WO1995018161A1

WO1995018161A1 - Binders based on cyclo-olefinic, if required peroxygenated copolymers, their preparation, coating media containing the same and their use

Info

Publication number: WO1995018161A1
Application number: PCT/EP1994/004260
Authority: WO
Inventors: Carmen Flosbach; Peter Schreiber; Walter Schubert; Astrid TÜCKMANTEL
Original assignee: Herberts Gesellschaft mit beschränkter Haftung
Priority date: 1993-12-24
Filing date: 1994-12-21
Publication date: 1995-07-06
Also published as: JPH07252461A

Abstract

Binders that are particularly useful in coating media for scratch- and acid-resistant coatings, in particular for the automobile industry and for coating polyolefine substrates, are disclosed, as well as their preparation. These binders are produced by radical-initiated polymerisation of 99.5 to 5 % by weight of one or several (meth)acrylic monomers and if required one or several additional radically polymerisable monomers different from the first in the presence of 0.5 to 95 % by weight of one or several cyclo-olefine homopolymers, cyclo-olefine copolymers, peroxygenated cyclo-olefine homopolymers and/or peroxygenated cyclo-olefine copolymers free from olefinic double bonds.

Description

Binding agents based on cycloolefinic, if appropriate

Peroxygenated copolymers, their preparation, containing them

Coating agents and their use. The invention relates to polymers based on cycloolefinic homo- and copolymers (COC), which can be peroxygenated, and free-radically polymerizable monomers, which are suitable as binders for the preparation of coating agents. Such coating agents are particularly suitable for the production of scratch-resistant and acid-resistant coatings. They can be used, for example, for the production of automotive paints and for the coating of polyolefin substrates.

In recent years, the requirements for chemical resistance, in particular sulfuric acid resistance, of automotive top coats and clear coats have been increased significantly. One way of resistance to

Increasing automotive paints compared to acids consists in their hydrophobization.

Attempts have been made to achieve such hydrophobization by using fluorine-containing monomers, as described in US Pat. Nos. 4,929,666 and 5,006,624. Such paints are ecologically unsafe because their disposal, e.g. through combustion, may be associated with the formation of toxic fluorine compounds.

Patent Abstracts of Japan, C-339, April 15, 1986 describes heat-resistant graft polymers of vinyl monomers on unsaturated cyclopentadiene polymers. However, as described in Patents Abstracts of Japan, C-432, June 30, 1987, they are not suitable for the coating of polyolefins.

The object of the invention is to provide polymers or binders which are suitable for acid-resistant coatings do not cause toxicity problems which have improved scratch resistance and which also enable improved adhesion to plastic substrates, in particular to polyolefins.

It has been shown that this object can be achieved by the provision of coating compositions which contain one or more reaction products as a binder or binder component, and which are peroxygenated by polymerization of free-radically polymerizable monomers in the presence of cycloolefinic homo- and / or copolymers (COC) can be and are free of olefinic double bonds are obtained. Without being bound by any theory, it is assumed that at least some of the (meth) acrylic monomers and / or others

Monomers are grafted onto the COC. The invention therefore relates to binders which are suitable for coating agents and are obtainable by free-radically initiated polymerization of

99.5 to 5% by weight, preferably 99.5 to 70% by weight, of one or more

(Meth) acrylic monomers and optionally additionally one or more radically polymerizable monomers different therefrom, in the presence of

0.5 to 95% by weight, preferably 0.5 to 30% by weight, of one or more

Cycloolefin homopolymer Cycloolefin copolymers, peroxygenated cycloolefin homopolymers and / or peroxygenated cycloolefin copolymers which are free of olefinic double bonds.

The binders obtained in this way are suitable for preparing solvent-containing and / or water-containing coating compositions which are suitable for producing scratch-resistant and acid-resistant coatings. They adhere well to plastic surfaces, especially non-polar plastic surfaces such as polyolefin surfaces, polyethylene, polypropylene and / or cycloolefin copolymers. The coating agents also form an object of the invention.

The coating compositions of the invention can in addition to the inventive Containers contain one or more crosslinkers, one or more organic solvents and / or water, as well as other additives and auxiliaries customary in paint. In addition to the binders according to the invention, they can also contain one or more further film-forming binders which are not crosslinkers for the binders according to the invention.

The cycloolefin homopolymers and cycloolefin copolymers free of olefinic double bonds used according to the invention are referred to below as COC. For example, known homopolymers and copolymers. Such conventional COC resins are described, for example, in EP-A-0 407 870, EP-A-0 485 893 and EP-A-0 503 422. The

Peroxygenated COC are, for example, known homo- and copolymers which have been peroxygenated by reaction with oxygen. Usual COC resins, which can serve as the basis for the peroxigenated COC resins, are described, for example, in the aforementioned EP-A. The peroxygenated COC are therefore homo- and oxygen-containing

Copolymers of cycloolefin monomers. The oxygen is preferably in a peroxidic function as a peroxide and / or as a hydroperoxide. The oxygen content is, for example, 0.01 to 50% by weight, preferably

0.05 to 20 wt .-%, particularly preferably 0.1 to 10 wt .-% based on the total weight of the homo- or copolymer.

Examples of usable cycloolefin homopolymers and cycloolefin copolymers contain

A) 20 to 100 wt .-% based on the total mass of

Monomers, units used for their preparation, obtained from at least one monounsaturated cycloolefin monomer and

B) 0 to 80% by weight, based on the total mass of the monomers, units used for their preparation, obtained from at least one monounsaturated acyclic olefin monomer. They can be prepared, for example, by polymerizing or copolymerizing monounsaturated cycloolefin monomers with the acyclic monounsaturated olefin monomers which may also be used. This can be done using customary methods, such as those described in the above-mentioned EP-A publications. For example, they can be obtained by radical-initiated polymerization or copolymerization.

To produce the peroxigenized COC, for example, oxygen can be introduced into the polymers obtained as described above by reaction with gaseous oxygen, which can optionally be diluted by inert gas, in the presence of radicals. The reaction can be carried out in the presence of auxiliaries, such as solvents, dispersants and free radical initiators. The reaction mixture can be heterogeneous or homogeneous with respect to the polymer used. As

Radical formers can be used as water-soluble or water-insoluble radical formers, such as are used, for example, in the polymerization of olefinically unsaturated monomers. It can

for example, radical initiators are used, as described below for the preparation of the binders by radical copolymerization.

Specific examples of usable peroxygenated cycloolefin homopolymers and cycloolefin copolymers include, for example

A) 0.1 to 100 wt .-% based on the total mass of their

Production of monomers used, units of at least one monounsaturated cycloolefin monomer and

B) 0 to 80% by weight, based on the total mass of the monomers used for their preparation, units of at least one

monounsaturated acyclic olefin monomers and

C) 0.01 to 50 wt .-%, based on the total weight of the polymer of oxygen, which is directly bound to carbon atoms of the polymer backbone.

Preferred examples of the monoolefinically unsaturated monomers for the preparation of the cycloolefin components are compounds of the general Formulas I, II, III, IV, V, VI and VII

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are the} same or different and represent a hydrogen atom or a C ₁ -C ₈ alkyl radical, the same

Residues in the different formulas can have a different meaning and n is a number from 2 to 10.

Compounds of the formulas I and III are particularly preferred, in particular norbornene and tetraacyclododecene, it being possible for these to be substituted, for example, by (C ₁ -C ₈ ) -alkyl.

Preferred acyclic olefins with no more than one olefinic double bond are alpha-olefins with 2 to 20 carbon atoms, for example ethylene or propylene. The COC used according to the invention particularly preferably contains a cycloolefin component and an alpha-olefin component. Preferred are COC, the norbornene or tetracyclododecene, which may be substituted, for example, by (C ₁ -C ₆ ) alkyl, with ethylene as a comonomer. Copolymers containing ethylene / norbornene are of particular importance.

In the peroxygenated COC, the oxygen is preferably in a peroxidic function as a peroxide and / or hydroperoxide.

The COC used according to the invention has component A (cycloolefin content), for example, in a proportion of from 20 to 100% by weight, preferably 20 to 90% by weight, based on the total mass of the monomers used.

The peroxygenic COC used according to the invention has component A (cycloolefin component), for example, in a proportion of 0.1 to 100% by weight, preferably 1 to 100, particularly preferably 10 to 90% by weight, based on the total mass of the monomers used .

The oxygen content is, for example, 0.01 to 50% by weight, preferably 0.05 to 20% by weight, particularly preferably 0.1 to 10% by weight, based on the total weight of the polymer. The proportion of component B (acyclic olefin component) is, for example, 0 to 80% by weight, preferably 10 to 80% by weight, particularly preferably 2 to 50% by weight, based on the total mass of the monomers used.

The weight average molecular weight (Mw) is preferably between 5000 and 100000 g / mol. The glass transition temperature is preferably -20-200 ° C, particularly preferably 0-200 ° C.

The polymers (COC-containing binders) obtained by polymerizing the monomers used according to the invention in the presence of the COC preferably have a number average molecular weight (Mn) of 5000 to 100000, particularly preferably 5000 to 20,000.

For the polymerization in the presence of the COC and / or peroxygenated COC, all known monofunctional (meth) acrylic monomers can optionally be differentiated together with others. racikaliscn copolymerizable monomers are used, which preferably have only a single olefinic double bond. The proportion of additional monomers can e.g. 0 to 50 wt .-%, preferably 0 to 40 wt .-%, based on the weight of the (meth) acrylic monomers.

The expression (meth) acrylic is synonymous with acrylic unc / cer methacrylic, which can be substituted.

Examples of (meth) acrylic monomers are (meth) acrylic esters, such as alkyl (meth) acrylates, which also have other functional grues, such as hydroxyl groups, amino groups, especially tert-amine crucians, glycidyl functions or carboxy-functionalized monomers.

Examples of this are long-chain, branched or unbranched unsaturated monomers, such as alkyl (meth) acrylates with C ₈ -C ₁₈ chains in the alkyl part, for example ethylhexyl (meth) acrylate, octyl (meth) acrylate, 3,5,5-trimethylhexyl (meth ) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylet, hexacecyl (meth) acrylate, octadecyl (meth) acrylate, lauryl acrylate, isobornyl (meth) acrylate, 4-tertiary butylcyclohexyl methacrylate. Other examples are short or medium-chain, branched or unbranched unsaturated monomers, such as alkyl (meth) acrylates with C ₁ -C ₇ chains in the alkyl part, for example methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate ,, butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate.

The (meth) acrylic monomers used can carry, for example, primary or secondary hydroxy functions. Examples of monomers with primary hydroxy functions are hydroxyalkyl esters of acrylic acid and / or methacrylic acid with a primary OH group and a C ₂ -C ₃ -hydroxyalkyl radical with hydroxyethyl (meth) acrylate, and also hydroxyalkyl esters of acrylic acid and / or methacrylic acid with one primary OH group and a C ₄ - C ₁₈ hydroxyalkyl residue such as butanediol monoacrylate, hydroxyhexyl acrylate, hydroxyoctyl acrylate and the corresponding methacrylates and reaction products of hydroxyethyl (meth) acrylate with caprolactone.

Examples of monomers with secondary OH functions are: hydroxypropyl (meth) acrylate, adducts of glycidyl (meth) acrylate and saturated short-chain fatty acids with C ₁ -C ₃ -alkyl radicals, for example acetic acid or propionic acid, and adducts of Cardura E (glycidyl ester of versatic acid) ) with unsaturated COOH-functional compounds such as acrylic or. Methacrylic acid, maleic acid, crotonic acid, adducts from Cardura E with unsaturated anhydrides such as maleic anhydride, reaction products from glycidyl (meth) acrylate with saturated branched or unbranched fatty acids with C ₄ -C ₂₀ -alkyl radicals, eg butanoic acid, caproic acid, lauric acid, palmitic acid, stearic acid, stearic acid Arachidonic acid.

Examples of carboxy-functionalized monomers are acrylic acid, methacrylic acid and crotonic acid.

It is also possible to use glycidyl-functionalized monomers. Examples of such monomers are glycidyl (meth) acrylate, 1,2-epoxybutyl acrylate or 2,3-epoxycyclopentyl acrylate.

Other copolymerizable glycidyl monomers are e.g. (Meth) allyl glycidyl ether or 3,4-epoxy-1-vinylcyclohexane.

It is also possible, for example, to use (meth) acrylic monomers with terminal tert-amino groups. Examples of such monomers are tert-aminomethyl methacrylate or tert-aminopropyl methacrylate. If such monomers are used, the simultaneous use of glycidyl-functionalized monomers should be avoided, otherwise gelling of the polymer cannot be ruled out.

Radically polymerizable monomers that can be used with the (meth) acrylic monomers are, for example, vinyl aromatic monomers, such as styrene and styrene derivatives, such as vinyl toluenes, chlorostyrenes, o-, m- or p-methylstyrene, 2,5-dimethylstyrene, p-methoxystyrene, p-tert-butylstyrene, p-dimethylaminostyrene, p-acetamidostyrene and m-vinylphenol. Vinyl toluenes and in particular styrene are preferably used.

Examples of usable carboxyl-functionalized monomers are crotonic acid, unsaturated anhydrides such as maleic anhydride, and also half esters of maleic anhydride by addition of saturated aliphatic alcohols, such as e.g. Ethanol, propanol, butanol and / or isobutanol.

Examples of other suitable ethylenically unsaturated monomers are the alkyl esters of maleic, fumaric, tetrahydrophthalic, crotonic, isocrotonic, vinyl acetic and itaconic acids, e.g. corresponding methyl, ethyl, propyl, butyl, isopropyl, isobutyl, pentyl, amyl, isoamyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 3,5,5-trimethylhexyl, decyldodecyl , Hexadecyl, octadecyl and octadecenyl esters.

In the context of the invention it is particularly preferred that the monomers used have only one olefinically unsaturated double bond. However, it is also possible to use small amounts of monomers with at least two polymerizable, olefinically unsaturated double bonds.

However, the proportion of these monomers is preferably less than 5% by weight, based on the total weight of the monomers.

Examples of such compounds are hexanediol diacrylate, hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, hexamethylene bismethacrylamide, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and similar compounds.

In the synthesis of the binders according to the invention, the free-radically polymerizable monomers are reacted in the presence of one or more COC and / or peroxygenated COC. If the possibly peroxygenated COC are liquid materials, the addition of solvents can be used to be dispensed with. However, it is possible to work in the presence of solvents so that a liquid reaction medium is achieved. It is beneficial to keep the amount of solvent as small as possible. Examples of solvents that can be used are conventional solvents, such as aromatic hydrocarbons or esters, for example xylene or butyl acetate.

The amount of COC or peroxygenated COC is selected so that it is 0.5 to 95% by weight, based on the total solids content of the finished product

Binder is.

According to one embodiment of the process according to the invention, the optionally peroxygenated COC can optionally be introduced with a little solvent. In general, the total amount of COC and / or peroxygenated COC to be used is presented. For the polymerization of the monomers, this optionally peroxygenated COC matrix can be heated, for example to temperatures in the order of 100 to 150 ° C, e.g. up to 140 ° C.

The monomers can then be introduced into this matrix. This can be done, for example, by dropping, for example over a period of 3 to 5 hours.

The monomers or the monomer mixture used can contain initiators. This is not necessary, but it is also possible if peroxygenated COC are used. The peroxy groups of the peroxygenated COC can then serve as initiators. If work is carried out in the presence of initiators, these can, if they are not already present in the monomer mixture, be added to the monomer mixture with a slight time lag or metered in separately. You can then continue for a longer period, e.g. be polymerized for several hours. It is then possible to adjust to a desired solids content, for example in the order of 30 to 60% by weight, for example 50% by weight, using a conventional paint solvent.

The binders are produced by radical copolymerization. The amount of monomer is adjusted so that the desired Specifications regarding molar mass, OH group ratio, OH number and acid number can be achieved. The preparation takes place, for example, as radical solution polymerization in the presence of a radical initiator, as is known to the person skilled in the art. Examples of radical initiators are dialkyl peroxides, such as di-tert-butyl peroxide, di-cumyl peroxide; Diacyl peroxide such as dibenzoyl peroxide, dilauroyl peroxide; Hydroperoxides, such as cumene hydroperoxide, tert-butyl hydroperoxide; Peresters such as tertiary butyl perbenzoate, tertiary butyl perpivalate, tertiary butyl per 3,5,5-trimethylhexanoate, tertiary butyl per 2-ethylhexanoate; Peroxide dicarbonates such as di-2-ethylhexyl peroxydicarbonate, dicyclohexyl peroxydicarbonate; Perketals such as 1,1-bis (tert-butylperoxy) 3,5,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane; Ketone peroxides, such as cyclohexanone peroxide, methyl isobutyl ketone peroxide and azo compounds, such as 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2methylbutyronitrile), 1,1'-azobis-cyclohexane carbonitrile , Azo-bis-isobutyro-nitrile, CC-cleaving initiators such as benzpinacol 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. If an aqueous emulsion is to be created, the solvent used in the production is removed (instead of the solids setting by adding customary paint solvents). This can be done, for example, by distillation, if appropriate under vacuum. The resin concentrate obtained, which has a high solids content, for example 90% by weight, can then, if acidic groups are contained in the resin, be mixed with a conventional base, e.g. Ammonia or an organic amine, e.g.

Triethylamine to be neutralized. The neutralized resin concentrate obtained can be emulsified in water. This can be done, for example, with vigorous stirring and if necessary with heating, for example at temperatures from 30 to 80 ° C, e.g. 50 ° C.

It is also possible in the manufacture of the resins with basic monomers Groups, for example those containing tertiary amines, are also polymerized. The resin containing basic groups and prepared in this way can then be neutralized with acids, for example inorganic or organic acids, such as formic acid, acetic acid and then emulsified in water.

If the resin does not contain acidic, basic or ionic groups, it can be emulsified using a conventional, non-ionic emulsifier. This can be done continuously or discontinuously. This happens e.g. by homogenizing the resin concentrate and the nonionic emulsifier, optionally with heating, for example to temperatures from 30 to 80 ° C, e.g. 60 ° C. Such a mixture can be emulsified in a conventional homogenization device. Examples of this are rotor / stator homogenizers, which operate at speeds of, for example, 8000 to 10,000 revolutions per minute. The emulsifiers are used, for example, in amounts of 3 to 30% by weight, based on the resin concentrate. It is assumed that the procedure according to the invention fixes the COC in the binder matrix formed by polymerizing the monomers. Without being bound to a specific theory here, it is assumed that, on the one hand, the polymerization of

Monomers in the presence of the COC form a semi-interpenetrating network, on the other hand, however, at least also during the polymerization

Part of the monomers is grafted onto the COC matrix. It is believed that this achieves the favorable weather resistance of coatings made on the basis of the binders according to the invention.

The binders according to the invention are particularly suitable for the production of coating compositions. Such coating agents can contain, in addition to the binders of the invention, customary lacquer additives, in particular crosslinking agents.

In the production of the binders according to the invention, the functional groups of the monomers used remain obsolete. It is therefore possible to choose crosslinkers depending on the type of functional groups of the binders used. The following combinations of

Binding agents based on COC and crosslinking agents specified:

1) COC, in which, inter alia, hydroxy- and / or carboxy-functionalized (meth) acrylic monomers are polymerized, with crosslinking agents based on la) polyisocyanates, which can be blocked, and / or

lb) melamine resins, or

lc) polyepoxides, which can optionally be catalyzed with acids or basic catalysts. 2) COC, in which, inter alia, epoxy and optionally hydroxy-functionalized (meth) acrylic monomers are copolymerized, with crosslinkers based on

2a) Carboxy-functionalized compounds, the cross-linking

can optionally be catalyzed with acids or bases, and optionally

2b) melamine resins, or 2c) polyamines, which can optionally be blocked.

3) COC, in which, inter alia, epoxy-functionalized (meth) acrylic monomers are polymerized, part of the glycidyl functions being subsequently esterified with alpha, beta-unsaturated carboxylic acids, as a result of which unsaturated groups are incorporated in the resin, as described in DE-A- 40 27 259 is inseminated, with crosslinkers based on

3a) polyamines, which may be capped, or

3b) components with several C-H-acidic groups in the molecule,

a basic catalyst optionally being added can, or

3c) transesterification crosslinkers with several groups capable of transesterification

Molecule.

Examples of polyisocyanates la) are diisocyanates, such as customary aliphatic, cycloaliphatic and aromatic diisocyanates, e.g. 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate; 3,5,5-trimethyl-1-isocyanate-3-isocyanatomethylcyclohexane; m-xylylene diisocyanate, p-xylylene diisocyanate; Tetramethyl diisocyanate, isophorone diisocyanate or cyclohexane-1,4-diisocyanate.

The polyisocyanates can be linked to prepolymers with a higher molecular weight. Examples include adducts of tolylene diisocyanate and trimethylolpropane, a biuret formed from 3 molecules of hexamethyl diisocyanate, as well as the trimers of hexamethylene diisocyanate and the trimers of isophorone diisocyanate.

The isocyanate groups of the polyisocyanates used may be completely blocked. Common capping agents can be used, e.g. Malonic acid dimethyl ester, malonic acid diethyl ester, acetoacetic ester, caprolactone, 1,2-propanediol and / or butanone oxime and the other capping agents known to the person skilled in the art. Examples of melamine resins Ib) are conventional crosslinking resins, such as e.g. Methyl etherified melamines, such as the commercial products Cymel 325, Cymel 327, Cymel 350 and Cymel 370, Maprenal MF 927.

Further examples of melamine resins 1b) which can be used are butanol- or isobutanol-etherified melamines, such as, for example, the commercial products Setamin US 138 or Maprenal MF 610; mixed etherified melamines which are etherified with both butanol and methanol, such as Cymel 254, and hexamethyloxymethylmelamine (HMM melamines) such as Maprenal 900 or Maprenal 904, the latter of which may require an external acid catalyst such as p-toluenesulfonic acid for crosslinking. The acid catalyst can be blocked ionically with amines such as, for example, triethylamine or non-ionically, such as with Cardura E, the glycidyl ester of versatic acid. The binders according to the invention, as described under 1), can be crosslinked with the uncapped polyisocyanates in a further temperature range, for example between 20 ° C. and 180 ° C., the range between 20 ° C. and 80 ° C. being preferred.

When using blocked polyisocyanates and / or melamine resins, baking temperatures between 80 ° C and 180 ° C are preferred.

Examples of polyepoxides 1c) which contain acid groups, e.g. Can crosslink COOH group-containing binder 1 are di- or polyfunctional epoxy compounds which are produced using, for example, di- or polyfunctional epoxy compounds, such as diglycidyl or polyglycidyl ether of (cyclo) aliphatic or aromatic hydroxy compounds such as ethylene glycol, glycerol, 1,2 - and 1,4-cyclohexanediol, bisphenols such as bisphenol A, polyglycidyl ethers of phenol formaldehyde novolaks, polymers of ethylenically unsaturated groups which contain epoxy groups, such as glycidyl (meth) acrylate, N-glycidyl (meth) acrylamide, and / or allyl glycidyl ether, optionally copolymerized with various other ethylenically unsaturated monomers, glycidyl ethers of fatty acids with 6-24 C atoms, epoxidized polyalkadienes, such as epoxidized polybutadiene, hydantoin-epoxy resins, glycidyl group-containing resins, such as polyesters or polyurethanes, which contain one or more glycidyl groups per molecule, and mixtures of the named resins and compounds gene.

If appropriate, the crosslinking can be additionally catalyzed using catalysts which are used, for example, in an amount between 0.1% and 10%, based on the total solid resin content.

These are e.g. Phosphonium salts such as benzyl triphenylphonium acetate, chloride, bromide or iodide, or e.g. Ammonium compounds such as Tetraethylammonium chloride or fluoride.

Examples of carboxy-functionalized compounds 2a) which can crosslink the epoxy-functionalized binders under 2) are carboxy Functionalized poly (meth) acrylic copolymers and / or one or more carboxy-functionalized polyesters. According to a preferred embodiment of the invention, the carboxy-functionalized poly (meth) acrylic copolymers have a number average molecular weight (Mn) of 1000 to 10000 g / mol. The correspondingly usable carboxy-functionalized polyesters preferably have a calculated molecular weight of 500 to 2000 g / mol. The acid number of these starting materials is 15 to 200 mg KOH / g, preferably 30 to 140 mg KOH / g and particularly preferably 60 to 120 mg KOH / g.

In the production of the carboxyl group-containing poly (meth) acrylic copolymers or polyesters, the carboxyl groups can be introduced directly by using building blocks containing carboxyl groups, for example when building up polymers such as (meth) acrylic copolymers. Examples of suitable carboxyl-containing monomers that can be used for this purpose are unsaturated carboxylic acids, such as e.g. Acrylic, methacrylic, itacon, croton, isoerotonic, aconitic, maleic and fumaric acid, half esters of maleic and fumaric acid as well as ß-carboxyethyl acrylate and adducts of hydroxyalkyl esters

Acrylic acid and / or methacrylic acid with carboxylic anhydrides, e.g. the phthalic acid mono-2-methacryloyloxyethyl ester.

In the present description and the claims, the

Expression (meth) acrylic used. This means acrylic and / or methacrylic.

When producing the (meth) acrylic copolymers or polyesters containing carboxyl groups, it is also possible, however, to first of all build up a polymer containing hydroxyl and optionally carboxyl groups with an OH number of 15 to 200 mg KOH / g and the carboxyl groups in whole or in part in a second stage by reacting the hydroxyl- and optionally carboxyl-containing polymers with carboxylic anhydrides.

Carboxylic anhydrides suitable for addition to the hydroxyl-containing polymers are the anhydrides of aliphatic, cycloaliphatic and aromatic saturated and / or unsaturated di- and polycarboxylic acids, such as, for example, the anhydrides of phthalic acid, tetra hydrophthalic acid, hexahydrophthalic acid, succinic acid, maleic acid,

Itaconic acid, glutaric acid, trimellitic acid and pyromellitic acid and their halogenated or alkylated derivatives.

Anhydrides of phthalic acid, tetrahydro- and hexahydrophthalic acid and 5-methylhexahydrophthalic anhydride are preferably used.

Examples of suitable hydroxyalkyl esters of alpha.beta-unsaturated

Carboxylic acids with primary hydroxyl groups for the preparation of hydroxy-functional poly (meth) acrylates are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamylacrylate, hydroxyhexyl acrylate, hydroxyoctyl acrylate and the corresponding methacrylates. Examples of usable hydroxyalkyl esters with a secondary hydroxyl group are 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate and the corresponding methacrylates.

Advantageously, the hydroxyl-functionalized component can be at least partially a reaction product of one mole of hydroxyethyl acrylate and / or hydroxyethyl methacrylate and an average of 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 used at least in part as the hydroxy-functionalized component. Glycidyl esters of strongly branched monocarboxylic acids are available under the trade name "Cardura". The reaction of acrylic acid or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary alpha carbon can take place before, during or after the polymerization reaction.

In addition to the monomers mentioned above, other ethylenically unsaturated monomers can also be used in the preparation of the (meth) acrylic copolymers. The selection of the other ethylenically unsaturated monomers is not critical. It is only necessary to ensure that the incorporation of these monomers does not lead to undesirable properties of the copolymer. Particularly suitable as a further ethylenically unsaturated component are alkyl esters of acrylic and methacrylic acid, such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth ) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) 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 octadecenyl (meth) acrylate.

Instead of the above-mentioned alkyl esters of acrylic and methacrylic acid or together with these alkyl esters, further ethylenically unsaturated monomers can be used for the production of (meth) acrylic copolymers, the selection of these monomers largely depending on the desired properties of the coating agents in terms of hardness, elasticity, Compatibility and polarity aimed.

Examples of other suitable ethylenically unsaturated monomers are the alkyl esters of maleic, fumaric, tetrahydrophthalic, croton, isocrotonic, vinyl acetic and itaconic acids, such as e.g. corresponding methyl, ethyl, propyl, butyl, isopropyl, isobutyl, pentyl, amyl, isoamyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 3,5,5-trimethylhexyl, decyldodecyl , Hexadecyl, octadecyl and octadecenyl esters.

Small portions of monomers with at least two polymerizable, olefinically unsaturated double bonds can also be used. The proportion of these monomers is preferably less than 5% by weight, based on the total weight of the monomers.

Another suitable component is a monovinyl aromatic compound fertilizer It preferably contains 8 to 10 carbon atoms per molecule.

Examples of suitable compounds are styrene, vinyl toluenes, alpha

Methylstyrene, chlorostyrenes, o-, m- or p-methylstyrene, 2,5-dimethylstyrene, p-methoxystyrene, p-tert-butylstyrene, p-dimethylaminostyrene, p-acetamidostyrene and m-vinylphenol. Vinyl toluenes and in particular styrene are preferably used.

The carboxyl group-containing polyesters can be constructed from aliphatic and / or cycloaliphatic di-, by the usual methods (see, for example, B. Vollmert, floor plan of macromolecular chemistry, E. Voll-mert-Verlag Karlsruhe 1982, Volume II, page 5 ff. Tri- or higher alcohols, optionally together with monohydric alcohols and from aliphatic, aromatic and / or cycloaliphatic carboxylic acids as well as higher polycarboxylic acids. Examples of suitable alcohols are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-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-dimethylclcyclohexane , Glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, etherification products of diols and polyols, for example Di- and triethylene glycol, polyethylene glycol, neopentyl glycol ester of hydroxypivalic acid.

Examples of suitable carboxylic acids are adipic, azelaine, 1,3- and 1,4-cyclohexanedicarboxylic acids, tetrahydrophthalic, hexahydrophthalic, endomethylene tetrahydrophthalic acid, isophthalic acid, o-phthalic acid, terephthalic acid or their anhydrides and their derivatives capable of esterification.

The calculated molecular weights of the polyesters are, for example, between 500 and 2000 g / mol.

The carboxy-functional poly (meth) acrylic copolymers and polyester which can be used can be "chain extended" with a lactone. The lactones (cyclic esters) attach to carboxyl groups, when the ring is opened and a new terminal carboxyl group is formed. On

An example of a particularly preferred lactone is epsilon-caprolactone. Examples of other lactones are gamma-butyrolactone and lactones, such as beta-priolactone, delta-valerolactone, delta-butyrolactone, zeta-enantholactone, eta-caprylolactone. Lactones of this type can be substituted:

Examples include 6-methyl-epsilon-caprolactone, 3-methyl-epsilon-caprolactone, 5-methyl-epsilon-caprolactone, 5-phenol-epsilon-caprolactone, 4-methyl-delta-valerolactone, 3,5-dimethyl-epsilon-caprolactone , and mixtures thereof.

The reaction with the lactone can, for example, take place immediately after the resin synthesis, that is to say after the synthesis of the poly (meth) acrylic polymer and / or of the polyester. The reaction takes place, for example, at an elevated temperature, for example at temperatures up to 100.degree. The reaction can be carried out, for example, with stirring for up to 10 hours, for example.

It may be advantageous to precondense the OH-functional resins and COOH-functional resins described.

The catalysts which can accelerate crosslinking between the epoxy-functionalized polysiloxanes 2) and component 2a) are those described in the description of component 1c). The quantitative ratios of components 2) and 2a) are preferably chosen so that the ratio of the epoxy groups and carboxy groups is between 1: 1.5 and 1.5: 1, preferably 1: 1.2 and 1.2: 1.

The melamine resins mentioned under 2b) are the same as those described under lb) above.

Component 2c) is a polyamine component with at least two functional groups of the formula R ⁴ HN-, where R is a hydrogen atom or a straight or branched alkyl radical with 1 to 10 carbon atoms or cycloalkyl radical with 3 to 8, preferably 5 or 6 carbon atoms. Suitable polyamines are diamines and amines with more than two amino groups, where the amino groups can be primary and / or secondary. In addition, adducts consisting of polyamines having at least two primary amino groups and at least one, preferably one, secondary amino group, with epoxy compounds, polyisocyanates and acryloyl compounds are also suitable as polyamines. Aminoamides and adducts of carboxyl-functionalized acrylates with imines which have at least two amino groups are also suitable.

Examples of suitable di- and polyamines are described, for example, in EP-A-0 240 083 and EP-A-0 346 982. Examples of these are aliphatic and / or cycloaliphatic amines having 2 to 24 carbon atoms, which contain 2 to 10 primary amino groups, preferably 2 to 4 primary amino groups, and 0 to 4 secondary amino groups.

Representative examples of this are ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, 4,7-dioxa-decan1,10-diamine, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, isophoronediamine, diethylenetriamine, dipropylenetriamine, 2,2-bis- (4-aminocyclohexyl) propane; Polyether polyamines, e.g. those with the tradename Jeffamine or Jefferson Chemical Company, bis (3-aminopropyl) ethylamine, 3-amino-1- (methylamino) propane and 3-amino-1- (cyclohexylamino) propane.

Also common are polyamines based on adducts of polyfunctional amine components with di- or polyfunctional epoxy compounds, for example those which are produced using, for example, di- or polyfunctional epoxy compounds, such as di-glycidyl or polyglycidyl ether of (cyclo) aliphatic or aromatic Hydroxy compounds such as ethylene glycol, glycerol, 1,2- and 1,4-cyclohexanediol, bisphenols such as bisphenol A, polyglycidyl ethers of phenol formaldehyde novolaks, polymers of ethylenically unsaturated groups which contain epoxy groups, such as glycidyl (meth) acrylate, N-glycidyl ( meth) acrylamide and / or allyl glycidyl ether, optionally copolymerized with various other ethylenically unsaturated monomers, glycidyl ether of fatty acids with 6 to 24 carbon atoms, epoxidized polyalkadienes, such as epoxidized polybutadiene, hydantoin-epoxy resins, glycidyl group-containing resins, such as polyesters or polyurethanes, which contain one or more glycidyl groups per molecule, and mixtures of the named resins and compounds.

The addition of the polyamines to the epoxy compounds mentioned takes place with the ring opening of the oxirane grouping. The reaction can take place, for example, in a temperature range of 20-100 ° C, but preferably between 20-60 ° C. Optionally, 0.1-2% by weight of a Lewis base such as triethylamine or an ammonium salt such as tetrabutylammonium iodide can be used for catalysis.

Suitable polyamines are also polyamine-isocyanate adducts. Common isocyanates for polyamine-isocyanate adducts are aliphatic, cycloaliphatic and / or aromatic di-, tri- or tetraisocyanates, which can be ethylenically unsaturated. Examples include 1,2-propylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, 2,3-butylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, w, w'-dipropyl ether diisocyanate, 1,3- Cyclopentane diisocyanate, 1,2- and 1,4-cyclohexane diisocyanate,

Isophorone diisocyanate, 4-methyl-1,3-diisocyanate-cyclohexane, transvinylidene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 3,3'-dimethyldicyclohexylmethane-4,4'-diisocyanate, tolylene diisocyanate, 1, 3-bis (1-isocyanato -1-methylethyl) benzene, 1,4-bis (1-isocyanato-1-methylethyl) benzene, 4,4'-diisocyanatodiphenyl, 3,3'-dichloro-4,4'-diisocyanatodiphenyl, adducts of 2 moles of a diisocyanate , e.g. Hexamethylene diisocyanate or isophorone diisocyanate to one mole of a diol, e.g. Ethylene glycol, the adduct of 3 moles of hexamethylene diisocyanate and 1 mole of water (available under the trade name Desmodur N from Bayer AG), the adduct of 1 mole of trimethylolpropane and 3 moles of toluene diisocyanate (available under the trade name Desmodur L from Bayer AG) and the adduct from 1 mole

Trimethylolpropane and 3 moles of isophorone diisocyanate.

The addition of polyamines to the isocyanate compounds mentioned takes place, for example, in a temperature range of 20-80 ° C., preferably 20-60 ° C. Optionally, 0.1 to 1% by weight of a tertiary amine, such as triethylamine and / or 0.1-1% by weight of a Lewis acid, such as dibutyltin laurate, can be catalyzed. As mentioned, the polyamines can also be adducts with acryloyl compounds. Examples of di- or polyfunctional acryloylungesättigte compounds for the manufacture of polyamine adducts are described in U.S. Patent No. 4,303,563, for example, ethylene glycol diacrylate, diethylene glycol diacrylate, trimethylene, 1,3-butylene glycol diacrylate, 1,6-hexamethylene, trimethylolpropane, and Pentaerytrituoltetraacrylat Pentaerytrituoltriacrylat. Further examples of polyfunctional acryloyl-unsaturated acrylates that can be used are:

1) Urethane acrylates obtained by the reaction of an isocyanate group of a polyisocyanate with a hydroxyacrylate, e.g. Hexamethylene diisocyanate and hydroxyethyl acrylate, the preparation is described in US Pat. No. 3,297,745,

2) Polyether acrylates obtained by transesterification of a hydroxy-terminated polyether with acrylic acid, described in US Pat. No. 3,380,831.

3) Polyester acrylates obtained by esterification of a hydroxyl-containing polyester with acrylic acid, described in US Pat. No. 3,935,173.

4) polyfunctional acrylates obtained by the reaction of a hydroxyl functionalized acrylate, e.g. Hydroxyethyl acrylate with a) dicarboxylic acids with 4 - 15 C atoms,

b) polyepoxides with terminal glycidyl groups,

c) polyisocyanates with terminal isocyanate groups, described in US Pat. No. 3,560,237, 5) acrylate-terminated polyesters, are degraded by the reaction of

Acrylic acid, a polyol with at least three hydroxy functions and a dicarboxylic acid, described in US Pat. No. 3,567,494,

6) Polyacrylate obtained by the reaction of acrylic acid with an epoxidized oil containing epoxy functions, such as soybean oil or

Linseed oil described in U.S. Patent 3,125,592, 7) Polyacrylate obtained by the reaction of acrylic acid with epoxy groups of a diglycidyl ether of bisphenol A, described in US-PS

3,373,075.

8) Polyacrylate obtained by the reaction of acrylic acid on

Epoxy functionalized vinyl polymer, e.g. Polymers with glycidyl acrylate or vinyl glycidyl ether described in U.S. Patent 3,530,100,9) polyacrylate obtained by the reaction of acrylic anhydride with polyepoxides described in U.S. Patent 3,676,398.

10) Acrylate urethane esters obtained by the reaction of a hydroxyalkyl acrylate with a diisocyanate and a hydroxyl functionalized alkyd resin described in U.S. Patent 3,676,140.

11) Acrylate urethane polyester obtained by the reaction of a polycaprolactone diol or triol with an organic polyisocyanate and with a hydroxyalkyl acrylate described in U.S. Patent 3,700,634.

12) Urethane polyacrylate, obtained by the reaction of a hydroxy-functionalized polyester with acrylic acid and a polyisocyanate, described in US Pat. No. 3,759,809. The acryloyl end groups of the di- or polyacrylic monomers or the polyacrylates from Examples 1) to 12) can be functionalized with polyamines. The attachment can e.g. in a temperature range of 20-100 ° C, preferably at 40-60 ° C. Another method for synthesizing an amine-functionalized hardener is described in EP-A-0 002 801. Here acrylic ester copolymers are amidized with diamines with elimination of alcohol. The reactive group obtained has the following structure:

R ⁵ = H or CH ₃ ,

R ⁶ = alkylene groups with 2 or 3 carbon atoms, which can be the same or different

n = 0, 1, 2 or 3

the rest coming from the acrylic ester copolymer backbone.

The acrylic acid ester copolymer has a number average molecular weight Mn of 1000-20000, preferably 2000-5000. Examples of possible comonomers are esters of (meth) acrylic acid such as e.g. Methyl, ethyl, eutyl, cyclohexyl (meth) acrylate, hydroxyethyl (meth) arylate, hydroxyprcpyl (meth) acrylate, furthermore (meth) acrylic acid, styrene and vinyl toluene. Methyl acrylate is particularly preferred since this monomer is particularly easily accessible to aminolysis. The proportion of (meth) acrylate in the copolymer is 2 to 35% by weight. The copolymers are prepared by solution polymerization in customary solvents such as toluene, xylenes, acetates, e.g. B. butyl acetate or ethyl glycol acetate, ethers such as tetrahydrofuran or aromatic mixtures such as the commercial product Solvesso 100. The synthesis of

Copolymers are known to the person skilled in the art and require no further

Explanation. The polyamines used in aminolysis must contain at least two primary or secondary amine groups and have already been described.

Reaction products from the reaction of a (meth) acrylic acid copolymer with alkyleneimines as described in cer EP-A-0 179 954 can also be used as hardeners. The functional gruccs obtained have the structure:

R ⁵ = H or CH ₃

R ⁷ = alkylene group with 2 to 4 carbon atoms,

the rest being as defined above.

In addition to (meth) acrylic acid, the copolymer can contain esters of (meth) acrylic acid or vinyl compounds such as styrene. The comonomers that can be used, for example, have already been described in the definition of the hydroxyl-containing poly (meth) acrylates b). Examples of alkyleneimines are e.g. Propylene or butylene imine.

Examples of polyamines which can likewise be used according to the invention as hardeners are also those which are prepared by reacting copolymers of alpha-dimethyl-m-isopropenylbenzyl isocyanate (TMI) which have a number average molecular weight (Mn) of 1000 to 10,000 with mono- or diketimines that contain either an OH or sec.NH grouping.

All customary vinyl polymerizable monomers without OH functionality, such as esters of (meth) acrylic acid such as e.g. Methyl, ethyl, butyl, isobutyl, ethylhexyl, cyclohexyl and / or lauryl

(Meth) acrylate can be selected, styrene, vinyl toluene and / or methyl styrene. The copolymers are prepared by conventional free-radical solution polymerization, as is known to the person skilled in the art. Work is carried out, for example, in aprotic organic solvents. e.g. Toluene and xylene, and esters, e.g. Butyl acetate.

Common radical initiators such as peroxides and azo compounds are generally used for this purpose. The reaction takes place e.g. with heating, for example to temperatures of 80 to 140 ° C.

The monomeric TMI can range from 2 to 40% by weight, based on: the weight of all monomers are copolymerized, but preferably in a range from 2 to 25% by weight. The isocyanate-terminated copolymer is then reacted with one or more mono- and / or diketenimines and / or mono- and / or dialdimines functionalized with OH or sec.NH.

The production of the ketimines and / or aldimines (in the following the term "ketimines" is used for simplicity, which, however, is also intended to include aldimines) is carried out e.g. by reacting alkanolamines or

Di- or triamines, which have at least one primary amino group, in the case of

Di- or triamines additionally carry a secondary amine function with

Aldehydes and / or ketones with elimination of water.

Examples of alkanolamines are:

Monoethanolamine, monopropanolamine, monohexanolamine or 2-amino-2-hydroxypropane.

Examples of di- and triamines which carry at least one primary amino group and one secondary amino group are:

N-methylpropylamine, diethylenetriamine, dipropylenetriamine or bishexamethyltriamine.

For the preparation of the TMI-acrylate / ketimine adducts, the primary amino groups of the amines mentioned above must be blocked. Here, the primary amines are reacted with aldehydes or ketones with elimination of water to give boat bases or aldimines or ketimines. Examples of such aldehydes and ketones are:

C ₃ - C ₁₀ compounds, the hexyl aldehyde, octyl aldehyde, diisopropyl ketone and / or methyl isobutyl ketone. The last two compounds are particularly preferred because they show little tendency to undergo side reactions. The OH- or sec.NH-functionalized mono- or diketimines are preferably used in deficiency in the addition to the isocyanate-terminated copolymers, preferably 90-95% of the isocyanate groups are reacted with OH or NH groups. The remaining excess isocyanate groups are urethanized in a final reaction step with monoalcohols such as ethanol, propanol or butanol. For the synthesis of the ketimine or aldimine-functionalized (blocked) polyamines, for example, a TMI copolymer is first prepared by free-radical solution polymerization. An alkanolamine or di- or triketimine, which carries both at least one primary and a secondary amine function, is then introduced with the desired blocking agent, aldehyde or ketone, in an organic solvent which forms an azeotropic mixture with water. The water of reaction formed is distilled off azeotropically by heating this mixture.

It is favorable to carry out the preparation under inert gas. The blocking agent can be used in excess, which can be distilled off after the reaction. It is expedient to choose a ketone / aldehyde as the capping agent which itself forms an azeotrope with water, so that an additional organic solvent can be dispensed with. To add the OH- or sec.NH-functionalized ketimine or aldimine to the isocyanate-terminated copolymer, the ketimine is used in e.g. 80 ° C under inert gas and the copolymer in e.g. metered in for two hours. With the help of a Lewis acid, e.g. Dibutyltin laurate can optionally catalyze the reaction. After the end of the metering, if the ketimine is in deficit, an alcohol, e.g. Added butanol. If necessary, e.g. about 10 to 30 min. touched.

The above preparation is merely an example of a procedure. For example, it is also possible to work in such a way that the copolymer is initially introduced and the ketimine is added.

The terminated (free) amino groups of the polyamine hardener component can be blocked, for example with ketones or aldehydes with the formation of Schiff bases. All the polyamines described so far have a very high reactivity with the binder components according to the invention, which can manifest itself in a very short pot life. For this reason, it may be expedient to react the terminated amine groups of the polyamines mentioned with aldehydes or ketones with elimination of water to give bases or aldimines or ketimines. Examples of aldehydes and ketones which can be used for capping are C ₃ -C ₁₀ compounds, such as hexylaldehyde, octylaldehyde, diisopropyl ketone and / or methyl isobutyl ketone. The last two compounds are particularly preferred because they show little tendency to undergo side reactions.

The quantitative ratio of epoxy-functionalized COC- (meth) acrylate 2) to 2c) in the curable lacquer is preferably chosen so that the ratio between epoxy groups and amine functions is between 1: 1.5 and 1.5: 1, preferably 1: 1.2 and 1.2: 1.

The COC, as they are mentioned above as component 3), can contain, for example, polymerized epoxy-functionalized (meth) acrylic monomers. Some of the glycidyl functions present can be esterified with alpha, beta-unsaturated carboxylic acids, as a result of which unsaturated groups are incorporated in the resin; this is described, for example, in DE-A-40 27 259.

The partial reaction of glycidyl groups with alpha, beta-unsaturated carboxylic acid to form component 3) can e.g. in such a way that one or more alpha, beta-unsaturated carboxylic acids are introduced into a heated (e.g. 50 to 100 ° C, e.g. 80 ° C) polysiloxane / acrylic resin solution until the desired acid number is reached. This can be done, for example, by dropping. The mixture is stirred until the acid number is preferably below 1 mg KOH / g.

Examples of usable acids are mono- or polyunsaturated monocarboxylic acids with, for example, 2 to 10, preferably 3 to 6, carbon atoms Men, such as cinnamic acid, crotonic acid, citraconic acid, mesaconic acid, dihydrolevulinic acid, sorbic acid and preferably acrylic acid and / or methacrylic acid.

The amount of acid is preferably such that there is a ratio between acryloyl groups and epoxy groups of 8: 2 to 2: 8, preferably 7: 3 and 3: 7.

Polyamines can be used as crosslinker component 3a). Such polyamines correspond to the polyamines already described above under 2c).

The ratio between epoxy and acryloyl groups to amine functions is chosen so that it is between 1: 1.5 and 1.5: 1, preferably between 1: 1.2 and 1.2: 1.

The CH-acidic component 3b) which can be used as a crosslinking agent for component 3) according to the invention can e.g. are produced by transesterification of an aliphatic beta-ketocarboxylic acid ester with a polyol.

Suitable beta-ketocarboxylic acid esters are, for example, esters of acetoacetic acid or alkyl-substituted acetoacetic acids, such as alpha- and / or gamma-methylacetoacetic acid. Suitable esters of these acids are those with aliphatic alcohols, preferably lower alcohols with 1 to 4 carbon atoms, such as methanol, ethanol or butanol.

According to a preferred embodiment of the invention, suitable polyols for the reaction with the beta-ketocarboxylic acid esters are monomers and polymers which are selected from: i) polyols from the group of straight or branched alkane diols and polyols having 2 to 12 carbon atoms, ii) Hydroxyl group-containing poly (meth) acrylates or poly (meth) acrylamides based on (meth) acrylic acid hydroxyalkyl esters or (meth) acrylic acid-hydroxyalkylamides each having 2 to 12 carbon atoms in the alkyl part, optionally copolymerized with alpha, beta-unsaturated monomers, with a number average of Molecular weight (Mn) from 1000 to 10000, iii) hydroxyl-containing poly (meth) acrylates based on

(Meth) acrylic acid hydroxyalkyl esters with 2 to 12 carbon atoms in the alkyl part and optionally copolymerizable alpha, beta-unsaturated monomers which are modified with cyclic esters of hydroxycarboxylic acids with 4 to 6 carbon atoms, with a number average molecular weight (Mn) of 1,000 to 10,000, and iv) polyester -Polyols or polyether polyols each with a

Number average molecular weight (Mn) from 500 to 2000.

Suitable alkane di- and polyols of group i) are those with straight and branched chains with 2 to 12 carbon atoms. They contain at least two hydroxyl functions, but preferably at least three. Examples include propanediol, butanediol, hexanediol, glycerin, trimethylolpropane and pentaerythritol. Examples of hydroxyl-containing poly (meth) acrylates ii) based on (meth) acrylic acid hydroxyalkyl esters with 2 to 12 carbon atoms in the alkyl part are hydroxyalkyl esters of acrylic acid or methacrylic acid with alcohols with at least two hydroxyl groups, such as 1,4-butanediol, mono (meth) acrylate , 1,6-hexanediol mono (meth) acrylate or 1,2,3-propanetriol mono (meth) acrylate. Examples of hydroxyl-containing poly (meth) acrylamides ii) based on (meth) acrylic acid hydroxyalkylamides are amides of acrylic acid or methacrylic acid with hydroxyalkylamines or di

(hydroxyalkyl) amines each having 2 to 12 carbon atoms in the alkyl part, which may have one or more hydroxyl groups, such as acrylic acid hydroxyethylamide. The term (meth) acrylic used in the present description and the claims is intended to mean and / or methacrylic.

The hydroxyl-containing poly (meth) acrylates of component ii) can be homopolymers or copolymers. They have a number average molecular weight from 1000 to 10,000, preferably from 3000 to 6000. Copolymerizable monomers for the preparation of the copolymers are alpha, beta unsaturated monomers, radically polymerizable monomers from the group of the esters of alpha, beta-unsaturated carboxylic acids, such as acrylic acid or methacrylic acid, examples of the alcohol components of the esters being methyl, ethyl, propyl alcohol and their isomers and higher

Are homologues. Further examples are diesters of maleic or fumaric acid, the alcohol component being the same as mentioned above. Other examples are vinyl aromatic compounds such as styrene, alpha methyl styrene and vinyl toluene. Other examples are vinyl esters of short-chain carboxylic acids, such as vinyl acetate, vinyl propionate and vinyl butyrate.

The hydroxyl group-containing poly (meth) acrylates of component iii) defined above can be modified poly (meth) acrylate homo- and copolymers, as are described under ii), the hydroxyl groups of which are wholly or partially with cyclic esters, such as e.g. of hydroxycarboxylic acids with 4 to 6 carbon atoms, such as butyrolactone or caprolactone. The modified poly (meth) acrylates of component iii) obtained have a number average molecular weight Mn of 1,000 to 10,000.

Examples of the polyester polyols and polyether polyols of component iv) are those with a number average molecular weight Mn of 500 to 2000. Specific examples are reaction products of di- or

Tricarboxylic acids, such as adipic acid or trimellitic acid, with polyols, the polyols being present in excess. Further examples are reaction products of di- or triols, such as propanediol or butanediol or

Glycerin, with ethylene oxide or propylene oxide. The C-H-acidic component can be synthesized, for example, over several stages. The polyol is first transesterified with the aliphatic beta-ketocarboxylic acid ester after removal of any solvent present.

The transesterification of the polyol can be carried out, for example, in such a way that the polyol, if appropriate freed from solvent by applying a vacuum, is initially introduced. The beta-ketocarboxylic acid ester is then added in excess, for example added dropwise. The reaction takes place at elevated temperature; the alcohol released is removed from the system. A catalyst can also be added to accelerate the reaction. Examples of such catalysts are acids such as formic acid or p-toluenesulfonic acid. It is favorable to increase the reaction temperature continuously during the transesterification (for example in steps of 10 ° C / 20 min) until a temperature is reached which is just below (about 10 ° C) below the boiling point of the beta-ketocarboxylic acid ester. After quantitative transesterification, the excess beta-ketocarboxylic acid ester is removed, for example by applying a vacuum. The mixture can then be cooled and adjusted to a desired solids content using an inert solvent.

The hardener component 3b) can also contain 2-acetoacetoxy-ethyl methacrylate as a reactive diluent to adjust the viscosity.

Acetoacetic ester functionalized components can be increased in their CH acidity by reacting the beta-carbonyl groups with primary and / or secondary monoamines, e.g. DE-A-39 32 517. Component 3b) preferably contains one or more mixed in

Catalysts in the form of Lewis bases or Brönstedt bases, the conjugated acids of the latter having a pKA value of at least 10. Lewis bases, such as e.g. those of the group of cycloaliphatic amines, such as diazabicyclooctane (DABCO), tert.-aliphatic amines, such as triethylamine, tripropylamine, N-methyldiethanolamine, N-methyldiisopropylamine or N-butyl-diethanolamine, and amidines such as diazabicyloundecane (DBU), and guin, and such as N, N, N ', - N'-tetramethylguanidine. Further examples are alkyl or aryl substituted phosphanes, e.g. Tributylphosphine, triphenylphosphine, tris-p-tolylphosphine, methyldiphenylphosphine, and also hydroxy- and amine-functionalized phosphines, e.g. Trishydroxymethylphosphine and tris-dimethylamino-ethylphosphane.

Examples of the Brönstedt bases that can be used are alcoholates, such as sodium or potassium ethylate, quaternary ammonium compounds, such as alkyl,

Aryl or benzylammonium hydroxides or halides, such as, for example, tetraethyl or tetrabutylammonium hydroxide or fluoride, and trialkyl or Triaryl phosphonium salts or hydroxides.

The amount of the catalysts is, for example, 0.01 to 5% by weight, preferably 0.02 to 2% by weight, based on the total solids content of components 3) and 3b).

The crosslinkers mentioned under 3c) are those which contain at least two groups capable of transesterification, which come from, for example, one or more of the following groups, which may be the same or different:

where R = alkyl and preferably H,

where alkyl and alkylene preferably have 1 to 6 carbon atoms, and wherein the carboxyl or carponamide groups defined above for the radicals W ₁ , W ₂ and W ₃ are each bonded to the group CR via the carbon atom and the group CR via at least one of the radicals W ₁ , W ₂ and / or W ₃ is bound to a polymeric or oligomeric unit. The functionality of component 3c) averages over 2 per molecule.

As mentioned above, the functionality of component 3c) is in Medium above 2. This means that monofunctional molecules can also be used in a mixture with higher-functionality molecules. The crosslinker components 3c) described above contain with W "at least one ester group which can crosslink with compounds containing hydroxyl groups in the sense of a transesterification action.

The crosslinker compounds are preferably essentially free of primary, secondary or tertiary amino groups, since these can adversely affect the storage stability and the light resistance.

The following are examples of crossester components 3c) capable of transesterification, which fall under the above preferred general formula. These examples are divided into three groups A1, A2 and A3 below.

Group A1 contains on average at least two groups in the molecule which are derived from methane tricarboxylic acid monoamide units or acetoacetic acid ester-2-carboxylic acid amides.

Suitable compounds A1 are, for example, reaction products of malonic diesters such as dimethyl malonate, diethyl, dibutyl, dipentyl or acetoacetic esters such as methyl acetoacetate, ethyl or butyl pentyl with polyisocyanates.

Examples of such isocyanates which can be used according to the invention are cycloaliphatic, aliphatic or aromatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylene diisocyanate, 1,12-dodecane diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate, 1-isocyanato -3,3,5-trimethyl-5-isocyanato-methylcylohexane (= isophorone diisocyanate IPDI), perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2 , 4- and 2,6-tolylene diisocyanate, diphenylmethane-2,4'- and / or -4,4'-diisocyanate, 3,2'- and / or 3,4-diisocyanato-4-methyl-diphenylmethane, naphthylene 1,5-diisocyanate, triphenylmethane-4,4'-triisocyanate, tetramethylxylylene diisocyanate or

Mixtures of these compounds. In addition to these simple isocyanates, those are also suitable which contain heteroatoms in the radical linking the isocyanate groups. Examples include carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups, acylated urea groups and polyisocyanates containing biuret groups.

The known polyisocyanates, which are mainly used in the production of lacquers, e.g. Biuret, isocyanurate or urethane groups containing modification products of the simple polyisocyanates mentioned above, in particular tris (6-isocyanatohexyl) biburet or low molecular weight polyisocyanates containing urethane groups, such as those obtained by reacting excess IPDI with simple polyhydric alcohols

Molecular weight range 62-300, especially with trimethylolpropane can be obtained. Of course, any mixtures of the polyisocyanates mentioned can also be used to produce the polyisocyanates of the invention

Products are used.

Suitable polyisocyanates are also the known prepolymers containing terminal isocyanate groups, as are accessible in particular by reacting the simple polyisocyanates mentioned above, especially diisocyanates, with inadequate amounts of organic compounds having at least two groups which are reactive toward isocyanate groups. As such, a total of at least two amino group and / or hydroxyl group-containing compounds with a number average molecular weight of 300 to 10,000, preferably 400 to 6000, are preferably used. The corresponding polyhydroxyl compounds, e.g. the hydroxypolyesters, hydroxypolyethers and / or hydroxyl group-containing acrylate resins known per se in polyurethane chemistry are used.

In these known prepolymers, the ratio of isocyanate groups to hydrogen atoms reactive towards NCO corresponds to 1.05 to 10: 1, preferably 1.1 to 3: 1, the hydrogen atoms preferably originating from hydroxyl groups. The nature and proportions of the starting materials used in the preparation of the NCO prepolymers are preferably chosen so that the NCO prepolymers a) have an average NCO functionality of 2 to 4, preferably 2 to 3 and b) a number average molecular weight from 500 to 10,000, preferably from 800 to 4000.

However, reaction products of esters and partial esters of polyhydric alcohols of malonic acid with monoisocyanates are also suitable as compound A1.

Polyhydric alcohols are e.g. di- to pentavalent alcohols such as

Ethanediol, the various propane, butane, pentane and hexanediols, polyethylene and polypropylene diols, glycerin, trimethylolethane and propane, pentaerythritol, hexanetriol and sorbitol. Suitable monoisocyanates are e.g. aliphatic isocyanates such as n-butyl isocyanate, octadecyl isocyanate, cycloaliphatic isocyanates such as cyclohexyl isocyanate, araliphatic isocyanates such as benzyl isocyanate or aromatic isocyanates such as phenyl isocyanate.

Also suitable are the corresponding malonic esters of aeryl resins, polyesters, polyurethanes, polyethers, polyester amides and imides containing OH groups and / or reaction products of malonic acid semiesters such as malonic acid monoethyl ester with aliphatic and aromatic epoxy resins, e.g. epoxy group-containing acrylate resins, glycidyl ethers of polyols such as hexanediol, neopentyl glycol, diphenylolpropane and methane and glycidyl group-containing hydantoins, and also mixtures of these compounds.

The examples of the following group A2 show a suitable curing component which contains at least two groups of the formula (II)

or structural units of the formula (II ')

contains, in which mean:

the latter group being bonded to the CH group via the C atom;

may be the same or different and represent a hydrocarbon radical, preferably an alkyl radical having 1 to 12, preferably 1 to 6, carbon atoms, which can also be interrupted by oxygen or an N-alkyl radical.

the latter group being bonded to the CR group via the C atom,

The number of group (II) in the hardener that can be used is preferably 2 to 20 and in particular 2 to 10, the larger numerical values relating to oligomeric or polymeric products and representing mean values here.

The curing component A2 which can be used according to the invention preferably has the formula (III)

in which X, Y and K are as defined above, R ^{2 is} the remainder of a polyol

or the radical R ^{2 of} a polycarboxylic acid

represents and n is at least 2, preferably 2 to 20, in particular 2 to 10. In the case of oligomeric or polymeric curing components, these figures are again average values.

Also preferred are curing components which fall under group A2 and which are obtained by non-quantitative transesterification of compounds of the formula (IV) or of the formula (V)

with polyols R ² (OH), where Y, K and R ^{1 have} the meaning given above, and the radicals R ^{1 can be} identical or different,

The polyols R ² (OH) mentioned above can be a polyhydric alcohol which preferably contains 2 to 12, in particular 2 to 6, carbon atoms. Examples include: ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), di-ß-hydroxyethylbutanediol, hexanediol (1,6), 0ctanediol (1.8), neopentyl glycol,

Cyclohexanediol- (1,6), 1,4-bis (hydroxymethyl) cyclohexane, 2,2-bis (4-hydroxycylohexyl) propane, 2,2-bis (4- (β-hydroxyethoxy) phenyl) -propane, 2- Methyl 1,3-propanediol, glycerol, trimethylolpropane, hexanetriol (1,2,6), butanetriol (1,2,4), tris (ß-hydroxyethyl) isocyanurate, trimethylolethane, pentaerythritol and their hydroxyalkylation products, further Fiethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, tripropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols and xylylene glycol. Polyesters obtained from or with lactones, for example epsilon-caprolactone or hydroxycarboxylic acids, such as, for example, hydroxypivalic acid, gamma-hydroxydecanoic acid, gamma-hydroxycaproic acid, thioglycolic acid, can also be used. In the case of such polyhydric alcohols, the index n in the above formula (III) preferably stands for 2 to 4.

Alternatively, the polyol can be an oligomeric or polymeric polyol compound (polyol resin) whose number average molecular weight, Mn,

(determined by means of gel chromatography; polystyrene standard), usually in the range from about 170 to 10,000, preferably about 500 to about 5000. In special cases, however, Mn can be 10,000 g / mol and more. Polymers, polycondensates or polyaddition compounds are suitable as oligomers / polymers. The hydroxyl number is generally 30 to 250, preferably 45 to 200 and in particular 50 to 180 mg KOH / g. These OH group-containing compounds can optionally also contain other functional groups, such as carboxyl groups. Examples of such polyols are polyether polyols, polyacetal polyols, polyester amide polyols, polyamide polyols, epoxy resin polyols or other reaction products with CO ₂ , phenol resin polyols, polyurea polyols, polyurethane polyols, cellulose esters and ether polyols, partially saponified homo- and copolymersalcohols, polyalkylene polyols, vinyl acetate polyols, vinyl alcohols . Polyether polyols, polyester polyols are preferred. Acrylate resins and polyurethane polyols. Such polyols, which can also be used in a mixture, are described, for example, in DE-OS 31 24 784.

Examples of polyurethane polyols result from the reaction of di- and polyisocyanates with an excess of di- and / or polyols. Appropriate Nete isocyanates are, for example, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate and isocyanates, formed from three moles of a diisocyanate such as hexamethylene diisocyanate or isophorone diisocyanate, and biurets which result from the reaction of three moles of a diisocyanate with one mole of water. Suitable polyurea polyols can be obtained in a similar manner by reacting di- and polyisocyanates with equimolar amounts of amino alcohols, for example ethanolamine or diethanolamine.

Examples of polyester polyols are the known polycondensates of di- or polycarboxylic acids or their anhydrides, such as phthalic anhydride, adipic acid etc., and polyols such as ethylene glycol, trimethylolpropane, glycerol etc.

Suitable polyamide polyols can be obtained in a similar manner to the polyesters by at least partially replacing the polyols with polyamines such as isophorone diamine, hexamethylene diamine, diethylene triamine, etc.

Examples of polyacrylate polyols or polyvinyl compounds containing OH groups are the known copolymers of hydroxyl-containing (meth) acrylic acid esters or vinyl alcohol and other vinyl compounds, such as styrene or (meth) acrylic acid esters. The above polycarboxylic acids R ² (CO ₂ H) _n , where n here is preferably 2 to 4, can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally substituted, for example by halogen atoms, and / or saturated. Examples of such carboxylic acids and their derivatives are: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 1,3- and 1,4-cyclic acid and tetrahydrofluoric acid, endodehydrochloric acid, endogenous tetrachloroacetic acid, and tetranoic acid their hexachloro derivative, glutaric acid, maleic acid, fumaric acid, dimeric and trimeric fatty acids, such as oleic acid, optionally in a mixture with monomeric fatty acids or cyclic monocarboxylic acids, such as benzoic acid, p-tert-butylbenzoic acid re or hexahydrobenzoic acid. Furthermore, the reaction products of the above-mentioned polyols R ² (OH) _n with cyclic carboxylic acid anhydrides. Depending on the type of polyol or polycarboxylic acid component, the hardening component A2 which can be used according to the invention is more or less viscous liquids or solids which are largely soluble at least in the conventional paint solvents and preferably less than 5% by weight, in particular contain less than 1% by weight of crosslinked fractions. The transesterification equivalent weight, which is a measure of the amount of groups (II) or structural units (II ') in (A2), is generally between 100 and 5000, preferably 200 and 2000, and the number average molecular weight Mn is generally between 200 and 10,000, preferably between 500 and 5000 (determined by gel chromatography; polystyrene standard). Processes for the preparation of such compounds are described in more detail in EP-A-0 310 011.

Further examples of the hardener component which can be used according to the invention are those of type A3, in which the group capable of transesterification is derived from a compound having the grouping -CO-CRR ³ -COOR ⁴ , in which R ^{3 is} C ₁ -C ₈ -alkyl, H, preferably hydrogen and R ⁴ = Alkvl such as

Is methyl, ethyl, butyl, t-butyl.

The above groupings of A3 can be attached to at least one polyvalent monomeric or polymeric compound. For example, they can be bound to at least one compound from the group of mono- or polyhydric alcohols, polymers containing OH groups, polyamine and polymercaptans. In terms of the transesterification function, they are multi-valued. For example, they can be esterified by a polyepoxide with a grouping dicarboxylic acid monoester, e.g. Malonic acid monoesters. Component A3 is thus obtained with one transesterifiable group per epoxy group. Aromatic or aliphatic polyepoxides can be used here.

Further examples of suitable dicarboxylic acid monoesters are malonic acid monoalkyl esters, acetone dicarboxylic acid monoalkyl esters, where the alkyl radical can be straight-chain or branched with 1 to 6 atoms, for example methyl, ethyl, n-butyl or t-butyl. The hardener components 3c) can be produced in conventional solvents. It is expedient to use solvents which do not later interfere with the production of the coating agent. It is also favorable to keep the organic solvent content as low as possible. If the hardener component 3c) contains polar groups, for example amide or urethane groups, then easy dispersion in water is possible. This can optionally also be supported by the fact that the crosslinker components contain neutralizable ionic groups, for example carboxyl groups, in the oligomer or polymer structure. Such crosslinkers with ionic

Groups can be well dispersed in water. The content of organic solvents can be reduced to low values without significantly increasing the viscosity of the crosslinking agent solution. The ratio between 3) and 3c) is preferably chosen so that the

Ratio of cer OH functions 3) obtained by the addition reaction of the alpha, beta-unsaturated acids to the glycidyl groups and the groups capable of transesterification between 1: 1.5 and 1.5: 1, preferably between 1: 1.2 and 1 , 2: 1 lies. In addition, the unsaturated bonds contained in the resin 3) can also be polymerized in the presence of radical initiators, as a result of which a further crosslinking effect is achieved. The initiators described above for polymerizing the monomers can be used, for example, as radical initiators.

The binder compositions according to the invention can be formulated in a customary manner to form coating compositions. This is generally done by adding solvents or water. Suitable organic solvents for the production of coating agents. for example, paints are those that can also be used in the production of the individual components 1), 1a) - 1c), 2), 2a) - 2c, 3), 3a) - 3c). Examples of such solvents are organic solvents, such as aliphatic and aromatic hydrocarbons, for example toluene, xylene, mixtures of aliphatic and / or aromatic hydrocarbons, esters, ethers and alcohols. These are common paint solvents. To produce the coating compositions from the inventive Binders can also be prepared in aqueous solutions. Suitable emulsifiers, such as those on the

Lacquer sector are common.

Customary additives, such as are customary in the paint sector, for example, can be added to produce the coating compositions. Examples of such additives are pigments, for example transparent or opaque color pigments such as titanium dioxide or carbon black and effect pigments such as metal flake pigments and / or pearlescent pigments.

The binder compositions according to the invention are particularly suitable for coating compositions which are said to have high scratch resistance and acid resistance.

Other examples of additives are fillers such as Talc and silicates; Plasticizers, light stabilizers, stabilizers and leveling agents, such as silicone oils. The coating agents produced from the binders according to the invention can be adjusted to the desired application viscosity by appropriately regulating the addition of solvents and / or water and / or additives. The coatings produced from the coating compositions can be cured in a wide temperature range, for example from -10 ° C. to 200 ° C., and depend on the particular type of crosslinking reaction.

The coating compositions produced from the binders according to the invention are suitable for coatings which adhere to a large number of substrates, such as, for example, wood, textiles, plastic, glass, ceramic, plaster, cement and in particular metal. It has proven to be particularly advantageous that they give excellent adhesion to non-polar plastic substrates, in particular polyolefin surfaces, for example polyethylene, polypropylene and / or cycloolefin copolymers. The coating agents can also be used in the multi-layer process. For example, they can be applied to common primers, basecoats, fillers or already existing top coats are applied.

A particularly preferred area of application for the binders according to the invention is the provision of coating agents for coatings which are said to have high scratch resistance and acid resistance.

The present invention thus also relates to processes for the production of coatings on various substrates, in which a coating agent prepared from the binders according to the invention is applied to the substrate, whereupon drying and curing is carried out. The invention also relates to the use of the binder compositions according to the invention in paints, in particular automotive top coats or clear coats. In any case, films with good hardness and good water and solvent resistance, chemical resistance, scratch resistance and high dirt-repellent effect are obtained with the coating compositions prepared from the binders according to the invention, the dirt-repellent effect being retained over long periods even under unfavorable weather conditions.

The coating compositions according to the invention can be applied in the customary manner

This is done, for example, by dipping, spraying, brushing or by electrostatic means. It may be advantageous to first apply and bake or harden a first clear coat, which can consist of a commercially available, conventionally organically dissolved or aqueous clear coat, and then as a second coat

To apply COC-containing clear coat. Of course, it is also possible to use the COC lacquer as the first layer.

In the following examples, parts (T) and percentages (%) each relate to the weight, unless stated otherwise.

A cycloolefinic copolymer which was free from olefinic double bonds and contained about 20 mol% of norbornene, 80 mol% of ethylene was used as COC resin I; Glass temperature 162 ° C, Mn 2000 g / mol, Mw 7000 g / mol, Mw / Mn = 3.45. A cycloolefinic copolymer based on norbornene and ethylene was used as the peroxygenated COC resin II; Solution viscosity [η] _O = 20 ml / g, measured at 60 ° C in decalin; Mw = 11500; Dispersion index = 2.7; Hydroperoxide content = 3.5% based on the solid resin.

Example 1 Production of a Copolymer According to the Invention Based on a COC

In a 4-liter three-necked flask equipped with a stirrer, dropping funnel and reflux condenser, 150 T of COC resin I (5% based on the total batch)

382.5 T xylene and heated to boiling. It becomes a mixture of 7.5 T acrylic acid at reflux

324.6 T butyl methacrylate

286.5 T styrene

375T methyl methacrylate

618 T hydroxypropyl methacrylate

43.5 T of tert-butyl perbenzoate were metered in continuously over the course of 6 hours. Then again

80.1 T xylene and 3.9 T tert-butyl perbenzoate were added and the mixture was re-polymerized for 4 hours at reflux. Then 308.1 T xylene and 420.3 T butyl acetate 98/100 are added.

The polymer has a solids content of 60.3%, an acid number of 19.5 and a viscosity of 2250 mPas and has a very slightly opaque, colorless appearance.

Example 2 Production of a copolymer according to the invention based on a COC

In a 4 liter three-necked flask equipped with a stirrer, dropping funnel and reflux condenser

300 T of COC resin I (10% based on the total batch)

690 T xylene

34.5 T tert-butyl perbenzoate submitted and heated to boiling. After stirring at reflux for 15 minutes, a mixture is formed

6 T acrylic acid

257.4 T butyl methacrylate

272.4 T styrene

252 T methyl methacrylate

489 x hydroxypropyl methacrylate

34.5 T of tert-butyl perbenzoate were metered in continuously over the course of 6 hours. A further 80.1 parts of xylene and 3 parts of tert-butyl perbenzoate are then added and the mixture is stirred under reflux for 4 hours.

160.8 parts of xylene are then added and the mixture is adjusted to a solids content of 55.0% with 420.3 parts of butyl acetate 98/100.

A slightly opaque, colorless COC lap polymer with a viscosity of 30300 mPas (Höppler at 25 ° C.) and an acid number of 19 mg KOH / g solid resin body is obtained.

Comparative experiment A

Attempts were made to stir the COC resin I into a copolymer which was prepared in accordance with the monomer formulation of Example 1. In a 4 liter three-necked flask equipped with a stirrer, dropping funnel and reflux condenser

532.5 T xylene submitted and heated to boiling. A mixture is refluxed within 6 hours

7.5 T acrylic acid

324.6 T butyl methacrylate

286.5 T styrene

375T methyl methacrylate

618 T hydroxypropyl methacrylate

43.5 T of tert-butyl perbenzoate were metered in continuously. Then another 80.1 parts of xylene and 3.9 parts of tert-butyl perbenzoate are added and the mixture is re-polymerized for 4 hours at reflux. Then 308.1 T xylene and 420.3 T butyl acetate 98/100 are added.

150 parts of a COC resin I are added to the OH-functional acrylate resin with stirring.

Even after long stirring at reflux, it is not possible to incorporate the COC product.

Example 3

Production of a copolymer according to the invention based on a peroxygenated COC

In a 4-liter three-necked flask equipped with a stirrer, a funnel and a reflux condenser

150 T of the peroxygenated COC resin II and 382.5 T xylene and heated to boiling. A mixture is formed at reflux

7.5 T acrylic acid

324.6 T butyl methacrylate

286.5 T styrene

375T methyl methacrylate

618 T hydroxypropyl methacrylate

37.95T of tert-butyl perbenzoate were metered in continuously over the course of 6 hours. Then another 80.1 parts of xylene and 3.9 parts of tert-butyl perbenzoate are added and the mixture is re-polymerized for 4 hours at reflux. Then 283.65 T xylene and 420.3 T butyl acetate 98/100 are added.

The polymer has a solids content of 60.1% and a viscosity of 2400 mPas. The acid number is 19 mg KOH / gFH.

Its appearance is colorless and slightly opaque.

Comparative experiment B

532.5 T xylene submitted and heated to boiling. A mixture is refluxed within 6 h

7.5 T acrylic acid

324.6 T butyl methacrylate

286.5 T styrene

375T methyl methacrylate 618 T hydroxypropyl methacrylate

43.5 T of tert-butyl perbenzoate were metered in continuously. Then another 80.1 parts of xylene and 3.9 parts of tert-butyl perbenzoate are added and the mixture is refluxed for 4 hours

post-polymerized. Then 308.1 T xylene and 420.3 T butyl acetate 98/100 are added. 150 parts of the peroxygenated COC resin II are added to the OH-functional acrylate resin with stirring.

Example 4

Production of paints The COC acrylic resin from Example 2 and the OH-functional resin from the comparative experiment are adjusted to a viscosity of 30 seconds AK4 with a butanol-etherified melamine resin in a ratio of resin: melamine resin 70:30 based on solid resin weight and with butyl acetate 98/100 . The varnishes are applied onto glass plates, with a dry film thickness of 40 μm. The mixture was then baked at 140 ° C. for 20 minutes.

The paint films were coated with 38% H ₂ SO ₄ . dropped at 65 ° C. The paint film based on the resin from Example 2 was destroyed after 24 minutes, the film based on the resin from the comparison test after 16 minutes.

Claims

Claims:

1. Binding agents suitable for coating agents, obtainable by free-radically initiated polymerization of

99.5 to 5% by weight of one or more (meth) acrylic monomers and

optionally additionally one or more different, radically polymerizable monomers, in the presence of

0.5 to 95% by weight of one or more cycloolefin homopolymers,

Cycloolefin copolymer, peroxygenated

Cycloolefin homopolymer and / or

peroxygenated cycloolefin copolymers that are free of olefinic double bonds.

2. Binder according to claim 1, characterized in that the cycloolefin homopolymer or the cycloolefin copolymer contains: A) 20 - 100 wt .-%, based on the total mass of the

Production of monomers used, obtained from at least one monounsaturated cycloolefin monomer and

B) 0 to 80% by weight, based on the total mass of the monomer units used, obtained from at least one acyclic monounsaturated olefin monomer.

3. Binder according to claim 1, characterized in that the

peroxygenated cycloolefin homopolymer or the peroxygenated cycloolefin copolymer contains:

A) 0.1 - 100 wt .-%, based on the total mass of his Production of monomers used, units obtained from at least one monounsaturated cycloolefin monomer, and B) 0 to 80% by weight, based on the total mass of monomers used, units obtained from at least one

monounsaturated acyclic olefin monomers and

C) 0.01 to 50 wt .-%, based on the total weight of the polymer of oxygen, which is directly attached to a carbon atom of the

Polymer backbone is bound.

4. Binder according to claim 1, 2 or 3, characterized in that the cycloolefin homopolymer, the cycloolefin copolymer, the

peroxygenated cycloolefin homopolymer and / or the peroxygenated

Cycloolefin copolymer as an acyclic olefin component contains one based on one or more monounsaturated alpha-olefins having 2 to 20 carbon atoms.

5. Binder according to one of the preceding claims, characterized in that the cycloolefin homopolymer, the cycloolefin copolymer, the peroxygenated cycloolefin homopolymer and / or that

peroxygenated cycloolefin copolymer a weight average of

Molecular weight (Mw) from 5000 to 100000 g / mol.

6. Binder according to one of the preceding claims, characterized in that the (meth) acrylic monomers and different, radically polymerizable monomers each have no more than one olefinic double bond.

7. Binder according to one of claims 1 to 6, characterized in that the (meth) acrylic monomers are alkyl (meth) acrylates having 1 to 18 carbon atoms in the alkyl part.

8. Binder according to claim 7, characterized in that at least part of the alkyl (meth) acrylates one or more drimae or has secondary hydroxy functions or an epoxy function in the alkyl part.

9. Binder according to one of the preceding claims, characterized in that at least some of the (meth) acrylic monomers have a carboxyl group and / or that one or more radically copolymerizable monomers which have one or more carboxyl groups were also used in the preparation of the binders.

10. A process for the preparation of the binder according to any one of claims 1 to 9, characterized in that 0.5 to 30 wt .-% of one or more cycloolefin homopolymer, cycloolefin copolymer, peroxygenated cycloolefin homopolymer and / or peroxygenated cycloolefin copolymer as in one of claims 1 to 5 defined, presented in liquid form, optionally dissolved in a solvent, and therein

99.5 to 70 wt .-% of one or more (meth) acrylic monomers and optionally additionally one or more different, radically polymerizable monomers, as defined in one of claims 1 and 6 to 9, polymerized in the presence of a radical initiator, the % By weight on the sum of

Solids contents of the monomers and cycloolefin homopolymers used, cycloolefin copolymers peroxygenated

Cycloolefin homopolymer and peroxygenated cycloolefin copolymers.

11. Coating agent for the production of coatings, containing one or more binders according to one of claims 1 to 9, or produced by the method of claim 10, in addition to one or more crosslinking agents and customary paint additives and optionally pigments and / or fillers.

12. coating agent according to claim 11, characterized in that it contains one or more customary solvents.

13. coating agent according to claim 11, characterized in that it is an aqueous coating agent which may contain one or more organic solvents.

14. Coating agent according to one of claims 11 to 13, characterized in that the binders are hydroxy- and / or carboxy-functionalized and contain as crosslinking agent one or more polyisocyanates, which may be capped and / or melamine resins, or one or more polyepoxides.

15. Coating agent according to one of claims 11 to 13, characterized in that the binders are epoxy-functionalized and additionally optionally hydroxy-functionalized and contain one or more carboxy-functionalized compounds and optionally one or more melamine resins or one or more polyamines, which may be capped, as crosslinking agents .

16. Coating agent according to one of claims 11 to 13, characterized in that the binders are epoxy- and acryloyl-functionalized and as crosslinking agent one or more polyamines, which may be blocked, one or more compounds with several CH-acids

Groups in the molecule or one or more crosslinkers with several transesterifiable groups per molecule are contained.

17. Use of the binders according to one of claims 1 to 9, or produced by the method of claim 10, for the production of scratch-resistant and acid-resistant coatings.

18. Use of the binders according to one of claims 1 to 9, or produced by the method of claim 10, for the production of coatings on plastic substrates.