DE19835913A1 - Through high-energy radiation and / or thermally curable substances and preparations - Google Patents

Abstract

The invention relates to radiation-hardening and/or heat-hardening substances and preparations with an oligomer or polymer basic structure, comprising at least one terminal or lateral vinyl ether group (a) and at least one group (b) that is different from said vinyl ether groups (a) and co-reacts with said groups (a), whereby, on average, at least one vinyl ether group (a) and one co-reactive group (b) are present for each oligomer or polymer molecule. The invention also relates to preparations containing the inventive material and to the uses of said preparation in or as a binder for liquid enamelling systems, coating powders, or as or in adhesives, casting agents and impregnating agents for electronics or electro-technics and for the production of shaped bodies.

Description

The invention relates to high-energy radiation and / or thermally curable substances and preparations and their use according to the invention gene.

The starting point for the present invention were considerations on the Field of UV-curable lacquers for use in liquid Form and powder coatings. Such paint systems win for the sake of Solvent saving more and more areas of application. A major problem with known UV varnishes, however, is the inhibition of curing on the varnish surface due to atmospheric oxygen. This inhibition must be carried out with lamps very high energy density and an acceleration of hardening Amincoinitiators are dubbed. These amines are often the cause for unpleasant smells.

With UV powder coatings, additional problems arise from the contradicting demands for good blocking resistance of the powder at the Storage and good flow of the melted paint film. For good block The glass transition temperature and melting point should be as high as possible be for good flow and application on thermosensitive substrates but as low as possible to avoid a hardening reaction before the formation of a to avoid optimal surface smoothness and damage to the substrate the. The melt should also improve the surface smoothness  have a low viscosity and the reaction only after Ver use delay. These ideas can be with powder coatings, their Curing on one of the known thermally activated reactions between Resin and hardener, e.g. B. polyepoxy resin and dicarboxylic acid based, only difficult to realize because at the same time as the melting process uses a viscosity-increasing reaction. For radiation-curable powder coatings however, there should be a separation of the melting process and crosslinking to be possible. To meet this requirement are state of the art various approaches have become known.

US-A-4,129,488 and US-A-4,163,810 disclose UV curable powders paints with special spatial arrangements of ethylenically unsaturated poly mere. The binder consists of an epoxy polyester polymer, at which the epoxy adduct is spatially arranged in such a way that it by means of a linear polymer chain at a spatial distance from the Polyester adduct is arranged. The polymer also contains a che mixed bound photo initiator.

EP-A 0 650 978, EP-A 0 650 979 and EP-A 0 650 985 Copolymers disclosed, the essential component of which is proportional high proportion of monomers with the structural element of methacrylic acid and is used as a binder for UV-curable powder coatings are cash. The copolymers are characterized by a relatively narrow molecule lar weight distribution.

EP-A 0 410 242 binders for UV-curable powder coatings known, which consist of polyurethanes, the certain (meth) acryloyl group have pen, without crosslinking component or peroxides can and are therefore stable in storage. For networking with UV radiation The addition of photoinitiators is necessary.  

Furthermore, EP-A 0 636 669 is a curable by UV light Known binder for powder coatings, which consists of unsaturated polymers, which may contain cyclopentadiene and a crosslinking agent which Has vinyl ether, vinyl ester or (meth) acrylic groups.

WO-A-93/25596 discloses polyacrylates as topcoats for automobiles, that are functionalized in a variety of ways with double bonds.

DE-A-42 26 520 discloses liquid compositions which made of unsaturated polymer in the form of unsaturated polyester and compounds exists that contain (meth) acryloyl groups and / or vinyl ether groups. These compositions can both by means of radical images as well cross-linked by radiation curing and used as a binder for paints become. When crosslinking by UV radiation, it is necessary to use Fotoini tiators to add.

In the case of the UV lacquers according to the prior art mentioned, this results in Problems from the need for high sensitivity to light and Transfer of the known oxygen inhibition of the surface additionally Use coinitiators, usually amines. The fission products of this Photoinitiators remain in the hardened paintwork and are the cause from unpleasant smells.

Furthermore, prior art is known from EP-A-0 322 808 become a liquid bandage that is curable by high-energy radiation means disclosed that from a mixture of an ethylenically unsaturated Polyester component, which is also an ethylenically unsaturated polyester oligo may contain meres, and an unpolymerized vinyl ether component consists. The vinyl ether component is selected so that it Average of at least two vinyl ether groups per molecule of vinyl ether  Contains component with the ethylenic double bonds of the polye ster component can react.

The present invention was based on this prior art based on the task of providing substances and preparations in whose Use in high-energy radiation and / or thermally curable Paint systems no oxygen inhibition of the paint surface occurs, so that on the use of odorous amines and other coinitia tors can be dispensed with, and which also a wider application can be supplied.

This object is achieved by substances with an oligomeric or polymeric basic structure solved, each terminal and / or lateral at least one vinyl ether group a) and at least one of the vinyl ether groups a) different, preferably co-reactive with groups a) have copolymerizable group b), on average at least one vinyl ether group a) and one coreactive group b) per oligomer or Polymer molecule are present.

Coating systems that have such substances show in a surprising way high UV reactivity and no oxygen inhibition of the surface curing in air. This has the advantage that the use of Amines and other coinitiators can be dispensed with.

Hardening to a B-state, i.e. H. a partially hardened state, where the hardening is interrupted and started again later can, is possible.

It should be mentioned in connection with the substances according to the invention the problem known per se to the person skilled in the art that with the usual, under  statistical reaction conditions taking place polymer structure or polymer-analog functionalization also polymer molecules are formed can only in one way, e.g. B. with the vinyl ether groups a) or are not functionalized at all. Since such less or not at all functionalized polymeric basic structures the properties of the inventions polymers according to the invention, it is preferred that To control manufacturing processes so that the smallest possible proportion of such less or not at all functionalized polymeric basic structures arise. Suitable methods for this are known to the person skilled in the polymer. This includes u. a. the use of surpluses under later re separation of unreacted substances or, if applicable, the whereabouts of the Excess in the finished paint binder. It has been shown that possibly still remaining portions of the success according to the invention in use of the claimed substances essentially do not impair.

This is attributed to the use of the substances according to the invention in by high-energy radiation and / or thermally curable paint systems outstandingly high UV reactivity to be observed without the occurrence of a Oxygen inhibition of the surface due to the fact that the inventions substances according to the invention by functionalizing the polymeric basic structure self-networking can take place while in the prior art Compositions of mixtures of substances are present that are only among themselves need to be networked.

The schematic structural principle of the substances according to the invention can be illustrated as follows:

According to the structural principle shown, the functional groups a) and b) can be linked at the same point and / or different points to the oligomeric or polymeric basic structure, and terminate them at will. The functional groups a) and b) can also be present more than once on the same group. So z. B. react on a terminal NH ₂ group two glycidyl methacrylates or on a terminal epoxy group a molecule of ethanolamine divinyl ether. Furthermore, polymeric basic structures which have several OH groups at the side or terminal at the same point can be vinylated. The value for n is between 0 and 6, preferably 1 or 2.

The oligomeric or polymeric basic structure can by C-C linkages be formed which have double and / or triple bonds and / or are selected from ester, ether, urethane, amide, imide, imidazole, Ketone, sulfide, sulfone, acetal, urea, carbonate and siloxane linkage exercises.

Furthermore, the oligomeric or polymeric basic structure can be linear, ver branches, ring-shaped or dentrimer.

The substances according to the invention are preferably polymer-analogous Implementation of functional polymers with compounds that are functional Groups a) or b) and at least one further group having the functional groups of the oligomeric or polymeric basic structure can react.

As a co-reactive, preferably copolymerizable functional group b) come in particular maleate, fumarate, itaconate, (meth) acrylate, allyl, Epoxy, alkenyl, cycloalkenyl, vinylaryl and cinnamate groups and / or structural units of the general formula I are preferred.  

When using structural units of the general formula I as functional group b) stand out in the paint systems during manufacture due to a low sensitivity to heat and still a good one Baking hardenability under atmospheric oxygen, short curing times with combined ter application of heat, UV light, in powder coatings by a good Block resistance of the powder during storage and a very good surface smoothes out the paintwork obtained from it.

In a preferred embodiment, the structural units of the general formula I in the coreactive groups b) in the form of esters des (oligo) dihydrodicyclopentadienols with mono- or polyfunctional Carboxylic acids of the general formula II may be incorporated.

An important class of polymers according to the invention are epoxy resins. Multiple epoxy-functional polymers, oligo, are suitable as basic structures mer or monomeric compounds, e.g. B. of the bisphenol A epoxy type compounds or of the type of bisphenol A epoxy resins, by reaction with compounds that are reactive with epoxy groups. The epoxy groups can be functionalized with compounds containing vinyl ether groups a) and thus coreactive groups b) and at least one further group  have that can react with epoxides. Examples of the invention Compounds of this kind are the products of partial implementations of known commercial epoxy resins with (meth) acrylic acid and / or compounds according to the general formula given below III and an aminovinyl compound such as aminobutyl vinyl ether or Dietha nolamine divinyl ether or the reaction products of polyacrylates with copolymer incorporated glycidyl (meth) acrylate with such compounds or the reaction products of polyurethane resins, which are also used of hydroxy-functional epoxy compounds, e.g. B. Glycid (2,3-Epoxypro panol-1), can be obtained with such compounds.

Polyurethane resins represent another important polymer according to the invention class represents the implementation of multi-functional Isocyanatver bonds with acrylates and vinyl compounds, hydroxy or amino acrylic laten and hydroxy or aminovinylates, optionally with Mitverwen formation of further compounds reactive with isocyanate groups, such as Hy droxy compounds can be obtained.

As isocyanate compounds commercially available and known compounds can be used, such as. B. tolylene diisocyanate (TDI), 4,4'-methylene di (phenyl isocyanate) (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI), further C ₂ -C ₁₂ alkylene diisocyanates, further C ₂ -C ₁₂ cycloalkylene diisocyanates, naphthalene diisocyanates , further alkaryl diisocyanates, such as phenylene diisocyanates, diphenyl diisocyanates and the various positional isomers of these compounds. In addition, the more isocyanate-functional biuretization and isocyanuration products derived from these isocyanates, such as the isocyanates trimerized or oligomerized via urethdione groups, and the higher isocyanates obtainable from the simple isocyanates mentioned above by dimerization or oligomerization with amines or water are also suitable.

Polyisocyanates, the diisocyanurate groups, are of particular importance exhibit. Here are the trimerization products mentioned above te diisocyanates to mention.

To prepare the binders according to the invention, the isocyanates mentioned or mixtures of these isocyanates are reacted with those compounds which are reactive with the isocyanates and which, in addition to the groups reactive with isocyanates, also have groups a) and b). Compounds which are reactive with isocyanates and which do not have groups a) or b) can also be used. The compounds to be reacted with the isocyanates can be mono- or polysubstituted with isocyanates, reactive, linear, branched, aromatic, cycloaliphatic, araliphatic, heterocyclic and / or as desired. Examples are C ₁ - C ₂₀ -Hydroxyalkylvinylether as Hydroxyethylmonovinylether, hydroxybutyl monovinyl ether, cyclohexanedimethanol monovinyl ether, Hexandiolmonovinylet forth, ethylene glycol monovinyl ether, and poly Propylenglykolmonovinylether alkylenglykolmonovinylether and diethanolamine, Aminopropylvi vinyl ether, C ₁ -C ₂₀ hydroxyalkyl (meth) acrylic esters such as hydroxyethyl acrylate, Hydroxybutyl acrylate and polyalkylene glycol monoacrylates, allyl alcohol, dihydrodicyclopentadienol, hydroxyl group-containing adducts of dicyclopentadienol (DCPD) with glycols according to the general formula V given below, ethylene glycol, polyethylene glycol, pentylene glycol, polypropylene glycol, hexane glycol, hexane diol glycol, hexanediol glycol, hexanediol glycol, hexanediol glycol, hexanediol glycol, hexanediol, phenol glycol, hexanediol glycol, hexanediol, phenol glycol, hexanediol, methylene glycol, methanediol, methanediol, hexanediol, hexanediol, hexanediol, hexanediol, hexanediol, hexanediol, hexanediol, hexanediol, hexanediols conditions such as allyl alcohol, partially etherified polyfunctional hydroxyl compounds, e.g. Example, trimethylolethane monoallyl ether, trimethylol ethane diallyl ether, trimethylol propane monoallyl ether, trimethylol propane diallyl ether, pentaerythritol monoallylet forth, pentaerythritol diallyl ether, alkylene diols such as butene-2-diol-1,4 and oxalkylated alkylene diols, preferably ethoxylated-1,4-dioxylated with ethoxylated-2-ethoxylated and a 1 to 10 alkylene oxide per mole of butene-2-diol-1,4.

The selection and combination of the desired starting connections gene depends on the desired properties of those to be produced Fabrics. The setting of a desired molecular weight and given If necessary, the viscosity can be increased by using monofunctional Ver bindings are made. The above measures and the selection of one suitable polymerization technology, if necessary with the use of solutions means and the control of the polymerization by catalysts are the Specialist possible due to his specialist knowledge.

The term polyurethane is also intended to be used in the context of this invention Include compounds whose main chain is not only via urethane compounds gene is linked, but also those compounds that are ester or Have ether chain links, d. H. the polyester urethanes and polyether urethanes no

Saturated and unsaturated polyester resins according to the invention with Grup pen a) and b) are functionalized, represent another important polymer class for the binders of the invention. To build the poly ester resins come with the usual and known carboxylic acids with <2 Carboxyl groups and / or their anhydrides and / or their esters and Hy droxyl compounds with <2 OH groups in question. It can also be mono  will use functional connections, e.g. B. the molecular weight regulate the importance of polycondensates.

As carboxylic acid components such. B. α, β-ethylenically unsaturated Carboxylic acids, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, Citraconic acid, saturated aliphatic carboxylic acids or their anhydrides, such as succinic acid, adipic acid, suberic acid, sebacic acid, azelaic acid, natural fatty acids and polymerized natural fatty acids such as linseed oil fat acid, dimer and polymer linseed fatty acid, castor oil, castor oil fatty acid, saturated cycloaliphatic carboxylic acids or their anhydrides, such as tetrahy drophthalic acid, hexahydrophthalic acid, endomethylene tetrahydrophthalic acid, Norbonenedicarboxylic acid, aromatic carboxylic acids or their anhydrides, like phthalic acid in its isomer forms, also tri- and tetracarboxylic acids or their anhydrides, such as trimellitic acid, pyromellitic acid, with allyl alcohol get partially esterified polycarboxylic acids, e.g. B. Trimellithsäuremonoallylester or Pyromellithsuredurediallylester in question, wherein benzophenone carboxylic acids from are of particular importance because of this copolymer UV-light excitable Structures can be built.

As hydroxyl components such. B. optionally alkoxylated, at least two valuable aliphatic and / or cycloaliphatic alcohols such as ethylene glycol, Propylene glycol, polyethylene glycols, polypropylene glycols, butanediol isomers, Hexanediol, trimethylolpropane, pentaerythritol, neopentyl glycol, cyclohexanedi methanol, bisphenol A, hydrogenated bisphenol A, OH polyfunctional polymers re, such as hydroxyl-modified polybutadienes or hydroxyl groups load-bearing polyurethane prepolymers, glycerin, mono- and diglycerides from saturated and unsaturated fatty acids, especially monoglycerides from Linseed oil or sunflower oil in question. Furthermore come unsown alcohols, such as polyfunctional (partially) etherified with allyl alcohol Hydroxyl compounds, e.g. B. trimethylolethane monoallyl ether, trimethylolethane  diallyl ether, trimethylol propane monoallyl ether, trimethylol propane diallyl ether, Pentaerythritol monoallyl ether, pentaerythritol diallyl ether, butene-2-diol-1,4 and alkoxylated butene-2-diol-1,4.

If monofunctional substances are used to regulate the molecular weight are used, these are preferably monofunctional alcohols, such as ethanol, Propanol, butanol, hexanol, decanol, isodecanol, cyclohexanol, benzyl alcohol hol or allyl alcohol. Under the term polyester in the sense of the present The invention also includes polycondensates in addition to the ester groups Have amide and / or imide groups, as they are by using Amino compounds can be obtained. Such are modified polyesters e.g. B. known from DE-A-157 00 273 and DE-A-172 00 323. This polye steramides or polyesterimides may have special requirements, e.g. B. be in terms of heat resistance, chemical resistance, hardness and scratch resistance often better than pure polyester.

The double bonds of the unsaturated polyesters used can also DCPD can be attached, which enables endomethylene tetrahy incorporate drophthalic acid structures according to the general formula IV.

These endomethylene tetrahydrophthalic acid structures can be attached to the chains permanent double bonds of the polyester and / or at the terminal double bond such as z. B. on substances according to the general formula III leads to be present.  

Groups a) and b) can be introduced by Co-condensation and / or by polymer-analogous reactions on polyesters done with functional groups. Examples of cocondensation are Use of trimethylolpropane di and monoallyl ether, pentaerythritol di and monoallyl ether, butene-2-diol-1,4, alkoxylated butene-2-diol-1,4 and Allyl alcohol.

Examples of polymer-analogous reactions on polyesters with functional ones Groups are e.g. B. Additions to incompletely condensed linear and / or branched prepolymeric polyester resins containing both free hydroxyl groups also have free OH groups. These can be attached to the carboxyl group pen with unsaturated glycidyl compounds and vinyl ethers become. The free carboxyl groups with unsaturated are preferred first termed glycidyl compounds converted to an acid-catalyzed polymer prevention of vinyl ethers. Suitable unsaturated glycidylver bonds are e.g. B. glycidyl (meth) acrylate, undecenoic acid glycidyl ester, (Meth -) - acrylation products of polyfunctional epoxy resins and / or allyl glycidether, preferably glycidyl (meth) acrylate being added. In the An these reactions are then the hydroxyl groups with Di Isocyanates and hydroxyvinyl ethers implemented.

However, it is preferred first of all to use diisocyanates with isocyanate groups with different reactivity, e.g. B. isophorone diisocyanate to react with a semi-equivalent amount of hydroxyvinyl ethers and then to bring these reaction products with the prepolymeric polyesters to react. In the reactions mentioned, hydroxyl-functional acrylates can be used in addition to the hydroxyvinyl ethers. Purely hydroxyl-functional prepoly mere polyesters can also be carried out in the manner described last with hydroxy vinyl ethers and hydroxyl-functional compounds which have groups b), for. B. hydroxyalkyl (meth) acrylates or allyl alcohol. The introduction of groups according to the general formula I is also possible in this way by using commercially available dihydricclopentadienol. However, it is preferred to introduce groups according to general formula I into the polyester via the cocondensation of the half esters of maleic acid with dihydrodicyclopentadienol according to general formula III. These half esters can be obtained in a smooth reaction from maleic anhydride (MSA), water and dicyclopentadiene (DCPD) or by a direct addition of DCPD to MSA. It is also possible to add DCPD directly to other acids and / or acidic polyesters. These reactions are usually worse and require catalysis, for. B. with BF ₃ etherate.

Next it is z. B. from US-A-5,252,682 known that in the reaction of DCPD and MSA side reactions according to the formula scheme V subordinate net can take place. These by-products also serve as an introduction of structures according to the general formula I.

Hydroxy-functional compounds for the introduction of groups according to the general formula I are dihydrodicyclopentadienyl alcohol and preferred the adducts from DCPD, which can be obtained inexpensively under acid catalysis Glycols according to formula VI.

Polyacrylate resins which are functional according to the invention with groups a) and b) are another important polymer class according to the invention and are by copolymerization of acrylic esters, possibly with other copolymerizable compounds obtained.

A preferred method for the production of polyacrylates is the solution medium-free, radical substance polymerization in the stirred reactor, if necessary under pressure or particularly preferably in continuous continuous reactors at temperatures above the melting temperature of the polymers formed, preferably above 140 ° C.

This method gives low molecular weight polyacrylates and narrow molecular weight distribution, which is particularly true for powder coatings because of the resulting narrower melting range and the lower Melt viscosity is very desirable. There is also no need for the substance polymer rization the need to remove an auxiliary solvent, and it it is possible to incorporate pigments and coating aids directly into the melt The polyacrylate resins according to the invention can also be used in solution means are manufactured.

Examples of components for the construction of polyacrylate resins are known esters of acrylic acid and methacrylic acid with aliphatic, cy cloaliphatic, araliphatic and aromatic alcohols with 1 to 40 Suitable carbon atoms, such as. B. methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, Ben cyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, furfuryl (meth) acrylate and  the esters of 3-phenylacrylic acid and its various forms of isomerism, such as methyl cinnamate, ethyl cinnamate, butyl cinnamate, benzyl cinnamate, cyclo hexylcinnamate, isoamylcinnamate, tetrahydrofurfurylcinnamate, furfurylcinna mat, acrylamide, methacrylamide, methylolacrylamide, methylolmethacrylamide, Acrylic acid, methacrylic acid, 3-phenylacrylic acid, hydroxyalkyl (meth) acrylates, such as ethyl glycol mono (meth) acrylate, butyl glycol mono (meth) acrylates, hexane diol mono (meth) acrylate, glycol ether (meth) acrylates, such as methoxyethyl glycol mono (meth) acrylate, ethyloxyethyl glycol mono (meth) acrylate, butyloxyethyl glycol mono (meth) acrylate, phenyloxyethyl glycol mono (meth) acrylate, glycidyl acrylate, glycidyl methacrylate, amino (meth) acrylates, such as 2-aminoethyl (meth) acrylate.

Other components are monomers which can be copolymerized by free radicals, such as styrene, 1-methylstyrene, 4-tert-butylstyrene, 2-chlorostyrene, vinyl esters of Fatty acids with 2 to 20 carbon atoms, such as vinyl acetate, vinyl propionate, Vinyl ethers of alkanols having 2 to 20 carbon atoms, such as vinyl isobutyl ether, vinyl chloride, vinylidene chloride, vinyl alkyl ketones, dienes, such as buta diene and isoprene and esters of maleic and crotonic acid in question. Ge suitable monomers are also cyclic vinyl compounds, such as vinyl pyridine, 2-methyl-1-vinylimidazole, 1-vinylimidazole, 5-vinylpyrrolidone and N-vinyl pyrrolidone. Allylic unsaturated monomers can also be used such as As allyl alcohol, allyl alkyl esters, monoallyl phthalate and allyl phthalate. Acrolein and methacrolein and polymerizable isocyanates also come in Question.

The incorporation of the vinyl ether groups a) and the co-reactive groups b) can by copolymerization in the preparation of the polyacrylates or preferred by subsequent polymer-analogous implementation. Polymerizes well Bare compounds that are also reactive with vinyl ethers are e.g. B. copolymerizable epoxy compounds, such as glycidyl (meth) acrylate or  Dihydrodicyclopentadienol (meth) acrylate, dihydrodicyclopentadienyl ethacrylate and dihydrodicyclopentadienyl cinnamate. The epoxy groups of copolymeri Based glycidyl (meth) acrylate can be directly after a cationic Me polymerize mechanism with vinyl ethers, but are also anchor groups for polymer-analogous functionalization reactions of the polymers, e.g. B. for one leadership of acrylic double bonds by reaction with (meth) acrylic acid and / or for the introduction of vinyl ether groups by reaction with Aminovinyl ether compounds, such as. B. Diethanolamine divinyl ether.

Dihydrodicyclopentadienyl groups of copolymerized dihydrodicyclopenta dienyl compounds can be started by UV radiation and / or thermally with radical-providing compounds directly with vinyl ether groups copolymerize or crosslink.

In principle, the invention is not limited to the poly mentioned leave. It may be advantageous to mix different polymer great to use. Mixtures of are particularly preferred set relatively soft and elastic, by itself no non-blocking Powder-forming polyurethane resins or polyacrylate resins with hard, good non-blocking polyester resins.

The various methods of functionalization mentioned can be found in any combination in uniform polymeric precursors or mixtures against different polymeric precursors. So one stands Type modular system available that allows the properties of the Adapt powder coatings to different requirements.

The substances according to the invention can also be combined with others, with the vinyl ether groups a) and / or the groups b) reactive and reactive therewith preferably solid compounds are mixed, such as. B. unsaturated,  preferably semi-crystalline polyesters, monomeric and / or polymeric acrylics ten, vinyl esters, vinyl ethers, allyl esters and allyl ethers, e.g. B. polyester acrylates, polyether acrylates, polyurethane acrylates and polyurethane vinyl ethers. The disturbing oxygen inhibition of the Surface suppressed in an advantageous manner.

The substances according to the invention can be copolymer-built photoinitiators have as they are explained in more detail below.

The invention also relates to preparations containing the substance according to the invention contain. The preparation according to the invention can have at least one Contain compound that is thermally or under high energy radiation Provides radicals and / or cations.

The invention also relates to uses of the preparation according to the invention tung. This includes use as or in a binder for liquid Paint systems, with or without the use of solvents, paint dispersion or powder coatings.

Such coating systems are when using the preparations according to the invention can be crosslinked with a surprisingly high reactivity and also show without Coinitiators do not inhibit surface oxygen. Next they are with thermally radical-providing compounds can be hardened by baking.

In the coating systems mentioned, curing takes place using conventional Photoi initiators of Norrish I or II type or with catalysts that are thermal Deliver radicals, such as peroxides, azo starters or C-C-labile compounds, such as B. those of the Pinacol type. Furthermore, combinations are the Have maleic and / or fumaric acid groups, in many cases in lacquer usual layer thicknesses can be hardened by baking in air.  

Copolymer photoini bound as photoinitiators are particularly preferred tiators. As copolymeric photoinitiators such. B. copolymerizable Descendants of benzophenone and compounds derived from EP-A-486 897, DE-A-38 20 463, DE-A-40 07 318 are known and in particular such compounds include those of aromatic or partially aromatic Ketones are derived and have thioxanthone structures used become. Also by adding z. B. Hydroxybenzophenone on copolymeri based epoxy compounds, such as. B. glycidyl (meth) acrylate, copoly More photo initiators can be installed. In particular polymers which, for. B. have copolymer-bound benzophenone groups, are with high Emp sensitivity UV-crosslinkable. This reactivity is further increased if at the same time structural units of the general formula I as functional Group b) are present.

If the coating systems containing the preparations according to the invention also have compounds that are thermally or under high energy Radiation and / or cations can provide the Purely thermal curing, e.g. B. by baking in air and / or by high-energy radiation with starters such as peroxides, azo starters or C-C unstable connections occur.

Such coating systems can be used for coating and / or painting most surfaces can be used. The surfaces can do everything common flat or shaped as well as fiber or particle-like substrates any materials, such as metal, wood, plastic, glass, ceramics, silicon um and other be more. The choice of the polymers to be combined Basic structure and the coreactive groups b) for the binder of the respective powder coating is carried out according to the requirements of the intended Use so that the finished paint coatings meet the requirements suffices. The basic principles in choosing the  polymeric basic structure and the co-reactive groups b) of the basis monomers to adjust the basic properties of the coatings Polymer chemist and known to the expert.

The requirements placed on the finished paint coatings can be quite different. For example, for clear top coats of metallic Paintwork in automobiles highly resistant to yellowing and weathering required, scratch resistance and gloss retention with high hardness.

With a coil-coat varnish, i.e. H. a varnish painted with the sheet metal, then wound up and later processed with deformation, maximum elasticity and adhesion are important. Even the price of the Monomers can be a selection criterion if for certain applications not a high quality of the paintwork, but a low price is required.

So z. B. the hardness, the glass transition temperature and the softening temperature of the polymers due to higher proportions of "hard" monomers, such as e.g. B. styrene or the (meth) acrylates of C1 to C3 alcohols be while z. B. butyl acrylate, ethylhexyl acrylate or tridecyl acrylate as "Soft" monomers lower these properties, but the elasticity improve action. Minor proportions of (meth) acrylic acid or (meth) acrylamide improve adhesion.

The influences of molecular weight and the molecular weight distribution, the control of the polymerization by controller, temperature sensing and Catalyst selections are generally known.

Monomers that have other functional groups in addition to the double bond can also wear for additional thermally activated crosslinking  reaction. As a rule, however, they are subordinate Amounts used and then improve z. B. liability, electrostatic Chargeability, the flow behavior of the paints and the surface smoothness. Descendants of 3-phenylacrylic acids improve further than built-in ones Stabilizers the weather resistance of the paintwork.

The paint preparations can also be pigments and / or customary paint aids such as flow aids, venting aids, other network and Contain dispersants, dyes and fillers. With paint powders too aqueous dispersions, so-called powder slurries, possible to the powder to make lacquers accessible to a liquid application.

Aqueous dispersions can also be produced, for example by (partial) - Neutralization of polymer-bound amino groups or dispersion with Help from protective colloids. It is advantageous to have a pH of <7 adjust to ver an acid catalyzed saponification of the vinyl ether avoid.

The invention also relates to the use of the preparation according to the invention tion as or in adhesives. These adhesives can melt as well Liquid system, as a solution or dispersion in suitable solvents or Water can be applied. The hardening can also be thermal and / or with high-energy radiation, preferably UV light.

The preparation according to the invention can also be used as a pouring and soaking agent can be used for electronics and / or electrical engineering. You can the preparations from the melt as a liquid system at room temperature me or as a solution or dispersions in suitable solvents or Water can be applied. Here too, the hardening can be thermal and / or with high-energy radiation, preferably UV light.  

Another use according to the invention relates to the production of Preparations for the production of moldings, the flat-shaped and / or may contain disordered fibrous reinforcing agents. Such reinforcing agents can, for example, glass fibers and / or others Fillers and reinforcing materials. Pigments may also be included.

The invention will be explained in more detail below with the aid of examples become:

Examples example 1 Polyurethane with vinyl ether and acrylate groups

Weigh in a stirred flask with an inlet vessel and a reflux condenser

387 g hexamethylene diisocyanate (2.3 mol)
185 g vinylcyclohexyl ether
1.50 g of tert-butyl cresol
0.75 g hydroquinone monomethyl ether
0.15 g phenothiazine
0.6 g dibutyltin dilaurate

The mixture is heated to 80 ° C. under a gentle stream of nitrogen and a dissolved mixture of:

90 g 1,4-butanediol (1 mol)
174 g of hydroxyethyl acrylate (1.5 mol)
58 g 1,4-butanediol monovinyl ether (0.5 mol)
30 g trimethylolpropane (0.22 mol)
50 g of vinylcyclohexyl ether (solvent) were added dropwise.

An exothermic reaction takes place. The temperature is increased by light Cool at 80 to 90 ° C and add another hour after the end of the feed Kept at 80 ° C. Thereafter, isocyanate is no longer detectable in the IR spectrum. After cooling, a waxy, slightly yellowish substance results a melting point of approx. 80 ° C.

Example 2 Polyurethane with vinyl ether and acrylate groups

The following are weighed into a stirred flask with an inlet vessel and a reflux condenser:

289 g Basonat HI 100 (trimerized hexamethylene diisocyanate with 21.8% NCO)
111 g vinylcyclohexyl ether
1 g of tert-butyl cresol
0.5 g hydroquinone monomethyl ether
0.1 g phenothiazine
0.4 g dibutyltin dilaurate (as catalyst)

The mixture is heated to 80 ° C. under a gentle stream of nitrogen and a dissolved mixture of:

11.4 g 1,4-butanediol (0.125 mol)
87 g hydroxyethyl acrylate (0.75 mol)
58 g of 1,4-butanediol monovinyl ether (0.5 mol) were added dropwise.

There is an exothermic reaction, the temperature is slightly increased Cool at 80 to 90 ° C and add another hour after the end of the feed  Kept at 80 ° C. Thereafter, isocyanate is no longer detectable in the IR spectrum. After cooling, a clear, colorless resin solution results.

Example 3 Polyacrylate with aminovinyl ether and acrylate groups

The following are weighed into a stirred flask with an inlet vessel and a reflux condenser:

486 g of butyl acetate, the template is brought to 85 ° C. Then who as the inlet I:
300 g methyl methacrylate
200 g glycidyl methacrylate (1.41 mol)
300 g butyl acrylate
200 g of ethyl hexyl acrylate and
10 g mercaptoethanol

in 90 minutes and as feed II:
30 g 2,2'Azobis (2-methylbutyronitrile) Wako-Starter V59, dissolved in
190 g butyl acetate

added in 120 minutes. It is polymerized at 85 ° C for 3 hours, cooled to 50 ° C and

67.6 g acrylic acid (0.94 mol)
0.7 g of tert-butyl cresol
0.35 g hydroquinone monomethyl ether
0.07 g phenothiazine and
0.7 g dimethylaminopyridine
added and stirred at 95 to 100 ° C for 8 hours. A resin solution with an acid number of 6.2 is then obtained. This solution is cooled to 60 ° C and there are:

74 g diethanolamine divinyl ether (0.47 mol)
dropped in an hour. There is a slightly exothermic reaction. After a further 3 hours at 80 ° C, the mixture is cooled. The result is a viscous yellowish resin solution.

Example 4 Polyacrylate with aminovinyl ether and dihydrodicyclo pentadienyl groups

The following are weighed into a stirred flask with an inlet vessel and a reflux condenser:

486 g of butyl acetate, the initial charge is brought to 85 ° C., then as feed I:
200 g methyl methacrylate
106.5 g glydidyl methacrylate (0.75 mol)
300 g butyl acrylate
200 g of ethyl hexyl acrylate
100 g dihydrodicyclopentadienyl acrylate and
10 g mercaptoethanol in 90 minutes and as feed II:
30 g 2,2'Azobis (2-methylbutyronitrile) Wako-Starter V59, dissolved in:
180 g butyl acetate
added in 120 minutes, it is post-polymerized at 85 ° C for 3 hours, cooled to 60 ° C and it is

118 g diethanolamine divinyl ether (0.75 mol)
added in an hour under a slightly exothermic reaction. After a further 3 hours at 80 ° C., a viscous, slightly yellowish resin solution results.

Example 5 Polyacrylate with aminovinyl ether, acrylate and dihydro dicyclopentadienyl groups

The following are weighed into a stirred flask with an inlet vessel and a reflux condenser:

486 g of butyl acetate, the initial charge is brought to 85 ° C., then as feed I:
200 g methyl methacrylate
100 g dihydrodicyclopentadienyl acrylate
200 g glycidyl methacrylate (1.41 mol)
300 g butyl acrylate
200 g of ethyl hexyl acrylate and
10 g mercaptoethanol

in 90 minutes and as feed II:
30 g 2,2'Azobis (2-methylbutyronitrile) Wako-Starter V 59, dissolved in
180 g butyl acetate

added in 120 minutes. It is polymerized at 85 ° C for 3 hours, cooled to 50 ° C and
67.6 g acrylic acid (0.94 mol)
0.7 g of tert-butyl cresol
0.35 g hydroquinone monomethyl ether
0.07 g phenothiazine and
0.7 g dimethylaminopyridine

added and stirred at 95 to 100 ° C for 8 hours. A resin solution with an acid number of 6.2 is then obtained. This solution is cooled to 60 ° C and it will be

74 g diethanolamine divinyl ether (0.47 mol)
dropped in an hour. There is a slightly exothermic reaction. After a further 3 hours at 80 ° C, the mixture is cooled.

The result is a viscous yellowish resin solution.

Comparative Example 1 Comparative example polyacrylate only with acrylate group pen

The following are weighed into a stirred flask with an inlet vessel with a reflux condenser:

486 g of butyl acetate, the initial charge is brought to 85 ° C., then feed I
300 g methyl methacrylate
200 g glycidyl methacrylate (1.41 mol)
300 g butyl acrylate
200 g of ethyl hexyl acrylate and
10 g mercaptoethanol in 90 minutes and as feed II:
30 g of 2,2'-azobis (2-methylbutyronitrile) Wako-Starter V 59, dissolved in 180 g of butyl acetate

added in 120 minutes. It is polymerized at 85 ° C for 3 hours, cooled to 50 ° C and

101 g acrylic acid (1.39 mol)
0.7 g of tert-butyl cresol
0.35 g hydroquinone monomethyl ether
0.07 g phenothiazine and
0.7 g dimethylaminopyridine

added and stirred at 95 to 100 ° C for 8 hours. To after cooling, a clear, viscous resin solution is obtained the acid number 7.9.

Test paints

The preparation of the test lacquers and the production of the test panels took place in a laboratory protected against UV light. The constituents of the test varnishes were premixed in glass bottles with a stirring spatula, these mixtures were stored in a drying cabinet at 50 ° C. for one hour and stirred again. After cooling to room temperature, clear viscous solutions resulted in all cases. The solutions were then drawn onto a degreased, bare steel sheet using a doctor blade with a gap height of 60 μm. The sheets with solutions L6 to L14 and VL1 to VL3 were then stored in a vacuum drying cabinet at 40 ° C. overnight to remove the solvent butyl acetate. Afterwards there are liquid viscous resin films on all test panels. The test panels were then irradiated under a UV light mercury vapor lamp with an emission maximum at approx. 365 nm and an energy output of 19 mJ / cm ² at the level of exposure until the films were still undone after 10 minutes under an acetone-damp cotton ball remained. If a surface inhibition of the films was observed, an uncrosslinked, acetone-soluble layer then present was first wiped off and the swellability of the crosslinked layer underneath was assessed.

Test results

The examples show that the procedure according to the invention is exceptional high UV light sensitivity and an oxygen inhibition of the Surface is avoided.

Claims (16)

1. With high-energy radiation and / or thermally curable substances an oligomeric or polymeric basic structure, the end and / - or laterally at least one vinyl ether group a) and at least one different from the vinyl ether groups a), with the groups a) have co-active group b), with on average at least one Vinyl ether group a) and one coreactive group b) per oligomer or Polymer molecule are present. 2. Substances according to claim 1, characterized in that the co-reactive Groups b) are copolymerizable with the vinyl ether groups a). 3. Fabrics according to claim 1 or 2, characterized in that the oligo mere or polymeric basic structure formed by C-C linkages is, which have double and / or triple bonds and / or out are selected from ester, ether, urethane, amide, imide, imidazole, Ketone, sulfide, sulfone, acetal, urea, carbonate and siloxane ver ties. 4. Fabrics according to one of claims 1 to 3, characterized in that the oligomeric or polymeric basic structure is linear, branched, ring-shaped or is built dentrimer. 5. Substances according to one of claims 1 to 4, characterized in that the co-reactive groups b) are selected from maleinate, fumarate, itaconate, (meth) acrylate, allyl, epoxy, alkenyl, cycloalkenyl, Have vinylaryl and cinnamate groups and / or structural units of the general formula I. 6. Substances according to claim 5, characterized in that the Structural units of the general formula I in the co-reactive groups b) in the form of esters of (oligo) dihydrodicyclopentadienol with mono- or polyfunctional carboxylic acids according to the general formula II are built. 7. Substances according to claim 5 or 6, characterized in that the structural units of the general formulas I and II in the co-reactive groups b) in the form of (oligo) -dihydrodicyclopentadienol semesters of maleic acid and fumaric acid according to the general formula III are built and the Connection to the basic structure via ester and / or amide groups is established. 8. Fabrics according to one of claims 1 to 7, characterized in that they have copolymer built-in photoinitiators. 9. Preparation containing a substance according to one of claims 1 to 8 contains. 10. Preparation according to claim 9, characterized in that it at least least contains a compound that is thermally or under high energy Radiation provides radicals and / or cations. 11. Use of the preparation according to claim 9 or 10 as or in a binder for liquid coating systems, with or without use of solvents or paint dispersions. 12. Use of the preparation according to claim 9 or 10 as or in a binder for powder coatings. 13. Use according to claim 11 or 12, characterized in that additionally pigments and / or auxiliaries customary in paint are included. 14. Use of the preparation according to claim 9 or 10 as or in Adhesives. 15. Use of the preparation according to claim 9 or 10 as or in Pouring and impregnating agents for electronics and / or electrical engineering. 16. Use of the preparation according to claim 9 or 10 for the Her position of shaped bodies.