Title of Invention	COMPOSITION SUITABLE FOR COLOURING CERAMIC MANUFACTURED ARTICLES AT THEIR SURFACE, PROCESS FOR COLOURING AND COLOURED ARTICLES OBTAINABLE THEREBY
Abstract	Composition suitable for colouring ceramic manufactured articles at their surface and to a depth of at least 1 mm in shades from pink to purple to violet, said composition consisting of a solution in water or inmixture of water with a water soluble organic solvent of a monovalent gold thiolate that during the normal ceramic fire cycle releases corrosive vapours in quantity not higher than 2g502/g AU deposited, comprised in the formulas Au-5-R-X and Au-5-R-H where R stands for a linear or branched bivalent radical of aliphatic or aromatic or cycloaliphatic or heterocyclic type, optionally with substituents, such as for example aminic, amidic, hydroxylic, hydrocarbylic or carbonylic groups or CONH-, in the chain; X stands for a monovalent group selected out of -COOH, 5020H,-OH,-CONH2,-NH2;-0-P(0)(OH)2, in which H atoms may be replaced by alkyl groups and wherein acid groups may be salified with amines or alkaline or alkaline earth metals and basic groups may optionally be salified with organic acids.

Title of Invention

COMPOSITION SUITABLE FOR COLOURING CERAMIC MANUFACTURED ARTICLES AT THEIR SURFACE, PROCESS FOR COLOURING AND COLOURED ARTICLES OBTAINABLE THEREBY

Abstract

Composition suitable for colouring ceramic manufactured articles at their surface and to a depth of at least 1 mm in shades from pink to purple to violet, said composition consisting of a solution in water or inmixture of water with a water soluble organic solvent of a monovalent gold thiolate that during the normal ceramic fire cycle releases corrosive vapours in quantity not higher than 2g502/g AU deposited, comprised in the formulas Au-5-R-X and Au-5-R-H where R stands for a linear or branched bivalent radical of aliphatic or aromatic or cycloaliphatic or heterocyclic type, optionally with substituents, such as for example aminic, amidic, hydroxylic, hydrocarbylic or carbonylic groups or CONH-, in the chain; X stands for a monovalent group selected out of -COOH, 5020H,-OH,-CONH2,-NH2;-0-P(0)(OH)2, in which H atoms may be replaced by alkyl groups and wherein acid groups may be salified with amines or alkaline or alkaline earth metals and basic groups may optionally be salified with organic acids.

Full Text	Filed of the invention The present invention relates to composition suitable for colouring ceramic manufactured articles at their surface, process for colouring and coloured articles obtainable thereby. In particular, the composition of the invention consists of water solutions or solutions of water and water-miscible solvents, of gold organic complexes compatible with other colouring cations optionally present in the solution releasing low quantities of corrosive vapours during the firing cycle. Said solutions allow the obtainment of ceramic manufactured articles in shades from pink to purple to violet after a firing cycle ranging from 750°C to 1,300°C. State of the art The use of coloured ceramic manufactured articles as well as the compositions and process adopted to obtain the relevant colours have been known since long. One of the methods most commonly used consists in the addition of powdered pigments. In particular inorganic oxides and mineral colouring matters, to the ceramic mixture (vitrified stoneware) before firing. The ceramic manufactured article is thus coloured through Its whole thickness, although with large consumption of colouring matter, which is the most expensive component. According to a process used, the surface of the ceramic material is caused to absorb, either after partial firing (as disclosed e.g. in German patent 2,012,304) or simply after moulding and before firing (as disclosed e.g. in Swiss patent 575,894) a water solution of Inorganic salts or metal complexes (as disclosed e.g. In Sprechsal vol. 119, NO 10, 1986, in EP 0704411 and in Indian Patent No. 191994) which become stable colours at high temperature during the ceramic firing cycle. The water solution is applied to the ceramic material before final firing. This process is particularly advantageous because it allows the colouring of very thin layers: therefore, it is widely used for flat manufactured articles (such as e.g. floor and wall tiles). Another problem to be solved when using colours in a water solution is the obtainable depth of colour penetration into the ceramic material. In fact, it was experimentally found that the depth of penetration depends on several parameters, such as the viscosity and surface tension of the colouring solution, the application temperature, the quantity of water optionally sprayed on the manufactured article once the colouring solution has been applied. The water solution is applied to the ceramic manufactured article by immersion, spraying, disk, and silk-screen techniques. Of cardinal importance is the application technique: in particular, the quantity of colouring solution that may be applied by disk and spraying techniques is as high as 400 to 600 g/m2; by silk-screen type techniques it usually amounts to 100 to 200 g/m2 and sometimes even to 400 g/m2, when thickened screens made of a small number of threads are used. Silk-screen type techniques are very much in demand, being the only techniques allowing graphic decorations and drawings, which otherwise cannot be obtained, and requiring lower quantities of colouring matter. When said techniques are used, the colouring solutions are to be thickened with appropriate thickening agents, e.g. modified glucomannans, starch and modified starch derivatives, cellulose and modified cellulose derivatives, or other polymeric substances, soluble or dispersible in a water solution. Colour penetration into the ceramic material before firing can be obtained by spraying relatively high quantities of water on the manufactured article after application of the colouring solution. However, the resulting colours are less intense than those obtained using other techniques. Colour penetration into the material is particularly important in the case of "smoothed" vitrified stoneware tiles. The term "smoothed" means that the vitrified stoneware surface has been abraded with diamond wheels by 0.8 to 1.5 mm and subsequently smoothed or polished with appropriate felt until obtaining a glassy surface. It follows that colour penetration into stoneware articles to be smoothed after firing must reach a depth of 1.6 mm min. other methods have been developed for the smoothing of very thin (1 to 10 \|a) surface layers of the manufactured article. Prior art The use of water solutions of gold compounds for the colouring also in-depth of ceramic manufactured articles is well known. The compounds disclosed in German patent 4,320,072 for said application substantially are gold chlorides also reported in the preceding literature (cf. "Encyclopedia der technischen Chemie". F. Ullmann. 1929, vol. 4. pp. 837-838). However, the gold chloride solution suffers from the inconvenience of being strongly acid, as it contains hydrochloric acid. In the absence of excess hydrochloric acid, the solution is unstable and the gold compound hydrolyses easily with formation of insoluble compounds. It follows that the solution is corrosive and impairs the apparatus used. In particular, in the case of silk-screen type technique, it rapidly impairs the printing screen. WO 97/21646 discloses the use of gold sodium thiosulphate solutions. Na3Au(S2O3)2, stabilised with sodium sulphite, for ceramic surfaces colouring by water solution absorption. From the compositions of solutions 1, 2. and 3 described therein, it is possible to calculate that 4.7 g SO2 or 5.88 g SO3, or an intermediate value in the case of mixtures thereof is released per g Au deposited on the surface. In both cases (use of gold chloride and gold thiosulphate), high amounts of strongly corrosive vapours rapidly impairing the heater metal structures, are released. Therefore, vapours are to be abated to prevent the emission of same into the environment. The use of precious metals water solutions in high concentrations, in the form of thiol derivatives, to obtain thin metal films for decorative purposes, e.g. for dishes, or for electronic purposes, e.g. for printed circuits, is already known. The following are examples of said use: 1. US patent No. 5.545,452 discloses the use of Au thiolates water solutions with a metal content of 2 to 25% by wi. (column 3, rows 10 to 20) to obtain thin metal films for decorative purposes (column 1, rows 38 to 40); 2. EP No. 514,073, like the US patent above, discloses the use of thiolates water solutions to obtain thin films made of Au or other precious metals to decorate the outer surface, and not the inside, of baked ceramic manufactured articles. Technical problem Considering that it is very simple to colour ceramic materials by disk, spraying and silk-screen techniques, the ceramic industry is highly interested in the possibility of using colouring water solutions based on gold to be applied by said techniques, and offering the advantage of • releasing the lowest possible quantity of very noxious or corrosive vapours in the heater; • being compatible with water solutions of organic derivatives of other cations used for the superficial and in-depth colouring of ceramic manufactured articles. Therefore, it is an object of the present invention to provide colouring formulations in the form of water solutions, which • release low quantities of corrosive vapours (≤2 g SO2/g Au deposited); • are compatible with water solutions of organic derivatives of other cations used for the superficial and in-depth colouring of ceramic manufactured articles; • colour the ceramic manufactured articles at their surface and to a depth of at least 1 mm. The Applicant, who has full-fledged experience in the production and sale of colouring matters for ceramic tiles, has now found that water solutions or water mixtures with alcohols or other water-miscible organic solvents, of monovalent gold organic derivatives, can be used to obtain - after firing - colour shades varying from pink to purple to violet on manufactured articles consisting of a conventional ceramic mixture. The water or hydroalcoholic solutions being an object of the present invention are particularly useful for colouring tiles of vitrified stoneware, either at their surface or to a depth of 1 to 3 mm from their surface. In-depth colouring is essential for maintaining the manufactured article decoration after smoothing. It is, therefore, a fundamental feature of the present invention to use water solutions or water mixtures with hydrophilic organic solvents, of gold organic complexes, which are compatible with derivatives of other cations and release low quantities of corrosive vapours (≤2 g SO2/g Au deposited). Said solutions are used to treat ceramic articles before firing. This makes it possible, after firing, to obtain pink, pufple and violet coloured articles, when solutions contain gold only, or new colour shades when solutions are mixed with derivatives of one or several of the following cations: Fe, Cr, Co, Mn, Cu, Ru, Pd, Zr, V, Ni, Sb, W, Zn, Sn. The gold compounds that may be used according to the present invention belong to the class of monovalent gold thiolates, wherein Au is bound to an S atom, and are substantially represented by the following general formulas: Au-S-R-X and Au-S-R-H where R stands for a linear or branched bivalent radical of aliphatic or aromatic or cycloaliphatic or heterocyclic type, optionally with substituents, such as for example aminic. amidic, hydroxylic, carboxyiic, hydrocarbylic or carbonylic groups or CONH-, in the chain; X stands for a monovalent group selected out of -COOH, SO2OH, -OH, -CONH2, "NH2; -O-P(O)(OH)2, in which H atoms may be replaced by alkyl groups and wherein acid groups may be salified with amines or alkaline or alkaline earth metals and basic groups may optionally be salified with organic acids. In particular, monovalent Au thiolates to be used according to the present invention may be in the form of alkaline, alkaline earth metal salts or of variously substituted amines. The water solutions of Au compounds according to the invention are stable, substantially neutral and release a quantity of corrosive vapours of 2 g SO2 max./g Au deposited on the manufactured article surface to be coloured. Said solutions are used in quantities corresponding to 0.1 to 20 g Au (as element) per m2 of surface to be coloured. By way of example, the gold thiolates that may be used according to the invention derive from: The compatibility of the gold thiolates according to the invention with the ceramic colouring systems based on metallic compounds (in particular of Fe. Ni. Cr. Co, Sn, Mn, Cu. Ru, Pd, Zr, V, Sb. W. Zn, Sn) in aqueous solutions has been ascertained through stability tests of the aqueous solutions containing beside Au thiolate also one or more compounds of the above mentioned metals and also through ceramic coloration tests by the same aqueous solutions after ageing. Unforeseable very valuable colours were obtained. Gold thiolates to be used according to the invention may generally be prepared by causing an Au(lll), in the form of a tetrachloroauric acid, to react in water solution with a thioether S(R')2. giving the reduction of Au(!ll) to Au(l). and then with the desired thiol HSR" (R" = -RX or -RH as per the general formulas shown above): This method, described in Inorganic Synthesis, 23 (1985) pp. 191-195, is based on some reactions reported therein. A typical process for applying colouring compositions according to the invention consists in the following steps: a) drying at 100°C of the article to be coloured to a water residue of 0.5% by wt. max.; a.1) pre-treatment, if any, of the dried article with water up to a max, quantity of 300 g/m2 manufactured article; b) treatment of the pre-treated article with a water solution of the colouring composition in a quantity of 30 to 600 g/m2 of the final coloured surface; b.1) post-treatment, if any, of the treated article with water up to a max. quantity of absorbed water of 300 g/m2 ceramic manufactured article; c) equalisation of the post-treated article at room temperature for 8 hours to homogenise the solution absorption; d) oven firing according to the usual ceramic cycle at a temperature of 1,000 to 1,300°C . The concentration of Au thiolate solution to be used according to the invention generally ranges from 0.1 to 2% Au (expressed as element). Some examples of the colours obtained by experimental runs are shown in the Table 1 reported hereinafter. All runs were carried out on the basis of the following process: 1) drying at 100°C of two 33x33 cm supports made of mixture A to a water residue of 0.5% by wt. max.; 2) supports cooling to room temperature; 3) deposition of 0.4 g of each solution on 10 cm2 of surface of each support; 4) supports equalisation at room temperature for 2 hrs and for additional 2 hrs in a thermoventilated oven at 60°C to homogenise the solutions absorption; 5) oven firing according to the usual ceramic cycle; 6) removal of a surface layer (0.8-0.9 mm) and smoothing; 7) colour detection on non-smoothed and smoothed support; 8) non-smoothed support cutting and penetration depth detection. Table 1 Ex. Complexing agent Colour before Colour after Penetration no % element smoothing smoothing (mm) 1 D.L mercaptosuccinic acid. 0.4% gold Parma red Pink 1.2 2 acetylcysteine, 0.4% gold Pink Light pink 2 3 thiolactic acid, 0.4% gold Pink Light pink 2 4 cysteine, 0.4% gold Parma red Pink 1.4 The composition of the ceramic mixture used is as follows (% by wt.) SiO2, 64.4%; AIA 21.8%; K2O 3.8%; Na2O 0.8%; CaO 0.6%; MgO 0.1%; TiO2 0.3%; Fe2O3 0.2%; ZrSi04 5%; H2O to 100%. Colours are as per the Colour Atlas. Example 5 Compatibility of some Au thiolates with other cations Compatibility tests were carried out with the following water solutions: Au acetylcysteinate prepared with the method disclosed in the following at page 11, line 6 and diluted up to 0.4% Au, Au mercaptosuccinate (0.4% Au), cobalt ammonium citrate (2% Co), Ni ammonium citrate (2% Ni); chromium ammonium citrate (2% Cr), iron ammonium citrate (Fe 2%), tin glycolate (Sn 2%). The mixtures consist of Au derivative solution (50%) and of another cation solution (50%). The results obtained, after the days reported below, are as follows: Au acetylcysteinate Au mercaptosuccinate Co 30 days, clear solution 30 days, clear solution 60 days, clear solution 60 days, clear solution colour turned from reddish violet to wine red Ni 30 days, clear solution 30 days, clear solution 60 days, clear solution 60 days, clear solution Cr 30 days, clear solution 30 days, clear solution 60 days, slightly opaque sol. 60 days, slightly opaque sol. Fe 30 days, clear solution 30 days, clear solution 60 days, clear solution 60 days, clear solution Sn 30 days, clear solution 30 days, clear solution 60 days, clear solution 60 days, clear solution Example 6 The connpatibillty of some Au thiolate according to the invention with other colouring cations has been tested in comparison with two Au compounds of the prior art, namely NaAuC4 and gold-sodium thiosulphate Na3Au(S2O3)2. The obtained results are reported in Tables 3 and 4. The tested products in form of aqueous solutions containing 1% by w. Au are prepared as follows. Product (1) Au thiolacetate (Au-TL/3) 30 g aqueous solution of tetrachloroauric acid (corresponding to 1 g Au) is added with aqueous solution of NaOH up to a pH of 8 (solution A). Thiolactic acid 1.65 g is dissolved in 30 g H2O and added with NH4OH aqueous solution 30% by w. up to a pH = 7 (solution B). The solution B is added to the solution A, then the mixture is added with NH4OH up to pH 9 and with H2O up to a total weight of 100 g. Product (2) Au sodium thiosulphate (Au-Bk.Giulini) Comparison test. In 91.6 g of H2O are dissolved 1.7 g Na3Au(S2O3)2 and 6.7 g of Na sulphite (molar ratio Au/Na2SO3 = 0.9/10) as disclosed by W097/21646 in Table 3. This ratio is the best as it regards the stabilization of the solution as declared by the Applicant: no precipitate occurs in the solution when it comes in contact with a piece of metal. Product (3) Au acetylcysteine (Au/CST) 30 g of aqueous solution of tetrachloroauric acid (corresponding to 1 g Au) are added with NaOH aqueous solution up to a pH of 8 (solution A). N-acetylcystelne 5.1 g in 30 g H2O are added with NH4OH aqueous solution 30%, up to a pH of 7 (solution B). The solution B is added to the solution A. then the mixture is added with NH4OH up to pH 9.5 and with H2O up to a total amount of 100 g. Product (4) Au acetylcysteine (Au-CST/9) 30 g of aqueous solution of tetrachloroauric acid (= 1 g Au) are added with NaOH aqueous solution up to a pH 8 (solution A), N-acetylcysteine 5.1 g in 30 g H2O are added with NaOH aqueous solution up to a pH 7 (solution B). The solution B is added to the solution A, then the mixture is added with NaOH up to pH 9 and with H2O up to a total amount of 100 g. Product (5) Au acetylcysteine (Au-CST/2) 30 g of aqueous solution of tetrachloroauric acid (= 1 g Au) are added with NaOH aqueous solution up to a pH of 8 (solution A). N-acetylcysteine 2.55 g in 30 g H2O are added with NH4OH 30% aqueous solution up to a pH 7 (solution B). The solution B is added to the solution A, then the mixture is added with NH4OH up to a pH 9.5 and with H2O up to a total amount of 100 g. Product (6) NaAuCl4 (Au-CI) Comparison test. 30 g of aqeuous solution of tetrachloroauric acid (= 1 g Au) are added with NaOH aqueous solution up to a pH of 2.5 and with H2O up to a total amount of 100 g. Product (7) Au acetylcysteine (Au-CST/10) 30 g of aqueous solution of tetrachloroauric acid (= 1 g Au) are added with NaOH aqueous solution up to a pH of 8 (solution A). N-acetylcysteine 2.55 g in 30 g H2O are added with NaOH aqueous solution up to a pH 7 (solution B). The solution B is added to the solution A, then the mixture is added with NaOH up to a pH of 9.5 and with a H2O up to a total amount of 100 g. In the following Table 2 are reported the tested products with the neutralizing agent used (NaOH or NH^OH) and the molar ratio between Au and SO2 (or SO3) developed during the ceramic firing of the treated manufactured articles. The Au acetylcysteine solutions products 3 and 4 have been prepared using an excess of acetylcysteine and consequently these solutions show a content of S higher then in the products 5 and 7. The use of an excess of acetylcysteine affords an higher stability of the Au-acetylcysteine solution. The tests reported in the following tables 3 and 4 have been carried out with solutions consisting of mixtures of Au derivative solution (50%) and of other cations solutions (50%) Table 3 - Comparative tests for Au-acetylcysterine and Au-thiolactate, reference product Na-Au thiosulphate (Au-Bk.Giulini) d = days XXX = crystals ppt = precipitate sol. = solution Fe citr/13 = 10 g hydrate iron citrate Aldrich (Fe 18 ÷ 19%) in 20 g H2 0 are added with 10 g of NH4OH 30%, find pH = 7; Fe = 4.5 ÷ 4.75% by w. Table 4 - Comparative tests for Au-acetylcysterine: reference product Na Au CI4 (Au-CI) d = days XXX = crystals ppt = precipitate sol. = solution Claims 1. Composition suitable for colouring ceramic manufactured articles at their surface and to a depth of at least 1 mm in shades from pink to purple to violet, said composition consisting of a solution in water or in mixture of water with a water soluble organic solvent of a monovalent gold thiolate that during the normal ceramic fire cycle releases corrosive vapours in quantity not higher than 2gSO2 /g An deposited, comprised in the formulas Au-S-R-X and Au-S-R-H where R stands for a linear or branched bivalent radical of aliphatic or aromatic or cycloaliphatic or heterocyclic type, optionally with substituents, such as for example aminic, amidic, hydroxylic, carboxylic, hydrocarbylic or carbonylic groups or CONH-. in the chain; X stands for a monovalent group selected out of -COOH, SO2OH. -OH, -CONH2, -NH2; -O-P(O)(OH)2, in which H atoms may be replaced by alkyl groups and wherein acid groups may be salified with amines or alkaline or alkaline earth metals and basic groups may optionally be salified with organic acids. 2. The composition as claimed in claim 1, wherein the concentration of gold thiolate in the solution correponds to a content of 0,1% to 2% of Au (expressed as element). 3. Composition as claimed in claim 1 wherein the release of corrosive vapours is not higher than IgSOg/g Au. 4. The composition as claimed in claim 1, wherein Au thiolate derives from one of the following thio-compounds: (N) acetyl-cysteine; 4-mercaptopyridine; 2-mercaptopyridine; 2-mercaptoacetyl-glycine; mercaptopropionyi-glycine; 3-mercaptopropionyl-glycine; (d,l) mercaptosuccinic acid; cysteine; 2-mercapto-propionic acid. 5. The composition as claimed in claim 1 containing, in addition to Au thiolate, other metal compounds having colouring properties for the ceramic material, selected from the organic or inorganic derivatives of the following elements: Co, Cr, Ni, Ru. Mn. Sb, W, Cu, Fe, Zr, V, Zn. Pd, Sn. 6. The composition as claimed in claim 1, containing in addition to Au thiolate selected from Au thiolactate and/or Au acetylcysteinate and/or Au mercptosuccinate, other metal compounds having colouring properties for the ceramic material selected from the following compounds: Cobalt ammonium citrate; Chromium acetate; Chromium ammonium citrate; Nickel ammonium citrate, Ru giycolate; Ru ammonium citrate; Mn ammonium citrate; NaSb tartrate; KSb tartrate, NaW citrate; Cu ammonium citrate. Fe ammonium citrate; sodium metavanadate; V giycolate; V ammonium citrate; Zn ammonium citrate, Pd giycolate; Pd ammonium citrate, Sn giycolate. 7. Process for colouring ceramic manufactured articles obtained by moulding a conventional ceramic mixture, said process using the composition as claimed in claim 1 and consisting in the following steps: a) drying at 100°C of the article to be coloured to a water residue of 0.5% by wt. max.; a.1) pre-treatment, if any, of the dried article with water up to a max. quantity of 300 g/m2 manufactured article; b) treatment of the pre-treated article with a water solution of the colouring composition in a quantity of 30 to 600 g/m2 of the final coloured surface; b,1) post-treatment, if any, of the article treated with water up to a max. quantity of absorbed water of 300 g/m2 ceramic manufactured article; c) equalisation of the post-treated article at room temperature for 8 hours to homogenise the solution absorption; d) oven firing according to the usual ceramic cycle at a temperature of 1,000 to 1,300°C. 8. The process as claimed in claim 5, wherein the solution of the colouring composition, thickened with appropriate thickening agents, is applied to the ceramic manufactured article in step (b) by the silk-screen technique. 9. Vitrified stoneware tiles coloured at their surface and to a depth of at least 1 mm, in shades from pink to purple, to violet, by the process as claimed in any of claim 7 and 8. 10. Vitrified stoneware tiles according to claim 9 wherein the superficial layer has been removed by smoothing to a depth of 1.5 mm and final polishing. 11. The process as claimed in claim 6, wherein the treatment with a gold thiolate solution is carried out so as to apply 0.1 to 20 g Au (as element) per nn2 of surface to be coloured. 12. Composition suitable for colouring ceramic manufactured articles substantially as hereinbefore described. 13. Process for colouring ceramic manufactured articles substantially as hereinbefore described. 14. Vitrified stoneware tiles substantially as hereinbefore described. Dated this 20 day of February 2001

Full Text

Filed of the invention
The present invention relates to composition suitable for colouring ceramic manufactured articles at their surface, process for colouring and coloured articles obtainable thereby.
In particular, the composition of the invention consists of water solutions or solutions of water and water-miscible solvents, of gold organic complexes compatible with other colouring cations optionally present in the solution releasing low quantities of corrosive vapours during the firing cycle.
Said solutions allow the obtainment of ceramic manufactured articles in shades from pink to purple to violet after a firing cycle ranging from 750°C to 1,300°C.
State of the art
The use of coloured ceramic manufactured articles as well as the compositions and process adopted to obtain the relevant colours have been known since long. One of the methods most commonly used consists in the addition of powdered pigments. In particular inorganic oxides and mineral colouring matters, to the ceramic mixture (vitrified stoneware) before firing. The ceramic manufactured article is thus coloured through Its whole thickness, although with large consumption of colouring matter, which is the most expensive component.
According to a process used, the surface of the ceramic material is caused to absorb, either after partial firing (as disclosed e.g. in German patent 2,012,304) or simply after moulding and before firing (as disclosed e.g. in Swiss patent 575,894) a water solution of Inorganic salts or metal complexes (as disclosed e.g. In Sprechsal vol. 119, NO 10, 1986, in EP 0704411 and in Indian Patent No. 191994) which become stable colours at high temperature during the ceramic firing cycle.
The water solution is applied to the ceramic material before final firing. This process is particularly advantageous because it allows the colouring of very thin layers: therefore, it is widely used for flat manufactured articles (such as e.g. floor and wall tiles).

Another problem to be solved when using colours in a water solution is the obtainable depth of colour penetration into the ceramic material. In fact, it was experimentally found that the depth of penetration depends on several parameters, such as the viscosity and surface tension of the colouring solution, the application temperature, the quantity of water optionally sprayed on the manufactured article once the colouring solution has been applied. The water solution is applied to the ceramic manufactured article by immersion, spraying, disk, and silk-screen techniques.
Of cardinal importance is the application technique: in particular, the quantity of colouring solution that may be applied by disk and spraying techniques is as high as 400 to 600 g/m2; by silk-screen type techniques it usually amounts to 100 to 200 g/m2 and sometimes even to 400 g/m2, when thickened screens made of a small number of threads are used.
Silk-screen type techniques are very much in demand, being the only techniques allowing graphic decorations and drawings, which otherwise cannot be obtained,
and requiring lower quantities of colouring matter. When said techniques are used,
the colouring solutions are to be thickened with appropriate thickening agents, e.g.
modified glucomannans, starch and modified starch derivatives, cellulose and
modified cellulose derivatives, or other polymeric substances, soluble or
dispersible in a water solution.
Colour penetration into the ceramic material before firing can be obtained by
spraying relatively high quantities of water on the manufactured article after
application of the colouring solution. However, the resulting colours are less
intense than those obtained using other techniques.
Colour penetration into the material is particularly important in the case of
"smoothed" vitrified stoneware tiles.
The term "smoothed" means that the vitrified stoneware surface has been abraded
with diamond wheels by 0.8 to 1.5 mm and subsequently smoothed or polished
with appropriate felt until obtaining a glassy surface.
It follows that colour penetration into stoneware articles to be smoothed after firing
must reach a depth of 1.6 mm min.

other methods have been developed for the smoothing of very thin (1 to 10 |a) surface layers of the manufactured article. Prior art
The use of water solutions of gold compounds for the colouring also in-depth of ceramic manufactured articles is well known. The compounds disclosed in German patent 4,320,072 for said application substantially are gold chlorides also reported in the preceding literature (cf. "Encyclopedia der technischen Chemie". F. Ullmann. 1929, vol. 4. pp. 837-838). However, the gold chloride solution suffers from the inconvenience of being strongly acid, as it contains hydrochloric acid. In the absence of excess hydrochloric acid, the solution is unstable and the gold compound hydrolyses easily with formation of insoluble compounds. It follows that the solution is corrosive and impairs the apparatus used. In particular, in the case of silk-screen type technique, it rapidly impairs the printing screen.
WO 97/21646 discloses the use of gold sodium thiosulphate solutions. Na3Au(S2O3)2, stabilised with sodium sulphite, for ceramic surfaces colouring by water solution absorption.
From the compositions of solutions 1, 2. and 3 described therein, it is possible to calculate that 4.7 g SO2 or 5.88 g SO3, or an intermediate value in the case of mixtures thereof is released per g Au deposited on the surface. In both cases (use of gold chloride and gold thiosulphate), high amounts of strongly corrosive vapours rapidly impairing the heater metal structures, are released. Therefore, vapours are to be abated to prevent the emission of same into the environment.
The use of precious metals water solutions in high concentrations, in the form of thiol derivatives, to obtain thin metal films for decorative purposes, e.g. for dishes, or for electronic purposes, e.g. for printed circuits, is already known. The following are examples of said use:
1. US patent No. 5.545,452 discloses the use of Au thiolates water solutions with a metal content of 2 to 25% by wi. (column 3, rows 10 to 20) to obtain thin metal films for decorative purposes (column 1, rows 38 to 40);

2. EP No. 514,073, like the US patent above, discloses the use of thiolates water solutions to obtain thin films made of Au or other precious metals to decorate the outer surface, and not the inside, of baked ceramic manufactured articles. Technical problem
Considering that it is very simple to colour ceramic materials by disk, spraying and silk-screen techniques, the ceramic industry is highly interested in the possibility of using colouring water solutions based on gold to be applied by said techniques, and offering the advantage of
• releasing the lowest possible quantity of very noxious or corrosive vapours in the heater;
• being compatible with water solutions of organic derivatives of other cations used for the superficial and in-depth colouring of ceramic manufactured articles.
Therefore, it is an object of the present invention to provide colouring formulations in the form of water solutions, which
• release low quantities of corrosive vapours (≤2 g SO2/g Au deposited);
• are compatible with water solutions of organic derivatives of other cations used for the superficial and in-depth colouring of ceramic manufactured articles;
• colour the ceramic manufactured articles at their surface and to a depth of at least 1 mm.
The Applicant, who has full-fledged experience in the production and sale of
colouring matters for ceramic tiles, has now found that water solutions or water
mixtures with alcohols or other water-miscible organic solvents, of monovalent
gold organic derivatives, can be used to obtain - after firing - colour shades
varying from pink to purple to violet on manufactured articles consisting of a
conventional ceramic mixture.
The water or hydroalcoholic solutions being an object of the present invention are
particularly useful for colouring tiles of vitrified stoneware, either at their surface or
to a depth of 1 to 3 mm from their surface.
In-depth colouring is essential for maintaining the manufactured article decoration
after smoothing.

It is, therefore, a fundamental feature of the present invention to use water
solutions or water mixtures with hydrophilic organic solvents, of gold organic
complexes, which are compatible with derivatives of other cations and release low
quantities of corrosive vapours (≤2 g SO2/g Au deposited).
Said solutions are used to treat ceramic articles before firing. This makes it
possible, after firing, to obtain pink, pufple and violet coloured articles, when
solutions contain gold only, or new colour shades when solutions are mixed with
derivatives of one or several of the following cations: Fe, Cr, Co, Mn, Cu, Ru, Pd,
Zr, V, Ni, Sb, W, Zn, Sn.
The gold compounds that may be used according to the present invention belong
to the class of monovalent gold thiolates, wherein Au is bound to an S atom, and
are substantially represented by the following general formulas:
Au-S-R-X and Au-S-R-H
where R stands for a linear or branched bivalent radical of aliphatic or aromatic or
cycloaliphatic or heterocyclic type, optionally with substituents, such as for
example aminic. amidic, hydroxylic, carboxyiic, hydrocarbylic or carbonylic groups
or CONH-, in the chain;
X stands for a monovalent group selected out of -COOH, SO2OH, -OH, -CONH2,
"NH2; -O-P(O)(OH)2, in which H atoms may be replaced by alkyl groups and
wherein acid groups may be salified with amines or alkaline or alkaline earth
metals and basic groups may optionally be salified with organic acids.
In particular, monovalent Au thiolates to be used according to the present
invention may be in the form of alkaline, alkaline earth metal salts or of variously
substituted amines.
The water solutions of Au compounds according to the invention are stable,
substantially neutral and release a quantity of corrosive vapours of 2 g SO2 max./g
Au deposited on the manufactured article surface to be coloured.
Said solutions are used in quantities corresponding to 0.1 to 20 g Au (as element)
per m2 of surface to be coloured.
By way of example, the gold thiolates that may be used according to the invention
derive from:

The compatibility of the gold thiolates according to the invention with the ceramic colouring systems based on metallic compounds (in particular of Fe. Ni. Cr. Co, Sn, Mn, Cu. Ru, Pd, Zr, V, Sb. W. Zn, Sn) in aqueous solutions has been ascertained through stability tests of the aqueous solutions containing beside Au thiolate also one or more compounds of the above mentioned metals and also through ceramic coloration tests by the same aqueous solutions after ageing. Unforeseable very valuable colours were obtained.
Gold thiolates to be used according to the invention may generally be prepared by causing an Au(lll), in the form of a tetrachloroauric acid, to react in water solution with a thioether S(R')2. giving the reduction of Au(!ll) to Au(l). and then with the desired thiol HSR" (R" = -RX or -RH as per the general formulas shown above): This method, described in Inorganic Synthesis, 23 (1985) pp. 191-195, is based on some reactions reported therein.
A typical process for applying colouring compositions according to the invention consists in the following steps:
a) drying at 100°C of the article to be coloured to a water residue of 0.5% by wt.
max.;
a.1) pre-treatment, if any, of the dried article with water up to a max, quantity of 300 g/m2 manufactured article;
b) treatment of the pre-treated article with a water solution of the colouring
composition in a quantity of 30 to 600 g/m2 of the final coloured surface;
b.1) post-treatment, if any, of the treated article with water up to a max. quantity of absorbed water of 300 g/m2 ceramic manufactured article;
c) equalisation of the post-treated article at room temperature for 8 hours to
homogenise the solution absorption;
d) oven firing according to the usual ceramic cycle at a temperature of 1,000 to
1,300°C .
The concentration of Au thiolate solution to be used according to the invention generally ranges from 0.1 to 2% Au (expressed as element). Some examples of the colours obtained by experimental runs are shown in the Table 1 reported hereinafter.

All runs were carried out on the basis of the following process:
1) drying at 100°C of two 33x33 cm supports made of mixture A to a water residue of 0.5% by wt. max.;
2) supports cooling to room temperature;
3) deposition of 0.4 g of each solution on 10 cm2 of surface of each support;
4) supports equalisation at room temperature for 2 hrs and for additional 2 hrs in a thermoventilated oven at 60°C to homogenise the solutions absorption;
5) oven firing according to the usual ceramic cycle;
6) removal of a surface layer (0.8-0.9 mm) and smoothing;
7) colour detection on non-smoothed and smoothed support;
8) non-smoothed support cutting and penetration depth detection.

Table 1
Ex. Complexing agent Colour before Colour after Penetration
no % element smoothing smoothing (mm)
1 D.L mercaptosuccinic
acid. 0.4% gold Parma red Pink 1.2
2 acetylcysteine, 0.4% gold Pink Light pink 2
3 thiolactic acid, 0.4% gold Pink Light pink 2
4 cysteine, 0.4% gold Parma red Pink 1.4
The composition of the ceramic mixture used is as follows (% by wt.)
SiO2, 64.4%; AIA 21.8%; K2O 3.8%; Na2O 0.8%; CaO 0.6%; MgO 0.1%; TiO2 0.3%; Fe2O3 0.2%; ZrSi04 5%; H2O to 100%.
Colours are as per the Colour Atlas.
Example 5
Compatibility of some Au thiolates with other cations
Compatibility tests were carried out with the following water solutions: Au acetylcysteinate prepared with the method disclosed in the following at page 11, line 6 and diluted up to 0.4% Au, Au mercaptosuccinate (0.4% Au), cobalt ammonium citrate (2% Co), Ni ammonium citrate (2% Ni); chromium ammonium citrate (2% Cr), iron ammonium citrate (Fe 2%), tin glycolate (Sn 2%).
The mixtures consist of Au derivative solution (50%) and of another cation solution (50%).

The results obtained, after the days reported below, are as follows:
Au acetylcysteinate Au mercaptosuccinate
Co 30 days, clear solution 30 days, clear solution
60 days, clear solution 60 days, clear solution
colour turned from reddish violet to wine red
Ni 30 days, clear solution 30 days, clear solution
60 days, clear solution 60 days, clear solution
Cr 30 days, clear solution 30 days, clear solution
60 days, slightly opaque sol. 60 days, slightly opaque sol.
Fe 30 days, clear solution 30 days, clear solution
60 days, clear solution 60 days, clear solution
Sn 30 days, clear solution 30 days, clear solution
60 days, clear solution 60 days, clear solution
Example 6
The connpatibillty of some Au thiolate according to the invention with other
colouring cations has been tested in comparison with two Au compounds of the
prior art, namely NaAuC4 and gold-sodium thiosulphate Na3Au(S2O3)2. The
obtained results are reported in Tables 3 and 4.
The tested products in form of aqueous solutions containing 1% by w. Au are
prepared as follows.
Product (1) Au thiolacetate (Au-TL/3)
30 g aqueous solution of tetrachloroauric acid (corresponding to 1 g Au) is added
with aqueous solution of NaOH up to a pH of 8 (solution A). Thiolactic acid 1.65 g
is dissolved in 30 g H2O and added with NH4OH aqueous solution 30% by w. up to
a pH = 7 (solution B). The solution B is added to the solution A, then the mixture is
added with NH4OH up to pH 9 and with H2O up to a total weight of 100 g.
Product (2) Au sodium thiosulphate (Au-Bk.Giulini)
Comparison test.

In 91.6 g of H2O are dissolved 1.7 g Na3Au(S2O3)2 and 6.7 g of Na sulphite (molar ratio Au/Na2SO3 = 0.9/10) as disclosed by W097/21646 in Table 3. This ratio is the best as it regards the stabilization of the solution as declared by the Applicant: no precipitate occurs in the solution when it comes in contact with a piece of
metal.
Product (3) Au acetylcysteine (Au/CST)
30 g of aqueous solution of tetrachloroauric acid (corresponding to 1 g Au) are
added with NaOH aqueous solution up to a pH of 8 (solution A). N-acetylcystelne
5.1 g in 30 g H2O are added with NH4OH aqueous solution 30%, up to a pH of 7
(solution B). The solution B is added to the solution A. then the mixture is added
with NH4OH up to pH 9.5 and with H2O up to a total amount of 100 g.
Product (4) Au acetylcysteine (Au-CST/9)
30 g of aqueous solution of tetrachloroauric acid (= 1 g Au) are added with NaOH
aqueous solution up to a pH 8 (solution A), N-acetylcysteine 5.1 g in 30 g H2O are
added with NaOH aqueous solution up to a pH 7 (solution B). The solution B is
added to the solution A, then the mixture is added with NaOH up to pH 9 and with
H2O up to a total amount of 100 g.
Product (5) Au acetylcysteine (Au-CST/2)
30 g of aqueous solution of tetrachloroauric acid (= 1 g Au) are added with NaOH
aqueous solution up to a pH of 8 (solution A). N-acetylcysteine 2.55 g in 30 g H2O
are added with NH4OH 30% aqueous solution up to a pH 7 (solution B). The
solution B is added to the solution A, then the mixture is added with NH4OH up to
a pH 9.5 and with H2O up to a total amount of 100 g.
Product (6) NaAuCl4 (Au-CI)
Comparison test.
30 g of aqeuous solution of tetrachloroauric acid (= 1 g Au) are added with NaOH
aqueous solution up to a pH of 2.5 and with H2O up to a total amount of 100 g.
Product (7) Au acetylcysteine (Au-CST/10)
30 g of aqueous solution of tetrachloroauric acid (= 1 g Au) are added with NaOH
aqueous solution up to a pH of 8 (solution A). N-acetylcysteine 2.55 g in 30 g H2O
are added with NaOH aqueous solution up to a pH 7 (solution B). The solution B is

added to the solution A, then the mixture is added with NaOH up to a pH of 9.5
and with a H2O up to a total amount of 100 g.
In the following Table 2 are reported the tested products with the neutralizing
agent used (NaOH or NH^OH) and the molar ratio between Au and SO2 (or SO3)
developed during the ceramic firing of the treated manufactured articles.
The Au acetylcysteine solutions products 3 and 4 have been prepared using an
excess of acetylcysteine and consequently these solutions show a content of S
higher then in the products 5 and 7. The use of an excess of acetylcysteine
affords an higher stability of the Au-acetylcysteine solution.

The tests reported in the following tables 3 and 4 have been carried out with solutions consisting of mixtures of Au derivative solution (50%) and of other cations solutions (50%)

Table 3 - Comparative tests for Au-acetylcysterine and Au-thiolactate, reference product Na-Au thiosulphate (Au-Bk.Giulini)

d = days
XXX = crystals
ppt = precipitate
sol. = solution
Fe citr/13 = 10 g hydrate iron citrate Aldrich (Fe 18 ÷ 19%) in 20 g H2 0 are added
with 10 g of NH4OH 30%, find pH = 7; Fe = 4.5 ÷ 4.75% by w.

Table 4 - Comparative tests for Au-acetylcysterine: reference product Na Au CI4 (Au-CI)

d = days XXX = crystals ppt = precipitate sol. = solution

Claims
1. Composition suitable for colouring ceramic manufactured articles at their
surface and to a depth of at least 1 mm in shades from pink to purple to violet,
said composition consisting of a solution in water or in mixture of water with a
water soluble organic solvent of a monovalent gold thiolate that during the
normal ceramic fire cycle releases corrosive vapours in quantity not higher than
2gSO2 /g An deposited, comprised in the formulas Au-S-R-X and Au-S-R-H
where R stands for a linear or branched bivalent radical of aliphatic or aromatic
or cycloaliphatic or heterocyclic type, optionally with substituents, such as for
example aminic, amidic, hydroxylic, carboxylic, hydrocarbylic or carbonylic
groups or CONH-. in the chain;
X stands for a monovalent group selected out of -COOH, SO2OH. -OH, -CONH2, -NH2; -O-P(O)(OH)2, in which H atoms may be replaced by alkyl groups and wherein acid groups may be salified with amines or alkaline or alkaline earth metals and basic groups may optionally be salified with organic acids.
2. The composition as claimed in claim 1, wherein the concentration of gold thiolate in the solution correponds to a content of 0,1% to 2% of Au (expressed as element).
3. Composition as claimed in claim 1 wherein the release of corrosive vapours is not higher than IgSOg/g Au.
4. The composition as claimed in claim 1, wherein Au thiolate derives from one of the following thio-compounds: (N) acetyl-cysteine; 4-mercaptopyridine; 2-mercaptopyridine; 2-mercaptoacetyl-glycine; mercaptopropionyi-glycine; 3-mercaptopropionyl-glycine; (d,l) mercaptosuccinic acid; cysteine; 2-mercapto-propionic acid.
5. The composition as claimed in claim 1 containing, in addition to Au thiolate, other metal compounds having colouring properties for the ceramic material, selected from the organic or inorganic derivatives of the following elements: Co, Cr, Ni, Ru. Mn. Sb, W, Cu, Fe, Zr, V, Zn. Pd, Sn.
6. The composition as claimed in claim 1, containing in addition to Au thiolate selected from Au thiolactate and/or Au acetylcysteinate and/or Au

mercptosuccinate, other metal compounds having colouring properties for the ceramic material selected from the following compounds: Cobalt ammonium citrate; Chromium acetate; Chromium ammonium citrate; Nickel ammonium citrate, Ru giycolate; Ru ammonium citrate; Mn ammonium citrate; NaSb tartrate; KSb tartrate, NaW citrate; Cu ammonium citrate. Fe ammonium citrate; sodium metavanadate; V giycolate; V ammonium citrate; Zn ammonium citrate, Pd giycolate; Pd ammonium citrate, Sn giycolate.
7. Process for colouring ceramic manufactured articles obtained by moulding a
conventional ceramic mixture, said process using the composition as claimed in
claim 1 and consisting in the following steps:
a) drying at 100°C of the article to be coloured to a water residue of 0.5% by wt.
max.;
a.1) pre-treatment, if any, of the dried article with water up to a max. quantity of 300 g/m2 manufactured article;
b) treatment of the pre-treated article with a water solution of the colouring
composition in a quantity of 30 to 600 g/m2 of the final coloured surface;
b,1) post-treatment, if any, of the article treated with water up to a max. quantity of absorbed water of 300 g/m2 ceramic manufactured article;
c) equalisation of the post-treated article at room temperature for 8 hours to
homogenise the solution absorption;
d) oven firing according to the usual ceramic cycle at a temperature of 1,000 to
1,300°C.
8. The process as claimed in claim 5, wherein the solution of the colouring composition, thickened with appropriate thickening agents, is applied to the ceramic manufactured article in step (b) by the silk-screen technique.
9. Vitrified stoneware tiles coloured at their surface and to a depth of at least 1 mm, in shades from pink to purple, to violet, by the process as claimed in any of claim 7 and 8.

10. Vitrified stoneware tiles according to claim 9 wherein the superficial layer has been removed by smoothing to a depth of 1.5 mm and final polishing.
11. The process as claimed in claim 6, wherein the treatment with a gold thiolate

solution is carried out so as to apply 0.1 to 20 g Au (as element) per nn2 of surface to be coloured.

12. Composition suitable for colouring ceramic manufactured articles
substantially as hereinbefore described.
13. Process for colouring ceramic manufactured articles substantially as
hereinbefore described.
14. Vitrified stoneware tiles substantially as hereinbefore described.
Dated this 20 day of February 2001

Documents:

in-pct-2001-245-che-abstract.pdf

in-pct-2001-245-che-claims filed.pdf

in-pct-2001-245-che-claims granted.pdf

in-pct-2001-245-che-correspondnece-others.pdf

in-pct-2001-245-che-correspondnece-po.pdf

in-pct-2001-245-che-description(complete)filed.pdf

in-pct-2001-245-che-description(complete)granted.pdf

in-pct-2001-245-che-form 1.pdf

in-pct-2001-245-che-form 19.pdf

in-pct-2001-245-che-form 26.pdf

in-pct-2001-245-che-form 3.pdf

in-pct-2001-245-che-form 5.pdf

in-pct-2001-245-che-other documents.pdf

in-pct-2001-245-che-pct.pdf

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Patent Number

211991

Indian Patent Application Number

IN/PCT/2001/245/CHE

PG Journal Number

02/2008

Publication Date

11-Jan-2008

Grant Date

13-Nov-2007

Date of Filing

20-Feb-2001

Name of Patentee

M/S. GRAZIANO VIGNALI

Applicant Address

Via Della Pace, 2-40037 Sasso Marconi

Inventors:

#	Inventor's Name	Inventor's Address
1	GUIZZARDI, Fabrizio	Via Gabella, 1 I-40129 Bologna

PCT International Classification Number

C04B 41/81

PCT International Application Number

PCT/EP99/06086

PCT International Filing date

1999-08-19

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	MI98A001913	1998-08-21	Italy