Stable pigment dispersion compositions

Abstract

The invention provides a method of forming a pigment dispersion that is stable at elevated temperatures, wherein the dispersion comprises a pigment, a solvent, and a dispersant that is a salt of a polyether-functionalized polyacid.

Description

Technical Field

[0001] The technology disclosed in this invention relates to a pigment dispersion that is stable at elevated temperatures and can be used to prepare colored polymers. Summary of the Invention

[0002] The present invention relates to a method for forming a pigment dispersion that is stable at elevated temperatures, comprising the steps of: (1) preparing a dispersion comprising (a) a solvent having a boiling temperature (T), wherein the solvent comprises or is composed of ethylene glycol or ethylene glycol oligomers, (b) a pigment, such as carbon black, and (c) a dispersant, (2) adding a material having a boiling point above the temperature (T), and (3) heating the dispersion to at least the boiling temperature (T) of the solvent.

[0003] The dispersants used in this invention include salts of P and X. P is a polyether-functionalized polybasic acid intermediate formed by the reaction of the following substances: (i) polybasic acid Z, (ii) optionally, a polyether monophilic nucleophilic reagent C, and (iii) optionally, a nonpolymeric monophilic nucleophilic reagent D. X is an alkali metal, an alkaline earth metal, ammonia, an amine, or a mixture thereof.

[0004] In the dispersant used in the method described herein, the polybasic acid Z has the formula (A). n -(B) m -(E) t -(G) q In polybasic acid Z, A is a repeating carboxylic acid unit with the following structure:

[0005] R is selected from H, CH3, or CH2COOH, and R' is selected from H or COOH, provided that when R is H, R' can only be COOH. In polybasic acid Z, B is an alkyl or aryl repeating unit having 2 to 30 carbon atoms, optionally substituted with a halide, ether, or nitro group, provided that B is substantially free of acid functional groups or contains no acid functional groups. Additionally, in polybasic acid Z, E is a repeating unit having the following structure:

[0006] Where R´´ is H or CH3, and Y is -P(=O)-(OH). k Or -S-(=O)2-OH, and W is a direct link between a main chain carbon atom and a P or S atom of Y, or a hydrocarbon-like linking group having 1 to 7 carbon atoms, wherein the hydrocarbon-like linking group optionally includes an ether, ester, or amide linking group, and k is 1 or 2. Additionally, in the polybasic acid Z, G is a repeating unit having the following structure:

[0007] R´´ is H or CH3, J is ethylene oxide or propylene oxide, wherein at least 50% or at least 70% of J is ethylene oxide, L is H or a straight or branched, saturated or unsaturated chain having 1 to 20 carbon atoms, optionally containing a carbonyl group to form an ester with the oxygen atom between J and L, and r is 1 to 100. In the polybasic acid Z, n is 10 to 200 or 20 to 100, m is 0 to 40 or 0 to 20, t is 0 to 20, and q is 0 to 70, provided that n is at least 30% of all repeating units (n+m+t+q). The polyether monophilic nucleophilic reagent C contains 6 to 70 ethylene glycol repeating units, and optionally contains propylene glycol repeating units and / or butanediol repeating units, provided that at least 50% or at least 70% of all repeating units are ethylene glycol. The polyether monophilic nucleophilic reagent C also contains a single alcohol, primary amine, or secondary amine group. The nonpolymeric monophilic nucleophilic reagent D is a straight or branched, saturated or unsaturated alkyl or aryl chain having 1 to 22 carbon atoms and containing a single alcohol, primary or secondary amine group, and optionally one or more tertiary amine, halide or nitro groups, provided that D is substantially free of acid groups or contains no acid groups.

[0008] In polyether-functionalized polybasic acid P, if q is 1 or greater, 0% to 50% of the total moles of repeating unit A reacts with C, or if q is 0, 10% to 50% of the total moles of A reacts with C. Additionally, in polyether-functionalized polybasic acid P, 0% to 30% of the total moles of A reacts with D. In the dispersant described above, one or more carboxylic acid repeating units of A react with polyether nucleophile C and / or nonpolymeric nucleophile D to form one or more bonds, wherein these bonds are selected from (i) ester bonds formed by the reaction product of the alcohol group of polyether nucleophile C and / or nonpolymeric nucleophile D with the carboxylic acid repeating unit of A; (ii) salt bonds and / or amide bonds formed by the reaction product of the primary or secondary amine of polyether nucleophile C and / or nonpolymeric nucleophile D with the carboxylic acid repeating unit of A; or (iii) imide bonds formed by the reaction product of the primary amine group of polyether nucleophile C and / or nonpolymeric nucleophile D with the same repeating unit A or two adjacent carboxylic acids of adjacent repeating unit A.

[0009] The present invention also includes the use of the above-mentioned dispersant to provide stable pigment dispersions at elevated temperatures. Detailed Implementation

[0010] Definitions. To simplify this disclosure, we will use parentheses around "methyl" to indicate that the named molecule may optionally include a methyl substituent, such as (meth)acrylic acid will refer to methacrylic acid and / or acrylic acid, and methyl (meth)acrylate will refer to methacrylate and / or acrylate. We intend that the polyethers used herein may be random polyethers or block polyethers, and we do not intend that they limit the polyether to a single block or multiple blocks of any particular repeating unit. We will use the symbol C(=O)-OH to represent any form of carboxylic acid, such as the acid form, salt form, or, if two carboxylic acids are physically adjacent and capable of forming an anhydride ring, the anhydride form. If C(=O)-OH is adjacent to the nitrogen of an amide bond, we also expect it to be capable of converting to C(=O)- as part of an imide. We will use the term "hydrocarbon group" to describe a hydrocarbon group with one hydrogen atom removed. A hydrocarbon group in this specification will mean a hydrocarbon-like group, and for every four carbon atoms in the group, it may include at most one oxygen or nitrogen atom, but preferably only carbon and hydrogen atoms. An alkylene group will mean a hydrocarbon with two hydrogen atoms removed. For every two carbon atoms in the group, the alkylene group will optionally also include at most one oxygen or nitrogen atom, but preferably only carbon and hydrogen atoms. To avoid ambiguity, when counting carboxylic acid groups or carbonyl groups, we count the anhydrides of dicarboxylic acids and imides as two carbonyl groups.

[0011] This invention relates to a method for forming a pigment dispersion that is stable at elevated temperatures. The method comprises the following steps: (1) preparing a dispersion comprising (a) a solvent having a boiling temperature (T), wherein the solvent comprises or is composed of ethylene glycol or ethylene glycol oligomers, (b) a pigment, and (c) a dispersant; (2) adding a material having a boiling point above the temperature (T); and (3) heating the dispersion to a temperature at least equal to the boiling temperature (T) of the solvent. The invention also includes the use of the dispersant to provide a stable pigment dispersion at elevated temperatures.

[0012] The solvents used in this invention include ethylene glycol or ethylene glycol oligomers, or mixtures thereof. In one embodiment, the solvent comprises or is composed of ethylene glycol. In another embodiment, the solvent comprises or is composed of ethylene glycol oligomers. When the solvent comprises or is composed of ethylene glycol oligomers, these oligomers may contain 2 to 5 repeating ethylene glycol units. If the dispersion used in this invention comprises one or more other cosolvents, these solvents may be selected from water, alkanols, alkanonic acids and alkanoic acid esters, and other solvents known to those skilled in the art. In one embodiment, the solvent will have a boiling temperature of at least 180°C, or at least 190°C, or at least 195°C, or at least 200°C. For example, ethylene glycol has a boiling temperature of 197°C. In embodiments in which a mixture of solvent or ethylene glycol oligomers is used, the boiling temperature refers to the initial boiling temperature, or the temperature at which any component of the mixture boils.

[0013] The dispersants used in this invention include salts of P and X. P is a polyether-functionalized polybasic acid intermediate formed via a reaction of: (i) a polybasic acid Z, (ii) optionally, a polyether monophilic nucleophilic reagent C, and (iii) optionally, a nonpolymeric monophilic nucleophilic reagent D. X is an alkali metal, an alkaline earth metal, ammonia, an amine, or a mixture thereof.

[0014] Polybasic acid Z has formula (A) n -(B) m -(E) t -(G) q In polybasic acid Z, A is a repeating carboxylic acid unit with the following structure:

[0015] R is selected from H, CH3, or CH2COOH, and R' is selected from H or COOH, provided that when R is H, R' can only be COOH. A can be derived from a free radical polymerizable unsaturated monomer having one or more carboxylic acid groups (such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, mesocarboxylic acid, or citraconic acid, or mixtures thereof).

[0016] B is an alkyl or aryl repeating unit having 2 to 30 carbon atoms, which is optionally substituted with a halide, ether, or nitro group, provided that B is substantially free of acid functional groups or contains no acid functional groups. For example, B can be derived from free radical polymerizable monomers containing carbon-carbon double bonds but without carboxyl groups or from acids derived from sulfur or phosphorus. Such repeating units of B will be derived from styrene, ethylene, propylene, butene, (meth)acrylic acid, and C1-C... 18(Meth)acrylates of alcohols and hydroxy methacrylates (such as hydroxyethyl methacrylate, hydroxybutyl methacrylate, vinyl acetate), (meth)acrylamide, vinyl-substituted heterocycles (such as vinylpyrrolidone, vinylimidazole, vinylcarbazole, 2-vinylpyridine and 4-vinylpyridine).

[0017] E is a repeating unit with the following structure:

[0018] Where R´´ is H or CH3, and Y is -P(=O)-(OH). k Or -S-(=O)2-OH, and W is a direct link between a main chain carbon atom and a P or S atom of Y, or a hydrocarbon-like linking group having 1 to 7 carbon atoms, wherein the hydrocarbon-like linking group optionally includes an ether, ester, or amide linking group, and k is 1 or 2. In one embodiment, E is derived from an anionic monoene-bonded unsaturated monomer containing a sulfonic acid group and / or a phosphate group and / or a phosphonic acid group, wherein the sulfonic acid group and / or the phosphate group and / or the phosphonic acid group can be in free acid form or a salt. As used herein, the terms "phosphate group" and "phosphonic acid group" of phosphorus-containing repeating units refer to oxyacids of phosphorus having a POH moiety, wherein the hydrogen atom is ionizable. The terms "phosphate group" and "phosphonic acid group" also include salts of oxyacids of phosphorus. In the salt or base form of phosphate, the phosphate group has a cation, such as an alkaline earth or alkaline earth metal ion that substitutes for at least one acid proton, ammonium, substituted ammonium, quaternary ammonium, or pyridinium ion. In the salt or base form of sulfonic acid, the sulfonic acid group has a cation, such as an alkaline earth or alkaline earth metal that has substituted at least one acid proton, ammonium, substituted ammonium, quaternary ammonium, or pyridinium ion.

[0019] Examples of anionic monoolefinic unsaturated monomers containing a sulfonic acid group (which may be in the form of a free acid or a salt) include allyl sulfonic acid, methyl allyl sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, vinyl benzyl sulfonic acid, allyloxybenzene sulfonic acid, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, acryloyloxymethylsulfonic acid, 2-(acryloyl)oxyethanesulfonic acid, 3-(acryloyl)oxypropanesulfonic acid, 4-(acryloyl)oxybutanesulfonic acid, methacryloyloxymethylsulfonic acid, 2-(methacryloyl)oxyethylsulfonic acid, 3-(methacryloyl)oxypropylsulfonic acid, 4-(methacryloyl)oxybutylsulfonic acid, and their salts.

[0020] Examples of anionic monoene-bonded unsaturated monomers containing phosphoric acid or phosphonic acid groups (which may be in the form of free acids or salts) include monovinyl phosphate, monoallyl phosphate, 3-butenylphosphonic acid, mono-3-butenyl phosphate, mono(4-vinyloxybutyl) phosphate, [(meth)acrylate hydroxyalkyl ester, hydroxyalkyl(meth)acrylamide or their polyalkoxyl derivatives with a molecular weight Mn of 150-700, such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate, N-hydroxyethylpropyl Phosphate esters of [enamides, N-hydroxyethyl methacrylamide hydroxyl poly(ethylene oxide) (meth)acrylates and polypropylene glycol (meth)acrylates], mono(2-hydroxy-3-vinyloxypropyl) phosphate esters, mono(1-phosphonomethyl-2-vinyloxyethyl) phosphate esters, mono(3-allyloxy-2-hydroxypropyl) phosphate esters, mono(2-allyloxy-1-phosphonomethylethyl) phosphate esters, their salts and / or esters, especially C1-C8 monoalkyl, dialkyl and (if suitable) trialkyl esters of monomers containing phosphate and / or phosphonic acid groups. Other suitable phosphonic acid monomers are disclosed in WO 99 / 25780 A1 and include vinylphosphonic acid, allylphosphonic acid, 2-acrylamido-2-methylpropanephosphonic acid, α-phosphonostyrene, and 2-methacrylamido-2-methylpropanephosphonic acid. Other suitable phosphorus-functionalized monomers are 1,2-ene-bonded unsaturated (meth)acrylate (hydroxy)oxyphosphonic alkyl ester monomers disclosed in US 4,733,005, including methacrylate (hydroxy)oxyphosphonic methyl ester. A preferred monomer is vinylphosphonic acid or its hydrolyzable ester.

[0021] G is a repeating unit with the following structure:

[0022] Wherein R´´´ is H or CH3, J is ethylene oxide or propylene oxide, wherein at least 50% or at least 70% of J is ethylene oxide, L is H or a straight or branched, saturated or unsaturated chain having 1 to 20 carbon atoms, optionally containing a carbonyl group to form an ester with the oxygen atom between J and L, and r is 1 to 100 or 10 to 50.

[0023] In the polyacid Z, n is 10 to 200 or 20 to 100, m is 0 to 40 or 0 to 20, t is 0 to 20, and q is 0 to 70, provided that n is at least 30% of all repeating units (n+m+t+q). In one embodiment, the polyacid Z will be primarily poly(meth)acrylic acid (e.g., >50% of the repeating units will be conventional repeating units from polymeric acrylic acid). In one embodiment, the polyacid will contain 5% to 50% of repeating units from maleic acid or maleic anhydride. In another embodiment, the polyacid Z may comprise a number of copolymers, such as poly(meth)acrylic acid-maleic acid copolymer; polyacrylic acid-itaconic acid copolymer; polyacrylic acid-AMPS acid copolymer; polyitaconic acid-acrylic acid copolymer; polyitaconic acid-acrylamic acid copolymer; etc., instead of poly(meth)acrylic acid.

[0024] The polyether monophilic nucleophilic reagent C comprises 6 to 70 ethylene glycol repeating units, and optionally includes propylene glycol repeating units and / or butanediol repeating units, provided that at least 50% or at least 70% of all repeating units are ethylene glycol. In one embodiment, C comprises 1 to 15, or even 1 to 10 propylene glycol repeating units. The polyether monophilic nucleophilic reagent C also comprises a single alcohol, primary amine, or secondary amine group.

[0025] Polyether mononuclear ether reagents can be derived from poly(epoxide) monoalkyl ether monoamines. Exemplary monoamine compounds of this type can be used as Surfonamine. ® amine or Jeffamine ™ The amine was purchased commercially from Huntsman Corporation. Surfonamine ® Specific examples of amines are L-100 (molar ratio of propylene oxide to ethylene oxide is 3:19), L-207 (molar ratio of propylene oxide to ethylene oxide is 10:32), L-200 (molar ratio of propylene oxide to ethylene oxide is 3:41), and L-300 (molar ratio of propylene oxide to ethylene oxide is 8:58).

[0026] When C contains a single alcohol group, C can be derived from poly(epoxy) monoalkyl ethers. These monoalkyl ethers are available from a variety of sources, such as Sigma-Aldrich, Croda, BASF, Dow, and Ineos.

[0027] The nonpolymeric monophilic nucleophilic reagent D is a straight or branched, saturated or unsaturated alkyl or aryl chain having 1 to 22 carbon atoms and containing a single alcohol, primary or secondary amine group, and optionally one or more tertiary amine, halide or nitro groups, provided that D is substantially free of acid groups or contains no acid groups.

[0028] In some embodiments where the nonpolymerized monophilic nucleophilic reagent D comprises a primary amine, the primary amine may include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecanamine, octadecylamine, nonadecanamine, eicosamine, or mixtures thereof. In some embodiments, the amine may include benzylamine, 2-phenylethylamine (commonly referred to as phenylethylamine), 3-phenylpropylamine, 4-phenylbutylamine, or mixtures thereof. In one embodiment, the primary amine may include benzylamine or 2-phenylethylamine. In one embodiment, the primary amine may include 2-phenylethylamine.

[0029] In some embodiments where the nonpolymerized monophilic nucleophilic reagent D comprises a secondary amine, the secondary amine may be, for example, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, N,N-diisopropylamine, N,N-diisobutylamine, diisopentylamine, piperidine, N,N-dimethylpiperidin-4-amine, N,N-dibenzylamine, N-benzylmethylamine, N-phenyl-N-propylamine, N-methyl-Phenethylamine, N-methyl-N-(1-phenylethyl)amine, 4-bromo-N-methylbenzylamine, or 4-fluoro-N-methylbenzylamine.

[0030] Specific examples of suitable monofunctional nucleophiles D containing a hydroxyl functional group include alcohols having optionally substituted C1-22 alkylene groups, such as methanol, ethanol, propan-1-ol, propan-2-ol, butanol, isobutanol, neopentyl alcohol, hexanol, octyl-1-ol, 2-ethylhexanol, decanol, dodecyl alcohol, oleyl alcohol, stearyl alcohol, dodecyl alcohol, cyclohexanol, benzyl alcohol, phenol, octylphenol, nonylphenol, phenylethanol, fluorinated alcohols such as 1H,1H,2H,2H-perfluoro-1-decyl alcohol, and those marketed under the trademark Isofol. ™ C8-22 branched alcohol (obtained from Sasol).

[0031] The polybasic acid Z can be prepared by methods known to those skilled in the art, and then functionalized by any method known in the art, using a polyether mononuclear agent C and optionally a nonpolymeric nucleophile D. For example, the polybasic acid can be prepared by esterification or amidation of poly(meth)acrylic acid or poly(meth)acrylic acid / maleic acid copolymers using any known polymerization technique or combination of polymerization techniques, employing bulk, solution, suspension, or emulsion methods; or by polymerization of (meth)acrylic acid with (meth)acrylates and / or amides; or by polymerization of (meth)acrylic acid with maleic acid (or maleic anhydride), (meth)acrylates and / or amides, and maleate esters and / or amides. Polymerization can include radical, anionic, cationic, atom-transfer, or group-transfer polymerization methods, or combinations thereof.

[0032] In the dispersants described herein, one or more carboxylic acid repeating units of A react with a polyether nucleophile C and / or a nonpolymeric nucleophile D to form one or more bonds, wherein these bonds are selected from (i) ester bonds formed by the reaction product of an alcohol group of a polyether nucleophile C and / or a nonpolymeric nucleophile D with a carboxylic acid repeating unit of A; (ii) salt bonds and / or amide bonds formed by the reaction product of a primary or secondary amine of a polyether nucleophile C and / or a nonpolymeric nucleophile D with a carboxylic acid repeating unit of A; or (iii) imide bonds formed by the reaction product of a primary amine group of a polyether nucleophile C and / or a nonpolymeric nucleophile D with the same repeating unit A or two adjacent carboxylic acids of an adjacent repeating unit A.

[0033] In another embodiment, polymeric intermediate P can be obtained by reacting a polybasic acid Z (often with a number average molecular weight between 700 and 50,000 or 700 and 28,000) as an aqueous solution or solid with a polyether mononuclear kinase reagent C and optionally a nonpolymeric nucleophile D, or by reacting the above substances, optionally in the presence of a catalyst (such as an acid or base catalyst). In one embodiment of polymeric intermediate P, if q is 1 or greater, 0% to 50% of the total moles of repeating unit A reacts with C. In another embodiment of polyether intermediate P, if q is 0, 10% to 50% of the total moles of A reacts with C. In one embodiment, 0% to 30% of the total moles of A reacts with D. Polymeric intermediate P is then reacted with X at a P to X weight ratio of 30:1 to 1:1 or 15:1 to 1:1 to form a salt. The reactions described herein are carried out under conditions known and understood to be useful by those skilled in the art.

[0034] The dispersants used in this invention include salts of P and X. X is an alkali metal, an alkaline earth metal, ammonia, an amine, or a mixture thereof.

[0035] In some embodiments, the salt can be formed by using ammonia, amine, quaternary ammonium, or pyridinium cation as X. Examples of amines are methylamine, diethylamine, ethanolamine, diethanolamine, hexylamine, 2-ethylhexylamine, and octadecylamine. Quaternary ammonium cations can be quaternary ammonium cations or benzyl ammonium cations. Quaternary ammonium cations can contain one or two alkyl groups having 6 to 20 carbon atoms. Examples of quaternary ammonium cations are tetraethylammonium, N-octadecyl-N,N,N-trimethylammonium; N,N-bisdodecyl-N,N-dimethylammonium, N-benzyl-N,N,N-trimethylammonium, and N-benzyl-N-octadecyl-N,N-dimethylammonium cations.

[0036] In other embodiments, the salt can be formed by using an alkali metal or an alkaline earth metal as X. For example, monovalent alkali metals (Li, Na, K, Rb, Cs, and Fr) or divalent alkaline earth metals (Be, Mg, Ca, Sr, Ba, and Ra) can be used. In some exemplary embodiments, lithium, sodium, and potassium can be used.

[0037] In another embodiment, X can be a polyamine, such as poly(ethyleneamine), alkylene polyamine, or polyallylamine or poly(C) 2-6 (-alkylene imine), for example, in one embodiment, polyethylene imine. The polyamine or polyalkylene imine can be linear or branched. The number average molecular weight of the polyamine or polyalkylene imine can be from 140 g / mol to 100,000 g / mol; more ideally from 140 to 75,000; or preferably from 200 to 10,000 or 20,000. In some embodiments, each molecule of X can have a total of at least four primary amine groups and / or secondary amine groups, more ideally at least six primary amine groups and / or secondary amine groups.

[0038] Examples of polyamines that can be used as X in this invention include, but are not limited to: amino-functionalized polyamino acids, such as polylysine purchased from Aldrich Chemical Co.; amino-functionalized silicones, which are marketed under the trade name Tegomer. ® ASi2122 was purchased from Degussa AG; it is a polyamide, marketed under the trade name Polypox. ® Aradur ® Or "Starburst" ® Dendritic compounds were purchased from Aldrich Chemical Co.; polyallylamine and poly(N-alkyl)allylamine, under the trade name PAA, were purchased from Nitto Boseki; polyvinylamine was purchased from Mitsubishi Kasei, under the trade name Lupamin. ® Purchased from BASF AG; polyalkylene imides, such as polyethylimide, which is marketed under the trade name Epomin ® Purchased from Nippon Shokubai Co., Ltd., and marketed under the trade name Lupasol ® Purchased from BASF AG; and polypropylene imide, marketed under the trade name Astramol. ® Purchased from DSMAG. Linear polyethylene imides can be prepared by hydrolysis of poly(N-acyl)alkylimides, as exemplified by Takeo Saegusa et al. MacromoleculesAs described in Volume 5, 1972, page 4470. Polypropylene imide dendrites are commercially available from DSM Fine Chemicals, and poly(amide) dendrites are available as “Starburst” dendrites from Aldrich Chemical Company. Alkylene polyamines can be characterized as materials having less than 2%, typically less than 1% (by weight) of a boiling point below about 200°C, and including vessel feet, such as ethylene polyamine vessel feet available from Dow Chemical Company (Freeport, Texas).

[0039] When X is polyimide, in one exemplary embodiment it is poly(C) 2-6 (-alkylimide) or polyethylimide (PEI). Polyimides can be linear, or especially branched.

[0040] Since both P and X can have multiple coreactive groups, there may be more than one bond between them in some cases (as defined above). It is also generally accepted that more than one P can be bonded to a single X. Similarly, there may be more than one X chemically bonded to a single P.

[0041] In the dispersant used in this invention, polymer intermediate P and substance X react together, such that the -CO2H or -CO2 of P... - It reacts with the amine, metal, or other basic groups of X to produce ionic salt bonds and / or covalent bonds, or a mixture of ionic salt bonds and covalent bonds. The weight ratio of P to X is 30:1 to 1:1, or 15:1 to 1:1, or 14:1, 13:1, 12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, or 2:1.

[0042] In one embodiment, the reaction product or copolymer product of P and X can be present as a pure polymer or a polymer in an organic solvent. This can be achieved by dissolving the pure reaction product or copolymer product in a solvent, or by synthesizing the reaction product or copolymer product in a solvent. In one embodiment, the solvent comprises or consists of ethylene glycol, ethylene glycol oligomers, or mixtures thereof.

[0043] In some embodiments, the reaction products of P and X can be further functionalized to adapt their properties and application performance to specific requirements. If desired, the following modification reactions can be combined to obtain multi-modified polybasic acid polyaddition compounds. When two or more modification reactions are carried out sequentially, sufficient groups should be ensured to be reactive in one or more subsequent reactions within the molecule.

[0044] The modification is an advantageous embodiment of the present invention and can be achieved in the following ways: a) The reaction of one or more remaining free amino groups of an amine polyamine with isocyanates, lactones, acid anhydrides, epoxides, cyclic carbonates or (meth)acrylates. b) The remaining free amino groups of an amine polyamine react with mono- or polycarboxylic acids, inorganic acids, phosphoric acids, and acids or strong acids containing polyoxometalates to form salts and / or react. c) One or more of the remaining free amino groups of amine polyamines are oxidized to nitrogen oxides; d) Quaternization of one or more remaining free amino groups in a polyamine; or e) The reaction of one or more remaining free amino groups of an amine polymetallic substance with a polymer capped with one or more monoamino reactive groups of MW 150-3000.

[0045] Modification of any remaining amino groups can be carried out in a manner known to those skilled in the art. For example, salt formation and quaternization of the amino nitrogen atom can be achieved using inorganic acids, strong acids, alkyl sulfates, alkyl or aralkyl halides, halocarboxylic acid esters, alkyl oxalate esters, or epoxides. This quaternization is preferred when, for example, the amino group will react with the binder system introduced into the pigment paste and cause flocculation. Suitable reagents for this purpose include hydrochloric acid, acetic acid, sulfuric acid, alkyl sulfonic acids, alkyl hydrogen sulfates, or aryl sulfonic acids. Quaternizing agents include dimethyl sulfate, benzyl chloride, methyl halides (such as methyl chloride, methyl bromide, and methyl iodide), dimethyl oxalate, acid-containing ethylene oxide, propylene oxide, and styrene oxide, as well as propane sulpholactone (or butane sulpholactone).

[0046] Salt formation and / or reaction of one or more remaining free amino groups of amine polyamines with mono- or polycarboxylic acids or phosphoric acid-containing compounds are disclosed in JP9,157,374, US2010 / 0017973, and US2013 / 0126804. Specific examples of suitable monocarboxylic acids include optionally substituted C-type compounds. 1-50 Aliphatic monocarboxylic acids, such as acetic acid, propionic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, stearic acid, arachidic acid, erucic acid, benzyl acid, methoxyacetic acid, and mixtures of fatty acids derived from naturally occurring oils (such as sunflower oil, rapeseed oil, castor oil, and olive oil), under the trade name Isocarb. ™ (ex Sasol) obtained branched alkyl carboxylic acids, Unicid ™ Acid (it is a linear C that is commercially available from Baker Hughes) 25-50Synthetic primary acids) and aromatic carboxylic acids (such as benzoic acid, salicylic acid, and naphtholic acid). Specific examples of suitable polycarboxylic acids include succinic acid, malonic acid, adipic acid, sebacic acid, malic acid, fumaric acid, citric acid, and tartaric acid. Specific examples of suitable phosphoric acid-containing acids include phosphoric acid and phosphorous acid. Specific examples of suitable acids containing polyoxometalates include phosphomolybdic acid, phosphotungstic acid, and silicomolybdic acid.

[0047] Reactions of one or more remaining free amino groups of a polyamine with acid anhydrides are disclosed in US 6,878,799 and US 7,767,750. Specific examples of suitable acid anhydrides include maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trimellitic anhydride, C... 1-20 Alkenyl and alkyl succinic anhydrides.

[0048] Reactions of one or more remaining free amino groups of amine polymers are disclosed in JP4,031,471. Specific examples of suitable epoxides include styrene oxide, propylene oxide, and ethylene oxide.

[0049] One or more remaining free amino groups of an amine polymer are reacted with polymers capped with carboxylic acids, sulfonic acids, sulfuric acids, phosphonic acids, phosphoric acids, isocyanates, epoxides, (meth)acrylates, acetoacetoxy groups, or cyclic carbonates. When carboxylic acid-capped polymers are used, the reaction products can be in the form of amides and / or corresponding salts; when sulfonic acid, sulfuric acid, phosphonic acid, and phosphoric acid-capped polymers are used, the reaction products can be salts, and a covalent bond is formed between the NH functional group of the amino group and: i) isocyanate-capped polymers to give urea; ii) epoxide-capped polymers to open the epoxide group to give an amino alcohol; and iii) (meth)acrylate-capped polymers formed by Michael addition between double bonds. These monoreactive capped polymers can be based on polyesters, polyethers, polyether / polyester, polyamides, polyesteramides, poly(meth)acrylates, polyurethanes, and mixtures thereof. Particularly useful monoreactive polymers have been disclosed in various patents.

[0050] Suitable examples of carboxylic acid-terminated polyesters, polyesteramides, and polyamide polymers are disclosed in US4,224,212, US4,861,380, US5,700,395, US5,760,257, US6,197,877, US8,202,935, JP4,866,255, JP8,010,601, JP9,157,361, WO2006 / 113258, and WO2007 / 039605, wherein: a) Polyesters are polymers derived from the following substances: One or more hydroxycarboxylic acids and / or lactones, optionally in the presence of an initiator molecule containing a carboxylic acid or ester functional group; or one or more diols and one or more diacids / anhydrides, optionally in the presence of an initiator molecule containing a carboxylic acid or ester functional group; b) Polyesteramides are derived from the polymerization of the following substances: One or more hydroxycarboxylic acids and / or lactones and one or more aminocarboxylic acids and / or lactams, optionally in the presence of an initiator molecule containing a carboxylic acid or ester functional group; and c) Polyamides are derived from the polymerization of the following substances: One or more aminocarboxylic acids and / or lactams, optionally in the presence of an initiator molecule containing a carboxylic acid or ester functional group; or one or more diamines and one or more diacids / anhydrides, optionally in the presence of an initiator molecule containing a carboxylic acid or ester functional group.

[0051] Specific examples of suitable hydroxycarboxylic acids and lactones include ricinoleic acid, 12-hydroxystearic acid, 6-hydroxyhexanoic acid, 5-hydroxyvalerate, 12-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, 5-hydroxydecanoic acid, 4-hydroxydecanoic acid, 10-hydroxyundecanoic acid, lactic acid, glycolic acid, β-propiolactone, β-butyrolactone, and optionally C. 1-6 -alkyl-substituted ε-caprolactone and optionally C 1-6 -alkyl-substituted δ-valerolactones (such as ε-caprolactone and 7-methyl-ε-caprolactone, 3-methyl-ε-caprolactone, 5-methyl-ε-caprolactone, 6-methyl-ε-caprolactone, 4-methyl-ε-caprolactone, 5-tetrabutyl-ε-caprolactone, 4,4,6-trimethyl-ε-caprolactone and 4,6,6-trimethyl-ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone or mixtures thereof).

[0052] Specific examples of suitable diols include alkylene glycols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexanediol, and diols with ether bonds such as diethylene glycol, dipropylene glycol, tripropylene glycol, and triethylene glycol. Examples of suitable polyalkylene glycols include mixed block and random copolymers of polyethylene glycol, polypropylene glycol, polybutanediol, and polyethylene glycol (Pluronic and reverse Pluronic from BASF) (MW less than 1000).

[0053] Specific examples of suitable dicarboxylic acids and anhydrides include maleic anhydride, succinic anhydride, glutaric anhydride, fumaric acid, malonic acid, adipic acid, sebacic acid, phthalic anhydride, and cyclohexanedicarboxylic anhydride.

[0054] Specific examples of suitable aminocarboxylic acids include sarcosine, β-alanine, 4-aminobutyric acid, 6-aminohexanoic acid, and 11-aminoundecanoic acid.

[0055] Specific examples of suitable lactams include laurolactam and caprolactam.

[0056] Specific examples of suitable diamines include alkyl diamines such as ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, isomers of butanediamine, pentanediamine, hexanediamine, heptanediamine, 1,12-diaminododecane, diaminocyclohexane, and diamines having ether bonds, such as 1,2-bis(2-aminoethoxy)ethane. Examples of suitable polyether diamines include Jeffamine diamines, such as D230, D400, and ED600, which are commercially available from Huntsman.

[0057] Examples of suitable initiator molecules containing carboxylic acid or ester groups include optionally substituted C24 groups as described above. 1-50 Aliphatic monocarboxylic acids and their methyl or ethyl esters.

[0058] Examples of suitable phosphate, sulfate, and sulfonate-terminated polyester polymers are disclosed in US 4,861,380 and US 6,197,877, wherein the polyesters are derived from the polymerization of hydroxycarboxylic acids and / or lactones as disclosed above using initiator molecules containing hydroxy or amino functional groups. Specific examples of suitable initiator molecules containing hydroxy functional groups include alcohols having optionally substituted C1-50 alkylene groups, such as methanol, ethanol, propan-1-ol, propan-2-ol, butanol, isobutanol, neopentyl alcohol, hexanol, octyl-1-ol, 2-ethylhexanol, decanol, dodecyl alcohol, oleyl alcohol, stearyl alcohol, dodecyl alcohol, cyclohexanol, benzyl alcohol, phenol, octylphenol, nonylphenol, phenylethanol, fluorinated alcohols such as 1H,1H,2H,2H-perfluoro-1-decyl alcohol, and those marketed under the trademark Isofol ™ C8-36 branched alcohols and Unilin purchased from Sasol ™ Alcohols (they are linear C-type alcohols obtained from Baker Hughes) 25-50 Synthetic primary alcohols). Specific examples of suitable initiator molecules containing amino functional groups include amines, such as butylamine, dodecylamine, and stearylamine.

[0059] Suitable examples of (meth)acrylate-terminated polyesters, polyesteramides, and polyamide polymers are disclosed in EP713894, JP3,488,001, JP2010222522, and US8,202,935, wherein the polyesters are derived from the polymerization of hydroxycarboxylic acids and / or lactones, as disclosed above, and the polymerization uses: i. Direct initiator molecules, such as 2-hydroxyethyl acrylate; ii. An initiator molecule containing a hydroxyl functional group, which then undergoes an transesterification reaction with (meth)acrylate; iii. An initiator molecule containing a carboxylic acid or ester functional group as described above, and then reacted with a (meth)acrylate containing a hydroxyl functional group (such as 2-hydroxyethyl acrylate or an epoxy functional group, such as glycidyl methacrylate).

[0060] Examples of suitable phosphate, sulfate, and sulfonate-terminated polyethers, polyether / polyesters, polyether / polyurethanes, and polyether / polyester / polyurethane polymers are disclosed in US 5,130,463, US 5,151,218, US 6,111,054, US 6,310,123, US 7,595,416, and US 8,202,935, wherein the polyethers are derived from the polymerization of ethylene oxide and alkylene oxides (such as ethylene oxide, propylene oxide, butane oxide, and styrene oxide) using initiator molecules containing hydroxyl or amino functional groups as disclosed above. These polyether monohydric alcohols can be further reacted with one or more hydroxycarboxylic acids or lactones as disclosed above, or with diols and diacids as described above, to obtain polyether polyester polymers containing alcohol groups, which can then be phosphorylated as disclosed in US 5,130,463. Polyether monohydric alcohols and polyether polyester monohydric alcohols can be further reacted with diols and diisocyanates as disclosed above to obtain polyether polyurethanes and polyether polyester polyurethane polymers containing alcohol groups, respectively. These polymers can then be phosphorylated, as disclosed in US 5,130,463. Specific examples of suitable diisocyanates include hexamethylene diisocyanate (HDI), 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), α,α-tetramethylxylene diisocyanate (TMXDI), diphenylmethane-4,4′-diisocyanate (4,4′-MDI), diphenylmethane-2,4′-diisocyanate (2,4′-MDI), and dicyclohexylmethane-4,4′-diisocyanate (HMDI).

[0061] Examples of suitable (meth)acrylate-terminated polyether polymers are disclosed in US7,923,474 and JP2010222522.

[0062] Examples of suitable carboxylic acid-terminated polyether polymers are disclosed in JP4,248,207, US7,767,750, US7,671,119, US7,872,070, US8,076,409 and US8,168,713, wherein the polymers are derived from i) the reaction of a polyalkylene glycol monosubstituted ether with a halocarboxylate (such as sodium monochloroacetate) followed by acidification with hydrochloric acid; ii) the reaction of a polyalkylene glycol monosubstituted ether with acrylonitrile followed by hydrolysis in the presence of an acid (such as hydrochloric acid); and iii) the reaction of a polyether amine with an acid anhydride.

[0063] Examples of suitable isocyanate-terminated polyester and polyether polymers are disclosed in JP4,031,471, JP7,149,855 and WO2007 / 039605. Examples of suitable epoxide or acetylacetoxy or cyclic carbonate-terminated polyacrylate polymers are disclosed in US5,100,969.

[0064] The dispersions used in this invention also include one or more pigments, or other particulate solid materials. In one embodiment, the solid is an organic pigment, such as any of the recognized categories of pigments described in the section entitled “Pigments” in the third edition and subsequent revisions of the Colour Index (1971) and its supplements. Examples of organic pigments include those derived from: azo, diazo, trizo, condensed azo, azo lakes, naphthol pigments, anthraquinones, anthraquinones, anthraquinones, benzimidazolones, carbazoles, pyrrolopyrrolediones, flavanones, indigo pigments, indanones, isodibenzoanthrones, isoyindanones, isoyindolones, isoyindolones, isoanthrone violet, metal complex pigments, oxazines, dinaphthalenes, violet ketones, pinanthrones, pyrazoloquinazolinones, quinacridones, quinophthalones, thioindigo, triarylcarbide pigments, triphenyldioxazines, xanthocyanins and phthalocyanine series, especially copper phthalocyanine and its nucleohalogenated derivatives, as well as lakes of acid dyes, basic dyes and mordant dyes. Carbon black, although strictly speaking an inorganic pigment, behaves more like an organic pigment in its dispersion properties. In one embodiment, the organic pigment is phthalocyanine (especially copper phthalocyanine), monoazo, diazo, indanone, anthraquinone, quinacridone, pyrrolopyrroledione, dinaphthalene, and carbon black.

[0065] Examples of inorganic pigments include metal oxides (such as titanium dioxide, rutile titanium dioxide, and surface-coated titanium dioxide), titanium oxides in various colors (such as yellow and black), iron oxides in various colors (such as yellow, red, brown, and black), zinc oxide, zirconium oxide, and aluminum oxide), oxygen-containing metal compounds (such as bismuth vanadate, cobalt aluminate, cobalt stannate, cobalt zincate, zinc chromate, and mixed metal oxides of two or more of manganese, nickel, titanium, chromium, antimony, magnesium, cobalt, iron, or aluminum), Prussian blue, vermilion, ultramarine, zinc phosphate, zinc sulfide, molybdates and chromates of calcium and zinc, metallic effect pigments (such as aluminum flakes, copper, and copper / zinc alloys), and pearlescent flakes (such as lead carbonate and bismuth oxychloride).

[0066] Inorganic solids include expanders and fillers, such as ground and precipitated calcium carbonate, calcium sulfate, calcium oxide, calcium oxalate, calcium phosphate, calcium phosphonate, barium sulfate, barium carbonate, magnesium oxide, magnesium hydroxide, natural magnesium hydroxide or brucite, precipitated magnesium hydroxide, magnesium carbonate, dolomite, aluminum hydroxide, aluminum hydroperoxide or boehmite, calcium silicate and magnesium silicate, aluminosilicates (including nano-clay), kaolinite, montmorillonite (including bentonite, lithium montmorillonite and saponite), mica, talc (including muscovite, gold... Mica, lepidolite, and chlorite; chalk; synthetic precipitated silica; pyrolytic silica; metal fibers and powders; zinc, aluminum, glass fibers; refractory fibers; carbon black (including single-walled and multi-walled carbon nanotubes, reinforced and unreinforced carbon black); graphite; buckyballs; bituminous materials; graphene; diamond; alumina; quartz; silica gel; wood flour; wood chips (including softwood and hardwood); sawdust; powdered paper / fibers; cellulose fibers (such as kenaf, sisal, flax, cotton). Cotton linters, jute, ramie, rice husks or bran, wine coconut, cattail reeds, coconut fiber, coconut shell fiber, oil palm fiber, kapok, banana leaves, calomel, fenugreek, agave fiber leaves, flax leaves, abaca, bagasse, rice straw, bamboo strips, wheat flour, MDF, etc.; vermiculite, zeolite, hydrotalcite, fly ash from power plants, incinerated sewage sludge ash, volcanic ash, blast furnace slag, asbestos, chrysotile, tremolite, crocidolite, wollastonite, palygorskite, etc.; micro-particle ceramic materials. (such as alumina, zirconium oxide, titanium dioxide, cerium dioxide, silicon nitride, aluminum nitride, boron nitride, silicon carbide, boron carbide, mixed silicon-aluminum nitrides and metal titanates); particulate magnetic materials, such as magnetic oxides of transition metals (typically iron and chromium), such as γ-Fe2O3, Fe3O4 and cobalt-doped iron oxides, ferrites (such as barium ferrites); and metal particles, such as aluminum, iron, nickel, cobalt, copper, silver, gold, palladium and platinum, and their alloys.

[0067] Other available solid materials include flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, hexabromocyclododecane, ammonium polyphosphate, melamine, melamine cyanurate, antimony oxide, and borates.

[0068] In one specific embodiment of the invention, the pigment comprises or is composed of carbon black.

[0069] The dispersions of the present invention can be prepared by methods known and understood by those skilled in the art. In some embodiments, the dispersions used in the methods of the present invention comprise 0.5% to 40% by weight of a pigment, 0.5% to 40% by weight of the dispersant described herein, and 20% to 99% by weight of a solvent. As described herein and understood by those skilled in the art, small amounts of other additives may be included in the dispersion. In one embodiment, the solvent is primarily or solely ethylene glycol. In another embodiment, the solvent is primarily or solely an ethylene glycol oligomer having 2 to 5 repeating ethylene glycol units.

[0070] In one embodiment, the dispersant used in the method of the present invention has a pH greater than or equal to 5, or even greater than or equal to 7, when measured in a 50% ethylene glycol solution of the dispersant.

[0071] After preparing a dispersion comprising a solvent, a dispersant, and a pigment (all as described above), the method of the present invention further includes the step of adding a material with a boiling point above temperature (T) to the dispersion, wherein temperature (T) is the boiling point of the solvent. In one embodiment, the solvent comprises ethylene glycol or an ethylene glycol oligomer having 2 to 5 repeating units, or is composed of ethylene glycol or an ethylene glycol oligomer having 2 to 5 repeating units. In such embodiments, temperature T may be at least 180°C, or 190°C, or 195°C, or even at least 200°C. The substance with a boiling point above temperature (T) may include other solvents, but may also include reactive monomer components. In one specific embodiment, the substance with a boiling point above temperature (T) comprises a monomer formed from the reaction product of a lower aliphatic glycol with dimethyl terephthalate or the reaction product of a lower aliphatic glycol with terephthalic acid. The substance with a boiling point above temperature (T) may also include bis(2-hydroxyethyl) terephthalate, 2-hydroxyethyl terephthalic acid, or mixtures thereof.

[0072] After mixing a substance with a boiling temperature higher than (T) with the dispersion described herein, or simultaneously with mixing, the mixture is heated to a temperature of at least T or higher. In some embodiments, the mixture is heated to temperatures above 180°C, or 190°C, or 195°C, or 200°C, or even at least 250°C (e.g., 200°C to 300°C, or even 250°C to 295°C). The dispersant of the present invention unexpectedly provides a pigment dispersion stable at elevated temperatures.

[0073] In one embodiment, the colored polymer prepared by the method of the present invention is polyethylene terephthalate (PET). Methods for preparing PET are known to those skilled in the art and are described in references, such as U.S. Patent Publication No. 2003 / 0105214, which is incorporated herein by reference. In this method, monomers used to prepare the PET polymer are formed via transesterification or esterification reactions. These monomers are prepared by transesterification or esterification of dimethyl terephthalate with a lower aliphatic diol (such as ethylene glycol or monoethylene glycol) or terephthalic acid with a lower aliphatic diol (such as ethylene glycol or monoethylene glycol). The products of the transesterification or esterification reactions include bis(2-hydroxyethyl) terephthalate or 2-hydroxyethyl terephthalic acid. In one embodiment of the invention, the dispersion described herein is mixed with the product of an ester exchange or esterification reaction, and then heated to a temperature of at least 180°C, or at least 190°C, or at least 195°C, or at least 200°C, or even at least 250°C (e.g., 200°C to 300°C), or even 250°C to 295°C.

[0074] In one embodiment, the polymer prepared by the method of the present invention comprises 0.01% to 20% by weight of the polymer, further for example 0.1% to 2% by weight, or even 0.4% to 1.6% by weight. In one exemplary embodiment, the pigment comprises carbon black.

[0075] The following examples provide an illustration of the invention. These examples are non-exhaustive and are not intended to limit the scope of the invention.

[0076] Example

[0077] A series of polymer intermediates (Z) were prepared as follows: Intermediate 1: Aqueous polyacrylic acid (49.5% reactive) (Carbosperse) ™ K-732 (500.00 parts) and Surfonamine ® L-207 (920.81 parts) was heated at 120°C to remove water for 7.5 hours, yielding a clear, pale yellow, viscous liquid. Acid value = 128.23 mg KOH g -1 Amine value = 21.72 mg KOH g -1 The active ingredient content is 97.5%.

[0078] Intermediate 2: Aqueous polyacrylic acid (49.5% active) (Carbosperse) ™ K-732 (250.00 parts) and Surfonamine ®L-207 (460.41 parts) was heated at 120°C to remove water for 12.5 hours, yielding a clear, colorless, viscous liquid. Acid value = 122.68 mg KOH g -1 Amine value = 10.75 mg KOH g -1 The active ingredient content is 98.6%.

[0079] Intermediate 3: Aqueous polyacrylic acid (49.5% reactive) (Carbosperse) ™ K-732 (50.00 parts) and Surfonamine ® L-207 (92.08 parts) was heated at 150°C and the water was removed for 24.0 hours to obtain a clear, pale yellow, viscous liquid. Acid value = 105.55 mg KOH g -1 Amine value = 4.37 mg KOH g -1 The active ingredient content is 99.7%.

[0080] Intermediate 4: Aqueous polyacrylic acid (49.5% reactive) (Carbosperse) ™ K-732 (50.00 parts) and Surfonamine ® L-100 (46.04 parts) was heated at 120°C and the water was removed for 7.5 hours to obtain a clear, amber-colored viscous gel. Acid value = 201.33 mg KOH g -1 Amine value = 16.10 mg KOH g -1 The active ingredient content is 99.7%.

[0081] Intermediate 5: Aqueous polyacrylic acid (49.5% reactive) (Carbosperse) ™ K-732 (240.00 parts) and Surfonamine ® L-207 (441.99 parts) was heated at 120°C and the water was removed for 7.3 hours. The resulting substance was heated to 140°C, and phenylethylamine (53.56 parts) was added over 30 to 45 minutes. The resulting substance was heated at 150°C and the water was removed for 6.75 hours, yielding a pale yellow viscous liquid. Acid value = 45.22 mg KOH g -1 Amine value = 7.76 mg KOH g -1 The active ingredient content is 99.2%.

[0082] Intermediate 6: Aqueous polyacrylic acid (49.5% reactive) (Carbosperse) ™K-732 (50.00 parts) and polyethylene glycol monomethyl ether MW 750 (85.64 parts) were heated at 160°C and water was removed for 24.0 hours to obtain an opaque yellowish-gray solid. Acid value = 62.61 mg KOH g -1 Active ingredient content = 100.0%.

[0083] Intermediate 7: Aqueous polyacrylic acid (49.5% reactive) (Carbosperse) ™ K-732 (50.00 parts) and polyethylene glycol monomethyl ether MW 2000 (92.08 parts) were heated at 160°C and water was removed for 24.0 hours to obtain a hard, opaque paste-like solid. Acid value = 89.98 mg KOH g -1 Active ingredient content = 100.0%.

[0084] Intermediate 8: Aqueous polyacrylic acid (49.5% reactive) (Carbosperse) ™ K-732 (250.00 parts) and polyethylene glycol monomethyl ether MW 1000 (230.20 parts) were heated at 160°C and water was removed for 24.0 hours to obtain a clear, amber-colored viscous liquid. Acid value = 152.63 mg KOH g -1 The active ingredient content is 99.8%.

[0085] Intermediate 9: 75.00 parts of hydrated polyacrylic acid (49.5% active) (Carbosperse K-732) and 182.47 parts of polyetheramine (Surfonamine L-300) were heated at 120°C to remove water for 21 hours, yielding a clear brown solid. Acid value = 89.34 mg KOH -1 - Amine value = 3.31 mg KOH g -1 Active ingredient content = 100.00%.

[0086] Intermediate 10: 53.48 parts of hydrated polyacrylic acid (49.5% active) (Carbosperse K-732) and 98.53 parts of polyetheramine (Surfonamine L-300) were heated at 120°C and the water was removed for 13 hours to obtain an opaque yellow solid. Acid value = 121.14 mg KOH g -1 Amine value = 4.73 mg KOH g -1 Active ingredient content = 100.00%.

[0087] Intermediate 11: 150.00 parts of hydrated polyacrylic acid (49.5% active) (Carbosperse K-732) and 212.71 parts of polyetheramine (Surfonamine L-207) were heated at 120°C to remove water for 19 hours, yielding a clear, dark amber-colored viscous liquid. Acid value = 151.60 mg KOH g -1 Amine value = 11.61 mg KOH g -1 The active ingredient content is 99.49%.

[0088] The following are examples of dispersant preparations or provided examples. The pH of the dispersant was measured using a 50% ethylene glycol solution of the dispersant: Example 1: Intermediate 5 (30.00 parts) and deionized water (20.00 parts) were heated at 50°C for 1 hour, and then cooled. 2-Dimethylamino-2-methylpropanol (80% aqueous solution) (2.33 parts) was added to the resulting mixture, and the mixture was stirred for 2 hours to obtain a clear yellow solution. Active ingredient content = 58.6%, pH = 7.

[0089] Example 2: Intermediate 5 (60.00 parts) and deionized water (40.00 parts) were heated at 50°C for 1 hour, and then cooled. 2-Dimethylamino-2-methylpropanol (80% aqueous solution) (2.33 parts) was added to the resulting mixture, and the mixture was stirred for 2 hours to obtain a clear yellow solution. Active ingredient content = 58.2%, pH = 9.

[0090] Example 3: 50.00 parts of the solution from Example 2 and 7.03 parts of hydrochloric acid solution (0.5M aqueous solution) were stirred for 2 hours to obtain a clear yellow solution. Active ingredient content = 52.61, pH = 7.

[0091] Example 4: Intermediate 1 (220.00 parts) and deionized water (220.00 parts) were heated at 50°C for 1 hour. 2-Dimethylamino-2-methylpropanol (80% aqueous solution) (72.84 parts) and deionized water (43.70 parts) were added to the resulting mixture, and the mixture was heated for 1.5 hours to obtain a clear, colorless solution. Active ingredient content = 50.0%, pH = 10.

[0092] Example 5: Intermediate 1 (25.00 parts) and ethylene glycol (50.00 parts) were heated at 60°C for 1 hour. Polyethyleneimine MW1800 (Epomin) was added. ™ SP-018 (2.50 parts) was added to the obtained substance and heated for 1.5 hours to obtain a clear, pale yellow solution. Active ingredient content = 39.2%, pH = 8.

[0093] Example 6: Intermediate 1 (25.00 parts) and ethylene glycol (50.00 g) were heated at 60°C for 1 hour. Polyethyleneimine MW1800 (Epomin) was added. ™ SP-018 (3.75 parts) was added to the obtained substance and heated for 2 hours to obtain a clear, yellow, viscous solution. Active ingredient content = 35.6%, pH = 9.

[0094] Example 7: Intermediate 1 (25.00 parts) and ethylene glycol (50.00 parts) were heated at 60°C for 1 hour. Polyethyleneimine MW1800 (Epomin) was added. ™ SP-018 (5.00 parts) was added to the resulting substance and heated for 2 hours to obtain a clear, yellow, viscous solution. Active ingredient content = 37.0%, pH = 10.

[0095] Example 8: Intermediate 2 (230.00 parts) and ethylene glycol (253.00 parts) were heated at 60°C for 1 hour. Polyethyleneimine MW1800 (Epomin) was added. ™ SP-018 (23.00 parts) was added to the obtained substance and heated for 1 hour to obtain a clear, yellow, viscous solution. Active ingredient content = 49.0%, pH = 7.

[0096] Example 9: Intermediate 1 (25.00 parts) and ethylene glycol (50.00 parts) were heated at 60°C for 1 hour. Polyethyleneimine MW600 (Epomin) was added. ™ SP-006 (2.50 parts) was added to the resulting substance and heated for 1 hour to obtain a clear yellow solution. Active ingredient content = 35.5%, pH = 7.

[0097] Example 10: Intermediate 3 (25.00 parts) and ethylene glycol (27.50 parts) were heated at 60°C for 1 hour. Polyethyleneimine MW1800 (Epomin) was added. ™ SP-018 (2.50 parts) was added to the resulting substance and heated for 3 hours to obtain a clear, yellow, gel-like solution. Active ingredient content = 49.2%, pH = 6.

[0098] Example 11: Intermediate 4 (25.72 parts) and ethylene glycol (28.29 parts) were heated at 60°C for 1 hour. Polyethyleneimine MW1800 (Epomin) was added. ™ SP-018 (2.57 parts) was added to the resulting substance and heated for 3 hours to obtain a clear, yellow, gel-like solution. Active ingredient content = 48.3%, pH = 6.

[0099] Example 12: Intermediate 5 (35.00 parts) and ethylene glycol (38.50 parts) were heated at 60°C for 1 hour. Polyethyleneimine MW1800 (Epomin) was added. ™ SP-018 (3.50 parts) was added to the obtained substance and heated for 1 hour to obtain a clear yellow solution. Active ingredient content = 49.9%, pH = 8.

[0100] Example 13: Intermediate 6 (25.00 parts) and ethylene glycol (27.50 parts) were heated at 60°C for 1 hour. Polyethyleneimine MW1800 (Epomin) was added. ™ SP-018 (2.50 parts) was added to the resulting substance and heated for 1 hour to obtain a clear, yellow, gel-like solution. Active ingredient content = 49.4%, pH = 7.

[0101] Example 14: Intermediate 7 (194.00 parts) and ethylene glycol (320.10 parts) were heated at 60°C for 1 hour. Polyethyleneimine MW1800 (Epomin) was added. ™ SP-018 (19.40 parts) was added to the resulting substance and heated for 2.25 hours to obtain a clear amber solution. Active ingredient content = 39.6%, pH = 6.

[0102] Example 15: Intermediate 9 (158.36 parts) and ethylene glycol (348.39 parts) were heated at 60°C for 0.25 hours. Polyethyleneimine MW1800 (Epomin SP-018) (15.84 parts) was added to the resulting mixture, and the mixture was heated for 1 hour to obtain a clear yellow solution. Active ingredient content = 33.7%, pH = 6.

[0103] Example 16: Intermediate 10 (83.32 parts) and ethylene glycol (91.65 parts) were heated at 60°C for 0.25 hours. Polyethyleneimine MW1800 (Epomin SP-018) (8.33 parts) was added to the resulting mixture, and the mixture was heated for 0.75 hours. Ethylene glycol (158.13 parts) was added to the resulting mixture, and the mixture was heated for 5.75 hours, yielding a clear yellow solution. Active ingredient content = 26.6%, pH = 6.

[0104] Example 17: Intermediate 11 (201.35 parts) and ethylene glycol (221.49 parts) were heated at 60°C for 0.25 hours. Polyethyleneimine MW1800 (Epomin SP-018) (20.14 parts) was added to the resulting mixture, and the mixture was heated for 2.33 hours. Ethylene glycol (157.70 parts) was added to the resulting mixture, and the mixture was heated for 4.5 hours to obtain a clear amber solution. Active ingredient content = 36.1%, pH = 6.

[0105] Comparative Example 1: Intermediate 1

[0106] Comparative Example 2: Example 7 of Patent WO2012125609A1

[0107] Comparative Example 3: Morwet D-809 (Nouryon)-Naphthalenesulfonic acid-formaldehyde condensate

[0108] Comparative Example 4: Orotan SN(Dow)-Naphthalenesulfonic acid-formaldehyde condensate

[0109] Test 1 - High Temperature Test 200°C: 1.05 g of the example or comparative example to be tested (100% active material excluding ethylene glycol or water, i.e., 2.10 g of 50% active material will be used) and 7.45 g of ethylene glycol (this value is reduced due to the amount of inactive material added as part of the example or comparative example, i.e., 6.40 g for 50% active material) were placed in a 32 mL vial and shaken until the sample was completely dissolved. Glass beads (17.00 g) and carbon black (Special Black 4, 1.50 g) were placed in the vial and the vial was sealed. The material was then ground on a horizontal shaker for 16 hours to produce a grinding base. The grinding base (1.00 g) was removed from the vial and placed in a 32 mL vial. Ethylene glycol (6.75 g) was added to the vial and the contents were stirred until homogeneous to produce a diluted grinding base. The vial was heated to 200°C. Once the diluted grinding base reaches 200°C, it is inspected to determine its homogeneity. Heterogeneous materials have a much larger proportion of pigment at the bottom of the vial, while homogeneous materials are acceptable. The results are summarized in Table 1.

[0110] Table 1

[0111] Experiment 2: Addition of a material with a boiling point higher than that of ethylene glycol solvent (bis(2-hydroxyethyl) terephthalate (“BHET”): The material obtained from Experiment 1 was transferred to Experiment 2. BHET (7.75 g) was added to a vial at 200°C. Once the BHET melted, the sample was stirred and heated for another hour. This process was repeated twice more, resulting in a total addition of 23.25 g of BHET and a total heating time of 3 hours. The sample was then allowed to cool to room temperature. Once cooled, the sample was first examined to determine homogeneity, where heterogeneous samples either had black spots throughout, a layer of black material at the bottom, or both. Next, the color was determined. A homogeneous sample with a black color was acceptable. The results are summarized in Table 2.

[0112] Table 2

[0113] This experiment demonstrates that the pigment dispersion described herein can be used at elevated temperatures (e.g., the temperatures required for polymerizing PET polymers).

[0114] Each of the foregoing references is incorporated herein by reference, including any prior application claiming priority thereto, whether or not specifically listed above. Reference to any document is not an admission that such document is prior art or constitutes general knowledge to any person skilled in the art. Unless expressly stated in the examples or otherwise, all numerical quantities of matter, reaction conditions, molecular weight, number of carbon atoms, etc., specified in this specification should be understood to be modified by the word “about.” It should be understood that the upper and lower limits of the quantities, ranges, and proportions described herein can be combined independently. Similarly, the ranges and quantities of each element of the invention can be used in conjunction with the ranges or quantities of any other element.

[0115] As used herein, the transitional term "comprising," synonymous with "comprising," "containing," or "characterized in," is inclusive or open-ended and does not exclude additional, unlisted elements or method steps. However, in every instance of "comprising" herein, it is intended that the term, as an alternative, narrower embodiment, also encompass the phrases "consistently composed of" and "composed of," wherein "composed of" excludes any unstated elements or steps, while "consistently composed of" allows the inclusion of additional, unlisted elements or steps that do not materially affect the essential and novel characteristics of the composition or method under consideration.

[0116] While certain representative embodiments and details have been shown to illustrate the purpose of this invention, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the invention. In this respect, the scope of the invention is defined only by the following claims.

Claims

1. A method for forming a pigment dispersion that is stable at elevated temperatures, comprising: (1) Preparing a dispersion, the dispersion comprising (a) A solvent having a boiling temperature (T), wherein the solvent comprises ethylene glycol or an ethylene glycol oligomer; (b) Pigments; and (c) A dispersant comprising a salt of P and X; Wherein P is a polyether-functionalized polybasic acid intermediate formed by the reaction of the following substances: (i) polybasic acid Z, (ii) optionally, polyether monophilic nucleophilic reagent C, and (iii) optionally, nonpolymeric monophilic nucleophilic reagent D, and X is an alkali metal, alkaline earth metal, ammonia, amine or a mixture thereof. (i) Wherein the polybasic acid Z has formula (A) n -(B) m -(E) t -(G) q ; Where A is a repeating carboxylic acid unit with the following structure: R is selected from H, CH3, or CH2COOH, and R' is selected from H or COOH, provided that when R is H, R' can only be COOH. B is an alkyl or aryl repeating unit having 2 to 30 carbon atoms, wherein the repeating unit is optionally substituted with a halide, ether, or nitro group, provided that B does not contain an acid functional group. E is a repeating unit with the following structure: Where R´´ is H or CH3, and Y is -P(=O)-(OH). k Or -S-(=O)2-OH, and W is a direct connection between the main chain carbon atom and the P or S atom of Y or a hydrocarbon linking group having 1 to 7 carbon atoms, wherein the hydrocarbon linking group optionally includes an ether, ester or amide linking group, and k is 1 or 2. G is a repeating unit with the following structure: Wherein R´´´ is H or CH3, J is ethylene oxide or propylene oxide, wherein at least 50% of J is ethylene oxide, L is H or a straight or branched, saturated or unsaturated chain having 1 to 20 carbon atoms, optionally containing a carbonyl group to form an ester with the oxygen atom between J and L, and r is 1 to 100. Where n is 10 to 200, m is 0 to 40, t is 0 to 20, and q is 0 to 70, provided that n is at least 30% of all repeating units (n+m+t+q); (ii) wherein the polyether mononuclear reagent C comprises 6 to 70 ethylene glycol repeating units and optionally comprises propylene glycol repeating units and / or butanediol repeating units, provided that at least 50% of all repeating units are ethylene glycol, and wherein the polyether mononuclear reagent C comprises a single alcohol, primary amine or secondary amine group. (iii) The nonpolymeric monophilic nucleophilic reagent D is a straight or branched, saturated or unsaturated alkyl or aryl chain having 1 to 22 carbon atoms and containing a single alcohol, primary or secondary amine group, and optionally one or more tertiary amine, halide or nitro groups, provided that D does not contain acid groups. If q is 1 or greater, then 0% to 50% of the total number of moles of repeating unit A reacts with C; if q is 0, then 10% to 50% of the total number of moles of A reacts with C, and 0% to 30% of the total number of moles of A reacts with D. (2) Add a substance with a boiling point higher than the boiling temperature (T); as well as (3) Heat the dispersion to at least the boiling temperature (T) of the solvent.

2. The method according to claim 1, wherein one or more carboxylic acid repeating units of A react with a polyether monophilic nucleophile C and / or a nonpolymeric monophilic nucleophile D to form one or more bonds, wherein the bonds are selected from (i) ester bonds formed by the reaction product of an alcohol group of a polyether monophilic nucleophile C and / or a nonpolymeric monophilic nucleophile D with a carboxylic acid repeating unit of A; (ii) salt bonds and / or amide bonds formed by the reaction product of a primary or secondary amine of a polyether monophilic nucleophile C and / or a nonpolymeric monophilic nucleophile D with a carboxylic acid repeating unit of A; or (iii) imide bonds formed by the reaction product of a primary amine group of a polyether monophilic nucleophile C and / or a nonpolymeric monophilic nucleophile D with the same repeating unit A or two adjacent carboxylic acids of adjacent repeating units A.

3. The method according to claim 1, wherein the weight ratio of P to X is 30:1 to 1:

1.

4. The method according to claim 1, wherein the weight ratio of P to X is 15:1 to 1:

1.

5. The method according to any one of claims 1 to 4, wherein A is derived from (meth)acrylic acid, maleic acid, itaconic acid, or a mixture thereof.

6. The method according to any one of claims 1 to 4, wherein C comprises 1 to 15 propylene glycol repeating units.

7. The method according to any one of claims 1 to 4, wherein C comprises 1 to 10 propylene glycol repeating units.

8. The method according to any one of claims 1 to 4, wherein X is an amine.

9. The method of claim 8, wherein X is an amine selected from polyethyleneimine, alkanolamine, or mixtures thereof.

10. The method of claim 8, wherein X comprises a plurality of amine groups.

11. The method according to any one of claims 1 to 4, wherein the pigment comprises carbon black.

12. The method according to any one of claims 1 to 4, wherein the pigment is composed of carbon black.

13. The method according to any one of claims 1 to 4, wherein the solvent comprises ethylene glycol.

14. The method according to any one of claims 1 to 4, wherein the solvent is composed of ethylene glycol.

15. The method according to any one of claims 1 to 4, wherein the solvent comprises an ethylene glycol oligomer having 2 to 5 ethylene glycol repeating units.

16. The method according to any one of claims 1 to 4, wherein the solvent comprises an ethylene glycol oligomer having 2 to 5 ethylene glycol repeating units.

17. The method according to any one of claims 1 to 4, wherein the dispersion comprises 0.5% to 40% by weight of pigment, 0.5% to 40% by weight of dispersant, and 20% to 99% by weight of solvent.

18. The method according to any one of claims 1 to 4, wherein the substance with a boiling point above the boiling temperature (T) is selected from bis(2-hydroxyethyl) terephthalate, 2-hydroxyethyl terephthalic acid, or mixtures thereof.

19. The method according to any one of claims 1 to 4, wherein the boiling temperature (T) is at least 180°C.

20. The method according to any one of claims 1 to 4, wherein the boiling temperature (T) is at least 190°C.

21. The method according to any one of claims 1 to 4, wherein the boiling temperature (T) is at least 195°C.

22. The method according to any one of claims 1 to 4, wherein the boiling temperature (T) is at least 200°C.

23. The method according to any one of claims 1 to 4, wherein the boiling temperature (T) is 200°C to 300°C.

24. The method according to any one of claims 1 to 4, wherein the boiling temperature (T) is 250°C to 295°C.

25. The method of claim 1, wherein the solvent comprises an ethylene glycol oligomer.

26. The method of claim 1, wherein the solvent is composed of an ethylene glycol oligomer.

27. The method of claim 1, wherein at least 70% of J is ethylene oxide.

28. The method of claim 1, wherein n is 20 to 100.

29. The method of claim 1, wherein m is 0 to 20.

30. The method of claim 1, wherein at least 70% of all repeating units are ethylene glycol.

31. Use of a dispersant to provide a stable pigment dispersion at a temperature of at least 180°C, wherein said dispersant comprises: Salts of P and X; wherein P is a polyether-functionalized polyacid intermediate formed by the reaction of the following substances: (i) polyacid Z, (ii) optionally, polyether monophilic nucleophilic reagent C, and (iii) optionally, nonpolymeric monophilic nucleophilic reagent D, and X is an alkali metal, alkaline earth metal, ammonia, amine or a mixture thereof. (i) Wherein the polybasic acid Z has formula (A) n -(B) m -(E) t -(G) q ; Where A is a repeating carboxylic acid unit with the following structure: R is selected from H, CH3, or CH2COOH, and R' is selected from H or COOH, provided that when R is H, R' can only be COOH. B is an alkyl or aryl repeating unit having 2 to 30 carbon atoms, wherein the repeating unit is optionally substituted with a halide, ether, or nitro group, provided that B does not contain an acid functional group. E is a repeating unit with the following structure: Where R´´ is H or CH3, and Y is -P(=O)-(OH). k Or -S-(=O)2-OH, and W is a direct connection between the main chain carbon atom and the P or S atom of Y or a hydrocarbon linking group having 1 to 7 carbon atoms, wherein the hydrocarbon linking group optionally includes an ether, ester or amide linking group, and k is 1 or 2. G is a repeating unit with the following structure: Wherein R´´´ is H or CH3, J is ethylene oxide or propylene oxide, wherein at least 50% of J is ethylene oxide, L is H or a straight or branched, saturated or unsaturated chain having 1 to 20 carbon atoms, optionally containing a carbonyl group to form an ester with the oxygen atom between J and L, and r is 1 to 100. Where n is 10 to 200, m is 0 to 40, t is 0 to 20, and q is 0 to 70, provided that n is at least 30% of all repeating units (n+m+t+q); (ii) wherein the polyether mononuclear reagent C comprises 6 to 70 ethylene glycol repeating units and optionally comprises propylene glycol repeating units and / or butanediol repeating units, provided that at least 50% of all repeating units are ethylene glycol, and wherein the polyether mononuclear reagent C comprises a single alcohol, primary amine or secondary amine group. (iii) The nonpolymeric monophilic nucleophilic reagent D is a straight or branched, saturated or unsaturated alkyl or aryl chain having 1 to 22 carbon atoms and containing a single alcohol, primary or secondary amine group, and optionally one or more tertiary amine, halide or nitro groups, provided that D does not contain acid groups. If q is 1 or greater, then 0% to 50% of the total number of moles of repeating unit A reacts with C; if q is 0, then 10% to 50% of the total number of moles of A reacts with C, and 0% to 30% of the total number of moles of A reacts with D.

32. Use of the dispersant according to claim 31, wherein the dispersion comprises: Solvent, wherein the solvent comprises ethylene glycol or ethylene glycol oligomers; and pigment.

33. Use of the dispersant according to claim 32, wherein the solvent is composed of ethylene glycol or an ethylene glycol oligomer.

34. Use of the dispersant according to any one of claims 31 to 33, wherein one or more carboxylic acid repeating units of A react with a polyether monophilic nucleophile C and / or a nonpolymeric monophilic nucleophile D to form one or more bonds, wherein the bonds are selected from (i) ester bonds formed by the reaction product of an alcohol group of a polyether monophilic nucleophile C and / or a nonpolymeric monophilic nucleophile D with a carboxylic acid repeating unit of A; (ii) salt bonds and / or amide bonds formed by the reaction product of a primary or secondary amine of a polyether monophilic nucleophile C and / or a nonpolymeric monophilic nucleophile D with a carboxylic acid repeating unit of A; or (iii) imide bonds formed by the reaction product of a primary amine group of a polyether monophilic nucleophile C and / or a nonpolymeric monophilic nucleophile D with the same repeating unit A or two adjacent carboxylic acids of adjacent repeating units A.

35. Use of the dispersant according to any one of claims 31 to 33, wherein the weight ratio of P to X is 30:1 to 1:

1.

36. Use of the dispersant according to any one of claims 31 to 33, wherein the weight ratio of P to X is 15:1 to 1:

1.

37. Use of the dispersant according to any one of claims 31 to 33, wherein A is derived from (meth)acrylic acid, maleic acid, itaconic acid, or mixtures thereof.

38. Use of the dispersant according to any one of claims 31 to 33, wherein C comprises 1 to 15 propylene glycol repeating units.

39. Use of the dispersant according to any one of claims 31 to 33, wherein C comprises 1 to 10 propylene glycol repeating units.

40. Use of the dispersant according to any one of claims 31 to 33, wherein X is an amine.

41. Use of the dispersant according to claim 40, wherein X is an amine selected from polyethyleneimine, alkanolamine, or mixtures thereof.

42. Use of the dispersant according to claim 40, wherein X comprises a plurality of amine groups.

43. Use of the dispersant according to any one of claims 31 to 33, wherein the pigment comprises carbon black.

44. Use of the dispersant according to any one of claims 31 to 33, wherein the pigment is composed of carbon black.

45. Use of the dispersant according to claim 32, wherein the solvent comprises ethylene glycol.

46. ​​Use of the dispersant according to claim 32, wherein the solvent is composed of ethylene glycol.

47. Use of the dispersant according to claim 32, wherein the solvent comprises an ethylene glycol oligomer having 2 to 5 ethylene glycol repeating units.

48. Use of the dispersant according to claim 32, wherein the solvent comprises an ethylene glycol oligomer having 2 to 5 ethylene glycol repeating units.

49. Use of the dispersant according to claim 32, wherein the dispersion comprises 0.5% to 40% by weight of the pigment, 0.5% to 40% by weight of the dispersant, and 20% to 99% by weight of the solvent.

50. Use of the dispersant according to claim 31, wherein the temperature is at least 190°C.

51. Use of the dispersant according to claim 31, wherein the temperature is at least 195°C.

52. Use of the dispersant according to claim 31, wherein the temperature is at least 200°C.

53. Use of the dispersant according to claim 31, wherein at least 70% of J is ethylene oxide.

54. Use of the dispersant according to claim 31, wherein n is 20 to 100.

55. Use of the dispersant according to claim 31, wherein m is 0 to 20.

56. Use of the dispersant according to claim 31, wherein at least 70% of all repeating units is ethylene glycol.

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