CA2001003C - Olefinically unsaturated compounds, a process for the production of copolymers containing isocyanate groups, the copolymers thus obtained and coating compositions or sealing compounds containing the copolymers - Google Patents

Abstract

Polymers based on olefinically unsaturated compounds having a molecular weight from 252 to 800 which contain (i) 7 to 24% by weight of urethane moieties and (ii) 5 to 17% by weight of isocyanate moieties bonded to tertiary carbon atoms which in turn form a part of a cycloaliphatic ring.
are useful as one of the components of a two component binder system for coating compositions or sealing compositions hardenable by the weight of moisture.

Description

~~o~.v~~
OLEFINICALLY UNSATURATED COMPOUNDS A PROCESS FOR THE
PRODUCTION OF COPOLYMERS CONTAINING ISOCYANATE
GROUPS. THE COPOLYMERS THUS OBTArNED AND
COATING COMPOSITIONS OR SEALING COMPOUNDS
CONTAINING THE COPOLYMERS
This inventian relates to olefinically unsaturated compounds containing isocyanate groups attached to tertiary carbon atoms, to a process fox the production of copolymers using these compounds, to the corresponding copolymers and to coating compositions or sealing compounds containing the copolymers as binder component.
BACKGROUND OF THE INVENTION
Copolymers containing free isocyanate groups and their use as binder component in Two-cor.~.ponent ccating composi tions are known.
Thus, DE-OSS 3 245 294, 3 245 295 and 3 245 298 for example describe isocyanate-functional copolymers which are produced using vinyl isocyanate as unsaturated NCO-func-tional monomer, while US-PS 3,004,527, 4,219,632, 4,401, 794 and 4,510,298 describe isocyanate-functional copolymers which are produced using isocyanatoethyl methacrylate as NCO-functional monomer. Where these two NCO functional monomers are used for the production of copolymers, the copolymers obtained contain primary isocyanate groups.
However, these primary isocyanate groups are too reactive to the nitrogen-containing crosslinking agents commonly used, such as for example polyketimines or polyoxazolanes, so that the pot lives obtained where the copolymers are used in two-component coating systems are not long enough.
Copolymers containing chemically incorporated, ter tiary aliphatic isocyanate groups are described, for ex-ar.~le, in US 4 754 011, CA 1 246 783, J 61 120-667-A
(C.A. 105 192 987), J 61 120-862-A (C.A. 105 192 967), J 61 126-177-A (C.A. 105 192 991) or J 61 126-178-A (C.A. 105 Le A 26 444 1 r ~~0~:~~3 192 992). In these cases, the isocyanate group is intro-duced through the use of m-isopropenyl-a, a-dimethylbenzyl isocyanate as the isocyanate-functional copolymerizable monomer. However, where this monomer is used for radical copolymerization with other unsaturated monomers, such as for example esters of (meth)acrylic acid or styrene, rel-atively large quantities of residual monomers are always found because the quasi-a-methyl styrene structure of the m-isopropenyl-a, a-dimethylbenzyl isocyanate copolymerizes only inadequately with the other monomers mentioned above on account of unfavorable copolymerization parameters.
Even corresponding reactivation with additional quantities of radical initiators fails to produce any significant in-crease in the monomer conversion, i.e. any real reduction in the residual monomer content. Large amounts of residual monomers in binders for coating purposes are of course harmful to health, so that binders are unsuitable for this application.
Japanese specification 54 419 as laid open (C. A. _100 211 228).

2 0 describes copolymers containing isocyanate groups which have been produced using reaction products of hydroxyethyl acrylate with diisocyan-atotoluene or with diisocyanatohexane. These copolymers are intended to be used for the production of adhesives.
Quite apart from the problems involved in the production of olefinically unsaturated monomers from hydroxyethyl acryl-ate and diisocyanates containing isocyanate groups of the same or substantially the same reactivity (the reaction of the starting materials mentioned generally always leads to large quantities of unwanted 2:1 adducts),~the isocyanate groups present in the copolymers of this prior publication are those of comparatively high reactivity which are unsuitable for the production of two-component lacquers in combination With nitrogen-containing crosslinking agents on account of the inadequate pot lives.
Le A 26 444 2 i~~~~.~~a~
Basically the same observations apply to the copoly-mers according to Japanese specification 267 523 as laid open (C.A. 106 157 585) which are also intended for the production of adhesives and in the production of which reaction products of isophorone diisocyanate with hydroxyethyl acrylate are used as the monomers containing isocyanate groups.
Accordingly, the object of the present invention is to provide new, olefinically unsaturated isocyanates suitable as isocyanate-functional monomers and also copolymers containing them as constituents which are not attended by the disadvantages of the prior art.
This object is achieved by the provision of the ole finically unsaturated monoisocyanates described in detail hereinafter and the copolymers produced with them.
BRIEF DESCRIPTION OF THE INVENTION
The present invention relates to olefinically unsat urated compounds having a molecular weight in the range from 252 to 800, characterized by (i) a content of 7 to 24% by weight of urethane groups and (ii) a content of 5 to 17% by weight of isocyanate groups which are attached to tertiary carbon atoms which in turn are part of a cycloaliphatic ring.
The present invention also relates to a process for the production of copolymers containing isocyanate groups, which have a weight average molecular weight of 1,000 to 100,000, by radically initiated copolymerization of ole-finically unsaturated monomers free from isocyanate groups with olefinically unsaturated monoisocyanates in such a quantity that the resulting copolymers contain from 0.1 to 13% by weight of chemically incorporated isocyanate groups for an average NCO functionality of the copolymers of at least 2, characterized in that unsaturated compounds of the type according to the invention are used as the olefinic-T~ A 2f 444 ~~D1.U(~~
ally unsaturated monoisocyanates.
The present invention also relates to copolymers con-taining isocyanate groups having a weight average molecular weight of from 1,000 to 100,000 of olefinically unsaturated compounds, characterized by an average NCO functionality of at least 2 and a content of 0.1 to 13% by weight of iso-cyanate groups attached to tertiary carbon atoms which, in turn, are part of a cycloaliphatic ring.
Finally, the invention also relates to coating compo sitions and sealing compounds containing as binder a two component system of a polyisocyanate component and a poly amine component containing blocked amino groups, character ized in that the polyisocyanate component consists of co polymers of the last-mentioned type.
DETAILED DESCRIPTION OF THE INVENTION
The olefinically unsaturated compounds according to the invention are monoolefinically unsaturated monoisocyan-ates which preferably have a molecular weight of from about 252 to 800, i.e. an NCO content of 5 to 17% by weight, and a content of 7 to 24% by weight of urethane groups. The isocyanate group in the compounds according to the inven-tion is attached to a tertiary carbon atom which, in turn, is part of a cycloaliphatic ring.
The olefinically unsaturated compounds according to the invention are prepared by reaction of special starting diisocyanates, which contain one aliphatically bound pri mary isocyanate group and one cycloaliphatically bound tertiary isocyanate group, with hydroxyl-functional, ole finically unsaturated compounds in such a way that one molecule hydroxyl compound is used per mol diisocyanate.
Polymerization inhibitors, such as for example 2,6-di-tert.-butyl-4-methylphenol or hydroquinone monomethyl ether, may optionally be added.
The starting diisocyanates are aliphatic-cycloali-phatic diisocyanates having an NCO content of from 20 to 50% by weight and preferably from 30 to 48% by weight _4_ T '. T '1 C A A A

n s~~~.~~~
which, in addition to a sterically unhindered, aliphatic-ally bound isocyanate group, may contain a sterically hin-dered isocyanate group attached to a tertiary carbon atom which, in turn, is part of a cycloaliphatic ring. Suitable starting diisocyanates are those corresponding to formula (I) or mixtures of those corresponding to formula (I) R1 \ / NCO
C
RZ\ ~ R3 (I) C
Ro / ~ ( R5 ) n-CHZNCO
in which R1 is an alkyl radical containing 1 to 4 carbon atoms, preferably a methyl radical, RZ and R3 are the same or different and represent a difunc-tional, linear or branched saturated hydrocarbon radi-cal containing 1 to 4 and preferably 1 to 3 carbon atoms, the sum of the carbon atoms in these radicals preferably being from 3 to 6 and more especially 4 or 5, R4 represents hydrogen or an alkyl radical containing 1 to 4 carbon atoms, preferably hydrogen or a methyl radical, RS is a difunctional, linear or branched, saturated ali-phatic hydrocarbon radical containing 1 to 4 and more especially 1 to 3 carbon atoms and n = 0 or 1.
Particularly preferred diisocyanates are, for example, 1-isocyanato-1-methyl-4(3)-isocyanatomethyl cyclohexane, which is generally present as a mixture of the 4- and 3-isocyanatomethyl isomers, 1-isocyanato-1-methyl-4-(4-iso-cyanatobut-2-yl)-cyclohexane or 1-isocyanato-1,2,2-trime-thyl-3-(2-isocyanatoethyl)-cyclopentane. However, other Le A 26 444 5 suitable diisocyanates are, for example, 1-isocyanato-1-n-butyl-3-(4-isocyanatobut-1-yl)-cyclopentane, 1-isocyanato-1-ethyl-4-n-butyl-4-(4-isocyanatobut-1-yl)-cyclohexane or 1-isocyanato-1,2-dimethyl-3-ethyl-3-isocyanatomethylcyclo-pentane.
The corresponding diisocyanates are described in de-tail in EP-A-0 153 561 and may be produced by the processes described therein.
Suitable hydraxyfunctional, olefinically unsaturated l0 compounds are any organic compounds containing an alcoholic hydroxyl group and an olefinic double band. These com pounds preferably have a molecular weight of 58 to 600.
Suitable compounds of this type are, for example, hydroxy ethyl acrylate, 2- and 3-hydroxypropyl acrylate, 2-, 3- and 4-hydroxybutyl acrylate, hydroxyethyl methacrylate, 2- and 3-hydroxypropyl methacrylate, hydroxyethyl vinyl ether, 2-, 3- and 4-hydroxybutyl vinyl ether, allyl alcohol, reac-tion products of unsaturated carboxylic acids, such as acrylic acid for example, with epoxides, reaction products of the hydroxyfunctional, olefinically unsaturated monomers mentioned by way of example above with E-caprolactone, bu-tyrolactone, ethylene oxide or propylene oxide.
The reaction of the special diisocyanates with the hy droxyfunctional, olefinically unsaturated monomers mention ed by way of example above is best carried out in such a way that 1 mol hydroxyl compound is used per mol diisocyan-ate.
The reaction may be carried out both in the presence and in the absence of a solvent inert to isocyanate and hy-droxyl groups. The reaction temperature is in the range from 0 to 100°C and preferably in the range from 20 to 80°C. In addition, catalysts such~as, for example, ter-tiary amines, organic zinc or tin compounds or other com-pounds which catalyze a urethanization reaction, may also be added in small c3uantities. The reaction products ob-he A 26 444 6 s~~~~.~~.~
tained are generally monoadducts of the special starting diisocyanates and the particular hydroxyfunctional, ole-finically unsaturated compounds used which may be used without additional working up or purification processes for the production of the isocyanate-functional copolymers ac-cording to the invention.
The monomers Free from isocyanate groups which are co-polymerized with the olefinically unsaturated monoisocyan-ates according to the invention in the process according to the invention are the usual, preferably monoolefinically unsaturated monomers which are already used as monomers in the process according to the prior art mentioned above.
Typical examples are esters of acrylic and methacrylic acid, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tent-butyl acrylate, 2-ethyl hexyl acrylate, cyclohexyl methacrylate, methyl methacry-late, n-butyl methacrylate, isobutyl methacrylate or 2-ethyl hexyl methacrylate: aromatic vinyl compounds, such as for example styrene, vinyl toluene, a-methyl styrene, cx-ethyl styrene, nucleus-substituted diethyl styrenes op-tionally representing isomer mixtures, isopropyl styrenes, butyl styrenes and methoxystyrenes; vinyl ethers, such as for example ethyl vinyl ether, n-propyl vinyl ether, iso-propyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether; vinyl esters, such as for example vinyl acetate, vinyl propionate and vinyl butyrate.
Mixtures of the monomers mentioned by way of example may of course be used to carry out the copolymerization.
The copolymers are produced, i.e. the process accord-ing to the invention is carried out, by copolymerization of the monomers mentioned by way of example, the olefinically unsaturated monoisocyanates essential to the invention being used in such a quantity that the resulting copolymers contain from 0.1 to 13% by weight and preferably from 1 to 10% by weight of free isocyanate groups. In practice, this Le A 26 444 ~o~~~~~
means that, in general, the ratio by weight of monomers containing isocyanate groups to monomers free from isocyan-ate groups of the type mentioned by way of example is from 0.01:1 to 24:1. The copolymerization is carried out by standard radical polymerization processes, such as for ex-ample bulk or solution polymerization. The monomers are copolymerized at temperatures in the range from 60 to 200 ° c and preferably at temperatures in the range from 80 to 160°C in the presence of radical formers and, optionally, molecular weight regulators.
The copolymerization is preferably carried out in inert solvents at solids contents of 30 to 95% by weight.
Suitable solvents are, for example, aromatic hydrocarbons, such as benzene, toluene, xylene; esters, such as ethyl acetate, butyl acetate, methyl glycol acetate, ethyl glycol acetate, methoxypropyl acetate: ethers, such as tetrahydro-furan, dioxane, diethylene glycol dimethyl ether; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ke-tone.
The copolymerization may be carried out continuously or discontinuously. Normally, the monomer mixture and the initiator are introduced uniformly and continuously into a polymerization reactor and the corresponding quantity of polymer is continuously removed at the same time. It is thus possible with advantage to produce chemically sub-stantially uniform copolymers. Chemically substantially uniform copolymers may also be produced by allowing the re-action mixture to run at a constant rate into a stirred vessel without removal of the polymer.
It is also possible, for example, initially to intro-duce part of the monomers, for example in solvents of the type mentioned, and to add the remaining monomers and aux-iliaries either separately or together to the monomers ini-tially introduced at the reaction temperature.
In general, the polymerization is carried out at an Le A 26 444 8 i~~~~.~~a~
excess pressure of 0 to 20 bar. The initiators are used in quantities of 0.05 to 15% by weight, based on the total quantity of monomers.
Suitable initiators are standard radical initiators such as, for example, aliphatic azo compounds, such as azo diisobutyronitrile, azo-bis-2-methyl valeronitrile, 1,1' azo-bis-1-cyclohexane nitrile and 2,2'-azo-bis-isobutyric acid alkyl ester; symmetrical diacyl peroxides, for example acetyl, propionyl or butyryl peroxide, bromine-, vitro-, methyl- or methoxy-substituted benzoyl peroxides, lauryl peroxides; symmetrical peroxydicarbonates, for example diethyl, diisopropyl, dicyclohexyl and also dibenzoyl per-oxydicarbonate: tart.-butyl peroctoate, tart.-butyl per-benzoate or tart.-butyl phenyl peracetate, and also peroxy-carbonates such as, for example, tart.-butyl-N-(phenylper-oxy)-carbonate or tart.-butyl-N-(2-,3- or 4-chlorophenyl-peroxy)-carbonate; hydroperoxides, such as for example tart.-butyl hydroperoxide, cumene hydroperoxide; dialkyl peroxides, such as dicumyl peroxide, tart.-butyl cumyl peroxide or di-tart.-butyl peroxide.
To regulate the molecular weight of the copolymers, standard regulators may be used during their production, including for example tart.-dodecyl mercaptan, n-dodecyl mercaptan or diisopropyl xanthogene disulfide. The molec-ular weight regulators may be added in quantities of from 0.1 to 10% by weight, based on the total quantity of mono-mars.
In addition, the copolymers have a molecular weight (weight average), as determined by gel permeation chroma-tography, of from 1,000 to 100,000, preferably from 1,500 to 75,000 and more preferably from 2,000 to 50,000.
The solutions of the copolymers obtained during the copolymerization reaction may be used in accordance with the invention without further working up. However, it is of course also possible to free the copolymers from any Le A 26 444 9 residues of unreacted monomers still present and from solvent by distillation and to use the copolymers obtained as distillation residue in accordance with the invention.
Two-component systems of a polyisocyanate component A) and a hardener B) are present as binder in the coating com positions or sealing compounds according to the invention.
The polyisocyanate component A) is one of the isocyanate functional copolymers according to the invention. The hardener component B) is an organic polyamine containing blocked amino groups. °'Blocked amino groups" are under-stood to be groups which react with water with release of primary and/or secondary amino groups. Particularly pre-ferred blocked polyamines B) are compounds which contain aldimine, ketimine, oxazolane, hexahydropyrimidine and/or tetrahydroimidazole groups and which, at the same time, may also contain several of these groups.
The blocked polyamines B) have a weight average molec-ular weight in the range from 86 to 10,000 and preferably in the range from 250 to 4,000 and, on a statistical aver-age, contain from 1 to 50, preferably from 2 to 10 and more preferably from 2 to 4 structural units corresponding to the following general formulae ~ ~~Re I R ~ C NLRB and/or R ~C=N--> > >
(II) (III) (IV) in which R6 and R~ may be the same or different and represent hydro-gen, aliphatic hydrocarbon radicals containing from 1 to 18 carbon atoms, cycloaliphatic hydrocarbon radi-cals containing from 5 to 10 carbon atoms, araliphatic hydrocarbon radicals containing from 7 to 18 carbon Le A 26 444 10 ~oo~:oo~
atoms or phenyl radicals; the two substituents Rs and R~ may also form a 5-membered or 6-membered cycloali phatic ring together with the adjacent carbon atom and, preferably, at most one of these substituents is hydrogen, and R8 is a difunctional aliphatic hydrocarbon radical con-taining 2 to 6 carbon atoms, with the proviso that 2 or 3 carbons are arranged between the twa nitrogen atoms.
The molecular weights mentioned may be determined by the method of gel permeation chromatography (molecular weights above 1,000) or from the stoichiometry of the starting materials used for the production of the compounds (molecular weights up to 1,000).
Components B) preferably used are, for example, those containing hexahydropyrimidine or tetrahydroimidazole structures corresponding to general formula (II), in which Rs and R~ may be the same or different and represent ali-phatic hydrocarbon radicals containing 2 to ZO carbon atoms; one of these substituents may also be hydrogen and R~ may be an optionally alkyl-substituted ethylene or tri-methylene radical.
The blocked polyamines of the type mentioned are pro duced in known manner by reaction of corresponding alde hydes or ketones with the corresponding polyamines.
Aldehydes or ketones suitable for the production of the compounds B) containing hexahydropyrimidine or tetra-hydroimidazole groups are, for example, those corresponding to the following general formula:
Rs C=O
R~
which preferably have a molecular weight of from 72 to 200 Le A 26 444 11 ~r~~~~o~
(ketones) or from 58 to 250 (aldehydes).
Examples of such aldehydes and ketones are acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketane, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, methyl isoamyl ketone, methyl heptyl ketone, diethyl ketone, ethyl butyl ketone, ethyl amyl ke-tone, diisopropyl ketone, diisobutyl ketone, cyclohexanone, isophorone, methyl-tert.-butyl ketone, 5-methyl-3-hepta-none, 4-heptyl ketone, 1-phenyl-2-propanone, acetophenone, methyl nonyl ketone, 3,3,5-trimethyl cyclohexanone, formal-dehyde, acetaldehyde, propionaldehyde, butyraldehyde, iso-butyraldehyde, trimethyl acetaldehyde, 2,2-dimethyl propan-al, 2-ethyl hexanal, 3-cyclohexene-1-carboxaldehyde, hexan-al, heptanal, octanal, valeraldehyde, benzaldehyde, tetra-hydrobenzaldehyde, hexahydrobenzaldehyde, acrolein, croton-aldehyde, propargylaldehyde, p-tolylaldehyde, 2-methyl pen-tanal, 3-methyl pentanal, phenyl ethanal, 4-methyl pen-tanal.
Aldehydes and ketones preferably used for the produc-tion of the compounds containing hexahydropyrimidine or tetrahydroimidazole groups are butyraldehyde, isobutyral-dehyde, trimethyl acetaldehyde, 2,2-dimethyl propanal, 2-ethyl hexanal, hexanal, 3-cyclohexane-1-carboxaldehyde, heptanal, octanal, hexahydrobenzaldehyde, 2 -methyl pentan-al, cyclohexanone, cyclopentanone, methyl isopropyl ketone, acetone, 3,3,5-trimethyl cyclohexanone and methyl cyclo-hexanone.
It is of course also possible to use mixtures of dif ferent ketones and aldehydes and also mixtures of ketones with aldehydes to obtain special properties.
The polyamines used for the production of the com-pounds containing hexahydropyrimidine or tetrahydroimidaz-ole groups are, in particular, organic compounds containing at least two primary and/or secondary amino groups.
Suitable polyamines are, for example, those corre-Le A 26 444 12 sponding to the following general formula R9-NH-R8-NH-Rlo in which RB is as defined above and Ra and Rlo may be the same or different and represent hydro-gen, aliphatic hydrocarbon radicals containing from 1 to 10 and preferably from 1 to 4 carbon atoms, cyclo-aliphatic hydrocarbon radicals containing from 5 to 10 and preferably 6 carbon atoms or aromatic hydrocarbon radicals containing from 7 to 15 and preferably 7 car-bon atoms, the hydrocarbon radicals mentioned, partic-ularly the aliphatic hydrocarbon radicals mentioned, optionally containing heteroatoms, such as oxygen, nitrogen or sulfur in the form of ether, ester, amide, urethane, oxirane, ketone, lactam, urea, thioether, thioester or lactone groups; the radicals may also contain reactive hydroxyl or amino groups.
Particularly preferred polyamines are those in which R9 and Rxo may be the same or different and represent hydro-gen and/or C1-Cs alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert.-butyl, n-pentyl or n-hexyl radicals, or in which at least one of the sub-stituents Rg and R9 is a group of the type obtained by addition of an amine hydrogen atom onto an olefinically unsaturated compound. Olefinically unsaturated compounds suitable for the production of modified polyamines such as these are, for example, derivatives of (meth)acrylic acid, such as esters, amides, nitriles or, for example, aromatic vinyl compounds, such as styrene, a-methyl styrene, vinyl toluene or, for example, vinyl esters, such as vinyl ace-tate, vinyl propionate, vinyl butyrate or, for example, vinyl ethers, such as ethyl vinyl ether, polyvinyl ether, butyl vinyl ether, or monoesters and diesters of fumaric Le A 26 444 13 acid, malefic acid or tetrahydrophthalic acid.
Rs and/or Rlo may also represent an aminoalkyl or hy-droxyalkyl radical containing, for example, 2 to 4 carbon atoms.
Especially preferred polyamines are ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,2- and 1,3-butylenediamine, diethylenetriamine and derivatives of these polyamines.
Compounds containing oxazolane groups of general formula (III) suitable for use as component B) are pref erably those in which Rs and R~ may be the same or differ ent and represent hydrogen or aliphatic hydrocarbon radi cals containing 1 to 18 and more especially 1 to 8 carbon atoms, or in which the substituents Rs and R~, together with the carbon atom of the heterocyclic ring, form a cycloali-phatic ring containing in all from 4 to 9 carbon atoms, more especially a cyclohexane ring, with the proviso that at most one of the substituents Rs and R, is hydrogen, and Rs is an alkenyl radical containing 2 to 4 and preferably 2 to 3 carbon atoms, with the proviso that at least 2 carbon atoms are arranged between the oxygen atom and the nitrogen atom.
The oxazolane-containing component B) is produced in known manner by reaction of corresponding aldehydes or ke-tones having the following formula Rs C=O
R~
with suitable hydroxyamines of the type mentioned in more detail hereinafter.
Basically, suitable aldehydes or ketones are those of the type already mentioned by way of example in the fore going. Preferred aldehydes or ketones in this case are ~e A 26 444 14 butyraldehyde, isobutyraldehyde, trimethylacetaldehyde, 2,2-dimethyl propanal, 2-ethyl hexanal, 3-cyclohexene-1-carboxaldehyde, hexahydrobenzaldehyde, cyclopentanone, cy-cloh:exanone, methyl cyclopentanone, methyl cyclohexanone, 3,3,5-trimethyl cyclohexanone, cyclobutanone, methyl cyclo-butanone, acetone, methyl ethyl ketone and methyl isobutyl ketone.
It is of course also possible to use mixtures of dif-ferent ketones and aldehydes and also mixtures of ketones with aldehydes to obtain special properties.
Hydroxyamines are, in particular, organic compounds which contain at least one aliphatic amino group and at least one aliphatically bound hydroxyl group. The hydroxy-amines generally have a molecular weight in the range from 61 to 500 and preferably in the range from 61 to 300.
Suitable hydroxyamines are, for example, bis-(2-hydroxyethyl)-amine, bis-(2-hydroxypropyl)-amine, bis-(2-hydroxybutyl)-amine, bis-(3-hydroxypropyl)-amine, bis-(3-hydroxyhexyl)-amine, N-(2-hydroxypropyl)-N-(2-hydroxy-ethyl)-amine, 2-(methylamino)-ethanol, 2-(ethylamino) ethanol, 2-(propylamino)-ethanol, 2-(butylamino)-ethanol, 2-amino-2-methyl-1-propanol,2-amino-2-ethyl-1-propanol,2 amino-2-propyl-1-propanol, 2-amino-2-methylpropane-1,3 diol, 2-amino-3-methyl-3-hydroxybutane, propanolamine, ethanolamine.
Particularly preferred hydroxyamines are bis-2-hy-droxyethyl)-amine, bis-(2-hydroxypropyl)-amine, bis-(2-hy-droxybutyl)-amine, bis-(3-hydroxyhexyl)-amine, 2-(methyl-amino)-ethanol, 2-(ethylamino)-ethanol, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1-propanol, propanolamine and ethanolamine.
Preferred compounds containing aldimine or ketimine groups are those which contain structural units having the following general formula Le A 26 444 15 ~~~.~.~~,3 R6 a ' c=rr- ( Iv) R~
in which Rs and R~ may be the same or different and represent hydro-gen or aliphatic hydrocarbon radicals containing 1 to 8 carbon atoms which may also be attached together l0 with the carbon atom to form a cycloaliphatic ring, more especially a cyclohexane ring.
In principle, the aldehydes or ketones already men-tioned by way of example in the foregoing are suitable for the production of these compounds. Preferred aldehydes or ketones in this case are butyraldehyde, isobutyraldehyde, trimethyl acetaldehyde, 2,2-dimethyl propanal, 2-ethyl hexanal, 3-cyclohexene-1-carboxaldehyde, hexahydrobenz-aldehyde and, in particular, ketones which have a boiling point below 170°C and which show high volatility at room temperature, including for example methyl isobutyl ketone, methyl isoprapyl ketone, diethyl ketone, diisobutyl ketone, methyl tert.-butyl ketone.
It is of course also possible to use mixtures of dif ferent ketones or aldehydes and also mixtures of ketones with aldehydes to obtain special properties.
The polyamines used for the production of component B) containing ketimine or aldimine groups are, in particular, organic compounds containing at least two aliphatically and/or cycloaliphatically bound primary amino groups. How-ever, the use of polyamines containing aromatic amino groups is also possible, although less preferred. The polyamines generally have a molecular weight of from 60 to 500 and preferably from 88 to 400, although it is also possible to use relatively high molecular weight, amino-terminated prepolymers as the polyamine component in the ~e A 26 444 16 production of component B).
Particularly preferred polyamines are diprimary ali-phatic or cycloaliphatic diamines such as, for example, tetramethylenediamine, hexamethylenediamine, isophorone-diamine, bis-(4-aminocyclohexyl)-methane, bis-aminomethyl hexahydro-4,7-methanoindane, 1,4-cyclohexanediamine, 1,3-cyclohexandiamine, 2-methyl cyclohexanediamine, 4-methyl cyclohexanediamine, 2,2,5-trimethyl hexanediamine, 2,2,4-trimethyl hexanediamine, butane-1,4-diol bis-(3-aminopro-pyl)-ether, 2,5-diamino-2,5-dimethyl hexane, bis-amino-methyl cyclohexane, bis-(4-amino-3,5-dimethylcyclohexyl)-methane or mixtures thereof.
Tetramethylenediamine, hexamethylenediamine, isophor onediamine, bis-aminomethyl cyclohexane, 1,4-cyclohexane diamine, bis-aminomethyl hexahydro-4,7-methanoindane and bis-(4-aminocyclohexyl)-methane are particularly preferred.
In addition tp these preferred diamines, prepolymers terminated by primary amino groups, i.e. compounds contain ing at least two terminal amino groups and having a molec ular weight of from 500 to 5,000 and preferably from 500 to 2,000, may also be used for the production of the aldimines or ketimines. These compounds include, for example the aminopolyethers known per se from polyurethane chemistry, of the type described for example in EP-A 0 081 701, or re-action products - for example containing amide, urea, ure-thane or secondary amino groups - of at least difunctional carboxylic acids, isocyanates or epoxides with diamines of the type mentioned by way of example above, these reaction products also containing at least two primary amino groups.
Mixtures of such relatively high molecular weight poly-amines with the low molecular weight polyamines mentioned may also be used.
Aromatic polyamines which, in principle, are also suitable, but less preferred, for the production of the aldimines or ketimines include, for example, 2,4- and 2,6-Le A 26 444 17 W~Q~.~fl;~
diaminotoluene, 1,4-diaminobenzene or 4,4'-diaminodiphenyl methane.
Component B), which may contain aldimine, ketimine, oxazolane, hexahydropyrimidine or tetrahydroimidazole groups, is prepared by reaction of the starting components, generally in such quantitative ratios that the amino com-pounds are present in a 1 to 1.5-fold molar excess, based on the carbonyl groups, according to the particular reac-tion required. Catalytic quantities of acidic substances, such as for example p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, aluminium(III) chloride, tin com-pounds, may optionally be used to accelerate the reaction.
The reaction is generally carried out at a temperature in the range from 60 to 180°C, the reaction being carried out in the presence of an entraining agent to remove the water of reaction until the calculated quantity of water has been eliminated or until no more water is eliminated.
The entraining agent and any unreacted starting mater-ials present axe then removed by distillation. Suitable entraining agents are, for example, toluene, xylene, cy clohexane, octane. The crude products thus obtained may be used without further purification as component B) for the production of the binder combinations. Where the purity of component B) has to meet particularly stringent require ments, it is also possible to obtain components B) in pure form, for example by distillation.
The preferred, blocked polyamines of component B) also include those which contain 2 to 10 structural units corre-sponding to general formula (II), (III) or (IV) and which are obtained by linkage of different compounds containing such structural units to form, for example, ester, ether, amide, urea and/or urethane bonds.
The compounds containing structural units correspond ing to the above formulae, which are to be linked to one another in this way, must contain at least one primary or Le A 26 444 18 secondary amino group or at least one hydroxyl group in non-blocked form. Suitable modifying agents, which are suitable for linking the compounds mentioned, are for example, polyisocyanates, polyepoxides, polycarboxylic acids and polyacryloyl compounds.
Polyisocyanates suitable for this modification reac-tion are, for example, aliphatic, cycloaliphatic, arali-phatic, aromatic and heterocyclic polyisocyanates of the type described, for example, by W. Siefken in 5ustus Liebigs Annalen der Chemie, 562, pages 75 to 1346, for example 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyan-atomethyl cyclohexane, 2,4- and 2,6-hexahydrotolylene di-isocyanate, hexahydro-1,3- and -1,4-phenylene diisocyanate, perhydro-2,4'- and/or -4,4'-Biphenyl methane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluyene diisocyanate, 2"6-toluylene diisocyanate, di-phenyl methane-2,4°- and/or -4,4'-diisocyanate, naphthy-lene-1,5-diisocyanate, mixtures of these and other polyiso-cyanates, palyisocyanates containing carbodiimide groups (for example DE-OS 10 92 007), polyisocyanates containing allophanate groups (for example GB-P 944,890), polyiso-cyanates containing isocyanurate groups (for example DE-PS
10 22 789, DE-PS 12 22 067), polyisocyanates containing urethane groups (for example US-P 3,394,164) or polyiso-cyanates obtained by reaction of at least difunctional hy-droxy compounds with excess, at least difunctional iso-cyanates, polyisocyanates containing biuret groups (for example DE-PS 11 01 394) and prepolymers or polymers con-taining at least two isocyanate groups.
Representatives of these compounds, which may be used in accordance with the invention, are described, for ex ample, in High Polymers, Vol. XVI, "Polyurethanes, Chem Le A 26 444 19 ~D(~~.~~~
istry and Technology", Interscience Publishers, New York/
London, VoI. I, 1962, pages 32 to 42 and 45 to 54 and Vol.
II, 1964, pages 5 - 6 and 198 - 199 and in Kunststoff Hand-buch, Vol. VII, Vieweg-Hochtlen, Carl-Hanser-Verlag, Miinchen, 1966, pages 45 to 72.
Polyepoxides suitable for the modification reaction mentioned above are, for example, aliphatic, cycloalipha-tic, araliphatic, aromatic and heterocyclic compounds con-taining at least two epoxide groups, such as for example epoxidized esters of aliphatic, polybasic acids with un-saturated monohydric alcohols, glycidyl ethers of poly-hydroxy compounds, glycidyl esters of polycarboxylic acids, copolymers containing epoxide groups.
Polycarboxylic acids suitable for the modification reaction are, for example, aliphatic, cycloaliphatic, aral iphatic, aromatic and heterocyclic compounds containing at least two carboxyl groups, such as for example adipic acid, dimeric fatty acid, phthalic acid, terephthalic acid, iso phthalic acid, fumaric acid, malefic acid, succinic acid, trimellitic acid, pyromellitic acid, copolymers containing (meth) aczylic acid, acidic polyesters or acidic polyamides.
Instead of the acids mentioned by way of example, it is also possible to use the corresponding anhydrides (pro viding the acids in question form intramolecular anhy 2S Brides) or the corresponding simple alkyl esters, particu larly methyl esters, fox the modification reaction.
Compounds containing at least two olefinic double bonds of the type mentioned above, which are suitable for the modification reaction, are in particular derivatives of acrylic acid or methacrylic acid, such as far example hexanediol-bis-(meth)acrylate, trimethylolpropane tris-(meth)acrylate, gentaerythritol tetra-(meth)acrylate, OH-functional polyesters or polyacrylates esterified with acrylic acid, diethylene glycol dimethacrylate, reaction products of polyisocyanates with hydroxyalkyl (meth)acry-Le A 26 444 20 i~~~~.~~a~
late.
zn the modification reaction to produce components B) of relatively high functionality, it is also possible to use mixtures of different blocked amines which contain at least one free hydroxyl or amino group reactive to the modifying agent.
Polyamines containing ketimine or aldimine groups, which still contain at least one free primary or secondary amino group or a free hydroxyl group, are obtained, for example, by reaction of at least difunctional amines with ketones and/or aldehydes in such equivalent ratios that at least one amino group remains free.
Even where, for example, polyamines containing at least one secondary amino group in addition to primary amino groups are used, the reaction with aldehydes or ketones results in the formation of aldimines or ketimines which contain at least one free secondary amino group (where an equivalent ratio of primary amino groups to car-bonyl groups of 1:1 has been used) or which contain free primary amino groups in addition to at least one secondary amino group (where the carbonyl compounds have been used in less than the equivalent quantity, based on the primary amino groups). Primary/secondary polyamines such as these are, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylene tetramine.
Compounds containing oxazolane groups, which also have at least one reactive primary or secondary amino group or a hydroxy group, are obtained for example by reaction of hydroxyamines containing at least one other hydroxy group and/or primary or secondary amino group in addition to a hydroxy group and a secondary amino group or by reactian of suitable hydroxyamines containing a hydroxy group and a primary amino group in suitable equivalent ratios with ke-tones and/or aldehydes of the type described, for example, Le A 26 444 21 in the foregoing. Suitable hydroxyamines are, for example, bis-2-hydroxyethyl)-amine, bis-(2-hydroxypropyl)-amine, bis-(2-hydroxybutyl)-amine, bis-(3-hydroxyprapyl)-amine, bis-(3-hydroxyhexyl)-amine, N-(2-hydroxypropyl)-N-(6-hy-droxyhexyl)-amine, 2-amino-2-methyl-1-propanol, 2-amino-2-methylpropane-1,3-diol, 2-amino-3-methyl-3-hydroxybutane, aminoethanol.
The hydroxyamines containing oxazolane groups, which also have at least one free primary or secondary amino group or a hydroxy group, are prepared by reaction of the starting components mentioned in such an equivalent ratio of amino or hydroxy groups to aldehyde or ketone groups that at least one primary or secondary amino group or a hy-droxy group is not blocked and is available for the subse-quent reaction with the reactant used as modifying agent.
Compounds containing hexahydropyrimidine or tetrahy-droimidazole groups, which also have at least one reactive primary or secondary amino group or a hydroxy group, are obtained for example by reaction of hydroxyamines contain-ing two secondary amino groups in addition to at least one hydroxy group, such as for example N-methyl-N'-4-hydroxy-tetramethylenediamine, or by reaction of polyamines con-taining at least one primary amino group or at least two other secondary amino groups in addition to at least one secondary amino group, such as for example N-methyl-1,3-diaminoethane, N-methyl-1,3-diaminopropane, N-methyl.-1,3-diaminobutane, diethylenetriamine, N-methyl diethylenetri-amine, N,N-bis-(3-aminopropyl)-amine, N,N'-dimethyl di-ethylenetriamine.
The compounds containing hexahydropyrimidine or tetra-hydraimidazole groups, which also have at least one free primary or secondary amino group or a hydroxyl group, are prepared by reaction of the starting compounds mentioned in such an equivalent ratio of amino or hydroxy groups to al-dehyde or ketone groups that at least one primary or sec-Le A 26 444 22 x:.~~~.~~a'~
ondary amino group or a hydroxyl'group is-not blocked and is available for the subsequent reaction with the reactant used as modifying agent.
The following structural units, which are suitable for the synthesis of relatively high molecular weight compon ents B) of the type in question containing ester, ether, amide, urethane, urethane bonds, are mentioned by way of example for the purposes of further illustration:
- bisketimine of diethylenetriamine and acetone H
CH °CsN CH2-CH2-N-CH2-CN2-N= 'CH3 - aldimine of isophoronediamine and isobutyraldehyde ,H
H3 H2-N=C~H H3 H~, ~CN3 C"3 2 - oxazolane of diethanolamine and isobutyraldehyde HO-CHZ-CHZs%

- hexahydropyrimidine of N-methyl-1,3-diaminopropane and cyclohexanone he A 26 444 23 If the modifying agents mentioned by way of example above are reacted With hexahydropyrimidines or tetrahydro-imidazoles containing free primary or secondary amino or hydroxyl groups, hexahydropyrimidines or tetrahydroimida-zoles of higher functionality are formed. The same applies to the modification of aldimines or ketimines and to the modification of oxazolanes.
However, if the modifying agents are reacted with mix tures of hexahydropyrimidines, tetrahydroimidazoles, ald imines, ketimines and/or oxazolanes containing free primary or secondary amino or hydroxyl groups, crosslinking compon-ents B) are formed in which hexahydropyrimidines, tetra-hydroimidazoles, ketimines, aldimines and/or oxazolanes are chemically linked to one another.
Accordingly, various compounds suitable as component B) may be obtained by these modification or crosslinking reactions.
The modification reaction is normally carried out in a solvent of the type mentioned by way of example above at reaction temperatures of 30 to 180°C, optionally using a water separator.
In general, an equivalent ratio is selected between reactive groups of the blocked polyamines and the reactive groups of the "modifying agent". However, it is also possible to use the "modifying agents" in a sub-stoichiometric quantity, for example in 0.75 to 0,99 times the equivalent quantity.
Polyamines suitable as component B), which may be ob tained by the modification reactions mentioned, are for ex ample compounds corresponding to the following formulae:
O b CH3N~~~~ C' -~- ( CHZ ) 6-NH-CI CH3 Tie A 26 444 24 CH3~~~CI-Nfi-CH
1/ltiH-C-I~ II
-C-AIH-(CH2)6-NH-C-0(CHZ)2-N~~O
polyol ~ II i~ .cH2cH2-N=c.
0-C-Nti- ( CH2 ) 6-Nti-C-N
~CHZCH2-N=C~
a~ n ( ~HZ)6_~_C_ _CH3 nII
-c-HN- c cH2 a 6 I! n /~ (CH2)b-NH-C-0-(CH2)2s~

CH3- ~ -CHZ-CH-CH2- a ~ZCH-CHZ-NH-tCH2)6-NeC~
I
OH OH
~Le A 26 444 25 f H~~~~H2CH2-O-C-tCH2)6-C-OCHZCH2-H~~ ,.
~Fi II I' i H2CH2-N=CY
CH3-N~-CH2CH2-C-O-tCH2)6-O-C-CH2GHZ-,H
CH2CH2-N=CY
In addition to the essential components A) and B), the binders according to the invention may optionally contain auxiliaries and additives of various kinds as further com-ponents C). These various auxiliaries and additives in-clude, for example, solvents and diluents, levelling aids, antioxidants, fillers, pigments and W absorbers.
The binders or binder combinations according to the invention are prepared by mixing the starting components A) and B) and, optionally, the additives and auxiliaries C) with one another. Where solvents or diluents are used as component C), they may already have been added to one or more of the individual components or,. alternatively, may be added to the mixture of components A) and B). In one pos-sible embodiment in particular, the solvents or diluents are actually present during the preparation of one or more starting components, as described for example in the fore-going with reference to the production of the copolymers.
The solvents or diluents should be substantially anhydrous to ensure an adequate pot life of the mixtures. Solvents or diluents are generally used in the quantities necessary to establish suitable processing viscosities of the combin-ations according to the invention. The solvent content of the binders according to the invention to be used in ac-~~e A 26 444 26 Y ~~~~.~~a~
cordance with the invention is generally between 14 and 800 by weight.
However, it is also possible in principle by using suitable, comparatively low molecular weight copolymers A) to reduce the solvent or diluent content even further or to eliminate the need to use such auxiliaries altogether.
In one preferred embodiment, compounds B) which con-tain no groups reactive to isocyanate groups in the absence of moisture and of which the blocked amino groups consist solely of hexahydropyrimidine, tetrahydroimidazole, ald-imine, ketimine and/or oxazolane groups of the type men-tioned are used as sole blocked polyamines. The preferred combinations according to the invention produced in this way contain 40 to 90 parts by weight of copolymers A) and 10 to 60 parts by weight of compounds B) containing hexa-hydropyrimidine, tetrahydroimidazole, ketimine, aldimine or oxazalane groups.
The quantitative ratios in which components A) and B) are used are generally selected in such a way that, for every blocked amino group of component B), there is a total of 0.2 to 8 and preferably 0.5 to 4 isocyanate groups of component A). In general, a larger excess of the groups just mentioned within the ranges mentioned will be selected when the other components contain reactive groups which re-act with isocyanate groups in the absence of moisture.
Groups such as these include in particular primary or sec-ondary amino groups which may be present in component B), for example in addition to the blocked amino groups, and also alcoholic hydroxyl groups which may be present in com-ponent B) in addition to the blocked amino groups. In gen-eral however, alcoholic hydroxyl groups are substantially inert to tertiary isocyanate groups under the prevailing conditions (room temperature), so that the hydroxyl groups only have to be considered when they are used in the form of substantially involatile alcohols which do not evaporate Le A 26 444 27 ~:00~.003 during the use of the combinations according to the inven-tion and may be considered as reactant for component A), for example at relatively high temperatures of the type prevailing during the hardening of coatings.
Complex mixtures containing urea groups (through re-action of the isocyanate groups with amino groups) are formed where the binders according to the invention are produced by mixing of the individual components, partic-ularly when compounds containing free primary or secondary amino groups in addition to the blocked amino groups are used as component B). Accordingly, the expression "bind-ers" in the context of the invention encompasses not only pure mixtures of the individual components A) and B) , as mentioned above, but also systems in which reaction prod-ucts of this type are present in addition to the individual components or which essentially consist solely of such re-action products. In all variants of the production of the binders according to the invention by mixing of the indi-vidual components, the type of individual components and the quantitative ratios between them are preferably selec-ted in such a way that the molar ratio of tertiary isocyan-ate groups to blocked amino groups on completion of the re-action, which may take place spontaneously, between isocy-anate groups on the one hand and primary or secondary amino groups on the other hand is from 0.2:1 to 8:1 and more es-pecially from 0.5:1 to 4:1, in which case an excess of iso-cyanate groups should again be considered where the indi-vidual components used contain alcoholic hydroxyl groups which may be considered in addition to the blocked amino groups as reactant for the isocyanate groups in the use according to the invention.
Tn addition, in the context of the invention. "blocked polyamines B) containing hydrogen atoms reactive to terti-ary isocyanate groups°' are understood to be not only blocked polyamines of the type mentioned which contain re-Le A 26 444 28 ~~o~.c~~;~
active hydrogen atoms in chemically bound form, but also those which are present in admixture with excess polyamine or hydroxylamine used for their production.
So far as the suitability of the binder combinations according to the invention is concerned, it is largely im material whether the possibly spontaneous reaction between the copolymers A) and the groups reactive to tertiary iso cyanate groups has already come completely to an end. Tf desired, however, it is also possible to terminate this re action before the use according to the invention by brief heating to 40 to 100°C. For the rest, the binders accord-ing to the invention are preferably produced at room tem-perature.
The binders according to the invention are generally liquid at room temperature (often because of the presence of solvents), show adequate stability in storage in the absence of water and, after application to a substrate, generally harden rapidly in the presence of atmospheric moisture.
In general, crosslinked films are obtained even at room temperature. The basically very rapid hardening pro-cess may be further accelerated by drying at higher tem-peratures. Drying times of 10 to 30 minutes at temper-atures of 80 to 130°C are advantageous.
Where blocked amino groups particularly stable to hydrolysis are used, this forced drying at elevated tem-peratures may be necessary to obtain the optimal property spectrum.
The coating compositions and sealing compounds con taming the binders according to the invention may contain the auxiliaries and additives normally used in lacquers, in cluding for example pigments, fillers, levelling aids, an tioxidants or UV absorbers.
These auxiliaries and additives should be largely anhydrous and are preferably incorporated in the starting Le A 26 444 29 components, generally in component A), before the produc-tion of the binders.
The lacquers and coating compositions containing the products according to the invention as binders generally have a pot life of 3 to 48 hours in the absence of mois ture. However, the pot life may be corrected upwards or downwards as required through the choice of suitable re-actants. The coating compositions (lacquers) and sealing compounds may be applied to any, optionally pretreated, substrates, including for ~2xample metals, wood, glass, ceramics, stone, concrete, plastics, textiles, leather, cardboard or paper, by spray coating, spread coating, dip coating, flood coating, casting, roll coating, trowelling.
In the following Examples, all parts and percentages are by weight, unless otherwise stated.
EXAMPLES
I) General procedure for the production of the olefin-ically unsaturated compounds al to a3 containing ter-tiary isocyanate groups:
The starting components are introduced under nitrogen into a 2-liter reaction vessel equipped with a stirrer, cooling and heating system and stirred at 40°C until the theoretical isocyanate content is reached.
The compositions of the starting components are shown in Table d together with the isocyanate content of the iso-cyanate-functional monomers obtained, Le A 26 444 30 ~tl~~.U~3 Table 1 (Quantities in g) Starting components al az as 1-Isocyanato-1-methyl-4(3)-iso-970 970 970 cyanatomethyl cyclohexane Hydroxyethyl acrylate 580 - -4-Hydroxybutyl acrylate - 720 -Hydroxyethyl methacrylate - - 650 2,6-di-tert.-butyl-4-methylphenol0.8 0.8 0.8 Isocyanate content (%) 13.7 12.5 13.1 Color value (APHA) 10 10 10 II) General procedure for the production of the copolymers A1 to AB containing tertiary isocyanate groups Part I is initially introduced into a 3-liter reaction vessel equipped with a stirrer, cooling and heating system and is heated to the reaction temperature. Part II and part III are then added at the same time in a nitrogen at mosphere over a total period of 2 hours and 2.5 hours, res pectively. The mixture is then stirred for 2 hours at the reaction temperature.
The reaction temperatures and the compositions of parts I to III are shown in Table 2 together with the char-acteristic data of the copolymers obtained.
Le A 26 444 31 e~r~~~.~~~
d' M

O d' t0 O O tn N O
ei~ O
V' O

00 CO O t0 N 10 N e-1 O CO
CO
CO

iQ', 1D M v-1 (~
M
~i M

N

O~ O~

O 10 t0 O 01 01 N O
v0 vp CO

CO M ~O N In Op N
M l~
M

R~, 1p N e-I M
N
N
d' d H

00 O ~O N O d' M O
N O
CO
d' .p ~ CO t~ O1 N 1p r-1 ll1 In N
O

M e-I r-i N
ri If1 ri I~ O

V' O N ~0 O 01 M O
V' I'~
~O

00 1D f~ t'y N d' c0 t11 00 M
CO

~0 H ri lC7 d' d' d' 01 er N 1D ~D O tf1 V' O

O

~ 1f1 O Il1 N

R,' 00 N M
N

H

V' M

N d V' CO O tn d' O N
O d~
N
O

en 00 e-1 \O I~ O !n M
IWC cr In dC f~ N r1 t~
v-1 ~

H

M N

N O V~ O O In M O
s~ t~
dW
D

N ~D CO ip O O In d' tf7 ri tn CO

le N rl e-I
rl a1' e-i d' r~

tf'f O~

O ~

'd' 01 l11 O fn e-I M
01 ei R', CO M -1 ri N
tW

ri dP

O

ro " I

O
~-l il N 1 r-1 ~

a~ +~ to cn ro o e' d o ~, ro ro~rt U ~ dP ~
~ ~

rlrorof~roal o +

H
~

1~ N i~ QI Li .1-~
N N M U W
1-'I
>'I
~'1 ro ~

ro N .aJ O r1 ~ f~ O O :~
+~ ro ro O
U
1..~
.~
~

+~ ~ E3 '~ .1.~ rl ro U M
ro U
U
IJ

a ro ~-1,-~ ~ ro ~ ~ cu U N +~
.~
ro ro a~
x ~
la s~

ro +~ ~ ~ ro ~
l O ,~ x s~
~ ~ a~
a~ a~
a~
~
~

a N + i, U t~ U rl ~r .6. O ?~
5r.~ f~ U
f~ ~

d! U U U .-1 H U -.-1 to ' d' ~., Q1 "~f' U i-~
N r-I ~
x O O
O

N fC H H ft) I-1 dP 'J tr C1 ,Q rl j'-a ro ro ',~1 I~.
~s '?r W-i ./', ~""
~', H GI N H 47 Vl 1:." 1 N O
.1.7 O
rl .1.7 ,i;
,'sy O
O
O

d ~--I .~"., N .t:'.r1 G) ~.1 tp ~-i .-d 'Cf O
r-1 U
O
,fir r-1 r-1 ~~1 O
.4"' .(~.~
~-.
L.' r-I O d.' 1~ ~.1 .i.l '~, ,~y C: O N
O ',!~ +! ~1 rl 'J~ '?r N U
.G~
.~,' 'fir 'fir .Ll r-1 .1.!

.O , Sd S.~?,.L', I-1 .~ .-I O r~1 f-I , .1..1 i-~ ~ r-I
.l.l O rl Ul O
-6~
.4' .1->
O
U
W
O
O
O

it O ro ro ro I O
?a ~ 4l ~ i~ >r O O
Ul O
O i.~
.W O
O ri Ul U
>r U
U
U

H U G.~SCPC1WcnWCGH~;WGpHUNZ"~,~ t~aE-~>CWW rt3t4D'.~~U

III) Preparation of components B) capable of crosslinking 513 g cyclohexane and 456 g isobutyraldehyde are introduced under nitrogen into a 2-liter reaction vessel equipped with a stirrer, cooling and heating system. 529.8 g 1-amino-3-methylaminopropane are added dropwise at 10°C
(ice bath cooling), after which the mixture is stirred far 1 hour at 10'C and then heated at the reflux temperature until no more water is eliminated. Cyclohexane and excess isobutyraldehyde are then distilled off and the hexahydro-pyrimidine crosslinker B1 is obtained.

In a 3-liter reaction vessel equipped with a stirrer, cooling and heating system, 680 g isophoronediamine, 1000 g methyl isobutyl ketone and 560 g toluene are refluxed under nitrogen on a water separator until the theoretical quantity of Water has been eliminated (144 g) or until no more water is eliminated. Toluene and excess methyl iso-butyl ketone are then distilled off and the bisketimine crosslinker BZ is obtained.

a) 1050 g diethanolamine and 615 g cyclohexane are intro duced under nitrogen into a 4 liter reaction vessel equip ped with a stirrer, cooling and heating system. 1408 g 2 ethyl hexanal are then added dropwise at room temperature, the temperature slowly rising. The mixture is then kept at the reflux temperature until the separation of water is complete. Cyclohexane and excess 2-ethyl hexanal are then distilled off. An oxazolane, the intermediate stage B3a), is obtained.
b) Preparation of B3 200.6 g of an isocyanurate polyisocyanate based on Le A 26 444 33 ~~1.~~~
hexamethylene diisocyanate, consisting essentially of N,N',N"-tris-(6-isocyanatohexyl)-isocyanurate, and 207 g butyl acetate are introduced under nitrogen into a reaction vessel equipped with a stirrer, cooling and heating system and heated to 60°C. After the dropwise addition of 286.7 g of the oxazolane intermediate stage B3a), the mixture is kept at 70°C for 10 hours. A 70% solution of the cross-linker B3, containing 3 oxazolane groups on a statistical average, is obtained.
IV) Preparation of the binder combinations according to the invention The components A) containing tertiary isocyanate groups and the polyamine components B) are mixed together at room temperature and adjusted to a processible viscos ity, optionally by addition of more auxiliaries C).
The films are coated onto metal test plates using a film drawing tool (wet film thickness 180 ~,m). The films applied and stored at room temperature were all tack-free after 60 minutes at the longest. After ageing, i.e. 24 hours at room temperature, clear, crosslinked, solvent-resistant films characterized by excellent mechanical properties and very good optical properties are obtained.
The lacquer mixtures prepared all had a pat life of several hours.
The compositions of the binder combinations and the solvent resistances (degree of crosslinking) are shown in Table 3 below.
Solvent resistance is tested by a wiping test using a cotton wool plug impregnated with methyl isobutyl ketone (MIBK). The number of double wipes for which the film re-mains visibly unchanged is shown. No film was subjected to more than 200 double wipes.
he A 26 444 34 ~
,.
ai 0 0 0oav 00 lL7 N N 1~rl e-1 ,t;O

lI1 O r1 O O CON

I~ tt1 N N /~/~ e-i ,o ".,O

t9 O r-1 O O CON

1p t11 N N /~A r1 ,OO

In O r-1 In In N N /~/W 1 J

t~ O .-1 O O ~DN

in M N J~I~ .-1 M

M _ .~a vo 0 O O t0N

M tn M N /~/~ H

N

O

O t"'~

N tn N N /~/W -1 tT ZT fi ~".,O

M O r1 O O ~ON

r~t lC1 M N A /~ ri ?.e ~-.

e-1 ~ O
N dl N

W O N
~ O
.i.1 N

~ N ~
O ~
d N ! ~ cr -II N 1lf ~ii' ~ .rrW
N N
~
rl t1 W N .l.a O
~ t~
f~ N

.-. ~ ~ ~
. m ,-I ~a ~ 3 ~

o ~ ~ s .~ a ~ ~
U

-ri .~ ./.1 N -rl ~ O -ri "~ ~
Q) +~ ~ ~ U d R.mr b N -f~ ~C
+.~
.-!

M Id N N rtf W rl !-1 LT ?t N N
RJ
.R

U ~', (.," (~ .-i",~ .N
f..~ r-I
O N

a~ -~ o o ~ ~ ~ ~ s~
a~ ~s o o o a ~, ,~ ~, a ~ a~ x ~, ~a a~ ~s a ~
s~

.ci ~ ~ ~ ~ ~ +~oo ~ ~
~ b -~
~

R~ O O ~ ~ O H d O
W W ?v ~
?a H ~ U U fa ?C W ~ ~
ttf U
,1.~ ~
O .~

~~O~.DO~
0p N

Is v0 O rl v0 O O t0 t0 ri In ti' N /~ e-i ri !~ N

O O ~-1 In O p op N

e-I In tf1 N /~ rl .O N

N O wi a~ O O GO N

rl 111 ~ N /~ /~ rl >s ,C;O

O O rl M O O CO N

rl l11 t0 N /~ /1 rl of N

,O O

n o rl N O O ~O N

e-I In W N /~ /W --I

M

M N

~'.,O

In O r1 rl O O lD N

e1 tl1 CO N /~ /1 ri N N

d' O t-1 O O O CO N

ri tn 1p N !~ /~ rl N

.t"rO

00 O .-1 O! In 1~ N I~ I~ r-I

O ~1 1 hd ~

r-i .~, O
fl) O

fly O II7 O
.~
tn ~ -.i ~ d.' U1 ~
~.I d N d' x a~ w !~ m a~ --~

w o +~ o +~ s~
c~ a~

_ _ O ~ ~ ~ $ ~ U
~ ~
~

.~ y U N
.a r4 .b~ d~ N ~-1 +~ ~ O .-1 ~
Cl .N !~.. 1~, U 119W rtf t ~i ~ .i~
r-I ~,' M fd O Gl ft! W ~-1 ~-1 N N
lC tT
.tl ~r U >~ ~ ~ .-i$ +~
1.~ .-~
~ QS

c~ ..~ o o rl a ra ~ s~
ar ~s o o o a o,~ a~ xa~ o,~a~~as~

,s~ ~ ~+~ ~1 .~ oa ~ ~
s~ +1 ~
-~
b Rf (~, O O~ 'T~O N O O
4-1 W ~
.~., '.a H ~ U ~ e~ x w ~ ~
~s o .u ~u o ,~

Q

(f~ .~",O

d' O d If1CO N

N lf1 r-I N /~ /~ rl ,L,''O

O e-I

M O CO O CO N

N lf1 r-1 M h /~ ri is b~ tT

,4"O

O ~-I

N O O~ O CO N

N lf1 e-1 C1 /~ /~ rl tn ,C'.,O

O ed r-1 O 00 O 00 N

N lL1 '-I i~'1 /~ /~ ~i ,C'.,O

O v-1 O O t~ lL11flN

N lfl N M /~ /~ rl M

M M

xr O

O ~'1 ~1 O l~ In 10 N

e-I 1!1 N N1 A /~ ~i N M

,L;O

Q e~

e-1 !IZ N c1 /~ /~ r-1 b~ tn tT

,C'.,O

O ml I~ O er O 1p N

e-1 111 N M /~ /~ rl Gl f-1 1 f.i ~

ml ~ O
O G!
N

1~ ~-1 O J~
~ W
flS

1~ U1 lif V' i.1 Q) ~
N

N W
.~, N
~ W

e9' W N ~ O ~
~ f N
~ V' ~ _ W
~

ail b~ O o N o 3 p, O .4~ ~ .-I ~
.C ~
~ U
N

r1 .E.) .a.) ~ r1 +~
~~' LT
Q! O
-r1 .N a: s~ U N W rt ~r ~.a .N .N
r-i U ~ ~ ~ ~ ~
a N

c~ - t r ~

O r-I o o r-i!~ rl i.a ~1 N to ~ 0 1 ~ ~,~, a~ xa~ w~sma~sa .a n, 1 ~e ~.~ ~-,.u m ~ ~
a.l ~
r .'.1 ~s U U~ 0 M i ~

H ~ x p 0 ~Ut , ~~.~ C,~
,'

Claims (8)

1. Olefinically unsaturated compounds having a molecular weight from 252 to 800 which contain (i) 7 to 24% by weight of urethane moieties and (ii) 5 to 17% by weight of isocyanate moieties bonded to tertiary carbon atoms which in turn form a part of a cycloaliphatic ring.

2. Olefinically unsaturated compounds according to claim 1 having the formula wherein R1 is an alkyl containing 1 to 4 carbon atoms, R2 and R3 are the same or different and each represents a difunctional, linear or branched saturated hydrocarbon moiety containing 1 to 4 carbon atoms with the sum of the R1 and R3 carbon atoms being from 3 to 6, R4 represents hydrogen or alkyl containing 1 to 4 carbon atoms, R5 is a difunctional, linear or branched, saturated aliphatic hydrocarbon moiety containing 1 to 4 carbon atoms, n is 0 or 1, and Z is the dehydroxylated remainder of hydroxy-containing olefinically unsaturated compound.

3. Olefinically unsaturated compounds according to claim 2 wherein R2, R3 and R5 are each alkylene.

4. Olefinically unsaturated compounds according to claim 2 wherein Z is the dehydroxylated remainder of hydroxy-ethyl acrylate, 2- and 3-hydroxypropyl acrylate, 2-, 3- and 4-hydroxybutyl acrylate, hydroxyethyl methacrylate, 2- and 3-hydroxypropyl methacrylate, hydroxyethyl vinyl ether, 2-, 3- and 4-hydroxybutyl vinyl ether or allyl alcohol.

5. A process for the production of copolymers containing isocyanate moieties, which have a weight average molecular weight of 1,000 to 100,000, determined by gel permeation chromatography which comprises radically-initiated copolymerizing olefinically unsaturated monomers free from isocyanate groups with olefinically unsaturated monoisocyanates in a quantity such that the resulting copolymer contains from 0.1 to 13% by weight of chemically incorporated isocyanate groups for an average NCO functionality of the copolymers of at least 2, wherein the olefinically unsaturated monoisocyanates are olefinically unsaturated compounds having a molecular weight from 252 to 800 which contain (i) 7 to 24% by weight of urethane moieties and (ii) 5 to 17% by weight of isocyanate moieties bonded to tertiary carbon atoms which in turn form a part of a cycloaliphatic ring.

6. A process as claimed in claim 5 wherein the olefinically unsaturated monoisocyanates are of the formula wherein R1 is an alkyl containing 1 to 4 carbon atoms, R2 and R3 are the same or different and each represents a difunctional, linear or branched saturated hydrocarbon moiety containing 1 to 4 carbon atoms with the sum of the R1 and R3 carbon atoms being from 3 to 6, R4 represents hydrogen or alkyl containing 1 to 4 carbon atoms, R5 is a difunctional, linear or branched, saturated aliphatic hydrocarbon moiety containing 1 to 4 carbon atoms, n is 0 or 1, and Z is the dehydroxylated remainder of hydroxy-containing olefinically unsaturated compound.

7. Copolymers containing isocyanate groups having a weight average molecular weight of from 1,000 to 100,000, determined by gel permeation chromatography, of olefinically unsaturated compounds, having an average NCO functionality of at least 2 and a content of 0.1 to 13% by weight o~ isocyanate moieties attached to tertiary carbon atoms which, in turn, form a part of a cycloaliphatic ring.

8. Coating compositions or sealing compounds hardenable by the effect of moisture which contain as a binder a two-component system of polyisocyanate component and a polyamine component containing blocked amino groups, wherein the polyisocyanate component consists of the copolymers claimed in claim 7.