Pigment composition

Abstract

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

Description

[0001] The disclosed technology relates to compositions comprising reaction products (e.g., dispersants) and metal oxide ceramic pigments that exhibit their full color intensity and / or hue upon firing at elevated temperatures, as well as methods for preparing and / or using such compositions. The compositions are particularly suitable as inkjet ink compositions for digital printing on substrates such as ceramic or glass articles (etc.).

[0002] Substrates subjected to firing, such as ceramic tiles, have been decorated using printing methods employing water-based ink compositions, typically using electrostatic dispersants (such as polyacrylic acid dispersants). These methods generally produce substrates that are already matched to each other, without variation between individual units. To achieve variation between individual units, digital inkjet methods have been developed and are accepted in the industry; however, due to limitations in the inkjet nozzle technology utilized in these methods, they cannot use water-based ink compositions and instead employ solvent-based ink compositions that require special dispersants with steric hindrance stability.

[0003] As an example of such substrates, recent trends in ceramic tiles have led to the use of larger tiles, which has presented challenges in applying a uniform surface treatment (before the coloring layer) and a final glaze layer using traditional curtain coating methods. (Typically, at least three coats are used to coat and print ceramic tiles: a first glaze layer, a coloring layer on top of the first glaze layer, and a second glaze layer on top of the coloring layer.) Given these challenges, the industry has begun using new “numerical value” methods to apply the first and final coatings. This change has resulted in shorter drying times between coatings, requiring intermediate coloring layers to be compatible with the first and final layers, which are typically water-based compositions. Under these conditions, many existing ink compositions (used in the coloring layer) have shown incompatibility with water-based first and final layers.

[0004] Therefore, the disclosed technology provides compositions that can be used in coloring layers, which are compatible with water-based first and / or final layers, thereby solving the problem of incompatibility between ink compositions and water-based first and / or final layers.

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

[0006] The following implementation schemes for this topic are proposed:

[0007] 1. A composition comprising: (a) a water-compatible liquid organic medium; (b) a mixed metal oxide ceramic pigment in particulate form that exhibits its full color intensity and / or hue upon firing at elevated temperatures; and (c) a reaction product comprising at least reactant A, reactant B, and reactant C; wherein reactant A is represented by the following general formula (A):

[0008] (A)

[0009] Wherein, for each molecule of reactant A independently: R 1 R is a terminal group; 2 For each repeating unit, it is independently H or COOH; R 3 Each repeating unit is independently H, CH3, or CH2COOH; R 4 For each repeating unit, independently H or C1 to C 36 hydrocarbon group; R 5 For each repeating unit, independently H or C1 to C 36 hydrocarbon group; R 6 For terminal groups; n is an integer from 10 to 1400; and m is 0, or an integer from 1 to 140; where R is a terminal group in the repeating unit. 2 When R is COOH, in the repeating unit 3 H is a constant; and where, if m is not 0, then n is at least 10 times m; wherein the reactant B is represented by the following general formula (B):

[0010] (B)

[0011] Wherein, for each molecule of reactant B independently: R 7 It is a C1 to C4 hydrocarbon group; R 8 For each repeating unit to be independently H or CH3, the condition is R.8 H;R in at least 70% of the repeating units. 9 It is a C1 to C4 hydrocarbon group; and z is an integer from 10 to 80; wherein the reactant C is represented by the following general formula (C):

[0012] (C)

[0013] Wherein, for each molecule of reactant C independently: R 10 It is a C1 to C4 hydrocarbon group; R 11 For each repeating unit to be independently H or CH3, the condition is R. 11 H;R in at least 40% of the repeating units. 12 For each repeating unit, it is independently a C1 to C5 hydrocarbon group; x is an integer from 6 to 50; and y is 0, or an integer from 1 to 20, provided that R 11 When H is present in 100% repeating 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 reactant A is present in an amount of 10% to 25% by weight, reactant B is present in an amount of 10% to 40% by weight, and reactant C is present in an amount of 40% to 80% by weight, all based on the total weight of reactant A, reactant B and reactant C.

[0014] 2. The composition according to embodiment 1, based on the total weight of the composition, comprises 20% to 79% by weight of a liquid organic medium.

[0015] 3. The composition according to any one of Embodiment 1 or Embodiment 2, wherein the composition comprises 20% to 60% by weight of mixed metal oxide ceramic pigments based on the total weight of the composition.

[0016] 4. The composition according to any one of embodiments 1 to 3, wherein the composition comprises 1% to 20% by weight of the reaction product based on the total weight of the composition.

[0017] 5. The composition according to any one of embodiments 1 to 4, wherein R 2 For H.

[0018] 6. The composition according to any one of embodiments 1 to 4, wherein R 2 It is COOH.

[0019] 7. The composition according to any one of embodiments 1 to 6, wherein R3 Each repeating unit is independently either H or CH3.

[0020] 8. The composition according to any one of embodiments 1 to 6, wherein R 3 Each repeating unit is independently either H or CH2COOH.

[0021] 9. The composition according to any one of embodiments 1 to 5, wherein R 3 Each repeating unit is independently CH3 or CH2COOH.

[0022] 10. The composition according to any one of embodiments 1 to 8, wherein R 3 For H.

[0023] 11. The composition according to any one of embodiments 1 to 5, 7 or 9, wherein R 3 It is CH3.

[0024] 12. The composition according to any one of embodiments 1 to 5 or 8 to 9, wherein R 3 It is CH2COOH.

[0025] 13. The composition according to any one of embodiments 1 to 12, wherein R 4 For each repeating unit, independently H or C1 to C 20 Hydrocarbon group.

[0026] 14. The composition according to any one of embodiments 1 to 13, wherein R 4 For H.

[0027] 15. The composition according to any one of embodiments 1 to 12, wherein R 4 C1 to C 36 Hydrocarbon group.

[0028] 16. The composition according to any one of embodiments 1 to 13 or 15, wherein R 4 C1 to C 20 Hydrocarbon group.

[0029] 17. The composition according to any one of embodiments 1 to 16, wherein R 5 For each repeating unit, independently H or C1 to C 20 Hydrocarbon group.

[0030] 18. The composition according to any one of embodiments 1 to 17, wherein R 5 For H.

[0031] 19. The composition according to any one of embodiments 1 to 16, wherein R5 C1 to C 36 Hydrocarbon group.

[0032] 20. The composition according to any one of embodiments 1 to 17 or 19, wherein R 5 C1 to C 20 Hydrocarbon group.

[0033] 21. The composition according to any one of embodiments 1 to 20, wherein n is an integer from 10 to 250.

[0034] 22. The composition according to any one of embodiments 1 to 20, wherein n is an integer from 20 to 1400.

[0035] 23. The composition according to any one of embodiments 1 to 22, wherein n is an integer from 20 to 150.

[0036] 24. The composition according to any one of embodiments 1 to 23, wherein m is 0, or an integer from 1 to 25.

[0037] 25. The composition according to any one of embodiments 1 to 24, wherein m is 0, or an integer from 1 to 15.

[0038] 26. The composition according to any one of embodiments 1 to 25, wherein m is 0.

[0039] 27. The composition according to any one of embodiments 1 to 23, wherein m is an integer from 1 to 140.

[0040] 28. The composition according to any one of embodiments 1 to 24 or 27, wherein m is an integer from 1 to 25.

[0041] 29. The composition according to any one of embodiments 1 to 25 or 27 to 28, wherein m is an integer from 1 to 15.

[0042] 30. The composition according to any one of embodiments 1 to 29, wherein z is an integer from 10 to 50.

[0043] 31. The composition according to any one of embodiments 1 to 29, wherein z is an integer from 20 to 80.

[0044] 32. The composition according to any one of embodiments 1 to 31, wherein z is an integer from 20 to 50.

[0045] 33. The composition according to any one of embodiments 1 to 32, wherein in at least 15% of the repeating units, y is 0 and R 11 It is CH3.

[0046] 34. The composition according to any one of embodiments 1 to 32, wherein in 100% repeating units, y is an integer from 1 to 20 and R 11 For H.

[0047] 35. The composition according to any one of embodiments 1 to 34, wherein reactant A is present in an amount of 10% to 20% by weight based on the total weight of reactant A, reactant B and reactant C.

[0048] 36. The composition according to any one of embodiments 1 to 35, wherein reactant B is present in an amount of 10% to 25% by weight based on the total weight of reactant A, reactant B and reactant C.

[0049] 37. The composition according to any one of embodiments 1 to 36, wherein reactant C is present in an amount of 55% to 80% by weight based on the total weight of reactant A, reactant B and reactant C.

[0050] 38. The composition according to any one of embodiments 1 to 37, wherein the mixed metal oxide ceramic pigment comprises two or more elements in cationic form selected from the group consisting of aluminum, magnesium, calcium, cadmium, cobalt, chromium, iron, indium, manganese, nickel, praseodymium, antimony, selenium, silicon, tin, vanadium, zinc and zirconium.

[0051] 39. The composition according to any one of embodiments 1 to 38, wherein the mixed metal oxide ceramic pigment comprises two or more elements in cationic form selected from the group consisting of aluminum, calcium, cobalt, chromium, iron, manganese, praseodymium, antimony, silicon, tin, zinc and zirconium.

[0052] 40. A method for digital printing on a ceramic article, the method comprising: (a) depositing a first glaze composition onto the ceramic article; (b) while the glaze composition is still wet, depositing an ink composition comprising a composition according to any one of embodiments 1 to 39 onto the ceramic article; and (c) heating the ceramic article such that the mixed metal oxide ceramic pigment exhibits its full color intensity and / or hue.

[0053] 41. The method according to embodiment 40, wherein the first glaze composition comprises water.

[0054] 42. The method according to any one of embodiments 40 or 41, wherein the method comprises depositing a second glaze composition onto the ink composition while at least the ink composition is still wet prior to the heating.

[0055] 43. The method according to any one of embodiments 40 to 42, wherein the second glaze composition is deposited onto the ink composition while both the ink composition and the first glaze composition are still wet.

[0056] 44. The method according to any one of embodiments 40 to 43, wherein the second glaze composition comprises water.

[0057] 45. The method according to any one of embodiments 40 to 44, wherein the second glaze composition is the same as the first glaze composition.

[0058] 46. ​​The method according to any one of embodiments 40 to 44, wherein the second glaze composition is different from the first glaze composition.

[0059] 47. The method according to any one of embodiments 40 to 46, wherein the heating comprises heating the ceramic article to a temperature greater than 600°C.

[0060] 48. The method according to any one of embodiments 40 to 47, wherein the heating comprises heating the ceramic article to a temperature of 1,000°C to 1,250°C.

[0061] The various features and implementation schemes of this subject matter will be described below in a non-restrictive manner.

[0062] As used herein, the term "hydrocarbon group" refers to a group having carbon atoms directly connected to the remainder of the molecule, wherein the group comprises at least carbon and hydrogen atoms. If the hydrocarbon group contains more than one carbon atom, these carbons do not necessarily have to be connected to each other. For example, at least two carbons may be connected via suitable elements or groups. In various embodiments, the term "hydrocarbon group" refers to a group having carbon atoms directly connected to the remainder of the molecule, wherein the group consists of carbon, hydrogen, and optionally one or more heteroatoms, provided that the heteroatoms do not alter the predominantly hydrocarbon nature of the substituent. Heteroatoms may connect at least two carbons in the hydrocarbon group and optionally no more than two non-hydrocarbon substituents. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, sulfur, nitrogen, oxygen, phosphorus, and silicon. When the hydrocarbon group contains heteroatoms, optionally, no more than two heteroatoms will be present for every ten carbon atoms in the hydrocarbon group. Suitable non-hydrocarbon substituents will also be apparent to those skilled in the art and include, for example, halogenated, hydroxyl, alkoxy, mercapto, alkyl mercapto, nitro, nitroso, and thionyl groups.

[0063] Therefore, examples of hydrocarbon groups in this technical context include: (i) hydrocarbon groups selected from aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl, cyclodienyl), and aromatic groups; (ii) substituted hydrocarbon groups selected from those defined in (i) that are substituted by no more than two non-hydrocarbon substituents and / or one or more hydrocarbon substituents, wherein the non-hydrocarbon substituents are selected from the group consisting of: halogen, hydroxyl, alkoxy, mercapto, alkyl mercapto, nitro, nitroso, and thionyl; and / or (iii) hydrocarbon groups containing heteroatoms selected from those defined in (i) that contain one or more heteroatoms in a ring or chain, provided that no more than two heteroatoms are present for every ten carbon atoms in the group, wherein the heteroatoms are selected from sulfur, nitrogen, oxygen, phosphorus, and silicon. Hydrocarbon groups containing heteroatoms may be substituted by no more than two non-hydrocarbon substituents and / or one or more hydrocarbon substituents. In some embodiments, the term "hydrocarbon group" refers to a group having carbon atoms directly connected to the remainder of the molecule, wherein the group consists of carbon atoms and hydrogen atoms.

[0064] It is known that some of the substances described herein can interact in the final formulation, such that the composition of the final formulation may differ from those initially added. The resulting products, including those formed when compositions of this subject matter are used in their intended use, may not be readily described. However, all such modifications and reaction products are included within the scope of this subject matter, which includes compositions prepared by mixing the components described herein.

[0065] As used herein, the indefinite article “a” / “an” is intended to mean one or more. As used herein, the phrase “at least one” / “at least one” means one or more of the following terms. Therefore, “a” / “an” and “at least one” / “at least one” are used interchangeably. For example, “at least one of A, B or C” means that in alternative embodiments, only one of A, B or C may be included, and any mixture of two or more of A, B and C may be included.

[0066] As used herein, the term “substantially free” means that a component does not include any intentional addition of materials that are “substantially free” in that component. For example, the component may include materials that are “substantially free” in that component at levels not exceeding impurity levels, which may be the result of incomplete chemical reactions and / or unintentional / undesired (but possibly unavoidable) reaction products.

[0067] As used herein, the transitional term “comprising,” synonymous with “comprising,” “containing,” or “characterized in,” is inclusive or open-ended and does not exclude additional, unlisted elements or method steps. However, in every use of “comprising” herein, it is intended that the term also cover the phrases “consistently composed of” and “composed of” as alternative embodiments, wherein “consisting of” excludes any elements or steps not specified, and “consisting of” allows the inclusion of additional, undescribed elements or steps that do not substantially affect the essential or essential and novel characteristics of the composition or method under consideration.

[0068] This subject matter relates to a composition comprising: (a) a water-compatible liquid organic medium; (b) a mixed metal oxide ceramic pigment in particulate form that exhibits its full color intensity and / or hue upon firing at elevated temperatures; and (c) a reaction product of at least reactants A, B, and C, all as described below. The reaction product can be characterized as a dispersant for the mixed metal oxide ceramic pigment, capable of at least partially dispersing the pigment in the liquid organic medium. In the context of the phrase “a reaction product of at least reactants A, B, and C,” “at least” means that other reactants and / or components may be present in the reaction, provided that the characteristics of the resulting reaction product remain substantially unchanged.

[0069] In some 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 document, “substantially all” means that the reaction is designed to maximize the reaction of reactants B and C; however, due to slight variations in stoichiometry and / or reaction conditions (potentially affecting reaction kinetics and other factors), a small amount of reactants B and C may remain unreacted, as will be understood by those skilled in the art. Furthermore, because the reaction is designed in this way to force the reaction of reactants B and C to consume as many reactants as possible, some unreacted reactant A will be present in the reaction products.

[0070] Reactant A is represented by the following general formula (A):

[0071] (A)

[0072] Wherein, for each molecule of reactant A independently: R 1 R is a terminal group; 2 For each repeating unit, it is independently H or COOH; R 3Each repeating unit is independently H, CH3, or CH2COOH; R 4 For each repeating unit, independently H or C1 to C 36 hydrocarbon group; R 5 For each repeating unit, independently H or C1 to C 36 hydrocarbon group; R 6 The terminator is a terminal group; n is an integer from 10 to 1400; and m is 0, or an integer from 1 to 140. In some embodiments, when R is in a repeating unit... 2 When R is COOH, in the repeating unit 3 For H. In some embodiments, if m is not 0, then n is at least 10 times m. As used herein, the phrase "independently for each molecule" means that the variable can vary between molecules of the components described by a general formula including such variables, thereby forming a mixture of molecules that can have different choices individually for each variable, but it is also contemplated that the variable can be the same for all molecules. Similarly, the phrase "independently for each repeating unit" means that the variable can vary between repeating units in a single molecule, but it is also contemplated that the variable can be the same for all repeating units. As those skilled in the art will understand, one or more carboxylic acid groups present in reactant A can be in the form of a salt or anhydride without substantially affecting the reactant product and / or its properties, since it is generally known that a certain amount of carboxylic acid groups can naturally form a salt or anhydride.

[0073] In some embodiments, reactant A is present in an amount of 10% to 25% by weight (such as 10% to 20% by weight, 10% to 15% by weight, 15% to 25% by weight, 15% to 20% by weight, or 20% to 25% by weight) based on the total weight of reactants A, B, and C. Non-limiting examples of suitable materials that can be used as reactant A include polyacrylic acid, polyacrylic acid-co-maleic acid, and / or polyacrylic acid-co-itaconic acid, optionally co-reacted with monounsaturated monomers such as acrylates and / or methacrylates, for example, butyl acrylate and / or butyl methacrylate.

[0074] Reactant B is represented by the following general formula (B):

[0075] (B)

[0076] Wherein, for each molecule of reactant B independently: R 7 It is a C1 to C4 hydrocarbon group; R 8 Each repeating unit is independently H or CH3; R 9 It is a C1 to C4 hydrocarbon group; and z is an integer from 10 to 80.

[0077] In some embodiments, reactant B is present in an amount of 10 wt% to 40 wt% (such as 10 wt% to 35 wt%, 10 wt% to 30 wt%, 10 wt% to 25 wt%, 10 wt% to 20 wt%, 10 wt% to 15 wt%, 15 wt% to 40 wt%, 15 wt% to 35 wt%, 15 wt% to 30 wt%, 15 wt% to 25 wt%, 15 wt% to 20 wt%, 20 wt% to 40 wt%, 20 wt% to 35 wt%, 20 wt% to 25 wt%, 25 wt% to 40 wt%, 25 wt% to 35 wt%, 25 wt% to 30 wt%, 30 wt% to 40 wt%, 30 wt% to 35 wt%, or 35 wt% to 40 wt%) based on the total weight of reactant A, reactant B, and reactant C. Non-limiting examples of suitable materials that can be used as reactant B include α-terminated polyetheramines (including, but not limited to, those marketed under the name Surfonamine). ® Those L100, L200, L207, or L300 purchased from Huntsman.

[0078] Reactant C is represented by the following general formula (C):

[0079] (C)

[0080] Wherein, for each molecule of reactant C independently: R 10 It is a C1 to C4 hydrocarbon group; R 11 Each repeating unit is independently H or CH3; R 12 Each repeating unit is independently a C1 to C5 hydrocarbon group; x is an integer from 6 to 50; and y is 0, or an integer from 1 to 20. In some embodiments, when R is in 100% of the repeating units... 11 When H is the integer part, y is greater than 0.

[0081] In some embodiments, based on the total weight of reactants A, B, and C, reactant C is present in a concentration of 40 wt% to 80 wt% (e.g., 40 wt% to 75 wt%, 40 wt% to 70 wt%, 40 wt% to 65 wt%, 40 wt% to 60 wt%, 40 wt% to 55 wt%, 40 wt% to 50 wt%, 40 wt% to 45 wt%, 45 wt% to 80 wt%, 45 wt% to 75 wt%, 45 wt% to 70 wt%, 45 wt% to 65 wt%, 45 wt% to 60 wt%, 45 wt% to 55 wt%, 45 wt% to 50 wt%, 50 wt% to 80 wt%, 50 wt% to 75 wt%). The substance is present in amounts of 5 wt%, 50 wt% to 70 wt%, 50 wt% to 65 wt%, 50 wt% to 60 wt%, 50 wt% to 55 wt%, 55 wt% to 80 wt%, 55 wt% to 75 wt%, 55 wt% to 70 wt%, 55 wt% to 65 wt%, 55 wt% to 60 wt%, 55 wt% to 60 wt%, 60 wt% to 80 wt%, 60 wt% to 75 wt%, 60 wt% to 70 wt%, 60 wt% to 65 wt%, 65 wt% to 80 wt%, 65 wt% to 75 wt%, 65 wt% to 70 wt%, 70 wt% to 80 wt%, or 75 wt% to 80 wt%. Non-limiting examples of suitable materials that can be used as reactant C include: water-soluble lubricants, such as Synalox. ™ 50-30B, Synalox ™ 55-70B; polyesters derived from polyethylene glycol monomethyl ether, ε-caprolactone and δ-valerolactone; and / or polyesters derived from polyethylene glycol monomethyl ether, ε-caprolactone and L-lactide.

[0082] In some embodiments, the composition comprises 20% to 79% by weight (e.g., 20% to 78.5% by weight, 20% to 78% by weight, 20% to 77.5% by weight, 20% to 77% by weight, 20% to 76.5% by weight, 20% to 76% by weight, 20% to 75.5% by weight, 20% to 75% by weight, 20% to 74% by weight, 20% to 73% by weight, 20% to 72% by weight, 20% to 71% by weight, 20% to 70% by weight, 20% to 65% by weight, 20% to 60% by weight, 20% to 55% by weight) based on the total weight of the composition. %, 20% to 50% by weight, 20% to 45% by weight, 20% to 40% by weight, 20% to 35% by weight, 20% to 30% by weight, 20% to 25% by weight, 25% to 79% by weight, 25% to 78.5% by weight, 25% to 78% by weight, 25% to 77.5% by weight, 25% to 77% by weight, 25% to 76.5% by weight, 25% to 76% by weight, 25% to 75.5% by weight, 25% to 75% by weight, 25% to 74% by weight, 25% to 73% by weight, 25% to 72% by weight, 25% to 71% by weight % by weight, 25% to 70% by weight, 25% to 65% by weight, 25% to 60% by weight, 25% to 55% by weight, 25% to 50% by weight, 25% to 45% by weight, 25% to 40% by weight, 25% to 35% by weight, 25% to 30% by weight, 30% to 79% by weight, 30% to 78.5% by weight, 30% to 78% by weight, 30% to 77.5% by weight, 30% to 77% by weight, 30% to 76.5% by weight, 30% to 76% by weight, 30% to 75.5% by weight, 30% to 75% by weight, 30% to 7 4% by weight, 30% to 73% by weight, 30% to 72% by weight, 30% to 71% by weight, 30% to 70% by weight, 30% to 65% by weight, 30% to 60% by weight, 30% to 55% by weight, 30% to 50% by weight, 30% to 45% by weight, 30% to 40% by weight, 30% to 35% by weight, 35% to 79% by weight, 35% to 78.5% by weight, 35% to 78% by weight, 35% to 77.5% by weight, 35% to 77% by weight, 35% to 76.5% by weight, 35% to 76% by weight, 35% to 75% by weight.5% by weight, 35% to 75% by weight, 35% to 74% by weight, 35% to 73% by weight, 35% to 72% by weight, 35% to 71% by weight, 35% to 70% by weight, 35% to 65% by weight, 35% to 60% by weight, 35% to 55% by weight, 35% to 50% by weight, 35% to 45% by weight, 35% to 40% by weight, 40% to 79% by weight, 40% to 78.5% by weight, 40% to 78% by weight, 40% to 77.5% by weight, 40% to 77% by weight, 40% to 76.5% by weight, 40% by weight 40% to 76% by weight, 40% to 75.5% by weight, 40% to 75% by weight, 40% to 74% by weight, 40% to 73% by weight, 40% to 72% by weight, 40% to 71% by weight, 40% to 70% by weight, 40% to 65% by weight, 40% to 60% by weight, 40% to 55% by weight, 40% to 50% by weight, 40% to 45% by weight, 45% to 79% by weight, 45% to 78.5% by weight, 45% to 78% by weight, 45% to 77.5% by weight, 45% to 77% by weight, 45% to 76.5% by weight 45% by weight to 76% by weight, 45% by weight to 75.5% by weight, 45% by weight to 75% by weight, 45% by weight to 74% by weight, 45% by weight to 73% by weight, 45% by weight to 72% by weight, 45% by weight to 71% by weight, 45% by weight to 70% by weight, 45% by weight to 65% by weight, 45% by weight to 60% by weight, 45% by weight to 55% by weight, 45% by weight to 50% by weight, 50% by weight to 79% by weight, 50% by weight to 78.5% by weight, 50% by weight to 78% by weight, 50% by weight to 77.5% by weight, 50% by weight to 77% by weight, 50% by weight to 76.5% by weight, 50% by weight 50% to 76% by weight, 50% to 75.5% by weight, 50% to 75% by weight, 50% to 74% by weight, 50% to 73% by weight, 50% to 72% by weight, 50% to 71% by weight, 50% to 70% by weight, 50% to 65% by weight, 50% to 60% by weight, 50% to 55% by weight, 55% to 79% by weight, 55% to 78.5% by weight, 55% to 78% by weight, 55% to 77.5% by weight, 55% to 77% by weight, 55% to 76.5% by weight, 55% to 76% by weight, 55% to 75% by weight.5% by weight, 55% to 75% by weight, 55% to 74% by weight, 55% to 73% by weight, 55% to 72% by weight, 55% to 71% by weight, 55% to 70% by weight, 55% to 65% by weight, 55% to 60% by weight, 60% to 79% by weight, 60% to 78.5% by weight, 60% to 78% by weight, 60% to 77.5% by weight, 60% to 77% by weight, 60% to 76.5% by weight, 60% to 76% by weight, 60% to 75.5% by weight, 60% to 75% by weight, 60% to 74% by weight, 60% to 73% by weight, 60% to 7 2% by weight, 60% to 71% by weight, 60% to 70% by weight, 60% to 65% by weight, 65% to 79% by weight, 65% to 78.5% by weight, 65% to 78% by weight, 65% to 77.5% by weight, 65% to 77% by weight, 65% to 76.5% by weight, 65% to 76% by weight, 65% to 75.5% by weight, 65% to 75% by weight, 65% to 74% by weight, 65% to 73% by weight, 65% to 72% by weight, 65% to 71% by weight, 65% to 70% by weight, 70% to 79% by weight, 70% to 78.5% by weight, 70% to 78% by weight, 70% to 77.5% by weight, 70% to 77% by weight, 70% to 76.5% by weight, 70% to 76% by weight, 70% to 75.5% by weight, 70% to 75% by weight, 70% to 74% by weight, 70% to 73% by weight, 70% to 72% by weight, 70% to 71% by weight, 71% to 79% by weight, 71% to 78.5% by weight, 71% to 78% by weight, 71% to 77.5% by weight, 71% to 77% by weight, 71% to 76.5% by weight, 71% to 76% by weight, 71% to 75.5% by weight, 71% to 75% by weight. 71% to 74% by weight, 71% to 73% by weight, 71% to 72% by weight, 72% to 79% by weight, 72% to 78.5% by weight, 72% to 78% by weight, 72% to 77.5% by weight, 72% to 77% by weight, 72% to 76.5% by weight, 72% to 76% by weight, 72% to 75.5% by weight, 72% to 75% by weight, 72% to 74% by weight, 72% to 73% by weight, 73% to 79% by weight, 73% to 78.5% by weight, 73% to 78% by weight, 73% to 77.5% by weight, 73% to 77% by weight, 73% to 76% by weight.5% by weight, 73% to 76% by weight, 73% to 75.5% by weight, 73% to 75% by weight, 73% to 74% by weight, 74% to 79% by weight, 74% to 78.5% by weight, 74% to 78% by weight, 74% to 77.5% by weight, 74% to 77% by weight, 74% to 76.5% by weight, 74% to 76% by weight, 74% to 75.5% by weight, 74% to 75% by weight 75% by weight, 75% by weight to 79% by weight, 75% by weight to 78.5% by weight, 75% by weight to 78% by weight, 75% by weight to 77.5% by weight, 75% by weight to 77% by weight, 75% by weight to 76.5% by weight, 75% by weight to 76% by weight, 75% by weight to 75.5% by weight, 75.5% by weight to 79% by weight, 75.5% by weight to 78.5% by weight, 75.5% by weight to 78% by weight, 75.5% by weight to 77.5% by weight, 75% by weight 0.5% to 77% by weight, 75.5% to 76.5% by weight, 75.5% to 76% by weight, 76% to 79% by weight, 76% to 78.5% by weight, 76% to 78% by weight, 76% to 77.5% by weight, 76% to 77% by weight, 76% to 76.5% by weight, 76.5% to 79% by weight, 76.5% to 78.5% by weight, 76.5% to 78% by weight, 76.5% by weight Liquid organic media comprising 77.5% to 77.5% by weight, 76.5% to 77% by weight, 77% to 79% by weight, 77% to 78.5% by weight, 77% to 78% by weight, 77% to 77.5% by weight, 77.5% to 79% by weight, 77.5% to 78.5% by weight, 77.5% to 78% by weight, 78% to 79% by weight, 78% to 78.5% by weight, or 78.5% to 79% by weight.

[0083] A water-compatible liquid organic medium can be any suitable organic liquid that imparts water compatibility to the composition as a whole. In this document, "water-compatible" means that the composition as a whole will maintain its dispersion integrity when in contact with water. For example, if the composition is an ink composition for digital printing, and the ink composition is printed onto an article that has previously been coated with a water-based coating (e.g., a glaze composition), and the water-based coating is still wet, the ink composition will remain in the place where it was printed to allow the printed image to substantially remain in the state intended for printing. In some embodiments, "water-compatible" means that the composition is miscible with or soluble in water. For example, when the composition comes into contact with water, it will absorb water rather than form an emulsion or dissociate from the water, similar to how oil and water dissociate due to their incompatibility.

[0084] In some embodiments, the liquid organic medium is substantially organic. In some embodiments, the main component of the liquid organic medium is organic. In some embodiments, the liquid organic medium is at least 50% (e.g., 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 some embodiments, the liquid organic medium is substantially composed of at least one organic liquid. In some embodiments, the liquid organic medium is substantially free of or contains no water.

[0085] In some embodiments, the liquid organic medium comprises at least one glycol ether, such as at least one of tripropylene glycol methyl ether or propylene glycol n-butyl ether.

[0086] In some embodiments, the composition comprises 20% to 60% by weight (e.g., 20% to 55% by weight, 20% to 50% by weight, 20% to 45% by weight, 20% to 40% by weight, 20% to 35% by weight, 20% to 30% by weight, 20% to 25% by weight, 25% to 60% by weight, 25% to 55% by weight, 25% to 50% by weight, 25% to 45% by weight, 25% to 40% by weight, 25% to 35% by weight, 25% to 30% by weight, 30% to 60% by weight, 30% to 55% by weight, 30% by weight) based on the total weight of the composition. Mixed metal oxide ceramic pigments (up to 50 wt%, 30 wt% to 45 wt%, 30 wt% to 40 wt%, 30 wt% to 35 wt%, 35 wt% to 60 wt%, 35 wt% to 55 wt%, 35 wt% to 50 wt%, 35 wt% to 45 wt%, 35 wt% to 40 wt%, 40 wt% to 60 wt%, 40 wt% to 55 wt%, 40 wt% to 50 wt%, 40 wt% to 45 wt%, 45 wt% to 60 wt%, 45 wt% to 55 wt%, 45 wt% to 50 wt%, 50 wt% to 60 wt%, 50 wt% to 55 wt% or 55 wt% to 60 wt%).

[0087] In some embodiments, based on the total weight of the composition, the composition comprises 1% to 20% by weight (such as 1.5% to 20% by weight, 2% to 20% by weight, 2.5% to 20% by weight, 3% to 20% by weight, 3.5% to 20% by weight, 4% to 20% by weight, 4.5% to 20% by weight, 5% to 20% by weight, 6% to 20% by weight, 7% to 20% by weight, 8% to 20% by weight, 9% to 20% by weight, 10% to 20% by weight, 15% to 20% by weight, 1% to 15% by weight, 1.5% to 15% by weight, 2% to 15% by weight, 2.5% to 15% by weight, 3% to 20% by weight). % to 15% by weight, 3.5% to 15% by weight, 4% to 15% by weight, 4.5% to 15% by weight, 5% to 15% by weight, 6% to 15% by weight, 7% to 15% by weight, 8% to 15% by weight, 9% to 15% by weight, 10% to 15% by weight, 1% to 10% by weight, 1.5% to 10% by weight, 2% to 10% by weight, 2.5% to 10% by weight, 3% to 10% by weight, 3.5% to 10% by weight, 4% to 10% by weight, 4.5% to 10% by weight, 5% to 10% by weight, 6% to 10% by weight, 7% to 10% by weight, 8% to 10% by weight % by weight, 9% to 10% by weight, 1% to 9% by weight, 1.5% to 9% by weight, 2% to 9% by weight, 2.5% to 9% by weight, 3% to 9% by weight, 3.5% to 9% by weight, 4% to 9% by weight, 4.5% to 9% by weight, 5% to 9% by weight, 6% to 9% by weight, 7% to 9% by weight, 8% to 9% by weight, 1% to 8% by weight, 1.5% to 8% by weight, 2% to 8% by weight, 2.5% to 8% by weight, 3% to 8% by weight, 3.5% to 8% by weight, 4% to 8% by weight, 4.5% to 8% by weight, 5% to 8% by weight, 6% to 8% by weight 7% to 8% by weight, 1% to 7% by weight, 1.5% to 7% by weight, 2% to 7% by weight, 2.5% to 7% by weight, 3% to 7% by weight, 3.5% to 7% by weight, 4% to 7% by weight, 4.5% to 7% by weight, 5% to 7% by weight, 6% to 7% by weight, 1% to 6% by weight, 1.5% to 6% by weight, 2% to 6% by weight, 2.5% to 6% by weight, 3% to 6% by weight, 3.5% to 6% by weight, 4% to 6% by weight, 4.5% to 6% by weight, 5% to 6% by weight, 1% to 5% by weight, 1.5% to 5% by weight, 2% to 5% by weight, 2%.5% to 5% by weight, 3% to 5% by weight, 3.5% to 5% by weight, 4% to 5% by weight, 4.5% to 5% by weight, 1% to 4.5% by weight, 1.5% to 4.5% by weight, 2% to 4.5% by weight, 2.5% to 4.5% by weight, 3% to 4.5% by weight, 3.5% to 4.5% by weight, 4% to 4.5% by weight, 1% to 4% by weight, 1.5% to 4% by weight, 2% to 4% by weight, 2.5% to 4% by weight, 3% to 4% by weight The reaction products are present in amounts ranging from 3.5% to 4% by weight, 1% to 3.5% by weight, 1.5% to 3.5% by weight, 2% to 3.5% by weight, 2.5% to 3.5% by weight, 3% to 3.5% by weight, 1% to 3% by weight, 1.5% to 3% by weight, 2% to 3% by weight, 2.5% to 3% by weight, 1% to 2.5% by weight, 1.5% to 2.5% by weight, 2% to 2.5% by weight, 1% to 2% by weight, or 1% to 1.5% by weight.

[0088] In some implementations, R 2 For H. In some implementations, R 2 It is COOH.

[0089] In some implementations, R 3 Each repeating unit is independently H or CH3. In some implementations, R 3 For each repeating unit, it is independently H or CH2COOH. In some embodiments, R 3 Each repeating unit is independently CH3 or CH2COOH. In some embodiments, R 3 For H. In some implementations, R 3 For CH3. In some implementations, R 3 It is CH2COOH.

[0090] In some implementations, R 4 For each repeating unit, independently H or C1 to C 36 (such as C1 to C) 34 C1 to C 32 C1 to C 30 C1 to C 28 C1 to C 26 C1 to C 24 C1 to C 22 C1 to C 20 C1 to C 18 C1 to C 16 C1 to C 14C1 to C 12 C1 to C 10 C1 to C8, C1 to C6, C1 to C4, C1 to C2, C2 to C 36 C2 to C 34 C2 to C 32 C2 to C 30 C2 to C 28 C2 to C 26 C2 to C 24 C2 to C 22 C2 to C 20 C2 to C 18 C2 to C 16 C2 to C 14 C2 to C 12 C2 to C 10 C2 to C8, C2 to C6, C2 to C4, C4 to C 36 C4 to C 34 C4 to C 32 C4 to C 30 C4 to C 28 C4 to C 26 C4 to C 24 C4 to C 22 C4 to C 20 C4 to C 18 C4 to C 16 C4 to C 14 C4 to C 12 C4 to C 10 C4 to C8, C4 to C6, C6 to C 36 C6 to C 34 C6 to C 32 C6 to C 30 C6 to C 28 C6 to C 26 C6 to C 24 C6 to C 22 C6 to C 20 C6 to C 18 C6 to C 16 C6 to C 14 C6 to C 12 C6 to C 10 C6 to C8, C8 to C 36 C8 to C 34 C8 to C 32 C8 to C 30 C8 to C 28 C8 to C 26 C8 to C 24 C8 to C 22 C8 to C20 C8 to C 18 C8 to C 16 C8 to C 14 C8 to C 12 C8 to C 10 C 10 To C 36 C 10 To C 34 C 10 To C 32 C 10 To C 30 C 10 To C 28 C 10 To C 26 C 10 To C 24 C 10 To C 22 C 10 To C 20 C 10 To C 18 C 10 To C 16 C 10 To C 14 C 10 To C 12 C 12 To C 36 C 12 To C 34 C 12 To C 32 C 12 To C 30 C 12 To C 28 C 12 To C 26 C 12 To C 24 C 12 To C 22 C 12 To C 20 C 12 To C 18 C 12 To C 16 C 12 To C 14 C 14 To C 36 C 14 To C 34 C 14 To C 32 C 14 To C 30 C 14 To C 28C 14 To C 26 C 14 To C 24 C 14 To C 22 C 14 To C 20 C 14 To C 18 C 14 To C 16 C 16 To C 36 C 16 To C 34 C 16 To C 32 C 16 To C 30 C 16 To C 28 C 16 To C 26 C 16 To C 24 C 16 To C 22 C 16 To C 20 C 16 To C 18 C 18 To C 36 C 18 To C 34 C 18 To C 32 C 18 To C 30 C 18 To C 28 C 18 To C 26 C 18 To C 24 C 18 To C 22 C 18 To C 20 C 20 To C 36 C 20 To C 34 C 20 To C 32 C 20 To C 30 C 20 To C 28 C 20 To C 26 C 20 To C 24 C 20 To C 22 C22 To C 36 C 22 To C 34 C 22 To C 32 C 22 To C 30 C 22 To C 28 C 22 To C 26 C 22 To C 24 C 24 To C 36 C 24 To C 34 C 24 To C 32 C 24 To C 30 C 24 To C 28 C 24 To C 26 C 26 To C 36 C 26 To C 34 C 26 To C 32 C 26 To C 30 C 26 To C 28 C 28 To C 36 C 28 To C 34 C 28 To C 32 C 28 To C 30 C 30 To C 36 C 30 To C 34 C 30 To C 32 C 32 To C 36 C 32 To C 34 Or C 34 To C 36 ) hydrocarbon group. In some embodiments, R 4 For H. In some implementations, R 4 It is a C1 hydrocarbon group. In some embodiments, R 4 It is a C2 hydrocarbon group. In some embodiments, R 4 It is a C4 hydrocarbon group. In some embodiments, R 4It is a C6 hydrocarbon group. In some embodiments, R 4 It is a C8 hydrocarbon group. In some embodiments, R 4 C 10 Hydrocarbon group. In some embodiments, R 4 C 12 Hydrocarbon group. In some embodiments, R 4 C 14 Hydrocarbon group. In some embodiments, R 4 C 16 Hydrocarbon group. In some embodiments, R 4 C 18 Hydrocarbon group. In some embodiments, R 4 C 20 Hydrocarbon group. In some embodiments, R 4 C 22 Hydrocarbon group. In some embodiments, R 4 C 24 Hydrocarbon group. In some embodiments, R 4 C 26 Hydrocarbon group. In some embodiments, R 4 C 28 Hydrocarbon group. In some embodiments, R 4 C 30 Hydrocarbon group. In some embodiments, R 4 C 32 Hydrocarbon group. In some embodiments, R 4 C 34 Hydrocarbon group. In some embodiments, R 4 C 36 Hydrocarbon group.

[0091] In some implementations, R 5 For each repeating unit, independently H or C1 to C 36 (such as C1 to C) 34 C1 to C 32 C1 to C 30 C1 to C 28 C1 to C 26 C1 to C 24 C1 to C 22 C1 to C 20 C1 to C 18 C1 to C 16 C1 to C 14 C1 to C 12 C1 to C 10 C1 to C8, C1 to C6, C1 to C4, C1 to C2, C2 to C 36C2 to C 34 C2 to C 32 C2 to C 30 C2 to C 28 C2 to C 26 C2 to C 24 C2 to C 22 C2 to C 20 C2 to C 18 C2 to C 16 C2 to C 14 C2 to C 12 C2 to C 10 C2 to C8, C2 to C6, C2 to C4, C4 to C 36 C4 to C 34 C4 to C 32 C4 to C 30 C4 to C 28 C4 to C 26 C4 to C 24 C4 to C 22 C4 to C 20 C4 to C 18 C4 to C 16 C4 to C 14 C4 to C 12 C4 to C 10 C4 to C8, C4 to C6, C6 to C 36 C6 to C 34 C6 to C 32 C6 to C 30 C6 to C 28 C6 to C 26 C6 to C 24 C6 to C 22 C6 to C 20 C6 to C 18 C6 to C 16 C6 to C 14 C6 to C 12 C6 to C 10 C6 to C8, C8 to C 36 C8 to C 34 C8 to C 32 C8 to C 30 C8 to C 28 C8 to C 26 C8 to C 24 C8 to C 22 C8 to C 20 C8 to C 18 C8 to C 16 C8 to C 14 C8 to C12 C8 to C 10 C 10 To C 36 C 10 To C 34 C 10 To C 32 C 10 To C 30 C 10 To C 28 C 10 To C 26 C 10 To C 24 C 10 To C 22 C 10 To C 20 C 10 To C 18 C 10 To C 16 C 10 To C 14 C 10 To C 12 C 12 To C 36 C 12 To C 34 C 12 To C 32 C 12 To C 30 C 12 To C 28 C 12 To C 26 C 12 To C 24 C 12 To C 22 C 12 To C 20 C 12 To C 18 C 12 To C 16 C 12 To C 14 C 14 To C 36 C 14 To C 34 C 14 To C 32 C 14 To C 30 C 14 To C 28 C 14 To C 26 C 14 To C 24 C14 To C 22 C 14 To C 20 C 14 To C 18 C 14 To C 16 C 16 To C 36 C 16 To C 34 C 16 To C 32 C 16 To C 30 C 16 To C 28 C 16 To C 26 C 16 To C 24 C 16 To C 22 C 16 To C 20 C 16 To C 18 C 18 To C 36 C 18 To C 34 C 18 To C 32 C 18 To C 30 C 18 To C 28 C 18 To C 26 C 18 To C 24 C 18 To C 22 C 18 To C 20 C 20 To C 36 C 20 To C 34 C 20 To C 32 C 20 To C 30 C 20 To C 28 C 20 To C 26 C 20 To C 24 C 20 To C 22 C 22 To C 36 C 22 To C 34 C 22To C 32 C 22 To C 30 C 22 To C 28 C 22 To C 26 C 22 To C 24 C 24 To C 36 C 24 To C 34 C 24 To C 32 C 24 To C 30 C 24 To C 28 C 24 To C 26 C 26 To C 36 C 26 To C 34 C 26 To C 32 C 26 To C 30 C 26 To C 28 C 28 To C 36 C 28 To C 34 C 28 To C 32 C 28 To C 30 C 30 To C 36 C 30 To C 34 C 30 To C 32 C 32 To C 36 C 32 To C 34 Or C 34 To C 36 ) hydrocarbon group. In some embodiments, R 5 For H. In some implementations, R 5 It is a C1 hydrocarbon group. In some embodiments, R 5 It is a C2 hydrocarbon group. In some embodiments, R 5 It is a C4 hydrocarbon group. In some embodiments, R 5 It is a C6 hydrocarbon group. In some embodiments, R 5 It is a C8 hydrocarbon group. In some embodiments, R 5 C 10Hydrocarbon group. In some embodiments, R 5 C 12 Hydrocarbon group. In some embodiments, R 5 C 14 Hydrocarbon group. In some embodiments, R 5 C 16 Hydrocarbon group. In some embodiments, R 5 C 18 Hydrocarbon group. In some embodiments, R 5 C 20 Hydrocarbon group. In some embodiments, R 5 C 22 Hydrocarbon group. In some embodiments, R 5 C 24 Hydrocarbon group. In some embodiments, R 5 C 26 Hydrocarbon group. In some embodiments, R 5 C 28 Hydrocarbon group. In some embodiments, R 5 C 30 Hydrocarbon group. In some embodiments, R 5 C 32 Hydrocarbon group. In some embodiments, R 5 C 34 Hydrocarbon group. In some embodiments, R 5 C 36 Hydrocarbon group.

[0092] In some implementations, n is 10 to 1400 (such as 10 to 1300, 10 to 1200, 10 to 1100, 10 to 1000, 10 to 900, 10 to 800, 10 to 700, 10 to 600, 10 to 500, 10 to 400, 10 to 300, 10 to 250, 10 to 200, 10 to 150, 10 to 100, 10 to 90, 10 to 80, 10 to 70, 10 to 60, 10 to 50, 10 to 40, 10 to 30, 10 to 20, 20 to 1400, 20 to 1300, 20 to 1200, 20 to 1100, 20 to 1000, 20 to 900, 20 to 800, 20 to 700, 20 to 600, 20...). To 500, 20 to 400, 20 to 300, 20 to 250, 20 to 200, 20 to 150, 20 to 100, 20 to 90, 20 to 80, 20 to 70, 20 to 60, 20 to 50, 20 to 40, 20 to 30, 30 to 1400, 30 to 1300, 30 to 1200, 30 to 1100, 30 to 1000, 30 to 900, 30 to 800, 30 to 700, 30 to 600, 30 to 500, 30 to 400, 30 to 300, 30 to 250, 30 to 200, 30 to 150, 30 to 100, 30 to 90, 30 to 80, 30 to 70, 30 to 60, 30 to 50, 30 to 40, 40 to 1400 40 to 1300, 40 to 1200, 40 to 1100, 40 to 1000, 40 to 900, 40 to 800, 40 to 700, 40 to 600, 40 to 500, 40 to 400, 40 to 300, 40 to 250, 40 to 200, 40 to 150, 40 to 100, 40 to 90, 40 to 80, 40 To 70, 40 to 60, 40 to 50, 50 to 1400, 50 to 1300, 50 to 1200, 50 to 1100, 50 to 1000, 50 to 900, 50 to 800, 50 to 700, 50 to 600, 50 to 500, 50 to 400, 50 to 300, 50 to 250, 50 to 200, 50 to 150 50 to 100, 50 to 90, 50 to 80, 50 to 70, 50 to 60, 60 to 1400, 60 to 1300, 60 to 1200, 60 to 1100, 60 to 1000, 60 to 900, 60 to 800, 60 to 700, 60 to 600, 60 to 500, 60 to 400, 60 to 300, 60 to 250, 60 to 200, 60 to 150, 60 to 100, 60 to 90, 60 to 80, 60 to 70, 70 to 1400, 70 to 1300, 70 to 1200, 70 to 1100, 70 to 1000, 70 to 900, 70 to 800, 70 to 700, 70 to 600, 70 to 500, 70 to 40070 to 300, 70 to 250, 70 to 200, 70 to 150, 70 to 100, 70 to 90, 70 to 80, 80 to 1400, 80 to 1300, 80 to 1200, 80 to 1100, 80 to 1000, 80 to 900, 80 to 800, 80 to 700, 80 to 600, 80 to 500, 80 To 400, 80 to 300, 80 to 250, 80 to 200, 80 to 150, 80 to 100, 80 to 90, 90 to 1400, 90 to 1300, 90 to 1200, 90 to 1100, 90 to 1000, 90 to 900, 90 to 800, 90 to 700, 90 to 600, 90 to 500, 90 to 400, 90 to 300, 90 to 250, 90 to 200, 90 to 150, 90 to 100, 100 to 1400, 100 to 1300, 100 to 1200, 100 to 1100, 100 to 1000, 100 to 900, 100 to 800, 100 to 700, 100 to 600, 100 to 500 100 to 400, 100 to 300, 100 to 250, 100 to 200, 100 to 150, 150 to 1400, 150 to 1300, 150 to 1200, 150 to 1100, 150 to 1000, 150 to 900, 150 to 800, 150 to 700, 150 to 600, 150 to 500 150 to 400, 150 to 300, 150 to 250, 150 to 200, 200 to 1400, 200 to 1300, 200 to 1200, 200 to 1100, 200 to 1000, 200 to 900, 200 to 800, 200 to 700, 200 to 600, 200 to 500, 200 to 400 200 to 300, 200 to 250, 250 to 1400, 250 to 1300, 250 to 1200, 250 to 1100, 250 to 1000, 250 to 900, 250 to 800, 250 to 700, 250 to 600, 250 to 500, 250 to 400, 250 to 300, 300 to 1400 00, 300 to 1300, 300 to 1200, 300 to 1100, 300 to 1000, 300 to 900, 300 to 800, 300 to 700, 300 to 600, 300 to 500, 300 to 400, 400 to 1400, 400 to 1300, 400 to 1200, 400 to 1100, 4 00 to 1000, 400 to 900, 400 to 800, 400 to 700, 400 to 600, 400 to 500, 500 to 1400, 500 to 1300, 500 to 1200, 500 to 1100, 500 to 1000, 500 to 900, 500 to 800, 500 to 700, 500 to 600600 to 1400, 600 to 1300, 600 to 1200, 600 to 1100, 600 to 1000, 600 to 900, 600 to 800, 600 to 700, 700 to 1400, 700 to 1300, 700 to 1200, 700 to 1100, 700 to 1000, 700 to 900, 700 to 800, 800 to 1400, 800 to 1300, 800 to 1200, 800 to 1100 Integers ranging from 800 to 1000, 800 to 900, 900 to 1400, 900 to 1300, 900 to 1200, 900 to 1100, 900 to 1000, 1000 to 1400, 1000 to 1300, 1000 to 1200, 1000 to 1100, 1100 to 1400, 1100 to 1300, 1100 to 1200, 1200 to 1400, 1200 to 1300, or 1300 to 1400.

[0093] In some implementations, m is 0, or 1 to 140 (such as 1 to 130, 1 to 120, 1 to 110, 1 to 100, 1 to 90, 1 to 80, 1 to 70, 1 to 60, 1 to 50, 1 to 40, 1 to 30, 1 to 25, 1 to 20, 1 to 15, 1 to 10, 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 140, 2 to 130, 2 to 120, 2 to 110, 2 to 100, 2 to 90, 2 to 80, 2 to 70, 2 to 60, 2 to 50, 2 to 40, 2 to 30, 2 to 25, 2 to 20, 2 to 15, 2 to 10, 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 to 5, 2 to 4, 2 to 3, 3 to 1). 40, 3 to 130, 3 to 120, 3 to 110, 3 to 100, 3 to 90, 3 to 80, 3 to 70, 3 to 60, 3 to 50, 30 to 40, 3 to 30, 3 to 25, 3 to 20, 3 to 15, 3 to 10, 3 to 9, 3 to 8, 3 to 7, 3 to 6, 3 to 5, 3 to 4, 4 to 140, 4 to 130, 4 to 120 4 to 110, 4 to 100, 4 to 90, 4 to 80, 4 to 70, 4 to 60, 4 to 50, 4 to 40, 4 to 30, 4 to 25, 4 to 20, 4 to 15, 4 to 10, 4 to 9, 4 to 8, 4 to 7, 4 to 6, 4 to 5, 5 to 140, 5 to 130, 5 to 120, 5 to 110, 5 to 100, 5 to 90, 5 to 80, 5 to 70, 5 to 60, 5 to 50, 5 to 40, 5 to 30, 5 to 25, 5 to 20, 5 to 15, 5 to 10, 5 to 9, 5 to 8, 5 to 7, 5 to 6, 6 to 140, 6 to 130, 6 to 120, 6 to 110, 6 to 100, 6 to 90, 6 to 80, 6 to 70, 6 to 60, 6 to 50, 6 to 40 6 to 30, 6 to 25, 6 to 20, 6 to 15, 6 to 10, 6 to 9, 6 to 8, 6 to 7, 7 to 140, 7 to 130, 7 to 120, 7 to 110, 7 to 100, 7 to 90, 7 to 80, 7 to 70, 7 to 60, 7 to 50, 7 to 40, 7 to 30, 7 to 25, 7 to 20, 7 to 15, 7 to 10, 7 to 9 7 to 8, 8 to 140, 8 to 130, 8 to 120, 8 to 110, 8 to 100, 8 to 90, 8 to 80, 8 to 70, 8 to 60, 8 to 50, 8 to 40, 8 to 30, 8 to 25, 8 to 20, 8 to 15, 8 to 10, 8 to 9, 9 to 140, 9 to 130, 9 to 120, 9 to 110, 9 to 100, 9 Up to 90, 9 to 80, 9 to 70, 9 to 60, 9 to 50, 9 to 40, 9 to 30, 9 to 25, 9 to 20, 9 to 15, 9 to 10, 10 to 140, 10 to 130, 10 to 120, 10 to 110, 10 to 100, 10 to 90, 10 to 80, 10 to 70, 10 to 60, 10 to 50, 10 to 40,10 to 30, 10 to 25, 10 to 20, 10 to 15, 15 to 140, 15 to 130, 15 to 120, 15 to 110, 15 to 100, 15 to 90, 15 to 80, 15 to 70, 15 to 60, 15 to 50, 15 to 40, 15 to 30, 15 to 25, 15 to 20, 20 to 140, 20 to 130, 20 to 120, 20 to 110, 20 to 100, 20 to 90, 20 to 80, 20 to 70, 20 to 60, 20 to 50, 20 to 4 0, 20 to 30, 20 to 25, 25 to 140, 25 to 130, 25 to 120, 25 to 110, 25 to 100, 25 to 90, 25 to 80, 25 to 70, 25 to 60, 25 to 50, 25 to 40, 25 to 30, 30 to 140, 30 to 130, 30 to 120, 30 to 110, 30 to 100, 30 to 90, 30 to 80, 30 to 70, 30 to 60, 30 to 50, 30 to 40, 40 to 140, 40 to 130, 40 to 120 40 to 110, 40 to 100, 40 to 90, 40 to 80, 40 to 70, 40 to 60, 40 to 50, 50 to 140, 50 to 130, 50 to 120, 50 to 110, 50 to 100, 50 to 90, 50 to 80, 50 to 70, 50 to 60, 60 to 140, 60 to 130, 60 to 120, 60 to 110, 60 to 100, 60 to 90, 60 to 80, 60 to 70, 70 to 140, 70 to 130, 70 to 120, 70 to 1 10. Integers of 70 to 100, 70 to 90, 70 to 80, 80 to 140, 80 to 130, 80 to 120, 80 to 110, 80 to 100, 80 to 90, 90 to 140, 90 to 130, 90 to 120, 90 to 110, 90 to 100, 100 to 140, 100 to 130, 100 to 120, 100 to 110, 110 to 140, 110 to 130, 110 to 120, 120 to 140, 120 to 130, or 130 to 140.

[0094] In some implementations, R 7 It is a C1 to C4 hydrocarbon group (such as C1 to C3, C1 to C2, C2 to C4, C2 to C3, C3 to C4, C1, C2, C3 or C4).

[0095] In some implementations, R 8 For H. In some implementations, R 8 For CH3. In some embodiments, R is present in at least 70% (such as at least 75%, at least 80%, at least 85%, at least 90%, or at least 95%) of the repeating units. 8 For H.

[0096] In some implementations, R 9 It is a C1 to C4 hydrocarbon group (such as C1 to C3, C1 to C2, C2 to C4, C2 to C3, C3 to C4, C1, C2, C3 or C4).

[0097] In some implementations, z is an integer from 10 to 80 (such as 10 to 70, 10 to 60, 10 to 50, 10 to 40, 10 to 30, 10 to 20, 20 to 80, 20 to 70, 20 to 60, 20 to 50, 20 to 40, 20 to 30, 30 to 80, 30 to 70, 30 to 60, 30 to 50, 30 to 40, 40 to 80, 40 to 70, 40 to 60, 40 to 50, 50 to 80, 50 to 70, 50 to 60, 60 to 80, 60 to 70, or 70 to 80).

[0098] In some implementations, R 10 It is a C1 to C4 hydrocarbon group (such as C1 to C3, C1 to C2, C2 to C4, C2 to C3, C3 to C4, C1, C2, C3 or C4).

[0099] In some implementations, R 11 For H. In some implementations, R 11 For CH3. In some embodiments, 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 the repeating units, R 11 For H. In some embodiments, 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 the repeating units, R 11 It is CH3.

[0100] In some implementations, R 12 Each repeating unit is independently a C1 to C5 hydrocarbon group (such as C1 to C4, C1 to C3, C1 to C2, C2 to C5, C2 to C4, C2 to C3, C3 to C5, C3 to C3, C4 to C5, C1, C2, C3, C4 or C5).

[0101] In some implementations, x is an integer from 6 to 50 (such as 6 to 40, 6 to 30, 6 to 20, 6 to 15, 6 to 10, 6 to 9, 6 to 8, 6 to 7, 7 to 50, 7 to 40, 7 to 30, 7 to 20, 7 to 15, 7 to 10, 7 to 9, 7 to 8, 8 to 50, 8 to 40, 8 to 30, 8 to 20, 8 to 15, 8 to 10, 8 to 9, 9 to 50, 9 to 40, 9 to 30, 9 to 20, 9 to 15, 9 to 15, 9 to 10, 10 to 50, 10 to 40, 10 to 30, 10 to 20, 10 to 15, 15 to 50, 15 to 40, 15 to 30, 15 to 20, 20 to 50, 20 to 40, 20 to 30, 30 to 50, 30 to 40, or 40 to 50).

[0102] In some implementations, y is 0, or an integer from 1 to 20 (such as 1 to 15, 1 to 10, 1 to 8, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 20, 2 to 15, 2 to 10, 2 to 8, 2 to 6, 2 to 5, 2 to 4, 2 to 3, 3 to 20, 3 to 15, 3 to 10, 3 to 8, 3 to 6, 3 to 5, 3 to 4, 4 to 20, 4 to 15, 4 to 10, 4 to 8, 4 to 6, 4 to 5, 5 to 20, 5 to 15, 5 to 10, 5 to 8, 5 to 6, 6 to 20, 6 to 15, 6 to 10, 6 to 8, 8 to 20, 8 to 15, 8 to 10, 10 to 20, 10 to 15, or 15 to 20).

[0103] Mixed metal oxide ceramic pigments can be any suitable mixed metal oxide material, known to provide desired pigment properties when fired at elevated temperatures. Mixed metal oxide ceramic pigments can comprise solids containing at least two different metals in the same or different oxidation states. In some embodiments, the mixed metal oxide ceramic pigment comprises two or more elements in cationic form selected from the following: aluminum, magnesium, calcium, cadmium, cobalt, chromium, iron, indium, manganese, nickel, praseodymium, antimony, selenium, silicon, tin, vanadium, zinc, and zirconium. In some embodiments, the mixed metal oxide ceramic pigment comprises two or more elements in cationic form selected from the following: aluminum, calcium, cobalt, chromium, iron, manganese, praseodymium, antimony, silicon, tin, zinc, and zirconium.

[0104] When referring to the mixed metal oxide ceramic pigments described herein, the phrase "to exhibit its full color intensity and / or hue after firing at elevated temperatures" means firing the pigment (typically after application to a substrate) until it provides the desired color / hue characteristics of the pigment, as is known to those skilled in the art. Furthermore, herein, the term "firing" means simply heating the article as is known in the fields of ceramics and glass manufacturing.

[0105] The term "particulate form" (refer to mixed metal oxide ceramic pigments) simply means that the pigment is in a solid form containing discrete particles.

[0106] Suitable non-limiting pigments for coloring ceramic or glass products include Pigment Yellow 159 (Zr-Si-Pr, praseodymium zircon or praseodymium 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, chromium tin 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 BASFSicocer ® Cyan 2500; 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.

[0107] The compositions described herein can be prepared by any conventional method known for preparing such compositions, which can be, include, or contain dispersions for coloring ceramic articles fired above 600°C or for annealing or tempering glasses above 400°C. Therefore, the solid, liquid media, and reaction products can be mixed in any order, followed by mechanical treatment of the mixture to reduce the solid particles to a suitable size, for example by ball milling, bead milling, pebble milling, or plastic milling until a dispersion is formed. It is anticipated that various particle size and dispersion equipment can be used sequentially to minimize total grinding time and cost, allowing large-particle pigments to be dispersed together with the dispersant in a continuous medium, initially premixed or pre-milled to the desired particle size range, and then transferred to a bead mill for further decomposition of the microparticles into D... 50 200-1000 (e.g., 200-600) nanometer diameter (measured by volume average particle size).

[0108] This subject matter also relates to a method for digital printing on a substrate, the method comprising: (a) depositing a first glaze composition onto the substrate; (b) depositing an ink composition comprising the glaze composition onto the substrate while the glaze composition is still wet; and (c) heating the substrate such that the mixed metal oxide ceramic pigment exhibits its full color intensity and / or hue. In some embodiments, the substrate may be a ceramic article. In some embodiments, the substrate may be a glass article. In some embodiments, the first glaze composition comprises water. In some embodiments, the method comprises depositing a second glaze composition onto the ink composition while at least the ink composition is still wet prior to the heating. In some embodiments, the deposition of the second glaze composition onto the ink composition is performed while both the ink composition and the first glaze composition are still wet. In some embodiments, the second glaze composition comprises water. In some embodiments, the second glaze composition is the same as the first glaze composition. In some embodiments, the second glaze composition is different from the first glaze composition. In some embodiments, the heating includes heating the substrate to a temperature 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 some embodiments, the heating includes heating the substrate to 400°C to 1500°C (such as 400°C to 1,250°C, 400°C to 1,000°C, 400°C to 900°C, 400°C to 800°C, 400°C to 700°C, 400°C to 600°C, 400°C to 500°C, 500°C to 1,500°C, 500°C to 1,250°C, 500°C to 1,000°C, 500°C to 900°C, 500°C to 800°C, 500°C to 700°C, 400°C to 600°C, 400°C to 500°C, 500°C to 1,500°C, 500°C to 1,250°C, 500°C to 1,000°C, 500°C to 900°C, 500°C to 1,250°C, 500°C to 1,000°C, 500°C to 800°C, 500°C to 700°C, 500°C to 600°C, 600°C to 1,500°C, 600°C to 1,250°C, 600°C to 1,000°C). Temperatures of 0°C, 600°C to 900°C, 600°C to 800°C, 600°C to 700°C, 700°C to 1,500°C, 700°C to 1,250°C, 700°C to 1,000°C, 700°C to 900°C, 700°C to 800°C, 800°C to 1,500°C, 800°C to 1,250°C, 800°C to 1,000°C, 800°C to 900°C, 900°C to 1,500°C, 900°C to 1,250°C, 900°C to 1,000°C, 1,000°C to 1,500°C, 1,000°C to 1,250°C, or 1,250°C to 1,500°C.

[0109] This subject matter also relates to a method for digital printing on ceramic articles, the method comprising: (a) depositing a first glaze composition onto the ceramic article; (b) depositing an ink composition comprising the above composition onto the ceramic article while the glaze composition is still wet; and (c) heating the ceramic article such that the mixed metal oxide ceramic pigment exhibits its full color intensity and / or hue. In some embodiments, the first glaze composition comprises water. In some embodiments, the method comprises depositing a second glaze composition onto the ink composition while at least the ink composition is still wet prior to the heating. In some embodiments, the deposition of the second glaze composition onto the ink composition is performed while both the ink composition and the first glaze composition are still wet. In some embodiments, the second glaze composition comprises water. In some embodiments, the second glaze composition is the same as the first glaze composition. In some embodiments, the second glaze composition is different from the first glaze composition. In some embodiments, the heating comprises heating the ceramic article to a temperature 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 some embodiments, the heating includes heating the ceramic article to 600°C to 1,500°C (such as 600°C to 1,250°C, 600°C to 1,000°C, 600°C to 900°C, 600°C to 800°C, 600°C to 700°C, 700°C to 1,500°C, 700°C to 1,250°C, 700°C to 1,000°C, 700°C to 900°C). Temperatures ranging from 700°C to 800°C, 800°C to 1,500°C, 800°C to 1,250°C, 800°C to 1,000°C, 800°C to 900°C, 900°C to 1,500°C, 900°C to 1,250°C, 900°C to 1,000°C, 1,000°C to 1,500°C, 1,000°C to 1,250°C, or 1,250°C to 1,500°C.

[0110] Ceramic articles encompass a wide variety of usable and decorative items formed from clay and porcelain, which acquire additional strength through elevated temperature treatment (such as from about 400°C to about 1200°C). This elevated temperature treatment melts the inorganic material, thereby providing additional mechanical strength and / or resistance to liquids. Ceramic articles can include, but are not limited to, tiles, cups, jars, earthenware pots, other storage containers, bowls, plates, utensils, jewelry, bricks, etc., of various sizes and shapes. Ceramic articles can be intended for interior residential use or for exterior purposes, such as in building construction.

[0111] Glassware includes both functional and decorative glass products. Glass differs from ceramics in that ceramics are typically at most translucent, while glass (unless heavily colored) is usually transparent at a thickness of about 0.5 mm, allowing reading number 10 through glass panes under normal sunlight conditions. Glassware can have a high concentration of silica, such as at least 50% by weight based on the entire glass portion of the product. Examples of glass compositions include lead oxide glass with 59 wt% silica, 2 wt% Na₂O, 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% Al₂O₃; soda-lime-silica window glass with about 72 wt% silica, 14.2 wt% Na₂O, 25 wt% MgO, 10 wt% CaO, and 0.6 wt% Al₂O₃; and fused silica glass with 95+ wt% silica. Glass articles may include, but are not limited to, window panes (including curved and non-flat panes), tubes, vials, bottles, beakers, flasks, glass, cups, plates, bowls, plates, lenses, vessels, jars, spheres / spheres, etc.

[0112] The subject matter disclosed herein can be better understood by referring to the following embodiments, which are only used to further illustrate the subject matter disclosed herein. The exemplary embodiments should not be construed as limiting the subject matter in any way.

[0113] Comparative Example 1: Ingredients: Carbosperse ™ K752 - Polyacrylic acid MW 2000, a 63% solution of active material in water, produced by Lubrizol; polyetheramine A - MW1650, a polyetheramine (derived from C...). 12-15 The reaction of alcohol with propylene oxide, followed by base-catalyzed addition of the resulting polyether alcohol to acrylonitrile, and subsequent hydrogenation to yield an amine (85% active material); and polyether alcohol A-MW1570 (derived from C... 12-15 (Reaction of alcohol with propylene oxide). Carbosperse ™ K752 (24.52 parts), polyetheramine A (22.6 parts), and polyether alcohol A (84.27 parts) were heated to 120°C under nitrogen atmosphere using a trap assembled with the reaction vessel for 2 hours. The temperature was then increased to 140°C and held for 3 hours. The temperature was then increased to 180°C and held for another 24 hours, resulting in a brown liquid.

[0114] Comparative Example 2: 23.21 parts of polyacrylic acid (Carbosperse K752, from Lubrizol, molecular weight 2000, 63% active solids in water solution), 20.70 parts of polyetheramine (Surfonamine L207, from Huntsman, molecular weight 2000), and 80.01 parts of polypropylene glycol monobutyl ether (from Sigma-Aldrich, molecular weight 1000) were heated to 80°C under nitrogen atmosphere for 1 hour. The reaction mixture was then heated to 140°C for 3 hours using an attached Dean-Stark condenser to remove water. The reaction temperature was then increased to 180°C and maintained for 24 hours. An amber liquid was obtained, with Mn = 10540 and Mw = 26180, as determined by gel permeation chromatography against the polystyrene standard in tetrahydrofuran (doped with 1% acetic acid).

[0115] Comparative Example 3: 61.9 parts of polyether alcohol from MW1600 (derived from the reaction of a C12-15 alcohol with propylene oxide), 7.57 parts of 1,2,4-benzenetricarboxylic anhydride, and 0.7 parts of orthophosphoric acid were combined and heated to 120°C under nitrogen with stirring and a condenser. After 24 hours, 7.96 parts of polyether amine from MW1650 (derived from the reaction of a C12-15 alcohol with propylene oxide, followed by base-catalyzed addition of the resulting polyether alcohol to acrylonitrile, and subsequent hydrogenation to give an amine (85% active material)) were added. After 3 hours, the condenser was removed. After 16.5 hours, a clear brown liquid with an acid value of 62.85 mg KOH / g was obtained.

[0116] Comparative Example 4: 25 parts of polyacrylic acid (Carbosperse K752, from Lubrizol, molecular weight 2000, 63% active solids in water solution), 21.58 parts of polyetheramine (Surfonamine L207, from Huntsman, molecular weight 2000), and 53.95 parts of poly(ethylene glycol) methyl ether (from Ineos, molecular weight 1000) were heated to 80°C under nitrogen cover for 1 hour. The reaction mixture was then heated to 140°C for 3 hours using an attached Dean-Stark condenser to remove water. The reaction temperature was then increased to 180°C and maintained for 24 hours. An amber liquid was obtained with an acid value of 26.1 mg KOH g. -1 .

[0117] Comparative Example 5: 25 parts of polyacrylic acid (Carbosperse K752, from Lubrizol, molecular weight 2000, 63% active solids in water solution), 21.6 parts of polyetheramine (Surfonamine B200, from Huntsman, molecular weight 2000), and 53.99 parts of polypropylene glycol monobutyl ether (from Sigma-Aldrich, molecular weight 1000), were heated to 80°C under nitrogen cover for 1 hour. The reaction mixture was then heated to 140°C for 3 hours using an attached Dean-Stark condenser to remove water. The reaction temperature was then increased to 180°C and maintained for 24 hours. An amber liquid was obtained with an acid value of 33.7 mg KOH g. -1 .

[0118] Intermediate A: 500 mwt (70.0 parts) of polyethylene glycol monomethyl ether, ε-caprolactone (91.08 parts), and δ-valerolactone (91.11 parts) were stirred at 120°C for 1 hour under nitrogen atmosphere. A solution of 80% zirconium butoxide (IV) in 1-butanol (0.95 parts) was added, and the reaction was heated to 180°C for 18 hours. An amber liquid was obtained, wherein Mn = 2660 and Mw = 3690, as determined by gel permeation chromatography against the polystyrene standard in tetrahydrofuran.

[0119] Intermediate B: 500 mwt (70.05 parts) of polyethylene glycol monomethyl ether, ε-caprolactone (91.14 parts), and L-lactide (90.82 parts) were stirred at 120°C for 1 hour under nitrogen atmosphere. A solution of 80% zirconium butoxide (IV) in 1-butanol (0.95 parts) was added, and the reaction was heated to 180°C for 18 hours. An amber liquid was obtained, wherein Mn = 2080 and Mw = 3140, as determined by gel permeation chromatography against the polystyrene standard in tetrahydrofuran.

[0120] Example 1: Polyacrylic acid (Carbosperse) ™ K752, produced by Lubrizol, molecular weight 2000, 63% active solids in water solution, 85.20 parts), polyetheramine (Surfonamine) ™ L207 (from Huntsman, molecular weight 2000, 60.19 parts) and polyalkylene glycol (Synalox) ™50-30B (from Dow, molecular weight 1000, 265.08 parts) was heated to 80°C under nitrogen cover for 1 hour. The reaction mixture was then heated to 140°C for 3 hours using an attached Dean-Stark condenser to remove water. The reaction temperature was then increased to 180°C and maintained for 24 hours. An amber liquid with an acid value of 27.9 mg KOH / g was obtained.

[0121] Example 2: Polyacrylic acid (Carbosperse) ™ K732, produced by Lubrizol, molecular weight 6000, 50% active solids in water solution, 105.15 parts), polyetheramine (Surfonamine) ™ L207 (from Huntsman, molecular weight 2000, 62.39 parts) and polyalkylene glycol (Synalox) ™ 50-30B (from Dow, molecular weight 1000, 270.10 parts) was heated to 80°C under nitrogen cover for 1 hour. The reaction mixture was then heated to 140°C for 3 hours using an attached Dean-Stark condenser to remove water. The reaction temperature was then increased to 180°C and maintained for 24 hours. An amber liquid was obtained with an acid value of 24.9 mg KOH / g.

[0122] Example 3: Polyacrylic acid (Carbosperse) ™ K752, produced by Lubrizol, molecular weight 2000, 63% active solids in water solution, 101.13 parts), polyetheramine (Surfonamine) ™ L207 (from Huntsman, molecular weight 2000, 91.85 parts) and polyalkylene glycol (Synalox) ™ 55-70B (from Dow, molecular weight 1600, 352.21 parts) was heated to 80°C under nitrogen cover for 1 hour. The reaction mixture was then heated to 140°C for 3 hours using an attached Dean-Stark condenser to remove water. The reaction temperature was then increased to 180°C and maintained for 24 hours. An amber liquid with an acid value of 26.0 mg KOH / g was obtained.

[0123] Example 4: Polyacrylic acid (Carbosperse) ™ K732, produced by Lubrizol, molecular weight 6000, 50% active solids in water solution, 127.45 parts), polyetheramine (Surfonamine) ™ L207 (from Huntsman, molecular weight 2000, 90.80 parts) and polyalkylene glycol (Synalox) ™55-70B (from Dow, molecular weight 1600, 354.02 parts) was heated to 80°C under nitrogen cover for 1 hour. The reaction mixture was then heated to 140°C for 3 hours using an attached Dean-Stark condenser to remove water. The reaction temperature was then increased to 180°C and maintained for 24 hours. An amber liquid was obtained with an acid value of 33.25 mg KOH / g.

[0124] Example 5: 20 parts of polyacrylic acid (Carbosperse K752, from Lubrizol, molecular weight 2000, 63% active solids in water solution), 17.95 parts of polyetheramine (Surfonamine L207, from Huntsman, molecular weight 2000), and intermediate A (78.64 parts) were heated to 80°C under nitrogen sealing for 1 hour. The reaction mixture was then heated to 140°C for 3 hours using an attached Dean-Stark condenser to remove water. The reaction temperature was then increased to 180°C and maintained for 24 hours. An amber liquid was obtained with an acid value of 27.5 mg KOH g. -1 .

[0125] Example 6: 20 parts of polyacrylic acid (Carbosperse K752, from Lubrizol, molecular weight 2000, 63% active solids in water solution), 17.95 parts of polyetheramine (Surfonamine L207, from Huntsman, molecular weight 2000), and intermediate B (78.64 parts) were heated to 80°C under nitrogen sealing for 1 hour. The reaction mixture was then heated to 140°C for 3 hours using an attached Dean-Stark condenser to remove water. The reaction temperature was then increased to 180°C and maintained for 24 hours. An amber liquid was obtained with an acid value of 39.8 mg KOH g. -1 .

[0126] In a 30 mL wide-mouth flask, Comparative Examples 1 to 2 and Examples 1 to 4 (0.3 parts) were dissolved in tris(propylene glycol) methyl ether (a mixture of isomers, dowanol TPM, 4.7 parts). Then, pigment Beige 36032 (from Colorobbia, 5 parts) was added, followed by borosilicate glass beads (1 mm diameter, 28 parts). The contents were then ground for 60 minutes at 60 Hz with an acceleration of 90 gravitational equivalents on a LabRAM II sonic stirrer (from Resodyne). The physical form of the resulting ground material was then observed, with fluid ground materials considered acceptable, and recorded in Table 1.

[0127] Table 1

[0128]

[0129] Grinding material preparation

[0130] In a 30 mL wide-mouth flask, Comparative Examples 3 to 4 and Examples 5 to 6 (0.3 parts) were dissolved in tris(propylene glycol) methyl ether (a mixture of isomers, dowanol TPM, 4.7 parts). Then, pigment Beige 36032 (from Colorobbia, 5 parts) was added, followed by borosilicate glass beads (1 mm diameter, 17 parts). The contents were then ground for 60 minutes at 60 Hz with an acceleration of 90 gravitational equivalents on a LabRAM II sonic stirrer (from Resodyne). The physical form of the resulting ground material was then observed, with fluid ground materials considered acceptable, as recorded in Table 2.

[0131] Table 2

[0132]

[0133] Water compatibility

[0134] Then 15% by weight of distilled water was added to each of the resulting grinding media (i.e., 1.5 g of water was added to 10 g of grinding media), and the mixture was stirred manually. The mixture was then transferred to a petri dish and evidence of agglomeration and an increase in viscosity after 10 minutes were observed. Acceptance was defined as no change in flow across the petri dish or a lack of homogeneity observed in the grinding media, and failure was defined as a significant increase in viscosity to form an obvious gel and / or a splitting of the material to form two layers, as recorded in Table 3.

[0135] Table 3

[0136]

[0137] Unless explicitly stated in the examples or otherwise, or required by the context, all numerical quantities of substances, reaction conditions, molecular weights, number of carbon atoms, etc., specified in this specification should be understood to be modified by the word “about.” As used herein, the term “about” means that the value of a given quantity is within ±20% of the specified value. In other embodiments, the value is within ±15% of the specified value. In other embodiments, the value is within ±10% of the specified value. In other embodiments, the value is within ±5% of the specified value. In other embodiments, the value is within ±2.5% of the specified value. In other embodiments, the value is within ±1% of the specified value. In other embodiments, the value is implemented in a composition substantially similar to that including the literal amounts described herein, within the range of explicitly described values ​​that will be understood by one of ordinary skill in the art based on the disclosure provided herein.

[0138] It should be understood that the upper and lower limits of the quantities, ranges, and ratios described herein can be combined independently, and any quantity within the disclosed range is considered to provide a minimum or maximum value within a narrower range in alternative embodiments (provided, of course, that the minimum quantity of the range must be lower than the maximum quantity of the same range). Similarly, the ranges and quantities of each element of the subject matter disclosed herein can be used in conjunction with the ranges or quantities of any other element.

[0139] 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 the art that various changes and modifications can be made therein without departing from the scope of the subject matter. In this regard, the scope of the invention is defined only by the following claims.

Claims

1. A composition comprising: a. A water-compatible liquid organic medium; b. A mixed metal oxide ceramic pigment in particulate form that exhibits its full color intensity and / or hue after firing at elevated temperatures; and c. At least the reaction products of reactant A, reactant B, and reactant C; The reactant A is represented by the following general formula (A): (A) in, For each molecule of reactant A independently: R 1 It is a terminal group; R 2 Each repeating unit is independently either H or COOH; R 3 Each repeating unit is independently H, CH3, or CH2COOH; R 4 For each repeating unit, independently H or C1 to C 36 hydrocarbon group; R 5 For each repeating unit, independently H or C1 to C 36 hydrocarbon group; R 6 It is a terminal group; n is an integer between 10 and 1400; and m is 0, or an integer from 1 to 140; Where R is in the repeating unit 2 When R is COOH, in the repeating unit 3 For H; and in, If m is not 0, then n is at least 10 times m; The reactant B is represented by the following general formula (B): (B) Wherein, for each molecule of reactant B independently: R 7 It consists of C1 to C4 hydrocarbon groups; R 8 For each repeating unit to be independently H or CH3, the condition is R 8 H is present in at least 70% of the repeating units; R 9 It is a C1 to C4 hydrocarbon group; and z is an integer between 10 and 80; The reactant C is represented by the following general formula (C): (C) Wherein, for each molecule of reactant C independently: R 10 It consists of C1 to C4 hydrocarbon groups; R 11 For each repeating unit to be independently H or CH3, the condition is R 11 H is present in at least 40% of the repeating units; R 12 Each repeating unit is independently a C1 to C5 hydrocarbon group; x is an integer between 6 and 50; and y is 0, or an integer from 1 to 20, provided that R 11 When H is in a 100% repeating unit, y is greater than 0; In this reaction, 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 The reactant A is present in an amount of 10% to 25% by weight, the reactant B is present in an amount of 10% to 40% by weight, and the reactant C is present in an amount of 40% to 80% by weight, all based on the total weight of reactants A, B, and C.

2. The composition according to claim 1, wherein, based on the total weight of the composition, the composition comprises 20% to 79% by weight of the liquid organic medium.

3. The composition according to any one of claims 1 or 2, wherein the composition comprises 20% to 60% by weight of the mixed metal oxide ceramic pigment based on the total weight of the composition.

4. The composition according to any one of claims 1 to 3, wherein the composition comprises 1% to 20% by weight of the reaction product based on the total weight of the composition.

5. The composition according to any one of claims 1 to 4, wherein R 2 For H.

6. The composition according to any one of claims 1 to 5, wherein R 3 For H.

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

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

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

10. The composition according to any one of claims 1 to 9, wherein in at least 15% of the repeating units, y is 0 and R 11 It is CH3.

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

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

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

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

15. A method for digital printing on ceramic articles, the method comprising: a. Depositing the first glaze composition onto the ceramic article; b. While the glaze composition is still wet, deposit an ink composition comprising the composition according to any one of claims 1 to 14 onto the ceramic article; and c. Heat the ceramic article so that the mixed metal oxide ceramic pigment exhibits its full color intensity and / or hue.

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

17. The method of claim 16, wherein the second glaze composition is deposited onto the ink composition while both the ink composition and the first glaze composition are still wet.

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

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

Images