DE2203492A1 - Epoxide reaction prodt coating material - contg alkyd resin polyester and/or acrylate resin - Google Patents

Abstract

The coating material of the parent patent contains reaction prodts. of epoxy cpds. (I) (contg. >1 epoxy gp) aminotriazine-formaldehyde-condensates and polycarboxylic acid (derivs). In this addn. alkyd resin, polyester and/or acrylate resin included. The coating material esp. suitable for powder coating techniques such as coil-coating produces hard, flexible coatings which are solvent resistant.

Description

5 COLOGNE 1. 24 ·. January 1972

BARBAHOSSAPLATZ 4 (LLOYDHAUS) TEL. 232587/246216

The invention relates to coating agents with a content of reaction products that result from the reaction of epoxy compounds with more than one epoxy group (I), aminotriazine-formaldehyde condensates or their derivatives (II) and polycarboxylic acids or their derivatives (III) in a further development of the patent application P 17 4-5 039 · 4 and which are characterized are that the binder made of alkyd resins or polyesters and / or acrylate resins and reaction products that by reacting epoxy compounds with more than one epoxy group (I), aminotriazine-formaldehyde condensates or their derivatives (II) and polycarboxylic acids or their derivatives (III) existed.

The term epoxy compounds with more than one epoxy group For the purposes of the invention, epoxy compounds which have more than one epoxy group per average molecular weight and such networking are accessible. Particularly suitable epoxy compounds are diepoxides with a molecular weight below 1000.

Of the aminotriazine sormaidehyde condensates that can be considered, z. B. Methylolmelaminen such as SJrimethylolmelamin, or their derivatives, e.g. B. melamine methylol ether, reaction products of aminotriazine-formaldehyde condensates with polycarboxylic acids or their derivatives are very good eexamethoxymethy! melamine and / or tetramethoxymethyl-diamino-4-phenyl-1,3-5-triazine are suitable.

Of the aliphatic polycarboxylic acids, e.g. B. adipic acid, trimethyladijpinsäure, or «, their derivatives, z. B. maleic anhydride, gives itaeonic acid or its derivatives, for example itaeonic anhydride, C-traconic anhydride, itaconic acid dimethylesier, excellent results and can alone or preferably in conjunction with cyclic acid anhydrides _? in particular phthalic anhydride can be used.

3098212/4081

5 COLOGNE-1, January 24, 1972

BARBAROSSAPLATZ 4 CLLOYDHAUSJ - 2 - TEL 232587/248216

With the exception of itaconic acid or its derivatives, preference is given to cyclic or heterocyclic polycarboxylic acids or their derivatives are used, for. B. phthalic acid, phthalic anhydride, Terepiithalic acid monomethyl ester, cyclohexane-1,2-diacid anhydride, Furan-carboxylic acid-2-anhydride, pyridinedicarboxylic acid, ■ tris-earboxy-ethyl isocyanurate, benzenetricarboxylic acid anhydride, ^ phthalic anhydride, benzophenonedicarboxylic anhydride, benzene tetracarboxylic dianhydride.

The production of the Uiisetzungprodukte, which in the context of this Invention is not claimed separately, is carried out by reacting epoxy compounds with more than one epoxy group (I), Jussinotriazine -]? Ormaldehyde condensates or their derivatives (II) and polycarboxylic acids or their derivatives (III) with one another at elevated temperature.

Clay the alkyd resins or polyesters contain hydroxyl groups? particularly suitable. Particularly suitable are those containing hydroxyl groups Polyesters based on aliphatic and aromatic saturated dicarboxylic acids and di- and trihydric alcohols or styrene-modified or styrene-containing unsaturated, in particular hydroxyl-containing polyesters, the also with monocarboxylic acids, e.g. B. benzoic acid, may be modified. The term modified with styrene means that where appropriate also proportions of polystyrene can be included.

Of the acrylate materials, those commercially available are preferred Products in solvent-free or solvent-based Form used, especially those containing unsaturated Athylencarbonsäurehydroxyalkylestern, z. B. Hydroxyalkyl methacrylate such as hydroxyethyl methacrylate or metha ^ rylic acid hydroxypropyl ester.

309831/1061

5 COLOGNE 1, January 24, 1972

■ BARBAROSSAPLATZ 4 CLLOYDHAUS) - 5 - TEL 232587/246216

Of course, the alkyd resins or polyesters and / or acrylate resins to be used must with the new reaction products, possibly also with each other, be compatible. This means that they are not only mixable with each other, but must continue to condense in the film to form absolutely homogeneous coatings even after they have been applied to a substrate. The compatibility can at any time by means of measures familiar to the specialist. be averaged. It is also possible, if necessary, to check the compatibility through a precondensation of alkyd resin, or. Polyester and / or acrylate resin with the new reaction products by measures known per se, e.g. B. joint heating in the melt, in the form, in the presence of solvents, to achieve or improve. Also that i.a. from the usage term dependent weight ratio of the alkyd resins or polyester and / or the aerylate resins to the new reaction products can be easily determined by conventional tests and is preferably 20 to 80 percent by weight, in particular up to 50 percent by weight, based on the binding agent of the coating agent, the term binding agent having the usual meaning and the comprises film-forming constituents of the coating composition. Of course other substances common in the production of coating agents, e.g. B. dyes, color pigments, hardeners, Solvents, graphite, fillers, wetting agents, suspending agents, or other resins, e.g. B. phenoplasts, especially o-eresol-formaldehyde condensates, can also be used as long as these resins are compatible with the cold or heat, or with further condensation in the film is achieved.

The new coating agents stand out with the appropriate composition with very good lacquer properties and give coatings of high hardness and elasticity, combined with excellent solvent resistance. The new coating agents can in a known manner, for. B. painting, spraying, rolling, electrostatic spraying, solvent-free or containing solvents on any documents, e.g. B. metal, plastic, wood, paper, cardboard, are applied and harden in the film by hardeners or the application of heat to infusible or thermoplastic coatings at higher temperatures.

" ⁴ " 309831/1061

5 COLOGNE 1, 24. '"January 1972

BARBAROSSAPLATZ 4 CLLOYDHAUS) - 4 - TEL 232587/246216

With the appropriate composition, the new coating agents are excellent as powder coating agents or as solvent-free or low-solvent coating agents for roller application after the so-called. "Goil coating process ¹¹ suitable.

Coating agents in powder form are suitable as those containing hydroxyl groups Alkyd resins or polyesters, in particular those containing terephthalic acid and already in powder form as acrylate resins Commercially available copolymers, while for liquid, solvent-free coating agents, hydroxyl-containing, fatty acid-free polyesters with a hydroxyl content above 4 # are preferred.

Since both the production of the new conversion products and If these are themselves new, their use as or for coating agents could not be foreseen. It is also surprising that the new reaction products with a variety of alkyd resins or polyesters or acrylate resins are readily compatible and on these substances, which by themselves no or result in only unsatisfactory coatings, exert a crosslinking effect, which leads to coatings with excellent properties leads.

The following examples illustrate the new coating agents and the production of the new conversion products contained therein.

Example 1; Production of the conversion product A:

60 parts of hexamethoxymethylmelamine are ^{mixed at 40 °} C. with 60 parts of a diepoxide based on "bisphenol A ^M and epichlorohydrin, molecular weight 500, epoxy value 0.45, and 19 parts of finely powdered itaconic acid are added with slow stirring. This is followed by stirring reacted for about 24 hours at 70 ^° C. A clear, very slightly yellowish ^{soft resin which is highly viscous at 20 °} C. and has an acid number of 61 results.

"5 _
309831/1061

5 COLOGNE 1. 24 ·. January 1972

BARBAROSSAPLATZ 4 (LLOYDHAUSJ - 5 - TEL 232587/246216

4-0 parts of the implementation product "A" are now mixed with 60 ropes of a styrene-containing, unsaturated, hydroxyl-containing polyester, known under the trade name "Roskydal TJe 6087", styrene content approx Layer thickness of about 0.020 millimeters applied. After drying for 15 minutes at -160 ⁰ G, a hard elastic clear coating results.

Example 2; Production of the reaction product "B";

80 parts of hexamethoxymethylmelamine are mixed at 5O ⁰ G with 40 parts of the diepoxide used in Example 1 and then added 23 parts of finely powdered phthalic anhydride and 7 parts of finely powdered itaconic acid. The reaction is now carried out to an acid number of 63 for about 72 hours at 50 ° C. with very slow stirring. A clear, very slightly yellowish soft resin which is viscous ^{at 20 ° C. results.}

50 parts of the reaction product “B” are mixed with 100 parts of the unsaturated polyester “Roskydal Ue 6087” used in Example 1 and rolled onto degreased sheet steel in a layer thickness of 0.005 millimeters. After baking for about 90 seconds at 230 ⁰ O, a similarly elastic coating results with the following values: Cross-cut according to DIN 53151, characteristic value 0, Erichsen depression according to DIN 53 156: 9.7 millimeters, sharp bend of the steel sheet of Ο, ΟδΟ millimeter thickness around the sheet thickness : no flaking, no cracking, combination of cross-cut and Erichsen indentation: 9.7 millimeters, cross-cut characteristic value 0; Resistance to xylene when a cotton ball soaked in lylene is rubbing on the cover with the application of pressure: no attack.

309831/1081

5 COLOGNE January 1st, 1972

BARBAROSSAPLATZ 4 CLLOYDHAUS) - 6 - TEL 232587/246216

Example 3: Production of the reaction product "G";

80 parts of hexamethoxymethylmelamine and 80 parts of the diepoxide used in Example 1 are mixed at 40 g. Now finely powdered Benzoltetracarbonsäure- (1,2,4,5) is dianhydride was added and a temperature of 50 with slow stirring for about 30 minutes - 55 ⁰ G held for about 90 minutes. The reaction can be recognized by the onset of a brownish discoloration, which then becomes more reddish and gradually lighter and clearer, as well as the formation of small bubbles, and it ends at an acid number of 25. The result is a clear soft resin which appears slightly brownish in a thick layer and which is still flowable at 20 G.

50 parts of the Ums etzungs product is ¹¹ G "are mixed with 50 parts of a hydroxyIgruppenhaltigen polyester, whose preparation is described below, are mixed. After application to degreased steel sheet in a layer thickness of 0.040 millimeters and baking for 10 minutes at 16O ⁰ G resulting excellent hard-elastic coatings.

Production of the hydroxyl-containing polyester;

156 parts of neopentyl glycol, 230 parts of triethylene glycol, 480 parts of glycerol (10Q # ig), 3 parts of zinc acetate · 2 H ₂ O, 300 parts of adipic acid, and 220 parts of benzoic acid are "in the presence of 80 parts of Iylene at 158 ⁰ G to 192 ⁰ G in a conventional apparatus equipped with stirrer, heating and water azeotropically until the acid number - / on 5 reacted After cooling to 110 ° 0 300 parts Gyclohsxan-1,2-dicarboxylic anhydride are added, and again at a temperature up to a maximum of 202 ⁰ G up. converted to the acid number of 12, and terminates the reaction then with gentle Yacuum at an acid number of 9. This results in a clear, well-flowable at 20 ⁰ C hydroxyl-bearing polyester.

- 7 -309831/1061

5 COLOGNE 1, January 24, 1972

BARBAROSSAPLATZ 4 CLLOYDHAUS) - 7 - TEL. 232587/246216

Example 4:

30 parts of the reaction product "B" are mixed with 70 parts of an acrylate resin solution, 50% in xylene / butanol 3: 1? known under
the trade name "luprenal 300 S ^M , as well as 20 parts of Ethy! glycolacetat and 5 parts of butylene glycol mixed and ^{precondensed at" 70 0} C for 30 minutes. After application on sheet steel in one
Layer thickness of 0.025 mm and baking for 10 minutes at 180 G ⁰ resulting hard-elastic coatings.

309831/1061

Claims (6)

"R _ 5 COLOGNE 1, January 24, 1972" * BARBAROSSAPLATZ A CLLOYDHAUSi TEL. 232587/246216 P_a_t_e_n_t_a_n_s_p_r_ü_c_h_e_2 1. Coating agents with a content of reaction products that by reacting epoxy compounds with more than one epoxy group (I), aminotriazine-formaldehyde condensates or their derivatives (II) and polycarboxylic acids or their derivatives (III) obtained in a further development of patent application P 17 45 039.4 were characterized · that the binder is made of alkyd resins and / or polyesters and / or acrylate resins and reaction products that are produced by reacting epoxy compounds with more as an epoxy group (I), aminotriazine-formaldehyde condensates or their derivatives (II) and polycarboxylic acids or their derivatives (III) were obtained. 2. Coating agent according to claim 1, characterized in that Reaction products are included, the aminotriazine-formaldehyde condensates by reaction of epoxy compounds with more than one epoxy group (I) or its derivatives (II) and itaconic acid or its derivatives (III) were obtained. 3. Coating agent according to Claims 1 and 2, characterized in that that styrene and / or polystyrene containing unsaturated polyesters are included. 4. Coating agent according to claims 1 to 3, characterized in that that hydroxyl-containing polyesters are included. 5. Coating agent according to claim 4, characterized in that hydroxyl-containing polyesters based on aliphatic and aromatic saturated dicarboxylic acids and di- and tri-valent ones Alcohols are included. 6. Coating agent according to Claims 1 to 5, characterized in that that up to 50 percent by weight of the binder consist of reaction products that result from the reaction of diepoxides with a molecular weight below 1000 (I), hexamethoxymethylmelamine and / or tetramethoxymethyl-diamino-4-phenyl-1,3,5-triazine (II) and itaconic acid and / or cyclic acid anhydrides (III). 309831/1061