Neutralized multiamine dispersant composition

Abstract

Compositions are described that include: (a) a polymeric dispersant that includes (i) an average of at least two polyether pendant groups per molecule, and (ii) an average of at least two amine groups per molecule, and (b) a functionalized acid component that includes a sulfonic acid and / or a phosphoric acid functionalized with at least one of an aromatic or an aliphatic functional group, wherein at least about 60 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component. Pigment dispersions and ink formulations that include these compositions are also described, as well as various methods of making and / or using the compositions, pigment dispersions, and / or ink formulations.

Description

[Technical field]

[0001] The disclosed technology relates to compositions comprising polymeric dispersants having an average of at least two amine groups per molecule that are at least partially neutralized (e.g., basified) with a functionalized acid moiety. Pigment dispersions and ink formulations comprising these compositions, as well as methods of making and / or using these materials, are also described. [Background technology]

[0002] Many conventional packaging inks are made around a common formulation of pigment, binder, adhesion promoter, and solvent. Exemplary ink formulations are described, for example, in JP 2017-39896(A). In many cases, the binder acts as a dispersing aid and prevents re-agglomeration of pigment particles after grinding. However, in other cases, the use of custom dispersants significantly improves ink properties such as stability, pigment content, and color development. In general, polymeric dispersants can be acid-functional, amine-functional, or non-ionic. However, due to compatibility issues that can occur when using amine-functional dispersants with other formulation ingredients in the formulation, non-ionic or acid-based dispersants have been used in this application.

[0003] An important pigment used in packaging inks is Pigment Yellow 13. To disperse Yellow 13 using a polymeric dispersant, it has been observed that it is highly preferred that the functional group of the dispersant contains an amine group, providing sufficient anchorage of the dispersant to the pigment surface. One binder used in packaging inks is nitrocellulose, for example, as seen in WO 2018-199802(A), and it has been found that amine-functional dispersants interact adversely with this binder, resulting in gel formation over time, which is devastating for a fully formulated ink composition. Similarly, organometallic complexes such as titanates have a long history in the formulation of packaging inks to provide adhesion to low surface energy substrates such as polyethylene or oriented polypropylene when used in combination with a binder, for example, as seen in WO 2012 / 028882(A1). However, organometallic complexes are highly susceptible to undesirable reactions with amine-functional dispersants, again forming gels and / or increasing viscosity.

[0004] Polymeric dispersants having multiple amine groups are described, for example, in the following documents: U.S. Patent Nos. 7,767,750 (B2), 8,859,675 (B2), 8,987,374 (B2), and 9,416,280 (B2). These documents do not disclose polymeric dispersants having an average of at least two amine groups per molecule, wherein at least about 60 percent of the amine groups present in the polymeric dispersant are each individually neutralized (e.g., basified) with a molecule of a functionalized acid component. The disclosed technology thus provides compositions comprising a polymeric dispersant having an average of at least two amine groups per molecule, where at least about 60 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of a functionalized acid component as described herein. These compositions, by using sulfonate or phosphate counterions to form amine salts, have been found to at least partially alleviate problematic interactions that amine-functionalized dispersants may have with other formulation ingredients, resulting in suitable performance with certain formulation ingredients, such as additives (e.g., organometallic complexes) and / or binders (e.g., nitrocellulose). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2017-39896 A [Patent Document 2] JP 2018-199802 A [Patent Document 3] International Publication No. 2012 / 028882 [Patent Document 4] U.S. Patent No. 7,767,750 [Patent Document 5] U.S. Patent No. 8,859,675 [Patent Document 6] U.S. Pat. No. 8,987,374 [Patent Document 7] U.S. Patent No. 9,416,280 Summary of the Invention

[0006] The subject matter disclosed herein provides a composition comprising: (a) a polymeric dispersant comprising: (i) an average of at least two polyether pendant groups per molecule, where the at least two polyether pendant groups are composed of monomeric units, where at least half of the monomeric units are poly(ethylene oxide) and / or poly(propylene oxide) monomeric units, and where the at least two polyether pendant groups comprise at least 50 weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant; and (ii) an average of at least two amine groups per molecule, where the at least two amine groups are not present in the at least two polyether pendant groups; and (b) a functionalized acid component comprising a sulfonic acid and / or a phosphoric acid functionalized with at least one of an aromatic or an aliphatic functional group, where at least about 60 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component.

[0007] Also provided is a pigment dispersion comprising: (a) a pigment; (b) a polymeric dispersant for the pigment comprising: (i) an average of at least two polyether pendant groups per molecule, where the at least two polyether pendant groups are composed of monomer units, where at least half of the monomer units are poly(ethylene oxide) monomer units and / or poly(propylene oxide) monomer units, and where the at least two polyether pendant groups constitute at least 50 weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant; and (ii) an average of at least two amine groups per molecule, where the at least two amine groups are not present in the at least two polyether pendant groups; and (c) a functionalized acid component comprising a sulfonic acid and / or a phosphoric acid functionalized with at least one of an aromatic or an aliphatic functional group, where at least about 60 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component.

[0008] Also provided is an ink formulation that includes: (a) the pigment dispersion described herein; (b) a solvent; (c) a binder; and (d) at least one additional additive.

[0009] 1. A method of making a pigment dispersion, comprising the steps of combining, in any order, a pigment, a polymeric dispersant for the pigment, and a functionalized acid component, and the optional step of grinding the pigment, wherein: (a) the polymeric dispersant comprises (i) an average of at least two polyether pendant groups per molecule, the at least two polyether pendant groups being composed of monomeric units, at least half of the monomeric units being poly(ethylene oxide) monomeric units and / or poly(propylene oxide) monomeric units, the at least two polyether pendant groups comprising at least 50 weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant; and (ii) an average of Also provided is a method of preparing a pigment comprising: (a) a pigment having a pigment pendant group and a functionalized acid component; and (b) a functionalized acid component comprising a sulfonic acid and / or a phosphoric acid functionalized with at least one of an aromatic or an aliphatic functional group; (c) at least about 60 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component; and (d) an optional step of grinding the pigment is (i) not performed, (ii) performed on the pigment alone prior to addition of the polymeric dispersant and / or the functionalized acid component, or (iii) performed on a combination of the pigment and the polymeric dispersant and / or the functionalized acid component.

[0010] Also provided is a method of making an ink formulation comprising, in order: (a) carrying out the method of forming a pigment dispersion described herein; and (b) adding the following formulation ingredients to the pigment dispersion: (i) a solvent, (ii) a binder, and (iii) at least one additional additive. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The following embodiments of the present subject matter are contemplated.

[0012] 1. A composition comprising: (a) a polymeric dispersant comprising: (i) an average of at least two polyether pendant groups per molecule, where the at least two polyether pendant groups are composed of monomeric units, where at least half of the monomeric units are poly(ethylene oxide) and / or poly(propylene oxide) monomeric units, and where the at least two polyether pendant groups constitute at least 50 weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant; and (ii) an average of at least two amine groups per molecule, where at least two amine groups are not present in the at least two polyether pendant groups; and (b) a functionalized acid component comprising a sulfonic acid and / or a phosphoric acid functionalized with at least one of an aromatic or an aliphatic functional group, where at least 60 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component.

[0013] 2. The composition of embodiment 1, wherein the polymeric dispersant contains an average of 2 to 200 polyether pendant groups per molecule.

[0014] 3. The composition of any one of the preceding embodiments, wherein from 50% to substantially all of the monomeric units of the polyether pendant groups are poly(ethylene oxide) and / or poly(propylene oxide) monomeric units.

[0015] 4. The composition according to any one of embodiments 1 to 3, wherein the ratio of the number of poly(ethylene oxide) monomer units to the number of poly(propylene oxide) monomer units is from 0:100 to 90:10.

[0016] 5. The composition of any one of the preceding embodiments, wherein the polyether pendant groups comprise at least 65 percent by weight of the polymeric dispersant, based on the total weight of the polymeric dispersant.

[0017] 6. The composition of any one of the preceding embodiments, wherein the polymeric dispersant contains an average of 2 to 500 amine groups per molecule.

[0018] 7. The composition of any one of the preceding embodiments, wherein the functionalized acid component comprises a sulfonic acid functionalized with at least one of an aromatic or an aliphatic functional group.

[0019] 8. The composition of any one of the preceding embodiments, wherein the functionalized acid component comprises dodecylbenzenesulfonic acid.

[0020] 9. The aromatic functional group is an optionally substituted C6-C 10 The composition of any one of embodiments 1 to 8, wherein the group is aromatic.

[0021] 10. The aliphatic functional group is a linear or branched, saturated or unsaturated C8-C 22 The composition of any one of embodiments 1 to 9, wherein the group is a hydrocarbon group.

[0022] 11. The functionalized acid component comprises at least one compound according to the general formula: [ka] In the formula, R 1 Linear or branched, saturated or unsaturated, C8-C 22 is a hydrocarbon group, R 2 Aromatic functional groups, optionally substituted C6-C 10 7. The composition of any one of embodiments 1-6, wherein: m is an aromatic group; W is phosphorus or sulfur; m is 1 or 2; when W is sulfur, m is 1 or 2; when W is phosphorus, m is 1; n is 1 or 2; when W is sulfur, n is 1; when W is phosphorus, n is 2; s is 0 or 1; and t is 0 or 1, with the proviso that s and t cannot both be 0.

[0023] 12. The composition of embodiment 11, wherein W is sulfur.

[0024] 13. The composition of embodiment 11 or 12, wherein s is 1 and t is 1.

[0025] 14. The composition of any one of the preceding embodiments, wherein at least about 75 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component.

[0026] 15. The composition of any one of the preceding embodiments, wherein at least about 95 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component.

[0027] 16. A pigment dispersion comprising: (a) a pigment; and (b) a polymeric dispersant for the pigment comprising: (i) an average of at least two polyether pendant groups per molecule, where the at least two polyether pendant groups are composed of monomer units, where at least half of the monomer units are poly(ethylene oxide) monomer units and / or poly(propylene oxide) monomer units, and where the at least two polyether pendant groups constitute at least 50 weight percent of the polymeric dispersant based on the total weight of the polymeric dispersant; and (ii) an average of at least two amine groups per molecule, where the at least two amine groups are not present in the at least two polyether pendant groups; and (b) a functionalized acid component comprising a sulfonic acid and / or a phosphoric acid functionalized with at least one of an aromatic or an aliphatic functional group, where at least 60 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component.

[0028] 17. The pigment dispersion according to embodiment 16, wherein the polymeric dispersant contains an average of 2 to 200 pendant polyether groups per molecule.

[0029] 18. The pigment dispersion according to embodiment 16 or 17, wherein from 50% to substantially all of the monomer units of the polyether pendant groups are poly(ethylene oxide) and / or poly(propylene oxide) monomer units.

[0030] 19. The pigment dispersion according to any one of embodiments 16 to 18, wherein the ratio of the number of poly(ethylene oxide) monomer units to the number of poly(propylene oxide) monomer units is from 0:100 to 90:10.

[0031] 20. The pigment dispersion according to any one of embodiments 16 to 19, wherein the polyether pendant groups constitute at least 65 percent by weight of the polymeric dispersant, based on the total weight of the polymeric dispersant.

[0032] 21. The pigment dispersion of any one of embodiments 16 to 20, wherein the polymeric dispersant contains an average of 2 to 500 amine groups per molecule.

[0033] 22. The pigment dispersion of any one of embodiments 16 to 21, wherein the functionalized acid component comprises a sulfonic acid functionalized with at least one of an aromatic or an aliphatic functional group.

[0034] 23. The pigment dispersion of any one of embodiments 16 to 22, wherein the functionalized acid component comprises dodecylbenzenesulfonic acid.

[0035] 24. The aromatic functional group is an optionally substituted C6-C 10 24. The pigment dispersion of any one of embodiments 16 to 23, wherein the group is aromatic.

[0036] 25. The aliphatic functional group is a linear or branched, saturated or unsaturated C8-C 22 25. The pigment dispersion of any one of embodiments 16 to 24, wherein the group is a hydrocarbon group.

[0037] 26. The functionalized acid component comprises at least one compound according to the following general formula: [ka] In the formula, R 1 Linear or branched, saturated or unsaturated, C8-C 22 is a hydrocarbon group, R 2 Aromatic functional groups, optionally substituted C6-C 10 26. The pigment dispersion of any one of embodiments 16 to 25, wherein: m is an aromatic group; W is phosphorus or sulfur; m is 1 or 2; when W is sulfur, m is 1 or 2; when W is phosphorus, m is 1; n is 1 or 2; when W is sulfur, n is 1; when W is phosphorus, n is 2; s is 0 or 1; and t is 0 or 1, with the proviso that s and t cannot both be 0.

[0038] 27. The pigment dispersion according to embodiment 26, wherein W is sulfur.

[0039] 28. The pigment dispersion according to embodiment 26 or 27, wherein s is 1 and t is 1.

[0040] 29. The pigment dispersion according to any one of embodiments 16 to 28, wherein at least about 75 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component.

[0041] 30. The pigment dispersion according to any one of embodiments 16 to 29, wherein at least about 95 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component.

[0042] 31. An ink formulation comprising: (a) the pigment dispersion of any one of embodiments 16 to 30; (b) a solvent; (c) a binder; and (d) at least one additional additive.

[0043] 32. The ink formulation of embodiment 31, wherein the solvent is a polar solvent.

[0044] 33. The ink formulation of embodiment 31 or 32, wherein the binder is a polymeric binder.

[0045] 34. The ink formulation of any one of embodiments 31-33, wherein the at least one additional additive comprises 1 to 5 additional additives.

[0046] 35. The ink formulation of any one of embodiments 31-34, wherein the at least one additional additive comprises at least one of a humectant, a stabilizer, an adhesion promoter, a wax, or a defoamer.

[0047] 36. A method of producing a pigment dispersion, comprising combining, in any order, a pigment, a polymeric dispersant for the pigment, and a functionalized acid component, and optionally grinding the pigment, wherein (a) the polymeric dispersant comprises (i) an average of at least two polyether pendant groups per molecule, the at least two polyether pendant groups being composed of monomeric units, at least half of the monomeric units being poly(ethylene oxide) monomeric units and / or poly(propylene oxide) monomeric units, the at least two polyether pendant groups comprising at least 50 weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant, and (ii) and (b) the functionalized acid component comprises a sulfonic acid and / or a phosphoric acid functionalized with at least one of an aromatic or an aliphatic functional group, (c) at least 60 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component, and (d) the optional step of grinding the pigment is (i) not performed, (ii) performed on the pigment alone prior to addition of the polymeric dispersant and / or the functionalized acid component, or (iii) performed on a combination of the pigment and the polymeric dispersant and / or the functionalized acid component.

[0048] 37. The method of embodiment 36, wherein the polymeric dispersant and the functionalized acid component are combined prior to the addition of the pigment, and the optional step of grinding the pigment is carried out before or after the pigment is added to the combination of the polymeric dispersant and the functionalized acid component.

[0049] 38. The method of embodiment 36, wherein the polymeric dispersant and the pigment are combined, the optional step of grinding the pigment is performed on the combination of the polymeric dispersant and the pigment, and then the functionalized acid component is added to the pigment composition.

[0050] 39. The method of any one of embodiments 36 to 38, wherein the polymeric dispersant contains an average of 2 to 200 polyether pendant groups per molecule.

[0051] 40. The method of any one of embodiments 36-39, wherein from 50% to substantially all of the monomeric units of the polyether pendant groups are poly(ethylene oxide) and / or poly(propylene oxide) monomeric units.

[0052] 41. The method of any one of embodiments 36 to 40, wherein the ratio of the number of poly(ethylene oxide) monomer units to the number of poly(propylene oxide) monomer units is 0:100 to 90:10.

[0053] 42. The method of any one of embodiments 36-41, wherein the polyether pendant groups constitute at least 65 weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant.

[0054] 43. The method of any one of embodiments 36 to 42, wherein the polymeric dispersant contains an average of 2 to 500 amine groups per molecule.

[0055] 44. The method of any one of embodiments 36-43, wherein the functionalized acid component comprises a sulfonic acid functionalized with at least one of an aromatic or an aliphatic functional group.

[0056] 45. The method of any one of embodiments 36-44, wherein the functionalized acid component comprises dodecylbenzenesulfonic acid.

[0057] 46. ​​Aromatic functional groups are optionally substituted C6-C 10 The method of any one of embodiments 36 to 45, wherein the group is aromatic.

[0058] 47. The aliphatic functional group is a linear or branched, saturated or unsaturated C8-C 22 The method of any one of embodiments 36 to 46, wherein the is a hydrocarbon group.

[0059] 48. The functionalized acid component comprises at least one compound according to the following general formula: [ka] In the formula, R 1 Linear or branched, saturated or unsaturated, C8-C 22 is a hydrocarbon group, R 2 Aromatic functional groups, optionally substituted C6-C 10 48. The method of any one of embodiments 36-47, wherein: m is an aromatic group; W is phosphorus or sulfur; m is 1 or 2; when W is sulfur, m is 1 or 2; when W is phosphorus, m is 1; n is 1 or 2; when W is sulfur, n is 1; when W is phosphorus, n is 2; s is 0 or 1; and t is 0 or 1, with the proviso that s and t cannot both be 0.

[0060] 49. The method of embodiment 48, wherein W is sulfur.

[0061] 50. The method of embodiment 48 or 49, wherein s is 1 and t is 1.

[0062] 51. The method of any one of embodiments 36-50, wherein at least about 75 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component.

[0063] 52. The method of any one of embodiments 36-59, wherein at least about 95 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component.

[0064] 53. A method of making an ink formulation comprising, in order: (a) carrying out the method of any one of embodiments 36-52 to form a pigment dispersion; and (b) adding the following formulation ingredients to the pigment dispersion: (i) a solvent, (ii) a binder, and (iii) at least one additional additive.

[0065] 54. The method of embodiment 53, wherein the solvent is a polar solvent.

[0066] 55. The method of embodiment 53 or 54, wherein the binder is a polymeric binder.

[0067] 56. The method of any one of embodiments 53-55, wherein the at least one additional additive comprises 1 to 5 additional additives.

[0068] 57. The method of any one of embodiments 53-56, wherein the at least one additional additive comprises at least one of a wetting agent, a stabilizer, an adhesion promoter, a wax, or an antifoaming agent.

[0069] Various features and embodiments of the present subject matter are described below, by way of non-limiting example.

[0070] As used herein, the indefinite article "a" / "an" is intended to mean one or more. As used herein, the phrase "at least one" means one or more 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 alternative embodiments may include only one of A, B, or C, or any mixture of two or more of A, B, and C.

[0071] As used herein, the term "substantially" means that a given quantity 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.

[0072] As used herein, the term "substantially free" means that a component does not contain the intentional addition of a material that the component is "substantially free of." For example, a component may contain "substantially free" material below the impurity level that may be the result of an incomplete chemical reaction and / or an unintended / undesirable (but perhaps unavoidable) reaction product.

[0073] 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, unrecited elements or method steps. However, in each occurrence of "comprising" herein, the term is also intended to encompass, as alternative embodiments, the phrases "consisting essentially of" and "consisting of," where "consisting" excludes any unspecified elements or steps, and "consisting essentially of" permits the inclusion of additional, unrecited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.

[0074] A composition is provided that includes: (a) a polymeric dispersant comprising: (i) an average of at least two polyether pendant groups per molecule, where the at least two polyether pendant groups are composed of monomeric units, where at least half of the monomeric units are poly(ethylene oxide) and / or poly(propylene oxide) monomeric units, and where the at least two polyether pendant groups constitute at least 50 weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant; and (ii) an average of at least two amine groups per molecule, where at least two amine groups are not present in the at least two polyether pendant groups; and (b) a functionalized acid component comprising a sulfonic acid and / or a phosphoric acid functionalized with at least one of an aromatic or an aliphatic functional group, where at least 60 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component. When describing an acid component functionalized with at least one of an aromatic or an aliphatic functional group herein, what is meant is that the acid component is functionalized with either an aromatic or an aliphatic functional group, and optionally, any of these functional groups are further functionalized with other types of functional groups. For example, the acid component can be functionalized with an aromatic functional group, and optionally, the aromatic functional group can be further functionalized with an aliphatic functional group, or vice versa.

[0075] As used herein, the term "polyether pendant group" refers to a polyether group attached to the backbone of a polymeric dispersant. In certain embodiments, the polyether pendant group may be created by joining together multiple alkylene oxide monomer units (e.g., ethylene oxide and / or propylene oxide monomer units), possibly in combination with other monomer units, via known methods to form a polyether group, and then attaching the polyether group to the backbone via known methods. This method of creating a polymeric dispersant provides the simplest conceptual understanding of what is meant by the terms "polyether pendant group" and "backbone."

[0076] In certain embodiments, it is possible to "grow" polyether pendant groups from the backbone of a polymeric dispersant by adding an alkylene oxide monomer unit (e.g., ethylene oxide and / or propylene oxide monomer unit) to the backbone, and then sequentially adding additional alkylene oxide monomer units (e.g., ethylene oxide and / or propylene oxide monomer units) to the first one to create the pendant group. (This method may result in a polymeric dispersant that is the same or very similar to that created in the method described in the previous paragraph.) In this context, the term "polyether pendant group" will be understood to mean the portion of the polymeric dispersant that begins with the first alkylene oxide monomer unit attached to the backbone and continues to the additional alkylene oxide monomer units attached to the first alkylene oxide monomer unit. The "backbone" is considered to be the portion of the polymeric dispersant that is not a polyether pendant group.

[0077] In either of the methods described in the previous two paragraphs, the polyether pendant group is terminated with a monomeric unit that remains relatively unreactive, as is well known in the art, compared to the monomeric units that make up the majority of the polyether pendant group. In certain embodiments, substantially all of the monomeric units of the polyether pendant group can be alkylene oxide monomeric units (e.g., ethylene oxide and / or propylene oxide monomeric units). By "substantially all" we mean that (i) all of the monomeric units of the polyether pendant group other than the terminal monomeric units are alkylene oxide monomeric units, and / or (ii) a minority of the monomeric units can be other than alkylene oxide monomeric units due to unintentional impurities in the monomeric units used to make the polyether pendant group.

[0078] As used herein, the terms "poly(alkylene oxide) monomer unit" and "alkylene oxide monomer unit" are used interchangeably. Similarly, the terms "poly(ethylene oxide) monomer unit" and "ethylene oxide monomer unit" are used interchangeably, and the terms "poly(propylene oxide) monomer unit" and "propylene oxide monomer unit" are used interchangeably. All of these terms refer to the individual monomer units that are joined together (directly or indirectly) to form the polyether pendant groups described herein.

[0079] In certain embodiments, the polymeric dispersant comprises an average of 2 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, or 55) to 200 (e.g., 190, 180, 170, 160, 150, 140, 130, 120, 110, 100, 95, 90, 85, 80, 75, 70, 65, or 60) polyether pendant groups per molecule. In certain embodiments, the polymeric dispersant comprises an average of 2 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100) to 200 (e.g., 190, 180, 170, 160, 150, 140, 130, 120, or 110) polyether pendant groups per molecule.

[0080] In certain embodiments, 50% to substantially all of the monomeric units of the polyether pendant group are poly(ethylene oxide) and / or poly(propylene oxide) monomeric units. In certain embodiments, substantially all of the monomeric units of the polyether pendant group are poly(ethylene oxide) and / or poly(propylene oxide) monomeric units. In certain embodiments, 50% (e.g., 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%) to 99% of the monomeric units of the polyether pendant group are poly(ethylene oxide) and / or poly(propylene oxide) monomeric units. In certain embodiments, 50% (e.g., 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90%) to 95% of the monomeric units of the polyether pendant group are poly(ethylene oxide) and / or poly(propylene oxide) monomeric units. In certain embodiments, 50% (e.g., 55%, 60%, 65%, 70%, 75%, 80%, or 85%) to 90% of the monomeric units of the polyether pendant group are poly(ethylene oxide) and / or poly(propylene oxide) monomeric units. In certain embodiments, 50% (e.g., 55%, 60%, 65%, 70%, 75%, or 80%) to 85% of the monomeric units of the polyether pendant group are poly(ethylene oxide) and / or poly(propylene oxide) monomeric units. In certain embodiments, 50% (e.g., 55%, 60%, 65%, 70%, or 75%) to 80% of the monomeric units of the polyether pendant group are poly(ethylene oxide) and / or poly(propylene oxide) monomeric units. In certain embodiments, 50% (e.g., 55%, 60%, 65%, or 70%) to 75% of the monomeric units of the polyether pendant group are poly(ethylene oxide) and / or poly(propylene oxide) monomeric units. In certain embodiments, 50% (e.g., 55%, 60%, or 65%) to 70% of the monomeric units of the polyether pendant group are poly(ethylene oxide) and / or poly(propylene oxide) monomeric units.In certain embodiments, 50% (e.g., 55%, or 60%) to 65% of the monomeric units of the polyether pendant group are poly(ethylene oxide) and / or poly(propylene oxide) monomeric units. In certain embodiments, 50% (e.g., 55%) to 60% of the monomeric units of the polyether pendant group are poly(ethylene oxide) and / or poly(propylene oxide) monomeric units. In certain embodiments, 50% to 55% of the monomeric units of the polyether pendant group are poly(ethylene oxide) and / or poly(propylene oxide) monomeric units.

[0081] In certain embodiments, the ratio of the number of poly(ethylene oxide) monomer units to the number of poly(propylene oxide) monomer units is 0:100 (e.g., 10:90, or 20:80) to 100:0 (e.g., 90:10, 80:20, 70:30, 60:40, 50:50, 40:60, or 30:70). In certain embodiments, the ratio of the number of poly(ethylene oxide) monomer units to the number of poly(propylene oxide) monomer units is 0:100, 10:90, 17:83, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, or 100:0.

[0082] In certain embodiments, the polyether pendant groups comprise at least 65 (e.g., 70, 75, 80, 85, 90, or 95) weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant. In certain embodiments, the polyether pendant groups comprise 65 (e.g., 70, 75, 80, 85, or 90) to 95 weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant. In certain embodiments, the polyether pendant groups comprise 65 (e.g., 70, 75, 80, or 85) to 90 weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant. In certain embodiments, the polyether pendant groups comprise 65 (e.g., 70, 75, or 80) to 85 weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant. In certain embodiments, the polyether pendant groups comprise 65 (e.g., 70, or 75) to 80 weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant. In certain embodiments, the polyether pendant groups comprise 65 (e.g., 70) to 75 weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant. In certain embodiments, the polyether pendant groups comprise 65 to 70 weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant. In certain embodiments, the polyether pendant groups comprise 65 (e.g., 70, 75, 80, 85, 90, or 95) weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant.

[0083] In certain embodiments, the polymeric dispersant has an average of 2 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, or 240) to 500 (e.g., 490, 480, 470, 460, 450, 440, 430, 420, 410, 400, 390, 380, 370, 360, 350, 340, 330, 320, 310, 300, 290, 280, 270, 260, or 250) amine groups. In certain embodiments, the polymeric dispersant has an average of 2 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, or 190) to 500 (e.g., 490, 480, 470, 460, 450, 440, 430, 420, 410, 400, 390, 380, 370, 360, 350, 340, 330, 320, 310, 300, 290, 280, 270, 260, 250, 240, 230, 220, 210, or 200) amine groups. In certain embodiments, the polymeric dispersant has an average of 2 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, or 290) to 500 (e.g., 490, 480, 470, 460, 450, 440, 430, 420, 410, 400, 390, 380, 370, 360, 350, 340, 330, 320, 310, or 300) amine groups.

[0084] In certain embodiments, the functionalized acid component comprises a sulfonic acid functionalized with at least one of an aromatic or an aliphatic functional group.

[0085] In certain embodiments, the functionalized acid component comprises dodecylbenzenesulfonic acid. An exemplary commercially available dodecylbenzenesulfonic acid is Maranil® DBS / LC available from BASF.

[0086] In certain embodiments, the aromatic functional group is an optionally substituted C-C 10 In certain embodiments, the aromatic functional group is a C-C 10 In certain embodiments, the aromatic functional group is a substituted C-C 10 In certain embodiments, the aromatic functional group is an optionally substituted C-C 10 In certain embodiments, the aromatic functional group is a C-C 10 In certain embodiments, the aromatic functional group is a substituted C-C 10 In certain embodiments, the aromatic functional group is an optionally substituted C6-C8 aromatic group. In certain embodiments, the aromatic functional group is a C6-C8 aromatic group. In certain embodiments, the aromatic functional group is a substituted C6-C8 aromatic group. In certain embodiments, the aromatic functional group is an optionally substituted C6 aromatic group. In certain embodiments, the aromatic functional group is a C6 aromatic group. In certain embodiments, the aromatic functional group is a substituted C6 aromatic group. In certain embodiments, the aromatic functional group is an optionally substituted C8 aromatic group. In certain embodiments, the aromatic functional group is a C8 aromatic group. In certain embodiments, the aromatic functional group is a substituted C8 aromatic group. In certain embodiments, the aromatic functional group is an optionally substituted C 10 In certain embodiments, the aromatic functional group is 10 In certain embodiments, the aromatic functional group is a substituted C 10 It is an aromatic group.

[0087] In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C-C 22In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C-C 20 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C-C 18 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C-C 16 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C-C 14 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C-C 12 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C-C 10 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C8 hydrocarbon group. In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 10 ~C 22 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 10 ~C 20 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 10 ~C 18 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 10 ~C 16 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 10 ~C 14 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 10 ~C 12 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 10 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 12 ~C 22In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 12 ~C 20 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 12 ~C 18 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 12 ~C 16 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 12 ~C 14 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 12 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 14 ~C 22 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 14 ~C 20 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 14 ~C 18 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 14 ~C 16 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 14 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 16 ~C 22 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 16 ~C 20 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 16 ~C 18 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 16In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 18 ~C 22 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 18 ~C 20 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 18 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 20 ~C 22 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 20 In certain embodiments, the aliphatic functional group is a linear or branched, saturated or unsaturated C 22 It is a hydrocarbon group.

[0088] In certain embodiments, the functionalized acid component comprises at least one compound according to the general formula: [ka] During the ceremony, R 1 is a linear or branched, saturated or unsaturated C8-C 22 is a hydrocarbon group (in an alternative embodiment, R 1 may be a hydrocarbon radical of one of the various embodiments described above; R 2 is an aromatic functional group, optionally substituted C6-C 10 is an aromatic group (in an alternative embodiment, R 2 may be one of the aromatic groups of the various embodiments described above; W is phosphorus or sulfur; m is 1 or 2; when W is sulfur, m is 1 or 2; when W is phosphorus, m is 1; n is 1 or 2, when W is sulfur, n is 1, and when W is phosphorus, n is 2; s is 0 or 1; t is 0 or 1; However, both s and t cannot be 0.

[0089] In certain embodiments, W is sulfur. In certain embodiments, W is phosphorus. In certain embodiments, W is sulfur, m is 1, and n is 1. In certain embodiments, W is sulfur, m is 2, and n is 1. In certain embodiments, W is phosphorus, m is 1, and n is 2.

[0090] In certain embodiments, s is 1 and t is 1. In certain embodiments, s is 0 and t is 1. In certain embodiments, s is 1 and t is 0.

[0091] In certain embodiments, at least 60 (e.g., 65, 70, 75, 80, 85, 90, or 95) percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component. In certain embodiments, substantially all of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component. In this context, "substantially all" means that the number of amine groups neutralized with molecules of the functionalized acid component is as high as is physically / chemically possible in the environment.

[0092] As present in the polymeric dispersant, each amine group may be independently primary, secondary, or tertiary. In certain embodiments, the presence of amine groups within the polyether pendant group may be undesirable as it may cause the polyether pendant group to prefer to associate with the pigment surface rather than be solvated in the liquid medium, or otherwise render the polyether pendant group unsuitable for the purpose of dispersing the pigment (associated with the backbone amine group) in the liquid medium.

[0093] Suitable polymeric dispersants according to the present subject matter are disclosed, for example, in U.S. Patent Nos. 7,767,750 (B2), 8,859,675 (B2), 8,987,374 (B2), and 9,416,280 (B2). It should be noted that these documents may disclose polymeric dispersants that are outside the broadest embodiment of the present subject matter. However, these documents disclose many embodiments of suitable polymeric dispersants that fall within the scope of the present subject matter, and are therefore exemplary of the polymeric dispersants described herein.

[0094] In certain embodiments, the compositions described above do not include materials that interfere with the neutralization of the amine groups with the functionalized acid component. In certain embodiments, materials that may interfere with the neutralization of the amine groups with the functionalized acid component are not added to the compositions described herein until the desired amount of neutralization has occurred.

[0095] Also provided is a pigment dispersion comprising: (a) a pigment; (b) a polymeric dispersant for the pigment, the polymeric dispersant comprising: (i) an average of at least two polyether pendant groups per molecule, the at least two polyether pendant groups being composed of monomer units, at least half of the monomer units being poly(ethylene oxide) monomer units and / or poly(propylene oxide) monomer units, the at least two polyether pendant groups comprising at least 50 weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant; and (ii) an average of at least two amine groups per molecule, the at least two amine groups being absent from the at least two polyether pendant groups; and (c) a functionalized acid component comprising a sulfonic acid and / or a phosphoric acid functionalized with at least one of an aromatic or an aliphatic functional group, wherein at least 60 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component. In certain embodiments, the pigment dispersion comprises (a) a pigment and (b) any one of the compositions previously described herein.

[0096] There is further provided an ink formulation comprising: (a) the pigment dispersion described hereinabove; (b) a solvent; (c) a binder; and (d) at least one additional additive.

[0097] In certain embodiments, the solvent is a polar solvent.

[0098] In certain embodiments, the binder is a polymeric binder.

[0099] In certain embodiments, the at least one additional additive comprises 1 to 5 additional additives.

[0100] In certain embodiments, the at least one additional additive comprises at least one of a wetting agent, a stabilizer, an adhesion promoter, a wax, or an antifoaming agent.

[0101] In certain embodiments, materials that may interfere with the neutralization of the amine groups with the functionalized acid component are not added to the ink formulations described herein until the desired amount of neutralization has occurred.

[0102] 1. A method of making a pigment dispersion, comprising the steps of combining, in any order, a pigment, a polymeric dispersant for the pigment, and a functionalized acid component, and the optional step of grinding the pigment, wherein: (a) the polymeric dispersant comprises (i) an average of at least two polyether pendant groups per molecule, the at least two polyether pendant groups being composed of monomeric units, at least half of the monomeric units being poly(ethylene oxide) monomeric units and / or poly(propylene oxide) monomeric units, the at least two polyether pendant groups comprising at least 50 weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant; and (ii) an average of Also provided is a method of preparing a pigment comprising: (a) a pigment having a pigment pendant group and a functionalized acid component; and (b) a functionalized acid component comprising a sulfonic acid and / or a phosphoric acid functionalized with at least one of an aromatic or an aliphatic functional group; (c) at least 60 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component; and (d) an optional step of grinding the pigment is (i) not performed, (ii) performed on the pigment alone prior to addition of the polymeric dispersant and / or the functionalized acid component, or (iii) performed on a combination of the pigment and the polymeric dispersant and / or the functionalized acid component.

[0103] In certain embodiments, the polymeric dispersant and the functionalized acid component are combined prior to the addition of the pigment, and the optional step of grinding the pigment is performed before or after the pigment is added to the combination of the polymeric dispersant and the functionalized acid component. In certain embodiments, the polymeric dispersant and the functionalized acid component are combined prior to the addition of the pigment, and the optional step of grinding the pigment is performed before or after the pigment is added to the combination of the polymeric dispersant and the functionalized acid component. In certain embodiments, the polymeric dispersant and the functionalized acid component are combined prior to the addition of the pigment, and the optional step of grinding the pigment is performed before the pigment is added to the combination of the polymeric dispersant and the functionalized acid component. In certain embodiments, the polymeric dispersant and the functionalized acid component are combined prior to the addition of the pigment, and the optional step of grinding the pigment is performed after the pigment is added to the combination of the polymeric dispersant and the functionalized acid component.

[0104] In certain embodiments, the polymeric dispersant and the pigment are combined, the optional step of grinding the pigment is performed on the combination of the polymeric dispersant and the pigment, and then the functionalized acid component is added to the pigment composition. In certain embodiments, the polymeric dispersant and the pigment are combined, the optional step of grinding the pigment is performed on the combination of the polymeric dispersant and the pigment, and then the functionalized acid component is added to the pigment composition.

[0105] In certain embodiments, the polymeric dispersant for the pigment and the functionalized acid component together may be comprised of any one of the compositions previously described herein.

[0106] There is further provided a method of making an ink formulation, the method comprising, in order: (a) carrying out the method for making a pigment dispersion described above to form a pigment dispersion; and (b) adding the following formulation ingredients to the pigment dispersion: (i) a solvent, (ii) a binder, and (iii) at least one additional additive.

[0107] In certain embodiments, the solvent is a polar solvent.

[0108] In certain embodiments, the binder is a polymeric binder.

[0109] In certain embodiments, the at least one additional additive comprises 1 to 5 additional additives.

[0110] In certain embodiments, the at least one additional additive comprises at least one of a wetting agent, a stabilizer, an adhesion promoter, a wax, or an antifoaming agent.

[0111] In certain embodiments of the methods described above, materials that may interfere with the neutralization of the amine groups with the functionalized acid component are not added to the ink formulations described herein until the desired amount of neutralization has occurred. Such materials may include resins, binders, and / or additional additives, as would be apparent to one skilled in the art. EXAMPLES

[0112] The subject matter disclosed herein may be better understood with reference to the following examples, which are provided merely to further illustrate the subject matter disclosed herein and are not to be construed as limiting the subject matter in any manner.

[0113] Comparative Example 1: Example 1, column 11, lines 35-57 of U.S. Patent No. 7,767,750(B2), issued Aug. 3, 2010 to inventor Dean Thetford and assignee The Lubrizol Corporation.

[0114] Comparative Example 2: Intermediate A was made by charging 200 parts of SURFONAMINE® B-200 polyetheramine (from Huntsman International LLC) with 11.6 parts of 2-hydroxyethyl acrylate and 0.03 parts of 2,6-di-tertbutyl-4-methylphenol to a reaction vessel, followed by stirring at 70° C. for 48 hours. 250 parts of ethyl acetate and 67.6 parts of tolylene-2,4-diisocyanate were charged to a separate reaction vessel under nitrogen, followed by stirring and charging 289.7 parts of Intermediate A and 125 parts of ethyl acetate over 10 minutes. Then 15.78 parts of 1,1′-((3-(dimethylamino)propyl)imino)bis(2-propanol) and 32.55 parts of ethyl acetate were charged to the vessel over 10 minutes. The mixture was then heated to 65° C. for 1 hour, followed by charging 95.13 parts of SURFONAMINE® B-200 polyetheramine and 94.7 parts of ethyl acetate, followed by stirring for an additional 2 hours at 65° C. to provide the dispersant of Comparative Example 2.

[0115] Comparative Example 3: A dispersant was produced according to the process described in Example 7, column 11, lines 45-53 (see Comparative Example C at column 10, lines 25-48) of U.S. Patent No. 9,416,280(B2), issued August 16, 2016 to inventor Stuart N. Richards and assignee Lubrizol Limited, using 24 parts EF60, 50 parts Jeffamine M2005, and 0.93 parts DMAPA in ethyl acetate. The resulting mixture was adjusted to 40.0 weight percent solids by adding additional ethyl acetate.

[0116] Comparative Example 4: A dispersion was made by adding 0.25 parts of acetic acid to 1.75 parts of Comparative Example 1, followed by mechanical stirring for about 1 minute until the material appeared homogenous, and then placing the container on a set of rollers to provide gentle mixing for about 30 minutes.

[0117] Comparative Example 5: A dispersion was made by adding 0.13 parts of benzoic acid to 1.87 parts of Comparative Example 1, followed by mechanical stirring for about 1 minute until the material appeared homogenous, and then placing the container on a set of rollers to provide gentle mixing for about 30 minutes.

[0118] Example 1: A dispersant was prepared by stirring a mixture of 225 parts of Comparative Example 1 and 309.38 parts of ethanol at 50° C. for 1 hour, followed by the addition of 84.38 parts of dodecylbenzenesulfonic acid and stirring at 50° C. for an additional hour.

[0119] Example 2: A mixture of 6.15 parts of Comparative Example 2 and 22.48 parts of ethanol was mechanically stirred for about 1 minute until the material appeared homogenous, then the container was placed on a set of rollers to provide gentle mixing for about 30 minutes. 0.47 parts of dodecylbenzenesulfonic acid was then added to the mixture, followed by mechanical stirring for about 1 minute until the material appeared homogenous, then the container was placed on a set of rollers to provide gentle mixing for about 30 minutes to create a dispersion.

[0120] Example 3: A mixture of 7.14 parts Comparative Example 3, 19.52 parts ethanol, and 2.17 parts ethyl acetate was mechanically stirred for about 1 minute until the material appeared homogeneous, and then the container was placed on a set of rollers to provide gentle mixing for about 30 minutes. 0.47 parts dodecylbenzenesulfonic acid was then added to the mixture, followed by mechanical stirring for about 1 minute until the material appeared homogeneous, and then the container was placed on a set of rollers to provide gentle mixing for about 30 minutes to create a dispersion.

[0121] Example 4: A dispersant was made by charging 35 parts of Comparative Example 3 to a reaction flask and stirring under nitrogen, charging 0.21 parts of benzenesulfonic acid to the reaction vessel along with 0.21 parts of ethyl acetate, and then heating the reaction mixture to 50°C for 1 hour using a condor attached to the flask.

[0122] Example 5: A dispersant was made by charging 35 parts of Comparative Example 3 to a reaction flask and stirring under nitrogen, charging 0.21 parts of phenylphosphonic acid to the reaction vessel along with 0.21 parts of ethyl acetate, and then heating the reaction mixture to 50°C for 1 hour using a condor attached to the flask.

[0123] To determine whether a particular dispersant may be suitable for use in an ink (e.g., an ink used for printing packaging materials), two types of experiments may be performed, as described below: a compatibility test, and one or both of dispersion test A and dispersion test B. A particular dispersant may be considered suitable for use in a (packaging) ink if it passes the compatibility test and at least one of dispersion test A or dispersion test B.

[0124] Each of the dispersants described in the previous examples and comparative examples was tested according to one of the compatibility test and dispersion test A or dispersion test B, and the results are reported in Table 1 below. The compatibility test is a measure of whether the dispersant is compatible with the ink medium. The dispersion test A and dispersion test B are methods to determine whether the dispersant is capable of dispersing a particular pigment, and each test may represent whether other similar pigments can pass the same test, and thus indicate that the dispersant is suitable for use with other similar pigments. Thus, passing at least one of the compatibility test and dispersion test A or dispersion test B indicates that a particular dispersant is suitable for use with at least one type of pigment.

[0125] Compatibility Test ("CT"): A varnish solution was made by dissolving 4 parts nitrocellulose varnish (DLX 3-5 from Nobel NC Co., Ltd.) in 5 parts ethanol and 1 part ethyl acetate. Separately, 2 parts dispersant was dissolved in 3 parts ethanol solvent. Five parts of the varnish solution were added to the mixture and stirred, followed by 2 parts of an organotitanate (TYZOR® IAM from Dorf Ketal Chemicals India Pvt Ltd) and stirring until homogeneous. After storage at room temperature for 2 weeks, the mixture was observed and gel formation and / or turbidity was recorded as a compatibility test failure, while a flowable clear fluid was recorded as a compatibility test pass.

[0126] Dispersion Test B ("DTB"): 3.39 parts of dispersant were dissolved in 22.48 parts ethanol and 3.39 parts ethyl acetate. 15.75 parts of Pigment Blue 15:4 were added and stirred to wet out the pigment. 125 parts of 3 mm glass beads were added and the resulting mixture was dispersed for 1 hour using a DAS 200 disperser (available from LAU GmbH) to produce a millbase. The viscosity of the millbase was measured using a TA rheometer using a parallel plate setup at 250 μm gap, 25° C. 38 seconds -1 A viscosity value of 2 Pa·s or more at a shear rate of 38 seconds was deemed to be a failure of Dispersion Test B. -1 A value of less than 2 Pa·s at a shear rate of 1000 μm was considered to pass the dispersion test B. [Table 1]

[0127] Except in the examples, or where otherwise expressly indicated, or where required by context, all numerical amounts herein specifying amounts of ingredients, reaction conditions, molecular weights, numbers of carbon atoms, and the like, 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 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 stated value that would be understood by one of skill in the art, based on the disclosure provided herein, to function substantially similarly to a composition containing the literal amounts recited herein.

[0128] It should be understood that the upper and lower quantity, range, and ratio limits described herein may be independently combined, and that any amount within a disclosed range is contemplated as providing a narrower minimum or maximum value in alternative embodiments (provided, of course, that the minimum amount of a range must be lower than the maximum amount of that same range). Similarly, the ranges and amounts for each element of the subject matter disclosed herein can be used together with ranges or amounts for any of the other elements.

[0129] 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 modifications and improvements can be made without departing from the scope of the subject matter, which scope should be limited only by the claims that follow.

Claims

1. 1. A composition comprising: a. a polymeric dispersant, i. an average of at least two polyether pendant groups per molecule, said at least two polyether pendant groups being composed of monomeric units, at least half of said monomeric units being poly(ethylene oxide) and / or poly(propylene oxide) monomeric units, and said at least two polyether pendant groups comprising at least 50 weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant; ii. a polymeric dispersant comprising an average of at least two amine groups per molecule, said at least two amine groups not being present in said at least two polyether pendant groups; b. a functionalized acid component comprising a sulfonic acid and / or a phosphoric acid functionalized with at least one of an aromatic or an aliphatic functional group; a composition wherein at least 60 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component.

2. The composition of claim 1, wherein the polymeric dispersant contains an average of 2 to 200 pendant polyether groups per molecule.

3. 2. The composition of claim 1, wherein from 50% to substantially all of the mer units of the polyether pendant groups are poly(ethylene oxide) and / or poly(propylene oxide) mer units.

4. 2. The composition of claim 1, wherein the ratio of the number of poly(ethylene oxide) monomer units to the number of poly(propylene oxide) monomer units is from 0:100 to 90:

10.

5. 2. The composition of claim 1, wherein the polyether pendant groups comprise at least 65 percent by weight of the polymeric dispersant, based on the total weight of the polymeric dispersant.

6. The composition of claim 1, wherein the polymeric dispersant contains an average of 2 to 500 amine groups per molecule.

7. The composition of claim 1 , wherein the functionalized acid component comprises a sulfonic acid functionalized with at least one of an aromatic or an aliphatic functionality.

8. The composition of claim 1 , wherein the functionalized acid component comprises dodecylbenzenesulfonic acid.

9. The aromatic functional group is an optionally substituted C ６ ~C １０ The composition of claim 1 wherein the group is aromatic.

10. The aliphatic functional group is a linear or branched, saturated or unsaturated C ８ ~C ２２ The composition of claim 1 which is a hydrocarbon group.

11. The functionalized acid component comprises at least one compound according to the general formula: 【Chemistry 5】 During the ceremony, R １ is a linear or branched, saturated or unsaturated C ８ ~C ２２ is a hydrocarbon group, R ２ is an aromatic functional group, optionally substituted C ６ ~C １０ is an aromatic group, W is phosphorus or sulfur; m is 1 or 2; when W is sulfur, m is 1 or 2; when W is phosphorus, m is 1; n is 1 or 2, when W is sulfur, n is 1, and when W is phosphorus, n is 2; s is 0 or 1; t is 0 or 1; The composition of claim 1 , with the proviso that s and t cannot both be 0.

12. The composition of claim 11 wherein W is sulfur.

13. The composition of claim 11 , wherein s is 1 and t is 1.

14. 2. The composition of claim 1, wherein at least about 75 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component.

15. 2. The composition of claim 1, wherein at least about 95 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component.

16. A pigment dispersion comprising: a. Pigment; b) a polymeric dispersant for said pigment, said polymeric dispersant comprising the composition of any one of claims 1 to 15.

17. 1. An ink formulation comprising: a. The pigment dispersion according to claim 16; b. a solvent; c. a binder; d. at least one additional additive.

18. A method of making a pigment dispersion, comprising combining, in any order, a pigment, a polymeric dispersant for said pigment, and a functionalized acid component, and optionally milling said pigment; a. The polymer dispersant is i. an average of at least two polyether pendant groups per molecule, said at least two polyether pendant groups being composed of monomeric units, at least half of said monomeric units being poly(ethylene oxide) and / or poly(propylene oxide) monomeric units, and said at least two polyether pendant groups comprising at least 50 weight percent of the polymeric dispersant, based on the total weight of the polymeric dispersant; ii. an average of at least two amine groups per molecule, said at least two amine groups being absent from said at least two polyether pendant groups; b. the functionalized acid component comprises a sulfonic acid and / or a phosphoric acid functionalized with at least one of an aromatic or an aliphatic functional group; c. at least 60 percent of the amine groups present in the polymeric dispersant are each individually neutralized with a molecule of the functionalized acid component; d. the optional step of grinding the pigment comprises: i. Not implemented; ii. performed on the pigment alone, prior to the addition of the polymeric dispersant and / or the functionalized acid component; or iii. The method is carried out on a combination of the pigment, the polymeric dispersant and / or the functionalized acid component.

19. 20. The method of claim 18, wherein the polymeric dispersant and the functionalized acid component are combined prior to addition of the pigment, and the optional step of grinding the pigment is performed before or after the pigment is added to the combination of the polymeric dispersant and the functionalized acid component.

20. 20. The method of claim 18, wherein the polymeric dispersant and the pigment are combined, the optional step of grinding the pigment is performed on the combination of the polymeric dispersant and the pigment, and then the functionalized acid component is added to the pigment composition.

Images