Metal preparation and coatings made therefrom

Abstract

The present invention is directed to metal preparations containing metal particles, in particular noble metal particles, to the use of such metal preparations 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.

1 . Metal preparation comprising
 A) from 5 to 60% by weight of metal particles wherein said metal particles
 (i) exhibit a d 50  value, measured by the volume related laser diffraction method, in the range of from 30 to 300 nm, 
 (ii) exhibit an average aspect ratio, measured by scanning electron microscopy or transmission electron spectroscopy, in the range of from 1.0 to 1.5, and 
 (iii) are selected from Ag, Au, Ru, Ir, Pd, Pt, Cu Nb, or an alloy comprising at least one thereof, 
   B) from 0.2 to 50% by weight of at least one organic compound of one or more elements selected from Si, Ge, B, P, Nb, Sn, Zn, Zr, Ti, Sb, Al, Bi, alkali metal or alkaline earth metal,   C) from 10 to 85% by weight of a solvent,   D) from 0.1 to 50% by weight of a polymeric binder, and   E) from 0.01 to 30% by weight of at least one metal compound that is soluble in organic solvent, wherein the metal comprises at least one from Ag, Au, Ru, Ir, Pd, Pt, Os, and Rh,   wherein the percentages are based on the total weight of the metal preparation.   
     
     
         2 . Metal preparation as claimed in  claim 1 , characterized in that the metal particles are noble metal particles selected from Ag, Au, Ru, Ir, Pd, Pt, or an alloy comprising at least one thereof. 
     
     
         3 . Metal preparation as claimed in  claim 1 , characterized in that the metal particles are of silver or a silver containing alloy having a silver content of at least 50% by weight, based on the weight of the alloy. 
     
     
         4 . Metal preparation as claimed in  claim 1 , characterized in that organic compound B is an alcoholate, carboxylate, citrate, acetylacetonate and/or tartrate of the elements selected from Si, Ge, B, P, Nb, Sn, Zn, Zr, Ti, Sb, Al, Bi, alkali metal and alkaline earth metal. 
     
     
         5 . Metal preparation as claimed in  claim 1 , characterized in that the Si containing organic compound is a silicon comprising polymer such as a polysilazane compound, a polysiloxane compound, a silicone resin, a silicone-modified alkyd resin, a silicone-polyester resin, and/or a silsesquioxane polymer. 
     
     
         6 . Metal preparation as claimed in  claim 1 , characterized in that solvent C 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 solvent:
 preferably wherein the solvent is selected from at least one of the group of alcohols, aromatic solvents, ketones, esters, ethers, ether-alcohols, saturated and unsaturated aliphatic hydrocarbons, or amides.   
     
     
         7 . (canceled) 
     
     
         8 . Metal preparation as claimed in  claim 1 , wherein the polymeric binder D comprises at least one of celluloses, polyamides, polyesters, polyethers, polyvinyls, polyacetals, polyvinylacetals, polysulfone, phenolic resin, ketone resin, epoxy resin, maleic resin and rosin resin. 
     
     
         9 . Metal preparation as claimed in  claim 1 , wherein metal compound E that is soluble in organic solvent at least one a resinate, a sulforesinate, a thiolate, a carboxylate or an alcoholate. 
     
     
         10 . Metal preparation as claimed in  claim 1 , further comprising, as ingredient F, from 0 to 5% by weight of at least one metal salt compound, wherein the metal comprises at least one from Co, Ni, Cu, Cr, Fe, and Mn:
 preferably characterized in that the metal salt compound is at least one from a resinate, a sulforesinate, a thiolate, a carboxylate or an alcoholate;   or   further comprising, as Ingredient G, from 0 to 10% by weight of a rheology modifying additive;   preferably characterized in that rheology modifying additive G comprises at least one of the additives from pine oil, castor oil, a fatty acid, a fatty acid derivative, a natural or a synthetic wax;   or   further comprising, as ingredient H, from 0 to 10% by weight of a dispersant;   preferably wherein dispersant H comprises at least one of polyacrylic acid, polyacrylates and their copolymers, polyurethanes polyvinylpyrrolidone, non-ionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants;   or   further comprising, as ingredient I, at least one additive.   
     
     
         11 - 16 . (canceled) 
     
     
         17 . Process for the production of a metal preparation as claimed in  claim 1 , characterized in that the ingredients are intimately mixed with each other and a ready-to-use metal preparation is obtained;
 preferably characterized in that the mixing is carried out employing a rotor-stator-homogenizer, a triple-roll mill, or a Speedmixer®.   
     
     
         18 . (canceled) 
     
     
         19 . Gold, platinum, or silver colored decorative elements on articles exhibiting a surface, such as porcelain, china, bone china, ceramic, glass or enamel, comprising a metal preparation as claimed in  claim 1 . 
     
     
         20 . Solid coating on a substrate, comprising, based on the total weight of the solid coating, at least 60%, preferably at least 80%, by weight of metal particles of at least one metal selected from Ag, Au, Ru, Ir, Pd, Pt, Cu, No, or an alloy comprising at least one thereof, and further comprising at least 5% by weight, based on the total weight of the solid coating, of a glass matrix comprising at least one oxide of SiO 2 , GeO 2 , B 2 O 3 , P 4 O 10 , NbO 2 , Nb 2 O 3 , SnO, SnO 2 , ZnO, ZrO 2 , TiO 2 , Al 2 O 3 , Bi 2 O 3 , Sb 2 O 3 , alkali metal oxide, and/or alkaline earth metal oxide. 
     
     
         21 . Solid coating on a substrate as claimed in  claim 20 , characterized in that the metal particles are of silver or a silver comprising alloy having a silver content of at least 50% by weight, based on the total weight of the alloy. 
     
     
         22 . Solid coating on a substrate as claimed in  claim 20 , characterized in that the glass matrix additionally contains one or more metals or metal oxides, the metal(s) selected from Ni, Cu, Cr, Fe, Mn, Ag, Au, Rh, Ru, Ir, Pd, Os and Pt. 
     
     
         23 . Solid coating on a substrate as claimed in  claim 20 , comprising 5 to 40% by weight of the glass matrix, based on the total weight of the solid coating:
 preferably comprising from 10 to 30% by weight of the glass matrix, based on the total weight of the solid coating.   
     
     
         24 . (canceled) 
     
     
         25 . Solid coating on a substrate as claimed in  claim 20 , characterized in that the solid coating is composed of two layers lying on top of each other, wherein a first layer is located directly on the substrate and constitutes a densely packed metallic layer comprising aggregated metal particles, and wherein the second layer is located on top of the first layer and is a glass-like layer comprising at least one oxide of SiO 2 , GeO 2 , B 2 O 3 , P 4 O 10 , NbO 2 , Nb 2 O 3 , SnO, SnO 2 , ZnO, ZrO 2 , TiO 2 , A 2 O 3 , Bi 2 O 3 , Sb 2 O 3 , alkali metal oxide, and/or alkaline earth metal oxide. 
     
     
         26 . Solid coating on a substrate as claimed in  claim 20 , characterized in that the substrate is an article exhibiting an outer surface of porcelain, china bone china, ceramic, glass or enamel. 
     
     
         27 . Process for the production of a metal comprising coating on a substrate, characterized in that a metal preparation as claimed in  claim 1  is applied onto a substrate and subsequently thermally treated at a temperature in the range of from 500° C. to 1250° C. 
     
     
         28 . Process as claimed in  claim 27 , characterized in that the substrate is an article exhibiting a silicatic surface, such as porcelain, china, bone china, ceramic, glass or enamel;
 or   characterized in that the metal preparation is directly applied onto the substrate;   or   characterized in that the metal preparation is applied onto the substrate by means of a transfer medium pre-coated with the said metal preparation;   or   characterized in that the metal preparation is applied onto the substrate or transfer medium employing a printing process;   preferably characterized in that the metal preparation is applied onto the substrate or transfer medium employing thermoplastic screen printing, ink jet printing, tampon printing, or offset printing.   
     
     
         29 - 32 . (canceled) 
     
     
         33 . Process as claimed in  claim 27 , characterized in that the substrate coated with the metal preparation is partly or in total covered by an additional protective layer prior to thermally treating the coating.