Pigment compositions

Abstract

A composition is described, including: (a) a liquid organic medium which is compatible with water; (b) a mixed metal oxide ceramic pigment in particulate form which develops its full color intensity and / or hue after firing at elevated temperature; and (c) a reaction product of at least a reactant A, a reactant B, and a reactant C as described herein; wherein substantially all individual molecules of reactant C react with one acid group present in reactant A to form an ester, and substantially all individual molecules of reactant B react with (i) one acid group present in reactant A to form an amide, or (ii) two acid groups present in reactant A to form an imide. Methods of making and using such compositions are also described.

Description

PIGMENT COMPOSITIONS

[0001] The disclosed technology relates to compositions including a reaction product (e.g., a dispersant) and a metal oxide ceramic pigment which develops its full color intensity and / or hue after firing at elevated temperature, as well as methods of making and / or using such compositions. The compositions may, among other things, be used as, or in, ink jet ink compositions for digitally printing on substrates, such as ceramic articles or glass articles (among others).

[0002] Substrates which are subjected to firing, such as ceramic tiles, have been decorated using printing methods which employ water-based ink compositions which generally use electrostatic dispersants (such as polyacrylic acid dispersants). Such methods have generally resulted in substrates which matched each other, without variations from unit to unit. To achieve variation from unit to unit, a digital inkjet process has been developed and has been accepted in the industry, but these processes have not been able to employ water-based ink compositions because of limitations in the inkjet nozzle technology utilized in the processes, and instead used solvent-based ink compositions which require special dispersants employing steric stabilization.

[0003] Recent trends in ceramic tiles, as one example of such substrates, have led to using larger tiles, which has caused some challenges in applying a uniform surface treatment (prior to the coloration layer) and final glaze layer using traditional curtain-coating methods. (In general ceramic tiles are coated and printed using a least three coating layers: a first glaze layer, a coloration layer on top of the first glaze layer, and a second glaze layer on top of the coloration layer.) In view of these challenges, the industry has begun using a new “digital value” method to apply the first and final coating layers. This change has resulted in less drying time between coating layers, which requires the middle coloration layer to be compatible with the first and final layers, which are generally aqueous compositions. In these conditions, many existing ink compositions (which are used in the coloration layer) have shown incompatibility with the aqueous-based first and final layers.

[0004] The disclosed technology, therefore, provides a composition which may be used in the coloration layer which is compatible with the aqueous-based first and / or final layers, solving the problem of incompatibility of an ink composition with the aqueous first and / or final layers.

[0005] Provided is a composition comprising: (a) a liquid organic medium which is compatible with water; (b) a mixed metal oxide ceramic pigment in particulate form whichdevelops its full color intensity and / or hue after firing at elevated temperature; and (c) a reaction product of at least a reactant A, a reactant B, and a reactant C as described herein; wherein substantially all individual molecules of reactant C react with one acid group present in reactant A to form an ester, and substantially all individual molecules of reactant B react with (i) one acid group present in reactant A to form an amide, or (ii) two acid groups present in reactant A to form an imide. Methods of making and using such compositions are also described.

[0006] The following embodiments of the present subject matter are contemplated:

[0007] 1. A composition comprising: (a) a liquid organic medium which is compatible with water; (b) a mixed metal oxide ceramic pigment in particulate form which develops its full color intensity and / or hue after firing at elevated temperature; and (c) a reaction product of at least a reactant A, a reactant B, and a reactant C; wherein the reactant A is represented by the following general formula (A):wherein, independently for each molecule of the reactant A: R1is a terminal group; R2is, independently for each repeat unit, H or COOH; R3is, independently for each repeat unit, H, CH3, or CH2COOH; R4is, independently for each repeat unit, H or a Ci to C36 hydrocarbyl group; R5is, independently for each repeat unit, H or a Ci to C36 hydrocarbyl group; R6is a terminal group; n is an integer from 10 to 1400; and m is 0 or an integer from 1 to 140; wherein when R2is COOH in a repeat unit, R3is H in the repeat unit; and wherein, if m is not 0, n is at least 10 times greater than m; wherein the reactant B is represented by the following general formula (B):wherein, independently for each molecule of the reactant B: R7is a Ci to C4 hydrocarbyl group; R8is, independently for each repeat unit, H or CH3, with the proviso that R8is H inat least 70% of repeat units; R9is a Ci to C4 hydrocarbyl group; and z is an integer from 10 to 80; wherein the reactant C is represented by the following general formula (C):wherein, independently for each molecule of the reactant C: R10is a Ci to C4 hydrocarbyl group; R11is, independently for each repeat unit, H or CH3, with the proviso that R11is H in at least 40% of repeat units; R12is, independently for each repeat unit, a Ci to C5 hydrocarbyl group; x is an integer from 6 to 50; and y is 0 or an integer from 1 to 20, with the proviso that when R11is H in 100% of repeat units, y is greater than 0; wherein substantially all individual molecules of reactant C react with one acid group present in reactant A to form an ester, and substantially all individual molecules of reactant B react with (i) one acid group present in reactant A to form an amide, or (ii) two acid groups present in reactant A to form an imide; and wherein the reactant A is present in an amount of from10 to 25 weight percent, the reactant B is present in an amount of from 10 to 40 weight percent, and the reactant C is present in an amount of from 40 to 80 weight percent, all based on the total combined weight of reactant A, reactant B, and reactant C.

[0008] 2. The composition of embodiment 1, comprising from 20 to 79 percent by weight of the liquid organic medium, based on the total weight of the composition.

[0009] 3. The composition of either embodiment 1 or embodiment 2, comprising from20 to 60 percent by weight of the mixed metal oxide ceramic pigment, based on the total weight of the composition.

[0010] 4. The composition of any one of embodiments 1 to 3, comprising from 1 to 20 percent by weight of the reaction product, based on the total weight of the composition.

[0011] 5 The composition of any one of embodiments 1 to 4, wherein R2is H.

[0012] 6. The composition of any one of embodiments 1 to 4, wherein R2is COOH.

[0013] 7. The composition of any one of embodiments 1 to 6, wherein R3is, independently for each repeat unit, H or CH3.

[0014] 8. The composition of any one of embodiments 1 to 6, wherein R3is, independently for each repeat unit, H or CH2COOH.

[0015] 9. The composition of any one of embodiments 1 to 5, wherein R3is, independently for each repeat unit, CH3 or CH2COOH.

[0016] 10, The composition of any one of embodiments 1 to 8, wherein R3is H.

[0017] 11. The composition of any one of embodiments 1 to 5, 7, or 9, wherein R3isCH3.

[0018] 12. The composition of any one of embodiments 1 to 5, or 8 to 9, wherein R3isCH2COOH.

[0019] 13. The composition of any one of embodiments 1 to 12, wherein R4is, independently for each repeat unit, H or a Ci to C20 hydrocarbyl group.

[0020] 14. The composition of any one of embodiments 1 to 13, wherein R4is H.

[0021] 15. The composition of any one of embodiments 1 to 12, wherein R4is a Ci toC36 hydrocarbyl group.

[0022] 16. The composition of any one of embodiments 1 to 13, or 15, wherein R4is aCi to C20 hydrocarbyl group.

[0023] 17. The composition of any one of embodiments 1 to 16, wherein R5is, independently for each repeat unit, H or a Ci to C20 hydrocarbyl group.

[0024] 18. The composition of any one of embodiments 1 to 17, wherein R5is H.

[0025] 19. The composition of any one of embodiments 1 to 16, wherein R5is a Ci toC36 hydrocarbyl group.

[0026] 20. The composition of any one of embodiments 1 to 17, or 19, wherein R5is aCi to C20 hydrocarbyl group.

[0027] 21. The composition of any one of embodiments 1 to 20, wherein n is an integer from 10 to 250.

[0028] 22. The composition of any one of embodiments 1 to 20, wherein n is an integer from 20 to 1400.

[0029] 23. The composition of any one of embodiments 1 to 22, wherein n is an integer from 20 to 150.

[0030] 24. The composition of any one of embodiments 1 to 23, wherein m is 0 or an integer from 1 to 25.

[0031] 25. The composition of any one of embodiments 1 to 24, wherein m is 0 or an integer from 1 to 15.

[0032] 26. The composition of any one of embodiments 1 to 25, wherein m is 0.

[0033] 27. The composition of any one of embodiments 1 to 23, wherein m is an integer from 1 to 140.

[0034] 28. The composition of any one of embodiments 1 to 24, or 27, wherein m is an integer from 1 to 25.

[0035] 29. The composition of any one of embodiments 1 to 25, or 27 to 28, wherein m is an integer from 1 to 15.

[0036] 30. The composition of any one of embodiments 1 to 29, wherein z is an integer from 10 to 50.

[0037] 31. The composition of any one of embodiments 1 to 29, wherein z is an integer from 20 to 80.

[0038] 32. The composition of any one of embodiments 1 to 31, wherein z is an integer from 20 to 50.

[0039] 33. The composition of any one of embodiments 1 to 32, wherein y is 0 and R11is CH3 in at least 15% of repeat units.

[0040] 34. The composition of any one of embodiments 1 to 32, wherein y is an integer from 1 to 20 and R11is H in 100% of repeat units.

[0041] 35. The composition of any one of embodiments 1 to 34, wherein the reactant A is present in an amount of from 10 to 20 weight percent, based on the total combined weight of reactant A, reactant B, and reactant C.

[0042] 36. The composition of any one of embodiments 1 to 35, wherein the reactant B is present in an amount of from 10 to 25 weight percent, based on the total combined weight of reactant A, reactant B, and reactant C.

[0043] 37. The composition of any one of embodiments 1 to 36, wherein the reactant C is present in an amount of from 55 to 80 weight percent, based on the total combined weight of reactant A, reactant B, and reactant C.

[0044] 38. The composition of any one of embodiments 1 to 37, wherein the mixed metal oxide ceramic pigment comprises two or more elements in cationic form selected from aluminum, magnesium, calcium, cadmium, cobalt, chromium, iron, indium, manganese, nickel, praseodymium, antimony, selenium, silicon, tin, vanadium, zinc, and zirconium.

[0045] 39. The composition of any one of embodiments 1 to 38, wherein the mixed metal oxide ceramic pigment comprises two or more elements in cationic form selected from aluminum, calcium, cobalt, chromium, iron, manganese, praseodymium, antimony, silicon, tin, zinc, and zirconium.

[0046] 40. A process for digital printing on a ceramic article comprising: (a) depositing a first glaze composition onto the ceramic article; (b) while the glaze composition is still wet, depositing an ink composition comprising the composition of any one of embodiments1 to 39 onto the ceramic article; and (c) heating the ceramic article such that the mixed metal oxide ceramic pigment develops its full color intensity and / or hue.

[0047] 41. The process of embodiment 40, wherein the first glaze composition comprises water.

[0048] 42. The process of either embodiment 40 or embodiment 41, wherein the process comprises depositing a second glaze composition onto the ink composition while at least the ink composition is still wet, prior to said heating.

[0049] 43. The process of any one of embodiments 40 to 42, wherein said depositing a second glaze composition onto the ink composition occurs while both the ink composition and the first glaze composition are still wet.

[0050] 44. The process of any one of embodiments 40 to 43, wherein the second glaze composition comprises water.

[0051] 45. The process of any one of embodiments 40 to 44, wherein the second glaze composition is the same as the first glaze composition.

[0052] 46. The process of any one of embodiments 40 to 44, wherein the second glaze composition is different from the first glaze composition.

[0053] 47. The process of any one of embodiments 40 to 46, wherein said heating comprises heating the ceramic article to a temperature of greater than 600 °C.

[0054] 48. The process of any one of embodiments 40 to 47, wherein said heating comprises heating the ceramic article to a temperature of from 1,000 °C to 1,250 °C.

[0055] Various features and embodiments of the present subject matter will be described below by way of non-limiting illustration.

[0056] As used herein, the term “hydrocarbyl” refers to a group having a carbon atom directly attached to the remainder of the molecule, where the group includes at least carbon and hydrogen atoms. If the hydrocarbyl group comprises more than one carbon atom, then those carbons need not necessarily be linked to each other. For example, at least two of the carbons may be linked via a suitable element or group. In various embodiments, the term “hydrocarbyl” refers to a group having a carbon atom directly attached to the remainder of the molecule, where the group consists of carbon, hydrogen, optionally one or more heteroatoms provided the heteroatoms do not alter the predominantly hydrocarbon nature of the substituent. The heteroatom may link at least two of the carbons in the hydrocarbyl group, and optionally no more than two non-hydrocarbon substituents. Suitable heteroatoms will be apparent to those skilled in the art and include, for instance, sulphur, nitrogen, oxygen, phosphorus and silicon. Where the hydrocarbyl contains heteroatoms, optionally,no more than two heteroatoms will be present for every ten carbon atoms in the hydrocarbyl group. Suitable non-hydrocarbon substituents will also be apparent to those skilled in the art and include, for instance, halo, hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulphoxy.

[0057] Examples of hydrocarbyl s within the context of the present technology therefore include: (i) hydrocarbon groups selected from aliphatic (e.g. alkyl or alkenyl), alicyclic (e.g. cycloalkyl, cycloalkenyl, cycloalkadienyl), and aromatic groups; (ii) substituted hydrocarbon groups, selected from hydrocarbon groups defined in (i) substituted with no more than two non-hydrocarbon substituents and / or one or more hydrocarbon substituents, the non-hydrocarbon substituents being selected from the group consisting of halo, hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulphoxy; and / or (iii) hetero-containing hydrocarbon groups, selected from hydrocarbon groups defined in (i) containing one or more heteroatom in the ring or chain, provided that the group has no more than two heteroatoms present for every ten carbon atoms in the group, the heteroatoms being selected from sulphur, nitrogen, oxygen, phosphorus and silicon. The hetero-containing hydrocarbon groups may be substituted with no more than two non-hydrocarbon substituents and / or one or more hydrocarbon substituents. In certain embodiments, the term “hydrocarbyl” refers to a group having a carbon atom directly attached to the remainder of the molecule, where the group consists of carbon and hydrogen atoms.

[0058] It is known that some of the materials described herein may interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. The products formed thereby, including the products formed upon employing the composition of the present subject matter in its intended use, may not be susceptible of easy description. Nevertheless, all such modifications and reaction products are included within the scope of the present subject matter; the present subject matter encompasses the composition prepared by admixing the components described herein.

[0059] As used herein, the indefinite article “a” / “an” is intended to mean one or more than one. As used herein, the phrase “at least one” means one or more than one of the following terms. Thus, “a” / “an” and “at least one” may be used interchangeably. For example “at least one of A, B or C” means that just one of A, B or C may be included, and any mixture of two or more of A, B and C may be included, in alternative embodiments.

[0060] As used herein, the term “substantially free of’ means that a component does not include any intentional addition of the material which the component is “substantially free of’. For example, the component may include a material which the component is“substantially free of’ at no more than impurity levels, which may be the result of incomplete chemical reactions and / or unintended / undesired (but perhaps unavoidable) reaction products.

[0061] As used herein, the transitional term “comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps. However, in each recitation of “comprising” herein, it is intended that the term also encompass, as alternative embodiments, the phrases “consisting essentially of’ and “consisting of,” where “consisting of’ excludes any element or step not specified and “consisting essentially of’ permits the inclusion of additional un-recited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.

[0062] The present subject matter relates to a composition comprising: (a) a liquid organic medium which is compatible with water; (b) a mixed metal oxide ceramic pigment in particulate form which develops its full color intensity and / or hue after firing at elevated temperature; and (c) a reaction product of at least a reactant A, a reactant B, and a reactant C, all as described below. The reaction product may be characterized as a dispersant for the mixed metal oxide ceramic pigment, the dispersant being capable of at least partially dispersing the pigment into the liquid organic medium. In the context of the phrase “a reaction product of at least a reactant A, a reactant B, and a reactant C”, “at least” means that other reactants and / or ingredients could be present in the reaction, as long as the properties of the resulting reaction product are substantially unchanged.

[0063] In certain embodiments, substantially all individual molecules of reactant C react with one acid group present in reactant A to form an ester, and substantially all individual molecules of reactant B react with (i) one acid group present in reactant A to form an amide, or (ii) two acid groups present in reactant A to form an imide. In this context, “substantially all” means that the reaction is designed such that reaction of reactants B and C is maximized, but there could be minor amounts of reactants B and C remaining unreacted due to slight variations in stoichiometry and / or reaction conditions (potentially impacting reaction kinetics and other factors), as would be understood by a person of ordinary skill in the art. Further, because the reaction is designed in this way, to force reaction of reactants B and C to consume as much of those reactants as possible, there will be some unreacted reactant A present in the reaction product.

[0064] The reactant A is represented by the following general formula (A):wherein, independently for each molecule of the reactant A: R1is a terminal group; R2is, independently for each repeat unit, H or COOH; R3is, independently for each repeat unit, H, CH3, or CH2COOH; R4is, independently for each repeat unit, H or a Ci to C36 hydrocarbyl group; R5is, independently for each repeat unit, H or a Ci to C36 hydrocarbyl group; R6is a terminal group; n is an integer from 10 to 1400; and m is 0 or an integer from 1 to 140. In certain embodiments, when R2is COOH in a repeat unit, R3is H in the repeat unit. In certain embodiments, if m is not 0, n is at least 10 times greater than m. As used herein, the phrase “independently for each molecule” means that a variable may vary from molecule to molecule of a component which is described by a general formula including such variables, thereby forming a mixture of molecules which individually may have a different selection for each variable, but it is also contemplated that the variable may be the same for all molecules. Similarly, the phrase “independently for each repeat unit” means that a variable may vary from repeat unit to repeat unit in a single molecule, but it is also contemplated that the variable may be the same for all repeat units. As would be understood by a person of skill in the art, one or more of the carboxylic acid groups present in reactant A could be in a salt form or an anhydride form without substantially impacting the reactant product and / or its properties, as it is generally known that certain amounts of carboxylic acid groups may naturally form salts or anhydrides.

[0065] In certain embodiments, the reactant A is present in an amount of from 10 to 25 (such as from 10 to 20, from 10 to 15, from 15 to 25, from 15 to 20, or from 20 to 25) weight percent, based on the total combined weight of reactant A, reactant B, and reactant C. Nonlimiting examples of suitable materials which may be used as reactant A include polyacrylic acid, polyacrylic-co-maleic acid, and / or polyacrylic-co-itaconic acid, optionally co-reacted with mono-unsaturated monomers, such as acrylates and / or methacrylates, for example butyl acrylate and / or butyl methacrylate.

[0066] The reactant B is represented by the following general formula (B):wherein, independently for each molecule of the reactant B: R7is a Ci to C4 hydrocarbyl group; R8is, independently for each repeat unit, H or CH3; R9is a Ci to C4 hydrocarbyl group; and z is an integer from 10 to 80.

[0067] In certain embodiments, the reactant B is present in an amount of from 10 to 40 (such as from 10 to 35, from 10 to 30, from 10 to 25, from 10 to 20, from 10 to 15, from 15 to 40, from 15 to 35, from 15 to 30, from 15 to 25, from 15 to 20, from 20 to 40, from 20 to 35, from 20 to 30, from 20 to 25, from 25 to 40, from 25 to 35, from 25 to 30, from 30 to 40, from 30 to 35, or from 35 to 40) weight percent, based on the total combined weight of reactant A, reactant B, and reactant C. Non-limiting examples of suitable materials which may be used as reactant B include alpha-terminated polyether amines (including but not limited to those commercially available from Huntsman under the trade names Surfonamine® LI 00, L200, L207, or L300).

[0068] The reactant C is represented by the following general formula (C):wherein, independently for each molecule of the reactant C: R10is a Ci to C4 hydrocarbyl group; R11is, independently for each repeat unit, H or CH3; R12is, independently for each repeat unit, a Ci to C5 hydrocarbyl group; x is an integer from 6 to 50; and y is 0 or an integer from 1 to 20. In certain embodiments, when R11is H in 100% of repeat units, y is greater than 0.

[0069] In certain embodiments, the reactant C is present in an amount of from 40 to 80 (such as from 40 to 75, from 40 to 70, from 40 to 65, from 40 to 60, from 40 to 55, from 40 to 50, from 40 to 45, from 45 to 80, from 45 to 75, from 45 to 70, from 45 to 65, from 45 to 60, from 45 to 55, from 45 to 50, from 50 to 80, from 50 to 75, from 50 to 70, from 50 to65, from 50 to 60, from 50 to 55, from 55 to 80, from 55 to 75, from 55 to 70, from 55 to65, from 55 to 60, from 60 to 80, from 60 to 75, from 60 to 70, from 60 to 65, from 65 to80, from 65 to 75, from 65 to 70, from 70 to 80, from 70 to 75, or from 75 to 80) weightpercent, based on the total combined weight of reactant A, reactant B, and reactant C. Nonlimiting examples of suitable materials which may be used as reactant C include: water soluble lubricants, e.g. synalox™ 50-30B, synalox™ 55-70B; polyesters derived from polyethylene glycol monomethyl ether, s-caprolactone, and 5-valerolactone; and / or polyesters derived from polyethylene glycol monomethyl ether, s-caprolactone, and L- lactide.

[0070] In certain embodiments, the composition comprises from 20 to 79 (such as from 20 to 78.5, from 20 to 78, from 20 to 77.5, from 20 to 77, from 20 to 76.5, from 20 to 76, from 20 to 75.5, from 20 to 75, from 20 to 74, from 20 to 73, from 20 to 72, from 20 to 71, from 20 to 70, from 20 to 65, from 20 to 60, from 20 to 55, from 20 to 50, from 20 to 45, from 20 to 40, from 20 to 35, from 20 to 30, from 20 to 25, from 25 to 79, from 25 to 78.5, from 25 to 78, from 25 to 77.5, from 25 to 77, from 25 to 76.5, from 25 to 76, from 25 to75.5, from 25 to 75, from 25 to 74, from 25 to 73, from 25 to 72, from 25 to 71, from 25 to 70, from 25 to 65, from 25 to 60, from 25 to 55, from 25 to 50, from 25 to 45, from 25 to 40, from 25 to 35, from 25 to 30, from 30 to 79, from 30 to 78.5, from 30 to 78, from 30 to77.5, from 30 to 77, from 30 to 76.5, from 30 to 76, from 30 to 75.5, from 30 to 75, from 30 to 74, from 30 to 73, from 30 to 72, from 30 to 71, from 30 to 70, from 30 to 65, from 30 to 60, from 30 to 55, from 30 to 50, from 30 to 45, from 30 to 40, from 30 to 35, from 35 to 79, from 35 to 78.5, from 35 to 78, from 35 to 77.5, from 35 to 77, from 35 to 76.5, from 35 to 76, from 35 to 75.5, from 35 to 75, from 35 to 74, from 35 to 73, from 35 to 72, from 35 to 71, from 35 to 70, from 35 to 65, from 35 to 60, from 35 to 55, from 35 to 50, from 35 to 45, from 35 to 40, from 40 to 79, from 40 to 78.5, from 40 to 78, from 40 to 77.5, from 40 to 77, from 40 to 76.5, from 40 to 76, from 40 to 75.5, from 40 to 75, from 40 to 74, from 40 to 73, from 40 to 72, from 40 to 71, from 40 to 70, from 40 to 65, from 40 to 60, from 40 to 55, from 40 to 50, from 40 to 45, from 45 to 79, from 45 to 78.5, from 45 to 78, from 45 to 77.5, from 45 to 77, from 45 to 76.5, from 45 to 76, from 45 to 75.5, from 45 to 75, from 45 to 74, from 45 to 73, from 45 to 72, from 45 to 71, from 45 to 70, from 45 to 65, from 45 to 60, from 45 to 55, from 45 to 50, from 50 to 79, from 50 to 78.5, from 50 to 78, from 50 to 77.5, from 50 to 77, from 50 to 76.5, from 50 to 76, from 50 to 75.5, from 50 to 75, from 50 to 74, from 50 to 73, from 50 to 72, from 50 to 71, from 50 to 70, from 50 to 65, from 50 to 60, from 50 to 55, from 55 to 79, from 55 to 78.5, from 55 to 78, from 55 to 77.5, from 55 to 77, from 55 to 76.5, from 55 to 76, from 55 to 75.5, from 55 to 75, from 55 to 74, from 55 to 73, from 55 to 72, from 55 to 71, from 55 to 70, from 55 to 65, from 55 to 60, from 60 to 79, from 60 to 78.5, from 60 to 78, from 60 to 77.5, from 60 to 77, from 60 to 76.5, from60 to 76, from 60 to 75.5, from 60 to 75, from 60 to 74, from 60 to 73, from 60 to 72, from 60 to 71, from 60 to 70, from 60 to 65, from 65 to 79, from 65 to 78.5, from 65 to 78, from 65 to 77.5, from 65 to 77, from 65 to 76.5, from 65 to 76, from 65 to 75.5, from 65 to 75, from 65 to 74, from 65 to 73, from 65 to 72, from 65 to 71, from 65 to 70, from 70 to 79, from 70 to 78.5, from 70 to 78, from 70 to 77.5, from 70 to 77, from 70 to 76.5, from 70 to 76, from 70 to 75.5, from 70 to 75, from 70 to 74, from 70 to 73, from 70 to 72, from 70 to 71, from 71 to 79, from 71 to 78.5, from 71 to 78, from 71 to 77.5, from 71 to 77, from 71 to 76.5, from 71 to 76, from 71 to 75.5, from 71 to 75, from 71 to 74, from 71 to 73, from71 to 72, from 72 to 79, from 72 to 78.5, from 72 to 78, from 72 to 77.5, from 72 to 77, from72 to 76.5, from 72 to 76, from 72 to 75.5, from 72 to 75, from 72 to 74, from 72 to 73, from73 to 79, from 73 to 78.5, from 73 to 78, from 73 to 77.5, from 73 to 77, from 73 to 76.5, from 73 to 76, from 73 to 75.5, from 73 to 75, from 73 to 74, from 74 to 79, from 74 to 78.5, from 74 to 78, from 74 to 77.5, from 74 to 77, from 74 to 76.5, from 74 to 76, from 74 to 75.5, from 74 to 75, from 75 to 79, from 75 to 78.5, from 75 to 78, from 75 to 77.5, from 75 to 77, from 75 to 76.5, from 75 to 76, from 75 to 75.5, from 75.5 to 79, from 75.5 to 78.5, from 75.5 to 78, from 75.5 to 77.5, from 75.5 to 77, from 75.5 to 76.5, from 75.5 to 76, from76 to 79, from 76 to 78.5, from 76 to 78, from 76 to 77.5, from 76 to 77, from 76 to 76.5, from 76.5 to 79, from 76.5 to 78.5, from 76.5 to 78, from 76.5 to 77.5, from 76.5 to 77, from77 to 79, from 77 to 78.5, from 77 to 78, from 77 to 77.5, from 77.5 to 79, from 77.5 to 78.5, from 77.5 to 78, from 78 to 79, from 78 to 78.5, or from 78.5 to 79) percent by weight of the liquid organic medium, based on the total weight of the composition.

[0071] The liquid organic medium which is compatible with water may be any suitable organic liquid which imparts compatibility with water into the composition as a whole. By “compatible with water” in this context, it is meant that the composition as a whole will maintain its dispersion integrity when contacted with water. For example, if the composition is an ink composition for digital printing, and the ink composition were printed onto an article which had previously been coated with an aqueous coating (e.g., a glaze composition), and the aqueous coating was still wet, the ink composition would remain where it was printed to allow the printed image to remain substantially as it was intended to be printed. In certain embodiments, “compatible with water” means that the composition is miscible in or with water. For example, when the composition is contacted with water, the composition would absorb the water, rather than forming an emulsion or dissociating from the water similarly to how oil and water dissociate due to their incompatibility.

[0072] In certain embodiments, the liquid organic medium is substantially organic. In certain embodiments, a major portion of the liquid organic medium is organic. In certain embodiments, the liquid organic medium is at least 50% (such as at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99%) organic. In certain embodiments, the liquid organic medium consists essentially of, or consists of, at least one organic liquid. In certain embodiments, the liquid organic medium is substantially free of, or free of, water.

[0073] In certain embodiments, the liquid organic medium comprises at least one glycol ether, for example at least one of tripropylene glycol methyl ether or propylene glycol n- butyl ether.

[0074] In certain embodiments, the composition comprises from 20 to 60 (such as from 20 to 55, from 20 to 50, from 20 to 45, from 20 to 40, from 20 to 35, from 20 to 30, from 20 to 25, from 25 to 60, from 25 to 55, from 25 to 50, from 25 to 45, from 25 to 40, from 25 to 35, from 25 to 30, from 30 to 60, from 30 to 55, from 30 to 50, from 30 to 45, from 30 to40, from 30 to 35, from 35 to 60, from 35 to 55, from 35 to 50, from 35 to 45, from 35 to40, from 40 to 60, from 40 to 55, from 40 to 50, from 40 to 45, from 45 to 60, from 45 to55, from 45 to 50, from 50 to 60, from 50 to 55, or from 55 to 60) percent by weight of the mixed metal oxide ceramic pigment, based on the total weight of the composition.

[0075] In certain embodiments, the composition comprises from 1 to 20 (such as from1.5 to 20, from 2 to 20, from 2.5 to 20, from 3 to 20, from 3.5 to 20, from 4 to 20, from 4.5 to 20, from 5 to 20, from 6 to 20, from 7 to 20, from 8 to 20, from 9 to 20, from 10 to 20, from 15 to 20, from 1 to 15, from 1.5 to 15, from 2 to 15, from 2.5 to 15, from 3 to 15, from3.5 to 15, from 4 to 15, from 4.5 to 15, from 5 to 15, from 6 to 15, from 7 to 15, from 8 to 15, from 9 to 15, from 10 to 15, from 1 to 10, from 1.5 to 10, from 2 to 10, from 2.5 to 10, from 3 to 10, from 3.5 to 10, from 4 to 10, from 4.5 to 10, from 5 to 10, from 6 to 10, from 7 to 10, from 8 to 10, from 9 to 10, from 1 to 9, from 1.5 to 9, from 2 to 9, from 2.5 to 9, from 3 to 9, from 3.5 to 9, from 4 to 9, from 4.5 to 9, from 5 to 9, from 6 to 9, from 7 to 9, from 8 to 9, from 1 to 8, from 1.5 to 8, from 2 to 8, from 2.5 to 8, from 3 to 8, from 3.5 to 8, from 4 to 8, from 4.5 to 8, from 5 to 8, from 6 to 8, from 7 to 8, from 1 to 7, from 1.5 to 7, from 2 to 7, from 2.5 to 7, from 3 to 7, from 3.5 to 7, from 4 to 7, from 4.5 to 7, from 5 to 7, from 6 to 7, from 1 to 6, from 1.5 to 6, from 2 to 6, from 2.5 to 6, from 3 to 6, from 3.5 to 6, from 4 to 6, from 4.5 to 6, from 5 to 6, from 1 to 5, from 1.5 to 5, from 2 to 5, from 2.5 to 5, from 3 to 5, from 3.5 to 5, from 4 to 5, from 4.5 to 5, from 1 to 4.5, from 1.5 to 4.5,from 2 to 4.5, from 2.5 to 4.5, from 3 to 4.5, from 3.5 to 4.5, from 4 to 4.5, from 1 to 4, from1.5 to 4, from 2 to 4, from 2.5 to 4, from 3 to 4, from 3.5 to 4, from 1 to 3.5, from 1.5 to 3.5, from 2 to 3.5, from 2.5 to 3.5, from 3 to 3.5, from 1 to 3, from 1.5 to 3, from 2 to 3, from2.5 to 3, from 1 to 2.5, from 1.5 to 2.5, from 2 to 2.5, from 1 to 2, from 1.5 to 2, or from 1 to 1.5) percent by weight of the reaction product, based on the total weight of the composition.

[0076] In certain embodiments, R2is H. In certain embodiments, R2is COOH.

[0077] In certain embodiments, R3is, independently for each repeat unit, H or CH3. In certain embodiments, R3is, independently for each repeat unit, H or CH2COOH. In certain embodiments, R3is, independently for each repeat unit, CH3 or CH2COOH. In certain embodiments, R3is H. In certain embodiments, R3is CH3. In certain embodiments, R3is CH2COOH.

[0078] In certain embodiments, R4is, independently for each repeat unit, H or a Ci to C36 (such as Ci to C34, Ci to C32, Ci to C30, Ci to C28, Ci to C26, Ci to C24, Ci to C22, Ci to C20, Ci to Ci8, Ci to Ci6, Ci to C14, Ci to C12, Ci to C10, Ci to Cs, Ci to Ce, Ci to C4, Ci to C2, C2 to C36, C2 to C34, C2 to C32, C2 to C30, C2 to C28, C2 to C26, C2 to C24, C2 to C22, C2 to C20, C2 to Ci8, C2 to Ci6, C2 to C14, C2 to C12, C2 to C10, C2 to Cs, C2 to Ce, C2 to C4, C4 to C36, C4 to C34, C4 to C32, C4 to C30, C4 to C28, C4 to C26, C4 to C24, C4 to C22, C4 to C20, C4 to Ci8, C4 to Cie, C4 to C14, C4 to C12, C4 to C10, C4 to Cs, C4 to Ce, Ce to C36, Ce to C34, Ce to C32, Ce to C30, Ce to C28, Ce to C26, Ce to C24, Ce to C22, Ce to C20, Ce to Ci8, Ce to Cie, Ce to C14, Ce to C12, Ce to C10, Ce to Cs, Cs to C36, Cs to C34, Cs to C32, Cs to C30, Cs to C28, Cs to C26, Cs to C24, Cs to C22, Cs to C20, Cs to C18, Cs tO C16, Cs to C14, Cs to C12, Cs to C10, C10 to C36, C10 to C34, C10 to C32, C 10 to C30, C10 to C28, C10 to C26, C10 to C24, C10 to C22, C10 to C20, C10 to C18, C10 to C16, C10 to C14, C10 to C12, C12 to C36, C12 to C34, C12 to C32, C12 toC30, C12 to C28, C12 to C26, C12 to C24, C12 to C22, C12 tO C20, C12 tO C18, C12 tO C16, C12 tOC14, C14 to C36, C14 to C34, C14 to C32, C14 to C30, C14 tO C28, C14 tO C26, C14 tO C24, C14 tOC22, C14 to C20, C14 to C18, C14 to C16, C16 tO C36, C16 tO C34, C16 to C32, C 16 to C30, C16 toC28, C16 tO C26, C16 tO C24, C16 tO C22, C16 tO C20, C16 tO C18, C18 tO C36, C18 tO C34, C18 tOC32, C18 tO C30, C18 tO C28, C18 tO C26, C18 tO C24, C18 tO C22, C18 tO C20, C20 tO C36, C20 tOC34, C20 tO C32, C20 tO C30, C20 tO C28, C20 tO C26, C20 tO C24, C20 tO C22, C22 tO C36, C22 toC34, C22 tO C32, C22 tO C30, C22 tO C28, C22 tO C26, C22 tO C24, C24 tO C36, C24 to C34, C24 toC32, C24 to C30, C24 to C28, C24 to C26, C26 to C36, C26 to C34, C26 to C32, C26 to C30, C26 toC28, C28 to C36, C28 to C34, C28 to C32, C28 to C30, C30 to C36, C30 to C34, C30 to C32, C32 toC36, C32 to C34, or C34 to C36) hydrocarbyl group. In certain embodiments, R4is H. Incertain embodiments, R4is a Ci hydrocarbyl group. In certain embodiments, R4is a C2 hydrocarbyl group. In certain embodiments, R4is a C4 hydrocarbyl group. In certain embodiments, R4is a Ce hydrocarbyl group. In certain embodiments, R4is a Cs hydrocarbyl group. In certain embodiments, R4is a C10 hydrocarbyl group. In certain embodiments, R4is a C12 hydrocarbyl group. In certain embodiments, R4is a C14 hydrocarbyl group. In certain embodiments, R4is a Ci6 hydrocarbyl group. In certain embodiments, R4is a Cis hydrocarbyl group. In certain embodiments, R4is a C20 hydrocarbyl group. In certain embodiments, R4is a C22 hydrocarbyl group. In certain embodiments, R4is a C24 hydrocarbyl group. In certain embodiments, R4is a C26 hydrocarbyl group. In certain embodiments, R4is a C28 hydrocarbyl group. In certain embodiments, R4is a C30 hydrocarbyl group. In certain embodiments, R4is a C32 hydrocarbyl group. In certain embodiments, R4is a C34 hydrocarbyl group. In certain embodiments, R4is a C36 hydrocarbyl group.

[0079] In certain embodiments, R5is, independently for each repeat unit, H or a Ci to C36 (such as Ci to C34, Ci to C32, Ci to C30, Ci to C28, Ci to C26, Ci to C24, Ci to C22, Ci to C20, Ci to Ci8, Ci to Ci6, Ci to C14, Ci to C12, Ci to C10, Ci to Cs, Ci to Ce, Ci to C4, Ci to C2, C2 to C36, C2 to C34, C2 to C32, C2 to C30, C2 to C28, C2 to C26, C2 to C24, C2 to C22, C2 to C20, C2 to Ci8, C2 to Cie, C2 to C14, C2 to C12, C2 to C10, C2 to Cs, C2 to Ce, C2 to C4, C4 to C36, C4 to C34, C4 to C32, C4 to C30, C4 to C28, C4 to C26, C4 to C24, C4 to C22, C4 to C20, C4 to Ci8, C4 to Cie, C4 to C14, C4 to C12, C4 to C10, C4 to Cs, C4 to Ce, Ce to C36, Ce to C34, Ce to C32, Ce to C30, Ce to C28, Ce to C26, Ce to C24, Ce to C22, Ce to C20, Ce to Ci8, Ce to Cie, Ce to C14, Ce to C12, Ce to C10, Ce to Cs, Cs to C36, Cs to C34, Cs to C32, Cs to C30, Cs to C28, Cs to C26, Cs to C24, Cs to C22, Cs to C20, Cs to C18, Cs tO C16, Cs to C14, Cs to C12, Cs to C10, C10 to C36, C10 to C34, C10 to C32, C 10 to C30, C10 to C28, C10 to C26, C10 to C24, C10 to C22, C10 to C20, C10 to C18, C10 to C16, C10 to C14, C10 to C12, C12 to C36, C12 to C34, C12 to C32, C12 toC30, C12 to C28, C12 to C26, C12 to C24, C12 to C22, C12 tO C20, C12 tO C18, C12 tO C16, C12 tOC14, C14 to C36, C14 to C34, C14 to C32, C14 to C30, C14 tO C28, C14 tO C26, C14 tO C24, C14 tOC22, C14 to C20, C14 to C18, C14 to C16, C16 tO C36, C16 tO C34, C16 to C32, C 16 to C30, C16 toC28, C16 tO C26, C16 tO C24, C16 tO C22, C16 tO C20, C16 tO C18, C18 tO C36, C18 tO C34, C18 tOC32, C18 tO C30, C18 tO C28, C18 tO C26, C18 tO C24, C18 tO C22, C18 tO C20, C20 tO C36, C20 tOC34, C20 tO C32, C20 tO C30, C20 tO C28, C20 tO C26, C20 tO C24, C20 tO C22, C22 tO C36, C22 toC34, C22 tO C32, C22 tO C30, C22 tO C28, C22 tO C26, C22 tO C24, C24 tO C36, C24 to C34, C24 toC32, C24 to C30, C24 to C28, C24 to C26, C26 to C36, C26 to C34, C26 to C32, C26 to C30, C26 toC28, C28 to C36, C28 to C34, C28 to C32, C28 to C30, C30 to C36, C30 to C34, C30 to C32, C32 toC36, C32 to C34, or C34 to C36) hydrocarbyl group. In certain embodiments, R5is H. In certain embodiments, R5is a Ci hydrocarbyl group. In certain embodiments, R5is a C2 hydrocarbyl group. In certain embodiments, R5is a C4 hydrocarbyl group. In certain embodiments, R5is a Ce hydrocarbyl group. In certain embodiments, R5is a Cs hydrocarbyl group. In certain embodiments, R5is a C10 hydrocarbyl group. In certain embodiments, R5is a C12 hydrocarbyl group. In certain embodiments, R5is a C14 hydrocarbyl group. In certain embodiments, R5is a Ci6 hydrocarbyl group. In certain embodiments, R5is a Cis hydrocarbyl group. In certain embodiments, R5is a C20 hydrocarbyl group. In certain embodiments, R5is a C22 hydrocarbyl group. In certain embodiments, R5is a C24 hydrocarbyl group. In certain embodiments, R5is a C26 hydrocarbyl group. In certain embodiments, R5is a C28 hydrocarbyl group. In certain embodiments, R5is a C30 hydrocarbyl group. In certain embodiments, R5is a C32 hydrocarbyl group. In certain embodiments, R5is a C34 hydrocarbyl group. In certain embodiments, R5is a C36 hydrocarbyl group.

[0080] In certain embodiments, n is an integer from 10 to 1400 (such as from 10 to 1300, from 10 to 1200, from 10 to 1100, from 10 to 1000, from 10 to 900, from 10 to 800, from10 to 700, from 10 to 600, from 10 to 500, from 10 to 400, from 10 to 300, from 10 to 250, from 10 to 200, from 10 to 150, from 10 to 100, from 10 to 90, from 10 to 80, from 10 to 70, from 10 to 60, from 10 to 50, from 10 to 40, from 10 to 30, from 10 to 20, from 20 to 1400, from 20 to 1300, from 20 to 1200, from 20 to 1100 from 20 to 1000, from 20 to 900, from 20 to 800, from 20 to 700, from 20 to 600, from 20 to 500, from 20 to 400, from 20 to 300, from 20 to 250, from 20 to 200, from 20 to 150, from 20 to 100, from 20 to 90, from 20 to 80, from 20 to 70, from 20 to 60, from 20 to 50, from 20 to 40, from 20 to 30, from 30 to 1400, from 30 to 1300, from 30 to 1200, from 30 to 1100 from 30 to 1000, from 30 to 900, from 30 to 800, from 30 to 700, from 30 to 600, from 30 to 500, from 30 to 400, from 30 to 300, from 30 to 250, from 30 to 200, from 30 to 150, from 30 to 100, from 30 to 90, from 30 to 80, from 30 to 70, from 30 to 60, from 30 to 50, from 30 to 40, from 40 to 1400, from 40 to 1300, from 40 to 1200, from 40 to 1100 from 40 to 1000, from 40 to 900, from 40 to 800, from 40 to 700, from 40 to 600, from 40 to 500, from 40 to 400, from 40 to 300, from 40 to 250, from 40 to 200, from 40 to 150, from 40 to 100, from 40 to 90, from 40 to 80, from 40 to 70, from 40 to 60, from 40 to 50, from 50 to 1400, from 50 to 1300, from 50 to 1200, from 50 to 1100 from 50 to 1000, from 50 to 900, from 50 to 800, from 50 to 700, from 50 to 600, from 50 to 500, from 50 to 400, from 50 to 300, from 50 to 250, from 50 to 200, from 50 to 150, from 50 to 100, from 50 to 90, from 50 to 80, from 50 to 70, from 50to 60, from 60 to 1400, from 60 to 1300, from 60 to 1200, from 60 to 1100 from 60 to 1000, from 60 to 900, from 60 to 800, from 60 to 700, from 60 to 600, from 60 to 500, from 60 to 400, from 60 to 300, from 60 to 250, from 60 to 200, from 60 to 150, from 60 to 100, from 60 to 90, from 60 to 80, from 60 to 70, from 70 to 1400, from 70 to 1300, from 70 to 1200, from 70 to 1100 from 70 to 1000, from 70 to 900, from 70 to 800, from 70 to 700, from 70 to 600, from 70 to 500, from 70 to 400, from 70 to 300, from 70 to 250, from 70 to 200, from 70 to 150, from 70 to 100, from 70 to 90, from 70 to 80, from 80 to 1400, from 80 to 1300, from 80 to 1200, from 80 to 1100 from 80 to 1000, from 80 to 900, from 80 to 800, from 80 to 700, from 80 to 600, from 80 to 500, from 80 to 400, from 80 to 300, from 80 to 250, from 80 to 200, from 80 to 150, from 80 to 100, from 80 to 90, from 90 to 1400, from 90 to 1300, from 90 to 1200, from 90 to 1100 from 90 to 1000, from 90 to 900, from 90 to 800, from 90 to 700, from 90 to 600, from 90 to 500, from 90 to 400, from 90 to 300, from 90 to 250, from 90 to 200, from 90 to 150, from 90 to 100, from 100 to 1400, from 100 to 1300, from 100 to 1200, from 100 to 1100 from 100 to 1000, from 100 to 900, from 100 to 800, from 100 to 700, from 100 to 600, from 100 to 500, from 100 to 400, from 100 to 300, from 100 to 250, from 100 to 200, from 100 to 150, from 150 to 1400, from 150 to 1300, from 150 to 1200, from 150 to 1100 from 150 to 1000, from 150 to 900, from 150 to 800, from 150 to 700, from 150 to 600, from 150 to 500, from 150 to 400, from 150 to 300, from 150 to 250, from 150 to 200, from 200 to 1400, from 200 to 1300, from 200 to 1200, from 200 to 1100 from 200 to 1000, from 200 to 900, from 200 to 800, from 200 to 700, from 200 to 600, from 200 to 500, from 200 to 400, from 200 to 300, from 200 to 250, from 250 to 1400, from 250 to 1300, from 250 to 1200, from 250 to 1100 from 250 to 1000, from 250 to 900, from 250 to 800, from 250 to 700, from 250 to 600, from 250 to 500, from 250 to 400, from 250 to 300, from 300 to 1400, from 300 to 1300, from 300 to 1200, from 300 to 1100 from 300 to 1000, from 300 to 900, from 300 to 800, from 300 to 700, from 300 to 600, from 300 to 500, from 300 to 400, from 400 to 1400, from 400 to 1300, from 400 to 1200, from 400 to 1100 from 400 to 1000, from 400 to 900, from 400 to 800, from 400 to 700, from 400 to 600, from 400 to 500, from 500 to 1400, from 500 to 1300, from 500 to 1200, from 500 to 1100 from 500 to 1000, from 500 to 900, from 500 to 800, from 500 to 700, from 500 to 600, from 600 to 1400, from 600 to 1300, from 600 to 1200, from 600 to 1100 from 600 to 1000, from 600 to 900, from 600 to 800, from 600 to 700, from 700 to 1400, from 700 to 1300, from 700 to 1200, from 700 to 1100 from 700 to 1000, from 700 to 900, from 700 to 800, from 800 to 1400, from 800 to 1300, from 800 to 1200, from 800 to 1100 from 800 to 1000, from 800 to 900, from 900 to 1400, from 900 to 1300, from 900to 1200, from 900 to 1100 from 900 to 1000, from 1000 to 1400, from 1000 to 1300, from 1000 to 1200, from 1000 to 1100, from 1100 to 1400, from 1100 to 1300, from 1100 to 1200, from 1200 to 1400, from 1200 to 1300, or from 1300 to 1400).

[0081] In certain embodiments, m is 0 or an integer from 1 to 140 (such as from 1 to 130, from 1 to 120, from 1 to 110, from 1 to 100, from 1 to 90, from 1 to 80, from 1 to 70, from 1 to 60, from 1 to 50, from 1 to 40, from 1 to 30, from 1 to 25, from 1 to 20, from 1 to 15, from 1 to 10, from 1 to 9, from 1 to 8, from 1 to 7, from 1 to 6, from 1 to 5, from 1 to 4, from 1 to 3, from 1 to 2, from 2 to 140, from 2 to 130, from 2 to 120, from 2 to 110 from 2 to 100, from 2 to 90, from 2 to 80, from 2 to 70, from 2 to 60, from 2 to 50, from 2 to 40, from 2 to 30, from 2 to 25, from 2 to 20, from 2 to 15, from 2 to 10, from 2 to 9, from 2 to 8, from 2 to 7, from 2 to 6, from 2 to 5, from 2 to 4, from 2 to 3, from 3 to 140, from 3 to 130, from 3 to 120, from 3 to 110 from 3 to 100, from 3 to 90, from 3 to 80, from 3 to 70, from 3 to 60, from 3 to 50, from 30 to 40, from 3 to 30, from 3 to 25, from 3 to 20, from 3 to 15, from 3 to 10, from 3 to 9, from 3 to 8, from 3 to 7, from 3 to 6, from 3 to 5, from 3 to 4, from 4 to 140, from 4 to 130, from 4 to 120, from 4 to 110 from 4 to 100, from 4 to 90, from 4 to 80, from 4 to 70, from 4 to 60, from 4 to 50, from 4 to 40, from 4 to 30, from 4 to 25, from 4 to 20, from 4 to 15, from 4 to 10, from 4 to 9, from 4 to 8, from 4 to 7, from 4 to 6, from 4 to 5, from 5 to 140, from 5 to 130, from 5 to 120, from 5 to 110 from 5 to 100, from 5 to 90, from 5 to 80, from 5 to 70, from 5 to 60, from 5 to 50, from 5 to 40, from 5 to 30, from 5 to 25, from 5 to 20, from 5 to 15, from 5 to 10, from 5 to 9, from 5 to 8, from 5 to 7, from 5 to 6, from 6 to 140, from 6 to 130, from 6 to 120, from 6 to 110 from 6 to 100, from 6 to 90, from 6 to 80, from 6 to 70, from 6 to 60, from 6 to 50, from 6 to 40, from 6 to 30, from 6 to 25, from 6 to 20, from 6 to 15, from 6 to 10, from 6 to 9, from 6 to 8, from 6 to 7, from 7 to 140, from 7 to 130, from 7 to 120, from 7 to 110 from 7 to 100, from 7 to 90, from 7 to 80, from 7 to 70, from 7 to 60, from 7 to 50, from 7 to 40, from 7 to 30, from 7 to 25, from 7 to 20, from 7 to 15, from 7 to 10, from 7 to 9, from 7 to 8, from 8 to 140, from 8 to 130, from 8 to 120, from 8 to 110 from 8 to 100, from 8 to 90, from 8 to 80, from 8 to 70, from 8 to 60, from 8 to 50, from 8 to 40, from 8 to 30, from 8 to 25, from 8 to 20, from 8 to 15, from 8 to 10, from 8 to 9, from 9 to 140, from 9 to 130, from 9 to 120, from 9 to 110 from 9 to 100, from 9 to 90, from 9 to 80, from 9 to 70, from 9 to 60, from 9 to 50, from 9 to 40, from 9 to 30, from 9 to 25, from 9 to 20, from 9 to 15, from 9 to 10, from 10 to 140, from 10 to 130, from 10 to 120, from 10 to 110 from 10 to 100, from 10 to 90, from 10 to 80, from 10 to 70, from 10 to 60, from 10 to 50, from 10 to 40, from 10 to 30, from 10 to 25, from 10 to 20, from 10 to 15, from 15 to 140, from 15 to 130, from 15 to 120, from 15to 110 from 15 to 100, from 15 to 90, from 15 to 80, from 15 to 70, from 15 to 60, from 15 to 50, from 15 to 40, from 15 to 30, from 15 to 25, from 15 to 20, from 20 to 140, from 20 to 130, from 20 to 120, from 20 to 110 from 20 to 100, from 20 to 90, from 20 to 80, from 20 to 70, from 20 to 60, from 20 to 50, from 20 to 40, from 20 to 30, from 20 to 25, from 25 to 140, from 25 to 130, from 25 to 120, from 25 to 110 from 25 to 100, from 25 to 90, from 25 to 80, from 25 to 70, from 25 to 60, from 25 to 50, from 25 to 40, from 25 to 30, from 30 to 140, from 30 to 130, from 30 to 120, from 30 to 110 from 30 to 100, from 30 to 90, from 30 to 80, from 30 to 70, from 30 to 60, from 30 to 50, from 30 to 40, from 40 to 140, from 40 to 130, from 40 to 120, from 40 to 110 from 40 to 100, from 40 to 90, from 40 to 80, from 40 to 70, from 40 to 60, from 40 to 50, from 50 to 140, from 50 to 130, from 50 to 120, from 50 to 110 from 50 to 100, from 50 to 90, from 50 to 80, from 50 to 70, from 50 to 60, from 60 to 140, from 60 to 130, from 60 to 120, from 60 to 110 from 60 to 100, from 60 to 90, from 60 to 80, from 60 to 70, from 70 to 140, from 70 to 130, from 70 to 120, from 70 to 110 from 70 to 100, from 70 to 90, from 70 to 80, from 80 to 140, from 80 to 130, from 80 to 120, from 80 to 110 from 80 to 100, from 80 to 90, from 90 to 140, from 90 to 130, from 90 to 120, from 90 to 110 from 90 to 100, from 100 to 140, from 100 to 130, from 100 to 120, from 100 to 110, from 110 to 140, from 110 to 130, from 110 to 120, from 120 to 140, from 120 to 130, or from 130 to 140).

[0082] In certain embodiments, R7is a Ci to C4 (such as Ci to C3, Ci to C2, C2 to C4, C2 to C3, C3 to C4, Ci, C2, C3, or C4) hydrocarbyl group.

[0083] In certain embodiments, R8is H. In certain embodiments, R8is CH3. In certain embodiments, R8is H in at least 70% (such as at least 75%, at least 80%, at least 85%, at least 90%, or at least 95%) of repeat units.

[0084] In certain embodiments, R9is a Ci to C4 (such as Ci to C3, Ci to C2, C2 to C4, C2 to C3, C3 to C4, Ci, C2, C3, or C4) hydrocarbyl group.

[0085] In certain embodiments, z is an integer from 10 to 80, such as from 10 to 70, from 10 to 60, from 10 to 50, from 10 to 40, from 10 to 30, from 10 to 20, from 20 to 80, from 20 to 70, from 20 to 60, from 20 to 50, from 20 to 40, from 20 to 30, from 30 to 80, from 30 to 70, from 30 to 60, from 30 to 50, from 30 to 40, from 40 to 80, from 40 to 70, from 40 to 60, from 40 to 50, from 50 to 80, from 50 to 70, from 50 to 60, from 60 to 80, from 60 to 70, or from 70 to 80.

[0086] In certain embodiments, R10is a Ci to C4 (such as Ci to C3, Ci to C2, C2 to C4, C2 to C3, C3 to C4, Ci, C2, C3, or C4) hydrocarbyl group.

[0087] In certain embodiments, R11is H. In certain embodiments, R11is CH3. In certain embodiments, R11is H in at least 40% (such as at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%) of repeat units. In certain embodiments, R11is CH3 in at least 15% (such as at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, or at least 60%) of repeat units.

[0088] In certain embodiments, R12is, independently for each repeat unit, a Ci to C5 (such as Ci to C4, Ci to C3, Ci to C2, C2 to C5, C2 to C4, C2 to C3, C3 to C5, C3 to C3, C4 to C5, Ci, C2, C3, C4, or C5) hydrocarbyl group.

[0089] In certain embodiments, x is an integer from 6 to 50, such as from 6 to 40, from6 to 30, from 6 to 20, from 6 to 15, from 6 to 10, from 6 to 9, from 6 to 8, from 6 to 7, from7 to 50, from 7 to 40, from 7 to 30, from 7 to 20, from 7 to 15, from 7 to 10, from 7 to 9, from 7 to 8, from 8 to 50, from 8 to 40, from 8 to 30, from 8 to 20, from 8 to 15, from 8 to 10, from 8 to 9, from 9 to 50, from 9 to 40, from 9 to 30, from 9 to 20, from 9 to 15, from 9 to 10, from 10 to 50, from 10 to 40, from 10 to 30, from 10 to 20, from 10 to 15, from 15 to 50, from 15 to 40, from 15 to 30, from 15 to 20, from 20 to 50, from 20 to 40, from 20 to 30, from 30 to 50, from 30 to 40, or from 40 to 50.

[0090] In certain embodiments, y is 0 or an integer from 1 to 20 (such as from 1 to 15, from 1 to 10, from 1 to 8, from 1 to 6, from 1 to 5, from 1 to 4, from 1 to 3, from 1 to 2, from 2 to 20, from 2 to 15, from 2 to 10, from 2 to 8, from 2 to 6, from 2 to 5, from 2 to 4, from 2 to 3, from 3 to 20, from 3 to 15, from 3 to 10, from 3 to 8, from 3 to 6, from 3 to 5, from 3 to 4, from 4 to 20, from 4 to 15, from 4 to 10, from 4 to 8, from 4 to 6, from 4 to 5, from 5 to 20, from 5 to 15, from 5 to 10, from 5 to 8, from 5 to 6, from 6 to 20, from 6 to 15, from 6 to 10, from 6 to 8, from 8 to 20, from 8 to 15, from 8 to 10, from 10 to 20, from 10 to 15, or from 15 to 20).

[0091] The mixed metal oxide ceramic pigment may be any suitable mixed metal oxide material which is known to provide the desired pigment properties when fired at elevated temperature. The mixed metal oxide ceramic pigment may comprise a solid containing at least two different metals in the same or different oxidation states. In certain embodiments, the mixed metal oxide ceramic pigment comprises two or more elements in cationic form selected from aluminum, magnesium, calcium, cadmium, cobalt, chromium, iron, indium, manganese, nickel, praseodymium, antimony, selenium, silicon, tin, vanadium, zinc, and zirconium. In certain embodiments, the mixed metal oxide ceramic pigment comprises twoor more elements in cationic form selected from aluminum, calcium, cobalt, chromium, iron, manganese, praseodymium, antimony, silicon, tin, zinc, and zirconium.

[0092] When referring to the mixed metal oxide ceramic pigments described herein, the phrase “which develops its full color intensity and / or hue after firing at elevated temperature” means that the pigment is fired (generally after being applied to a substrate) until it provides the expected color / hue properties of the pigment, as would be known to those of ordinary skill in the relevant art. Further, the term “fired” in this context means simply heating the article as is known in the art of ceramics and glass manufacturing.

[0093] The term “particulate form”, referring to the mixed metal oxide ceramic pigment, simply means that the pigment is in a solid form comprising discrete particles.

[0094] Suitable, non-limiting pigments for coloration of ceramic articles or glass articles are Pigment Yellow 159 (Zr-Si-Pr, zircon praseodymium yellow or praseodymium yellow zircon) such as BASF Sicocer® F Yellow 2200; Pigment Red 232 (Zr-Si-Fe zircon) such as BASF Sicocer® F Coral 2300; Pigment Red 233 (Ca-Sn-Si-Cr, chrome tin pink sphene); Pigment Brown 33 (Zn-Fe-Cr, Spinel) such as BASF Sicocer® Brown 2700; Pigment Blue 72 (Co-Al-Cr, Cobalt Spinel blue); Pigment Blue 28 (Co- Al spinel) such as BASF Sicocer® Blue 2501; Pigment Blue 36 (Co-Al spinel) such as BASF Sicocer® Cyan2500; Pigment Black 27 (Co-Mn-Fe-Cr spinel) such as BASF Sicocer® Black 2900; and Pigment White 12 (Zr-Si) such as BASF Sicocer® White EDT / AK-4409 / 2.

[0095] The composition described herein may be prepared by any of the conventional methods known for preparing such compositions, which may be, include, or comprise dispersions for coloration of ceramic articles fired above 600 °C or for glasses annealed or tempered above 400°C. Thus, the solid, the liquid medium and the reaction product may be mixed in any order, the mixture then being subjected to a mechanical treatment to reduce the particles of the solid to an appropriate size, for example, by ball milling, bead milling, gravel milling or plastic milling until the dispersion is formed. It is anticipated that a variety of particle size and dispersing equipment can be used sequentially to minimize total milling time and expense, such that a large particle size pigment can be dispersed in a continuous media with the dispersant, an initial pre-mix or pre-mill grinding to a desired particle size range, and then transfer to a bead type mill to further break down particulate particles into the D50 200-1000 (such as 200-600) nanometre diameter (by volume average particle size measurements).

[0096] The present subject matter further relates to a process for digital printing on a substrate comprising: (a) depositing a first glaze composition onto the substrate; (b) whilethe glaze composition is still wet, depositing an ink composition comprising the composition described above onto the substrate; and (c) heating the substrate such that the mixed metal oxide ceramic pigment develops its full color intensity and / or hue. In certain embodiments, the substrate may be a ceramic article. In certain embodiments, the substrate may be a glass article. In certain embodiments, the first glaze composition comprises water. In certain embodiments, the process comprises depositing a second glaze composition onto the ink composition while at least the ink composition is still wet, prior to said heating. In certain embodiments, said depositing a second glaze composition onto the ink composition occurs while both the ink composition and the first glaze composition are still wet. In certain embodiments, the second glaze composition comprises water. In certain embodiments, the second glaze composition is the same as the first glaze composition. In certain embodiments, the second glaze composition is different from the first glaze composition. In certain embodiments, said heating comprises heating the substrate to a temperature of greater than 400 °C, greater than 500 °C, greater than 600 °C, such as greater than 700 °C, greater than 800 °C, greater than 900 °C, or greater than 1,000 °C. In certain embodiments, said heating comprises heating the substrate to a temperature of from 400 °C to 1,500 °C (such as from 400 °C to 1,250 °C, from 400 °C to 1,000 °C, from 400 °C to 900 °C, from 400 °C to 800 °C, from 400 °C to 700 °C, from 400 °C to 600 °C, from 400 °C to 500 °C, from 500 °C to 1,500 °C, 500 °C to 1,250 °C, from 500 °C to 1,000 °C, from 500 °C to 900 °C, from 500 °C to 800 °C, from 500 °C to 700 °C, from 500 °C to 600 °C, from 600 °C to 1,500 °C, from 600 °C to 1,250 °C, from 600 °C to 1,000 °C, from 600 °C to 900 °C, from 600 °C to 800 °C, from 600 °C to 700 °C, from 700 °C to 1,500 °C, from 700 °C to 1,250 °C, from 700 °C to 1,000 °C, from 700 °C to 900 °C, from 700 °C to 800 °C, from 800 °C to 1,500 °C, from 800 °C to 1,250 °C, from 800 °C to 1,000 °C, from 800 °C to 900 °C, from 900 °C to 1,500 °C, from 900 °C to 1,250 °C, from 900 °C to 1,000 °C, from 1,000 °C to 1,500 °C, from 1,000 °C to 1,250 °C, or from 1,250 °C to 1,500 °C).

[0097] The present subject matter further relates to a process for digital printing on a ceramic article comprising: (a) depositing a first glaze composition onto the ceramic article; (b) while the glaze composition is still wet, depositing an ink composition comprising the composition described above onto the ceramic article; and (c) heating the ceramic article such that the mixed metal oxide ceramic pigment develops its full color intensity and / or hue. In certain embodiments, the first glaze composition comprises water. In certain embodiments, the process comprises depositing a second glaze composition onto the ink composition while at least the ink composition is still wet, prior to said heating. In certainembodiments, said depositing a second glaze composition onto the ink composition occurs while both the ink composition and the first glaze composition are still wet. In certain embodiments, the second glaze composition comprises water. In certain embodiments, the second glaze composition is the same as the first glaze composition. In certain embodiments, the second glaze composition is different from the first glaze composition. In certain embodiments, said heating comprises heating the ceramic article to a temperature of greater than 600 °C, such as at least 700 °C, at least 800 °C, at least 900 °C, or at least 1,000 °C. In certain embodiments, said heating comprises heating the ceramic article to a temperature of from 600 °C to 1,500 °C (such as from 600 °C to 1,250 °C, from 600 °C to 1,000 °C, from 600 °C to 900 °C, from 600 °C to 800 °C, from 600 °C to 700 °C, from 700 °C to 1,500 °C, from 700 °C to 1,250 °C, from 700 °C to 1,000 °C, from 700 °C to 900 °C, from 700 °C to 800 °C, from 800 °C to 1,500 °C, from 800 °C to 1,250 °C, from 800 °C to 1,000 °C, from 800 °C to 900 °C, from 900 °C to 1,500 °C, from 900 °C to 1,250 °C, from 900 °C to 1,000 °C, from 1,000 °C to 1,500 °C, from 1,000 °C to 1,250 °C, or from 1,250 °C to 1,500 °C).

[0098] Ceramic articles include a variety of useful and decorative items formed from clay and porcelain that develop additional strength from an elevated temperature treatment (such as about 400 °C to about 1200 °C) which fuses the inorganic material, providing additional mechanical strength and / or resistance to liquids. Ceramic articles may include, but are not limited to, tiles in various sizes and shapes, cups, jars, crocks, other storage vessels, bowls, plates, utensils, jewelry, bricks, etc. Ceramic articles may be intended for use inside a dwelling or for exterior use such as in building construction.

[0099] Glass articles include functional and decorative glass articles. Glass differs from ceramic in that ceramic is generally translucent at best where glass (unless intensely coloured) is generally transparent in thicknesses of about 0.5 mm such that size ten type can be read through glass panes under normal sunlight conditions. Glass articles may have high concentrations of silica, such as of at least 50% by weight based on the entire glass portion of the article. Examples of glass compositions include lead-oxide glass at 59 wt.% silica, 2 wt.% Na?O, 25 wt.% PbO, 12 wt.% K2O, 0.4 wt.% alumina and 1.5 wt.% Zn; sodium borosilicate glass with about 81 wt.% silica, 12 wt.% B2O3, 4.5 wt.% Na2O, and 2 wt.% AI2O3; soda-lime-silica window glass with about 72 wt.% silica, 14.2 wt.% Na2O, 25 wt.% MgO, 10 wt.% CaO, and 0.6 wt.% AI2O3; and fused silica glass with 95+wt.% silica. Glass articles may include, but are not limited to, glass panes (including curved and non-flatpanes), tubes, vials, bottles, beakers, flasks, glasses, cups, plates, bowls, pans, lenses, vessels, jars, spheres / balls, etc.

[0100] The subject matter disclosed herein may be better understood with reference to the following examples, which are set forth merely to further illustrate the subject matter disclosed herein. The illustrative examples should not be construed as limiting the subject matter in any manner.

[0101] Comparative Example 1 : Ingredients: Carbosperse™ K752 - poly acrylic acid MW 2000 63% active in water ex Lubrizol; Polyetheramine A - a polyetheramine of MW1650 (derived from a C12-15 alcohol reacted with propylene oxide followed by base catalysed addition of the resultant polyether alcohol to acrylonitrile and subsequent hydrogenation to give an amine (85% active)); and Polyetheralcohol A - a polyetheralcohol of MW1570 (derived from a C12-15 alcohol reacted with propylene oxide). The Carbosperse™ K752 (24.52 parts), the Polyetheramine A (22.6 parts), and the Polyetheralcohol A (84.27 parts) were heated to 120 °C under nitrogen with a trap fitted to the reaction vessel for 2 hours. The temperature was then increased to 140 °C for 3 hours. The temperature was then increased to 180 °C for a further 24 hours, yielding a brown liquid.

[0102] Comparative Example 2: Polyacrylic acid (Carbosperse K752 ex Lubrizol, 2000 molecular weight, 63% active solids in water, 23.21 parts), poly ether amine (Surfonamine L207 ex Huntsman, 2000 molecular weight, 20.70 parts) and polypropylene glycol monobutyl ether (ex Sigma-Aldrich, 1000 molecular weight, 80.01 parts) were heated to 80 °C under a nitrogen blanket for 1 hour. The reaction mixture was heated to 140 °C with an attached Dean-Stark condenser for 3 hours to remove water. The reaction temperature was then increased to 180 °C for 24 hours. An amber liquid was obtained with with Mn = 10540 and Mw = 26180 as determined by gel permeation chromatography in tetrahydrofuran spiked with 1% acetic acid against polystyrene standards.

[0103] Comparative Example 3: A poly etheralcohol of MW1600 (61.9 parts), (derived from a Cl 2- 15 alcohol reacted with propylene oxide), 1,2,4-benzenetricarboxylic acid anhydride (7.57 parts), and ortho-phosphoric acid (0.7 parts) were combined and heated to 120 °C under nitrogen with stirring and a condenser fitted. After 24 hours, poly etheramine of MW1650 (7.96 parts, derived from a C12-15 alcohol reacted with propylene oxide followed by base catalysed addition of the resultant polyether alcohol to acrylonitrile and subsequent hydrogenation to give an amine (85% active)) was added. After 3 hours, the condenser was removed. After 16 and half hours, a brown clear liquid was obtained with an acid value of 62.85 mgKOH / g.

[0104] Comparative Example 4: Polyacrylic acid (Carbosperse K752 ex Lubrizol, 2000 molecular weight, 63% active solids in water, 25 parts), polyether amine (Surfonamine L207 ex Huntsman, 2000 molecular weight, 21.58 parts) and poly(ethylene glycol) methyl ether (ex Ineos, 1000 molecular weight, 53.95 parts) were heated to 80 °C under a nitrogen blanket for 1 hour. The reaction mixture was heated to 140 °C with an attached Dean-Stark condenser for 3 hours to remove water. The reaction temperature was then increased to 180 °C for 24 hours. An amber liquid was obtained with acid value = 26.1 mg KOH g’1-

[0105] Comparative Example 5: Polyacrylic acid (Carbosperse K752 ex Lubrizol, 2000 molecular weight, 63% active solids in water, 25 parts), polyether amine (Surfonamine B200 ex Huntsman, 2000 molecular weight, 21.6 parts) and polypropylene glycol monobutyl ether (ex Sigma-Aldrich, 1000 molecular weight, 53.99 parts) were heated to 80 °C under a nitrogen blanket for 1 hour. The reaction mixture was heated to 140 °C with an attached Dean-Stark condenser for 3 hours to remove water. The reaction temperature was then increased to 180 °C for 24 hours. An amber liquid was obtained with acid value = 33.7 mg KOH g'1.

[0106] Intermediate A: Polyethylene glycol monomethyl ether 500 mwt (70.0 parts), s-caprolactone (91.08 parts) and 5-valerolactone (91.11 parts) were stirred under nitrogen at 120 °C for 1 hour. Zirconium (IV) butoxide 80% in 1-butanol (0.95 parts) was added and the reaction was heated to 180 °C for 18 hours. An amber liquid was obtained with Mn = 2660 and Mw = 3690 as determined by gel permeation chromatography in tetrahydrofuran against polystyrene standards.

[0107] Intermediate B: Polyethylene glycol monomethyl ether 500 mwt (70.05 parts), s-caprolactone (91.14 parts) and L-lactide (90.82 parts) were stirred under nitrogen at 120 °C for 1 hour. Zirconium (IV) butoxide 80% in 1-butanol (0.95 parts) was added and the reaction was heated to 180 °C for 18 hours. An amber liquid was obtained with Mn = 2080 and Mw = 3140 as determined by gel permeation chromatography in tetrahydrofuran against polystyrene standards.

[0108] Example 1 : Polyacrylic acid (Carbosperse™ K752 ex Lubrizol, 2000 molecular weight, 63% active solids in water, 85.20 parts), poly ether amine (Surfonamine™ L207 ex Huntsman, 2000 molecular weight, 60.19 parts) and polyalkylene glycol (Synalox™ 50- 30B ex Dow, 1000 molecular weight, 265.08 parts) were heated to 80 °C under a nitrogen blanket for 1 hour. The reaction mixture was heated to 140 °C with an attached Dean-Starkcondenser for 3 hours to remove water. The reaction temperature was then increased to 180 °C for 24 hours. An amber liquid was obtained with an acid value of 27.9 mgKOH / g.

[0109] Example 2: Polyacrylic acid (Carbosperse™ K732 ex Lubrizol, 6000 molecular weight, 50% active solids in water, 105.15 parts), poly ether amine (Surfonamine™ L207 ex Huntsman, 2000 molecular weight, 62.39 parts) and polyalkylene glycol (Synalox™ 50- 30B ex Dow, 1000 molecular weight, 270.10 parts) were heated to 80 °C under a nitrogen blanket for 1 hour. The reaction mixture was heated to 140 °C with an attached Dean-Stark condenser for 3 hours to remove water. The reaction temperature was then increased to 180 °C for 24 hours. An amber liquid was obtained with acid value = 24.9 mgKOH / g.

[0110] Example 3 : Polyacrylic acid (Carbosperse™ K752 ex Lubrizol, 2000 molecular weight, 63% active solids in water, 101.13 parts), poly ether amine (Surfonamine™ L207 ex Huntsman, 2000 molecular weight, 91.85 parts) and polyalkylene glycol (Synalox™ 55- 70B ex Dow, 1600 molecular weight, 352.21 parts) were heated to 80 °C under a nitrogen blanket for 1 hour. The reaction mixture was heated to 140 °C with an attached Dean-Stark condenser for 3 hours to remove water. The reaction temperature was then increased to 180 °C for 24 hours. An amber liquid was obtained with acid value = 26.0 mgKOH / g.

[0111] Example 4: Polyacrylic acid (Carbosperse™ K732 ex Lubrizol, 6000 molecular weight, 50% active solids in water, 127.45 parts), polyether amine (Surfonamine™ L207 ex Huntsman, 2000 molecular weight, 90.80 parts) and polyalkylene glycol (Synalox™ 55- 70B ex Dow, 1600 molecular weight, 354.02 parts) were heated to 80 °C under a nitrogen blanket for 1 hour. The reaction mixture was heated to 140 °C with an attached Dean-Stark condenser for 3 hours to remove water. The reaction temperature was then increased to 180 °C for 24 hours. An amber liquid was obtained with acid value = 33.25 mgKOH / g.

[0112] Example 5: Polyacrylic acid (Carbosperse K752 ex Lubrizol, 2000 molecular weight, 63% active solids in water, 20 parts), polyether amine (Surfonamine L207 ex Huntsman, 2000 molecular weight, 17.95 parts) and Intermediate A (78.64 parts) were heated to 80 °C under a nitrogen blanket for 1 hour. The reaction mixture was heated to 140 °C with an attached Dean-Stark condenser for 3 hours to remove water. The reaction temperature was then increased to 180 °C for 24 hours. An amber liquid was obtained with acid value = 27.5 mg KOH g'1.

[0113] Example 6: Polyacrylic acid (Carbosperse K752 ex Lubrizol, 2000 molecular weight, 63% active solids in water, 20 parts), polyether amine (Surfonamine L207 ex Huntsman, 2000 molecular weight, 17.95 parts) and Intermediate B (78.64 parts) were heated to 80 °C under a nitrogen blanket for 1 hour. The reaction mixturewas heated to 140 °C with an attached Dean-Stark condenser for 3 hours to remove water. The reaction temperature was then increased to 180 °C for 24 hours. An amber liquid was obtained with acid value = 39.8 mg KOH g'1.

[0114] Comparative Examples 1 to 2 and Examples 1 to 4 (0.3 parts) were dissolved in tri(propylene glycol) methyl ether (mixture of isomers, dowanol TPM, 4.7 parts) in a 30 mL volume jar. Pigment beige 36032 (ex Colorobbia, 5 parts) was then added, followed by borosilicate glass beads (1 mm diameter, 28 parts). The contents were then milled on a LabRAM II acoustic mixer (ex Resodyne) with an acceleration of 90 gravitation force equivalents at 60 Hz for 60 minutes. The resultant physical form of the millbases was then observed with a fluid millbase been regarded as a pass, reported in Table 1.Table 1

[0115] Millbase preparation

[0116] Comparative Examples 3 to 4 and Examples 5 to 6 (0.3 parts) were dissolved in tri(propylene glycol) methyl ether (mixture of isomers, dowanol TPM, 4.7 parts) in a 30 mL volume jar. Pigment beige 36032 (ex Colorobbia, 5 parts) was then added, followed by borosilicate glass beads (1 mm diameter, 17 parts). The contents were then milled on a LabRAM II acoustic mixer (ex Resodyne) with an acceleration of 90 gravitation force equivalents at 60 Hz for 60 minutes. The resultant physical form of the millbases was then observed with a fluid millbase been regarded as a pass, as reported in Table 2.Table 2

[0117] Water Compatibility

[0118] 15 weight % of distilled water was then added to each of the resultant millbases (i.e. 1.5g of water was added to 10g of millbase), which were then stirred manually before transferring to a watch glass and observing evidence of agglomeration and increased viscosity after 10 minutes, where a pass is where no changes in flow across the watch glass or observation of lack of homogeneity of millbase, and where a fail is when the viscosity greatly increases to form a obvious gel and or where the material splits to form 2 layers, as reported in Table 3.Table 3

[0119] Except in the Examples, or where otherwise explicitly indicated or required by context, all numerical quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word “about”. As used herein, the term “about” means that a value of a given quantity is within ±20% of the stated value. In other embodiments, the value is within ±15% of the stated value. In other embodiments, the value is within ±10% of the stated value. In other embodiments, the value is within ±5% of the stated value. In other embodiments, the value is within ±2.5% of the stated value. In other embodiments, the value is within ±1% of the stated value. In other embodiments, the value is within a range of the explicitly-described value which would be understood by those of ordinary skill, based on the disclosures provided herein, to perform substantially similarly to compositions including the literal amounts described herein.

[0120] It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined, and that any amount within a disclosed range is contemplated to provide a minimum or maximum of a narrower range in alternative embodiments (with the proviso, of course, that the minimum amount of a range must be lower than the maximum amount of the same range). Similarly, the ranges and amounts for each element of the subject matter disclosed herein may be used together with ranges or amounts for any of the other elements.

[0121] While certain representative embodiments and details have been shown for the purpose of illustrating the subject matter disclosed herein, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departingfrom the scope of the subject matter. In this regard, the scope of the invention is to be limited only by the following claims.

Claims

What is claimed is:

1. A composition comprising: a. a liquid organic medium which is compatible with water; b. a mixed metal oxide ceramic pigment in particulate form which develops its full color intensity and / or hue after firing at elevated temperature; and c. a reaction product of at least a reactant A, a reactant B, and a reactant C; wherein the reactant A is represented by the following general formula (A):wherein, independently for each molecule of the reactant A:R1is a terminal group;R2is, independently for each repeat unit, H or COOH;R3is, independently for each repeat unit, H, CH3, or CH2COOH;R4is, independently for each repeat unit, H or a Ci to C36 hydrocarbyl group;R5is, independently for each repeat unit, H or a Ci to C36 hydrocarbyl group;R6is a terminal group; n is an integer from 10 to 1400; and m is 0 or an integer from 1 to 140; wherein when R2is COOH in a repeat unit, R3is H in the repeat unit; and wherein, if m is not 0, n is at least 10 times greater than m; wherein the reactant B is represented by the following general formula (B):wherein, independently for each molecule of the reactant B: R7is a Ci to C4 hydrocarbyl group;R8is, independently for each repeat unit, H or CH3, with the proviso that R8is H in at least 70% of repeat units;R9is a Ci to C4 hydrocarbyl group; and z is an integer from 10 to 80; wherein the reactant C is represented by the following general formula (C):wherein, independently for each molecule of the reactant C:R10is a Ci to C4 hydrocarbyl group;R11is, independently for each repeat unit, H or CH3, with the proviso that R11is H in at least 40% of repeat units;R12is, independently for each repeat unit, a Ci to C5 hydrocarbyl group; x is an integer from 6 to 50; and y is 0 or an integer from 1 to 20, with the proviso that when R11is H in 100% of repeat units, y is greater than 0; wherein substantially all individual molecules of reactant C react with one acid group present in reactant A to form an ester, and substantially all individual molecules of reactant B react with (i) one acid group present in reactant A to form an amide, or (ii) two acid groups present in reactant A to form an imide; and wherein the reactant A is present in an amount of from 10 to 25 weight percent, the reactant B is present in an amount of from 10 to 40 weight percent, and the reactant C is present in an amount of from 40 to 80 weight percent, all based on the total combined weight of reactant A, reactant B, and reactant C.

2. The composition of claim 1, comprising from 20 to 79 percent by weight of the liquid organic medium, based on the total weight of the composition.

3. The composition of either claim 1 or claim 2, comprising from 20 to 60 percent by weight of the mixed metal oxide ceramic pigment, based on the total weight of the composition.

4. The composition of any one of claims 1 to 3, comprising from 1 to 20 percent by weight of the reaction product, based on the total weight of the composition.

5. The composition of any one of claims 1 to 4, wherein R2is H.

6. The composition of any one of claims 1 to 5, wherein R3is H.

7. The composition of any one of claims 1 to 6, wherein n is an integer from 20 to 150.

8. The composition of any one of claims 1 to 7, wherein m is 0.

9. The composition of any one of claims 1 to 8, wherein z is an integer from 20 to 50.

10. The composition of any one of claims 1 to 9, wherein y is 0 and R11is CH3 in at least 15% of repeat units.

11. The composition of any one of claims 1 to 9, wherein y is an integer from 1 to 20 and R11is H in 100% of repeat units.

12. The composition of any one of claims 1 to 11, wherein the reactant A is present in an amount of from 10 to 20 weight percent, based on the total combined weight of reactant A, reactant B, and reactant C.

13. The composition of any one of claims 1 to 12, wherein the reactant B is present in an amount of from 10 to 25 weight percent, based on the total combined weight of reactant A, reactant B, and reactant C.

14. The composition of any one of claims 1 to 13, wherein the reactant C is present in an amount of from 55 to 80 weight percent, based on the total combined weight of reactant A, reactant B, and reactant C.

15. A process for digital printing on a ceramic article comprising: a. depositing a first glaze composition onto the ceramic article; b. while the glaze composition is still wet, depositing an ink composition comprising the composition of any one of claims 1 to 14 onto the ceramic article; and c. heating the ceramic article such that the mixed metal oxide ceramic pigment develops its full color intensity and / or hue.

16. The process of claim 15, wherein the process comprises depositing a second glaze composition onto the ink composition while at least the ink composition is still wet, prior to said heating.

17. The process of claim 16, wherein said depositing a second glaze composition onto the ink composition occurs while both the ink composition and the first glaze composition are still wet.

18. The process of any one of claims 15 to 17, wherein said heating comprises heating the ceramic article to a temperature of greater than 600 °C.

19. The process of any one of claims 15 to 18, wherein said heating comprises heating the ceramic article to a temperature of from 1,000 °C to 1,250 °C.

Images