MXPA97008923A - Coating compositions containing a functionality of sil - Google Patents

Abstract

The present invention relates to a sprayable coating composition, which contains at least one soluble film-forming silicon-containing compound, which has, on average, more than one functionalized silicon group, a volatile organic carrier , a component of polymeric microparticles, and a catalyst, to a substrate coated with the composition, to a process for coating the substrate to provide a protective finish, the substrate protected with the finish, to certain oligomeric compounds and to a process for the same.

Description

COATING COMPOSITIONS CONTAINING A SILAN FUNCTIONALITY BACKGROUND OF THE INVENTION Field of the Invention This invention is directed to a coating composition useful for providing a finish on a variety of substrates. In particular, this invention is directed to an organosilane composition useful for the finishing of automobiles and trucks.

State of the Art It is well known that consumers prefer cars and trucks with an exterior finish that have an attractive aesthetic appearance that include high brightness and excellent DOl (image distinction). Although finishes have been obtained even more aesthetically attractive, the deterioration of the finish over the course of time, as a result of which the exterior finish of a car or truck loses its luster or other aspects of its aesthetic appearance, is the most appreciable of all . An observed cause Rff.026042 Increasingly this deterioration is the attack of the finish caused by the exposure to the chemical attack of the environment. The chemical agents that can cause the attack of a finish include acid rain and chemical smoke. In order to protect and preserve the aesthetic qualities of the finish on a vehicle, it is generally known to provide a clear (non-pigmented) top coat on a colored (pigmented) base coat, so that the base coat remains unaffected even during prolonged exposure to the coat. environment or environmental conditions. It is also generally known that alkoxysilane polymers, due to the strong binding of siloxane when cured, exhibit excellent chemical resistance. They are exemplary of the prior literature describing the silane polymers for coating, U.S. Pat. Nos. 5,244,696 and 5,223,495. There is a continuing need for a clear, commercially practical coating finish that has an excellent appearance, including high brightness and DOl, that is also resistant to acid attack caused by chemical attack. To be commercially practical, such a clear coating should not be prone to breakage. It is also important that the finish has good resistance to scratching and damage and that it is derived from compositions that are characterized by low levels of volatile organic chemicals such as solvents and the like. Finally, such a clear coating must be capable of application over a variety of base coatings and must have excellent adhesion.

BRIEF DESCRIPTION OF THE INVENTION This invention relates to a liquid, curable, sprayable coating composition, comprising: i) at least one compound containing the silyl group, having at least two functional groups of the formula, -SiRnX3-n / a groups that are attached or attached to the compound by a silicon-carbon bond where: n is 0, 1 or 2; R is oxysilyl or unsubstituted hydrocarbyl or hydrocarbyl substituted with at least one substituent containing an element selected from the group of O, N, S, P, Si; and X is a hydrolyzable portion selected from the group of alkoxy with Ci to C, aryloxy with C6 to C20, acyloxy with Ci to Ce, hydrogen, halogen, amine, amide, imidazole, oxazolidinone, urea, carbamate, and hydroxylamine; the compound having a number average molecular weight between about 300 and 3000 and a volatility such that not more than about 30 parts by weight of the compound containing the silyl group per 100 parts of the compound are evaporated during curing; ii) a second component containing the reactive silyl group for film formation, optional, which, together with i, yields a functionality of -SiRnX3-n average of more than one, 20 iii) microparticles of the polymer, substantially insoluble in the liquid coating composition, in an amount of 5 to 100 parts per 100 parts by weight of all the other components forming the film; and iv) from 0 to about 100 parts by weight of a liquid organic carrier, based on the weight of i, ii, and iii); and v) sufficient catalyst to effect crosslinking. The term "compound" as used herein, excludes all polymers of random chain lengths such as those obtained in the polymerization of vinyl initiated by free radicals. The term "component" in the article (ii) includes the polymers, oligomers, compounds and mixtures thereof. The average number of silyl groups in the composition, when (i) e (ii) both are present, it will always be greater than one. The invention also includes a process for coating a substrate with the above coating composition. The invention further includes certain oligomeric compounds (i), (see Examples A and B); a process for making the oligomer, (see Examples C and D); and a substrate having adhered thereto a coating derived from the composition described. The composition of the invention is especially useful for the formation of a clear topcoat over a pigmented basecoat. Such a clear top coat can be applied over a variety of colored coatings, such as colored coatings based on an organic solvent or colored powder coatings.

DETAILS OF THE INVENTION The Compound Containing Silyl (i) The compound (i) is selected from at least one of the following groups 1 to 12. 1. ) Silanes with amino function that have been reacted with isocyanate.

[A] 25 * - 100 * 0 Catalyst or UV wherein: R is a portion independently selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene, and a low molecular weight polymer; R1 is independently alkyl with C? -C? 6; R2 is independently H or alkyl with C? -C? 2; R3 is a portion independently selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene, and a low molecular weight polymer; n is an integer from 2 to 12; and m is 1 to 16. The representative low molecular weight polymer values for R and R3 are polyester, polyurethane, polyether, polyamine and the like. Preferred for R1 are the alkyls of Ci to C4, more preferably Ci to C2. The alkyl substituents can be linear or cyclic and the amine function can be primary or secondary. By "low molecular weight" is meant a number no greater than about 3000 (numerical average). When R and / or R3 are the low molecular weight polymers, m = 1. Hereinafter, in groups 2 to 10, R, R1, R2, R3, n and m are as defined above, except where indicated. The following reactions do not need to be carried out until they are completed as long as the product contains at least two silyl groups. 2. ) The silane with amino function is reacted with anhydride.

Both R groups can be taken together and when taken together a cycloalkyl ring structure with C3-C2 is formed. 3. ) The silane with amino function that has been reacted with an epoxide.

R4 is independently selected from H and alkyl with C? -C? 2; or R4 can be taken together to form a cycloalkyl with C3-C12. 4. ) The silane with amino function that has been reacted with acid.

. ) The silane with epoxy function that has been reacted with amine.

P] 25 * -50 * C With catalyst without Catalyst where R2 is H, then n is 1-12. 6. ) The silane with epoxy function that has been reacted with an anhydride. where R can be taken together as defined in group 2 above. The acid group can be further reacted at 100 ° -150 ° C with the catalyst to have the disubstitution in each anhydride, in which case n is 1 to 12. 7. ) The silane with epoxy function that has been reacted with an acid. 8 ) The reaction of [A] + n [B]. n is 1 or 2; n is 2 when R2 is H. 9. ) Isocyanate-containing alkoxysilanes that have been reacted with a polyol.

R-foH], * n NCO-ER3j-¡H-OR * ) The reaction of [A] + n [C], n is 1 or 2; n is 2 when R2 is H.

With respect to the Compounds of Group 9, one mole of 1, 4-cyclohexanedimethanol can be reacted with 2 moles of isocyanatopropyltrimethoxysilane to give a silane compound having two trimethoxysilyl groups per molecule. Alternatively, one mole of pentaerythritol can be reacted with 3 moles of methylhexahydrophthalic anhydride having 3 carboxylic acid groups and 1 hydroxyl group. The carboxylic acid compound can then be reacted with 3 moles of the glycidyl ester of a branched, aliphatic carboxylic acid of 10 carbon atoms to give a polyol compound having 4 hydroxyl groups. The polyol compound can then be reacted with 3 moles of isocyanatopropyltrimethoxysilane to give a silane compound having 1 hydroxyl group and 3 trimethoxysilyl groups. 11. Another method for making the silane compounds is to react a compound having two or more carbon-carbon double bonds with trichlorosilane in the presence of a catalyst and then treat the resulting adduct with an alcohol. Useful compounds having two or more C-C double bonds have the formula: A- [BS] R * nR 3j where: A is an aliphatic, cycloaliphatic or benzene radical, with and free valences, each of such free valences is going to be a carbon atom different from the carbocyclic ring formed by A; each B is independently a covalent bond, an alkylene group, or a substituted alkylene group having either one or more ether oxygens (as in -OR3-) and / or the ester groups (as in -C (0) OR3 - u -0 (0) CR3-) wherein the ether oxygens are between the alkylene segments and wherein the ester groups are between A and R3 or between an alkylene segment and R3, wherein the alkylene group and the substituted alkylene group, which is comprised of the alkylene segments, are independently defined as those having 1 to 20 carbon atoms, preferably 1 to 10, and more preferably 1 to 5 carbon atoms; and is 2, 3, 4, 5 or 6; each R 1 attached to the silicon atom is independently alkyl containing 1 to 20 carbon atoms or phenyl; each R2 attached or attached to the silicon atom is independently halogen, alkoxy containing 1 to 20 carbon atoms, phenoxy, acyloxy containing 1 to 20 carbon atoms, or oxysilyl; each R3 is independently an alkylene group containing 2 to 20 carbon atoms; and each n is independently 0, 1 or 2.

For example, one mole of 5-vinyl-2-norbornene can be reacted with 2 moles of trichlorosilane and the resulting compound can be reacted with 6 moles of methanol to replace the chlorine atoms with methoxy groups. The resulting silane compound will have two trimethoxysilyl groups. Alternatively, one mole of limonene can be reacted with 2 moles of trichlorosilane and the resulting compound can be reacted with 6 moles of methanol to replace the chlorine atoms with methoxy groups. The resulting silane compound will have two trimethoxysilyl groups. Alternatively, one mole of trivinylcyclohexane can be reacted with 3 moles of trichlorosilane and the resulting compound can be reacted with 9 moles of methanol to replace the chlorine atoms with methoxy groups. The resulting silane compound will have three trimethoxysilyl groups. Other useful compounds for this hydrosilylation reaction include the terpenes similar to myrcene, ocimene, allozymene, dipentene, entadiene, fellandrene, terpinene, terpinolene, isoterpinolene, pinenos, and also 4-vinyl-l-cyclohexene, dicyclopentadiene, cyclododecatriene, norbornadiene, and its isomers. 12. Another contemplated method for making the compound (i) is to react an unsaturated alcohol with an acid or anhydride to produce an unsaturated ester. This ester is hydrosilylated to form an adduct which is then treated with alcohol. Alternatively, the process can be initiated with an unsaturated acid or ester transesterified with an alcohol, the polyfunctionality can be supplied by one or more of the acid, anhydride, ester, or alcohol reagents. It is contemplated that the definition of compound (i) employed herein also include oligomers formed from precursors B or C, independently, through their organofunctionality (epoxide or isocyanate).

Component (ii) Containing the Optional Silyl Group The coating composition of this invention may include a number of ingredients to improve the preparation of the composition as well as to improve the final properties of the coating composition and the finish. For example, it is often desirable to include about 20 to 90%, preferably 20 to 60%, by weight of the composition, of a reactive silane polymer that forms a film.

Such a polymer typically has a number average molecular weight of about 500 to 10,000. The silane polymer is the product of the polymerization of about 30-95%, preferably 40-60%, by weight of the monomers containing a compound other than the ethylenically unsaturated silane and about 5-70%, preferably 40-60%, by weight of the monomers containing the ethylenically unsaturated silane, based on the weight of the organosilane polymer. The monomers containing the compound other than the ethylenically unsaturated silane, suitable, are the alkyl acrylates, alkyl methacrylates and mixtures thereof, wherein the alkyl groups have 1-12 carbon atoms, preferably 3-8 carbon atoms. The film-forming component of the coating composition is referred to as the "binder" and is dissolved, emulsified or otherwise dispersed in an organic solvent or liquid carrier. The binder generally includes all components that contribute to the solid organic portion of the cured composition. In general, pigments, and chemical additives such as stabilizers are not considered part of the binder. The non-binder solids other than the pigments typically do not exceed about 5% by weight of the composition. The term "binder" includes the reactive silane compound, the organosilane polymer, the dispersed polymer, and all other optional film-forming components. The coating composition contains about 50-100% by weight of the binder and about 0-50% by weight of the organic solvent carrier. Suitable alkyl methacrylate monomers used to form the organosilane polymer are methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, methacrylate nonyl, lauryl methacrylate and the like. Suitable alkyl acrylate monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, nonyl acrylate, lauryl acrylate and the like. Cycloaliphatic methacrylates and acrylates can also be used, such as trimethylcyclohexyl methacrylate, trimethylcyclohexyl acrylate, isobutylcyclohexyl methacrylate, t-butyl cyclohexyl acrylate, and t-butyl cyclohexyl methacrylate. Also, aryl acrylate and aryl methacrylates, such as benzyl acrylate, can be used. and the benzyl methacrylate. Mixtures of two or more of the monomers mentioned above are also suitable. In addition to the alkyl acrylates and methacrylates, other monomers containing compounds other than the polymerizable silanes, up to about 50% by weight of the polymer, can be used in the acrylosilane polymer for the purpose of achieving the desired properties such as hardness; appearance; resistance to damage, acid attack and scratches, and the like. Exemplary of such other monomers are styrene, methyl styrene, acrylamide, acrylonitrile, methacrylonitrile, and the like. A silane-containing monomer useful in the formation of the acrylosilane polymer is an alkoxysilane having the following structural formula: wherein R is either CH3, CH3CH2, CH30, or CH3CH20; R1 and R2 are CH3 or CH3CH2; and R3 is either H, CH3, or CH3CH2; and n is 0 or a positive integer from 1 to 10. Preferably, R is CH30 or CH3CH20 and n is 1.

Typical examples of such alkoxysilanes are acryloxy alkyl silanes, such as gamma-acryloxypropyltrimethoxysilane and methacryloxy alkyl silanes, such as gamma-methacryloxypropyltrimethoxysilane, and gamma-methacryloxypropyltris (2-methoxyethoxy) silane. Other suitable alkoxysilane monomers have the following structural formula: wherein R, R1 and R2 are as described above and n is 0 or a positive integer from 1 to 10. Examples of such alkoxysilanes are vinylalkoxysilanes, such as vinyltrimethoxysilane, vinyltriethoxysilane and vinyltris (2-methoxyethoxy) silane. Other examples of such alkoxysilanes are allylkoxysilanes such as allytrimethoxysilane and allyltriethoxysilane. Other suitable silane-containing monomers are acyloxysilanes, including acryloxysilane, methacryloxysilane and vinylacetoxysilanes, such as vinylmethyldiacetoxysilane, acryloxypropyltriaketoxysilane, and ethacryloxypropyltriaketoxysilane. Of course, mixtures of the silane-containing monomers are also suitable. The functional silane macromonomers can also be used in the formation of the silane polymer. These macromonomers are the product of the reaction of a silane-containing compound, having a reactive group such as epoxide or isocyanate, with a monomer containing a compound other than the ethylenically unsaturated silane having a reactive group, typically a hydroxyl or an epoxide group, which is coreactive with the silane monomer. An example of a useful macromonomer is the product of the reaction of an ethylenically unsaturated monomer with hydroxy function such as a hydroxyalkyl acrylate or methacrylate having 1-8 carbon atoms in the alkyl group and an isocyanatoalkyl alkoxysilane such as isocyanatopropyltriethoxysilane. Typical of such functional silane macromonomers are those having the following structural formula: wherein R, R1, and R2 are as described above; R4 is H or CH3, Rs is an alkylene group having 1-8 carbon atoms and n is a positive integer from 1-8. In addition to the organosilane polymer, other solution crosslinking polymers and / or film formers can be included in the composition of the present application. Examples are acrylics, cellulosics, aminoplasts, urethanes, polyesters, epoxides or mixtures thereof. An optional, preferred film-forming polymer is a polyol, for example, a polymer in acrylic polyol solution of polymerized monomers. Such monomers can include any of the above-mentioned acrylates and / or alkyl methacrylates and, in addition, the hydroxy alkyl acrylates or methacrylates. The polyol polymer preferably has a hydroxyl number of about 50-200 and a weight average molecular weight of about 1,000-200,000 and preferably about 1,000-20,000. To provide the functionality of hydroxy in the polyol, up to about 90% by weight, preferably 20 to 50%, of the polyol, comprises the polymerized functional hydroxy monomers. Suitable monomers include hydroxyalkyl acrylates and methacrylates, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyisopropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyisopropyl methacrylate, hydroxybutyl methacrylate, and the like, and mixtures thereof. thereof. Other polymerizable monomers may be included in the polyol polymer, in an amount of up to about 50% by weight. Such polymerizable monomers include, for example, styrene, methylstyrene, acrylamide, acrylonitrile, methacrylonitrile, methacrylamide, methylol methacrylamide, methylol acrylamide and the like, and mixtures thereof. In addition to the silane-forming polymer (ii) described hitherto, the reactive component (ii) can also be a monofunctional silane or an oligomer containing a silane, which is outside the definition of the compound (i).

The Microparticles of the Polymer (III) This component of the coating composition of the invention is a polymer dispersed in an organic (substantially non-aqueous) medium. This component has been described until now as a non-aqueous dispersion polymer (NAD), a microgel, a non-aqueous latex, or a polymer colloid. In general, the dispersed polymer is stabilized by steric stabilization effected by the attachment or fixation of a solvated polymeric or oligomeric layer at the interface of the particle's medium. In the dispersed polymers of the present composition, the dispersed phase or particle, covered by a steric barrier, will be referred to as the "macromolecular polymer" or "core". The stabilizer that forms the steric barrier, attached or fixed to this core, will be referred to as the "macromonomer chains" or "arms". The dispersed polymers solve the problem of breaking and are used in an amount ranging from about 10 to 60% by weight, preferably about 15 to 40%, more preferably about 20 to 30%, of the total binder in the composition. The ratio or proportion of the silane compound to the dispersed polymer component of the composition suitably ranges from 5: 1 to 1: 2, preferably 4: 1 to 1: 1. To accommodate these relatively high concentrations of the dispersed polymers, it is desirable to have reactive groups on the arms of the dispersed polymer, such reactive groups make the polymers compatible with the continuous phase of the system. The dispersed polymer contains approximately -90%, preferably 50-80%, by weight, based on the weight of the dispersed polymer, of a high molecular weight core having a weight average molecular weight of about 50,000-500,000. The preferred average particle size is 0.05 to 0.5 microns. The arms, attached or fixed to the core, make up about 10-90%, preferably 20-59%, by weight of the dispersed polymer, and have a weight average molecular weight of about 1,000-30,000, preferably 1,000 to 10,000. The macromolecular nucleus of the dispersed polymer typically comprises the polymerized ethylenically unsaturated monomers. Suitable monomers include styrene, acrylate or alkyl methacrylate, ethylenically unsaturated monocarboxylic acid, and / or silane-containing monomers. Monomers such as methyl methacrylate contribute to a high Tg (vitreous transition temperature) while monomers such as butyl acrylate or 2-ethylhexyl acrylate contribute to a low Tg. Other optional monomers are acrylates, hydroxyalkyl methacrylates or acrylonitrile. Groups such as hydroxy in the core can react with the silane groups in the silane compound to produce an additional bond with the film matrix. If a crosslinked core is desired, allyl diacrylate or allyl methacrylate can be used. Alternatively, an epoxy functional monomer such as glycidyl acrylate or methacrylate can be used to react with the functional comonomers of carboxylic acid and cross-link the core; or the core may contain the silane functionality. A preferred feature of the dispersed polymers is the presence of the macromonomer arms which contain hydroxy groups adapted to react with the organosilane compound. It is not known with certainty that the portion of these hydroxy functional groups reacts with the organosilane compound because of the numerous and complicated sets of reactions that occur during baking and curing. However, it can be said that a substantial portion of these functionalities in the arms, preferably most of them, react and crosslink with the film former of the composition, which in some cases exclusively consist of an organosilane compound. . The arms of the dispersed polymer must be anchored securely to the macromolecular core. For this reason, the arms are preferably anchored by the covalent bonds. The anchor should be sufficient to hold the arms to the dispersed polymer after they react with the film-forming compound. For this reason, the conventional method of anchoring by the adsorption of the skeleton portion of a graft polymer may be insufficient. The arms or macromonomers of the dispersed polymer serve to prevent the nucleus from flocculating forming a steric barrier. The arms, typically in contrast to the macromolecular nucleus, are believed capable, at least temporarily, of being dissolved or solvated in the medium or carrier of the organic solvent of the composition. They can be in the extended configuration of the chain with their hydroxy functional groups available for reaction with the silane groups of the compound containing the film-forming silane and the polymer. Such arms comprise about 3 to 30% by weight, preferably 10 to 20%, based on the weight of the macromonomer, of the monomers containing the functionality of ethylenically unsaturated hydroxy, polymerized, and about 70-95% by weight, based on in the weight of the macromonomer, of at least one other ethylenically unsaturated, polymerized monomer, without such crosslinking functionality. Combinations of such hydroxy monomers with other minor amounts of crosslinking functional groups, such as silane or epoxy, on the arms, they are also adequate. The arms of the macromonomer attached or fixed to the core can contain the polymerized monomers of the alkyl methacrylate, alkyl acrylate, each having 1-12 carbon atoms in the alkyl group, as well as the glycidyl acrylate or the glycidyl methacrylate or the ethylenically unsaturated monocarboxylic acid for anchoring and / or crosslinking. Useful, typical hydroxy-containing monomers are hydroxyalkyl acrylates or methacrylates. A preferred composition for a dispersed polymer having a hydroxy functionality comprises a core consisting of about 25% by weight of hydroxyethyl acrylate, about 4% by weight of methacrylic acid, about 46.5% by weight of methyl methacrylate, about 18% by weight. % by weight of methyl acrylate, about 1.5% by weight of glycidyl methacrylate and about 5% of styrene. The macromonomer bound or attached to the core contains 97.3% by weight of the prepolymer and about 2.7% by weight of glycidyl methacrylate, the latter for crosslinking or anchoring. A preferred prepolymer contains about 28% by weight of butyl methacrylate, about 15% by weight of ethyl methacrylate, about 30% by weight of butyl acrylate, about 10% by weight of hydroxyethyl acrylate, about 2% by weight of acrylic acid, and about 15% by weight of styrene.

The dispersed polymer can be produced by the dispersion polymerization of the monomers in an organic solvent in the presence of a steric stabilizer for the particles. The process has been described as one of the polymerization of the monomers in an inert solvent in which the monomers are soluble but the resulting polymer is not soluble, in the presence of a dissolved amphoteric stabilizing agent.

The Carrier (iv) Conventional solvents and diluents can be employed as carriers in the composition of this invention to assist in sprayable, flow, and homogeneous and uniform deposition. Typical carriers include toluene, xylene, butyl acetate, acetone, methyl isobutyl ketone, methyl ethyl ketone, methanol, isopropanol, butanol, hexane, acetone, ethylene glycol monoethyl ether, naphtha VM &PR, mineral spirits, heptane and other aliphatic hydrocarbons , cycloaliphatics, aromatics, esters, ethers, ketones, and the like. They may be used in amounts of 0 to about 440 grams (or a higher amount) per liter of the coating composition. Preferably, they are employed in amounts not exceeding about 340 grams per liter of the composition. Other useful carriers will be readily suggested by those skilled in the art.

The Catalyst (v) Typical catalysts are dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin dioxide, dibutyl tin dioctoate, tin octoate, aluminum titanate, aluminum chelates, zirconium chelate and the like. Tertiary amines and acids (blocked or unblocked) or combinations thereof are also useful for the catalysis of the silane bond. Preferably, these catalysts are used in the amount of about 0.1 to 5.0% by weight of the composition. Other useful catalysts will be readily suggested by a person skilled in the art.

Crosslinking Agents, Stabilizers, Pigments The present coating composition may include an additional crosslinking agent, for example, monomeric or polymeric alkylated melamine formaldehyde resin that is partially or fully alkylated. A preferred crosslinking agent is a methylated and butylated or isobutylated melamine formaldehyde resin having a degree of polymerization of about 1 to 3. In general, this melamine formaldehyde resin contains about 50% butylated groups or isobutylated groups and 50% methylated groups. Such crosslinking agents typically have a number average molecular weight of about 300-600 and a weighted average molecular weight of about 500-1500. Examples of the commercially available resins are "Cymel" 1168, "Cymel" 1161, "Cymel" 1158, "Resi ine" 4514 and "Resimine" 354. Preferably, the crosslinking agent is used in the amount of about 0-35. % by weight, based on the weight of the binder. Other crosslinking agents contemplated are urea formaldehyde, benzoguanamine formaldehyde and blocked polyisocyanates. To improve the resistance to environmental agents of a clear finish produced by the present coating composition, an ultraviolet light stabilizer or a combination of ultraviolet light stabilizers may be added in the amount of about 0.1-5% in Weight based on the weight of the binder. Such stabilizers include ultraviolet light absorbers, selectors, dampers, and hindered amine light stabilizers. Also, an antioxidant can be added in the amount of about 0.1-5% by weight based on the weight of the binder. Typical ultraviolet light stabilizers include benzophenones, triazoles, triazines, benzoates, hindered amines and mixtures thereof. The composition may also include agents for flow control such as Resiflow® S (acrylic terpolymer solution), BYK 320 and 325 (silicone additives); rheology control agents such as microgel and cellulose acetate butyrate, smoking silica; water purifiers or absorbers such as tetrasilicate, trimethyl orthoformate, triethyl orthoformate, and the like. When the present coating composition is used as a base coat, the typical pigments that can be added include the following: metal oxides such as titanium dioxide, zinc oxide, iron oxides of various colors, carbon black, filler pigments such such as talc, china clay, barites, carbonates, silicates and a wide variety of organic colored pigments such as quinacridones, copper phthalocyanines, perylenes, azo pigments, indantrone blue, carbazoles such as carbazole violet, isoindolinones, isoindolones, thioindigo, benzimidazolinones, metallic flake pigments such as aluminum flakes, and the like. The pigments may be introduced into the coating composition by first forming a base for grinding or dispersing the pigment with any of the polymers mentioned above used in the coating composition or with another compatible polymer or dispersant by conventional techniques, such as mixing at high speed. high, grinding with sand, grinding in a ball mill, grinding by crushing or milling with two rollers. The base for grinding is then mixed or combined with the other constituents used in the coating composition.

Application Techniques The coating composition can be applied by conventional techniques such as spraying, electrostatic spraying, submerging, brush painting, flow coating and the like. The preferred techniques are spraying and electrostatic spraying. After application, the composition is typically baked at 100-150 ° C for about 15-30 minutes to form a coating of about 0.000254-0.00762 cm (0.1-3.0 thousandths of an inch) thick. However, curing at room temperature is also effective. When the composition is used as a clear coating, it is applied over the colored coating which can be dried to a tack-free state and cured or preferably dried instantaneously for a short period before the clear coating is applied. It is customary to apply a clear topcoat over a basecoat carrying the solvent, by means of a "wet-humid phase" application, that is, the topcoat is applied to the basecoat without completely drying the basecoat. The coated substrate is then heated for a predetermined period of time to allow simultaneous curing of the clear and base coatings. The application on the base coat carrying the water normally requires some drying period of the base coat before the application of the clear coat. The coating composition of this invention is typically formulated as a single package or package system although systems of two packages or packages are possible as will be apparent to a person skilled in the art. The system of a single package or container has been found to have a prolonged storage duration.

A steel panel of the automobile or other substrate has several layers of coatings. The substrate is typically first coated with a layer of inorganic oxidation-proof iron or zinc phosphate, on which is provided a primer or primer which can be an electrocoated primer or a repair primer. Optionally, a surfactant-priming agent can be applied over the primer coating to provide the best appearance and / or improved adhesion of the base coat to the primer or primer coating. A colored coating or pigmented base coat is then applied over the surfactant-primer. A clear top coat (clear coating) is then applied to the pigmented base coat (colored coat). The colored coating and the clear coating preferably have a thickness of about 0.000254-0.00635 cm (0.1-2.5 mils) and 0.00254-0.00762 cm (1.0-3.0 mils). A composition of this invention, depending on the presence of pigments or other conventional components, can be used as a base coat, a clear coat, or a primer or primer. The composition is useful for coating other substrates as well as such glass fibers reinforced with polyester, injection molded polyurethanes, partially crystalline polyamides and other plastic and metal substrates which will be readily apparent to a person skilled in the art.

EXAMPLES All parts and percentages are by weight unless otherwise indicated. Molecular weights were determined by gel permeation chromatography using a polystyrene standard. All the microparticles used to make the compositions described in the following Examples were made by the procedure of Example 1. The coating compositions in the following Examples were made by combining the mentioned ingredients, in the mixed order, with complete or perfect mixing. The commercially available materials used in the Examples are: A composition of this invention was prepared in a 350 gram batch by combining the following ingredients according to this recipe: Properties Calculated Solids 75. 45 Solids in \ folupen 68.08 Satin of ßalcn 8. 66 Cbptenidb of foliar Qrgánioos (VDC) 2.12 The compound (1) is an adduct formed of 1 mol of cyclohexanedimethanol and 2 mol of 3-isocyanatopropyltrimethoxysilane. It was prepared by charging 260 g of cyclohexanedimethanol and 1 g of a 10% solution of dibutyltin dilaurate in xylene to a vessel. Then, the 3-isocyanatopropyltrimethoxysilane was added dropwise by feeding it at a rate of 15 ml per minute during which the temperature was raised to 90 ° C. Then the reaction was maintained at 90 ° C for 2 hours. The microparticle compound (iii) was formed as follows. First, a dispersing agent was made by copolymerizing the following monomers and then reacting the resulting copolymer with glycidyl methacrylate to place some polymerizable carbon-carbon double bonds on the molecule.

Dispersing Monomers 14. 73% Styrene 27.52% Butyl acrylate 43.88% Butyl acrylate 9.83% Hydroxyethyl acrylate 2.30% Methacrylic acid 1.5% Glycidyl methacrylate (reacted with the previous polymer) Next, a mixture of the monomers was polymerized in the presence of the above dispersant in a hydrocarbon solvent that dissolves the monomers but not the resulting polymer. The ratio was about 36 parts of the dispersant with respect to about 64 parts of the microparticle monomer mixture, which has the composition: Monomers % Styrene 18.0% Methyl Acrylate 36.5% Methyl Methacrylate 25.0% Hydroxyethyl Acrylate 4.0% Methacrylic Acid Monomers (Contd.) 1. 5% Glycidyl methacrylate The resulting microparticle dispersion comprised the microparticles of the polymer in a hydrocarbon diluent and was sterically stabilized against flocculation by the relatively non-polar chains of the dispersing polymer.

Example 2 A composition of this invention was prepared in a 23.5 gram batch by combining the following ingredients according to this formula: Compound (i) was prepared by hydrosilation of the limonene with 2 moles of trichlorosilane at 90 ° C under pressure for 8 hours in the presence of the 2,2'-azobis (2-methylbutanonitrile) initiator to obtain the disubstituted trichlorosilane. Then, after the methanol treatment and the simultaneous removal of the hydrogen chloride, the trichlorosilane is converted to trimethoxysilane. The final product was l-methyl-2-trimethoxysilyl-4- (1-methy1-2-trimethoxysilylethyl) cyclohexane and the isomers.

Microgel A dispersed polymer microgel was prepared by charging the following constituents in a polymerization reactor equipped with a heat source and a reflux condenser. The microgel when used in the following examples, was prepared by this procedure.

Parts in Weight Portion I Mineral Alcohols (eg 157-97,614 210 ° C) Heptane 37,039 2,2'-azobis (2-1,395 methylbutanonitrile) Stabilizer of 4,678 methacrylate copolymer Methyl methacrylate monomer 15,187 Portion II Methyl methacrylate monomer 178,952 Styrene monomer 75,302 Monomer of hydroxyethyl acrylate 23,455 Mineral spirits (range of 32,387 pe from 157-210 ° C) Heptane 191.896 N, N-dimethylethanolamine 1.108 Monomer of glycidyl methacrylate 2.816 (Continued) Parts in Weight Stabilizer of 58,271 methacrylate copolymer Methacrylate acid monomer 2,816 Portion III Toluene 12,938 Heptane 30,319 2,2'-azobis (2- 2,024 methylbutanonitrile) Portion IV Heptane 16,204 Portion V Melamine formaldehyde resin 246,300 methylated / butylated Total 1067,300 Portion I was charged to the reaction vessel and heated to its reflux temperature. It was refluxed for 60 minutes. Then, portions II and III were added simultaneously for a period of 180 minutes, while maintaining the resulting reaction mixture at its reflux temperature. Then the IV portion was emptied into the reactor and the reaction mixture is refluxed for 120 minutes. The excess solvent (246.3 parts) was then removed and the reactor contents cooled to 10i.66 ° C (215 ° F). After cooling, portion V was added and mixed 30 minutes while continuing to cool to 60 ° C (140 ° F). The resulting dispersion was 70.0% by weight solids.

Acrylosilane resin A solution of the polymer was prepared by charging the following constituents in the continuous stirred tank polymerization reactors equipped with heat sources and reflux condensers. The acrylosilane resin when used in the following examples was prepared by this procedure.

Parts by weight Portion I Styrene monomer 138.560 Cyclohexyl methacrylate monomer 138.560? -methacryloxypropyltrimethoxy-360.256 silane monomer Isobutyl methacrylate monomer 55.424 Ethylene glycol butyl ether acetate 14.549 (Continued) Parts in Weight Mineral spirits (range: 14,549 157-210 ° C) Portion II T-butyl peroxyacetate 22.170 Ethylene glycol butyl ether acetate 46,556 Mineral spirits (range: 46,556 157-210 ° C) Portion III T-butyl peroxyacetate 2770 Acetate of ethylene glycol butyl ether 5.820 Mineral spirits (range: 5,820 157-210 ° C) Portion IV t-butyl peroxyacetate 2.770 Ethylene glycol butyl ether acetate 5.820 Mineral spirits (range: 5,820 157-210 ° C) Total 866,000 In the specification the resin was charged to each reactor of a continuous stirred tank polymerization system at the following levels: R1 = 45%, R2 = 50% and R3 = 60%. The reactors were then heated under reduced pressure to the following specifications: R1 = 210 ° C, 1759 kg / cm2 (25 psi), R2 = 150 ° C, 1337 kg / cm2 (19 psi) and R3 = 135 ° C, pressure atmospheric The feeds of each portion and the transfers between the reactors were then initiated. Portion I was fed to R1 at a flow rate of 43.2 parts / hour, portion II was fed to Rl at a flow rate of 6.9 parts / hour, portion III was fed to R2 at a rate of 0.86 parts / hour and portion IV was fed to R3 at a rate of 0.86 parts / hour. The final product was continuously transferred from R3 to a storage tank. The resulting acrylosilane resin was 85.0% by weight solids.

Acrylic Polyol Resin A polymeric solution was prepared by charging the following constituents in the continuous stirred tank polymerization reactors equipped with heat sources and reflux condensers. The acrylic polyol resin when used in the following examples was prepared by this procedure.

Parts by weight Portion I Hydroxypropyl monomer 232,300 Isobutyl methacrylate monomer 132,800 Styrene monomer 199,100 Butyl acrylate monomer 99,600 Aromatic hydrocarbons (range 30,800 pe of 155-177 ° C) Portion II T-butyl peroxyacetate 56,440 Aromatic hydrocarbons ( 105.400 pe range of 155-177 ° C) Portion III t-butyl peroxyacetate 4.980 Aromatic hydrocarbons (range 9,300 pe of 155-177 ° C) Portion IV T-butyl peroxyacetate 4.980 Aromatic hydrocarbons (range 9,300 of pe 155 -177) Total 885,000 In the specification the resin was charged to each reactor of a continuous stirred tank polymerization system at 10% capacity. The reactors were then heated under pressure to the following specifications: ^ = 190 * 0, 1.4074 kg / cm2 (20 psi), R2 = 155 ° C, 1055 kg / cm2 (15 psi) and R3 = 133 ° C, atmospheric pressure . The feeds of each portion and the transfers between the reactors were then initiated. Portion I was fed to R1 at a flow rate of 6.64 parts / minute, portion II was fed to R1 at a flow rate of 1541 parts / minute, portion III is fed to R2 at a rate of 0.136 parts / minute and portion IV was fed to R3 at a rate of 0.136 parts / minute. The final product was continuously transferred from R3 to a storage tank. The resulting acrylic polyol resin was at 80.0% by weight of the solids.

Silice dispersion A dispersion of silica was made by first preparing a dispersing polymer and then dispersing the silica by a grinding process. The silica dispersion when used in the following examples was prepared by this procedure.

Dispersant Resin Parts in Weight Portion I Xylene 165,794 Portion II Butyl methacrylate monomer 349,686 Hydroxypropyl acrylate 233,131 Portion III t-butyl peroxyacetate 17,485 Xylene 28,615 Portion IV Xylene 4,995 Portion V Xylene 45,294 Total 845,000 Portion I was charged to the reaction vessel and heated to its reflux temperature. Portion II was then added over a period of 400 minutes simultaneously with portion III initiated at the same time as portion II but added over a period of 415 minutes, while maintaining the resulting reaction mixture at its reflux temperature. Portion IV was added to the reactor and the reaction mixture was refluxed for 40 minutes. Heating was removed and then portion V was added to thin the batch. The resulting acrylic dispersing resin was 70.0% by weight solids.

Silice dispersion Parts in Weight Portion I Xylene 35,000 Butanol 20,000 Resin Dispersant 36,000 Portion II Silice Fusionado Amorphous Hydrophobic 9,000 Total 100,000 The portion I is charged to a mill of a horizontal medium previously loaded with the zirconia medium at a level of 122.58 kg (270 pounds) for a mill of 94.62 1 (25 gallons). The mill temperature is maintained at 37.77-48.88 ° C (100-120 ° F). Then portion II is added at a slow speed followed by milling at high speed for 20 minutes. The dispersion was then filtered through a 10 micron filter to obtain the final product.

Example 3 A composition of this invention was prepared in a 350 gram batch by combining the following ingredients according to this formula: Compound (i) was prepared by hydrosilation of one mole of 1,2,4-trivinylcyclohexane with 3 moles of trichlorosilane in the presence of the platinum catalyst to obtain the 1,2,4-tris (trichlorosilylethyl) cyclohexane and the subsequent treatment with methanol for the conversion to tris (2-trimethoxysilylethyl) cyclohexane. A method known in the art. The compound (ii) was prepared using the following recipe. The double functional acrylosilane resin, so called because it contains both the alkoxysilane and the hydroxy functionality, when used in the following examples, is prepared by this process.

Acrylosin Resin with Double Function Parts in Weight Portion I n-amyl acetate 1089.25 2-Ethylhexanol 1089.25 Portion II 2-Ethylhexanol 472.01 N-amyl acetate 472.01 2,2'-azobis (2-methylbutanonitrile) 798.67 Portion III Styrene monomer 2939.90 Cyclohexyl methacrylate 2155.99 Methacrylate of i-butyl 783.90 Monomer of α-methacryloxypropyltrimethoxy-979.97 silane Hydroxyethyl methacrylate 2939.90 Portion IV n-amyl acetate 22.51 T-butyl peroxyacetate 49.02 Total 13792.38 Portion I was charged to the reaction vessel and heated to its reflux temperature (160-170 ° C).

Then portions II and III were added simultaneously over a period of 480 minutes while maintaining the resulting reaction mixture at its reflux temperature. The reaction is maintained at reflux for 15 minutes after portions II and III are all inside. Then the temperature is reduced to 130 ° C, the IV portion is added to the reactor and the reaction mixture is maintained at 130 ° C for 1 hour. The resulting double function acrylosilane resin was 77.1% by weight of the solids.

Example 4 A composition of this invention was prepared in a 350 gram batch by combining the following ingredients according to this recipe: Compound (i) was prepared by hydrosilation of the vinylnorbornene. Then, 100 g of the vinylnorbornene, 320 g of trichlorosilane and 0.6 g of the divinyl platinum complex are heated in a reactor under pressure at 115 ° C for 4 hours. Excess trichlorosilane is removed under vacuum. A mixture of 115 g of anhydrous methanol and 530 g of trimethyl orthoformate under vacuum is added dropwise to the reaction product. After the addition is complete 15 g of triethylamine are added and the reaction mixture is refluxed for 2 hours. The volatile substances are separated and the solids are removed by filtration. The reaction mixture is then distilled at 80-100 ° C, 0.03-0.10 Torr to give the product of 2-trimethoxysilyl-5- (2-trimethoxysilylethyl) norbornane.

Example 5 A composition of this invention was prepared in a 350 gram batch by combining the following ingredients according to this recipe: Cfcppc-eicicp Melamine Binder 10.00 B? Tal? L, l li-dliiea < B UV. 4.40 Flow Agent 0.20 Acrylosilane Resin 31.00 Microparticles 20.00 Silane Compound 33.00 C ^ talisadcr acid 1.20 Tin Catalyst 0.20 Total 100.00 Compound (i) was prepared using the following recipe. The star polyester was prepared first according to the recipe shown below. Silanated star polyester, when used in the following examples, was prepared by this procedure.

Star Polyester Parts in Weight • Portion I Butyl Acetate 38,300 Methylhexahydrophthalic Anhydride 282,300 Portion II Pentaerythritol 68,120 Portion III Cardura-E, glycidyl ester of 375,580 with Cyl Portion IV Butyl Acetate 1,914 Portion V Dibutyltin Lauralate 0.696 Butyl Acetate 4.350 (Cont.) Parts by weight Portion VI Butyl Acetate 98,740 Total 870,000 Portion I was charged to the reaction followed by Portion II. The batch was heated to reflux and refluxed for 1 hour. Portion III was then added over a period of 30 minutes. After the reflux maintenance period, Portions IV, V and VI were added and the reaction was refluxed for 1 hour or until the acid number was less than 3. Portion VI was then added and the batch was filtered and He cooled. The resulting star polyester resin was 80.0% by weight solids. Compound (i) was prepared by reacting 1500 g of Star Polyester with 410 g of 3-isocyanatopropyltrimethoxysilane in the presence of a small amount of tin catalyst. These reagents were added to a suitable container with a nitrogen atmosphere to exclude moisture. The batch was stirred for three hours during which the temperature could reach approximately 60 ° C (140 ° F).

After cooling the vessel was sealed and the reaction was allowed to continue overnight.

Example 6 A composition of this invention was prepared in a 350 gram batch by combining the following ingredients according to this recipe: The compound (i) was prepared using the following recipe. The star polyester should be prepared first according to the recipe shown in Example 5. Then the compound (i) was prepared as shown in Example 5 except that 1860 g of the star polyester was reacted with 762 g of the -isocyanatopropyltrimethoxysilane. Compound (i) in this example had a higher silane content than in Example 5.

Example 7 A composition of this invention was prepared in a 350 gram batch by combining the following ingredients according to this recipe: Compound (i) was prepared as shown in Example 1. In this example, compound (i) was used with the double functional acrylosilane.

Example 8 A composition of this invention was prepared in a 350 gram batch by combining the following ingredients according to this recipe: Compound (i), the silanated star polyester in this example was prepared as shown in Example 5 except that 3720 g of the star polyester and 1524 g of the 3-isocyanatopropyltrimethoxysilane were used in the preparation.

Example 9 A composition of this invention was prepared in a 350 gram batch by combining the following ingredients according to this recipe: The compound (i) the star polyester silanated in this example was prepared as shown in Example 8 Example 10 A composition of this invention was prepared in a 350 gram batch by combining the following ingredients according to this recipe: The star polyester used in this example was prepared as shown in Example 5 except that the glycidyl ester of the C 1 carboxylic acid was replaced with the glycidyl ester of the carboxylic acid with C 5 on a molecular basis. Compound (i), the silanated star polyester was prepared as shown in Example 5 except that 3720 g of the star polyester and 1524 g of the 3-isocyanatopropyltrimethoxysilane were used in the preparation.

Example 11 A composition of this invention was prepared in a batch of 2500 grams by combining the following ingredients according to this recipe: Example 12 A composition of this invention was prepared in a 700 gram batch by combining the following ingredients according to this recipe: Properties Calculated Solids in Satin 75.40 Kiss of the Gallon 8.68 Solids in 70.01 Ctptenido de Qrgániaoß Nfolát ± les (WC) 2.14 Catalyst Binder Melan? Na 10.00 rtil nor ll 11 stkk «Be uv Uv 4.40 Flow Agent 0.20 Acryosi Resin \ rWo 25.00 MLcroparticles 20.00 Silane Cbppjesto 39.00 Catalyst Acid 1.20 Catalyst of Effetan 0.20 Total 100.00 Compound (i), the star-shaped polyester in this example was prepared as shown in the Example 8 Example 13 A composition of this invention was prepared in a 700 gram batch by combining the following ingredients according to this recipe: Compound (i), the silanated star polyester in this example was prepared as shown in Example 8.

Example 14 A composition of this invention can be prepared in a 1000 gram batch by combining the following ingredients according to this recipe: Compound (i) can be prepared by mixing in a suitable vessel equipped with a nitrogen layer, 2 moles of 3-aminopropyltrimethoxysilane with 1 mole of 1,6-hexanediisocyanate) at room temperature and allowing it to stand until the isocyanate peak is present. absent from the infrared spectrum. The final product is bis (3-trimethoxysilylpropylureido) exano.

Example 15 A composition of this invention can be prepared in a batch of 1000 grams by combining the ingredients according to the recipe given in Example 14 substituting Compound (i) shown below. Compound (i) can be prepared for this example by mixing in a suitable vessel equipped with a nitrogen atmosphere 2 moles of epoxypropyltrimethoxysilane with 1 mole of cyclohexane-1,2-dicarboxylic acid and heating at 120 ° C. The reaction is allowed to continue until substantially all of the acid has been reacted as shown by the determination of the acid number. The final product is bis (3-trimethoxysilyl-2-hydroxypropyl) cyclohexane-1,2-dicarboxylate.

Example 16 A composition of this invention can be prepared in a batch of 1000 grams by combining the ingredients according to the recipe given in Example 14 which replaces Compound (i) shown below. Compound (i) can be prepared for this example by mixing in a suitable vessel with a nitrogen atmosphere, 2 moles of allyl alcohol with 1 mole of dimethyl adipate and heating to 90 ° C. The methanol is distilled from the reaction until a quantitative amount is obtained. One mole of the intermediate product, diallyl adipate, is hydrosilated with 2 moles of trimethoxysilane by the methods known in the art to produce the disilaged product. The final product is bis (3-trimethoxysilylpropyl) adipate.

Example 17 A composition of this invention can be prepared in a batch of 1000 grams by combining the ingredients according to the recipe given in Example 14 substituting Compound (i) shown below. The compounds (i) can be prepared for this example by mixing in a suitable vessel equipped with a nitrogen atmosphere, 3 moles of methyl vinylacetate with 1 mole of trimethylolpropane and heating to 90 ° C. The methanol is distilled from the reaction until a quantitative amount is obtained. The final product is the tri-ester of 4-trimethoxysilylbutyric acid of trimethylolpropane.

Example 18 A composition of this invention was prepared in a 500 gram batch by combining the following ingredients according to this recipe: Pre-conditions pa mia c solids ßi teso 84.82 Teso del Galón 8.88 Solids in \ falunen 80.12 GopbaiidD de Orgánicos \ fol tües (WC) 1.35 Cbpposici? N Binding Mamaliria 5 .00 Acrylosilane Resin 27.80 MJcnjpBt'l.ioil as 15.00 Ctppuesto Silano 51.00 Catalyst Acid 1.00 Catalyst Tin 0.20 Total 100.00 Example A A composition of the invention was prepared according to the recipe of Example 2 with the exception that compound (i) was where x, y and z are independently from 1 to 3.

Example B A composition of the invention was prepared according to the recipe of Example 4 with the exception that compound (i) was where x, y and z are independently 1 to 3, Example C A process for making the compound (i) described in Example A is as follows.

A mixture of bis (trimethoxysilyl) limonene (470 g, 1.24 mol), water (16 g, 0.89 mol) and the amine salt of dodecylbenzenesulfonic acid (5.0 g) is reacted for 12 hours at room temperature. The volatiles (57.6 g) were removed under vacuum. The cloudy product was diluted with 500 ml of anhydrous hexanes and filtered through dry silica gel 60 and dried decolorizing activated carbon under nitrogen. The volatile substances were removed under vacuum. The product was a colorless liquid, with a viscosity of 6.4 poises, containing < 7% of the starting monomer (by GC), a dimer as a main component (> 50% by weight) and a small amount of the trimer (by mass spectroscopy KIDS). The oligomers showed solid residues of 93.6% against the monomer, significantly improved, when the small samples were heated for 1 hour at 104.44 ° C (220 ° F). Compounds were also manufactured in which the viscosities in poises were 1.0, 1.4, 3.2, 5.2, 6.1, 14, 15 and 16.

Example D A process for making the compound (i) described in Example B is as follows. A mixture of 5- (2-trimethoxysilylethyl) -trimethoxysilylnorbornane (290 g, 0.80 mol), water (9.0 g, 0.50 mol) and the amine salt of dodecylbenzenesulfonic acid (3.0 g) is reacted for 12 hours at room temperature. The volatile substances were removed under vacuum. The cloudy product was diluted with 300 ml of anhydrous hexanes and filtered through dry silica gel 60 and dry decolorizing activated carbon under nitrogen. The volatile substances were removed under vacuum. Production: 170 g, colorless liquid, viscosity 1.6 poise, containing < 15% of the starting monomer (by GC), a dimer as a main component (> 50% by weight) and a small amount of the trimer (by mass spectroscopy KIDS). The oligomers showed significantly improved solid residues against the monomer, when the small samples were heated for 1 hour at 104.44 ° C (220 ° F). The compounds were also made where the viscosities in poises were 1.2 and 1.5.

It is noted that in relation to this date the best method known by the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, property is claimed as contained in the following

Claims (10)

1. This invention relates to a liquid coating composition, curable or hardenable, which can be sprayed, characterized in that it comprises: i) at least one compound containing the reactive silyl group, film former, having at least two functional groups; of the formula -SiRnX3-n, the functional groups are attached or bound to the compound by a silicon-carbon bond, wherein: n is 0, 1 or 2; R is oxysilyl or unsubstituted hydrocarbyl or hydrocarbyl substituted with at least one substituent containing an element selected from the group of 0, N, S, P, Si; and X is a hydrolyzable portion selected from the group of alkoxy with Ci to C4, aryloxy with C6 to C20, acyloxy with Ci to C6, hydrogen, halogen, amine, amide, imidazole, oxazolidinone, urea, carbamate, and hydroxylamine; the compound has a numerical pro- tein molecular weight between about 300 and 3000 and a volatility in such a way that it does not 5 more than about 30 parts by weight of the compound containing the silyl group per 100 parts of the compound will evaporate during curing; ii) a second component that contains a Optional reactive film-forming silyl group, which, together with and, produces an average functionality of -SiRnX3-n of more than one; iii) polymeric microparticles, substantially insoluble in the liquid coating composition, in an amount of 5 to 100 parts per 100 parts by weight of all other film-forming components; Iv) from 0 to about 100 parts by weight of a liquid organic carrier, based on the weight of i, ii, and iii; and v) sufficient catalyst to effect crosslinking. 25

2. A composition according to claim 1, characterized in that the compound (i) is selected from at least one member of group A to J: wherein: R is a portion selected from the group alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene and a low molecular weight polymer; R1 is alkyl with C? -C16; R2 is H or alkyl 'with C? -C12; R3 is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene and a low molecular weight polymer; n is an integer from 2 to 12; and m is 1 to 16; wherein: R is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene and a low molecular weight polymer, or both R groups are taken together to form the cycloalkyl with C3-C12; R1 is alkyl with C? -Cj.6; R2 is H or alkyl with C? -C12; R3 is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene and a low molecular weight polymer; n is an integer from 2 to 12; and m is from 1 to 16; wherein: R is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene. and a low molecular weight polymer; R1 is alkyl with C? -C? 6; R2 is H or alkyl with C? -C? 2; R is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene and a low molecular weight polymer; R4 is independently selected from H and alkyl with C? -C? 2; or R4 can be taken together to form a cycloalkyl with C3-C12; n is an integer from 2 to 12; and m is 1 to 16; nde: R is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene and a low molecular weight polymer; R1 is alkyl with Cj.-C? 6; R2 is H or alkyl with C? -C12; R3 is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene and a low molecular weight polymer; n is an integer from 2 to 12; and m is from 1 to 16; nde: R is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene and a low molecular weight polymer; . R1 is alkyl with C1-C6; R2 is H or alkyl with C? -C12; when R2 is H, then n is 1 to 12; R3 is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene and a low molecular weight polymer; R4 is independently selected from H and alkyl with C? -C? 2; or R4 can be taken together to form a cycloalkyl with C3-C? 2; n is an integer from 2 to 12; and m is from 1 to 16; wherein: R is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene, and a low molecular weight polymer; or both R groups are taken together to form cycloalkyl with C3-C? 2; R1 is alkyl with Ci-C; R3 is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene and a low molecular weight polymer; R4 is independently selected from H and alkyl with C? -C? 2; or R4 can be taken together to form a cycloalkyl with C3-C12; n is an integer from 2 to 12; and m is from 1 to 16; wherein: R is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene and a low molecular weight polymer; R1 is alkyl with C? -C? 6; R3 is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene and a low molecular weight polymer; R4 is independently selected from H and alkyl with C? ~ C? 2; or R4 can be taken together to form a cycloalkyl with C3-C? 2; n is an integer from 2 to 12; and m is from 1 to 16; nde: R is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene and a low molecular weight polymer; R1 is alkyl with C? -C? 6; R2 is H, alkyl with C? -C? 2 or R is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene and a low molecular weight polymer; R 4 is independently selected from H and alkyl with C 1 -C 12; or R4 can be taken together to form a cycloalkyl with C3-C? 2; and m is from 1 to 16; (I) R u-f-O-CNH-IRS -SKORife nde: R is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene and a low molecular weight polymer; R1 is alkyl with C? -C? 6; R3 is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene and a low molecular weight polymer; n is an integer from 2 to 12; and m is from 1 to 16; Y wherein: R is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene, and a low molecular weight polymer; R1 is alkyl with C? -C? 6; R2 is H, alkyl with C? -C? 2 or R3 is a portion selected from the group of alkyl, cycloalkyl, heterocyclic, aryl, alkoxy, aralkyl, alkene, cycloalkene and a polymer of low molecular weight; and m is 1 to 16.

3. A composition according to claim 1, characterized in that it has the formula: characterized in that: A is a cycloaliphatic radical, or a benzene radical, with and free valences, each such free valence is for a carbon atom different from the carbocyclic ring formed by A; each B is independently a covalent bond, an alkylene group, or a substituted alkylene group having either one or more ether oxygens or ester groups wherein the ether oxygens are between the alkylene segments and wherein the ester groups are between A and R3 or between an alkylene segment and R3, wherein the alkylene group and the substituted alkylene group, which is comprised of the alkylene segments, are independently 1 to 20 carbon atoms; and is 2, 3, 4, 5 or 6; each R1 attached or attached to the silicon atom is independently alkyl containing 1 to 20 carbon atoms or phenyl; each R2 attached or attached to the silicon atom is independently halogen, alkoxy containing 1 to 20 carbon atoms, phenoxy, acyloxy containing 1 to 20 carbon atoms, or oxysilyl; each R3 is independently an alkylene group containing 2 to 20 carbon atoms; and each n is independently 0, 1 or 2.

4. A composition according to claim 1, characterized in that the compound (i) is the product of the reaction of an unsaturated alcohol with an acid or anhydride, or, the product of the reaction of an alcohol with an unsaturated acid or ester; and component (ii) is the product of the polymerization of about 30 to 95% by weight of the monomers containing a compound other than the ethylenically unsaturated silane and about 5 to 70% by weight of the monomer containing the ethylenically unsaturated silane, with based on the weight of the organosilane polymer.

5. A composition according to claim 4, characterized in that the monomer containing the silane is at least one element of group A a C: (A) CHa-C 9 COCHa- (CH 2) n- CHj-R SHOR 2 OR 2 wherein R is either CH 3, CH 3 CH 2, CH 30, or CH 3 CH 20; R1 and R2 are CH3 or CH3CH2; R3 is either H, CH3, or CH3CH2; and n is 0 or a positive integer from 1 to 10; (B) wherein R is either CH3, CH3CH2, CH30, or CH3CH20; R1 and R2 are CH3 or CH3CH2; R3 is either H, CH3, or CH3CH2; and n is 0 or a positive integer from 1 to 10; Y (C) wherein R is either CH3, CH3CH2, CH30, or CH3CH20; R1 and R2 are CH3 or CH3CH2; R3 is either H, CH3, or CH3CH2; R 4 is H or CH 3, R 5 is an alkylene group having 1 to 8 carbon atoms and n is 0 or a positive integer from 1 to 8.

6. A composition according to claim 2, characterized in that the compound (i) is the product of the reaction of the cyclo silane formed from the cyclohexanedimethanol and 3-isocyanatopropyltrimethoxysilane, or, the reaction product of the silanated polyester formed from the methylhexahydrophthalic anhydride, pentaerythritol and epoxidized ester of the carboxylic acid with Cio.

7. A method for protecting a substrate, characterized in that it comprises coating the substrate with a composition according to claim 1.

8. A substrate, characterized in that it is coated with a protective coating derived from a composition according to claim 1.

9. A compound containing the silyl group reactive for the formation of the film, characterized in that it contains at least one element of group A and B: wherein x, y and z are independently 1 to 3; Y where x, y and z are independently 1 to 3.

10. A process for manufacturing an oligomeric compound containing the silyl group reactive for film formation, characterized in that it comprises the steps of: i) reacting a silane selected from the group of disilylated limonene and disilylated vinyl norbornene with a controlled amount of water in the presence of a catalyst, ii) separating the methanol from the reaction product of (i) to complete the oligomerization, and iii) optionally removing (a) the insoluble byproducts from step (ii) and (b) the inert solvent employed to facilitate the removal of insoluble byproducts; whereby the reactive compound that is formed has at least 4 silyl groups.