, the silane indicated in Table 1 was premixed with trimethylol propane-triacetoacetate to form the Adduct. Components A and B were separately prepared then mixed to form a primer. In Test Nos. 9-16, the silane was not premixed. Rather, Component A and Component B were prepared. In preparing Component A, trimethylol propane-triacetoacetate and the relevant silane were separately added. Components A and B were mixed to form a primer. In Test No. 17 the silane was added to Component B. In Test Nos. 18-20, Component B and the silane were each Independently added to Component A. The priijiers for Comparative Test Nos. I and I contain no si lane. They were prepared in the same manner as the primers for Test Nos. 9-16, omitting the silane. In all Tests the primers were applied by spray gun to a dry-layer thickness of about 20 to 25 pm. At spraying viscosity (30-35 s ISO-cup 4) the VOC for the primers was 350 g/1. Table 1 reports the results of the following adhesion tests. Variously aged primers (specifically, one day, one week and one month after primer preparation) of Test Nos. 1-16 and Comparative Test Nos. I and II were applied to Alclad 2024T3 substrates which had been cleaned with Sikkens®B2. The coated substrates were aged for one week, after which the already-described modified DIN 53151 cross-hatch method was used to test both initial adhesion and wet adhesion after 2 weeks of water immersion. Test No. 17 was carried out in a similar fashion, except only wet adhesion of a one-day-aged primer was tested. Test Nos. 18-20 were also carried out in the manner as described for Test Nos. 1-16, except only one-day-aged primers were tested. Table 2 reports the results of the following adhesion tests. The primers of Test Nos. 1-16 and Comparative Tests I and II were applied to Alclad 2024T3 substrates which had been cleaned with S1kkens®B2 and a Scotch-Br1te®pad, After one day the primers were sprayed over with the topcoat Aviox® Finish available from AD Aerospace Finishes VoF, Sassenheim, the Netherlands. The coated substrates were aged for one week, after which the already described modified DIN 53151 cross-hatch method was used to test both initial adhesion and wet adhesion after 2 weeks of water immersion and DIN 65472 was used to test filiform corrosion (FFC) resistance. Test No. 17 was carried out In a manner consistent with Test Nos. 1-16 except the Alclad 2024T3 substrate was pretreated first with alkaline cleaning, then with alkaline etching and finally with nitric acid pickling. Only testing indicated In / Table-2 was performed for Test No. 17. Test Nos. 18-20 were carried out in a manner consistent with Test Nos. 1-16 except the primers were sprayed over with the topcoat Aerodur® C21/100 UVR available from AD Aerospace Finishes VoF, Sassenheim, the Netherlands. Only testing indicated in Table 2 was performed for Test Nos. 18-20. In Tables 1 and 2, "Ratio PolyAc/Crosslinker" means the ratio of acetoacetate groups to groups capable of crosslinking with the acetoacetate groups. Primer Formulation: Test Nos. 1-16 and Comparative Test Nos. I and II SZPr391 strontium zinc phosphorsilicate available from Haloa. 10 Y-25, a Theology modifier available from Chemise. Our cop ending application no.883/MAS/96 relates to 'a process for the preparation of a coating having improved substrate-adhesion'. The composition claimed therein limits the amount of the cross linker and organosilane is optional. The composition is also not solvent based. Average molecular weight of polyacetoacetate is restricted to less than 1000. WE CLAIM: 1. A process for the preparation of a coating, comprising the steps of preparing an organic solvent containing coating composition by combining (a) an organic solvent, (b) a polyacetoacetate having acetoacetate groups and having a number average molecular weight in the range of 1000 to 5000 (c) a crosslinker having at least two groups capable of crosslinking with the acetoacetate groups, and (d) at least one organosilane in which coating composition, the organosilane is present in an adhesion enhancing amount, and drying and/or curing the coating composition at a temperature between 5°C and 100°C. 2. The process as claimed in claim 1, wherein the organosilane is of the following general formula: wherein Z is an amino group, an amino-containing group, an epoxy group, an epoxy-containing group, a mercapto group, a mercapto-containing group, a vinyl group, or a vinyl-containing group, an isocyanate group, an isocyanate- containing group, an ureido group, an ureido-containing group, an imidazole group or an imidazole-containing group, R is an aliphatic, alicyclic or aromatic group, R' is an alkoxy group or alkoxyalkoxy group, R" is an alkyl group having 1 to about 8 carbon atoms, x is 0 to 20, a is 0 to 3, b is 1 to 4, c is 0 to 3 and 3. The process as claimed in claim 1, wherein comprising a mixture of organosilanes. 4. The process as claimed in claim 3, wherein Z is selected from the group consisting of NJ, NH2CH2NH, CH2(0)CHCH20, SH, H2NCONH, CH3NH and CH2=C(CH3)COO. 5. The process as claimed in claim 2, wherein R is selected from the group consisting of alkylene and alkenylene group. 6. The process as claimed in claim 2, wherein R' is an alkoxy or alkoxyalkoxy group having 1 to 10 carbon atoms. 7. The process as claimed in claim 2, wherein R is CH2, R' is OCH3 or OC2H5, X is 3, a is 1, b is 3 and cis 0. 8. The process as claimed in claim 1, wherein the organosilane is selected from the group consisting of NH2(CH2)3Si(OCH3)3, NH2CH2NH(C2)3Si(OCH3)3, CH2(0)CHCH20(GH2)3Si(OCH3)3, SH(CH2)3 Si(OCH3)3, and mixtures thereof 9. The process as claimed in claim 1, wherein the ratio of acetoacetate groups to groups capable of crosslinking with acetoacetate groups is 1.1 to 2. 10. The process as claimed in claim 1, wherein the crosslinker is selected from the group consisting of amine, ketimine, aldimine, acryloyl and methacryloyl functional compounds, polymers and copolymers thereof and mixtures thereof. 11. The process as claimed in claim 1, wherein the crosslinker is a blocked primary amino group-containing compound comprising the condensation product of (I) an aldehyde or a ketone and (ii) a polyamine having 2 to 6 primary amino groups. 12. The process as claimed in claim 1, wherein the coating composition comprises at least one pigment component, 13. The process as claimed in claim 12, wherein the pigment is substantially chromate-free and is present in a pigment volume concentration of 10 to 40. 14. The process as claimed in claim 12, wherein the pigment is selected from the group consisting of barium metaborate, zinc phosphate, aluminium phosphate and mixtures thereof. 15. The process as claimed in claim 1, wherein the organosilane is present in an amount of 1 to 10 weight % based on binder solids. 16. The process as claimed in claim 1, wherein the ratio of acetoacetate groups to groups capable of crosslinking with acetoacetate groups is between 1.1 and 1.5. 17. The process as claimed in claim 1, wherein the coating composition comprises at least one additional binder component, selected from the group consisting of isocyanates, epoxies, oxazolidines and mixtures thereof. 18. The process as claimed in claim 1, wherein the coating composition is a primer. 19. The process as claimed in claim 1, wherein the coating composition has a volatile organic content (VOC) below 420 g/1. 20. A method of coating a substrate, comprising coating a substrate with a coating as claimed in any one of the preceding claims. 21. The method as claimed in claim 20, wherein the substrate is selected from the group consisting of aluminium, steel, galvanized steel and plastic. 22. A process for the preparation of a coating substantially as herein described. 23. A method of coating a substrate substantially as herein described.

Full Text

The present invention relates to a process for the preparation of a coating and a method of coating a substrate with the coating.
Coating compositions of this type are generally known from, for example, US-A-3668183, Polyenamine Coatings: I. Formulation of Coatings and Determination of Film Properties K.L. Hoy and C.H. Carder, ' Journal of Paint Technology, Vol. 46, No. 591, April 1974, pages 70-75, and "Polyenamine Coatings: II. Chemical Methods of Improving Film Properties", C.H. Carder and H.O. Colomb, Jr., Journal of Paint Technology, Vol. 46, No. 591, April 1974, pages 76-78. referred to respectively as "Polyenamine Coatings I" and "Polyenamine Coatings 11". Such coating compositions, when properly formulated and applied to a substrate, form a coating having highly desirable properties, such as hardness, flexibility and toughness. There is however, a continuing difficulty in that such coatings frequently do not adequately adhere to the substrate on which they are applied.
US-A-3668183 generally discloses the production of polyenamine resins by the reaction of polyacetcacetates with blocked polyamines. Also disclosed there is the possible use of a silicone component in the polyacetoacetate end cap to improve acid resistance.
WO-A-94/21738 discloses a crosslinkable liquid carrier-based coating composition comprising organic polymer(s) having acetoacetyl group functionality, a polyamine compound{s) having at least two acetoacetyl-reactive amino groups per molecule and a non-polymeric monoacetoacetyl compound(s) selected from a specific group of such compounds. The ratio of acetoacetyl groups of the acetoacetyl functional polymer(s) to the number of acetoacetyl-reactive amino

wherein
Z is an amino group, an amino-containing group, an epoxy group, an epoxy-containing group, a mercapto group, a mercapto-containing group, a vinyl group, a vinyl-containing group, an isocyanate group, an isocyanate-containing group, an ureido group, an ureido-containing group, an imidazole group or an imidazole-containing group,
R is an aliphatic, alicylic or aromatic group,
R' is an alkoxy group or alkoxyalkoxy groups,
R" is an alkyl group having 1 to about 8 carbon atoms,
X is 0 to about 20.
a is 0 to 3, preferably 0 to 2,
bis 1 to 4, 1 to 3,
c is 0 to 3, and preferably 0 to 2, and
the sum of a + b + c is 4.
Preferred organosilanes are aminosilanes, epoxysilanes, mercaptosilanes, vinylsilanes, ureidosilanes, imidazolsilanes and isocyanatosilanes.
Polyacetoacetates are acetoacetate-functionai compounds having at least two acetatoacetate groups. Polyacetoacetates are well known in the art, for example as demonstrated in the already mentioned US-A-3668183, US-A-5021537, "PoTyenamine Coatings I" and "Poiyenamine

Coatings. 11". They can be described as the partial or complete acetoacetylation product of a monomeric polyalcohol having at least two free hydroxyl groups or an oligomeric or polymeric condensation derivative of such polyalcohols. The production of polyacetoacetates, "acetoacetylation", may be accomplished by various reaction schemes. Some examples are transesterification of alkyl acetoacetates, such as methyl, ethyl or t-butyl acetoacetate with polyols or the reaction of polyol or polythiol with diketene, or the diketene-acetone adduct 2,2,6-trimethyl-l,3-dioxin-4H-one. Such compounds and synthesis mechanisms are well known in the art (see for example US-A-3668183 and "The Acetoacetyl Functionality: A New Approach to Thermoset Coatings", R.J. Clemens, et al.. Proceedings: XVI^^ International Conference in Organic Coatings Science and Technology. 9-13 July 1990, Athens, Greece, page 127 et seq., and "Comparison of Methods for the Preparation of Acetoacetylated Coating Resins", J.5. Witzeman et al.. Journal of Coating Technology 62, No. 789, 101 (1990)) and need not be further detailed here.
Preferably, polyacetoacetates used in the current invention are partial or couplet acetoacetylation products of (1) roonoroeric polyalcohols having 2 its 6 hydroxyl groups. (2) partial esters of polyalcohols with monocariioxyT 1 c acids (the carboxylic acids having 2 to 22 and preferably 5 to 18 carbon atoms), the partial esters having at least 2 unreacted hydroxyl groups, (3) polymeric condensates having at least 2 hydroxyl groups, suitable polymeric condensates being, for non-limiting example, polyesters, polyethers and/or polyurethanes (see, for example. The Chemistry of Organic Film Formers. D.H. Solomon, Robert E. Krieger Publishing Co., 1977) and (4) addition polymers containing at least two (2) hydroxyl groups.
Some examples of monomeric polyalcohols having 2 to 6 hydroxyl groups which can be conveniently converted into polyacetoacetates include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,4-butanediol,

1,5-pentanediol, neopentyl glycol, 1,6-hexanediol. 2-ethyl-2-butyl-propanediol, 2-methylpropanediol, 3-(nethyl-l,5-pentanediol, di-ethylene glycol, triethylene glycol, 1,4-cyclohexyldimethanol, dipropylene glycol, trimethylolethane, trimethylolpropane, glycerol, di-trimethylolpropane, pentaerythritol and the like.
Suitable partial esters of polyalcohols with monocarboxylic acids containing 2 to 22, preferably 5 to 18 carbon atoms, the partial esters having at least 2 unreacted hydroxyl groups, include for example the reaction product of a triol, e.g. trimethylolpropane, with a monocarboxylic acid in a, for example, 1:1 molar ratio. Other suitable partial esters are the reaction products of a tetrol e.g. pentaerythritol, with a monocarboxylic acid in, for example, 1:1 or 1:2 molar ratio. Useful monocarboxylic acids are: acetic acid, hexanoic acid, 2-ethylhexanoic acid, nonaoic acid, 3,5,5-trimethylhexanoic acid, benzoic acid, oleic acid, linoleic acid, dehydrated castor oil fatty acid, and the like. It is well known that esterification of polyalcohols with monocarboxylic acids in a stoichiometric excess of the hydroxyl component generally yield a mixture of products with different degrees of esterification and having different hydroxyl functionalities. In addition to single alcohols and acids, mixtures of one or both reactants may also be used.
Usually monomeric polyalcohols like trimethylolpropane, di-trimethylolpropane, pentaerythritol and other alcohols with 3 or more hydroxyl groups are partially esterified, however, if desired, polymeric preformed polyalcohols such as polyester-, polyether- and polyurethane polyols, and addition polymers, all containing 2 or more hydroxyl groups can be partially esterified with monocarboxylic acids and used as polyacetoacetate precursors.

Partialmonocarboxylic acid esters of polyepoxy compounds represent a further group of suitable precursors for polyacetoacetate.
Polyester polyols having at least 2 hydroxy!groups are suitable precursors for preparing polyacetoacetates. Usually the polyester polyols are made by the condensation of polyhydric alcohols and polycarboxylic acids or anhydrides, with or without the use of a monobasic acid, at temperatures at about 150°C to about 260°C and with a stoichiometric excess of the alcohol component. Suitable polyesters have a number average molecular weight of about 200 to about 5000, a hydroxyl number of about 50 to about 500 and a acid number of about 0 to about 50, preferably from 0 to about 20. Examples of polycarboxylic acids and anhydrides suitable for the preparation of polyester polyols include succinic acid, adipic acid, azaleic acid, terephthalic acid, l,4-cyc1ohexaned1carboxylic acid, fumaric acid, maleic acid, maleic anhydride, hexahydrophthalic anhydride, trimellitic anhydride and the like. Useful polyhydric alcohols (also sometimes referred to as "polyalcohols"), are ethylene glycol, diethylene glycol, 1.2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,5-hexanedlol, 1,4-cyclohexanediiDethanol, 2-methyl-l,3-propanediol, r.eopentyl glycol, 2-ethyl-2-butylpropanediol, glycerol, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, di-triraetnyiolpropane and other low molecular polyalcohols. Further classes of suitable polyalcohols for the production of polyesterpolyols are the reaction products of wjnoroeric polyalcohols with lactones, for example epsilon-caprolacton, alkoxylated polyalcohols such as the reaction products of glycerol, trimethylolpropane, neopentylglycol, water, ethylene glycol, Bisphenol A and the like with alkylene oxides, for example ethylene oxide, propylene oxide and mixtures thereof. The polyalcohols may be replaced partially or completely by mono- or polyepoxides e.g. the glycidyl ester of a C9-C11 branched aliphatic acid (available as Cardura® ElO from Shell) or diglycidyl ethers based on Bisphenol A- Polylactone polyesterpolyols are a next group of

suitable precursors. These polyols are formed from the reaction of a lactone, e.g. epsilon caprolactone, and a polyalcohol, for example, those already mentioned above, such as ethylene glycol, trimethylolpropane, neopentyl glycol, and ethoxylated trimethyl ol propane.
Polyurethanes with at least 2 hydroxyl groups are a further class of suitable polyacetoacetate precursors. Preparation of these polyurethanes usually involves the reaction of polyisocyanates with a stoichiometric excess of a monomeric or polymeric polyalcohols. The isocyanate component is selected from n-functional isocyanates wherein n is a number ranging from 2 to 5 preferably from 2 to 4 and especially from 3 to 4. The isocyanate component may include a single such n-functional isocyanate or combinations thereof.
As specific examples of suitable n-functional isocyanates may be mentioned, for example, di isocyanates such as 1,6-hexane diisocyanate (commercially available, for example, under the trade designation HMDI from Bayer), isophorone di isocyanate (commercially available, for example, under the trade designation IPDI from Huels), tetrafflethylxylene di isocyanate (commercially available, for example, under the trade designation m-TMXDI from Cytec), 2-methyl-l,5-pentane di isocyanate, 2,2,4-tr1methyl-1,6-hexane diisocyanate, 1,12-dodecane di isocyanate and methylene b1s(4-cyclohexyl Isocyanate) (commercially available, for example, Desmodur® W from Bayer), and higher functional Isocyanates such as a biuret of 1,6-hexane diisocyanate (commercially available, for example, as Desmodur® N from Bayer), an isocyanurate of 1,6-hexane diisocyanate (commercially available, for example, as Desmodur® N-3390 from Bayer), an isocyanurate of isophorone diisocyanate (commercially available, for example, as Desmodur® Z-4370 from Bayer), a reaction product of tetramethylxylene diisocyanate and trimethylol propane (cormnercially available, for example, as Octane® 3160 from Cytec), and a reaction product of one mole of trimethylol

propane and 3 moles of toluene diisocyante (commercially available, for example, as Desmodur® L from Bayer).
Polyether polyois having at least 2 hydroxyl groups represent a further useful group of precursors for polyacetoacetates. Poly(oxyalkylene)diols, triols and tetrols are generally preferred. Usually this type of polyol is made from the reaction of alkylene oxides wherein the alkylene group contains 2-8 carbon atoms with monomeric poiyalcohols, for example, those already mentioned above, such as glycerol, trimethylolpropane, pentaerythritol, sorbitol and the like, or preformed polymeric poiyalcohols containing 2-6 hydroxyl groups such as polyester and polylactonepolyols. The reaction products of polyepoxides with monoalcohols and/or poiyalcohols, preferably having 2-6 hydroxyl groups can also be used as polyacetoacetate precursors.
Suitable poiyalcohols for the preparation of polyurethane polyois are for example the monomeric types already mentioned above, such as ethylene glycol, neopentyl glycol, 6-hexanediol, 1,2-propanediol, diethyl ene glycol, 2-ethyl-2-butyl-l,3-propane did, triroethylol propane, glycerol, ditrimethylol propane, pentaerythritol and the like. Other suitable poiyalcohols are partial esters from poiyalcohols with monocarboxylic acids. Further usable poiyalcohols include for example polyesterpolyols and polyetherpolyols, preferably containing 2-6 hydroxylgroups. Addition polyois having 2-6 hydroxyl may also be employed. The preparation of polyurethane polyois is well-known in the art.
Addition polymers having at least 2 hydroxyl groups are a very useful class of precursors for polyacetoacetates. Usually these hydroxyl-functional compounds are prepared by radical polymerization of ethylenically unsaturated monomers having one or more hydroxyl groups, generally in the presence of one or more
comonomers which do not contain hydroxy! groups. A preferred group of hydroxy!-functional monomers are the hydroxyalkyl acrylates and hydroxyalkyl methacrylates. Representative monomers include: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydoxypropyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate and the like. Other useful hydroxy-functional monomers include the reaction product from methacrylic acid or acrylic acid with a monoepoxide, for example the glycidylether of a C9-C11 branched aliphatic acid, ethoxylated and propoxylated hydroxy-alkyl(meth)acrylates, ally! alcohol, and reaction products of hydroxyalkyl(meth)acrylates with lactones such as epsilon-caprolactone.
Suitable non-hydroxyl-functional ethylenically unsaturated comonomers are, for example, the acrylic or methacrylic esters of monoalcohol having 1-18 carbon such as ethyl(meth)acrylate, butyl(meth)acrylate, methyl(raeth)acrylate, 2-ethyl-hexylacrylate and the like. Examples of other copolymerizable monomers include, for example, methacrylic acid, acrylic acid, glycidyl methacrylate, styrene, vinyl toluene, dibutyl maleate, vinyl acetate, vinyl versatate. allylglycfdyl ether, itaconlc acid, naleic acid and the like. A preferred number average molecular weight for addition polyols is about ECO to about 5000. An hydroxyl number of about 50 to 300 is preferred for the addition polyol. A preferred acid number is about 0 to 50.
An alternative and very convenient method for the preparation of acetoacetate functional addition polymers consists of (co)polymering one or more acetoacetate functional ethylenically unsaturated monomers. Preferred acetoacetate functional monomers are the acetoacetic acid esters of hydroxyalkyl (meth)acrylates such as 2-{acetoacetoxy)ethyl methacrylate, 2-(acetoacetoxy)ethyl acrylate, 2-(acetoacetoxy)propyl methacrylate, 2-(acetoacetoxy)propyl acrylate, 4-(acetoacetoxy)butyl acrylate and the like, allyl acetoacetate and the acetoacetic acid ester of the reaction product of a hydroxyalkyl

(meth)acrylate with a lactone, or the acetoacetic acid ester of the reaction product of (meth)acrylic acid or a hydroxyalkyl (meth)acrylate with an alkylene oxide. Usually the acetoacetate functional monomers are copolymerized with non-acetoacetate functional monomers such as alkyl (meth)acrylates, the alkyl group having 1 to 18 carbon atoms, hydroxyalkyl (meth)acrylates, styrene, acrylic acid, methacrylic acid, maleic anhydride, dibutyl fumarate, acrylonitrile, acrylamide, vinyl toluene or other ethylenically unsaturated monomers. "(Meth)acrylate" is a shorthand indication of both acrylate and methacrylate.
All above-described polyalcohols are easily acetoacetylated by transesterification with alkyl acetoacetates of which the lower alkyl acetoacetates, having alkyl groups with 1 to 5 carbon atoms, are preferred such as methyl-, ethyl- or t-butyl acetoacetate. Another preferred method of acetoacetylation consists of reacting any of the nffintioned polyalcohols with diketene. Both methods are suitable for partial or complete conversion of the hydroxyl groups into acetoacetate groups.
Preparation of polyacetoacetates are well known in the art and may be found, for example, in the above mentioned paper by Witzman et al.
The polyacetoacetates of the current invention typically have a number average molecular weight (Mn) of about 200 to about 5000. More typically, they have a number average molecular weight less than 1000.
Particularly for use in reduced VOC coating compositions, the polyacetoacetates used in the current invention preferably have a number average molecular weight of about 200 to about 3000 and more preferably, about 250 to about 1000. Even more preferably, the polyacetoacetates for such uses have a number average molecular weight of about 250 to about 750, most preferably about 250 to about 500.

The pojyacetoacetates of this invention are acetoacetate-functional compounds which may be crosslinked via their acetoacetate groups. Cross! inkers for these acetoacetate-functional compounds of the current invention are well-known. Such crossllnkers are compounds having one or more groups capable of crosslinking with acetoacetate groups. For some examples, see US-A-3668183, EP-A-199087 and EP-A-240083,
Depending on the ultimately desired coating characteristics, the ratio of acetoacetate groups in the polyacetoacetate group to groups in the crosslinker capable of crosslinking can be varied. The ratio is generally in the range of about 0.5 to about 2. The preferred ratio of acetoacetate groups in the polyacetoacetate to groups capable of crosslinking with acetoacetate is greater than 1, preferably between about 1.1 and about 2, more preferably between about 1.1 and about 1.5.
As some examples of crossllnkers for polyacetoacetates herein described may be mentioned the following general classes of compounds and their derivatives and acidify cations: polyfunctional amines, ketimines, aldiraines, acryloyl and methacryloyl-functional polymers, copolymers and mixtures thereof.
Preferred crossllnkers are blocked primary amino group-containing compounds comprising the condensation product of (i) an aldehyde or a ketone and (ii) a polyamine having 2 to 6 (preferably 2 to 4) primary amino groups and a molecular weight of about 60 to about 1500, most preferably about 60 to about 1000.
Such blocked primary amino group-containing compounds are well known in the art from, for non-limiting example, EP-A-199087, EP-A-240083. US-A-5214086, US-A-4504630, US-A-4503174, US-A-4251597. WO-A-94/21738 and US-A-3975251.

Preferred blocking agents are ketones and aldehydes having 3-10 carbon atoms and more preferably having 3-8 carbon atoms. Examples of suitable blocking agents include acetone, methylethylketone, methylisobutylketone, diethyl ketone, methylacrylketone, ethylamylketone, isobutyraldehyde, hexanaldehyde, heptanaldehyde, pentanone, cyclohexanone, isophorone, hydroxycitronellal and decanone.
Blocked primary amino group-containing compounds preferred for use in the current invention include, for example, the ketimines and aldimines prepared from the reaction of a ketone or aldehyde with aliphatic, cycloaliphatic or arylaliphatic amines containing 2 or more, preferably 2 to 4, primary amine groups and from 2 to 200 carbon atoms. Examples of suitable amines Include: ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethy1enedi ami ne, decamethylenedi ami ne, 4,7-dioxadecane-l,10-diamine, dodecamethylenediamine, 4,9-dioxadodecane-l,12-d1aniine.
7-methyl-4,10-d1oxatridecane-l,13-diamine, 1,2-diaminodicyclohexane, 1,4-diaminocyclohexane, 4,i'-:-l2n1nodicyclohexy1 irethane, isophorone diamine, bis(3-methyl-4-aannccyclohexyl)raethane,
2,2-bis{4-aminocyclohexyl), nitrile tr1s{ethane) amine, bis(3-am1nopropy1) methylamine, 2-am1no-l-(methyl amino)propane, 3-amino-l-{cyclohexylamino)prapane, N-(2-hydroxyethyl)ethylene diamine, l,4-xyly1enediam1ne and 4-aminomethyl, l,8-octaned1am1ne.
A particularly preferred group of polyamines that are useful in the practice of the present Invention can be represented by the following structural formula:
H2N-(R'-NH)^-R-NH2

where the groups R and R' can be the same or different and represent an alkylene group containing from 2 to 6 and preferably from 2 to 4 carbon atoms and n is a number from 1 to 6 and preferably from 1 to 3. Included in the definition of alkylene group are cycloalkylene groups and alkylene groups containing an ether-oxygen atom. Examples of representative polyalkylene polyamines include diethylenetriamine, dipropylenetriamine and dibutylenetriamine. These polyamines have two primary amino groups and one secondary amino group.
Also preferred as crosslinkers for polyacetoacetates are the ketimines and aldimines obtained from the adduct reaction of a partially ketone-or aldehyde-blocked polyamine with a mono- or polyfunctional epoxy, isocyanate, maleinate, fumarate, acryloyl or methacryloyl compound whereby the reacting components are chosen in such a way that the adduct contains at least 2 imine groups.
Preferred polyamines are the above-mentioned amines of the structural formula H2N-{R'-NH)n-R-NH2 wherein n, R and R' are as described above. Other preferred polyamines for the formation of adducts have the structure R-NH-R'-NH2 wherein R is an alkyl or alkenyl group containing up to 20 carbon atoms and R' is an alkylene group containing 2-12 carbon atoms.
As examples of preferred epoxy compounds may be mentioned the di- or polyglycldylethers of {cyclo)aliphatic or aromatic hydroxyl compounds such as ethylene glycol, butanediol, polypropyleneglycol, Bisphenol-A, Bisphenol-F; hydrogenated Bisphenol-A, hydrogenated Bisphenol-F, phenol formaldehyde novolaks, etc. Other suitable epoxy compounds are monofunctional glycidylethers and glycidylesters such a phenylglycidylether, 2-ethylhexylglycidylether, the glycidylester of a C9-C11 branched aliphatic acid (available under the tradename Cardura ElO from Shell) and the like. 01glycidylesters of dicarboxyllc acids containing for instance 6-24 carbon atoms can also be conveniently

used. ,Further examples of suitable epoxy compounds are disclosed in EP 0 199 087, US 5,288,802, and EP 240 083. The epoxy resins are known to a skilled person and need no further description.
Examples of suitable isocyanate compounds for the preparation of adducts with partially blocked polyamines include aliphatic, cycloaliphatic or aromatic mono-, di-, tri- or tetraisocyanates and polyisocyanate prepolymers thereof. Preferred isocyanates include 1,6-hexane diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, 2,2,4-trimethyl-1,6-hexane diisocyanate, 1,12-dodecane diisocyanate, methylene bis(4-cyclohexyl isocyanate), 2,4- and 2,6-toluene diisocyanate, 4,4-dlphenylmethane diisocyanate, xylene diisocyanate, the biuret of 1,6-hexane diisocyanate, the isocyanurate of 1,6-hexane diisocyanate, the isocyanurate of isophorone diisocyanate, the uretdione of 1,6-hexane diisocyanate, etc. Other preferred isocyanates are the reaction products of diols or triols with a stoichiometric excess of di- or tri isocyanate, for the reaction product of Isophorone diisocyanate or 1,6-hexane diisocyanate with a diol such as ethylene glycol, 1,2-propanediol and the Hke or with a triol such as triraethylol propane and the reaction product of tetramethylxylene dilsocyante with trimethylol propane. Additional suitable isocyanates are disclosed in EP-A- 199 087 and EP-A-139 513.
Examples of suitable acryloyl or methacryloyl Include the {meth)acry1ic acid esters of mono-, di-, tri- or polyvalent hydroxyl compounds such as butanol, 2-ethylhexanol, ethylene glycol, neopentylglycol, 1,6-hexanediol, trimethylolpropane, ethoxylated trimethylolpropane, ditriraethylolpropane, pentaerythritol, diethylene glycol, polypropylene glycol, polyesterdiols and -triols, and polyurethanediols and -triols. The reaction products of {meth)arylic acid with epoxy compounds e.g. the glycidylether of Bisphenol A are also suitable for adduct formation with partially blocked polyamines.

A further group of suitable reaction partners are maleate and fumarate compounds such as diethyl maleate, dibutyl fumarate and unsaturated polyesters containing one or more maleate or fumarate groups. Suitable unsaturated polyesters include, for example, the polycondensation product of maleic anhydride with neopentyl glycol. The unsaturated polyester resins are well-known in the art and need no further description for skilled persons.
Particularly suitable ketimes are obtained by the reaction of a diisocyanate (such as hexamethylene diisocyanate) with a diketimine obtained from one mole dialkylene triamine (such as dipropylene triamine) and 2 moles ketone, as detailed in EP-A-199087 and EP-A-240083.
In addition to the polyacetoacetate and crosslinker, the binder may comprise additional binder components such as Isocyanates, epoxides, and oxazolldlnes.
The organosllanes useful in the current invention are of the following general

Z is an anion group, an aim no-containing group, an epoxy group, an epoxy-containing group, a mercapto group, a mercapto-containing group, a vinyl group, a vinyl-containing group, an isocyanate group, an isocyanate-containing group, an ureido group, an ureldo-containing group, an imidazole group or an iraidazole-containing group.

R isan aliphatic, alicyclic or aromatic group,
R'is an alkoxy group or alkoxyalkoxy group,
R" is an alkyl group having 1 to about 8 carbon atoms,
X is 0 to about 20,
a is 0 to 3, preferably 0 to 2,
b is 1 to 4, preferably 1 to 3,
c is 0 to 3, preferably 0 to 2, and
the sum ofa + b + cis4.
Typically, R is an alkylene group, e.g. methylene.
Typically R' is a lower alkoxy or alkoxyalkoxy , e.g. ethoxy, propoxy, isopropoxy, ethoxyethoxy, etc. and, most commonly, aethoxy.
As preferred organosilanes may be mentioned l«H2(CH2)3Si(0CH3)3, NH2CH2NH(CH2)3SI(OCH3)3. CH2(0)CH2CH2O(CH2)3Si(OCH3)3. SH{CH2)3Si{0CH3)3, and mixtures thereof.
Some oreganos lanes useful in the current invention are listed below.
Aminosilanes
H2N(CH2)3Si{0C2H5)3 3-Aminopropyl-triethoxysilane
H2N(CH2)3Si(CH3)(OC2H5)2 3-Ami nopropyl-methyl-diethoxysi1ane
H2N(CH2)3Si(OCH3)3 3-Ami nopropyl-trimethoxysi1ane
H2N(CH2)3Si C(0C2H4)20083)13 3-Aminopropyl-tris(2-methoxyethoxy-

H3C-NHICH2)sSi(OCH3)3 N-Methyl-3-ami nopropyl-trimethoxy-
silane H2N(CH2)2NH(CH2)3Si(OCH3)3 N-Aminoethyl-3-aminopropyl-tri-
methoxy-silane
^ H2N(CH2)2NH(CH2)3Si(CH3)(0CH3)2 N-Ami noethyl-3-aminopropyl-methyl -
dimethoxysilane (CH30)3-Si(CH2)3NH{CH2)3)Si(0CH3)3 N,N-Bis(trimethoxysilylpropyl)amine
Mercaptosllanes
HS(CH2)3Si(0C2H5)3 3-Mercaptopropyl-triethoxysilane
HS(CH2)3Si(0CH3)3 3-Mercaptopropyl-trimethoxysilane
HS(CH2)3Si(CH3)(OCH3)2 3-Mercaptopropyl-methyl-dimethoxy-
silane
Vinyl si lane
H2C=C{CH3{C00(CH2)3Si(0CH3)3 3-Methacryloxypropyl-trimethoxysilane
CH2=CHSi{0C2H5)3 Vinyltriethoxysilane
CH2=CHSi(0CH3)3 Vinyltrirnethcxysilane
CK2=CHS1(0C2H40CH3)3 Vinyl-tris(2-ia£thoxy-ethoxy)silane
Epoxysilanes
0
/\ H2C-CH-CH2O(CH2)3Si{0CH3)3 3-Glycidyloxypropyl-trimethoxysilane
{CH2)2S1(0CH3)3 2-(3.4-Epoxycyclohexyl)ethyltri-
OI^^HJ methoxysilane

Isocyanatosilane
0 = C = N{CH2)3Si(OC2H5)3 3-Isocyanatopropyltriethoxysilane
A particularly effective "adhesion-enhancing amount" of organosilanes is about 1 to about 10 we1ght% based on binder solids, preferably about 1.5 to about 5 weight%.
The coating compositions of the current Invention are typically, though not necessarily, formulated as well-known "two-pack" systems. Thus, in general the oreganos lane may be placed with either the crossllnker or with the polyacetoacetate. Further, the organosilane may be added as a "third component", that is, it may be added independently rather than with the crossllnker or polyacetoacetate. Independent addition of the organosilane is particularly desirable when the organosilane is capable of crosslinking with one of the binder components. Depending on the organosilane used, it may be present as either a "free" additive (that is, unreacted) or it may be present In the form of a reaction product with another component of the coating composition.

The coating compositions of this invention may also contain a pigment component. The pigment component of this invention may be any of the generally well-known pigments or mixtures thereof used in coating formulations, as reported, e.g., in Pigment Handbook. T.C. Patton, Ed.. Wiley-Interscience. New York. 1973. The coating composition disclosed herein has been found to be particularly useful for pigment components which are substantially chromate-free. Non-limiting examples of such substantially chromate-free pigments are barium metaborate. zinc phosphate, aluminum triphosphate and mixtures thereof. Preferably, the pigment component, if employed, is present in a pigment volume concentration of about 10 to about 40.
Coating compositions of the instant invention have been found to be particularly useful as primer coats, especially for aluminum substrates. Typically, when the current coating comopositions are formulated for use as such primer coats, the above-described substantially chromate-free pigments are employed.
The coating composition generally contains an organic solvent which is commonly applied, for instance, in the Industrial preparation of paint, such as aliphatic or acrobatic hydrocarbons, esters, ethers, alcohols, ketones and ether acetates. However, the amount of solvent Is typically lower than what Is company required In that the current Invention may be formulated as a "high solids" (low solvent) coating composition. Such compositions are also referred to a "low VOC" coating compositions. Current "high solids" formulations have a VOC preferably below 420 g/1 and more preferably below 350 g/1. "VOC" refers to the "volatile organic content", which Is normally expressed as grams organic volatiles per liter organic component.
The coating composition of the current invention may also contain other additives usual for such formulations. A particularly preferred additive is a water scavenger, such as a molecular sieve. Other

typical .additives may be, for non-limiting example, dispersing agents, for instance, soya lecithin; fillers; reactive diluents; plasticizers; levelling agents, for instance, acrylate oligomers; anti-foaming agents, for instance, silicone oil; metal salts of organic acids, such as cobalt of ethyl hexanoate, dibutyl tin dilaurate; chelating agents; rheology control agents, for instance, bentonites, pyrolized silica, hydrogenated castor oil derivatives and adducts of a di- or triisocyanate and a monoamine; catalysts, such as phosphoric acid, phosphoric esters, and carboxylic acids; antioxidants, such as substituted phenols; and UV stabilizers, such as, benzophenones, triazoles, benzoates and hindered bipiridylamines.
The coating composition may be applied to the substrate in any suitable manner, such as by roller coating, spraying, brushing, flow coating, or dipping. It is preferred that the composition Is applied by spraying.
Suitable substrates include plastic in metals, such as Iron, steel, galvanized steel and, as earlier iner.rioned, the preferred aluminium. Prior to applying a coating of the current invention, the surface may be prepared In conventional ways, far example, cleaning (with, for example, solvent or a water based alkaline cleaner), mechanically treating For example, abrasion) and/or conversion coating (phosphorizing, chromating or anodizing).
A temperature above ambient is not necessary to dry and cure the coating conq)os1t1ons disclosed herein; however, heat may be applied. Thus, the full range of temperatures, from, for example, about S'C to about lOO'C can be used to cure and/or dry the coating compositions of this invention.

Accordingly, the present invention provides a process for the preparation of a coating, comprising the steps of preparing an organic solvent containing coating composition by combining (a) an organic solvent, (b) a polyacetoacetate having acetoacetate groups and having a number average molecular weight in the range of 1000 to 5000, (c) a crosslinker having at least two groups capable of crosslinking with the acetoacetate groups, and (d) at least one organosilane in which coating composition, the organosilane is present in an adhesion enhancing amount, and drying and/or curing the coating composition at a temperature between 5°C and 100°C.
Accordingly, the present invention also provides a method of coating a substrate, wherein a substrate is coated with a coating as described above.
The current invention is further disclosed and explained with reference to the following representative, though non-limiting, examples.

EXAMPLES
The adhesion and corrosion resistance of coating compositions according to the current invention were tested as detailed below.
Preparation of polyacetoacetates
The polyacetoacetates used in the following examples were prepared by transesterification of the polyols with ethyl acetoacetoacetate or t-butyl acetoacetate according to the methods described by Witzeman J.S. in Journal of Coating Technology 62, No. 789. 101 (1990). The acetoacetate of Test Nos. 1-20 and Comparative Tests I and II was prepared by acetoacetylation of a precondensate from ditn'methylolpropane (1 mole) and isononaoic acid (0.6 mole).
Preparation of ketimfne resin
The ketimine resin used in the following exam{5les is the adduct of 1,6-hexane diisocyanate (1 mole) with 2 moles-of the di retiming from dipropylene triamine and methyl isobutyl ketone. The ketimine resin was prepared according to the method described in EP-A-240083, and was used in the form of an 85% solution in a mixture of xylene and methyl isobutyl ketone.
Adhesion Test
To test adhesion, a "modified" DIN 53151 cross-hatch method was used to test initial adhesion, adhesion after water immersion and adhesion after immersion in hydraulic oil. In conventional cross-hatch adhesions tests, several grids are made wherein each grid has equal spacing in both the horizontal and vertical directions, for example, in one grid the spacing between the cuts is 0.1 mm in both the horizontal and vertical directions, in another grid the spacing is 0.2

mm, in another the spacing is 0.3 mm, etc. As a modification, the adhesion tests reported here were performed by using one grid wherein in both the horizontal and vertical directions the spacing between cuts was increased by 0.1 mm over the next previous cut; that is, the spacing between the first two cuts was 0.1 mm, between the second and third cuts was 0,2 mm, between the third and fourth cuts 0.3 mm, etc. until a spacing of 1.1 mm was acheived.
Test Nos. 1-20 and Comparative Test Nos. I and II
In Test Nos. 1-20, four (4) different si lanes were added, in separate tests, to the primer formulations described below. Various si lane concentration levels as well as the manner of adding the si lane to the coating composition (primer) were also tested. In Comparative Test Nos. I and II no si lanes were added. Otherwise, Comparative Test Nos. I and II were carried out in the same manner as Test Nos. 1-17. Results are reported in Tables 1 and 2.
In Test Nos. 18-20 the ratio acetoacetate groups to crosslinking groups was varied.
Experimental Method: Test Wos. 1-20 and Comparative Test Nos. I and II
In Test Nos. 1-8, the silane indicated in Table 1 was premixed with trimethylol propane-triacetoacetate to form the Adduct. Components A and B were separately prepared then mixed to form a primer.
In Test Nos. 9-16, the silane was not premixed. Rather, Component A and Component B were prepared. In preparing Component A, trimethylol propane-triacetoacetate and the relevant silane were separately added. Components A and B were mixed to form a primer. In Test No. 17 the silane was added to Component B. In Test Nos. 18-20, Component B and the silane were each Independently added to Component A.

The priijiers for Comparative Test Nos. I and I contain no si lane. They were prepared in the same manner as the primers for Test Nos. 9-16, omitting the silane.
In all Tests the primers were applied by spray gun to a dry-layer thickness of about 20 to 25 pm. At spraying viscosity (30-35 s ISO-cup 4) the VOC for the primers was 350 g/1.
Table 1 reports the results of the following adhesion tests. Variously aged primers (specifically, one day, one week and one month after primer preparation) of Test Nos. 1-16 and Comparative Test Nos. I and II were applied to Alclad 2024T3 substrates which had been cleaned with Sikkens®B2. The coated substrates were aged for one week, after which the already-described modified DIN 53151 cross-hatch method was used to test both initial adhesion and wet adhesion after 2 weeks of water immersion. Test No. 17 was carried out in a similar fashion, except only wet adhesion of a one-day-aged primer was tested. Test Nos. 18-20 were also carried out in the manner as described for Test Nos. 1-16, except only one-day-aged primers were tested.
Table 2 reports the results of the following adhesion tests. The primers of Test Nos. 1-16 and Comparative Tests I and II were applied to Alclad 2024T3 substrates which had been cleaned with S1kkens®B2 and a Scotch-Br1te®pad, After one day the primers were sprayed over with the topcoat Aviox® Finish available from AD Aerospace Finishes VoF, Sassenheim, the Netherlands. The coated substrates were aged for one week, after which the already described modified DIN 53151 cross-hatch method was used to test both initial adhesion and wet adhesion after 2 weeks of water immersion and DIN 65472 was used to test filiform corrosion (FFC) resistance. Test No. 17 was carried out In a manner consistent with Test Nos. 1-16 except the Alclad 2024T3 substrate was pretreated first with alkaline cleaning, then with alkaline etching and finally with nitric acid pickling. Only testing indicated In

/
Table-2 was performed for Test No. 17. Test Nos. 18-20 were carried out in a manner consistent with Test Nos. 1-16 except the primers were sprayed over with the topcoat Aerodur® C21/100 UVR available from AD Aerospace Finishes VoF, Sassenheim, the Netherlands. Only testing indicated in Table 2 was performed for Test Nos. 18-20.
In Tables 1 and 2, "Ratio PolyAc/Crosslinker" means the ratio of acetoacetate groups to groups capable of crosslinking with the acetoacetate groups.
Primer Formulation: Test Nos. 1-16 and Comparative Test Nos. I and II

SZPr391 strontium zinc phosphorsilicate available from Haloa.
10 Y-25, a Theology modifier available from Chemise.

Our cop ending application no.883/MAS/96 relates to 'a process for the preparation of a coating having improved substrate-adhesion'.
The composition claimed therein limits the amount of the cross linker and organosilane is optional. The composition is also not solvent based. Average molecular weight of polyacetoacetate is restricted to less than 1000.

WE CLAIM:
1. A process for the preparation of a coating, comprising the steps of preparing an organic solvent containing coating composition by combining (a) an organic solvent, (b) a polyacetoacetate having acetoacetate groups and having a number average molecular weight in the range of 1000 to 5000 (c) a crosslinker having at least two groups capable of crosslinking with the acetoacetate groups, and (d) at least one organosilane in which coating composition, the organosilane is present in an adhesion enhancing amount, and drying and/or curing the coating composition at a temperature between 5°C and 100°C.
2. The process as claimed in claim 1, wherein the organosilane is of the following general formula:

wherein Z is an amino group, an amino-containing group, an epoxy group, an
epoxy-containing group, a mercapto group, a mercapto-containing group, a
vinyl group, or a vinyl-containing group, an isocyanate group, an isocyanate-
containing group, an ureido group, an ureido-containing group, an imidazole
group or an imidazole-containing group,
R is an aliphatic, alicyclic or aromatic group,
R' is an alkoxy group or alkoxyalkoxy group,
R" is an alkyl group having 1 to about 8 carbon atoms,
x is 0 to 20,
a is 0 to 3,
b is 1 to 4,
c is 0 to 3 and

3. The process as claimed in claim 1, wherein comprising a mixture of organosilanes.
4. The process as claimed in claim 3, wherein Z is selected from the group consisting of NJ, NH2CH2NH, CH2(0)CHCH20, SH, H2NCONH, CH3NH and CH2=C(CH3)COO.
5. The process as claimed in claim 2, wherein R is selected from the group consisting of alkylene and alkenylene group.
6. The process as claimed in claim 2, wherein R' is an alkoxy or alkoxyalkoxy group having 1 to 10 carbon atoms.
7. The process as claimed in claim 2, wherein R is CH2,
R' is OCH3 or OC2H5, X is 3, a is 1, b is 3 and cis 0.
8. The process as claimed in claim 1, wherein the organosilane is selected from
the group consisting of NH2(CH2)3Si(OCH3)3, NH2CH2NH(C2)3Si(OCH3)3,
CH2(0)CHCH20(GH2)3Si(OCH3)3, SH(CH2)3 Si(OCH3)3, and mixtures thereof

9. The process as claimed in claim 1, wherein the ratio of acetoacetate groups to groups capable of crosslinking with acetoacetate groups is 1.1 to 2.
10. The process as claimed in claim 1, wherein the crosslinker is selected from the group consisting of amine, ketimine, aldimine, acryloyl and methacryloyl functional compounds, polymers and copolymers thereof and mixtures thereof.
11. The process as claimed in claim 1, wherein the crosslinker is a blocked primary amino group-containing compound comprising the condensation product of (I) an aldehyde or a ketone and (ii) a polyamine having 2 to 6 primary amino groups.
12. The process as claimed in claim 1, wherein the coating composition comprises at least one pigment component,
13. The process as claimed in claim 12, wherein the pigment is substantially chromate-free and is present in a pigment volume concentration of 10 to 40.
14. The process as claimed in claim 12, wherein the pigment is selected from the group consisting of barium metaborate, zinc phosphate, aluminium phosphate and mixtures thereof.
15. The process as claimed in claim 1, wherein the organosilane is present in an amount of 1 to 10 weight % based on binder solids.

16. The process as claimed in claim 1, wherein the ratio of acetoacetate groups to
groups capable of crosslinking with acetoacetate groups is between 1.1 and 1.5.
17. The process as claimed in claim 1, wherein the coating composition comprises
at least one additional binder component, selected from the group consisting of
isocyanates, epoxies, oxazolidines and mixtures thereof.
18. The process as claimed in claim 1, wherein the coating composition is a primer.
19. The process as claimed in claim 1, wherein the coating composition has a
volatile organic content (VOC) below 420 g/1.
20. A method of coating a substrate, comprising coating a substrate with a coating
as claimed in any one of the preceding claims.
21. The method as claimed in claim 20, wherein the substrate is selected from the group consisting of aluminium, steel, galvanized steel and plastic.
22. A process for the preparation of a coating substantially as herein described.
23. A method of coating a substrate substantially as herein described.

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Patent Number

220407

Indian Patent Application Number

882/MAS/1996

PG Journal Number

30/2008

Publication Date

25-Jul-2008

Grant Date

28-May-2008

Date of Filing

24-May-1996

Name of Patentee

AD AEROSPACE FINISHES V.O.F.

Applicant Address

RIJKSSTRAATWEG 31, 2171 AJ SASSENHEIM,

Inventors:

#	Inventor's Name	Inventor's Address
1	NICOLAAS ANTONIUS MARIA SCHOONDERWOERD

PCT International Classification Number

C09D3/82

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA