JP2002522580A - Materials and preparations curable by high energy irradiation and / or heat - Google Patents

Abstract

  (57) [Summary] The present invention relates to oligomers having at least one vinyl ether group a) and at least one vinyl ether group a), which are different from at least one vinyl ether group a) in the terminal and / or lateral positions, and which are co-reactive with the group a) High-energy radiation and / or having, on average, at least one vinyl ether group a) and one co-reactive group b) present per oligomer or polymer molecule. It relates to a substance which can be cured by heat. The invention also relates to preparations containing the substances according to the invention and to the use of the preparations as binders in liquid coating systems, powder coatings, adhesives, electronics and / or electrical engineering. It also relates to the use as or in casting agents and impregnating agents and to the production of moldings.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to substances and formulations which are curable by high energy irradiation and / or heat and their use according to the invention.

The starting point of the present invention was the consideration for the field of paints curable under UV light for use in liquid paints and powder paints. Such coating systems are gaining field of use one after another for solvent saving reasons. However, a major problem with known UV paints is the inhibition of curing of the paint surface by oxygen in the air. This deterrence has to be avoided by accelerating the curing by lamps with significantly higher energy densities and amine co-initiators. These amines often cause unpleasant odors.

[0003] In the case of UV-powder paints, there are, in addition, other problems arising from the conflicting requirements of good blocking resistance of the powders on storage and good leveling of the melted paint film. The glass transition point and melting point should be as high as possible for good blocking resistance, while good leveling to avoid curing reactions and substrate damage before forming optimal surface smoothness And must be low for application on heat-sensitive substrates. Similarly, for improved surface smoothness, the melt has a low viscosity and the reaction must start with some delay. These assumptions are difficult to achieve with powder coatings based on the known thermal activation reaction between a resin and a curing agent, e.g., a polyepoxide resin and a dicarboxylic acid curing agent, since the melting process and the This is because the reaction for increasing the viscosity has already started. In the case of radiation-curable powder coatings, on the contrary, the separation between the melting process and the crosslinking must be possible. To meet these requirements, various methods are known in the prior art.

[0004] US Pat. No. 4,129,488 and US Pat.
No. 4,163,810 discloses UV curable powder coatings having the special spatial requirements of ethylenically unsaturated polymers. According to this, the binder consists of an epoxide-polyester-polymer, wherein the epoxide adduct is spatially separated from the polyester adduct by means of a linear polymer chain. It is arranged in a way. The polymer additionally contains a photoinitiator chemically bonded.

[0005] EP-A-0 650 978, EP-A-0 650 978
-A) 0650979 and EP-A-065098.
No. 5 discloses a copolymer in which a substantial component is a monomer having a relatively high proportion of a methacrylic acid structural element and which can be used in powder coatings curable using UV light as a binder. ing. This copolymer is characterized by a relatively narrow molecular weight distribution.

[0006] EP-A 0 410 242 discloses polyurethanes having certain (meth) acryloyl groups, which can be crosslinked without using crosslinking components or peroxides and are therefore storage-stable. Binders for UV-crosslinkable powder coatings are known. Addition of a photoinitiator is required for crosslinking using UV irradiation.

[0007] Furthermore, according to EP-A-0 636 669, an unsaturated polymer optionally containing cyclopentadiene and a crosslinking agent having vinyl ether groups, vinyl ester groups or (meth) acryl groups UV light-curable binders for powder coatings are known.

[0008] WO 93/25596 discloses polyacrylates as topcoats for motor vehicles which have been functionalized with double bonds in various ways.

[0009] DE-A 42 226 520 discloses a liquid composition comprising an unsaturated polymer in the form of an unsaturated polyester and a compound having (meth) acryloyl and / or vinyl ether groups. are doing. These compositions can also be crosslinked with radical formers or by radiation curing and used as binders for paints. At the time of crosslinking by UV irradiation, it is necessary to add a photoinitiator.

The problem with these prior art UV coatings is that additional co-initiators, usually amines, need to be added for high light sensitivity and to avoid known surface oxygen suppression. Happens. The decomposition products of these photoinitiators remain in the cured coating and cause unpleasant odors.

Further according to EP-A 0 322 808, it consists of a mixture of an ethylenically unsaturated polyester component which may also comprise an ethylenically unsaturated polyester oligomer and a non-polymerized vinyl ether component. A liquid, high energy radiation curable binder is disclosed, and one prior art is known. In this case, the vinyl ether component is selected so as to have on average at least two vinyl ether groups per molecule of the vinyl ether component capable of reacting with the ethylenic double bond of the polyester component.

Starting from these prior arts, the present invention provides an unpleasant odor when used in high-energy radiation and / or heat-curable paint systems without oxygen suppression of the paint surface. It was based on the task of providing substances and preparations which avoid the use of evolving amines and other co-initiators and which have a wider field of use.

According to the invention, the object is to provide at least one vinyl ether group a) and at least one vinyl ether group a) in both terminal and / or lateral positions.
In contrast to (a), it has an oligomeric or polymeric substructure with a group (b) which is co-reactive, preferably copolymerizable, with an average of at least one vinyl ether group (a) And one co-reactive group b) was solved by the substances present per oligomer or polymer molecule.

Paint systems with such substances surprisingly do not show a high UV-reactivity and no oxygen suppression of the surface when cured in air. This has the advantage that the use of amines and other co-initiators can be avoided.

It is also possible to cure to the B-state, ie a partially cured state in which the curing is interrupted and can then be started again.

It is to be noted that, in connection with the substances according to the invention, also in the case of customary, randomly generated polymer structures as well as polymer-like functionalizations under the reaction conditions, the polymer molecules are, for example, vinyl ether There is a problem known to the expert that only one type having a group a) or having no functionalization can be formed. Such a little or no functionalized polymeric substructure can impair the properties of the polymers according to the invention, so that a low proportion of such a little or no functionalized polymeric substructure is as low as possible. It is advantageous to adjust the production method to produce Suitable methods for this are known to the polymer expert. Among these are the excess use of non-reactive substances or, if appropriate, the subsequent separation of excess residues in the final paint binder. Residues which may still remain do not substantially affect the performance of the invention when using the claimed substances.

The fact that the oxygen suppression of the surface does not take place even with the extremely high UV reactivity observed during the use of the substances according to the invention in paint systems capable of high-energy irradiation and / or heat curing is according to the invention. In the case of substances, self-crosslinking can take place by functionalization of the polymer substructure, whereas in the prior art it can be attributed to the fact that it is a composition of a substance mixture that must first be crosslinked with each other.

The general structural principle of the substance according to the invention can be illustrated as follows.

[0019]

[Outside 1]

According to the structural principle represented here, the functional groups a) and b) are linked to the oligomeric or polymeric substructure at the same or different positions, or can terminate these as appropriate. . The functional groups a) and b) can be present once or multiple times on the same group. That is, for example, one glycidyl methacrylate can react with one terminal NH ₂ group or one molecule of ethanolamine divinyl ether can react with one terminal epoxide group. In addition, polymeric substructures having multiple OH groups at the same lateral or terminal position can be vinylated. The value of n is
It is between 0 and 6, preferably 1 or 2.

The oligomeric or polymeric substructure can be formed by CC-bonds with double and / or triple bonds and / or ester, ether, urethane, amide bonds Imide bond, imidazole bond, ketone bond, sulfide bond, sulfone bond, acetal bond, urea bond, carbonate bond and siloxane bond.

Furthermore, the oligomeric or polymeric substructure can be configured in a linear, branched, cyclic or dendritic manner.

Advantageously, the substance according to the invention is a compound having a functional polymer and a functional group a) or b) and at least one other group capable of reacting with a functional group of the oligomeric or polymeric substructure. And a polymer-like reaction with

As co-reactive, preferably copolymerizable, functional groups b), in particular maleate groups,
Fumarate, itaconate, (meth) acrylate, allyl, epoxide, alkenyl, cycloalkenyl, vinylaryl and cinnamate groups and / or preferably of the general formula I

[0025]

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The structural unit corresponds to:

If the structural units of the general formula I are used as functional groups b), the coating systems have a low sensitivity to heat during production and nevertheless good baking properties in oxygen in the air It is characterized by a short curing time under the combined application of heat, UV light, in the case of powder coatings a good blocking resistance of the powders on storage and a significantly better surface smoothness of the coatings obtained therefrom. .

In a preferred embodiment, the structural units of the general formula I comprise, in the co-reactive group b), (oligo) -dihydrodicyclopentadienol and the general formula II

[0029]

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Can be incorporated in the form of an ester with a monofunctional or polyfunctional carboxylic acid.

An important class of polymers according to the invention is epoxide resins. The basic structure may be a multiply epoxy-functionalized polymer, oligomeric or monomeric compound, for example the type of bisphenol-A-epoxide compound or the type of bisphenol-A-epoxide resin by reaction with a compound that is reactive with epoxide groups. It is suitable. Epoxide groups can be functionalized with compounds having a vinyl ether group a) and thus a co-reactive group b) and at least one group capable of reacting with other epoxides. Examples of compounds of this type according to the invention include commercially available epoxide resins known per se and (meth) acrylic acid and / or

[0032]

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Or a reaction product of a polyacrylate having glycidyl (meth) acrylate incorporated into a copolymer or a product from a partial reaction with an amino compound, such as aminobutyl vinyl ether or diethanolamine vinyl ether, or an amino compound, or Obtained from the reaction product of a polyurethane resin with a hydroxyl-functional epoxide compound, such as glycid (2,3-epoxypropanol-1), together with such a compound.

Polyurethane resins are another important class of polymers according to the invention, which are multifunctional isocyanate compounds and acrylates and vinyl compounds, hydroxyacrylates or aminoacrylates and hydroxyvinylates or aminovinylates. , Optionally with a compound reactive with another isocyanate, such as a hydroxyl compound.

As the isocyanate compound, compounds which are commercially available and known per se, for example, toluylene diisocyanate (TDI), 4,4′-methylene-di (phenol isocyanate) (MDI), and isophorone diisocyanate (IPDI) , hexamethylene diisocyanate (HMDI), other _C 2 _{-C 12} - alkylene diisocyanate, other _C 2 _{-C 12} - cycloalkylene diisocyanate, naphthalene diisocyanate, other alkyl aryl diisocyanates, For example, phenylene diisocyanate, diphenyl diisocyanate and various positional isomers of these compounds can be used. In addition, higher isocyanate-functional biuretized and isocyanurated products derived from these isocyanates, such as isomerates trimerized and oligomerized via uretdione groups, and monoisocyanates Higher isocyanates obtained from the above isocyanates by dimerization or oligomerization with amines or water correspond.

Of particular interest are polyisocyanates having diisocyanurate groups.
In this case, mention may in particular be made of the trimerized products of the diisocyanates mentioned above.

In order to prepare the binders according to the invention, the above-mentioned isocyanates or mixtures of these isocyanates are separated from groups which are reactive with isocyanates and which are reactive with isocyanates by other groups a) and reacting with the compound having b). Also, the base a
Compounds which do not have a) or b) and which are reactive with isocyanates can also be used. The compound to be reacted with the isocyanate is linear or branched, aromatic, alicyclic, araliphatic, heterocyclic and / or optionally substituted one or more times with the isocyanate. be able to. Examples thereof include C ₁ -C ₂₀ -hydroxyalkyl vinyl ethers such as hydroxyethyl monovinyl ether, hydroxybutyl monovinyl ether, cyclohexane dimethanol monovinyl ether, hexanediol monovinyl ether, ethylene glycol monovinyl ether, propylene glycol monovinyl ether and polyalkylene glycol monovinyl. vinyl ethers and diethanolamine divinyl ether, aminopropyl vinyl ether, C 1 _-C 20 _- hydroxyalkyl (meth) - acrylic esters, such as hydroxyethyl acrylate, hydroxybutyl acrylate and polyalkylene glycol monoacrylate, allyl alcohol, dihydro dicyclopentadienyl enol, And one of the following Adduct having a hydroxyl group to the glycol dicyclopentadiene enol according to formula V (DCPD),
Ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butanediol isomer, hexanediol, neopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, unsaturated hydroxyl compounds such as allyl alcohol, partially etherified polyfunctional hydroxyl compounds For example, trimethylolethane monoallyl ether, trimethylolethanediallyl ether, trimethylolpropane monoallyl ether,
Trimethylolpropane diallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, alkylene diols such as butene-2-diol-1,4 and alkoxylated alkylene diols, preferably ethoxylated and propoxylated butene-2- Butene-2 having a degree of alkoxylation of 1 to 10 alkylene oxides per mole of diol-1,4
-Diol-1,4.

The selection and combination of each of the desired starting compounds will depend on the desired properties of the material made therefrom. Adjustment of the desired molecular weight and, if appropriate, viscosity can be achieved by the simultaneous use of monofunctional compounds. The means mentioned above and the selection of suitable polymerization techniques, optionally the simultaneous use of solvents and the control of the polymerization by means of catalysts, are possible for the expert on the basis of his / her expertise.

The concept of polyurethanes is, within the scope of the present invention, not only compounds whose main chains are linked via urethane compounds, but also compounds having an ester or ether chain component, such as polyester urethanes and polyethers Must contain urethane.

Saturated and unsaturated polyester resins which are functionalized according to the invention with the groups a) and b) are another important polymer class for the binders according to the invention. At that time, the carboxyl group 2 which is commonly used and known for the constitution of the polyester resin is used.
More than one carboxylic acid and / or their anhydrides and / or their esters and hydroxyl compounds with more than two OH groups are relevant. Alternatively, monofunctional compounds can be used together, for example to adjust the molecular weight of the polycondensate.

As the carboxylic acid component, for example, α, β-ethylenically unsaturated carboxylic acid such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, saturated aliphatic carboxylic acid and anhydrides thereof such as succinic acid Acids, adipic acid, coric acid, sebacic acid, azelaic acid, natural fatty acids and polymerized natural fatty acids such as linseed oil fatty acids, dimer linseed oil fatty acids and polymer linseed oil fatty acids, castor oil, castor oil fatty acids, saturated cycloaliphatic carboxylic acids And their anhydrides, for example, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, norbonenedicarboxylic acid, aromatic carboxylic acids and their anhydrides, for example phthalic acid in its isomeric form, also tricarboxylic acids and Tetracarboxylic acid and this Anhydrides such as trimellitic acid, pyromellitic acid and polycarboxylic acids partially esterified with allyl alcohol, such as monoallyl trimellitic acid or diallyl pyromellitic acid, with benzophenonecarboxylic acid being particularly important Yes, because UV copolymerizable structures can be incorporated via this copolymer.

As the hydroxy component, for example, at least 2 optionally alkoxylated
Divalent aliphatic and / or cycloaliphatic alcohols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, butanediol isomer, hexanediol, trimethylolpropane, pentaerythritol, neopentyl glycol, cyclohexanedimethanol, bisphenol A Hydrogenated bisphenol A, OH polyfunctional polymers such as hydroxyl-modified polybutadiene or polyurethane prepolymers having hydroxyl groups, glycerin, mono- and diglycerides of saturated and unsaturated fatty acids,
In particular, monoglycerides of linseed oil or sunflower oil are applicable. Furthermore, polyfunctional hydroxyl compounds (partially) etherified with unsaturated alcohols, for example allyl alcohol, for example trimethylolethane monoallyl ether, trimethylolethanediallyl ether, trimethylolpropane monoallyl ether, trimethylolpropanediallyl Ethers, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, butene-2-diol-1,4 and alkoxylated butene-2-diol-1,4 also apply.

If monofunctional substances are used for controlling the molecular weight, these are preferably monofunctional alcohols, such as ethanol, propanol, butanol, hexanol, decanol, isodecanol, cyclohexanol, benzyl alcohol or allyl Alcohol. The concept of polyesters within the scope of the present invention also includes polycondensates having amide and / or imide groups in addition to the ester groups, for example those obtained using amino compounds together. Modified polyesters of this type are known, for example, from DE-A 1 57 00 273 and DE-A 17 200 233. These polyesteramides or polyesterimides have special requirements,
For example, with respect to heat resistance, chemical resistance, hardness and scratch resistance, they are often more satisfactory than pure polyesters.

DCPD can also be added to the double bonds of the unsaturated polyesters used, so that the general formula IV

[0045]

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The endmethylene tetrahydrophthalic acid structure of can be incorporated.

In this endomethylene tetrahydrophthalic acid structure there are double bonds and / or terminal double bonds of the polyester linked in the chain, for example those introduced via substances according to the general formula III. be able to.

The introduction of the groups a) and b) according to the invention can be effected by cocondensation and / or by polymer-analogous reactions on polyesters with functional groups. Examples of co-condensation include trimethylolpropane diallyl ether and trimethylolpropane monoallyl ether, pentaerythritol diallyl ether and pentaerythritol monoallyl ether, butene-2-diol-1,4, alkoxylated butene-2-diol-1, 4 and allyl alcohol at the same time.

Examples of polymer-like reactions to functionalized polyesters are, for example, polyesters which are incompletely condensed linear and / or branched prepolymers and which still have free hydroxyl groups as well as free OH groups This is an addition to resin. These can react an unsaturated glycidyl compound and vinyl ether with a carboxyl group. Advantageously, the free carboxyl groups are first reacted with an unsaturated glycidyl compound in order to prevent acid-catalyzed polymerization of the vinyl ether. Suitable unsaturated glycidyl compounds are, for example, glycidyl (meth) acrylates, glycidyl undecenoate, polyfunctional epoxide resins and / or (meth) acrylated products of allyl glycidyl ethers, preferably glycidyl (meth) ) Add acrylate. Following this reaction, the hydroxyl group is reacted with diisocyanate and hydroxyvinyl ether.

Advantageously, however, firstly a diisocyanate having various reactive isocyanate groups, for example isophorone diisocyanate, is reacted with a half equivalent of hydroxyvinyl ether, and the reaction product is then prepolymerized. With polyester in the form of In the above reaction, a hydroxyl-functional acrylate can additionally be used together with the hydroxyvinyl ether. The pure hydroxyl-functional prepolymeric polyesters can also be reacted in the manner described lastly and also with hydroxyvinyl ethers and hydroxyl-functional compounds having groups b), for example hydroxyalkyl (meth) acrylates or allyl alcohol. General formula I
In this manner, the introduction of the group by is also possible by the simultaneous use of commercially available dihydrodicyclopentadienol. However, advantageously, the general formula I
Are introduced into the polyesters via cocondensation of maleic acid with a half ester of dihydrodicyclopentadienol of the general formula III. These half esters are obtained in a facile reaction from maleic anhydride (MSA), water and dicyclopentadiene (DCPD), and by direct addition of DCPD to MSA. In addition, DCPD can be added directly to other acids and / or acidic polyesters. However, these reactions are often difficult to proceed, and
For example, a catalyst using etherified BF ₃ is required.

Further, for example, from US Pat. No. 5,252,682, DCP
In the reaction of D with MSA, the formula V

[0052]

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The side reaction due to may occur subordinately. It is known that this side reaction also helps to introduce the structure according to general formula I.

The hydroxy-functional compounds for the introduction of groups according to general formula I are dihydrodicyclopentadienyl alcohols and, advantageously, cost-effectively of formula VI

[0055]

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Is an adduct to glycol of DCPD obtained using an acidic catalyst according to

Polyacrylate resins which are functionalized according to the invention with the groups a) and b) are another important class of polymers according to the invention, which are acrylic esters and optionally other copolymerizable compounds. Obtained by copolymerization.

Preferred processes for the preparation of polyacrylates are solvent-free radical bulk polymerization in a stirred reactor under pressure, more preferably than at temperatures above the melting point of the polymer formed, particularly preferably at temperatures above the melting point of the polymer formed. Is carried out in a continuous flow reactor at 140 ° C. or higher.

This process results in polyacrylates having a low molecular weight and a narrow molecular weight distribution, which is particularly desirable in the case of powder coatings because of the narrow melting range and low melt viscosity obtained therefrom. In addition, no co-solvent removal is required during bulk polymerization, and it is possible to incorporate the pigment and coating aid directly into the melt. The polyacrylate resins according to the invention can also be produced in solvents.

As components for the construction of the polyacrylate resins, for example, the known acrylic and methacrylic acids and aliphatic, cycloaliphatic, araliphatic and aromatic carbon atoms of 1 to
Esters with alcohols having 40 are preferred, for example methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) Acrylate, t-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, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, furfuryl (meth) acrylate and esters of 3-phenylacrylic acid and various isomers thereof Body forms such as methyl cinnamate, ethyl cinnamate, butyl cinnamate, benzyl cinnamate, cyclohexyl cinnamate, isoamyl cinnamate, tetrahydrofurfuryl cinnamate, furfuryl cinnamate, acrylamide, methacrylamide, Methylol acrylamide, methylol methacrylamide, acrylic acid, methacrylic acid, 3-phenylacrylic acid,
Hydroxyalkyl (meth) acrylates, such as ethyl glycol mono (meth) acrylate, butyl glycol mono (meth) acrylate, hexanediol mono (meth) acrylate, glycol ether (meth) acrylates, such as methoxyethyl glycol mono (meth) acrylate, ethyl Oxyethyl glycol mono (meth) acrylate, butyloxyethyl glycol mono (meth) acrylate, phenyloxyethyl glycol mono (meth) acrylate,
Glycidyl acrylate, glycidyl methacrylate, amino (meth) acrylate, such as 2-aminoethyl (meth) acrylate.

As another component, a monomer capable of undergoing radical copolymerization, for example, styrene, 1-methylstyrene, 4-t-butylstyrene, 2-chlorostyrene, carbon atoms of 2 to 2
Vinyl esters of zero fatty acids, 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 butadiene and isoprene And esters of maleic acid and crotonic acid. Suitable monomers are or cyclic vinyl compounds such as vinylpyridine, 2-methyl-1-vinylimidazole, 1-vinylimidazole,
-Vinylpyrrolidone and N-vinylpyrrolidone. Also, allylic unsaturated monomers such as allyl alcohol, allyl alkyl esters, monoallyl phthalate and allyl phthalate can be used. Also included are acrolein and methacrolein and polymerizable isocyanates.

The incorporation of the vinyl ether groups a) and the co-reactive groups b) can be effected by copolymerization in the preparation of the polyacrylates or, preferably, by a subsequent polymer-analogous reaction. Good polymerizable compounds which are additionally reactive with vinyl ethers are, for example, copolymerizable epoxide compounds such as glycidyl (meth) acrylate or dihydrodicyclopentadienol (meth) acrylate, dihydrodicyclopentadienyl ethane Acrylate and dihydrodicyclopentadienyl cinnamate. The epoxide groups of the copolymerizable glycidyl (meth) acrylate can be polymerized directly with vinyl ethers according to a cationic mechanism, but also with an anchor group for the polymer-like functionalization reaction of the polymer, such as reaction with (meth) acrylic acid. For the introduction of acrylic double bonds and / or for the introduction of vinyl ether groups by reaction with aminovinyl ether compounds such as diethanolamine divinyl ether.

The dihydrodicyclopentadienyl group of the copolymerizable dihydrodicyclopentadienyl compound can be directly copolymerized and crosslinked with the vinyl ether group by UV irradiation and / or thermal initiation using a radical-supplying compound.

Basically, the invention is not limited by the type of polymer described above. It may be advantageous to use mixtures of different polymer types. Particularly advantageously, in this case, a polyurethane resin or a polyacrylate resin which adjusts relatively softly and elastically and forms a powder which itself is not blocking-resistant, and a polyester resin which is hard and has good blocking resistance. A mixture comprising:

The various methods described above for functionalization can be performed in a single polymer precursor or a mixture of various polymer precursors in any combination. That is, a kind of unit system can be used in which the properties of the powder coating can be adapted to greatly different requirements.

The substances according to the invention are also compounds which are reactive and preferably solid with the other vinyl ether groups a) and / or groups b) which are co-reactive therewith, for example unsaturated and preferably partially crystalline Polyesters, monomeric and / or polymeric acrylates, vinyl esters, vinyl ethers, allyl esters and allyl ethers such as polyester acrylates, polyether acrylates, polyurethane acrylates and polyurethane vinyl ethers can also be mixed. Also, in such a mixture, oxygen suppression of harmful surfaces is advantageously suppressed.

The substances according to the invention can have a photoinitiator incorporated in the copolymer as described in detail below.

The present invention also relates to preparations containing the substances according to the invention. The preparations according to the invention can then comprise at least one compound in which thermal or high-energy irradiation supplies radicals and / or cations.

The present invention also relates to the use of the preparation according to the invention. This includes the use as or in binders for liquid coating systems, coating dispersions or powder coatings, with or without solvents.

Such coating systems are surprisingly highly reactive and can be crosslinked when using the preparations according to the invention and do not show surface oxygen suppression without the use of co-initiators. .
In addition, they can be baked using thermal radical-generating compounds.

The curing takes place in the above-mentioned coating systems with the customary Norrish I or II type photoinitiators or thermally radical-forming catalysts, such as peroxides, azo initiators or C—C -With unstable compounds, for example compounds of the pinacol type. In addition, combinations having maleic acid groups and / or fumaric acid groups can often be cured to the customary layer thickness by baking the paint in air.

Particular preference is given to photoinitiators bound to copolymers as photoinitiators. As copolymeric photoinitiators, for example, benzophenone and EP-A (EP-A)
No. 4,868,973, DE-A-38 20 463, DE-A-400 73 318, in particular derived from aromatic or partially aromatic ketones. A derivative which can be copolymerized with a compound containing a compound having a thioxanthone structure can be used. Also, copolymeric photoinitiators can be incorporated, for example, by addition of hydroxybenzophenone to a copolymerizable epoxide compound, such as glycidyl (meth) acrylate. In particular, for example, polymers having benzophenone groups attached to the copolymer can be crosslinked with high UV sensitivity. This reactivity is even higher when the structural units of the general formula I are present at the same time as functional groups b).

If the coating system comprising the preparation according to the invention additionally contains compounds which supply radicals and / or cations by thermal or high-energy irradiation, the curing is purely thermal, for example in air. And / or high energy irradiation with initiators such as peroxides, azo initiators or CC-labile compounds.

Such a coating system can be used for coating and / or painting various surfaces. The surface may very generally be a planar or molded and fibrous or particulate substrate of any material, such as metal, wood, synthetic resin, glass, ceramics, silicon and various others. The choice of the polymeric substructure to be combined for each powder coating binder as well as the co-reactive groups b) is such that, depending on the requirements of the intended use, the finished paint coating will meet the submitted requirements. Do. In doing so, the basic principles in the selection of the polymeric substructure and the co-reactive groups b) of the monomers on which it is based, which serve as the basis for the adjustment of the basic properties of the paint, are given to polymer chemists and experts. Is known.

The demands made on a finished paint coating will vary widely. For example, for topcoats of metallic coatings for motor vehicles, the highest yellowing and weathering resistance, scratch resistance and gloss retention are required at the same time as high hardness.

High elasticity and adhesion are problematic when the paint is applied in a coil-coat paint, ie a coiled steel sheet line (Blechbahn), then wound up and subsequently processed for shaping. Also, where a particular application requires a lower price instead of a higher quality coating, the price of the monomer is also a selection criterion.

That is, for example, the hardness, glass transition temperature, and softening temperature of a polymer are “hard”.
It can be increased by the proportion of monomers such as styrene or (meth) acrylates of C ₁ -C ₃ alcohols, whereas, for example, butyl acrylate, ethylhexyl acrylate or tridecyl acrylate reduces these properties as “soft” monomers, Instead, it improves elasticity. A lower proportion of (meth) acrylic acid or (meth) acrylamide improves the adhesion.

The influence of the molecular weight and the molecular weight distribution, the control of the polymerization by the selection of regulators, temperature control and catalysts are basically known.

[0079] Monomers having other functional groups in addition to the double bond can also be used for crosslinking reactions that allow for additional heat activation. Usually, however, they are used in small amounts, thereby improving, for example, paint adhesion, electrostatic charging, paint leveling and surface smoothness. Derivatives of 3-phenylacrylic acid further improve the weatherability of the coating as a built-in stabilizer.

The paint preparations can additionally contain pigments and / or customary paint auxiliaries, such as leveling auxiliaries, degassing auxiliaries, other wetting and dispersing agents, coloring materials and filling materials. . In the case of paint powders, aqueous dispersions, so-called powder slurries, are also possible in order to make the powder paints applicable for liquid applications.

Aqueous dispersions can also be prepared, for example, by (partial) neutralization of the polymer-bound amino groups or by dispersion using protective colloids. At that time, it is advantageous to adjust the pH to 7 or more in order to avoid saponification of the vinyl ether by the acid catalyst.

The present invention also relates to the use of the preparations according to the invention as or in an adhesive. These adhesives can be applied from the melt as a liquid system, as a solution or dispersion in a suitable solvent or water. Also in this case, the curing can be effected by thermal and / or high-energy irradiation, preferably by UV light.

The preparations according to the invention can additionally be used as casting and impregnating agents for electronics and / or electrical engineering. The preparations can be applied from the melt at room temperature as liquid systems or as solutions or dispersions in suitable solvents or water. Also in this case, the curing can be effected by thermal and / or high-energy irradiation, preferably by UV light.

Other uses according to the invention also relate to the production of preparations for the production of moldings which may comprise a fibrous reinforcement shaped and / or arranged in a plane. Such reinforcements may be, for example, glass fibers and / or other fillers and reinforcements. In addition, a pigment may be included.

Hereinafter, the present invention will be described in detail with reference to Examples.

EXAMPLES Example 1 Polyurethane with Vinyl Ether Groups and Acrylate Groups The following are weighed into a stirred flask with a feed vessel and a reflux condenser.

387 g of hexamethylene diisocyanate (2.3 mol), 185 g of vinylcyclohexyl ether, 1.50 g of t-butylcresol, 0.75 g of hydroquinone monomethyl ether, 0.15 g of phenothiazine, 0.6 g of dibutyltin laurate.

The mixture was heated to 80 ° C. under a gentle stream of nitrogen, and the following dissolved mixture was added dropwise over 1 hour.

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

An exothermic reaction occurs. The temperature is lightly cooled to 80-90 ° C, one more after the addition is complete.
Hold at 80 ° C. for time. Thereafter, no isocyanate is detected in the IR spectrum. After cooling, a waxy, pale yellow substance having a melting point of about 80 ° C. is obtained.

Example 2 Polyurethane with Vinyl Ether and Acrylate Groups The following are weighed into a stirred flask with a feed vessel and a reflux condenser.

Basonat HI100 (trimerized hexamethylene diisocyanate, NCO content 21.8%) 289 g, vinylcyclohexyl ether 111 g, t-butylcresol 1 g, hydroquinone monomethyl ether 0.5 g, phenothiazine 0.1 g 0.4 g of dibutyltin laurate (as catalyst).

The mixture was heated to 80 ° C. under a gentle stream of nitrogen, and the following dissolved mixture was added dropwise over 1 hour.

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

An exothermic reaction took place and the temperature was slightly cooled to 80-90 ° C.
Hold at 80 ° C. for time. Thereafter, no isocyanate is detected in the IR spectrum. After cooling, a clear, colorless resin solution was obtained.

Example 3 Polyacrylate Having Amino Vinyl Ether Groups and Acrylate Groups The following are weighed into a stirred flask having a feed vessel and a reflux condenser.

486 g of butyl acetate, the charge is heated to 85 ° C. Next, 300 g of methyl methacrylate, 200 g of glycidyl methacrylate (1.41 mol), 300 g of butyl acrylate, 200 g of ethylhexyl acrylate, and 10 g of mercaptoethanol were used as feed I within 90 minutes, and 190 g of butyl acetate as feed II in 90 minutes. 30 g of 2,2'-azobis (2-methylbutyronitrile) Wako-Starater V59 dissolved in 120 minutes are added within 120 minutes. Polymerize at 85 ° C. for 3 hours, cool to 50 ° C., and then add 67.6 g of acrylic acid (0.94 mol), 0.7 g of t-butylcresol, 0.35 g of hydroquinone monomethyl ether, 0.07 g of phenothiazine, and Add 0.7 g of dimethylaminopyridine and stir for 8 hours at 95-100 ° C. Thereby, a resin solution having an acid value of 6.2 is obtained. The solution is cooled to 60 ° C. and 74 g of diethanolamine divinyl ether (0.47 mol) are added dropwise within one hour. A slightly exothermic reaction occurs. Cool for another 3 hours after 80 ° C. A high viscosity yellow resin solution is obtained.

Example 4 Polyacrylate Having Aminovinyl Ether Groups and Dihydrodicyclopentadienyl Groups The following are weighed into a stirred flask having a feed vessel and a reflux condenser.

486 g of butyl acetate, the charge was heated to 85 ° C., then as charge I 200 g of methyl methacrylate, 106.5 g of glycidyl methacrylate (0.75 mol), 300 g of butyl acrylate, 200 g of ethylhexyl acrylate, 200 g of dihydrodiamine 30 g of 2,2′-azobis (2-methylbutyronitrile) Wako-Starter V59 in which 100 g of cyclopentadienyl acrylate and 10 g of mercaptoethanol were dissolved within 90 minutes and as feed II in 180 g of butyl acetate Is added within 120 minutes. After polymerization for 3 hours at 85 ° C. and cooling to 60 ° C., 118 g of diethanolamine divinyl ether (0.75 mol) are then added dropwise within 1 hour under a slightly exothermic reaction. Cooling after an additional 3 hours at 80 ° C. produces a high viscosity, pale yellow resin solution.

Example 5: Polyacrylate having aminovinylether groups, acrylates and dihydrocyclopentadienyl groups The following are weighed into a stirred flask with a feed vessel and a reflux condenser.

486 g of butyl acetate, the charge was heated to 85 ° C., and then as charge I, 200 g of methyl methacrylate, 100 g of dihydrodicyclopentadienyl acrylate, 200 g of glycidyl methacrylate (1.41 mol), 300 g of butyl acrylate , 200 g of ethylhexyl acrylate and 10 g of mercaptoethanol within 90 minutes and, as infeed II, 30 g of 2,2′-azobis (2-methylbutyronitrile) Wako-Starter V59 120 g in 180 g of butyl acetate. Add within minutes. Polymerize at 85 ° C. for 3 hours, cool to 50 ° C., and then add 67.6 g of acrylic acid (0.94 mol), 0.7 g of t-butylcresol, 0.35 g of hydroquinone monomethyl ether, 0.07 g of phenothiazine, and Add 0.7 g of dimethylaminopyridine and stir for 8 hours at 95-100 ° C. Thereby, a resin solution having an acid value of 6.2 is obtained. The solution is cooled to 60 ° C. and 74 g of diethanolamine divinyl ether (0.47 mol) are added dropwise within one hour. A slightly exothermic reaction occurs. Cool for another 3 hours after 80 ° C. A highly viscous yellow resin solution forms.

Comparative Example 1: Comparative Example Having Only Acrylate Groups Polyacrylate The following were weighed and placed in a stirred vessel having a feeding container and a reflux condenser.

486 g of butyl acetate, The charge is heated to 85 ° C. in a vessel. Next, 300 g of methyl methacrylate, 200 g of glycidyl methacrylate (1.41 mol), 300 g of butyl acrylate, 200 g of ethylhexyl acrylate, and 10 g of mercaptoethanol were used as the feed I within 90 minutes, and 180 g of butyl acetate was used as the feed II. 30 g of 2,2'-azobis (2-methylbutyronitrile) Wako-Starter V59 dissolved in the above are added within 120 minutes. After polymerization at 85 ° C. for 3 hours, cool to 50 ° C., then 101 g of acrylic acid (1.39 mol), 0.7 g of t-butylcresol, 0.35 g of hydroquinone monomethyl ether, 0.07 g of phenothiazine, and dimethylamino 0.7 g of pyridine is added and stirred for 8 hours at 95-100 ° C. After cooling, a clear, high-viscosity resin solution having an acid value of 7.9 is obtained.

[0104] Test paints L1 100gB1 + 50gTEGDVE + 5gBDMK L2 100gB1 + 50gHDA + 5gBDMK L3 100gB2 + 3gBDMK L4 100gB2 + 50gTEGDVE + 5gBDMK L5 100gB2 + 50gHDA + 5gBDMK L6 156gB3 (about 100g resin content) + 3gBDMK L7 156gB3 (resin content of about 100g) + 50gTEGDVE + 3gBDMK L8 156gB3 (resin content of about 100g ) +50 g HDA +3 g BDKM L9 156 gB4 (resin content about 100 g) +3 gBDKM L10 156 gB4 (resin content about 100 g) +50 gTEGDVE +3 gBDDMK L11 156 gB4 (resin content about 100 g) +50 gHDA +12 gDMB 56gB5 (resin content about 100g) + 3gBDKM L13 156gB5 (resin content about 100g) + 50gTEGDVE + 3gBDKML14 156gB5 (resin content about 100g) + 50gHDA + 3gBDDMK VL1 162gVB1 (resin content about 2g +50 g TEGDVE +3 g BDDM VL3 162 g VB1 (resin content about 100 g) +50 g HDA +3 g BDDM BDKM = benzyldimethyl ketal (photoinitiator), TEGDVE = triethylene glycol divinyl ether, HDA = hexanediol diacrylate.

The preparation of the test paints and the production of the test plates were carried out in a laboratory protected against UV light. The components of the test paint were premixed in a glass bottle with a stirring spatula, and the mixture was kept at 50 ° C. for 1 hour in a drier and mixed well again. After cooling to room temperature, a clear, high-viscosity solution was obtained in all cases. The solution is then placed at intervals 60
It was applied on a fresh steel plate degreased using a μm doctor blade. Then, the plate coated with the solutions L6 to L14 and VL1 to VL3 was left overnight at 40 ° C. in a vacuum dryer to remove the solvent butyl acetate. As a result, a liquid high-viscosity resin film was formed on the test plate. Emission maximum about 365 nm and energy capability 1
The test plate was irradiated under a UV light-mercury vapor lamp with 9 mJ / cm ² on the irradiation surface until the film under the cotton ball wetted with acetone after 10 minutes still did not erode the film. If surface inhibition of the membrane was observed, the existing uncrosslinked, acetone-soluble layer was wiped first to determine the swellability of the underlying crosslinked layer.

Test Findings Paint Paint Findings after UV irradiation L1 30 seconds: Acetone resistance, no surface inhibition ^* L2 60 seconds: Acetone resistance, no surface inhibition L3 90 seconds: Acetone resistance, no surface inhibition L4 30 seconds: Acetone resistance, no surface inhibition L5 60 seconds: acetone resistance, no surface inhibition L6 90 seconds: acetone resistance, no surface inhibition L7 30 seconds: acetone resistance, no surface inhibition L8 60 seconds: acetone resistance, surface inhibition None L9 120 seconds: acetone resistance, no surface inhibition L10 30 seconds: acetone resistance, no surface inhibition L11 60 seconds: acetone resistance, no surface inhibition L12 30 seconds: acetone resistance, no surface inhibition L13 30 seconds: resistance Acetone properties, no surface inhibition L14 30 seconds: Acetone resistance, no surface inhibition VL1 300 seconds: Adhesive Acetone resistance under surface inhibition VL2 240 seconds: Acetone resistance, no surface inhibition VL3 240 seconds: Acetone resistance under adhesive surface inhibition ^* Surface inhibition: Thin adhesive or non-adhesive surface layer that remains uncrosslinked and remains acetone soluble Below, the layer is acetone insoluble.

These examples show that the method according to the invention achieves an unusually high UV light sensitivity and avoids surface oxygen suppression.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/00 C09D 5/00 Z 4J038 5/03 5/03 4J040 129/10 129/10 4J100 157/06 157/06 C09J 129/10 C09J 129/10 157/06 157/06 // C08F 299/00 C08F 299/00 (72) Inventor Horst Binder Lampertheim Schwimmbadstraße 24 F-term (reference) 4F071 AA30 AA31 AA36 AA39 AH12 BA02 BB01 BC07 4J011 AC04 QB01 QB02 QB13 QB15 QB17 QB23 QB25 QB29 SA22 SA64 UA01 VA01 WA02 WA06 WA07 XA02 4J027 AA01 AA08 AB01 AB06 AB07 AB01 AB01 AB01 AH03 BA01 CA34 CB10 CC02 CC05 CD01 CD06 CD08 CD09 4J034 FA01 FA04 FB01 FB03 FC01 FC03 FC04 FC05 FD01 FD04 FD05 FD 07 GA51 GA54 HA01 HA07 HC03 HC12 HC13 HC17 HC22 HC35 HC46 HC52 HC61 HC64 HC67 HC71 HC73 QB11 RA07 RA08 4J036 AD10 CA11 CA20 CA21 CB08 HA02 JA01 JA06 4J038 FA221 FA241 FA261 FA271 FA281 FA291 NA01 NA10 PA02 PA17 4J040 FA221 FA231 FA271 FA271 FA271 FA271 FA271 FA271 FA271 JB08 KA13 LA06 LA11 4J100 AL03P AL04P AL05P AL08R AL10Q BA02H BA15H BA31H BC37H BC37R CA04 CA05 CA31 DA02 HA62 HC11 HC29 HC48 JA01 JA03

Claims (16)

[Claims] 1. In each case, at least one vinyl ether group a) and at least one vinyl ether group a) are present at the terminal and / or lateral positions with a group b) which is co-reactive with the group a). It has an oligomeric or polymeric substructure, wherein on average at least one vinyl ether group a) and one co-reactive group b) are present per oligomer or polymer molecule, Or a substance that can be cured by heat. 2. The substance according to claim 1, wherein the co-reactive group b) is copolymerizable with the vinyl ether group a). 3. The oligomeric or polymeric substructure is formed by a CC bond having a double bond and / or a triple bond, and / or an ester bond, an ether bond, a urethane bond, an amide bond, and an imide. 3. The substance according to claim 1, wherein the substance is selected from a bond, an imidazole bond, a ketone bond, a sulfide bond, a sulfone bond, an acetal bond, a urea bond, a carbonate bond and a siloxane bond. 4. The method according to claim 1, wherein the oligomeric or polymeric substructure is linear, branched,
4. The substance according to claim 1, wherein the substance is in the form of a ring or a tree. 5. The co-reactive group b) comprises a maleate group, a fumarate group, an itaconate group, a (meth) acrylate group, an allyl group, an epoxide group, an alkenyl group,
Cycloalkenyl, vinylaryl and cinnamate groups and / or general formula I The substance according to any one of claims 1 to 4, wherein the substance is selected from the structural units: 6. A structural unit of the general formula I in which the (oligo) -dihydrodicyclopentadienol and the general formula II in the co-reactive group b) 6. The substance according to claim 5, which is incorporated in the form of an ester with a monofunctional or polyfunctional carboxylic acid according to 7. Structural units of the general formulas I and II in the co-reactive group b) Are incorporated in the form of (oligo) -dihydrodicyclopentadienol half-esters of maleic acid and fumaric acid, and the compounds for the substructure are made via ester groups and / or amide groups The substance according to claim 5. 8. A substance according to claim 1, which has a photoinitiator incorporated in the copolymer. 9. A preparation comprising the substance according to claim 1. 10. The preparation according to claim 9, wherein the thermal or high-energy irradiation comprises at least one compound providing radicals and / or cations. 11. Use of the preparations according to claim 9 or 10 as or in a binder for liquid paint systems or paint dispersions with or without solvents. 12. Use of the preparations according to claim 9 or 10 as or in a binder for powder coatings. 13. Use according to claim 11, which additionally comprises auxiliaries customary for pigments and / or paints. 14. The method according to claim 9, wherein the adhesive is or in the adhesive.
Use of the described preparation. 15. Use of the preparations according to claim 9 or 10 as or in casting agents and impregnants for electronics and / or electronics. 16. Use of the preparation according to claim 9 or 10 for the production of a shaped body.