DE19634721C2 - Coating agents containing modified polyester containing fluorine and the use of the coating agents - Google Patents

Description

The invention relates to solvent-free, solvent-containing, water thinnable or powder coating materials containing fluorine containing modified polyester and the use of the coating medium. In general, those contained in the coating compositions modified polyester has a fluorine content of 0.01 to 10 wt .-%, preferably at least 0.2% by weight of fluorine and very particularly preferably more than 0.5% by weight Fluorine, on.

These coating compositions can work together depending on their total settlement physically drying, oxidative drying and / or moisture curing, cold curing, especially as a two-component system, thermosetting and / or be radiation-curable and can be analogous to known coatings means, e.g. B. on the basis of polyesters, polyester acrylates, polycarbonate diols, polybutadiene polyols, polyester urethane acrylates, polyester urethane resins, combinations of polyester or polyester urethane resins with amino plastic and / or reversibly blocked polyisocyanates, so that no further explanations are necessary.

The production of fluorine-containing polyesters is state of the art and mentioned for example in WO-91/09025 and the literature cited therein. Coating agents, especially of the type claimed, cannot be removed.

DE-44 18 309 A1 describes perfluoroalkyl group-containing, water-soluble, emulsifiable or dispersible resins based on the reaction of

• a) Perfluoroalkyl groups containing defined sulfonamides (general Formula),
• b) Components with oxyethylene units and reactive towards 1,2-epoxides Groups, according to claim 1 also an acid group-containing, polyoxyalkylene modified polyester containing oxyethylene units is used,
• c) a component which contains 1,2-epoxy groups and
• d) optionally further components which are reactive towards 1,2-epoxides Have groups, with the proviso that the amount of those present in the resin Oxyethylene units is 5 to 95% by weight of the total resin.

The resins are used as a treatment, protection and impregnation agent for rock materials, textile materials, leather and paper as well as emulsifying, wetting and auxiliaries for the preparation of aqueous perfluoroalkyl compounds of the preparations used (claim 5).

In the examples, polyether esters are used and the resins according to the examples play 1 to 7 have a fluorine content of 29.3 to 43.9% by weight and cannot be painted over due to the high fluorine content (anti-graffiti Equipment, cf. P. 5, line 33), which in practice means that this Resins for conventional coating agents, e.g. B. in automotive painting, in the absence of a missing, but always necessary repair option, not are operational. In addition, these resins are not thermosetting. Also from the description, the examples and the claims (cf. e.g. claim 5) there is no other matter.  

DE-195 47 448 A1 relates to polyurethane coating compositions which are differ practically from the prior art only in that these reaction mixtures known per se additionally characterizing one contain fluorinated monohydric alcohol other than fluorinated polyoxetane (cf. Description, p. 2, lines 5-15 and claim 20). From this the expert can neither the task of producing in the coating according to the invention agents containing defined modified polyester and their manufacture derive lung.

Claim 1 of DE-195 47 448 A1 reads: Reaction product of a reaction mixture, comprising:

• a) a fluorinated monohydric alcohol other than fluorinated poly (oxetane), wherein at least 20 percent of the total hydrogen and halogen atoms of said fluorinated alcohol are fluorine atoms;
• b) a non-fluorinated polyol consisting of a polyether, a poly ester or a hydrogenated polyol polyol or combinations thereof; and
• c) a polyisocyanate of the formula R (NCO) _n , where n is 1.7 to 5, and R has 4 to 100 carbon atoms, and R is not a polyether or polyester, the ratio of isocyanate groups to hydroxyl groups being 1: 1 to 50: 1 is.

The ratio of isocyanate groups to hydroxyl groups from 1: 1 to 50: 1 be indicates that the hydroxyl groups of components (a) and (b), where (b) too Can be polyester, must be fully reacted with isocyanate groups and there may be a large excess of isocyanate groups.

So much for the reaction mixture for the preparation of the reaction products as polyols Polyester, it should be noted that it is known in the art that these polyesters have a ratio of isocyanate groups to hydroxyl Groups of 1: 1 (see claim 1) as a two-component system only with strong limited storage stability of the reaction mixture can be used, because after only a few hours it becomes unusable due to very strong viscos increase in activity with subsequent gelation occurs. The Kompo can do that too nente (a) practically nothing to change, since their amount is completely indefinite and according to claim 3 can also be only 1% by weight of the reaction mixture. In addition, it is also known prior art that even with two Component systems with insufficient or excess of isocyanate groups Hydroxyl groups, usually in the range of 0.8 to 1.2 NCO- to -OH, the Processing time of such systems is very limited.

In fact, reaction mixtures of DE-195 47 448 A1 can only be used with other connections are implemented or networked if they have excess Contain isocyanate groups.

From the description of DE-195 47 448 A1, for example page 2, line 41-45, and page 4, lines 16-29, the examples and the subclaims 2 and 8 it can be clearly seen that the reaction mixtures excess, preferably contain blocked isocyanate groups (see examples, etc.), to form a coating (= reaction product) with polyamines the substrate is cross-linked (see page 4, lines 15-16 and examples), so that these reaction mixtures were practically modified blocked polyisocyanates.  

In contrast, modified in the coating compositions of the invention Contain polyesters with a fluorine content of 0.01 to 10 wt .-%, the carboxyl and / or have hydroxyl groups and therefore none at all can contain closed isocyanate groups.

The fluorine content of reaction products according to DE-195 47 448 A1 is complete indefinite and cannot be derived from the description or the claims can be derived, especially since the fluorine content of the fluorinated monovalent Alcohols (a) is undetermined since at least 20 percent of the total water Substance and halogen atoms of said fluorinated alcohol are fluorine atoms (see claim 1).

In contrast, the fluorine content is that in the coating according to the invention agents containing modified polyester 0.01 to 10 wt .-%, preferred at least 0.2% by weight fluorine, and is based on those located at the chain end Fluorine-containing groups.

Next in the manufacture of the coating in the invention modified polyester contained neither reaction mixtures according to DE-195 47 448 A1 still fluorinated monohydric alcohols as such ver applies.

The object of the invention is therefore seen in coating compositions according to the above and below explanations and claims to make available, which are analogous to known solvents free, solvent-based, water-dilutable or powdered Be Allow layering agents to be used, however due to the fact that some or all of them are used wise contained modified polyester with a content of 0.01 to 10 wt .-% fluorine to improve coatings, e.g. B. in relation to chemicals, Water and weather resistance, trouble-free formation of coatings, to lead.

The subject of the invention are coating compositions according to the claims and the use of the bean said coating agents.

For the production of the modified polyesters contained in the coating compositions according to the invention, all carboxyl group-containing polyesters known from numerous publications in coating technology, e.g. B. saturated or unsaturated polyesters, or known per se, already with other conventional modifiers, for. B. styrene, vinyl toluene, alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, diisocyanates, modified poly esters, such as those mentioned or described in DE-OS 39 33 890, for example. Of course, these polyesters other than the carboxyl groups, other functional groups, e.g. B. NH ₂ - and / or NH groups, for. B. according to DE-OS 39 33 890, acetoacetate groups, especially hydroxyl groups. The carboxyl groups of the polyesters can result from polycarboxylic acids which have not been completely reacted with polyols in the production of polyesters or the use of hydroxycarboxylic acids, in particular dimethylol propionic acid, or in the usual way by partially reacting polyesters containing hydroxyl groups with polycarboxylic acids or their anhydrides, in particular trimellitic anhydride, hexahydrophthalic anhydride, Succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride.

In the manufacture of automotive clearcoat or transparent topcoats for the well-known multi-layer coating (coloring basecoat + clearcoat / trans Parent top coat, especially with joint hardening of the base layer and clear coat) is made of aliphatic or cycloaliphatic carboxyl group-containing polyesters, preferably those using Cyclo hexanedicarboxylic acids or their anhydrides, e.g. B. 1,4- and / or 1,3-cyclohexane dicarboxylic acid and / or hexahydrophthalic anhydride, and aliphatic and / or cycloaliphatic polyols, e.g. B. neopentyl glycol, trimethylol propane, Cyclohexanedimethanol, diols based on hydrogenated bisphenol A. were made, e.g. B. according to WO 95/01407 or EP 0 706 546.

For the production of laminates, in particular glass fiber reinforced starting from unsaturated polyesters which are customary per se.

The reaction products claimed according to the invention for reaction with the above carboxyl group-containing polyesters, preferably with an acid number of 10 to 200, in particular 40 to 100, and optionally further functional groups, in particular with a hydroxyl content of at least 3%, are obtained by reaction of epoxy compounds with at least two epoxy groups, e.g. B. in the literature, z. BM Paquin, epoxy compounds and epoxy resins, Springer-Verlag, Berlin / Göttingen / Heidelberg, 1958, EP 0 617 726, EP 0 447 360, described epoxy compounds, in particular commercially available diepoxides such as liquid epoxy resins based on bisphenol A, aliphatic or at room temperature cycloaliphatic epoxy resins, in particular based on cyclohexanedi methanol, diglycidyl hexahydrophthalate, 3,4-epoxy-6-methyl-cyclohexyl methyl-3,4-epoxy-6-methylcyclohexane carboxylate, triglycidyl isocyanurate and / or epoxy resins with more than one epoxy group per average molecular weight z. B. at room temperature solid epoxy resins based on bisphenol A, and / or acrylic copolymers with more than one epoxy group per average molecular weight, in particular with at least two epoxy groups per average molecular weight, preferably with an average molecular weight below 5000, especially below 3000, z. B. using an appropriate amount of glycidyl (meth) acrylate and / or other epoxy (meth) acrylates, e.g. B. according to DE-OS 195 37 887, and / or allyl glycidyl ether Herge provided acrylic copolymers, which may optionally also contain hydroxyl groups, and fluorine-containing carboxylic acids or their anhydrides, preferably fluorine-containing aromatic carboxylic acids or their anhydrides, for. B fluorobenzoic acid, 4,5-difluorophthalic anhydride, and / or half-esters of fluorine-containing monohydric alcohols, e.g. B. 2-fluoroethanol, 3-fluoro benzyl alcohol, preferably 2,2,2-trifluoroethanol, and dicarboxylic acids or their anhydrides, e.g. B. succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, preferably hexahydrophthalic anhydride, and / or perfluorocarboxylic acids of the general formula F- (CF ₂ ) _n -COOH, where n is an integer from 5 to 21, preferably per- or pentadeca- fluoroctanoic acid, optionally with the use of phosphoric acid and / or fluorine-free carboxylic acids or their anhydrides, e.g. As acrylic acid, methacrylic acid, methacrylic anhydride, crotonic acid, aliphatic monocarboxylic acids with at least 7 carbon atoms, for. B. pelargonic acid, cycloaliphatic, heterocyclic or aromatic monocarboxylic acids, for. B. furan carboxylic acid, cyclohexanol carboxylic acid, cyclohexanone carboxylic acid, adamantane carboxylic acid, abietic acid, nicotinic acid, benzoic acid, polycarboxylic acids or their anhydrides, half esters of polycarboxylic acids or their anhydrides and monohydric alcohols, glycol or polyglycol ethers or fatty alcohols.

In the production of these reaction products, the processes known for the reaction with the epoxy compounds, which are usually also known for the reaction of fluorine-free carboxylic acids or their anhydrides, are used, for. B. according to DE-OS / DE-PS 17 95 852 or 17 45 053 or other patents, for. B. solvent-free reaction or reaction carried out in the presence of organic solvents at temperatures of 35 to 180 ° C, preferably 120 to 150 ° C, optionally under pressure and / or inert atmosphere, for. B. N ₂ , and / or in the presence of suitable catalysts for the epoxy-carboxy reaction, for. B. alkali metal hydroxides, e.g. B. lithium hydroxide monohydrate, sodium carbonate, organometal salts, e.g. B. lithium octoate, tertiary amines, triethylbenzyl ammonium chloride, phosphines, these catalysts are usually used in an amount of 0.1 to 5 wt .-%, preferably 0.1 to 1 wt .-%, based on the reactants. When reacting the epoxy compounds with the claimed perfluorocarboxylic acids, it may be advantageous to use temperatures as low as possible, in particular below 100.degree.

The reaction of the carboxyl-containing polyester, preferably with a Average molecular weight below 5000, in particular from 500 to 3000, with the reaction products takes place at elevated temperature, for. B. 60 to 160 ° C, in particular 80 to 130 ° C, in the melt or in the presence of orga African solvent, e.g. B. xylene, optionally in an inert atmosphere and / or in the presence of customary catalysts for the epoxy / carboxy reaction.

The modified contained in the coating compositions of the invention Polyesters have carboxyl and / or hydroxyl groups, which are used for crosslinking are suitable with conventional crosslinking agents and contain as crosslinking agents medium z. B. epoxy compounds, β-hydroxyalkylamides, polycarboxylic acids or their anhydrides, aminoplasts and / or polyisocyanates and / or reversible blocked polyisocyanates.

The coating compositions according to the invention preferably contain Ver wetting agents in whole or in part with monohydric alcohols, e.g. B. methanol and / or butanol, etherified aminoplasts and / or carboxyl group-containing Derivatives of fully or partially etherified aminoplasts, their use in coating compositions the skilled worker is familiar with, e.g. B. urea and / or Aminotriazine-formaldehyde resins, preferably with methanol and / or butanol fully or partially etherified melamine-formaldehyde resins, hexamethoxymethyl melamine, tetramethoxybenzoguanamine, tetramethoxymethylglycoluril, carboxyl group-containing reaction products of hexamethoxymethylmelamine and polycarboxylic anhydrides,  z. B. according to DE-PS 35 37 855, and / or polyisocyanates, the Use in coating compositions is also quite familiar to the person skilled in the art is preferably polyisocyanates based on trimerized hexamethy Lendiisocyanat or trimerized isophorone diisocyanate, and / or the expert also common blocked polyisocyanates, preferably those that in Journal of Coatings Technology, March 1995, Vol. 67, No. 842, page 33- 40, and in Farbe & Lack, issue July 1996, pages 51-58, are described, z. B. with methanol blocked tetramethylxylylene diisocyanate (TMXDI) or isophoronediiso mixed blocked with 3,5-dimethylpyrazole and 1,2,4-triazole diisocyanate isocyanurate.

The coating compositions of the invention can in addition to the modifi graced polyesters still other resins, e.g. B. polyurethane resins, polyester urethane resins, phenolic resins, polyesters other than those claimed, e.g. B. on the Based on caprolactone polyols, epoxy resins or modified epoxy resins, Acrylic copolymers, preferably with hydroxyl and / or epoxy groups also in the form of their solution, emulsion or dispersion in water, z. B. aqueous polyurethane dispersions, preferably in Kombina tion with crosslinking agents of the type described above.

The paint raw materials and paint technology suitable for combination with polyesters Compatibility tests are just as familiar to the person skilled in the art as the quantities ratios of the components and the composition of coating agents for the respective purpose and therefore no longer need to be explained become.

The coating compositions of the invention can be used as a function of their composition analogous to known coating compositions on the Use base of polyesters and this is based on the literature, for example refer to the explanations in DE-OS 39 33 890, column 1, lines 47-68, and ff. Column 2, lines 1-39.

The solvent-free solvents according to the invention are preferably containing, water-dilutable or powdered coating agents composed that they are thermosetting, e.g. B. at temperatures of 60 up to 180 ° C and in the case of coil coating processes also briefly at metal temperatures up to about 250 ° C, e.g. B. 10 s / 230 ° C.

A particular use of the coating compositions according to the invention is those for the production of coatings or coatings in the coil coating process (Coil coating) or for the production of coatings during painting of packaging containers, e.g. B. cans or drinks cans, or for forth provision of automotive paints, especially transparent top coats or Clear coats for multi-layer coating, with the transparent top coat or clear varnish on a vented or pre-dried base layer What base layer and top coat or clear coat layer together be branded. For example, a powder clear coat based an epoxy group-containing acrylic copolymer as a crosslinking binder component one or more of the modified polyesters with carboxyl groups contain.  

Special uses of the coating compositions according to the invention are also the production of chemical-resistant polyurethane varnishes in combination with polyisocyanates or blocked polyisocyanates, especially of 2K Systems, e.g. B. with commercially available "paint polyisocyanates" based on trimerized hexamethylene diisocyanate and / or trimerized isophorondi isocyanate, or the production of laminates, especially glasfaserver strengthened, by means of coating agents according to the invention, the modified unsaturated polyester, dissolved in styrene.

The content of the modified polyesters in the coating according to the invention funds can fluctuate within wide limits, as can be seen from the previous standing statements results and is among other things from the intended use of the coating agent and the fluorine content of the modifi contained therein graced polyester.

The coating compositions according to the invention can, for example, have one mode treated polyester modified with drying fatty acids (fluor containing drying alkyd resin), as an oxidative drying self-binding contain agents, or coating agents according to the invention for radical Networking, e.g. B. by means of peroxides and catalysts or by means of photoiniti UV curing hardeners, contain essential as a binding component saturated modified polyesters, dissolved in suitable monomers, e.g. B. styrene, Hexanediol diacrylate, tripropylene glycol diacrylate.

On the other hand, modified poly esters only in minor amounts, e.g. B. less than 10 wt .-%, based contain on binders, especially to ensure trouble-free training of the Surfaces of coating compositions according to known composition to effect the order.

Of course, the coating compositions according to the invention can also usual additives and auxiliaries, e.g. B. pigments, graphite, fillers, solutions medium, water, drying agents, e.g. B. cobalt octoate, hardener, e.g. B. acid hardeners, z. B. p-toluenesulfonic acid, also in blocked form, neutralizing agent, z. B. tertiary amines, catalysts or accelerators for crosslinking cracks ions, organic metal compounds, e.g. B. metal chelates, e.g. B. Titanyl acetylacetonate, dibutyltin dilaurate, dispersant, rheology aid, z. B. thickening and thixotropic agents, e.g. B. hydrophobicized pebbles acid, polyurethanes, copolymers, e.g. B. based on (meth) acrylic acid, Polymerization initiators, e.g. B. peroxides, photoinitiators, e.g. B. on the Base of benzophenone, UV absorber, e.g. B. based on benzotriazole, HALS (hindered amine light stabilizer) compounds, reactive thinners, e.g. B. Diacrylates, polyols, surfactants e.g. B. fluorosurfactants, silicone oil, included.

The coating compositions of the invention can be applied to substrates according to usual methods, e.g. B. painting, spraying, dipping, rolling, electro static order.

Metal, wood or plastic are particularly suitable as substrates, whether probably also other substrates, e.g. B. paper, textile materials come.  

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.

Preparation of the reaction product R

In a conventional apparatus, 100 parts of a commercially available room temperature liquid epoxy resin based on bisphenol A and epichlor hydrine with a molecular weight of 700 and an epoxy value of 0.53-0.55 ("Eurepox 730" from Schering AG, Bergkamen DE) and 15 parts of perfluorooctanoic acid ("Fluorad acid FC 26" from 3M-Company, European Technical Center, Zwijndrecht, Belgium) using 0.2 part of tetraethylammonium bromide as a catalyst at 90 to 100 ° C taking into account the initially exothermic reaction until Acid number of 4.8 implemented. The reaction product is practically colorless Resin which is still flowable at room temperature and has a fluorine content of 8.98% by weight.

Production of the fluorine-containing modified polyester F

A 83% solution of the carboxyl-containing polyester D according to DE-PS 38 11 497 in a mixed solvent of butyl glycol and n-butanol in Weight ratio 5: 2 with 8 parts of the reaction product R in one usual equipment at 90 to 100 ° C using 0.1 part of lithium hydroxide monohydrate and 0.1 part tetraethylammonium bromide as catalysts implemented up to the acid number of 36. The almost colorless end product (fluor. Ent modified modified polyester in solution) has a solids content 84.3% by weight and a fluorine content of 0.79% by weight (solid resin). Diluted with xylene to a solids content of approx. 60.7% by weight the viscosity 56 s / DIN 4 mm / 21 ° C.

example 1

100 parts of the above solution of the modified polyester F are with 25 parts of hexamethoxymethylmelamine mixed and diluted with 42 parts of xylene. Solids content approx. 65.6% by weight, viscosity 53 s / DIN 4 mm / 21 ° C. After this Application on aluminum sheet in a dry film thickness of approx. 5 µm and baking for 10 min / 180 ° C results in a colorless, glossy hard elastic cover that deforms around the sheet thickness without cracking leaves.

Example 2

60 parts of the above solution of the modified polyester F are with 5 parts of 2- (dimethylamino) ethanol neutralized, with 10 parts of desalted Diluted water and mixed with 15 parts of hexamethoxymethylmelamine, followed by is diluted with 110 parts of demineralized water. The watery colloidal Solution (Tyndall effect) has a solids content of approx. 32.8% by weight pH around 8.8 and a viscosity of 183 s / DIN 4 mm / 20 ° C. Immediately after Apply to degreased steel sheet in a dry film thickness of approx. 20 µm is baked for 15 min / 160 ° C. The result is a colorless high shiny coating that deforms around the sheet thickness without cracking leaves.  

Preparation of the reaction product R3

102 parts of 3,4-epoxy are in a conventional apparatus at room temperature cyclohexylmethyl-3 ', 4'-epoxy-cyclohexane-carboxylate (commercial product e.g. "Diepoxid 126" from Degussa AG) while stirring and observing the exothermic Reaction 5 parts of trifluoroacetic anhydride, taking its boiling into account point (40 ° C) gradually added dropwise so that the temperature does not rise above 36 ° C. As soon as the exothermic reaction has ended, 40 to 45 ° C until the acid number below 2 implemented. The reaction product is a clear, slightly yellowish soft resin that is easily flowable at room temperature with a fluorine content of approx. 2.53% by weight.

Preparation of the modified polyester G containing fluorine

134 parts of a 60% solution of polyester D according to DE-PS 38 11 497 in a mixed solvent (74.87% aromatic petroleum distillate solvent with a density of 0.874 and boiling limits of 162-177 ° C, 12.84% butyl glycol and 12.29% diacetone alcohol) - viscosity of the solution approx. 222 s / DIN 4 mm / 22 ° C - are in the presence of 0.1 part of benzyltriethylammonium chloride as a catalyst 12 parts of the reaction product R3 at 120 ° C. in a conventional apparatus taking into account the slightly exothermic reaction, the permissible Peak temperature can rise to 140 ° C. It will continue at 120 to 130 ° C to the acid number of 21 (solid resin) and then with Diluted 5 parts butyl glycol and 5 parts diacetone alcohol; Viscosity 144 s / DIN 8 mm / 24 ° C.

Example 3

111 parts of the above solution of the fluorine-containing modified poly esters G with 24 parts of hexamethoxymethylmelamine, 14 parts of butanol and 20 parts of xylene to a clear coating agent with a viscosity of 128 s / DIN 4 mm / 23 ° C mixed. After application to degreased sheet steel in a dry film layer thickness of approx. 25 µm and a baking time of 10 min / 160 ° C results in a colorless, high-gloss, hard-elastic coating.

Preparation of the reaction product R4

In a conventional apparatus 100 parts of the for the preparation of the reaction product R3 used cycloaliphatic diepoxide with 43 parts of the Half ester from hexahydrophthalic anhydride and 2,2,2-trifluoroethanol Room temperature mixed and with slow heating taking into account the upper Exothermic reaction starting at a temperature of 80 ° C at a max. point temperature of 160 ° C until the exothermic reaction subsides, after which the acid number was 6. Then continue at 13 to 140 ° C until acid number of practically 0 implemented. The reaction product is a clear light  yellowish solid resin almost completely tack-free at room temperature with a Fluorine content of approx. 6.74% by weight. Viscosity approx. 46 s / DIN 8 mm / 21 ° C of the 67% Solution in "Solvesso 100" (petroleum distillate solvent as for polyester G according to its manufacturing example).

Preparation of the modified polyester H containing fluorine

In a conventional apparatus, 134 parts of the 60% solution of the Production of the fluorine-containing modified polyester G used Polyester D in the presence of 0.2 parts of benzyltriethylammonium chloride Catalyst at 120 to 140 ° C gradually 16 parts of a 67% solution of the reaction product R4 metered in "Solvesso 100" and up to the acid number implemented under 26 (solution). Viscosity approx. 260 s / DIN 4 mm / 22 ° C.

Example 4

150 parts of the above solution of the modified polyester H are with 40 parts of an 80% solution of a commercially available methoxymethylmelamine resin in isobutanol (medium to high etherification, low methylol content, medium to high imino functionality, viscosity 2500-7500 mPa.s / 23 ° C) and 20 parts of butanol to a clear coating agent with a viscosity of 159 s / DIN 4 mm / 22 ° C mixed. After application to degreased sheet steel in a dry film layer thickness of approx. 20 µm and a baking time of 15 min / 160 ° C results in a colorless, high-gloss, hard-elastic coating.

Claims (6)

1. Coating agent with a content of a modified polyester which contains 0.01 to 10% by weight of fluorine, in particular 0.2 to 10% by weight of fluorine, and carboxyl and / or hydroxyl groups and whose fluorine content is at the end of the chain Fluorine-containing groups can be produced by reacting a carboxyl-containing polyester with a reaction product containing at least one free epoxy group from the reaction of epoxy compounds with at least two epoxy groups and / or epoxy resins with more than one epoxy group per average molecular weight and / or acrylic copolymers with more than one Epoxy group per average molecular weight and 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, where n is an integer from 5 to 21 means, if necessary under Use of phosphoric acid and / or fluorine-free carboxylic acids or their anhydrides and / or half-esters of polycarbonic acids or their anhydrides and monohydric alcohols, glycol ethers, poly glycol ethers and / or fatty alcohols. 2. Coating composition according to claim 1, characterized in that the Polyester is modified with drying fatty acids and as oxidative drying self-binding agent is included. 3. Coating composition according to claims 1 and 2, characterized in that there are also other resins and, where appropriate, conventional crosslinking agents and / or contains conventional additives and auxiliary substances. 4. Coating composition according to claims 1 and 3, characterized in that it is polyester, acrylic copolymers, polyurethane resins and / or polyester contains urethane resins. 5. Coating composition according to claims 1, 3 and 4, characterized in that it is a completely or partially etherified aminoplast and / or or their carboxyl-containing derivatives and / or polyisocyanates and / or contains reversibly blocked polyisocyanates. 6. Use of the coating compositions according to claims 1 and 3 to 5 for Manufacture of automotive paints or for the production of coatings in the band painting process or for the production of chemical-resistant coatings or for the production of laminates.