DE19901118A1 - Solid, modified cyclo-aliphatic epoxy resins, useful for production of especially weather-resistant coating powder for cars - Google Patents

Abstract

Solid, modified, possibly fluorinated cycloaliphatic epoxy resins, obtained by reacting liquid cycloaliphatic polyepoxides with no ether links with cyclic monocarboxylic acids and/or hydroxy-acids and/or half-esters and possibly smaller amounts of fluorine-containing acids, anhydrides or half-esters and/or perfluorocarboxylic acids. Modified cycloaliphatic epoxy resins containing more than one epoxide group per average molecule and optionally 0.01-2 wt% fluorine, in the form of fusible and/or dispersible solid resins with good storage stability, are obtained by reacting: (A) liquid cycloaliphatic polyepoxides containing essentially no ether oxygen links with (B) cyclic monocarboxylic acids and/or cyclic hydroxy-carboxylic acids and/or half-esters with at least one ring structure derived from diacids or anhydrides and monohydric alcohols, glycol mono-alkyl ethers, polyglycol mono-alkyl ethers or fatty alcohols, and optionally with (C) smaller amounts of fluorine-containing carboxylic acids or anhydrides and/or half-esters of fluorine-containing monohydric alcohols and diacids or anhydrides and/or perfluoro-acids of formula F-(CF2)n-COOH. n = 5-21 . The reaction is carried out at elevated temperature, optionally in presence of organic solvents and/or catalysts for the epoxy/carboxy reaction, using 0.1-0.49 mols carboxy component (B) and less than 0.1 mol fluoro compound (C) per epoxide group in (A). An Independent claim is also included for the process as described above, carried out at above 60 deg C.

Description

The invention relates to storage-stable, meltable and / or soluble and / or dispersible, modified cycloaliphatic at room temperature Epoxy resins with more than one epoxy group per average molecular weight, optionally with a fluorine content of 0.01 to 2% by weight their manufacture and their use, in particular for the manufacture of Coating agents, preferably solvent-free, solvent-containing, especially low-solvent (high solids), water-dilutable or powder shaped coating compositions, very particularly preferably powder topcoats, ins special transparent powder topcoats or powder clearcoats for automobiles series painting, in the case of a pigmented color-providing base layer, preferably with a metallic effect, applied a powder clear coat and together is hardened with the base layer, or powder topcoats for coating of automotive parts, e.g. B. Clear powder coating for coating aluminum rims, according to the description below and the claims.

The production and use of epoxy resins are known in the art and in the literature including patent publications, e.g. B. A. M. Paquin, epoxy compounds and epoxy resins, Springer-Verlag, Berlin / Göttingen / Heidelberg 1958, W. A. Riese, Solvent-Free Painting Systems, Curt R. Vincentz Verlag, Hanover 1967, Wagner / Sarx, lacquer synthetic resins, Carl Hanser Verlag, Munich 1971, Dr. P. Oldring PhDBA, Waterborne & Solvent Based Epoxies and their End User Applications, Sita Technology Limited, London 1996, Stoye / Feitag, Lackharze, Carl Hanser Verlag, Munich / Vienna 1996, technical information Mations (leaflets) from manufacturers, described in detail.

The technically and economically most important epoxy resins are based built up of bisphenol A. Liquid epoxy resins are used on this basis for the production of solvent-free, low-solvent or water thinable coating agents, e.g. B. in combination with polyamines, poly aminoamides and / or ketimines as hardeners, or in combination with others Hardeners, e.g. B. polycarboxylic anhydrides, as the basis for casting resins or mold masses used, while solid epoxy resins based on bisphenol A in combination with suitable crosslinking agents, e.g. aminoplasts and / or blocked polyisocyanates, for the production of solvent-based Coating agents are used; however, it is of greater importance is, suitable epoxy resins based on bisphenol A, z. B. with enamel points from 70 to 105 ° C, for the production of powder coating means, e.g. B. in combination with conventional hardeners, e.g. B. polycarboxylic acid anhydrides, polycarboxylic acids, polyesters containing carboxyl groups, dicyandiamide or its derivatives. They also usually become special suitable solid epoxy resins based on bisphenol A, e.g. B. "Epicote 1004 "(Shell) modified with fatty acids and used as an epoxy resin ester position of air or oven drying coating agents used.  

Epoxy resins based on bisphenol A or a comparable base, e.g. B. bisphenol F, phenol or cresol novolac polyglycidyl ether compared to their advantages, e.g. B. excellent adhesion to metal and high Chemical resistance, but also disadvantages. The most serious disadvantage is their lack of weather resistance, which results in gloss in top coats loss and chalking in outdoor weathering, so that in general Manufacture of weatherproof top coats powder coatings on the Basis of carboxyl-containing polyesters and triglycidyl isocyanurate or β-hydroxyalkylamides or based on polyesters containing hydroxyl groups and suitable storage-stable polyisocyanates, e.g. B. blocked (cyclo) ali phatic polyisocyanates or elimination-free polyisocyanates based on of uretdiones. For the production of clear powder coating for The automotive serial painting, however, are epoxy in numerous patents group-containing acrylic copolymers and acidic hardeners, e.g. B. carboxyl groups containing acrylic copolymers, carboxyl-containing cycloaliphatic poly esters, polycarboxylic acids or their anhydrides, modified polycarboxylic acid anhydrides, have been proposed and some have found their way into practice.

Cycloaliphatic epoxy resins are liquid or semi-solid at room temperature and are generally used as the basis for casting resins, e.g. B. in combination with polycarboxylic anhydrides, e.g. B. hexahydrophthalic anhydride, as a hardener, or for the production of radiation-curable, e.g. B. UV curable, coating used or are in minor amounts in coating materials, e.g. B. solvent-thinnable stoving varnishes based on carboxyl group-containing acrylic copolymers, as hardeners.

Fatty acid-modified cycloaliphatic epoxy resins are not known. The reason for this is obvious that the person skilled in the art of this modification couldn't expect any epoxy resin esters that could be used for paint production because it is known that the reaction of epoxy resins which are liquid at room temperature based on bisphenol A, e.g. B. "Epikote 828" (Shell), and fatty acids in practice compared to epoxy resin esters based on solid epoxy resins like "Epikote 1004" did not give usable results.

Because cycloaliphatic epoxy resins are liquid or semi-solid at room temperature are, as already stated above, they are therefore produced of powdery coating agents in analogy to solid aromatic Epoxy resins, especially those based on bisphenol A, are not considered.

The use of these cycloaliphatic epoxy resins for the production of powder painting is therefore only possible to a limited extent if selected combinations are observed Settlements and manufacturing conditions, e.g. B. according to EP-0 462 053 B1 or EP-0 770 650 A1, and relates either to the combination with solid colloidal Condensation polymers of urea or melamine with high formaldehyde defined pore volume (EP-0 462 053 B1) or powder coatings on the basis of carboxyl group-containing poly (meth) acrylates and as hardeners epoxy resins with a molecular weight up to 1500, the epoxy resins at least 70 wt .-% polyglycidyl ester of aliphatic and cycloaliphatic polycarbonate include acids (EP-0 770 650 A1).  

If liquid epoxy resins are used at room temperature (10 to 25 ° C) are used preferably in the form of solid mixed phases (solid Solutions) made up of liquid and solid epoxy at room temperature resins are formed, as described in EP-A-0 536 085, the in EP-0 770 650 A1, page 5, lines 10 to 13.

In contrast, the present invention relates to solid, room temperature modified cycloaliphatic epoxy resins, both by their own are characterized as well as by their production ("stand-by Process) and EP-0 770 650 A1 are not to be found or derived therefrom can be directed.

From the above patent publications it can also be seen that polyglycidyl esters of aliphatic or cycloali which are liquid at room temperature phatic polycarboxylic acids compared to the other components in clearly less amount is present, e.g. B as a hardener according to EP-0 770 650 A1, page 6, table with triglycidyl isocyanurate (TGIC) as hardener for comparison with Hexahydrophthalic acid diglycidyl ester and hexahydrotrimellitic acid triglycidyl esters, and in so far not analogous to solid aromatic epoxy resins, in particular based on bisphenol A.

The new object of the invention - cf. Schulte, patent law with EPC, new edited and expanded edition, Carl Heymanns Verlag KG, Berlin / Bonn / Munich 1994, §1, 37 (pp. 19-21) and ~, 21 (pp. 120-121) - is therefore included in it seen, modified cycloaliphatic epoxy resins solid at room temperature to provide, which is in broad analogy to fixed aro Matic epoxy resins, especially based on bisphenol A, for the Her provision of coating agents, preferably powder coating medium, and by conventional hardening agents, e.g. B. polycarboxylic acid hydride, carboxyl group-containing polyester, after application to a base by exposure to heat, e.g. B. 120 to 200 ° C, preferably 140 to 160 ° C, too Cure weather-resistant coatings (coatings).

The object of the invention is noted that at room temperature solid cycloaliphatic epoxy resins, especially diepoxides, are not known are, although at room temperature liquid cycloaliphatic epoxy resins have long been on the market, like the literature, for example W. A. Riese, Löser free painting systems, Curt R. Vincentz Verlag, Hanover 1967, page 222, Formula can be seen, nevertheless, the expert has the invention Task not given, which is obviously due to the fact that he regarded this task as impossible from the outset.

In addition, should also be based on analogy to solid epoxy resins Bisphenol A solid modified cycloaliphatic epoxy resins are available be made, which are suitable for further modifications, in particular for provision of fatty acid-modified cycloaliphatic epoxy resins or Epoxy resin esters are suitable and in contrast to the known fatty acid modifi graced epoxy resins or epoxy resin esters based on bisphenol A. lead to weather-resistant coatings (coatings).  

Analog use is understood to mean that the modified cycloaliphatic epoxy resins according to the invention at ent speaking composition of the same or similar comparable solid epoxy Resins based on bisphenol A for the production of solvent-free, solvent-based, water-dilutable or powder coating let use medium. The same applies to inventions modified with fatty acids modified cycloaliphatic epoxy resins or epoxy resin esters according to the invention to.

This object is accomplished according to the claims and implementations below solved.

From my DE-PS 17 95 852 it is known to use epoxy compounds with at least two epoxy groups in the molecule based on bisphenol A and one mole Specular weight below 500 and an epoxy value greater than 0.3 at temperatures over 60 ° C with 0.1 to 1.5 moles, based on one mole of the epoxy compound, aromatic monocarboxylic acids which, in addition to the carboxyl group, also contain an amino or may contain hydroxyl group, e.g. B. benzoic acid, p-tert-butylbenzoe acid, p-aminobenzoic acid, optionally in the presence of fatty acids or fat oils to implement and the reaction products for the production of Stove enamels, e.g. B. in combination with hexamethoxymethylmelamine (examples 2 and 3) to use.

In my DE-PS 17 45 035, which is an addition to my DE-PS 17 95 852, will instead of aromatic monocarboxylic acids other cyclic or hetero cyclic monocarboxylic acids or half esters of cyclic polycarboxylic acids used with monohydric alcohols, glycol monoethers or fatty alcohols and numerous connections in the underlying disclosure listed, which were only partially adopted in DE-PS 17 45 035.

Knowing these patents, it is nevertheless not obvious to a person skilled in the art now instead of the epoxy resins based on liquid at room temperature of bisphenol A now liquid cycloaliphatic epoxy resins according to the Claims analogous to my previous patents with those claimed there and implement the described connections. This results from itself from the fact that a corresponding implementation is still unknown and solid cycloaliphatic epoxy resins, e.g. B. for the production of powder coatings analogous to solid epoxy resins based on bisphenol A, likewise not are known, which is obviously due to an existing prejudice of the professional world suggests any analogy to these patents. In addition, the modified cyclo according to the invention differ aliphatic epoxy resins compared to my DE-PS 17 95 852 and 17 45 035 by a different and selected composition and will be preferred used for the production of powder coatings. They also contain inventions modified cycloaliphatic epoxy resins according to the invention, if appropriate 0.01 to 2 wt% fluorine.  

The following are other patent publications to be considered Made executions.

DE-41 39 877 A1 relates to cast resin for use in manufacture of insulating materials for high-voltage switchgear that from one by molecular enlargement to an epoxy equivalent greater than 200 modifi adorned ring epoxidized cycloaliphatic epoxy resin based on 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate or bis (3,4-epoxy cyclohexylmethyl) adipate or a mixture of these substances and a hardener and dolomite as a filler (description p. 2, lines 48-52 and claim 1).

In the description on page 2, lines 57-62, the molecular size of the Basic materials for higher-viscosity compounds of the three listed per se known methods in lines 62-63 the addition of dicarboxylic anhydrides or dicarboxylic acids in the deficit, the molecular enlargement takes place with the formation of ester groups.

Modified cycloaliphatic epoxy resins according to the invention, in particular with a melting point above 30 ° C, or their use in the production of Powder coatings or epoxy resin esters cannot or cannot be taken from it can be derived from it.

From the description on page 2, lines 66-68 and ff. Page 3, lines 1-8, and the case play molding material A, B and C and claims 2 and 3 can be seen that the molecular enlargement is preferably carried out by bisphenol A as a diol.

According to the description on p. 3, lines 17-30 and claim 6, they can be used as hardeners Dicarboxylic anhydrides used also in a mixture with half esters of these Anhydrides and mono- and difunctional alcohols and / or mono- or Dicarboxylic acids are used.

However, a connection with the present invention is not discernible. since these mixtures are used as hardening agents and accordingly as is known, to insoluble and infusible end products or molding materials to lead.

EP-0 051 275 A1 relates to a reactive curable binder mixture based on

• A) defined aliphatic and / or cycloaliphatic epoxy compounds (cf. claim 1, lines 3-4 and 16-21 and formula sheet),
• B) defined polycarboxylic acid units based on an oligomeric and / or polymeric polymerization and / or condensation product with ur originally free OH groups of the group polyester and polymers, the over an ester group is linked to a carbocyclic polycarboxylic acid so that there is still a free COOH group in the o-position to this ester bond located on the acid residue (cf. claim 1, lines 5-12 and lines 23-30, ff. P. 26, lines 1-8) and  
• C) a defined catalyst component in the form of alkali and / or earth alkali salts (cf. claim 1, lines 53-12 and lines 23-30, ff. page 26 under C), lines 9-17).

It is readily apparent to the person skilled in the art that these are two or three-component systems with limited shelf life in space temperature.

Although used to produce the reactive binder mixture as a component A) cycloaliphatic epoxy compounds which are liquid even at room temperature, for example epoxidized cyclohexene and / or cyclopentene derivatives Formulas III to VI according to the formula sheet (see p. 4, lines 20-23) sets, however, the expert does not find any indication in how he invented modified cycloaliphatic epoxy resins according to the invention or can. To this extent, these statements go beyond the known state of the art Technology not out.

DE-34 41 043 C2 relates to coating compositions and methods for Manufacture of an anti-corrosive coating.

As can be seen from the description, examples and claims the coating composition as an essential component a defined High molecular weight reaction product based on the implementation of aro matic epoxy resins and defined aromatic components such as more robust polyhydroxyphenols with neighboring hydroxy groups (component B 1, cf. Claim 1) and / or defined phosphorus compounds, for. B. Phosphoric acid (component B 3, claim 1), is based.

A connection with the modified cycloaliphatic according to the invention Epoxy resins are not visible.

DE-41 16 957 A1 relates to radiation-crosslinkable coating compositions which, in addition to one or more latent hardeners, photoinitiator (s) and, if appropriate, other fillers, additives and auxiliaries and solvents, contain the following binder components:

• a) an olefinically unsaturated ester of an epoxy novolak and
• b) a binder obtained by reacting an epoxy compound with more than one epoxy group per molecule, with one or more carbon acids in the molar ratio of the epoxy groups to the carboxyl groups of 1: 0.5 to 0.9 and subsequent reaction of the reaction product with a or more unsaturated isocyanatocarbamate esters by reaction of compounds with at least two isocanate groups with hydroxyl groups containing acrylic, methacrylic or cyanoacrylic acid esters (Claim 1).

The binder component a) does not relate to the present invention since it is an olefinically unsaturated ester of an epoxy novolak or epoxy novolac resin and thus aromatic structure.

According to p. 3, line 14, binders of component b) from EP-B- 0 194 360 known and on p. 6, Examples 5-7, the preparation of this Binder component according to EP-B-0 194 360 (see p. 6, line 25) by Um setting of a phenol novolak epoxy resin with a functionality of about 3.5 with lactic acid (Example 5), an o-cresol novolak epoxy resin a functionality of about 6.5 with lactic acid (Example 6) or one Bisphenol A novolak epoxy resin with a functionality of about 8 with Lactic acid (Example 7) as a structural component for further reaction with the Unsaturated isocyanatocarbamate esters as defined above.

It is apparent that Examples 5-7 are also the present invention do not affect, because they are completely different structural components and end products.

For Examples 5-7 it should also be noted that these are mol ratios of 1 mole of an aromatic novolak epoxy resin with a different functionality from 3.5 (example 5) to 8 (example 7) to 1.2 mol (Example 5) to 1.63 mol of lactic acid, so that it is a The completely open question is how much carboxyl groups there are on an epoxy group (equi valence). The wording in claim 1 can also do this b) Line 56-57 that first in the molar ratio of the epoxy groups the carboxyl groups of 1: 0.5 to 0.9 should not be changed.

In claim 4 it is said that the coating composition according to the claims 1-3 characterized in that the epoxy resin component as a binder component b) additions of mono- or bifunctional epoxy compounds contains.

Since the binder component b) as a structural component for further implementation a reaction with the defined unsaturated isocyanatocarbamate esters Product of an epoxy compound with more than one epoxy group per molecule with carboxylic acid (s), technically one could perhaps do the same understand that the mono- or bifunctional epoxy compounds are not are contained in the binder component b) as an additive, which is formal is spoken, but also for reaction with carboxylic acid (s) into consideration to be pulled.

According to p. 3, line 14, binders of component b) are from EP-B-0 194 360 known. According to p. 3, lines 31-38, those there are particularly preferred Novolak epoxy resins and on page 3, lines 39-41, it says: "This Epoxy resins can be used prior to implementation for better viscosity adjustment before reaction with carboxylic acid additions of mono- and bifunctional light epoxy compounds, so-called reactive diluents, are added "(cf. also analogously to claim 4).  

On p. 3, lines 27-30, are shown as preferred representatives of peracids epoxidized polyunsaturated compounds epoxidized cycloolefins such as B. 3,4-Diepoxy-6-methyl-tetrahydro-benzyl-3,4-diepoxy-6-methyl-tetra hydro-benzoate, vinylcyclohexene dioxide u. a. as well as the diglycidyl esters Based on anhydrides such as hexahydrophthalic or methylnadic acid anhydride called.

The formulation that the compounds mentioned were preferred Acting as representative of a group does not imply that that group as such is preferably used. Rather, page 3 is lines 39-41 and claim 4 that these bifunctional epoxy compounds are known as reactive thinner as an additive for binder component b) for better viscosity act setting.

However, it should not be disputed that the on page 3, line 27- 30, epoxidized cycloolefins mentioned basically for reaction with mono carboxylic acids analogous to the long-known epoxy / carboxy reaction (cf. e.g. B. Wagner / Sarx, Lackkunstharze, Carl Hanser Verlag Munich 1971, p. 181, Formula 3.37 and Stoye / Freitag, lacquer resins, Carl Hanser Verlag Munich / Vienna 1996, p. 241, table 7.11 under 7.67) are suitable.

On page 3, lines 42-45, it says: "Everyone can be carboxylic acids common monocarboxylic acids are used. Examples of this are the un branched monocarboxylic acids, such as formic acid, acetic acid, propionic acid, Lactic acid, stearic acid and also branched monocarboxylic acids such as benzoin acid or cinnamic acid and phenylacetic acid and preferably unsaturated Carboxylic acids of the acrylic acid and methacrylic acid type. "

These statements reflect practically only the known state of the technique.

A selection of cyclic monocarboxylic acids such as the aromatic Benzoic acid is not evident, especially not in connection with the on p. 3, lines 27-30, called cycloaliphatic diepoxides, rather are aliphatic mono with the exception of benzoic acid and phenylacetic acid carboxylic acids listed, of which acrylic and methacrylic acid are preferred.

At no point is there any hint that the average specialist could cause attempts to produce the modes according to the invention initiated cycloaliphatic epoxy resins and nowhere the latter are disclosed or suggested in any form.

Nor can it be overlooked that in the manufacture of the binders component b) first epoxy compounds, preferably based on Novo sheet (see description on page 3, lines 31-38, examples and claim 3) with monocarboxylic acids - cf. my previous statements - implemented are, but then continue with unsaturated isocyanato carbamate esters are implemented, which is not the subject of the present is the invention.  

It is also the known and undeniable goal in the manufacture of radiation-curable, e.g. B. UV-curable, coating agents, as low as possible viscous and solvent-free or at least low-solvent coating medium to develop, since it contains organic solvents and / or water these volatile and non-curable components before Radiation curing must first escape from the coating (coating / film), to avoid blistering / pinholes - consistent thus p. 2, lines 56-62 and p. 3, lines 39-41.

Also the objective in the production of radiation-curable coating means thus leads from the modified cycloalipha according to the invention table epoxy resins.

DE-43 09 196 A1 relates to curable powdery mixtures containing

• A) a reaction product
  A1) Compounds with at least two 1,2-epoxy groups per molecule and epoxy equivalent weights from 160 to 600 and
  A2) aromatic dicarboxylic acids or their mixtures with compounds from the group (cyclo) aliphatic dicarboxylic acids, monocarboxylic acids and / or monohydric phenols and
  A3) optionally cyclic anhydrides and
• B) a hardener, polyester containing carboxyl groups as hardener with exception of.

According to p. 3, lines 5-7, the epoxy compounds used as component A1) bonds on average at least two 1,2-epoxy groups per molecule thus represent polyepoxide compounds, and usually have a glass transition temperature (Tg) of at least 10 ° C.

On p. 3, lines 7-8, it states that these polyepoxide compounds both saturated and unsaturated as well as aliphatic, cycloaliphatic, aroma can be table and heterocyclic and can also have hydroxyl groups.

On page 3, lines 26-39, (poly) glycidyl are also available as polyepoxide compounds esters listed, examples of cycloaliphatic polyglycidyl esters in line 39 is called hexahydrophthalic acid diglycidyl ester.

On page 3, lines 42-47, it says: "These polyepoxide compounds (An Note: Component A1) can also be mixed with one another and if necessary can also be used in a mixture with monoepoxides, whereby it should be noted that the mixture of 1,2-epoxy compounds has a glass transition temperature of min at least 10 ° C. If 1,2-epoxy compounds are used in the mixture  with low glass temperatures, these can only be used to a small extent and only in combination with a corresponding high-melting 1,2-epoxy compound be used so that the glass temperature of component A at least Is 10 ° C.

Modified cycloaliphatic epoxy resins according to the invention are thus not to be removed or suggested to the expert.

On the contrary, DE-43 09 196 A1 leads from the present invention away, as the structural components considered therein at room temperature liquid epoxy compounds, whereby hexahydrophthalic acid (p. 3, line 39) and tetrahydrophthalic acid diglycidyl ester (p. 3, line 68), according to the above, only to a small extent and only in combination with corresponding high-melting 1,2-epoxy compounds be set so that the glass transition temperature (Tg) of component A) at least Is 10 ° C.

In addition, on page 4, lines 32-35 it says: "If component A2) is a Mixture of aromatic dicarboxylic acid with (cyclo) aliphatic dicarbon represents acids, monocarboxylic acids and / or aromatic alcohols, is the amount of this stock in addition to the aromatic dicarboxylic acid parts usually 0.1 to 20 wt .-%, preferably 1 to 5 wt .-%, based on aromatic dicarboxylic acid. "

This information also continues from the present invention.

Furthermore, polyepoxide compounds based on cycloolefins or cyclo alkenes not considered as component A1).

With regard to DE-44 34 279 A1, reference is made to the above statements referred to DE-43 09 196 A1, since between the two publications extensive identity exists with the exception that in DE-44 34 279 A1 component A2) consists of cyclic carboxylic acid anhydrides, while component A2) of DE-43 09 196 A1 aromatic dicarboxylic acids or their mixture with compounds from the group (cyclo) aliphatic dicarbon acids, monocarboxylic acids and / or monohydric alcohols. Furthermore are carboxyl in DE-44 34 279 A1 in contrast to DE-43 09 196 A1 Group-containing polyesters not exempted as curing agents, but preferred (see p. 5, line 7).

Since neither of the publications considered above The object of the invention is also the modified cycloali according to the invention phatic epoxy resins are visible or can be derived from them, will solve the problem on the explanations below and the Claims referred.  

The terms storage stable, meltable and / or soluble and / or dispersible need no explanation per se; however, it should be noted that the term soluble includes both solubility in solvent or water and the term dispersible both non-aqueous dispersions (NAD = None- Aqueous dispersion) and - preferably - aqueous dispersions finally watery powder slurries.

The term liquid at room temperature means that as the starting products cycloaliphatic polyepoxide compounds used at room temperature ture from 10 to 25 ° C as liquids of different viscosities can.

The term fixed means that the modified cyclo aliphatic epoxy resins at room temperature (10 to 25 ° C) no longer flows are capable and preferably have melting points above 30 ° C.

Examples of liquid starting materials used at room temperature Cycloaliphatic polyepoxide compounds are the literature, for example EP-0 444 710 B1, pp. 14-15; U.S. Patent 3,859,314; DE-23 19 815 C2 and EP-0 051 275 A1, p. 23, formula sheet; W. A Riese, Solvent-free paint systems, Curt R. Vincentz Verlag, Hanover 1967, p. 222 and p. 228; Karsten, paint raw material tables 9th edition, Curt R. Vincentz Verlag, Hanover 1992, p. 495 take and for example those based on cycloaliphatic poly amines, e.g. B. isophoronediamine, cycloaliphatic polycarboxylic acids, e.g. B. Tetrahydrophthalic acid, or cycloolefins or cycloalkenes, e.g. B. Cyclo pentadiene, dicyclopentadiene, terpenes, e.g. B. Limonene (= 1.8 (9) p-mentadiene or 1-methyl-4-isopropenyl-1-cyclohexene).

Mixtures of different cycloaliphatic can of course also Polyepoxide compounds are used.

The term that these polyepoxide compounds preferably have no oxygen ether linkages, e.g. B. -CH-CH ₂ -O-, means that the latter are either practically nonexistent or only present in a small amount unavoidable in the preparation of the polyepoxide compounds by side reactions.

Polyglycidyl esters are preferably more cycloaliphatic as starting materials Polycarboxylic acids or their anhydrides, especially cyclo diglycidyl esters aliphatic dicarboxylic acids, preferably hexahydrophthalic acid, methylhexa hydrophthalic acid, tetrahydrophthalic acid, 1,3- or 1,4-cyclohexanedicarbon acid, camphoric anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride (3,6-endo methylene-1,2,3,6-tetrahydrophthalic anhydride). Most notably Preferred starting materials are polyepoxide compounds, in particular Diepoxides, based on cycloolefins or cycloalkenes, e.g. B. Bis- (3,4-epoxy-cyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxy cyclohexane carboxylate, limonene dioxide, vinyl cyclohexene dioxide, 2- (3,4-epoxy cyclohexyl-5,5-spiro-3,4-epoxy) -cyclohexane-m-dioxane, used and limonene dioxide and 3,4-epoxy-cyclohexylmethyl-3 ', 4'-epoxy-cyclohexane-carboxylate or their mixtures expressly preferred.  

The production of these polyepoxide compounds is state of the art for example, the preferred cycloaliphatic diepoxide compounds by epoxidation of cycloolefins or cycloalkenes by means of Halogen-free peracids obtained, the latter also "in-situ", for example as formed from acetic acid or propionic acid / hydrogen peroxide mixtures can be. Cycloaliphatic diepoxides are very particularly preferred compounds with two cycloaliphatic ring structures in the molecule on the Base of cycloolefins or cycloalkenes used.

The term cyclic monocarboxylic acids encompasses aromatic, heterocyclic and cycloaliphatic monocarboxylic acids.

Examples of aromatic monocarboxylic acids to be used according to the invention are benzoic acid, p-tert-butylbenzoic acid, dimethoxybenzoic acid, methyl benzoic acid, 3,4,5-trimethoxybenzoic acid, 2,4,6-trimethylbenzoic acid, benzo phenon-2-carboxylic acid, naphthalene carboxylic acid, phenoxyacetic acid, phenylacetic acid acid, 3-phenylpropionic acid. Benzoic acid and especially are preferred preferably used p-tert-butylbenzoic acid.

Examples of heterocyclic monocarboxylic acids to be used according to the invention are quinaldic acid, coumarin-3-carboxylic acid, 2-furanacrylic acid, furan-2-carbon acid, nicotinic acid, isonicotinic acid, tetrahydrofuran-2-carboxylic acid. Preferential furan-2-carboxylic acid and / or tetrahydrofuran-2-carboxylic acid and / or nicotinic acid and / or isonicotinic acid.

Examples of cycloaliphatic monocarbon to be used according to the invention Acids are cyclobutane carboxylic acid, cyclopropane carboxylic acid, cyclododecane carboxylic acid, cyclohexane carboxylic acid, cyclohexanone carboxylic acid, cyclopentane carboxylic acid, d-campholic acid, adamantane carboxylic acid, monocarboxylic acids, the are derived from cyclopentadiene or dicyclopentadiene, e.g. B. Commercial pro products such as TCD carboxylic acids, e.g. B. TCD carboxylic acid S (tricyclo [5.2.1.02.6] hecan 8-carboxylic acid) from Ruhrchemie, Holten, hydrogenated natural resin acids, e.g. B. Perhydro or tetrahydroabietic acid. Cyclohexane carbon is preferred acid and / or adamantane carboxylic acid and / or TCD monocarboxylic acids and / or Cyclododecane carboxylic acid used.

Examples of cyclic hydroxycarboxylic acids to be used according to the invention are 2-hydroxybenzoic acid (salicylic acid), 3-hydroxybenzoic acid, 4-hydroxy benzoic acid, benzilic acid, 1-hydroxynaphthalene-2-carboxylic acid, 2-hydroxycinnamon acid, hydroxyphenylacetic acid, hydroxynicotinic acid and cyclohexanolcarbon acid. Salicylic acid and / or 4-hydroxybenzoic acid and / or cyclohexanol carboxylic acid used.

Examples of half esters to be used according to the invention with at least one Cyclic ring structure in the molecule are made in a known manner by implementation of cyclic dicarboxylic acids or their anhydrides with aliphatic or cyclic monohydric alcohols or, by reaction of saturated or unsaturated aliphatic dicarboxylic acids or their anhydrides with cyclic get monohydric alcohols.  

Examples of dicarboxylic acids and their anhydrides are adipic acid and amber acid anhydride, citraconic anhydride, dodecenyl succinic anhydride, glutar acid anhydride, fumaric acid, itaconic acid, itaconic anhydride, sebacic acid, Phthalic anhydride, isophthalic acid, terephthalic acid and their derivatives such as Dimethyl terephthalate, hexahydrophthalic anhydride, tetrahydrophthal acid anhydride, tetrachlorophthalic anhydride, maleic anhydride, camphor acid anhydride, 1,4-cyclohexanedicarboxylic acid and 5-norbornene-2,3-dicarboxylic acid anhydride.

Examples of monohydric aliphatic alcohols are methanol, ethanol, pro panol, methoxypropanol, diacetone alcohol, 2,4-dimethyl-3-pentanol, butanol, Methoxybutanol, neopentyl alcohol, 2-methyl-1-butanol, amyl alcohol, isoamyl alcohol, ethylhexanol, 4-methyl-2-pentanol and 3-methyl-3-buten-1-ol.

Examples of typical fatty alcohols are 1-decanol, lauryl alcohol, isooctanol, 1-heptanol, 1-hexanol, 1-nonanol, 1-octanol, stearyl alcohol, 1-tetradecanol and 1-undecanol, with stearyl alcohol being preferred.

Examples of glycol monoethers are methyl glycol, ethyl glycol, butyl glycol and the 1,2-propylene glycol monomethyl already listed as methoxypropanol ether.

Examples of polyglycol monoethers are based on the known etherification of polyglycols, in particular with a molecular weight of about 300 to about 3000 based on polyethylene glycols or polypropylene glycols built up, e.g. B. triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tetrahydrofurfuryl alcohol polyethylene glycol ether.

Examples of cyclic monohydric alcohols are benzyl alcohol, cyclohexanol, Tetrahydrofurfuryl alcohol, methoxybenzyl alcohol, 2-methylcyclohexanol, cyclo dodecanol, cyclootanol, cyclopentanol, cyclopropylmethanol and ethylbenzyl alcohol as well as tricyclic monohydric alcohols, which differ from cyclopentadiene or derive dicyclopentadiene or perhydrogenated natural resin acids and in Trade as TCD alcohols (e.g. from Ruhrchemie, Holten) or as hydroabietyl alcohol, e.g. B. "Abitol-E" supplied by Hercules BV, 2280 HV Rijswijk, NL and, for example, in DE-195 08 544 A1, page 3, lines 36-39, are listed, or 1-adamantol, borneol and isoborneol.

Particularly suitable half esters are those from the implementation of relatively short chain saturated aliphatic dicarboxylic acids or their anhydrides, e.g. B. Succinic anhydride, glutaric anhydride, adipic acid, and cyclic saturated monohydric alcohols, especially benzyl alcohol, cyclohexanol, tricyclic alcohols such as TCD alcohols, and very particularly preferably 1-adamane tol, borneol and in particular isoborneol and cyclododecanol, or from Conversion of cyclic dicarboxylic acids or their anhydrides, preferably Phthalic acid and / or its derivatives, e.g. B. phthalic anhydride, tetrahydro phthalic anhydride, hexahydrophthalic anhydride, terephthalic acid dimethyl esters, and 5-norborene-2,3-dicarboxylic anhydride, and cyclic monovalent Alcohols, especially benzyl alcohol, cyclohexanol, cyclododecanol, tetrahydro furfuryl alcohol and isoborneol.  

Through the use of half esters from cyclic dicarboxylic acids or their Anhydrides and polyglycol monoalkyl ethers with sufficient hydrophilic groups or oxygen ether bonds in their structure can be used the modified cycloaliphatic epoxy resins according to the invention Position of water-dilutable coating agents can be effected.

The use of mixtures of cyclic monocarboxylic acids and / or cyclic hydroxycarboxylic acids and / or the listed half esters, especially mixtures of the preferably used monocarboxylic acids and / or the preferably used hydroxycarboxylic acids and / or the preferred used half-star, because this has the properties of the Invention modified cycloaliphatic epoxy resins depending on "Control" their use particularly well. Very particularly preferred are mixtures containing salicylic acid and / or cyclohexanol carboxylic acid and / or contain in particular 4-hydroxybenzoic acid in an amount that on a Epoxy group of the polyepoxide compounds used as starting products 0.1 to 0.11 mol of these hydroxycarboxylic acids, preferably 0.04 to 0.08 mol 4-hydroxybenzoic acid, are used and p tert-butylbenzoic acid and / or half-esters from cyclic dicarboxylic acids or their anhydrides and cyclic monohydric alcohols, especially the preferred used half esters of the type described above, used become.

The use of mixtures is to be understood as either such used or the individual components in succession at the inventions production according to the polyepoxide used as starting materials connections are added.

Selection and amount of the claimed monocarboxylic acids and / or hydroxycarbon As already stated, acid and / or half-esters are based on the Ver use of the modified cycloaliphatic epoxy resins according to the invention. When used to produce pigmented coating agents have the claimed modifiers (monocarboxylic acids, hydroxycar bonic acids) preferably aromatic ring structures. When using for the production of transparent coating materials, e.g. B. powder clearcoat, are, however, preferably or predominantly modifiers with cyclo aliphatic and / or heterocyclic ring structure used and the amount of the modifiers with aromatic ring structure so limited that the modified cycloaliphatic epoxy resins 0 to 20% aromatic ring structures in the molecule or per average molecular have weight.

Regarding the manufacturing method according to the invention it is noted that the Ver driving conditions in the implementation of polyepoxide compounds and monocarbon acids are known in the art and are familiar to the person skilled in the art, that the reaction is more or less exothermic and depending on Ver driving conditions, e.g. B. Time / temperature curve, selection and amount of optionally used catalysts for the epoxy / carboxy reaction, Absence or presence of organic solvents, e.g. B. from in the paint industry commonly used solvents, e.g. B. xylene, inert  Atmosphere, e.g. B. nitrogen, more or less side reactions, e.g. B. Ver etherification reactions can occur, so that the optimal Verfahrenbe conditions not calculated, but by empirical tests, also series attempts to determine and reproducible must be determined and this is, for example, the literature and chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, Volume 2, Prepolymers and Reactive Diluents for UV and EB curable Formulations, edited by P.K.T. Oldring, published by SITA Technology, London 1991, pages 37-68, and the references referenced therein.

The production according to the invention is preferably carried out in two or more stages carried out, the implementation in the first stage generally at relatively low temperature, e.g. B. 80 to 110 ° C, up to an acid number below 10, preferably below 5, and only then the Temperature is increased, preferably in the range from 111 to max. 170 ° C, ins particularly 115 to 130 ° C until the reaction is complete or essentially has subsided or ended, which is particularly evident in the parameters Easily control melting point, viscosity and acid number. Given if it can also be done so that the hot melt on a sub location, e.g. B. "Teflon" coated steel sheet, in a greater layer thickness, e.g. B. 1 to 5 mm, applied and a thermal post-treatment, for. B. at 140 to 170 ° C, is subjected to a final product with significantly increased Obtain melting point. When using cyclic hydroxycarbon acids, in particular 4-hydroxybenzoic acid, it is recommended the amount limit to 0.1 mol per epoxy group and their use if necessary to be provided only after implementation with other modifiers, because 4-hydroxybenzoic acid due to the phenolic position in the para position Hydroxyl group to considerable molecular enlargement through side reactions, e.g. B. etherification reactions. This effect can also with Advantage to be taken advantage of from the outset by a relatively small Use of 4-hydroxybenzoic acid to achieve higher melting points.

Examples for the production of the modified cyclo according to the invention aliphatic epoxy resins optionally containing fluorine Carboxylic acids or their anhydrides are fluorobenzoic acid, 4- (trifluoromethyl) - benzoic acid, pentafluorobenzoic acid, 2,2,3,3,3-pentafluoropropionic acid, tri fluoroacetic anhydride and 4,5-difluorophthalic anhydride.

The modified cycloaliphati in the preparation of the invention epoxy resins optionally containing fluorine-containing dicarbon Acid half-esters are obtained by reacting dicarboxylic acids or their anhydrides and fluorine-containing monohydric alcohols.

Examples of dicarboxylic acids and their anhydrides are given above on p. 13, lines 1-8, are listed and are carried out according to the execution made there preferred.  

Monohydric alcohols containing fluorine, including perfluoroalcohols are from the literature, for example US-PS 31 71 861, US-PS 32 83 012, EP-0 582 667 B1, p. 8 under Fluorochemical Alcohols, known and / or in Commercially available, e.g. B. Dupont commercial products (Zonyl Ba-L or Zonyl BA), from 3M-Company (L-9704 = 1,1-dihydroheptafluorobutanol), from Asahi Glass or Hoechst. Further examples are 2-fluoroethanol, 3-fluorobenzyl alcohol, 4-fluorobenzyl alcohol, 2,3,4,5,6-pentafluorobenzyl alcohol, 4- (trifluoromethyl) - benzyl alcohol, hydroxybenzotrifluoride, hexafluoro-2-propanol, heptafluoro-1 butanol, pentadecafluoro-1-octanol and preferably 2,2,2-trifluoroethanol.

Dicarboxylic acid semiesters from cyclic dicarboxylic acids are preferred or their anhydrides, very particularly preferably hexahydrophthalic anhydride, and 2,2,2-trifluoroethanol are used.

The modified cycloaliphati in the preparation of the invention epoxy resins are optionally used perfluorocarboxylic acids from the literature, e.g. B. US-PS 31 45 222, known and / or commercially available Lich, e.g. B. the preferably used perfluorooctanoic acid or pentadeca fluoroctanoic acid as "Fluorad acid FC 26" from 3M Deutschland GmbH, Neuss.

The modified in the manufacture of the invention if necessary cycloaliphatic epoxy resins with fluorine-containing compounds used of the type described above will not be prepublished to mine lichten patent application 196 34 721.1-43 in relation to the other bean wanted modifiers (fluorine-free monocarboxylic acids, hydroxycarbon acids, half esters) only in a very small amount if appropriate co-used, so that a significant difference in terms of novelty against about my patent application 196 34 721.1-43. In addition, the modified cycloalipatic epoxy resins according to the invention of 196 34 721.1-43 not for the production of fluorine-containing polyesters used, but directly as such for the production of coating materials used and are moreover by a fluorine content of 0.01 to 2 wt .-% as well as by their properties, e.g. B. melting point.

Since fluorine compounds in the manufacture of the modified according to the invention cycloaliphatic epoxy resins may have a catalytic effect must have to be determined on a case-by-case basis whether this fluorine compound before, during or after the other claimed fluorine-free modifications decorative agents are used.

Preferably modified in the manufacture of the invention cycloaliphatic epoxy resins containing the claimed carboxyl groups Compounds used in such an amount that 0.2 to an epoxy group up to 0.4 mol of these compounds are used and in one use or the use of cyclic hydroxycarboxylic acids, preferably 4-hydroxy benzoic acid, not more than 0.11 mol per epoxy group can be used.

The modified cycloaliphatic according to the invention preferably have Epoxy resins have a melting point of 30 to 150 ° C, especially 70 to 110 ° C.  

The possible fluorine content of the modified cycloaliphati according to the invention epoxy resins is 0.01 to 2% by weight, preferably 0.1 to 1% by weight, and is generally based on pendant fluorine-containing groups, in particular Trifluoromethyl and / or perfluoroalkyl groups.

The new modified cycloaliphatic epoxy resins are one hand through their properties (stable in storage, meltable and / or soluble and / or disper greedy; solid at room temperature, preferably with a melting point of 30 to 150 ° C, especially 70 to 110 ° C), on the other hand by their chemical Constitution (more than one epoxy group per average molecular weight and "stand-by-process" and a possible fluorine content of 0.01-2% by weight, preferably characterized by pendant fluorine-containing groups).

From the "stand-by process" it is readily apparent that the Invention according to modified cycloaliphatic epoxy resins in the molecule the cycloaliphatic polyepoxide compound used as starting raw materials have at least one additional cyclic ring structure and ins contain in particular at least three cyclic ring structures in the molecule, preferably at least two of which are cycloaliphatic in structure it is obvious to the person skilled in the art that the starting raw materials for the preparation position of the modified cycloaliphatic epoxy resins according to the invention on the one hand, preferably cycloaliphatic liquid at room temperature Diepoxidverbindungen with two cycloaliphatic ring structures in the molecule based on cycloolefins or cycloalkenes and cyclic monocarbon acids and / or cyclic hydroxycarboxylic acids and / or cyclic half esters from dicarboxylic acids or their anhydrides and monohydric alcohols are, on the other hand when using cycloaliphatic diepoxides with only a cyclic ring structure and monocarboxylic acids and / or hydroxycarbon acids with two or more cyclic ring structures in the molecule, e.g. B. Adaman tancarboxylic acid, TCD monocarboxylic acid, and / or half-esters from cyclic di carboxylic acids or their anhydrides, e.g. B. hexahydrophthalic anhydride, Nor bonendicarboxylic acid anhydride, also modified cyclo according to the invention aliphatic epoxy resins with at least three cyclic ring structures lie, which must also be taken into account that also by side reactions such as etherification additional cyclic ring structures arise.

Since cycloaliphatic diepoxide compounds are preferably used, contain the modified cycloaliphatic epoxy resins according to the invention preferably more than one epoxy group, but less than two epoxy groups and at least one secondary hydroxyl group and at least one ester bond, which are caused by the known epoxy / carboxy reaction, in Molecule or per average molecular weight.  

The modified cycloaliphatic epoxy resins according to the invention are preferably for the production of fatty acid-modified epoxy resins or Epoxy resin esters used for the production of air or oven drying, solvent-based, especially low-solvent, or water-diluted possible coating agents, in particular weather-resistant pigmented or transparent top coats, e.g. B. clear varnish are suitable.

Production and use of fatty acid-modified epoxy resins or Epoxy resin esters based on bisphenol A are known in the literature, e.g. B. the publications mentioned at the beginning, described in detail and the Expert so familiar that further explanations are unnecessary because Production and use of the modified cycloalipha according to the invention table epoxy resins analog or largely analog production and use Known epoxy resin ester based on bisphenol A epoxy resins, e.g. B. "Epikote 1004" (Shell), but with the advantageous difference, that are based on fatty acid-modified epoxy resins or epoxy resin esters the basis of the modified cycloaliphatic epoxy resins according to the invention also have weather-resistant top coats produced, as already stated.

The modified cyclo according to the invention are very particularly preferred aliphatic epoxy resins as a binder component for the production of pig mented or transparent powder coatings, especially high-gloss powders topcoats, used and can by the usual for epoxy resins and be Known curing agents at temperatures of 120 to 200 ° C, preferably 130 up to 180 ° C, very particularly preferably 140 to 160 ° C, crosslinked or hardened become.

In particular, the modified cycloaliphatic according to the invention Epoxy resins in combination with hardeners containing carboxyl groups, e.g. B. Poly carboxylic acids, polycarboxylic anhydrides, modified polycarboxylic anhydrides, carboxyl group-containing acrylic copolymers and / or carboxyl group-containing Polyester, used for the production of powder top coats, the latter of course, if necessary, also conventional additives and auxiliaries, for. B. Accelerators, degassing agents, leveling agents, light stabilizers, rheological Tools can contain.

The modified cycloaliphatic according to the invention are special Epoxy resins in combination with carboxyl-containing polyesters Position of so-called hybrid systems used, which in itself state of the art Technology are and for example in David A. Bate BSc. (Hons), The Science of Powder Coatings, Chemistry, Formulation and Application, published by SITA Technology, London 1990. The advantage is there in that compared to the prior art through the use of the Invention according to modified cycloaliphatic epoxy resins instead of epoxy Resins also weather-resistant pigmented or transparent powder coating lacquers can be produced, whereby for the production of powder clear lacquer according to the prior art cycloaliphatic polyesters are used, for. B. according to WO-95/01407 or EP-0 706 546.  

The optimal mixing ratio and the paint compatibility of carboxyl-containing polyesters and the modified according to the invention Cycloaliphatic epoxy resins can easily be determined by simple experiments are and is preferably in the range of 25-75 wt .-% according to the invention modified cycloaliphatic epoxy resins to 75 to 25 wt .-% polyester, in particular in the range 40-60% by weight of modified cyclo according to the invention aliphatic epoxy resins to 40-60 wt .-% polyester.

Of course, the modified cycloaliphati according to the invention epoxy resins but also for the production of powder coatings, in particular Powder clearcoat can be used in which the carboxyl-containing poly esters in whole or in part by carboxyl suitable for powder coating production group-containing copolymers, in particular acrylic copolymers, preferably with anhydride groups, were replaced. It is also possible to invent modified cycloaliphatic epoxy resins according to the invention in mixtures with others for the curing of carboxyl-containing polyesters and / or car Boxyl group-containing acrylic copolymers suitable curing agents, for. B. Triglycidyl isocyanurate (TGIC), modified triglycidyl isocyanurate, β-hydroxyalkylamides to be used as hardeners.

One of the specially preferred use of the modified according to the invention Cycloaliphatic epoxy resins is used as a binder component Provision of powder clearcoat for automotive OEM painting or car handsets and refer to page 1, paragraph 1. This use also relates to powder clearcoats based on epoxy groups, optionally additional hydroxyl-containing acrylic copolymers and hardeners containing carboxyl groups, especially polycarboxylic acids, e.g. B. Dodecanedioic acid, very particularly preferably polycarboxylic anhydrides, where in powder coating production instead of the above acrylic copolymers all or part, preferably up to 50% by weight, of the invention modified cycloaliphatic epoxy resins can be used.

It is noted that powder coatings based on epoxy groups Acrylic copolymers and hardeners containing carboxyl groups number of items are richer patent publications; for example, EP-0 509 393 B1 and DE-44 27 225 A1 and the documents cited therein.

The modified cycloaliphatic epoxy resins according to the invention have this use, among others, has the advantage of being in contrast no residual solvent from the production of the acrylic copolymers (Solution polymerization) included, so that shelf life and trickle ability of powder clearcoats can be improved and this is based on my patent application 198 08 857.4 dated March 03, 1998, page 1 and the therein drawn publications.

Of course, the use of the modified according to the invention cycloaliphatic epoxy resins in general to understand that the former general mine as a binder component in conventional coating agents, independently on their composition, for example thermosetting coating compositions based on polyesters and aminoplasts and / or polyisocyanates, the optionally blocked or latent NCO groups, e.g. B. uretdione,  in different, even less, e.g. B. below 10 wt .-%, based on binders, can be included, provided they are compatible with paint technology is present, which is easy due to tests or tests familiar to a person skilled in the art is to be determined.

Are modified according to the invention for the production of coating compositions Cycloaliphatic epoxy resins with fluorine content are used, so the through causes a known fluorine content benefits, especially improvement of Weather, water and chemical resistance from the coating means obtained coatings (coating / film). Powder coatings with a content of fluorine-containing modified cycloaliphatic tables according to the invention Epoxy resins also show improved shelf life and flow ability.

Of course, using the modifi invention decorated cycloaliphatic epoxy resins produced coating optionally also conventional additives and auxiliaries or additives, for. B. Rheology aids, e.g. B. acrylic copolymers with low glass transition temperature, crosslinking catalysts or accelerators, e.g. B. Imidazole or its derivatives, e.g. B. 1,2-dimethylimidazole, boron trifluoride complexes, e.g. B. boron trifluoride-urea complex, boron trifluoride-triethanol complex, organic metal compounds, e.g. B. dibutyltin dilaurate, dibutyltin diacetate, Metal chelates, especially metal acetylacetonates, preferably titanyl and / or zirconium (IV) acetylacetonate, acid catalysts, e.g. B. p-toluenesulfone acid, blocked p-toluenesulfonic acid, degassing agent, e.g. B. benzoin, UV Absorber, HALS (hindered amine light stabilizer) compounds, photoiniti ators, e.g. B. benzophenone derivatives, polymerization initiators contain. Water-thinnable coating agents can also be used as neutralizers medium, e.g. B. tert. Amines, e.g. B. 2- (dimethylamino) ethanol.

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

100 parts of 3,4-epoxycyclohexylmethyl-3 ', 4', epoxycyclohexane carboxylate (commercial product "Diepoxid 126" from Degussa; Viscosity according to DIN 53177, the 25 ° C 200-450 mPa.s) heated to 100 ° C and after and after taking into account the exothermic reaction (approximate value during the course of 2h) 55 parts of p-tert-butylbenzoic acid were added with stirring, so that the temperature does not rise above 110 ° C. The acid number of the clear, light yellowish reaction product was then 17.8. Now the temperature increased to 130 ° C over the course of an hour and then continued while increasing the temperature up to max. 160 ° C to the acid number below 2 vice versa sets, after which the melt was placed in a Teflon shell.

The end product is a clear, slightly yellowish, thin, colorless layer Hard resin with a melting point of around 75 ° C.  

Example 2

100 parts of that used in Example 1 are used in a conventional apparatus cycloaliphatic epoxy resin heated to 110 ° C and gradually in Ver run for about an hour with 45 parts of the half ester from phthalic acid anhydride and benzyl alcohol (phthalic acid monobenzyl ester) implemented. Connecting end is reacted at 120-130 C to an acid number of practically zero (dir worth about 75 min).

The end product is a clear, yellowish, thin layer of colorless hard resin with a melting point of about 40 ° C.

Example 3

63 parts of that used in Example 1 are used in a conventional apparatus cycloaliphatic epoxy resin heated to 110 ° C and in the course of about one hour with 10 parts of adamantane carboxylic acid at a temperature of 110-120 ° C implemented. Then with 11 parts of furan-2-carboxylic acid at 116- Max. 130 ° C taking into account the clearly exothermic reaction to the acid Number less than 5 implemented (guide value about 1.5 hours).

The end product is a clear, slightly yellowish / brownish hard resin with one Melting point of about 55 ° C and is colorless in a thin layer.

Example 4

Analogous to the preceding examples, 80 parts of the ver applied cycloaliphatic epoxy resin with 39 parts of cyclohexane carboxylic acid at 110 to max. 130 ° C converted to an acid number of practically zero (dir worth about 2h), with 0.1 part of lithium hydroxide monohydrate as a catalyst were used.

It results in clear brownish no longer flowing at room temperature capable end product.

Example 5

80 parts of the cycloaliphatic diepoxide used in Example 1 are over a period of about 3 hours at a temperature of 104 to 110 ° C and after with 10 parts of 4-hydroxybenzoic acid to an acid number below 5 implemented. Then continue at 110 to max. 116 ° C implemented until Melting point is about 40 ° C (guide value about 1h) and the melt into one Teflon-coated aluminum shell transferred.

The end product is practically colorless.

Example 6

The resin or end product from Example 5 is poured from the melt into a conventional tin can press-in lid (diameter approx. 8.3 mm), so that the layer thickness is several millimeters. Thereafter, this sample is placed in an oven kept at a set temperature of 165 _o C and held therein until the melting point of the resin is about 65 ° C, after 15 min was the case. The color of the resin (practically colorless) has not changed compared to the resin from Example 5 as a result of the temperature aftertreatment.

Example 7

80 parts of that used in Example 1 are used in a conventional apparatus Cycloaliphatic diepoxide heated to 110 ° C and with 7 parts of a half ester mixture "H" (colorless, more viscous liquid at room temperature) from the mixture or the joint production of the half esters from the order Settling of hexahydrophthalic anhydride and 5-norbonen-2,3-dicarboxylic acid mixed anhydride in a molar ratio and tetrahydrofurfuryl alcohol. After which the temperature has reached 110 ° C again, 1 part of 4-hydroxybenzoic acid added and the temperature increased to 115 ° C. Now in the course of 37 parts of the above half-ester "H" were metered in about one hour and the temperature was maintained until the acid number was 22 and one removed Sample a solid resin, which at room temperature (20 ° C) still an adhesive (sub jective test by thumb pressure). After that it will continue reacted while increasing the temperature to 125 to 130 ° C until the melting point is about 53 ° C, with an acid number of 14 was present.

The end product is a slightly yellowish clear in a thin layer, e.g. B. 0.5 mm, colorless solid resin (melting point approx. 53 ° C, acid number 14).

Example 8

70 parts of that used in Example 1 are used in a conventional apparatus cycloaliphatic diepoxide and 30 parts of limonene dioxide (commercially available Isomer mixture) heated to 90 ° C and in the course of about an hour added 16 parts of adamantane carboxylic acid to this temperature, which is practical immediately dissolves clearly, the acid number compared to the theoretical acid number of the pure mixture does not fall significantly and was 38. After that at this temperature gradually in portions over the course of about one Hour 4 parts of 4-hydroxybenzoic acid added and up to an acid number of 40 implemented. Now, gradually over the course of about two hours 19 parts of furan-2-carboxylic acid were added in portions, the temperature is continuously increased to 120 ° C until the melting point is about 61 ° C (Acid number 7).

The end product is a clear yellowish / brownish solid resin (melting point approx. 61 ° C, acid number 7), which is practically colorless in a thin layer.

Claims (24)

1. Storage-stable, meltable and / or soluble and / or dispersible, modified at room temperature, modified cycloaliphatic epoxy resins with more than one epoxy group per average molecular weight, optionally with a fluorine content of 0.01 to 2 wt .-%, can be prepared by reacting essentially free of oxygen ether linkages, liquid at room temperature cycloaliphatic polyepoxide compounds and cyclic monocarboxylic acids and / or cyclic hydroxycarboxylic acids and / or half esters from dicarboxylic acids or their anhydrides and monohydric alcohols, glycol monoalkyl ethers, polyglycol monoalkyl ethers or fatty alcohols, the half esters optionally having at least one cyclic ring structure with the use of minor amounts, based on the above fluorine-free compounds containing carboxyl groups, fluorine-containing carboxylic acids or their anhydrides and / or dicarboxylic acid semiesters of fluorine-containing alk ohol 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, at elevated temperature, optionally in the presence of organic solvents and / or catalysts for the epoxy - / Carboxy reaction, with 0.1 to 0.49 mol of the above carboxyl group-containing compounds being used for an epoxy group and the amount of the optionally also used carboxyl group-containing fluorine compounds due to the above-described fluorine content of 0.01 to 2% by weight. %, based on the end product, is limited and is less than 0.1 mol of the carboxyl group-containing fluorine compounds per epoxy group. 2. Modified cycloaliphatic epoxy resins according to claim 1, characterized through a melting point of 30 to 150 ° C. 3. Modified cycloaliphatic epoxy resins according to claim 2, characterized through a melting point of 40 to 110 ° C. 4. Modified cycloaliphatic epoxy resins according to claims 1 to 3, characterized in that it is cyclo based on polyglycidyl esters aliphatic polycarboxylic acids and / or cycloaliphatic polyepoxide compound are based on cycloolefins or cycloalkenes. 5. Modified cycloaliphatic epoxy resins according to claims 1 to 4, characterized in that they are cyclo based on diglycidyl esters aliphatic dicarboxylic acids and / or cycloaliphatic diepoxide compounds are based on cycloolefins or cycloalkenes.   6. Modified cycloaliphatic epoxy resins according to claims 1 to 5, characterized by at least three cyclic ring structures in the molecule. 7. Modified cycloaliphatic epoxy resins according to claim 6, characterized ge indicates that they have at least two cycloaliphatic ring structures exhibit. 8. Modified cycloaliphatic epoxy resins according to claims 1 to 7, characterized by at least four cycloaliphatic ring structures in the Molecule. 9. Modified cycloaliphatic epoxy resins according to claims 1 to 8, characterized in that they have more than one but less than two Epoxy groups and at least one secondary hydroxyl group and at least have an ester bond per average molecular weight. 10. Modified cycloaliphatic epoxy resins according to claims 1 to 9, characterized in that the fluorine content on attached fluorine-containing Groups based. 11. Modified cycloaliphatic epoxy resins according to claim 10, characterized characterized in that the attached groups trifluoromethyl and / or per are fluoroalkyl groups. 12. Process for the preparation of stable, meltable and / or soluble and / or dispersible, modified at room temperature, modified cycloaliphatic epoxy resins with more than one epoxy group per average molecular weight, optionally with a fluorine content of 0.01 to 2% by weight, according to claims 1 to 11, characterized in that in wesent union free of oxygen ether bonds, liquid at room temperature cyclo aliphatic polyepoxide compounds and cyclic monocarboxylic acids and / or cyclic hydroxycarboxylic acids and / or half esters of dicarboxylic acids or their anhydrides and monohydric alcohols, glycol monoalkyl ethers, polyglycol monoalkyl ethers or fatty alcohols, where the half esters have at least one cyclic ring structure, optionally with the use of subordinate amounts, based on the above fluorine-free carboxyl-containing compounds, fluorine-containing carboxylic acids or their hydrides and / or he 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 as an integer from 5 to 21, at temperatures above 60 ° C., optionally in the presence organic solvents and / or catalysts for the epoxy / carboxy reaction, are converted, 0.1 to 0.49 mol of the compounds containing carboxyl groups being used on an epoxy group and the amount of fluorine compounds optionally containing carboxyl groups used being less than 0, Is 1 mole per epoxy group. 13. The method according to claim 12, characterized in that Poylglycidyl esters of cycloaliphatic polycarboxylic acids and / or cycloaliphatic poly epoxy compounds based on cycloolefins or cycloalkenes ver be applied.   14. The method according to claim 13, characterized in that diglycidyl ester cycloaliphatic dicarboxylic acids and / or cycloaliphatic diepoxide compound be based on cycloolefins or cycloalkenes. 15. The method according to claims 12 to 14, characterized in that cycloaliphatic polyepoxide compounds based on cycloolefins or cycloalkenes which have at least two cycloaliphatic ring structures in the Have molecule are used. 16. The method according to claims 12 to 15, characterized in that Half esters of cyclic dicarboxylic acids or their anhydrides and cyclic monohydric alcohols can be used. 17. The method according to claim 16, characterized in that half-esters of cycloaliphatic dicarboxylic acids or their anhydrides and cycloaliphatic monohydric alcohols can be used. 18. The method according to claims 12 to 17, characterized in that Mixtures of cyclic monocarboxylic acids and / or cyclic hydroxycarbon acids and / or dicarboxylic acid semiesters with at least one cyclic ring structure can be used. 19. The method according to claims 12 to 18, characterized in that cyclic hydroxycarboxylic acids are used or used. 20. The method according to claim 19, characterized in that 4-hydroxy benzoic acid is used. 21. Use of the epoxy resins according to the preceding claims for Her provision of fatty acid-modified epoxy resins or epoxy resin esters. 22. Use of the epoxy resins according to claims 1 to 20 or of epoxy resin esters according to claim 21 as a binder component for the production of solvent-free, solvent-based or water-dilutable coating agents. 23. Use of the epoxy resins according to claims 1 to 20 as a binder component for the production of powder coating materials, given if in aqueous dispersion. 24. Use according to claim 23 as a binder component for the production pigmented or transparent powder topcoats, especially powders clear varnish for automotive serial multi-layer painting or for automotive or motor vehicle parts.