NCO-FREE RESINS USEFUL AS A SUBSTITUTE FOR POLYURETHANES

Abstract: Compositions obtained by curing an acetoacetylated polymer poly(meth)acrylic or polyester-based resin and an NCO-free urethane polymer having vinylic end groups is disclosed.

Description: Description NCO-Free Resins Useful As a Substitute for Polyurethanes Technical Field The present invention relates to NCO-free resins an coatings possessing the outstanding performanc characteristics of polyurethanes. Background Art For the past several decades, urethane coatings, blocked urethanes, etc. have been very successfully used as polymers for coating and engineering polymers. They have been formulated to achieve outstanding results for the industry. Most commonly, urethanes are prepared by a reaction in which free isocyanates (NCO) are reacted with various other groups in a two-package system. Recent environmental toxological studies however indicate that it is very desirable to eliminate f ee NCO groups from uncured polymers coatings. This would prevent exposure of this toxic material to humans during manufacture, application and in the final product, and the product would be very stable because no NCO groups would be available to react with moisture, etc. To date no satisfactory solution to this problem is available. There is thus a strongly felt need for NCO-free resins and coatings possessing the outstanding performance of urethane materials. Notably there is a strongly felt need for NCO-free resins and coatings possessing the following advantagest high gloss, high impact resistance, good hardness and flexibility, good solvent and chemical resistance, good UV resistance in weathering, and good room temperature cure. Disclosure of the Invention Accordingly, one object of this invention is to provi novel NCO-free resins and cured products thereof possessi the outstanding performance characteristics of uretha materials. ∑t is another object of this invention to provide nov NCO-free resins and cured products thereof possessing hi gloss characteristics. It is another object of this invention to provide nov NCO-free resins and cured products thereof possessing hi impact resistance. It is another object of this invention to provide nov NCO-free resins and cured products thereof possessing go hardness and flexibility characteristics. ∑t is another object of this invention to provide nov NCO-free resins and cured products thereofpossessing go solvent and chemical resistance. It is another object of this invention to provide nov NCO-free resins and cured products -thereof possessing go UV resistance and weathering characteristics. It is another object of this invention to provide nov NCO-free resins which cure rapidly at room temperature. It is another object of this invention to provide a t component kit for preparing NCO-free resins and cur products thereof which have a long life. The inventor has now discovered NCO-free resins a coatings which satisfy all of the above objects of th invention, and other objects which will become apparent fr TITUTESHEET the description of the invention given hereinbelow. These NCO-free resins and coatings are obtained curing a two-component mixture. The first component of t mixture is at least one polymer carrying acetoacet groups. The second component of this mixture is at lea one NCO-free urethane bearing at least two unsaturated e groups (i.e. vinylic end groups). This mixture is cured i the presence of a catalyst having a pKa of 12 to 14. Best Mode for Carrying Out the Invention The present invention uses two different polymer possessing acetoacetyl groups: an acetoacylate (meth)acrylic resin and an acetoacetylated polyester. Thes two different polymers possessing acetoacetyl groups can b either used individually or together in preparing the cure products provided by this invention which includes coatings articles, adhesives, etc. (vide infra). Acetoacetylated-(meth)acrylic resins In one embodiment, the acetoacetylated acrylic resin i obtained by copolymerizing a mixture containing 10 to 6 wt.%, preferably 15 to 35 wt.%, of at least one monomer o formula (I): CH 2 *C(R 1 )-CO-0-CH2CH 2 -0-CO-CH 2 -CO-CH3 (I) and 40 to 90 wt.%, preferably 65 to 85 wt.%, of at least on alkyl (meth)aerylate of formula (II): CH 2 «C(R 1 )-CO-0-R (II) wherein R is a C 1 _ 12 linea or branched saturated alky group and R 1 is a hydrogen atom or a methyl group. In another embodiment, the acetoacylated (meth)acryli resin is obtained by copolymerizing a mixture containing t same ratios as above of at least one monomer of formula ( together with at least one alkyl (meth) erylate of formu (II), and in addition 10 to 50 wt.% of styrene. These acetoacetylated (meth)acrylic resins have molecular weight, fl n , of from 10,000 to 16,000, preferab 13,000 to 15,000. (M R * number average molecular weight.) The acetoacylated (meth)acrylic resins may be prepar by polymerization of the monomers by conventional metho ° using conventional polymerization catalysts. T polymerization is preferably carried out using free-radica forming catalysts in solution or in emulsion. Convention emulsifiers and/or protective colloids may be used when t copolymers are prepared in aqueous emulsion. 5 When the polymer is prepared in solution, in additi to water, suitable organic solvents which can be us include aromatic ^ hydrocarbons such as benzene, toluene a xylene, ketones- * such as methylethyIketone, esters saturated carboxylic acids such as ethylacetat 0 butylacetate and methylglycolacetate, alcohols such methanol, ethanol, isopropanol, nbutanol, isobutanol a glycols and also glycol ethers, for example the methyleth of ethylene glycol. Acetoacetylated polyester resin; 5 The polyester functionalized with acetoacetyl grou can be obtained in one of two ways. In one embodiment, the polyester and a C 1 acetoacetate, e.g. methyl acetoacetate, are subjected to transesterification reaction. The polyester used has 0 molecular weight, R R , of 1,000 to 10,000, preferably 1,2 to 8,000, and possesses hydroxyl groups. The hydroxy grou containing polyesters may contain, as the acid deri HEET - 5 - moiety, moieties derived from benzoic acid, p-t-buty benzole acid, capric acid, caproic acid, dimethylo propionic aci'd, α-ethyl butyric acid, 2-ethyl hexanoic acid adipic acid, azelaic acid, dimethyl glutarate, fumaric acid isophthalic acid, aleic anhydride, terephthalic acid citric acid, trimellitic anhydride, pyromelliti dianhydride, and combinations of two or more of these. The hydroxy compound derived moiety may be derived fro arayl alcohol, benzyl alcohol, butyl alcohol, cetyl alcoho (hexadecanol), ethyl alcohol, α-ethyl hexyl alcohol, hexy alcohol, isobutyl alcohol, isopropyl alcohol, methy alcohol, octyl alcohol, pentyl alcohol, propyl alcohol, 1,3 butane diol, 1,4-butane diol, 1,2-, 1,3- or 1,4 cyclohexanedimethanol, diethylene glycol, dimethylo propionic acid, dipropylene glycol, ethylene glycol, Este Oiol 204, 1,6-hexanediol, hexylene glycol, neopentyl glycol 1,5-pentanediol, propylene glycol, tetraethylene glycol triethylene glycol, trimethylene glycol trimethylpentanediol, glycerine, trimethylol ethane trimethylol 'propane, tris(hydroxyethyl)isocyanurate pentaerythritol, and combinations of of two or more o these. The polyesters have a hydroxyl group content of fro 150 to 900 equivalent weight (solids), preferably 150 to 75 equivalent weight, -OH (solids). The transesterification reaction is carried out usin conventional methods using conventional transesterificatio catalysts. The polyester is reacted with the C 1-4 alky acetoacetate in the presence of a transesterificatio catalyst to give the acetoacetoxy-resin and a low molecula weight C 1-4 alkyl alcohol which is distilled off. Any wel known transesterification catalyst may be used, e.g. an aci catalyst like trichloroacetic acid. At least 75% and up t 100%, of the polyester hydroxyl group are este ified. In another embodiment, the polyester functional! with acetoacetyl groups is obtained by subjecting standard free radical graft polymerization react conditions an unsaturated polyester with a monomer formula (I): CH 2 *C(R 1 )-CO-0-CH 2 CH 2 -0-CO-CH 2 -CO-CH 3 (I) to obtain a product in which at least 70% and up to 100% the ethylenically unsaturated groups in the unsatura polyester have been reacted. The unsaturated polyester starting material used ha molecular weight, fl n , of from 1,500 to 8,000 prefera 1,500 to 3,500. The diacid component of the unsatura polyester includes, for example, moieties derived f fumaric acid, maleic acid, itaconic acid, citraconic ac mesaconic, aconitric acid, and mixtures of two or more these diacids. Unsaturated polyesters containing fuma and/or maleic acid-derive moieties are preferred. The diol component of the unsaturated polyes includes, for example, moieties derived from ethylene glycol, propylene glycol, diethylene gly (HOCH 2 CH 2 OCH 2 CH 2 OH), triethylene glycol (HO(C 2 H 4 0) 2 CH 2 O polyethylene glycol, dipropylene glycol (mixed isomer polypropylene glycol, 1,3-butane diol, 1,4-butane diol, 1 hexanediol, neopentyl glycol, 1,2-, 1,3- or 1 cyclohexanedimethanol, 2,2,4-trimethyl pentane di bisphenol A, trimethylolethane, trimethylolpropa dicyelopentadiene glycol, dimethylol propionic acid. Es Diol 204, hexylene glycol, 1,5-pentane diol, tetraethyl glycol, monools of allyl ethers, and mixtures of at le two of the diols. The unsaturated polyester may optiona contain from 10 to 50 wt.% of styrene-derived units. EET NCO-free urethane functlonalized with unsaturated end groups: The NCO-free urethane polymer may be a urethane polym having at least two (meth)aerylate end groups. This polym can be obtained using one of twc different procedures. In the first procedure, a C 2 „ 12 linear, branched cyclic alkyl or arylpolyol having an -average of from 2 to hydroxyl groups per molecule is reacted together with a C 12 linear, branched or cyclic saturated alkyl or ar diisocyanate, triisocyanate or tetraisocyanate, or a mixtu of these, at a temperature of from 5 to 20*C using any kno conventional catalyst. The reactants are then heated to temperature of from 40 to 150°C and held at this temperatu for a period of time sufficient to reduce the NCO content the reaction mixture to 4 to 20 wt.%. A hydroxy substituted alkyl (meth)aerylate of formul (III)* CH 2 «C(R 1 )-CO-0-R 2 -OH (III) wherein R 1 is a hydrogen atom or a methyl group, and R 2 is C 2 _ linear or branched saturated alkylene is then added t the reaction mixture. Together with the hydroxy-substitute alkyl (meth)aerylate of formula (III) other vinyl group containing monomers and polymers may be added optionall with suitable stabilizers. These vinyl containing monomer can be any monomer processing an α,β-unsaturated ester functionality. The stabilizer may, for example, th monomethyl ether hydroquinoline (METHQ) which may be used i an amount of 100 to 500 ppm, preferably 150 to 250 ppm. The reaction temperature is maintained at 40 to 150° until the NCO content of the reaction mixture approaches wt.%, i.e. until the NCO content is not more than 4 wt.% preferably not more than 2 wt.%, and most preferably no more than 1 wt.%. At this time an aliquot of a C 1-4 alk alcohol, such as methanol, ethanol, etc. is added whi maintaining the reaction temperature at from 40 to 150 until no detectable NCO is obtained. The C 1-4 alkyl alcoh is added in an amount corresponding to a OB to NCO ratio at least 1.5, preferably 1.5 to 3.0, most preferably 1.5 2.0 The temperature is maintained at 40 to 150*C until t NCO content reaches a 0.0% NCO is determined by the standa ASTM D 2572-70 (di-butylamine). Thus in this embodiment, among others, a NCO-fr urethane functionalized with unsaturated end groups and formula (VI) is obtained: (CH 2 =C(R 1 CO-0-R 2 -0-CO-NH-B-NH-CO-Ot p A (VI) In formula (VI), p is an integer of from 2 to 4. Each R 1 independently a hydrogen atom or a methyl group. Each R 2 independently a c 2 -3 linear or branched satura alkylene. Each # B is independent a C 2 _ i2 linear or branc saturated alkylene, or a C 4 _ 12 cyclic saturated alkylene, a C 6 . 12 arylene. And A is a C 2 _ 12 linear or branc saturated alkylene group or a C 4 _ 1 cyclic satura alkylene group. The material of formula (VI) is obtained when diisocyanate is used. However it will be recognized t products having different structures are obtained w triisocyanates and/or tetraisocyanates are used. In another embodiment, using the process outli above, a diol is sequentially reacted with a diisocyana then with a hydroxy-substituted alkyl (meth)aerylate formula (III) and then with the C χ _ 4 alkyl alcohol to obt a product of formula (IV): CH g « C(R 1 )-C0-O-R 2 -0fCO-NH-B-NH-CO-0-A-0» nt 1 -CO-NH-B-NH-CO-0-R 2 -0-CO-C(R i )*CH 2 (IV). In formula (VI) each R 1 is independently hydrogen methyl. Each R 2 is independently a C 2 _ 3 linear or branch saturated alkylene. Each B is independently a C 2 _ 12 line or branched saturated alkylene, or a C 4 _ 12 cyclic saturat alkylene, or a C 6 _ 12 arylene. Each A is independently a C 12 linear or branched saturated alkylene, or a C 4 _ 12 cycl saturated alkylene. And n is 1 to 4 for coatings and 1 10 for elastomers. In another embodiment, the NCO-free uretha functionalized with unsaturated terminal groups is obtain by reacting a diisocyanate and/or a triisocyanate and/or tetraiisocyanate with a hydroxy-substituted alk (meth)aerylate of formula (III) to obtain a product of t formula (V): (CH 2 « C(R 1 tCO-0-R 2 -0-CO-NH m X (V) wherein variables R 1 and R 2 are as defined above, X is th diisocyanate, triisocyanate or tetraiisocyanate nucleus or mixture thereof, and m is 2, 3 or 4. To obtain the compound of formula (V) the diisocyanat and/or triisocyanate and/or tetraiisocyanate is reacted wit the hydroxy substituted alkyl (meth)acrylate formula (III at a temperature of from 40 to 150°C for a length of tim necessary to reduce the NCO content of the reaction mixtur to 4 to 20 wt.%. The hydroxy substituted alky (meth)aerylate may be used together with other α,ø unsaturated esters and with vinyl containing monomers an polymers and with suitable stabilizers. The reaction temperature is maintained until the NC content approaches 0 wt.%, i.e. is less than 4 wt.% preferably less than 2 wt.% and most preferably less than wt.%, at which time an aliquot of a C 1-4 alcohol similar t that described above is added while maintaining the reactio temperature until no detectable NCO is obtained (i.e. unt the NCO content is 0.0% as defined by ASTM D 2572-70 (d butylamine). As discussed supra, the Cl-4 allyl alcohol added in an amount corresponding to a NCO to OH ratio of least 1.5, preferably 1.5 to 20. The product thus obtain has a molecular weight fi R , of 200 to 8,000 preferably 400 4,000. When the NCO-free urethane • functionalized wi unsaturated end groups is prepared (e.g. from a diol obtain the material of formula (IV) or from a polyol obtain the material of formula (VI)), it will be appreciat that a molar excess of the , isocyanate (viz. t diisocyanate, triisocyanate and/or tetraiisocyanate) ov the hydroxy compound must be used in the preparation of t prepolymer. In this reaction formation of the isocyanat prepolymer may be assisted by the use of catalysts known the art to assist polyurethane formation. For exampl these include tertiary amines, and methyl salts, e. stannouβ octoate and particular dibutyl tin dilaurate. The reaction of the hydroxy compound and the Isocyana may produce a viscous urethane prepolymer and, especial when the degree of polymerization is large, the prepolym may be solid. It is desirable in these circumstances th the reaction of the hydroxy compound and the isocyanate effected in the presence of an inert diluent. Similarl where the urethane prepolymer is very viscous or soli further reaction of the prepolymer is desirably effected the presence of an inert-diluent. The diluent should be substantially free of grou which are reacted with isocyanate groups, at least to su an extent that the diluent does not interfere with t formation of the prepolymer. In the preparation of t material of formula (VI), the diluent can of course be t hydroxy substituted (meth)acrylate of formula (III). ET When the urethane prepolymer is prepared in an ine diluent, the prepolymer may be separated from the diluen e.g. by evaporation of the diluent or by the addition to t diluent of a rt n-solvent or the prepolymer. The C 2 _ 12 linear, branched or cyclic alkyl or ar polyol which can be used in the present invention inclu methylene glycol, propylene glycol, butylene glycol glycerine, trimethylolethane (TME), trimethylolpropane (TM and pentaerythritol, or combinations of these materials. Examples of diols and polyols which do not have cycli groups in the chain include, for example, ethylene glyco and propylene glycol, in which case A has the structure Butylene glycol, diethylene glycol 1,3-butane diol, 1,4 butane diol, dipropylene glycol, 1,6-hexanediol, hexylen glycol, neopentyl glycol, 1,5-pentanediol, tetraethylen glycol, triethylene glycol, trimethylene glycol, tri ethy pentane diol, trimethylol ethane, or trimethylol propane and derivatives of these materials in which one or more o the carbon atoms are substituted by atoms or groups whic are unreactive towards hydroxyl and isocyanate group may b used. Examples, of diols containing cyclic groups which ma be used in the preparation of the urethane prepolyme include, for example, cycloalkane diols, e.g. 1,2-, 1,3- o 1,4-cyclohexane diol and a diol having the structure in which' case the group A in the urethane prepolymer has t structure respectively. Other suitable diols include, for exampl cycloalkane dialkanols, e.g. 1,2-, 1,3- or 1,4-cyclohexa dimethanol or 1,2-, 1,3- or 1,4-cyclohexane diethano polycycloalkane diols, polycycloalkane dialkanols, ar dialkanols and condensates of alkylene oxides with aromat compounds containing two phenolic groups. Other diols which can be used are diols of t structure that is, oxyalkylated derivatives of phenolic compoun where R4 and R5 are hydrogen atoms or C 1-4 alkyl grou e.g. methyl, and Ar is a divalent aromatic group in wh each free valency is on an aromatic carbon atoms, and which a+b together preferably total not more than 8 and a preferably not greater than b+3. Ar may be mononuclear, e.g. as in phenylene, fu polynuclear as in naphthalene or anthracene, or prefera has the structure EET - 13 - in which Y ,is a divalent link, e.g. -0-, -S0 2 -, -CO- -CH 2 - or a substituted derivative of -CH 2 - e.g. CH, I 3 -c- I CH 3 Suitably, one of the groups R 4 and R 5 is hydrogen a the other is methyl, or both R 4 and Rg are hydrogen. Th is, the diol may be prepared by reaction of propylene oxi or ethylene oxide with a phenolic compound having t structure HO-Ar-OH, preferably Preferably a+b is not greater than 4. Diisocyanates containing cyclic groups which may used to prepare the urethane prepolymer include, f example, diisocyanates in which the chain between the fr valencies is provided with at least one aromatic group or least one cycloaliphatic group, or in which the cha between the free valencies includes in combination at lea one aromatic and at least one cycloaliphatic group * Cycloaliphatic diisocyanates include for exampl diisocyanates of the structure: where -Y- is a divalent link which may be, for example, -CH 2 - or substituted derivative thereof, -0-, -S0 2 -, -CO-, and the isocyanate groups are linked meta- or para- to the groups ϊ. A particular example is 4,4'- dicyclohexylmethane diisocyanate. Aromatic diisocyanates which may be used include, for examples, 2,4- or 2,6-tolylene diisocyanate, or mixtures thereof, in which case the divalent group B or X has the structure or a combination of said structures. Another suitable aromatic diisocyanate is that having the structure (CH 2 ) m -NC0 where m is a whole number chosen such that there ar preferably not more than 20 atoms between cyclic groups i the urethane prepolymer derived therefrom. A suitabl diisocyanate having the latter structure is xylylen diisocyanate. Another suitable diisocyanate is that having th structure: - E SHEET where Y is a divalent link which may have the designatio hereinbefore described and in which the isocyanate grou are linked meta or para to the group Y. A preferred examp is 4,4'-diisocyanatodiphenyl methane. Diisocyanates which do not contain cyclic groups may used in the production of the urethane prepolymer. Suitab such diisocyanates include, for example, tetramethyle diisocyanate, penta ethylene diisocyanate and hexamethyle diisocyanate, in which case the divalent group B or X wi have the structure -(CH 2 ) 4 -, -(CH 2 ) 5 - or -(CH 2 ) 6 -. Preferred isocyanates are 1,6-hexamethylenediisocyana (HDI), trimethylhexamethylenediisocyanate (TMDI isophoronediisocyanate (IPDI), toluene diisocyanate (TD and 4,4'-diphenyl methane diisocyanate (MDI), a combinations of these. A polyisocyanate-containing material may be obtained reacting a polyoi of the formula RfOH) χ with a diisocyanate of the formula OCN-R'-NCO where the diisocyanate is used in a molar amount of 2( relative to the polyol. The reaction product obtained h the structure (Urethane-} (NCO) χ and is reacted with a hydroxy-substituted alk (meth)aerylate of the formula CH 2 « C(H,MetCO-0-R"-OH which is used in a molar amount of 2(x) to provide a produ of the formula [Urethane* (CO-C(H,Me)«CH 2 ) χ . In the above description, R is C 5 _ 10 o li ear or branched cyclic alkyl, x is an integer of from 4 to 10, R' is C 6 _ linear or branched or cyclic alkyl, and R M is C 2-6 linear branched or cyclic alkyl. Examples of RfOH) χ include, wh R » C 5 and x * 4, pentaerythritol, a material of the formu HO-CH 2 -C(CH 2 OH) 3 Also when R is C 6 _ 10 o alkyl, x may be > 4, e.g. the hydrox substituted polyester may be used for RfOH) χ . Uses: The materials obtained by curing the two componen used in the present invention may be used in any applicati in which polyurethanes are used. These applications inclu acoustic foams, building products, contact lense craniofacial reconstruction, cushioning, fibers, films, fo insulation, insulation, mouth protectors, packing recreational surfaces, coatings, fabric coatings, concre waterproofing, leather coatings, magnetic tape binder elastomeric blends, sealing applications, etc. A salient advantage of the compositions of the prese invention is their curing characteristics. The compositio readily cure at temperatures below 120*C, preferably bel 100*C, and they can also be cured easily at ro temperature. One of the uses of the present compositions is coating varied articles which may be coated wi polyurethane coatings. These articles include e.g BSTITUTE SHEET automobiles (e.g. exterior of automobiles, etc.), fabri (e.g. raincoats, clothing, shoes, umbrellas), etc. The articles may be obtained by using known procedures used wi polyurethanes. The present compositions can also be used sealants (e.g. for double pane windows). Coatings and articles in accordance with the prese invention are obtained by curing at least one of t polymers functionalized with acetoacetyl groups togeth with at least one NCO-free urethane functionalized wi unsaturated end groups in the presence of a catalyst. T catalysts used must have a pKa of form 12 to 14. Suitab catalysts which may be used include l,8-diazo-(5.4.0] bicycloundecene, tetramethyl guanidine, 1,4 dihydropyridines, and 2-allyl-N-alkyl imidazoline. The acetoacetylated acrylic resin and/ acetoacetylated polyester resin component, on the one han and the NCO-free resin component, on the other hand, ar reacted in an amount of 1 to 0.8 to 1.2, respectivel preferably 1 to' ca. 1, these amounts being measured i equivalents of acetoacetyl groups to equivalents of vinyli groups in the NCO-free resin. The catalyst is used in a amount of 0.2 to 3.0 wt.%, preferably 0.2 to 1.0 wt.% These amounts are based on the amount of resin solid. The two-component coating systems of the presen invention are isocyanate-free. They are easy to apply usin known techniques, requiring the use of only conventiona existing equipment without the need for taking specia safety precautions. The coatings and articles obtained fro these compositions possess the outstanding performanc characteristics of polyurethanes. Other features of the invention will become apparent i the course of the following descriptions of exemplar embodiments which are given for illustration of th invention and are not intended to be limiting thereof. The list below identifies the abbreviations used in th experimental section. MATERIALS SOURCE 1. Aoetoacetoxyethyl Methacrylate Monomer (AAEM) CAS No. 21282-97-3 EASTMAN CHEMICAL 2. Butyl Aery late Monomer (BA) CAS No. 141-32-2 ROHM & HAAS 3. Butyl Methacrylate Monomer (BMA) CAS No. 97-88-1 ROHM & HAAS 4. n-Butyl Acetate CAS No. 123-86-4 UNION CARBIDE 5. BYK 300 (Paint Additive) BYL MALLINCKRODT CHEMISCHE PRODUKTE 6. BYK 306 (Paint Additive) BYK MALLINCKRODT CHEMISCHE PRODUKTE 7. Desmodur H 1,6-Hexamethylene Diisocyanate (HDI) CAS No.822-06-0 MOBAY CHEMICAL CORP. 8., Desmodur W Methylene Bis(4-cyclohexylisocyanate) CAS No. MOBAY CHEMICAL CORP. 9. 1,8-Diaza-bicyclo[5 f ,0Jundecene-7 (Amicure DBU / DBU) CAS No. 6674-22-2 AIR PRODUCTS 10. Ektapro EEP Solvent (EEP) CAS No. EASTMAN CHEMICAL 11. 1,6-Hexanedlol Diacrylate (HD0DA) CAS No. 13048-33-4 INTEREZ 12. High Flass Naphtha (Unlcal 86) CAS No. WARUM CHEMICAL 13. Hydroxyethyl Aerylate Monomer ( OCYL 420 / HEA) CAS No.818-61-1 ROHM & HAAS 14. Hydroxypropyl Aerylate Monomer (ROCYL 430 / HPA) CAS No. 25584-83-2 ROHM & HAAS BSTITUTE SHEET 15. Isophorone Diisocyanate (IPDI) CAS No. 4098-71-9 HUELS 16. IPDI-T 1890 L (IsocyanuraΛ of IPDI) CAS No. HUELS 17. Isocyanate 81 (Modified 4,4 , -Diphenylmethane Diisocyanate) CAS No. BASF 18. 4,4'-Diphenyl Methane Diisocyanate (MONDUR M, MDI) CAS No. MOBAY 19 * Mercapto Ethanol CAS No. 60-24-2 ALDRICH/BASF 20. Methyl Methacrylate Monomer (MMA) CAS No. 80-62-6 ROHM & HAAS 21. MPA-2000 (Anti-setting agent) CAS No. NL CHEMICALS 22. Styrene Monomer CAS No. 100-42-5 POLYSAR 23. TIOXIDE RCR 60• (Titanium Dioxide, Pigment) CAS No. 13463-67-7 TIOXIDE CORP. 24. Toluene Diisocyanate (MONDUR TD-80 TDI) CAS No. MOBAY 25. Trimethylolpropane Ethoxy Trlacrylate (TMPEOTA) CAS No. 28961-43-5 SARTOMER 26. Trimethylolpropane Trlacrylate (TMPTA) CAS No. 15625-89-5 INTEREZ 27. Trimethylol Ethane (TME) CAS No. 77-85-0 IMC 28. Trimethylol Propane (TMP) CAS No. 77-99-6 CELANESE • 29 * Trimethylhexamethylene Diisocyanate (TMDI) CAS No. 16938-22-0 HUELS 30. VAZO 67 2,2'-Azobis(2-Methylbutyronitrile) CAS No. 13472-08-7 DU PONT 31. VAZO 64 Azobisisobutyronitrile CAS No. 78-67-1 DU PONT 32. Xylol CAS No. 1330-20-7 HARRISONS & CROSSFIELD 33. Propylene Glycol Monomethyl Ether Acetate (EKTAS0LVE PM Acetate, PMA) CAS No. EASTMAN CHEMICAL 34. Monomethyl Ether of Hydroquinone (MEHQ) CAS No. 150-76-5 EASTMAN CHEMICAL 35. Dibutyltin Dilaurate (T-12, DBTL) CAS No. 77-58-7 M & T CHEMICAL 36. Methyl Ethyl Ketone (MEK) CAS No. 78-93-3 HARRISON & CROSSFIELD SUBSTITUTE SHEET FORMULATIONS OF TWO COMPONENT NCO-FREE WHITE PAINT RAW MATERIALS OF PART ONE: 1. White Paint - A — Resin A, 6X-75-146 2. White Paint - B — Resin B, GX-75-162 RAW MATERIALS OF PART TWO: 2. ETMPTA — Ethoxylated trimethylolpropane trlacrylate 4. NCO-free acrylic urethane-B (NFAU-B) — GX-81-170 5. NCO-free acrylic urethane-C (NFAU-C) — GX-87-3 6. NCO-free acrylic urethane-D (NFAU-D) — GX-87-37 7. NCO-free acrylic urethane D (NFAU-D) — GX-87-37 CATALYST: DBU — l,8-diazar(5,4,0]-bicycloundecene. NCO-FREE WHITE ACRYLIC ENAMEL FORMULATION PART ONE: White Paint-X Where, X « White Paint-A, White Paint-B or White Paint-A, and White Paint-B. PART TWO: Crosslinking Agent-Y Where, Y « TMPTA, ETMPTA or TMPTA and ETMPTA EQ. WT. Ratio of Part One/Part Two - 1/0.8-1 CATALYST: DBU, 0.4-1.0% TRS NCO-FREE WHITE ACRYLIC-URETHANE ENAMEL FORMULATION PART ONE: White Paint-X Where, X » White Paint-A, White Paint-B or White Paint-A, and White Paint-B. PART TWO: Crosslinking Agent-Y Where, Y * NFAU-A, NFAU-B, NFAU-C, NFAU-D, NFAU or mixture of both e.g., NFAU-A/NFA B, ETMPTA/NFAU-D, NFAU-D/NFAU-E etc. EQ. WT. Ratio of Part One/Part Two « 1/0.8-1.0 CATALYST: DBU, 0.4-1.0% TRS Preparation of hydroxy-qroup containing polyester: GX-60-178 (GX-59-67): RAW MATERIALS A. Neopentyl Glycol (EASTMAN) 944.4 GMS B. Pentaerylthritol (CELANESE) 126.6 GMS C. Isophthalic Acid (AMOCO) 874.9 GMS D. Adipic Acid (BASF) 493.9 GMS E. Benzole Acid (BAYER) 143.8 GMS 2583.5 GM§ PROCEDURE 1. Charge neopentyl glycol and adipic acid into a 5-L flas equipped with agitator, sample tube, thermometer nitrogen purge, packed partial condenser, water trap an total condenser. 2. Increase temperature to 130+5C. at 130C weigh i isophthalic acid, pentaerylthritol and benzole acid. 3. Heat to 215+5C (max.) and maintaining an exit vapo temperature at 100+5C (max.) on partial condenser unti the distillate exit temperature falls below 90C. Allo reaction mixture to cool to 150C. 4. Remove the packed partial condenser and start additio of xylol to establish solvent reflux processing and hol at 215+5C until an acid value of 10 is reached. 5. Cool to 150C and dilute to 80 NVM% with n-butyl acetate SPECIFICATIONS: Solids content % 80 Viscosity 88", Z4-5 AN 10 Color. • WPG (IMP.) 11.0 Solvent. n-butyl acetate -OH,Eq.Wt.(solids) 708 EET - 25 - Preparation of hydroxy-group containing polyester: GX-Jfό-163 (GX-S9-8dϊ * ■ — " JUSJ RAW MATERIALS A. Adipic Acid (BASF) 1523.5 GMS B. Trimethylol Propane (CELANESE) 561.0 GMS c. Propylene Glycol (DOW) 816.0 GMS 2900.5 GMS PROCEDURE 1. Charge adipic acid, trimethylol propane, and propylen glycol into a 5-L flask equipped with agitator, sampl tube, thermometer, nitrogen sparge, packed partia condenser, water trap and total condenser. 2. Heat to 215+5C (max.) and maintaining an exit vapo temperature at 100+5C (max.) on partial condenser unti the distillate exit temperature falls below 90C. Allo reaction mixture to cool to 150C. 3. Remove the packed partial condenser and start additio of xylol to establish solvent reflux processing and hol at 215+5C until an acid value of < 5 is reached. SPECIFICATIONS: ; Solids content % 96 Viscosity 88 N , Z4-5 25 AN 1.5 Color 1 WPG (IMP.) 11.4 Solvent xylol -OH, Eq.Wt. (solids) 192 Preparation of hvdroxy-σroup containing polyester: GX-60-156 (GX-59-79) ' . : RAW MATERIALS A. Adipic Acid (BASF) 1385.0 GMS B. Trimethylol Propane (CELANESE) 510.0 GMS C. Ethylene Glycol (STANCHEM) 605.0 GMS 2500.0 GMS PROCEDURE 1. Charge adipic acid, trimethylol propane, and ethyle glycol into a 5-L flask equipped with agitator, samp tube, thermometer, nitrogen sparge, packed parti condenser, water trap and total condenser. 3. Heat to 215+5C (max.) and maintaining an exit vap temperature at 100+5C (max.) on partial condenser unt the distillate exit temperature falls below 90C. All reaction mixture to cool to 150C. 4. Remove the packed partial condenser and start additi of xylol to establish solvent reflux processing and ho at 215+5C until an acid value of < 5 is reached. 5. Cool to 150C:and dilute to 80 NVM% with n-butyl acetat SPECIFICATIONS: Solids content % 97 Viscosity 52", Z3-4 AN 0.5 Color 1 WPG (IMP.) 11.8 Solvent xylol -OH,Eq.Wt.(solids) 181 NCO-FREE ACRYLIC WHITE PAINT A PAR 1 GRIND PASTE GX-82-10(GX-75-106) PREMIX GP-GX-75-146 (NCO-free acrylic) 268.5 GMS Xylol 80.5 GMS EEP 40.0 GMS MFA-2000X 3.6 GMS BYK 300 2.9 GMS DISPERSE AT HIGH SPEED IN A COWELS STIRRER FOR 15 MINUTES SIFT IN Tioxide RCR 60 220.0 GMS DISPERSE AT HIGH SPEED AGAIN FOR 30 MINUTES AND THEN SANDMILL TO 7H MILL CLEANUP GP-GX-75-146 68.3 GMS Xylol 20.0 GMS PREMIX FOR MILL FLUSH Xylol i 60.0 GMS EEP 30.0 GMS LETDOWN MIXTURE GP-GX-75-146 214.7 GMS n-Butyl acetate 40.0 GMS PREMIX FOR LETDOWN SPECIFICATIONS: Viscosity (Stormer) 62 KU Dispersion (Hegmen) 7 H Hiding (Criptometer) 894 SAG (thousand of an inch)... 4 - 5 Solids content %, by wt. • 48.0 - 28 - NCO-FREE ACRYLIC RESIN (GX-75-146) RAW MATERIALS A. Methyl methacrylate 5 Butyl methacrylate Acetoacetoxyethyl methacrylate B. VAZO 64 PMA/Xylol (20/80) C. Xylol 10 D. Mercapto ethanol PROCEDURE 1. Charge RM-C into 3 L flask. Place RM-A and RM-B in respective addition funnels. 2. Heat xylol to 105-1-5 C and then start addition of RM-A 15 and RM-B at a rate indicated on data and results. Maintain temperature at 105+5 C. 3. Once RM-A and RM-B are completely added, wait for one hour then take the first sample and add 0.3 g of VAZO 64 into reaction flask. 204. For every 30 minutes, take sample add add 0.3 g of VAZO 64. 5. If the solids content of sample reached 49.5% of NVM, add another 0.3 g of VAZO 64 and wait for 30 minutes. Then turn off heat, add 0.3 CC of RM-D. 25 CHARACTERISTICS NVM % 50-l A.N 204-1 Viscosity U Color l 30 WPG 9.904-0.05 Solvent. Xylol Mn 15145 Polydisp 1.7965 EET - 29 - NCO-FREE ACRYLIC WHITE PAINT A PART 1 GRIND PASTE GX-82-1KGX-75-108) PREMIX GP-GX-75-162 *Acrylic polymer) 250.0 GMS Xylol 90.0 GMS High flash napht ..- 30.0 GMS MPA--2000X 3.6 GMS BYK 300 3.0 GMS HSD AT HIGH SPEED FOR 15 MINUTES SIFT IN Tioxide RCR 60 280.0 GMS HSD FOR 30 MINUTES AND THEN SANDMILL TO 7H MILL CLEANUP GP-GX-75-162 65.0 GMS Xylol 22.0 GMS PREMIX FOR MI L FLUSH Xylol 60.0 GMS High flash napth. • 20.0 GMS PREMIX FOR MILL RINSE LETDOWN MIXTURE GP-GX-75-162 200.5 GMS Xylol 30.0 GMS PREMIX FOR LETDOWN SPECIFICATION: Viscosity 63 KU Dispersion 7 H Hiding 970 SAG 4 - 5 Solids content %, BY wt 56.7 - 30 - NCO-FREE ACRYLIC RESIN (GX-75-162) RAW MATFRIALS A. Butyl acrylate 294.6 GMS Styrene 232.8 GMS Acetoacetoxyethyi methacrylate ...... 232.4 GMS B. VAZO 64 8.0 GMS PMA/Xylol (20/80) 255.0 GMS C. Xylol 250.0 GMS D. Mercapto ethanol 0.3 CC PROCEDURE 1. Charge RM-C (xylol) into 3 L flask. Place RM-A (monomers) and RM-B (initiator solution) in respective addition funnels. 2. Heat xylol to 1054-5 C and then start addition of RM-A and RM-B at a rate indicated on data and results. Maintain temperature at 1054-5 C. 3. Once RM-A and RM-B are completely added, wait for one hour then take first sample and add 0.3 g of VAZO 67 into reaction flask. 4. For every 3Q minutes, take sample add add 0.3 g of VAZO 67. 5. If the solids content of sample reached 59.5% NVM, add one more 0.3 g of VAZO 67 and wait for at least 30 minutes, then remove heat, add 0.3 CC of RM-D (mercapto ethanol). SPECIFICATIONS NVM % 604-1 A.N 204-1 Viscosity V Color 1 WPG 10.00+0.05 Solvent Xylol Mn 13390 Polydisp 2.5530 - 31 - NFAU - A NCO-FREE ACRYLIC URETHANE GX-87-52 RAW MATERIALS A. IPDI-T 1890 L E. Hydroxypropyl acrylate MEHQ n-Butyl acetate D. n-Butyl acetate........ PROCEDURE 1. Charge RM-A, RM-D and RM-C into reactor at R.T. 2. Heat to 754-5 C and maintain at 754-5 C when RM-B is added within one hour under dry pressure air. 3. Hold the reactor temperature at 754-5 C until NCO% drop to 1.0 % cool to 604-5 C and 20 ml of MEOH is added. 4. Maintain at-60+5 C until NCO% ■ 0.0 SPECIFICATIONS NVM % 73.8 Viscosity (Gardner). 58' Z3-4 Color (Gardner) 1 NCO% 0.0 WPG (IMP.) (SP. GR.) 10.57 Solvent n-butyl acetate εq.He. ............. ' 387.89 (solids) 525.1 (73.87 %) NFAU - B NCO-FREE ACRYLIC UREThANE GX-81-170 (GX-75-159) RAW MATERIALS A. Trimethylol propane (TMP) .... MEK B. Isophorone diisocyanate (IPDI) MEK C. Hydroxyethyl acrylate (HEA) HQME D. T-12 MEK . GMS PROCEDURE 1. Charge RM-A into reactor at room temperature. 2. Hold at 20-30 C when RM-B is added within 15 minutes. 3. Heat to 804-5 C and maintain at 804-5 C until NCO% reduced to 10. 4. Continue to-hold at 804-5 C with RM-C is added within 15 minutes. 5. Maintain the reaction solution at 804-5 C until NCO% drops to 0.5, cool to 604-5 C and then 15 ml of methanol is added. 6. Hold at 604-5 C until NC0% * 0. SPECIFICATIONS NVM % 78 Viscosity Z6 Red. Vis 10.8", W at 70% NVM Color l NCO% 0.0 WPG 10.63 Solvent MEK SUBSTITUTE SHEET NFAU - C NCO-FREE ACRYLIC URETHANE GX-87-3 (GX-75-160) RAW MATERIALS A. Trimethylol propane (TMP) . MEK B. Desmodur H MEK C. Hydroxyethyl acrylate (HEA) HQME D. T-12 MEK 1344.11 GMS PROCEDURE 1. Charge RM-A into reactor at room temperature. 2. Hold at 20-25 C when RM-B is added within 15 minutes. 3. Cool down to 154-5 C when RM-D is added within 5 minutes. ; 4. Heat to 50--60 C and maintain at 50-60 C until NCO% reduced to a value of 12.0 (4-20% (9-12 preferred)]. 5. Hold at 50-60 C when RM-C is added within 15 minutes. 6. Maintain at 50-60 C until NCO* reduced to 0.5 and then 15 ml of methanol is added. 7. Bold at 50-60 C until NCO% » 0. SPECIFICATIONS NVM % 72.57 Viscosity 11", V Color 1 NCO% 0.0 WPG 10.47 Solvent MEK NFAU - D GX-87-37 (GX-75-167 ) RAW MATERIALS A. Trimethy hexamethylene diisocyanate (TMDI) 210.00 GMS B. Hydroxypropyl acrylate (HPA) 247.00 GMS C. DBTL (T-12) .25 GMS D. MEK .05 GMS 571.30 GMS PROCEDURE 1. Charge RM-A, RM-D and RM-C into reactor at room temperature. 2. Heat to 654-5 C and hold at 654-5 C when RM-B and RM-E are added. 3. Maintain the reaction temperature at 654-5 C until NCO% down into 1.0 and 15 ml of methanol is added. 4. Hold at 654-5 C until NCO% ■ 0. SPECIFICATIONS Solids Content 78.3 Viscosity C Color 1 NCO% 0.0 WPG (IMP) 10.41 Solvent MEK SUBSTITUTE SHEET PROCEDURE 1 * Charge RM-A into reactor at room temperature. 2. Hold at 20-25 C when RM-B is added (30 minutes) under N and then RM-D is added. 3. Heat to 654-5 C and maintain at 654-5 C until NCO% reduced to 10.0%. 4. Continue to hold at 654-5 C when RM-C is added within one hour. 5. Maintain at 654-5 C until NCO% down to 1.0% and then 15 ml of methanol is added. 6. Hold at 654-5 C until NCO% » 0. SPECIFICATIONS Solids content % 75.0 Viscosity • 12 N , w-X Colour •••••• 1 NCO% 0.0 WPG (IMP) 10.23 GP-GX-81-155 NCO-FREE ACRYLIC PAINT COLOR: RED GRIND PASTE PREMIX GP-GX-75-162 Acrylic polymer 125.0 GMS Xylol 45.0 GMS MPA-2000X 3.6 GMS BYK 300 3.0 GMS HSD AT HIGH SPEED FOR 15 MINUTES SIFT IN Moly Orange 2565 65.1 GMS Host Violet ER02 8.9 GMS Bon-Maroon-6002 0.9 GMS HSD FOR 30 MINUTES AND THEN SANDMILL TO 7H MILL CLEANUP GP-GX-75-162 105.0 GMS Xylol 15.0 GMS PREMIX FOR MILL FLUSH Xylol 95.0 GMS LETDOWN MIXTURE GP-GX-75-162 368.0 GMS Xylol 100.00 GMS PREMIX FOR LETDOWN SPECIFICATION: Viscosity 58 KU Dispersion • 7 H Hiding 646 SAG 6 - 7 Solids content %, By V 41.2 Total paint 934.5 GMS SUBSTITUTE SHEET GP-GX-81-137 NCO-FREE ACRYLIC PAINT COLOR: GREEN GRIND PASTE PREMIX GP-GX-75-162 Xylol HPA-2000X BYK 300 BSD AT HIGH SPEED FOR 15 MINUTES SIFT IN I.A.F. Compound Sandor-Green-GLS LT Yel 09-425 2p Irgalit-Blue-BCA Tioxide RCR 60 Regal 400R Black BSD FOR 30 MINUTES AND THEN SANDMILL TO 7H MILL CLEANUP GP-GX-75-162 74.8 GMS Xylol 30.0 GMS PREMIX FOR MILL FLUSH Xylol 82.7 GMS FOR MILL RINSE LETDOWN MIXTURE GP-GX-75-162 543.9 GMS Xylol 92.1 GMS PREMIX FOR LETDOWN SPECIFICATION: Viscosity 60 KU Dispersion 7 H Hiding 726 SAG 6 - 7 Solids content %, By V. 43.63 Total paint 990.3 GMS - 38 - GP-GX-81-148 NCO-FREE ACRYLIC PAINT COLOR: YELLOW GRIND PASTE PREMIX GP-GX-75-162 236.4 GMS Xylol 127.2 GMS MPA-2000X 3.8 GMS BYK 300 3.1 GMS BSD AT HIGH SPEED FOR 15 MINUTES SIFT IN Light Yel 2361 142.2 GMS Tioxide RCR 60 52.3 GMS Chrome Yel 2165 47.4 GMS Ferrite-Yel-305 7.2 GMS HSD FOR 30 MINUTES AND THEN.SANDMILL TO 7H MILL CLEANUP GP-GX-75-162 100.0 GMS Xylol 39.1 GMS PREMIX FOR MILL FLUSH Xylol , 80.9 GMS • LETDOWN MIXTURE GP-GX-75-162 236.4 GMS Xylol 42.7 GMS PREMIX FOR LETDOWN SPECIFICATION: Viscosity 61 KU Dispersion 7 H Hiding 894 SAG 4 - 5 Solids content %, By V 40.8 Total paint 1118.7 GMS ET FORMULATIONS OF TWO COMPONENT NCO-FREE WHITE PAINT RAW MATERIALS OF PART ONE: 1. White Paint - A — Resin A, GX-75-146 2. White Paint - B — Resin B, GX-75-162 RAW MATERIALS OF PART TWO: 1. TMPTA — Trimethylolpropane trlacrylate. 2. ETMPTA — Ethoxyl ted trimethylolpropane trlacrylate 3. NCO-free acrylic urethane-A (NFAU-A) — GX-81-161 4. NCO-free acrylic urethane-B (NFAU-B) — GX-81-170 5. NCO-free acrylic urethane-C (NFAU-C) — GX-87-3 6. NCO-free acrylic urethane-D (NFAU-D) — GX-87-37 7. Acrylic urethane-E — GX-87-44 CATALYST: DBU — l,8-diaza-[5,4,0]-bicycloundecene. NCO-FREE WHITE ACRYLIC ENAMEL FORMULATION: PART ONE: White Paint-X Where, X - White Paint-A, White Paint-B or White Paint-A, and White Paint-B. PART TWO: Crosslinking Agent-Y Where, Y = TMPTA, ETMPTA or TMPTA and ETMPTA. EQ.WT. Ratio of Part One/Part Two « 1/0.8-1 CATALYST: DBU, 0.4-1.0% TRS NCO-FREE WHITE ACRYLIC-URETHANE ENAMEL FORMULATION: PART ONE: White Paint-X Where, X "White Paint-A, White Paint-B or White Paint-A and White Paint-B. PART TWO: Crosslinking Agent-Y Where, Y ■ NFAU-A, NFAU-B, NFAU-C, NFAU-D NFAU-E or mixture of both e.g., NFAU-A/NFAU-B, NFAU-D/NFAU-E etc. .WT. Ratio of Part One/Part Two * 1/0.8-1.0 CATALYST: DBU, 0.4-1.0% TRS Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein. SUBSTITUTE SHEET

Claims: Claims 1. A cured polymer comprising a first component and a second component, wherein said first component comprises at least one acetoacetylated polymer resin and wherein said second component comprises at least one NCO-free urethane polymer having vinylie end groups. 2. The cured polymer of Claim 1, wherein said acetoacetylated (meth)acrylic resin is a copolymer obtained by copolymerizing 10 to 60 wt.% of a monomer of the formula (I) CH 2 -C(R 1 )-C00-CH 2 CH 2 -0-C0-CH 2 -C0-CH 3 (I) with 90 to 40 wt.% of an alkyl (meth)acrylate of the formula (II) CH 2 -C(R 1 )-C0-0R (II) wherein R is C 1 _ 12 linear or branched saturated alkyl, and R 1 is H or CH 3 . 3. The cured polymer of Claim 2, wherein said NCO- free urethane polymer is a polymer of the formula (IV) CH Λ- ϊ -C(R 1 )-CO-0-R 2 -0 * fCO-NH-B-NH-CO-Q-A-rO+n I I 1 -CO-NH-B-NH-CO-0-R2-0-C0-C(Rϊ A )-CH 2 (IV). whereint each Rl independently is H or CH~ each R 2 Independently is a C 2 _ 3 linear or branched saturated alkylene moiety; each B is independently a C 2 _ 12 linear or branched saturated alkylene moiety, or a C._ 12 cyclic saturated alkylene moiety, or a C 6 _ 14 arylβne , oiβty) each A is independently a C 2 _ 12 linβar oχ . branched saturated alkylene moiety, or a C 4 _ 12 cycUc saturated alkylene moiety, or a g _ 14 arylene moiety; and n is an integer of from 1 to 10. 4. The cured polymer of Claim 2, wherein said NCO- free urethane polymer is a polymer of the formula (V)t (CH2--C( 1 *CO-0-R -0-CO-NH+ X (V) whereint each R independently is H or CH 3 ; 2 Bach R is independently a C,_ 3 linear or branched saturated alkylene moiety; X is a C 2_i2 linear or branched saturated alkylene moiety, or a c 4 _ 12 cyclic saturated alkylene moiety, or a C- 14 arylene moiety; and is 2, 3 or 4. 5. The cured polymer of Claim 2, wherein said NCO- free urethane polymer is a polymer obtained byt (1) reacting a reaction mixture of a C_ . linear, branched or cyclic alkyl or aryl polyol having an average of 2 to 4 hydroxyl groups per molecule and a 2 _ 14 linear, branched or cyclic saturated alkyl or aryl diisocyanate, triisocyanate, tetraiisocyanate, or a mixture thereof, at 5 to 20*C, using a molar ration of OH groups to NCO groups lower than 1.0; (2) raising the temperature of the mixture of step SUBSTITUTE SHEET (1) to 40 to 150*C and maintaining said temperature at 40 to 150*C until an NCO content of 4 to 20 wt.% in the reaction mixture is reached; (3) adding a hydroxyl substituted alkyl (meth)acrylate of formula (III) CH 2 -C(R 1 )-C0-0-R 2 -0H (III) whereini R 1 is H or CH 3 ; and 2 is a C 3 linear or branched saturated alkylene moiety; and maintaining the temperature at 40 to 150*C until the NCO content of the mixture is below 2 wt.%; (4) adding to the reaction mixture a C. 4 alcohol in an amount appropriate to obtain a ratio of OH groups to NCO groups greater than 1.5; and (5) obtaining a NCO-free urethane polymer. 6. The cured polymer of Claim 2, wherein said acetoacetylated (meth)acrylic resin is obtained by reacting said monomer of formula (I) with said alkyl (meth)acrylate of formula (II) and styrene. 7. The cured polymer of Claim 1, further comprising a catalyst having a pKa of 12 to 14. 8. The cured polymer of Claim 1, wherein said acetoacetylated polymer is an acetoacetylated polyester obtained by either (1) subjecting an hydroxyl group- containing polyester and a C j . alkyl acetoacetate to a transesterification reaction, or (2) subjecting an unsaturated polyester and at least one monomer of formula (I) CH 2 -C(R 1 )-COO-CH 2 CH 2 -0-CO-CH 2 -CO-CH 3 (J . wherein R is H or CH 3 to a graft polymerization reaction. 9. The cured polymer of Claim 8, wherein said NCO- free urethane polymer is a polymer of the formula (IV) whereini each R independently is H or CH 3 ; 2 each R independtly is a C 2 _ 3 linear or branched saturated alkylene moiety; each B is independently a C. .. linear or branched saturated alkylene moiety, or a C 4 _ 12 cyclic saturated alkylene moiety, or a C fi _ 14 arylene moiety; each A is an independently C 2 _ 12 linear or branched saturated alkylene moiety, or a C. 12 cyclic saturated alkylene moiety, or a C 6 _ l4 arylene moiety; and n is an integer of from 1 to 10. 10. The cured polymer of Claim 8, wherein said NCO- free urethane polymer is a polymer of the formula (V)ι (CH, « C( 1 *tCO-0-R 2 -0-CO-NHf- Σ (V) whereint each R independently is H or CH 3 ; TITUTE SHEET each R is an independently C 2 _ 3 linear or branched saturated alkylene moiety; X is a C 2 _ 12 linear or branched saturated alkylene moiety, or a C 4 _ 12 cyclic saturated alkylene moiety, or a C 6-14 ar y lenβ noiety; and a is 2, 3 or 4. 11. The cured polymer of Claim 8, wherein said NCO- free urethane polymer is a polymer obtained byi (1) reacting a mixture of a 2 - 2 linear, branched or cyclic alkyl or aryl polyol having an average of 1 to 4 hydroxyl groups per molecule and a C 2 . 2 linear, branched or cyclic alkyl or aryl polyol having an average of 1 to 4 hydroxyl groups per molecule and a C_ 12 linear, branched or cyclic saturated alkyl or aryl diisocyanate, triisocyanate, tetraiisocyanate, or mixture thereof, at 5 to 20 # C; (2) raising the temperature of the mixture of step (1) to 40 to 150*C and maintaining said temperature at 40 to 150*C with an NCO content of 4 to 20 wt.% in the reaction mixture is reached; (3) adding a hydroxyl substituted alkyl (meth)acrylate of formula (III) CH 2 -C(R 1 )-CO-0-R 2 -OH (III) whereint R-l is H or CH 3 ; and 2 R is a C- 3 linear or branched saturated alkylene moiety; and maintaining the temperature at 40 to 150*C until the NCO content of the mixture is below 2 wt.%; (4) adding to the reaction mixture a C 1-4 alcohol in an amount appropriate to obtain a ratio of OH groups to NCO groups greater than 1.5; and (5) obtaining a NCO-free urethane polymer. 12. An article coated with a coating obtained by curing a first component and a second component, wherein said first component is at least one acetoacetylated polymer resin and wherein said second component is at least one NCO-free urethane polymer having vinylie end groups. 13. The coated article of Claim 12, wherein said acetoacetylated polymer resin is an acetoacetylated(meth)acrylic copolymer resin obtained by copolymerizing IP to 60 wt.% of a monomer of the formula (.1) CH 2 s C(R 1 )-COO-CH2CH2-0-CO-CH 2 -CO-CH3 " (I) with 90 to 40 wt.% of an alkyl (meth)acrylate of the formula (II) CH 2 "C(R 1 )-CO-OR (II) wherein R is C 1 . 12 linear or branched saturated alkyl, and R 1 is B or CH 3 . 14. The coated article of Claim 12, wherein said NCO-free urethane polymer is a polymer of the formula (IV) SUBSTITUTE SHEET CH 2 »C(R 1 )-CO-0-R 2 -O CO-NH-B-NH-CO-0-A-Ot n , ' -C0-NH-B-NH-C0-O-R 2 -O-CO-C(R 1 ) « CH 2 (IV). wherein: each R 1 independently is H or CH 3 ; each R 2 independently is a C 2 . 3 linear or branched saturated alkylene moiety; each B is independently a C 2 _ 12 linear or branched saturated alkylene moiety, or a C 4 „ 12 cyclic saturated alkylene moiety, or a Cg -14 arylene moiety; each A is independently a C 2 _ 1 linear or branched saturated alkylene moiety, or a C 4 _ 12 cyclic saturated alkylene moiety, or a C g _ 14 arylene moiety; and n is an integer of from 1 to 10. IS. The coated article of Claim 12, wherein said NCO-free urethane polymer is a polymer of the formula C*)« (CH 2 « C(R 1 tCO-0-R 2 -0-CO-NHt m X (V) wherein: each R 1 independently is H or CH 3 ; each R 2 is independently a C 2 . 3 linear or branched saturated alkylene moiety; X is a C 2 _i2 linear or branched saturated alkylene moiety, or a C 4 _ 12 cyclic saturated alkylene moiety, or a c 6-14 arylene moiety; and m is 2, 3 or 4. 16. The coated article of Claim 12, wherein said NCO-free urethane polymer is a polymer obtained by: (1) reacting a mixture of a C 2 _ι 2 linear, branched or cyclic alkyl or aryl polyol having an average of 2 to 4 hydroxyl groups per molecule and a C 2 _ 12 linear, branched or cyclic saturated alkyl or aryl diisocyanate, triisocyanate, tetraiisocyanate, or a mixture thereof, at 5 to 20*C, using a molar ratio of OH groups to NCO groups lower than 1.0 (2) raising the temperature of the mixture, of step (1) to 40 to 150°C and maintaining said temperature at 40 to 150*C with an NCO content of 4 to 20 wt.% in the reaction mixture is reached; (3) adding a hydroxyl substituted alkyl (meth)acrylate of formula (III) CH 2 *C(R 1 )-CO-0-R 2 -OH (III) wherein: R 1 is H or CH 3 ; and R 2 is a C 2 -3 linear or branched saturated alkylene moiety; and maintaining the temperature at 40 to 150 β C until the NCO content of the mixture is below 2 wt.%; (4) adding to the reaction mixture a C 1 _ 4 alcohol in an amount appropriate to obtain a ratio of OH groups to NCO groups greater than 1.5; and (5) obtaining a NCO-free urethane polymer. 17. The coated article of Claim 13, wherein said BSTITUTE SHEET acetoacetylated (meth)acrylic resin is obtained by reacting said monomer of formula (I) with said alkyl (meth)aerylat^ of formula (II) and styrene. 18. The coated article of Claim 12, wherein said acetoacetylated polymer is acetoacetylated polyester obtained by either (1) subjecting a hydroxy group- containing polyester and a C 1-4 alkylacetoacetate to a transesterification reaction, or -(2) subjecting an unsaturated polyester and at least one monomer of formula (I) CH 2 β C(R 1 )-COO-CH 2 CH 2 -0-CO-CH 2 -CO-CH 3 (I) wherein R 1 is H or CH 3 to a graft polymerization reaction. 19. The coated article of Claim 18, wherein said NCO-free urethane polymer is a polymer of the formula (IV) CH 9 «C(R 1 )-CO-Q-R 2 -OfCO-NH-B-NH-CO-0-A-0» n l' -CO-NH-B-NH-CO-0-R 2 -0-CO-C(R 1 )«CH 2 (IV). wherein: each 1 independently is H or CH 3 ; each R 2 independently is a C 2 . 3 linear or branched saturated alkylene moiety; each B is independently a. C 2 _ 12 linear or branched saturated alkylene moiety, or a C 4 _ 1 cyclic saturated alkylene moiety, or a C 6 _ 14 arylene moiety; each A is independently a C 2-12 linear or branched saturated alkylene moiety, or a C 4 _ 12 cyclic saturated alkylene moiety, or a C 6 _ 12 arylene moiety; and n is an integer of from 1 to 10. 20. The coated article of Claim 18, wherein said NCO-free urethane polymer is a polymer of the formula (V): (CH 2 * B C(R 1 tCO-0-R 2 -0-CO-NH πι X (V) wherein: each R 1 independently is H or CH 3 ; each R 2 is independently a C 2 . 3 linear or branched saturated alkylene moiety; X is a C 2 _ 12 linear or branched saturated alkylene moiety, or a C 4 _ 12 cyclic saturated alkylene moiety, or a c 6-14 arylene moiety; and m is 2, 3 or 4. 21. The coated article of Claim 12, wherein said NCO-free urethane polymer is a polymer obtained by: (1) reacting a reaction mixture of a C 2 _ 12 linear, branched or cyclic alkyl or aryl polyol having an average of 2 to 4 hydroxyl groups per molecule and a C 2 _ 12 linear, branched or cyclic saturated alkyl or aryl diisocyanate, triisocyanate, tetraiisocyanate, or mixture thereof, at 5 to 20°C; (2) raising the temperature of the mixture of step (1) to 40 to 150*C and maintaining said temperature at 40 to 150*C with an NCO content of 4 to 20 wt.% in the reaction mixture reached; (3) adding a hydroxyl substituted alkyl (meth)acrylate of formula (III) CH 2 - B C(R 1 )-CO-0-R 2 -OH (III) wherein: R 1 is H or CH 3 ; and R 2 is a C . 3 linear or branched saturated alkylene moiety; and maintaining the temperature at 40 to 150°C until the NCO content of the mixture is below 2 wt.%; (4) adding to the reaction mixture a C lβ . 4 alcohol in an amount appropriate to obtain a ratio of OB groups to NCO groups greater than 1.5; and (5) obtaining a NCO-free urethane polymer. 22. An article obtained by curing a first component and a second Component, wherein said first component comprises at least one an acetoacetylated polymer resin and wherein said second component comprises at least one NCO-free urethane polymer having vinylie end groups. 23. The article of Claim 22, wherein said article is an automobile, a fabric-based article or a shoe. 24. A double pane window, comprising two panes of glass bound to each other with an adhesive composition obtained by curing at least one acetoacetylated polymer resin with at least one NCO-free urethane polymer having vinylie end groups.

Inventors: CHAN PAUL SHAU LUNG, CHAN, PAUL, SHAU, LUNG
Applicants: GUERTIN BROS COATINGS AND SEAL, GUERTIN BROS. COATINGS AND SEALANTS, LTD.
Application year: 1990
Main classification: C09D175
IPC codes: C08L33, C08L67, C08L75, C09D167, C09D175