Polymers for inkjet ink compositions

Abstract

Disclosed herein are polymers that can be incorporated into pigment dispersions and inkjet ink compositions comprising a first monomer selected from the group consisting of ethylenically unsaturated hydrophobic monomers, and a second monomer selected from the group consisting of maleic anhydrides, maleic acids, and salts, esters, imides, and amides thereof. The polymer may have a portion of a second monomer functionalized with at least one organic group having a calcium index value greater than or equal to the calcium index value of the phenylphosphonic acid. Additionally and / or alternatively, the at least one polymer may be cross-linked by a second monomer. Dispersions and inkjet ink compositions comprising such polymers may further comprise at least one pigment and a liquid carrier. Methods of making such polymers are also disclosed.

Description

[0001] This application is a divisional application of a Chinese patent application (Invention title: Polymers for inkjet ink compositions, Filing date: 31 October 2017; Application number: 2017800676980). TECHNICAL FIELD

[0002] Disclosed herein are polymers comprising an ethylenically unsaturated hydrophobic monomer and a maleic anhydride and / or maleic acid (or salts, esters, imides, and amides thereof) monomer, and compositions comprising these monomers, which are useful in inkjet ink applications. BACKGROUND

[0003] In inkjet printing of pigment-based inks, individual ink droplets are deposited on a substrate with the goal of rapidly forming pigment aggregates on the substrate. This approach can be challenging for plain and coated papers, including those papers having low-solubility salts (e.g., calcium and magnesium salts). Slow pigment aggregation can result in average or below average image quality, manifested as low optical density, poor speckling, and the like.

[0004] Other challenges include maintaining the stability of such pigment-based dispersions. Thus, there is a need to develop new pigment-based inkjet ink compositions to address these challenges. SUMMARY

[0005] One embodiment provides a polymer comprising, consisting essentially of, or consisting of:

[0006] a first monomer selected from an ethylenically unsaturated hydrophobic monomer, and a second monomer selected from maleic anhydride, maleic acid, and salts, esters, imides, and amides thereof,

[0007] wherein at least a portion of the second monomer is functionalized with at least one organic group having a calcium index value greater than the calcium index value of phenylphosphonic acid.

[0008] Another embodiment provides a composition comprising, consisting essentially of, or consisting of:

[0009] at least one pigment;

[0010] a liquid carrier; and

[0011] at least one polymer comprising a first monomer selected from an ethylenically unsaturated hydrophobic monomer, and a second monomer selected from maleic anhydride, maleic acid, and salts, esters, imides, and amides thereof,

[0012] wherein a portion of the second monomer is functionalized with at least one organic group having a calcium index value greater than or equal to the calcium index value of phenylphosphonic acid.

[0013] Another embodiment provides a composition comprising, consisting essentially of, or consisting of:

[0014] at least one pigment;

[0015] a liquid carrier; and

[0016] at least one polymer encapsulating the at least one pigment, wherein the at least one polymer comprises a first monomer selected from an ethylenically unsaturated hydrophobic monomer, and a second monomer selected from maleic anhydride, maleic acid and salts, esters, imides and amides thereof, wherein the ethylenically unsaturated hydrophobic monomer comprises the formula wherein R 1 and R 2 are independently selected from the group consisting of H, C1-C 12 alkyl, C5-C 20 aryl and C6-C 20 alkylaryl, and the carbon atoms of R 1 and R 2 may be optionally substituted with at least one heteroatom selected from the group consisting of O, N and S, and

[0017] wherein the at least one polymer is crosslinked by the second monomer.

[0018] Another embodiment provides a method of making a polymer (e.g., a polymer capable of binding divalent metal ions, such as calcium and / or magnesium binding polymers) comprising:

[0019] (a) combining:

[0020] (i) at least one polymer comprising a first monomer selected from an ethylenically unsaturated hydrophobic monomer, and a second monomer selected from maleic anhydride, maleic acid and salts, esters, imides and amides thereof, and

[0021] (ii) at least one reagent comprising an amino group and at least one organic group having a calcium index value greater than the calcium index value of phenylphosphonic acid; and

[0022] (b) forming a polymer.

[0023] Another embodiment provides a method of making a polymer comprising,

[0024] (a) combining:

[0025] (i) at least one polymer comprising a first monomer selected from an ethylenically unsaturated hydrophobic monomer, and a second monomer selected from maleic anhydride, maleic acid and salts, esters, imides and amides thereof, wherein the ethylenically unsaturated hydrophobic monomer comprises the formula wherein R 1 and R 2 are independently selected from the group consisting of H, C1-C 12 alkyl, C5-C 20aryl and C6-C 20 alkaryl, and R 1 and R 2 The carbon atoms of the aryl group can be optionally substituted with at least one heteroatom selected from O, N and S, and

[0026] (ii) at least one crosslinking agent selected from epoxy-containing compounds; and

[0027] (b) forming a polymer.

[0028] In particular, the present application comprises:

[0029] 1. A composition comprising:

[0030] at least one pigment;

[0031] a liquid carrier; and

[0032] at least one polymer comprising a first monomer selected from ethylenically unsaturated hydrophobic monomers, and a second monomer selected from maleic anhydride, maleic acid and salts, esters, imides and amides thereof,

[0033] wherein a portion of the second monomer is functionalized with at least one organic group having a calcium index value greater than or equal to the calcium index value of phenylphosphonic acid.

[0034] 2. The composition of item 1, wherein the at least one organic group comprises at least two phosphonic acid groups, esters thereof, or salts thereof.

[0035] 3. The composition of item 1, wherein the at least one organic group comprises at least one geminal diphosphonic acid group, esters thereof, or salts thereof.

[0036] 4. The composition of item 1, wherein the at least one organic group comprises at least one group comprising the formula or salts thereof, wherein Q is H, R, OR, SR, or NR2, wherein R can be the same or different, selected from H, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 hydroxyalkyl, C1-C6 acyl, aralkyl, alkaryl, and aryl. 18 alkyl, C1-C 18 acyl, aralkyl, alkaryl, and aryl.

[0037] 5. The composition of item 1, wherein the at least one organic group comprises at least one group comprising the formula or salts thereof, wherein n is an integer from 1 to 9.

[0038] 6. The composition of item 1, wherein the at least one organic group comprises at least one group comprising the formula or salts thereof, and wherein R is selected from H, C1-C6 alkyl, aryl.

[0039] 7. The composition of clause 1, wherein the at least one organic group comprises at least one heterocyclic group comprising at least one OH group or a salt thereof.

[0040] 8. The composition of clause 1, wherein the at least one organic group comprises at least one phosphonic acid group or a salt thereof, and at least one second ionic, ionizable, or basic group located ortho or located geminal to the at least one phosphonic acid group or a salt thereof.

[0041] 9. The composition of clause 1, wherein the at least one organic group comprises at least one nitroso group and at least one OH group or a salt thereof.

[0042] 10. The composition of clause 1, wherein the at least one organic group comprises at least one aryl or alkyl polyacid group comprising at least three carboxylic acids.

[0043] 11. The composition of clause 1, wherein the at least one organic group comprises a heteroaryl group comprising at least one carboxylic acid group or a salt thereof.

[0044] 12. The composition of clause 1, wherein the at least one organic group comprises an azoarene group comprising at least two OH groups, at least two NH2 groups, or at least one OH group and at least one NH2 group and has the formula wherein Ar 1 and Ar 2 are the same or different, are arylene or aryl and at least one of Ar 1 or Ar 2 is arylene.

[0045] 13. The composition of clause 1, wherein the at least one organic group comprises at least one group selected from the group consisting of carboxylic acid, sulfonic acid, phosphonic acid, hydroxyl, amine, and ester, amide, and salts and esters thereof.

[0046] 14. The composition of any one of clauses 1-13, wherein the calcium index value of the at least one organic group is greater than the calcium index value of 1,2,3-benzene tricarboxylic acid.

[0047] 15. The composition of any one of clauses 1-14, wherein the portion of the second monomer functionalized with the at least one organic group comprises at least 3 mol% of the total amount of the second monomer.

[0048] 16. The composition of any one of clauses 1-15, wherein the ethylenically unsaturated hydrophobic monomer comprises the formula wherein R 1 and R 2 are independently selected from the group consisting of H, C1-C 12 alkyl, C5-C 20 aryl, and C6-C20 alkaryl, and wherein R 1 and R 2 the carbon atoms of R

[0049] 17. The composition of any one of clauses 1-15, wherein the ethylenically unsaturated hydrophobic monomer comprises the formula wherein R 1 and R 2 are independently selected from the group consisting of H, C1-C 12 alkyl, C5-C 20 aryl, C6-C 20 aralkyl, and C6-C 20 alkaryl.

[0050] 18. The composition of any one of clauses 1-15, wherein the ethylenically unsaturated hydrophobic monomer is selected from the group consisting of styrene, -methylstyrene, ethylene, propylene, 1-butene, isobutylene, butadiene, and methyl vinyl ether.

[0051] 19. The composition of any one of clauses 1-15, wherein the ethylenically unsaturated hydrophobic monomer is selected from the group consisting of styrene.

[0052] 20. The composition of any one of clauses 1-15, wherein the ethylenically unsaturated hydrophobic monomer is selected from the group consisting of ethylenically unsaturated esters.

[0053] 21. The composition of clause 20, wherein the ethylenically unsaturated ester is selected from the group consisting of vinyl acetate, allyl acetate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, n-octyl acrylate, benzyl acrylate, acrylonitrile, and acrylamide.

[0054] 22. The composition of any one of clauses 1-21, wherein the second monomer comprises maleic anhydride.

[0055] 23. The composition of any one of clauses 1-21, wherein the second monomer comprises maleic acid, and salts, esters, imides, and amides thereof.

[0056] 24. The composition of any one of clauses 1-21, wherein the second monomer comprises a mixture of maleic anhydride and maleic acid, and salts, esters, imides, and amides thereof.

[0057] 25. The composition of any one of clauses 1-24, wherein the second monomer is present in the at least one polymer in an amount of 10 to 60 mol%, relative to the at least one polymer.

[0058] 26. The composition of any of clauses 1-25, wherein the first monomer is present in the at least one polymer in an amount of 40 to 90 mol% relative to the at least one polymer.

[0059] 27. The composition of any of clauses 1-25, wherein the first monomer is present in the at least one polymer in an amount of 67 to 80 mol% relative to the at least one polymer.

[0060] 28. The composition of any of clauses 1-27, wherein the at least one pigment is unmodified.

[0061] 29. The composition of any of clauses 1-27, wherein the at least one pigment is self-dispersing.

[0062] 30. The composition of any of clauses 1-29, wherein the at least one polymer is adsorbed to the at least one pigment.

[0063] 31. The composition of any of clauses 1-29, wherein the at least one polymer encapsulates the at least one pigment.

[0064] 32. The composition of any of clauses 1-29, wherein the at least one polymer is crosslinked.

[0065] 33. The composition of any of clauses 1-29, wherein the at least one polymer is crosslinked by a second monomer.

[0066] 34. The composition of any of clauses 1-29, wherein the at least one polymer is crosslinked by a carboxylate-containing group of a second monomer.

[0067] 35. The composition of any of clauses 1-29, wherein the at least one polymer is crosslinked by at least 10% of carboxylate-containing groups of a second monomer.

[0068] 36. The composition of any of clauses 1-35, wherein the at least one polymer is crosslinked by at least one bond selected from the group consisting of amide, imide, and ester bonds.

[0069] 37. The composition of any of clauses 1-35, wherein the at least one polymer is crosslinked by at least one bond selected from the group consisting of ether and thioether bonds.

[0070] 38. The composition of any of clauses 1-35, wherein the at least one polymer is crosslinked by at least one bond selected from the group consisting of ester bonds.

[0071] 39. The composition of clause 38, wherein the ester bond results from a reaction between an epoxy-containing compound and a carboxylate-containing group of a second monomer.

[0072] 40. The composition of clause 39, wherein the epoxy-containing compound is selected from the group consisting of a diglycidyl ether compound and a triglycidyl ether compound.

[0073] 41. The composition of clause 39, wherein the epoxy-containing compound is selected from the group consisting of trimethylolpropane triglycidyl ether.

[0074] 42. The composition of any one of clauses 31-41, wherein the at least one polymer has an acid value of less than 325.

[0075] 43. The composition of any one of clauses 31-41, wherein the at least one polymer has an acid value of from 50 to 325.

[0076] 44. The composition of any one of clauses 31-43, wherein the composition has a pH of from 8 to 11.

[0077] 45. The composition of any one of clauses 1-44, wherein the at least one polymer is a random copolymer.

[0078] 46. The composition of any one of clauses 1-44, wherein the at least one polymer is an alternating copolymer.

[0079] 47. The composition of any one of clauses 1-46, wherein the at least one polymer is present in an amount of from 0.1 wt% to 25 wt%, relative to the total weight of the inkjet ink composition.

[0080] 48. The composition of any one of clauses 1-47, wherein at least a second portion of the second monomer is functionalized with at least one second organic group comprising the formula wherein R 3 and R 4 are independently selected from the group consisting of H, C1-C 10 alkyl, C4-C 18 aryl, C4-C 18 heteroaryl, and C3-C 20 heterocycloalkyl, and A is selected from the group consisting of C1-C 10 alkylene, C3-C 20 cycloalkylene, C3-C 20 heterocycloalkylene, arylene, heteroarylene, and C2-C 20 ether.

[0081] 49. The composition of any one of clauses 1-47, wherein at least a second portion of the second monomer is functionalized with at least one second organic group comprising a formula selected from the group consisting of: , , , , , 、 、 、 and .

[0082] 50. The composition of any of clauses 1-47, wherein at least a second portion of the second monomer is functionalized with at least one second organic group comprising the formula wherein R 3 , R 4 , and R 5 are independently selected from the group consisting of H, C1-C 10 alkyl, C4-C 18 aryl, C4-C 18 heteroaryl, and C3-C 20 heterocycloalkyl, and A is selected from the group consisting of C1-C 10 alkylene, C3-C 20 cycloalkylene, C3-C 20 heterocycloalkylene, arylene, heteroarylene, and C2-C 20 ether.

[0083] 51. The composition of any of clauses 48-50, wherein the at least one second organic group is bonded to the second portion of the second monomer through an amide, imide, and ester linkage.

[0084] 52. The composition of any of clauses 1-51, wherein the liquid carrier is aqueous.

[0085] 53. The composition of any of clauses 1-52, wherein the composition is an aqueous dispersion.

[0086] 54. The composition of any of clauses 1-53, further comprising at least one surfactant.

[0087] 55. The composition of any of clauses 1-54, further comprising at least one durability polymer.

[0088] 56. The composition of any of clauses 1-55, further comprising at least one viscosity modifier.

[0089] 57. The composition of any of clauses 1-56, further comprising at least one polymeric binder.

[0090] 58. The composition of any of clauses 1-57, wherein the composition is an inkjet ink composition.

[0091] 59. A polymer comprising:

[0092] a first monomer selected from the group consisting of ethylenically unsaturated hydrophobic monomers, and a second monomer selected from the group consisting of maleic anhydride, maleic acid and salts, esters, imides and amides thereof,

[0093] wherein at least a portion of the second monomer is functionalized with at least one organic group having a calcium index value greater than the calcium index value of phenylphosphonic acid.

[0094] 60. The polymer of clause 59, wherein the first monomer is selected from the group consisting of styrene.

[0095] 61. A method of making a polymer, comprising:

[0096] (a) combining:

[0097] (i) at least one polymer comprising a first monomer selected from the group consisting of ethylenically unsaturated hydrophobic monomers, and a second monomer selected from the group consisting of maleic anhydride, maleic acid and salts, esters, imides and amides thereof, and

[0098] (ii) at least one reagent comprising an amino group and at least one organic group having a calcium index value greater than the calcium index value of phenylphosphonic acid; and

[0099] (b) forming the polymer.

[0100] 62. The method of clause 61, wherein the combining is in the presence of at least one base selected from the group consisting of NH4OH, NaOH and KOH.

[0101] 63. The method of clause 61 or 62, wherein the method further comprises:

[0102] combining the at least one polymer with at least one crosslinking agent.

[0103] 64. The method of clause 63, wherein the at least one crosslinking agent is selected from the group consisting of epoxy-containing compounds.

[0104] 65. The method of clause 63 or 64, wherein the at least one crosslinking agent further comprises boric acid.

[0105] 66. The method of any one of clauses 63-65, wherein prior to or simultaneously with combining the at least one polymer with at least one crosslinking agent, the method further comprises hydrolyzing the at least one polymer.

[0106] 67. A composition comprising:

[0107] at least one pigment;

[0108] a liquid carrier; and

[0109] at least one polymer encapsulating the at least one pigment, wherein the at least one polymer comprises a first monomer selected from an ethylenically unsaturated hydrophobic monomer, and a second monomer selected from maleic anhydride, maleic acid and salts, esters, imides and amides thereof, wherein the ethylenically unsaturated hydrophobic monomer comprises the formula wherein R 1 and R 2 are independently selected from H, C1-C 12 alkyl, C5-C 20 aryl and C6-C 20 alkylaryl, and the carbon atoms of R 1 and R 2 may optionally be substituted with at least one heteroatom selected from O, N and S, and

[0110] wherein the at least one polymer is crosslinked by the second monomer.

[0111] 68. The composition of clause 67, wherein the second monomer is selected from maleic anhydride, maleic acid and salts thereof.

[0112] 69. The composition of any one of clauses 67 or 68, wherein the at least one polymer is crosslinked by the carboxylate groups of the second monomer.

[0113] 70. The composition of any one of clauses 67 or 68, wherein the at least one polymer is crosslinked by at least 10% of the carboxylate groups of the second monomer.

[0114] 71. The composition of any one of clauses 67-70, wherein the at least one polymer is crosslinked by at least one bond selected from amide, imide and ester bonds.

[0115] 72. The composition of any one of clauses 67-70, wherein the at least one polymer is crosslinked by at least one bond selected from ether and thioether bonds.

[0116] 73. The composition of any one of clauses 67-70, wherein the at least one polymer is crosslinked by at least one bond selected from ester bonds.

[0117] 74. The composition of clause 73, wherein the ester bond results from a reaction between an epoxy-containing compound and a carboxylate-containing group of the second monomer.

[0118] 75. The composition of clause 74, wherein the epoxy-containing compound is selected from a diglycidyl ether compound and a triglycidyl ether compound.

[0119] 76. The composition of clause 74, wherein the epoxy-containing compound is selected from trimethylolpropane triglycidyl ether.

[0120] 77. The composition of any of clauses 67-76, wherein the ethylenically unsaturated hydrophobic monomer comprises the formula wherein R 1 and R 2 are independently selected from the group consisting of H, Ci-C 12 alkyl, C5-C 20 aryl, C6-C 20 aralkyl, and C6-C 20 alkaryl.

[0121] 78. The composition of any of clauses 67-76, wherein the ethylenically unsaturated hydrophobic monomer is selected from the group consisting of styrene, -methylstyrene, ethylene, propylene, 1 -butene, isobutylene, butadiene, and methyl vinyl ether.

[0122] 79. The composition of any of clauses 67-76, wherein the ethylenically unsaturated hydrophobic monomer is selected from the group consisting of styrene.

[0123] 80. The composition of any of clauses 67-79, wherein the at least one polymer has an acid value of less than 325.

[0124] 81. The composition of any of clauses 67-79, wherein the at least one polymer has an acid value of from 50 to 325.

[0125] 82. The composition of any of clauses 67-81, wherein the composition has a pH of from 8 to 11.

[0126] 83. The composition of any of clauses 67-82, wherein the second monomer is present in the at least one polymer in an amount of from 10 to 60 mol%, relative to the at least one polymer.

[0127] 84. The composition of any of clauses 67-83, wherein the first monomer is present in the at least one polymer in an amount of from 40 to 90 mol%, relative to the at least one polymer.

[0128] 85. The composition of any of clauses 67-84, wherein a portion of the second monomer is functionalized with at least one organic group comprising the formula wherein R 3 and R 4 are independently selected from the group consisting of H, Ci-C 10 alkyl, C4-C 18 aryl, C4-C 18 heteroaryl, and C3-C 20 heterocycloalkyl, and A is selected from the group consisting of Ci-C 10 alkylene, C3-C 20 cycloalkylene, C3-C 20C2-C10alkylene, C3-C10cycloalkylene, C3-C10heterocycloalkylene, arylene, heteroarylene, and C2-C10ether. 20 ether.

[0129] 86. The composition of any of clauses 67-84, wherein a portion of the second monomers are functionalized with at least one organic group comprising a moiety selected from the group consisting of: and .

[0130] 87. The composition of any of clauses 67-84, wherein a portion of the second monomers are functionalized with at least one organic group comprising a moiety of the formula wherein R 3 , R 4 and R 5 are independently selected from the group consisting of H, C1-C 10 alkyl, C4-C 18 aryl, C4-C 18 heteroaryl, and C3-C 20 heterocycloalkyl, and A is selected from the group consisting of C1-C 10 alkylene, C3-C 20 cycloalkylene, C3-C 20 heterocycloalkylene, arylene, heteroarylene, and C2-C 20 ether.

[0131] 88. The composition of any of clauses 85-87, wherein the at least one organic group is bonded to the second monomer by at least one bond selected from the group consisting of amide, imide, and ester bonds.

[0132] 89. The composition of any of clauses 67-88, wherein the at least one pigment is unmodified.

[0133] 90. The composition of any of clauses 67-88, wherein the at least one pigment is self-dispersing.

[0134] 91. The composition of any of clauses 67-90, wherein the liquid carrier is aqueous.

[0135] 92. The composition of any of clauses 67-91, wherein the composition is an aqueous dispersion.

[0136] 93. The composition of any of clauses 67-92, further comprising at least one surfactant.

[0137] ​​​​​​​​94. The composition of any of clauses 67-93, further comprising at least one durable polymer.

[0138] 95. The composition of any of clauses 67-94, further comprising at least one viscosity modifier.

[0139] 96. The composition of any of clauses 67-95, further comprising at least one polymeric binder.

[0140] 97. The composition of any of clauses 67-96, wherein the composition is an inkjet ink composition.

[0141] 98. A method of making a polymer, comprising:

[0142] (a) combining:

[0143] (i) at least one polymer comprising a first monomer selected from an ethylenically unsaturated hydrophobic monomer, and a second monomer selected from maleic anhydride, maleic acid and salts, esters, imides and amides thereof, wherein the ethylenically unsaturated hydrophobic monomer comprises the formula wherein R 1 and R 2 are independently selected from H, C1-C 12 alkyl, C5-C 20 aryl and C6-C 20 alkylaryl, and the carbon atoms of R 1 and R 2 may be optionally substituted with at least one heteroatom selected from O, N and S, and

[0144] (ii) at least one crosslinking agent selected from an epoxy-containing compound; and

[0145] (b) forming a polymer.

[0146] 99. The method of clause 98, wherein the at least one crosslinking agent further comprises boric acid.

[0147] 100. The method of clause 98 or 99, wherein prior to or concurrently with combining the at least one polymer with at least one crosslinking agent, the method further comprises hydrolyzing the at least one polymer.

[0148] 101. The method of any of clauses 98-100, wherein the second monomer is selected from maleic anhydride, maleic acid and salts thereof.

[0149] 102. The method of any of clauses 98-101, wherein the at least one crosslinking agent selected from an epoxy-containing compound reacts with the carboxylate-containing group of the second monomer.

[0150] 103. The composition of any one of clauses 98-102, wherein the epoxy group containing compound is selected from the group consisting of a diglycidyl ether and a triglycidyl ether compound.

[0151] 104. The composition of any one of clauses 98-102, wherein the epoxy group containing compound is selected from the group consisting of trimethylolpropane triglycidyl ether. BRIEF DESCRIPTION OF DRAWINGS

[0152] Figure 1A is a photograph of PigDisp-27 exposed to dipropylene glycol on a microscope slide; and

[0153] Figure 1B is a photograph of PigDisp-28 exposed to dipropylene glycol on a microscope slide. DETAILED DESCRIPTION

[0154] Disclosed herein is a composition comprising, consisting essentially of, or consisting of:

[0155] at least one pigment;

[0156] a liquid carrier; and

[0157] at least one polymer that is crosslinked and / or capable of binding calcium and / or other divalent metals.

[0158] In one embodiment, the at least one polymer is capable of binding calcium and / or other divalent metals. In one embodiment, the at least one polymer comprises a first monomer selected from the group consisting of an ethylenically unsaturated hydrophobic monomer, and a second monomer selected from the group consisting of maleic anhydride, maleic acid and salts, esters, imides and amides thereof, wherein a portion of the second monomer is functionalized with at least one organic group having a calcium index value greater than or equal to the calcium index value of phenylphosphonic acid. In one embodiment, the at least one organic group has a calcium index value greater than or equal to the calcium index value of 1,2,3-benzene tricarboxylic acid (1,2,3-benzenetricarboxylic acid).

[0159] Another embodiment provides a composition comprising, consisting essentially of, or consisting of:

[0160] at least one pigment;

[0161] a liquid carrier; and

[0162] at least one polymer encapsulating the at least one pigment, wherein the at least one polymer comprises a first monomer selected from the group consisting of an ethylenically unsaturated hydrophobic monomer, and a second monomer selected from the group consisting of maleic anhydride, maleic acid and salts, esters, imides and amides thereof, wherein the ethylenically unsaturated hydrophobic monomer comprises the formula , wherein R 1 and R 2Independently selected from H, C1-C 12 Alkyl, C5-C 20 Aryl and C6-C 20 Alkyl aryl, and R 1 and R 2 The carbon atom may optionally be replaced by at least one heteroatom selected from O, N, and S, and

[0163] The at least one polymer is crosslinked by a second monomer.

[0164] In one embodiment, a composition comprising the at least one polymer encapsulating a pigment exhibits enhanced stability relative to a composition comprising a self-dispersing pigment and / or a composition comprising a pigment and a polymeric dispersant comprising the same monomer, wherein the polymeric dispersant is not crosslinked.

[0165] In one embodiment, the "olefinically unsaturated" monomer contains a polymerizable C=C group. Exemplary olefinically unsaturated hydrophobic monomers include acrylate and methacrylate groups, vinyl and allyl groups. In one embodiment, the olefinically unsaturated hydrophobic monomer has the formula... , where R 1 and R 2 Independently selected from H, C1-C 20 Alkyl (e.g., C1-C) 12 (or C1-C6 alkyl), C5-C 20 Aryl (e.g., C5-C) 12 Aryl, C6-C 12 Aryl, C5-C 10 Aryl, C6-C 10 Aryl), C6-C 20 Arylalkyl (aryl-substituted alkyl, e.g., C6-C) 12 Aryl group, C6-C 10 Aryl groups and C6-C 20 Alkyl (alkyl-substituted aryl, e.g., C6-C) 12 Alkyl, C6-C 10 (Alkyl aryl). R 1 and R 2 It can be a straight chain or a branched chain. In one implementation, R 1 and R 2 The carbon atom may optionally be replaced with at least one heteroatom selected from O, N, and S. In one embodiment, R 1 and R 2 Independently selected from H, C1-C 12 Alkyl, C5-C 20 Aryl, C6-C 20 Araneyl and C6-C 20Alkylaryl. In another embodiment, R 1 and R 2 are independently selected from the group consisting of H, C1-C 12 alkyl, C6-C 12 aryl, C6-C 12 aralkyl, and C6-C 12 alkaryl. In yet another embodiment, R 1 and R 2 are independently selected from the group consisting of H, C1-C 12 alkyl, and C5-C 12 aryl (e.g., C5-C 10 aryl) or H, C1-C 12 alkyl, and C6-C 12 aryl (e.g., C6-C 10 aryl). In yet another embodiment, R 1 and R 2 are independently selected from the group consisting of H and C5-C 12 aryl (e.g., C5-C 10 aryl) or H and C6-C 12 aryl (e.g., C6-C 10 aryl).

[0166] In one embodiment, the ethylenically unsaturated hydrophobic monomer is selected from ethylenically unsaturated hydrophobic monomers containing a vinyl group, e.g., -alkenes. Exemplary monomers containing a vinyl group include ethylene, propylene, 1 -butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 2-methyl- 1-butene, 3,3-dimethyl- 1-pentene, 2-methyl- 1-heptene, 4,4-dimethyl- 1-heptene, 3,3-dimethyl- 1-hexene, 4-methyl- 1-pentene, isobutylene, diisobutylene, styrene, -methylstyrene, and vinyltoluene, and mixtures thereof.

[0167] In one embodiment, the ethylenically unsaturated hydrophobic monomer is selected from ethylenically unsaturated esters, e.g., ethylenically unsaturated esters of aliphatic acids, wherein the acid moiety has 3-8 carbon atoms, e.g., 3-6 carbon atoms, and the ester moiety has 1-8, e.g., 1-6 or 1-4 carbon atoms. Exemplary ethylenically unsaturated esters include vinyl acetate, allyl acetate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, n-octyl acrylate, benzyl acrylate, acrylonitrile, and acrylamide. In one embodiment, the first monomer can comprise two or more different ethylenically unsaturated hydrophobic monomers.

[0168] In one embodiment, the ethylenically unsaturated hydrophobic monomer is selected from the group consisting of styrene, - methylstyrene, ethylene, propylene, 1 -butene, isobutylene, butadiene, methyl vinyl ether. In one embodiment, the ethylenically unsaturated hydrophobic monomer is selected from the group consisting of styrene and - methylstyrene.

[0169] In one embodiment, the second monomer is selected from the group consisting of maleic anhydride, maleic acid and salts, esters, imides and amides thereof, for example from the group consisting of maleic anhydride, maleic acid and salts thereof. For example, the second monomer can comprise maleic anhydride, or maleic acid, or a mixture of maleic anhydride and maleic acid (and / or salts, esters, imides and amides thereof). The second monomer can be unsubstituted (except for the portion functionalized with the at least one organic group). Alternatively, the second monomer can be substituted, for example with at least one group selected from the group consisting of Ci-C6alkyl and halogen. Exemplary substituted second monomers include methyl maleic anhydride, dimethyl maleic anhydride, fluoromaleic anhydride and methyl ethyl maleic anhydride.

[0170] In one embodiment, the second monomer is present in the at least one polymer in an amount of 10 to 60 mol% relative to the at least one polymer, for example in an amount of 10 to 50 mol%, 10 to 40 mol%, 10 to 35 mol%, 20 to 60 mol%, 20 to 50 mol%, 20 to 40 mol%, 20% to 35 mol% relative to the at least one polymer. In one embodiment, the at least one polymer comprises the first monomer in an amount of 40 to 90 mol%, 50 to 90 mol%, 40 to 80 mol%, or 50 to 80 mol%. In another embodiment, the at least one polymer comprises the first monomer in an amount of 67 to 80 mol% and the second monomer in an amount of 20 to 33 mol% relative to the at least one polymer. The at least one polymer can be a random copolymer or an alternating copolymer.

[0171] In one embodiment, the first monomer is selected from styrene. In one embodiment, the at least one polymer is selected from a styrene-maleic anhydride (SMA) polymer, wherein a portion of the maleic anhydride monomers are functionalized with the at least one organic group. In one embodiment, the styrene-maleic anhydride polymer can be prepared by polymerization of styrene or styrene-like monomers and maleic anhydride or derivatives thereof. For example, the styrene-maleic anhydride polymer can be a copolymer of styrene and maleic anhydride. In one embodiment, some or all of the maleic anhydride monomers are hydrolyzed to maleic acid, resulting in a polymer comprising styrene, maleic anhydride, and maleic acid (and salts thereof) monomers. Additional monomers, such as acrylates and methacrylates, can also be present. In one embodiment, the additional monomers are present at low levels. For example, the styrene-maleic anhydride polymer can be a polymer of styrene, maleic anhydride, and additional monomers, the molar ratio of polymerized styrene and maleic anhydride to other polymerized monomers being greater than 1 / 1, such as greater than 5 / 1, greater than 10 / 1, and greater than 20 / 1. These polymers can be prepared using any method known in the art, including using continuous monomer feed polymerization as well as using one-pot (one-step) polymerization methods. In one embodiment, the styrene-maleic anhydride polymer is prepared using continuous monomer feed methods.

[0172] Other examples of styrene-maleic anhydride polymers include functionalized styrene-maleic anhydride polymers (in addition to the portion that is functionalized with the at least one organic group), which are polymers prepared by polymerization of styrene and maleic anhydride monomers that have been further reacted (e.g., reacted with an alcohol to form an ester group or reacted with an amine to form an amide or imide group). Specific examples of functionalized styrene-maleic anhydride polymers include polymers comprising half-esters or amides of styrene monomers and polymerized maleic anhydride (thus including polymers comprising monomers of the formula or wherein R is selected from the group consisting of C1-C 20 alkyl, aralkyl, alkaryl, and aryl groups, such as selected from the group consisting of C6-C 18 alkyl, aralkyl, and aryl groups. Partially functionalized styrene-maleic anhydride polymers, in which some but not all of the polymerized maleic anhydride monomers have been functionalized, can also be used. Examples of these polymers include styrene-maleic anhydride-maleate polymers and styrene-maleic anhydride-maleic amide polymers. In addition, polymers comprising monomers of polymerized styrene and monomers of polymerized maleic anhydride imide can also be used.

[0173] The at least one polymer can be prepared using conventional polymerization techniques. - olefin maleic anhydride copolymers, which can be prepared, for example, by any of a number of conventional polymerization processes, including those set forth in U.S. Reissue Patent No. Re. 28,475 and U.S. Patent Nos. 3,553,117; 3,560,455; 3,560,456; 3,560,457; 3,488,311; 4,522,992; 4,358,573; 4,871,823; 4,859,752; and 5,336,727, the disclosures of which are incorporated herein by reference. The at least one polymer can be prepared, for example, in pure olefin at 160 °C; in a solvent of aromatic hydrocarbon that dissolves the monomers but not the polymer (precipitation polymerization or suspension polymerization); or in a solvent of ketone that dissolves both the reactants and the polymer (solution polymerization). In one embodiment, the temperature of the solution polymerization is 60-80 °C. The free radical initiator is typically AIBN or benzoyl peroxide.

[0174] In one embodiment, a portion of the second monomer is functionalized with at least one organic group having a calcium index value greater than or equal to the calcium index value of phenylphosphonic acid. In one embodiment, the at least one organic group is capable of binding calcium and / or other divalent metals. In one embodiment, the binding capacity of divalent metals can be quantified by calcium index value as described in U.S. Patent No. 8,858,695, the disclosure of which is incorporated herein by reference. The “calcium index value” refers to a measure of the ability of an organic group to coordinate or bind calcium ions in solution. The higher the calcium index value, the stronger or more effective the group can coordinate calcium ions. The calcium index value can also be used to represent the binding capacity of other divalent metal ions, such as magnesium.

[0175] The calcium index value can be determined by any method known in the art. For example, the calcium index value can be measured with a method in which UV-Vis spectroscopy is used to measure the amount of calcium coordinated by a compound in a standard solution containing soluble calcium ions and a color indicator. Alternatively, for compounds with strong colors, NMR methods can be used to measure the calcium index value.

[0176] In one embodiment, the “calcium index value” is according to the methods described in U.S. Patent No. 8,858,695, e.g., Method A or Method B, column 29, line 45 to column 31, line 37, the disclosure of which is incorporated herein by reference. For either method used, a compound corresponding to the desired organic group to be tested is selected. In the test compound, the at least one organic group can be bonded to any residue, as long as the atoms responsible for binding calcium ions are separated from the residue by at least two bonds. The residue can comprise or consist of hydrogen, C1-C 10 ​alkyl (substituted or unsubstituted) or C4-C 18 aryl (substituted or unsubstituted), for example, the compound to be tested can contain an organic group bonded to hydrogen, C1-C 10 alkyl (substituted or unsubstituted) or C4-C 18 aryl (substituted or unsubstituted). For example, for a 3,4,5-tricarboxyphenyl functional group and its salts, 1,2,3-benzene tricarboxylic acid can be selected. In this example, the residue is hydrogen and the oxygen atoms of the carboxylic acid are at least two bonds from the hydrogen residue.

[0177] In one embodiment, reference to a calcium index value means a value greater than or equal to that of a reference material. In one embodiment, the reference is phenylphosphonic acid. Thus, the calcium index value of the at least one organic group is greater than or equal to the calcium index value of phenylphosphonic acid. In another embodiment, the reference is 1,2,3-benzene tricarboxylic acid. In one embodiment, the calcium index value is greater than or equal to 2.53, for example greater than or equal to 2.8, greater than or equal to 3.0, or greater than or equal to 3.2, determined using UV-Vis spectroscopy (or Method A), as described in more detail below.

[0178] Method A. For this method, a series of solutions were prepared at pH 9 containing 0.087 mM Congo Red indicator, 5 mM cesium chloride, 1 wt% Mw 350 polyethylene glycol methyl ether, and calcium chloride at concentrations from 0 to 7 mM (0.2, 0.5, 1, 2, 3, 4, 4.5, 5, 6, and 7 mM). UV-Vis spectra of these solutions were recorded using a UV-2501PC within 1 hour of their preparation. These spectra were used to generate a calibration curve relating absorbance at 520 nm to calcium concentration.

[0179] Test solutions were then prepared at pH 9 containing 0.087 mM Congo Red indicator, 1 wt% Mw 350 polyethylene glycol methyl ether, 5 mM calcium chloride, and the cesium salt of the compound of interest such that the ionic concentration at pH 9 was 5 mM. The uncomplexed calcium concentration was determined by comparison to the calibration curve. The calcium index value was then calculated as . Measurements were made in duplicate and averaged.

[0180] Method B. For compounds that produce high color levels and thus are difficult to use in Method A, a second method was developed. For this method, a series of solutions were prepared at pH 9 containing 0.087 mM Congo Red indicator, 1 wt% Mw 350 polyethylene glycol methyl ether, and calcium chloride at concentrations from 0 to 7 mM (0.2, 0.5, 1, 2, 3, 4, 4.5, 5, 6, and 7 mM). UV-Vis spectra of these solutions were recorded using a UV-2501PC within 1 hour of their preparation. These spectra were used to generate a calibration curve relating absorbance at 520 nm to calcium concentration. 43 CaCO3, HCl / D2O, NaOH / D2O, D2O, and water to prepare 43CaCl2 is 0.01 M, NaCl is 0.01 M, 10% D2O and aqueous solution at pH 8 or 9. The pH is chosen to ionize the compound under study and to solubilize the compound. A portion of the solution weighing approximately 0.65 g is added to a 5 mm NMR tube and weighed to the nearest 0.001 g. The unbound 43 Ca chemical shift, proton resonance frequency is 400.13 MHz. A solution of the compound under study (ligand) is added in successive increments from 0.2 - 1.0 M. After each addition, the 43 Ca chemical shift is measured and the difference between the chemical shift of the sample and the chemical shift of the unbound calcium is calculated. The successive increments are planned so that the ratio is 0.25, 0.5, 1, 2, 3, 4, 6 and 8, where is the total concentration of complexed, protonated and free anions from the ligand and is the total concentration of calcium in all species present. The calcium index value (NMR) is calculated as where X is determined by fitting the parameters X and in the following equation:

[0181]

[0182] so as to minimize the RMS difference between the data and the chemical shift predicted by the equation, where:

[0183] is the chemical shift of the sample 43 Ca chemical shift minus the difference between the chemical shift of the free aqueous 43 Ca 2+ ;

[0184] is the calculated difference between the chemical shift of the free 43 Ca chemical shift minus the difference between the chemical shift of the free 43 Ca 2+ ;

[0185] is the total concentration of complexed, protonated and free anions from the ligand;

[0186] is the total concentration of calcium in all species present;

[0187] X is a fitting parameter; and

[0188] is the proton dissociation constant of the ligand LH.

[0189] Without wishing to be bound by any theory, the presently claimed polymeric dispersant can result in improved print performance due to interaction or binding with calcium salts and / or other divalent metal salts (e.g., magnesium) present in or on the substrate. The divalent metal salt can be a coating on the substrate or added subsequently, e.g., by printing with a fixer containing the metal salt. The initially stable dispersion can rapidly destabilize upon contact with the substrate. Alternatively, or in addition, the destabilization can be caused by a change in pH upon contact with the substrate, which can be advantageous for the polymeric dispersant comprising the linking functionality described above. It is believed that the rapid post-print destabilization due to the change in pH, interaction with calcium and / or other divalent metal salts, or a combination thereof, results in a printed image with good overall properties, such as optical density, edge acuity (sharpness), and / or inter-color bleed.

[0190] In one embodiment, the at least one organic group functionalized second monomer portion is used in mol% of the total amount of second monomer (sum of functionalized and non- functionalized second monomer). In one embodiment, the at least one organic group functionalized second monomer portion is at least 3 mol%, such as at least 5 mol%, at least 7 mol%, or at least 10 mol%, relative to the total amount of second monomer. In one embodiment, the at least one organic group functionalized second monomer portion is at most 75 mol% of the total second monomer, such as at most 60 mol%, at most 50 mol%, or at most 40 mol% of the total amount of second monomer. In one embodiment, the at least one organic group functionalized second monomer portion is 3 mol% to 75 mol% of the total amount of second monomer, such as 5 mol% to 75 mol%, 3 mol% to 60 mol%, 5 mol% to 60 mol%, 3 mol% to 50 mol%, 5 mol% to 50 mol%, 3 mol% to 40 mol%, or 5 mol% to 40 mol%.

[0191] In one embodiment, a portion of the second monomer is functionalized with the at least one organic group through a number of reactions known in the art, such as reaction with a carboxylic acid and / or an acid anhydride. In one embodiment, an alcohol or amine containing the at least one organic group can be reacted with maleic anhydride or acid, optionally in the presence of a base, as desired. In one embodiment, a primary amine containing the at least one organic group can be reacted with maleic anhydride or acid in the presence of a base to form an amide group that bonds the at least one organic group to the polymer.

[0192] In one embodiment, the at least one organic group comprises at least one group selected from the group consisting of carboxylic acid, sulfonic acid, phosphonic acid, hydroxyl, amine, and esters, amides, and salts and esters thereof.

[0193] In one embodiment, the at least one organic group is selected from one or more of the following:

[0194] at least one phosphonic acid group (e.g., at least two phosphonic acid groups), partial esters thereof, and salts thereof, e.g., geminal diphosphonic acid groups, partial esters thereof, and salts thereof;

[0195] at least one heterocyclic group comprising at least one OH group (e.g., at least two OH groups) and salts thereof;

[0196] at least one phosphonic acid group or salt thereof and at least one second ionic, ionizable, or basic group located in the ortho position or in the para position to the phosphonic acid group, and salts thereof;

[0197] aryl or alkyl polyacid groups comprising at least three carboxylic acids;

[0198] heteroaryl groups comprising at least one carboxylic acid group, and salts thereof;

[0199] aryl groups comprising at least one nitroso group and at least one OH group, and salts thereof; and

[0200] azoarene groups comprising at least one OH group, at least one NH2 group, or at least one OH group and at least one NH2 group and having the formula wherein Ar 1 and Ar 2 (which can be the same or different) are arylene or aryl and at least one of Ar 1 or Ar 2 is arylene.

[0201] In one embodiment, the at least one organic group comprises at least two phosphonic acid groups, esters thereof, or salts thereof.

[0202] In one embodiment, the at least one organic group can comprise at least one geminal diphosphonic acid group, partial ester thereof, and salt thereof, i.e., the at least one organic group can comprise at least two phosphonic acid groups, partial esters thereof, and salts thereof, which are directly bonded to the same carbon atom. Such groups can also be referred to as 1,1-diphosphonic acid groups, partial esters thereof, or salts thereof. Thus, for example, the at least one organic group can comprise a group comprising the formula Q is bonded to the para position and can be H, R, OR, SR, or NR2, wherein R (which can be the same or different) is H, C1-C18 saturated or unsaturated, branched or unbranched alkyl, C1-C 18 saturated or unsaturated, branched or unbranched acyl, aralkyl, alkaryl, or aryl. For example, Q can be H, R, OR, SR, or NR2, where R (which can be the same or different) is H, C1-C6 alkyl, or aryl. In one embodiment, Q is H, OH, or NH2. Further, the at least one organic group can include a group comprising the formula where Q is as described above and n is 0-9, for example 1 to 9, 0 to 3, or 1 to 3. In one embodiment, n is 0 or 1. Further, the at least one organic group can include a group comprising the formula where Q and n are as described above and Y is an arylene, heteroarylene, alkylene, vinylene, alkarylene, aralkylene, cyclic or heterocyclic group. In one embodiment, Y is an arylene, for example, phenylene, naphthylene, or biphenylene, which can be further substituted with any group, for example, one or more alkyl or aryl groups. When Y is an alkylene, examples include, but are not limited to, substituted or unsubstituted alkylene groups, which can be branched or unbranched and can be substituted with one or more groups, for example, aromatic groups. Examples include, but are not limited to, C1-C 12 groups such as methylene, ethylene, propylene, or butylene.

[0203] Y can be further substituted with one or more groups selected from, but not limited to, R', OR', COR', COOR', OCOR', carboxylate, halogen, CN, NR'2, SO3H, sulfonate, sulfate, NR'(COR'), CONR'2, imide, NO2, phosphate, phosphonate, , SOR', NR'SO2R', and SO2NR2', where R' (which can be the same or different) is independently hydrogen, branched or unbranched C1-C 20 substituted or unsubstituted saturated or unsaturated hydrocarbon, for example, alkyl, alkenyl, alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkaryl, or substituted or unsubstituted aralkyl.

[0204] In one embodiment, the at least one organic group can include a group comprising the formula where Y, Q, and n are as described above. Sp is a spacer group, as used herein, is a linkage between two groups. Sp can be a bond or a chemical group. Examples of chemical groups include, but are not limited to , , , , , , , and cyclic imides derived therefrom, and cyclic imides derived therefrom, and cyclic imides derived therefrom, and cyclic imides derived therefrom (including phthalimides and maleimides of these), sulfonamide groups (including and groups), arylene groups, alkylene groups, and the like. R", which can be the same or different, represents hydrogen or an organic group, such as a substituted or unsubstituted aryl or alkyl group. As shown in the structure above, the group comprising at least two phosphonic acid groups and salts thereof is bonded to Y through a spacer group, Sp. In one embodiment, Sp is where R" is H or C1-C6alkyl.

[0205] Additionally, the at least one organic group can include at least one group comprising the formula R can be H, C1-C 18 saturated or unsaturated, branched or unbranched alkyl, C1-C 18 saturated or unsaturated, branched or unbranched acyl, aralkyl, alkaryl, or aryl. In one embodiment, R is H, C1-C6alkyl, or aryl.

[0206] In one embodiment, the at least one organic group can include more than two phosphonic acid groups, partial esters thereof, and salts thereof, and can comprise, for example, more than one type of group (e.g., two or more), wherein each type of group comprises at least two phosphonic acid groups, partial esters thereof, and salts thereof. For example, the at least one organic group can include a group comprising the formula Y and Q are as described above. In one embodiment, Y is an arylene group, a heteroarylene group, an alkylene group, an alkarylene group, or an aralkylene group. In this formula, p is 1 to 4, for example, p is 2.

[0207] ​​​​​​​​​​​​​​​​​​​​In one embodiment, the at least one organic group can include at least one o-bisphosphonic acid group, partial esters thereof, and salts thereof, meaning that these groups are adjacent to one another. Thus, the at least one organic group can include two phosphonic acid groups, partial esters thereof, and salts thereof, bonded to adjacent or vicinal carbon atoms. Such groups are sometimes also referred to as 1,2-bisphosphonic acid groups, partial esters thereof, or salts thereof. The groups comprising two phosphonic acid groups, partial esters thereof, and salts thereof can be aromatic groups or alkyl groups, thus the o-bisphosphonic acid groups can be o-alkyl or o-arylbisphosphonic acid groups, partial esters thereof, and salts thereof. For example, the at least one organic group can be a group comprising the formula , partial esters thereof, and salts thereof, wherein the acid, ester, or salt groups are located in the ortho position to one another.

[0208] In one embodiment, the at least one organic group includes at least one phosphonic acid group or salt thereof and at least one second ionizable, or basic group, and salts thereof, located in the ortho position or in the geminal position to the phosphonic acid group.

[0209] In one embodiment, the at least one organic group is selected from , , , , , , partial esters thereof, and salts thereof.

[0210] In one embodiment, the at least one organic group includes at least one heterocyclic group (e.g., heteroaryl) comprising at least one OH group, for example at least two OH groups, and salts thereof. The heterocyclic group can be a nitrogen-containing heteroaryl group, for example a pyridyl or quinolyl group, and the at least one organic group is a hydroxypyridyl or hydroxyquinolyl group. The hydroxyl group can be located on the heteroaryl group such that it is geometrically close to the heteroatom, for example in the ortho position to the heteroatom. Such groups can be in the form of a salt. For example, the at least one organic group can include a 2-hydroxypyridyl or 2-hydroxy-quinolyl group, and an 8-hydroxy-quinolyl group and salts thereof. Other isomers or tautomers are also known to those skilled in the art. In one embodiment, the at least one organic group includes an 8-hydroxy-quinolyl group. Additionally, the at least one organic group can further include additional organic groups, including those described above for Y. For example, an electron-withdrawing group, for example a chloro or nitro group, can be included to lower the pKa of the OH group. In one embodiment, the organic group can include at least one heterocyclic group (e.g., heteroaryl) comprising at least one OH group, and salts thereof.

[0211] In one embodiment, the at least one organic group can further include at least one heteroaryl group including at least two OH groups. When two OH groups are present, the OH groups can be located ortho to each other on the heteroaryl group. When more than two OH groups are present, at least two of the OH groups can be located ortho to each other on the heteroaryl group. For example, the at least one organic group can be a dihydroxy-pyridyl group, such as a 2,3-dihydroxy-pyridyl group (which can also be referred to as a 3-hydroxy-2-pyridyl group), a 3,4-dihydroxy-pyridyl group (which can also be referred to as a 3-hydroxy-4-pyridyl group), a 2,3-dihydroxy-quinolyl group (which can also be referred to as a 3-hydroxy-2-quinolyl group), or a 3,4-dihydroxy-quinolyl group (which can also be referred to as a 3-hydroxy-4-quinolyl group). Other isomers and tautomers are also known to those skilled in the art.

[0212] In one embodiment, the at least one organic group includes at least one phosphonic acid group, partial esters thereof, and salts thereof and at least one second ion, ionizable group, or basic group. The second group is not a phosphonic acid group or salt thereof. In one embodiment, the second ion or ionizable group is a carboxylic acid group, a sulfonic acid group, or a salt thereof. In one embodiment, the basic group is a Lewis base, such as an OH group (hydroxyl) or an amino group. In one embodiment, the two groups are located geminal to each other, meaning directly bonded to the same carbon atom. Thus, for example, when the second ion or ionizable group is a carboxylic acid group or salt thereof, the at least one organic group can include a group including the formula and salts thereof. Q, which is bonded to the geminal position, can be any of the above. In one embodiment, Q is H. Additionally, the at least one organic group can include a group including the formula and salts thereof, where n is 0 to 9, such as 0 to 3. Further, the at least one organic group can include a group including the formula and salts thereof, where Y is as described above. In one embodiment, Y is an arylene group. Further, the at least one organic group can include a group including the formula and salts thereof, where Y and Sp (which is a spacer group) are as described above. In one embodiment, Y is an arylene group.

[0213] In one embodiment, the at least one organic group can include at least one phosphonic acid group, partial esters thereof, and salts thereof and at least one hydroxyl group or salt thereof, such as a group including the formula and salts thereof, where Y is as described above. In one embodiment, Y is an arylene group and the phosphonic acid group and the hydroxyl group are located ortho to each other. When the groups are located geminal, the at least one organic group can include at least one group including the formula and / or salts thereof, where R is H or a C1-C6 alkyl group. In one embodiment, R is H. Additionally, the at least one organic group can include at least one group including the formula The group and its salt, wherein n is 0 to 9, for example 0 to 3. Furthermore, the at least one organic group may include the formula... and its salt or and its salt groups, wherein Y and Sp are as described above.

[0214] In one embodiment, the at least one organic group comprises an aryl or alkyl polyacid group containing at least three carboxylic acids. In one embodiment, at least two carboxylic acid groups are in the ortho position, meaning they are bonded to adjacent atoms (e.g., adjacent carbon atoms). For example, the at least one organic group is an aryl polyacid group containing at least three carboxylic acids, such as 1,2,3- or 1,2,4-tricarboxylic acids, or 1,2,3,4- or 1,2,4,5-tetracarboxylic acid groups.

[0215] In one embodiment, the at least one organic group comprises a heterocyclic group containing at least one carboxylic acid group or a salt thereof. The heteroaryl group can be any known in the art. In one embodiment, the heteroaryl group is a nitrogen-containing heteroaryl group, such as pyridyl, pyrimidinyl, pyrroloyl, quinolinyl, or pyrazinyl. In one embodiment, the at least one organic group comprises two carboxylic acid groups and their salts. These acid groups can be located at any position on the heteroaryl ring. In one embodiment, the acid groups can be located ortho or meta relative to each other. Furthermore, when the heteroaryl group contains at least one nitrogen atom, both acid groups can be adjacent to the nitrogen atom (i.e., ortho). Thus, for example, the heteroaryl group can be a 2,6-pyridyl-dicarboxylic acid group.

[0216] In one embodiment, the at least one organic group comprises an aryl group containing at least one nitrosyl group and at least one OH group, or a salt thereof. These two groups may be located at any position on the aryl group. In one embodiment, the aryl group is phenyl, and the nitrosyl group and the OH group are ortho-ortho to each other. The aryl group may further contain other substituents, such as alkyl, halogen, ether, etc., including electron-withdrawing groups, such as chlorine and nitro groups, which are capable of lowering the pKa of the at least one organic group, regardless of its tautomerism. For example, the at least one organic group may be a nitrosophenolic group, such as the inclusion group. Groups or inclusion formulas The group, where Z is an electron-withdrawing group, such as chlorine or nitro.

[0217] In one embodiment, the at least one organic group comprises an azo aromatic group. For example, the at least one organic group may include an inclusion group. The group, in which Ar 1 and Ar 2 (They may be the same or different) are arylene, such as phenylene or naphthylene, or aryl, such as phenyl or naphthyl, and Ar 1Or Ar 2 At least one of them is an aryl group. In this embodiment, the azo aromatic group has at least one or at least two OH groups, at least one or at least two NH2 groups, or at least one OH group and at least one NH2 group. Therefore, for example, the azo aromatic group may have the formula... (dihydroxyazo aromatic group), (diaminoazo aromatic group) or or (Amino-hydroxyazo aromatic group). Other combinations are also possible. In one embodiment, the OH and / or NH2 groups are located adjacent to the azo group (N=N group). For example, the at least one organic group may be a structure containing... The group may also include electron-withdrawing groups, such as chlorine or nitro, on the aryl and / or arylene groups. For example, the at least one organic group may be a structure containing... The group, where Z is an electron-withdrawing group such as chlorine or nitro.

[0218] In one implementation, at least a portion of the second monomer is contained in the form -AN(R) 3 (R) 4 Functionalization of at least one organic group of ) (or for polymers containing at least one organic group having a desired calcium index value, at least a second portion of the second monomer is functionalized with at least one second organic group), wherein R 3 and R 4 Independently selected from H, C1-C 10 Alkyl, C4-C 18 Aryl, C4-C 18 heteroaryl and C3-C 20 Heterocyclic alkyl, and A is selected from C1-C1. 10 Alkylene, C3-C 20 Cycloalkylene, C3-C 20 Heterocyclic alkyl groups (where at least one ring atom of the alkyl group is a heteroatom selected from O, N, and S), aryl groups, heteroaryl groups (where at least one ring atom of the heteroaryl group is a heteroatom selected from O, N, and S), and C2-C 20 Ether. In another embodiment, at least a portion of the second monomer is functionalized with at least one organic group selected from the following formula (or, for polymers containing at least one organic group having a desired calcium index value, at least a second portion of the second monomer is functionalized with at least one second organic group): , , , , , , , , and In yet another embodiment, at least a second portion of the second monomer is functionalized with at least one organic group comprising the formula (or, for polymers containing at least one organic group having a desired calcium index value, at least a second portion of the second monomer is functionalized with at least a second organic group), wherein R 3 , R 4 , and R 5 are independently selected from the group consisting of H, Ci-C 10 alkyl, C4-C 18 aryl, C4-C 18 heteroaryl, and C3-C 20 heterocycloalkyl, and A is selected from the group consisting of Ci-C 10 alkylene, C3-C 20 cycloalkylene, C3-C 20 heterocycloalkylene, arylene, heteroarylene, and C2-C 20 ether. In any of these embodiments, the at least one organic group is bonded to the portion of the second monomer through amide, imide, and ester linkages, for example through amide linkages and ester linkages.

[0219] In one embodiment, the at least one polymer can be used as a polymeric dispersant to disperse pigments in a liquid medium, such as an aqueous medium. Dispersion can be carried out by methods known in the art, such as mixing (e.g., with a high shear mixer), sonication, milling (e.g., with a media or ball mill), and the like. In one embodiment, crosslinking is carried out by adding a crosslinking agent to the polymericly dispersed pigments.

[0220] In one embodiment, the composition comprises pigments that are polymericly dispersed pigments comprising at least one polymer adsorbed to or encapsulating the pigments (e.g., polymerically encapsulated pigments). In another embodiment, the at least one polymer is crosslinked by a second monomer. For example, polymerically encapsulated pigments can include polymericly dispersed pigments in which the at least one polymer is crosslinked with a plurality of crosslinking agents. The pigments can be any of the pigments described herein, such as unmodified or untreated pigments, or modified (self-dispersing) pigments.

[0221] In one embodiment, the at least one polymer is crosslinked by at least one linkage selected from the group consisting of amide, imide, ester, ether, and thioether linkages (e.g., amide, ester, and ether linkages, or amide and ester linkages). For example, crosslinking agents such as multifunctional reagents (e.g., di-, tri-, etc.) containing two or more epoxy, thiol (mercapto), and amine groups, and mixtures thereof, can be used to form linkages, for example, in reaction with carboxylate-containing groups of the second monomer. In one embodiment, the second monomer of at least two different polymers (e.g., comprising maleic anhydride, maleic acid and salts thereof, esters, imides, and amides, etc.) can react with the crosslinking agent. In one embodiment, the crosslinking agent is selected from the group consisting of epoxy-containing compounds, for example, di- or tri-epoxy-based compounds, for example, trimethylolpropane polyglycidyl ether, for example, to form crosslinked polymers comprising ester linkages. In one embodiment, the ester linkage results from the reaction between an epoxy-containing compound (e.g., di- and tri-glycidyl ether compounds, for example, trimethylolpropane polyglycidyl ether) and a carboxylate-containing group of the second monomer. In another embodiment, the crosslinking agent is selected from the group consisting of aminoethylthiol.

[0222] In one embodiment, the at least one polymer is crosslinked by a carboxylate-containing group of the second monomer, for example, anhydride, carboxylic acid and salts thereof, ester, imide, and amide, or carboxylic acid and salts thereof. In one embodiment, the at least one polymer can hydrolyze to produce a carboxylate-containing group (e.g., carboxylic acid or carboxylic acid salt) if containing an anhydride, carboxylic acid and salts thereof, ester, imide, and amide, which can react with the crosslinking agent. The hydrolysis to produce the carboxylic acid or carboxylic acid salt can be performed prior to or concurrently with the addition of the crosslinking agent.

[0223] In another embodiment, the at least one polymer is crosslinked by at least 10% of the carboxylate-containing groups of the second monomer, for example, 10% to 50%, 10% to 40%, or 10% to 30% of the carboxylate-containing groups of the second monomer. In one embodiment, the amount of carboxylate-containing groups targeted for crosslinking (“%Target CO2”) can be determined by the amount of crosslinking agent added.

[0224] In one embodiment, the acid value of the crosslinked at least one polymer (“An(xlink)”) is less than 325. In one embodiment, the acid value of the at least one polymer is defined as a theoretical value related to the acid value of the starting polymer (“AN(SP)”) and the percentage of carboxylate targeted for crosslinking (“%Target CO2”), which conforms to the following equation:

[0225]

[0226] In one embodiment, the acid number AN(xlink) of the at least one polymer is less than 300, less than 275, less than 250, or less than 200. In another embodiment, the acid number AN(xlink) of the at least one polymer is from 50 to 325, for example, an acid number from 50 to 300, 50 to 275, 50 to 250, 50 to 225, 50 to 200, 75 to 325, 75 to 300, 75 to 275, 75 to 250, 75 to 225, 75 to 200, 90 to 325, 90 to 300, 90 to 275, 90 to 250, 90 to 225, or 90 to 200.

[0227] In one embodiment, the at least one polymer is present in the composition in an amount of from 0.1 wt% to 25 wt%, for example, from 0.1 wt% to 20 wt%, from 0.2 wt% to 25 wt%, from 0.2 wt% to 20 wt%, from 0.5 wt% to 25 wt%, or from 0.5 wt% to 20 wt%, relative to the total weight of the inkjet ink composition.

[0228] In one embodiment, the weight average molecular weight (M w ) of the at least one polymer (e.g., the at least one polymer crosslinked by the second monomer) is at least 1000, for example, at least 2000 or at least 3000 (for uncrosslinked polymers). In another embodiment, the M w is less than or equal to 200,000, for example, less than 150,000, less than 100,000, or less than 70,000. In one embodiment, the M w is from 1000 to 200,000, for example, from 1000 to 150,000, from 1000 to 100,000, from 1,000 to 70,000, from 2000 to 200,000, from 2000 to 150,000, from 2000 to 100,000, from 2000 to 70,000, from 3000 to 200,000, from 3000 to 150,000, from 3000 to 100,000, or from 3000 to 70,000.

[0229] In one embodiment, the pH of the composition comprising the at least one polymer (e.g., the at least one polymer crosslinked by the second monomer) is from 8 to 11, for example, a pH from 8.5 to 11, from 8 to 10.5, from 8.5 to 10.5, from 8 to 10, or from 8.5 to 10. In one embodiment, the composition is a dispersion (e.g., an aqueous dispersion) comprising, consisting essentially of, or consisting of the at least one polymer, at least one pigment, and a liquid carrier (e.g., an aqueous solution or water).

[0230] Another embodiment provides a method of making a polymer (e.g., a polymer capable of binding divalent metal ions, for example, a calcium and / or magnesium binding polymer) comprising:

[0231] (a) combining:

[0232] (i) at least one polymer comprising: a first monomer selected from an ethylenically unsaturated hydrophobic monomer, and a second monomer selected from maleic anhydride, maleic acid and salts, esters, imides and amides thereof, and

[0233] (ii) at least one agent comprising an amino group and at least one organic group having a calcium index value greater than that of phenylphosphonic acid; and

[0234] (b) forming a polymer.

[0235] In one embodiment, the combining is conducted in the presence of at least one base selected from NH4OH, NaOH and KOH. In one embodiment, the at least one agent comprises an amino group selected from a primary amine.

[0236] Another embodiment provides a method of making a polymer, comprising,

[0237] (a) combining:

[0238] (i) at least one polymer comprising: a first monomer selected from an ethylenically unsaturated hydrophobic monomer, and a second monomer selected from maleic anhydride, maleic acid and salts, esters, imides and amides thereof, wherein the ethylenically unsaturated hydrophobic monomer comprises the formula wherein R 1 and R 2 are independently selected from H, C1-C 12 alkyl, C5-C 20 aryl and C6-C 20 alkaryl, and the carbon atoms of R 1 and R 2 may be optionally substituted with at least one heteroatom selected from O, N and S, and

[0239] (ii) at least one crosslinking agent selected from an epoxy-containing compound; and

[0240] (b) forming a polymer.

[0241] In one embodiment, any of the methods described herein further comprise combining the polymer with at least one crosslinking agent, for example selected from an epoxy-containing compound, for example a di- or tri-epoxy-based compound disclosed herein, for example trimethylolpropane triglycidyl ether. In one embodiment, the method comprises combining the polymer with the at least one crosslinking agent and boric acid. In one embodiment, the at least one crosslinking agent selected from an epoxy-containing compound reacts with the carboxylate-containing group of the second monomer.

[0242] In one embodiment, wherein the at least one polymer is combined with at least one crosslinking agent prior to or simultaneously, the method further comprises hydrolyzing the at least one polymer. Hydrolysis can be performed by any method known in the art, for example by adding water and / or at least one base, for example at least one base selected from the group consisting of NH4OH, NaOH, and KOH. In one embodiment, hydrolysis results in carboxylate-containing groups (e.g., carboxylic acid or carboxylate salt groups) of a second monomer that can react with the at least one crosslinking agent. In one embodiment, the pH of the composition (e.g., a solution containing the polymer) is from 8 to 11, for example from 8.5 to 11 or from 8.5 to 10.5, when the crosslinked polymer is formed.

[0243] pigment

[0244] In one embodiment, the inkjet ink composition comprises at least one pigment, which can be unmodified or modified. The pigment is a solid material, which is typically in the form of a particle or readily forms a particle, for example a press cake. In one embodiment, the modified pigment has at least one moiety (fragment) attached, for example an acid group (and partial salts, partial esters, salts, and esters thereof) and an organic group. In another embodiment, the modified pigment is an oxidized pigment, which can further comprise a moiety attached. In one embodiment, the modified pigment is self-dispersible, such that no external dispersant is needed to disperse the pigment (self-dispersible pigment).

[0245] In one embodiment, wherein the pigment is unmodified, the at least one polymer can further act as a dispersant. In one embodiment, wherein the pigment is modified, the at least one polymer can further act as an additive. In either embodiment, the polymer can improve one or more print performance properties, for example O.D., spot, and durability.

[0246] The unmodified pigment can be any type of pigment routinely used by those skilled in the art, for example black pigments and other colored pigments, including blue, black, brown, cyan, green, white, violet, magenta, red, orange, or yellow pigments. Mixtures of different pigments can also be used. Representative examples of black pigments include various carbon blacks (Pigment Black 7), for example channel blacks, furnace blacks, gas blacks, and lamp blacks, and include, for example, carbon blacks sold under the following names by Cabot Corporation: Regal® ® , Black Pearls® ® , Elftex® ® , Monarch® ® , Mogul® ® , and Vulcan® ® carbon blacks (e.g., Black Pearls®® 2000, Black Pearls ® 1400, Black Pearls ® 1300, Black Pearls ® 1100, Black Pearls ® 1000, Black Pearls ® 900, Black Pearls ® 880, Black Pearls ® 800, Black Pearls ® 700, Black Pearls ® 570, Black Pearls ® L, Elftex ® 8, Monarch ® 1400, Monarch ® 1300, Monarch ® 1100, Monarch ® 1000, Monarch ® 900, Monarch ® 880, Monarch ® 800, Monarch ® 700, Regal ® 660, Mogul ® L, Regal ® 330, Regal ® 400, Vulcan® P). Carbon blacks available from other suppliers can be used. Suitable classes of color pigments include, for example, anthraquinone, phthalocyanine blue, phthalocyanine green, diazonium, monoazo, indanthrone, quinolonoquinolone, and (thio)indigoid. These pigments are commercially available in powder or press cake form from many sources, including BASF Corporation, Engelhard Corporation, Sun Chemical Corporation, Clariant, and Dianippon Ink and Chemicals (DIC). Examples of other suitable color pigments are described in Colour Index, 3rd Edition (The Society of Dyers and Colourists, 1982). In one embodiment, the pigment is a cyan pigment, such as Pigment Blue 15, Pigment Blue 15:3, Pigment Blue 15:4, or Pigment Blue 60, a magenta pigment, such as Pigment Red 122, Pigment Red 177, Pigment Red 185, Pigment Red 202, or Pigment Violet 19, a yellow pigment, such as Pigment Yellow 74, Pigment Yellow 128, Pigment Yellow 139, Pigment Yellow 155, Pigment Yellow 180, Pigment Yellow 185, Pigment Yellow 218, Pigment Yellow 220, or Pigment Yellow 221, an orange pigment, such as Pigment Orange 168, a green pigment, such as Pigment Green 7 or Pigment Green 36, or a black pigment, such as carbon black.

[0247] In one embodiment, the pigment is a high structure carbon black, such as a carbon black having the following properties:

[0248] ; and

[0249] The ratio of STSA / BET is 0.7 to 1.

[0250] In one embodiment, the ratio of STSA / BET is 0.8 to 1, such as 0.9 to 1. In one embodiment, the carbon black has a STSA of 160 to 220 m 2 / g. In another embodiment, the carbon black has a BET surface area of at least 150 m 2 / g, such as at least 170 m 2 / g, at least 190 m2 / g, ranging from 190 to 275 m 2 / g. In another embodiment, the compressed OAN (COAN) of the carbon black is at least 120 mL / 100 g, for example, at least 130 mL / 100 g. OAN and COAN can be determined according to ASTM-D2414. Surface area measurements can be determined according to ASTM-D6556. Further details regarding this carbon black can be found in U.S. Patent No. 9,388,300, the disclosure of which is incorporated herein by reference.

[0251] In one embodiment, the self-dispersing pigment is carbon black oxide. In one embodiment, "carbon black oxide" is a carbon black pigment typically with a pH < 7.0, characterized by surface-bound ionic or ionizable groups, such as one or more of the following: alcohols (phenols, naphthols), lactones, carbonyl compounds, carboxyl compounds (e.g., carboxylic acids), acid anhydrides, ethers, and quinones. The degree of oxidation of the carbon black determines the surface concentration of these groups. In one embodiment, carbon black oxide is obtained by oxidizing unmodified carbon black (e.g., pigments selected from channel black, furnace black, gas black, and lampblack). Exemplary unmodified carbon black includes carbon black commercially available from Cabot Corporation under the name Regal. ® Black Pearls ® Elftex ® Monarch ® Mogul ® and Vulcan ® For example, Black Pearls ® 1100, Black Pearls ® 900, Black Pearls ® 880, BlackPearls ® 800, Black Pearls ® 700, Black Pearls ® 570, Elftex ® 8. Monarch ® 900, Monarch ® 880, Monarch ® 800, Monarch ® 700, Regal ® 660 and Regal ®330. Exemplary oxidants for carbon black include oxygen, ozone, peroxides such as hydrogen peroxide, persulfates such as sodium persulfate and potassium persulfate, hypohalates such as sodium hypochlorite, nitric acid, and transition metal-containing oxidants such as permanganates, osmium tetroxide, chromium oxide, cerium ammonium nitrate, and mixtures thereof (e.g., gaseous oxidants such as a mixture of oxygen and ozone).

[0252] In another implementation, the carbon black oxide is obtained from commercial sources, such as Black Pearls. ® 1400, Black Pearls ® 1300, Black Pearls ® 1000, Black Pearls ® L, Monarch ® 1000, Mogul ® L and Regal ® 400, which can be purchased commercially from Cabot Corporation.

[0253] In one embodiment, the pigment is linked to at least one organic group, wherein the "linked" organic group is distinguishable from the adsorbed group because Soxhlet extraction for several hours (e.g., at least 4, 6, 8, 12, or 24 hours) does not remove the linked group from the pigment. In another embodiment, the organic group is linked to the pigment if it cannot be removed after repeated washing with a solvent or solvent mixture that dissolves the starting organic treatment material but cannot disperse the treated pigment. In yet another embodiment, "linked" refers to a bond such as a covalent bond, for example, a pigment bonded or covalently bonded to a nucleophile or organic group.

[0254] In one embodiment, the at least one organic group may be an aliphatic group, a cyclic organic group, or an organic compound having both an aliphatic and a cyclic moiety, such as arylene, heteroarylene, and alkylene. In one embodiment, the organic group is linked by a diazonium salt derived from a primary amine, which can form the diazonium salt even transiently. Other linking methods are described below. The organic group may be substituted or unsubstituted, branched or unbranched. Aliphatic groups include, for example, groups derived from alkanes, alkenes, alcohols, ethers, aldehydes, ketones, carboxylic acids, and carbohydrates. Cyclic organic groups include, but are not limited to, alicyclic hydrocarbon groups (e.g., cycloalkyl, cycloalkenyl), heterocyclic hydrocarbon groups (e.g., pyrrolyl, pyrrololinyl, piperidinyl, morpholinyl, etc.), aryl (e.g., phenyl, naphthyl, anthracene), and heteroaryl (imidazolyl, pyrazolyl, pyridinyl, thiophene, thiazolyl, furanyl, indolyl, and triazolyl, such as 1,2,4-triazolyl and 1,2,3-triazolyl).

[0255] Arylene, heteroarylene, and alkylene groups can be unsubstituted or substituted. Exemplary arylene groups include phenylene, naphthylene, and biphenylene, and exemplary heteroarylene groups include phenylene, naphthylene, and biphenylene groups having a ring carbon replaced by one or more oxygen or nitrogen atoms. In one embodiment, the arylene group is C5-C 20 Arylene. Heteroarylene groups can be arylene groups as defined herein in which one or more ring carbon atoms are replaced by a heteroatom, such as N, O, and S. In addition to being a ring atom, the heteroatom can also be bonded to other groups. Alkylene groups can be branched or unbranched. Alkylene groups can be C1-C 12 Alkylene, such as methylene, ethylene, propylene, or butylene.

[0256] In one embodiment, the at least one linking organic group comprises at least one ionic group, ionizable group, or a mixture of ionic and ionizable groups. Ionic groups can be anionic or cationic, and can be associated with a counterion of opposite charge, including inorganic or organic counterions, such as Na + , K + , Li + , NH4 + , NR'4 + , acetate, NO3 2- , , , OH - , or Cl - , where R' represents hydrogen or an organic group, such as a substituted or unsubstituted aryl or alkyl group. Ionizable groups are groups that are capable of forming ionic groups in the use medium. Anionic groups are negatively charged ionic groups that can be produced from groups having ionizable substituents (anionizable groups), such as acidic substituents. Cationic groups are positively charged organic ionic groups that can be produced from ionizable substituents that form cations (cationizable groups), such as protonated amines. Specific examples of anionic groups include , , , ; or , and specific examples of anionizable groups can include , , , or , where R' represents hydrogen or an organic group, such as a substituted or unsubstituted aryl or alkyl group. In addition, specific examples of cationic or cationizable groups include alkyl amines or aryl amines that can be protonated in an acidic medium to form an ammonium group where R' represents an organic group, such as a substituted or unsubstituted aryl or alkyl group. Organic ionic groups include those described in U.S. Patent No. 5,698,016, the disclosure of which is incorporated herein by reference.

[0257] For example, the linking group can be an organic group, such as a benzoic acid group (benzoate group), a phthalic acid group, a tricarboxybenzene acid group, a benzene sulfonic acid group (bulfonate group), or a salt thereof. In one embodiment, surface modification can also be used to introduce ionic or ionizable groups onto the surface of the pigment, such as chlorination and sulfonylation.

[0258] In one embodiment, the at least one organic group attached to the pigment is capable of binding calcium (e.g., has a defined calcium index value), including those described in PCT Patent Publication No. WO 2007 / 053564, the disclosure of which is incorporated herein by reference, such as the groups described herein as being capable of binding calcium. For example, the organic group includes at least one diphosphonic acid group, partial ester thereof, or salt thereof, such as a group having the formula where Q is bonded to geminal positions and can be H, R, OR, SR, or NR2, where R" (which can be the same or different) is as defined above, or can be H, C1-C 18 saturated or unsaturated, branched or unbranched alkyl, C1-C 18 saturated or unsaturated, branched or unbranched acyl, aralkyl, alkaryl, or aryl. In addition, U.S. Patent Nos. 5,672,198, 5,922,118, 6,042,643, and 6,641,656 disclose modified pigments having various linking groups, including phosphonic acid groups, the disclosures of which are incorporated herein by reference.

[0259] In one embodiment, the pigment (carbon black or color pigment) is modified (e.g., has an organic group attached) by diazotization treatment with at least one organic group, for example, as detailed in U.S. Patent Nos. 5,554,739; 5,630,868; 5,672,198; 5,707,432; 5,851,280; 5,885,335; 5,895,522; 5,900,029; 5,922,118; 6,042,643; 6,506,245, 6,534,569; 6,641,653, 7,223,302, 6,398,858 and 6,494,943 (high shear conditions) 6,372,820; 6,368,239; 6,350,519; 6,337,358; 6,103,380; 7,173,078; 7,056,962; 6,942,724; 6,929,889; 6,911,073; 6,478,863; 6,472,471; WO 2011 / 143533; and 8,858,695, the disclosures of which are incorporated herein by reference. In one embodiment, attachment is provided by a diazotization reaction, wherein the at least one organic group has a diazonium salt substituent. In another embodiment, direct attachment can be formed by using a diazotization and stable free radical method, described for example in U.S. Patent Nos. 6,068,688; 6,337,358; 6,368,239; 6,551,393; 6,852,158, the disclosures of which are incorporated herein by reference, which utilizes the interaction of at least one transition metal compound with at least one organic halide compound in the presence of one or more free radical trapable particulates or the like to produce free radicals. In yet another embodiment, the pigment (carbon black or color pigment) can be modified (e.g., have an organic group attached) by using the following methods: U.S. Patent Nos. 5,837,045, 6,660,075 and WO 2009 / 048564 (reaction with an organic compound containing a C--C double or triple bond activated by at least one substituent) or U.S. Patent Publication No. 2004 / 0171725, 6,664,312, 6,831,194 (reaction with an acid anhydride component), 6,936,097, U.S. Patent Publication Nos. 2001 / 0036994, 2003 / 0101901 (reaction with an organic group having a group), Canadian Patent No. 2,351,162, European Patent No. 1394221 and PCT Publication Nos. WO 01 / 51566 (reaction between at least one electrophile and at least one nucleophile), WO04 / 63289, WO 2010 / 141071 (reaction with The reaction, where A is a heteroatom) and WO 99 / 23174, the contents of which are incorporated herein by reference.

[0260] In one embodiment, the dispersion may be formulated to provide a certain amount of pigment such that the final amount in the inkjet ink composition effectively provides the desired image quality (e.g., optical density) without adversely affecting the performance of the inkjet ink. In one embodiment, the amount of colorant (e.g., pigment) present is from 1% to 15% by weight, for example, from 1% to 10% by weight, relative to the total weight of the composition, for example, from 2% to 10% by weight, from 3% to 10% by weight, from 2% to 7% by weight, or from 3% to 7% by weight, relative to the total weight of the composition.

[0261] Dispersion and inkjet ink composition

[0262] In one embodiment, the composition comprises a liquid carrier. In one embodiment, the liquid carrier is aqueous. In one embodiment, the composition comprises a pigment to produce a dispersion, such as an aqueous dispersion, such as an inkjet ink composition. In one embodiment, the composition, dispersion, or inkjet ink composition comprises a liquid carrier containing at least 40% water (aqueous solution), such as at least 45% water or at least 50% water.

[0263] In one embodiment, the composition, dispersion, or inkjet ink composition comprises at least one organic solvent present in an amount of 1% to 50% relative to the total weight of the inkjet ink composition, or in other amounts disclosed herein. The at least one organic solvent may also be present in addition to at least 40% water (or at least 45% water or at least 50% water). In one embodiment, the organic solvent is soluble or miscible in water. In another embodiment, the organic solvent is chemically stable to aqueous hydrolysis conditions (e.g., reaction with water under thermal aging conditions, including, for example, the hydrolysis of esters and lactones). In one embodiment, the dielectric constant of the organic solvent is lower than that of water, for example, a dielectric constant of 20. Examples of suitable organic solvents include: low molecular weight diols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, triethylene glycol monomethyl ether or monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and tetraethylene glycol monobutyl ether); alcohols (e.g., ethanol, propanol, isopropanol, n-butanol, sec-butanol, and tert-butanol, 2-propyn-1-ol (propynyl alcohol), 2-buten-1-ol, 3-buten-2-ol, 3-butyn-2-ol and cyclopropanol); diols containing about 2 to about 40 carbon atoms (e.g., 1,3-pentanediol, 1,4-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 2,6-hexanediol, neopentanediol (2 2-Dimethyl-1,3-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2,6-hexanetriol and poly(ethylene-co-propylene) glycols and their reaction products with alkylene oxides (including ethylene oxide, including ethylene oxide and propylene oxide); triols containing about 3 to about 40 carbon atoms (e.g., glycerol, trimethylolethane, trimethylolpropane, 1,3,5-pentanetriol, 1,2,6-hexanetriol, etc. and their reaction products with alkylene oxides (including ethylene oxide, propylene oxide and mixtures thereof); polyols (e.g., pentaerythritol); amides (e.g., dimethylformaldehyde and dimethylacetamide); ketones or ketols (e.g., acetone and diacetone alcohol); ethers (e.g., tetrahydrofuran and diacetone alcohol). Alkane); lactams (e.g., 2-pyrrolidone, N-methyl-2-pyrrolidone and... -Caprolactam); urea or urea derivatives (e.g., di-(2-hydroxyethyl)-5,5,-dimethylhydantoin (dantacol) and 1,3-dimethyl-2-imidazolidineone); inner salts (e.g., betaine); and hydroxyamide derivatives (e.g., acetylethanolamine, acetylpropanolamine, propylcarboxyethanolamine, and propylcarboxypropanolamine, and their reaction products with epoxides). Other examples include sugars (e.g., maltitol, sorbitol, gluconolactone, and maltose); sulfoxide derivatives (symmetric and asymmetric) containing about 2 to about 40 carbon atoms (e.g., dimethyl sulfoxide, methyl ethyl sulfoxide, and alkylphenyl sulfoxide); and sulfone derivatives (symmetric and asymmetric) containing about 2 to about 40 carbon atoms (e.g., dimethyl sulfone, methyl ethyl sulfone, sulfolane (tetramethylene sulfone, cyclosulfone), dialkyl sulfone, alkylphenyl sulfone, dimethyl sulfone, methyl ethyl sulfone, diethyl sulfone, ethylpropyl sulfone, methylphenyl sulfone, methyl sulfolane, and dimethyl sulfolane). Organic solvents may include mixtures of organic solvents.

[0264] The amount of solvent can vary depending on various factors, including the nature of the solvent (solubility and / or dielectric constant), the type of colorant, and the desired properties of the resulting inkjet ink composition. The solvent can be used in an amount of 1 to 40 weight %, including an amount of 1 to 30 %, or an amount of 1 to 20 %, based on the total weight of the inkjet ink composition. In another embodiment, the amount of solvent is greater than or equal to about 2 weight %, including greater than or equal to about 5 % and greater than or equal to about 10 weight %, based on the total weight of the aqueous dispersion or inkjet ink composition.

[0265] In one embodiment, the ink composition (e.g., inkjet ink composition) includes at least one surfactant, for example when the pigment is not self-dispersible. The at least one surfactant can enhance the colloidal stability of the composition or modify the interaction of the ink with a printing substrate (e.g., printing paper) or with the ink printing head. Various anionic, cationic, and nonionic dispersants can be used with the ink compositions of the present application, either neat or as aqueous solutions. In one embodiment, the surfactant is present in an amount of 0.05 to 5 weight %, for example in an amount of 0.1 to 5 weight %, or 0.5 to 2 weight %, relative to the total weight of the inkjet ink composition.

[0266] Representative examples of anionic dispersants or surfactants include, but are not limited to, higher fatty acid salts, higher alkyl dicarboxylic acid salts, sulfuric ester salts of higher alcohols, higher alkyl sulfonic acid salts, alkyl benzene sulfonic acid salts, alkyl naphthalene sulfonic acid salts, naphthalene sulfonic acid salts (Na, K, Li, Ca, etc.), condensates between formalin polycondensates, higher fatty acids, and amino acids, dialkyl sulfosuccinic acid ester salts, alkyl sulfosuccinic acid salts, naphthenic acid salts, alkyl ether carboxylic acid salts, acylated peptides, alkyl ether phosphoric acid salts, and alkyl phosphoric acid salts, alkyl phosphonic acid salts and diphosphonic acid salts, including hydroxylated or aminated derivatives. For example, polymers and copolymers of styrene sulfonic acid salts, unsubstituted and substituted naphthalene sulfonic acid salts (e.g., alkyl or alkoxy substituted naphthalene derivatives), aldehyde derivatives (e.g., unsubstituted alkyl aldehyde derivatives, including formaldehyde, acetaldehyde, propionaldehyde, etc.), maleic acid salts, and mixtures thereof can be used as anionic dispersing aids. The salts include, for example, Na + , Li + , K + , Cs + , Rb + , and substituted and unsubstituted ammonium cations. Representative examples of cationic surfactants include aliphatic amines, quaternary ammonium salts, sulfonium salts, sulfonium salts, phosphonium salts, and the like.

[0267] Representative examples of nonionic dispersants or surfactants that can be used in the inkjet ink of the present application include fluorine derivatives, silicone derivatives, acrylic copolymers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene secondary alcohol ethers, polyoxyethylene styrol ethers, ethoxylated acetylene diols, polyoxyethylene lanolin derivatives, ethylene oxide derivatives of alkyl phenol formalin condensates, polyoxyethylene polyoxypropylene block polymers, fatty acid esters of polyoxyethylene polyoxypropylene alkyl ether polyoxyethylenated compounds, polyethylene oxide condensation type glycol fatty acid esters, fatty acid monoglycerides, fatty acid esters of polyglycerol, fatty acid esters of propylene glycol, sucrose fatty acid esters, fatty acid alkylol amides, polyoxyethylene fatty acid amides, and polyoxyethylene alkyl amine oxides. For example, ethoxylated mono- or di-alkyl phenols can be used. These nonionic surfactants or dispersants can be used alone or in combination with the anionic and cationic dispersants described above.

[0268] In one embodiment, the inkjet ink composition comprises a polymer disclosed herein as the first polymer, and further comprises a second polymer, which is a polymeric dispersant, such as a natural or synthetic polymeric dispersant. Specific examples of natural polymeric dispersants include proteins, such as gelatin, gelatin, casein, and albumin; natural rubbers, such as gum arabic and gum tragacanth; glucosides, such as saponin; alginic acid and alginic acid derivatives, such as alginic acid propylene glycol ester, triethanolamine alginate, and ammonium alginate; and cellulose derivatives, such as methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, and ethylhydroxy cellulose. Specific examples of polymeric dispersants include synthetic polymeric dispersants, including polyvinyl alcohol, polyvinylpyrrolidone, acrylic or methacrylic resins (often written as “(meth)acrylic”) such as poly(meth)acrylic acid, acrylic-(meth)acrylonitrile copolymer, (meth)acrylic acid-potassium-(meth)acrylonitrile copolymer, vinyl acetate-(meth)acrylate copolymer, and (meth)acrylic acid-(meth)acrylate copolymer; styrene-acrylic or methacrylic resins such as styrene-(meth)acrylic acid copolymer, styrene-(meth)acrylic acid-(meth)acrylate copolymer, styrene- methylstyrene-(meth)acrylic acid copolymer, styrene-methylstyrene-(meth)acrylic acid-(meth)acrylate copolymer; vinyl naphthalene-acrylic or methacrylic acid copolymer; vinyl naphthalene-maleic acid copolymer; and vinyl acetate copolymers such as vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate-maleate copolymer, vinyl acetate-tiglic acid copolymer, and vinyl acetate-acrylic acid copolymer; and salts thereof. - methylstyrene-(meth)acrylic acid-(meth)acrylate copolymer; vinyl naphthalene-acrylic or methacrylic acid copolymer; vinyl naphthalene-maleic acid copolymer; and vinyl acetate copolymers such as vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate-maleate copolymer, vinyl acetate-tiglic acid copolymer, and vinyl acetate-acrylic acid copolymer; and salts thereof. - methylstyrene-(meth)acrylic acid-(meth)acrylate copolymer; vinyl naphthalene-acrylic or methacrylic acid copolymer; vinyl naphthalene-maleic acid copolymer; and vinyl acetate copolymers such as vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate-maleate copolymer, vinyl acetate-tiglic acid copolymer, and vinyl acetate-acrylic acid copolymer; and salts thereof.

[0269] In one embodiment, the viscosity of the inkjet ink composition is 1-25 cP. It should be understood that the viscosity can be adjusted by various methods. In one embodiment, a polymeric binder can be used in conjunction with the inkjet ink compositions disclosed herein to adjust the viscosity of the composition and / or to provide other desirable properties, such as durability (e.g., at least one durable polymer). Suitable polymeric binders include, but are not limited to, water-soluble polymers and copolymers, such as gum arabic, polyacrylate, polymethacrylate, polyvinyl alcohol (Elvanol ® Selvol™ from Sekisui Specialty Chemicals), hydroxypropyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone (e.g., Luvitec ® Kollidon ® Kollidon ® polyvinyl ether, starch, polysaccharide, polyethyleneimine with or without derivatization with ethylene oxide and propylene oxide; Jeffamine ® polyetheramine (Huntsman); and the like. Additional examples of water-soluble polymeric compounds include various dispersants or surfactants described above, including, for example, styrene-acrylic acid copolymers (e.g., Joncryl ® resin from BASF), styrene-acrylic acid-alkyl acrylate terpolymers, styrene-methacrylic acid copolymers (e.g., Joncryl ® resin from BASF), styrene-maleic acid-alkyl acrylate terpolymers, styrene-methacrylic acid-alkyl acrylate terpolymers, styrene-maleic acid half-ester copolymers, vinyl naphthalene-acrylic acid copolymers, alginic acid, polyacrylic acid or salts thereof and derivatives thereof. Additionally, the binder can be added or present in the form of a dispersion or latex. For example, the polymeric binder can be a latex of an acrylate or methacrylate copolymer (e.g., NeoCryl ® resin from Koninklijke DSM N.V., AC and AS polymers from Alberdingk-Boley) or can be a water-dispersible polyurethane (e.g., ABU polymers from Alberdingk-Boley) or polyester (e.g., Eastman AQ™ polymers from Eastman Chemical). Polymers, such as those listed above, as well as variations and related materials useful as binders for inkjet inks are included in Ethacryl ® dispersant from BASF.Resin, NeoCryl from Koninklijke DSM N.V. ® Resin, and AC and AS polymers Alberdingk-Boley.

[0270] In one embodiment, the polymeric binder is selected from polyurethanes. Exemplary polyurethanes include polyurethanes comprising at least one polyether and at least one diisocyanate. In one embodiment, the at least one polyether comprises a monomer comprising Formula (I):

[0271] (I)

[0272] wherein R1may be substituted or unsubstituted and is selected from the group consisting of C1-C 10 alkylene, C3-C 20 cycloalkylene, C3-C 20 heterocycloalkylene (at least one ring atom is a heteroatom selected from the group consisting of O, N, and S), C5-C 20 arylene, C3-C 20 heteroarylene (at least one ring atom is a heteroatom selected from the group consisting of O, N, and S), C6-C 20 alkyl arylene, polyether moieties, and combinations thereof. In one embodiment, R1is unsubstituted. In one embodiment, R1is substituted with at least one substituent selected from the group consisting of C1-C 10 alkyl and C5-C 20 aryl. In one embodiment, R1is selected from polyether moieties, such as polyethylene glycol moieties, polypropylene glycol moieties, polytetramethylene oxide (polybutylene oxide) moieties, and combinations thereof. In one embodiment, the at least one polyether is formed from a diol monomer, such as by polymerization of a diol monomer. Exemplary diol monomers include C1-C 10 alkylene diols, such as propylene glycol, polytetramethylene oxide diol (polybutylene oxide diol), 1,6-hexanediol, 1,5-pentanediol, and 2-butyl-2-ethylpropyl diol. In another embodiment, the diol monomer comprises a monomer of Formula (I), for example, the diol monomer is C1-C 10 polyalkylene glycol, polyether glycol, or any other diol conforming to Formula (I). In one embodiment, the at least one polyether is polypropylene glycol, such as polypropylene glycol having a number average molecular weight of 400 g / mol to 6000 g / mol. In one embodiment, the at least one polyether is present in an amount of 30 weight percent to 95 weight percent relative to the weight of the polyurethane.

[0273] In one embodiment, the at least one diisocyanate has Formula (II):

[0274] (II)

[0275] wherein R2may be substituted or unsubstituted and selected from the group consisting of C1-C 10 alkylene, C3-C 20 cycloalkylene, C3-C 20 heterocycloalkylene (at least one ring atom is a heteroatom selected from the group consisting of O, N, and S), C5-C 20 arylene, C3-C 20 heteroarylene (at least one ring atom is a heteroatom selected from the group consisting of O, N, and S), and combinations thereof. In one embodiment, R2is unsubstituted. In one embodiment, R2is substituted with at least one substituent selected from the group consisting of C1-C 10 alkyl and C5-C 20 aryl. For example, R2may be hexamethylene or phenylene optionally substituted with methyl, or cyclohexylene optionally substituted with methyl, , , or .

[0276] In one embodiment, the at least one diisocyanate is selected from the group consisting of toluene diisocyanates, such as toluene 2,4-diisocyanate (2,4-TDI) and toluene 2,6-diisocyanate (2,6-TDI), hexamethylene diisocyanate (HDI), 4,4'-methylene diphenyl diisocyanate (4,4’-MDI), 2,4'-methylene diphenyl diisocyanate (2,4’-MDI), 2,2'-methylene diphenyl diisocyanate (2,2’-MDI), methylene bis(4-cyclohexyl diisocyanate) (HDMI), meta-tetramethylxylene diisocyanate (m-TMXDI), and isophorone diisocyanate (IPDI). In one embodiment, the diisocyanate is selected from the group consisting of toluene diisocyanates (e.g., toluene 2,4-diisocyanate, toluene 2,6-diisocyanate), isophorone diisocyanate, and combinations thereof. In one embodiment, the at least one diisocyanate is present in an amount of 3 wt% to 50 wt% relative to the polyurethane.

[0277] In one embodiment, the at least one polyurethane further comprises a monomer comprising at least one hydrophilic group in addition to the at least one polyether and the at least one diisocyanate. In one embodiment, the monomer comprising at least one hydrophilic group has the formula (III):

[0278] (III)

[0279] wherein R3comprises at least one hydrophilic group bonded to one moiety, which can be substituted or unsubstituted, selected from the group consisting of C1-C 10 alkylene, C3-C 20Cycloalkylene, C3-C 20 Heterocycloalkylene (at least one ring atom is a heteroatom selected from O, N, and S), C5-C 20 Arylene, C3-C 20 Heteroarylene (at least one ring atom is a heteroatom selected from O, N, and S), C6-C 20 Alkylarylene. In one embodiment, the "hydrophilic group" is capable of forming a hydrogen bond with water. In one embodiment, the at least one hydrophilic group is selected from the group consisting of hydroxyl, carboxylic acid, sulfonic acid, phosphonic acid, polyether (e.g., polyethylene glycol, polypropylene glycol, and the like), and salts and ethers thereof. In one embodiment, the at least one hydrophilic group is selected from the group consisting of carboxylic acid and salts and ethers thereof. In one embodiment, the R3moieties are unsubstituted. In another embodiment, the R3moieties are substituted with at least one substituent selected from the group consisting of C1-C 10 Alkyl and C5-C 20 Aryl. One exemplary monomer of Formula (III) is dimethylol propionic acid (DMPA).

[0280] In one embodiment, the molar ratio between the at least one diisocyanate and the polyol or diol based monomer in the polyurethane is from 0.5: 1 to 3: 1. In another embodiment, the at least one polyurethane is characterized by a NCO / OH ratio, which is the ratio of the moles of isocyanate groups to the moles of hydroxyl groups of all diol monomers (e.g., the at least one polyether alone, or if present, the sum of the at least one polyether and the monomer containing at least one hydrophilic group), in one embodiment, the NCO / OH ratio is from 0.85 to 1.15, for example, from 0.85 to 1.1, from 0.9 to 1.15, or from 0.9 to 1.1.

[0281] In one embodiment, the acid value of the at least one polyurethane corresponds to the amount of monomer containing at least one hydrophilic group, for example, carboxylic acid groups, or any hydrophilic group disclosed herein. For example, the acid value of the at least one polyurethane (AN(PU)) can be calculated from the following equation:

[0282]

[0283] In one embodiment, the acid value of the at least one polyurethane is from 10 to 100 mg KOH / g polyurethane, for example, from 10 to 80, from 10 to 70, from 10 to 60, from 10 to 50, from 10 to 40, from 10 to 35, from 15 to 100, from 15 to 80, from 15 to 70, from 15 to 60, from 15 to 50, from 15 to 40, from 15 to 35, from 20 to 100, from 20 to 80, from 20 to 70, from 20 to 60, from 20 to 50, from 20 to 40, or from 20 to 35 mg KOH / g polyurethane.

[0284] In one embodiment, the inkjet ink further comprises at least one water soluble compound having a hydroxyl number of at least 80, wherein the at least one water soluble compound is selected from the group consisting of ethoxylated C3-C 20 polyols, such as ethoxylated triols, ethoxylated tetraols, ethoxylated pentaols, and ethoxylated hexaols. In one embodiment, the ethoxylated C3-C 20 polyols are selected from the group consisting of ethoxylated glycerol, ethoxylated pentaerythritol, ethoxylated trimethylolpropane, ethoxylated glucoside, and ethoxylated glucose. In another embodiment, the at least one water soluble compound is selected from the group consisting of polyols containing three or more hydroxyl groups (e.g., xylitol and sorbitol) and polyether polyols. The at least one water soluble compound can be present in an amount ranging from 1 wt% to 60 wt%, relative to the total weight of the inkjet ink composition.

[0285] Exemplary rheological additives for adjusting the viscosity of the inkjet ink composition include, but are not limited to, alkali-swellable emulsions (e.g., Rheovis® AS rheology control additive from BASF), hydrophobically modified alkali-swellable emulsions (e.g., Rheovis® HS rheology control additive from BASF), hydrophobically modified polyurethanes (e.g., Rheovis® PU rheology control additive from BASF), and hydrophobically modified polyethers (e.g., Rheovis® PE rheology control additive from BASF). ® AS rheology control additive), hydrophobically modified alkali-swellable emulsions (e.g., Rheovis ® HS rheology control additive), hydrophobically modified polyurethanes (e.g., Rheovis ® PU rheology control additive), and hydrophobically modified polyethers (e.g., Rheovis ® PE rheology control additive).

[0286] In one embodiment, the inkjet ink composition can further comprise a dye to alter the color balance and adjust optical density. Exemplary dyes include food dyes, FD&C dyes, acid dyes, direct dyes, reactive dyes, derivatives of phthalocyanine sulfonic acid, including copper phthalocyanine derivatives, sodium salts, ammonium salts, potassium salts, and lithium salts.

[0287] In one embodiment, the inkjet ink composition comprises one or more polymers selected from the group consisting of polymeric dispersants and polymeric binders, as disclosed herein, in an amount ranging from 0.1 wt% to 20 wt%, relative to the total weight of the composition, such as in an amount ranging from 0.1 wt% to 10 wt%, 0.1 wt% to 5 wt%, 0.2 wt% to 20 wt%, 0.2 wt% to 10 wt%, 0.2 wt% to 5 wt%, 0.5 wt% to 20 wt%, 0.5 wt% to 10 wt%, or 0.5 wt% to 5 wt%, relative to the total weight of the composition.

[0288] In one embodiment, in addition to the surfactant, the inkjet ink composition can further include one or more suitable additives to impart a number of desirable properties while maintaining the stability of the composition. Other additives are well known in the art and include humectants, biocides and fungicides, pH control agents, drying promoters, penetrants, and the like. The amount of a particular additive will vary depending on various factors, but is typically present in an amount of 0.01% to 40% by weight of the inkjet ink composition. In one embodiment, the at least one additive is present in an amount of 0.05% to 5% by weight, for example, in an amount of 0.1% to 5% by weight, or in an amount of 0.5% to 2% by weight, relative to the total weight of the inkjet ink composition.

[0289] A humectant and a water-soluble organic compound in addition to the at least one organic solvent can also be added to the inkjet ink composition of the present application, for example, to prevent nozzle clogging as well as to provide paper penetration (penetrant), improved drying (drying promoter), and anti-curling properties. In one embodiment, the humectant and / or water-soluble compound is present in an amount of 0.1% to 50%, for example, in an amount of 1% to 50%, 0.1% to 30%, 1% to 30%, 0.1% to 10%, or 1% to 10%.

[0290] Specific examples of humectants and other water-soluble compounds that can be used include: low molecular weight glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and dipropylene glycol; glycols containing from about 2 to about 40 carbon atoms such as 1,3-pentanediol, 1,4-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 2,6-hexanediol, neopentyl glycol (2,2-dimethyl-1,3-propanediol), 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2,6-hexanetriol, poly(ethylene-co-propylene) glycol, and the like, and reaction products thereof with alkylene oxides (including ethylene oxide, including ethylene oxide and propylene oxide); triol derivatives containing from about 3 to about 40 carbon atoms including glycerol, trimethylolpropane, 1,3,5-pentanetriol, 1,2,6-hexanetriol, and the like, and reaction products thereof with alkylene oxides (including ethylene oxide / propylene oxide and mixtures thereof); neopentyl glycol, (2,2-dimethyl-1,3-propanediol), and the like, and reaction products thereof with alkylene oxides (including ethylene oxide and propylene oxide in any desired molar ratio to form materials having a wide range of molecular weights); thiodiglycol; pentaerythritol and lower alcohols such as ethanol, propanol, isopropanol, n-butanol, sec-butanol, and t-butanol, 2-propyn-1-ol (propargyl alcohol), 2-buten-1-ol, 3-buten-2-ol, 3-butyn-2-ol, and cyclopropyl alcohol; amides such as dimethylformamide and dimethylacetamide; ketones or ketone alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxolane; and the like. In one embodiment, the humectant and / or water-soluble compound is present in an amount of 0.1% to 50%, for example, in an amount of 1% to 50%, 0.1% to 30%, 1% to 30%, 0.1% to 10%, or 1% to 10%. alkylphenylsulfoxides, etc.; and sulfone derivatives (symmetrical and asymmetrical sulfones) containing from about 2 to about 40 carbon atoms, such as dimethyl sulfone, methyl ethyl sulfone, cyclobutyl sulfone (tetramethyl sulfone, cyclic sulfone), dialkyl sulfones, alkyl phenyl sulfones, dimethyl sulfone, methyl ethyl sulfone, diethyl sulfone, ethyl propyl sulfone, methyl phenyl sulfone, methyl cyclobutyl sulfone, dimethyl cyclobutyl sulfone, etc. These materials can be used individually or in combination.

[0291] Biocides and / or fungicides can also be added to the aqueous dispersion or inkjet ink composition disclosed herein. Biocides are important in preventing bacterial growth, as bacteria are typically larger than inkjet nozzles and can cause clogging and other printing problems. Examples of useful biocides include, but are not limited to, benzoate or sorbate salts, and isothiazolinones. In one embodiment, the biocide and / or fungicide is present in an amount of 0.05 wt% to 5 wt%, 0.05 wt% to 2 wt%, 0.1 wt% to 5 wt%, or 0.1 wt% to 2 wt%, relative to the total weight of the composition.

[0292] One embodiment provides a composition comprising at least one pigment, a liquid carrier, and at least one polymer comprising a first monomer and a second monomer selected from maleic anhydride, maleic acid and salts, esters, imides and amides thereof, as described herein (e.g., selected from maleic anhydride, maleic acid, and salts thereof). The first monomer can be selected from ethylenically unsaturated hydrophobic monomers comprising the formula wherein R 1 and R 2 are independently selected from H, C1-C 12 alkyl, C5-C 20 aryl, C6-C20 Araneyl and C6-C 20 Alkyl aryl, and R 1 and R 2 The carbon atom may optionally be replaced by at least one heteroatom selected from O, N, and S (e.g., R). 1 and R 2 Independently selected from H, C1-C 12 Alkyl, C5-C2 aryl, C6-C 20 Araneyl and C6-C 20 Alkyl or H, C1-C 12 Alkyl, C5-C 20 (Aryl). In one embodiment, the first monomer is styrene. At least a portion of the second monomer may be functionalized with at least one organic group having a calcium index value greater than that of phenylphosphonic acid. Alternatively, the at least one polymer is crosslinked via the second monomer, for example, via a carboxyl group of the second monomer. In one embodiment, the polymer is linked by at least one bond selected from ester bonds, wherein the ester bond may be obtained from a reaction between an epoxy-containing compound (e.g., di- and triglycidyl ether compounds, such as trimethylolpropane polyglycidyl ether) and a carboxyl group of the second monomer. In one embodiment, the composition consists essentially of at least one (crosslinked) polymer, at least one pigment, and a liquid carrier (e.g., water). In one embodiment, the pH of the composition (e.g., an aqueous dispersion) is 8 to 11. In one embodiment, the acid value of the composition (e.g., an aqueous dispersion) is 50 to 300.

[0293] Example

[0294] Definitions

[0295] NaAL = sodium alendronate.

[0296] NaOH = Sodium hydroxide.

[0297] SMA 2000 = Low molecular weight styrene-maleic anhydride copolymer, wherein the molar ratio of styrene to maleic anhydride is approximately 2:1 (SMA 2000). ® 2000 polymers, from Total Petrochemicals & Refining USA, Inc.

[0298] SMA 3000 = Low molecular weight styrene-maleic anhydride copolymer, wherein the molar ratio of styrene to maleic anhydride is approximately 3:1 (SMA 3000). ® 3000 polymers, from Total Petrochemicals & Refining USA, Inc.

[0299] SMA EF40 = Low molecular weight styrene-maleic anhydride copolymer, wherein the molar ratio of styrene to maleic anhydride is approximately 4:1 (SMA EF40). ® EF40 polymer, from Total Petrochemicals & Refining USA, Inc.

[0300] Joncryl 683 = Styrene-acrylic resin (from BASF's Joncryl) ® 683 resin).

[0301] Acidic ion exchange resin = Purolite ® C107E ion exchange resin (from Purolite).

[0302] TMPTGE = Trimethylolpropane triglycidyl ether from Sigma Aldrich.

[0303] SURFYNOL 465 = SURFYNOL ® 465 surfactant is a nonionic surfactant from Air Products.

[0304] TEGMBE = triethylene glycol monobutyl ether.

[0305] XIRAN ® SZ25010 resin is a low molecular weight styrene-maleic anhydride copolymer, with a maleic anhydride content of 25%, and is sourced from Polyscope Polymers, BV.

[0306] XIRAN ® SZ15010 resin is a low molecular weight styrene-maleic anhydride copolymer, with a maleic anhydride content of 15%, and is sourced from Polyscope Polymers, BV.

[0307] DMAPA = 3-(dimethylamino)-1-propylamine.

[0308] Polymer Examples

[0309] Examples of polymers A through D describe the synthesis of polymers comprising a first monomer selected from olefinically unsaturated hydrophobic monomers and a second monomer selected from maleic anhydride, wherein a portion of the second monomer is functionalized with at least one organic group having a calcium index value greater than or equal to that of phenylphosphonic acid. Examples of polymers E and G describe the synthesis of comparative polymers having a first monomer selected from olefinically unsaturated hydrophobic monomers and a second monomer selected from maleic anhydride, wherein no second monomer is functionalized with at least one organic group having a calcium index value greater than or equal to that of phenylphosphonic acid. Example of polymer H describes the synthesis of a comparative polymer having a monomer selected from olefinically unsaturated hydrophobic and hydrophilic monomers, wherein no monomer is selected from maleic anhydride, maleic acid, or its salts, esters, imides, and amides. Examples of polymers I and J describe the synthesis of polymers comprising a first monomer selected from olefinically unsaturated hydrophobic monomers and a second monomer selected from maleic anhydride, wherein the polymer is hydrolyzed. Polymer-K is an example of a polymer comprising a first monomer selected from olefinically unsaturated hydrophobic monomers and a second monomer selected from maleic anhydride, wherein a portion of the second monomer is functionalized with at least one organic group having a calcium index value greater than or equal to that of phenylphosphonic acid, and wherein a portion of the second monomer is functionalized with (dimethylamino)-1-propylamine. Polymer-L is an example describing a polymer comprising a first monomer selected from olefinically unsaturated hydrophobic monomers and a second monomer selected from maleic anhydride, wherein a portion of the second monomer is functionalized with (dimethylamino)-1-propylamine.

[0310] Polymer-A

[0311] 100 g of SMAEf40 polymer powder and 320 g of deionized (DI) water were added to a 1-liter cylindrical reactor equipped with a temperature monitor, stirrer, and condenser. A NaAL solution was prepared by dissolving sodium alendronate trihydrate (31.6 g) in a mixture of 122 g of deionized water and 58.4 g of 40 wt% NaOH solution. The NaAL solution was added to the reactor with stirring. The resulting mixture was heated to 90 °C. Heating was carried out for 11 hours. During this period, the initial emulsion gradually became clear and homogeneous. After cooling to room temperature, the solution was transferred to a stainless steel beaker, where the pH was adjusted from the initial value of 11-12 to 8.5-10 by stirring the solution in the presence of acidic resin. The solution was then filtered through a glass frit to remove the ion exchange beads, yielding a clear, colorless liquid. 31P NMR was used to determine the amount of bisphosphonate groups attached to the polymer. A final solution of polymer-A was obtained: 19.2% solids, pH = 9.60, and 13% of the initial charge of NaAL covalently bonded to the polymer. For polymer-A, the portion of the second monomer functionalized with bisphosphonate groups (calcium index value greater than that of phenylphosphonic acid) was 13 mol of the total second monomer.

[0312] Polymer-B

[0313] 100 g of SMAEf40 polymer powder and 360 g of DI water were added to a 1-liter cylindrical reactor equipped with a temperature monitor, stirrer, and condenser. A NaAL solution was prepared by dissolving sodium alendronate trihydrate (56.9 g) in a mixture of 126 g of deionized water and 74 g of 40 wt% NaOH solution. The NaAL solution was added to the reactor with stirring. The resulting mixture was heated to 90°C. Heating was carried out for 11 hours. During this period, the initial emulsion gradually became clear and homogeneous. After cooling to room temperature, the solution was transferred to a stainless steel beaker, where the pH was adjusted from the initial value of 11-12 to 8.5-10 by stirring the solution in the presence of acidic resin. The solution was then filtered through a glass frit to remove the ion exchange beads, yielding a clear, colorless liquid. 31 P NMR was used to determine the amount of bisphosphonate groups attached to the polymer. A final solution of polymer-B was obtained: 17.6% solids, pH = 9.75, and 11% of the initial charge covalently bonded to the polymer with NaAL. For polymer-B, the portion of the second monomer functionalized with bisphosphonate groups (calcium index value greater than that of phenylphosphonic acid) was 11 mol of the total second monomer.

[0314] Polymer-C

[0315] 80 g of SMA3000 polymer powder and 200 g of DI water were added to a 1-liter cylindrical reactor equipped with a temperature monitor, stirrer, and condenser. A NaAL solution was prepared by dissolving sodium alendronate trihydrate (31.7 g) in a mixture of 122 g of deionized water and 29.3 g of 40 wt% NaOH solution. The NaAL solution was added to the reactor with stirring. The resulting mixture was heated at 80°C for 11 h. During this time, the initial emulsion gradually became clear and homogeneous. After cooling to room temperature, the solution was transferred to a stainless steel beaker, where the pH was adjusted from an initial value of 11–12 to 8.5–10 by stirring in the presence of an acidic resin. The solution was filtered through a glass frit to remove ion exchange beads, yielding a clear, colorless liquid. The amount of bisphosphonate groups attached to the polymer was determined using ICP analysis, first by dialyzing a small portion of the polymer solution with deionized water using a dialysis tube (e.g., Spectro / Por® Dialysis Membrane, MWCO 2kD) with a suitable molecular weight cutoff (i.e., MWCO 2kD). The final solution of polymer-C was obtained: 12.7% solids, pH = 9.62, and 11% of the initial charge covalently bonded to the polymer with NaAL. For polymer-C, this portion of the second monomer, functionalized with bisphosphonate groups (calcium index value greater than that of phenylphosphonic acid), constituted 11 mol of the total second monomer.

[0316] Polymer-D

[0317] 80 g of SMA2000 polymer powder and 200 g of DI water were added to a 1-liter cylindrical reactor equipped with a temperature monitor, stirrer, and condenser. A NaAL solution was prepared by dissolving sodium alendronate trihydrate (42.5 g) in a mixture of 164 g of deionized water and 78.4 g of 40 wt% NaOH solution. The NaAL solution was added to the reactor with stirring. The resulting mixture was heated at 80°C for 8 h. During this time, the initial emulsion gradually became clear and homogeneous. After cooling to room temperature, the solution was transferred to a stainless steel beaker, where the pH was adjusted from an initial value of 11–12 to 8.5–10 by stirring the solution in the presence of an acidic resin. The solution was filtered through a glass frit to remove ion exchange beads, yielding a clear, colorless liquid. The amount of bisphosphonate groups attached to the polymer was determined using ICP analysis, first by dialyzing a small portion of the polymer solution with deionized water using a dialysis tube (e.g., Spectro / Por® Dialysis Membrane, MWCO 2kD) with a suitable molecular weight cutoff (i.e., MWCO). The final solution of polymer-D was obtained: 14.7% solids, pH = 9.58, and 22% of the initial charge covalently bonded to the polymer with NaAL. For polymer-D, this portion of the second monomer, functionalized with bisphosphonate groups (calcium index value greater than that of phenylphosphonic acid), constituted 22 mol% of the total second monomer.

[0318] Polymer-E

[0319] Polymer-E is an aqueous solution of the sodium salt of SMA 2000, which can be prepared by hydrolysis in the presence of NaOH solution. The final solution of Polymer-E has a solid content of 28.7% and a pH of 9.83.

[0320] Polymer-F

[0321] Polymer-F is an aqueous solution of the sodium salt of SMA 3000, which can be prepared by hydrolysis in the presence of NaOH solution. The final solution of Polymer-F has a solid content of 17.2% and a pH of 9.75.

[0322] Polymer-G

[0323] Polymer-G is an aqueous solution of the sodium salt of SMA EF40, which can be prepared by hydrolysis in the presence of NaOH solution and a small amount of Polymer-F (as a hydrolysis aid), wherein the amount of SMA 3000 added is 5.3% by weight of SMA EF40. The final solution of Polymer-G has the following properties: 20.9% solids and pH 9.90.

[0324] Polymer-H

[0325] Polymer-H is an aqueous solution of the sodium salt of Joncryl 683, which can be prepared by neutralizing the Joncryl 683 polymer with NaOH solution. The final solution of Polymer-H has a solid content of 22.6% and a pH of 8.84.

[0326] Polymer-I

[0327] Add 285 g of XIRAN to a 1-liter cylindrical reactor equipped with a temperature monitor, top stirrer, and condenser. ® SZ25010 resin powder (acid value, AN(SP) = 285) and 1044 g of DI water were added. 137.5 g of 40% NaOH solution was added to the polymer and water mixture. The resulting mixture was heated at 95°C for 10 h. During this period, the initial emulsion gradually became clear and homogeneous as the polymer was completely hydrolyzed, producing a solution with 22.1% solids and a pH of 10.1.

[0328] Polymer-J

[0329] Add 285g of XIRAN to a 1-liter cylindrical reactor equipped with a temperature monitor, top stirrer, and condenser. ® SZ15010 resin granules (acid value, AN(SP) = 156) and 1169 g of DI water were added. 75.3 g of 40% NaOH solution was added to the polymer and water mixture. The resulting mixture was heated at 95°C for 10 h. During this period, the initial emulsion gradually became clear and homogeneous as the polymer was completely hydrolyzed, producing a solution with 19.8% solids and a pH of 10.4.

[0330] Polymer-K

[0331] 30 g of SMA3000 polymer powder, 0.91 mL of 3-(dimethylamino)-1-propylamine (DMAPA) from Sigma Aldrich, and 180 g of DI water were added to a 0.5 L cylindrical reactor equipped with a temperature monitor, stirrer, and condenser. A NaAL solution was prepared by dissolving sodium alendronate trihydrate (2.6 g) in a mixture of 20 g of deionized water and 4.4 g of 40 wt% NaOH solution. The NaAL solution was added to the reactor with stirring. The resulting mixture was heated to 90 °C. Heat for 2 hours. Then add 13.6 g of 40% by weight NaOH solution and heat the mixture at 90°C. Heating was applied for 6 hours. During this period, the initial emulsion gradually became clear and homogeneous. A final solution of polymer-K was obtained: 15.8% solids, pH = 8.59. 31 P NMR was used to determine the amount of bisphosphonate groups attached to the polymer, and P NMR was used to determine the amount of bisphosphonate groups attached to the polymer. 1 The amount of dimethylamino groups attached to the polymer was determined by ¹H NMR. For polymer-K, the portion of the second monomer functionalized with diphosphonate groups (calcium index value greater than that of phenylphosphonic acid) was 3.3 mol% of the total second monomer. The second monomer functionalized with organic groups is 8.5 mol of the total second monomer.

[0332] Polymer-L

[0333] Add 30 g of SMA® EF40 polymer powder, 0.56 g of 3-(dimethylamino)-1-propylamine (DMAPA) from Sigma Aldrich, and 130 g of DI water to a 0.5 L cylindrical reactor equipped with a temperature monitor, stirrer, and condenser. After mixing, add 0.5 g of 40% by weight NaOH solution and heat the resulting mixture at 94°C for 2 h. Then add another 10.6 g of 40% by weight NaOH solution and heat the mixture at 94°C. Heating was carried out for 8 hours. During this period, the initial emulsion gradually became clear and homogeneous. A final solution of polymer-L was obtained: 14.1% solids, pH = 8.59. 1 ¹H NMR was used to determine the amount of dimethylamino groups attached to the polymer. For polymer-L, dimethylamino groups (having the formula...) were used... The second monomer functionalized with organic groups constitutes 8.4 mol of the total second monomer.

[0334] Pigment Dispersion Examples

[0335] Examples of pigment dispersions, PigDisp-1-5, are aqueous dispersions of yellow pigment, stabilized by polymer. Examples of pigment dispersions, PigDisp-6-9, are aqueous dispersions of cyan pigment, stabilized by polymer. Examples of pigment dispersions, PigDisp-10-21, are aqueous dispersions of magenta pigment, stabilized by polymer. Examples of pigment dispersions, PigDisp-22-24, are aqueous dispersions of black pigment, stabilized by polymer. The pigment dispersions are prepared as follows.

[0336] PigDisp-1 and PigDisp-2

[0337] Polymer-G (560 g solution, 20.9% solids in water) was combined with 724 g of DI water and 272 g of PigmentYellow 74 (in dry powder form). The mixture was then heated for approximately 10 minutes. The sample was sonicated using a Misonix® probe sonicator for approximately 7 hours to obtain a low-viscosity yellow dispersion. A small portion of this dispersion (approximately 50 g) was centrifuged at 2,500 G for 20 minutes, followed by decantation to separate the product. A final solution of polymer-G-dispersed yellow pigment, PigDisp-1, was obtained, containing 15.5% solids and an average particle size of 198 nm (determined using a Microtrac® Particle Size Analyzer).

[0338] Add 5.87 g of TMPTGE, 3.6 g of boric acid, and 190 g of DI water to the remaining dispersion (2014 g of solution, 18.2% solids content). Heat the resulting mixture at 65°C. The solution was heated for 4 h. After cooling to room temperature, it was diluted to 10% solids and then centrifuged at 2,500 G for 20 min. The solution was then purified and concentrated by percolation using a 3,000 MW cutoff (MW cut-off) polysulfone membrane to obtain PigDisp-2: 16.5% solids with an average particle size of 162 nm (determined using a Microtrac® particle size analyzer).

[0339] PigDisp-3

[0340] Polymer-A (829 g solution, 19.2% solids in water) was combined with 917 g of DI water and 370 g of PigmentYellow 74 (in dry powder form). The mixture was then heated for approximately 10 minutes. The solution was sonicated using a Misonix® probe sonicator for approximately 7 hours to obtain a low-viscosity yellow dispersion. The solution was then diluted to 10% solids and centrifuged at 2,500 G for 20 minutes. Subsequently, the solution was purified and concentrated by percolation using a 3,000 MW-cut polysulfone membrane to obtain PigDisp-3: 18.5% solids with an average particle size of 170 nm (determined using a Microtrac® particle size analyzer).

[0341] PigDisp-4

[0342] Polymer-A (112 g solution, 19.2% solids in water) was combined with 124 g of DI water and 50 g of PigmentYellow 74 (in dry powder form). The mixture was then heated in approximately 10... The mixture was sonicated using a Misonix® probe sonicator for approximately 1 hour to obtain a low-viscosity yellow dispersion. 1.21 g of TMPTGE (% target CO2 = 15%), 0.74 g of boric acid, and 144 g of DI water were added to the dispersion. The resulting mixture was then heated at 65°C. Heating was performed for 4 h. After cooling to room temperature, the solution was centrifuged at 2,500 G for 20 min. After centrifugation, the solution (first diluted to 12% solids) was purified and concentrated by percolation using a 3,000 MW-retained polysulfone membrane to obtain PigDisp-4: 20.1% solids with an average particle size of 177 nm (determined using a Microtrac® particle size analyzer).

[0343] PigDisp-5

[0344] PigDisp-5 is a Pro-Jet™ APD1000 yellow colorant, an aqueous dispersion of pigment yellow, and is commercially available from FUJIFILM Imaging Colorants, Inc. This dispersion is stabilized using a polyacrylate dispersant.

[0345] Evaluation of PigDisp 1-5

[0346] The dispersion examples PigDisp-1-4 were evaluated by performing sedimentation tests, in which these dispersions were left to stand on a workbench at room temperature for a period of time. Their sedimentation performance was based on the following criterion grading:

[0347] Difference = The dispersion separates into two layers within ≤4 days, with the top layer containing a small or reduced amount of pigment, while the bottom layer has a pigment concentration much higher than its initial concentration;

[0348] Good = dispersion remains uniform (i.e., little or no layer separation) for 5 days or longer.

[0349] Table 1

[0350]

[0351] Table 1 shows that, for both non-crosslinked and crosslinked samples, pigment dispersions stabilized by polymer-A exhibited better sedimentation performance than those stabilized by polymer-G. The main difference between polymer-A and polymer-G is that polymer-A is a functionalized SMA EF40 polymer with bisphosphonate groups attached to the polymer, while polymer-G does not contain any such functional groups. The calcium index value of phenylphosphonic acid is 2.53, measured using method A as described in column 29, lines 45 through 30, lines 44 of U.S. Patent 8,858,695, including a list of calcium index values ​​for various compounds in Table 5A, the disclosure of which is incorporated herein by reference. Based on previous work on -CH2(PO3) 2- The calcium index value of the diphosphonate group was determined to be approximately 3.45 by measurement (Table 5A of U.S. Patent No. 8,858,695).

[0352] Considering the ability of polymers to bind polyvalent metal ions (e.g., magnesium and calcium), and taking into account functional groups, hydrophobicity, and other factors, a magnesium sensitivity test was developed. The Mg sensitivity test was performed as follows: (1) one drop (approximately 0.05 g) of the dispersion example PigDisp-3-5 (as is) was added to a series of 10–15 mL MgCl2 solutions with different levels of molar concentration: 1.0 mM, 2.0 mM, 3.0 mM, and 5.0 mM; (2) the sample was shaken and then allowed to stand at room temperature for one hour; and (3) the lowest molar concentration of MgCl2 was recorded when complete precipitation of the pigment dispersion was observed (i.e., clear separation of water and pigment precipitate). After testing all these examples, the MgCl2 molar concentrations at which complete pigment precipitation was achieved are summarized in Table 2. The lower the MgCl2 concentration required for precipitation, the greater the sensitivity to magnesium and / or calcium ions, which indicates the ability of calcium and / or magnesium to bind.

[0353] Table 2

[0354]

[0355] PigDisp-3 and PigDip-4, which contain polymer-A and bisphosphonate-functionalized SMA EF40 polymers, exhibit better calcium and / or magnesium binding capacity than PigDisp-5, a polymer-stable dispersion that does not contain any monomers selected from maleic anhydride, maleic acid and its salts, esters, imides and amides.

[0356] PigDisp-6

[0357] Polymer-A (202 g solution, 19.2% solids in water) was combined with 223 g of DI water and 90 g of PigmentBlue 15:4 (in dry powder form). The mixture was then heated for approximately 10 minutes. The mixture was sonicated using a Misonix® probe sonicator for approximately 1 hour to obtain a low-viscosity cyan dispersion. 4.37 g of TMPTGE (% target CO2 = 30%), 2.68 g of boric acid, and 257 g of DI water were added to the dispersion. The resulting mixture was then heated at 65°C. Heating was carried out for 5 h. After cooling to room temperature, the solution was first diluted to approximately 13% solids, followed by centrifugation at 2,500 G for 20 min. After centrifugation, the solution was purified and concentrated by percolation using a 3,000 MW-cut polysulfone membrane to obtain PigDisp-6: 20.7% solids with an average particle size of 152 nm (using Microtrac). ® (Measured by particle size analyzer).

[0358] PigDisp-7

[0359] Polymer-B (220 g solution, 17.6% solids in water) was combined with 205 g of DI water and 90 g of PigmentBlue 15:4 (in dry powder form). The mixture was then heated for approximately 10 minutes. Using Misonix ® The sample was sonicated using a probe sonicator for approximately 1 hour to obtain a low-viscosity cyan dispersion. 4.37 g of TMPTGE (% target CO2 = 30%), 2.68 g of boric acid, and 257 g of DI water were added to the dispersion. The resulting mixture was then heated at 65°C. Heating was carried out for 5 h. After cooling to room temperature, the solution was first diluted to approximately 12% solids, and then centrifuged at 2,500 G for 20 min. After centrifugation, the solution was purified and concentrated by percolation using a 3,000 MW-retained polysulfone membrane to obtain PigDisp-7: 20.4% solids with an average particle size of 157 nm (determined using a Microtrac® particle size analyzer).

[0360] PigDisp-8

[0361] Polymer-E (47 g solution, 28.7% solids in water) was combined with 213 g of DI water and 40 g of PigmentBlue 15:4 (as a filter cake, the amount of which was determined by its solids content). The mixture was then boiled in approximately 10... The solution was sonicated for approximately 1 hour using a Misonix® probe sonicator to obtain a low-viscosity cyan dispersion. The resulting solution was centrifuged at 2,500 G for 20 minutes, followed by decantation to separate the product. A final solution of polymer-E dispersed cyan pigment PigDisp-8 was obtained, with 13.7% solids and an average particle size of 163 nm (determined using a Microtrac® particle size analyzer).

[0362] PigDisp-9

[0363] PigDisp-9 is an aqueous dispersion of Pro-Jet™ APD1000 cyan pigment and is commercially available from FUJIFILM Imaging Colorants, Inc. This dispersion is stabilized using a polyacrylate dispersant.

[0364] Evaluation of PigDisp 6-9

[0365] For these cyan dispersions, the Mg sensitivity test was performed as follows: (1) one drop (approximately 0.05 g) of the dispersion example PigDisp-6-9 (as is) was added to a series of 10–15 mL MgCl2 solutions with different molar concentrations: 1.0 mM, 2.0 mM, 3.0 mM, and 5.0 mM; (2) the sample was shaken and then allowed to stand at room temperature for one hour; and (3) the lowest molar concentration of MgCl2 was recorded when complete precipitation of the pigment dispersion was observed (i.e., clear separation of water and pigment precipitate). After testing all these examples, the MgCl3 molar concentrations at which complete pigment precipitation was achieved are summarized in Table 3. The lower the MgCl2 concentration required for precipitation, the greater the sensitivity to magnesium and / or calcium ions, which indicates the ability of calcium and / or magnesium to bind.

[0366] Table 3

[0367]

[0368] PigDisp-6 and PigDip-7, containing polymers A and B respectively and bisphosphonate-functionalized SMA EF40 polymers, exhibited better calcium and / or magnesium binding capacity than PigDisp-8 and PigDisp-5. PigDisp-8 is a cyan dispersion of unfunctionalized SMA 2000 dispersion that does not have functional groups with a calcium index greater than or equal to that of phenylphosphonic acid, and PigDisp-5 is a polymer-stable dispersion that does not contain any monomers selected from maleic anhydride, maleic acid and its salts, esters, imides, and amides. Compared to polymer-A, polymer-B contains a higher amount of bisphosphonate groups linked to the SMA EF40 polymer.

[0369] PigDisp-10

[0370] Polymer-A (762 g solution, 19.2% solids in water) was combined with 1444 g of DI water and 340 g of Pigment Violet 19 (in dry powder form). The mixture was then heated in approximately 10... The mixture was sonicated using a Misonix® probe sonicator for approximately 7 hours to obtain a low-viscosity, magenta-colored dispersion. 10.7 g of TMPTGE, 6.53 g of boric acid, and 273 g of DI water were added to the dispersion. The resulting mixture was then heated at 65°C. Heating was carried out for 4 h. After cooling to room temperature, the solution was first diluted to approximately 10% solids, and then centrifuged at 2,500 G for 20 min. After centrifugation, the solution was purified and concentrated by percolation using a 3,000 MW-retained polysulfone membrane to obtain PigDisp-10: 17.1% solids with an average particle size of 168 nm (determined using a Microtrac® particle size analyzer).

[0371] PigDisp-11

[0372] Polymer-G (617 g solution, 20.9% solids in water) was combined with 1228 g of DI water and 300 g of Pigment Violet 19 (in dry powder form). The mixture was then heated for approximately 10 minutes. The sample was sonicated using a Misonix® probe sonicator for approximately 6 hours to obtain a low-viscosity, magenta-colored dispersion. 9.14 g of TMPTGE, 5.61 g of boric acid, and 222 g of DI water were added to the dispersion. The resulting mixture was then heated at 65°C. Heating was carried out for 4 h. After cooling to room temperature, the solution was first diluted to approximately 10% solids, and then centrifuged at 2,500 G for 20 min. After centrifugation, the solution was purified and concentrated by percolation using a 3,000 MW-retained polysulfone membrane to obtain PigDisp-11: 18.3% solids with an average particle size of 161 nm (determined using a Microtrac® particle size analyzer).

[0373] PigDisp-12

[0374] Polymer-H (59 g solution, 22.6% solids in water) was combined with 215 g of DI water and 40 g of PigmentRed 122 (as a filter cake, the amount of which was determined by its solids content). The mixture was then boiled in approximately 10... The solution was sonicated for approximately 0.5 h using a Misonix® probe sonicator to obtain a low-viscosity cyan dispersion. The resulting solution was centrifuged at 2,500 G for 20 min, followed by decantation to separate the product. A final solution of polymer-H dispersed magenta pigment PigDisp-12 was obtained: 14.0% solids and an average particle size of 106 nm (determined using a Microtrac® particle size analyzer).

[0375] PigDisp-13

[0376] PigDisp-13 is an aqueous dispersion of Pro-Jet™ APD1000 magenta pigment, commercially available from FUJIFILM Imaging Colorants, Inc. This dispersion is stabilized using a polyacrylate dispersant.

[0377] PigDisp-14-15

[0378] Polymer-A (34 g solution, 19.2% solids in water) was combined with 38 g of DI water and 15 g of PigmentViolet 19 (in dry powder form). The mixture was then heated in approximately 10... The sample was sonicated for approximately 0.5 hours using a Misonix® probe sonicator to obtain a low-viscosity, magenta-colored dispersion. 43 g of DI water was added to the dispersion to obtain PigDisp-14: 16.6% solids with an average particle size of 184 nm (determined using a Microtrac® particle size analyzer).

[0379] Add 35 g of PigDisp-14, 0.13 g of TMPTGE (% target CO2 = 20%), and 0.08 g of boric acid to a separate reactor. Heat the resulting mixture at 65°C. Heating was carried out for 5 hours. After cooling to room temperature, the final solution of PigDisp-15 was obtained, with an average particle size of 200 nm (determined using a Microtrac® particle size analyzer).

[0380] PigDisp-16-17

[0381] Polymer-B (37 g solution, 17.6% solids in water) was combined with 35 g of DI water and 15 g of PigmentViolet 19 (in dry powder form). The mixture was then heated in approximately 10... The sample was sonicated for approximately 0.5 hours using a Misonix® probe sonicator to obtain a low-viscosity, magenta-colored dispersion. 43 g of DI water was added to the dispersion to obtain PigDisp-16: 16.6% solids with an average particle size of 183 nm (determined using a Microtrac® particle size analyzer).

[0382] Add 35 g of PigDisp-16, 0.13 g of TMPTGE (% target CO2 = 20%), and 0.08 g of boric acid to a separate reactor. Heat the resulting mixture at 65°C. Heating was carried out for 5 hours. After cooling to room temperature, the final solution of PigDisp-17 was obtained, with an average particle size of 205 nm (determined using a Microtrac® particle size analyzer).

[0383] PigDisp-18-19

[0384] Polymer-D (44 g solution, 14.7% solids in water) was combined with 27 g of DI water and 15 g of PigmentViolet 19 (in dry powder form). The mixture was then heated in approximately 10... The mixture was sonicated for approximately 0.5 hours using a Misonix® probe sonicator to obtain a low-viscosity, magenta-colored dispersion. 43 g of DI water was added to the dispersion to obtain PigDisp-18: 16.6% solids with an average particle size of 171 nm (determined using a Microtrac® particle size analyzer).

[0385] Add 35 g of PigDisp-18, 0.19 g of TMPTGE (% target CO2 = 17%), and 0.12 g of boric acid to a separate reactor. Heat the resulting mixture at 65°C. Heating was carried out for 5 hours. After cooling to room temperature, the final solution of PigDisp-19 was obtained, with an average particle size of 220 nm (determined using a Microtrac® particle size analyzer).

[0386] PigDisp-20-21

[0387] Polymer-C (51 g solution, 12.7% solids in water) was combined with 20 g of DI water and 15 g of PigmentViolet 19 (in dry powder form). The mixture was then heated in approximately 10... The sample was sonicated for approximately 0.5 hours using a Misonix® probe sonicator to obtain a low-viscosity, magenta-colored dispersion. 43 g of DI water was added to the dispersion to obtain PigDisp-20: 16.6% solids with an average particle size of 166 nm (determined using a Microtrac® particle size analyzer).

[0388] Add 35 g of PigDisp-20, 0.16 g of TMPTGE (% target CO2 = 18%), and 0.10 g of boric acid to a separate reactor. Heat the resulting mixture at 65°C. Heating was carried out for 5 hours. After cooling to room temperature, the final solution of PigDisp-21 was obtained, with an average particle size of 179 nm (determined using a Microtrac® particle size analyzer).

[0389] PigDisp 10-21 evaluation

[0390] For these magenta dispersions, the Mg sensitivity test was performed as follows: (1) One drop (approximately 0.05 g) of the dispersion example PigDisp-10-21 (as is) was first added to a series of 10–15 mL MgCl2 solutions with different molar concentrations: 1.0 mM, 2.0 mM, 3.0 mM, and 5.0 mM; (2) After initial shaking, the mixture was allowed to stand at room temperature for one hour; (3) The lowest molar concentration of MgCl2 was recorded when complete precipitation of the pigment dispersion was observed (i.e., clear separation of water and pigment precipitate). After testing all these examples, the MgCl4 molar concentrations at which complete pigment precipitation was achieved are summarized in Table 2. The lower the MgCl2 concentration required for precipitation, the greater the sensitivity to magnesium and / or calcium ions, which indicates the ability of calcium and / or magnesium to bind.

[0391] Table 4

[0392]

[0393] PigDisp-10 and PigDip-14-17, containing polymer-A and polymer-B, bisphosphonate-functionalized SMA EF40 polymers respectively, as well as PigDisp-18-19, containing polymer-D, bisphosphonate-functionalized SMA 2000 polymer, and PigDisp-20-21, containing polymer-C, bisphosphonate-functionalized SMA 3000 polymer, exhibit better calcium and / or magnesium binding capacity than PigDisp-11 and PigDisp-12-13. PigDisp-11 is an unfunctionalized SMA EF40 stable magenta dispersion that does not have functional groups with a calcium index value greater than or equal to that of phenylphosphonic acid, and PigDisp-12-13 is a polymer stable dispersion that does not contain any monomers selected from maleic anhydride, maleic acid and its salts, esters, imides and amides. Compared to polymer-A, polymer-B contains a higher amount of bisphosphonate groups attached to the SMA EF40 polymer.

[0394] For these magenta dispersions, Ca sensitivity testing was performed as follows: (1) one drop (approximately 0.05 g) of the dispersion examples PigDisp-10 and PigDisp-12-17 (as is) was added to a series of 10–15 mL CaCl2 solutions with different molar concentrations: 1.0 mM, 2.0 mM, 3.0 mM, and 5.0 mM; (2) the samples were shaken and allowed to stand at room temperature for one hour; and (3) the lowest molar concentration of CaCl2 was recorded when complete precipitation of the pigment dispersion was observed (i.e., clear separation of water and pigment precipitate). The CaCl2 molar concentrations of these samples are summarized in Table 5. The lower the CaCl2 concentration required for precipitation, the greater the sensitivity to magnesium and / or calcium ions, which indicates the ability of calcium and / or magnesium to bind.

[0395] Table 5

[0396]

[0397] For the magenta dispersion, the Ca sensitivity test showed the same results as the Mg sensitivity test (Table 4). PigDisp-10 and PigDip-14-17, containing polymer-A and polymer-B, respectively, and bisphosphonate-functionalized SMA EF40 polymers, exhibited better calcium and / or magnesium binding capacity than PigDisp-12-13, a polymer-stable dispersion that does not contain any monomers selected from maleic anhydride, maleic acid and its salts, esters, imides, and amides.

[0398] PigDisp-22

[0399] Polymer-A (112 g solution, 19.2% solids in water) was combined with 124 g of DI water and 50 g of BlackPearls 900 (from Cabot Corporation). The mixture was then heated in approximately 10... The mixture was sonicated for approximately 10 minutes using a Misonix® probe sonicator to obtain a low-viscosity black dispersion. 0.90 g of TMPTGE (% target CO2 = 10%), 0.56 g of boric acid, and 144 g of DI water were added to the dispersion. The resulting mixture was then heated at 65°C. Heating was carried out for 5 hours. After cooling to room temperature, the solution was first diluted to approximately 13% solids, and then centrifuged at 2,500 G for 20 minutes. After centrifugation, the solution was purified and concentrated by percolation using a 3,000 MW-retained polysulfone membrane to obtain PigDisp-22: 20.6% solids with an average particle size of 102 nm (determined using a Microtrac® particle size analyzer).

[0400] PigDisp-23

[0401] Polymer-G (772 g solution, 20.9% solids in water) was combined with 999 g of DI water and 375 g of BlackPearls 900 (from Cabot Corporation). The mixture was then heated in approximately 10... The mixture was sonicated using a Misonix® probe sonicator for approximately 1 hour to obtain a low-viscosity black dispersion. 8.1 g of TMPTGE, 4.967 g of boric acid, and 750 g of DI water were added to the dispersion. The resulting mixture was then heated at 65°C. Heating was carried out for 4 h. After cooling to room temperature, the solution was first diluted to approximately 10% solids, and then centrifuged at 2,500 G for 20 min. After centrifugation, the solution was purified and concentrated by percolation using a 3,000 MW-retained polysulfone membrane to obtain PigDisp-23: 17.1% solids with an average particle size of 101 nm (determined using a Microtrac® particle size analyzer).

[0402] PigDisp-24

[0403] PigDisp-24 is an aqueous dispersion of Pro-Jet™ APD1000 Black, a black pigment, and is commercially available from FUJIFILM Imaging Colorants, Inc. This dispersion is stabilized using a polyacrylate dispersant.

[0404] Evaluation of PigDisp 22-24

[0405] For these black dispersions, the Mg sensitivity test was performed as follows: (1) one drop (approximately 0.05 g) of dispersion example PigDisp-22-24 (as is) was added to a series of 10–15 mL MgCl2 solutions with different levels of molar concentration: 1.0 mM, 2.0 mM, 3.0 mM, and 5.0 mM; (2) the sample was shaken and then allowed to stand at room temperature for four hours; and (3) the lowest molar concentration of MgCl2 was recorded when complete precipitation of the pigment dispersion was observed (i.e., clear separation of water and pigment precipitate). After testing all these examples, the MgCl6 molar concentrations at which complete pigment precipitation was achieved are summarized in Table 2. The lower the MgCl2 concentration required for precipitation, the greater the sensitivity to magnesium and calcium ions, which indicates the ability of calcium and / or magnesium to bind.

[0406] Table 6

[0407]

[0408] PigDisp-22, containing polymer-A and bisphosphonate-functionalized SMA EF40 polymers, exhibits better calcium and / or magnesium binding capacity than PigDisp-23 and PigDisp-24. PigDisp-23 is an unfunctionalized SMA EF40-stable magenta dispersion that does not have functional groups with a calcium index value greater than or equal to that of phenylphosphonic acid. PigDisp-24 is a polymer-stable dispersion that does not contain any monomers selected from maleic anhydride, maleic acid and its salts, esters, imides and amides.

[0409] PigDisp-25

[0410] Polymer-K (136 g solution, 15.8% solids in water, pH = 8.59) was combined with 90 g of DI water and 50 g of Pigment Yellow 74 (in dry powder form). The mixture was then heated in approximately 10... Using Misonix ® The sample was sonicated using a probe sonicator for approximately 3 hours to obtain a low-viscosity yellow dispersion. 1.41 g of TMPTGE (% target CO2 = 14%), 0.89 g of boric acid, and 140 g of DI water were added to the dispersion (274 g solution, 25.2% solids content). The resulting mixture was then heated at 65°C. Heating was carried out for 4 h. After cooling to room temperature, the solution was diluted to 10% solids and then centrifuged at 2,500 G for 20 min. The solution was then purified and concentrated by percolation using a 3,000 MW MW-cut polysulfone membrane to obtain a yellow PigDisp-25 dispersion: 19.34% solids, pH = 9.38, and an average particle size of 158 nm (using Microtrac). ® (Particle size analysis). For this yellow dispersion, its Mg sensitivity was tested as described in the evaluation of PigDisp 1-5. PigDisp-25, containing polymer-K, bisphosphonate-functionalized SMA 3000 polymer, exhibited better calcium and / or magnesium binding capacity than PigDisp-5, a yellow, polymer-stable dispersion free of any monomers selected from maleic anhydride, maleic acid and its salts, esters, imides, and amides.

[0411] PigDisp-26 to PigDisp-34

[0412] Dispersions PigDisp-26 to PigDisp-34 were prepared to investigate the effect of stability on crosslinking. Stability was assessed by solvent stability testing, which was performed on the dispersions according to the following method:

[0413] Place a 50 µL drop of solvent onto a microscope slide, then place a 5 µL drop of dispersion (with a solids loading of approximately 18–20%) on top of the solvent drop. Use the microscope cover to flatten the droplet and record the appearance of the colorant particles. When the dispersion has good compatibility, the pigment particles will mix with the liquid and flow, coloring the liquid region. When the dispersion has poor compatibility, the pigment particles will aggregate and not diffuse with the liquid.

[0414] Table 7 below lists the acid value and target CO2 percentage ("%CO2") of the polymer for each dispersion.

[0415] Table 7

[0416]

[0417] PigDisp-26

[0418] Polymer-I (298 g solution, 22.1% solids in water) was combined with 424 g of DI water and 198 g of carbon black, which was prepared according to the method described in U.S. Patent No. 9,388,300 and has the following properties: BET surface area = 265 m² 2 / g, STSA = 197 m 2 / g, OAN = 175 mL / 100 g, and COAN = 135 mL / 100 g. Then the mixture is heated for approximately 10... Using Misonix ® The sample was ultrasonically treated with a probe ultrasonic instrument for about 2 hours to obtain a low-viscosity black dispersion with a solid content of 25.8% and a pH of 9.80.

[0419] PigDisp-27

[0420] PigDisp-26 (250 g) was diluted to approximately 12% solids and then centrifuged at 2,500 G for 20 min. After centrifugation, the solution was purified and concentrated by percolation using a 3,000 MW MW-cut polysulfone membrane to obtain a non-crosslinked carbon black PigDisp-27 dispersion: 20.8% solids, pH = 9.41, and an average particle size of 146 nm (achieved using Microtrac). ® (Measured by particle size analyzer).

[0421] PigDisp-28

[0422] Add 2.80 g of TMPTGE, 2.58 g of boric acid, and 115.16 g of DI water to 250 g of PigDisp-26. Heat the resulting mixture at 65°C. Heating was carried out for 5 h. After cooling to room temperature, the solution was diluted to approximately 12% solids and then centrifuged at 2,500 G for 20 min. After centrifugation, the solution was purified and concentrated by percolation using a 3,000 MW-cut polysulfone membrane to obtain a crosslinked carbon black dispersion: 18.10% solids, pH = 8.83, and an average particle size of 148 nm (using Microtrac). ® (Measured by particle size analyzer).

[0423] Evaluation of PigDisp-27-28

[0424] Solvent stability tests were performed on PigDisp-27 (non-crosslinked carbon black dispersion) and PigDisp-28 (crosslinked carbon black dispersion) using various solvents. The results are listed in Table 8 below.

[0425] Table 8

[0426]

[0427] When exposed to the solvents listed in Table 8, the non-crosslinked dispersion PigDisp-27 immediately becomes unstable, as evidenced by the aggregation of large pigment particles impacting the microscope slide. In contrast, the crosslinked dispersion PigDisp-28 diffuses and disperses in the solvent, demonstrating its stability upon exposure to the solvent.

[0428] The comparison of solvent stability is also shown in Figure 1A and 1B These are photographs of PigDisp-27 and PigDisp-28 on microscope slides exposed to dipropylene glycol, respectively. It can be seen that... Figure 1A The non-crosslinked dispersion PigDisp-27 in the mixture is aggregated, while Figure 1B The cross-linked dispersion PigDisp-28 in the slide is uniformly distributed throughout the slide without any visible aggregation.

[0429] PigDisp-29

[0430] Polymer-I (124 g solution, 22.1% solids in water, pH = 10.1) was combined with 135.6 g of DI water and 118 g of Pigment Green 7 cake (42.9% solids). The mixture was then heated in approximately 10... Using Misonix ® The sample was ultrasonically treated with a probe ultrasonic instrument for about 2 hours to obtain a low-viscosity green dispersion with a solid content of 25.2%.

[0431] PigDisp-30

[0432] PigDisp-29 (75 g) was diluted to approximately 15% solids and then centrifuged at 2,500 G for 10 min. Following centrifugation, the solution was purified and concentrated by percolation using a 3,000 MW MW-cut polysulfone membrane to obtain a non-crosslinked green PigDisp-30 dispersion: 19.10% solids, pH = 9.21, and an average particle size of 147 nm (achieved using Microtrac). ® (Measured by particle size analyzer).

[0433] PigDisp-31

[0434] Add 2.04 g of TMPTGE, 3.13 g of boric acid, and 41 g of DI water to 150 g of PigDisp-29. Heat the resulting mixture at 65°C. Heating was carried out for 5 h. After cooling to room temperature, the solution was diluted to approximately 15% solids and then centrifuged at 2,500 G for 10 min. After centrifugation, the solution was purified and concentrated by percolation using a 3,000 MW-cut polysulfone membrane to obtain a crosslinked green PigDisp-31 dispersion: 17.87% solids, pH = 8.46, and an average particle size of 151 nm (using Microtrac). ® (Measured by particle size analyzer).

[0435] Evaluation of PigDisp-30-31

[0436] Solvent stability tests were performed on PigDisp-30 (non-crosslinked green dispersion) and PigDisp-31 (crosslinked green dispersion) using various solvents. The results are listed in Table 9 below.

[0437] Table 9

[0438]

[0439] When exposed to the solvents listed in Table 9, the non-crosslinked dispersion PigDisp-30 immediately becomes unstable, as evidenced by the aggregation of large pigment particles impacting the microscope slide. In contrast, the crosslinked dispersion PigDisp-31 diffuses and disperses in the solvent, demonstrating its stability upon exposure to the solvent.

[0440] PigDisp-32

[0441] Polymer-J (90 g solution, 19.8% solids in water, pH = 10.4) was combined with 160 g of DI water and 40 g of Pigment Violet 19 (in powder form). The mixture was then heated in approximately 10... Using Misonix ® The sample was ultrasonically treated with a probe ultrasonic instrument for about 2 hours to obtain a low-viscosity magenta dispersion with a solid content of 20.1%.

[0442] PigDisp-33

[0443] First, PigDisp-32 (130 g) was diluted to approximately 15% solids and then centrifuged at 2,500 G for 10 min. After centrifugation, the solution was purified and concentrated by percolation using a 3,000 MW-cut polysulfone membrane to obtain a non-crosslinked, magenta-red PigDisp-33 dispersion: 22.9% solids, pH = 8.8, and an average particle size of 162 nm (using Microtrac). ® (Measured by particle size analyzer).

[0444] PigDisp-34

[0445] Add 0.86 g of TMPTGE and 1.24 g of boric acid to 130 g of PigDisp-32. Heat the resulting mixture at 65°C. Heating was carried out for 5 h. After cooling to room temperature, the solution was first diluted to approximately 15% solids, and then centrifuged at 2,500 G for 10 min. After centrifugation, the solution was purified and concentrated by percolation using a 3,000 MW-cut polysulfone membrane to obtain a crosslinked magenta PigDisp-34 dispersion: 18.56% solids, pH = 8.62, and an average particle size of 166 nm (using Microtrac). ® (Measured by particle size analyzer).

[0446] Evaluation of PigDisp-33-34

[0447] Solvent stability tests were performed on PigDisp-33 (non-crosslinked magenta dispersion) and PigDisp-34 (crosslinked magenta dispersion) using various solvents. The results are listed in Table 10 below.

[0448] Table 10

[0449]

[0450] When exposed to the solvents listed in Table 10, the non-crosslinked dispersion PigDisp-33 immediately becomes unstable, as evidenced by the aggregation of large pigment particles impacting the microscope slide. In contrast, the crosslinked dispersion PigDisp-34 diffuses and disperses in the solvent, demonstrating its stability upon exposure to the solvent.

[0451] PigDisp-35

[0452] Polymer-L (152 g solution, 14.1% solids in water) was combined with 72.5 g of DI water and 50 g of PigmentYellow 74 (in dry powder form). The mixture was then heated in approximately 10... Using Misonix ® The sample was sonicated using a probe sonicator for approximately 3 hours to obtain a low-viscosity yellow dispersion. 1.13 g of TMPTGE, 0.70 g of boric acid, and 140 g of DI water were added to the dispersion (288 g solution, 26% solids content). The resulting mixture was then heated at 65°C. Heating was carried out for 4 h. After cooling to room temperature, the solution was diluted to 10% solids and then centrifuged at 2,500 G for 20 min. The solution was then purified and concentrated by percolation using a 3,000 MW-cut polysulfone membrane to obtain yellow PigDisp-35: 20.16% solids with an average particle size of 165 nm (using Microtrac). ® (Measured by particle size analyzer).

[0453] Unless otherwise stated herein or in obvious contradiction in the context, the terms “a,” “an,” and “the” shall be construed as encompassing both the singular and plural. Unless otherwise stated, the terms “comprising,” “having,” “including,” and “containing” shall be construed as open-ended terms (i.e., meaning “including but not limited to”). Unless otherwise stated herein, descriptions of numerical ranges herein are intended only as a way of abbreviating each individual value falling within that range, and each individual value is incorporated into this specification as if it were individually referenced herein. Unless otherwise stated herein or in obvious contradiction in the context, all methods described herein may be performed in any suitable order. Unless otherwise stated, the use of any and all instances or exemplary language provided herein (e.g., “such as”) is intended only to better illustrate the invention and not to limit its scope. No language in the specification should be construed as indicating that any unclaimed element is essential to the practice of the invention.

Claims

1. A composition comprising: At least one pigment; Liquid carrier; and At least one polymer encapsulating the at least one pigment, wherein the at least one polymer comprises a first monomer selected from olefinically unsaturated hydrophobic monomers, and a second monomer selected from maleic anhydride, maleic acid and its salts, esters, imides and amides, wherein the olefinically unsaturated hydrophobic monomer comprises the formula... , where R 1 and R 2 Independently selected from H, C1-C 12 Alkyl, C5-C 20 Aryl and C6-C 20 Alkyl aryl, and R 1 and R 2 The carbon atom may optionally be replaced by at least one heteroatom selected from O, N, and S, and The at least one polymer is crosslinked by a second monomer. The first monomer is present in the at least one polymer in an amount of 40 to 90 mol%, relative to the at least one polymer. The second monomer is present in the at least one polymer in an amount of 10 to 60 mol%, relative to the at least one polymer. in, The at least one polymer has an acid value of 90 to 325, the acid value being based on the following equation: Wherein, "AN(xlink)" is the acid value of the at least one crosslinked polymer, "AN(SP)" is the acid value of the starting polymer, and "%targetCO2" is the percentage of carboxylate groups in the target second monomer used for crosslinking.

2. The composition of claim 1, wherein the second monomer is selected from maleic anhydride, maleic acid and its salts.

3. The composition of any one of claims 1 or 2, wherein the at least one polymer is crosslinked via the carboxylate group of the second monomer.

4. The composition of any one of claims 1 or 2, wherein the at least one polymer is crosslinked by at least 10% of the carboxylate groups of the second monomer.

5. The composition of any one of claims 1-4, wherein the at least one polymer is crosslinked by at least one bond selected from amides, imides and esters.

6. The composition of any one of claims 1-4, wherein the at least one polymer is crosslinked by at least one bond selected from ester bonds.

7. The composition of claim 6, wherein the ester bond is derived from a reaction between an epoxy-containing compound and a carboxyl group of a second monomer.

8. The composition of claim 7, wherein the epoxy-containing compound is selected from diglycidyl ether compounds and triglycidyl ether compounds.

9. The composition of claim 7, wherein the epoxy-containing compound is selected from trimethylolpropane triglycidyl ether.

10. The composition of any one of claims 1-9, wherein the olefinically unsaturated hydrophobic monomer comprises... , where R 1 and R 2 Independently selected from H, C1-C 12 Alkyl, C5-C 20 Aryl, C6-C 20 Araneyl and C6-C 20 Alkyl aryl.

11. The composition of any one of claims 1-9, wherein the olefinically unsaturated hydrophobic monomer is selected from styrene, -Methylstyrene, ethylene, propylene, 1-butene, isobutene, butadiene, and methyl vinyl ether.

12. The composition of any one of claims 1-9, wherein the olefinic unsaturated hydrophobic monomer is selected from styrene.

13. The composition of any one of claims 1-12, wherein the acid value of the at least one polymer is less than 325.

14. The composition of any one of claims 1-12, wherein the acid value of the at least one polymer is 50 to 325.

15. The composition of any one of claims 1-14, wherein the pH of the composition is 8 to 11.

16. The composition of any one of claims 1-15, wherein a portion of the second monomer is contained in a specific formulation. Functionalization of at least one organic group, wherein R 3 and R 4 Independently selected from H, C1-C 10 Alkyl, C4-C 18 Aryl, C4-C 18 heteroaryl and C3-C 20 Heterocyclic alkyl, and A is selected from C1-C1. 10 Alkylene, C3-C 20 Cycloalkylene, C3-C 20 Heterocyclic alkyl, aryl, heteroaryl and C2-C 20 ether.

17. The composition of any one of claims 1-15, wherein a portion of the second monomer is functionalized with at least one organic group selected from the following formula: , , , , , , , , and .

18. The composition of any one of claims 1-15, wherein a portion of the second monomer is contained in a specific formulation. Functionalization of at least one organic group, wherein R 3 R 4 and R 5 Independently selected from H, C1-C 10 Alkyl, C4-C 18 Aryl, C4-C 18 heteroaryl and C3-C 20 Heterocyclic alkyl, and A is selected from C1-C1. 10 Alkylene, C3-C 20 Cycloalkylene, C3-C 20 Heterocyclic alkyl, aryl, heteroaryl and C2-C 20 ether.

19. The composition of any one of claims 16-18, wherein the at least one organic group is bonded to the second monomer by at least one bond selected from amides, imides and esters.

20. The composition of any one of claims 1-19, wherein the at least one pigment is unmodified.

21. The composition of any one of claims 1-19, wherein the at least one pigment is self-dispersible.

22. The composition of any one of claims 1-21, wherein the liquid carrier is aqueous.

23. The composition of any one of claims 1-22, wherein the composition is an aqueous dispersion.

24. The composition of any one of claims 1-23, further comprising at least one surfactant.

25. The composition of any one of claims 1-24, further comprising at least one durable polymer.

26. The composition of any one of claims 1-25, further comprising at least one viscosity improver.

27. The composition of any one of claims 1-26, further comprising at least one polymeric adhesive.

28. The composition of any one of claims 1-27, wherein the composition is an inkjet ink composition.

29. A method for preparing a polymer, comprising: (a) Combine the following: (i) A polymer comprising at least one of the following: a first monomer selected from olefinically unsaturated hydrophobic monomers, and a second monomer selected from maleic anhydride, maleic acid and its salts, esters, imides and amides, wherein the olefinically unsaturated hydrophobic monomer comprises the following formula: , where R 1 and R 2 Independently selected from H, C1-C 12 Alkyl, C5-C 20 Aryl and C6-C 20 Alkyl aryl, and R 1 and R 2 The carbon atom may optionally be replaced by at least one heteroatom selected from O, N, and S, and (ii) at least one crosslinking agent selected from epoxy-containing compounds; and (b) Formation of polymers, The at least one polymer is crosslinked by a second monomer. The first monomer is present in the at least one polymer in an amount of 40 to 90 mol%, relative to the at least one polymer. The second monomer is present in the at least one polymer in an amount of 10 to 60 mol%, relative to the at least one polymer. Wherein, the at least one polymer has an acid value of 90 to 325, the acid value being based on the following equation: Wherein, "AN(xlink)" is the acid value of the at least one crosslinked polymer, "AN(SP)" is the acid value of the starting polymer, and "%targetCO2" is the percentage of carboxylate groups in the target second monomer used for crosslinking.

30. The method of claim 29, wherein before or simultaneously with incorporating the at least one polymer with the at least one crosslinking agent, the method further comprises hydrolyzing the at least one polymer.

31. The method of any one of claims 29-30, wherein the second monomer is selected from maleic anhydride, maleic acid and its salts.

32. The method of any one of claims 29-31, wherein the at least one crosslinking agent selected from epoxy-containing compounds reacts with the carboxylate-containing group of the second monomer.

33. The method of any one of claims 29-32, wherein the epoxy-containing compound is selected from diglycidyl ether and triglycidyl ether compounds.

34. The method of any one of claims 29-32, wherein the epoxy-containing compound is selected from trimethylolpropane triglycidyl ether.

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