COATING COMPOSITION CONTAINING METAL PARTICLES

Abstract

The present invention is directed to a coating composition containing metal particles, in particular noble metal particles, to the use of such a coating composition for the production of attractive metallic decorative elements on articles having an outer silicatic surface such as of porcelain, ceramic, china, bone china, glass or enamel, to metallic coatings on such substrates and to a process for the production of coatings of this kind.

Claims

1. Coating composition, comprising A) 5 to 40% by weight of metal particles exhibiting a d.sub.50 value in the range of from 30 to 300 nm, the d.sub.50 value measured by the volume related laser diffraction method, wherein the metal particles are selected from the group consisting of Ag, Au, Ru, Ir, Pd, Pt, Cu, Nb, or of an alloy containing at least one of these, B) 1 to 30% by weight of an organic compound of one or more elements selected from the group consisting of Si, Ge, Nb, Sn, Zn, Zr, Ti, Sb, Al, Bi, alkali metal or alkaline earth metal, with the proviso that at least an oxygen or nitrogen containing organic compound of Si is present, C) 5 to 25% by weight of a binder containing at least one compound selected from the group of polyvinylacetales, D) 10 to 70% by weight of a solvent, E) 0 to 10% by weight of a rheology modifying additive, and F) 0 to 5% by weight of at least one metal salt compound, wherein the metal is selected from the group consisting of Co, Ni, Cu, Cr, Fe, Mn, Au, Rh, Ru, Ir, Os and Pt, based on the weight of the coating composition which adds to 100%.

2. Coating composition according to claim 1, characterized in that the metal particles are noble metal particles selected from the group consisting of Ag, Au, Ru, Ir, Pd, Pt, or of an alloy containing at least one of these.

3. Coating composition according to claim 1, characterized in that the metal particles are of silver or of a silver containing alloy having a silver content of at least 50% by weight, based on the weight of the alloy.

4. Coating composition according to claim 1, characterized in that the organic compound B) is an alcoholate, carboxylate, citrate, acetylacetonate and/or tartrate of the elements, selected from Ge, Nb, Sn, Zn, Zr, Ti, Sb, Al, Bi, alkali metal and/or alkaline earth metal.

5. Coating composition according to claim 1, characterized in that the oxygen or nitrogen containing organic compound of Si is a polysilazane compound, a polysiloxane compound, a silicone resin and/or a silsesquioxane polymer.

6. Coating composition according to claim 1, characterized in that binder C) comprises polyvinylbutyral.

7. Coating composition according to claim 1, characterized in that solvent D) is an organic solvent or a mixture of organic solvents, having a water content in the range of from 0 to at most 10% by weight, based on the total weight of the solvents.

8. Coating composition according to claim 1, characterized in that the rheology modifying additive D) is pine oil, castor oil, a fatty acid, a fatty acid derivative, a natural or a synthetic wax.

9. Coating composition according to claim 1, characterized in that the metal salt compound is a resinate, a sulforesinate, a thiolate, a carboxylates or an alcoholate of at least one of the elements Co, Ni, Cu, Cr, Fe, Mn, Au, Rh, Ru, Ir, Os and Pt.

10. Process for the production of a coating composition according to claim 1, characterized in that compounds A) to F) are intimately mixed with each other and a ready-to-use coating composition is achieved.

11. Process according to claim 10, characterized in that further additives are added.

12. Process according to claim 10, characterized in that the mixing is carried out by a rotor-stator-homogenizer or a Speedmixer.

13. A method for the manufacture of metallic, gold or silver colored decorative elements on articles exhibiting an outer surface of porcelain, china, bone china, ceramic, glass or enamel, which comprises applying a coating composition according to claim 1.

14. Metal particles containing solid coating on a substrate, comprising, based on the weight of the solid coating, at least 60% by weight of metal particles of at least one metal, selected from the group consisting of Ag, Au, Ru, Ir, Pd, Pt, Cu, Nb, or of an alloy containing at least one of these, and comprising at least 5% by weight, based on the weight of the solid coating, of a glass matrix consisting of SiO.sub.2 or comprising SiO.sub.2 and at least one of alkali metal oxides, alkaline earth metal oxides, GeO.sub.2, Nb.sub.2O.sub.3, SnO, SnO.sub.2, ZnO, ZrO.sub.2, TiO.sub.2, Al.sub.2O.sub.3, Bi.sub.2O.sub.3 and Sb.sub.2O.sub.3.

15. Metal particles containing solid coating on a substrate according to claim 14, characterized in that the metal particles are of silver or of a silver containing alloy having a silver content of at least 50% by weight, based on the weight of the alloy.

16. Metal particles containing solid coating on a substrate according to claim 14, characterized in that it additionally contains one or more metals or metal oxides, the metal selected from the group Co, Ni, Cu, Cr, Fe, Mn, Au, Rh, Ru, Ir, Os and Pt.

17. Metal particles containing solid coating on a substrate according to claim 14, characterized in that it comprises 5 to 40% by weight of the glass matrix, based on the weight of the solid coating.

18. Metal particles containing solid coating on a substrate according to claim 17, characterized in that it comprises 5 to 20% by weight of the glass matrix, based on the weight of the solid coating.

19. Metal particles containing solid coating on a substrate according to claim 14, characterized in that the solid coating is composed of two layers lying on top of each other, whereby a first layer is located directly on the substrate and constitutes a densely packed metallic layer comprising aggregated metal particles exhibiting a d.sub.50 value in the range of from 50 to 300 nm, the d.sub.50 value measured by the volume related laser diffraction method, wherein the metal particles are selected from the group consisting of Ag, Au, Ru, Ir, Pd, Pt, Cu, Nb, or of an alloy containing at least one of these, and wherein the second layer is located on top of the first layer and is a glass-like layer comprising at least SiO.sub.2.

20. Metal particles containing solid coating on a substrate according to claim 12, characterized in that the substrate is an article exhibiting an outer surface of porcelain, china, bone china, ceramic, glass or enamel.

21. Process for the production of a metal containing coating on a substrate, characterized in that a metal particles containing coating composition according to claim 1 is applied onto a substrate and is subsequently thermally treated at a temperature in the range of from 500 C. bis 1250 C. in an oxygen containing atmosphere.

22. Process according to claim 21, characterized in that the substrate is an article exhibiting a surface of porcelain, china, bone china, ceramic, glass or enamel.

23. Process according to claim 21, characterized in that the metal particles containing coating composition is directly applied onto the substrate.

24. Process according to claim 21, characterized in that the metal particles containing coating composition is applied onto the substrate by means of a transfer medium pre-coated with the metal particles containing coating composition.

25. Process according to claim 21, characterized in that the metal particles containing coating composition is applied onto said substrate or onto a transfer medium by means of a printing process.

26. Process according to claim 21, characterized in that the substrate coated with the metal particles containing coating composition is partly or in total covered by an additional protective layer prior to thermally treating the coating.

Description

EXAMPLE 1

[0088] 0.361 g of Mowital B 45 H, dissolved in dipropylene glycol monomethyl ether (DPM) (17% solids content, product of Kuraray Europe GmbH, CAS-No. 68648-78-2) are metered into a container equipped with a stirrer. 0.013 g of Durazan 1066 (CAS-No. 346577-55-7), 0.602 g of a paste of silver nano-sized particles (d.sub.50 of 70 nm, d.sub.90 of 115 nm, in TPM (50% solids content in tripropylene glycol monomethyl ether) and 0.031 g of rhodium(II) 2-ethylhexanoat (2% in 2-ethylhexanol) are subsequently added under stirring.

[0089] The resulting paste is applied onto a glass plate by means of a brush. The glass plate coated with the coating composition is then fired at a temperature of 580 C. in air. The solvents evaporate and the organic compounds of the coating composition burn without remainings at this temperature. The resulting solid coating layer on the glass plate is composed of a glossy lower metallic layer of silver colour and an upper protective glass-like layer.

[0090] The layer is composed of 92.2% by weight of silver, 0.2% by weight of rhodium and 7.6% by weight of SiO.sub.2, based on the weight of the layer.

EXAMPLE 2

[0091] 2.4 g of polyvinylbutyral binder (Mowital B 60 H, product of Kuraray Europe GmbH), dissolved in 17.6 g dipropylene glycol monomethylether, are metered into a container equipped with a stirrer. 1.0 g of sodium acetate is added and dissolved in the binder solution. 5 g of a Silsesquioxane polymer preparation (MP 60LAN, product of Merck KGaA), 60 g of a paste of silver nanosized particles (d.sub.50 of 70 nm, 50 g solids in tripropylene glycol monomethyl ether), 3 g of a rhodium(III)-2-ethylhexanoate solution (2% in ethylhexanol), and 1.5 g of bismuth(III)-2-ethylhexanoate solution (70% in xylene) are subsequently added under stirring.

[0092] The resulting paste is applied onto a glass plate by means of a brush. The glass plate coated with the coating composition is then fired at a temperature of 580 C. in air. The solvents evaporate and the organic compounds of the coating composition burn without remainings at this temperature. The resulting solid coating layer on the glass plate is composed of a glossy lower metallic layer of silver colour and an upper protective glass-like layer.

[0093] The layer is composed of 93.3% by weight of silver, 4.1% by weight of SiO.sub.2, 1.2% by weight of Na.sub.2O, 1.2% by weight of Bi.sub.2O.sub.3 and 0.2% by weight of rhodium, based on the weight of the layer.