MXPA98001461A - Reusable copolymers that include vinyl silanum and vinyl esters of acid grease ramific - Google Patents

Abstract

A copolymer composition and a coating comprising the copolymer composition containing a vinyl silane of the formula (See Formula) wherein R 1 is an aryl or alkyl group having 1 to 10 carbon atoms and R 2 is a hydrolyzable group; of branched fatty acid vinyl having the formula (See Formula) wherein R3, R4, R5 are hydrogen or alkyl groups with 1 to 12 carbon atoms and where the total of R3, R4 and R5 contains at least 3 carbon atoms and optionally at least one olefinically unsaturated compound

Description

REUSABLE COPOLYMERS THAT INCLUDE VINYL-S ILANO AND VINYL ESTERS OF BRANCHED FATTY ACID BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a curable resin and more particularly to a curable resin having hydrolysable silyl groups on the side chains.

State of the Art US Patent No. 5,459,205 discloses a curable resin based on hydrolysable silyl group prepolymers, copolymerized with short chain vinyl derivatives, such as vinyl acetate, vinyl propionate, and monomers with silane functional group, such as trialkoxy-vinyl -s ilano. European Patent No. EP 0 396 914 discloses topcoating compositions based on a mixture of a hydroxyl group resin and a hydrolysable silyl group-containing polymer. No publication describes the REF: 26794 copolymers comprising vinyl esters of acidc g J- a. or w or branched Japanese Patent Nos. 63/027564, 04057820 and 04288376 disclose high molecular weight coating compositions containing vinyl silane monomers, vinyl ethers and vinyl esters of branched fatty acids, which are modified with fluorine.

Nothing in the prior art teaches curable resins such as those described herein. The compositions of this invention give an excellent balance of resistance to solvents, resistance to chemicals, hardness, Llexibility and adhesion to a variety of substrates. More specifically, such compositions can be used in automotive topcoat formulations, where they give an exterior finish that has attractive aesthetic appearance, including high luster, excellent image distinctiveness (DOI) and protection against attack by environmental chemicals.

BRIEF DESCRIPTION OF THE INVENTION This invention relates to a crosslinkable polymer composition having a weight average molecular weight below about 40,000, and an acid value below 20 mg KOH / gram derived from A, B, and optionally C, wherein: A is 5 to 95% of A, B and C of a vinyl silane having the formula: CH2 = CH-Si- (R2) 3.m wherein Ri is an aryl or alkyl group having from 1 to 10 carbon atoms, and R2 is a hydrolyzable group; B is 5 to 95% by weight of a branched fatty acid vinyl ester having the formula FU wherein R3, R4, R5 are hydrogen or alkyl groups with 1 to 12 carbon atoms and wherein the total of R3, R and R = contain at least 3 carbon atoms; Y C is 0 to 90% by weight of a different polymerizable olefinically unsaturated compound.

The preferred ranges of A, B and C are: A is 10 to 60% B is 10 to 90% C is 5 to 60% Miás preferred soi A is 10 to 50% B is 10 to 50% C is 10 to 50% Preferred vinyl silanes are those in which m = 0 and R2 is methoxy or ethoxy.

Preferred vinyl esters are those derived from branched fatty acids such as pivalic acid wherein R3 R4 and R5 are each methyl; Versatic acid 9, 10 or 11 where the total number of carbon atoms in R3 R4 and R5 are 7, 8, and 9, respectively. The most preferred branched fatty acids are Versatile 9 and Versatile 10.

Preferred molecular weights are between about 1,000 to 15,000 (average weight).

Preferred compositions have hydroxyl values (by titration, mg KOH / gram) of about 20 to 160. More preferred are values of about 50 to 130.

Optional component C is preferably selected from vinyl aromatic (meth) acrylates, and derivatives of maleic, fumaric and itaconic acids.

This invention also relates to 3 component coating compositions comprising, as component (i), a combination of A, B or A, B and C; as component (ii) a non-aqueous dispersion of a polymer in a substantially non-aqueous medium and, as component (iii), a melamine and / or isocyanate crosslinking agent. Preferred coating compositions comprise: (i) from 20 to 80 weight percent of a composition A, B and optionally C; (ii) from 10 to 40 weight percent of a non-aqueous dispersion of a polymer in a substantially non-aqueous medium; Y (iii) from 10 to 70 weight percent of a crosslinking agent selected from one or both of an isocyanate and melamine crosslinker.

Preferred coating compositions are those wherein (i) is present from about 40 to 70 weight percent and contains a combination of A, B and C; (ii) it is present from about 10 to 30 weight percent and (iii) from 10 to 50 percent. Also included within the scope of this invention are substrates coated with the coating composition described herein.

DETAILS OF THE INVENTION Component (i) The polymeric compositions of this invention have particular utility in coatings that exhibit good resistance to usual wear and chemical attack. Such coatings typically comprise crosslinkers such as melamine resins, blocked or unblocked isocyanates, and mixtures thereof. Other components can be added as will be obvious to someone of skill in the art, to obtain improved properties. A catalyst typically added to catalyze the crosslinking of the silane portions of the silane polymer with itself and with other components of the composition, including the dispersed polymer. Typical of such catalysts are dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin dioxide, dibutyl tin dioctate, tin octoate, aluminum titanate, aluminum chelate, zirconium chelate and the like. Tertiary amines and acids or combinations thereof are also useful for catalyzing the silane bond, preferably, these catalysts are used in the amount of about 0.1 to 5.0% by weight of the composition.

To improve the resistance to environmental conditions of a clear finish, produced by the present coating composition, an ultraviolet light stabilizer, or a combination of ultraviolet light stabilizers in the amount of about 0.1 to 5% by weight, can be added, based on the weight of the binder. Such stabilizers include ultraviolet light absorbers, filters, dampers and specific hindered amine light stabilizers. An antioxidant may also be added, in the amount of 0.1 to 5% by weight, based on the weight of the binder.

Typical ultraviolet light stabilizers that are useful include benzophenones, triazoles, triazines, benzoates, hindered amines and mixtures thereof. The composition may also include conventional formulation additives such as flow control agents such as Resiflow® S (polybutylacrylate), BYK 320 and 325 (high molecular weight polyacrylates), rheology control agents, such as fumed silica; water scrubbers such as tetrasilicate, trimetyl ortho-formate, triethyl orthoformate, and the like.

When the present composition is used as a clear coating (topcoat) on a pigmented color coating (basecoat) to provide a clearcoat / clearcoat finish, small amounts of pigment can be added to the clearcoat to eliminate yellowing undesirable. The composition can also be pigmented and used as the color coating, or as a monolayer or even as a prescriber or dresser. The composition has excellent adhesion to a variety of substrates, such as previously painted substrates, cold-rolled steel, phosphatized steel, and steel coated with conventional primers by electrodeposition. The present composition shows excellent adhesion to the preparers, for example, those comprising cross-linked epoxy polyesters and various epoxy resins, as well as alkyd resin repair preparers. The present composition can be used to coat plastic substrates such as glass fiber reinforced with polyester, injection molded urethanes and partially crystalline polyamides.

When the present coating composition is used as a base coat, the typical pigments that can be added to the composition include the following: metal oxides such as titanium dioxide, zinc oxide, iron oxides of various colors, carbon black, filler pigments 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 , red thioindigo, benzi idazolinones, metallic flake pigments such as aluminum flake, and the like.

The pigments can be introduced into the coating composition first by the formation of a grinding base dispersion or pigment with any of the aforementioned polymers, used in the coating compositions or with another compatible polymer or dispersant, by conventional techniques , such as high speed mixing, sand grinding, ball milling, attrition grinding or attrition or milling by two rollers. The grinding base is then mixed with the other constituents used in the coating composition.

Conventional solvents and diluents are used to disperse and / or dilute the aforementioned polymers, to obtain the coating composition. Typical solvents and diluents include toluene, xylene, butyl acetate, acetone, methyl isobutyl ketone, methyl ethyl ketone, methanol, isopropanol, butanol, hexane, acetone, ethylene glycol, monoethyl ether, naphtha, mineral spirits, heptane and other aliphatic, cycloaliphatic, and aromatic hydrocarbons, esters, ethers, ketones, and the like.

The coating composition can be applied by conventional techniques such as spraying, electrostatic spraying, dipping, brush application, flow coating and the like. The preferred techniques are spraying and electrostatic spraying. After application, the composition is typically baked at 100 ° to 150 ° C for about 15 to 30 minutes, to form a coating thickness of about 2.5 microns to 76 microns (0.1 to 3.0 mils). When this composition is used as a clear coating, it is applied over the color coating which can be dried to a stick-free state, and cured or preferably dried instantly for a short period before the clear coating is applied. The color coating / clear coating finish is then baked as mentioned above, to provide a dry and cured finish.

It is customary to apply a clear topcoat over a basecoat by means of a "wet on wet" application, for example, the topcoat is applied to the basecoat, without fully curing or drying the basecoat. The coated substrate is then heated for a period of time to allow simultaneous cure of the base and clear coatings.

After curing the clear topcoating compositions of the present invention, a portion of the silane-containing polymer can migrate and laminate to the top of the clear coating, particularly when the organosilane polymer is used in combination with a polyol, to produce a clear, durable coating, resistant to environmental conditions. Such stratification has been shown by electronic scanning chemical analysis (ESCA) of a cross-section of the cured layer of the topcoat.

The coating composition can be formulated with a single package system having a prolonged shelf life.

For a two component system, a polyfunctional organic isocyanate compound can be used without particular limitation, as long as the isocyanate compound has at least two isocyanate groups in the molecule. Preferred functional isocyanate compounds are isocyanate compounds having 2 to 3 isocyanate groups in the molecule.

Typical examples of the polyfunctional organic isocyanate compounds are, for example, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, diisocyanate. of xylylene, lysine methyl ester diisocyanate, -NCO (CH2) 6-NCO Or a trimer and isophorone diisocyanate (isocyanurate), and the like.

When the curable resin of the present invention is used in exterior coatings, the use of the aliphatic isocyanate or the alicyclic isocyanate is preferable to the use of the aromatic isocyanate, from the standpoints of resistance to environmental conditions and resistance to yellowing.

The contemplated vinyl silane monomers useful as component (A) include: ^ OCH3 ^ OCH2CH3 ^ OCH2CH2OCH3CH2 = CH- Sr-OCH2CH2OCH3 ^ OCH2CH2OCH3 CH3 The vinyl esters contemplated of branched fatty acids (B) include: R, and to those in which R3 + R4 + R5 = 8 carbon atoms, = 9 carbon atoms, = 10 carbon atoms; Y Optional component C includes: alkyl methacrylate monomers such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, nonyl methacrylate, lauryl methacrylate and the like. Similarly, suitable alkyl acrylate monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, nonyl acrylate, sodium acrylate, lauryl and the like. The methacrylates and cycloaliphatic acrylates may also be used such as trimethylcyclohexyl methacrylate, trimethylcyclohexyl acrylate, t-butyl-cyclohexyl acrylate, or t-butyl-cyclohexyl methacrylate. The aryl acrylate and the aryl methacrylates can also be used, such as benzyl acrylate and benzyl methacrylate. Of course, mixtures of two or more of the aforementioned monomers are also suitable.

In addition to the alkyl acrylates or methacrylates, other polymerizable monomers, up to about 50% by weight of the silane-free polymer, can be used in the acrylosilane polymer for the purpose of achieving the desired properties such as hardness, usual wear resistance of appearance, and the like. Exemplary of other monomers are styrene, methylstyrene, acrylamide, acrylonitrile, methacrylonitrile, and the like.

To provide the hydroxyl functional group in the polyol, suitable monomers include hydroxyalkyl acrylates and methacrylates, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyisopropyl acrylate, hydroxypropyl methacrylate, methacrylate. hydroxyisopropyl, hydroxybutyl methacrylate, and the like, and mixtures thereof.

Other monomers with silane functional group can be used such as: or other trialkoxy derivatives Preferred polymerizable compounds (C) which can be included in the formulation include reaction products of e-caprolactone and hydroxyalkyl (meth) acrylates, reaction products of maleic acid, itaconic acid, and hemiesters with monofunctional epoxide esters such as Cardura ElO (Shell), epoxides such as ethylene oxide, propylene oxide, cyclohexene oxide, and glycidyl ethers such as phenyl glycidyl ether and the like. Other possible polymerizable compounds are urethane adducts of hydroxyalkyl (meth) acrylate and diisocyanates to form a monomer with an isocyanate functional group. Such monomers can also be modified with derivatives of amino and / or hydroxyl functional groups to form polymerizable intermediates with urethane or urea functional groups.

The most preferred component (C) are the following reaction products: R6-0-CO-CH = CH-CO-0-R7 wherein Rd and R are the same or different, and are selected from alkylene, cycloalkylene, aryl, aralkylene, and alkaryl, of up to about 20 carbon atoms, interrupted by or substituted with heteroatoms and / or hydroxyl groups. Examples of such reaction products are the following: R * CH3- (CH,) 3 - CH, CH 15 CH3 - (CH2) 2- - CH2 ~ CH, - > R- , Component (ii) This component of the coating composition of the invention is a polymer dispersed in an organic medium (substantially non-aqueous). This component has been described to date as a non-aqueous polymer dispersion (NAD), a microgel, a non-aqueous latex, or a polymer colloid. In general, the dispersed polymer is stabilized by spherical stabilization achieved by coupling a solvated polymer or oligomeric layer at the particle media interface.

In the dispersed polymers of the present composition, the dispersed phase or particle, protected by a spherical barrier, is referred to as the "macromolecular polymer" or "core". The stabilizer that forms the steric barrier, coupled to this nucleus, is referred to as the "macromonomeric chains" or "arms".

The dispersed polymers solve the cracking problem and are used in an amount ranging from about 10 to 60% by weight, preferably from about 15 to 40%, more preferably from about 20 to 30%, of the total binder in the composition. The proportion of the silane compound to the dispersed polymeric compound of the composition is suitably in the range of 5: 1 to 1: 2, preferably 4: 1 to 1: 1. To accommodate these relatively high concentrations of dispersed polymers, it is desirable to have reactive groups on the arms of the dispersed polymer, which reactive groups make the polymers compatible with the continuous phase of the system.

The dispersed polymer contains about 10 to 90%, preferably 50 to 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 to 500,000. The preferred average particle size is 0.05 to 0.5 microns. The arms, coupled to the core, constitute approximately 10 to 90%, preferably 20 to 59% by weight of the dispersed polymer, and have a weight average molecular weight of from about 1,000 to 30,000, preferably from 1,000 to 10,000.

The macromolecular nucleus of the dispersed polymer typically comprises polymerized, ethylenically unsaturated monomers. Suitable monomers include styrene, acrylate or alkyl methacrylate, ethylenically unsaturated monocarboxylic acid, and / or silane-containing monomers. Such monomers as methyl methacrylate contribute to high Tg (vitreous transition temperature) while monomers such as methyl acrylate or 2-ethylhexyl acrylate contribute to a low Tg. Other optional monomers are the hydroxyalkyl acrylates, methacrylates or acrylonitrile. Such functional groups such as the hydroxyl in the core can react with the silane groups in the silane compound to produce additional bond within the film matrix. If a crosslinked core is desired, allyl diacrylate or allyl methacrylate can be used. Alternatively, a monomer with an epoxy functional group, such as acrylate or glycidyl methacrylate, may be used to react with the monocarboxylic acid functional group comonomers and cross-link the core; or the core may contain silane functional group.

A preferred feature of the dispersed polymers is the presence of macromonomeric arms containing hydroxyl groups, adapted to react with the organosilane compound. It is known with certainty which portion of these hydroxyl functional groups reacts with the organosilane compound, due to the reaction groups that occur during baking and curing. However, it can be said that a substantial portion of these functional groups in the arms, preferably most of them, do react and crosslink with the film former of the composition, which in some may consist exclusively of a compound of organosilane The arms of the dispersed polymer must be securely anchored to the macromolecular core. For this reaction, the arms are preferably anchored by 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 anchoring method by absorption of the spinal column portion of a graft polymer may be insufficient.

The macromonomer arms of the dispersed polymer serve to prevent the core from flocculating by forming a spherical barrier. The arms, typically in contrast to the macromonomeric core, are believed to be capable, at least temporarily, of being solvated in the carrier or organic solvent medium of the composition. These can be in the extended chain configuration, with their hydroxyl functional groups available for reaction with the silane groups of the film-forming silane-containing compound, and the polymer. Such arms comprise approximately 3 to 30% by weight, preferably 10 to 20%, based on the weight of the macromonomer, of the monomers containing hydroxyl, ethylenically unsaturated, polymerized functional groups, and approximately 70 to 95% by weight, based on in the weight of the macromonomer, of at least one other polymerized, ethylenically unsaturated monomer without such crosslinking functionality. Combinations of such hydroxyl monomers with other minor amounts of crosslinking functional groups, such as silane or epoxy, on the arms, are also appropriate.

The macromonomeric arms coupled to the core may contain polymerized monomers of alkyl methacrylate, alkyl acrylate, each having 1 to 12 carbon atoms in the alkyl group, as well as glycidyl acrylate or glycidyl methacrylate or ethylenically unsaturated monocarboxylic acid for the anchoring and / or crosslinking. Typical useful hydroxyl-containing monomers are hydroxyalkyl acrylates or methacrylates A preferred composition for a dispersed polymer having a hydroxyl functional group, 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 of methyl acrylate, about 1.5% by weight of glycidyl methacrylate and about 5% by weight of styrene. The macromonomer coupled to the core contains 97.3% by weight of prepolymer and about 2.7% by weight of glycidyl methacrylate, the latter for crosslinking or the 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 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 polymerizing the monomers in an inert solvent, in which the monomers are soluble, but the resulting polymer is not soluble, in the presence of an amphoteric, dissolved stabilizing agent.

Component (nor The coating composition further includes, particularly in conjunction with a polyol polymer, an additional crosslinking agent, for example, conventionally known alkylated, monomeric or polymeric melamine formaldehyde resin, which is partially or completely alkylated. A preferred crosslinking agent is the methylated and butylated or isobutylated melamine formaldehyde resin, which has 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 to 600 and a weight average molecular weight of about 500 to 1,500. Examples of resins commercially available with Cymel * 1168, CymelR 1161, CymelR 1158, Resimine 4514 and Resimine "354. Preferably, the crosslinking agent is used in the amount of about 5 to 50% by weight, based on the weight of the binder of the composition Other crosslinking agents contemplated are urea formaldehyde, benzoguanamine formaldehyde and blocked polyisocyanates.

The compositions of this invention can be made by the same techniques as those used in the synthesis of acrylic resins and vinyl resins. An example of such a synthetic technology comprises dissolving or dispersing the monomers of the respective components in an organic solvent, and heating the solution in the presence of a radical polymerization initiator at a temperature of about 60 to 180 ° C, with constant agitation. The reaction time is generally from about 1 to 10 hours. As the organic solvent, the same alcohol, ether, ester and hydrocarbon can be used as the aforementioned solvents. In the case of a solvent of the hydrocarbon type, it is preferably used in combination with a different type of solvent from the point of view of solubility.

Examples of free radical initiators are those which are soluble in the polymerization medium such as azobis- (isobutyronitrile), azobis- (alpha, gamma-dimethyl-valeronitrile), azobisdimethyl-valeronitrile, tert-butyl perbenzoate, peracetate tert-butyl, diter-butyl peroxide, t-butyl peroxy-2-ethylhexanonate, and benzoyl peroxide. The free radical initiator is usually present in amounts of about 0.1 to 10 percent by weight based on the total weight of the polymerizable alf, beta-ethylenically unsaturated monomer.

Examples of the chain transfer agents are alkyl mercaptans such as tert-dodecyl mercaptan. When used, these materials are present in an amount of up to 5 weight percent, based on the weight of the polymerizable alpha, beta-ethylenically unsaturated monomers.

Among the organic solvents that can be used for polymerization are those that have a boiling point of at least 50 ° C and usually 110 ° to 180 ° C. These include, for example, ketones such as methyl amyl ketones, esters such as hexyl acetate and heptyl acetate; glycol ethers and glycol esters such as propylene glycol monoethyl ether acetate and isobutyl isobutyrate.

The following examples illustrate the invention. All parts and percentages are on a weight basis, unless otherwise indicated. Molecular weights were determined by gel permeation chromatography using a polystyrene standard.

EXAMPLE 1 Copolymer (mixture) of Veova 'Vinyl-Silane / Hydroxypropyl methacrylate A reactor equipped with a reflux condenser, stirrer, thermometer, nitrogen gas inlet and addition funnel, was charged with a first part consisting of 6 parts of Solvesso 100 (mixture of aromatic solvent, Exxon) and 4 parts of n. -butanol. This was heated to 125 ° C and part 2 consisting of 47.76 parts of Veova® 9 (Shell), vinyltrimethoxy-silane (Silquest® A171, OSI), 7.96 parts of hydroxypropyl methacrylate, 5.4 parts of t-butyl peroxy-isononanoate. Butyl (Trigonox® 42S, AKZO) and 1.5 parts of Solvesso® 100 was added dropwise to it from an addition funnel over a period of 5 hours.

After the completion of the addition, a third part of Solvesso® 100 (1 part) was added as a rinse solvent and the contents of the reactor were refluxed for 10 minutes. Subsequently, part 4 was added in 20 minutes, consisting of 0.6 parts of di-t-butyl peroxide (TrigonoxR B) and 0.4 parts of SslvessoR 100, followed by part 5 (0.5 parts of Solvesso 100) as a rinsing step and the contents of the reactor were refluxed for 2 hours. Part 6 consisting of a part of SoIvessoR-100 and 6.25 parts of n-butanol was finally added to the reactor.

Results of Solids 78.3% (1 hour Test: drying at 105 ° C) Viscosity Y- (Gardner-Holdt) Acid value 3.5 mg KOH / g Molecular weight at 2300 number (Mn) Molecular weight at 8800 weight (Mw) Examples 2 to 6 The procedure of Example 1 was followed E 1 • ¿- Ej. 3 Ej. 4 Ej.; J.6 Part 1 SolvessoR 6 6 6 10 10 100 n-butanol 4 4 4 Part 2 VeovaR 9 55 -7 O - - Veova "10 - - 47.76 47.76 63.68 71.64 Yes qu st '15 .92 23.88 23.88 15.92 7.96 A171 Metacri7. .96 7.96 - lato of hydroxyethyl Metacri7.96 hydroxypropyl lactate Tr: .gonox 5.4 21S Solvesso 1.5 1.5 1.5 3.5 3.5 .00 VAZO 67 Tpgonox 3.4 B Part 3 Solvesso 100 Part 4 TrigonoxR 0.5 0.6 0.6 0.6 0.6 B (AKZO) So vesso 0.5 0.4 0.4 0.4 0.4 100 Part 5 Soivesso 0.5 0.5 0.5 0.5 0.5 100 Part 6 Soivesso 7.25 7.25 n-tsutanoi 6.25 6.25 Result- Ex.2 Ex3 Ex .4 Ex .5 Ex .6 Two Test Solids 80.3 77.5 78.4 79.7 80.5 Viscssi- > Z6 X + l / 4 S I Q dad Value of 3.6 2.9 3.4 • 2 2.3 acid Weight 3000 3200 2300 1100 1100 molecular in number (Mn) Weight 24300 25700 7100 2200 2400 molecular weight (Mw) Procedure i Maleato adduct; Component C A reactor equipped with stirrer, thermometer, reflux condenser, nitrogen gas inlet and addition funnel was charged with 146 parts of trimethylpentanediol, 98 parts of maleic anhydride and 61 parts of methyl isobutyl ketone and the mixture was heated to reflux for 2 hours.

Part 2 consisting of 260 parts of Cardura® El (Shell) and 65 parts of Solvesso® 100 was then added to the reactor, and the contents heated to reflux until the acid value was less than 2.

Results of Solids 81% Test: Viscosity H Acid value 0.1 Molecular weight in number (Mn) 500 Weight TiOi? Cuiar in pso (Mw) 840 Procedure 2 Maleato adduct; Component C Procedure 1 was repeated except that the initial reactor charge was 108 parts of benzyl alcohol, 98 parts of Cardura® ElO and 51 parts of methyl isobutyl ketone.

Solid results 81.9% Test: Viscosity C Acid value 1.3 Molecular weight in number (Mn) 370 Molecular weight in weight (M) 710 Procedure 3 Maleato adduct; Component C First, 532 parts of the product of Process 1 were refluxed with 168 parts of hexyhydrophthalic anhydride and 50 parts of SolvessoR 100 for 2 hours. Subsequently, 260 parts of CarduraR ElO and 57 parts of Solvesso "1 100 were added and the mixture was heated to reflux until the acid value was below 2.

Results of Solids 80.5% Test: Viscosity U Acid value 03 Molecular weight in number (Mn) 650 Molecular weight in weight (Mw) 1370 EXAMPLES 7 to 11 The procedure of Example 1 was repeated, with the following changes Part 1 Ex 2 Ex 3 Ex 4 Ex 5 Ex 6 Maleate - 9.95 - Procedure 1 Maleate 19.80 Procedure 2 Maleate 39.8 Procedure 3 Solvesso '' 10 100 Part 2 Silquest 40 40.65 A1511 Silquest * 23.8 88 A1712 Veova '47.76 23.8 40 40.65 Tpgonox' 5.2 5.4 425 soivesso 1.5 1.7 2.2 1.5 TrigonoxR 3.7 B Part 3 Solvesso '"100 Part 4 Soivesso "0.4 0.4 0.8 0.4 0.1 i? N n U Tpgonox '0.6 0.2 0.6 0.4 100 Part 5 Soivesso "0.5 0.5 0.6 0.5 100 Silquest A151 comprises ^ OCH2CH3 SilquestR A171 comprises OCH, CH2 = CH-Sr-QCH3 \ OCH3 Part 6 Solvesso '100 n-Bu t no 1 5.5 Result- Ex.7 Ex 8 Ex. 9 Ex.10 Ex.

Solids 83.8 83 70.8 87.2 90 Viscosí- V + l / 2 Zl + 1/4 H A H dad Value of 5.5 4 5 4.3 0.2 acid Weight 800 1160 2400 1600 1600 mole cu- Lar in Number (Mn) Weight 1420 6100 13500 5300 5100 Molecular in Weight (Mw) EXAMPLE 12 A clear coating paint formulated with the copolymer of Example 5 was applied in a wet-on-wet form over a commercial blue base coat and baked for 30 minutes at 135 ° C. A clear, solvent resistant coating was obtained, with a luster of 85, hardness of Buc holz of 125 and good resistance to etching or attack by acid.

It is noted that in relation to this date, the best method known to 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 (7)

1. A crosslinkable copolymer composition having a weight average molecular weight below about 40,000, a hydroxyl value of about 20 to 160, and an acid value below about 20, derived from A, B and optionally C, wherein :

A is 5 to 95% of A, B and C of a vinyl silane having the formula:

(Rl) m

CH2 = CH-Si- (R2) 3.m

wherein R 1 is an aryl or alkyl group having 1 to 10 carbon atoms, and R 2 is a hydrolysable group;

B is 5 to 95% by weight of a branched fatty acid vinyl ester having the formula

CH2 = CH-O-CO- C - R4 R5

wherein R3, R4, Rs are hydrogen or alkyl groups with 1 to 12 carbon atoms and wherein the total of R3, R ^ and R = contain at least 3 carbon atoms; Y

C is 0 to 90% by weight of a different polymerizable olefinically unsaturated compound.

2. A composition according to claim 1, characterized in that it has a weight average molecular weight of between about 1,500 to 10,000, a hydroxyl value of about 20 to 160, and an acid value below 10.

3. A composition according to claim 2, characterized in that A is 10 to 60%, B is 10 to 90% and C is 5 to 60% of the total weight of A, B, v r.

4. A composition according to claim 3, characterized in that A is 10 to 50%, B is 10 to 50%, and C is 10 to 50% of the total weight of A, B and C.

p fnmpri? i "i Ón d P conformity to the .on caractßri?: because m = 0 R - is ¡x:

6. A composition according to claim 1, characterized in that R3 R4 and R = are logs a member of the acid group

10

7. Composition in accordance with i T? MnHii rcpa rc-? Oónrt 1 charac ter because QL lxa?.? í

fifteen . > u L OL. ? u uo l? i? ii S O n j-O ii-ua < ? n - CL m i T? nH i ar-i An r ^ n ~ / ~ * t- £ ir - i t a ^ a r-} ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ . ~ J t - * J -J t -ii Va.j_ - S iiiui.? 1-.U ac cx ^ - w? .- i: .ci, ^ í.c3.j.Lc:? '_c x _- d. • - • rj uii va ut _J.C a. _-Ld ^ v ^. USJ O ju - ^ ..: 20 5. _coxi_'1.3.ci2.r? sp.ts 10 sstZ5.n .io A. 01703 ^ 110 CLT 10 3. 60, 3 ^ *, t - - 'a. ~ J of 1 ^ S ^ ia O »- / o ^ -. C J.] - COO u? uai JS , /

-? iwwo -. ") S H i / - • a" • ^ \ n r- \ '-a ^ 5.' ~ '' - £ ^ ^ * ~ * ^ ~ < a p rn-n or t * • > r-? r ^. ^ i "-

molecular weight in weight from about 1,500 to 10,000, a hydroxyl value from about 20 to 160, and an acid value below about 10, with A present from 10 to 60%, B from 10 to 90% and C of 5 to 60% of the total weight of A, B and c.

10. A composition according to claim 7, characterized in that it has an average molecular weight of about 1,500 to 10,000, a hydroxyl value of from about 20 to 160, and an acid value below about 10, with A being present from 10 to 60. %, B from 10 to 90% and C from 5 to 60% of the total weight of A, B and C.

11. A coating composition according to claim 1, characterized in that it comprises

(i) from 20 to 80 weight percent of the composition of A, B and optionally C;

(ii) from 10 to 40 weight percent of a non-aqueous dispersion of a polymer in a substantially non-aqueous medium; and (iii) from 10 to 70 weight percent of a crosslinking agent selected from one or both of an isocyanate and melamine crosslinker.

12. A coating composition according to claim 11, characterized in that it comprises:

(i) from 40 to 70 weight percent of A, B and r - /

(ii) from 10 to 30 weight percent of a non-aqueous dispersion of the polymer; Y

(iii) from 10 to 50 weight percent of a crosslinker selected from isocyanate and melamine.

13. A composition according to claim 12, characterized in that the crosslinker is polyisocyanate.

14. A composition according to claim 12, characterized in that the crosslinker is derived from melamine formaldehyde.

15. A substrate, characterized in that it is coated with the composition according to claim 1.