EP1910485A1 - Coatings reparable by introduction of energy - Google Patents

Abstract

Coating compositions reparable by introduction of energy, coatings obtained therewith and reparable by introduction of energy, methods of producing them, and their use.

Description

Through energy input reparable coatings

description

The present invention relates to energy-recoverable Beschichtungsmas- sen, thus obtained by energy input reparable coatings, as well as processes for their preparation and their use.

Self-healing, thin polymer layers prepared by self-assembly techniques known to those skilled in the art are described in P. Bertrand, A. Jonas, A. Laschewsky, R. Legras, Macromol.Rap.Comm. (2000), 21 (FIG. 7), pp. 319 - 348. The disadvantage of this high ionic content in the film that the coatings have a high chemical resistance is that the polymer films can only heal physically after damage by repositioning the ionic charged polymer chains.

A two-component polyurethane varnish capable of curing scratches is described in WO 97/45475. The components consist of a water-dispersible polyisocyanate and a water-dispersible polymer having an OH number of 10-450 mg KOH / g.

A disadvantage of this disclosure is that the hydroxy group-bearing polymer makes no special contribution to self-healing (see comparative example).

The coating described in WO 2002/88215 can only heal scratches for a short time after application and is used as a repair varnish.

A disadvantage of the coatings disclosed here is that the hydroxyl-containing compounds used in the coatings contain aliphatic hydroxyl groups whose corresponding urethanes show a significant self-healing effect only at very high temperature above about 200 ° C.

A physical self-healing effect can also be achieved by using polysiloxanes reactive with polyisocyanates, as in WO 96/10595 A1. In addition, it is described to use blocked polyisocyanates, which can then react with a polyol component. As polyols, however, only normal polyacrilate polyols are described which do not make any particular contribution to self-healing (see comparative example).

Polyurethane based coatings are also used to heal scratches on glass. They make use of the flowability of polyurethanes in the film. Examples thereof for this US 4584229, EP 135404 A1, DE 2634816 and EP 635348 A1 called. All previously described self-healing lacquer systems according to the prior art use only a physical residual flowability of a coating after curing to heal the resulting scratches again. However, a sufficiently high flowability of the coatings requires a low crosslinking density. This leads to unsatisfactory mechanical resistance, the z. B. do not meet the requirements for automotive applications in terms of scratch resistance or chemical resistance.

A true chemical self-healing of a coating is described only in EP 355 028 A. In this case, a lower lacquer layer contains an aromatic ketone, which on UV exposure or under the influence of sunlight causes the crosslinking of lower lacquer layers and thus causes an annealing of mechanical defects by the formation of new chemical bonds , A disadvantage here is the lack of selectivity in the formation of new crosslinking points, since the crosslinking in the coating can proceed and then leads to embrittlement.

Furthermore, systems based on Diels Alder reaction products are described by Wudl et al. The disadvantage here is that a weather-unstable double bond is formed with each Diels Alder addition (Chen XX, Dam MA, Ono K. ₁ st A., Shen HB, Nutt SR, Sheran K., Wudl F. "A thermally re -mendable cross-linked polymer material "Science, 2002, 295, 1698-1702).

It is an object of the present invention to provide reparable coatings by energy input which are at least as scratch-resistant as the coatings known hitherto in the prior art and have improved reparability caused by energy input compared to comparable coatings.

The object is achieved by coating compositions containing as structural components

A) at least one compound having isocyanate-reactive groups (Y) whose reaction product is more easily cleaved with isocyanate, as the corresponding reaction product with a compound having primary hydroxyl groups, and optionally at least one further isocyanate-reactive group (Z), of (Y) is different, as well

B) at least one di- or polyisocyanate.

The cleavage of the bond between isocyanate groups and groups (Y) takes place by introducing heat and / or high-energy radiation and / or by applying Pressure, preferably by introducing heat and / or high-energy radiation and particularly preferably by introducing heat, for example thermally or by NIR radiation. Under the cleavage conditions, the groups (Y) and isocyanate groups are at least partially regressed and can be rejoined. The coating material therefore becomes more easily flowable than the coating when cleaved, scratches can heal by bleeding of the lower-viscosity coating composition and the crosslinking compound is crosslinked again after the energy input has been terminated by recombination of the bonds between the groups (Y) and isocyanate groups.

In this document, the term coating composition is understood to mean the uncured composition which contains coating medium (binder) and optionally pigment and / or other typical coatings additives.

The coating is understood to mean the applied and dried and / or cured coating composition.

The term "readily cleavable" is understood here that the cleavage reaction of the reaction product in groups (Y) and isocyanate groups proceeds under the reaction conditions selected at a rate which is faster than that of the cleavage of the corresponding reaction product with a compound having primary Hydroxy groups, especially methanol.

The novel compounds A) contain at least two isocyanate-reactive groups (Y) whose reaction product is readily cleavable with isocyanate, and optionally at least one further isocyanate-reactive group (Z).

In an alternative embodiment, compounds A) may be a mixture of compounds which contain exclusively at least two isocyanate-reactive groups (Y), with compounds containing exclusively isocyanate-reactive groups (Z).

It is a particular advantage of such compounds A) according to the invention which contain at least one group (Y) and at least one group (Z) in one molecule that the back-cleaved groups (Y) can not escape from the coating, since they still have groups (Z) are connected to the isocyanate group-containing component (B).

In a further alternative embodiment, the compounds A) may be those which each contain exactly one group (Y) and exactly one group (Z). Isocyanate-reactive groups (Y) whose reaction product with isocyanate is readily cleavable are those groups which can be used to block isocyanate groups.

Such groups are described in D.A. Wicks, Z.W. Wicks, Progress in Organic Coatings, 36, 148-172 (1999), 41, 1-83 (2001) and 43, 131-140 (2001).

Preferred groups (Y) are phenols, imidazoles, triazoles, pyrazoles, oximes, N-hydroxyimides, hydroxybenzoic acid esters, secondary amines, lactams, CH-acidic cyclic ketones, malonic esters or alkyl acetoacetates.

These groups mentioned may be connected in any way with the abovementioned compounds A).

Imidazolic groups as isocyanate-reactive groups, referred to herein for short as "imidazoles", are known, for example, from WO 97/12924 and EP 159117, triazoles from US 4482721, CH-acidic cyclic ketones are described, for example, in DE-A1 102 60 269, there especially in paragraph [0008] and preferably in paragraphs [0033] to [0037], particularly preferably cyclopentanone-2-carboxylic acid ester and in particular cyclopentanone-2-carboxylic acid ethyl ester.

Preferred imidazoles are, for example, those imidazoles which, in addition to the free NH group, also contain a further functional group, such as e.g. -OH, -SH, -NH-R, -NH2, -CHO, such as, for example, 4- (hydroxymethyl) imidazole, 2-mercapto-imidazole, 2-aminoimidazole, 1- (3-aminopropyl) imidazole, 4, 5-diphenyl-2-imidazolethiol, histamine, 2-imidazole-carboxaldehyde, 4-imidazole-carboxylic acid, 4,5-imidazole-dicarboxylic acid, L-histidine, L-camosine, and 2, 2 "-bis (4,5 dimethyl imidazole).

Suitable triazoles are 3-amino-1, 2,4-triazole, 4-amino-1, 2,4-triazole, 3,5-diamino-1, 2,4-triazole, 1H-1, 2,4-triazole-3-thiol , 5-methyl-1 H-1, 2,4-triazole-3-thiol and 3-amino-5-mercapto-1, 2,4-triazole.

Preference is given to phenols, oximes, N-hydroxyimides, lactams, imidazoles, triazoles, malonic esters and alkylacetonates; particularly preferred are lactams, phenols, imidazoles, triazoles and malonic esters, and very particular preference is given to phenols.

Phenols are understood as meaning those groups which consist of at least one aromatic or heteroaromatic, preferably aromatic ring system which carries at least one, preferably exactly one phenolic hydroxy group. The aromatic ring systems may be C ₆ to C ₂ o-aryl systems act, optionally arbitrarily substituted with halogen, Ci to _C20 alkyl, Ci to C ₂₀ -Alkyloyl, C ₆ to C ₂₀ - Aryloyl, Ci to C ₂₀ -alkenyloxycarbonyl, C ₆ to C ₂₀ -aryloxycarbonyl, Ci to C ₂₀ - alkylamidocarbonyl or C ₆ to C ₂₀ -Arylamidocarbonyl may be substituted. In the case of heteroaromatic systems, one or more, for example one, two or three, preferably one or two, more preferably one carbon atom of an aromatic ring system may be replaced by a nitrogen, oxygen or sulfur, preferably nitrogen atom.

The novel compounds A) contain on average at least 2, for example 2 to 20, preferably 2 to 10, more preferably 2 to 6, very particularly preferably 2 to 4 and in particular 2 to 3 groups (Y).

The groups (Y) within the compounds (A) may each be the same or different, preferably they are the same.

Groups (Y) can be present in compound A) in amounts of up to 5 mol / kg of compound A), preferably 0.1 to 5, particularly preferably 0.3 to 4.5, very particularly preferably 0.5 to 4 and in particular 1 to 3 mol / kg.

In addition, the compounds A) may optionally contain at least one, for example one to six, preferably one to four, particularly preferably one to three, very particularly preferably one to two and in particular exactly one further isocyanate-reactive group (Z).

Groups (Z) are isocyanate-reactive groups other than the groups (Y). These may be, for example, primary hydroxy, secondary hydroxy, tertiary hydroxy, primary amino or mercapto groups, preferably primary hydroxy or primary amino groups and more preferably primary hydroxy groups.

Primary hydroxy or amino groups are hydroxy or amino groups attached to a carbon atom attached to just one other carbon atom. Analogously, in the case of secondary hydroxyl or amino groups, the carbon atom bound to it is correspondingly bonded to two and to tertiary hydroxyl or amino groups having three carbon atoms.

The carbon atoms to which the hydroxy or amino groups are bonded may be cycloaliphatic or aliphatic carbon atoms, ie be part of a cycloaliphatic ring system or a straight or branched chain, but not an aromatic ring system.

Groups (Z) may be present in compound A) in amounts up to 5.5 mol / kg of compound A). Particularly in the case of primary hydroxyl groups as groups (Z), the OH number may be 0-300 mg KOH / g according to DIN 53240-2, preferably 0 to 250, more preferably 0 to 200, most preferably 10 to 150 and especially 50 to 150.

The compounds A) may preferably be polyethers or polyetherols, polyesters or polyesterols, polyurethanes or polyacrylates, and also their esterification products with (meth) acrylic acid, which in this document is abbreviated to methacrylic acid and acrylic acid, preferably acrylic acid. act that contain groups (Y).

Polyethers or polyetherols as compounds A) are, for example, compounds which are composed of diols or polyols which are optionally alkoxylated one or more times. In addition, at least one group carrying (Y) monomer is copolymerized into such compounds A or forms the starter molecule for an alkoxylation.

Di- or polyols are ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 1-dimethylethane-1, 2-diol, 2-butyl-2-ethyl-1, 3-propanediol, 2-ethyl-1 , 3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, 1, 2, 1, 3 or 1, 4-butanediol, 1, 6-hexanediol, 1, 10-decanediol, bis ( 4-hydroxycyclohexane) isopropylidene, tetramethylcyclobutanediol, 1, 2-, 1, 3- or 1, 4-cyclohexanediol, cyclooctanediol, norboranediol, pinanediol, decalindiol, 2-ethyl-1,3-hexanediol, 2,4-diethyl octane-1,3-diol, hydroquinone, bisphenol A, bisphenol F, bisphenol B, bisphenol S, 2,2-bis (4-hydroxycyclohexyl) propane, 1, 1, 1, 2, 1, 3- and 1, 4-cyclohexanedimethanol, 1, 2-, 1, 3- or 1, 4-cyclohexanediol, trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitone, erythritol, adonitol (Ribitol), arabitol (lyxite), xyNt, dulcitol (galactitol), maltitol or isomalt.

Each hydroxy group can independently of one another be alkoxylated one to twenty times, preferably one to ten times, particularly preferably one to five times, very particularly preferably one to three times and in particular one to two times.

Suitable alkylene oxides are, for example, ethylene oxide, propylene oxide, isobutylene oxide, vinyl oxirane and / or styrene oxide; preference is given to ethylene oxide, propylene oxide, and ethylene oxide is particularly preferred. The alkylene oxides can also be used in a mixture.

Further, polyTHF has a molecular weight between 162 and 2000, polyethylene glycol with a molecular weight between 106 and 2000, poly-1,3-propylene glycol with a molecular weight between 134 and 2000, and poly-1,2-propylene glycol with one molecular weight between 134 and 2000 as well as mixed polyethylene - / - 1, 2-propylene glycols with a molecular weight between 106 and 2000 in question. The polyetherols obtained can then be reacted, for example, at least partially with compounds which have at least one hydroxyl-reactive group and at least one group (Y) or at least one group which can be converted into a group (Y).

Examples are 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-hydroxy-4-methylbenzoic acid, 4-hydroxy-3-nitrobenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3 , 5-Dihydroxybenzoic acid, 2,4-dihydroxy-3,6-dimethylbenzoic acid, 3,4,5-trihydroxybenzoic acid, 5-hydroxyisophthalic acid or 4-hydroxyphthalic acid and their anhydrides, C 1 -C ₄ -alkyl ethers and C 1 - to C ₄ - Al kylester. Preference is given to 4-hydroxybenzoic acid, 5-hydroxyisophthalic acid and 4-hydroxyphthalic acid and their tert-butyl ethers, and 4-hydroxybenzoic acid is particularly preferred.

In the context of this document, C 1 -C ₄ -alkyl is understood as meaning methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl or tert-butyl.

For the reaction, the polyetherols are then at least partially reacted with these compounds, preferably in such a way that products A) are formed which contain at least two groups (Y).

This ensures that the hydroxyl-containing polyetherols are at least partially modified by reaction with preferably 4-hydroxybenzoic acid, so that it is at least in some of the terminal hydroxyl groups to phenolic hydroxy groups. If the phenolic hydroxy groups are etherified, preferably tert-butyl etherified, these protective groups can be removed in a subsequent step (see below).

The polyesters or polyesterols are the following compounds:

Polyesterpolyols are known, for example, from Ullmanns Enzyklopadie der technischen Chemie, 4th Edition, Volume 19, pages 62 to 65. Polyester polyols are preferably used which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols. The polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and may optionally be substituted, for example by halogen atoms, and / or unsaturated. Examples include: Oxalic, maleic, fumaric, succinic, glutaric, adipic, sebacic, dodecanedioic, o-phthalic, isophthalic, terephthalic, trimellitic, azelaic, 1,4-cyclohexanedicarboxylic or tetrahydrophthalic, hydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride, dimer fatty acids, their isomers and hydrogenation products, and esterifiable derivatives such as anhydrides or dialkyl esters, for example C 1 -C ₄ -alkyl esters, preferably methyl, ethyl or n-butyl esters, of said acids , Preference is given to dicarboxylic acids of the general formula HOOC- (CH ₂ ) y COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, particularly preferably succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.

Suitable polyhydric alcohols for the preparation of polyesterols are the diols and polyols listed above for the polyethers.

Alcohols of the general formula HO- (CH ₂ ) χ-OH are preferred, where x is a number from 1 to 20, preferably an even number from 2 to 20. Preferred are ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol. Further preferred is neopentyl glycol.

Also included are polycarbonate diols, e.g. by reaction of phosgene with an excess of the mentioned as synthesis components for the polyester polyols low molecular weight alcohols, into consideration.

Also suitable are lactone-based polyesterdiols, which are homopolymers or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules. Suitable lactones include preferably those derived from compounds of the general formula HO- (CH _{2) z} -COOH itself, where z is a number from 1 to 20 and a hydrogen atom of a methylene unit may also by a C _r -C ₄ Alkyl may be substituted. Examples are ε-caprolactone, β-propiolactone, gamma-butyrolactone and / or methyl-ε-caprolactone, 2-, 3- or 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid or pivalolactone and mixtures thereof. Suitable starter components are, for example, the low molecular weight dihydric alcohols mentioned above as the synthesis component for the polyesterpolyols. The corresponding polymers of ε-caprolactone are particularly preferred. Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers. Instead of the polymers of lactones, it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones. In addition, at least one group (Y) carrying monomer is polymerized into the compound A.

The polyesterols can be reacted, for example, at least in part, with compounds which have at least one hydroxyl-reactive group and at least one group (Y) or at least one group which can be converted into a group (Y).

Examples of these are 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-hydroxy-4-methylbenzoic acid, 4-hydroxy-3-nitrobenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid - Acid, 3,5-dihydroxybenzoic acid, 2,4-dihydroxy-3,6-dimethyl-benzoic acid, 3,4,5-trihydroxybenzoic acid, 5-hydroxyisophthalic acid or 4-hydroxyphthalic acid and their anhydrides, C 1 -C ₄ -alkyl ethers and C 1 to C ₄ alkyl esters. Preference is given to 4-hydroxybenzoic acid, 5-hydroxyisophthalic acid and 4-hydroxyphthalic acid and their tert-butyl ether, and 4-hydroxybenzoic acid is particularly preferred.

For the reaction, the polyesterols are then at least partially reacted with these compounds, preferably in such a way that products A) are formed which contain at least two groups (Y).

The suitable polyesters have a weight-average molecular weight of from 1000 to 50,000, preferably from 2,000 to 30,000, particularly preferably from 3,000 to 20,000, and very particularly preferably from 5,000 to 15,000.

Polyurethanes as compounds A are compounds which are composed of reaction products of diisocyanates or polyisocyanates with diols or polyols which are optionally alkoxylated one or more times and which in turn can then be reacted as described for the polyetherols or polyesterols aromatic carboxylic acids bearing phenolic groups.

Isocyanates are, for example, aliphatic, aromatic and cycloaliphatic di- and polyisocyanates having an NCO functionality of at least 1, 8, preferably 1, 8 to 5 and more preferably 2 to 4 in question, and their isocyanurates, biurets, urethanes, allophanates and uretdiones ,

The diisocyanates are preferably isocyanates having 4 to 20 carbon atoms and 2 NCO groups. Examples of conventional diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate,

Tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1, 4-, 1, 3 or 1, 2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane _J

1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate), 1, 3- or 1, 4-bis (isocyanatomethyl) cyclohexane, 2,4- or 2,6-diisocyanato-1 methylcyclohexane, 3 (or 4), 8 (or 9) -bis (isocyanatomethyl) -tricyclo [5.2.1.0 ²⁶ ] decane isomer mixtures, and also aromatic diisocyanates such as tolylene 2,4- or 2,6-diisocyanate and isomer mixtures thereof, m- or p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane and their mixtures of isomers, 1, 3 or 1, 4-phenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 1, 5-naphthylene diisocyanate, Diphenylene-4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate, tetramethylxylylene diisocyanate, 1,4-diisocyanatobenzene or diphenyl ether-4,4 ' diisocyanate.

There may also be mixtures of said diisocyanates.

Conceivable, although less preferred, monomeric isocyanates with more than

2 NCO groups.

Polyisocyanates having isocyanurate polyisocyanates ondiisocyanate uretdione, biuret groups, urethane groups or allophanate natgruppen polyisocyanates containing oxadiazinetrione groups or Iminooxadiazin- dione group-containing polyisocyanates, uretonimine-modified polyisocyanates based on linear or branched C ₄ -C ₂ o-alkylene , cycloaliphatic diisocyanates having a total of 6 to 20 carbon atoms or aromatic diisocyanates having a total of 8 to 20 carbon atoms or mixtures thereof.

The usable diisocyanates and polyisocyanates preferably have a content of isocyanate groups (calculated as NCO, molecular weight = 42) of 10 to 60% by weight, based on the diisocyanate and polyisocyanate (mixture), preferably 15 to 60% by weight and particularly preferably 20 up to 55% by weight.

Preferred are aliphatic or cycloaliphatic di- and polyisocyanates, e.g. the abovementioned aliphatic or cycloaliphatic diisocyanates, or mixtures thereof.

Particularly preferred are 1, 6-hexamethylene diisocyanate, 1, 3-bis (isocyanatomethyl) - cyclohexane, isophorone diisocyanate and di (isocyanatocyclohexyl) methane, very particularly preferred are isophorone diisocyanate and 1, 6-hexamethylene diisocyanate, particularly preferred is hexamethylene diisocyanate.

Further preferred 1) isocyanurate polyisocyanates of aromatic, aliphatic and / or cycloaliphatic diisocyanates. Particular preference is given here to the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on hexamethylene diisocyanate and isophorone diisocyanate. The isocyanurates present are, in particular, trisisocyanatoalkyl or trisisocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologs having more than one isocyanurate ring. The isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average NCO-

Functionality from 2.6 to 4.5.

2) uretdione diisocyanates having aromatic, aliphatic and / or cycloaliphatic bound isocyanate groups, preferably aliphatically and / or cycloaliphatically bonded and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate. Uretdione diisocyanates are cyclic dimerization products of diisocyanates.

The uretdione diisocyanates can be used in the preparations according to the invention as the sole component or in a mixture with other polyisocyanates, in particular those mentioned under 1).

3) biuret polyisocyanates having aromatic, cycloaliphatic or aliphatic bound, preferably cycloaliphatic or aliphatic bound isocyanate groups, in particular tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologues. These biuret polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 2.8 to 4.5.

4) polyisocyanates containing urethane and / or allophanate groups with aromatically, aliphatically or cycloaliphatically bonded, preferably aliphatically or cycloaliphatically bonded isocyanate groups, as described, for example, by reacting excess amounts of hexamethylene diisocyanate or isophorone diisocyanate with monohydric or polyhydric alcohols, e.g. Methanol, ethanol, / so-propanol, n-propanol, n-butanol, / so-butanol, se / c-butanol, tert.

Butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol), 2-ethylhexanol, n-pentanol, stearyl alcohol, cetyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1, 3 Propanediol monomethyl ether, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol or polyhydric alcohols, as listed above in the polyesterols, or mixtures thereof can be obtained. These urethane and / or allophanate polyisocyanates generally have a NCO content of 12 to 20 wt .-% and an average NCO functionality of 2.5 to 4.5.

5) oxadiazinetrione-containing polyisocyanates, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such oxadiazinetrione-containing polyisocyanates can be prepared from diisocyanate and carbon dioxide.

6) polyisocyanates containing iminooxadiazinedione groups, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such polyisocyanates containing iminooxadiazinedione groups can be prepared from diisocyanates by means of special catalysts.

7) Uretonimine-modified polyisocyanates.

The polyisocyanates 1) to 7) can be used in a mixture, if appropriate also in a mixture with diisocyanates.

Suitable polyhydric alcohols for preparing the polyurethanes listed above in the polyethers diols and polyols into consideration.

Preferred compounds A according to the invention are polyacrylates. Such preferred polyacrylates contain as structural components

(a) at least one polymerizable compound having at least one group (Y) or at least one group which can be converted into a group (Y),

(b) at least one ester of a monoalcohol with (meth) acrylic acid,

(c) at least one compound different from (a) and (b) having exactly one free-radically polymerizable C =C double bond, (d) optionally at least one ester of an alcohol having more than one hydroxy group with (meth) acrylic acid, exactly has a free-radically polymerizable C =C double bond,

(e) optionally different from (d) compounds having more than one free-radically polymerizable C = C double bond.

Compounds (a) are polymerizable compounds having at least one group (Y) or at least one group which can be converted into a group (Y).

These may be, for example, compounds which contain at least one, preferably exactly one ethylenic C =C double bond which is bonded to at least one, preferably exactly one phenol, imidazole, triazole, pyrazole, oxime, N-hydroxyimide, Hydroxybenzoic acid ester, secondary amine, lactam, CH-acidic eye- or at least one, preferably exactly one protected phenol, imidazole, triazole, pyrazole, oxime, N-hydroxyimide, hydroxybenzoic acid ester, secondary amine, lactam, CH-acid cyclic ketone, malonic acid ester or alkyl acetoacetate.

Examples of groups which can be converted into a group (Y) are protected groups, e.g. O-alkylated, preferably O-tert. alkylated, O-acylated or O-silylated phenols, oximes, N-hydroxyimides, hydroxybenzoic acid esters or N-sulfonated secondary amines.

Common protecting groups for the groups mentioned are described, for example, in Theodora W. Greene, Protective Groups in Organic Synthesis, 3rd ed., Wiley New York, 1999 or in Philip J. Kocienski, Protecting Groups, Thieme Stuttgart 2000.

Particularly preferred compounds (a) are protected styrene derivatives or cinnamic acid derivatives of the formula (I)

wherein

R ¹ and R ⁴ independently of one another are hydrogen or methyl,

R ⁴ additionally carboxyl (-COOH) or an ester group (-COOR ⁵ ),

R ² and R ⁵ independently of one another are C 1 to C ₂₀ -alkyl,

R ^{3 is} hydrogen, halogen, Ci to C ₂₀ -alkyl, Ci to C ₂₀ -alkyloyl, C ₆ to C ₂₀ -aryloyl, Ci to C ₂₀ -alkenyloxycarbonyl, C ₆ to C ₂₀ -aryloxycarbonyl, Ci to C ₂₀ -alkylamidocarbonyl , C ₆ to

C ₂₀ -arylamidocarbonyl or trisubstituted SiIyI and p is 0 to 2, preferably 0 to 1 and particularly preferably 0,

wherein the groups -COOR ⁵ and -OR ^{3 can} also together form a grouping -COO-.

Therein, the Ci to C _2O -AI ky I optionally be substituted and, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-Etylhexyl, 2 , 4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, hetadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1-dimethylbutyl, 1, 1,3,3-tetramethylbutyl, benzyl, 1 Phenylethyl, 2-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) -ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1, 2-di- (methoxycarbonyl) -ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1, 3-dioxolane 2-yl, 1, 3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1, 1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2- Trifluoroethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl.

Therein, the C ₆ to C ₂₀ -aryl may optionally be substituted and are, for example, phenyl, ToIyI, XyIyI, α-naphthyl, ß-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethyl phenyl, trimethylphe - nyl, ethylphenyl, diethylphenyl, / so-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, I as per pyl naphthyl, chlomaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2, 4,6

Trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl,

SiIyI can be, for example, trimethylsilyl, triethylsilyl, triphenylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, tert-butoxydimethylsilyl, tert-butoxydiphenylsilyl or thexyldimethylsilyl.

Halogen may mean fluorine, chlorine or bromine, preferably chlorine.

R ¹ is preferably hydrogen.

R ³ is preferably tert-butyl, tert-amyl, benzyl, acetyl, benzoyl, trimethylsilyl, tert-butyloxycarbonyl, benzyloxycarbonyl or phenylamidocarbonyl, more preferably tert-butyl or tert-amyl.

The group -OR ³ may be in position 2, 3 or 4 relative to the vinyl group, preferably in position 4.

When the group -OR ^{3 is} in position 4, there are preferably no substituents in the ortho position of this group -OR ³ . R ¹ and R ⁴ may be in either the cis or trans configuration.

Preferred compounds (a) are 4-methoxystyrene, 4-silyloxystyrene, 4-tert-butoxy-styrene, 4-tert-amyloxystyrene, 4-acetoxystyrene, 4-hydroxycinnamic acid or coumarin, more preferably 4-tert-butoxystyrene , Also, 1- (4-methoxyphenyl) -1-propene, methylisoeugenol (1, 2-dimethoxy-4- (1-propenyl) benzene, 1- (3,4-dimethoxyphenyl) -1-propene) and Isoeugenol (1- (4-hydroxy-3-methoxyphenyl) -1-propene.

Compounds (b) are esters of a monoalcohol with (meth) acrylic acid.

The monoalcohol may be aromatic, cycloaliphatic or, preferably, aliphatic, more preferably it is a cycloalkanol or alkanol, most preferably an alkanol.

Examples of monoalcohols are methanol, ethanol, isopropanol, n-propanol, n-

Butanol, iso-butanol, sec-butanol, tert-butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol), 2-ethylhexanol, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol, ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, 1, 3-propanediol monomethyl ether.

Preferred compounds (b) are (meth) acrylic acid ethyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid n-butyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid cyclohexyl ester and dihydrodicyclopentadienyl acrylate, particularly preferred are (meth) acrylic acid methyl ester, ( Meth) acrylic acid ethyl ester, (meth) acrylic acid n-butyl ester and (meth) acrylic acid 2-ethylhexyl ester.

Compounds (c) are compounds different from (a) and (b) with exactly one free-radically polymerizable C =C double bond.

Examples are vinyl aromatic compounds, e.g. Styrene, α-methylstyrene, α, β-unsaturated nitriles, e.g. Acrylonitrile, methacrylonitrile, α, β-unsaturated aldehydes, e.g. Acrolein, methacrolein,

Vinyl esters, e.g. Vinyl acetate, vinyl propionate, halogenated ethylenically unsaturated compounds, e.g. Vinyl chloride, vinylidene chloride, cyclic monounsaturated compounds, e.g. Cyclopentene, cyclohexene, cyclododene,

N-vinyl formamide,

Allylacetic acid, vinyl acetic acid, monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and their water-soluble alkali metal, alkaline earth metal or ammonium salts such as: Acrylic acid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylenemalonic acid, crotonic acid, fumaric acid, mesaconic acid and itaconic acid, maleic acid, N-vinylpyrrolidone N-vinyllactams, for example N-vinylcaprolactam,

N-vinyl-N-alkylcarboxamides or N-vinylcarboxamides, such as. N-vinylacetamide, N-vinyl-N-methylformamide and N-vinyl-N-methylacetamide, vinyl ethers, e.g. Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, iso-propyl vinyl ether, n-butyl vinyl ether, se / c-butyl vinyl ether, / so-butyl vinyl ether, tert-butyl vinyl ether, and mixtures thereof.

Preferred compounds (c) are styrene, vinyl acetate, acrylonitrile, acrylic acid, N-vinylpyrrolidone, N-vinylcaprolactam and ethyl vinyl ether, particularly preferred is styrene.

Compounds (d) are esters of an alcohol having more than one hydroxy group with (meth) acrylic acid.

Examples of such alcohols are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,1-dimethylethane-1,2-diol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-1 , 3-propanediol, 2-methyl-1, 3-propanediol, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, 1, 2, 1, 3 or 1, 4-butanediol, 1, 6-hexanediol, 1, 10-decanediol, bis ( 4-hydroxycyclohexane) isopropylidene, tetramethylcyclobutanediol, 1, 2-, 1, 3- or 1, 4-cyclohexanediol, cyclooctanediol, norbomandiol, pinanediol, decalindiol, 2-ethyl-1,3-hexanediol, 2,4-diethyl-octane 1, 3-diol, 2,2-bis (4-hydroxycyclohexyl) propane, 1, 1, 1, 2, 1, 3 and 1, 4-cyclohexanedimethanol, 1, 2, 1, 3 or 1 , 4-cyclohexanediol, trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, ditrimethylolpropane and dipentaerythritol.

The alcohols may optionally be alkoxylated one to ten times, preferably one to five times, more preferably one to three times and very particularly preferably one or two times per hydroxyl group, preferably ethoxylated and / or propoxylated and particularly preferably ethoxylated.

In this case, the compounds (d) can be compounds (d1) which have no other functional groups in addition to (meth) acrylate groups, or those compounds (d2) which have at least one other functional group. Examples of such functional groups are hydroxy groups, unsubstituted amino groups, N-monosubstituted amino groups, N, N-dialkyl-substituted amino groups and thiol groups.

Preferred compounds (d1) are 1, 2-ethanediol di (meth) acrylate, 1, 2

Propanediol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate.

Preferred compounds (d2) are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 4-aminobutyl (meth) acrylate, 6-aminohexyl (meth) acrylate, 2-thioethyl (meth) acrylate and 2-Dimethylaminoethyl (meth) acrylate.

The compounds (d1) and (d2) can also be used as mixtures, for example as technical mixtures of the acrylation of pentaerythritol, which usually have an OH number according to DIN 53240 of 99 to 115 mg KOH / g and predominantly of pentaerythritol triacrylate and Pentaerythritol tetraacrylate, and may contain minor amounts of pentaerythritol diacrylate.

Compounds (e) are optionally different from (d) compounds having more than one radically polymerizable C = C double bond.

Examples are divinylbenzene, butadiene, chloroprene or isoprene.

The polyacrylates usually contain the synthesis components in the following quantities (in mol%):

(a) 0.1 to 50, preferably 0.5 to 40, particularly preferably 1 to 30, very particularly preferably 5 to 25 and in particular 10 to 20 mol%,

(b) 50 to 99.9, preferably 60 to 99.5, particularly preferably 70 to 90, very particularly preferably 75 to 95 and in particular 80 to 90 mol%, (c) 0 to 50, preferably 1 to 40, particularly preferred From 5 to 35, very particularly preferably from 10 to 30, and in particular from 15 to 25, mol%,

(d) 0 to 5, preferably 0 to 4, particularly preferably 0 to 3, very particularly preferably 0.1 to 2.5 and in particular 1 to 2 mol%,

(e) 0 to 5, preferably 0 to 4, particularly preferably 0 to 3, very particularly preferably 0.1 to 2.5 and in particular 1 to 2 mol%,

with the proviso that the sum is 100 mol%. A common but not the only method for preparing such (co) polymers is free-radical or ionic (co) polymerization in a solvent or diluent.

The free-radical (co) polymerization of such monomers takes place, for example, in aqueous solution in the presence of polymerization initiators which decompose into free radicals under polymerization conditions, for example peroxodisulfates, H ₂ O ₂ -redoxysysteme or hydroxyperoxides, such as tert. Butyl hydroperoxide or cumene hydroperoxide. The (co) polymerization can be carried out in a wide temperature range, optionally under reduced or elevated pressure, usually at temperatures up to 100 ° C. The pH of the reaction mixture is usually adjusted in the range of 4 to 10.

However, the (co) polymerization can also be carried out continuously or batchwise in another manner known per se to those skilled in the art, e.g. as a solution, precipitate, water-in-oil emulsion, inverse emulsion, suspension or reverse suspension polymerization.

At this time, the monomer (s) is (co) polymerized using radical polymerization initiators.

Examples are those listed in Polymer Handbook Edition 1999, Wiley & Sons, New York.

These are, for example, peroxodisulfates, for example potassium, sodium or ammonium peroxodisulfate, peroxides, for example sodium peroxide or potassium peroxide, perborates, for example ammonium, sodium or potassium perborate, monopersulfates, for example ammonium, sodium or potassium hydrogen monopersulfate, and also salts of peroxycarboxylic acids, for example ammonium, sodium, potassium or magnesium monoperoxyphthalate.

Furthermore, hydrogen peroxide, for example as an aqueous solution in a concentration of 10 to 50% by weight, can be used.

It is also possible to use tert. Butyl hydroperoxide, tert. Amyl hydroperoxide, cumyl hydroperoxide, peracetic acid, perbenzoic acid, monoperphthalic acid or meta-chloroperbenzoic acid.

It is also possible to use ketone peroxides, dialkyl peroxides, diacyl peroxides or mixed acyl alkyl peroxides. Examples of diacyl peroxides are dibenzoyl peroxide and diacetyl peroxide. Examples of dialkyl peroxides are di-tert-butyl peroxide, di-cumyl peroxide, bis (α, α-dimethylbenzyl) peroxide and diethyl peroxide.

An example of mixed acyl-alkyl peroxides is tert. Perbenzoate. Ketone peroxides are, for example, acetone peroxide, butanone peroxide and 1, 1'-peroxy-bis-cyclohexanol.

Others are for example 1, 2,4-trioxolane or 9,10-dihydro-9,10-epidioxidoanthracene.

Into radicals are preferred decomposing azo compounds such as 2,2'-azo-bis (iso- butyronitrile), 2,2 ^1-azobis- (2-amidinopropane) hydrochloride or 4,4 ^1-azo-bis- (4 ¹ - cyano-pentanoic acid) or dialkyl peroxides such as di-tert-amyl peroxide, aryl-alkyl peroxides such as tert-butyl-cumyl peroxide, alkyl acyl peroxides such as tert-butyl-peroxy-2-ethylhexanoate, peroxydicarbonates such as di- (4 tert-butylcyclohexyl) peroxydicarbonate or hydroperoxides.

The synthesis components are usually used in the form of aqueous solutions or aqueous emulsions, the lower concentration being determined by the amount of water which is acceptable in (co) polymerization and the upper concentration by the solubility of the compound in question in water.

As a solvent or diluent, e.g. Water, alcohols, such as methanol, ethanol, n- or iso-propanol, n- or iso-butanol, glycols, ketones, such as acetone, ethyl methyl ketone, diethyl ketone or / so-butyl methyl ketone. Particular preference is given to nonpolar solvents such as, for example, xylene and its mixtures of isomers, Shellsol® A and solvent naphtha. Also possible are esters or ketones. Examples of these are n-butyl acetate, ethyl acetate, 1-methoxypropylacetate-2, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-ethoxyethyl propionate or butylglycol acetate.

In a preferred embodiment, the monomers are premixed and initiator added with any further additives dissolved in solvent. A particularly preferred embodiment is described in WO 01/23484 and there particularly on page 10, Z. 3 to Z. 24

If appropriate, the (co) polymerization can be carried out in the presence of polymerization regulators, such as, for example, hydroxylammonium salts, chlorinated hydrocarbons and thio compounds, for example tert-butylmercaptan, thioglycolic acid ethylacrylic esters, mercaptoethynol, mercaptopropyltrimethoxysilane, dodecylmercaptan, tert-dodecylmercaptan or alkali metal hypophosphites become. In (co) polymerization, these regulators, eg. B. in amounts of 0 to 0.8 parts by weight, based on 100 parts by weight of the (co) polymerizing monomers, are used by the molecular weight of the resulting (co) polymer is reduced. In the emulsion polymerization, dispersants, ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers can be used as surface-active compounds.

Suitable as such are both the protective colloids commonly used to carry out emulsion polymerizations and emulsifiers.

Suitable protective colloids are, for example, polyvinyl alcohols, cellulose derivatives or vinylpyrrolidone-containing copolymers. A detailed description of other suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, macromolecular substances, Georg-Thieme-Verlag, Stuttgart, 1969, pp. 411 to 420. Of course, mixtures of emulsifiers and / or or protective colloids. The dispersants used are preferably exclusively emulsifiers whose relative molecular weights, in contrast to the protective colloids, are usually below 1000. They may be anionic, cationic or nonionic in nature. Of course, in the case of the use of mixtures of surfactants, the individual components must be compatible with each other, which can be checked in case of doubt by hand on fewer preliminary tests. In general, anionic emulsifiers are compatible with each other and with nonionic emulsifiers.

The same applies to cationic emulsifiers, while anionic and cationic emulsifiers are usually incompatible with each other. Customary emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: 3 to 100: C ₄ to C _2), ethoxylated fatty alcohols (degree of ethoxylation: from 3 to 100, alkyl radical: C ₈ to Ci _8), as well as alkali and ammonium salts of alkyl sulfates (alkyl radical: C ₈ to Ci ₆₎ ethoxylated sulfuric acid monoesters of alkylphenols (degree of ethoxylation: from 3 to 100, alkyl radical: C ₄ to C _2), of alkylsulfonic acids (alkyl: C ₂ to C ₈₎ sulfonic acids and alkylacrylic ( Alkyl radical: Cg to Ci ₈ ). Further suitable emulsifiers, such as sulfosuccinic esters, can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme Verlag, Stuttgart, 1961, pages 192 to 208.

In general, the amount of dispersant used is 0.5 to 6, preferably 1 to 3 wt .-% based on the monomers to be radically polymerized.

The resulting polymers, polymer solutions or polymer dispersions can additionally be deodorized chemically and / or physically.

Any protective groups present in the compounds A are removed after their preparation and preferably before reaction with the compounds B. Common methods for removing the protective groups are described, for example, in Theodo. ra W. Greene, Protective Groups in Organic Synthesis, 3rd Ed., Wiley New York, 1999, or in Philip J. Kocienski, Protecting Groups, Thieme Stuttgart 2000.

In the case of the tertiary alkyl groups, in particular of phenols, the protecting group-containing compounds A are preferably reacted with at least one acid at a temperature of 20 to 100 ° C, preferably from 20 to 80 ° C and more preferably from 40 to 70 ° C over a Heated from 10 minutes to several hours.

Suitable acids are sulfuric acid, phosphoric acid, mineral acids such as hydrochloric acid, alkyl or arylsulfonic acid, for example methane, trifluoromethane, benzene, para-toluene or dodecylbenzenesulfonic acid, carboxylic acids such as acetic acid, or strongly acid ion exchanger.

The cleavage is preferably carried out in the presence of at least one reducing agent, for example those as described in WO 03/35596 of page 5, lines 36 to 37, page 7 and page 13, lines 5 to 2 30. Preference is given to the presence of triphenylphosphine, triphenyl phosphite, hypophosphorous acid or triethyl phosphite, particularly preferably hypophosphorous acid.

In a preferred embodiment, the cleavage of the protective groups is carried out under a gas which is inert under the reaction conditions.

In the case of the acyl groups as protective groups, especially of phenols, the protective group-containing compounds A are preferably with at least one base, for example sodium hydroxide, potassium hydroxide or lime, at a temperature of 20 to 100 ⁰ C, preferably from 20 to 80 ⁰ C and especially preferably heated from 40 to 70 ⁰ C over a period of 10 minutes to several hours.

In the case of the silyl groups as protective groups, in particular of phenols, the protective group-containing compounds A are preferably with at least one acid or a fluoride-containing compound, such as NaF, ammonium fluoride or tetra butylam- moniumfluorid, at a temperature of 20 to 100 ⁰ C, preferably from 20 heated to 80 ⁰ C and more preferably from 40 to 70 ° C over a period of 10 minutes to several hours.

In addition to the binder component A at least one further component B must be present, which contains at least one di- or polyisocyanate.

These may be, for example, di- or polyisocyanates, as listed above for the polyurethanes. Preferred di- and polyisocyanates are 1, 6

Diisocyanatohexane and isophorone diisocyanate and their polyisocyanates as listed above, in particular their isocyanurates. In a particularly preferred embodiment of the present invention, the component B comprises at least one polyisocyanate which contains at least one compound having at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group bound at least partially via allophanate groups.

Such polyisocyanates contain a content of allophanate groups (calculated as C ₂ N ₂ HO ₃ = 101 g / mol) of from 1 to 28% by weight, preferably from 3 to 25% by weight.

At least 20 mol%, preferably at least 25 mol%, particularly preferably at least 30 mol%, very particularly preferably at least 35 mol%, of the compound having at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group which form structural components of these polyisocyanates , in particular at least 40 mol% and especially at least 50 mol% of allophanate groups.

These polyisocyanates generally have a number average molecular weight M _n of less than 10,000 g / mol, preferably less than 5000 g / mol, more preferably less than 4000 and very particularly preferably less than 2000 g / mol (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).

The compounds having at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group can, for example monoesters of α, ß-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, Acrγlamidoglykolsäure, Methacr¬lami- doglykolsäure or Vinyl ethers, preferably (meth) acrylic acid and particularly preferably acrylic acid with diols or polyols which preferably have 2 to 20 C atoms and at least two hydroxyl groups, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1 , 3-propylene glycol, 1, 1-dimethyl-1, 2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1, 2, 1, 3 or 1, 4-butanediol, 1, 5-pentanediol , Neopentyl glycol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, 2-ethyl-1,4-butanediol, 1,4-dimethylolcyclohexane, 2,2-bis (4-hydroxycyclohexyl) propane, glycerol , Trimethylolethane , Trimethylolpropane, trimethylolbutane, pentaerythritol, ditrimethylolpropane, erythritol, sorbitol, poly-THF having a molecular weight between 162 and 2000, poly-1,3-propanediol having a molecular weight between 134 and 400, or polyethylene glycol having a molecular weight between 238 and 458 Also esters or Am ide of (meth) acrylic acid with amino alcohols z. For example, 2-aminoethanol, 2- (methylamino) ethanol, 3-amino-1-propanol, 1-amino-2-propanol or 2- (2-amino- ethoxy) ethanol, 2-mercaptoethanol or polyaminoalkanes such as ethylenediamine or diethylenetriamine, or vinylacetic acid.

Preference is given to using 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 1- _J- 4-butanediol mono (meth) acrylate, neopentylglycol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, glycerol mono- and di (meth) acrylate, trimethylolpropane mono- and di (meth) acrylate, pentaerythritol mono-, di- and tri (meth) acrylate and also 4-hydroxybutyl vinyl ether, 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 4-aminobutyl (meth) acrylate, 6-aminohexyl (meth) acrylate, 2-thioethyl (meth) acrylate, 2-aminoethyl (meth) acrylamide, 2-aminopropyl (meth) acrylamide, 3-amino-propyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, 2-hydroxy-propyl (meth) acrylamide or 3-hydroxypropyl (meth ) acrylamide. Particular preference is given to 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 1,4-butanediol monoacrylate, 3- (acryloyloxy) -2-hydroxypropyl (meth) acrylate and the monoacrylates of polyethylene glycol of molecular weight from 106 to 238 ,

In a preferred embodiment, the compound having at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group is selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate and 1, 4-butanediol monoacrylate, 1, 2- or 1,3-diacrylate of glycerol, trimethylolpropane diacrylate, pentaerythritol triacrylate, ditrimethylolpropane triacrylate and dipentaerythritol pentaacrylate, preferably from 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.

The formation of the adduct of isocyanate group-containing compound and the compound having at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group is generally carried out by mixing the components in any order, optionally at elevated temperature.

In this case, the compound containing isocyanate-reactive groups is preferably added to the compound containing isocyanate groups, preferably in several steps.

The isocyanate group-containing compound is more preferably initially introduced, and the compounds containing isocyanate-reactive groups are added. Subsequently, optionally desired further components can be added. In general, the reaction is carried out at temperatures between 5 and 100 ° C, preferably between 20 to 90 ° C and more preferably between 40 and 80 ° C and in particular between 60 and 80 ° C.

Preference is given to work under anhydrous conditions.

Anhydrous here means that the water content in the reaction system is not more than 5% by weight, preferably not more than 3% by weight and particularly preferably not more than 1% by weight, very particularly preferably not more than 0.75 and in particular not more than 0, 5% by weight.

Preferably, the reaction is carried out in the presence of at least one oxygen-containing gas, e.g. Air or air-nitrogen mixtures or mixtures of oxygen or an oxygen-containing gas with an inert gas under the reaction conditions, which have an oxygen content of less than 15, preferably less than 12, more preferably less than 10, most preferably less than 8 and in particular less than 6 vol% ,

The reaction may also be carried out in the presence of an inert solvent, e.g. Acetone, / so-butyl methyl ketone, toluene, xylene, butyl acetate, methoxypropyl acetate or ethoxyethyl acetate. Preferably, however, the reaction is carried out in the absence of a solvent.

In a preferred embodiment, the reaction is carried out under allophanatization conditions.

In a further preferred embodiment, such compounds are used, as described in WO 00/39183, p. 4, Z. 3 to p. 10, Z. 19, the disclosure of which is herewith part of the present document. Particularly preferred among these are those compounds which have as structural components at least one (cyclo) aliphatic isocyanate containing allophanate groups and at least one hydroxyalkyl (meth) acrylate, very particularly preferably the products Nos. 1 to 9 in Table 1 to S 24 of WO 00/39183.

The binder components A and B are generally mixed in approximately equimolar amounts, so that the ratio of (Y) and (Z) groups (in total) to isocyanate groups in B is from 5: 1 to 1: 2 , preferably from 3: 1 to 1: 1.5, particularly preferably from 2: 1 to 1: 1, 2, very particularly preferably 1, 5: 1 to 1: 1, 1 and in particular 1, 2: 1 to 1: 1, 1.

A further aspect of the present invention is the use of binder components A and B in coating formulations for the production of coatings which have an energy-input-repairable effect. By this is meant that scratches, cracks and / or delaminations formed in the coating can be at least partially reversed from the substrate.

In addition to components A and B, such coating formulations may still contain:

optionally at least one compound having one or more than one free-radically polymerizable double bond, optionally at least one photoinitiator and optionally further typical lacquer additives.

Compounds having one or more than one free-radically polymerizable double bond are, for example, those compounds which have 1 to 6, preferably 1 to 4 and particularly preferably 1 to 3 groups capable of free-radical polymerization.

Free-radically polymerizable groups are, for example, vinyl ether or (meth) acrylate groups, preferably (meth) acrylate groups and particularly preferably acrylate groups.

Radically polymerizable compounds are often subdivided into monofunctional (compound having a radically polymerizable double bond) and multifunctional (compound having more than one radically polymerizable double bond), polymerizable compounds.

Monofunctional, polymerizable compounds are those having exactly one free-radically polymerizable group; multifunctional, polymerizable compounds are those having more than one, preferably having at least two free-radically polymerizable groups.

Monofunctional, polymerizable compounds are, for example, esters of (meth) acrylic acid with alcohols having 1 to 20 C atoms, for example (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid-2 ethylhexyl ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dihydrodicyclopentadienyl acrylate, vinylaromatic compounds, eg styrene, divinylbenzene, α, β-unsaturated nitriles, eg acrylonitrile, methacrylonitrile , α, β-unsaturated aldehydes, for example acrolein, methacrolein, vinyl esters, for example vinyl acetate, vinyl propionate, halogenated ethylenically unsaturated compounds, for example vinyl chloride, vinylidene chloride, conjugated unsaturated compounds, for example butadiene, isoprene, chloroprene, monounsaturated compounds, for example ethylene, Propylene, 1-butene, 2-butene, isobutene, cyclic monounsaturated compounds, for example cyclopentene, cyclohexene, cyclododecene, N-vinylformamide, allylacetic acid e, vinylacetic acid, monoethylenically unsaturated carboxylic acids having 3 to 8 C atoms and their water-soluble alkali metal, alkaline earth metal or ammonium salts such as: acrylic acid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylenemalonic acid, crotonic acid, fumaric acid, mesaconic acid and itaconic acid, maleic acid , N-vinylpyrrolidone, N-vinyllactams, such as N-vinylcaprolactam,

N-vinyl-N-alkylcarboxamides or N-vinylcarboxamides, such as. N-vinylacetamide, N-vinyl-N-methylformamide and N-vinyl-N-methylacetamide or vinyl ethers, e.g. Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, / so-propyl vinyl ether, n-butyl vinyl ether, se / c-butyl vinyl ether, / so-butyl vinyl ether, tert-butyl vinyl ether, 4-hydroxy-butyl vinyl ether, and mixtures thereof.

Preferred among these are the esters of (meth) acrylic acid, particular preference is given to (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid n-butyl ester, (meth) acrylic acid 2-ethylhexyl ester and 2-hydroxyethyl acrylate, completely Particularly preferred are (meth) acrylic acid n-butyl ester, (meth) acrylic acid 2-ethylhexyl ester and 2-hydroxyethyl acrylate and especially 2-hydroxyethyl acrylate.

(Meth) acrylic acid in this specification stands for methacrylic acid and acrylic acid, preferably for acrylic acid.

Multifunctional, polymerizable compounds are preferably multifunctional (meth) acrylates which carry more than 1, preferably 2-10, more preferably 2-6, most preferably 2-4 and especially 2-3 (meth) acrylate groups, preferably acrylate groups.

These may be, for example, esters of (meth) acrylic acid with correspondingly at least dihydric polyhydric alcohols.

Such polyalcohols are, for example, at least divalent polyols, polyether or polyesterols or polyacrylate polyols having an average OH functionality of at least 2, preferably 3 to 10, suitable.

Examples of polyfunctional, polymerizable compounds are ethylene glycol diacrylate, 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,8 Octanediol diacrylate, neopentyl glycol diacrylate, 1, 1, 2, 1, 3 and 1, 4-cyclohexanedimethanol diacrylate, 1, 2, 1, 3 or 1, 4-cyclohexanediol diacrylate, trimethylolpropane triacrylate, ditri methylolpropane penta- or hexaacrylate, pentaerythritol tri- or tetraacrylate, glycerol di- or triacrylate, and di- and polyacrylates of sugar alcohols, such as sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xyNt, Dulcitol (galactitol), maltitol or isomalt, or of polyester polyols, polyetherols, polyTHF with a molecular weight between 162 and 2000, poly-1,3-propanediol with a molecular weight between see, 134 and 2000, polyethylene glycol having a molecular weight between 106 and 2000, as well as epoxy (meth) acrylates, urethane (meth) acrylates or polycarbonate (meth) acrylates.

Further examples are (meth) acrylates of compounds of the formula (Villa) to (VIIIc),

(Villa) (VIIIb) (VIIIc)

wherein

R ⁷ and R ⁸ independently of one another denote hydrogen or C 1 -C ₈ -alkyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,

k, I, m, q independently of one another are each an integer from 1 to 10, preferably 1 to 5 and particularly preferably 1 to 3, and

each Xi for i = 1 to k, 1 to I, 1 to m and 1 to q can be independently selected from the group -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CH ₃ ) -O- , -CH (CH ₃ ) -CH ₂ -O-, -CH ₂ --C (CH ₃ J ₂ -O-, -C (CH ₃ ) ₂ -CH ₂ -O-, -CH ₂ -CHVJn-O- , -CHVJn-CH ₂ -O-, -CH ₂ -CHPh-O- and -CHPh-CH ₂ -O-, preferably from the group -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CH ₃ ) -O- and -CH (CH ₃ ) -CH ₂ -O-, and more preferably -CH ₂ -CH ₂ -O-,

where Ph is phenyl and Vin is vinyl.

Therein optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Ci - Ci ₈ alkyl, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, Hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1, 1-dimethyl-propyl, 1, 1-dimethylbutyl, 1, 1,3,3- Tetramethylbutyl, preferably methyl, ethyl or n-propyl, most preferably methyl or ethyl.

Preference is given to (meth) acrylates of one to twenty times and more preferably three to ten times ethoxylated, propoxylated or mixed ethoxylated and propoxylated and in particular exclusively ethoxylated neopentyl glycol, trimethylolpropane, trimethylolethane or pentaerythritol.

Preferred multifunctional, polymerizable compounds are ethylene glycol diacrylate, 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,6. Hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, Polyestepoly- olenacrylate, Polyetherolacrylate and triacrylate of one to twenty times alkoxylated, particularly preferably ethoxylated trimethylolpropane.

Very particularly preferred multifunctional, polymerizable compounds are 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate and triacrylate of one to twenty times ethoxylated trimethylolpropane.

Polyester polyols are e.g. from Ullmann's Encyclopedia of Industrial Chemistry,

4th edition, Volume 19, pp. 62 to 65 known. Preference is given to using polyesterpolyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols. The polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic, and optionally, e.g. by halogen atoms, substituted and / or unsaturated. Examples include:

Oxalic, maleic, fumaric, succinic, glutaric, adipic, sebacic, dodecanedioic, o-phthalic, isophthalic, terephthalic, trimellitic, azelaic, 1,4-cyclohexanedicarboxylic or tetrahydrophthalic, hydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride, dimeric fatty acids, their isomers and hydrogenation products, and esterifiable derivatives such as anhydrides or dialkyl esters, for example C 1 -C ₄ -alkyl esters, preferably methyl, ethyl or n-butyl esters, of said acids , Preference is given to dicarboxylic acids of the general formula HOOC- (CH ₂ ) y COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, particularly preferably succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.

Suitable polyhydric alcohols for preparing the polyesterols are 1, 2-propanediol, ethylene glycol, 2,2-dimethyl-1, 2-ethanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 3-methylpentane-1, 5-diol, 2-ethylhexane-1, 3-diol, 2,4-diethyloctane-1, 3-diol, 1, 6-hexanediol, poly-THF with one mole mass between 162 and 2000, poly-1,3-propanediol with a molecular weight between 134 and 2000, poly-1,2-propanediol with a molecular weight between 134 and 2000, polyethylene glycol with a molecular weight between 106 and 458, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester , 2-ethyl-1, 3-propanediol, 2-methyl-1,3-propanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 1, 1, 1, 2, 1, 3 and 1, 4-cyclohexanedimethanol, 1, 2-, 1, 3- or 1, 4-cyclohexanediol, trimethylolbutane, trimethylolpropane, trimethylolethane, neopentyl glycol, Pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xyNt, dulcitol (galactitol), maltitol or isomalt, which may optionally be alkoxylated as described above.

Alcohols of the general formula HO- (CH ₂ ) χ-OH are preferred, where x is a number from 1 to 20, preferably an even number from 2 to 20. Preferred are ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol. Further preferred is neopentyl glycol.

Also included are polycarbonate diols, e.g. by reaction of phosgene with an excess of the mentioned as synthesis components for the polyester polyols low molecular weight alcohols, into consideration.

Also suitable are lactone-based polyesterdiols, which are homopolymers or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules. Suitable lactones include preferably those derived from compounds of the general formula HO- (CH _{2) z} -COOH itself, where z is a number from 1 to 20 and a hydrogen atom of a methylene unit may also by a C _r -C ₄ Alkyl may be substituted. Examples are ε-caprolactone, β-propiolactone, gamma-butyrolactone and / or methyl-ε-caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid or pivalolactone and mixtures thereof. Suitable starter components are, for example, the low molecular weight dihydric alcohols mentioned above as the synthesis component for the polyesterpolyols. The corresponding polymers of ε-caprolactone are particularly preferred. Lower polyester diols or polyether diols can also be used as

Starter be used for the production of lactone polymers. Instead of the polymers of lactones, it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones.

Furthermore, the multifunctional, polymerizable compound as listed above may be urethane (meth) acrylates, epoxy (meth) acrylates or carbonates (meth) acrylates.

Urethane (meth) acrylates are e.g. obtainable by reacting polyisocyanates with hydroxyalkyl (meth) acrylates or vinyl ethers and optionally chain extenders such as diols, polyols, diamines, polyamines or dithiols or polythiols. In addition, urethane (meth) acrylates dispersible in water without the addition of emulsifiers additionally contain ionic and / or nonionic hydrophilic groups which are present, for example. be incorporated by structural components such as hydroxycarboxylic acids in the urethane.

Such urethane (meth) acrylates essentially contain as structural components: (I) at least one organic aliphatic, aromatic or cycloaliphatic di- or polyisocyanate,

(II) at least one compound having at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group and

(III) optionally at least one compound having at least two isocyanate-reactive groups.

Possible employable components (I), (II) and (IM) may be the same as described above for the polyurethanes.

The urethane (meth) acrylates preferably have a number-average molecular weight M _{n of} from 500 to 20,000, in particular from 500 to 10,000, more preferably from 600 to 3,000 g / mol (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).

The urethane (meth) acrylates preferably have a content of 1 to 5, particularly preferably 2 to 4 moles of (meth) acrylic groups per 1000 g of urethane (meth) acrylate.

Epoxide (meth) acrylates are obtainable by reacting epoxides with (meth) acrylic acid. Suitable epoxides are, for example, epoxidized olefins, aromatic glycidyl ethers or aliphatic glycidyl ethers, preferably those of aromatic or aliphatic glycidyl ethers.

Epoxidized olefins may, for example, be ethylene oxide, propylene oxide, iso-butylene oxide, 1-butoxide, 2-butene oxide, vinyl oxirane, styrene oxide or epichlorohydrin. Preferred are ethylene oxide, propylene oxide, iso-butylene oxide, vinyl oxirane, styrene oxide or epichlorohydrin, particularly preferably ethylene oxide , Propylene oxide or epichlorohydrin and most preferably ethylene oxide and epichlorohydrin.

Aromatic glycidyl ethers are, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol B diglycidyl ether, bisphenol S diglycidyl ether, hydroquinone diglycidyl ether, alkylation products of phenol / dicyclopentadiene, for example 2,5-bis [(2, 3-E-epoxypropoxy) phenyl] octahydro-4,7-methano-5H-indene (CAS No. [13446-85-0]), tris [4- (2,3-epoxypropoxy) phenyl] methane isomers) CAS-No. [66072-39-7]), phenol based epoxy novolacs (CAS # [9003-35-4]) and cresol based epoxy novolacs (CAS # [37382-79-9]). Aliphatic glycidyl ethers include for example, 1, 4-butanediol, 1, 6-hexane diol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1, 1, 2 _J 2-tetrakis [4- (2 _J 3-epoxypropoxy) phenyl] ethane (CAS-No. [ 27043-37-4]), diglycidyl ethers of polypropylene glycol (α, ω-bis (2,3-epoxypropoxy) poly (oxypropylene) (CAS No. [16096-30-3]) and of hydrogenated bisphenol A (2 , 2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, CAS No. [13410-58-7]).

The epoxy (meth) acrylates and vinyl ethers preferably have a number average molecular weight M _{n of} from 200 to 20,000, particularly preferably from 200 to 10,000 g / mol and very particularly preferably from 250 to 3,000 g / mol; the content of (meth) acrylic or vinyl ether groups is preferably 1 to 5, more preferably 2 to 4 per 1000 g of epoxy (meth) acrylate or vinyl ether epoxide (determined by gel permeation chromatography with polystyrene as standard and tetrahydrofuran as eluent).

On average, carbonate (meth) acrylates preferably contain 1 to 5, in particular 2 to 4, particularly preferably 2 to 3 (meth) acrylic groups and very particularly preferably 2 (meth) acrylic groups.

The number average molecular weight M _{n of} the carbonate (meth) acrylates is preferably less than 3000 g / mol, more preferably less than 1500 g / mol, more preferably less than 800 g / mol (determined by gel permeation chromatography with polystyrene as standard, solvent tetrahydrofuran).

The carbonate (meth) acrylates can be obtained in a simple manner by transesterification of carbonic acid esters with polyhydric, preferably dihydric alcohols (diols, eg hexanediol) and subsequent esterification of the free OH groups with (meth) acrylic acid or else transesterification with (meth) acrylic esters, such as it eg in EP-A 92,269. They are also available by reacting phosgene, urea derivatives with polyvalent, e.g. dihydric alcohols.

Vinyl ether carbonates are also obtainable in an analogous manner by reacting a hydroxyalkyl vinyl ether with carbonic esters and optionally dihydric alcohols.

Also conceivable are (meth) acrylates or vinyl ethers of polycarbonate polyols, such as the reaction product of one of said diols or polyols and a carbonic acid ester and a hydroxyl-containing (meth) acrylate or vinyl ether.

Suitable carbonic acid esters are, for example, ethylene, 1, 2 or 1, 3-propylene carbonate, carbonic acid dimethyl, diethyl or dibutyl ester. Suitable hydroxyl-containing (meth) acrylates are, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, glycerol mono- and di (meth ) acrylate, trimethylolpropane mono- and di (meth) acrylate and also pentaerythritol mono-, di- and tri (meth) acrylate.

Suitable hydroxyl-containing vinyl ethers are e.g. 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether.

Particularly preferred carbonate (meth) acrylates are those of the formula:

wherein R is H or CH ₃ , X is a C ₂ -C ₈ alkylene group and n is an integer from 1 to 5, preferably 1 to 3.

R is preferably H and X is preferably C ₂ to do alkyls, for example 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene or 1,6-hexylene preferably C ₄ - to C ₈ -alkylene. Most preferably, X is C ₆ - alkylene.

The carbonate (meth) acrylates are preferably aliphatic carbonate (meth) acrylates.

Among the multifunctional polymerizable compound, urethane (meth) acrylates are particularly preferred.

Photoinitiators are socially active compounds which, when irradiated with electromagnetic radiation, form free radicals which cause a radical polymerization. This can be, for example, UV or IR radiation or electromagnetic radiation in the visible range.

Photoinitiators may be, for example, photoinitiators known to the person skilled in the art, for example those in "Advances in Polymer Science", Volume 14, Springer Berlin 1974 or in KK Dietliker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymerization, PKT Oldring (Eds), SITA Technology Ltd, London. Suitable examples include mono- or Bisacylphosphinoxide, as described for example in EP-A 7 508, EP-A 57 474, DE-A 196 18 720, EP-A 495 751 or EP-A 615 980, for example, 2.4 , 6-trimethylbenzoyldiphenylphosphine oxide (Lucirin ^® TPO from BASF AG), ethyl 2,4,6-trimethylbenzoylphenylphosphinate (Lucirin ^® TPO L from BASF AG), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure® 819 Ciba Spezialitätenchemie), benzophenones, hydroxyacetophenones, phenylglyoxylic acid and its derivatives or mixtures of these photoinitiators. Examples which may be mentioned are benzophenone, acetophenone, acetonaphthoquinone, methyl ethyl ketone, valerophenone, hexanophenone, α-phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, 4-morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxyacetophenone, β-methylanthraquinone, fert-butylanthraquinone, anthraquinone-carboxylic acid ester, benzaldehyde, α-tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1-indanone , 1, 3,4-triacetylbenzene, thioxanthen-9-one, xanthen-9-one, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-di- / so-propylthioxanthone,

2,4-dichlorothioxanthone, benzoin, benzoin / so-butyl ether, chloroxanthenone, benzoin tetrahydropyranyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin / so-propyl ether, 7-H-benzoin methyl ether, benz anthracen-7-one, 1-naphthaldehyde, 4,4'-bis (dimethylamino) benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, Michler's ketone, 1-acetonaphthone, 2-acetonaphthone, 1-benzoylcyclohexyl- clohexan-1-ol, 2-hydroxy-2,2-dimethylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, Acetophenone dimethyl ketal, o-methoxy benzophenone, triphenyl phosphine, tri-o-tolyl phosphine, benz [a] anthracene-7,12-dione, 2,2-diethoxyacetophenone, benzil ketals such as benzil dimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone and 2,3-butanedione.

Also suitable are non-yellowing or slightly yellowing photoinitiators of the phenylglyoxalic acid ester type, as described in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761.

Preferred among these photoinitiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, benzophenone, 1-benzoylcyclohexan-1-ol , 2-hydroxy-2,2-dimethylacetophenone and 2,2-dimethoxy-2-phenylacetophenone.

IR photoinitiators contain a sensitizer co-initiator mixture. Dyes, in particular cyanine, xanthylium or thiazine dyes, are frequently used as the sensitizer dye, and the co-initiators are, for example, boranate salts, sulfonium salts, iodonium salts, sulfones, peroxides, pyridine N-oxides or halomethyltriazines. As further paint typical additives, for example, antioxidants, stabilizers, activators (accelerators), fillers, pigments, dyes, antistatic agents, flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents can be used.

Furthermore, one or more thermally activatable initiators may be added, for example potassium peroxodisulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, azobis / so-butyronitrile, cyclohexylsulfonylacetyl peroxide, di- / so-propyl percarbonate, tert-butyl peroctoate or benzopinacol , and for example those thermally activatable initiators having a half life at 8O ⁰ C of more than 100 hours, such as di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, t-butyl perbenzoate, silylated pinacols, the z. B. commercially available under the trade name ADDID 600 from Wacker or hydroxyl-containing amine-N-oxides, such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6- Tetramethylpiperidine-N-oxyl etc.

Further examples of suitable initiators are described in "Polymer Handbook" 2nd ed., Wiley & Sons, New York.

Suitable thickeners besides free-radically (co) polymerized (co) polymers, customary organic and inorganic thickeners such as hydroxymethylcellulose or bentonite are also suitable.

As chelating agents, e.g. Ethylenediaminetic acid and its salts and ß-di-ketones are used.

Suitable fillers include silicates, e.g. Example by hydrolysis of silicon tetrachloride available silicates such as Aerosil ^® the Fa. Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonates, etc.

Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and benzotriazole (the latter available as Tinuvin ^® grades from Ciba-Spezialitatenchemie) and benzophenones. These may be used alone or together with suitable radical scavengers, for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, eg. For example, bis (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate can be used. Stabilizers are usually used in amounts of 0.1 to 5.0 wt .-%, based on the solid components contained in the preparation.

The coating compositions according to the invention can be both one-component and two-component. Two-component means that the components A and B and optionally other paint constituents are mixed together only shortly before application and then essentially only after the application to the Substrate react with each other. Mixing usually takes place in the case of two-component paints within a period of not more than 12 hours, preferably not more than 10, more preferably not more than 9, very preferably not more than 7, in particular not more than 5 and especially not more than 3 hours before application to the substrate.

In contrast, one-component (1K) coating compositions can be mixed together for a longer time before the application, to existing isocyanate groups in the form of blocked isocyanate groups with common blocking agents (see above) can be used.

The coatings obtained with the coating compositions of the invention generally have a glass transition temperature T ₉ above -30, preferably above -10 ° C. The upper limit is generally carried out at glass transition temperatures T ₉ of not more than 120, preferably not more than 100 ⁰ C (according to the DSC method (Differential Scanning Calorimetry) according to ASTM 3418/82, heating rate 10 ° C / min) ,

In a preferred embodiment of the present invention, the coating compositions according to the invention are radiation-curable or dual- or multi-cure-capable.

For the purposes of this document, the term "dual cure" or "multi-cure" denotes a curing process which takes place via two or more than two mechanisms, specifically selected from radiation, moisture, chemical, oxidative and / or thermosetting, preferably selected from radiative, moisture keits-, chemically and / or thermally curing, more preferably selected from radiation, chemical and / or thermal curing and most preferably radiation and chemical curing.

Radiation hardening in the sense of this document is defined as the polymerization of polymerisable compounds as a result of electromagnetic and / or particulate radiation, preferably UV light in the wavelength range of λ = 200 to 700 nm and / or electron radiation in the range of 150 to 300 keV and especially preferably with a radiation dose of at least 80, preferably 80 to 3000 mJ / cm ² .

The coating compositions according to the invention are particularly suitable for coating substrates such as wood, paper, textile, leather, fleece, plastic surfaces, glass, ceramics, mineral building materials, such as cement blocks and fiber cement boards, and in particular of metals or coated metals. The coating of the substrates with the coating compositions according to the invention is carried out by customary methods known to the person skilled in the art, wherein a coating composition according to the invention or a coating formulation containing it is applied to the substrate to be coated in the desired thickness and, if appropriate, dried. If desired, this process can be repeated one or more times.

The coating compositions may be prepared by a variety of application methods, such as e.g. Air pressure, airless or electrostatic spray method using one or two-component spray systems, but also by spraying, filling, doctoring, brushing, rolling, rolling, pouring, laminating, injection molding or coextrusion one or more times be applied.

The coating thickness is generally in a range of about 3 to 1000 g / m ² and preferably 10 to 200 g / m ² .

In addition, a process for coating substrates is disclosed, in which a coating composition according to the invention or a coating formulation containing it, optionally mixed with further typical coatings additives and thermally, chemically or radiation-curable resins, applied to the substrate and optionally dried, and with electron beams or UV exposure under oxygen-containing atmosphere or preferably under inert gas hardens, optionally at temperatures up to the height of the drying temperature and / or at temperatures up to 160 ⁰ C, preferably between 60 and 160 ⁰ C, thermally treated.

Radiation hardening takes place with high-energy light, eg UV light or electron beams. The radiation curing can be carried out at higher temperatures. Preference is given to a temperature above the T _{9 of} the radiation-curable binder. The drying and curing of the coatings is generally carried out under normal temperature conditions, ie without heating the coating. The mixtures according to the invention can, however, also used for the production of coatings by application at elevated temperature, eg at 40-250 ⁰ C, preferably 40-150 ° C and especially at 40 to 100 ° C dried and cured excluded. This is limited by the thermal stability of the substrate.

Furthermore, a process for coating substrates is disclosed, in which the coating composition of the invention or coating formulations containing it, optionally mixed with thermally curable resins, applied to the substrate, dries, and then with electron beams or UV exposure under oxygen-containing atmosphere or preferably under Inert gas cures, optionally at temperatures up to the height of the drying temperature. The method for coating substrates can also be carried out so that after application of the coating composition of the invention or paint formulations is first irradiated with electron beams or UV exposure under oxygen or preferably under inert gas to achieve a pre-curing, then at temperatures up to 16O ⁰ C. , preferably between 60 and 16O ⁰ C, thermally treated and then cured by electron beams or UV exposure under oxygen or preferably under inert gas.

Optionally, if several layers of the coating composition are applied one above the other, drying and / or radiation curing may take place after each coating operation.

Suitable radiation sources for radiation curing are, for example, low-pressure mercury lamps, medium-pressure lamps with high-pressure lamps and fluorescent tubes, pulse emitters, metal halide lamps, electronic flash devices, whereby a radiation curing without photoinitiator is possible, or Excimerstrahler. The radiation is cured by exposure to high-energy radiation, ie UV radiation or daylight, preferably light in the wavelength range of λ = 200 to 700 nm, particularly preferably from λ = 200 to 500 nm and most preferably λ = 250 to 400 nm, or by Irradiation with high-energy electrons (electron radiation, 150 to 300 keV). The radiation sources used are, for example, high-pressure mercury vapor lamps, lasers, pulsed lamps (flash light), halogen lamps or excimer radiators. The radiation dose for UV curing, which is usually sufficient for crosslinking, is in the range from 80 to 3000 mJ / cm ² .

Of course, several radiation sources can be used for the curing, e.g. two to four.

These can also radiate in different wavelength ranges.

The drying and / or thermal treatment can also be carried out in addition to or instead of the thermal treatment by NIR radiation, wherein NIR radiation here electromagnetic radiation in the wavelength range of 760 nm to 2.5 microns, preferably from 900 to 1500 nm is designated.

The irradiation may optionally also in the absence of oxygen, for. B. under inert gas atmosphere, are performed. As inert gases are preferably nitrogen, noble gases, carbon dioxide, or combustion gases. Furthermore, the irradiation can be carried out by covering the coating composition with transparent media. Transparent media are z. As plastic films, glass or liquids, eg. B. water. Particular preference is given to irradiation in the manner described in DE-A1 199 57 900.

As far as crosslinkers are included, which cause an additional thermal crosslinking, for example isocyanates, for example, simultaneously or even after the radiation curing, the thermal crosslinking by increasing the temperature to up to 15O ⁰ C, preferably up to 13O ⁰ C are performed.

For repair (self-healing) of the coatings of the invention, the coatings are heated to a temperature of at least 10 minutes, preferably at least 15 minutes, preferably at least 20 minutes, more preferably at least 30, most preferably at least 45 and more preferably at least 60 minutes at least 25, preferably at least 30 and more preferably at least 35 ⁰ C above the glass transition temperature of the coating.

Such heating can be carried out by treatment at a corresponding temperature (for example in an oven or belt furnace) or can additionally or exclusively also be carried out by heating with NIR radiation, in which case NIR radiation is electromagnetic radiation in the wavelength range from 760 nm to 2.5 μm, preferably from 900 to 1500 nm.

The coating compositions according to the invention can be used in particular as primers, fillers, pigmented topcoats and clearcoats in the field of industrial, in particular aircraft or large vehicle painting, wood, automotive, in particular OEM or automotive refinish, or decoration.

Ppm and percentages used in this specification, unless otherwise indicated, are by weight percent and ppm.

The following examples are intended to illustrate but not to limit the invention.

Examples

Preparation and Composition of Component A:

In a 2 liter vessel with pilot stirrer, the solvent was initially charged and warmed to 100 ⁰ C. Feed 1 was initially started and metered within 1 h 50 min. Subsequently, feed 2 was started and continued continuously over 2 h 45 min. After completion of feed 2 feed 3 was started at a temperature of 128 to 134 ⁰ C. The dosage of feed 3 was completed after 2 h 30 min. The polymerization was then continued for a further 3 hours at 133 to 136 ° C. At the end of the reaction, solvent was distilled off, so that the solids content was about 60%.

To split off the t-butyl group of 4- (t-butoxy) styrene units, 500 g of the solution polymer (only Examples 1 and 2) were heated to 50 ° C. and 5.9 g of hypophosphorous acid and 17.0 g of p-toluenesulfonic acid were added , The reaction mixture was stirred at 90 ^° C. for 4 h. It was then cooled to about 60 ⁰ C, diluted with 200 ml of i-propanol and neutralized with a total of 25 ml of 25% ammonia solution. The polymer solution was diluted with i-propanol and the precipitated salt was filtered off. The solvent was distilled off in vacuo. Subsequently, the resin was dissolved in n-butyl acetate to obtain a 50% resin solution. Two-component formulations:

Unless otherwise stated, the statements in the formulation refer to parts by weight in grams. To prepare the formulation, components A were dissolved in 50% n-butyl acetate, mixed with components B, and the catalyst DBTL (dibutyltin laurate) and optionally the photoinitiator added. The coatings were applied by means of a spiral blade to 150 microns on black colored glass plates, which enable gloss measurements. The layer thickness after drying and curing of the paint films was about 60 microns.

The coatings of test series "a" were cured by annealing at 150 ° C. for 30 minutes. Curing was checked by FT-IR spectroscopy on the films via the NCO absorption band at 2250 cm ^-1 .

The formulations of test series "b" additionally contained acrylate groups. Therefore, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one was added as a photoinitiator and the coatings after thermal curing of a UV exposure by means of two medium-pressure mercury UV lamps and an energy of 2 x 1200 mW / cm ² subjected. The fully cured paint films were each subjected twice to a scratch test and then annealed at 150 ° C for 30 min. After each step, the relative residual gloss was determined in percent by gloss measurement. The untreated lacquer films served as reference.

The scratch test was carried out by passing a Scrotch-Brite® nonwoven stretched onto a flat metal plate with a weight of 750 g over the paint surface. A double stroke corresponds to a double load

(*) As isocyanurate, an isocyanurate based on 1,6-hexamethylene diisocyanate having an NCO content (DIN EN ISO 11909) of about 22.0% by weight and a viscosity at 23 ° C. (in accordance with DIN EN ISO 3219) of approx 3200 mPas. (**) As polyisocyanatoacrylate was prepared analogously to WO 00/39183 as follows: 1, 6-hexamethylene diisocyanate (HDI) was provided under nitrogen blanketing and added to an amount of stabilized 2-hydroxyethyl acrylate, that the product has a content of acrylate groups of 2 mol / kg. The mixture was heated to 8O ⁰ C and was 200 wt. Ppm (based on diisocyanate) of the catalyst N ₁ N ₁ N-trimethyl-N- (2-hydroxypropyl) ammonium 2-ethylhexanoate to. The temperature slowly increased to 12O ⁰ C. It was allowed to react at this temperature and stopped the reaction by adding 250 ppm by weight (based on diisocyanate) of di-2- (ethylhexyl) phosphate at such a conversion that the final product after Removal of the monomer had an NCO content of 14.9%. The reaction mixture was subsequently freed from unreacted HDI in a thin-layer evaporator at 135 ^° C. and 2.5 mbar.

With the novel binder formulations 1 and 2, coatings were obtained which are capable of curing scratches under temperature. The gloss value increases significantly. This effect can be repeated. A direct comparison of the components A 1 and AV 1, which both have a comparable glass transition temperature, shows that lacquers with a marked self-healing effect can be obtained with the component A 1 according to the invention.

Claims

claims

1. coating compositions containing as structural components

A) at least one compound having isocyanate-reactive groups (Y) whose reaction product is more readily cleavable with isocyanate than the corresponding reaction product with a compound having primary hydroxy groups, and optionally at least one further isocyanate-reactive group (Z), which is different from (Y), as well as

B) at least one di- or polyisocyanate.

2. Coating composition according to claim 1, characterized in that the isocyanate-reactive groups (Y) are selected from the group consisting of phenols, imidazoles, triazoles, pyrazoles, oximes, N-hydroxyimides, Hydroxybenzoesäureestem, secondary amines, lactams, CH acid cyclic ketones, malonic esters and alkyl acetoacetates.

3. Coating composition according to one of the preceding claims, characterized in that the compound A) contains 2 to 20 groups (Y).

4. Coating composition according to one of the preceding claims, characterized in that the isocyanate-reactive groups (Z) are selected from the group consisting of primary hydroxyl groups, secondary hydroxyl groups, tertiary hydroxyl groups, primary amino groups and mercapto groups.

5. Coating composition according to claim 4, characterized in that up to 5.5 mol / kg of compound A) groups (Z) are contained in the compound A).

6. Coating composition according to one of the preceding claims, characterized in that the compound A is selected from the group of polyether, polyesters, polyurethanes and polyacrylates and their (meth) acrylates.

7. Coating composition according to one of claims 1 to 5, characterized in that the compound A comprises at least one polyacrylate.

8. Coating composition according to claim 7, characterized in that the polyacrylate contains as structural components

(a) at least one polymerizable compound having at least one group (Y) or at least one group which can be converted into a group (Y),

(b) at least one ester of a monoalcohol with (meth) acrylic acid,

253/05 GSZ / bw 19.07.05 (c) at least one compound different from (a) and (b) having exactly one free-radically polymerizable C =C double bond,

(d) optionally at least one ester of an alcohol having more than one hydroxy group with (meth) acrylic acid,

(e) optionally different from (d) compounds having more than one free-radically polymerizable C = C double bond.

9. Coating composition according to claim 8, characterized in that the synthesis components (a) at least one styrene derivative or cinnamic acid derivative of the formula (I)

wherein

R ¹ and R ⁴ independently of one another are hydrogen or methyl,

R ⁴ additionally carboxyl (-COOH) or an ester group (-COOR ⁵ ),

R ² and R ⁵ independently of one another Ci to C ₂₀ -AlkVl,

R ^{3 is} hydrogen, halogen, C ₁ to C _{2 o} -alkyl, C ₁ to C ₂₀ -alkyloyl, C ₆ to C ₂₀ -aryloyl,

Ci to C ₂₀ -alkyl kyloxycarbonyl, C ₆ to C ₂₀ aryloxycarbonyl, Ci to C ₂₀ -

Alkylamidocarbonyl, C ₆ to C ₂₀ arylamidocarbonyl or trisubstituted SiIyI and p is 0 to 2, preferably 0 to 1 and particularly preferably 0,

where the groups -COOR ⁵ and -OR ^{3 can} also together form a grouping -COO-,

contains.

10. Coating composition according to claim 9, characterized in that the styrene derivative is selected from the group consisting of 4-methoxystyrene, 4-silyloxystyrene, 4-tert-butoxystyrene, 4-tert-amyloxystyrene, 4-acetoxystyrene 4-hydroxycinnamic acid or coumarin ,

11. Coating composition according to claim 9, characterized in that at least one compound (c) is selected from the group consisting of styrene, vinyl acetate, acrylonitrile, acrylic acid, N-vinylpyrrolidone, N-vinylcaprolactam and E- ethylvinylether present.

12. Coating composition according to one of the preceding claims, characterized in that component B contains at least one polyisocyanate containing at least one compound having at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group, said compound at least partially via allophanate natgruppen is bound.

13. Coating composition according to one of the preceding claims, further comprising - optionally at least one compound having one or more than one free-radically polymerizable double bond,

optionally at least one photoinitiator and

- If necessary, further paint typical additives.

14. A process for the preparation of coatings, characterized in that binder components A and B according to one of claims 1 to 12 in a ratio of (Y) and (Z) groups (in total) in A to isocyanate groups in B of 5: 1 to 1: 2 mixed and reacted.

15. The method according to claim 14, characterized in that optionally additionally radiation-cured, the coating composition.

16. Use of coating compositions according to one of claims 1 to 13 for the production of coatings which have a reparable by energy input effect.

17. A coating obtainable by mixing and reacting binder components A and B according to any one of claims 1 to 12.

18. Coating according to claim 17, characterized in that it has a glass transition temperature of -30 to 120 ⁰ C.

19. A process for the thermal treatment of coatings according to one of

Claims 17 to 18, characterized in that the coatings are heated for a period of at least 10 minutes to a temperature which is at least 25 ° C above the glass transition temperature of the coating.

20. The method according to claim 19, characterized in that one carries out the heating with NIR radiation.