CROSSLINKABLE HYDROXY FUNCTIONAL POLYDIENE POLYMER COATING COMPOSTIONS AND A PROCESS FOR PREPARING THEM

Abstract: A crosslinkable phase-stable composition, in particular for coating primed and unprimed substrates comprising from 10 to 80 percent by weight of a hydroxy functional polydiene polymer having a functionality of at least 1.3, 8 to 60 percent by weight of an amino resin crosslinking agent, and 2 to 40 percent by weight of a reinforcing agent. The invention also encompasses a process to make such compositions by partially reacting the three components, preferably for 0.5 to 10 hours at 60 to 120 DEG C, and optionally in the presence of a small amount of catalyst, to give phase stable compositions and subsequently completely crosslinking the composition. The invention also encompasses a process for painting a substrate which comprises priming the substrate with a primer selected from the group consisting of epoxy resin primers and polyester resin primers, applying to the primed substrate a crosslinkable basecoat composition comprising from 10 to 80 percent by weight of a hydroxy functional polydiene polymer having a functionality of at least 1.3, from 8 to 60 percent by weight of an amino resin crosslinking agent, and from 2 to 40 percent by weight of a reinforcing agent, and applying over the base coat a clearcoat selected from the group consisting of dihydroxy polydiene-based clearcoats, polyester clearcoats, and acrylic clearcoats.

Description: CROSSLINKABLE HYDROXY FUNCTIONAL POLYDIENE POLYMER COATING COMPOSITIONS AND A PROCESS FOR PREPARING THEM This invention relates to novel crosslinkable phase-stable compositions comprised of hydroxy functional polydiene polymers, amino resm crosslinking agents, and reinforcing agents. More specifically, the invention relates to the use of particular di- and poly-hydroxy functional hydrogenated diene polymers in crosslinking with ammo resms to produce products which are particularly useful coating compositions which adhere well to substrates which have or have not been coated with a suitable primer. These coating compositions may contain pigment and may be used to "pamt" the substrate. Hydroxy functional polydiene polymers are well known. United States Patent No. 5,393,843 discloses that formulations containing these polymers, a melamme resm crosslinking agent, and an acid catalyst can be cured by baking under normal bake conditions. This same patent also discloses that these polymers can be mixed with isocyanates to yield compositions which cure at ambient temperature. However, the cured compositions are usually fairly soft and, although they can be very useful in some applications, they have limited adhesion. Attempts to increase hardness and adhesion by increasing crosslink density by simply mixing these components with a reinforcing agent, such as a low molecular weight diol or triol, and higher levels of crosslinking agent were unsuccessful because the reinforcing agent and crosslinking agents are relatively polar and are incompatible with the relatively nonpolar polydiene polymers. Incompatibility of the components leads to poor properties, such as gloss, the cured composition or, even worse, the compositions may phase separate upon storage prior to cure. Surprisingly, compositions have now been found which overcome problems of prior art adhesives, sealants or coatings. In particular, it has now surprisingly been found possible to provide phase- stable compositions which, hen cured, have an mcreased hardness and/or adhesion to apolar substrates. Accordingly, the present mvetion provides a crosslinkable phase-stable composition comprising from 10 to 80 percent by weight of a hydroxy functional polydiene polymer havmg a functionality of at least 1.3, from 8 to 60 percent by weight of an ammo resm crosslinking agent, and from 2 to 40 percent by weight of a reinforcing agent. For the purposes of this specification, a composition is defmed as phase-stable if the composition does not phase-separate upon standmg for two weeks at room temperature (20°C) . The composition of the present invention can e.g. be used as adhesive, sealant or coating. In particular, the composition is highly useful for coating and painting a variety of unprimed substrates, particular relatively nonpolar substrates, such as plastic surfaces mcludmg polyethylene, polypropylene, etc., and for painting and coating primed substrates. Steel is the most common substrate which often requires priming. The coating composition of this invention is a crosslinkable composition contammg a hydroxy functional polydiene polymer, an ammo resm crosslinking agent, and a reinforcing agent. The coatings of this invention will usually contain a pigment but it is not required. The preferred polymers for use herem are hydrogenated polydiene diols. The polymers must have a functionality of at least about 1.3 so that they will actually crosslink. In a more preferred embodiment of the invention, the polydiene polymer will have a functionality of at least about 1.9. In another preferred embodiment of the invention, the polydiene polymer will contain a substantial amount of a vmyl aromatic hydrocarbon, usually styrene, since coatings made from such polymers exhibit good adhesion to unprimed steel substrates as well . The composition of this invention is particularly suitable for coating automotive exterior parts. Typically, the composition of this invention can be applied directly to plastic automotive exterior parts. Further, as outlined above, the composition can be applied to primed substrates such as primed steel, m particular steel which has been primed with an epoxy resm based primer. The primer is typically applied by the cathodic electrodeposition (CED) process. If desired, the epoxy resm-primed steel is further coated with a primer/surfacer, which is usually based on a polyester resm, prior to application of the composition of this mvention. Following priming, if desired, the composition of this invention can be applied to the substrate. In the automotive industry the coating thus produced is commonly referred to as the basecoat. The basecoat typically contams pigment and is the actual "pamt" which goes onto the car. A clear coat is usually applied over the basecoat to preserve the colour. Accordingly, the invention presents novel compatible coating compositions which exhibit excellent adhesion to primed and unprimed substrates and provides a process for the preparation of these novel compositions. This invention thus provides a composition which may be used to "pamt" the entire exterior of an automobile. The hydroxy functional polydiene polymer, the ammo resm crosslinking agent, and the reinforcing agent are mutually incompatible and therefore cannot be used as merely a physical blend. As will be set out m more detail below, in order to make the crosslinkable phase- stable compositions of the present invention, the components are partially reacted (partially crosslinked) to overcome the mutual incompatibility. To accomplish partial reaction, the components are "cooked" m a vessel for some combmation of time, temperature, and catalyst concentration sufficient to give a composition which will not phase separate. Typical cooking conditions are 0.5 to 10 hours, preferably 1 to 4 hours, at 60 to 120°C, preferably 80 to 100°C, with about 0 to 0.4 parts by weight of a catalyst which is used to accelerate the reaction of the hydroxyls with the ammo resm. Complete crosslinking of the composition is accomplished after the catalyst concentration is mcreased to the requisite level and the composition is applied to the substrate and baked. Hydroxy functional polydiene polymers and other polymers containmg ethylenic unsaturation can be prepared by copolymerizing one or more olefins, particularly diolefins, by themselves or with one or more alkenyl aromatic hydrocarbon monomers. The copolymers may, of course, be random, tapered, block or a combination of these, as well as linear, radial or star . The hydroxy functional polydiene polymers may be prepared using anionic initiators or polymerization catalysts. Such polymers may be prepared usmg bulk, solution or emulsion techniques. When polymerized to high molecular weight, the polymer will, generally, be recovered as a solid such as a crumb, a powder, a pellet or the like. When polymerized to low molecular weight, it may be recovered as a liquid. In general, when solution anionic techniques are used, copolymers of conjugated diolefins, optionally with vmyl aromatic hydrocarbons, are prepared by contacting the monomer or monomers to be polymerized simultaneously or sequentially with an anionic polymerization initiator such as group IA metals, their alkyls, amides, silanolates, naphthalides, biphenyls or anthracenyl derivatives. It is preferred to use an organo alkali metal (such as sodium or potassium) compound m a suitable solvent at a temperature with the range from about -150°C to about 300°C, preferably at a temperature with the range from about 0°C to about 100°C. Particularly effective anionic polymerization initiators are organo lithium compounds having the general formula: R Lι n wherem R is an aliphatic, cycloaliphatic, aromatic or alkyl-substituted aromatic hydrocarbon radical havmg from 1 to about 20 carbon atoms and n is an integer of 1 to 4. Con ugated diolefins which may be polymerized anionically include those conjugated diolefins contammg from about 4 to about 24 carbon atoms such as 1, 3-butadιene, isoprene, piperylene, methylpentadiene, phenyl-butadiene, 3, -dιmethyl-l, 3- hexadiene, , 5-diethyl-l, 3-octadιene and the like. Isoprene and butadiene are the preferred conjugated diene monomers for use in the present invention because of their low cost and ready availability. Alkenyl (vmyl) aromatic hydrocarbons which may be copolymerized include vmyl aryl compounds such as styrene, various alkyl-substituted styrenes, alkoxy- substituted styrenes, vmyl naphthalene, alkyl- substituted vmyl naphthalenes and the like. The hydroxy functional polymers to be used m the compositions of this invention are generally diols when the polymer is linear. Radial and star polymers are also contemplated herein and such case, the polymers would be polyols wherein a hydroxy group is located at the ends of most or all of the arms of such polymerε. The hydroxy functional polydiene polymers may have number average molecular weights of from 500 to 500,000. Lower molecular weights require excessive crosslinking whereas higher molecular weights cause very high viscosity, making processmg very difficult. More preferably, the polymer is one having a number average molecular weight of from 1,000 to 50,000. Most preferably, the polymer is a predominately linear diol having a number average molecular weight of from 2,000 to 20,000 because this offers the best balance between cost, ability to use the mildest curing conditions, and achieving good processing behavior. Hydrogenated polybutadiene diols are preferred for use herein because they are easily prepared, they have low glass transition temperature, and they have excellent weatherability. The diols, dihydroxylated polybutadienes, are synthesized by anionic polymerization of conjugated diene hydrocarbon monomers with lithium initiators. Polyols can be synthesized m the same manner. This process is well known as described in U.S. Patents Nos. 4,039,593 and Re. 27,145. Polymerization commences with a monolithium, dilithium, or polylithium initiator which builds a living polymer backbone at each lithium site. Typical monolithium living polymer structures contammg conjugated diene hydrocarbon monomers are: X-B-Ll X-B1-B2-L1 X-A-B-Li X-A-B1-B2-L1 X-A-B-A-Li wherein B represents polymerized units of one or more conjugated diene monomers such as butadiene or isoprene, A represents polymerized units of one or more vmyl aromatic monomer such as styrene, and X is the residue of a monolithium initiator such as sec- butyllithium. B can also be a copolymer of a conjugated diene and a vmyl aromatic compound. Bl and B2 are formed of different dienes. Dihydroxylated polydiene diols used m this invention may also be prepared anionically such as described in United States Patents Nos. 5,391,663, 5,393,843, 5,405,911, and 5,416,168. The dihydroxylated polydiene polymer can be made usmg a di-lithium initiator, such as the compound formed by reaction of two moles of sec-butyllithium with one mole of diisopropenylbenzene. This dimitiator is used to polymerize a diene m a solvent typically composed of 90%w cydohexane and 10%w diethylether. The molar ratio of dimitiator to monomer determines the molecular weight of the polymer. The living polymer is then capped with two moles of ethylene oxide and terminated with two moles of methanol to yield the desired dihydroxy polydiene. Dihydroxylated polydiene polymers can also be made using a mono-lithium initiator which contams a hydroxyl group which has been blocked as the silyl ether. Details of the polymerization procedure can be found in U.S. Patent 5,376,745. A suitable initiator is hydroxypropyllithium m which the hydroxyl group is blocked as the tert-butyl-dimethylsilyl ether. This mono-lithium initiator can be used to polymerize isoprene or butadiene in hydrocarbon or polar solvent. The living polymer is then capped with ethylene oxide and terminated with methanol. The silyl ether is then removed by acid catalyzed cleavage in the presence of water yielding the desired polymer. A dihydroxy polybutadiene unsaturated polymer withm the scope of this mvention can have any butadiene microstructure. However, it preferably should have less than about 10? 1, 2-butadιene addition in order to minimize its viscosity. A dihydroxy polybutadiene polymer to be used after hydrogenation can also have any butadiene microstructure. However, it is preferred that it have no less than about 30% 1, 2-butadιene addition because, after hydrogenation, the polymer would be a waxy solid at room temperature if it contained less than about 30O 1, 2-butadιene addition and, when used in the process of this mvention, it would give a paste at room temperature instead of a low viscosity solution. Therefore, compositions based on a hydrogenated polybutadiene diol having less than about 30° 1, 2-butadιene addition would have to be coated onto a substrate while the composition was at a temperature high enough that the composition is a homogeneous, low viscosity liquid. Alternatively, the composition could be dispersed in water while it is hot and then be handled as a waterborne dispersion. Although a hydrogenated polybutadiene having a 1, 2-butadιene addition greater than about 30% will give compositions within this invention which are liquids at room temperature, it is preferred that the 1, 2-butadιene content should be between about 40 and 60o to minimize viscosity of the hydrogenated polybutadiene diol. When one of the conjugated dienes is 1, 3-butadιene and is to be hydrogenated, the anionic polymerization of the conjugated diene hydrocarbons is typically controlled with structure modifiers such as diethylether or glyme (1 , 2-dιethoxyethane) to obtain the desired amount of 1, 4-addιtιon. As described m U.S. Reissue Patent No. Re 27,145 the level of 1,2- addition of a butadiene polymer or copolymer can greatly affect elastomeric properties after hydrogenation. Linear unsaturated or hydrogenated polyisoprene diol polymers can also be used these compositions. A dihydroxy polyisoprene polymer withm the scope of this invention can have any isoprene microstructure. However, it preferably should have greater than 80" 1,4-addιtιon of the isoprene, preferably greater than 90° 1,4-addιtιon of the isoprene, m order to reduce the viscosity of the polymer. Polyisoprene diols of this type can be prepared by anionic polymerization in the absence of microstructure modifiers that increase 3,4-addιtιon of the isoprene. The diene microstructures are typically determmed by C 13 nuclear magnetic resonance (NMR) in chloroform. The preferred method of making the polymers of the present invention involves the use of lithium initiators havmg the structure: CH 3 R wherein each R is methyl, ethyl, n-propyl, or n-butyl and A" is an alkyl-substituted or non-substituted propyl bridging group, including -CH2-CH2-CH2- (1,3- propyl) , -CH 2 -CH (CH3) -CH 2 - (2-methyl-l, 3-propyl ) , and - CH 2 -C(CH 3 ) 2 -CH 2 - (2,2-dιmethyl-l, 3-propyl) , or an alkyl-substituted or non-substituted octyl bridging group, including -CH -CH -CH 2 -CH -CH 2 -CH -CH -CH 2 - (1,8-octyl), because these initiators will initiate polymerization of anionic polymers at surprisingly higher polymerization temperatures with surprisingly lower amounts of dead initiator (higher efficiency) than similar initiators wherein A" is replaced by alkyl-substituted or non-substituted butyl, pentyl, or hexyl bridging groups, such as -CH 2 -CH 2 -CH 2 -CH 2 - (1,4- butyl), -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 - (1, 5-pentyl) , or -CH 2 ~ CH 2 -CH -CH 2 -CH 2 -CH - (1,6-hexyl) . Certain hydroxylated polydiene polymers useful in the present invention have the structural formula (I) HO-A-OH or (HO-A) n -X wherein A is a homopolymer of a conjugated diolef monomer, a copolymer of two or more conjugated diolef monomers, or a copolymer of one or more conjugated diolef monomers with a monoalkenyl aromatic hydrocarbon monomer, where n>l and where X is the residue of a couplmg agent. During the preparation of these hydroxylated polydiene polymers, it is possible to make some mono- functional polymer havmg the structural formula HO-A, either by incomplete capping of the living polymer or by incomplete coupling via the coupling agent. Although it is preferred that the amount of th_s mono- functional polymer is minimal, satisfactory crosslinked compositions with this invention can be achieved even when the amount of mono-functional polymer is as high as 70°W of the hydroxylated polymer in the composition. Other hydroxylated polydiene polymers useful in the present invention have the structural formula ( I I ) HO-A- S z -B- OH o r ( HO-A-S z -B ) n -X o r HO-S z -A-B- S y -OH o r ( HO- S z -A-B ) n-χ wherem A and B are polymer blocks which may be homopolymer blocks of conjugated diolefm monomers, copolymer blocks of conjugated diolefm monomers, or copolymer blocks of diolefm monomers and monoalkenyl aromatic hydrocarbon monomers, where S is a v yl aromatic polymer block, where y and z are 0 or 1, where n is greater than or equal to 2, and where X is the residue of a coupling agent. These polymers may contain up to 60% by weight of at least one v yl aromatic hydrocarbon, preferably styrene. The A blocks and the B blocks can have a number average molecular weight of from 100 to 499,000, preferably 500 to 49,900, and most preferably 1000 to 19,900. The S block may have a number average molecular weight of from 500 to 50,000. Either the A or the B block may be capped with a mmiblock of polymer, 50 to 1000 number average molecular weight, of a different composition, to compensate for any initiation, tapering due to unfavorable copolymerization rates, or capping difficulties. It will be appreciated that the total number average molecular weight of the hydroxy functional polydiene polymer is kept withm the ranges given herem before. The molecular weights of the polymers are conveniently measured by Gel Permeation Chromatography (GPC) , where the GPC system has been appropriately calibrated. The polymers can be characterized from the data in the chromatogram by calculating the number- average molecular weight (Mn) , by calculating the weight-average molecular weight (Mw) or by measuring the "peak" molecular weight. The peak molecular weight is the molecular weight of the mam specie shown on the chromatogram. For anionically polymerized linear polymers, the polymer is nearly monodisperse (Mw/Mn ratio approaches unity) , and usually it is adequately descriptive to report the peak molecular weight of the narrow molecular weight distribution observed. Usually, the peak molecular weight value is between Mn and Mw. For polydisperse polymers the number average molecular weight should be calculated from the chromatograph and used. The materials used in the columns of the GPC are styrene-divinyl benzene gels or silica gels. The solvent is tetrahydrofuran and the detector is a refractive mdex detector. The polymers of this invention may be hydrogenated usmg procedures known to those skilled the art, for example using the procedure disclosed m U.S. Patent Reissue 27,145. The hydrogenation of these polymers and copolymers may be carried out by a variety of well established processes mcludmg hydrogenation in the presence of such catalysts as Raney Nickel, noble metals such as platinum and the like, soluble transition metal catalysts and titanium catalysts as m U.S. Patent 5,039,755. The polymers may have different diene blocks and these diene blocks may be selectively hydrogenated as for example described in U.S. Patent 5, 229, 464. The crosslinking agents which are useful in the present invention are ammo resms. For the purposes of this mvention, an ammo resm is a resm made by reaction of a material bearing NH groups with a carbonyl compound and an alcohol. The NH bearing material is commonly urea, melamme, benzoguanamme, glycoluπl, cyclic ureas, thioureas, guanidmes, urethanes, cyanamides, etc. The most common carbonyl component is formaldehyde and other carbonyl compounds mclude higher aldehydes and ketones. The most commonly used alcohols are methanol, ethanol, and butanol. Other alcohols include propanol, hexanol, etc. CYTEC (formerly American Cyanamid) sells a variety of these ammo resms, as do other manufacturers. CYTEC' s literature describes three classes or "types" of ammo resms that they offer for sale. Type 1 CH 2 OR CH 2 0R Y—N Y— \ \ CH 2 OH H Type 2 Type 3 where Y is the material that bore the NH groups, the carbonyl source is formaldehyde and R and R' are alkyl groups from the alcohol (s) used for alkylation. R" is an aliphatic group. R, R' and R" may contain up to 8 carbon atoms. Although this type of description depicts the ammo resms as monomeric material of only one pure type, the commercial resms exist as mixtures of monomers, dimers, trimers, etc. and any given resm may have some character of the other types. Dimers, trimers, etc. also contain methylene or ether bridges. Generally, Type 1 ammo resms are preferred m the - present invention. The following Type 1 ammo resms can for example be used to achieve the purpose of the present invention: CYMEL 303 - a melamme-formaldehyde resm where R is CH3, CYMEL 1156 - a melamme-formaldehyde resm where R is C4H9, CYMEL 1141 - a carboxyl modified melamme-formaldehyde resm where R is a mixture of CH3 and 1-C4H9, CYMEL 1170 - a glycoluril- formaldehyde resm where R is C4H9, and BEETLE 80 - a urea- formaldehyde resm where R is C4H9. All of these products are made by CYTEC and are described in the American Cyanamid publication 50 Years of Ammo Coating Resms, edited and written by Albert J. Kirsch, published m 1986 along with other ammo resms useful in the present invention. The butylated ammo resms generally have fairly good compatibility with the hydroxy functional polydiene polymers while the methylated ammo resms generally are incompatible with the hydroxy functional diene polymers. However, the ammo resins do not necessarily have to be compatible with the polymer and give phase stable mixtures when merely mixed together because the partial reaction disclosed in this invention can overcome this incompatibility, giving resms which will not phase separate. The reinforcing agent typically has at least two functional groups capable of reacting with the ammo resm crosslinking agent. Typically, the reinforcing agent will react with the crosslinking agent when the composition is heated. The number average molecular weight preferably is from 60 to 600, most preferably 60 to 120. Suitable functional groups mclude primary and secondary alcohols as well as dicarboxylic acids or anhydrides . The equivalent weight of the reinforcing agent will usually be at least 30 preferably at least 50, and usually at most 300, preferably at most 150 grams per mole of functional group, more preferably at most 100 grams per mole of functional group. The equivalent weight of the reinforcing agent is defined as the molecular weight of the reinforcing agent divided by the number of functional groups per molecule of the reinforcing agent. The functionality, that is the number of functional groups per molecule, of a reinforcing agent molecule should be at least two to be effective as reinforcing agent. It will be appreciated that the overall functionality m commercial grades of reinforcing agent molecules having a functionality of 2, may be lower due to impurities. Therefore, reinforcing agents having a functionality of at least 1.6, preferably at least 1.8, may also be used m the composition of the present mvention. Preferably, however, the functionality is at least 2.0 and can be as high as desired with the proviso that increasing the functionality increases the polarity which adversely affects the compatibility of the reinforcing agent with the polydiene diol. However, if the reinforcing agent can be blended or cooked mto the composition, the functionality is acceptable. Examples of reinforcing agents suitable for use m the present mvention mclude unsubstituted aliphatic diols such as ethylene glycol, 1,3-propane diol, 1,4- butane diol, 1,6-hexane diol, and dimer diol, substituted aliphatic diols such as 1,2-propane diol, 2-methyl-l, 3-propane diol (MP-diol from Arco) , neopentyl glycol, 2-ethyl-l, 3-hexane diol (PEP diol) , 2, 2, -trιmethyl-l, 3-pentane diol (TMPD diol) , and 2- butyl-2-ethyl-l, 3-propane diol (BEPD diol) , cycloaliphatic diols such as cydohexane dimethanol and 4, 4-ιsopropylιdenedιcyclohexanol (HBPA) , and aromatic diols such as 4, -ιsopropylιdenedιphenol (Bisphenol A) (BPA) . Triols such as glycerol, tπmethylol ethane, and trimethylol propane may also be used. Analogous unsubstituted and substituted carboxylic acids may also be used. Preferred materials for use herem are aliphatic diols havmg 5 to 40 carbon atoms, especially alkyl-substituted aliphatic diols such as PEP diol, TMPD diol, and BEPD diol because they are substituted, branched diols and, as such, are not as incompatible with the polydiene polymers as unsubstituted, straight cham diols. A proton-donating acid catalyst is often, but not always, required to achieve the purposes of the present mvention, i.e., crosslink the polydiene polymer and reinforcing agent using the ammo resm crosslinking agents described above. Sometimes, a catalyst is not necessary such as when CYMEL 1141 is the crosslinking agent because its acid functionality alone is sufficient to catalyze the partial reaction needed to obtain compatibility as well as subsequent crosslinking reactions. When a catalyst is used, it is normal that the amount of the acid catalyst used ranges from 0.05 to 4%w of the polymer/remforcer/ammo resm mixture to be certain there is sufficient acid. An excess, however, can be undesirable. Most preferably, an amount from 0.1 to 2%w of the polymer/remforcer/ ammo resm is used. The presence of a strong proton- donat g acid is normally required to catalyze the crosslinking reaction of many ammo resms which are useful in the present mvention. However, some medium strength and even relatively weak acids may also be effective depending upon the ammo resms used. Generally, the most active catalysts are those with the lowest pKa values. The following list of acid catalysts which may be used in the present invention is arranged accordmg to increasing pKa value: mineral acids, Cycat 4040 catalyst (p-toluene sulfonic acid), Cycat 500 catalyst (dinonylnaphthalene disulfonic acid) , Cycat 600 catalyst (dodecyl benzene sulfonic acid) , oxalic acid, maleic acid, hexamic acid, phosphoric acid, Cycat 296-9 catalyst (dimethyl acid pyrophosphate) , phthaiic acid and acrylic acid. Other acids which may be used are described m the aforementioned American Cyanamid Company publication. Also, 3M Brand Resm Catalyst FC-520 (diethylammonium salt of trifluoromethane sulfonic acid) may be used. Cycat 600 was found to be a very useful catalyst. The compatible compositions of the present invention are prepared by mixing the polydiene polymer, the ammo resm crosslinking agent, and the reinforcing agent together. An effort should be made to make the mixture as homogeneous as is reasonably possible. The components are then partially reacted (incompletely reacted) in an appropriate vessel. It is important that the reaction not proceed too far or the composition will be too high in viscosity, making application very difficult or impossible or the composition may even entirely crosslink in the vessel. But, enough reaction must be accomplished to overcome incompatibility of the components to give a resm which will not phase separate upon standmg, or more preferably, is homogeneous and clear. Thus, the mixture is partially reacted at least until a phase-stable composition is obtamed, that is a composition which does not phase separate upon standmg for two weeks at room temperature (20°C) . The reaction should not be allowed to proceed until the mixture starts to gel. When a mixture starts to gel, the viscosity increases substantially and in lab-scale experiments the mixture starts climbing up the stirring rod. Preferably, the mixture is partially reacted at most until the viscosity of the mixture is ten times the viscosity of the mixture at the start of the reaction. The required and desired levels of partial reaction can easily be determmed by a skilled person by no more than routme experimentation. Conditions for cooking a particular composition which will give a satisfactory product depend on €he composition and can be determmed empirically for each composition by routine experimentation. For example, it was found that when cooking a resm containing an acid-functional melamme resin, the acid on the res was usually sufficient to catalyze the reaction so little or no extra catalyst was needed. It was also found that cooking a resin containing a relatively incompatible methylated melamme at 100°C for 1 hour was not sufficient to give a phase stable composition, cooking 2 hours was satisfactory, and cooking 4 hours caused the resm to gel. Cooking another composition containing the more compatible butylated melamine resm for 1 hour at 100°C was satisfactory to give a clear, phase stable composition. Thus, satisfactory cooking conditions will be those combinations of catalyst concentration, cooking time, and cooking temperature which are sufficient to give a phase-stable, preferably clear composition. Thus, general recommendations are to do the reactions at 60 to 120°C for 0.5 to 10 hours, usually for 1 to 3 hours, in the presence of catalyst. It will be appreciated by those skilled in the art that the amount of catalyst to be applied in the partial reaction (cooking) step should be sufficient to catalyse the partial reaction step, but should not be sufficient to catalyse complete crosslinking of the composition. It belongs to the skills of the person skilled m the art to select the appropriate amount of catalyst. The catalyst can be the same one which will be needed to entirely crosslink the composition after it has been applied to the substrate and is baked. It is frequently found that the amount of catalyst needed m the partial reaction step is usually less than about half of the total catalyst needed to obtain the desired amount of crosslinking m the final product. The partially reacted mixture is then still m a physical form that allows convenient and easy application thereof as desired. The partially reacted mixture and the rest of the catalyst required for crosslinking are then mixed together and the mixture is applied to a substrate. The substrate is then baked to effect crosslinking. Preferably, the substrate is baked at 100 to 250°C for 0.01 to 2 hours. Although use of solvent may not be necessary, solvent can be mcluded n with the polymer/remforcer/ ammo resm mixture to reduce the viscosity such that the partially reacted mixture can be easily stirred durmg the partial reaction or to facilitate application of the finished resm (partially reacted mixture) . Suitable solvents mclude hydrocarbon solvents such as liquid aliphatic hydrocarboxy sometimes referred to as naphtha or mineral spirits, toluene, xylene, etc., and oxygenated solvents such as esters, ketones, ethers and alcohols. Two common solvents which are well suited and which were used m much of this work are naphtha and isobutyl acetate. If the partially reacted resm will be dispersed m water for application as a water based product, use of a water soluble solvent, such as BUTYL OXITOL or diacetone alcohol, may be advantageous. Solvent contents of up to 70%w of the polymer/remforcer/ammo resm/solvent mixture can be used. However, it is usual with these compositions that the solvent content is 40% by weight or less. For applications m which the resm must have low viscosity but m which solvent content must be low or even zero, it may be necessary to disperse the partially reacted resm m water and apply it as a waterborne composition. In this case, the partial reaction and subsequent dispersion should be done with little or no solvent present. Dispersion of the partially reacted resm m water can be accomplished by a process known to those skilled in the art, typically by the inversion process or by the direct emulsification process. In the inversion process, the surfactant is added to the organic phase which has been heated to a temperature high enough to give the resm a viscosity low enough that it can be efficiently stirred. Typical temperatures are from 40 to 90°C. While stirring the resm vigorously, as with a 4-bladed stirrer rotating at about 2000 rpm, water is slowly added. When a volume of water about equal to the volume of the organic phase has been added, the mixture will invert from organic continuous to water cont¬ inuous, thereby making the waterborne dispersion. More water is then added to reduce the viscosity to the desired range. In the direct emulsification process, surfactant is added to the required amount of water, typically about 150 parts by weight per 100 parts of organic resm. Typically, the organic resm is then dispersed in the soapy water with a high shear mixer, such as a Silverson mixer/emulsifler operating at about 6000 rpm. A wide variety of surfactants may be used, including anionic surfactants, nonionic surfactants and cationic surfactants. A particularly effective surfactant is the anionic surfactant made by neutralizing CYCAT 600 with a tertiary amine such as triethyl amme or dimethylam oethanol . This compound not only functions as the surfactant to stabilize the dispersion in water but, after the composition is applied to a substrate, the amme evaporates during the bake step, allowmg the CYCAT 600 to catalyze the cure with the ammo resm crosslinking agent. In the solids portion of the crosslinkable composition, the hydroxy functional polydiene polymer should comprise from 10 to 80 percent by weight (%w) of the polymer/reinforcing agent/crosslmk g agent composition. The reinforcing agent should comprise from 2 to 40%w of the composition, and the ammo resm crosslinking agent should comprise from 8 to 60%w of the composition. If the hydroxy functional polydiene polymer is used at less than 10%w, then the cured composition will be too brittle for most applications. If it is used at more than 80%, then the concentrations of crosslinker and remforcer will be too low and the composition will not cure to high strength and will be too soft for many applications. If the concentration of the re ^forcer is too low, then the cured composition will be too soft for many applications, and if it is too high, then the crosslink density will be too high and the composition will again be too brittle. If the concentration of the ammo resm is too low, then the strength will not be as high as desired, and if the concentration is too high, then homopolymerization of the ammo resm will cause the cured composition to be too brittle. The crosslinked materials of the present invention are most useful in coatmgs, especially m coatings for applications which require hard, glossy surfaces such as coatmgs for metal buildings or furniture or coatmgs for difficult to bond to substrates such as oily metal or plastic substrates. They are also useful in certam kinds of adhesives (mcludmg assembly adhesives, structural adhesives, laminating adhesives and contact adhesives), sealants, films (such as those requiring heat and solvent resistance), etc. However, it may be necessary for a formulator to combine a variety of ingredients together with the compositions of the present mvention m order to obtain products having the proper combination of properties (such as adhesion, cohesion, durability, low cost, etc.) for particular applications. Thus, a suitable formulation might be only the partially reacted resm consistmg of the polymers of the present invention, the reinforcing agent and the ammo resm curing agent. However, m many adhesive, sealant and coating applications, suitable formulations would also contain various combinations of resms, plasticizers, fillers, solvents, stabilizers, surfactants and other ingredients such as asphalt. The followmg are some typical examples of formulating ingredients for adhesives, sealants and coatings. In adhesive applications, as well as in coatmgs and sealants, it may be necessary to add an adhesion promoting or tackifying resm that is compatible with the composition. A common tackifying res is a diene- olefin copolymer of piperylene and 2-methyl-2-butene having a softening point of about 95°C. This resm is available commercially under the tradename Wmgtack 95 and is prepared by the cationic polymerization of 60% piperylene, 10% isoprene, 5% cyclo-pentadiene, 15% 2- methyl-2-butene and about 10% dimer, as taught m U.S. Patent No. 3,577,398. Other tackifying resms may be employed wherein the resinous copolymer comprises 20-80 weight percent of piperylene and 80-20 weight percent of 2-methyl-2-butene. The resms normally have ring and ball softening points as determined by ASTM method E28 between about 80°C and 115°C. In some cases, however, liquid resms may also be used. Other adhesion promotmg resms which are also useful m the compositions of this invention mclude hydrogenated ros s, esters of ros s, polyterpenes, terpenephenol resms, polymerized mixed olefins, aromatic resms mcludmg coumarone-mdene resms, polystyrene resms, v yl toluene-alpha methylstyrene copolymers and polyindene res s. To obtain good thermo-oxidative and color stability, it is preferred that the adhesion promotmg res be a saturated resm, e.g., a hydrogenated dicyclopentadiene resm such as Escorez 5000 series resm made by Exxon or a hydrogenated polystyrene or polyalphamethylstyrene resm such as Regalrez resm made by Hercules. The amount of adhesion promotmg resm employed varies from 0 to 200 parts by weight per hundred parts of partially reacted resm (phr) , preferably between 20 to 150 phr, most preferably 20 to 100 phr. The selection of which particular adhesion promotmg resm to use is, m large part, dependent upon the specific composition of the partially reacted resm employed in the respective adhesive composition. It belongs to the skill of the average skilled person m this field to select appropriate adhesive promotmg resms. The composition of the instant invention may contain plasticizers, such as rubber compounding oils. Rubber compounding oils are well-known in the art and mclude both high saturates content oils and high aromatics content oils. Preferred plasticizers are highly saturated oils, e.g. Tufflo 6056 and 6204 oil made by Arco and process oils, e.g. Shellflex 371 oil made by Shell. The amounts of rubber compounding oil employed m the mvention composition can vary from 0 to about 200 phr, preferably between about 0 to about 100 phr, and most preferably between about 0 and about 50 phr. This mvention provides a process for painting a substrate requiring priming, such as steel, which comprises: (a) coating the substrate with a primer selected from the group consisting of epoxy resm primers and polyester resm primers, (b) applying to the primed substrate a crosslinkable basecoat composition comprising from 10 to 80 percent by weight of a dihydroxylated polydiene polymer, from 8 to 60 percent by weight of an ammo resm crosslinking agent, and from 2 to 40 percent by weight of a reinforcing agent, and crosslinking the applied base coat composition and (c) applymg over the basecoat a clearcoat selected from the group consisting of dihydroxy polydiene-based clearcoats, polyester clearcoats, and acrylic clearcoats. The primers which may be used in the process of the present invention are those which are commonly used as primers for steel substrates mcludmg epoxy resm primers and polyester primers. Epoxy resm primers are normally based on the diglycidyl ether of Bisphenol A (DGEBA), such as EPON 828 resm (Shell Chemical) . To prepare the resm, the DGEBA is reacted with Bisphenol A (BPA) to generate a higher molecular weight epoxy resm which has secondary hydroxyl functional groups. The curing agent for this epoxy polyol is typically an ammo resm or a polyisocyanate. After being suitably formulated, the epoxy primer can be applied from solution a solvent such as xylene or it can be applied as a solvent free powder. A particularly desirable method of applymg the epoxy primer is by the cathodic electrodeposition (CED) process. A typical resm preparation and formulation of a waterborne epoxy primer which can be applied by the CED process is given in U.S. Patent 4,883,572. Again the DGEBA is reacted with BPA to give a higher molecular weight epoxy polyol. The epoxy groups on the resin are then reacted with a secondary amme, such as methylammoethanol, and the tertiary amine formed is ionized with an acid, such as lactic acid. The ionic species make the resm dispersable m water. After formulating the resm with suitable curing agent, corrosion inhibitor package, and various other components, the primer can be applied and cured by baking, typically for 20 mmutes at about 180°C. Polyester polyols can also be used m the primers. These polyester polyols are also normally cured with ammo resms or polyisocyanates. Typically, the polyester polyols are synthesized by carrying out a condensation reaction using a glycol or a mixture of glycols and an anhydride or diacid compound or a mixture of anhydrides or diacid compounds. The condensation reactions typically are done at temperatures of 175 to 235°C m a resm kettle which is capable of removing the water of condensation. Typical glycols used in the polyester polyol synthesis are the same as the reinforcing agents described above for use m the novel coating compositions of this invention. Especially preferred are ethylene glycol, 1,4-butane diol, and neopentyl glycol. The anhydrides and diacids which can be used in the polyester synthesis are well known. Anhydrides and diacids which are frequently used in polyesters for primers are phthaiic anhydride, isophthalic acid, and adipic acid. A fairly complete list of hydroxy functional and acid functional compounds which are used in polyesters is given m Bulletin IP-65c, "How to Process Better Coating Res s with Amoco PIA and TMA" from Amoco Chemical Company, 1992. Polyester primers can be applied from a solution organic solvent or as a solvent free powder. However, a preferred method of application is as a waterborne coating. The technology for preparation of waterborne polyester coating resms is known to those skilled in the art can for example be found m U.S. Patent 4,054,614. A polyester is prepared which has acid functional groups. These acid groups are neutralized with a tertiary amine, such as dimethylammoethanol, and the resm is dispersed in water. After formulation with suitable crosslinkers, corrosion inhibitors, and any other ingredients necessary to give good performance, the primer is applied and cured (cross- linked) by baking, typically for 30 mmutes at about 150°C. Curing agents for the primers are typically ammo resms or polyisocyanates. The ammo resms which are used are the same types which are described above for use in the compositions of this invention. Polyisocyanates used in primers are usually based on toluene diisocyanate (TDI) or 4,4-dιphenyl methane diisocyanate (MDI) . These diisocyanates are typically converted to triisocyanates by, for example, condensing 3 moles of diisocyanate to form an isocyanurate ring structure or by reaction of 3 moles of diisocyanate with a triol such as trimethylolpropane. The polyisocyanate will cure the polyol at ambient temperature a two component coating. Alternatively, the isocyanate groups can be blocked with a volatile blocking agent, such as phenol, and the blocked polyisocyanate will deblock when baked at temperatures of about 180°C, regenerating the polyisocyanate which w ll cure the polyol. The primary functions of the primer coating are to prevent corrosion of the substrate, to provide a surface which is smooth or which can be sanded smooth, and to provide a surface to which an additional coating will adhere. It has been found that the coatmgs of this invention adhere very well to these primers. The coatmgs (basecoats) of this invention will almost always be pigmented to provide the desired color to the coated part and also to protect the primer agamst degradation by sunlight and the environment. In other words, the basecoat is the "pamt" for the substrate. This pigmented coating based on the compositions of this mvention will frequently also be coated with a clearcoat coating (clearcoat) to improve the appearance of the coated part and also to protect the pigmented coating agamst degradation. Resms for the clearcoat coatmgs typically will contain either a polyester polyol or an acrylic polyol and the curing agent for the polyol will be either an ammo resm or a polyisocyanate. The polyester polyols m the clearcoat are very similar to those m the primer except that only alcohol and acid functional components which have good stability, especially to sunlight, will be used in the polyester synthesis. The acrylic polyols used in clearcoats are made by free radical polymerization, usually in solution m an organic solvent or m a suspension polymerization if the coating will be applied as a powder. There is a wide variety of acrylate and methacrylate monomers which are commercially available for use m acrylics. The acrylic monomers which will be used m polymerization will be selected to give the acrylic polyol the proper properties. Two of the important properties of the acrylic polyol are its glass transition temperature (which will usually be between 0 and 50°C) and its hydroxy equivalent weight (which will usually be between 200 and 1000) . Thus, a typical polymerization might use a combination of methyl methacrylate , butyl acrylate and hydroxy ethyl acrylate. The crosslinkers for the polyester polyol or acrylic polyol m the clearcoat will be quite similar to those in the primers except that only stable crosslinkers will be used. The ammo resms of the type described above for use m the compositions of this invention are used as crosslinkers for baked clearcoats. Only light stable isocyanates will be used. These are based on hexane diisocyanate (HDI) , isophorone diisocyanate (IPDI) or 4, -dιcyclohexyl methane diisocyanate (HMDI) . These diisocyanates will usually be converted to triisocyanates and they will be blocked if they will be used to cure the polyol m a bake system. The clearcoat coatmgs will usually be formulated with wetting agents to improve flow and reduce surface defects, and with stabilizers, especially to protect the clearcoat as well as the basecoat agamst degradation by sunlight. Optional components which may be added to the compositions of the present invention are stabilizers. Antioxidants are added to protect the compositions aga st heat degradation and oxidation during the preparation, storage, cure, and use of the compositions. Ultraviolet light stabilizers are added to protect the compositions agamst degradation caused by sunlight. Pigments will often be included m the coating (pamt) composition to give the pamted part the desired color and appearance. Various types of fillers can be mcluded in the formulation. This is especially true for exterior coatmgs or sealants which fillers are added not only to create the desired appeal but also to improve the performance of the coatmgs or sealants such as their weatherability. A wide variety of fillers can be used. Suitable fillers mclude calcium carbonate, clays, talcs, silica, zmc oxide, titanium dioxide and the like. The amount of filler usually is the range of 0 to about 65%w based on the solvent free portion of the formulation depending on the type of filler used and the application for which the coating or sealant is mtended. An especially preferred filler is titanium dioxide because it is very effective at improving resistance of compositions to degradation by exposure to sunlight. The only three ingredients that will always be used in all adhesives, coatmgs or sealants of this invention are the hydroxy functional diene polymer, the ammo resm crosslinking agent, and the reinforcing agent. Beyond these ingredients, the formulator will choose to use or not to use among the various resms, fillers and pigments, plasticizers, stabilizers and solvents disclosed herem. No definite rules can be offered about which ingredients will be used. The skilled formulator will choose particular types of ingredients and adjust their concentrations to give exactly the combination of properties needed in the composition for any specific adhesive, coating or sealant application. Thus, according to further aspect, the present invention relates to adhesives comprising the composition of this invention and a tackifying resm. Adhesives are frequently thm layers of sticky compositions which are used in protected environments (adhering two substrates together) . Therefore, unhydrogenated diene polymers will usually have adequate stability so resm type and concentration will be selected for maximum stickiness without great concern for stability, and pigments will usually not be used. Tackifying resms are well known to those skilled in the art and have for example been described m "Handbook of Adhesives", 3rd edition, van Nostrand Remhold New York. According to another aspect, the present invention relates to a coating comprising the composition of this invention, either a filler or a stabilizer or both and optionally a pigment. Coatings are frequently thin, non-sticky, pigmented compositions applied on a substrate to protect or decorate it. Therefore, hydrogenated diene polymers may be needed to give adequate durability. Resms will be selected to assure maximum durability and minimum dirt pick-up. Fillers and pigment will be selected carefully to give appropriate durability and color. Coatmgs will frequently contain relatively high solvent concentration or will be waterborne dispersions to allow easy application and give a smooth dry coating. Accordmg to yet another aspect, the present invention relates to a sealant comprising the composition of this invention and a tackifying resm. Sealants are gap fillers. Therefore, they are used in fairly thick layers to fill the space between two substrates. Since the two substrates frequently move relative to each other, sealants are usually low modulus compositions capable of withstanding this movement. Since sealants are frequently exposed to the weather, hydrogenated polymers are usually used. Resms and plasticizers will be selected to maintain low modulus and minimize dirt pick-up. Fillers and pigment will be selected to give appropriate durability and color. Since sealants are applied in fairly thick layers, solvent content is as low as possible to minimize shrinkage. A formulator skilled m the art will see tremendous versatility in the hydroxy functional diene polymer/remforcer/crosslmker compositions of this invention to prepare coatmgs, adhesives and sealants having properties suitable for many different applications . Examples The followmg examples demonstrate the utility of the inventive compositions containing hydroxy terminated polydiene polymers, ammo resm crosslinking agents, and reinforcing agents which have been cooked (partially reacted) to obtain compatibility and subsequently cured (crosslinked) . The polymers used m the examples are characterized Table 1 where Bd is an unhydrogenated polybutadiene block, EB is a hydrogenated polybutadiene block, and S/EB indicates a random copolymer block of styrene and hydrogenated butadiene. Table 1 Function¬ 1, 2-Bd Styrene Polymer Type M n ality Content, Content, %w %w A HO-EB-OH 3300 1.9 48 0 B HO-Bd-OH 3400 1.9 40 0 C HO-EB-OH 2000 1.9 84 0 D HO-EB-OH 2700 2.4 20 0 E HO-S/EB-OH 3500 1.85 40 26 F HO-S/EB-OH 4300 1.8 37 43 Thus, Polymer A was a hydrogenated polybutadiene diol having a number average molecular weight of 3300, an average functionality of 1.9 hydroxyls per molecule, and a 1, 2-Bd/l, 4-Bd addition ratio of 48/52. Polymer B was a diol similar to Polymer A except the polybutadiene was not hydrogenated. Polymer C was similar to Polymer A except the 1, 2-Bd/l, 4-Bd ratio was 84/16. Polymer D was similar to Polymer A except the average functionality was 2.4 hydroxyls per molecule and the 1, 2-Bd/l, 4-Bd ratio was 20/80. Polymers E and F were similar to Polymer A except they also contained 26%w and 43%w styrene copolymerized with the hydrogenated polybutadiene. The other components used in the examples are described in Table 2. Table 2 Component Supplier Description Crosslinking agents CYMEL 1141 CYTEC Acid-functional, methylated/butylated melanine/formaldehyde, eq wt 150-250 CYMEL 1156 CYTEC Liquid, butylated melamine/formaldehyde resin, 2.2 functionality CYMEL 303 CYTEC Liquid, methylated melamme/formaldehyde resin, 2.2 functionality DESMODUR BL-3175 Bayer Blocked HDI based trusocyanate Catalyst CYCAT 600 CYTEC Dodecylbenzene sulfonic acid DABCO T-l2 Air Products Dibutyl t n dilaurate Reinforcing Agents TMPD Diol Eastman 2,2, -trimethy1-1, 3- pentane diol, mp = 54°C BEPD Diol Eastman 2-butyl-2-ethyl-l, 3- propane diol, mp = 40°C HBPA Shell 4, 4-ιsopropylιdenedι- cyclohexanol, mp = 160°C BPA Shell 4, 4-ιsopropylιdenedι- phenol, mp = 155°C Solvents VM&P Naphtha HT Shell Aliphatic hydrocarbon mixture, bp = 119 - 139°C Isobutyl acetate Aldrich Isobutyl aceetate, bp = 116°C Table 2 (continued) Other Components DESMOPHEN 670A-80 Bayer Polyester polyol, 80%w in butyl acetate, 500 hydroxy eq wt DESMOPHEN 365 Bayer Acrylic polyol, 65%w in butyl acetate/xylene (3/1), 607 hydroxy eq wt TiPure R-706 DuPont Titanium dioxide pigment Coatings made according to the present mvention were evaluated for mechanical properties after they were applied to a substrate and cured by baking. The general appearance (clarity, gloss, adhesion, and mar resistance) of the coatmgs was judged visually and described qualitatively. The pencil hardness (gouge) of the coatmgs was measured accordmg to the ASTM D3363 method of pushing successively softer pencil leads across the coating until the pencil lead will no longer gouge through the coating. The hardness scale (softest to hardest) is 6B<5B<4B<3B<2B<B<HB<F<H<2H<3H<4H<5H<6H Rocker hardness was measured by ASTM D2134 using a Sward type hardness rocker. This test measures the number of rocks the rocker will make on the coating before the amplitude decreases from a fixed starting angle to a fixed ending angle. The value is expressed as the percentage of rocks the test sample gave relative to the number of rocks the rocker would make on a glass substrate. The methyl ethyl ketone (MEK) resistance of the coatmgs was measured according to the ASTM D4752 method of rubbing an MEK-moistened cloth across the coating for 100 cycles, or until breakthrough to the metal substrate occurred (one cycle equals one forward and one backward stroke) . It should be cautioned that, in cases where the coatmgs had poor adhesion to steel, the hardness and MEK resistance values may be misleading since the coatmgs may be merely scraped off the steel instead of being gouged through or rubbed through. This poor adhesion to steel would have the effect of making the coatmgs appear softer in the hardness test than they really are and making them appear poorly cured in the MEK resistance test when they actually may be well cured. Adhesion of the coatings was measured with the Crosshatch adhesion test, ASTM D3359, Method B. In this test, a lattice pattern is scribed through the coating, pressure sensitive tape is applied and removed, and the amount of coating removed with the tape is rated. The scale ranges from 5 (no adhesion loss) to 0 (greater than 65% adhesion loss) . An mtegral part of this invention is the process of cooking the components of these compositions to overcome their inherent incompatibility. Conditions of catalyst concentration, cooking time, and cooking temperature necessary to prepare phase stable compositions varied from one formulation to another and had to be determmed by trial and error for each formulation. Phase stable combinations of the polydiene polymer, reinforcing agent, and crosslinking agent could usually be obtamed by cooking them together in a resm kettle for about 1-3 hours at about 100°C using varying amounts of acid catalyst, CYCAT 600. The catalyst concentration, cooking time, and cooking temperature actually used for each composition is shown m the tables. For convenience, the cooks were typically done at 60%w solids content in solvent, either isobutyl acetate or VM&P naphtha, to give the resm a manageable viscosity. Viscosities at 25°C were measured on some of the compositions using a Brookfield viscometer. Prior to casting films, the acid catalyst content was typically mcreased to 1 part by weight (pbw) in order to accomplish cure during bake. Unless specified otherwise, coatmgs were applied on colΔ rolled steel panels (QD412 panels from Q-Panel Corp.) with a #52 wire wound rod and cured by baking 20 mmutes at 175°C. Coatings were applied on thermoplastic olefin panels (Himont ETA-3081 panels from ACT Corp.) and cured by baking 1 hour at 121°C. Comparative Example Table 3 presents properties of coatings made with Polymer A using the conventional technology of curing diols with melamine resins, without the reinforcing agents of this invention. Table 3 Composition, pbw 3-1 3-2 3-3 Polymer A 80 80 80 CYMEL 303 20 - - CYMEL 1156 - 20 - CYMEL 1141 - - 20 CYCAT 600 0.4 0.4 0 VM&P naphtha 67 67 - Isobutyl acetate - - 67 Cook Time, hr 1 1 1 Cook Temp. , °C 100 80 100 Appearance of Resm Phase stable? yes yes no Clarity clear clear grainy Viscosity @ 25°C, cps 15000 nd Properties on QD412 Thickness, mil 1.0 0.6 Pencil Hardness B 4B MEK Rubs 4 2 Crosshatch Adhesion 0 0 General Appearance Clarity clear clear Gloss high high Adhesion to Steel v. Poor v. Poor Mar Resistance v. poor v. Poor Properties on ETA-3081 Crosshatch Adhesion The results show that conditions of 0.4 pbw of catalyst and cooking 1 hour at 100°C were sufficient to give a phase stable composition with Formulation 3-1. The butylated melamme, CYMEL 1156, used in Formulation 3-2 is somewhat more compatible with Polymer A and so the somewhat more mild cooking temperature of 80°C was sufficient to give a phase stable composition. No combination of cooking time, temperature, and catalyst concentration was found which gave a satisfactory composition with Formulation 3.3. The acid functionality on the CYMEL 1141 seemed to catalyze the reaction so no CYCAT 600 was needed. In fact, when as little as 0.4 pbw of CYCAT 600 was added, the resm gelled quickly during the resm cook. When cook times shorter than 1 hour were used, the resms made were not phase stable and would separate upon standmg at room temperature. When cook times longer than 1 hour were used, the resm became too high in viscosity and, after several hours of cooking, the resm gelled. The results Table 3 show that both Formulations 3-1 and 3-2 had poor adhesion to unprimed steel but excellent adhesion to thermoplastic polyolefin (TPO) substrate. However, both compositions gave coatmgs which were very soft and weak, thus giving them very poor mar resistance and making them unsuitable for use m practical applications. The results of the Comparative Example show that, to be useful, coatmgs based on the hydroxy terminated polydiene polymers and melamme resms will have to be harder and stronger. This could be accomplished by also mcludmg a low molecular weight reinforcing agent (diol), such as TMPD diol or BEPD di , in the formulation. But these low molecular weight diols are quite polar and therefore have poor compatibility with the hydroxy terminated polydiene polymers described above and mixtures with them are not phase stable. However, this invention demonstrates that phase stable compositions can be prepared containing the reinforcing diols by carrying out the partial reaction of the components using the method of this invention as described above. The results of experiments which demonstrate this invention are given Tables 4, 5, 6 and 7. Example 1 - Effect of Melamme Resm and Reinforcing Agent (Diol) Type Table 4 presents results on formulations containing two low molecular weight, branched, reinforcing diols with two butylated melamme resms formulations contammg 40 pbw of Polymer A. Table 4 Composition, pbw 4-1 4-2 4-3 4-4 Polymer A 40 40 40 40 CYMEL 1156 40 40 CYMEL 1141 40 40 CYCAT 600 0.4 0.4 0 0 VM&P naphtha 67 67 67 67 Cook Time, hr 2 2 2 2 Cook Temp., °C 100 100 100 100 Appearance of Resm Phase stable? yes yes yes yes Clarity clear clear clear clear Viscosity @ 25°C, cps 125 230 170 205 Properties on QD412 Thickness, mil 1.3 1.0 1.0 0.9 Pencil Hardness HB 3B H H MEK Rubs >100 22 100 >100 Crosshatch Adhesion 0 0 1 0 Table 4 (continued) General Appearance Clarity clear clear clear clear Gloss high high high high Adhesion to Steel poor poor good poor Mar Resistance good good good good Properties on ETA-3081 Crosshatch Adhesion 5 The results show that both TMPD di and BEPD did can be cooked into resms based on Polymer A using either CYMEL 1156 or CYMEL 1141 to give phase stable compositions. Clear resms could be made with CYMEL 1156 using 0.4 pbw of CYCAT 600 catalyst. Since the acid group on CYMEL 1141 can catalyze the reactions, no CYCAT 600 was needed m the cooks with CYMEL 1141 to achieve phase stable blends. All four of the compositions have much better mar resistance than the Comparative Example. Formulations 4-1 and 4-2 in Table 4 have very poor adhesion to steel and can be rubbed off the steel readily with mild finger pressure. Formulations 4-3 and 4-4, conta mg the acid functional melamme resm, have much better adhesion m this qualitative test but still have low adhesion to steel in the Crosshatch adhesion test. All four formulations, however, have excellent adhesion to TPO which is generally considered to be a difficult substrate to adhere to. Example 2 - Effect of Concentration of Polymer A The results m Table 5 show the effect of the concentration of the hydroxy terminated diene polymer in formulations contammg TMPD diol with two butylated melamme resms. Table 5 Composition, pbw 5-1 5-2 5_-3 5-4 5-5 5-6 Polymer A 40 40 30 30 20 20 TMPD diol 20 20 20 20 30 30 CYMEL 1156 40 - 50 - 50 - CYMEL 1141 - 40 - 50 - 50 CYCAT 600 0.4 0 0.4 0 0.4 0 VM&P naphtha 67 67 67 67 67 67 Cook Time, hr 2 2 2 2 2 2 Cook Temp. , °C 100 100 100 100 100 100 Appearance of Resin Phase stable? yes yes yes yes yes yes Clarity clear clear clear clear clear clear Viscosity @ 25°C, cps 125 170 75 150 40 60 Properties on QD412 Thickness, mil 1.3 1.0 1.1 1.2 1.2 0.9 Pencil Hardness HB H B H H H MEK Rubs >100 100 >100 >100 >100 >100 Crosshatch Adhesion 0 1 0 0 0 0 General Appearance Clarity clear clear clear clear clear sl. haze Gloss high high high high high good Adhesion to Steel poor good poor good poor fair Mar Resistance good good excel excel excel excel Properties on ETA-3081 Crosshatch Adhesion 5 nd The results in Table 5 show that excellent resms can be obtained at concentrations of Polymer A of only 20 pbw. Again it was found that 0.4 pbw of CYCAT 600 was needed in the formulations containing CYMEL 1156 to achieve phase stable resins but no CYCAT 600 was needed in the formulations containing CYMEL 1141. All three of the coatings containing CYMEL 1156 had poor adhesion to steel while those containing CYMEL 1141 adhere somewhat better to steel. Formulations 5-1 through 5-5 had excellent adhesion to TPO. Adhesion to TPO was not determined (nd) on Formulation 5-6 but it too is expected to show excellent adhesion to TPO. Example 3 - Effect of Type of Hydroxy Terminated Polydiene Polymer The results in Table 6 show the effect of the type of hydroxy terminated diene polymer used in the composition containing TMPD diol and CYMEL 1141. Table 6 Composition, pbw 6-1 6-2 6-3 6-4 Polymer A 40 - - — Polymer B - 40 - - Polymer C - - 40 - Polymer D - - - 40 TMPD diol 20 20 20 20 CYMEL 1141 40 40 40 40 VM&P naphtha 67 67 67 67 Cook Time, hr 2 2 2 2 Cook Temp., °C 100 100 100 100 Appearance of Resin Phase stable? yes yes yes yes Clarity clear clear clear opaque Viscosity @ 25°C, cps 170 95 45 paste Properties on QD412 Thickness, mil 1.0 1.1 1.1 — Pencil Hardness H 4H H — MEK Rubs 100 >100 >100 -- Crosshatch Adhesion 1 5 4 -- General Appearance Clarity clear clear clear -- Gloss high high high — Adhesion to Steel good excel excel -- Mar Resistance good excel excel -- Properties on ETA-3081 Crosshatch Adhesion 5 3 3 — All four formulations were cooked for 2 hours at 100°C without addition of CYCAT 600 catalyst because CYMEL 1141 was used in all formulations. As is the case with nearly all the resms prepared in this work, all four resms were clear when hot after cooking was complete. Formulations 6-1, 6-2 and 6-3 remained clear when cooled to room temperature. However, Formulation 6-4 became an opaque, easily stirred paste when cooled to room temperature. Thus, practical applications Formulation 6-4 would have to be coated onto a substrate while it was still hot. Since equipment to do this was not available, Formulation 6-4 was not coated and tested. However, its properties would be expected to be similar to those of Formulation 6-1 based on Polymer A. Results on Formulations 6-1, 6-2, and 6-3 show that, although the compositions with Polymers B and C did not adhere to TPO as well as the composition with Polymer A, all three of Polymers A, B, and C are suitable for use in this invention. Although more sophisticated equipment may be needed to coat resms based on Polymer D, it is expected that Polymer D would also be suitable for use in this invention. Example 4 - Effect of Styrene Content n the Hydroxy Terminated Diene Polymer The results m Table 7 compare compositions made with hydroxy terminated polydiene polymers with varying styrene content with TMPD diol and the methylated melamme resm, CYMEL 303. Table 7 Composition, pbw 7-1 7-2 7-3 Polymer A 40 - - Polymer E - 40 - Polymer F - - 40 TMPD did 20 20 20 CYMEL 303 40 40 40 CYCAT 600 1 1 1 VM&P naphtha 67 67 67 Cook Time, hr 3 3 3 Cook Temp. , @C 100 100 100 Appearance of Resm Phase stable? no yes yes Clarity v. Hazy clear clear Viscosity @ 25°C, cps nd 540 1300 Table 7 (continued) Properties on QD412 Thickness, mil 1.2 1.1 Pencil Hardness 4B 3B MEK Rubs >100 15 Crosshatch Adhesion 0 0 General Appearance Clarity clear clear Gloss high high Adhesion to Steel poor poor Mar Resistance excel excel Properties on ETA-3081 Crosshatch Adhesion — 5 2 The results for Formulation 7-1 show that it was difficult to prepare this resm. Even under these fairly severe cooking conditions, the resm was hazy and phase separated upon standmg at room temperature. It is felt that a phase stable composition could be made with Formulation 7-1 with further work to optimize catalyst concentration and cooking conditions. The reason for this difficulty in preparing Formulation 7-1 is the limited compatibility of Polymer A with CYMEL 303. Results on Formulations 7-2 and 7-3 show that Polymers E and F gave much better resms m this formulation than did Polymer A. This shows the beneficial effect of mcludmg styrene m the did in improving compatibility with the melamme resm. In this formulation, neither resm gave good adhesion to steel but both adhered fairly well to the TPO. Example 5 - Adhesion of Various Coating Compositions to Primed Steel A selection of coating compositions based on dihydroxy functional polydiene polymers was tested on steel panels which were primed with the cathodic electrodeposition (CED) epoxy primer specified for use on Ford cars. The resms were also tested on unprimed steel. The compositions of the resms are given m Table 8. All of the resms were prepared by cooking them in a resm kettle for 2 hours at 100°C at 60%w solids in Shell VM&P Naphtha solvent. All the resms were clear, nearly colorless, fairly low viscosity liquids. They were applied to the substrates with a #52 wire rod and were cured by baking 30 mmutes at 121°C. Properties are shown in the Table 8. Table 8 Adhesion of Various Basecoats to Steelf Composition, pbw 8-1 8-2 8-3 8-4 8-5 8^ Polymer A 40 30 30 30 Polymer F (43% S) 40 Polymer E (26% S) 40 TMPD Diol 20 20 20 20 H HBBPPAA ee 20 BPA 20 CYMEL 1156 40 50 50 50 CYMEL 1141 40 40 CYCAT 600 1 1 1 1 1 1 V VMM&&PP NNaapphhtthhaa 67 67 67 67 67 67 Cook Time, hr 2 2 2 2 2 2 Cook Temp, C 100 100 100 100 100 100 Properties on Unprimed Steel 13 Thickness, mil 1.3 0.9 1.1 1.2 Pencil Hardness HB H 4H 4H Rocker Hardness 12 Crosshatch Adhesion 0 0 5 5 Properties on CED Primed Steel c Thickness, mil 2.0 2.1 1.9 1.9 2.0 2.1 Pencil Hardness H H H H 4H 3H Rocker Hardness 5 11 15 10 6 6 Crosshatch Adhesion 5 5 5 5 5 5 a Resms were cooked for 2 hours at 100°C with 0.4 pbw CYCAT 600 m a resm kettle. CYCAT level was raised to 1 pbw prior to casting films. Coatmgs were applied onto the substrates with #52 wire rod. They were cured by baking 30 mmutes at 121°C. k Unprimed steel substrate was QD412 panels from Q- Panel Corp. c CED primed steel was APR 16900 (Ford spec) from ACT. d pbw = parts by weight e Hydrogenated Bisphenol A The results of the Crosshatch adhesion test show that the coating compositions based on the two styrene- containing diols, Polymers E and F give good Crosshatch adhesion to unprimed steel since the acid functional melamine resin, CYMEL 1141, was used in these formulations. The results in Table 8 also show that all of the coating compositions gave excellent Crosshatch adhesion to the CED epoxy primed steel. Thus, any of these coating compositions would be a candidate for use in coatings over this epoxy primer. It is likely that the epoxy primer coating has residual functional groups which can react with the melamine resin in the coating composition giving excellent bonding between the primer and the coating composition. Example 6 - Basecoat/Clearcoat Combinations A system for painting a car would consist of at least three layers (primer/ basecoat/clearcoat) or four layers (primer/surfacer/basecoat/clearcoat) . Table 9 presents prototype formulations for a basecoat and three clearcoats mtended to demonstrate the suitability of resins based on Polymer A for use in automotive coatings Table 9 Basecoat/Clearcoat Combinations Coating Composition, pbw White Cooked Polyester Acrylic Basecoat 9-1 Clearcoat 9-2 Clearcoat 9-3 Clearcoat 9-4 5 Polymer A 40 30 DESMOPHEN 670A-80 87.5 DESMOPHEN 365 607 TMPD Diol 20 BEPD Diol 20 10 CYMEL 1156 40 50 CYMEL 303 30 DESMODUR BL-31 5 370 CYCAT 600 1 1 1 DABCO T-12 0.73 15 IRGANOX 1076 0.5 0.5 0.5 3.6 TINUVIN 328 1 2 2 14.6 TINUVIN 123 2 2 1 7.3 VM&P Naphtha HT 67 67 Xylene 28 253 20 TiPure R-706 100 The resms in Basecoat 9-1 and Clearcoat 9-2 were cooked for 2 hours at 100°C with 0.4 pbw of CYCAT u00. Before casting films, the catalyst level was mcreased to 1 pbw and the stabilizers (IRGANOX 1076, TINUVIN 328, and TINUVIN 123, supplied by Ciba Geigy) were added. Basecoat 9-1 used T1O2 at 50%w on a solids basis as the pigment. Clearcoat 9-3 was a polyester polyol cured with a melamine resm and Clearcoat 9-4 was an acrylic polyol cured with a blocked isocyanate. All coatmgs were thinned as required to achieve a sprayable viscosity usmg xylene/butanol (1/1) . The white Basecoat 9-1 was applied to three substrates; DEXFLEX 880 (purchased from Standard Plaque, Inc.) is a TPO which is typical of the type used m automobile bumpers, epoxy primed steel (APR 16900 purchased from Advanced Coating Technologies, Inc.) which is the CED epoxy primer specified for use by Ford, and primer/surfacer coated steel (APR 29401 purchased from Advanced Coating Technologies, Inc.) which is specified for use by Ford. After about a 5 mmute flash, Clearcoat 9-2 was applied over the coated epoxy primed steel, and the coatmgs were cured by baking 30 m utes at 121°C. The white Basecoat 9-1 on TPO was cured by baking 30 m utes at 121°C and Clearcoat 9-3 was applied and cured by baking 30 minutes at 121°C. The white Basecoat 9-1 on the primer/surfacer coated steel was cured by baking 30 m utes at 121°C. Clearcoat 9-4 was applied over the coated primer/surfacer panels and the clearcoat was cured by baking for 20 mmutes at 150°C. It was found that all three basecoat/clearcoat systems gave excellent adhesion in the Crosshatch adhesion test. These results demonstrate that basecoat compositions based on the dihydroxy polydiene polymers are suitable candidates for use m coatings not only for TPO but also for the primed metal parts of the car as well. They have excellent Crosshatch adhesion to TPO and to the primed metal substrates which are typically used by Ford. They also have excellent intercoat adhesion with polyester / melamine and acrylic / urethane clearcoats as well as to clearcoats made from another dihydroxy polydiene resin.

Claims: C L A I M S 1. A crosslinkable phase-stable composition comprising from 10 to 80 percent by weight of a hydroxy functional polydiene polymer having a functionality of at least 1.3, from 8 to 60 percent by weight of an ammo resm crosslinking agent, and from 2 to 40 percent by weight of a reinforcing agent. 2. The composition of claim 1 wherein the polydiene polymer has a functionality of at least 1.9. 3. The composition of claim 1 or 2 wherein the polydiene polymer is a polybutadiene did. . The composition of claim 3 wherein the polybutadiene diol is a hydrogenated polybutadiene did havmg no less than 30% by weight 1,2 butadiene addition. 5. The composition of claim 3 wherein the polybutadiene did is an unhydrogenated polybutadiene did, having less than 10% by weight 1,2 butadiene addition. 6. The composition of claim 1 or 2 wherein the polydiene polymer is an unhydrogenated or hydrogenated polyisoprene did having greater than 80^ by weight 1,4 isoprene addition. 7. The composition of claim 6 wherein the polyisoprene did has greater than 90% by weight 1,4 isoprene addition. 8. The composition of any one of the preceeding claims wherein the reinforcing agent has at least two functional groups capable of reacting with the cross- linking agent. 9. The composition of claim 8, wherein the reinforcing agent is an aliphatic did havmg 5 to 40 carbon atoms. 10. The composition of claim 1 wherein the polydiene polymer has the structural formula: HO-A-OH or (HO-A) n -X wherein A is a homopolymer of a conjugated diolefm monomer, a copolymer of two or more conjugated diolefm monomers, or a copolymer of one or more conjugated diolefm monomers with a monoalkenyl aromatic hydrocarbon monomer, where n>l, and where X is the residue of a couplmg agent. 11. The composition of claim 1 wherein the polydiene polymer has the structural formula: (II) HO-A-S z -B-OH or (HO-A-S z -B) n -X or HO-S z -A-B-S y -OH or (H0-S z -A-B) n -X wherein A and B are polymer blocks which may be homopolymer blocks of conjugated diolef monomers, copolymer blocks of conjugated diolefm monomers, or copolymer blocks of diolef monomers and monoalkenyl aromatic hydrocarbon monomers, where S is a vmyl aromatic polymer block, where y and z are 0 or 1 and at least one of y or 2 is 1, where n is greater than or equal to 2, and where X is the residue of a couplmg agent. 12. A coating comprising the composition of any one of claims 1-11 and either a filler or a stabilizer or both, and optionally a pigment. 13. An adhesive or sealant comprising the composition of any one of claims 1-11 and a tackifying resm. 14. A process for preparing a crosslinkable phase- stable composition comprising mixing from 10 to 80 percent by weight of a hydroxy functional polydiene polymer havmg a functionality of at least 1.3, from 8 to 60 percent by weight of an amino resm crosslinking agent and from 2 to 40 percent by weight of a reinforcing agent, and partially reacting the mixture, optionally m the presence of a crosslinking catalyst, such that a phase-stable composition is obtamed. 15. A process for making a compatible crosslinked composition which comprises the steps of: (a) mixing together from 10 to 80 percent by weight of a hydroxy functional polydiene polymer having a functionality of at least 1.3, from 8 to 60 percent by weight of an ammo resm crosslinking agent, and from 2 to 40 percent by weight of a reinforcing agent, (b) partially reacting the mixture optionally in the presence of crosslinking catalyst, such that a phase-stable composition is obtamed, (c) applymg the phase-stable composition to a substrate, and (d) crosslinking the applied composition, optionally m the presence of additional crosslinking catalyst. 16. The process of claim 15 wherein a crosslinking catalyst is used in a total amount of from 0.05 to 4 % by weight and less than one half is used m step (b) . 17. A method for painting a substrate which comprises: (a) priming the substrate with a primer selected from the group consisting of epoxy resm primers and polyester resm primers, (b) applymg to the primed substrate a crosslinkable basecoat composition comprising from 10 to 80 percent by weight of a hydroxy functional polydiene polymer having a functionality of at least 1.3, from 8 to 60 percent by weight of an ammo resm crosslinking agent, and from 2 to 40 percent by weight of a reinforcing agent, and crosslinking the applied basecoat composition, and (c) applymg over the basecoat a clearcoat selected from the group consisting of dihydroxy polydiene- based clearcoats, polyester clearcoats, and acrylic clearcoats . 18. Articles which have been coated with a coating as claimed in claim 12.

Inventors: ST CLAIR DAVID JOHN, ST. CLAIR, DAVID, JOHN
Applicants: SHELL INT RESEARCH, SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1996
Main classification: C08L19
IPC codes: C08L15, C08L19, C08L61, C09D115, C09D161, C09J115, C09J161