POLYMERS FOR INKJET INK COMPOSITIONS

Abstract

An inkjet ink composition comprising: 1 to 15% by weight, based on the total weight of the inkjet ink composition, of at least one pigment, a carrier fluid, and 0.1 to 25% by weight, based on the total weight of the inkjet ink composition, of at least one polymer comprising first monomers selected from ethylenically unsaturated, hydrophobic monomers, wherein the ethylenically unsaturated, hydrophobic monomers are selected from styrene, α-methylstyrene, ethylene, propylene, 1-butylene, isobutylene, butadiene, methyl vinyl ether, and ethylenically unsaturated esters. and second monomers selected from maleic anhydride, maleic acid and salts, esters, imides and amides thereof, wherein at least a portion of the second monomers is functionalized with at least one organic group having a calcium index value greater than the calcium index value of phenylphosphonic acid, and wherein the first monomers are provided in the at least one polymer in a proportion in the range of 40 to 90 mol% relative to the at least one polymer, and wherein the second monomers are provided in the at least one polymer in a proportion in the range of 10 to 60 mol% relative to the at least one polymer, and wherein the at least one polymer has an acid number of 90 to 325 according to the following equation: AN (xlink) = AN (SP) − (% CO 2 − Target) × AN (SP) where “AN(xlink)” represents the acid number of the at least one polymer being crosslinked, “AN(SP)” represents the acid number of the starting polymer, and “%CO2 target” represents the percentage of the carboxylate-containing target for crosslinking.

Description

FIELD OF INVENTION

[0001] Described herein are inkjet ink compositions comprising polymers comprising ethylenically unsaturated, hydrophobic monomers and maleic anhydride and / or maleic acid (or salts, esters, imides, and amides thereof) monomers. BACKGROUND

[0002] In inkjet printing with pigment-based inks, individual ink droplets are deposited onto a substrate to rapidly form pigment aggregates on the substrate. This process can be challenging with plain and coated papers, including those with few dissolved salts such as calcium and magnesium salts. Slow pigment aggregation can result in average or substandard image quality, manifesting as low optical density, poor grain, and so on.

[0003] Other challenges arise when maintaining the stability of such pigment-based dispersions. Accordingly, there is a need to develop new pigment-based inkjet compositions to overcome these challenges.

[0004] US 2007 / 0100023 A1 relates to an inkjet ink composition containing a liquid carrier, at least one dye, and at least one polymer having at least one functional group. At least one polymer is bound or adsorbed to the dye.

[0005] DE 10 2006 062 441 A1 describes an inkjet ink composition containing modified comb copolymers.

[0006] US 2006 / 0235108 A1 relates to an inkjet ink composition containing a pigment, an aqueous medium, a copolymer resin of a hydrophobic monomer and a hydrophilic monomer, and a urethane resin.

[0007] WO 20137005019 A2 describes an inkjet ink composition containing a pigment encapsulated with a crosslinked polymer and a liquid carrier.

[0008] US 2014 / 0132661 A1 relates to an inkjet ink composition comprising more than 1 wt.% of a pigment and more than 0.1 wt.% of a polymer E, which may be a copolymer E2 having a functional group of the type -CQ(PO3H2)2 with a calcium index higher than that of 1,2,3-benzenetricarboxylic acid. The first hydrophobic monomer of the copolymer may be propylene, ethylene, styrene, u.-methylstyrene, butadiene, or an unsaturated ester. The second monomer may be selected from acrylic esters, vinyl esters, vinyl cyano compounds, halogenated monomers, aromatic vinyl monomers, olefins, dienes, and vinyl monomers.

[0009] DE 690 03 013 T2 relates to aminophosphonate-containing polymers and their use in fine-particle slurries with a high solids content for inhibiting corrosion and the formation and deposition of scale in aqueous systems. SUMMARY

[0010] The present invention relates to an inkjet ink composition comprising: 1 to 15% by weight, based on the total weight of the inkjet ink composition, of at least one pigment, a carrier fluid, and 0.1 to 25% by weight, based on the total weight of the inkjet ink composition, of at least one polymer comprising first monomers selected from ethylenically unsaturated, hydrophobic monomers, wherein the ethylenically unsaturated, hydrophobic monomers are selected from styrene, α-methylstyrene, ethylene, propylene, 1-butylene, isobutylene, butadiene, methyl vinyl ether, and ethylenically unsaturated esters. and second monomers selected from maleic anhydride, maleic acid and salts, esters, imides and amides thereof, wherein at least a portion of the second monomers is functionalized with at least one organic group having a calcium index value greater than the calcium index value of phenylphosphonic acid, and wherein the first monomers are provided in the at least one polymer in a proportion in the range of 40 to 90 mol% relative to the at least one polymer, and wherein the second monomers are provided in the at least one polymer in a proportion in the range of 10 to 60 mol% relative to the at least one polymer, and wherein the at least one polymer has an acid number of 90 to 325 according to the following equation: AN(xlink)=AN(SP)−(%CO2−target)×AN(SP) where “AN(xlink)” represents the acid number of the at least one polymer being crosslinked, “AN(SP)” represents the acid number of the starting polymer, and “%CO2 target” represents the percentage of the carboxylate-containing target for crosslinking. BRIEF DESCRIPTION OF THE DRAWINGS Fig. Figure 1A is a photograph of PigDisp-27 exposed to dipropylene glycol on a microscope slide. Fig. Figure 1B is a photograph of PigDisp-28 exposed to dipropylene glycol on a microscope slide. DETAILED DESCRIPTION

[0011] an inkjet ink composition is described comprising: 1 to 15% by weight, based on the total weight of the inkjet ink composition, of at least one pigment, a carrier fluid, and 0.1 to 25% by weight, based on the total weight of the inkjet ink composition, of at least one polymer comprising first monomers selected from ethylenically unsaturated, hydrophobic monomers, wherein the ethylenically unsaturated, hydrophobic monomers are selected from styrene, α-methylstyrene, ethylene, propylene, 1-butylene, isobutylene, butadiene, methyl vinyl ether, and ethylenically unsaturated esters. and second monomers selected from maleic anhydride, maleic acid and salts, esters, imides and amides thereof, wherein at least a portion of the second monomers is functionalized with at least one organic group having a calcium index value greater than the calcium index value of phenylphosphonic acid, and wherein the first monomers are provided in the at least one polymer in a proportion in the range of 40 to 90 mol% relative to the at least one polymer, and wherein the second monomers are provided in the at least one polymer in a proportion in the range of 10 to 60 mol% relative to the at least one polymer, and wherein the at least one polymer has an acid number of 90 to 325 according to the following equation: AN(xlink)=AN(SP)−(%CO2−target)×AN(SP) where “AN(xlink)” represents the acid number of the at least one polymer being crosslinked, “AN(SP)” represents the acid number of the starting polymer, and “%CO2 target” represents the percentage of the carboxylate-containing target for crosslinking.

[0012] The at least one polymer can bind calcium and / or other divalent metals. 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-benzenetricarboxylic acid.

[0013] In one embodiment, the at least one polymer is crosslinked via the second monomers.

[0014] In one embodiment, an inkjet ink composition having the at least one polymer encapsulating the pigment has increased stability relative to an inkjet ink composition having a self-dispersed pigment and / or a composition having a pigment and a polymeric dispersant with the same monomers in which the polymeric dispersant is not crosslinked.

[0015] In one embodiment, the ethylenically unsaturated hydrophobic monomers are selected from ethylenically unsaturated esters, such as ethylenically unsaturated esters of an aliphatic acid, in which the acid residue has 3-8 carbon atoms and, for example, 3-6 carbon atoms and the ester residue has 1-8 and, for example, 1-6 or 1-4 carbon atoms. Exemplary ethylenically unsaturated esters are 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 monomers may comprise two or more different ethylenically unsaturated hydrophobic monomers.

[0016] In one embodiment, the ethylenically unsaturated, hydrophobic monomers are selected from styrene, α-methylstyrene, ethylene, propylene, 1-butylene, isobutylene, butadiene, and methyl vinyl ether. In one embodiment, the ethylenically unsaturated, hydrophobic monomers are selected from styrene and α-methylstyrene.

[0017] According to the invention, the second monomers are selected from maleic anhydride, maleic acid, and salts, esters, imides, and amides thereof, and e.g., from maleic anhydride, maleic acid, and salts thereof. For example, the second monomers may comprise maleic anhydride, maleic acid, or a mixture of maleic anhydride and maleic acid (and / or salts, esters, imides, and amides thereof). The second monomers may be unsubstituted (as opposed to the portion functionalized with the at least one organic group). Alternatively, the second monomers may be substituted, e.g., with at least one group selected from C1-C6 alkyl and halide. Exemplary substituted second monomers are methylmaleic anhydride, dimethylmaleic anhydride, fluoromaleic anhydride, and methylethylmaleic anhydride.

[0018] The second monomers are provided in the at least one polymer in a proportion of 10 to 60 mol% relative to the at least one polymer, e.g., in a proportion of 10 to 50 mol%, of 10 to 40 mol%, of 10 to 35 mol%, of 20 to 60 mol%, of 20 to 50 mol%, of 20 to 40 mol%, of 20% to 35 mol% relative to the at least one polymer. The at least one polymer contains the first monomers in a proportion of 40 to 90 mol%, of 50 to 90 mol%, of 40 to 80 mol%, or of 50 to 80 mol% relative to the at least one polymer. For example, the at least one polymer comprises the first monomers in a proportion of 67 to 80 mol% and the second monomers in a proportion 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.

[0019] In one embodiment, the first monomers are selected from styrene. In one embodiment, the at least one polymer is selected from styrene-maleic anhydride (SMA) polymers in which a portion of the maleic anhydride monomers is functionalized with the at least one organic group. In one embodiment, the styrene-maleic anhydride polymer can be prepared by the polymerization of styrene or a styrenic monomer 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 in minor amounts.For example, the styrene-maleic anhydride polymers may be a polymer of styrene, maleic anhydride, and an additional monomer with a molar ratio of the polymerized styrene and maleic anhydride to another polymerized monomer greater than 1 / 1, and for example, greater than 5 / 1, greater than 10 / 1, and greater than 20 / 1. Such polymers may be prepared using any method known in the art, including polymerization using a continuous monomer feed and also using a one-pot polymerization process. In one embodiment, the styrene-maleic anhydride polymer is prepared using a continuous monomer feed method.

[0020] Other examples of styrene-maleic anhydride polymers are functionalized styrene-maleic anhydride polymers (in addition to the part functionalized with the at least one organic group), which are polymers prepared by the polymerization of styrene and maleic anhydride monomers, which have been further reacted with, for example, alcohols to form ester groups, or with amines to form amide or imide groups. Specific examples of functionalized styrene-maleic anhydride polymers are polymers comprising styrene monomer and monomers of the half-ester or half-amide of polymerized maleic anhydride (i.e., monomers with formulas such as -(CH(COOH)-CH(COOR)- or -(CH(COOH)-CH(CONR2)-), where R is selected from C1-C 20 -alkyl, aralkyl, alkaryl and aryl groups and e.g. from C6-C 18,-alkyl, aralkyl, and aryl groups. Partially functionalized styrene-maleic anhydride polymers may also be used, in which some, but not all, of the polymerized maleic anhydride monomers have been functionalized. Examples of these polymers are styrene-maleic anhydride-maleic acid ester polymers and styrene-maleic anhydride-maleic acid amide polymer. In addition, polymers comprising polymerized styrene monomers and polymerized maleic anhydride imide monomers may also be used.

[0021] The at least one polymer can be prepared using conventional polymerization techniques. For example, alpha-olefin-maleic anhydride copolymers can be prepared by various conventional polymerization processes, including those of newly issued U.S. patent application Ser. No. 28,475 E and U.S. patent applications Nos. 3,553,117 A, 3,560,455 A, 3,560,456 A, 3,560,457 A, 3,488,311 A, 4,522,992 A, 4,358,573 A, 4,871,823 A, 4,859,752 A, and 5,336,727 A, which are incorporated herein by reference. The at least one polymer can be prepared, for example, in pure alkenes at 160°C, in solvents such as aromatic hydrocarbons which dissolve the monomers but precipitate the polymers (precipitation polymerization or suspension polymerization), or in solvents such as ketones which precipitate the reactants and the polymers (solution polymerization).In one embodiment, the temperature for solution polymerization is in the range of 60-80°C. The radical initiators are usually AIBN or benzoyl peroxide.

[0022] At least a portion of the second monomers 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 can bind calcium and / or other divalent metals. In one embodiment, the binding ability of divalent metals can be quantified by calcium index values, as described in U.S. Patent No. 8,858,695 B2, which is incorporated herein by reference. The "calcium index value" is a measure of the ability of an organic group to coordinate or bind calcium ions in a solution. The higher the calcium index value, the more strongly or effectively the group can coordinate calcium ions. The calcium index values ​​can also be used to indicate the binding ability of other divalent metal ions, such as magnesium.

[0023] Calcium index values ​​can be determined by any method known in the art. For example, the calcium index value can be measured using a method in which the amount of calcium coordinated by a compound in a standard solution containing soluble calcium ions and a color indicator is measured using UV-VIS spectroscopy. Alternatively, for compounds with a strong color, for example, the calcium index value can be measured using an NMR method.

[0024] In one embodiment, the "calcium index value" corresponds to the methods described in US patent US 8,858,695 B2, which is incorporated herein by reference, e.g., Method A or Method B in column 29, line 45 to column 31, line 37. For both methods, a compound was chosen that corresponds to a desired organic group to be tested. 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 be hydrogen, C1-C 10 -alkyl (substituted or unsubstituted) or C4-C 18 -aryl (substituted or unsubstituted), the compound to be tested being, for example, the hydrogen, C1-C 10 -alkyl (substituted or unsubstituted) or C4-C 18-aryl (substituted or unsubstituted) bonded group. For example, a 3,4,5-tricarboxyphenyl functional group and salts thereof and 1,2,3-benzenetricarboxylic acid can be selected. In this example, the radical is hydrogen, and the oxygen atoms of the carboxylic acids are separated from the hydrogen radical by at least two bonds.

[0025] According to the invention, a reference to the calcium index value means that the value is greater than or equal to that of phenylphosphonic acid as a reference material. The at least one organic group thus has a calcium index value that is greater than or equal to the calcium index value of phenylphosphonic acid. In another embodiment, the reference is 1,2,3-benzenetricarboxylic acid. In one embodiment, the calcium index value is greater than or equal to 2.53 and, for example, greater than or equal to 2.8, greater than or equal to 3.0, greater than or equal to 3.2, which is determined using UV-VIS spectroscopy (or Method A) as explained in more detail below.

[0026] Method A. For this method, a series of pH 9 solutions were prepared containing 0.087 mM Congo Red indicator, 5 mM cesium chloride, 1 wt.% MW350 polyethylene glycol methyl ether, and calcium chloride at concentrations ranging from 0 to 7 mM (0.2, 0.5, 1, 2, 3, 4, 4.5, 5, 6, and 7 mM). The UV-VIS spectra of these solutions were recorded within 1 hour of their preparation using a UV-2501PC. These spectra were used to construct a calibration curve relating absorbance at 520 nm to calcium concentration.

[0027] Test solutions were then prepared at pH 9 containing 0.087 mM Congo Red indicator, 1 wt% MW350 polyethylene glycol methyl ether, 5 mM calcium chloride, and the cesium salt of the relevant compound, such that the ion concentration at pH 9 was 5 mM. The concentration of uncomplexed calcium was determined by comparison with the calibration curve. The calcium index value was then expressed as log 10 ((0.005 - uncomplexed calcium) / (( uncomplexed calcium) 2 )) was calculated. Duplicate measurements were taken and then averaged.

[0028] Method B. For compounds that develop a high degree of color and are therefore difficult to use in Method A, a second method was developed. For this method, an aqueous solution containing 0.01M in 43 CaCl2, 0.01M in NaCl, 10% D2O and a pH of 8 or 9, from 43CaCO3, HCl / D2O, NaOH / D2O, D2O, and water. The pH was chosen to ionize and dissolve the compound under investigation. A portion of the solution weighing approximately 0.65 g was placed in a 5 mm NMR tube and weighed to the nearest 0.001 g. The chemical shift of the unbound 43 Ca was measured using a Bruker Avance II spectrometer with a proton resonance frequency of 400.13 MHz. A 0.2-1.0M solution of the compound under investigation (ligand) was added in successive increments. After this addition, the chemical 43 Ca shift was measured and δ, the difference between the sample shift and that of unbound calcium, was calculated. The successive increments were planned such that the L o / Ca o -ratio was 0.25, 0.5, 1, 2, 3, 4, 6 and 8, where L ois the total concentration of complex, protonated and free anions from the ligand and Ca o the total concentration of calcium in all species present. The calcium index value (NMR) was calculated as log 10 (X), where X is calculated by inserting the parameters X and δ m was determined in the following equation: δ=δm2{[1+(L0 / Ca0)+(1+H+ / Ka) / (XCa0)]−[1+(L0 / Ca0)+(1+H+ / Ka) / (XCa0)]2−4(L0 / Ca0)} such that the RMS difference between the data and the predicted chemical shifts is minimized by the equation, where: δ the difference in chemical 43 Ca shift of the sample vs. that of free, aqueous 43 Ca 2+ is, δ m the calculated difference in the chemical 43 Ca shift at infinite L / Ca vs. that of free 43 Ca 2+ is, L ois the total concentration of complexed, protonated and free anions of the ligand, Ca o the total concentration of calcium in all species present, X is a fitting parameter, and K a is the proton dissociation constant for the ligand LH.

[0029] Without wishing to be bound by any particular theory, the polymer dispersant claimed herein may enable improved printing performance through interaction or bonding with calcium salts and / or other divalent metal salts (e.g., magnesium) in or on the substrate. The divalent metal salts may be a coating on the substrate or may be added later, such as by printing with a fixation fluid containing metal salts. Initially stable dispersions may rapidly destabilize when in contact with a substrate. Alternatively, or additionally, destabilization may result from a change in pH or contact with the substrate, which may be advantageous for polymer dispersants comprising the pendant functional groups described above.It is assumed that rapid destabilization after printing caused by a change in pH, interaction with calcium and / or other divalent metal salts or mixtures thereof results in printed images with overall good properties such as optical density, edge sharpness and / or color bleed.

[0030] In one embodiment, the portion of the second monomers functionalized with the at least one organic group is expressed as mol% of the total amount of second monomers (sum of the functionalized and non-functionalized second monomers). In one embodiment, the portion of the second monomers functionalized with the at least one organic group is at least 3 mol% and, for example, at least 5 mol%, at least 7 mol%, or at least 10 mol% relative to the total amount of second monomers. In one embodiment, the portion of the second monomers functionalized with the at least one organic group is at most 75 mol% of the total second monomers and, for example, at most 60 mol%, at most 50 mol%, or at most 40 mol% of the total amount of second monomers.In one embodiment, the portion of the second monomers functionalized with the at least one organic group is in the range from 3 mol% to 75 mol% and, for example, from 5 mol% to 75 mol%, from 3 mol% to 60 mol%, from 5 mol% to 60 mol%, from 3 mol% to 50 mol%, from 5 mol% to 50 mol%, from 3 mol% to 40 mol% or from 5 mol% to 40 mol% of the total amount of second monomers.

[0031] In one embodiment, a portion of the second monomers is functionalized with the at least one organic group via a number of reactions known in the art, e.g., by reactions with carboxylic acids and / or anhydrides. In one embodiment, alcohols or amines containing the at least one organic group may react with the maleic anhydride or maleic acid, optionally in the presence of a base if required. In one embodiment, a primary amine containing the at least one organic group may react with the maleic anhydride or maleic acid in the presence of a base to form an amide group that links the at least one organic group to the polymer.

[0032] In one embodiment, the at least one organic group comprises at least one group selected from carboxylic acids, sulfonic acids, phosphonic acids, hydroxyls, amines and esters, amides and salts and esters thereof.

[0033] In one embodiment, the at least one organic group is selected from one or more of the following: • at least one phosphonic acid group (e.g. at least two phosphonic acid groups), partial esters thereof and salts thereof, such as a geminal bisphosphonic acid group, partial esters thereof and salts thereof, • at least one heterocyclic group comprising at least one OH group (e.g. at least two OH groups) and salts thereof, • at least one phosphonic acid group or a salt thereof and at least one second ionic, ionizable or basic group, vicinal or geminal to the phosphonic acid group, and salts thereof, • an acrylic or alkyl polyacid group comprising at least three carboxylic acids, • a heteroaryl group comprising at least one carboxylic acid group, and salts thereof, • an aryl group comprising at least one nitroso group and at least one OH group, and salts thereof. • an azoarene group 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 Ar 1 -N=N-Ar 2 where Ar 1 and Ar 2 which may be the same or different, are an arylene group or an aryl group and at least one of Ar 1 or Ar 2 is an arylene group.

[0034] In one embodiment, the at least one organic group comprises at least two phosphonic acid groups, esters thereof, or salts thereof.

[0035] In one embodiment, the at least one organic group may comprise at least one geminal bisphosphonic acid group, partial esters thereof, and salts thereof, so that the at least one organic group may comprise at least two phosphonic acid groups, partial esters thereof, and salts thereof that are directly bonded to the same carbon atom. Such a group may also be referred to as a 1,1-diphosphonic acid group, partial esters thereof, or salts thereof. The at least one organic group may thus comprise a group having the formula -CQ(PO3H2)2, partial esters thereof, and salts thereof. Q is bonded to the geminal position and may be H, R, OR, SR, or NR2, where R, which may be the same or different, is H, a saturated or unsaturated, branched or unbranched C1-C 18- Alkyl group, a saturated or unsaturated, branched or unbranched C1-C 18-acyl group, an aralkyl group, an alkaryl group, or an aryl group. Q can be, for example, H, R, OR, SR, or NR2, where R, which may be the same or different, is H, a C1-C6 alkyl group, or an aryl group. In one embodiment, Q is H, OH, or NH2. Furthermore, the at least one organic group can be a group having the formula -(CH2) n -CQ(PO3H2)2, partial esters thereof and salts thereof, wherein Q is as described above and n is between 0 and 9 and, for example, 1 to 9, 0 to 3 or 1 to 3. In one embodiment, n is either 0 or 1. Furthermore, the at least one organic group may be a group having the formula -Y-(CH2) n-CQ(PO3H2)2, partial esters thereof, and salts thereof, wherein Q and n are as described above, and Y is an arylene, heteroarylene, alkylene, vinylidene, alkarylene, aralkylene, cyclic, or heterocyclic group. In one embodiment, Y is an arylene group such as a phenylene, naphthalene, or biphenylene group, which may be further substituted by any group such as one or more alkyl groups or aryl groups. When Y is an alkylene group, it may be, for example, substituted or unsubstituted alkylene groups, which may be branched or unbranched, and may be substituted by one or more groups such as aromatic groups. Examples include C1-C 12 -Groups such as methylene, ethylene, propylene or butylene groups.

[0036] Y may be further substituted by one or more groups selected from, among others, R', OR', COR', COOR', OCOR', carboxylates, halogens, CN, NR'2, SO3H, sulfonates, sulfates, NR'(COR'), CONR'2, imides, NO2, phosphates, phosphonates, N=NR', SOR', NR'SO2R' and SO2NR2', where R', which may be the same or different, independently represents hydrogen, branched or unbranched, substituted or unsubstituted, saturated or unsaturated C1-C 20 -hydrocarbons and e.g. alkyl, alkenyl, alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkaryl or substituted or unsubstituted aralkyl.

[0037] In one embodiment, the at least one organic group may be a group having the formula -Y-Sp-(CH2) n-CQ(PO3H2)2, partial esters thereof, and salts thereof, wherein Y, Q, and n are as described above. Sp is a spacer group, which here is a connection between two groups. Sp can be a bond or a chemical group. Examples of chemical groups include -CO2-, -O2C-, -CO-, -OSO2-, -SO3-, -SO2-, -SO2C2H4O-, -SO2C2H4S-, -SO2C2H4NR''-, -O-, -S-, -NR''-, -NR''CO-, -CONR''-, -NR''CO2-, -O2CNR''-, -NR''CONR''-, -N(COR'')CO-, -CON(COR'')-, - NR''COCH(CH2CO2R'')- and cyclic imides thereof, -NR''COCH2CH(CO2R'')- and cyclic imides thereof, -CH(CH2CO2R'')CONR''- and cyclic imides thereof, - CH(CO2R'')CH2CONR'' and cyclic imides thereof (including phthalimides and maleimides thereof), sulfonamide groups (including -SO2NR''- and -NR''SO2- groups), arylene groups, alkylene groups and the like.R'', which may be the same or different, represents hydrogen or an organic group such as a substituted or unsubstituted aryl or alkyl group. As stated above in the construction, a group comprising at least two phosphonic acid groups and salts thereof is bonded to Y via the spacer group Sp. In one embodiment, Sp is -CO2-, -O2C-, -O-, -NR''CO- or -CONR''-, -SO2NR''-, -SO2CH2CH2NR''-, -SO2CH2CH2O- or -SO2CH2CH2S-, wherein R''H is a C1-C6 alkyl group.

[0038] Furthermore, the at least one organic group may comprise at least one group having the formula -CR=C(PO3H2)2, partial esters and salts thereof. R may be H, a saturated or unsaturated, branched or unbranched C1-C 18- Alkyl group, a saturated or unsaturated, branched or unbranched C1-C 18-acyl group, an aralkyl group, an alkaryl group, or an aryl group. In one embodiment, R is H, a C1-C6 alkyl group, or an aryl group.

[0039] In one embodiment, the at least one organic group may comprise more than two phosphonic acid groups, partial esters thereof, and salts thereof, and may, for example, comprise more than one group type (such as two or more), each group type comprising at least two phosphonic acid groups, partial esters thereof, and salts thereof. For example, the at least one organic group may comprise a group having the formula -Y-[CQ(PO3H2)2] p , partial esters thereof, and salts thereof. Y and Q are as described above. In one embodiment, Y is an arylene, heteroarylene, alkylene, alkarylene, or aralkylene group. In this formula, p is between 1 and 4, and for example, 2.

[0040] In one embodiment, the at least one organic group may comprise at least one vicinal bisphosphonic acid group, partial esters thereof, and salts thereof, meaning that these groups are adjacent to one another. The at least one organic group may comprise two phosphonic acid groups, partial esters thereof, and salts thereof bonded to adjacent carbon atoms. Such groups are sometimes also referred to as 1,2-diphosphonic acid groups, partial esters thereof, and salts thereof. The group comprising the two phosphonic acid groups, partial esters thereof, and salts thereof may be an aromatic group or an alkyl group, so the vicinal bisphosphonic acid group may be a vicinal alkyl or a vicinal aryldiphosphonic acid group, partial esters thereof, and salts thereof.For example, the at least one organic group may be a group having the formula -C3H3-(PO3H2)2, partial esters thereof, and salts thereof, wherein the acid, ester, or salt groups are located at ortho positions to each other.

[0041] In at least one embodiment, 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 vicinal or geminal to the phosphonic acid group and salts thereof.

[0042] In one embodiment, the at least one organic group is selected from -C(OH)(PO3H2)2, -CH2C(OH)(PO3H2)2, -CH2CH2C(OH)(PO3H2)2, -CH2CH2CH2C(OH)(PO3H2)2, -CH(PO3H2)2, -CH2CH(PO3H2)2, partial esters thereof, and salts thereof.

[0043] In one embodiment, the at least one organic group comprises at least one heterocyclic group (e.g., a heteroaryl group) comprising at least one OH group, e.g., at least two OH groups, and salts thereof. The heterocyclic group may be a nitrogen-containing heteroaryl group such as a pyridinyl group or a quinolinyl group, and the at least one organic group is a hydroxypyridinyl group or a hydroxyquinolinyl group. The hydroxy group may be positioned on the heteroaryl group such that it is geometrically close to the heteroatom, such as ortho to the heteroatom. Such a group may have a salt form. For example, the at least one organic group may comprise a 2-hydroxypyridinyl group or a 2-hydroxyquinolinyl group, and also an 8-hydroxyquinolinyl group and salts thereof. Other isomers or tautomers are known to those skilled in the art.In one embodiment, the at least one organic group comprises an 8-hydroxyquinolinyl group. Furthermore, the at least one organic group may further comprise additional organic groups, including those described above for Y. For example, electron-withdrawing groups such as chloro or nitro groups may be included to lower the pKa of the OH group. In one embodiment, the organic group may comprise at least one heterocyclic group (e.g., a heteroaryl group) comprising at least one OH group, and salts thereof.

[0044] In one embodiment, the at least one organic group may also comprise at least one heteroaryl group comprising at least two OH groups. If two OH groups are present, the OH groups may be located at positions ortho to each other on the heteroaryl group. If more than two OH groups are present, at least two of the OH groups are located at positions ortho to each other on the heteroaryl group. For example, the at least one organic group may be a dihydroxypyridinyl group such as a 2,3-dihydroxypyridinyl group (which may also be referred to as a 3-hydroxy-2-pyridonyl group), a 3,4-dihydroxypyridinyl group (which may also be referred to as a 3-hydroxy-4-pyridonyl group), a 2,3-dihydroxyquinolinyl group (which may also be referred to as a 3-hydroxy-2-quinolonyl group), or a 3,4-dihydroxyquinolinyl group (which may also be referred to as a 3-hydroxy-4-quinolonyl group).Further isomers and tautomers are known to the person skilled in the art.

[0045] In one embodiment, the at least one organic group comprises at least one phosphonic acid group, a partial ester thereof, and salts thereof, and at least one second ionic group, an ionizable group, or a basic group. The second group is not a phosphonic acid group or salts thereof. In one embodiment, the second ionic or ionizable group is a carboxylic acid group, a sulfonic acid group, or salts thereof. In one embodiment, the basic group is a Lewis base such as an OH group (a hydroxyl group) or an amino group. In one embodiment, these two groups are geminal to each other, meaning that they are directly bonded to the same carbon atom. For example, if the second ionic or ionizable group is a carboxylic acid group or salts thereof, the at least one organic group may comprise a group having the formula -CQ(PO3H2)(CO2H) and salts thereof.Q bonded to the geminal position may be any of those described above. In one embodiment, Q is H. Additionally, the at least one organic group may be a group having the formula -(CH2). n -CQ(PO3H2)(CO2H) and salts thereof, where n is 0 to 9 and e.g. 0 to 3. Furthermore, the at least one organic group may be a group having the formula -Y-(CH2) n -CQ(PO3H2)(CO2H) or salts thereof, wherein Y is as described above. In one embodiment, Y is an arylene group. Furthermore, the at least one organic group may also be a group having the formula -Y-Sp-(CH2) n -CQ(PO3H2)(CO2H) or salts thereof, wherein Y and Sp, which is a spacer group, are as described above. In one embodiment, Y is an arylene group.

[0046] In one embodiment, the at least one organic group may comprise at least one phosphonic acid group, a partial ester thereof, or salts thereof, and at least one hydroxy group or salts thereof, such as a group having the formula -Y-(PO3H2)(OH) and salts thereof, where Y is as described above. In one embodiment, Y is an arylene group, and the phosphonic acid group and the hydroxy group are located at positions ortho to each other. When these groups are geminal, the at least one organic group may comprise at least one group having the formula -CR(PO3H2)(OH) and / or salts thereof, where R is H or a C1-C6 alkyl group. In one embodiment, R is H. Furthermore, the at least one organic group may comprise at least one group having the formula -(CH2) n-CR(PO3H2)(OH) and salts thereof, wherein n is 0 to 9 and e.g. 0 to 3. Furthermore, the at least one organic group may be a group having the formula -Y-(CH2) n -CR(PO3H2)(OH) and salts thereof or a group with the formula -Y-Sp-(CH2) n -CR(PO3H2)(OH) and salts thereof, wherein Y and Sp are as described above.

[0047] In one embodiment, the at least one organic group comprises an aryl or alkyl polyacid group having at least three carboxylic acids. In one embodiment, at least two of the carboxylic acid groups are vicinal, 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 having at least three carboxylic acids, such as a 1,2,3- or 1,2,4-tricarboxylic acid group or a 1,2,3,4- or 1,2,4,5-tetracarboxylic acid group.

[0048] In one embodiment, the at least one organic group comprises a heteroaryl group comprising at least one carboxylic acid group or salts thereof. The heteroaryl group can be any group known in the art. In one embodiment, the heteroaryl group is a nitrogen containing a heteroaryl group such as a pyridinyl group, a pyrimidinyl group, a pyrrolyl group, a quinolinyl group, or a pyrazinyl group. In one embodiment, the at least one organic group comprises two carboxylic acid groups and salts thereof. These acid groups can be located anywhere on the heteroaryl ring. In one embodiment, the acid groups can be ortho or meta to each other. And when the heteroaryl group contains at least one nitrogen atom, the two acid groups can be adjacent (i.e., ortho) to the nitrogen atom. For example, the heteroaryl group can be a 2,6-pyridinyldicarboxylic acid group.

[0049] In one embodiment, the at least one organic group comprises an aryl group having at least one nitroso group and at least one OH group, or a salt thereof. The two groups can be located anywhere on the aryl group. In one embodiment, the aryl group is a phenyl group, and the nitroso and OH groups are located at positions ortho to each other. The aryl group can further comprise other substituents such as alkyl groups, halogen groups, ether groups, and the like, including electron-withdrawing groups such as chloro and nitro groups that can lower the pKa value of the at least one organic group regardless of its tautomeric form. For example, the at least one organic group can be a nitrosophenolic group such as a group having the formula -C3H3(OH)(NO) or a group having the formula -C6H2Z(OH)(NO), where Z is an electron-withdrawing group such as chloro or nitro.

[0050] In one embodiment, the at least one organic group comprises an azoarene group. For example, the at least one organic group may comprise a group having the formula Ar 1 -N=N-Ar 2 include, where Ar 1 and Ar 2 which may be the same or different, are an arylene group such as a phenylene or a naphthylene group or an aryl group such as a phenyl group or a naphthyl group and at least one of Ar 1 or Ar 2 is an arylene group. In this embodiment, the azoarene group comprises 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. The azoarene group can therefore have the formula -(HO)Ar 1 -N=N-Ar 2 (OH) (a bishydroxyazoarene group), -(H2N)Ar 1 -N=N-Ar 2 (NH2) (a bis-aminoazoarene group), or - (HO)Ar 1 -N=N-Ar2 (NH2) or -(H2N)Ar 1 -N=N-Ar 2 (OH) (an amino-hydroxyazoarene group). Other combinations are also possible. In one embodiment, the OH and / or NH2 groups are located at positions ortho to the azo group (the N=N group). For example, the at least one organic group can be a group having the structure -(HO)C6H3-N=N-C6H3(OH). Furthermore, electron-withdrawing groups such as chloro or nitro groups can be present in the aryl and / or arylene groups. For example, the at least one organic group is a group having the structure -(HO)C6H3-N=N-C6H3Z(OH), where Z is an electron-withdrawing group such as chloro or nitro.

[0051] In one embodiment, at least a portion of the second monomers is contacted with at least one organic group having the formula-AN(R 3 )(R 4) functionalized (or at least a second part of the second monomers is functionalized with at least one second organic group; for polymers containing at least one organic group with the desired calcium index values), where R 3 and R 4 independently from H, C1-C 10 -Alkyl, C4-C 18 -aryl, C4-C 18 -Heteroaryl and C3-C 20 -Heterocycloalkyl and A is selected from C1-C 10 -alkylene, C3-C 20 -Cycloalkylene, C3-C 20 -Heterocycloalkylene (wherein at least one ring atom of the cycloalkylene is a heteroatom selected from O, N and S), arylene, heteroarylene (wherein at least one ring atom of the heteroarylene is a heteroatom selected from O, N and S) and C2-C 20-ether. In another embodiment, at least a portion of the second monomers is selected from the group consisting of at least one organic group having a formula -CH2CH2-N(CH3)2, -CH2CH2CH2-N(CH3)2, -CH(CH3)CH2-N(CH3)2, -CH2CH2CH2CH2-N(CH3)2, -CH2CH2-N(CH2CH3)2, -CH2CH2CH2-N(CH2CH3)2, -CH2CH2CH2CH2-N(CH2CH3)2, -CH2CH2-NHCH2CH2OH, -CH2CH2-N(CH2CH2OH)2 or functionalized (or at least a portion of the second monomers is functionalized with at least one second organic group; for polymers containing at least one organic group with the desired calcium index value). In a further embodiment, at least a second portion of the second monomers is functionalized with at least one organic group having the formula -AN + (R 3 )(R 4 )(R 5) functionalized (or at least a second part of the second monomers is functionalized with at least one second organic group; for polymers having at least one organic group with the desired calcium index values), where R 3 , R 4 and R 5 independently from H, C1-C 10 -Alkyl, C4-C 18 -aryl, C4-C 18 -Heteroaryl and C3-C 20 -Heterocycloalkyl and A is selected from C1-C 10 -Alkylene, C3-C 20 Cycloalkylene, C3-C 20 -Heterocycloalkylene, arylene, heteroarylene and C2-C 20 -ether. In all of these embodiments, the at least one organic group is bonded to a portion of the second monomers via amide, imide, and ester bonds, and e.g., via amide and ester bonds.

[0052] In one embodiment, the at least one polymer can act as a polymer dispersant for dispersing a pigment in a liquid medium (e.g., an aqueous medium). Dispersing can be accomplished by methods known in the art, such as mixing (e.g., with a high-shear mixer), sonication, milling (e.g., with media or a ball mill), etc. In one embodiment, crosslinking is performed by adding crosslinking agents to the polymer-dispersed pigment.

[0053] In one embodiment, the inkjet ink composition comprises a pigment that is a polymer-dispersed pigment comprising the at least one polymer adsorbed to the pigment or encapsulating the pigment (e.g., a polymer-encapsulated pigment). In another embodiment, the at least one polymer is crosslinked via the second monomers. For example, polymer-encapsulated pigments can comprise polymer-dispersed pigments in which the at least one polymer is crosslinked with various crosslinking agents. The pigment can be any pigment described herein, such as an unmodified or otherwise untreated pigment or a modified (self-dispersed) pigment.

[0054] In one embodiment, the at least one polymer is crosslinked via at least one linkage selected from amide, imide, ester, ether, and thioether linkages (e.g., amide, ester, and other linkages or amide and ester linkages). For example, crosslinking agents such as multifunctional reagents (e.g., bifunctional, trifunctional, etc.) containing two or more epoxy, thiol, and amine groups, and mixtures thereof, can be used to form linkages, e.g., in reaction with carboxylate-containing groups of the second monomers. In one embodiment, the second monomers (e.g., maleic anhydride, maleic acid, and salts, esters, imides, and amides thereof) of at least two polymers can react with the crosslinking agents.In one embodiment, the crosslinking agents are selected from epoxy-containing compounds, such as di- or tri-epoxide-based compounds such as trimethylolpropane polyglycidyl ether, to form crosslinked polymers with ester linkages. In one embodiment, the ester linkage is derived from a reaction between epoxy-containing compounds (e.g., di- and triglycidyl ether compounds such as trimethylolpropane polyglycidyl ether) and carboxylate-containing groups of the second monomers. In another embodiment, the crosslinking agent is selected from aminoethanethiol.

[0055] In one embodiment, the at least one polymer is crosslinked via carboxylate-containing groups of the second monomer (anhydrides, carboxylic acids, and salts, esters, imides, and amides thereof). In one embodiment, the at least one polymer containing anhydrides, carboxylic acids, and salts, esters, imides, and amides thereof can be hydrolyzed to generate carboxylate-containing groups (e.g., carboxylic acid or carboxylate) that can react with the crosslinking agent. Hydrolysis can be performed to generate the carboxylic acid or carboxylate either before or simultaneously with the addition of the crosslinking agent.

[0056] In another embodiment, the at least one polymer is crosslinked via at least 10% of the carboxylate-containing groups of the second monomer and, 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 number of carboxylate-containing groups for crosslinking ("%CO2 target") can be determined based on the amount of crosslinking agent added.

[0057] The at least one polymer that is crosslinked has an acid number ("AN(xlink)") of 90 to 325. The acid number of the at least one polymer is defined as a theoretical value related to the acid number of the starting polymer ("AN(SP)") and the percentage of the carboxylate-containing target for crosslinking ("%CO2 target") according to the following equation: AN(xlink)=AN(SP)−(%CO2−target)×AN(SP)

[0058] The at least one polymer has an acid number AN(xlink) in the range from 90 to 325, from 90 to 300, from 90 to 275, from 90 to 250, from 90 to 225 or from 90 to 200.

[0059] In one embodiment, the at least one polymer is provided in the inkjet ink composition in an amount of 0.1 to 25 weight percent, e.g., 0.1 to 20 weight percent, 0.2 to 25 weight percent, 0.2 to 20 weight percent, 0.5 to 25 weight percent, or 0.5% to 20 weight percent relative to the total weight of the inkjet ink composition.

[0060] In one embodiment, the at least one polymer has an average molecular weight (M w ) of at least 1000 and eg of at least 2000 or at least 3000 (for the non-crosslinked polymer). In another embodiment, the M wless than or equal to 200,000 and e.g. none than 150,000, less than 100,000 or less than 70,000. In one embodiment, the M w in the range from 1000 to 200,000 and e.g. from 1000 to 150,000, from 1000 to 100,000, from 1000 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.

[0061] In one embodiment, the inkjet ink composition comprising the at least one polymer (e.g., the at least one polymer crosslinked via the second monomers) has a pH in the range of 8 to 11 and, for example, a pH in the range of 8.5 to 11, 8 to 10.5, 8.5 to 10.5, 8 to 10, or 8.5 to 10. In one embodiment, the inkjet ink composition is a dispersion (such as an aqueous dispersion) comprising, consisting essentially of, or consisting of the at least one polymer, at least one pigment, and a carrier liquid (e.g., an aqueous solution or water).

[0062] The polymer contained in the inkjet ink composition can be prepared by a process comprising: (a) Combine: (i) at least one polymer comprising first monomers selected from ethylenically unsaturated, hydrophobic monomers selected from styrene, α-methylstyrene, ethylene, propylene, 1-butylene, isobutylene, butadiene, methyl vinyl ether, and ethylenically unsaturated esters, and second monomers selected from maleic anhydride, maleic acid, and salts, esters, imides, and amides thereof, and (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 the phenylphosphonic acid, and (b) Forming the polymer.

[0063] The combining may be carried out in the presence of at least one base selected from NH4OH, NaOH, and KOH. In one embodiment, the at least one reagent comprises an amino group selected from a primary amine.

[0064] In one embodiment, the methods described herein further comprise combining the polymer with at least one crosslinking agent selected, for example, from epoxy-containing compounds such as the di- or triepoxide-based compounds described herein, such as 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 epoxy-containing compounds reacts with carboxylate-containing groups of the second monomers.

[0065] In one embodiment, the method further comprises, prior to or concurrently with combining the at least one polymer with the at least one crosslinking agent, hydrolyzing the at least one polymer. The hydrolysis may be carried out by any known method in the art, e.g., by adding water and / or at least one base such as a base selected from NH4OH, NaOH, and KOH. In one embodiment, the hydrolysis produces carboxylate-containing groups (e.g., carboxylic acid or carboxylate groups) of the second monomers that can react with the at least one crosslinking agent. In one embodiment, the composition after forming the crosslinked polymer (e.g., the solution with the polymer present therein) has a pH in the range of 8 to 11, and e.g., a pH of 8.5 to 11 or of 8.5 to 10.5. Pigments

[0066] The inkjet ink composition of the invention comprises 1 to 15 wt. % of at least one pigment, which may be unmodified or modified, based on the total weight of the inkjet ink composition. The pigments are solids that generally have the shape of a particle or may simply be formed into a particle, such as a presscake. In one embodiment, the modified pigment has at least one radical, such as acid groups (and partial esters, partial salts, and partial esters thereof) and organic groups. In another embodiment, the modified pigment is an oxidized pigment that may further have groups attached thereto. In one embodiment, the modified pigment is self-dispersible, so that no external dispersant is required to disperse the pigment (self-dispersed pigments).

[0067] In an embodiment where the pigment is unmodified, the at least one polymer can further function as a dispersant. In an embodiment where the pigment is modified, the at least one polymer can further function as an additive. In one embodiment, the polymer can improve one or more printing performance properties, such as optical density, grain, and durability.

[0068] The unmodified pigment may be any type of pigment commonly 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 may also be used. Examples of black pigments are various carbon blacks (Pigment Black 7) such as channel blacks, furnace blacks, gas blacks, and lamp blacks, and include, for example, carbon blacks known as Regal ® , Black Pearls ® , Elftex ® , Monarch ® , Mughal ® and Vulcan ® -Carbon blacks are available from Cabot Corporation (such as 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). However, carbon blacks from other suppliers can also be used. Suitable classes of colored pigments include anthraquinones, phthalocyanine blues, phthalocyanine greens, diazos, monoazos, pyranthrones, perylenes, heterocyclic yellows, quinacridones, quinolonoquinolones, and (thio)indigoids. Such pigments are commercially available in either powder or presscake form from various suppliers, including BASF Corporation, Engelhard Corporation, Sun Chemical Corporation, Clariant, and Dianippon Ink and Chemicals (DIC). Examples of other colored pigments are described in the Color 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.

[0069] In one embodiment, the pigment is a carbon black with a high structure such as a carbon black with the following properties: OAN≥170 mL / 100 g, and a STSA / BET ratio in the range of 0.7 to 1.

[0070] In one embodiment, the ratio of STSA / BET ranges from 0.8 to 1 and, for example, from 0.9 to 1. In one embodiment, the carbon black has an STSA in the range 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 and e.g. at least 170 m 2 / g, at least 190 m 2 / g in the range of 190 to 275 m 2 / g. In another embodiment, the carbon black has a compressed OAN (COAN) of at least 120 mL / 100 g and, for example, a COAN of at least 130 mL / 100 g. OAN and COAN can be determined according to ASTM-D2414. Surface area measurements can be made according to ASTM-D6556. Additional details regarding such a carbon black can be found in U.S. Patent No. 9,388,300, the disclosure of which is incorporated herein by reference.

[0071] In one embodiment, the self-dispersed pigment is an oxidized carbon black. In one embodiment, “oxidized carbon blacks” are carbon black pigments that generally have a pH < 7.0 and surface-bound ionic or ionizable groups such as alcohols (phenols, naphthols), lactones, carbonyls, carboxyls (e.g., carboxylic acids), anhydrides, ethers, and quinones. The degree of oxidation of carbon black can determine the surface concentration of these groups. In one embodiment, the oxidized carbon black is obtained by oxidizing an unmodified carbon black, such as pigments selected from channel blacks, furnace blacks, gas blacks, and lamp blacks. Exemplary unmodified carbon blacks are those commercially available from Cabot Corporation, such as Regal ® , Black Pearls ® , Elftex ® , Monarch ® , Mughal ® and Vulcan ® , such as Black Pearls ® 1100, Black Pearls ® 900, Black Pearls ®880, Black Pearls ® 800, Black Pearls ® 700, Black Pearls ® 570, Elftex ® 8, Monarch ® 900, Monarch ® 880, Monarch ® 800, Monarch ® 700, shelf ® 660 and shelf ® 330. Exemplary oxidizers for carbon blacks are oxygen gas, ozone, peroxides such as hydrogen peroxides, persulfates such as sodium and sodium hypochlorite, nitric acid, and transition metal-containing oxidizers such as permanganate salts, osmium tetroxide, chromium oxides, ceric ammonium nitrates, and mixtures thereof (e.g., mixtures of gaseous oxidizers such as oxygen and ozone).

[0072] In another embodiment, the oxidized soot is obtained from commercial suppliers such as Black Pearls ® 1400, Black Pearls ® 1300, Black Pearls ® 1000, Black Pearls ® L, Monarch ® 1000, Mughal ® L and shelf® 400, which are commercially available from Cabot Corporation.

[0073] In one embodiment, the pigment has at least one organic group attached thereto, where an "attached" group can be distinguished from an adsorbed group in that Soxhlet extraction for several hours (e.g., at least 4, 6, 8, 12, or 24 hours) does not separate the attached group from the pigment. In another embodiment, the organic group is attached to the pigment if the organic group cannot be removed after repeated washing with a solvent or mixture of solutions that can dissolve the organic starting material for treatment but cannot disperse the treated pigment. In a further embodiment, "attached thereto" means a bond such as a covalent bond, where, for example, a pigment is attached or covalently bonded to a nucleophile or an organic group.

[0074] In one embodiment, the at least one organic group can be an aliphatic group, a cyclic organic group, or an organic compound having at least one aliphatic portion and one cyclic portion, such as arylene, heteroarylene, and alkylene. In one embodiment, the organic group is attached via a diazonium salt derived from a primary amine, which can form a diazonium salt (even temporarily). Other methods for attachment are described below. The organic group can be substituted or unsubstituted and 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, among others, alicyclic hydrocarbon groups (for example, cycloalkyls, cycloalkenyls), heterocyclic hydrocarbon groups (for example, pyrrolidinyl, pyrrolinyl, piperidinyl, morpholinyl, etc.), aryl groups (for example, phenyl, naphthyl, anthracenyl) and heteroaryl groups (imidazolyl, pyrazolyl, pyridinyl, thienyl, thiazolyl, furyl, indolyl and triazolyl such as 1,2,4-triazolyl and 1,2,3-triazolyl).

[0075] The arylene, heteroarylene, and alkylene may be unsubstituted or substituted. Exemplary arylenes are phenylene, naphthylene, and biphenylene, and exemplary heteroarylenes are phenylene, naphthylene, and biphenylene having a ring carbon substituted by one or more oxygen or nitrogen atoms. In one embodiment, the arylene is a C5-C 20-arylene. Heteroarylenes can be an arylene as defined herein, wherein one or more ring carbon atoms are replaced by a heteroatom such as N, O, and S. The heteroatom can be a ring atom and can additionally be bonded to other groups. Alkylenes can be branched or unbranched. The alkylenes can be a C1-C 12 -alkylene such as methylene, ethylene, propylene or butylene.

[0076] In one embodiment, the at least one bound organic group comprises at least one ionic group, an ionizable group, or mixtures of an ionic group and an ionizable group. An ionic group may be anionic or cationic and may be bound to a counterion of opposite charge, such as Na + , K + , Li + , NH4 + , NR'4 + , acetate, NO3 - , SO4 2- , R'SO3 - , R'OSO3 - , OH - or Cl -be associated, where R' represents hydrogen or an organic group, such as a substituted or unsubstituted aryl or alkyl group. An ionizable group can form an ionic group in the medium used. Anionic groups are negatively charged ionic groups that can be generated from groups containing ionizable substituents that can form anions (anionizable groups), such as acidic substituents. Cationic groups are positively charged organic ionic groups that can be generated from ionizable substituents that can form cations (cationizable groups), such as protonated amines. Specific examples of anionic groups are -COO - , -SO3 - , -OSO3 - , -HPO3 - ; -OPO3 2- or-PO3 2-, and specific examples of anionizable groups may include -COOH, -SO3H, -PO3H2, -R'SH, or -R'OH, where R' represents hydrogen or an organic group such as a substituted or unsubstituted aryl or alkyl group. Furthermore, specific examples of cationic or cationizable groups include alkyl or arylamines, which can be protonated in an acidic medium to form ammonium groups -NR'2H + where R' represents an organic group such as substituted or unsubstituted aryl or alkyl groups. Organic ionic groups include those described in U.S. Patent No. 5,698,016, which is incorporated herein by reference.

[0077] For example, the attached group may be an organic group, such as a benzenecarboxylic acid group (-C6H4-COOH group), a benzenedicarboxylic acid group, a benzenetricarboxylic acid group, a benzenesulfonic acid group (a -C6H4-SO3H group), or salts thereof. In one embodiment, surface modification may also be used to introduce ionic or ionizable groups onto a pigment surface, such as chlorination and sulfonylation.

[0078] In one embodiment, the at least one organic group attached to the pigment can bind calcium (e.g., have defined calcium index values), such as the organic groups described in PCT Publication No. WO 2007 / 053564, which is incorporated herein by reference, wherein the groups can bind calcium as described herein. For example, the organic group comprises at least one geminal bisphosphonic acid group, partial esters thereof, or salts thereof, and e.g., a group having the formula -CQ(PO3H2)2, partial esters thereof, or salts thereof, wherein Q is attached to the geminal position and can be H, R, OR, SR, or NR2, wherein R", which can be the same or different, is as defined above or H, a saturated or unsaturated, branched or unbranched C1-C 18- Alkyl group, a saturated or unsaturated, branched or unbranched C1-C 18-acyl group, an aralkyl group, an alkaryl group, or an aryl group. Furthermore, US patent documents US 5,672,198 A, US 5,922,118 A, US 6,042,643 A, and US 6,641,656 B2, which are incorporated herein by reference, disclose modified pigments with various attached groups, including phosphonic and acidic groups.

[0079] In one embodiment, the pigment (carbon black or a colored pigment) is modified with at least one organic group via a diazonium treatment, which is explained, for example, in the following patents: US 5,554,739 A; US 5,630,868 A; US 5,672,198 A; US 5,707,432 A; US 5,851,280 A; US 5,885,335 A; US 5,895,522 A; US 5,900,029 A; US 5,922,118 A; US 6,042,643 A; US 6,506,245 B1, US 6,534,569 B2; US 6,641,653 B2, US 7,223,302 B2, US 6,398,858 B1 and US 6,494,943 B1 (higher shear conditions) US 6,372,820 B1; US 6,368,239 B1; US 6,350,519 B1; US 6,337,358 B1; US 6,103,380A; US 7,173,078 B2; US 7,056,962 B2; US 6,942,724 B2; US 6,929,889 B2; US 6,911,073 B2; US 6,478,863 B2; US 6,472,471 B2; WO 2011 / 143533 A2; and US 8,858,695 B2, which are incorporated herein by reference. In one embodiment, the bonding occurs via a diazonium reaction in which the at least one organic group has a diazonium salt substituent.In another embodiment, the direct bond can be formed using diazonium and stable free radical methods such as those described in US patent documents US 6,068,688 A; US 6,337,358 B1; US ​​6,368,239 B1; US ​​6,551,393 B2; US 6,852,158 B2, which are incorporated herein by reference, utilizing the reaction of at least one radical with at least one particle, a radical being generated from the interaction of the at least one transition metal compound with at least one halogen-organic compound in the presence of one or more particles capable of radial capture, etc. In a further embodiment, the pigment (carbon black or colored pigment) can be modified (e.g.for the attachment of organic groups) by applying the methods of US patent documents US 5,837,045 A, US 6,660,075 B2 and WO 2009 / 048564 A2 (reaction with organic compounds containing a C--C double bond or triple bond activated by at least one substituent) or US patent documents US 2004 / 0171725 A1, US 6,664,312 B2, US 6,831,194 B2 (reaction with an anhydride component), US 6,936,097 B2, US patent applications US 2001 / 0036994 A1, US 2003 / 0101901 A1 (reaction with organic groups containing an -N=NN- group), Canadian patent CA 2,351,162 A1 of European Patent EP 1394221 A1 and PCT publications WO 01 / 51566 A1 (reaction between at least one electrophile and at least one nucleophile), WO 2004 / 63289 A2, WO 2010 / 141071 A1 (reaction with H2N-AY, where A is a heteroatom) and WO 1999 / 23174 A1, which are incorporated herein by reference.

[0080] The dispersion is formulated to provide an amount of pigment such that a final amount of the inkjet ink composition can effectively exhibit the desired image quality (e.g., optical density) without compromising the performance of the inkjet ink. According to the invention, the pigment is provided in a range of 1 to 15 weight percent, e.g., 1 to 10 weight percent relative to the total weight of the inkjet ink composition, and e.g., in a range of 2 to 10 weight percent, 3 to 10 weight percent, 2 to 7 weight percent, or 3 to 7 weight percent relative to the total weight of the inkjet ink composition. Inkjet ink composition

[0081] The inkjet ink composition according to the invention comprises a carrier liquid. In one embodiment, the carrier liquid is aqueous. The inkjet ink composition also comprises a pigment. In one embodiment, the inkjet ink composition comprises a carrier liquid comprising at least 40% water (an aqueous solution) and, for example, at least 45% water or at least 50% water.

[0082] In one embodiment, the inkjet ink composition comprises at least one organic solvent, which is provided in a proportion in the range of 1% to 50% relative to the total weight of the inkjet ink composition, or in other proportions as specified herein. The at least one organic solvent may be provided in addition to at least 40% water (or at least 45% water, or at least 50% water). In one embodiment, the organic solvent may be dissolved in water or mixed with water. In another embodiment, the organic solvent is chemically stable under aqueous hydrolysis conditions (e.g., a reaction with water under heat-aging conditions such as the hydrolysis of esters and lactones). In one embodiment, the organic solvent has a dielectric constant below that of water,such as a dielectric constant in the range of about 10 to about 78 at 20°C. Examples of suitable organic solvents are low molecular weight glycols (such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, triethylene glycol monomethyl or monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and tetraethylene glycol monobutyl ether); alcohols (such as ethanol, propanol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, and tert-butyl alcohol, 2-propyn-1-ol (propargyl alcohol), 2-buten-1-ol, 3-buten-2-ol, 3-butyn-2-ol, and cyclopropanol); Diols containing between about 2 and 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 and poly(ethylene-co-propylene) glycol and their reaction products with alkylene oxides, including ethylene oxide and propylene oxide); triols containing from about 3 to about 40 carbon atoms (such as glycerin (glycerol), trimethylolethane, trimethylolpropane, 1,3,5-pentanetriol, 1,2,6-hexanetriol and the like, and their reaction products with alkylene oxides, including ethylene oxides, propylene oxides and mixtures thereof); polyols (such as pentaerythritol); amides (such as dimethylformaldehyde and dimethylacetamide); ketones or ketoalcohols (such as acetone and diacetone alcohol); ethers (such as tetrahydrofuran and dioxane); Lactams (such as 2-pyrrolidone, N-methyl-2-pyrrolidone and ε-caprolactam); ureas or urea derivatives (such as di-(2-hydroxyethyl)-5,5-dimethylhydantoin (Dantacol) and 1,3-Dimethyl-2-imidazolidinone); inner salts (such as betaine); and hydroxyamide derivatives (such as acetylethanolamine, acetylpropanolamine, propylcarboxyethanolamine, and propylcarboxypropanolamine, as well as their reaction products with alkylene oxides). Further examples are saccharides (such as maltitol, sorbitol, gluconolactone, and maltose); sulfoxide derivatives (symmetrical and asymmetric) containing from about 2 to about 40 carbon atoms (such as dimethyl sulfoxide, methylethyl sulfoxide, and alkylphenyl sulfoxides); and sulfone derivatives (symmetric and asymmetric) containing from about 2 to about 40 carbon atoms (such as dimethyl sulfone, methyl ethyl sulfone, sulfolane (tetramethylene sulfone, a cyclic sulfone), dialkyl sulfones, alkylphenyl sulfones, dimethyl sulfone, methyl ethyl sulfone, diethyl sulfone, ethylpropyl sulfone, methylphenyl sulfone, methylsulfolane, and dimethylsulfolane). The organic solvent may include mixtures of organic solvents.

[0083] The amount of solvent can be varied depending on various factors, including the properties of the solvent (solubility and / or dielectric constant), the type of pigment, and the desired performance of the resulting inkjet ink composition. The solvent can be used in amounts ranging from 1 to 40 weight percent based on the total weight of the inkjet ink composition, including from 1 to 30 weight percent or 1 to 20 weight percent. In another embodiment, the amount of solvent is greater than or equal to about 2 weight percent based on the total weight of the aqueous dispersion or inkjet ink composition, including greater than or equal to about 5 weight percent and greater than or equal to about 10 weight percent.

[0084] In one embodiment, an inkjet ink composition comprises at least one surfactant, e.g., when the pigment is not self-dispersible. The at least one surfactant may improve the colloidal stability of the composition or may improve the interaction of the ink with either the printing substrate, such as printing paper, or with the inkjet printhead. Various anionic, cationic, and non-ionic dispersants may be used in conjunction with the ink composition of the present invention, and these may be used neat or as an aqueous solution. In one embodiment, the surfactant is provided at a level of 0.05 to 5 wt.%, e.g., at a level of 0.1 to 5 wt.% or 0.5 to 2 wt.%, relative to the total weight of the inkjet ink composition.

[0085] Representative examples of anionic dispersants or surfactants include higher fatty acid salts, higher alkyl dicarboxylates, sulfonic acid ester salts of higher alcohols, higher alkyl sulfonates, alkylbenzenesulfonates, alkyl naphthalenesulfonates, naphthalenesulfonates (Na, K, Li, Ca, etc.), formalin polycondensates, condensates between higher fatty acids and amino acids, dialkyl sulfosuccinates, naphthenates, alkyl ether carboxylates, acylated peptides, α-olefin sulfonates, N-acrylmethyltaurine, alkyl ether sulfonates, secondary higher alcohol ethoxysulfates, polyoxyethylene alkylphenyl ether sulfates, monoglycyl sulfates, alkyl ether phosphates and alkyl phosphates, alkyl phosphonates and bisphosphonates including hydroxylated or aminated derivatives. For example, polymers and copolymers of styrenesulfonate salts, unsubstituted and substituted naphthalenesulfonate salts (e.g.Alkyl- or alkoxy-substituted naphthalene derivatives), aldehyde derivatives (such as unsubstituted alkylaldehyde derivatives including formaldehyde, acetaldehyde, propylaldehyde, etc.), maleic acid salts, and mixtures thereof are used as the anionic dispersing aids. Examples of salts are Na. + , Li + , K + , Cs + , Rb + and substituted and unsubstituted ammonium cations. Representative examples of cationic surfactants are aliphatic amines, quaternary ammonium salts, sulfonium salts, phosphonic salts, and the like.

[0086] Representative examples of nonionic dispersants or surfactants that can be used in inkjet inks of the present invention are fluorine derivatives, silicone derivatives, acrylic acid copolymers, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene secondary alcohol ethers, polyoxyethylene styrene ethers, ethoxylated acetylenic diols, polyoxyethylene lanolin derivatives, ethylene oxide derivatives of alkylphenol formalin condensates, polyoxyethylene polyoxypropylene block polymer, fatty acid esters of polyoxyethylene polyoxypropylene alkyl ether polyoxyethylene compounds, ethylene glycol fatty acid esters of the polyethylene oxide condensation type, fatty acid monoglycerides, fatty acid esters of polyglycerol, fatty acid esters of propylene glycol, sucrose fatty acid esters, fatty acid alkanolamides, polyoxyethylene fatty acid amides and polyoxyethylene alkylamine oxides. For example, ethoxylated monoalkyl or dialkylphenols can be used.These non-ionic surfactants or dispersants can be used alone or in combination with the above-mentioned anionic and cationic dispersants.

[0087] In one embodiment, the inkjet ink composition comprises the polymers specified herein as a first polymer and further comprises a second polymer that is a polymeric dispersant and is, for example, a natural polymer or a synthetic polymer dispersant. Specific examples of natural polymer dispersants are proteins such as glue, gelatin, casein, and albumin; natural gums such as gum arabic and gum tragacanth; glucosides such as saponin; alginic acid and alginic acid derivatives such as propylene glycol alginate, triethanolamine alginate, and ammonium alginate;and cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and ethylhydroxycellulose. Specific examples of polymeric dispersants, including synthetic polymeric dispersants, are polyvinyl alcohols, polyvinylpyrrolidones, acrylic or methacrylic resins (often written as "(meth)acrylic") such as poly(meth)acrylic acid, acrylic acid-(meth)acrylonitrile copolymers, potassium (meth)acrylate-(meth)acrylonitrile copolymers, vinyl acetate-(meth)acrylate ester copolymers, and (meth)acrylic acid-(meth)acrylate ester copolymers; Styrene-acrylic or methacrylic resins such as styrene-(meth)acrylic acid copolymers, styrene-(meth)acrylic acid-(meth)acrylate ester copolymer, styrene-α-methylstyrene-(meth)acrylic acid copolymer, styrene-α-methylstyrene-(meth)acrylic acid-(meth)acrylate ester copolymers; vinylnaphthalene-acrylic or methacrylic acid copolymer; vinylnaphthalene-maleic acid copolymer;and vinyl acetate copolymers such as vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinylethylene copolymer, vinyl acetate-maleate ester copolymers, vinyl acetate-crotonic acid copolymer, and vinyl acetate-acrylic acid copolymer; and salts thereof.

[0088] In one embodiment, the inkjet ink composition has a viscosity in the range of 1-25 mPa s (cP). It should be noted that the viscosity can be adjusted by various methods. In one embodiment, polymeric binders can be used in conjunction with the inkjet ink composition provided herein to adjust the viscosity of the composition and / or to provide other advantageous 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 salts, polymethacrylate salts, polyvinyl alcohols (Elvanol ®-Polyvinyl alcohol from DuPont, Selvol™ from Sekisui Specialty Chemicals), hydroxypropyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidinone (such as Luvitec ® -Polyvinylpyrrolidinone and Kollidon ® -Polyvinylpyrrolidinone from BASF), polyvinyl ethers, starch, polysaccharides, polyethyleneimines derived or not with ethylene oxide and propylene oxide; Jeffamine ® -Polyetheramines (Huntsman); etc. Other examples of water-soluble polymer compounds are various of the dispersants or surfactants described above, including, for example, styrene-acrylic acid copolymer (such as Joncryl ® resins from BASF), styrene-acrylic acid-alkyl acrylate terpolymer, styrene-methacrylic acid copolymers (such as Joncryl ®resins from BASF), styrene-maleic acid-alkyl acrylate terpolymers, styrene-methacrylic acid-alkyl acrylate terpolymer, styrene-maleic acid half-ester copolymers, vinylnaphthalene-acrylic acid copolymer, alginic acid, polyacrylic acids or their salts and their derivatives. In addition, the binder may be added or be present in a dispersion or latex form. For example, the polymeric binder may be a latex of acrylate or methacrylate copolymers (such as NeoCryl ® resins from Koninklijke DSM NV, the AC and AS polymers from Alberdingk-Boley) or can be a water-soluble polyurethane (such as ABU polymers from Alberdingk-Boley) or polyester (such as Eastman AQ™ polymers from Eastman Chemical). Polymers such as those mentioned above, and variations and related materials that can be used for binders in inkjet inks are listed in the Ethacryl ® -Dispersants from Lyondell Chemical Company, the Joncryl ®resins from BASF, the NeoCryl ® resins from Koninklijke DSM NV and the AC and AS polymers from Alberdingk-Boley.

[0089] In one embodiment, the polymeric binders are selected from polyurethanes. Exemplary polyurethanes include those containing at least one polyether and at least one diisocyanate. In one embodiment, the at least one polyether comprises a monomer having the formula (I): -O-R1-O- (I) where R1 may be substituted or unsubstituted and is selected from C1-C 10 -alkylene, C3-C 20 -Cycloalkylene, 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, a polyether radical, and combinations thereof. In one embodiment, R1 is unsubstituted. In one embodiment, R1 is substituted by at least one substituent selected from C1-C 10 -alkyl and C5-C 20 -aryl groups. In one embodiment, R1 is selected from a polyether residue, e.g., a polyethylene glycol residue, a polypropylene glycol residue, a polytetramethylene oxide residue, and combinations thereof. In one embodiment, the at least one polyether is formed from a diol monomer, for example, by polymerization of diol monomers. Exemplary diol monomers are C1-C 10 -Alkylenediols such as propylene glycol, polytetramethylene oxide diol, 1,6-hexanediol, 1,5-pentanediol and 2-butyl-2-ethylpropyldiol. In another embodiment, the diol monomer comprises the monomer having the formula (I), wherein the diol monomer is, for example, a C1-C 10-polyalkylene glycol, a polyether glycol, or another diol corresponding to formula (I). In one embodiment, the at least one polyether is polypropylene glycol, such as a polypropylene glycol with an average molecular weight in the range of 400 g / mol to 6000 g / mol. In one embodiment, the at least one polyether is provided in a proportion of 30 to 95 weight percent relative to the polyurethane.

[0090] In one embodiment, the at least one diisocyanate has the formula (II): OCN-R2-NCO (II) where R2 can be substituted or unsubstituted and consists of C1-C 10 -alkylene, C3-C 20 -Cycloalkylene, 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) and combinations thereof. In one embodiment, R2 is unsubstituted. In one embodiment, R2 is substituted by at least one substituent selected from C1-C 10 -alkyl and C5-C 20 -aryl groups. For example, R2 can be hexamethylene or phenylene optionally substituted by methyl, or cyclohexylene optionally substituted by methyl.

[0091] In one embodiment, the at least one diisocyanate is selected from toluene diisocyanates such as toluene-2,4-diisocyanate (2,4-TDI) and toluene-2,6-diisocyanate (2,6-TDI), hexamethylene diisocyanate (HDI), 4,4'-methylenediphenyl diisocyanate (4,4'-MDI), 2,4'-methylenediphenyl diisocyanate (2,4'-MDI), 2,2'-methylenediphenyl diisocyanate (2,2'-MDI), methylenebis(4-cyclohexyl diisocyanate) (HDMI), m-tetramethylxylene diisocyanate (m-TMXDI), and isophorone diisocyanate (IPDI). In one embodiment, the diisocyanate is selected from 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 provided in a proportion in the range of 3 to 50 percent by weight relative to the polyurethane.

[0092] In one embodiment, the at least one polyurethane comprises, in addition to the at least one polyether and the at least one diisocyanate, a monomer containing at least one hydrophilic group. In one embodiment, the monomer containing at least one hydrophilic group having the formula (III): -O-R3-O- (III) wherein R3 comprises at least one hydrophilic group linked to a radical which may be substituted or unsubstituted and is selected from C1-C 10 -alkylene, C3-C 20 -Cycloalkylene, 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, a "hydrophilic group" can be a water-bonding hydrogen. In one embodiment, the at least one hydrophilic group is selected from hydroxyls, carboxylic acids, sulfonic acids, phosphonic acids, polyethers (e.g., a polyethylene glycol, polypropylene glycol, etc.), and salts and ethers thereof. In one embodiment, the at least one hydrophilic group is selected from carboxylic acids and salts and ethers thereof. In one embodiment, the R3 radical is unsubstituted. In another embodiment, the R3 radical is substituted by at least one substituent selected from C1-C 10 -alkyl and C5-C 20 -aryl groups. An exemplary monomer with formula (III) is dimethylolpropionic acid (DMPA).

[0093] In one embodiment, the molar ratio between the at least one diisocyanate and a polyol or diol-based monomer in the polyurethane is in the range of 0.5:1 to 3:1. In another embodiment, the at least one polyurethane is characterized by an NCO / OH ratio that is the ratio of the molar amount of isocyanate groups / molar amount of hydroxyl groups of all diol monomers, ie, the at least one polyether alone or, if present, the sum of the at least one polyether and the monomer containing the at least one hydrophilic group. In one embodiment, the NCO / OH ratio is in the range of 0.85 to 1.15, e.g., from 0.85 to 1.1, from 0.9 to 1.15, or from 0.9 to 1.1.

[0094] In one embodiment, the at least one polyurethane has an acid number corresponding to the amount of the monomer containing at least one hydrophilic group and, for example, a carboxylic acid group or another hydrophilic group specified herein. For example, the acid number (AN(PU)) of the at least one polyurethane can be calculated from the following equation: AN(PU)=(Number of moles of monomers containing a hydrophilic group × 56.1 mgKOH ×1000) / (Total mass(g) of monomers

[0095] In one embodiment, the at least one polyurethane has an acid number in the range from 10 to 100 mg KOH / g polyurethane and, 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 in the range from 20 to 35 mg KOH / g polyurethane.

[0096] In one embodiment, the inkjet ink composition 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 ethoxylated C3-C 20 -polyols such as ethoxylated triols, ethoxylated tetraols, ethoxylated pentaols and ethoxylated hexaols. In one embodiment, the ethoxylated C3-C 20Polyols selected from ethoxylated glycerol, ethoxylated pentaerythritol, ethoxylated trimethylolpropane, ethoxylated glucoside, and ethoxylated glucose. In another embodiment, the at least one water-soluble compound is selected from polyols comprising three or more hydroxyl groups (e.g., xylitol and sorbitol) and polyether polyols. The at least one water-soluble compound may be present in a proportion ranging from 1 to 60 weight percent relative to the total weight of the inkjet ink composition.

[0097] Examples of rheological additives for adjusting the viscosity of an inkjet ink composition include alkali-swellable emulsions (such as the rheology-controlling additive Rheovis ® AS from BASF), hydrophobically modified alkali-swellable emulsions (such as the rheology-controlling additive Rheovis ®HS from BASF), hydrophobically modified polyurethanes (such as the rheology-controlling additive Rheovis ® PU from BASF), and hydrophobically modified polyethers (such as the rheology-controlling additive Rheovis ® PE from BASF).

[0098] In one embodiment, the inkjet ink composition may further comprise colorants for modifying the color balance and adjusting the optical density. Exemplary colorants include food colorings, FD&C colorants, acid colorants, direct colorants, reactive colorants, derivatives of phthalocyaninesulfonic acids, including copper phthalocyanine derivatives, sodium salts, ammonium salts, potassium salts, and lithium salts.

[0099] In one embodiment, the inkjet ink composition comprises one or more polymers selected from the polymeric dispersants and polymeric binders described herein, in an amount ranging from 0.1 to 20 weight percent relative to the total weight of the composition and, for example, in an amount ranging from 0.1 to 10, from 0.1 to 5, from 0.2 to 20, from 0.2 to 10, from 0.2 to 5, from 0.5 to 20, from 0.5 to 10, or from 0.5 to 5 weight percent relative to the total weight of the inkjet ink composition.

[0100] In one embodiment, the inkjet ink composition may further comprise, in addition to the surfactant, one or more suitable additives to provide a number of desired properties and maintain the stability of the inkjet ink composition. Other additives such as humectants, biocides and fungicides, pH adjusters, drying accelerators, penetrants, and the like are known in the art. The amount of a particular additive varies depending on various factors, but is generally provided at a level in a range between 0.01 and 40 weight percent based on the weight of the inkjet ink composition. In one embodiment, the at least one additive is provided at a level in the range of 0.05 to 5, e.g., from 0.1 to 5 or from 0.5 to 2 weight percent relative to the total weight of the inkjet ink composition.

[0101] Humectants and other water-soluble organic compounds may also be added as the at least one organic solvent to the inkjet ink composition of the present invention, e.g., to prevent nozzle clogging and provide paper penetration (penetrant), improved drying (drying accelerator), and anti-curling properties. In one embodiment, the humectant and / or water-soluble compound is provided at a level ranging from 0.1% to 50%, e.g., from 1% to 50%, from 0.1% to 30%, from 1% to 30%, from 0.1% to 10%, or from 1% to 10%.

[0102] Specific examples of humectants and other water-soluble compounds that may be used are low molecular weight glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and dipropylene glycol; Diols containing between about 2 and 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 their reaction products with alkylene oxides, including ethylene oxide, including ethylene oxide and propylene oxide;Triol derivatives containing between about 3 and about 40 carbon atoms, including glycerin, trimethylolpropane, 1,3,5-pentanetriol, 1,2,6-hexanetriol, and the like, and their reaction products with alkylene oxides, including ethylene oxide, propylene oxide, and mixtures thereof; neopentyl glycol, (2,2-dimethyl-1,3-propanediol), and the like, and their reaction products with alkylene oxides, including ethylene oxide and propylene oxide, in any desirable molar ratio to form materials having a wide range of molecular weights; thiodiglycol; Pentaerythritol and lower alcohols such as ethanol, propanol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol and tert-butyl alcohol, 2-propyn-1-ol (propargyl alcohol), 2-buten-1-ol, 3-buten-2-ol, 3-butyn-2-ol and cyclopropanol; amides such as dimethylformaldehyde and dimethylacetamide; ketones or keto alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane;Cellosolves such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, triethylene glycol monomethyl (or monoethyl) ether; carbitols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether; lactams such as 2-pyrrolidone, N-methyl-2-pyrrolidone and ε-caprolactam; ureas and urea derivatives; inner salts such as betaine and the like; thio (sulfur) derivatives of the above materials including 1-butanethiol; t-butanethiol, 1-methyl-1-propanethiol, 2-methyl-1-propanethiol; 2-methyl-2-propanethiol; thiocyclopropanol, thioethylene glycol, thiodiethylene glycol, trithio- or dithiodiethylene glycol and the like; Hydroxyamide derivatives including acetylethanolamine, acetylpropanolamine, propylcarboxyethanolamine, propylcarboxypropanolamine, and the like; reaction products of the above materials with alkylene oxides;and mixtures thereof. Further examples include saccharides such as maltitol, sorbitol, gluconolactone, and maltose; polyhydric alcohols such as trimethylolpropane and trimethylolethanes; N-methyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidinone; sulfoxide derivatives containing between about 2 and about 40 carbon atoms, including dialkyl sulfides (symmetric and asymmetric sulfoxides) such as dimethyl sulfoxide, methylethyl sulfoxide, alkylphenyl sulfoxides, and the like; and sulfone derivatives (symmetric and asymmetric sulfones) containing between about 2 and about 40 carbon atoms, such as dimethyl sulfone, methyl ethyl sulfone, sulfolane (tetramethylene sulfone, a cyclic sulfone), dialkyl sulfones, alkylphenyl sulfones, dimethyl sulfone, methyl ethyl sulfone, diethyl sulfone, ethylpropyl sulfone, methylphenyl sulfone, methylsulfolane, dimethylsulfolane, and the like. Such materials can be used alone or in combination.

[0103] Biocides and / or fungicides may be added to the inkjet ink compositions provided herein. Biocides are important to prevent bacterial growth because bacteria are often larger than the ink nozzles and can cause clogging and other printing problems. Examples of useful biocides include benzoate or sorbate salts and isothiazolinones. In one embodiment, the biocides and / or fungicides are provided at a level in the range of 0.05 to 5 weight percent, 0.05 to 2 weight percent, 0.1 to 5 weight percent, or 0.1 to 2 weight percent relative to the total weight of the inkjet ink composition.

[0104] In one embodiment of the inventive inkjet ink composition, the first monomer is styrene. At least a portion of the second monomers is functionalized with at least one organic group having a calcium index value greater than the calcium index value of phenylphosphonic acid. Additionally, the at least one polymer may be crosslinked via the second monomers, e.g., via carboxylate-containing groups of the second monomers. In one embodiment, the polymer is crosslinked via at least one compound selected from ester linkages, wherein the ester linkage may be derived from a reaction between epoxy-containing compounds (e.g., di- and triglycidyl ether compounds such as trimethylolpropane polyglycidyl ether) and carboxylate-containing groups of the second monomers.In one embodiment, the inkjet ink composition consists essentially of the at least one (crosslinked) polymer, at least one pigment, and a carrier liquid (e.g., water), in the amounts specified in claim 1. In one embodiment, the inkjet ink composition (e.g., an aqueous dispersion) has a pH in the range of 8 to 11. In one embodiment, the inkjet ink composition (e.g., an aqueous dispersion) has an acid number in the range of 90 to 300. EXAMPLESDefinitions NaAL = sodium alendronate. NaOH = sodium hydroxide. SMA 2000 = a styrene-maleic anhydride copolymer with a low molecular weight and approximately a 2:1 molar ratio of styrene and maleic anhydride (SMA ® 2000 Polymer from Total Petrochemicals & Refining USA, Inc.). SMA 3000 = a low molecular weight styrene-maleic anhydride copolymer with approximately a 3:1 molar ratio of styrene and maleic anhydride (SMA ® 3000 polymer from Total Petrochemicals & Refining USA, Inc.). SMA EF40 = a low molecular weight styrene-maleic anhydride copolymer with approximately a 4:1 molar ratio of styrene and maleic anhydride (SMA ® EF40 polymer from Total Petrochemicals & Refining USA, Inc.). Joncryl 683 = a styrene-acrylic resin (Joncryl ® 683 resin from BASF). Acidic ion exchange resin = Purolite ® C107E ion exchange resin (from Purolite). TMPTGE = Trimethylolpropane triglycidyl ether from Sigma Aldrich. SURFYNOL 465 = SURFYNOL ® 465 surfactant, a non-ionic surfactant from Air Products. TEGMBE = triethylene glycol monobutyl ether. XIRAN ®SZ25010 resin = a low molecular weight styrene-maleic anhydride copolymer with 25% maleic anhydride from Polyscope Polymers, BV. XIRAN ® SZ15010 resin = a low molecular weight styrene-maleic anhydride copolymer with 15% maleic anhydride from Polyscope Polymers, BV. DMAPA = 3-(Dimethylamino)-1-propylamine. Polymer examples

[0105] The examples of Polymer-A through Polymer-D describe the synthesis of polymers comprising first monomers selected from ethylenically unsaturated, hydrophobic monomers and second monomers selected from maleic anhydride, wherein a portion of the second monomers are functionalized with at least one organic group having a calcium index value greater than or equal to the calcium index value of phenylphosphonic acid. The examples of Polymer-E and Polymer-G describe the synthesis of a comparative polymer having first monomers selected from ethylenically unsaturated, hydrophobic monomers and second monomers selected from maleic anhydride, wherein none of the second monomers is functionalized with at least one organic group having a calcium index value greater than or equal to a calcium index value of phenylphosphonic acid.The example of Polymer-H describes the synthesis of a comparative polymer with monomers selected from ethylenically unsaturated, hydrophobic, and hydrophilic monomers, wherein none of the monomers is selected from maleic anhydride, maleic acid, or salts, esters, imides, and amides thereof. The examples of Polymer-I and Polymer-J describe the synthesis of polymers comprising first monomers selected from ethylenically unsaturated, hydrophobic monomers and second monomers selected from maleic acid, wherein the polymers are hydrolyzed.Polymer-K is an example of a polymer comprising first monomers selected from ethylenically unsaturated, hydrophobic monomers and second monomers selected from maleic anhydride, wherein a portion of the second monomers are functionalized with at least one organic group having a calcium index value greater than or equal to the calcium index value of phenylphosphonic acid, wherein a portion of the second monomers are functionalized with (dimethylamino)-1-propylamine. The example of Polymer-L describes a polymer comprising first monomers selected from ethylenically unsaturated, hydrophobic monomers and second monomers selected from maleic anhydride, wherein a portion of the second monomers are functionalized with (dimethylamino)-1-propylamine. Polymer-A

[0106] 100 g of SMA EF40 polymer powder and 320 g of deionized (DI) water were added to a 1-liter cylindrical reactor equipped with a temperature controller, a stirrer, and a compressor. A NaAL solution was prepared by dissolving sodium alendronate trihydrate (31.6 g) in a mixture of 122 g of DI water and 58.4 g of a 40 wt% NaOH solution. The NaAL solution was added to the reactor with stirring. The resulting mixture was heated to 90°C for 11 h. During this time, the initially milky slurry became clear and homogeneous. After cooling to room temperature, the solution was transferred to a stainless steel beaker, where its pH was adjusted from an initial value of 11-12 to a pH of 8.5-10 by stirring the solution in the presence of an acidic resin.A clear, colorless liquid was obtained by suction filtration through a glass frit to remove the ion exchange beads. 31 P NMR was used to determine the amount of bisphosphonate groups bound to the polymer. As a result, a solution of Polymer-A was obtained containing 19.2% solids and a pH of 9.60; and 13% of an initially charged NaAl was covalently bound to the polymer. For Polymer-A, the proportion of second monomers functionalized with bisphosphonate groups (with a calcium index value greater than that of phenylphosphonic acid) was 13 mol% of the total second monomers. Polymer-B

[0107] 100 g of SMA EF40 polymer powder and 360 g of deionized (DI) water were added to a 1-liter cylindrical reactor equipped with a temperature controller, a stirrer, and a compressor. A NaAL solution was prepared by dissolving sodium alendronate trihydrate (56.9 g) in a mixture of 126 g of DI water and 74 g of a 40 wt% NaOH solution. The NaAL solution was added to the reactor with stirring. The resulting mixture was heated to 90°C for 11 h. During this time, the initially milky slurry became clear and homogeneous. After cooling to room temperature, the solution was transferred to a stainless steel beaker, where its pH was adjusted from an initial value of 11-12 to a pH of 8.5-10 by stirring the solution in the presence of an acidic resin.A clear, colorless liquid was obtained by suction filtration through a glass frit to remove the ion exchange beads. 31 P NMR was used to determine the amount of bisphosphonate groups bound to the polymer. As a result, a solution of Polymer-B was obtained containing 17.6% solids and a pH of 9.75; and 11% of an initially charged NaAl was covalently bound to the polymer. For Polymer-B, the proportion of second monomers functionalized with bisphosphonate groups (with a calcium index value greater than that of phenylphosphonic acid) was 11 mol% of the total second monomers. Polymer-C

[0108] 80 g of SMA 3000 polymer powder and 200 g of DI water were added to a 1-liter cylindrical reactor equipped with a temperature controller, a stirrer, and a compressor. A NaAL solution was prepared by dissolving sodium alendronate trihydrate (31.7 g) in a mixture of 122 g of DI water and 29.3 g of a 40 wt% NaOH solution. The NaAL solution was added to the reactor with stirring. The resulting mixture was heated to 80°C for 11 h. During this time, the initially milky slurry became clear and homogeneous. After cooling to room temperature, the solution was transferred to a stainless steel beaker, where its pH was adjusted from an initial value of 11-12 to a pH of 8.5-10 by stirring the solution in the presence of an acidic resin. A clear, colorless liquid was obtained by suction filtration through a glass frit to remove the ion exchange beads.An ICP analysis method was used to determine the amount of bisphosphonate groups bound to the polymer. A small portion of the polymer solution was first dialyzed against deionized water using a dialysis tube with an appropriate cutoff molecular weight (MWCO) (e.g., Spectro / Por® dialysis membrane, MWCO 2 kD). As a result, a solution of Polymer-C was obtained containing 12.7% solids and a pH of 9.62; and 11% of an initially charged NaAL was covalently bound to the polymer. For Polymer-C, the proportion of second monomers functionalized with bisphosphonate groups (with a calcium index value greater than that of phenylphosphonic acid) was 11 mol% of the total second monomers. Polymer-D

[0109] 80 g of SMA 3000 polymer powder and 200 g of DI water were added to a 1-liter cylindrical reactor equipped with a temperature controller, a stirrer, and a compressor. A NaAL solution was prepared by dissolving sodium alendronate trihydrate (42.5 g) in a mixture of 164 g of DI water and 78.4 g of a 40 wt% NOH solution. The NaAL solution was added to the reactor with stirring. The resulting mixture was heated to 80°C for 8 h. During this time, the initially milky slurry became clear and homogeneous. After cooling to room temperature, the solution was transferred to a stainless steel beaker, where its pH was adjusted from an initial value of 11-12 to a pH of 8.5-10 by stirring the solution in the presence of an acidic resin. A clear, colorless liquid was obtained by suction filtration through a glass frit to remove the ion exchange beads.An ICP analysis method was used to determine the amount of bisphosphonate groups bound to the polymer. A small portion of the polymer solution was first dialyzed against deionized water using a dialysis tube with an appropriate cutoff molecular weight (MWCO) (e.g., Spectro / Por® dialysis membrane, MWCO 2kD). As a result, a solution of Polymer-D was obtained that had 14.7% solids and a pH of 9.58; and 22% of an initially charged NaAL was covalently bound to the polymer. For Polymer-D, the proportion of second monomers functionalized with bisphosphonate groups (with a calcium index value greater than that of phenylphosphonic acid) was 22 mol% of the total second monomers. Polymer-E

[0110] Polymer-E was an aqueous solution of the sodium salt of SMA 2000, which can be prepared by hydrolysis in the presence of a NaOH solution. The resulting solution of Polymer-E had 28.7% solids and a pH of 9.83. Polymer-F

[0111] Polymer-F was an aqueous solution of the sodium salt of SMA 3000, which can be prepared by hydrolysis in the presence of a NaOH solution. The resulting solution of Polymer-E had 17.2% solids and a pH of 9.75. Polymer-G

[0112] Polymer-G was an aqueous solution of the sodium salt of SMA EF40, which can be prepared by hydrolysis in the presence of a NaOH solution and a small amount of Polymer-F (as a hydrolysis aid). The added amount of SMA 3000 constituted 5.3 weight percent of SMA EF40. The resulting solution of Polymer-G had 20.9% solids and a pH of 9.90. Polymer-H

[0113] Polymer-H was an aqueous solution of the sodium salt of Joncryl 683, which can be prepared by neutralizing the Joncryl 683 polymer with a NaOH solution. The resulting solution of Polymer-H had 22.6% solids and a pH of 8.84. Polymer-I

[0114] In a cylindrical reactor with a volume of 1 liter, equipped with a temperature monitor, an overhead stirrer and a compressor, 285 g of a XIRAN ® SZ25010 resin powder (acid value AN(SP) = 285) and 1044 g of DI water were added. 137.5 g of a 40 wt.% NaOH solution was added to the mixed polymer and water slurry. The resulting mixture was heated to 95°C for 10 h. During this time, the initially milky slurry gradually became clear and homogeneous. When the polymer was fully hydrolyzed, the solution was 22.1% solids and had a pH of 10.1. Polymer-J

[0115] In a cylindrical reactor with a volume of 1 liter, equipped with a temperature monitor, an overhead stirrer and a compressor, 285 g of a XIRAN ® SZ25010 resin granules (acid number AN(SP) = 156) and 1169 g of DI water were added. 75.3 g of a 40 wt.% NaOH solution were added to the mixed polymer and water slurry. The resulting mixture was heated to 95°C for 10 h. During this time, the initially milky slurry gradually became clear and homogeneous. When the polymer was fully hydrolyzed, the solution had 19.8% solids and a pH of 10.1. Polymer-K

[0116] To a 0.5-liter cylindrical reactor equipped with a temperature controller, a stirrer, and a compressor, 30 g of SMA 3000 polymer powder, 0.91 ml of 3-(dimethylamino)-1-propylamine (DMAPA) from Sigma-Aldrich, and 180 g of DI water were added. A NaAL solution was prepared by dissolving sodium alendronate trihydrate (2.6 g) in a mixture of 20 g of DI water and 4.4 g of a 40 wt% NaOH solution. The NaAL solution was added to the reactor with stirring. The resulting mixture was heated to 90°C for 2 h. An additional 13.6 g of the 40 wt% NaOH solution was added, and the mixture was heated to 90°C for 6 h. During this time, the initially milky slurry gradually became clear and homogeneous. As a result, a solution of Polymer-K was obtained which had 15.8% solids and a pH of 8.59. 31P NMR was used to determine the amount of bisphosphonate groups bound to the polymer; and 1 H NMR was used to determine the amount of dimethylamino groups bound to the polymer. For Polymer-K, the fraction of the second monomers functionalized with bisphosphonate groups (with a calcium index value greater than that of phenylphosphonic acid) was 3.3 mol% of the total second monomers. The fraction of the second monomers functionalized with dimethylamino groups (organic groups with the formula -AN(R 3 )(R 4 )) was 8.5 mol% of the total second monomers. Polymer-L

[0117] In a 0.5-liter cylindrical reactor equipped with a temperature controller, a stirrer, and a compressor, 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 were added. After mixing, 0.5 g of a 40 wt. % NaOH solution was added, and the resulting mixture was heated to 94°C for 2 h. Another 10.6 g of the 40 wt. % NaOH solution was added, and the mixture was heated to 94°C for 8 h. During this time, the initially milky slurry gradually became clear and homogeneous. As a result, a solution of Polymer-L was obtained that had 14.1% solids and a pH of 8.59. 1 H NMR was used to determine the amount of dimethylamino groups bound to the polymer. For Polymer-L, the fraction of the second monomers bound with dimethylamino groups (organic group with the formula -AN(R3 )(R 4 )) were functionalized, 8.4 mol% of the total second monomers. Pigment dispersion examples

[0118] Pigment dispersion examples PigDisp-1-5 are aqueous yellow pigment dispersions stabilized by polymers. Pigment dispersion examples PigDisp-6-9 are aqueous cyan pigment dispersions stabilized by polymers. Pigment dispersion examples PigDisp-10-21 are aqueous magenta pigment dispersions stabilized by polymers. Pigment dispersion examples PigDisp-22-24 are aqueous black pigment dispersions stabilized by polymers. The pigment dispersions are prepared as follows. PigDisp-1 and PigDisp-2

[0119] Polymer-G (560 g of a 20.9% solids solution in water) was combined with 724 g of DI water and 272 g of Pigment Yellow 74 (as a dry powder). This mixture was then sonicated at approximately 10°C 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 and then decanted to isolate the product. The resulting solution was a Polymer-G-dispersed yellow pigment, PigDisp-1, with 15.5% solids and a mean particle size of 198 nm (determined using a Microtrac® particle size analyzer). PigDisp-1 and PigDisp-2

[0120] To the remaining dispersion (2014 g of a solution containing 18.2% solids), 5.87 g of TMPTGE, 3.6 g of boric acid, and 190 g of DI water were added. The resulting mixture was heated to 65°C for 4 h. After cooling to room temperature, the solution was diluted to 10% solids and then centrifuged at 2,500 G for 20 minutes. The solution was then purified by diafiltration using a polysulfone membrane tailored to 3,000 MW and concentrated to obtain PigDisp-2 with 16.5% solids and a mean particle size of 162 nm (determined using a Microtrac® particle size analyzer). PigDisp-3

[0121] Polymer-A (829 g of a 19.2% solids solution in water) was combined with 917 g of DI water and 370 g of Pigment Yellow 74 (as a dry powder). This mixture was then sonicated at approximately 10°C using a Misonix® probe sonicator for approximately 7 h to obtain a yellow dispersion with a low viscosity. The solution was then diluted to 10% solids and centrifuged at 2,500 G for 20 minutes. The solution was then purified by diafiltration using a polysulfone membrane tailored to 3,000 MW and concentrated to obtain PigDisp-3 with 18.5% solids and a mean particle size of 170 nm (determined using a Microtrac® particle size analyzer). PigDisp-4

[0122] Polymer-A (112 g of a 19.2% solids solution in water) was combined with 124 g of DI water and 50 g of Pigment Yellow 74 (as a dry powder). This mixture was then sonicated at approximately 10°C using a Misonix® probe sonicator for approximately 1 h to obtain a yellow dispersion with a low viscosity. To the dispersion were added 1.21 g of TMPTGE (%CO2 target = 15%), 0.74 g of boric acid, and 144 g of DI water. The resulting mixture was heated to 65°C for 4 h. After cooling to room temperature, the solution was centrifuged at 2,500 g for 20 minutes. After centrifugation, the solution was first diluted to 12% solids and then purified and concentrated by diafiltration using a 3,000 MW polysulfone membrane to obtain PigDisp-4 with 20.1% solids and a mean particle size of 177 nm (determined using a Microtrac® particle size analyzer). PigDisp-5

[0123] PigDisp-5 is a yellow dye Pro-Jet™ APD1000, which is an aqueous dispersion of a yellow pigment and is commercially available from FUJIFILM Imaging Colorants, Inc. This dispersion is stabilized using polyacrylate dispersants. Rating of PigDisp-5

[0124] The dispersion samples PigDisp-1-4 were evaluated by conducting settling experiments, where the dispersions were allowed to stand undisturbed at room temperature. Their settling performance was assessed based on the following criteria: Poor = dispersion separates into two layers in ≤ 4 days, with the upper layer containing a small or reduced amount of pigment, while the pigment concentration at bottom level is much higher than the initial concentration; Good = Dispersion remains uniform (i.e. little or no layer separation) for 5 days or longer; Table 1 Dispersion polymer Networking Weaning performance PigDisp-1 Polymer-G No Bad PigDisp-2 Polymer-G Yes Bad PigDisp-3 Polymer-A No Good PigDisp-4 Polymer-A Yes Good

[0125] Table 1 shows that in both the non-crosslinked and crosslinked samples, the pigment dispersions stabilized by Polymer-A exhibited better settling performance than the dispersions stabilized with Polymer-G. The main difference between Polymer-A and Polymer-G is that Polymer-A is a functionalized SMA EF40 polymer in which bisphosphonate groups are bonded to the polymer, whereas Polymer-G contains no such functionalized groups. The calcium index value of phenylphosphonic acid is 2.53, which was measured using Method A as described in US Patent 8,858,695 B2 at column 29, line 45 to column 30, line 44, which contains a list of calcium index values ​​for various compounds in Table 5A and is incorporated herein by reference. Based on the previous measurement of -CH2(PO3) 2-)2 (Table 5A of US patent US 8,858,695 B2) the calcium index value for the bisphosphonate group was determined to be approximately 3.45.

[0126] To assess the polymer's ability to bind polyvalent metal ions such as magnesium and calcium, taking into account the functional group and hydrophobicity, among other factors, a magnesium sensitivity test was developed. The Mg sensitivity test was performed as follows: (1) One drop (approximately 0.05 g) of each of the dispersion examples PigDisp-3-5 (as is) was added to a series of 10-15 ml MgCl2 solutions with varying molar concentrations: 1.0 mM, 2.0 mM, 3.0 mM, and 5.0 mM; (2) the samples were shaken and then allowed to stand undisturbed for one hour at room temperature; and (3) the lowest molar concentration of MgCl2 at which complete precipitation of the pigment dispersion (i.e., a clear separation of water and pigment precipitates) was observed was recorded.After testing all of these examples, their MgCl2 molar concentrations at which the pigments completely precipitated were recorded in Table 2. The lower the MgCl2 concentration required for precipitation, the greater the sensitivity to magnesium and / or calcium ions, thereby indicating the ability for calcium and / or magnesium binding. Table 2 Dispersion polymer Networking [MgCl 2 ], mM PigDisp-3 Polymer-A No 2,0 PigDisp-4 Polymer-A Yes 2,0 PigDisp-5 Polyacrylates Yes >5,0

[0127] PigDisp-3 and PigDip-4, which contain Polymer-A, i.e., a bisphosphonate-functionalized SMA EF40 polymer, exhibit better calcium and / or magnesium binding capacity than PigDisp-5, which is a polymer-stabilized dispersion not containing a monomer selected from maleic anhydride, maleic acid, and salts, esters, imides, and amides thereof. PigDisp-6

[0128] Polymer-A (202 g of a 19.2% solids solution in water) was combined with 223 g of DI water and 90 g of Pigment Blue 15:4 (as a dry powder). This mixture was then sonicated at approximately 10°C using a Misonix® probe sonicator for approximately 1 h to obtain a cyan dispersion with a low viscosity. 4.37 g of TMPTGE (%CO2 target = 30%), 2.68 g of boric acid, and 257 g of DI water were added to the dispersion. The resulting mixture was heated to 65°C for 5 h. 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 by diafiltration using a polysulfone membrane tailored to 3,000 MW and concentrated to yield PigDisp-6 with 20.7% solids and a mean particle size of 152 nm (determined using a Microtrac ®particle size analyzer). PigDisp-7

[0129] Polymer-B (220 g of a 17.6% solids solution in water) was combined with 205 g of DI water and 90 g of Pigment Blue 15:4 (as a dry powder). This mixture was then sonicated at approximately 10°C using a Misonix® probe sonicator for approximately 1 h to obtain a cyan dispersion with a low viscosity. 4.37 g of TMPTGE (%CO2 target = 30%), 2.68 g of boric acid, and 257 g of DI water were added to the dispersion. The resulting mixture was heated to 65°C 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 minutes. After centrifugation, the solution was purified and concentrated by diafiltration using a 3,000 MW polysulfone membrane to obtain PigDisp-7 with 20.4% solids and a mean particle size of 157 nm (determined using a Microtrac® particle size analyzer). PigDisp-8

[0130] Polymer-E (47 g of a 28.7% solids solution in water) was combined with 213 g of DI water and 40 g of Pigment Blue 15:4 (in the form of a presscake, the size of which was determined based on its solid content). This mixture was then sonicated at approximately 10°C using a Misonix® probe sonicator for approximately 1 h to obtain a cyan dispersion with a low viscosity. The resulting solution was centrifuged at 2,500 g for 20 seconds and then decanted to isolate the product. The result was a solution of Polymer-E-dispersed cyan pigment, PigDisp-8, with 13.7% solids and a mean particle size of 163 nm (determined using a Microtrac® particle size analyzer). PigDisp-9

[0131] PigDisp-9 is a Pro-Jet™ APD1000 Cyan, which is an aqueous cyan pigment dispersion commercially available from FUJIFILM Imaging Colorants, Inc. This dispersion is stabilized using polyacrylate dispersants. Rating of PigDisp-6-9

[0132] For these cyan dispersions, a Mg sensitivity test was performed as follows: (1) One drop (approximately 0.05 g) of each of the dispersion examples PigDisp-6-9 (as is) was added to a series of 10-15 ml MgCl2 solutions with varying molar concentrations: 1.0 mM, 2.0 mM, 3.0 mM, and 5.0 mM; (2) the samples were shaken and then allowed to stand undisturbed for one hour at room temperature; and (3) the lowest molar concentration of MgCl2 at which complete precipitation of the pigment dispersion (i.e., a clear separation of water and pigment precipitates) was observed was recorded. After testing all of these examples, their MgCl2 molar concentrations at which the pigments completely precipitated were recorded in Table 3.The lower the MgCl2 concentration required for precipitation, the greater the sensitivity to magnesium and / or calcium ions, thus indicating the ability for calcium and / or magnesium binding. Table 3 Dispersion polymer Networking [MgCl 2 ], mM PigDisp-6 Polymer-A Yes 2,0 PigDisp-7 Polymer-B Yes 2,0 PigDisp-8 Polymer-E No 3,0 PigDisp-9 Polyacrylates Yes 5,0

[0133] PigDisp-6 and PigDip-7, containing Polymer-A and Polymer-B, respectively, which is a bisphosphonate-functionalized SMA EF40 polymer, exhibited better calcium and / or magnesium binding capacity than PigDisp-8, which is a non-functionalized SMA 2000-dispersed cyan dispersion containing no functional groups with a calcium index value greater than or equal to the calcium index value of phenylphosphonic acid, and than PigDisp-5, which is a polymer-stabilized dispersion containing no monomer selected from maleic anhydride, maleic acid, and salts, esters, imides, and amides thereof. Larger amounts of bisphosphonate groups are bound to an SMA EF40 polymer in Polymer-B than in Polymer-A. PigDisp-10

[0134] Polymer-A (762 g of a 19.2% solids solution in water) was combined with 1444 g of DI water and 340 g of Pigment Violet 19 (as a dry powder). This mixture was then sonicated at approximately 10°C using a Misonix® probe sonicator for approximately 7 h to obtain a low-viscosity magenta dispersion. To the dispersion were added 10.7 g of TMPTGE, 6.53 g of boric acid, and 273 g of DI water. The resulting mixture was heated to 65°C 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 minutes. After centrifugation, the solution was purified and concentrated by diafiltration using a polysulfone membrane tailored to operate at 3,000 MW to obtain PigDisp-10 with 17.1% solids and a mean particle size of 168 nm (determined using a Microtrac® particle size analyzer). PigDisp-11

[0135] Polymer-G (617 g of a 20.9% solids solution in water) was combined with 1228 g of DI water and 300 g of Pigment Violet 19 (as a dry powder). This mixture was then sonicated at approximately 10°C using a Misonix® probe sonicator for approximately 6 h to obtain a low-viscosity magenta 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 heated to 65°C 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 minutes. After centrifugation, the solution was purified and concentrated by diafiltration using a 3,000 MW polysulfone membrane to obtain PigDisp-11 with 18.3% solids and a mean particle size of 161 nm (determined using a Microtrac® particle size analyzer). PigDisp-12

[0136] Polymer-H (59 g of a 22.6% solids solution in water) was combined with 215 g of DI water and 40 g of Pigment Red 122 (as a presscake, the size of which was determined based on its solid content). This mixture was then sonicated at approximately 10°C using a Misonix® probe sonicator for approximately 0.5 h to obtain a cyan dispersion with a low viscosity. The resulting solution was centrifuged at 2,500 g for 20 min and then decanted to isolate the product. The result was a solution of a Polymer-H-dispersed magenta pigment, PigDisp-12, with 14.0% solids and a mean particle size of 106 nm (using a Microtrac® particle size analyzer). PigDisp-13

[0137] PigDisp-13 is a Pro-Jet™ APD1000 magenta, which is an aqueous magenta pigment dispersion commercially available from FUJIFILM Imaging Colorants, Inc. This dispersion is stabilized using polyacrylate dispersants. PigDisp-14-15

[0138] Polymer-A (34 g of a 19.2% solids solution in water) was combined with 38 g of DI water and 15 g of Pigment Violet 19 (as a dry powder). This mixture was then sonicated at approximately 10°C using a Misonix® probe sonicator for approximately 0.5 h to obtain a magenta dispersion with a low viscosity. 43 g of DI water was added to the dispersion to obtain PigDisp-14 with 16.6% solids and a mean particle size of 184 nm (determined using a Microtrac® particle size analyzer).

[0139] To a separate reactor, 35 g of PigDisp-14, 0.13 g of TMPTGE (%CO2 target = 20%), and 0.08 g of boric acid were added. The resulting mixture was heated to 65°C for 5 h. After cooling to room temperature, a PigDisp-15 solution with a mean particle size of 200 nm (determined using a Microtrac® particle size analyzer) was obtained. PigDisp-16-17

[0140] Polymer-B (37 g of a 17.6% solids solution in water) was combined with 35 g of DI water and 15 g of Pigment Violet 19 (as a dry powder). This mixture was then sonicated at approximately 10°C using a Misonix® probe sonicator for approximately 0.5 h to obtain a magenta dispersion with a low viscosity. 43 g of DI water was added to the dispersion to obtain PigDisp-16 with 16.6% solids and a mean particle size of 183 nm (determined using a Microtrac® particle size analyzer).

[0141] To a separate reactor, 35 g of PigDisp-16, 0.13 g of TMPTGE (%CO2 target = 20%), and 0.08 g of boric acid were added. The resulting mixture was heated to 65°C for 5 h. After cooling to room temperature, a solution of PigDisp-17 with a mean particle size of 205 nm (determined using a Microtrac® particle size analyzer) was obtained. PigDisp-18-19

[0142] Polymer-D (44 g of a 14.7% solids solution in water) was combined with 27 g of DI water and 15 g of Pigment Violet 19 (as a dry powder). This mixture was sonicated at approximately 10°C using a Misonix® probe sonicator for approximately 0.5 h to obtain a magenta dispersion with a low viscosity. 43 g of DI water was added to the dispersion to obtain PigDisp-18 with 16.6% solids and a mean particle size of 171 nm (determined using a Microtrac® particle size analyzer).

[0143] To a separate reactor, 35 g of PigDisp-18, 0.19 g of TMPTGE (%CO2 target = 17%), and 0.12 g of boric acid were added. The resulting mixture was heated to 65°C for 5 h. After cooling to room temperature, a solution of PigDisp-19 with a mean particle size of 220 nm (determined using a Microtrac® particle size analyzer) was obtained. PigDisp-20-21

[0144] Polymer-C (51 g of a 12.7% solids solution in water) was combined with 20 g of DI water and 15 g of Pigment Violet 19 (as a dry powder). This mixture was then sonicated at approximately 10°C using a Misonix® probe sonicator for approximately 0.5 h to obtain a magenta dispersion with a low viscosity. 43 g of DI was added to the dispersion to obtain PigDisp-20 with 16.6% solids and a mean particle size of 166 nm (determined using a Microtrac® particle size analyzer).

[0145] To a separate reactor, 35 g of PigDisp-20, 0.16 g of TMPTGE (%CO2 target = 18%), and 0.10 g of boric acid were added. The resulting mixture was heated to 65°C for 5 h. After cooling to room temperature, a solution of PigDisp-21 with a mean particle size of 179 nm (determined using a Microtrac® particle size analyzer) was obtained. Rating of PgDisp-10-21

[0146] For these magenta dispersions, a Mg sensitivity test was performed as follows: (1) One drop (approximately 0.05 g) of each of the dispersion examples PigDisp-10-21 (as is) was added to a series of 10-15 ml MgCl2 solutions with varying molar concentrations: 1.0 mM, 2.0 mM, 3.0 mM, and 5.0 mM; (2) the samples were shaken and then allowed to stand undisturbed for one hour at room temperature; and (3) the lowest molar concentration of MgCl2 at which complete precipitation of the pigment dispersion (i.e., a clear separation of water and pigment precipitates) was observed was recorded. After testing all of these examples, their MgCl2 molar concentrations at which the pigments completely precipitated were recorded in Table 4.The lower the MgCl2 concentration required for precipitation, the greater the sensitivity to magnesium and / or calcium ions, which indicates the ability for calcium and / or magnesium binding. Table 4 Dispersion polymer Networking [MgCl 2 ], mM PigDisp-10 Polymer-A Yes 2,0 PigDisp-11 Polymer-G Yes 5,0 PigDisp-12 Polymer-H No >5,0 PigDisp-13 Polyacrylates Yes >5,0 PigDisp-14 Polymer-A No 2,0 PigDisp-15 Polymer-A Yes 2,0 PigDisp-16 Polymer-B No 2,0 PigDisp-17 Polymer-B Yes 2,0 PigDisp-18 Polymer-D No 3,0 PigDisp-19 Polymer-D Yes 3,0 PigDisp-20 Polymer-C No 3,0 PigDisp-21 Polymer-C Yes 3,0

[0147] PigDisp-10 and PigDisp-14-17, containing respectively Polymer-A and Polymer-B, which is a bisphosphonate-functionalized SMA EF40 polymer, and PigDisp-18-19, containing Polymer-D, which is a bisphosphonate-functionalized SMA 2000 polymer, and PigDisp-20-21, containing Polymer-C, which is a bisphosphonate-functionalized SMA 3000 polymer, exhibited better calcium and / or magnesium binding capacity than PigDisp-11, which is a non-functionalized, SMA EF40-stabilized magenta dispersion that does not contain functional groups with a calcium index value greater than the calcium index value of phenylphosphonic acid, and than PigDisp-12-13, which are polymer-stabilized dispersions that do not contain a monomer consisting of maleic anhydride, maleic acid, and Salts, esters, imides, and amides thereof. Larger amounts of bisphosphonate groups are bound to an SMA EF40 polymer in Polymer-B than in Polymer-A.

[0148] For these magenta dispersions, a Ca sensitivity test was performed as follows: (1) One drop (approximately 0.05 g) of each of the dispersion examples PigDisp-10 and PigDisp-12-17 (as is) was added to a series of 10-15 ml CaCl2 solutions with varying molar concentrations: 1.0 mM, 2.0 mM, 3.0 mM, and 5.0 mM; (2) the samples were shaken and then allowed to stand undisturbed for one hour at room temperature; and (3) the lowest molar concentration of CaCl2 at which complete precipitation of the pigment dispersion (i.e., a clear separation of water and pigment precipitates) was observed was recorded. After testing all of these examples, their CaCl2 molar concentrations at which the pigments completely precipitated were recorded 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 for calcium and / or magnesium binding. Table 5 Dispersion polymer Networking [CaCl 2 ], mM PigDisp-10 Polymer-A Yes 2,0 PigDisp-12 Polymer-H No >5,0 PigDisp-13 Polyacrylates Yes >5,0 PigDisp-14 Polymer-A No 2,0 PigDisp-15 Polymer-A Yes 2,0 PigDisp-16 Polymer-B No 2,0 PigDisp-17 Polymer-B Yes 2,0

[0149] For the magenta dispersions, the Ca sensitivity test yielded the same results as the Mg sensitivity test (Table 4). PigDisp-10 and PigDip-14-17, containing Polymer-A and Polymer-B, respectively, each a bisphosphonate-functionalized SMA EF40 polymer, exhibited better calcium and / or magnesium binding capacity than PigDisp-12-13, which is a polymer-stabilized dispersion that does not contain a monomer selected from maleic anhydride, maleic acid, and salts, esters, imides, and amides thereof. PigDisp-22

[0150] Polymer A (112 g of a 19.2% solids solution in water) was combined with 124 g of DI water and 50 g of Black Pearls 900 (from Cabot Corporation). This mixture was then sonicated at approximately 10°C using a Misonix® probe sonicator for approximately 10 min to obtain a black dispersion with a low viscosity. To this dispersion, 0.90 g of TMPTGE (%CO2 target = 10%), 0.56 g of boric acid, and 144 g of DI water were added. The resulting mixture was heated to 65°C for 5 h. After cooling to room temperature, the solution was first diluted to approximately 13% solids and then centrifuged at 2,500 g for 20 min. After centrifugation, the solution was purified and concentrated by diafiltration using a 3,000 MW polysulfone membrane to obtain PigDisp-22 with 20.6% solids and a mean particle size of 102 nm (determined using a Microtrac® particle size analyzer). PigDis-23

[0151] Polymer-G (772 g of a 20.9% solids solution in water) was combined with 999 g of DI water and 375 g of Black Pearls 900 (from Cabot Corporation). The mixture was then sonicated at approximately 10°C using a Misonix® probe sonicator for approximately 1 h to obtain a black dispersion with a low viscosity. 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 heated to 65°C for 4 h. After cooling to room temperature, the solution was first diluted to 10% solids and then centrifuged at 2,500 g for 20 minutes. After centrifugation, the solution was purified and concentrated by diafiltration using a 3,000 MW polysulfone membrane to obtain PigDisp-23 with 17.1% solids and a mean particle size of 101 nm (determined using a Microtrac® particle size analyzer). PigDisp-24

[0152] PigDisp-24 is a Pro-Jet™ APD1000 Black, which is an aqueous black pigment dispersion commercially available from FUJIFILM Imaging Colorants, Inc. This dispersion is stabilized using polyacrylate dispersants. Rating by PigDisp-22-24

[0153] For these black dispersions, a Mg sensitivity test was performed as follows: (1) One drop (approximately 0.05 g) of each of the dispersion examples PigDisp-22-24 (as is) was added to a series of 10-15 ml MgCl2 solutions with varying molar concentrations: 1.0 mM, 2.0 mM, 3.0 mM, and 5.0 mM; (2) the samples were shaken and then allowed to stand undisturbed for one hour at room temperature; and (3) the lowest molar concentration of MgCl2 at which complete precipitation of the pigment dispersion (i.e., a clear separation of water and pigment precipitates) was observed was recorded. After testing all of these examples, their MgCl2 molar concentrations at which the pigments completely precipitated were recorded in Table 6.The lower the MgCl2 concentration required for precipitation, the greater the sensitivity to magnesium and / or calcium ions, which indicates the ability for calcium and / or magnesium binding. Table 6 Dispersion polymer Networking [MgCl 2 ], mM PigDisp-22 Polymer-A Yes 2,0 PigDisp-23 Polymer-G Yes 3,0 PigDisp-24 Polyacrylates Yes 5,0

[0154] PigDisp-22, containing Polymer-A, which is a bisphosphonate-functionalized SMA EF40 polymer, exhibited better calcium and / or magnesium binding capacity than PigDisp-23, which is a non-functionalized SMA EF40-stabilized magenta dispersion that does not contain functional groups with a calcium index value greater than or equal to the calcium index value of phenylphosphonic acid, and than PigDisp-24, which is a polymer-stabilized dispersion that does not contain a monomer selected from maleic anhydride, maleic acid, and salts, esters, imides, and amides thereof. PigDisp-25

[0155] Polymer-K (136 g of a 15.8% solids solution in water with a pH of 8.59) was combined with 90 g of DI water and 50 g of Pigment Yellow 74 (in the form of a dry powder). This mixture was then mixed at approximately 10°C with a Misonix ®The mixture was sonicated in a probe sonicator for approximately 3 h to obtain a yellow dispersion with a low viscosity. To the dispersion (274 g of a solution containing 25.2% solids), 1.41 g of TMPTGE (%CO2 target = 14%), 0.89 g of boric acid, and 140 g of DI water were added. The resulting mixture was heated to 65°C for 4 h. After cooling to room temperature, the solution was diluted to 10% solids and then centrifuged at 2,500 g for 20 minutes. The solution was then purified and concentrated by diafiltration using a 3,000 MW polysulfone membrane to obtain a yellow PigDisp 25 dispersion with 19.34% solids, a pH of 9.38, and a mean particle size of 158 nm (determined using a Microtrac® particle size analyzer). A Mg sensitivity test was performed on this yellow dispersion as described for the evaluation of PigDisp 1-5.PigDisp-25, containing Polymer-K, which is a bisphosphonate-functionalized SMA 3000 polymer, exhibited better calcium and / or magnesium binding capacity than PigDisp-5, which is a yellow polymer-stabilized dispersion not containing a monomer selected from maleic anhydride, maleic acid, and salts, esters, imides, and amides thereof. PigDisp-26 to PigDisp-34

[0156] Dispersions PigDisp-26 to PigDisp-34 were prepared to investigate the effect of stability on crosslinking. Stability is assessed by a solvent stability test, which was performed on the dispersions as follows:

[0157] A 50 µl drop of the solution was placed on a microscope slide, and then a 5 µl droplet of the dispersion (containing approximately 18-20% solids) was placed on top of the drop of solution. A slide cover was used to flatten the droplet. The appearance of the color particles was recorded. If the dispersion has good compatibility, the pigments mix, flow with the liquid, and color the liquid area. If the dispersion has poor compatibility, the pigment particles agglomerate and do not disperse with the liquid.

[0158] The following Table 7 lists the acid number and percentage of CO2 target (“%CO2”) for the polymers of each dispersion. Table 7 Dispersion AN(SP) ON (xlink) %CO2 target PigDisp26 285 285 0 PigDisp27 285 285 0 PigDisp28 285 199 30 PigDisp29 285 285 0 PigDisp30 285 285 0 PigDisp31 285 199 30 PigDisp32 156 156 0 PigDisp33 156 156 0 PigDisp34 156 125 20 PigDisp-26

[0159] Polymer-I (298 g of a 22.1% solids solution in water) was prepared with 424 g of DI water and 198 g of carbon black according to the method described in US Patent No. 9,388,300, so that it had the following properties: BET surface area = 265 m 2 / g, STSA = 197 m 2 / g, OAN = 175 ml / 100 g, and COAN = 135 ml / 100 g. This mixture was then sonicated at approximately 10°C using a Misonix® probe sonicator for approximately 2 h to obtain a black dispersion with a low viscosity, 25.8% solids, and a pH of 9.80. PigDisp-27

[0160] 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 by diafiltration using a 3,000 MW polysulfone membrane and concentrated to obtain the non-crosslinked carbon black dispersion PigDisp-27 with 20.8% solids, a pH of 9.41, and a mean particle size of 146 nm (determined using a Microtrac® particle size analyzer). PigDisp-28

[0161] To 250 g of PigDisp-26, 2.80 g of TMPTGE, 2.58 g of boric acid, and 115.16 g of DI water were added. The resulting mixture was heated to 65°C 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 minutes. After centrifugation, the solution was purified by diafiltration using a polysulfone membrane tailored to 3,000 MW and concentrated to obtain a cross-linked carbon black dispersion with 18.10% solids, a pH of 8.83, and a mean particle size of 148 nm (determined using a Microtrac® particle size analyzer). Rating by PigDisp-27-28

[0162] The solution stability test was applied to PigDisp-27 (non-crosslinked carbon black dispersion) and PigDisp-28 (crosslinked carbon black dispersion) with various solvents. The results are listed in Table 8 below. Table 8 solvent PigDisp-27 (non-crosslinked) PigDisp-28 (cross-linked) Dipropylene glycol Agglomerated Good spread 2-Pyrollidone Agglomerated Good spread Triethylene glycol monobutyl ether Agglomerated Good spread 1,2-Hexanediol Agglomerated Good spread with few agglomerations 2-Methyl-1,3-propanediol Agglomerated Good spread with few agglomerations 1,4-Butanediol Agglomerated Good spread Tetraethylene glycol Agglomerated Good spread

[0163] The non-crosslinked dispersion PigDisp-27 was immediately destabilized upon exposure to the solvents listed in Table 8, resulting in large agglomerates of pigment particles bouncing outward onto the slide. In contrast, the crosslinked dispersion PigDisp-28 spread and dispersed into the solvent, indicating its stability upon contact with the solvent.

[0164] The contrast of solvent stability is also in Fig. 1A and Fig. 1B, which are photographs of PigDisp-27 and PigDisp-28 after contact with dipropylene glycol on the slide. It is clearly visible that the non-crosslinked dispersion of PigDisp-27 in Fig. 1A is agglomerated, while the cross-linked dispersion PigDisp-28 in Fig. 1B is evenly distributed over the slide without any visible agglomeration. PigDisp-29

[0165] Polymer-I (124 g of a 22.1% solids solution in water with a pH of 10.1) was combined with 135.6 g of DI water and 118 g of Pigment Green 7 (in the form of a presscake with 42.9% solids). This mixture was then sonicated at approximately 10°C using a Misonix® probe sonicator for approximately 2 h to obtain a low-viscosity green dispersion with 25.5% solids. PigDisp-30

[0166] PigDisp-29 (75 g) was diluted to approximately 15% solids and then centrifuged at 2,500 g for 10 min. After centrifugation, the solution was purified by diafiltration using a 3,000 MW polysulfone membrane and concentrated to obtain the non-crosslinked green dispersion PigDisp-30 with 19.10% solids, a pH of 9.21, and a mean particle size of 147 nm (determined using a Microtrac® particle size analyzer). PigDisp31

[0167] To 150 g of PigDisp-29, 2.04 g of TMPTGE, 3.13 g of boric acid, and 41 g of DI water were added. The resulting mixture was heated to 65°C 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 minutes. After centrifugation, the solution was purified by diafiltration using a polysulfone membrane tailored to 3,000 MW and concentrated to obtain a cross-linked green dispersion, PigDisp-31, with 17.87% solids, a pH of 8.46, and a mean particle size of 151 nm (determined using a Microtrac® particle size analyzer). Rating of PigDisp-30-31

[0168] The solution stability test was applied to PigDisp-30 (non-crosslinked green dispersion) and PigDisp-31 (crosslinked green dispersion) with various solvents. The results are listed in Table 9 below. Table 9 solvent PigDisp-30 (non-crosslinked) Pig-Disp-31 (networked) Dipropylene glycol Agglomerated Good spread 2-Pyrollidone Agglomerated Good spread Triethylene glycol monobutyl ether Agglomerated Good spread 1,2-Hexanediol Distribution with some agglomerations Good spread 2-Methyl-1,3-propanediol Agglomerated Good spread 1,4-Butanediol Agglomerated Good spread Tetraethylene glycol Agglomerated Good spread

[0169] The non-crosslinked dispersion PigDisp-30 was immediately destabilized upon exposure to the solvents listed in Table 9, resulting in large agglomerates of pigment particles bouncing outward onto the slide. In contrast, the crosslinked dispersion PigDisp-31 spread and dispersed into the solvent, indicating its stability upon contact with the solvents. PigDisp-32

[0170] Polymer-J (90 g of a 19.8% solids solution in water with a pH of 10.4) was combined with 160 g of DI water and 40 g of Pigment Violet 19 (powder form). This mixture was then sonicated at approximately 10°C using a Misonix® probe sonicator for approximately 2 h to obtain a low-viscosity magenta dispersion containing 20.1% solids. PigDisp-33

[0171] PigDisp-32 (130 g) was first diluted to approximately 15% solids and then centrifuged at 2,500 g for 10 minutes. After centrifugation, the solution was purified and concentrated using a 3,000 MW polysulfone membrane to obtain a non-crosslinked, magenta-colored PigDisp-33 dispersion with 22.9% solids, a pH of 8.8, and a mean particle size of 162 nm (determined using a Microtrac® particle size analyzer). PigDisp-34

[0172] To 130 g of PigDisp-32, 0.86 g of TMPTGE and 1.24 g of boric acid were added. The resulting mixture was heated to 65°C 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 minutes. After centrifugation, the solution was purified by diafiltration using a polysulfone membrane tailored to 3,000 MW and concentrated to obtain a cross-linked, magenta-colored PigDisp-34 dispersion with 18.56% solids, a pH of 8.62, and a mean particle size of 166 nm (determined using a Microtrac® particle size analyzer). Rating by PigDisp-33-34

[0173] The solution stability test was applied to PigDisp-33 (non-crosslinked magenta dispersion) and PigDisp-34 (crosslinked magenta dispersion) with various solvents. The results are listed in Table 10 below. Table 10 solvent PigDisp-33 (non-crosslinked) PigDisp-34 (cross-linked) Dipropylene glycol Agglomerated Good spread 2-Pyrollidone Agglomerated Good spread Triethylene glycol monobutyl ether Agglomerated Good spread 1,2-Hexanediol Agglomerated Good spread 2-Methyl-1,3-propanediol Agglomerated Good spread 1,4-Butanediol Agglomerated Good spread Tetraethylene glycol Agglomerated Good spread

[0174] The non-crosslinked dispersion PigDisp-33 was immediately destabilized upon exposure to the solvents listed in Table 10, resulting in large agglomerates of pigment particles bouncing outward onto the slide. In contrast, the crosslinked dispersion PigDisp-314 spread and dispersed into the solvent, indicating its stability upon contact with the solvents.

[0175] Polymer-L (152 g of a 14.1% solids solution in water) was combined with 72.5 g of DI water and 50 g of Pigment Yellow 74 (as a dry powder). This mixture was then sonicated at approximately 10°C using a Misonix® probe sonicator for approximately 3 h to obtain a yellow dispersion with a low viscosity. To the dispersion (288 g of a 26% solids solution) were added 1.13 g of TMPTGE, 0.70 g of boric acid, and 140 g of DI water. The resulting mixture was heated to 65°C for 4 h. After cooling to room temperature, the solution was diluted to 10% solids and then centrifuged at 2,500 g for 20 minutes. The solution was then purified by diafiltration using a polysulfone membrane tailored to 3,000 MW and concentrated to obtain a yellow dispersion PigDisp-35 with 20.16% solids and a mean particle size of 165 nm (determined using a Microtrac ®particle size analyzer).

Claims

[1] An inkjet ink composition comprising: 1 to 15% by weight, based on the total weight of the inkjet ink composition, of at least one pigment, a carrier fluid, and 0.1 to 25% by weight, based on the total weight of the inkjet ink composition, of at least one polymer comprising first monomers selected from ethylenically unsaturated, hydrophobic monomers, wherein the ethylenically unsaturated, hydrophobic monomers are selected from styrene, α-methylstyrene, ethylene, propylene, 1-butylene, isobutylene, butadiene, methyl vinyl ether, and ethylenically unsaturated esters. and second monomers selected from maleic anhydride, maleic acid and salts, esters, imides and amides thereof, wherein at least a portion of the second monomers is functionalized with at least one organic group having a calcium index value greater than the calcium index value of phenylphosphonic acid, and wherein the first monomers are provided in the at least one polymer in a proportion in the range of 40 to 90 mol% relative to the at least one polymer, and wherein the second monomers are provided in the at least one polymer in a proportion in the range of 10 to 60 mol% relative to the at least one polymer, and wherein the at least one polymer has an acid number of 90 to 325 according to the following equation: AN(xlink)=AN(SP)−(%CO2−target)×AN(SP) where “AN(xlink)” represents the acid number of the at least one polymer being crosslinked, “AN(SP)” represents the acid number of the starting polymer, and “%CO2 target” represents the percentage of the carboxylate-containing target for crosslinking. [2] The inkjet ink composition according to claim 1, wherein the at least one organic group comprises at least two phosphonic acid groups, esters thereof, or salts thereof. [3] The inkjet ink composition according to claim 1, wherein the at least one organic group comprises at least one geminal bisphosphonic acid group, esters thereof, or salts thereof. [4] The inkjet ink composition according to claim 1, wherein the at least one organic group comprises at least one group having the formula -CQ(PO3H2)2 or salts thereof, wherein Q is H, R, OR, SR or NR2 and wherein R, which may be the same or different, is selected from H, C1-C 18 -Alkyl, C1-C 18 -acyl, aralkyl, alkaryl and aryl. [5] The inkjet ink composition according to claim 1, wherein the at least one organic group comprises at least one group having the formula -(CH2) n-CQ(PO3H2)2 or salts thereof, where n is an integer in the range of 1 to 9. [6] The inkjet ink composition of claim 1, wherein the at least one organic group comprises at least one group having the formula -CR=C(PO3H2)2 or salts thereof and wherein R is selected from H, C1-C6 alkyl and aryl. [7] The inkjet ink composition according to claim 1, wherein the at least one organic group comprises at least one heterocyclic group comprising at least one OH group or salts thereof. [8] The inkjet ink composition of claim 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 vicinal or geminal to the at least one phosphonic acid group or salt thereof. [9] The inkjet ink composition according to claim 1, wherein the at least one organic group comprises at least one nitroso group and at least one OH group or a salt thereof. [10] The inkjet ink composition of claim 1, wherein the at least one organic group comprises at least one aryl or alkyl polyacid group comprising at least three carboxylic acids. [11] The inkjet ink composition according to claim 1, wherein the at least one organic group comprises a heteroaryl group comprising at least one carboxylic acid group or salts thereof. [12] The inkjet ink composition of claim 1, wherein the at least one organic group comprises at least one 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 having the formula Ar 1 -N=N-Ar 2 where Ar 1 and Ar 2, which may be the same or different, are an arylene or an aryl and at least one of Ar 1 or Ar 2 is an arylene. [13] The inkjet ink composition of claim 1, wherein the at least one organic group comprises at least one group selected from carboxylic acids, sulfonic acids, phosphonic acids, hydroxyls, amines and esters, amides, and salts and esters thereof. [14] The inkjet ink composition of any one of claims 1 to 13, wherein the at least one organic group has a calcium index value greater than the calcium index value of 1,2,3-benzenetricarboxylic acid. [15] The inkjet ink composition according to any one of claims 1 to 14, wherein the portion of the second monomers functionalized with the at least one organic group constitutes at least 3 mol% of the total amount of the second monomers. [16] The inkjet ink composition of any one of claims 1 to 15, wherein the ethylenically unsaturated hydrophobic monomers are selected from styrene. [17] The inkjet ink composition of claim 1, wherein the ethylenically unsaturated esters are selected from vinyl acetate, allyl acetate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, n-octyl acrylate, benzyl acrylate, acrylonitrile and acrylamide. [18] The inkjet ink composition of any one of claims 1 to 17, wherein the second monomers comprise maleic anhydride. [19] The inkjet ink composition according to any one of claims 1 to 18, wherein the first monomers are provided in the at least one polymer in a proportion in the range of 67 to 80 mol% relative to the at least one polymer. [20] The inkjet ink composition of any one of claims 1 to 19, wherein the at least one pigment is unmodified. [21] The inkjet ink composition of any one of claims 1 to 19, wherein the at least one pigment is self-dispersed. [22] The inkjet ink composition of any one of claims 1 to 21, wherein the at least one polymer is adsorbed to the at least one pigment. [23] The inkjet ink composition of any one of claims 1 to 21, wherein the at least one polymer encapsulates the at least one pigment. [24] The inkjet ink composition of any one of claims 1 to 21, wherein the at least one polymer is crosslinked. [25] The inkjet ink composition of any one of claims 1 to 21, wherein the at least one polymer is crosslinked via the second monomers. [26] The inkjet ink composition of any one of claims 1 to 21, wherein the at least one polymer is crosslinked by carboxylate-containing groups of the second monomers. [27] The inkjet ink composition of any one of claims 1 to 21, wherein the at least one polymer is crosslinked by at least 10% of the carboxylate-containing groups of the second monomer. [28] The inkjet ink composition according to any one of claims 1 to 27, wherein the at least one polymer is crosslinked via at least one compound selected from amide, imide and ester linkages. [29] The inkjet ink composition of any one of claims 1 to 27, wherein the at least one polymer is crosslinked via at least one compound selected from ether and thioether linkages. [30] The inkjet ink composition according to any one of claims 1 to 27, wherein the at least one polymer is crosslinked via at least one compound selected from ester bonds. [31] The inkjet ink composition of claim 30, wherein the ester bond is derived from a reaction between epoxy-containing compounds and carboxylate-containing groups of the second monomers. [32] The inkjet ink composition of claim 31, wherein the epoxy-containing compounds are selected from di- and triglycidyl ether compounds. [33] The inkjet ink composition of claim 31, wherein the epoxy-containing compounds are selected from trimethylolpropane triglycidyl ether. [34] The inkjet ink composition according to any one of claims 23 to 33, wherein the inkjet ink composition has a pH in the range of 8 to 11. [35] The inkjet ink composition of any one of claims 1 to 34, wherein the at least one polymer is a random polymer. [36] The inkjet ink composition of any one of claims 1 to 35, wherein the at least one polymer is an alternating copolymer. [37] The inkjet ink composition according to any one of claims 1 to 36, wherein at least a second portion of the second monomers is contacted with at least one second organic group having the formula -AN(R 3 )(R 4 ) is functionalized, where R 3 and R 4 independently from H, C1-C 10 -Alkyl, C4-C 18 -aryl, C4-C 18 -Heteroaryl and C3-C 20 -Heterocycloalkyl and A is selected from C1-C 10 -alkylene, C3-C 20 -Cycloalkylene, C3-C 20 -Heterocycloalkylene, arylene, heteroarylene and C2-C 20 -Ether is selected. [38] The inkjet ink composition of any one of claims 1 to 36, wherein at least a second portion of the second monomers is functionalized with at least one second organic group having a formula selected from -CH2CH2-N(CH3)2, -CH2CH2CH2-N(CH3)2, -CH(CH3)CH2-N(CH3)2, -CH2CH2CH2CH2-N(CH3)2, -CH2CH2-N(CH2CH3)2, -CH2CH2CH2-N(CH2CH3)2, -CH2CH2CH2CH2-N(CH2CH3)2, -CH2CH2-NHCH2CH2OH, -CH2CH2-N(CH2CH2OH)2 or. [39] An inkjet ink composition according to any one of claims 1 to 36, wherein at least a second portion of the second monomers is contacted with at least one second organic group having the formula -AN + (R 3 )(R 4 )(R 5 ) is functionalized, where R 3 , R 4 and R 5 independently from H, C1-C 10 -Alkyl, C4-C 18 -aryl, C4-C 18 -Heteroaryl and C3-C 20 -Heterocycloalkyl and A is selected from C1-C 10 -alkylene, C3-C 20-Cycloalkylene, C3-C 20 -Heterocycloalkylene, arylene, heteroarylene and C2-C 20 -Ether is selected. [40] The inkjet ink composition of any one of claims 37 to 39, wherein the at least one second organic group is bonded to the second portion of the second monomers via amide, imide and ester bonds. [41] The inkjet ink composition of any one of claims 1 to 40, wherein the carrier liquid is aqueous. [42] The inkjet ink composition according to any one of claims 1 to 41, wherein the inkjet ink composition is an aqueous dispersion. [43] The inkjet ink composition of any one of claims 1 to 41, further comprising at least one surfactant. [44] The inkjet ink composition of any one of claims 1 to 43, further comprising at least one viscosity modifier. [45] The inkjet ink composition of any one of claims 1 to 44, further comprising at least one polymeric binder.

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