DETENTION ADHESIVES ON THE BASIS OF RADIATIONHARDENABLE, (METH) ACRYLGRUPPENHALTIGEN POLYESTERS.

The subject of the available invention are radiation-hardenable, (meth) acrylic-group-functional polyesters, which are branched in the main chain and/or aliphatic Seitenketten possess and whose hydroxyl groups were replaced to maximally 70% by radiate-hardenable functional groups.

(Meth) acrylic-functional polyesters and/or polyester urethanes are well-known. They serve primarily as raw materials for lacquers, which with reactive solvents and photo initiators are interlaced to hard films. Without reactive monomers they are processed predominantly from solutions. By additives sticky-making resins know Oligooder polymers also surface-sticky coatings with such (meth) acrylierten to be manufactured.

The procedures for the production more makromerer i.e. with the help of their functional groups of radiate-hardenable polymere ones from polymers are various. Thus after DE-OS 28 38 691 and DE-OS 30 00 of 308 manufacture ways is described by Veresterung by hydroxyl polyesters with acrylic acid. The problem of this procedure lies in it, daß these ester reactions not vollstänig runs off and thus not converted monomers either by complicated distillation methods to be removed or by reaction with e.g. Epoxiden not be bound must. A procedure, which unites both ways, is described in the EP-PS 0,054,105. Another procedure is the conversion by hydroxyl polyesters with Säureanhydriden and afterwards with Glycidylestern of (meth) acrylic-functional monomers after the US-PS 4.158.618, whereby by use of halogenierten, cyclischen anhydrides an internal photo initiator into the polymers is built. Frequently the introduction is made from (Meth) groups of acrylics in polyesters by Diisocyanate, whereby either Isocyanatpräpolymer is manufactured, which in the further with a hydroxyalkyl (meth) acrylate is abreacted, or which is converted polyesters with an adduct from Diisocyanat and hydroxyalkyl (meth) acrylate (US-PS 4.174.307 and US-PS 4.164.486).

In the US-PS 4.174.307 (meth) acrylgruppenhaltige monomers or Oligomere with very low molecular weights are used. With (meth) the acrylierten polyesters after the US-PS 4.164.486 it concerns such, which contain dimer fatty acid and ethoxyliertes bisphenol A of their metal adhesion for improvement. Due to their composition these products are with ambient temperature and point with higher molecular weights so groß e viscosities up, daß they only from Löung and/or with additives of monomerer reactive solvents to be processed can. The production acrylic-functional Polyether by conversion with Isocyanatoalkyl (meth) acrylate describes the US-PS 4,233,425.

The well-known (meth) acrylic gruppenhaltigen polyesters, which are zugängig over Diisocyanate, is together, daß they are either predominantly linear by the functional polyester components developed or in case of a bypass of the main chain from polyesters of small condensation degrees develop. So far after the functionalization, particularly in case of branched high-molecular basis polyester high viscosities arise, become the products from solution and/or with groß EN additives of monomerer reactive solvents processes. In order to receive with coatings hard, scratch-proof films after the networking, further insatiated monomers are inserted and/or replaced hydroxyl groups despite the difficulties mentioned as completely as possible with polymerizationable groups of acrylics.

In the FR-A-2 121,191 a procedure for the production of coats is descriptive by hardening with ionizing radiation. Here hydroxylgruppenhaltige connections with Vinylisocyanat or vinylisocyanatgruppenhaltigen polymers or copolymers are converted. The reaction is implemented in such a way, daß as many hydroxyl groups as possible, at least two per molecule, to finalconstant Vinylurethangruppen to be converted.

It insisted from there the task to develop (meth) acrylgruppenhaltige Makromere on the basis from polyesters to which are still liquid with and/or despite higher molecular weight at ambient temperature and can be thus solvent-freely processed. At the same time reactive solvent and photo initiators should be caused by electronic irradiation a sufficient structure of coherence of the polyesters also when incomplete replacing the hydroxyl groups of the polyester by insatiated groups containing isocyanates without monomers.

The task posed could be solved thereby, daß such basis polyesters to be used, those over ester bridges or if necessary Etherbrücken to the main chain bound, aliphatic Seitenketten carry. These polyesters must, in order to ensure a sufficient coherence, to possess molecular weights of 1.000 to 10,000. By the bypass it is sufficient for the main chain further, the originally existing hydroxyl groups of the polyester to 30 to 70% by polymerizationable, insatiated, to replace functional groups which harden during radiation effect reactively. An additive of further monomerer insatiated connections to the reaching of a complete networking is thus not necessary. In order to receive again even with higher molecular weights still liquid products, muß with the basis polyesters amorphous products with glass transformation temperatures under 0 °C, preferably under -20 °C, concern. This can be achieved now on the one hand by the choice predominantly aliphatic Polycarbonsäuren and Polyolen. Examples of such aliphatic components are Dicarbonsäurediole with alkyl side chains of 2 to 18 carbon atoms, as well as Triole as for instance Trimethylolpropan, Glycerin, Pentaerythrit among other things. Just as elegantly is however the introduction of aliphatic Seitenketten, which is possible over Partialester of a Polycarbonsäure with aliphatic mono alcohols or over Partialester of a polyole with aliphatic mono carbonic acids or if necessary over Partialether of Polyolen with aliphatic mono alcohols, whereby the structure of the Partialester is so constituted, daß an average functionality from 2 to 3 results. When thereby a linear normal polyester understood functionality of 2, with which the number of the polyester connections amounts to a unit from Polycarbonsäure and polyole 2, whereby either no further Carboxyl-bzw. Hydroxyl groups at this unit are present or by mono carbonic acids and/or mono alcohols are locked. Accordingly a functionality of 3 at such a polyester unit from Polycarbonsäure + Polyalkohol results, if at this unit in center over a further Carboxyloder hydroxyl group a Seitenkette of the polyester is bound.

The subject of the invention from there radiate-hardenable Makromere on the basis is characterized of (meth) acrylic-functional polyester, da&szlig thereby;

1. a) Hydroxyl groups containing basis polyesters with middle molecular weights from 1.000 to 10,000 and with 20° C liquid condition, which alkyl side chains with 4 to 36 C-atoms contain in the alkyl group over groups of esters or Etherbrücken of third or higher polyester-forming functions to the main chain bound, to 30 to 70% of the hydroxyl groups of the polyesters according to a) with acrylate connections or Methacrylatverbindungen are converted, how
2. b1) Isocyanatoalkyl (meth) acrylate and/or
3. b2) Adducts from Dioder tri isocyanates or Polyisocyanaten or Isocyanatopraepolymeren of polyesters or Polyethern with low molecular weight with hydroxyl alkyl acrylates and/or. Hydroxyalkylmethacrylaten and/or
4. b3) methyl acrylamidoglykolat methylether and/or
5. b4) after conversion from 30 to 70% of the hydroxyl groups of the polyesters with a dicarbonic acid, tri carbonic acid or their anhydrides with in such a way formed groups of carboxyls under formation of groups of carboxyls with Glycidylacrylat or Glycidylmethacrylat and/or
6. b5) with Ethacrylsäure or acrylic acid or their derivatives are used.

As ester segment of the polyesters thereby the repeating grouping becomes from Di - or tri carbonic acid and ≁ as their hydrocarbon remainder and a Dioder Triol with ∼ when understood their hydrocarbon remainder, whereby the alkyl side chain is bound over third polyester screen end a function, i.e. a third group of carboxyls of the tri carbonic acid or a third hydroxyl group of the Triols.

The new polyesters are unvernetzt and to a large extent linear i.e. from normal main chains with only comparatively smaller, by trifunctional members of the main chain of conditioned Kettenverzweigung, developed, although tri carbonic acids and/or higher Polycarbonsäuren and if necessary Triole and/or more highly functional Polyole necessarily are to be along-used.

The new basis polyesters exhibit completely or predominantly a comb structure - simplifies in seen even projection - and/or a structure, in that the alkyl sides chain in as regelmä&szlig as possible; iger, statistic arrangement from the essentially linear and normal main chain of the polyesters stand out.

Into that erfindungsgemäß EN polyesters originate the alkyl side chains from mono carbonic acid remainders or from Monoalkanolresten, those at third functions, i.e. groups of carboxyls or Etherbrücken from tri carbonic acids or if necessary. Tetracarbonsäuren, or of Triolen or if necessary Tetraolen in the ester segments are bound. The alkyl side chains are essentially gleichmäß , i.e. the ester segments of the main chain from Dibzw bind industrial union along the main chain of the polyesters. Polycarbonsäuren, Dibzw. Polyolen and Dihydroxy monobzw. Hydroxydicarbonsäuren possess at least partial Carboxyloder Ethergruppen also to it bound alkyl residues of the mono carbonic acid and/or mono alcohols.

It is erfindungsgemäß necessarily, daß in a substantial functionality of the polyester-forming components of only 2 or few more in the polyester main chain is present, i.e. daß only 2 groups of carboxyls of the Polycarbonsäuren and/or only 2 hydroxyl groups of the Polyole or only on the average 2 polyester screen end Hydroxylbzw. Groups of carboxyls of a Hydroxypolycarbonsäure in the main chain of the polyesters are bound, although as basic materials tri carbonic acids and/or higher Polycarbonsäuren and Triole and/or higher Polyole zusätzlicl for dicarbonic acids and Diolen are used. The alkyl side chain mentioned carries the third group of carboxyls of the tri carbonic acids and 3 OH-group of the Triole by choice of the basic materials and manufacture conditions. It is erfindungsgemä&szlig from there; planned, preferably alkyl esters of at least trifunctional carbonic acids to use in special mono esters of tri carbonic acids and Diester of Tetracarbonsäuren, however also dialkyl esters of tri carbonic acids and if necessary tri alkyl ester of tetrafunktionellen carbonic acids and/or aliphatic mono esters of Triolen and Diester of Tetraolen, however also Diester of aliphatic carbonic acids of Triolen and tri esters of aliphatic carbonic acids of Tetraolen as basic materials beside the usual dicarbonic acids and Diolen and/or hydroxy acids. Glycidylester of mono carbonic acids and Monobis tri alkyl ester of tri carbonic acids are preferential, whereby during the polyester formation a group of alkyl esters of the mono carbonic acid in the polyester remains, while further groups of alkyl esters abgespalten in usual way become. Preferentially Trimethylolpropanester of mono carbonic acids are further. Erfindungsgemäß it is however in many cases also possible to go out in place of particularly mono esters with Polycarbonsäuren and/or mono carbonic acid esters with Polyolen with the individual components Triund higher Polycarbonsäuren plus mono alcohol and/or Triol or higher Polyole plus mono carbonic acid even for combinations of Polycarbonsäure and mono carbonic acid and/or polyole and Monoalkanol is possible. This procedure is not preferential.

Erfindungsgemäß it is preferentially, decided for the setting up the alkyl side chains branched alcohols in form of its esters or as individual component or branched out mono carbonic acids as their ester or as individual component to begin.

As basic materials know well-known aliphatic Di, trichloroethylene and higher Polycarbonsäuren, aromatic Di, Triund Polycarbonsäuren, Dihydroxy monocarbonsäuren and Hydro35 to xydicarbonsäuren as well as Monound dialkyl ester of the Diund mentioned more highly functional carbonic acids, mono, and/or dicarbonic acid esters of Diolen and higher Polyolen and/or Dimonocarbonsäureester and Monobzw. Dialkyl ester of Monobzw. Dihydroxymonobzw. Dicarbonic acids as well as Monound Dialkylether by Diolen and higher Polyolen as well as the mono carbonic acids and Monoalkanole themselves to be used.

For the setting up the main chain of the polyesters the following zweiund more-functional, polyester screen end of basic materials are preferential:

1. as triund more-functional Polycarbonsäuren, Trimellitsäure, Trimesinsäure, Hemellithsäure, Pyromellithsäure and their polyester screen end as well as much Trimellitsäureanhydrid and Trimellitsäuremonoalkylester, Trimellitsäure - mono alkyl esters as well as - prefers derivatives dialkyl ester and - tri alkyl esters.
2. as dicarbonic acids, e.g. Terephthalsäure, Hexahydrophthalsäure, Tetrahydrophthalsäure, Isophthalsäure, Phthalsäure and aliphatic dicarbonic acids with 2 to 12 carbon atoms as well as their polyester screen end of derivatives, like e.g. Azelainsäure, sebacic acid, Dodekansäure,
3. as Triole and more-functional Polyole Glycerin, Pentaerythrit and much prefers Trimethylolpropan, Trimethylolethan, Di-Trimethylolpropanether and their ester and Ether, Glycidylester of mono carbonic acids, particularly the so-called Versaticsäuren.
4. as Monobzw. Dihydroxycarbonsäure e.g. Hydroxybernsteinsäure (malic acid) and as Diole, aliphatic Diole with 2 to 6 carbon atoms such as mono ethyl glycol or Hexandiol as well as Etherdiole such as Diethylenglykol, tri ethyl glycol up to Polyether glycols with mol Gew. 1.000.

For the setting up the alkyl side chains are geradkettige or branched Alkanole or aliphatic mono carbonic acids with 4 to 36, preferably 4 to 18 carbon atoms and/or the Monooder if necessary Diester and/or Monooder if necessary Diether of the more dreioder more-functional Polyole, Polycarbonsäuren mentioned or hydroxy acids.

Very preferentially verzweigtkettige Alkanole, in particular 2-Ethylhexanol is if necessary tert or. - Butanol as well as verzweigtkettige aliphatic mono carbonic acids such as 2-Ethylhexansäure, Isononansäure or α , α - Dialkyl mono carbonic acids in form of the Versaticsäuren, e.g. with 9 to 11 carbon atoms. Decided satisfied polyester screen end basic materials are further preferentially, i.e. satisfied Diole and dicarbonic acids, satisfied tri carbonic acid esters or if necessary tri carbonic acid, satisfied Triole and particularly Glycidylester or if necessary Glycerin. In addition, smaller portions of insatiated basic materials can be used to approx. 2 mol %, e.g. maleic acid anhydride or fumaric acid.

Those erfindungsgemäß e task is particularly favourably solvable using Trimellitsäure-mono-2-ethylhexylester or a mixture of Trimellitsäureanhydrid and 2-Ethylhexanol. Further preferentially Trimethylolpropanmonoester are, particularly - the mono-2-ethylhexansäureester. Into that erfindungsgemäß EN polyesters is to amount to the molar ratio of ester segments of the main chain to Seitenketten 1 to 0.02 to 2.0. When understood ester segment of the main chain thereby the 2-wertige remainder from a dicarbonic acid remainder connected with a Diolrest, without consideration for whether this ester segment carries further groups of carboxyls or hydroxyl groups or does not carry. Such a molar ratio from 1,0 would be conceivable to 4.0, but is polyester, particularly linear polyesters to realise from a Dialkanolester of a Tetracarbonsäure and the Dialkanolester of a Tetraols only with difficulty. In contrast to this a polyester with the molar ratio mentioned 1.0 is producible to 2.0 with on the average an alkyl side chain per dicarbonic acid remainder and an alkyl side chain for each Diolrest, for example from Trimellitsäure-mono-2-ethylhexylester and Trimethylolpropan-2-ethylhexylester quite and meaningful. Molar ratios of ester segments of the main chain to the Seitenkette from 1,0 to 0.05 to 1.0 are preferential. The polyesters gemäß the invention have remarkable characteristics.

In particular a bypass of the polyester chains is avoided to a large extent, so daß the participating Diole and dicarbonic acids, but all Polyole on the average 2 hydroxyl groups for polyester formation do not only make, all Polycarbonsäuren likewise 2 groups of carboxyls available in an educated manner in the ester segments of the main chain contained and in hydroxy acids 2 of the functional groups to the formation of ester segments of the main chain to likewise contribute. A slight Kettenverzweigung of the polyester chains is however not avoidable and can be tolerated.

Into that erfindungsgemäß EN polyesters are the glass temperatures preferably under 0° C, very preferentially under minus 20° C.

At the same time the polyesters have a broad molar weight distribution and molecular weights of approximately 1,000 to approximately 10,000 or more, whereby 2,000 to 5,000 is preferential. The OH-number is appropriate for preferably 20-50 mg between 10 to 100, KOH/g. the polyesters is liquid with 20° C. The glass temperatures lie under it under minus 10° C, predominantly even substantially. The viscosities in (are appropriate for Pa.s) with 20° C between 70 and approx. 5.000. The new side chain polyesters have the special characteristic, daß with only small increase of the temperature substantial dropping of the viscosity the liquefaction takes place. Thus the task is solved to make polyesters available whose processing can take place solvent-freely. Due to their structure those are erfindungsgemäß EN polyester amorphously. Very remarkably is daß the task mentioned not only with aliphatic dicarbonic acid components or aliphatic Polycarbonsäurekomponenten, but with aromatic Dicarbonsäure-und Polycarbonsäurekomponenten, even with ausschließ lichem portion from aromatic Polycarbonsäuren to be solved can, although a polyester from for example Terephthalsäure and ethyl glycol is firm with 100° C and exhibits a glass temperature of 73° C, which can be not substantially lowered also by a use of a mixture of aromatic dicarbonic acids.

After the state of the art muß ten polyesters with deep glass transformation temperatures a high portion of aliphatic dicarbonic acid or Diole exhibit, whereby their adhesion is very small to polar surfaces with use as adhesive, particularly to metals.

Those erfindungsgemäß EN polyesters possess also with very high portions of aromatic components at the same time low fusion viscosity and deep glass transformation temperatures and exhibit an excellent adhesion to metal.

The glass transformation temperature of the descriptive polyesters is with same portions of aromatic dicarbonic acids substantially more deeply than those of the well-known polyesters.

The glass transformation temperature sinks with higher mol content of alkyl side chains and with increasing length of the alkyl side chains. Example for this shows table 1. to the characteristics is it however from small Einfluß whether the alkyl side chain is bound to the dicarbonic acid component or the Diolkomponente of the ester segments and whether the connection takes place via a Etherbrücke or a group of esters.

The substantially degraded fusion viscosity that erfindungsgemäß EN polyester is of special importance for the solvent-poor or solvent-free processing, whereby the degradation of the viscosity can be stopped by the number and the length of the Seitenketten. The additive of softeners or reactive solvents can be void from there, differently than with well-known polyesters.

For the use that erfindungsgemäß EN polyester is ma&szlig in particular their character as hydroxyl polyesters; giving, whereby a conversion with reactive or interlacable connections, like isocyanates, Melaminoder Benzoguanaminharzen, Epoxiden, silane star o. such is intended, by which those erfindungsgemäß EN polyesters become interlacable. Further a conversion of the Hydroxypolyester with carbonic acid anhydrides can and anschließ end to networking with Epoxiden or Polyoxazolinen and peroxide or the radiation hardening after functionalization with insatiated groups take place.

By the characteristics that erfindungsgemäß EN polyesters become coatings or adhesives more flexibly and more cold-resistantly. As reactive adhesives funktionalisierte products of that are erfindungsgemäß EN polyesters, particularly for the group of materials of same or different quality, as for instance metals, plastics, glass, ceramic(s), leather among other things applicable, whereby for the order smaller temperatures are necessary. The hardened masses point a very good elasticity with at the same time good firmness. As liquid polyesters the descriptive polyesters are particularly suitable due to their deep glass transformation temperatures for Kaschierund applications of detention sticking, whereby particularly at polar substrates a better adhesion is reached as with well-known liquid star. The degree of the tackness is further beeinflu&szlig by kind and quantity of the alkyl side chains; bar. Additives of sticky making resins, pigments, ageing protecting agents, fillers such as Silica, chalk are possible among other things. To the production that erfindungsgemäß EN polyesters can be followed essentially two ways. The mono carbonic acids and Monoalkanole can be converted (before the polyester formation) with more trioder more-functional dicarbonic acids or their anhydrides or their ester-forming derivatives, in particular the Methylestern and/or the more trioder more-functional Polyolen, to mono esters or if necessary the star or the Monoethern or if necessary Diethern. This procedure is in particular advisable with the schwerveresternden Versaticsäuren and if necessary also with branched alcohols such as 2-Ethylhexanol. The installation of Versaticsäuren is possible by use of the appropriate commercial Glycidylester, whereby preferably first with a dicarbonic acid, for example an aliphatic dicarbonic acid and in the second step with aromatic dicarbonic acid anhydrides it is converted on which further polyester raw materials can be added.

On the other hand mono carbonic acids and/or Monoalkanole can be present during the Veresterung and polyester formation, whereby also a Überschuß the monofunctional sidechain-forming connections possible and zweckmäß industrial union is. The transesterification and polyester formation can be promoted by catalysts. Further the statistic distribution knows through ester temperatures if necessary lowered and increased ester time to be promoted. Generally the temperatures with the Veresterung and polyester formation are to 200 to 240° C with 180 to 260° C, preferably. At the end of the polycondensation the pressure on 10 to 20 mbar is preferably lowered. Branched alkyl groups, particularly in trained esters of the tri carbonic acid alkyl esters and Glycidylversaticsäureester become erfindungsgemä&szlig with the polycondensation; practically did not abgespalten. It is possible, but does not prefer beginning Monoalkanole as well as tri carbonic acids or Triole and aliphatic mono carbonic acids as well as Triolen with the polycondensation and forming so the alkyl side chains during the polycondensation.

It is however decided to prefer to train appropriate mono esters or Monoether or the Diund tri ester with which all monofunctional alkyl side's groups up to one per mol abgespalten become.

Erfindungsgemäß it is preferentially, da&szlig in the new side polyesters; proceed from 90% or more of the ester segments no conventional branch chains polyester segments.

During the production of the polyesters is examinably, daß the alkyl residues of at the third function of tri carbonic acids bound mono alcohols and to the third function of Triolen bound mono carbonic acids did not abgespalten and in the hydroxyl polyesters are received, which is possible in a simple manner with analysis of the distillate of Veresterung and polycondensation. At first and second functions of polyester-forming components bound alkyl side chains, e.g. methanol into Dimethylterephthalat and two alkyl groups into tri carbonic acid tri alkyl star will however abgespalten and to step as free Alkanole or mono carbonic acids in the distillate up.

It becomes a Überschuß of Diolen plus Triolen and/or their esters or derivatives assigned opposite dicarbonic acids plus tri carbonic acids and/or their esters or derivatives and with the progressing of the polycondensation of the Überschuß the Diols removes, until Hydroxylzahlen are reached from 10 to 100 and acid numbers (sp) under 5, preferably under 3, very preferentially under 1.

With the distance of the last quantities of surplus Diol and sinking of the OH-numbers on the final value networking may not enter by splitting off from alkyl side chains, which is noticeable by stopping the agitator to a fast rise of the viscosity around at least one power of ten and developing tough reading tables of a mass. Such a spoiled beginning is to be repeated in the same way, whereby however a OH-number than measured of the spoiled beginning, higher around 5, the last is if necessary the final OH-number or the last temperature of the polycondensation is to be lowered around 10° C and/or be increased the pressure to 40 to 50 mbar is. A further way is the employment of tri carbonic acid tri alkyl star (see example 1) in place of same mol quantities of the mono esters or the ester after example Ib). Trimethylolpropan more monoester (example Ia) and particularly Glycidylester, in particular the all Versaticsäuren, proved than very stable.

The production that erfindungsgemäß EN hydroxyl polyester with alkyl side chains by a procedure for the production of polyesters with OH-numbers of 10 to 100 out zweiund more-functional basic materials, whereby in the Überschuß during the polyester formation existing Diole in the course of the polyester formation to be removed, thereby characterized, daß as difunktionelle polyester screen end of components aliphatic Diole and aliphatic, cyclo-aliphatic or aromatic dicarbonic acids, when trifunctional components, Trioder Polycarbonsäuren, Trioder Polyole or hydroxy acids, whose polyester screen end derivatives and Monoalkanole and/or aliphatic mono carbonic acids as free connection or as esters and/or Ether of the trifunctional polyester-forming components are used, whereby at least ever third or higher Carboxyloder hydroxyl function of the trifunctional polyester-forming components is present or more mole a Monoalkanol or an aliphatic mono carbonic acid than free connection or esters and/or Ether and is converted to polyesters.

The determination of the point of glass (Tg) became with a Differentialkalorimeter, Mod. DSC 1 of the company Perkin Elmer, accomplished. The final's group concentration becomes by the acid number sp, Hydroxylzahl OHZ, both in mg KOH/g and/or the carboxyl number of (C) in mVal.COOH/kg polymer after H. Pohl, Analytic. Chem. 26 (1954), 1614, measured.

The indicated molecular weights are average molecular weights (m) due to measurements of the gel permeation chromatography (GPC) and estimation due to the contained peaks, which indicate emphasis of the contained molecular weights, and/or, computes middle molecular weights (m) from the OH-number.

The use of the new polyesters is particularly preferential as detention adhesives, after 30 to 70% of the hydroxyl groups was replaced by Methacrylgruppen or groups of acrylics by networking with electron-beams or UV jets. In case of of UV jets a photo sensitizer, for example after polymer Paint Colour journal, becomes VOL. 175 (April 1985), pages 247 to 250, in quantities of 1% before the networking added. The polyesters can gemäß examples with actually arbitrary acrylic connections and Methacrylverbindungen, the named F, to be converted, the one further group, how group of isocyanates, reactive with hydroxyl groups, a Ethergruppe or a Glycidylgruppe contain, whereby in case of from Glycidylacrylaten and Methacrylaten first by conversion with dicarbonic acid a carboxyl polyester is to be manufactured. As detention adhesives thereby laminar coatings on paper, o.dgl., are understood plastic which the special characteristic of the continuous tackness to exhibit. This preferential use is not particularly contained for the stressed polyesters suitably, since detention adhesives are producible in this way, the Lösungsoder diluents, which disturb with the networking.

The special advantage of the radiation-interlacable Makromere is erfindungsgemäß so far the not attainable low viscosity. The Makromeren is steady in open Gefäß EN, even at temperatures to approx. 150° C.

In second stage the conversion takes place from 30 to 70% of the hydroxyl groups of the polyesters via acrylate connection and thus the replacement from 30 to 70% of the existing hydroxyl groups via groups of acrylates. The kind of the acrylate connections or Methacrylatverbindungen which can be used unimportant actually, as long as the respective connection exhibits a further group reactive with the hydroxyl group of the polyesters. In the simplest case can be used the acrylic acid, Methacrylsäure or acrylic chloride, Methacrylchlorid or the anhydrides of the acrylic acid and/or Methacrylsäure. This functionalization gemäß b5) is not preferential, because these connections are with difficulty manageable. The usual polymerization inhibitors, how under b2) must be described, added. Gemäß b1) can Isocyanato alkylacrylat or Isocyanato alkylmethacrylat for functionalization to be used, whereby alkyl has the meaning ethyl or Propyl.

Gemäß b2 know adducts in the relationship 1: 1 to be used, which exhibit a Isocyanatogruppe and an acrylate remainder and/or a Methacrylatrest. These adducts before the conversion with the hydroxyl polyesters made of on the one hand Diisocyanaten or if necessary Polyisocyanaten or Isocyanato to praepolymeren of polyesters or Polyethern with low molecular weight, which two groups of isocyanates in the molecule exhibit and on the other hand about equivalent mol quantities of hydroxyalkyl acrylates and/or Hydroxyalkylmethacrylate.

Preferentially Toluylendiisocyanat, Methylendiphenyl-4,4' are diisocyanat, Hexamethylendiisocyanat, Benzol-1,4-diisopropylisocyanat, Isophorondiisocyanat and further Diisocyanate as isocyanates. In the same way also tri isocyanates can be used, which are converted also with two mol hydroxyl alkyl acrylate. isocyanate praepolymere can be used in trained form, for example as Desmodur PF (Bavarian AG), or be manufactured out for example tri ethyl glycol by conversion with the Diisocyanaten mentioned. In the same way for example a conversion product of the Molekulargrö&szlig can; e 3 or 5 by 2 moles ethyl glycol and 1 mol of a dicarbonic acid with one the Diisocyanate to be converted and later with hydroxyl alkyl acrylates to the conversion come, so daß the adduct mentioned is formed. For the formation of the adducts temperatures from 50 to 120°C are sufficient. To be determined it is a conversion of isocyanates and Polyisocyanate up to a remainder of approx. 10% without admission from air humidity to be worked and by analysis. Further can gemäß b3 methyl acrylamidoglykolat methylether (MAGME) the company Dyno cyanamide C.V., Rotterdam or the appropriate to be Acrylamidoglykolat methylether used. Here a Umetherung takes place, whereby on the reaction conditions specified down freed methanol is removed. Further can gemäß b4 first a conversion preferentially from 30 to 70% of the hydroxyl groups of the polyester with a dicarbonic acid or with an anhydride of a dicarbonic acid, for example with Phthalsäureanhydrid or every other aliphatic or aromatic dicarbonic acid anhydride take place. This conversion takes place zweckmäß industrial union directly after formation of the polyester. By the quantity of the dicarbonic acid anhydride remain the desired quantity of the hydroxyl groups. Anschließ end become the groups of carboxyls with Glycidylacrylat or Glycidylmethacrylat, resulted from conversion of the dicarbonic acid or the dicarbonic acid anhydride, prefers under addition of a polymerization inhibitor, converted. If differently said, does not take place the conversion of the hydroxyl groups of the polyester with 1,0 to 1.1 mol of the materials b1 to b5 per mol of the OH-groups which can be converted with 60 to 150° C and pressures from 300 mbar to normal print under Ausschluß of air humidity.

In the same way the conversion with the acrylate connections or Methacrylatverbindungen can take place also out polyesters already manufactured at the temperatures mentioned. Arbitrary other acrylate connections and Methacrylatverbindungen can be used, which are able, with the hydroxyl groups or with groups of carboxyls of a carboxyl polyester (from the hydroxyl polyester by conversion with dicarbonic acid anhydrides develops) are reactive. In this way develops the acrylate-functional or methacrylatfunktionellen Makromere, which by radiation cross-linking detention adhesives supply, whereby in the used thin layer 2 to 5 Mrad by those surprisingly high reactivity of the funktionalisierten Makromere sufficient are. By the low viscosity of the funktionalisierten Makromere it is possible to lay on with 50 to at the most 100° C on paper or plastic foils, for example with a blade or through capers, for 5 to 200 g Makromere in a processing step and accomplish by radiation by means of an electron emitter (EB) or by UV jets the networking to the detention adhesive. During UV radiation cross-linking a photo initiator and/or a photo sensitizer in quantities from 0,5 to 1.5% the Makromeren is to be added, which can take place directly after production. Suitable photo initiators are in polymer Paint Colour journal, VOL. 175 (April 1985), pages 247 to 250, described. In the examples the examples of the functionalization marked by F and the examples of the networking are by V.

In a reactor with put on column, Kontrollsowie Kontaktthermometer is manufactured under agitating and nitrogen atmosphere from 464 g (2.417 mol) Trimellitsäureanhydrid and 990 g (7,615 mol) 2-Ethylhexanol of the tri esters with 0,75 g Octylenglykoltitanat as catalyst by Veresterung with 160 to 210° C in 5 hours under adherence to a column head temperature of approx. 102° C. If an acid number is reached of < 3 mg KOH/g, 333 g (3,142 mol) are admitted Diethylenglykol and the column is closed. After changing over to a distillation bridge one umgeestert and one abdestilliert in such a way with 200 to 230° C 2-Ethylhexanol, daß the vapour temperature 165° C does not exceed. If the vapour temperature falls at an interior temperature of 230° C on < 100° C, vacuum is put on (800 mbar falling on 300 mbar), so daß the vapour temperature within the range 100 to 165° C lies. Thus one umgeestert, until final characteristic numbers are reached. Then the vacuum with nitrogen is waived and the product is cooled.

Thereby in the distillate of the beginning 676 g 2-Ethylhexanol and 84 g Diethylenglykol were found. In made the product is calculated of it, daß 1 mol of 2-Ethylenhexanol per mol of Trimellitsäure bound and as alkyl side chain is contained, which is confirmed by analyses. The relationship from ester segments to alkyl side chains is 1: 1 mol.

With subsequent beginnings of this alkyl side chain polyester the distillate can be used as source for 2-Ethylhexanol, whereby during the polyester formation the quantity of Diethylenglykol is decreased according to the quantity already added.

13.57 kg of Glycidylester of the Versaticsäure 10 (Cardura (R) E10 Shell) 2 were warmed up in a reactor with put on column, Kontrollsowie Kontaktthermometer under agitating and nitrogen atmosphere to 110° C. The Glycidyl esters became then 4.35 kg of adipic acid and 67 g DYNAPOL A 1 V^(R) (1) admitted. The Glycidyladipatbildung took place under weak heat of reaction, which entailed a temperature increase on 140° C. The temperature of 140° C was held 30 min. Afterwards the addition took place from 8,81 kg Phthalsäureanhydrid and 5.52 kg of Diethylenglykol. Reactor contents were heated in 1 hr. 30 min. on 235° C. After 5 hr. with 235° C 22 g Octylenglykoltitanat were admitted and a vacuum was put on by 150 mbar. The pressure was continued to lower innherlab by 2 hr. 30 min. up to 10 mbar, afterwards on 5 mbar. After 4 hr. under these conditions the condensation was terminated by breaking the vacuum and cooling the product. The product had sp < a 1 mg KOH/g and a OHZ of 40 mg KOH/g as well as a viscosity V20 = 4,350 Pa.s.

The glass transformation temperature is with -15° C. M= 2,800 to 3.800 In the distillate only the Überschu&szlig became; the Diethylenglykols found, but practically no Versaticsäure. Accordingly the remainder of the Versaticsäure is bound as alkyl side chain at the Glycerinrest of the polyester, which was confirmed by analyses. The relationship from ester segments to alkyl side chains amounts to 1: 0.53 mol.

2) Versaticsäure of the number of total carbon of 10 with α , α '- Kettenverzweigung through predominantly groups of methyls with a smaller portion of groups of ethyls.

1) Adduct from phosphorous acid and 3 mol of Versaticsäure 10 (Cardura (R) 10 Shell) after_EP-A1 0,117,912, as protection from oxidative dismantling.

In a reactor with put on column, Kontrollsowie Kontaktthermometer are chargiert under agitating and nitrogen atmosphere with simultaneous heating: 13.42 kg Trimethylolpropan/2-Ethylhexansäure-monoester (example Ia), 1.88 kg mono ethyl glycol, 5.00 kg Hexandiol-1,6, 7.37 kg of adipic acid, 8.38 kg of Isophthalsäure and 45 g DYNAPOL A 1 Vth^(R) 2). With approx. 140° C begins the Wasserabspaltung, which under control of the column head temperature (approx. 105° C) is accomplished. After 2 to 3 hours the final temperature of 240° C is reached. After 5 to 6 hours 3.70 kg distillate resulted.

15 g Octylenglykoltitanat are admitted and put on vacuum. After approximately 3 hr. during pressure decrease on up to 10 mbar is reached final characteristic numbers. The vacuum is waived with nitrogen and the product is cooled.

In the distillate is the Überschuß ethyl glycol however practically not Hexandiol and 2-Ethylhexansäure. Accordingly the remainder of the 2-Ethylhexanols is bound as alkyl side chain at the Trimethylolpropanrest in the polyester, which is confirmed by analyses. The relationship of the ester segments to alkyl side chains amounts to 1: 0.40 mol.

Example 11 is accomplished as follows: 50.6 g mono ethyl glycol (0.817 mol) and 0.122 g Butyltitanatlösung 36.8% industrial union in 2-Ethylhexandiol-1,3 were warmed up with 97,0 g mono esters of the 2-Ethylhexansäure of the Trimethylolpropans 0.35 mol in a Rundkolben with put on column, thermometer and agitator under nitrogen atmosphere. With approx. 80° C the addition took place from 136 g dicarbonic acid mixture (C4-C6) (1 mol). In 30 minutes the temperature on 150° C, during reaction water splitting off beginning was increased. After 4 hours 240° C reached with sp of 14,5 mg a KOH/g. after further 60 minutes amounted to was put on sp 14.0 mg KOH/g. it a vacuum by 100 mbar and lowered on 20 mbar. After 3 hours by breaking the vacuum and cooling the product the condensation was terminated. The product had sp of 1,4 mg a KOH/g and a OHZ of 40 mg KOH/g and a glass temperature of under -20° C.

The examples 4 to 10 and the comparison examples A to C of the components in the molar ratios mentioned and same conditions as in, contained in the table 1, example 11 are made, whereby the same Überschuß by ethyl glycol one uses. The polycondensation is broken off with an acid number under 2 with reaching the OH-number of 40. The molar weights (m) lie between 2.600 and 3.500.

165.6 g 2-Ethylhexansäure (1.15 mol) were warmed up in a Rundkolben with put on column, thermometer and agitator under nitrogen atmosphere and 134.0 g Trimethylolpropan (1.0 mol) as well as 0.86 g esters of of the phosphorous acid (H3PO3) made of Versaticsäureglycidylester and H3PO3 and 0.137 g Butyltitanatlösung 36.8% industrial union admitted. After 60 minutes 185° C were reached, with splitting off beginning of the reaction water.

Now the reaction temperature on 255° C was increased. After 93.6% reaction water was abdestilliert, the put on column was removed and changed over to the lower way. With reaching sp of approx. 6.2 mg a KOH/g was terminated by cooling the product the condensation. In the product 1.0 mol of 2-Ethylhexansäure per mol of Trimethylolpropan is contained.

Example 2 is repeated, whereby however the quantity of the Glycidylesters is varied, i.e. on 2 (example 12), 20 (example 13), 40 (example 14) and 70 (example 15), whereby 98 mol % Diethylenglykol are contained in the product in example 12 and in the following 80, 60 and 30 mol % Diethylenglykol and the example 2 appropriate Überschuß Diethylenglykol in the beginning is used.

With rising content of Glycidylestern the glass temperature Tg and the viscosity sinks.

Example 3 is repeated, whereby however in the product and according to 60 mol % (example 16), 45 mol % (example 16) and 15 mol % (example 17) MEG is contained of 5 mol % (example 16), 20 mol % (example 17) and 50 mol % Trimethylolpropan-mono-2-ethylhexylester (example 18) with same portions of 35 mol % Hexandiol-1,6 and in each case 50 mol % Isophthalsäure and 50 mol % adipic acid. In the beginning a Überschu&szlig becomes; MEG added and with the progressing of the polycondensation removes. The products have a OHZ of 40.

According to the procedure of example 2 an alkyl side chain polyester made of the following basic materials: Glycidylester of Versaticsäure E10 (Cardura^(R) E10 = 8.89 kg; Hexandiol-1,6 = 7.66 kg; Neopentylglykol = 1.48 kg and the acid components adipic acid = 8.94 kg; Phthalsäureanhydrid = 6.04 kg as well as Dynapol A1V^(R) (see example 2) = 67 g; Octylenglykoltitanat = 22.5 G.

Characteristic number sp < 1, OHZ = 30, V20 = 795 Pa.s, TG = -31° C

According to the procedure of example 2 the polyester was made of the following basic material: Gylcidylester of Versaticsäure 10 (Cardura^R E10) 8,78kg; Hexandiol-1,6 = 6.89 kg; Neopentylglykol = 2.07 kg; Adipic acid = 5.89 kg; Phthalsäureanhydrid = 5.97 kg; Isophthalsäure = 3.35 kg as well as Dynapol A1V^(R) = 67 g and Octylenglykoltitanat = 22.5 G.

The received polyester had characteristic numbers: Acid number under 1, OHZ = 38, V20 = 2,610 Pa.s, TG = -22°C

According to the procedure of example 2 a polyester made of the basic materials: Adipic acid = 15.19 kg; Hexandiol-1,6 = 4.97 kg; Mono ethyl glycol = 1.87 kg; Trimethylolpropan mono more ethylhexylester (see example Ia) = 15.40 kg as well as Dynapol A1V^(R) = 30 g and Octylenglykoltitanat = 15 G. Characteristic numbers: Sp under 1, OHZ = 24, V20= 70,8 Pa.s, TG =-50°C

In a reactor IPDI, DBTL and the polymerization inhibitor are submitted and warmed up to 40° C. HEA becomes gleichmä&szlig under agitating during 3 hr.; industrial union meters. As soon as by exotherms reaction the temperature to 60° C rises, one cools, so daß the temperature 80° C does not exceed, however 50° C not to be fallen below. After terminated HEA addition so for a long time reactor contents are held 60° C, until the NCO content sank on 12,2% after 2 hr. Viscosity from 8.000 to 12.000mPa.s with 20° C. the product can be handled for short time at open air, muß however with longer keeping from air humidity in closed barrels to be protected.

The polyester after example 2 is cooled down directly after the production on 120° C and the vacuum adjusted to 400 mbar and/or a manufacturer polyester after example 2 is warmed up to 120° C with a vacuum by 400 mbar. Under agitating 100 kg each of the polyester admitted after example 2 12.5 kg of the adduct after example IIa and 1 hr. agitated to the NCO content to under 0,2% dropped.

The hydroxyl groups of the polyester were converted by this reaction to example 2 from originally a OH-number from 40 to 50%, so daß now in place of half of all hydroxyl groups of acrylate remainders stand. Such a product is called A 50. Viscosity with 50° C 114 Pa.s TG -5° C

In appropriate way such as example F1 the polyester is converted to example 2 with 7,5 kg (example F2) and with 17,5 kg (example F3) of the adduct to example IIa according to example F1. In example F2 the functionalization 30% of the existing hydroxyl group of the polyester (product A 30) amounts to. The viscosity with 50° C amounts to 192 Pa.s, TG -10° C.

The product of example F3 is funktionalisiert to 70% (product A 70). The viscosity with 40° C amounts to 310 Pa.s TG -4° C.

After the procedure of the example the polyester is brought to F1 after example 1 with 12,5 kg of the product after example IIa per 100 kg of the polyester to the reaction. A product with a 50% develops igen for functionalization of the hydroxyl groups. Viscosity with 50° C amounts to 35 Pa.s, TG -32°C.

The polyester after example 3 is brought to IIa according to the procedure of the example F1 with 12,5 kg of the adduct after example to the reaction. A funktionalisierter polyester with viscosity develops with 50° C of 88 Pa.s, TG -25° C.

The polyester after example 2 is warmed up to 150° C under agitating and shifted with 11,8 kg steel acid anhydride per 100 kg of the polyester. After 30 min. the Hydroxylzahl sank on 17 mg KOH/g, while the acid number reaches 18 mg KOH/g. Whereupon 9.1 kg become G˙ lycidylmethacrylat as well as 50 g Hydrochinon as polymerization inhibitor added and further 30 min. with 150 to 170° C under agitating converted. The product is cooled down and filled up. The acid number amounts to 2 mg KOH/g, the viscosity with 20° C amounts to 4,500 Pa.s, TG -10° C.

The polyester after example 2 is warmed up to 150° C under agitating. Per 100 kg of the polyester 4.6 kg become Methylacrylamidoglykolat more methylether (MAGME) as well as 50 g p-Toluolsulfonsäure and 50 g Hydrochinon admitted and anschließ end further 50 min. with 150° C react calmly. Develops a polyester, whose hydroxyl groups are acryliert to 50%.

Viscosity with 20° C 4,300 Pa.s, TG -15° C.

By means of a blade is laid on funktionalisierten polyesters specified on a paper of 80 g/m2 or an appropriate plastic foil of one in the examples F with 100° C with a pick-up by 20 g/cm2 and interlaced with a dose of 3 Mrad by means of an electron emitter (Elektrocurtain company Energy Sciences Int.).

Under V1 the order way specified and the polyesters specified there are used in the same way and at same temperatures, whereby as a photo initiator 1% Darocur is distributed always 1173 (companies notice) in the funktionalisierten polyester. The networking takes place via an irradiation time from 0.5 seconds. by means of an UV emitter, manufacturer: Company Theimer, with radiating power of 100 W/cm.

Also order temperatures can be selected by 50° C upward, as far as the funktionalisierten polyesters exhibit leading a low viscosity mentioned.

The characteristics of in such a way received detention adhesives are mentioned in the following table.

Into a 1 l-Rundkolben in each case 1 time is submitted to that in the following specified Diisocyanate at ambient temperature. Under agitating and introduction of nitrogen in the process of one hour 116 g Hydroxyethylacrylat are course-dripped. After further 30 minutes originally existing NCO content of the mixture lowered itself to the half value.

Similar to examples F8 are converted now 800 g of the polyester with aforementioned in each case the quantities of Diisocyanat Hydroxyethylacrylat adduct, described in example 22, in the table, so daß the resulting NCO content of the product than 0.1% is smaller.

In a 2-l-Rundkolben 700 g of the Trimellitsäure-2-ethylhexylesters become gemäß Example 14 with 202 g ethyl glycol under agitating and nitrogen introduction heated. The Wasserabspaltung begins the reaction water with approx. 180° C. over a Vigreux column and a distillation bridge at a head temperature from 100 to 105° C is abdestilliert.

Within three hours the temperature of 180° C on 210° C is increased. As ester catalyst now 0.6 g Oktylenglykoltitanat are added and a further hour with 210° C is agitated. Now further 0.3 g Oktylglykoltitanat are added and put on after removing the distillation mechanism a vacuum, which is lowered within 30 minutes on 10 mbar. It is continued to condense, until the desired characteristic data is reached by Hydroxylzahl = 40 mg KOH/g with acid number of smaller 1 mg KOH/g.

800 g of the polyester described in example F9 become anschlie&szlig with 8,2 g Trimellitsäureanhydrid with 150°C and; end with 80°C similar to example F9 with 20 g Isocyanatoethylmethacrylat converted, so daß the resulting NCO content 0.1% amounts to smaller.

Into a 1 l-Rundkolben at a temperature of 80° C 800 g of the polyester with 39 and/or 65 g of a 1:1, described in example F9, are converted - adduct from Toluylendiisocyanat and 2-Ethylhexanol (NCO= 13.8%). Thus a part of the hydroxyl groups is replaced by groups of urethanes. Anschließ end these products similar to example F9 with 26,7 and/or 20,0 g Isocyanato ethylmethacrylat funktionalisiert, so daß the resulting NCO content smaller than 0.1% lies.