MXPA99005487A - Coating agent- the manufacture and use thereof - Google Patents

Abstract

La composición de revestimiento adecuada para los laquerados multicapa, con una composición aglutinante que contiene:de 25a 75%en peso de copolímeros (met)acrílicos de carboxilo funcionales y/o poliésteres de carboxilo funcionales, la funcionalidad del carboxilo corresponde a un númeroácido de 15 a 300 mg KOH/g, de 25 a 75%en peso de resina de entre glosamiento de epóxido funcionalizadas, al menos una de las cuales es un copolímero (met)acrílico que se ha preparado co-utilizando (met)acrilato de tert-butilo;de 0 605 en peso de polioles que tienen al menos dos funciones hidroxilo en la molécula;de 0 a 40%de componentes que se entrecruzan con los grupos hidroxilo para formaréteres y/o de un agente de entrecruzamiento con base en triazina;de 0 a 405 en peso de poliisocianato;de 0 60%en, peso de al menos un polianhídrido orgánico con al menos dos grupos anhídridos deácido carboxílico cíclico por molécula, de 0 20%en peso de diluyentes reactivos con una función epóxido, de 0 a 10%en peso de uno o más catalizadores para la reacción de carboxilo y grupos epóxido.

Description

COATING COMPOSITIONS, ITS PREPARATION AND ITS USE DESCRIPTIVE MEMORY The invention relates to aqueous and / or solvent-containing coating agent compositions which are suitable for coatings that are baked at an elevated temperature, and in particular for the preparation of multilayer lacquers, for example in the motor vehicle sector. A baking lacquer in which the polymers contain carboxyl groups, such as for example acrylates based on acrylic acid or methacrylic acid and acrylates containing glisiryl groups, are mixed to give a curable composition known from DE-A-30 22 996. WO 84/00771 describes a multicomponent system in which four types of binder are mixed together and then the mixture is applied. The components are hydroxyl groups containing acrylate, anhydride acid, at least 50% being anhydrides of alkylhexahydrophthalic acid, epoxy resin and melamine resin. The systems have a high solids content. DE-A-23 33 384 discloses a binder based on acrylated polyesters which are obtained by polymerization of an acrylate containing hydroxyl groups in a polyester or alkyl resin containing hydroxyl groups. The crosslinking can be carried out with melamine resins and simultaneously epoxy resins. DE-A-38 00 389 describes the modification of copolymers containing hydroxyl groups with lactones, in particular with epsilon-caprolactone. US-A-4 501 829 discloses polyesters with hydroxyl and carboxyl groups that are reacted with lactones. The reaction is carried out in the hydroxyl groups. US-A-4 082 816 describes compositions of (meth) acrylic copolymers modified with caprolactone and containing carboxyl groups and melamine-formaldehyde resins. The coating compositions known in some cases lead to the formation of film of high hardness and good resistance to the corrosive action of the natural elements. However, such compositions do not meet the constantly increasing requirements of high acid resistance and solvent resistance. DE 44 16 282 discloses baking lacquers based on the crosslinking of acidic polyesters, which are urethanized with polyepoxides. DE 42 37 658 also describes carboxy-epoxy lacquers for baking systems. In such systems, the carboxyl group chains are elongated with caprolactone to increase their reactivity. These systems are distinguished by excellent resistance to chemicals. All the above systems have the common characteristic that they tend to run, especially at high coating thicknesses. EP-A-0 509 392 and EP-A-0 517 536 describe powder coating resins in which tert-butyl (meth) acrylate and glisiril methacrylate are copolymerized. It is said that said monomer combination leads to increased reactivity. The object of the invention is to provide a binder system which can be processed for aqueous coating compositions and / or which contains solvents which can be baked at elevated temperature and which lead to the coating with a good hardness, good resistance to the corrosive action of the natural elements and high elasticity, in which they are also resistant to acids and resistant to solvents. The coating compositions must also have good application reliability (reduced tendency to run) even at high coating thicknesses. In particular, the coating compositions should not show any yellowing in the baking and have a high storage stability. A high boiling resistance is an essential requirement. It has been found that such an object can be achieved by an aqueous coating composition or by containing solvents comprising a binder system based on functional (meth) acrylic carboxyl copolymers and / or polyesters with a functional epoxy (meth) acrylic copolymer as a crosslinking agent, the functional epoxide (meth) acrylic copolymer having been prepared using tert-butyl (meth) acrylate as the monomer unit. The invention thus provides a coating composition comprising a binder, solvent and / or water composition and optionally pigments and / or fillers and optionally conventional lacquer additives, which are characterized in that the binder composition comprises: A) 25 75 % by weight of one or more carboxy functional (meth) acrylic copolymers and / or one or more carboxyl functional polyesters, the functionality of the carboxyl in each case corresponds to an acid number of 15 to 300 mg KOH / g. B) 25 to 75% by weight of one or more functional epoxy crosslinking resins, at least one of said crosslinking resins being (meth) acrylic copolymer which has been prepared using tert-butyl (meth) acrylate as the monomer unit , C) 0 to 60% by weight of one or more polyols having at least two hydroxyl functions in the molecule and differing from a component A) optionally containing hydroxyl functions, D) 0 to 40% by weight of components that crosslink with hydroxyl groups for forming ethers, and / or a crosslinking agent based on triazine, E) 0 to 40% by weight of one or more polyisocyanates, which can optionally be covered, F). Or at 60% by weight of an anhydride component comprising at least one organic polyanhydride with at least two anhydride groups of cyclic carboxylic acid per molecule, G) 0 to 20% by weight of one or more diluents reactive with an epoxide function, H ) 0 to 10% by weight of one to more catalysts to catalyze the reaction of carboxyl and epoxide groups, The sum of the weight percent of the components A) to H) adding up to 100% by weight. According to a preferred embodiment of the invention, the functional epoxide crosslinking resin is based on (meth) acrylic copolymers which have been prepared using 3 to 50% by weight of tert-butyl (meth) acrylate, based on in the total weight of the monomer units. According to another preferred embodiment of the invention, a crosslinking component B) is used which comprises at least one crosslinking resin based on the (meth) acrylic copolymers that have been prepared using the following monomer units: b1) 5 a 60% by weight of one or more functional epoxide olefinically unsaturated monomers, in particular glycidyl (meth) acrylate, b2) 3 to 50% by weight tert-butyl (meth) acrylate, b3) 0 to 60% by weight of one or more aromatic vinyl functional monomers, b4) O at 20% by weight of one or more hydroxyl functional (meth) acrylic monomers, b5) 0 to 92% by weight of one or more monomers differing from b1) a b4), The sum of the weight% of b1 to b5 adds 100% by weight. It has surprisingly been found that aqueous or solvent-containing coating compositions according to the invention lead to coatings which, despite a possible expected formation of slit products during the advanced cross-linking reaction, achieve a high strength of boiling, the other requirements according to the object being at a high level without change. In component A) of the binder or coating compositions according to the invention, the carboxyl groups can be modified by the reaction with lactones. An "elongation of chains" of the carboxyl groups is carried out by the addition of lactones. Upon opening the ring of the lactone to be added, the carboxyl groups are originally esterified in the (meth) acrylic copolymer matrix and / or in the polyester matrix, but the carboxyl groups of lactone are released and formed from this Thus, reaction products containing carboxyl groups exposed in the short side chains corresponding to the lactone.

According to a preferred embodiment of the invention, the carboxy functionalized (meth) acrylic copolymers, which optionally contain urethane groups and which can be reacted with lactone, have a number average molecular weight (Mn) of 1,000 to 30,000 g / moles The functionalized carboxyl polyesters which optionally contain urethane groups and which can be used accordingly, preferably have a calculated molecular weight of 500 to 4,000 g / mol, such as for example 800 to 4,000 g / mol. The acid number of said starting materials is from 15 to 300 mg KOH / g, preferably from 30 to 250 mg KOH / g, and particularly preferably from 60 to 200 mg KOH / g. In the preparation of (meth) acrylic copolymers or polyesters containing carboxyl groups, each can optionally contain urethane groups and can be used as component A), carboxyl groups can be introduced directly by using units containing carboxyl groups, for example, in the increase of polymers, such as the (meth) acrylic co -omers. Examples of suitable monomers containing carboxyl groups and which can be used for this purpose are unsaturated carboxylic acids, such as, for example, acrylic, methacrylic, itaconic, crotonic, isocrotonic, aconitic, maleic and fumaric acids, the average esters of maleic acid and fumaric and carboxyalkyl esters of (meth) acrylic acid, ie, beta-carboxyethyl acrylate, and adducts of hydroxyalkyl esters of acrylic and / or pentacrylic acid with carboxylic acid anhydrides, such as for example 2-ester phthalic acid ( met) acryloxy-ethyl. The term (meth) acrylic is used in the present description and the claims of the patent. The foregoing refers to acrylic and / or metametacrylic. In the preparation of (meth) acrylic copolymers or polyesters containing carboxyl groups and optionally contain urethane groups, however, it is also possible first to increase a polymer containing hydroxyl groups and optionally also carboxyl groups and has an OH number of 15 to 300 mg / KOH / g, and to introduce all or some of the carboxyl groups and a second step by reaction with carboxylic acid anhydrides. In said process, the ratios in amounts are used so that optionally sufficient OH groups are still able to carry out a urethanization. The carboxylic acid anhydrides which are suitable for addition in the hydroxyl group containing polymers and which may contain carboxyl groups are the anhydrides of saturated and / or unsaturated aliphatic, cycloaliphatic and aromatic acids di- and polycarboxylic acids, such as, for example, the anhydrides of phthalic acid tetrahydrophthalic acid, hexahydrophthalic acid, succinic acid, maleic acid, itaconic acid, glutaric acid, trimellitic acid and pyromellitic acid, and halogenated or alkylated derivatives thereof.

The anhydrides of phthalic acid, tetrahydro- and hexahydrophthalic acid of 5-methylhexahydrophthalic acid anhydride are preferably used. Monomers which are suitable for the introduction of hydroxyl groups into poly (methyl) acrylic copolymers which optionally contain urethane groups are, for example, hydroxyalkyl esters of alpha, beta-unsaturated carboxylic acids, such as (meth) acrylic acid, that is, with primary hydroxyl groups, such as, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamyl acrylate, hydroxyaxyl acrylate, hydroxyoctyl acrylate and the corresponding methacrylates. Examples which may be mentioned of hydroxyalkyl esters with a secondary hydroxyl group which may be used are 2-hydroxypropyl acrylates, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate and the corresponding methacrylates. The functionalized hydroxyl component may advantageously be at least in part a reaction product of one mole of hydroxyethyl acrylate and / or hydroxyethyl methacrylate and on average two moles of epsilon-caprolactone. A reaction product of acrylic acid and / or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary alpha-carbon atom can also be cooled, at least in part, as the functionalized hydroxyl component. The glycidyl esters of highly branched monocarboxylic acids are obtained, for example, under the tradename "Cardura". The reaction of acrylic acid or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary alpha-carbon can be carried out before, during or after the polymerization reaction. In addition to the aforementioned monomers, the monomers which are also ethylenically unsaturated can also be used in the preparation of (meth) acrylic copolymers, the selection of the monomers which are also ethylenically unsaturated is not critical, and conventional olefinic monomers, with and without other functional groups, for the polymerization can be used. Preferably, the monomers are selected in a manner with which the skilled person is familiar in such a way that their incorporation does not lead to undesirable properties of the copolymer. Monomers which are also suitable ethylenically unsaturated are, for example, in particular alkyl esters of acrylic and methacrylic acid, such as, for example, methyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, ( meth) propyl acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) cyclohexyl acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, 3,5,5-trimethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate and octadecinyl (meth) acrylate. It is also possible to use modified silane monomers, such as, for example, gamma-methacryloxypropyltrimethoxysilane or gamma-methacryloxypropyltris (2-methoxy-ethoxy) -silane. Instead of the aforementioned alkyl esters of acrylic and methacrylic acid, or together with said alkyl esters, other ethylenically unsaturated monomers can be used for the preparation of (meth) acrylic copolymers, the selection of said monomers depends to a large extent on the properties of the coating compositions with respect to hardness, elasticity, compatibility and polarity. Examples of other suitable ethylenically unsaturated monomers are the alkyl esters of maleic, fumaric, tetrahydrophthalic, crotonic, isocrotonic, vinylacetic and itaconic acids, such as, for example, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, pentyl, amyl esters, isoamyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 3,5,5-trimethylhexyl, decyl, dodecyl, hexadecyl, octadecyl and octadecenyl corresponding. It is also possible to use small amounts of monomers with at least two polymerizable, olefinically unsaturated double bonds. The content of said monomers is preferably below 5% by weight, based on the total weight of monomers. Examples of such compounds are hexanediol diacrylate, hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, hexamethylenebismethacrylamide, trimethylpropanetriacrylate, trimethylpropanetrimethacrylate and the like. The aromatic monovinyl compounds are other suitable components. They preferably contain from 8 to 9 carbon atoms per molecule. Examples of suitable compounds are styrene, vinyltoluene, alpha-methylstyrene, chlorostyrene, o-, m- or p-methylstyrene, 2,5-dimethylstyrene, p-methoxystyrene, p-tert-butylstyrene, p-dimethylaminostyrene, p-acetamidostyrene and -vinylphenol. Preference is given to vinyltoluenes and, in particular, styrene. It is also possible to use silane-modified monomers, such as, for example, gamma-methacryloxypropyltrimethoxysilane or gamma-methacryloxypropyltris (2-methoxy-ethoxy) -silane. The copolymer binder component A) is prepared by free radical copolymerization. The amount of monomer is adjusted at this point, so that the desired specifications are achieved with respect to molecular weight, OH group ratio, OH number and acid number. It may be advantageous herein to dose a portion of the monomers in an alternating period with respect to one another. For the preparation of the copolymers, the monomers or the monomer mixture used may comprise initiators. If the monomer mixture does not comprise initiators, they can be added to the monomer mixture optionally in a slightly alternate period or dosed separately. Then, the polymerization can also be carried out over a relatively long period, that is, for several hours.

It is then possible to adjust the mixture to a desired solids content, for example in the order of 30 to 60% by weight, for example 50% by weight, with a conventional lacquer solvent. The preparation is carried out, for example, as polymerization of free radical solution in the presence of a free radical initiator, so that it is familiar to the skilled person. Examples of free radical initiators are dialkyl peroxides, such as di-tert-butyl peroxide, dicumyl peroxide; diacyl peroxide, such as dibenzoyl peroxide, dilaurayl peroxide; hydroperoxides, such as eumeno hydroperoxide, ether-butyl hydroperoxide, peresters, such as tert-butyl perbenzoate, tert-butyl perpivalate, per-2-ethyl-tert-butyl per-3,5,5-trimethylhexanoate. tert-butyl hexanoate; peroxide dicarbonates, such as di-2-ethylhexyl peroxyd carbonate, dicyclohexyl peroxydicarbonate; Perketals, such as 1,1-bis- (tert-butylperoxy) -3,5,5-trimethyl-cyclohexane, 1,1-bis- (tert-butylperoxy) -cyclohexane; ketone peroxides, such as cyclohexanone peroxide, methyl isobutyl ketone peroxide; and azo compounds, such as 2,2'-azo-bis (2,4-dimethyl-valeronitrile), 2,2'-azo-bis- (2-methylbutyronitrile), 1,1,1-azo-bis- cyclohexanecarbonitrile, azo-bis-isobutyronitrile; and and slit initiators, such as, for example, benzopinacol derivatives.

The polymerization initiators are generally added, for example, in an amount of 0.1 to 4% by weight, based on the weight of monomers. In another reaction step, the OH functions of the carboxylated functionalized (meth) acrylic copolymers can be reacted with mono-, di-, tri- or polyisocyanates for the possible urethanization of functionalized carboxyl (meth) acrylic copolymers. The amount of di-, tri- or polyisocyanates depends on the OH number of the (meth) acrylic copolymer and is selected in a manner familiar to the skilled person, so that gelation is avoided. For example, copolymers with an OH number of 30 to 100 mg KOH / g are reacted with di-, tri- or polyisocyanates, so that an OH number of the urethanized copolymer of 15 to 80 mg KOH / g results. A process can be followed herein, so that the functional (OH) -carboxyl and OH copolymer is initially introduced into the reaction vessel as a solution in an aprotic solvent and the optionally dissolved di-, tri- or polyisocyanate. in an aprotic solvent, such as for example xylene or butyl acetate, then it is mixed for a period of, for example 30 minutes to 3 hours, for example, from 5 ° C to 80 ° C. The term of the reaction is reached with the NCO number of the mixture is less than 0.1. In the case where the monoisocyanates are used, a particular amount of isocyanate is not necessary, and optionally all the OH functions of the (meth) acrylic copolymer can be achieved herein. The reaction conditions are the same for the di-, tri- or polyisocyanates. Of course, it is also possible to urethaneize the functional OH (meth) acrylic copolymers before the introduction of the carboxyl groups by reaction with acid anhydrides and only then add them into the acid. Examples of di-, tri- and polyisocyanates, which can also be used as a mixture, are described under the description of component E). Examples of monoisocyanates are, for example, reaction products of the diisocyanates described below for component (E) with monoalcohols, such as methane, butanol, hexanol and octanol, 1 mole of diisocyanate being reacted with one mole of alcohol. Other examples of monoisocyanates are alpha (meth) acrylate, alpha-dimethyl-m-isopropenylbenzyl isocyanate or isocyanate. Polyesters containing carboxylic groups and optionally containing urethane groups and can be used as components (A) can be increased by conventional methods from aliphatic and / or cycloaliphatic alcohols which are difunctional, trifunctional or have a greater functionality, optionally together with monohydric alcohols, and of aliphatic, aromatic and / or cycloaliphatic carboxylic acids, in particular dicarboxylic acids, and polycarboxylic acids of greater functionality. Examples of suitable alcohols are aliphatic diols, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, , 4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol , 1,4-dimethylolcyclohexane and aliphatic polyhydric alcohols, such as glycerol, trimethylethane, trimethylpropane and pentaerythritol, and etherification products of diols and polyols, i.e., di- and triethylene glycol, polyethylene glycol and the neopentyl glycol ester of hydroxypivalic acid. Examples of suitable carboxylic acids are adipic, acrylic, 1,3-and 1,4-cyclohexadicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid and endomethyltetrahydrophthalic acid, isophthalic acid, o-phthalic acid, terephthalic acid and anhydrides thereof and derivatives thereof. that have the ability to esterify. The calculated molecular weights of the polyesters are between 500 and 2000 g / moles. The carboxyl functional (meth) acrylic copolymers and polyesters which can be used as components (A) can be "elongated chain" with a lactone as explained above. The lactones (cyclic esters) are added to the carboxyl groups, the ring being open and a new terminal carboxyl group is formed. If the OH and COOH groups are present, the OH groups react considerably faster with lactones, carboxyl functional (meth) acrylic copolymers and carboxyl functional polyesters that are free of the OH groups are preferred for the preparation of the component (A). If the copolymers or polyester containing OH groups are initially used as starting substances, their OH groups preferably react completely or substantially with anhydrides to give carboxylic acids. An example of a particularly preferred lactone is epsilon-caprolactone. Examples of other lactones are gamma-butyrolactone and lactones such as beta-propiolactone, delta-valerolactone, delta-butyrolactone, zeta-enantolactone and eta-caprilolactone. These lactones can be substituted; examples of the above are 6-methyl-epsilon-caprolactone, 3-methyl-epsilon-caprolactone, 5-methyl-epsilon-caprolactone, 5-phenol-epsilon-carpolactone, 4-methyl-delta-valerolactone, 3,5- dimethyl-epsilon-carprolactone and mixtures thereof. The reaction with the lactone can be carried out, for example, directly after the synthesis of resin, that is, after the synthesis of the poly (meth) acrylic copolymer or the polyester. The reaction is carried out, for example, at elevated temperature, for example at temperatures up to 100 ° C. The reaction can be carried out, for example, with stirring, for example up to 10 hours. The functionalized carboxyl polyesters can be urethanized, as can the functionalized carboxylic acid (meth) acrylic copolymers already described. The reaction conditions and the polyisocyanates that can be used are the same as for the (meth) acrylic copolymers. The introduction of the urethane groups is possible by reaction of the functional carboxyl and OH polyesters, reaction of the carboxyl functional and OH functional polyesters of lactone modified with mono-, di- or tri- or polyisocyanates. The reaction of the functional carboxyl and OH polyesters prior to lactonization with polyisocyanates is preferred. It is possible in the present to uretanize a large proportion or total amount of OH groups, so that in the case of the lactone reaction said OH groups can no longer enter the reactions competent to carboxyl groups. It is also possible to introduce the urethane groups during the synthesis of the same polyester. The foregoing is effected by the replacement of all or a portion of the di- or tricaboxylic acids by di- or triisocyanates. The aforementioned routes 1) and 2) are preferred, and route 1) is particularly preferred. Examples of mono-, di-tri- or polyisocyanates that may be employed may be mentioned in the following description of component E). The coating compositions according to the invention comprise as component B) one or more functional epoxide crosslinking agents. The above are, for example, compounds with at least two epoxide functions in the molecule. The latter can have an epoxide equivalent weight of, for example, 200-700, preferably 250-500, and in particular 300-400, in each case based on the solid resin. The average molecular weight number (Mn) is preferably 200 to 10,000 g / moles. The glass transition temperature is preferably from -20 ° to 70 ° C, particularly preferred from 0 ° C to 50 ° C, and in particular 5 ° C to 40 ° C. The upper limit of preference is up to 50 ° C, for example up to 25 ° C. Examples of the above are conventional di- or polyepoxides, ie polyglycidyl ethers based on diethylene glycol, and propylene glycol or polypropylene glycol, for example with a number average molecular weight (Mn) of up to 2,000, triglycidyl ethers of glycerol and / or di- or polyphenols, such as bisphenol A. Other examples of di- or polyepoxides are those based on di- or polyglycidyl esters. Examples of the foregoing are reaction products of 1-hydroxy-2,3-epoxypropane with phthalic or terephthalic acid to give phthalic or terephthalic acid bis (2,3-epoxypropyl ester), or a diglycidyl ether of bisphenol A with trimellitic anhydride for give polyesters, for example with an average molecular weight number (Mn) of from 500 to 2,000. Examples that can also be used are copolymers functionalized glycidyl (meth) acrylics. Examples of the above are copolymers of glycidyl (meth) acrylate or 2,3-epoxycyclopentyl acrylate. Comonomers which may be selected are (meth) acrylic acid esters such as, for example, methyl, ethyl, butyl, isobutyl, ethylhexyl, cyclohexyl and / or lauryl esters, functionalized hydroxyl esters of (meth) acid acrylic, such as the hydroxyethyl and / or hydroxypropyl esters, and also also styrene, vinyltoluene and / or alpha-methylstyrene, as well as all alpha, beta-unsaturated monomers, as described above for component A). The average molecular weight number (Mn) can be, for example, between 1,000 and 10,000 and preferably 2,000 to 5,000. Other copolymerizable glycidyl monomers are, for example, glycidyl (meth) allyl ether or 3,4-epoxy-1-vinylcyclohexane. The copolymers are prepared by polymerization of free radical solution, which is known to the expert and does not require further explanation. According to a preferred embodiment of the invention, at least one of said crosslinking resins B) is composed of the following monomers: b1) 5 to 60% by weight of glycidyl (meth) acrylate b2) 3 to 50% by weight of tert-butyl (meth) acrylate b3) 0 to 60% by weight of one or more aromatic vinyl functional monomers. b4) 0 to 20% by weight of one or more hydroxyl functional (meth) acrylic monomers b5) 0 to 92% by weight of one or more monomers that differ from part B1) to B4). Examples of the monomers that can be used as in B3) to B5) are the monomers mentioned above in the text that can be used for the preparation of the poly (meth) acrylic copolymers of the component TO). In the case of the preparation of a glycidyl (meth) acrylate copolymer, it may be advantageous for a content of acidic monomers, such as, for example, (meth) acrylic acid, to be copolymerized in said copolymer. The above can be carried out, for example, up to an acid number of 3 to 30 mg KOH / g of solid resin. In order to avoid undesirable gelling of the resin, it is urgent here to select the suitably moderate polymerization conditions. In this way, it is advantageous not to exceed a polymerization temperature of, for example, 120 ° C and to keep the polymerization time as short as possible, for example up to 3 hours. Azo initiators are particularly suitable here for mild polymerization conditions. It is also possible to subject the binder components A and B at least partially to the precondensation in a further reaction step.

The foregoing can be effected, for example, by heating the components A and B. The desired degree of condensation can be determined, for example, from the reduction in the acid number; for example, it is possible to heat the components at a temperature of, for example, 80 to 120 ° C, by stirring, and continuing stirring until the acid number of the mixture has been reduced, for example from 2 to 5 mg KOH / g of solid resin. Obviously it is also possible to reduce the acid number further, but it must be ensured then that the viscosity of the mixture does not rise until gelation. The storage stability of the compositions can also be increased by precondensation of components A) and B). Precondensation between components A) and C) is also possible, and the conditions are the same as for the condensation of A) and B). It is also possible to synthesize the binder B) in the matrix of the binder C) and vice versa. Due to the foregoing, it is possible, for example, to initially introduce a part or all of the polyol of component C) in the reaction vessel, optionally with one or more organic solvents, and to react therein the monomers required for the preparation of the component functional epoxide B), or a portion thereof. For example, polyols C) can be initially introduced into the reaction vessel, optionally with a solvent, and heated, for example, at temperatures of 140 ° C. The monomers required for the preparation of the functional epoxide component B) can be dosed, optionally with initiators, for example during a period of up to 5 hours. The polyol component C) used in said process is preferably a polyester polyol, in particular one with an average molecular weight number Mn of 500 to 4000, preferably with an acid number below 15 mg KOH / g, and preferably with an OH number of 15 to 300 mg KOH / g. Said co-matrix polymer of B) and C) may have advantages in a mixture of B) and C), such as, for example, better compatibility and a more homogeneous mixture. The binder composition according to the invention and the coating compositions according to the invention may comprise one or more polyols with at least two hydroxyl functions in the molecule as component C). Said polyols can be selected, for example, from the OH-functional polyesters and (meth) acrylic copolymers, which can also be optionally urethanized, mentioned in the description of A) and for the preparation of A). The above can be those that are free of carboxyl groups or that contain carboxyl groups.

The latter are used in particular if component A) is free of hydroxyl groups. The binder composition according to the invention and the coating compositions according to the invention may comprise as component D) a crosslinking agent which reacts with the hydroxyl groups to form ethers. The foregoing may be, for example, one or more melamine resins. Examples of the above are etherified butanol or isobutanol melanins which are insoluble in water, such as, for example, the commercial products Setamin® US 138 or Maprenal® MF 610; etherified mixed melamines which are etherified butanol and methanol, such as, for example, CymeIR 254, and hexamethyloxymethylmelamine (melamine HMM), such as for example Cymel® 301 or Cymel® 303, being possible for an acid catalyst, such as for example p -toluenesulfonic, optionally added to the latter for crosslinking. Other examples of melamine resin crosslinking agents are conventional hydrophilic and therefore water soluble or melamine compatible resins, such as, for example, etherified methyl melamines, such as, for example, CymelR 325, CymelR 327, CymeIR 350 and Cymel® 370, and Maprenal® MF 927. The binder compositions and coating compositions according to the invention may also comprise a triazine-based crosslinking agent as crosslinking component D). An example for the above is a triazine triscarbamate of the general formula C3N3 (NHCOOR) s In said formula, R can be an alkyl radical having from 1 to 20 C atoms, an aryl radical having from 6 to 20 C atoms and / or an aralkyl radical having from 7 to 20 C atoms. The R radicals can be identical or different. Specific examples of said carbamate crosslinking agents are 2,4,6-tris- (methoxycarbonylamino) -1,5,5-triazine and 2,4,6-tris (butoxycarbonylamino) -1,5,5-triazine. The coating compositions according to the invention may comprise one or more free or covered polyisocyanates as the crosslinking agents which form urethane groups with OH groups (component E). Examples of polyisocyanates that can be used are cycloaliphatic, aliphatic or aromatic polyisocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylene disocyanate, 1,2-dodecane diisocyanate, 1, 3 and 1 , Cyclohexane-4-diisocyanate, 1-diisocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (= IPDI isophorone diisocyanate), 2,4'- and / or 4,4'-peridrodiphenylmethane-diisocyanate, 1, 3 - and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluylene diisocyanate, 2,4'- and / or 4,4'-diphenylmethane diisocyanate, 3,2'- and / or 3, 4- isocyanate-4-methyl-diphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ', 4"- triphenylmethane triisocyanate, tetramethylxyne diisocyanate or mixtures of said compounds In addition to said simple isocyanates, those containing heteroatoms in the radical bond of the isocyanate groups are also suitable. polyisocyanates containing carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups, acylated urea groups and biuret groups The polyisocyanates which are particularly suitable for the invention are the known polyisocyanates conventionally used in the preparation of lacquers, ie modification products of the aforementioned simple polyisocyanates containing biuret, isocyanurate or urethane groups, in particular tris- (6-isocyanatohexyl) -biuret or low molecular weight polyisocyanates containing urethane groups, such as those obtainable by the reaction of IPDI, employees in excess, with simple polymeric alcohols of the scala molecular weight 62-300, in particular with trimethylolpropane. Any desired mixture of the polyisocyanates mentioned can obviously also be used for the preparation of the products according to the invention. The suitable polyisocyanates are also the known prepolymers containing terminal isocyanate groups, so that they are accessible in particular by the reaction of the aforementioned simple polyisocyanates, especially diisocyanates, with excess amounts of organic compounds with at least 2 groups which are reactive to the other isocyanate groups. Such compounds which are preferably used are compounds containing at least two amino groups and / or hydroxyl groups in total and having an average molecular weight number of 300 to 10000m, preferably 400 to 6000. In said known prepolymers, the ratio of isocyanate groups to hydrogen atoms that are reactive to NCO preferably is 1.05 to 10: 1, preferably particularly 1.1 to 3: 1, the hydrogen atoms preferably originating from the hydroxyl groups. The nature and quantity ratios of the starting materials used in the preparation of NCO prepolymers are preferably selected so that the NCO polymers have an average NCO functionality of 2 to 4, preferably 2 to 3, and b) a number of average molecular weight from 500 to 10000, preferably 800 to 4000. The polyisocyanates can be used as free polyisocyanates; in that case, these are not covered. The coating compositions are then referred to as two-component systems (2C systems), in which the polyisocyanates are added immediately before use. If the isocyanate groups of the polyisocyanates are completely covered, the coated polyisocyanates can be added directly to the coating composition. The coating compositions are then defined as one-component systems (1C systems). The coating agent that can be used are conventional coating agents such as those used, for example, in the lacquer industry. Examples of coating agents that can be used are esters, such as dimethyl malonate, diethyl malonate and ethyl acetoacetate, lactams, such as elepsilon-caprolactam, acetanilide, acetylacetone, acetone oxime, substituted pyrazoles, such as dimethylpyrazole , propan-1,2-diol and / or oximes, such as butanone oxime. The coating of the polyisocyanates can be carried out, for example, by heating one or more polyisocyanates with the coating agent. For example, one or more polyisocyanates can be initially introduced into the reaction vessel and heated, for example, to about 80 ° C, with stirring, and the coating agent can be dosed (for example for a period of about 10 minutes) . The mixture is stirred until the NCO number is less than 0.1%. It is also possible to cover one or more polyisocyanates with a mixture of two or more coating agents. The advantage of using two or more different polyisocyanates and / or two or more coating agents is based on the fact that with the above the crosslinking can be carried out over a wide temperature range. If they are not coated, the free polyisocyanates are used in aqueous systems, it may be advantageous to equip the polyisocyanates with hydrophilic or hydrophobic groups. By using hydrophilic polyisocyanates, these can be dispersed in water more easily. By introducing hydrophobic groups, a more rapid diffusion of the hydrophobized polyisocyanates in the resin particles in aqueous systems can be carried out. The binder compositions according to the invention and therefore the coating agent compositions according to the invention may comprise one or more anhydride components f) as crosslinking agents which lead to the ester groups with OH groups. Component F) comprises at least one organic compound containing at least two cyclic carboxylic acid anhydride groups per molecule. The content of carboxylic acid anhydride groups (formally calculated as C4O3, molecular weight = 96) in said compounds is preferably from 5 to 88% by weight, preferably particularly from 6 to 30%. Suitable examples are the trimellitic anhydride adducts of the general formula (I). wherein R represents a divalent hydrocarbon radical having from 2 to 12 carbon atoms which optionally contains ether oxygen atoms. Possible compounds of formula I are, for example, the corresponding trimellitic anhydride esters of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, neopentiglycol, glycerol or trimethylpropane. Other suitable polyanhydrides are, for example, the benzophenone tetracarboxylic acid dianhydrides of the general formula (II) wherein X represents hydrogen or halogen, NO2, -COOH or -SO3H substituents and the two aromatic nuclei may be identical or different. Examples of the above are 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride; 2-bromo-3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride or 5-nitro-3,3', 4,4'-benzophenotetracarboxylic acid dianhydride. The 1,2,4,5-benzannetetracaboxylic acid dianhydride of the formula (III) for example, it is also suitable. Component F) preferably comprises in particular olefinically unsaturated monomers containing a statistical average of at least two cyclic carboxylic acid anhydride groups per molecule. The above are preferably copolymers of maleic anhydride and / or taconic anhydride with comonomers such as are used, for example, as monomers for component A) and which are described above by way of example. Copolymers based on maleic anhydride, styrene and / or alkyl esters of acrylic and / or methacrylic acid are particularly suitable. The copolymers preferably have a number average molecular weight (Mn) of 1, 500 to 75,000, preferably 2,000 to 50,000. The foregoing can, for example, be prepared in a manner completely analogous to copolymers A). The compositions may also comprise monoepoxide compounds G), preferably with an average molecular weight of up to 3,000, preferably particularly less than 1,000. In the case of said low molecular weights, said compounds can have a very positive influence on the viscosity properties of the lakes prepared therewith, although they then function as if they were reactive diluents. Examples of said compounds are, for example, the reaction products of a diglycidyl compound, for example, a diglycidyl ether, such as one mole of diglycidyl ether of bisphenol A and one mole of a saturated or unsaturated monocarboxylic acid, such as acetic acid, propionic acid or isononanoic acid. Other examples are the reaction products of hydroxyethyl epoxides, such as 1-hydroxy-2,3-epoxypropane, with aromatic polycarboxylic acids, such as phthalic or terephthalic acid, to give the corresponding polyesters, such as phthalic acid or terephthalic bis- (2,3-epoxypropyl ester), or reaction products of diglycidyl ethers, such as diglycidyl ether of dysphenol A, with acid anhydrides, such as trimellitic anhydride, to give the polyester by an average molecular weight number from 500 to 3,000, preferably up to 1,000.

Other examples are the reaction products of di- or polyepoxides, such as the polyglycidyl esters based on diethylene glycol, dipropylene glycol and polypropylene glycol with an average molecular weight number of up to 2,000 and triglycidyl esters of glycerol and / or polyphenols, such as Bisphenol A or F, with the aforementioned moncarboxylic acids. The glycidic esters of versatic acid with the commercial product Cardura E from Shell AG are particularly preferred. The binder composition according to the invention and therefore the coating agent compositions according to the invention may comprise one or more catalysts (component H) for the reaction of carboxyl groups with epoxide groups. The above are, in particular, catalysts that are soluble in organic solvents or in water or that are mixed with organic materials. Examples of suitable catalysts that are soluble in organic solvents or that are mixed with organic materials are the phosphonium salts, such as, for example, ethyltriphenylphosphonium acetate, phosphate, chlorine, bromine or iodine, butyltriphenylphosphonium acetate, phosphate, chlorine, bromine or iodine and benzyltriphenylphosphonium acetate, phosphate, chlorine, bromine or iodine, and the quaternary ammonium salts, such as, for example, alkylbenzyldimethylammonium chloride, benzyltrimethylammonium chloride, methyltrioctylammonium chloride, tetraethylammonium bromine, N-dodecylpyridinyl chlorine and tetraethylammonium iodine. Preferred catalysts which are soluble in organic solvents or that are mixed with organic materials are ethyltriphenylphosphonium acetate, phosphate, chlorine or bromine, butyltriphenylphosphonium acetate, phosphate, chlorine or bromine, benzyltriphenylphosphonium acetate, phosphate, chlorine or bromine and chlorine. dimethyltrioctylammonium.

Ethyltriphenylphosphonium phosphate can be obtained, for example, from ethyltriphenylphosphonium acetate by reaction with phosphoric acid. Other examples of catalysts are acids, such as sulfonic acids, ie p-toluenesulfonic acid. It is also possible to react the functionalized glycidyl resin with p-toluenesulfonic acid, for example at elevated temperature up to, for example, 80 ° C. In said reaction, the p-toluenesulfonic acid is added with the opening of the oxirane ring. During the baking of the finished lacquer, the p-toluenesulfonic acid separates again and can catalyze the crosslinking of COOH / epoxide. Other examples are dinonylnaphthalenedisulfonic acid, dinonylnaphthalenemonosulfonic acid and dodecylbenzenesulfonic acid. The acid catalysts can be partially neutralized, completely or in excess. Possible neutralizing agents are tertiary amines, such as, for example, triethylamine, dimethylethanolamine or dimethyloxazolidine.

The composition may comprise the catalyst, which is soluble in organic solvents and / or water or mixed with organic materials, in an amount of about 0 to about 10% by weight, preferably 0.3 to 2.0% by weight, based on the sum of the weights of components A) to G). It is also possible to join an amine catalyst with the mixture of functionalized COOH (meth) acrylic copolymer resin. The above is carried out rapidly by the copolymerization of amino monomers tertiary (meth) acrylamide during the synthesis of the functionalized COOH (meth) acrylic copolymer resin. Examples of said monomers are dimethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate-amide. The content in terms of the amount of said (meth) acrylates is preferably 0.5 to 10% by weight, preferably particularly 1 to 5% by weight, based on the total solids content of the (meth) acrylic copolymer resin of COOH functionalized. When the binder composition or the coating agent composition according to the invention is prepared, the ratios of preferential amounts are selected in such a way that the molar ratio of the reactive groups of 1: 3 to 3: 1 still prevails. between the resin comprising carboxyl groups of components A) and the epoxide component B), and, preferably, between the sum of the weights of components A) to C) and the weight of component D) a ratio of 65:35 at 98: 2 and / or between the sum of the weights of the components A) to C) and the weight of the polyisocyanate component E) a ratio of 60:40 to 95: 5. The coating compositions with the invention can comprise solvents, since they are conventional, for example, for the preparation of coating composition, for example lacquers. Said compositions can also be solvents, since they are used in the preparation of the individual components. Examples of said solvents are organic solvents, in particular conventional solvent for lacquers, such as aliphatic and aromatic hydrocarbons, for example toluene, silene and mixtures of aliphatic and / or aromatic hydrocarbons, esters, ethers and alcohol. Aqueous solutions can also be prepared for the preparation of the coating compositions of the binders according to the invention. Suitable emulsifiers that are conventional in the lacquer sector can optionally be used for that purpose. The solvent content in the coating compositions is, for example, from 2 to 20% by weight. The binder compositions according to the invention and the coating compositions according to the invention can also be found in aqueous form, in which case they are free of organic solvents or have only a relatively low content of organic solvents. The water content is, for example, from 10 to 70% by weight; the solvent content that is added to the water is, for example, from 0 to 20% by weight. For preparing the aqueous compositions it is possible, for example, to largely liberate the carboxyl-containing component A) from the organic solvents, ie by distillation, and then to neutralize some of the carboxyl groups, ie, with bases, such as the triethyleneamine or dimethylethanolamine, to then form an emulsion in water, which is optionally heated. The other resins can then optionally be emulsified in said emulsion, in which component A) acts as an emulsifying resin. This is done, for example, by heating the emulsifying resin at 60-80 ° C and adding the functional hydroxyl and / or epoxide resins, which are also heated to 60-80 ° C, over the course of 120 minutes during the agitation. The addition of all other resins and lacquer additives can also be carried out before emulsification. It is also possible, for example, to mix the functionalized COOH resin of component A), which has been largely freed from the solvents with the epoxy resin, which has been largely freed from the solvents, and to form an emulsion in a water / emulsifier mixture by a rotor / stator unit. It is also possible to emulsify the components separately and mix the emulsions. Possible emulsifiers are, for example, ethoxylated sorbitan fatty acid esters. For the preparation of the coating compositions according to the invention, conventional pigments, fillers and / or auxiliary substances and lacquer additives can be added. The above are conventional lacquer additives, so that they are customary in the lacquer sector. The quantities are based on the conventional family scale for the expert. For example, the coating compositions according to the invention may comprise from 2 to 60% by weight of 1 or more pigments and / or fillers. The amount of additives is, for example, 0.01 to 10% by weight. Examples of pigments are coloring pigments, such as titanium dioxide or carbon black, and effect pigments such as metal flake pigments and / or opalescent pigments. The coating compositions according to the invention comprise effect pigments together with coloring pigments or coloring pigments with fillers. Examples of fillers are conventional fillers in lacquers such as, for example, talc and silicates. Examples of additives are substances and auxiliary additives, such as plasticizers, light stabilizers, stabilizers of flow control agents such as silicone oils. The coating compositions prepared from the binders according to the invention are suitable for coatings that adhere to a large number of substrates, for example, wood, textiles, plastic, glass, ceramics and, in particular, metal; The coating compositions according to the invention can be applied by known methods such as, for example, spraying, dipping, rolling or knife cutting. In the above, the coating is applied from the coating compositions according to the invention, for example, as a topcoat coating, to the substrate which is optionally provided with other layers of lacquer.After an evaporation phase, the applied coating composition is crosslinked by heating. Baking temperatures are, for example, 20 to 180 ° C, preferably 60 to 150 ° C. The layer thickness of the baked film is, for example, 15 to 60 μm. At this point, a hard, glossy and acid-resistant lacquer coating was formed. A preferred embodiment is the application of the coating composition according to the invention as a coating of lacquer on a lacquer base, preferably an aqueous-based lacquer comprising coloring and / or effect pigments. The above can be carried out by the wet-on-wet process, or the basecoat if it is dried beforehand by heating. Particularly good adhesion of the two layers is obtained in the present. Basecoats, which comprise conventional topcoat pigment, for example, can be excessively lacquered with the coating compositions that have been formulated according to the invention as clear lacquer coatings without pigments; they preferably comprise effect pigments, such as, for example, metallic pigments. The polyester, polyurethane or (meth) acrylic copolymer resins are preferably used as the binder base of the basecoat. Such binders can optionally be crosslinked by cross-linking agents, i.e., melamine derivatives or isocyanate derivatives. It is also possible to add supercritical carbon dioxide as a lacquer solvent to the coating composition according to the invention, in particular as a clear lacquer and to apply the mixture. In addition to the formulation as clear lacquers, the coating compositions according to the invention can also be formulated as base lacquers, and also as fillers. The above are particularly suitable for the preparation of multilayer laquered, that is, in a motor vehicle sector. Conventional additives such as, for example, have been described above so that basecoats can be added for the formulation as basecoats or fillers. Compared with conventional basecoats, the basecoats according to the invention give, in particular, coatings with improved resistance to moist heat. The base lacquers according to the invention can be excessively lacquered with conventional clear lacquers by the number wet process, optionally after the brief surface drying.

Preferably, they are lacquered in excess with clear lacquers based on the coating compositions according to the invention. In the following examples, parts (P) and percentages are related to weight, unless stated otherwise.

EXAMPLE 1 Preparation of a 336.7 P polyester oligomer of trimethylolpropane, 366.8 P of adipic acid and 297 P of hexanediol are esterified with 5 P of hypophosphorous acid to an acid number of 20 KOH / g to 180 ° C at 230 ° C in the mixture in a 2-liter three-neck flask provided with a stirrer, separator, thermometer and reflux condenser. The condensation is then carried out in vacuo in an acid number of less 1.5 mg KOH / g. The product obtained in this way has a baking residue of 94.5% (1 h, 150 ° C), a viscosity of 3200 mPa. s (100%), a hydroxyl number of 466 mg KOH / g and a color number of 30 Hazen.

EXAMPLE 2 Preparation of a functional epoxy resin A 990 P of silex Solvesso 100 is initially introduced into a 3-liter 4-liter flask fitted with a stirrer, thermometer, safety funnel and reflux condenser and heated to 140 ° C with stirring. Over the course of 5 hours a mixture of 842.4 P glycidyl methacrylate 300.0 P tert-butyl acrylate 348.6 P styrene 383.4 P butyl acrylate 11.10 P di-tert-butyl peroxide 64.50 P tert-butyl-2-ethylhexanoate -butyl is added by dripping. The monomer mixture container and safety funnel is rinsed with 60 P Solvesso, which are added to the batch. Subsequently, the post-polymerization is carried out for 6 hours at 140 ° C. The functional epoxy resin has a solid content of 64.55 (1 h, 150 ° C) and a viscosity of 1,200 mPa.s.

Preparation of a 990 P epoxide functional resin B Solvesso 100 is initially introduced into a 4-liter 4-liter flask fitted with a stirrer, thermometer, safety funnel and reflux condenser and heated to 140 ° C, with stirring. Over the course of 5 h, a mixture of 842.40 P of glycidyl methacrylate 564.39 P of styrene 467.61 P of butyl acrylate 11.10 P of di-tert-butyl peroxide 64.50 p of tert-butyl peroxy-2-ethylhexanoate is added by drip. The monomer mix container and safety funnel is rinsed with 90 P Solvesso, which are added to the batch.

Subsequently, the post polymerization is carried out for 6 hours at 140 ° C. The resin has a solids content of 64.5% (1 h, 150 ° C) and a viscosity of 1,100 mPa.s.

Preparation of a functional epoxy resin C 990 P Solvesso 100 is initially introduced into a 4-liter three-necked flask fitted with a stirrer, thermometer, safety funnel and reflux condenser and heated to 140 ° C with stirring. Over the course of 5 hours, a mixture of 842.40 P of glycidyl methacrylate 245.79 P of styrene 324.93 P of butyl acrylate 300.00 P of tert-butyl acrylate 161.28 P of hydroxyethyl acrylate 11.10 P of di-tert-butyl peroxide 64.50 P for tert-butyl peroxy-2-etiihoxanoate is added dropwise. The monomer mixture container and safety funnel are rinsed with 60 P Solvesso, which are added to the batch. Subsequently, the polymerization is carried out for 6 hours at 140 ° C. The functional epoxy resin has a solid content of 64.5% (1 h, 150 ° C) and a viscosity of 1,600 mPa.s.

Preparation of a functional epoxy resin D 990 P Solvesso 100 is initially introduced into a 4-liter three-necked flask fitted with a stirrer, thermometer, safety funnel and reflux condenser and heated to 140 ° C, with stirring. Over the course of 5 h, a mixture of 842.40 P of glycidyl methacrylate 461.58 P of styrene 409.14 P of butyl acrylate 164.28 P of hydroxyethyl acrylate 1 1.10 P of di-tert-butyl peroxide 64.50 P of peroxy-2- tert-butyl ethylexanoate is added dropwise. The monomer mixture container and safety funnel are rinsed with 60 P Solvesso, which is added to the batch. Subsequently, the post-polymerization is carried out for 6 h 140 ° C. The functional epoxy resin has a solids content of 64.5% (1 h, 150 ° C) and a viscosity of 1650 mPa.s.

Preparation of a functional epoxide co-matrix polymer E 990 P of Solvesso 100 and 450 P of the oligomer described in example 1 is initially introduced into a 3-liter three-neck flask fitted with a stirrer, thermometer, safety funnel and reflux condenser and heat to 140 ° C, with stirring. Over the course of 5 h, a mixture of 842.40 P of glycidyl methacrylate 248.40 P of styrene 33.30 P of butyl acrylate 300.00 P of tert-butyl acrylate 1 1.10 P of di-tert-butyl peroxide 64.50 P of peroxy-2 - tert-butyl ether terephthalate is added by dripping. The monomer mixture container and the safety funnel are rinsed with 60 p Solvesso, which is added to the batch. Subsequently, the post-polymerization is carried out for 6 h at 140 ° C. The functional epoxy resin has a solids content of 64.5% (1 h, 150 ° C) and a viscosity of 1,400 mPa.s.

Preparation of a functional epoxide co-matrix polymer F. 990 P Solvesso 100 and 450 p of the oligomer described in example 1 are initially introduced into a 4-liter three-necked flask fitted with a stirrer, thermometer, safety funnel and reflux condenser and heated to 140 ° C, with stirring . Over the course of 5 h, a mixture of 842.40 P of glycidyl methacrylate 7.67 P of styrene 574.32 P of butyl acrylate 11.10 P of di-tert-butyl peroxide 64.50 P of tert-butyl peroxy-2-etherexenoate is added by dripping. The monomer mixture container and the safety funnel are rinsed with 60 P Solvesso, which is added to the batch.

Subsequently, the post-polymerization is carried out for 6 h at 140 ° C. The functional epoxy resin has a solids content of 64. 5% (1h, 150 ° C) and the viscosity of 1,500 mPa.s.

Example 3 Synthesis of an acid cross-linking agent based on the oligomer of example 1. 1.101.6 P of the product of example 1) and 300 P of xylene are mixed with 985.8 P of hexahydrophthalic anhydride in a 4-neck flask of 4 liters provided with an agitator, thermometer and a reflux condenser and the esterification is carried out at 140 ° C at a constant acid number. Then 312.6 P of epsilon-caprolacton is added. The reaction is carried out at 140 ° C until the theoretical solids content is reached. When the reaction is finished, the resin is diluted with 300 P of n-butanol. The functional carboxyl resin has a baking residue of 79.6% (1 h, 150 ° C), an acid number of 150 mg KOH / g solid resin and a viscosity of 1,400 mPa.s.

Preparation of a clear lacquer The following recipe was used for the preparation of a clear lacquer composition: 38.80 P of functional epoxide polymer of example 2). A, B, C, D or F 36.20 P of the acidic crosslinking agent of example 3). 9.00 P of n-butanol 9.00 P of methoxypropanol 5.00 P of butyl diglycol acetate 0.4 P of a commercially available flow control agent based on the 1.6 P silicone oil of light stabilizer (mixture of 1: 1 benzotriazole derivatives and a mine sterically impeded). The mixture is adjusted to a spray viscosity of 28 seconds of AK4 flow rate with a mixture of methoxypropanol and butyl glycol acetate. The clear lacquer is applied by the wet-on-wet method using a spray gun on a metal sheet coated with a commercially available water-based filler and a commercially available water-based base lacquer, allowed to evaporate at room temperature during 8 minutes and bake at 80 ° C for 5 minutes and then at 140 ° C for 17 minutes. The tests listed were carried out with the resulting coatings and the following characteristic values obtained.

Claims (6)

NOVELTY OF THE INVENTION CLAIMS

1. - A coating composition comprising a binder, solvent and / or water composition and optionally pigments and / or fillers and optionally conventional lacquer additives, characterized in that the binder composition contains: A) from 25 to 75% by weight of one or more carboxyl functional (meth) acrylic copolymers with an average molecular weight number of 1000 to 3000 g / mmoles and / or one or more carboxyl functional polyesters with an average molecular weight number of 500 to 4000 g / mmole, the functionality of the carboxyl in each case corresponds to an acid number of from 15 to 300 mg KOH / g, B) from 25 to 75% by weight of one or more epoxide-functionalized (meth) acrylic copolymers with an average molecular weight number from 200 to 10,000 g / moles, an oxide equivalent weight of 200 to 700 of a glass transition temperature of -20 to 70 ° C, which has been prepared co-using from 3 to 50% by weight, based on the total weight of monomer units or, of tert-butyl (meth) acrylate as a monomer unit, the ratio of the amounts of A) to B) being selected such that the molar ratio of its reactive groups is from 1: 3 to 3: 1. C) from 0 to 60% by weight of one or more polyols having at least two hydroxyl functions in the molecule and differing from a component A) optionally containing hydroxyl functions, D) from 0 to 40% by weight of crosslinking components with the hydroxyl groups to form ethers, and / or of a triazine-based crosslinking agent, E) from 0 to 40% by weight of one or more polyisocyanates, which can optionally be covered, F) from 0 to 60% by weight of an anhydride component comprising less than one organic polyanhydride with at least two cyclic carboxylic anhydride groups per molecule, G) from 0 to 20% by weight of one or more diluents reactive with an epoxide strength, H) from 0 to 10% by weight of one or more catalysts to catalyze the reaction of carboxyl and epoxide groups, the sum of% in weight of components A) to H) totaling 100% by weight.

2. The coating composition according to claim 1, further characterized in that the component B) is based on 3 to 50% by weight of tert-butyl (meth) acrylate as the monomer unit, based on the weight total of all monomer units.

3. The coating composition according to claim 1 or 2, further characterized in that component B) is based on a (meth) acrylic copolymer which is based on the following monomer units: b1) from 5 to 60% in weight of one or more functional epoxide olefinically unsaturated monomers, preferably (meth) acrylate glycidyl, b2) from 3 to 50% by weight of tert-butyl (meth) acrylate, b3) from 0 to 60% by weight of one or more aromatic vinyl functional monomers, b4) from 0 to 20% by weight of one or more hydroxyl functional (meth) acrylic monomers, b5) from 0 to 92% by weight of one or more monomers differing from b1) to b4), the sum of the % by weight of b1) to b5) adding 100% by weight.

4. The coating composition according to one of claims 1 to 3, further characterized in that it comprises as component A) one or more carboxyl functional (meth) acrylic copolymers or functional carboxyl polyesters, at least some of the carboxyl functions they react with lactone.

5. The coating composition according to one of claims 1 to 4, further characterized in that all or a part of component B) has been prepared by polymerization in the presence of component C).

6. The process for the production of multiple lacquered by the application of a size and optionally one or more intermediate layers to a substrate and the subsequent application of a base lacquer comprising color and / or defect pigments, with a lacquered in subsequent excess with a clear lacquer, it being possible for the base lacquer and the clear lacquer to be applied by the wet-on-wet and baking process, characterized in that the coating composition according to one of claims 1 to 5 is used as base lacquer and / or clear lacquer.