DE2851613A1 - Solvent soluble hydroxyl gp. contg. copolymers - made by reacting unsatd. mono:carboxylic acid with mono-glycidyl cpd. in vinyl monomer, and copolymerising with further vinyl monomers - Google Patents

Abstract

Prepn. of organic solvent-soluble, OH-contg. copolymers is claimed which are based on vinyl cpds., alpha, beta-unsatd. monocarboxylic acids (I) and monoglycidyl cpds. (II), in which the COOH gp. of the (I) is bound as an ester to the (II). The copolymers are made by first esterifying the (I) with the (II) in the presence of >=1 vinyl cpd. Subsequently, copolymerisation is carried out in an inert solvent, opt. with the addn. of further vinyl cpd(s). such that during the copolymerisation stage, >=2 further vinyl cpds. are present in addn. to the monomeric prod. from the esterification stage. The OH-contg. copolymers are obtd. as clear colourless organic solvent solns., which are free from the clouding and brown colour of prior art materials of this type. The process is suitable for industrial scale prodn. and is not critical w.r.t. reaction conditions. The prods. are useful as components in coating resin compsns. for use with crosslinking agents such as polyisocyanates and aminoplast resins.

Description

Process for the preparation of in organic solvents

soluble hydroxyl group-bearing copolymers In DE-PS 1 078 754 is a process for the production of esterified polyhydroxy copolymers described. This known method is characterized in that simultaneously and in the presence of an epoxy-carboxy catalyst and a catalyst for the Vinyl polymerization are implemented: (a) a short-chain nC, ß-unsaturated monocarboxylic acid, (b) a vinyl monomer with only one active addition polymerization capable, terminal CH2 = C <group and (c) a monoepoxide, which is an optionally alkyl-substituted, Alkylene oxide, an ether or ester with only one three-membered epoxy substituent is, the monoepoxide otherwise having no reactive group. Here must always simultaneously in the presence of an epoxy CarboKy catalyst and a catalyst be implemented for vinyl polymerization. Like reworking the examples there have shown, these known copolymers give yellow to brownish colored Solutions. The paint films produced therefrom show after the solvent has evaporated an undesirable yellow to brown color, making these products only a very may find limited application.

In FR-PS 1 390 572 there is also a method for production of esterified polyhydroxy copolymers described, the addition reaction takes place between the epoxy and carboxy groups during or after the copolymerization. The application of this process principle is by the inventor of the present invention Wprden described in the following patent specifications: DE-OS 2 054 231, CH-PS 523 951, DE-OS 2 021 141, DE-PS 26 26 900, DE-AS 26 03 259, DE-AS 26 59 853, .CH-PS 519 532, DE-OS 25 15 705, DE-OS 26 03 624, DE-OS 26 18 809, DE-OS 20 65 770.

The disadvantage of this known method is on a manufacturing scale in that for the complete reactions, namely esterification and copolymerization, relatively long reaction times (12 to 15 hours) are required. Find here unwanted side reactions take place because the carboxyl group of the 61ß-unsaturated Monocarboxylic acid before and after its copolymerization with the other monomers with reactive groups, e.g. with the hydroxyl groups and / or C-lycidyl groups below Ester formation, and the glycidyl groups with each other or with the hydroxyl groups below Ether binding structures, react. Such reactions are therefore against the reaction conditions are very sensitive, so that it is on an industrial scale Scale is required to adhere to the reaction parameters very precisely in order to produce copolymers with the desired properties in a comparable quality. In addition, even if the reaction is carried out very carefully, there is always a certain amount Ge7particle formation with particle diameters of about 5 to 25 .mu.m takes place from the Lacquer experts are referred to as "specks" in the lacquer films produced therefrom and do not allow a high performance finish to be achieved.

In DE-OS 16 68 510 there is also a method for creating of esterified polyhydroxy copolymers described, but the addition reaction between the epoxy and carboxy groups before, after or during the copolymerization is carried out. In the embodiment in which the esterification during or is carried out after the copolymerization, the statements made above apply explained type with the stated disadvantages. In the embodiment in which two reaction components, namely the α, ß-unsaturated monocarboxylic acid with the epoxy compound, which is a glycidyl ester of a tertiary aliphatic monocarboxylic acid represents, first alone in the absence of esterification catalysts to a precursor processed as an ester (as also in DE-PSS 27 09 784 and 27 09 782 takes place), there is the surprising disadvantage that the copolymer solutions clouded and the lacquer films produced therefrom as well are clouded. Furthermore, further difficulties can easily arise because the o &, ß-unsaturated carboxylic acid tends to polymerize with itself, whereby the homopolymers formed thereby also cause cloudiness. Such Findings are also supported by the information in DE-PS 1 038 754 column 9, lines 43 to column 10, line 8 and in DE-PS 26 26 900 column 10, lines 1 to 39 confirmed.

The object of the present invention is to provide those described above Disadvantages of the known processes, some of which are carried out on an industrial scale To improve significantly the type explained above, namely: 1. The copolymer solutions should be colorless and shiny. This means that the lacquer films produced therewith should also be "free of specks" or very "few specks".

2. The manufacturing process should also be used on a factory scale against the Reaction conditions be relatively insensitive, so that after determining the optimal Reaction parameters always even with small deviations from the reaction conditions useful, high-performance copolymers are obtained and undesirable Side reactions are largely avoided.

3. The manufacturing process should be particularly important when performing in Factory scale with a significantly reduced implementation time in the one-pot process be feasible, and the significantly reduced boiler occupancy time increases productivity of the manufacturing plant and thus the production costs to lower.

4. The manufacturing process should allow further improved To produce copolymers based on known or new monomer compositions.

5. The copolymers produced by the process should be non-adhesive, waterproof and elastic films on the various substrates result or be suitable as a binder for pigments, opaque paints and fleeces, as well as e can be used as a binder component, the produced therewith Coatings or flat structures have advantageous properties in various directions exhibit.

The object of the invention was achieved in that the esterification stage is carried out in a special way and then under certain conditions the Copolymerization takes place.

The invention relates to a process for the production of in organic solvents soluble hydroxyl group-bearing copolymers aut based on vinyl compounds, α, ßunsaturated monocarboxylic acids and monoglycidyl compounds, in which the carboxyl group of the, ß-unsaturated monocarboxylic acid with the nonoglycidyl compound linked as an ester, by heating and esterification and copolymerization means Polymerization initiators and optionally chain terminators, characterized in that that first the i, ß-unsaturated monocarboxylic acid with the monoglycidyl compound in Presence of at least one vinyl compound is esterified and subsequently the copolymerization is carried out in the presence of inert solvents, wherein optionally before or during the copolymerization further vinyl compound (s) is (are) added, with the proviso that when the Copolymerization stage in addition to the monomeric esterification product at least two further vinyl compounds must be present in the reaction mixture.

Acrylic acid, Methacrylic acid and / or crotonic acid, individually or as a mixture, used. These include also half esters of maleic and fumaric acid with saturated alcohols, the 1 to 10 Contain carbon atoms.

The monoepoxides include substituted alkyl compounds and ethers and esters, provided they have a three-membered epoxy ring contain.

Examples of alkyl-substituted monoepoxides are propylene oxide, butene-2-oxide, Itexene-2-oxide, octene-2-oxide and styrene oxide.

Examples of substituted ether monoepoxides are butyl glycidyl ether, Hexyglycidyl ether, octyl glycidyl ether and phenyl glycidyl ether.

Examples of ester monoepoxides are the glycidyl esters of the following acids: acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, isononanoic acid, α, A-dialkylalkane monocarboxylic acids in which the hydrogen atoms of the alkane monocarboxylic acid are substituted by alkyl radicals in the i-position to the carboxyl group that a tertiary carbon atom is present, with the formula where R1, R2 and R3 are alkyl groups and the total sum of the carbon atoms of all alkyl groups is 3 to 25. The glycidyl esters of α, α-dialkylalkanemonocarboxylic acids with 9 to 13 carbon atoms in the alkyl group are preferred.

The most preferred glycidyl ester of an α, α-dialkylalkane monocarboxylic acid has the empirical formula C13H24O3 As vinyl compounds, aromatic Vinyl compounds such as styrene, vinyl toluene, α-methylstyrene and halostyrene are used which, except for the vinyl group, did not enable any reaction with the carboxyl group Own group.

As vinyl compounds are the esters of acrylic, methacrylic and crotonic acid with saturated alcohols that contain 1 to 10 carbon atoms in the alcohol residue, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert .-, butyl, Amyl, Hexyl, heptyl, octyl, nonyl and decyl radicals, individually or as a mixture, can be used.

Examples of vinyl esters that can be used are: vinyl esters of α, α-dialkylalkane monocarboxylic acids with the formula where R1, R2 and R3 denote alkyl groups, and the total sum of the carbon atoms of all alkyl groups is 3 to 25, and of these, vinyl esters with the following empirical formula Og H19 -CO-O-CH = C2 are preferred. Vinyl acetate and vinyl propionate can also be used as vinyl esters.

As A, ß-ethylenically unsaturated compounds bearing hydroxyl groups can be hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate,, hydroxypropyl methacrylate as well as butanediol monoacrylate and / or butane monomethacrylate, individually or in a mixture, be used. Furthermore, ether esters bearing hydroxyl groups, such as polypropylene glycol monomethacrylate, are also used and / or polyethylene glycol monomethacrylate with average molecular weights between about 175 to about 390, useful.

First, the special implementation of the ester formation is carried out the addition reaction is described.

In the most general way of working, the α becomes α, ß-unsaturated Monocarboxylic acid with the nonoglycidyl compound in the presence of at least one other vinyl compound by heating to 80 to 18500 by 1: 1 addition reaction converted to the ester between the carboxyl group and the monoepoxy group. Possibly a polymerization inhibitor is used here. It is preferred here in a range of a very low Deficiency of α, ß-unsaturated Monocarboxylic acid to work up to valent, the molar ratio of monoepoxide: α, ßunsaturated Monocarboxylic acid 1: 0.98 to 1.

In a more preferred embodiment of the addition reaction is how worked above, but is an inert organic solvent or a Mixture of inert organic solvents also used, the addition reaction is preferably carried out in the llemperat-urbereich from 100 to 1800 a. As inert Solvents are those that do not contain active hydrogen atoms, useful, e.g. toluene, xylene or other aromatics with a boiling range of about 1000 C to about 1800 C, butyl acetate, monoglycol ether acetates, z .B. Ethyl glycol acetate, or Mixtures of monoglycol acetate and xylene, monoglycol acetates being exemplary Methyl glycol acetate, ethyl glycol acetate, isopropyl glycol acetate or n-butyl glycol acetate to be named. In carrying out this preferred embodiment, the inert organic solvents in double to four times the amount by weight, based on the weight of the monoepoxy compound.

In a more specific embodiment of the above preferred Addition process for the preparation of the ester is made using organic Solvent used in the range of amounts of total monomers selected so that in the reaction mixture intended for the addition reaction, 50 to 95 percent by weight Addition product are formed and 5 to 50 percent by weight (preferably 5 to 20 percent by weight) of one or more other monomeric vinyl compounds are present.

Due to the presence of the other monomeric vinyl compounds the preparation of the addition product surprisingly becomes a disruptive one Homopolymerization of the addition product avoided, like our own special investigations have revealed.

Should copolymers in the subsequent copolymerization stage with low average molecular weights of about 10,000 to 20,000 are produced, so is to work in the range given above for the addition reaction and in addition, in the reaction mixture before and during the addition reaction Chain regulator be present.

Should, however, be copolymers in the subsequent copolymerization stage are produced with higher average molecular weights of about 20,000 to 100,000, thus, in the presence of all of them, the addition reaction becomes polymerization reactions capable vinyl compounds carried out in the absence of chain regulators.

In all variants of the implementation of the addition implementation, the formation of the addition product monitored analytically and as soon as acid numbers from about 15 to about 21 are reached, the addition reaction is considered to have ended as far as that Addition product copolymerized to form hydroxyl group-containing copolymers which are intended for crosslinking with polyisocyanates.

The foregoing shows that the selection conditions according to Nature and amount of the other vinyl compounds when carrying out the addition reaction (before the copolymerization) and the presence or absence of chain regulators considerable influence on the properties of the in the subsequent copolymerization stage Exercise to be produced copolymers. Such a control option of the Properties already in the addition reaction for the subsequent copolymerization stage has not previously been known for the monomer mixtures in question and thus allows copolymers with known or new monomer composition with improved properties.

Further possible variations of this principle will be explained below and are illustrated by the examples.

After the addition product from derd ,, ß-unsaturated monocarboxylic acid and the monoepoxy compound prepared in the presence of at least one vinyl compound has been, may if necessary after establishing the monomer composition or, if necessary, by adding further monomers and polymerization initiators Chain regulators that take place copolymerization.

In a preferred embodiment, the above is explained Addition product in the presence of an inert solvent or mixture of solvents (e.g. xylene and ethyl glycol acetate) in the presence of several (e.g. four) others monomeric vinyl compounds and a chain regulator under reflux within 3 hours made. The polymerization reaction can be carried out by that the approach of the addition production with the vinyl compounds present continues is refluxed and a mixture of the required additional amount of vinyl monomers and polymerization initiators in the course of 3 to 5 hours is added and copolymerized in small proportions.

J) erartigo preferred embodiments are illustrated by the example 1 to 5 clarified.

In another preferred embodiment, this is the above explained addition product - as explained last - with column numbers 17 to 21 prepared and a mixture of the required additional amount of vinyl monomers, Hydroxyalkyl acrylates and / or hydroxyalkyl methacrylates, optionally and / or Ether esters bearing hydroxyl groups, chain terminators and polymerization initiators added continuously in small portions over the course of 4 to 5 hours and then is copolymerized for a further 3 hours after the end of the feed. It will Acid numbers from 6.2 to 7.0 and viscosities of the 50% strength copolymer solutions diluted with xylene from 120 to 280 seconds flow time, measured in the flow cup with 4 mm nozzle, (compare Examples 1 to 4) obtained.

A most preferred embodiment of the production explained above of the addition product in the presence of vinyl monomers, but in the absence of Vinyl monomers bearing hydroxyl groups, such as, for example, E-hydroxyalkyl acrylates and / or Hydroxyalkyl methacrylates and / or ether esters carrying hydroxyl groups leads after completion of the esterification by adding to one Acid number from 14-21 of the addition product formed. By ctic absence of hydroxyl groups carrying vinyl monomers in the preparation of the addition product can be used in the subsequent copolymerization with a shortened feed time of the feed mixture worked for about 3 hours, with final acid numbers of 4.5-6.5 and lower Viscosities of the 50% strength copolymer solution diluted with xylene of 50-300 seconds Flow time, measured in the flow cup with a 4 mm nozzle (see Examples 4 and 5) was obtained will. This preferred embodiment of the method is particularly advantageous used for the production of copolymers used for the production of polyisocyanate realtion paints should serve.

The production times of the copolymer solutions in the examples 1 to 5 are 9 to 11 hours and vary due to the feed times of the monomer mixture and the additives it contains. The actual condensation time for manufacture the addition product was left at 3 hours. The copolymerization time also became after addition of all ionomers also held for 3 hours.

It is noteworthy that you can namely times by controlling the feed the desired viscosities of the monomer mixture and the additives contained therein the copolymer solutions can achieve. With shortened feed times for the monomer mixtures higher viscosities are obtained, and lower viscosities are obtained with longer feed times. The feed times can - depending on the desired properties of the copolymer solutions - be set in certain ranges, e.g. between 30 ilinutes and 7 hours.

As polymerization initiators, for example, diacyl peroxide, e.g. dibenzoyl peroxide, perester, e.g. tertiary butyl peroctoate, and dialkyl peroxides, e.g. di.-tert.-butyl peroxide, as well as all peroxides, their half-lives in one Temperature range from 50 to 1500 C are used.

The peroxide content is about 0.5 to 5% by weight, based on the total Proportion of α, ß-ethylenically unsaturated monomers including the esterified Moncepoxyde.

As a chain regulator, for example, octyl mercaptan, Decyl mercaptan, lauryl mercaptan and the branched dodecyl mercaptan are used. The proportion of chain regulators, based on the total proportion of ethylenically unsaturated Monomers including the esterified monoepoxides is 0 to 2.5% by weight.

As soon as 95 to 100% of the addition product is produced, is with the addition of the polymerization initiator and / or with the mixture of the rest i, ß-ethylenically unsaturated monomers and the polymerization initiator and optionally Chain regulator started. The feed times are generally 15 to 5 minutes Hours.

After this addition has ended, the reaction will continue for 2 to 3 hours kept under reflux until the reaction is complete.

The invention is illustrated by the following examples, however, it should not be restricted to these: Example 1 In one with stirrer, reflux condenser and thermometer-equipped reaction vessel is refluxed at 140 to 14600 a mixture consisting of 293 g xylene, 150 g ethyl glycol acetate, 155 g glycidyl ester an α, α-dialkylalkane monocarboxylic acid with the following empirical formula Cl 3112403 with an epoxy equivalent of 245 to 253 (boiling range 5% -90% at 760 mm Hg 2510 - 2780 C) (= 23.5% by weight = 0.627 epoxy equivalent).

(The glycidyl ester is described in Shell Chemical's "Technical Bulletin RES / CAX / 1" entitled: "Shell Resin Intermediates Cardura B 10". Its structure can be represented by the following formula, which is based on a synthetic, saturated, high branched monocarboxylic acid with 10 carbon atoms is based, where R1, R2 and R3 represent straight-chain alkyl groups, of which at least one is always the methyl group), 45.0 g of acrylic acid (= 6.9% by weight = 0.625 equivalent), 3.0 g of polypropylene glycol monomethacrylate with an average molecular weight of 350 - 387 and a hydroxyl number of 145 - 160 (= 2.6% by weight). (The product can be represented by the following formula: where n is the numerical values 5 or 6), 9.6 g of hydroxyethyl methacrylate (= 8.3% by weight), 15.0 g of styrene (= 12.07% by weight), 15.0 g of methyl methacrylate ( = 12% by weight) and 7.4 g of dodecyl mercaptan were refluxed for three hours until the acid number 21 was reached in order to form the addition product. About 6.6 g of unreacted acrylic acid are present in this reaction batch. The acid number is based on the amount of monomers used, in the present case 35.4% by weight.

After the addition product has been prepared, the with The mixture still at 140 to 1460 C is the following mixture, which is at room temperature located in a dropping funnel, made of 30.0 g of folypropylene glycol monomethacrylate (= 2.5 % By weight) of the type already explained above, 100.0 g of hydroxyethyl methacrylate (= 8.3% by weight), 143.2 g of styrene (= 11.99% by weight), 143.2 g of methyl methacrylate (= 11.99% by weight), 7.4 g di-tert-butyl peroxide 6.7 g dodecyl mercaptan in four hours Add dropwise uniformly and then add an additional 3.0 hours copolymerized by refluxing.

The copolymer solution containing hydroxyl groups formed has a solids content of 62 wt .-%, an acid number of 7 and a viscosity of 152 seconds, measured in the nozzle with a diameter of 4 mm at the outlet nozzle 200 C, with the copolymer solution previously reduced to a concentration of 50% by weight was diluted with xylene.

In this example 1, the reaction of 155 g of glycidyl ester and 45 g of acrylic acid to the addition product in the presence of 3 g of propylene glycol monomethacrylate, 9.6 g of hydroxyethyl methacrylate, 15 g of styrene and 15 g of methyl methacrylate made, the ratio of the addition product to the vinyl monomers thereof being 85.8% by weight Is 14.2% by weight. In addition, the formation of the monomeric addition product in Presence of tertiary dodecyl mercaptan made.

Further research has shown this to be clear above One-pot process is feasible on a factory scale, taking about 3 hours for the formation of the addition product and about 7 hours for the formation of the copolymer are required so that the total preparation cooking time is only about 10 hours.

Example 2 The procedure given in Example 1 is followed, but are used: 294.0 g xylene, 150.0 g ethyl glycol acetate, 155.0 g glycidyl ester a @, @ -dialkylalkanemonocarboxylic acid of the type mentioned in Example 1 (= 23.5 % By weight = 0.627 epoxy equivalent (.45.0 g of acrylic acid (= 6.9% by weight = C, -25 acid equivalent), 12.6 g of hydroxyethyl methacrylate (= 1.31% by weight), 15.0 g styrene (= 2.27 wt. S6), 15.0 g of methyl methacrylate (= 2.27 C wt.%) And 0.7 g of dodecyl mercaptan are in about 3 hours at about 1440 C to the acid number 18.5 to form the Addition product kept under reflux. The acid number relates to the amount of the monomers used, in the present case to 35.4% by weight. The following Mixture, which is at room temperature, consisting of 130.0 g of hydroxyethyl methacrylate (= 19.72% by weight), 143.2 g of styrene (= 21.73% by weight), 143.2 g of methyl methacrylate (= 21.73 % By weight), 6.7 g of dodecyl mercaptan and 7.4 f of di.-tert.-butyl peroxide are obtained in 4 hours uniformly drop by drop into the reaction mixture, which is still at 140 to 1460 C. of the completed addition product was added with heating to reflux. After the addition of the monomer feed is complete, the same is continued for 3 hours Temperature copolymerized.

The copolymer solution obtained has a solids content of 62.5 % By weight and an acid number of 6.2. The viscosity of the previous to 50 wt. -96 with xylene diluted copolymer solution has an outflow time of 195 seconds at 200 C, measured in a flow cup with a 4 mm diameter of the discharge nozzle.

In this example 2, 200 g of monomeric addition product are used in the first stage from the glycidyl ester and acrylic acid In the presence of 12.6 g of hydroxyethyl methacrylate, 15 g of styrene and 15 g of methyl methacrylate were prepared. The addition product ratio to the other monomers is 82.44% by weight, -O / o to 17.56% by weight.

A small amount is involved in the preparation of the addition product Dodecyl mercaptan present. The monomer feed is used in the preparation of the copolymer also contain dodecyl mercaptan. The above example can also be used in Factory scale can be carried out as a one-top-two process, with the total cooking time approximately 10 hours.

Example 3 The procedure is as stated in Example 1, but the following are used: 294.0 g of xylene, 150.0 g of ethyl glycol acetate, 155.0 g of glycidyl ester of an α, α-dialkylalkane monocarboxylic acid (= 23.5% by weight = 0.627 Epoxy equivalent) of the type mentioned in Example 1, 45.0 g of acrylic acid (= 6.83,% by weight = 0.625 acid equivalent), 12.6 g of hydroxyethyl methacrylate (= 1.91% by weight), 15.0 g of styrene (= 2.27% by weight), 15.0 g of methyl methacrylate (= 2.27% by weight and 26.2 g of vinyl ester of a, Z'- -dialkylalkanemonocarboxylic acid with the formula C9H19-C0-0-CH = CH2 (= 3.98% by weight), the remainder being C9H19- largely due to the following structure can be marked. This mixture is reacted for 3 hours at about 1450 ° C. up to the acid number 17 to give the addition product - as described in Example 1, but here calculated at 37.7% by weight. Then the following mixture, which is at room temperature, consists of 130.0 g of hydroxyethyl methacrylate (= 19.73% by weight), 130.0 g of styrene (= 19.73% by weight), 130.0 g Methyl methacrylate (= 19.73% by weight), 6.7 g of dodecyl mercaptan and 7.4 g of di.-tert.-butyl peroxide were added dropwise uniformly at 146 ° C. in 4 hours and then copolymerized for a further 3 hours at the same temperature.

The copolymer solution has a solids content of 62% by weight and an acid number of 6.5. The viscosity of the previously diluted to 50% by weight with xylene Solution is 120 sec. Flow time, measured in the flow cup with 4 mm outlet nozzle at 200 C.

In this example, 200 g of monomeric addition product are made from the Glycidyl ester and acrylic acid in the presence of 12.6 g of hydroxyethyl methacrylate, 15 g of styrene, 15 g of methyl methacrylate and 26.2 g of vinyl ester were prepared. The relationship Addition product to the four other vinyl monomers is 74.4% by weight to 25.6 Wt%. During the preparation of the addition product, in the absence of dodecyl mercaptan worked.

Example 4 The procedure is as indicated in Example 1, but are used: 294.0 g xylene, 150.0 g ethyl glycol acetate, 155.0 g glycidyl ester an α, α-dialkylalkane monocarboxylic acid (= 23.5% by weight = 0.627 epoxy equivalent) of the type described in Example 1, 45.0 g of acrylic acid (= 6.82% by weight - = 0.625 acid equivalent), 25.0 g of styrene (= 3.79% by weight), 1.7 g of dodecyl mercaptan for 3 hours at about 145 C up to the acid number 20 to the addition product - as described in Example 1, but calculated here with 33.6 wt .-% -reacted and the following mixture, which is at room temperature, consisting of 142.6 g of hydroxyethyl methacrylate (= 21.65% by weight), 133.2 g of styrene (= -20.21% by weight), 158.2 g of methyl methacrylate (= 24% by weight), 6.7 g of di-tert-butyl peroxide and 7.4 g of dodecyl mercaptan in 4 hours added evenly at about 1460C and then another 2.5 hours at the copolymerized at the same temperature.

The copolymer solution has a solids content of 62.1 and one Acid number of 6.2. The viscosity of the solution previously diluted to 50% by weight with xylene is 280 seconds flow time, measured in the flow cup with 4 mm Outlet nozzle at 200 C.

In this example, 200 g of monomeric addition product are made from the Glycidyl ester and acrylic acid prepared in the presence of 25 g of styrene. The relationship Addition product to styrene is 88.88% by weight to 11.12% by weight. In the preparation of of the addition product was carried out in the presence of dodecyl mercaptan.

In addition, the feed contained the monomer mixture in the copolymerization Dodecyl mercaptan.

Example 5 The procedure is as indicated in Example 1, but are used: 400.0 g xylene, 209.0 g glycidyl ester of a single α, α Dialkylalkanemonocarboxylic acid of the type mentioned in Example 1 (= 34.83% by weight = 0.853 Epoxy equivalent), 61.0 g acrylic acid (= 10.16% by weight = 0.847 acid equivalent), 50.0 g styrene (= 5% by weight), 50.0 g butyl acrylate (= 5% by weight) and 0.7 g dodecyl mercaptan.

The mixture became the addition product for 3 hours at 1420 G up to an acid number of 15 - As described in Example 1, but calculated here with 48% by weight - implemented and the following mixture, which was at room temperature, consisting of 115.0 g styrene (= 22.5% by weight), 115.0 g butyl acrylate (= 22.5% by weight), 5.0 g dodecyl mercaptan and 6.5 g of di.-tert.-butyl peroxide was added dropwise uniformly over 3 hours and then copolymerized at 143O C for 3 hours. The copolymer solution has a solids content of 60 wt .-% and an acid number of 5. The viscosity of the Solution previously diluted to 50% with xylene is 50 seconds flow time, measured in the flow cup with 4 mm nozzle at 200 C.

In this example there are 270 g of addition product from the glycidyl ester and acrylic acid in the presence of 50 g of styrene and 50 g of butyl acrylate manufactured. The ratio of the addition product to the styrene and butyl acrylate is 73% by weight to 27% by weight.

Example 6 Production of a reactive lacquer: 100 parts by weight of copolymer solution from Example 2 and 40 parts by weight of a 75% solution of one in xylene / ethyl glycol acetate = 1: 1 aliphatic triisocyanate containing dissolved biuret groups, which obtained by reacting 3 moles of hexamethylene diisocyanate and one mole of water has been, with an NC0 content of 21 .We.-Vo, with a solvent mixture, consisting of xylene and butyl acetate = 1: 1 to a viscosity of 18 seconds The flow time, measured in a Din cup with an outlet nozzle of 4 mm at 200 ° C., is set.

Example 7 The procedure is as indicated in Example 1, but are used: 294.0 g xylene, 150.0 g ethyl glycol acetate, 150.0 g phenyl glycidyl ether (= 22.79% by weight = 1 epoxy equivalent), 72.0 g of acrylic acid (= 10.93% by weight = 1 acid equivalent), 60.0 g of styrene (= 9.12% by weight), 60.0 g of n-butyl acrylate (= 9.12% by weight) and 5.0 g of dodecyl mercaptan.

The mixture was 3 hours at 1460 C to the addition product with the Acid number 97 reacted, then the following mixture of 185.1 g of styrene (= 24.02 % by weight), 158.1 g of n-butyl acrylate (= 24.02% by weight), 2.0 g of dodecyl mercaptan and 6.5 g di.-tert.-butyl peroxide added dropwise uniformly over the course of three hours The copolymer solution was then copolymerized at 1450 ° C. for three hours a viscosity of 470 seconds flow time, measured in the flow cup with 4 mm Nozzle at 200 ° C. The finished copolymer has an acid number of 43.6.

Example 8 Production of a stoving enamel: 100 parts by weight of Copolymer solution, obtained according to Example 7, were 50 parts by weight of a Melamine-formaldehyde resin solution containing 50% solids and etherified with butanol mixed cold and applied to iron sheets with a dry film thickness of 50 μm and baked at 1200 C for 30 minutes.

The films were clear, hard on the surface and resistant to xylene obtained, which also have good adhesive strength and flexibility.

Example 9 - The procedure was as indicated in Example 7, but 130 g of n-butyl glycidyl ether were used instead of phenyl glycidyl ether.

The copolymer solution obtained had a viscosity of 170 seconds Flow time, measured in the flow cup with 4 mm nozzle at 200 C.

Example 10 Production of a stoving enamel 100 parts by weight of Copolymer solution, obtained according to Example 9, with 50 parts by weight of a 50.5 solids containing urea-formaldehyde resin solution etherified with isobutanol mixed cold and applied to steel sheets with a dry film thickness of 60 µm and baked at 1400 C for 30 minutes. It became clear, hard-surfaced, opposite Xylene-resistant films are obtained, which also have a good adhesive strength on the most diverse Have metal substrates such as aluminum and copper.

Example 11 The procedure is as stated in Example 1, but are used: 290 g xylene, 150 g ethyl glycol acetate, 178 g Glycidyl benzoate (= 27.04% by weight), = 1 epoxy equivalent), 72 g of acrylic acid (= 10.93% by weight = 1 acid equivalent), 60 g of styrene (= 9.12% by weight), 60 g of n-butyl acrylate (= g, 12% by weight) and 4 g of dodecyl mercaptan.

the mixture became the addition product at 145 ° C. for three hours the acid number 62 reacted, then the mixture of 144.1 g of styrene (21.89% by weight, Ó), 144.1 g of n-butyl acrylate (21.89% by weight) and 7.0 g of di-tert-butyl peroxide in three hours added drop by drop and then polymerized at 146 ° C. The copolymerization solution has a viscosity of 255 seconds flow time, measured in a flow cup with a 4 mm nozzle at 200 ° C. The copolymer has a The hydroxyl number is 85 and the acid number is 18.

Example 12 Production of a reactive lacquer: 100 g copolymer solution, obtained according to Example 11, and 20 g of a 75% solution of a xylene / ethylglycol acetate = 1: 1 dissolved aliphatic triisocyants containing biuret groups, which obtained by reacting three moles of hexamethylene diisocyanate and one mole of water was, with an NCO content of 21 wt .-%, with a solvent mixture, consisting of xylene / butyl acetate = 1 1 1 adjusted to spray viscosity and steel sheets coated with a dry film thickness of 45 µm and 10 days at room temperature hardened. The films had excellent gloss and durability to xylene.

Example 13 The procedure was as stated in Example 11, but instead of glycidyl benzoate, 128 g of octene-2-oxide were used.

The copolymer solution obtained had a viscosity of 120 seconds Flow time, measured in the flow cup with 4 mm nozzle at 200 C.

Example 14 Production of a stoving enamel: 100 parts by weight of Copolymer solution, obtained according to Example 13, were 60 parts by weight of a 50% solids containing urea-formaldehyde resin solution etherified with isobutanol mixed and applied to steel sheets with a dry film thickness of 50 µm and baked at 1500 C for 30 minutes.

The copolymers obtainable by the process of the invention can as component A in reactive lacquers together with a polyisocyanate component B be used.

It became shiny, resistant to xylene and super fuel Obtained films that also had high flexural strength.

Further advantageous embodiments of the invention are set out in the claims 1 to 23.

The following polyisocyanates, for example, can be used as component B: toluene-2,4-diisocyanate, Toluylene-2,6-diisocyanate, cyclohexylene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,5-naphthylene diisocyanate, 1- (isocyanatophenyl) ethyl isocyanate or xylylene diisocyanate, Fluorine-substituted diisocyanates, ethylene glycol diphenyl ether 2,2'-diisocyanate, diethylene glycol diphenyl ether 2,2'-diisocyanate, 1,1'-dinaphthyl-2,2'-diisocyanate, biphenyl-2,4'-diisocyanate, biphenyl-4,4'-diisocyanate, Benzophenone-3,3'-diisocyanate, fluorene-2,7-diisocyanate, anthraquinone-2,6-diisocyanate, Pyrene-3,8-diisocyanate, chrysene-2,8-diisocyanate, 1-methylbenzene-2,4,6-triisocyanate, Naphthalene-1,3,7-triisocyanate, biphenylmethane-2,4,4'-triisocyanate, triphenylmethane-4,4 ', 4' '- triisocyanate, 3'-methoxyhexane diisocyanate, octane diiso - #, # - diisocyanate-1, 4-diethylbenzene, t, -Diisocyanate-1,4-dimethylnaphthalene, cyclohexane-1,2-diisocyanate, 1-isopropylbenzene-2,4-diisocyanate, 1-chlorobenzene-2,4-diisocyanate, 1-fluorobenzene-2,4-diisocyanate, 1-nitrobenzene-2,4-diisocyanate, 1-chloro-4-methoxybenzene-2,5-diisocyanate, azobenzene-4,4'-diisocyanate, benzolazonaphthalene-4,4'-diisocyanate, Diphenyl ether-2, 4-diisocyanate and diphenyl ether-4'4'-diisocyanate and polyisocyanates based on isophorone diisocyanate with isocyanurate structures and one functionality between 3 and 4.

Furthermore, reaction products containing isocyanate groups become polyhydric Alcohols with polyisocyanates, for example the reaction product of 1 mole of trimethylolpropane with 3 moles of tolylene diisocyanate, and also trimerized or polymerized isocyanates called.

In addition, there is also a reaction product containing biuret groups from 1 mole of water and 3 moles of hexamethylene diisocyanate with an NCO content of 16 to 17% by weight in question. The last-mentioned reaction product is particularly preferred from water and hexamethylene diisocyanate. The NCO content of the reaction product applies for a 750 / cige solution in xylene / ethyl glycol acetate.

To use the copolymers, one brings the mixtures of solvent-based hydroxyl-containing copolymers A and polyisocyanate B in the simplest possible way Ways, for example after adding known auxiliaries such as leveling agents, pigments or dyes, by spraying, dipping, pouring, brushing or other suitable measures on the appropriate documents and dry the fabric at room temperature; In special cases, the coatings can be baked in, which is essentially the case according to the documents used and the requirements made by practice aimed at the coatings. The use of reactive melamine resins can also be used be beneficial. You can use the reactive melamine resins in amounts from 1 to 10 0% by weight, based on the weight of the binder component, by adding in particular an increase in gloss can be observed in the fabric.

When using the copolymers in the reactive lacquers already explained the implementation and the application of the surface structure to the base takes place in Solution. Suitable solutions are e.g. ethyl acetate, butyl ester, ether ester, Diethyl glycol diacetate and aromatics such as benzene, toluene or xylene. The concentration the solutions can fluctuate within wide limits and is essentially based on the solubility of the components. Solutions with a solids content are preferred from 20 to 80% by weight used When using the copolymers In reactive lacquers, components A and B are preferably used in the following amounts used: (A) 60 to 95% by weight of hydroxyl-containing copolymers, produced according to the invention, (B) 5 to 40 wt. 06 organic polyisocyanate, where (A) and (B) together must result in numerical values of 100% by weight.

A particularly preferred reactive varnish contains: (A) 63 to 68% by weight produced copolymers containing hydroxyl groups and (B) 32 to 37 wt .-% organic Triisocyanate, which by reaction of 3 moles of hexamethylene diisocyanate and 1 mole Water was obtained, where (A) and (B) must give numerical values of 100% by weight.

The main areas of application for the copolymers are - in combination with aliphatic and aromatic polyisocyanates or their mixtures - air and Oven-drying metal, wood and plastic paintwork. Such two-component paints are preferred when using air or force dried varnishes Properties are expected that are usually only offered by stoving enamels.

These new reactive lacquers are used as binders especially for the Automotive refinish sector as well as for bus and truck painting.

In combination with aliphatic polyisocyanates you get full-bodied, non-yellowing coatings with excellent weather resistance and gloss retention.

When crosslinking with aromatic polyisocyanates is with a certain yellowing is to be expected.

Reaction paints based on the invention show correspondingly their higher Cross-linking density compared to comparable good commercial products for the same The purpose is high scratch and abrasion resistance, combined with good solvent resistance To be highlighted is also the good resistance to water and chemicals.

In addition to air drying, such paints can be used in a wide temperature range to be branded; for example, the films are full in 30 minutes at 1300 ° hardened.

The coatings cured at room temperature are weatherproof burned-in films.

The copolymers have a high pigment absorption. For figmentation all neutral pigments and fillers are suitable.

Strongly basic pigments as well as pigments with soluble metal compounds can have a catalytic effect on the crosslinking, reducing the processing time the ready-mixed paint batches are shortened.

Investigations of the reaction solution obtained according to Example 6 for Proof of the technical progress achieved: 1. Determination of the pot life, i.e. the durability of the two-component paint at 200 C: flow time in seconds (flow nozzle 4 mm) onset 18 after 24 hours 19 after 48 hours 22 after 50 hours 24 after 72 Hours 42 gelled after 96 hours 250 after 100 hours This result shows that these paints have a surprisingly long pot life. If you lie in practice usual processing conditions - increase in viscosity by twice the initial viscosity, i.e. a maximum of 36 seconds flow time, this lacquer has a processing time of more than 60 hours. In addition, paint residues that are 96 hours old can get through Add freshly made paint solutions to be diluted and still well processed will.

2. Determination of the curing time of the paint films: This-produced Two-component paint solution is applied to a Open glass plate, so that a dry film thickness of approx. 40 µm results.

2a Determination of the pendulum hardness according to König at 200 C: pendulum hardness according to one day 30 seconds after two days 80 seconds after three days 150 seconds four days 188 seconds after seven days 200 seconds after ten days 201 seconds What is surprising here is that the clearcoat already cures after 4 days 200 C has reached its almost complete film hardness of 188 seconds. If you put this Result in relation to four days of open pot life, i.e. no gelling of the If lacquer solution occurs during this time, this result was surprising and not predictable.

2b Determination of the König pendulum hardness after baking 800 C and 30 minutes baking time: pendulum hardness 800 C 30 minutes 55 seconds after one day at 200 C 95 seconds after two days at 200 C 165 seconds after three Days at 200 C 189 seconds after seven days at 20 ° C 201 seconds after ten Tacgen at 20 ° C 200 seconds through the drying time of 30 minutes at 80 ° C Already after a further three days of drying at 200 ° C., the almost complete result is obtained Film hardness of 189 seconds pendulum hardness.

The resulting paint films are very hard on the surface and cannot be injured with the fingernail test. Also, these stand out Coatings due to very good lightfastness and resistance to solvents, such as xylene, toluene or acetone from. After 1 1/2 years of exposure to Florida at 5 ° C test panels laid out towards the south, these lacquer films show no cracking and only a gloss reduced by 1000 compared to the original gloss, the 11No - measured after Lange - amounts to.

Comparative studies to prove the technical progress achieved compared to the best competitive products on the market with regard to pot life: Copolymer according to analogous reaction- Analogous reaction- Example 2 the invention paint, but copoly paint, but copoly dung - reaction varnish merisate after admixture after admixture according to example 6 of game 2 game 1 1 Invention DE-PS 26 03 259- DE-PS 26 26 900 1 Determination of the pot life of the reactive lacquer by measuring the flow time in the DIN cup with a nozzle 4 mm in diameter at 20 ° C in seconds time - at the beginning 18 18 18 after 24 hours 19 25 28 after 48 hours 22 75 155 after 56 hours 26 280 not measurable, gelling: not measurable after 60 hours, gelled Comparative inquiries to prove the technical port step achieved compared to the best competing products on the market with regard to pot life: To determine the pot life, the copolymers prepared according to the invention listed in the table above were compared with the best competing products on the market with the aliphatic triisocyanate, which has been obtained by reacting 3 moles of hexamethylene diisocyanate and 1 mole of water. The mixing ratios of the copolymers with the polyisocyanate, based on the solids content, were 70% by weight copolymer: 30% by weight polyisocyanate.

The mixtures were made with a mixed solvent consisting of xylene-butyl acetate in a weight ratio of 1: 1 to a viscosity of 18 seconds Flow time, measured in a DIN cup with a 4 mm opening, diluted and the increase in viscosity was determined as a function of time at 200.degree. As as can be seen from the table above, are those prepared according to the invention Copolymers the known copolymers according to DE-PS 26 03 259 and DE-PS 26 26 900 clearly superior. The copolymers prepared according to the invention have a more favorable "pot life" in terms of slower viscosity increase or gelation. This suggests a much cheaper processing the reactive paints conclude.

The hydroxyl group-bearing copolymers, which after the process of the invention can be obtained, instead of the polyisocyanates, can also be patted with Polyisocyanates are used for the production of stoving enamels, e.g. in DE-OS 26 23 081 with the Eezeichnung11Bennlacke on the basis of film-forming hydroxyl group-containing copolymers soluble in inert organic solvents " is described. By the inventor of the present invention, for example, as masked polyisocyanates for this purpose in DE-OS or -AS 26 12 786 with the Designation "Blocked diisocyanates, ire heating from diisocyanatomethyl-norbonane and alkyl acetoacetate and their use as crosslinking agents ", in DE-OS or -AS 26 12 785 "Elocked diisocyanates, their preparation from 4,4'-diisocyanatodicyclohexylmethane and acetoacetic acid real alkyl esters and their use as crosslinking agents ", in DE-OS or -AS 26 12 784 "Blocked diisocyanates, their preparation from 1,6-hexamethylene diisocyanate and acetoacetic acid esters their use as crosslinking agents ", in DE-OS or -AS 26 12 783 "Blocked polyisocyanates from polyisocyanate containing biuret groups and Acetessigsällrealkylester '' and in DE-OS or -AS 26 12 638 "blocked Diisocyanates from 2,2,4-trimethylhexamethylene diisocyanate and alkyl acetoacetate and their use as crosslinking agents ".

Such as Examples 8, 10 and 14 of the present invention show, 70 to 95% by weight of hydroxyl-containing copolymers can be produced according to the invention, with 5 to 30% by weight of amino resins used as stoving enamels can be found, where the% by weight information must be 100% by weight.

All amino resins can be used here as amino resins that are compatible with acrylate copolymers and in large numbers are commercially available and are often based on urea and / or melamine-formaldehyde and are etherified with lower alkanols.

The solution of the finished copolymer is cooled and the Aminoplastlö solution introduced, the solvent content being adjusted so that the desired concentration is achieved. Pigments can then be added.

The stoving enamels according to the invention result in after stoving 90 to 1800 C films with excellent chemical resistance properties of all kinds such as solvents, acids and eyes as well as super fuels.

The baking varnishes can be dried at room temperatures. Hardening does not necessarily have to be done at 120 to 1400 G in 30 minutes to become. At 1600 0, for example, the burn-in time is reduced to around 15 minutes.

Preferred aminoplasts are condensation products from formaldehyde and melamine, with about 4 to 6 moles of formaldehyde either weak per mole of melamine acidic or weakly basic have reached the reaction and with butanol or isobutanol 80 to 100% ought to be drained. The resulting implementation products should have a molecular weight of 400 to 1200 and in organic solvents such as xylene and butanol or isobutanol and other alcohols can be soluble.

The mixed polymer and the aminoplast are in a ratio of 70 to 95 parts of the copolymer and from 5 to 30 parts of the aminoplast in the organic Solvent dissolved. The proportions of the copolymer and the alkylated aminoplasts are to be chosen so that the two components are both in the coating solution as well as in the finished film. Any suitable concentration of the mixed polymer can be used and the aminoplast in the solvent, e.g., from 1 to 50 percent by weight come. If a pigment is present, the total solids content is in the Coating mass between 5 and 75 percent by weight. The ratio of pigment to binder (Mixed polymers plus aminoplast) can be between 1:20 and 1: 4.

The following solvents can be used: hydrocarbons, such as Benzene, toluene, xylenes and aromatic naphthenes or Mixtures solchor solvent; Esters, such as ethyl, butyl, amyl, ethoxyethyl or methoxyethyl acetates, lactates or propionates; Ketones, such as acetone, methyl isopropyl ketone, methyl isobutyl ketone, Di-oxane, isophorone or cyclohexanone; Alcohols such as n-butanol, t-butanol, isopropyl alcohol, Amyl alcohols and cyclohexanol; Ethers, such as diethyl ether, monoethyT, monomethyl and monobutyl ether of ethylene glycol and various other solvents such as Dimethylformamide, dimethylacetamide, acetonitrile, nitrometal, ifitroethane, nitropropane or nitrobutane, as well as mixtures of 2 or more solvents of the same Group and from several or all of the groups listed above.

The following pigments can be added: inorganic pigments, such as chrome yellow, Prussian blue, Brunswick green; Titanium pigments, e.g. titanium dioxide, expanded titanium pigments (which are stretched with either precipitated or natural extenders, such as Alkaline metal sulfates, e.g. calcium sulfate and barium sulfate); toned titanium pigments, Titanates, such as barium, zinc, lead, and magnesium titanates. Other types of organic too Pigments can be used, e.g. zinc sulfide pigments such as zinc sulfide, lithopon, extended zinc sulfide pigments, such as calcium-based lithopon, with natural Extenders expanded zinc sulfide, zinc oxide or antimony oxide or organic pigments, i.e. organic dyes that are free from sulfonic acid, carboxylic acid or others are water-solubilizing C groups, The term "pigment" also includes others water-insoluble organic dyes, e.g. the calcium or barium lakes of azolaceous dyes.

The new stoving enamels can be applied to the substrates in any way applied, e.g. by brushing, spraying, dipping, rolling. You will be then dried and hardened by heating.

The calculation of reaction batches for the production of copolymers with a certain hydroxyl group content is from the same inventor in DE-AS 26 o3 259 in columns 5 and 6 and in DE-AS 26 26 900 in columns 5 to 8 been.,

Claims (16)

Claims: t. Process for the production of in organic Solvent-soluble hydroxyl-containing copolymers based on of vinyl compounds, α, ß-unsaturated monocarboxylic acids and monoglycidyl compounds, in which the carboxyl group of the i, ß-unsaturated monocarboxylic acid with the monoglycidyl compound linked as an ester, by heating and esterification and copolymerization means Polymerization initiators and optionally chain terminators, characterized in that that first the α, ß-unsaturated monocarboxylic acid with the monoglycidyl compound is esterified in the presence of at least one vinyl compound and thereafter the copolymerization is carried out in the presence of inert solvents, wherein optionally before or during the copolymerization further vinyl compound (s) is (are) added, with the proviso that when the Copolymerization stage in addition to the monomeric esterification product at least two more Vinyl compounds must be present in the reaction mixture. 2. The method according to claim 1, characterized in that first 2 up to 50 wt. 5b addition product by esterification of the α, ßunsaturated monocarboxylic acid is prepared with the monoglycidyl compound and then the one used to prepare the Addition product used reaction approach with 98 to 50 wt .-% other vinyl compounds is copolymerized, the sum of the reactants adding up to 100% by weight got to. 3. The method according to claim i or 2, characterized in that first 2 to 50% by weight of the addition product by esterification of the α, ß-unsaturated monocarboxylic acid with the glycidyl compound is produced and then the one to produce of the addition product used reaction mixture with 98 to 50 wt .-% of other vinyl compounds is copolymerized, of which 0 to 30% by weight is one or more vinyl compounds with a hydroxyl group in the molecule. 4. The method according to any one of claims 1 to 3, characterized in that that as other vinyl compounds styrene, acrylates and / or methacrylates with 1 to 12 carbon atoms are used in the alcohol residue. 5. The method according to any one of claims 1 to 4, characterized in that that as other vinyl compounds with a hydroxyl group in the molelnul hydroxyethyl acrylate, Hydroxypropyl acrylate, butanediol monoacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, Butanediol monomethacrylate, polypropylene glycol monomethacrylate and / or polyethylene glycol monomethacrylate with average molecular weights between about 175 to about 390. 6. The method according to any one of claims 1 to 5, characterized in that that first 10 to 40 wt .-, 4 addition product by esterification of acrylic acid and / or Methacrylic acid with a monoglycidyl ester or monoglycidyl ester mixture of aliphatic saturated monocarboxylic acids with 2 to 19 carbon atoms with a mixture of 30 to 88 wt .- styrene, vinyl esters of saturated monocarboxylic acids or mixtures such esters with 4 to 19 carbon atoms in the carboxylic acid molecule, ethyl acrylate, n-, iso-, sec. -, tert-butyl acrylate, methyl acrylate, ethyl methacrylate, n-, iso-, sec.-, tert.-3utyl methacrylate, methyl methacrylate and 2 to 30% by weight of hydroxyethyl acrylate, Hydroxypropyl acrylate, buttanediol monoacrylate, hydrohyethyl methacrylate, hydroxypropyl methacrylate, Butanediol monomethacrylate is copolymerized, the above weight percent must add up to 100% by weight / a. 7. The method according to any one of claims 1 to 6, characterized in that first 6 to 12 wt .-% acrylic acid with 18 to 39 wt .-% glycidyl ester of an α, α-dialkylalkanemonocarboxylic acid with the empirical formula C13H2403, the structure of about corresponds, in which R1, R2 and R3 represent straight-chain alkyl groups, in front of which at least one is the methyl group, are esterified to the addition product up to acid numbers 15 to 22, the molar ratio of glycidyl ester to acrylic acid being 1: 0.98 to 1, and then the reaction mixture obtained is reacted with 30 to 15 wt .-% styrene and / or vinyl toluene, 15 to 25 wt .-% methyl methacrylate, 15 to 25 wt .-, ° b hydroxyethyl methacrylate and the reaction is carried out until an acid number 6 to 9 is reached and the mentioned Gew.-SS must be supplemented to 100 Gew.- '. 8. The method according to any one of claims 1 to 6, characterized in that first 5 to 7 wt .- $ acrylic acid with 17 to 25 wt corresponds, where R1, R2 and R3 are straight-chain alkyl groups, of which at least one is the methyl group, are esterified to the addition product up to acid numbers 18 # 1, the molar ratio of glycidyl ester to acrylic acid being 1: 0.98 to 1, and then the reaction mixture obtained with 25 to 30% by weight of styrene, 15 to 20% by weight of methyl methacrylate, 15 to 20% by weight of hydroxyethyl methacrylate, up to 6% by weight of polypropylene glycol monomethacrylate, the structure of which has approximately the formula corresponds, where n is numbers from 5 to 6 and the average molecular weight is about 350 to 387 and 10 to 3 wt .-% vinyl ester of an α, α-dialkylalkanemonocarboxylic acid with approximately the formula C9H19-CO-O-CH = CH2, the grouping C9H19 largely the structure has, the wt .-% having to add up to 100 wt .-%, are copolymerized until acid numbers of 6 to 7 are present. 9. The method according to one or more of claims 1 to 8, characterized characterized in that the addition reaction of the &, ßunsaturated monocarboxylic acid with the monoglycidyl compound in the presence of 5 to 70% by weight of other vinyl compound (en) takes place, the percentages by weight of the components for the adduct and the other (s) vinyl compound (s) must add up to 100% by weight and the additional required amount of vinyl compounds added during copolymerization is, so that at the end of the copolymerization 2 to 50 wt .-% addition product and 98 up to 50% by weight of other vinyl compounds are present in copolymerized form. 10. The method according to any one of claims 1 to 9, characterized in, that the reaction of the ß-unsaturated monocarboxylic acid with the monoglycidyl compound to the monomeric addition product in the presence of at least one inert organic Solvent which does not contain active hydrogen atoms, by heating Reflux temperature takes place. 11. The method according to any one of claims 1 to 10, characterized in, that the reaction of the d ,, ß-unsaturated monocarboxylic acid with the monoglycidyl compound takes place to the monomeric addition product in the presence of a chain regulator. 12. The method according to any one of claims 1 to 10, characterized in that that the copolymerization by heating the reaction mixture that formed contains monomeric addition product, in the presence of inert organic solvents which contain no active hydrogen atoms9 at reflux temperature in The presence of polymerization initiators takes place. 130 Method according to one of Claims 1 to 12, characterized in that that the copolymerization by heating the reaction mixture that formed contains monomeric addition product, in the presence of inert organic solvents, which contain no active hydrogen atoms, under reflux and addition of polymerization initiator and vinyl compounds and continue to heat after the addition is complete until the copolymerization is complete0 14eProcess according to one of Claims 1 to 13, characterized in that the copolymerization with the addition of a chain regulator he follows. 150 Reaction lacquers based on copolymers containing hydroxyl groups based on vinyl compounds, α, ß-unsaturated monocarboxylic acids and Monoglycidyl compounds which are bonded as esters by addition, polyisocyanates, inert organic solvents and optionally others in reactive lacquers Usual additives, characterized in that components (A) and (B) are used in quantities of (A) 60 to 95% by weight of hydroxyl-containing copolymers, prepared according to of the invention, iB) 5 to 40 wt .-% organic polyisocyanate, where (A) and (B) together must result in numerical values of 100% by weight 6 are included based on copolymers containing hydroxyl groups based on vinyl compounds, ^ ', ß-unsaturated monocarboxylic acids and monoglycidyl compounds produced by addition are bound as esters, amino resins, organic solvents and optionally further additives commonly used in baking enamels9, characterized in that the components (A), and (C) in amounts of CA) 70 to 95% by weight of hydroxyl group-containing copolymers, prepared according to the invention, (C) 5 to 30% by weight of aminoplast resins, where (A) and (C) together must result in numerical values of 100 Gew0'o are included. 17. The method according to claim 6, characterized in that copolymers from a) 20 to 32 wt .-% styrene and / or vinyl toluene, b) 16 to 26 wt .-% methyl methacrylate, c) 26 to 16% by weight of hydroxyethyl methacrylate, optionally up to 7% by weight of hydroxyethyl methacrylate by means of polypropylene glycol monomethacrylate with the formula are replaced, where n is numbers from 5 to 6 and the average molecular weight is about 350 to 387, a) 6 to 9 gel, r .-% acrylic acid and / or methacrylic acid and e) 20 to 30 wt .-% glycidyl esters of aliphatic saturated Monocarboxylic acids having 9 to 15 carbon atoms are prepared, components d and e first being converted to the addition product in the presence of at least one of components a and / or b, optionally c, and then the components being copolymerized in the presence of inert solvents, components a, b, c, d and e are selected so that they add up to 100% by weight. 18. The method or claim 1, characterized in that copolymers from a) 10 to 29 wt .-% styrene and / or vinyl toluene, b) 18 to 26 wt .-% methyl methacrylate, c) 16 to 26% by weight of hydroxyethyl methacrylate, d) 7 to 12% by weight of acrylic acid and / or Methacrylic acid and e) 36 to 20% by weight of glycidyl esters of aliphatic saturated Monocarboxylic acids with 9 to 15 carbon atoms are produced, with the components d) and e) first to the addition product in the presence of at least one of the components a) and / or b) optionally c) are reacted and then the components are copolymerized in the presence of inert solvents, the components a, b, c, d and e are selected so that they are 100% by weight ore. 19. The method according to claim 1, characterized in that copolymers of a) 27 to 32 wt .-% styrene and / or vinyl toluene, b) 18 to 20 wt .-% methyl methacrylate, C1) 16 6 to 18 wt .-% hydroxyethyl methacrylate , c2) 2 to 6 wt .-% polypropylene glycol monomer methacrylate with the formula where n denotes numbers from r to 6 and the average molecular weight is about 350 to 387, d) 6 to 7% by weight of acrylic acid and / or methacrylic acid and e) 23 to 25% by weight of glycidyl esters of aliphatic saturated monocarboxylic acids with 9 to 15 carbon atoms wcrden prepared, wherein the components d) and e) are first converted to the addition product in the presence of at least one of the components a) and / or b) optionally c) and then the components are copolymerized in the presence of inert solvents, the components a, b , c, d and e are selected so that they add up to 100% by weight. 20. The method according to claim 1, characterized in that copolymers of 3 to 40 wt .-% a) styrene and / or vinyl toluene and / or b) methyl methacrylate, lo to 40 wt .-% b1) acrylic acid esters and / or methacrylic acid esters of aliphatic saturated monoalcohols with 2 to 12 0 atoms, lo to 30 wt .-% c) hydroxyethyl acrylate and / or hydroxyethyl methacrylate, polypropylene glycol monomethacrylate with the formula where n denotes numbers from 5 to 6 and the average molecular weight is about 350 to 387, 5 to 12% by weight d) acrylic acid and / or methacrylic acid and 35 to 15% by weight glycidyl esters of aliphatic saturated monocarboxylic acids having 9 to 15 carbon atoms are prepared, wherein components d) and e) are first converted to the addition product in the presence of at least one of components a) and / or b) optionally c) and then the components are copolymerized in the presence of inert solvents, components a, b , c, d and e are selected so that they add up to 100% by weight. 21. The method according to claim 1 or one of claims 17 to 20 thereby characterized in that for copolymers intended for polyisocyanate crosslinking are, the starting components are selected and implemented so that copolymers with a hydroxyl group content of about 2 to about 6% by weight, based on the weight of the starting monomers. 22. The method according to claim 21, characterized in that the starting components selected and reacted so long that copolymers with acid numbers of 2 to 12, preferably 3 to 6, can be obtained. 23. The method according to claim 20, characterized in that for copolymers, which are intended for crosslinking with amino resins, the starting components as follows are selected and implemented that copolymers with a hydroxyl group content from 2 to 4.5% by weight, o ', based on the weight of the starting monomers, and with an acid number of 10 to 50 can be obtained.