DE19939738A1 - Production of stable, modified, unsaturated cycloaliphatic epoxy resin for use e.g. in coating materials, involves reacting liquid cycloaliphatic diepoxide with special unsaturated half-ester compounds - Google Patents

Abstract

Production of stable, modified, unsaturated cycloaliphatic epoxy resins by reacting liquid cycloaliphatic diepoxides with half-esters of unsaturated dicarboxylic acids and unsaturated mono-alcohols, hydroxy-(cyclo)alkyl vinyl ethers, alkoxylated hydroxyalkyl (meth)acrylates or hydroxyl-containing reaction products, e.g. from glycidyl versatate and (meth)acrylic acid. A process for the production of stable liquid or semi-solid modified cycloaliphatic epoxy resins (MCE) (A) and/or fusible and/or soluble and/or dispersible solid MCE (B) with more than one epoxide group. At least one second hydroxyl group and at least one ester linkage per average mol. wt., optionally with a fluorine content of 0.01-3 wt% and a silicon content of 0.01-10 wt%. The process involves reacting liquid cycloaliphatic diepoxides (CDE) with (I) half-esters of unsaturated dicarboxylic acids (or anhydrides) (UDCA) and unsaturated mono-alcohols based on 2-10C olefins and/or (II) half-esters of UDCA with hydroxy-(cyclo)alkyl vinyl ethers and/or (III) half-esters of UDCA with hydroxyalkyl (meth)acrylates containing polyoxyalkylene units and/or reaction products with a sec. OH group from the reaction of glycidyl versatate (e.g. Cardura E10 (RTM)) with (meth)acrylic acid and/or products with an OH group from the reaction of caprolactone with hydroxyalkyl (meth)acrylates (optionally in presence of fluorine-containing acids or anhydrides) and/or dicarboxylic acid half-esters of fluorine-containing monohydric alcohols and diacids or their anhydrides and/or perfluoro-acids of formula F(CF2)nCOOH in which n = 5-21 and/or organosilicon compounds with group(s) which can react with epoxide, at elevated temperature, optionally in presence of organic solvent and/or inert gas and/or catalysts for the epoxide/carboxyl reaction and/or polymerisation inhibitors and using 0.02-0.49 equivalents of the modifier per epoxide group, to give MCE as described but with at least two olefinic double bonds connected to one another via ester linkages and also via one or more methylene and/or alkyl, cycloalkyl, alkylaryl-aryl or aralkyl groups. An Independent claim is also included for a process for the production of (A) and (B) with epoxide, sec. OH groups and ester linkages as above and also with at least one olefinic double bond, by reacting liquid CDE with (IV and V) half-esters of saturated diacids with hydroxy compounds as listed in sections (II) and (III) under conditions as above.

Description

The state of the art is in my unpublished patent applications gene DE-199 01 118.4, 199 04 232.2, 199 10 206.6, 199 22 032.8, 199 30 862.4, 199 30 863.2 and 199 30 864.0, so that there are repetitions remaining.

The subject of the invention is a process for the production of storage-stable modified cycloaliphatic epoxy resins according to the following claims and designs and the use of those produced by this method modified cycloaliphatic epoxy resins.

My DE-196 34 721 A1 relates to coating compositions with a content of Modified polyester containing fluorine and the use of coating means. In column 2, lines 65-68 and ff. Column 3 and ff. Column 4, Line 1-3, is the implementation of epoxy compounds with at least two epoxies groups, e.g. B. liquid at room temperature cycloaliphatic diepoxide compound and fluorine compounds containing carboxyl groups are described, however are carboxyl group-containing fluorine compounds in the present invention only used as an optional measure.

In contrast, the method according to the invention is not compared to the above Pre-published patent applications and DE-196 34 721 A1 new and leads to modified cycloaliphatic epoxy resins not described above, which moreover when used for the production of binder components or in the production of acrylics containing epoxy groups and hydroxyl groups copolymers with more than one epoxy group per average molecular weight offer very special advantages.

Regarding the terms storage stable, meltable and / or soluble and / or dispersing cash as well as liquid and solid is to the patent application 199 01 118.4, p. 11, lines 1-13 (paragraphs 1-3).

For the selection of cycloaliphatic diepoxyver liquid at room temperature Binding is based on the above unpublished patent application conditions, in particular 199 01 118.4, page 4, paragraph 4 to the last paragraph, and ff. Page 12, paragraph 1.

The manufacturing conditions in the method according to the invention are: also to patent application 199 01 118.4, page 14, last paragraph, and ff. page 15, paragraphs 1 and 2, and also to DE-196 34 721 A1, Column 2, lines 65-68 and ff. Column 3 and ff. Column 4, lines 1-3, referenced, whereby the person skilled in the art has no difficulty in making the statements made there Considerations corresponding to the method according to the invention term.

Preferably, in two or more stages, it is initially relatively low Temperature, preferably 40 to 70 ° C, and then higher Temperature, in particular 80 to 130 ° C, implemented.  

The manufacturing conditions depend on the selection and quantity of each Components mainly according to the intended use of the herge presented modified cycloaliphatic epxoid resins. For example for the production of liquid or semi-solid modified at room temperature cycloaliphatic epoxy resins particularly gentle conditions and low Temperatures, preferably in the range from 50 to 100 ° C., in particular 60-90 ° C., applied. The procedure is preferably such that 0.04 up to 0.4 mol equivalents, in particular 0.05 to 0.2 mol in the production of modified cycloaliphatic epoxy resins (A) and 0.2 to 0.4 equiva lente in the production of modified cycloaliphatic epoxy resins (B) using modifiers, preferably those containing carboxyl groups become.

Examples of used for the preparation of the half esters (I) and (II) Unsaturated dicarboxylic acids or their anhydrides are fumaric acid, itacon acid, maleic acid, maleic anhydride, citraconic anhydride, itaconic acid anhydride and dodecenyl succinic anhydride and mixtures of at least two of the above compounds, maleic anhydride and itaconic acid anhydride and mixtures thereof are preferred.

Examples of unsaturated to be used for the preparation of the half esters (I) are monohydric alcohols based on olefins with up to 10 carbon atoms 2-propen-1-ol (allyl alcohol), 2-butenol (methylallyl alcohol / crotyl alcohol), 1-buten-3-ol, 3-buten-1-ol, 2-methyl-3-buten-2-ol, 3-methyl-2-buten-1-ol, 3-methyl-3-buten-1-ol, 2-methyl-2-propen-1-ol, 1-octen-3-ol, trans-3-phenyl- 2-propen-1-ol, 9-decen-1-ol and 3,7-dimethyl-6-octen-1-ol or mixtures at least two of the above compounds, wherein 1-octen-3-ol and 9-decene 1-ol or mixtures thereof are preferred.

Examples of hydroxy- to be used for the preparation of the half esters (II) (Cyclo) alkyl vinyl ethers are 1,4-butanediol monovinyl ether and cyclohexane-1,4- dimethanol monovinyl ether.

Examples of unsaturated to be used for the preparation of the half esters (III) Most dicarboxylic acids or their anhydrides are with those for the manufacturers tion of the half esters (I) and (II) unsaturated dicarboxylic acids to be used or their anhydrides or their mixtures are identical, maleic anhydride and / or itaconic anhydride are again preferred.

Examples of hydroxy-10 to be used for the preparation of the half esters (III), alkyl (meth) acrylates are hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate 4-Hydroxy-n-butyl methacrylate and equivalent hydroxy (cyclo) alkyl (meth) acrylates such as e.g. B. 1,4-Cyclohexanedimethanol monomethacrylate. Examples of hydroxy to be used for the preparation of the half esters (III) are alkyl (meth) acrylates with polyoxyalkylene units in their structure primarily commercial products such as B. Polypropylene glycol monometh acrylate (average molecular weight e.g. 350-387, 5-6 oxyethylene Units in the structure; Commercial product "Blemmer-PP-1000" from Nippon Oils & Fats Co., Ltd., Tokyo, JP) or "RMA-150 M" (approx. 15 oxyethylene units), "RMA-450 M" (approx. 45 oxyethylene units). or "RMH-4000" (100 oxyethylene Units) by Nippon Nyukazi Co "Ltd., JP.  

The reaction products to be used for the preparation of the half esters (III) with a secondary hydroxyl group from the reaction of versatic acid glyci dylester and acrylic acid and / or methacrylic acid as a smooth equivalent for Acrylic acid has long been state of the art - cf. for example DE-OS 28 51 613, in particular claim 8, and are simple and Way by reaction (addition reaction) of 1 mol of versatic acid glycidyl esters, e.g. B. Commercial products such as "Cardura E 10" (Shell), and about 1 mole (meth) - acrylic acid produced.

The reaction products to be used for the preparation of the half esters (III) with a hydroxyl group from the reaction of caprolactone and hydroxyalkyl (Meth) acrylates are also state of the art - cf. for example EP-0 037 314 - and as commercial products, e.g. B. "Tone M 100" (Union Carbide Corporation, US and Union Carbide Europe S.A., CH).

Examples of those to be used to prepare the half esters (IU) and (U) Dicarboxylic acids and their anhydrides are both aliphatic as well as cycloaliphatic, aromatic or heterocyclic dicarboxylic acids or their anhydrides can be used. Adipic acid, Glutaric anhydride, succinic anhydride, camphoric anhydride, 1,3-cyclo hexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid anhydride, terephthalic acid or its equivalent dimethyl terephthalate, and very particularly preferably succinic anhydride, glutaric anhydride, Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic acid anhydride and / or 5-norbornene-2,3-dicarboxylic acid anhydride used.

Examples of hydroxy- to be used for the preparation of the half esters (IV) (Cyclo) alkyl vinyl ethers are to be used with those for the half esters (II) ends identical.

Examples of hydroxy to be used to prepare the half esters (V) alkyl (meth) acrylates are to be used with those for the half esters (III) the identical.

Examples of hydroxyalkyl to be used for the preparation of the half esters (V) (Meth) acrylates with polyoxyalkylene units in their structure are with those identical to that used for the half esters (III).

Examples of the reaction to be used to prepare the half esters (V) Products with a secondary hydroxyl group from the conversion of versatic acid glycidyl esters and (meth) acrylic acid are with those for the half esters (III) to be used identically.

Examples of the reaction to be used for the preparation of the half esters (U) products from the implementation of caprolactone and hydroxyalkyl (meth) acrylates are identical to those to be used for the half esters (III).  

The preparation of the half esters can be carried out according to methods known per se The technology takes place in an analogous manner as far as the claimed half esters not already belong to the state of the art and is not the subject of Invention.

Mixtures of the claimed half esters are preferably used and for this purpose is referred to the unpublished patent applications 199 22 032.8, Page 2, paragraph 3, and 199 04 232.2, page 2, last paragraph, referenced the statements made there by the expert without further ado can be transferred to the present invention.

Examples of optionally containing fluorine-containing carboxylic acids or their anhydrides are DE-196 34 721 A1 and not previously published clear patent application 199 01 118.4.

Examples of half-esters of dicarboxylic acids which may be used or their anhydrides are also the above-mentioned patent application conditions. Half-esters of maleic acid are very particularly preferred anhydride and / or itaconic anhydride and / or 5-norbonen-2,3-dicarboxylic acid anhydride and / or phthalic anhydride and / or tetrahydrophthalic anhydride and / or hexahydrophthalic anhydride and 2,2,2-trifluoroethanol and / or Heptafluoro-1-butanol and / or pentadecafluoro-1-octanol and / or hydroxybenzo trifluoride and especially half esters of maleic anhydride and 2,2,2-trifluor ethanol and / or 3-hydroxybenzotrifluoride and / or heptafluoro-1-butanol and / or pentadecafluoro-1-octanol used.

The possible fluorine content of the modified cycloaliphatic epoxy resins can also be brought about by completely or partially replacing the previous one standing carboxyl group-containing compounds not described above esters (R) can be used, can be produced by the epoxy known per se / Carboxy addition reaction by reaction of versatic acid glycidyl ester, e.g. B. "Cardura E 10", (about 1 mol) as component i) with carboxyl groups containing fluorine compounds of the type described above, preferably 4- (trifluoromethyl) benzoic acid and / or pentafluorobenzoic acid and / or half esters of maleic anhydride or mixtures containing it with phthal acid anhydride and / or tetrahydrophthalic anhydride and / or hexahydrophthalic acid anhydride and / or 5-norbornene-2,3-dicarboxylic acid anhydride and monovalent Fluorine-containing alcohols of the type described above, preferably 2,2,2-trifluoroethanol and / or 3-hydroxybenzotrifluoride and / or heptafluoro- 1-butanol and / or pentadecafluoro-1-octanol, (about 1 mole) as a component ii) and subsequent reaction of the fluorine-containing reaction product with a secondary hydroxyl group from the epoxy / carboxy reaction with Dicarboxylic acids or their anhydrides of the type described above preferably dicarboxylic anhydrides of the type described above, quite be particularly preferably maleic anhydride and / or phthalic anhydride and / or Tetrahydrophthalic anhydride and / or hexahydrophthalic anhydride and / or 5-Norbonen-2, 3-dicarboxylic anhydride, to the half ester (R).

The implementation of "Cardura E 10" is carried out analogously to the known epoxy / carboxy Reaction at elevated temperature, optionally in the presence of organic Solvents and / or catalysts for the epoxy / carboxy reaction, by leads.  

With respect to the optionally used organic silicon Ver binding is to the unpublished patent application 199 10 206.6 referenced, the integral part of the present patent application is.

According to patent application 199 10 206.6, half esters are preferably Page 3, Paragraph 4.

Half-esters of maleic anhydride and / or glutaric anhydride and / or phthalic anhydride and / or tetrahydrophthalic anhydride and / or hexahydrophthalic anhydride and / or 5-norborene-2,3-dicarboxylic acid anhydride are very particularly preferred, with mixtures of these containing maleic anhydride being particularly preferred, particularly preferred and organosilanols of the general formula

R _n SiX _4-n ,

where R is aliphatic, aromatic or heterocyclic radicals and X stands for OH, in particular with organosilanols known per se 1 to 3 hydroxyl groups from the precursor of the polysiloxane or silicone resin production, for example mentioned in patent application 199 10 206.6 Organosilanols and / or methylphenylsilanediol and / or diphenylsilanediol and / or particularly preferably dimethylsilanediol and / or those in the above Organosilanols described with a hydroxyl group.

The Mitver, if applicable, in the production according to the invention Use of fluorine compounds containing carboxyl groups and / or silicon orga African connections is to be understood in such a way that it said half-star (I) to (V) both in minor amounts, related on the molar ratios of the components, as well as in the same amount as well larger amounts compared to the half-esters (I) to (V) can be used, and that depending on the desired or required fluorine and / or Silicon content.

The fluorine content of the modes produced according to the invention is preferably cycloaliphatic epoxy resins from 0.1 to 1% by weight and / or the sili cium content 0.1 to 7 wt .-%. According to the inventions are very particularly preferred modified cycloaliphatic epoxy resins prepared according to the process, the both attached trifluoromethyl and / or perfluoroalkyl groups as well attached silicon-containing groups, especially according to the not pre-ver public patent application 199 10 206.6, have. making synergistic Effects occur.

Type and amount of the half esters (I) to (V) used within the scope of the claims depend primarily on the intended use of the invention produced modified cycloaliphatic epoxy resins and can not calculated, but must be carried out by empirical tests, including series tests, to be determined by the expert and this is based on the explanations in patent application 199 01 118.4, page 14, last paragraph, and ff. page 15 and the literature cited there.  

The possible use of catalysts in the implementation of epoxy compound with reactive compounds, e.g. B. containing carboxyl groups Connections is state of the art and need not be explained.

The possible use of polymerization inhibitors in the implementation or when combining compounds with polymerizable double bonds and functional groups that react with epoxy groups, e.g. B. Acrylic Acid, hydroxyalkyl (meth) acrylates is also state of the art and Polymerization inhibitors, e.g. B. hydroquinone monomethyl ether, are in all common in such connections, e.g. B. acrylic monomers, styrene, already for Improvement in shelf life included and therefore also needs no longer to be explained.

Modified cycloaliphatic epoxy resins produced according to the invention (B) preferably have a melting point of 30 to 120 ° C, especially 50 to 100 ° C. Those with fluorine and silicon are very particularly preferred content, in particular a fluorine content of 0.1 to 1 wt .-% and a sili cium content according to the above on page 5, penultimate para.

For using the modified cycloalipha produced according to the invention Table epoxy resins (A) and (B) according to the use claims are after standing made the following statements.

The use of cycloaliphatic epoxy liquid at room temperature resin is state of the art and this is based on the patent application 199 01 118.4, page 2, paragraph 2 and last paragraph, and the patent application 199 10 206.6, page 1, last paragraph, and the literature cited therein ver grasslands.

Cycloaliphatic epoxies that are liquid at room temperature are used in the paint field resins, mainly for qualitative, economic and technical reasons as well as 3, 4-epoxycyclohexylmethyl-3 ', 4'-epoxy in terms of occupational hygiene cyclohexane carboxylate (ECC), for the production of cationically UV-curable Coating agents used and for example in Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, Volume 5, Specialty Finishes, edited by P.K.T. Oldring, published by SITA Technology, London 1994.

The use of modified cycloalipha produced according to the invention table epoxy resins, in particular of (A), has compared to the state of the Technology in the production of cationically and radically radiation-curable Coating agents have the advantage of being chemically incorporated Modifiers with at least one double bond have a higher ver wetting-tight and / or improved elasticity and adhesion can be brought about can, so that in general to the usual to increase flexibility sentences, e.g. B. caprolactone polyols, epoxidized polybutadiene can be dispensed with can. Contain the modified epoxy produced according to the invention resins (A) and / or (B) sufficiently hydrophilic groups, e.g. B. by use of half esters (III) and / or (V) with polyoxyethylene units in their Structure, can also be water-dilutable or water-dispersible UV-curable Coating agents are produced.  

Modified cycloaliphatic epoxy produced according to the invention Resins (B) can also be used to produce UV-curable powder coatings be applied.

With paint compatibility with other binders, eg. B. Acrylic copolymers, hydroxyl- and / or carboxyl-containing polyesters, poly ester urethane resins, polyurethane dispersions, epoxy resins, the inventions. modified cycloaliphatic epoxy resins prepared in accordance with the invention can be combined with these binders and also in relation to them Lich lower amount, e.g. B. below 10 wt .-%, based on the total bandage medium, to round off or improve these binders, for. B. hardness, Elasticity, water resistance and / or chemical resistance thereof preserving coatings (coatings) contained in the coating compositions his. Varnish compatibility tests of different or under Different binders are simple routine for the person skilled in the art, so that explanations can be dispensed with.

By using modified epoxy produced according to the invention Resins containing fluorine and / or silicon can be so easy Way "introduced" into the total binder fluorine and / or silicon become.

When using the modified epoxy produced according to the invention Resins (A) and / or (B), preferably (8), for the production of fatty acid modes fected epoxy resins or epoxy resin esters or for the modification of Polyesters, preferably unsaturated polyesters, are used in the epoxy resin "introduced" esters or polyester practically unsaturated double bonds, which leads to improved drying and / or curing. Especially before known unsaturated polyesters are added, preferably with a Acid number from 20 to 60, with modified according to the invention cycloaliphatic epoxy resins, very particularly preferably with fluorine and Silicon content and / or at least two double bonds, modified.

For the production of fatty acid-modified epoxy resins or epoxy resin esters is referred to the corresponding sections in the patent applications 199 01 118.4 and 199 10 206.6.

For the production of modified polyesters is DE-196 34 721 A1 and the corresponding sections in patent applications 199 01 118.4 and 199 10 206.6.

For the production of modified poly modified cyclo esters produced by the process according to the invention aliphatic epoxy resins with 1.1 to 1.5 epoxy groups per average mole Specular weight used.

In the implementation of known carboxyl-containing acrylic copoly merisaten, preferably with an acid number of 10 to 100, in particular 20 to 50, and modified cycloaliphatic produced according to the invention  Epoxy resins with a fluorine and / or silicon content, preferably with 1.1 up to 1.5 epoxy groups per average molecular weight is special The advantage is that fluorine and / or silicon-containing groups, in particular trifluoromethyl and / or perfluoro alkyl groups and / or silicon-organic groups, to the above Acrylco allow polymers to be attached so that they are in the outer structure or Shell of the acrylic copolymers, so that, if necessary, on the one Set of unsaturated fluorine or silicon containing acrylic monomers of State of the art, e.g. B. 3-methacryloxypropyltrimethoxysilane, or ent speaking unsaturated vinyl monomers, e.g. B. vinyl triethoxysilane, or for example, perfluoroalkylethyl methacrylates, in whole or in part preferably entirely, can be dispensed with.

The reactions of carboxyl-containing acrylic copolymers with the Modified cycloaliphatic epoxy resins produced in accordance with the invention can be analogous to that of carboxyl-containing polyesters and fluorine and / or Silicon-containing modified cycloali prepared according to the invention phatic epoxy resins.

When using the modified cyclo produced according to the invention aliphatic epoxy resins, preferably according to claims 2 to 10 and a melting point below 100 ° C, epoxy groups and hydroxyl group-containing acrylic copolymers with more than one epoxy group per through Produce average molecular weight for the production of powder coatings are suitable.

Epoxy group-containing acrylic copolymers used for the production of powder coatings are suitable; belong to the state of the art and are extensive in Literature, especially the patent literature, for example David A. Bate BSc (Hons), The Science of Powder Coatings. Chemistry, Formulation and Appli cation, Volume 1, published by SITA Technology, London 1990, EP-0 728 163 B1, described. It is practical to produce these acrylic copolymers for the introduction of epoxy groups only the use of the commercially available Glycidyl methacrylate possible with suitable comonomers, in particular with high glass transition temperature (Tg), e.g. B. methyl methacrylate, isobornyl methacrylate, styrene, is copolymerized by solution polymerization and after solution polymerization, the solvent, e.g. B. xylene Vacuum distillation is removed as much as possible (see mine not before published patent application 198 08 857.4).

The particular advantage when using the products produced according to the invention modified epoxy resins, preferably according to the above guides on this page and most preferably with a fluorine and / or silicon content, in particular fluorine and silicon content in that, if necessary, on the use of glycidyl methacrylate and / or Fluorine-containing vinyl or acrylic monomers and / or silicon-containing All or part of acrylic or vinyl monomers, preferably entirely, ver can be dispensed and the preparation of the above acrylic copolymers by using the modified cycloali prepared according to the invention table epoxy resins as a graft base for the preparation of the above described acrylic copolymers, optionally by mass or substance  polymerization in the presence or in the lap of those produced according to the invention modified cycloaliphatic epoxy resins can be carried out.

Of course, when using the herge according to the invention presented modified cycloaliphatic epoxy resins for the production of Solvent-free, solvent-containing, especially low-solvent or "high solids", water-dilutable or powder coating means also conventional additives and auxiliaries or additives, eg. B. Rheology auxiliaries, crosslinking catalysts or accelerators, crosslinking or Hardening agents, degassing agents, light stabilizers, photoinitiators, ver be used and this is comparative to the state of the art and the explanations in 199 01 118.4, page 20, paragraph 3.

For example, the person skilled in the art can be cationic and / or radical Hardening suitable photoinitiators according to literature, e.g. B. Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, Volume 3, Photoinitiators for Free Badical and Cationic Polymerization by K.K. Dietliker, edited by P.K.T. Oldring, published by SITA Technology Ltd., London 1991, or Volume 5, Specialty Finishes as dressed above, select or refer to technical information from manufacturers or suppliers (technical data sheets and safety data sheets).

When using the modified cyclo produced according to the invention aliphatic epoxy resins for the production of epoxy and hydroxyl groups containing acrylic copolymers suitable for powder coating production with more as an epoxy group per average molecular weight, it may be advantageous a combination of these, preferably as a crosslinking or curing agent hardening agents containing carboxyl groups, e.g. B polyesters containing carboxyl groups and / or polycarboxylic acids or their anhydrides or modified polycarbonate acid anhydrides, in combination with crosslinking or hardening agents such as latent ones Polyisocyanates and / or aminoplasts containing NCO groups, e.g. B. "Powder link 1174 "to be used if secondary hydroxyl groups are used for adhesion sub support should not remain, but should be reduced or eliminated, especially at a low baking temperature.

The following examples serve to supplement the description and claims play the further explanation of the invention without the claim to full to raise consistency. The parts specified are parts by weight.  

example 1

In a conventional apparatus, 140 parts of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate (commercial product) are mixed with 30 parts of a half ester heated to 70 ° C. from the reaction of hexahydrophthalic anhydride and hydroxyethyl methacrylate and, at 70 ° C. up to warmed up with a clear solution. Now 0.2 parts of lithium hydroxide monohydrate are mixed in and the temperature is raised to 90 ° C. and reacted at this temperature until the acid number is below 2, whereupon the mixture is filtered off.
The end product is clear and yellowish (colorless in a thin layer) and has a viscosity of 83 s / DIN 8 mm / 21 ° C.

Example 2

140 parts of the diepoxide compound used in Example 1 are heated to 80 ° C. in a conventional apparatus and 1 part of 4- (trifluoromethyl) benzoic acid is added in portions at a temperature of 78-82 ° C. After a clear solution, 23 parts of the half ester of tetrahydrophthalic anhydride and polypropylene glycol monomethacrylate (commercial product "Blemmer-PP-1000" as described) are mixed and reacted at 85-90 ° C. to an acid number below 3.
The end product is clear and slightly yellowish (colorless in a thin layer) and has a viscosity of 37 s / DIN 8 mm / 21 ° C. Fluorine content approx. 0.18% by weight.

Example 3

In a conventional apparatus, 140 parts of the diepoxide compound used in Example 1 and 23 parts of the half ester of maleic anhydride and "Blemmer-PP-1000" are mixed, heated to 90 ° C. and reacted at this temperature to an acid number below 3.
The end product is clear and very slightly yellowish (almost colorless) and has a viscosity of 34 s / DIN 8 mm / 22 ° C.

Example 4

70 parts of the diepoxide compound used in Example 1 and 106 parts of the half ester used in Example 2 are mixed in a conventional apparatus, heated to 90 ° C. and reacted at this temperature. With an acid number of 42, 0.1 part of hydroquinone monomethyl ether is added and, after its dissolution, 0.2 part of titanylacetylacetonate is added, whereupon the reaction is continued until the acid number is 28.
The end product is liquid at room temperature, clear and slightly yellowish (colorless in a thin layer) and has a viscosity of 76 s / DIN 8 mm / 40 ° C.

Example 5

The binder heated to 60 ° C according to Example 4 is applied in a layer thickness of about 0.2 mm to degreased steel sheet and subjected to a heat treatment (baking) for 2 hours at 140 ° C in a drying cabinet.
The result is a clear, high-gloss, colorless, hard-elastic coating (coating) that can be bent around the sheet thickness without cracking or flaking.

Claims (14)

1. A process for the preparation of storage-stable, modified or semi-solid, modified cycloaliphatic epoxy resins (A) or storage-stable, meltable and / or soluble and / or dispersible, modified at room temperature, modified cycloaliphatic epoxy resins (8), where (A) and (8) optionally have a fluorine content of 0.01 to 3% by weight and / or a silicon content of 0.01 to 10% by weight, with more than one epoxy group per average molecular weight and at least one secondary hydroxyl group and at least one one ester bond per average molecular weight, characterized in that at room temperature liquid cycloaliphatic diepoxide compounds and (I) half esters of unsaturated dicarboxylic acids or their anhydrides and unsaturated monohydric alcohols based on olefins with up to 10 C atoms, and / or (II) Half esters of unsaturated dicarboxylic acids or their anhydrides and hydroxy alkyl vinyl ethers and the like nd / or hydroxycycloalkyl vinyl ethers and / or (III) half esters of unsaturated dicarboxylic acids or their anhydrides and hydroxyalkyl (meth) acrylates and / or hydroxyalkyl (meth) acrylates with polyoxyalkylene units in their structure and / or reaction products with a secondary hydroxyl group from the reaction of versatic acid glycidyl ester ("Cardura E 10" / Shell or equivalents) and (meth) acrylic acid and / or reaction products with a hydroxyl group from the reaction of caprolactone and hydroxyalkyl (meth) acrylates, optionally with the use of fluorine-containing carboxylic acids or their anhydrides and / or dicarboxylic acid half-esters of fluorine-containing monohydric alcohols and dicarboxylic acids or their anhydrides and / or perfluorocarboxylic acids of the general formula F- (CF ₂ ) _n -COOH with n = 5-21 as an integer and / or organosilicon compounds, which contain at least one group which is reactive with an epoxy group, at elevated temperature, optionally in the presence of organic solvents and / or inert atmosphere and / or catalysts for the epoxy / carboxy reaction and / or polymerization inhibitors, with 0.02 to 0.49 equivalents of the above compounds (modifiers) on an epoxy group are used, so that modified cycloaliphatic epoxy resins result which differ from those of the preamble of the claim in that they additionally contain at least two olefinically unsaturated double bonds, both by ester bonds and by one or more methylene groups and / or alkyl, cycloalkyl -, alkylaryl- aryl- or aralkyl- are connected to one another, 2. Process for the preparation of storage-stable, modified or semi-solid, modified cycloaliphatic epoxy resins (A) or vvn storage-stable, meltable and / or soluble and / or dispersible, modified cycloaliphatic epoxy resins (B) which are solid at room temperature, where (A) and (B) optionally have a fluorine content of 0.01 to 3% by weight and / or a silicon content of 0.01 to 10% by weight, with more than one epoxy group per average molecular weight and at least one secondary hydroxyl group and at least one ester bond per Average molecular weight and at least one olefinically unsaturated double bond per average molecular weight, characterized in that at room temperature liquid cycloaliphatic diepoxide compounds and (IV) half esters from saturated dicarboxylic acids or their anhydrides and hydroxyalkyl vinyl ethers and / or hydroxycycloalkyl vinyl ethers and / or (V) saturated esters from en dicarboxylic acids or their anhydrides and hydroxyalkyl (meth) acrylates and / or hydroxyalkyl (meth) acrylates with polyoxyalkylene units in their structure and / or hydroxycycloalkyl (meth) acrylates and / or reaction products with a secondary hydroxyl group from the reaction of versatic acid glycidyl esters and (Meth) acrylic acid and / or reaction products with a hydroxyl group from the reaction of caprolactone and hydroxy (cyclo) alkyl (meth) acrylics, optionally with the use of fluorine-containing carboxylic acids or their anhydrides and / or dicarboxylic acid semesters of fluorine-containing monohydric alcohols and Dicarboxylic acids or their anhydrides and / or per fluorocarboxylic acids of the general formula F- (CF ₂ ) _n -COOH with n as an integer from 5 to 21 and / or organosilicon compounds which contain at least one group which is reactive with an epoxy group elevated temperature, optionally in the presence of organic solvents and / or inert atmosphere and / or catalysts for the epoxy / carboxy reaction and / or polymerization inhibitors, are reacted, using 0.02 to 0.49 equivalents of the above compounds (modifiers) to an epoxy group. 3. The method according to claims 1 and 2, characterized in that at Based on room temperature liquid cycloaliphatic diepoxide compounds of cycloolefins or cycloalkenes can be used. 4. The method according to claims 1 to 3, characterized in that both Fluorine compounds as well as silicon-organic compounds can be used. 5. The method according to claims 1 to 4, characterized in that half esters of dicarboxylic acids or their anhydrides and organosilanols of the general formula R _n SiX _4-n , where R is aliphatic and / or aromatic and / or heterocyclic radicals and X stands for OH, can be used. 6. The method according to claim 5, characterized in that half esters of Dicarboxylic acids or their anhydrides and organosilanols known per se with one or two hydroxyl groups from the precursor of the polysiloxane or Silicone resin manufacturing can be used.   7. The method according to claims 1 to 6, characterized in that tri fluoroacetic anhydride and / or 4- (trifluoromethyl) benzoic acid and / or Pentafluorobenzoic acid and / or perfluorooctanoic acid and / or half esters of Maleic anhydride and / or itaconic anhydride and / or 5-norborene-2,3- dicarboxylic anhydride and 2,2,2-trifluoroethanol and / or pentadecafluoro-1- octanol and / or 2,3,4,5,6-pentafluorobenzyl alcohol and / or 3-hydroxybenzo trifluoride can be used. 8. The method according to claim 1 and claims 3 to 7, characterized in net that half ester (III) of maleic anhydride and polypropylene glycol monomethacrylate and / or reaction products with a secondary hydroxyl group from the reaction of versatic acid glycidyl ester with acrylic acid and / or methacrylic acid can be used. 9. The method according to claims 2 to 7, characterized in that half esters (V) of saturated dicarboxylic acids or their anhydrides and polypropylene glycol monomethacrylate and / or reaction products with a secondary Hydroxyl group from the reaction of versatic acid glycidyl ester with acrylic acid and / or methacrylic acid can be used. 10. The method according to claims 1 to 9, characterized in that the fluorine compounds containing carboxyl groups or those containing silicon Half-esters in minor amounts, based on one mole of the half-esters (I) to (V) can be used. 11. Use of the modified according to claims 1 to 10 Cycloaliphatic epoxy resins for the production of fatty acid-modified Epoxy resins or epoxy resin esters or for the modification of unsaturated carboxyl-containing polyesters or for modifying carboxyl groups containing acrylic copolymers or as a binder component for the production of solvent-free, solvent-based or water thinnable or powder coating materials. 12. Use according to claim 11 as a binder component for the production of cationically and / or radically radiation-curable, solvent-free, solvent-based or water-dilutable coating compositions or of Powder coatings. 13. Use of the modified according to claims 2 to 10 Cycloaliphatic epoxy resins for the production of epoxy groups and hydroxyl group-containing acrylic copolymers by mass or substance, solution or emulsion polymerization. 14. Use of the modified according to claims 2 to 10 Cycloaliphatic epoxy resins for the production of epoxy groups and hydroxyl group-containing acrylic copolymers with more than one epoxy group per Average molecular weight suitable for the production of powder coatings are.