专利摘要:
The present invention relates to an ink jet ink composition comprising: (a) a carbon black having the following properties: OAN> 170 ml / 100 g; and STSA in the range of 160 to 220 m2 / g; (b) at least one polymeric dispersing agent selected from polyoxyethylene / polyoxypropylene block copolymers, styrene-acrylic resins, styrene-methacrylic resins, styrene-maleic acid copolymers and styrene-maleic anhydride copolymers; (c) at least one surfactant selected from ethoxylated siloxanes, succinic acid esters and succinic acid salts; and (d) at least one polyurethane.
公开号:FR3043684A1
申请号:FR1661323
申请日:2016-11-21
公开日:2017-05-19
发明作者:Tianqi Liu；Robert J Anderson；Jinqi Xu；Jodi A Bates；Paul S Palumbo
申请人:Cabot Corp；
IPC主号:

专利说明:

INK COMPOSITIONS FOR INKJET FIELD OF THE INVENTION
[1] The present invention relates to ink jet ink compositions comprising high structure carbon blacks.
BACKGROUND [2] There is a continuing need for new carbon black materials to improve the performance of many applications. For example, in ink jet ink printing, manufacturers are looking for improved optical density of the printed product, for example when new types of papers and new printers are developed.
Detailed Description [3] An embodiment provides an ink jet ink composition comprising: (a) a carbon black having the following properties: OAN> 170 ml / 100 g; and STSA in the range of 160 to 220 m2 / g; (b) at least one dispersing agent selected from polyoxyethylene / polyoxypropylene block copolymers, styrene-acrylic resins, styrene-methacrylic resins, maleic-styrene acid copolymers, and maleic anhydride-styrene copolymers; (c) at least one surfactant selected from ethoxylated siloxanes, succinic acid esters, and succinic acid salts; and (d) at least one polyurethane.
[4] In one embodiment, the carbon blacks are tunnel blacks, furnace blacks and lamp blacks. In one embodiment, the carbon blacks described herein are furnace blacks. In one embodiment, the reactor for preparing furnace black carbon blacks is a multi-stage reactor, such as those described in US Pat. No. 7,829,057 or US Patent Application Publication No. 2007/015. As used herein, a "multi-stage reactor" is provided with two or more feedstock injection locations, one or more consecutive injection locations being positioned downstream of a first feed location. 'injection. In one embodiment, the carbon blacks described herein may be prepared as described in US Patent 9,056,994.
[5] In one embodiment, the carbon blacks are useful as pigments for example in inkjet ink compositions. In printing applications, there is a continuing need to develop pigment and ink formulations which, when deposited on a substrate such as paper, produce a printed product having a high optical density (OD). Often, a high OD is associated with larger particles as these have a lower tendency to penetrate the pores of the paper. However, larger particles generally tend toward poorer sedimentation performance, and disadvantageous for the long-term storage of inkjet ink formulations, for example in cartridges. It has been discovered that a combination of larger Oil Absorption Index (NAO) and Statistical Specific Surface Area (STSA) values (for example, within a range of BET surface values) can reach the compromise between OD and sedimentation.
[6] In one embodiment, ΙΌΑΝ is in the range of 170 to 220ml / 100g, for example 170 to 210ml / 100g, 180 to 220ml / 100g, 180 to 210ml / 100g, 190 to 220g. ml / 100 g, or 190 to 210 ml / 100 g. OAN can be determined according to ASTM-D2414. While not wishing to be bound by any theory, it is believed that the described NAO values may be an important factor in obtaining high optical density values.
[7] In one embodiment, the STSA is in the range of 160 to 220 m 2 / g, for example 160 to 210 m 2 / g, and in some applications, the STSA is in the range of 170 to 220 m 2 / g. g, from 170 to 210 m2 / g, from 180 to 220 m2 / g, or from 180 to 220 m2 / g. In one embodiment, the STSA is in the range of 130 m2 / g to 220 m2 / g, for example 130 m2 / g to 200 m2 / g. STSA values can be determined according to ASTM-D6556.
[8] Another embodiment provides a carbon black having the following properties: OAN> 170 ml / 100g; and STSA in the range of 160 to 220 m2 / g; and
An STSA / BET ratio in the range of 0.7 to 1.
[9] Another embodiment provides a carbon black having the following properties: OAN> 170 ml / 100 g; and STSA in the range of 160 to 220 m2 / g; and
BET specific surface in the range from 190 to 275 m2 / g.
[10] Without wishing to be bound by any theory, it is considered that high STSA values and a certain BET surface area range achieve good sedimentation performance, as indicated by lower sedimentation rates (%, as determined by the method of Example 6). In one embodiment, the BET surface area is in the range of 200 to 270 m 2 / g, such as a surface area in the range of 200 to 260 m 2 / g. The BET surface area can be determined according to ASTM-D6556. In one embodiment, the BET specific surface area is in the range of 150 m2 / g to 260 m2 / g, from 150 m2 / g to 220 m2 / g, from 160 m2 / g to 260 m2 / g, 160 m2 / g / g to 220 m2 / g, from 170 m2 / g to 260 m2 / g, from 170 m2 / g to 220 m2 / g, from 180 m2 / g to 260 m2 / g, or from 180 m2 / g to 220 m2 /boy Wut.
Another embodiment involves the discovery that good printing and sedimentation performance can be achieved with carbon blacks having a small internal volume, as determined by an STSA / BET ratio in the range of 0.7. 1. An STSA / BET ratio of 1 represents the limit when carbon black has virtually no internal porosity. In another embodiment, this STSA / BET ratio range may be useful for applications incorporating conductive carbon blacks.
[12] In one embodiment, the STSA / BET ratio ranges from 0.7 to 0.9, or an STSA / BET ratio is in the range of 0.7 to 0.8. In another embodiment, the STSA / BET ratio ranges from 0.8 to 1 or from 0.9 to 1. In one embodiment, an STSA / BET ratio in the range of 0.7 to 1 is obtained in one embodiment. minimizing etching during the formation of carbon black. In one embodiment, the carbon black may have the STSA and / or BET values described herein.
[13] In one embodiment, the carbon black has a compressed OAN (COAN) of at least 120ml / 100g, for example at least 125m 2 / 100g, at least 130ml / 100g, d at least 135 ml / 100 g, ie a COAN in the range of 120 to 145 ml / 100 g. COAN values can be determined according to ASTM D2414.
[14] In one embodiment, the carbon black has an OAN / COAN ratio in the range of 1.3 to 1.5, e.g., 1.3 to 1.45.
[15] Another embodiment relates to dispersions comprising the carbon blacks described herein. The dispersion may be aqueous or non-aqueous.
[16] In one embodiment, the carbon black is provided in the form having the consistency of, for example, a solid or semi-solid paste or putty (containing aqueous materials / solvents and / or or non-aqueous), a slurry in which the carbon black is supplied as an aqueous or non-aqueous dispersion, or as a loose powder which may be a free-flowing powder or a sticky powder. In one embodiment, the carbon black, whether in the form of a raw material, an oxidized black, or a modified black (e.g., having an organic group attached), may be provided under one embodiment. dry form, such as a powder, pellets, granules or a slab. In one embodiment, "dry" refers to a material substantially free of water and possibly free of volatile matter. In one embodiment, dry forms comprise a volatile material, such as about 50% or more of a volatile solvent.
[17] In one embodiment, the dispersion comprises pigments such as the carbon blacks described herein (e.g., self-dispersed carbon blacks comprising oxidized carbon blacks or carbon blacks having at least one group organic non-attached) and a liquid vehicle, for example an aqueous or non-aqueous vehicle. In one embodiment, the vehicle contains water, for example, the vehicle comprises an aqueous solution. In one embodiment, the aqueous solution contains more than 50% by weight of water, and may be for example water or mixtures of water with water-miscible solvents, such as alcohols. In one embodiment, the amount of pigment present in the dispersion may vary but is typically in an amount in the range of 0.1% to 30%, for example 1% to 25%, 1% to 20%, from 3% to 20%, from 3% to 15%, based on the total weight of the dispersion.
[18] Self-dispersed carbon blacks (e.g. oxidized or modified carbon blacks described herein) can provide useful properties when present in a dispersion. In one embodiment, the carbon black in the dispersion has a mean volume (mV) in the range of 0.07 to 0.18 μm, for example 0.1 to 0.18 μm. In another embodiment, the carbon black has a D10 in the range of 0.03 to 0.1 μm, for example 0.05 to 0.1 μm, such as a D10 in the range of 0.06 to 0.1 μm, or 0.07 to 0.1 μm. In another embodiment, the carbon black has a D50 in the range of 0.07 to 0.16 μm, for example 0.1 to 0.16 μm. In another embodiment, the carbon black has a D90 in the range of 0.15 to 0.25 μm, for example 0.18 to 0.25 μm, such as a D90 in the range of 0.15 to 0.24 μm, or a D90 in the range of 0.18 to 0.24 μm.
[19] The dispersion can be prepared using any method known in the art. For example, the modified pigment in a dry form can be combined with the liquid vehicle with agitation to produce a stable dispersion. Any equipment known in the art, such as a grinding media mill or other high shear mixing equipment may be used, and various conventional milling media may also be used. Other methods for forming the dispersion will be known to those skilled in the art.
[20] Another embodiment provides ink jet ink compositions comprising the dispersions described herein. The amount of modified pigment used in the ink jet ink composition can be varied, but is typically in an amount effective to provide the desired image quality (e.g., optical density) without adversely affecting the performance of the inkjet ink. In one embodiment, the pigment, such as the carbon blacks described herein (e.g., oxidized carbon blacks or carbon blacks having at least one non-attached organic group), is present in the jet ink composition. ink in a range of 0.1% to 20%, for example 1% to 20%, 1% to 10% or 3% to 8%, based on the total weight of the jet ink composition ink.
[21] Dispersants (surfactants and / or dispersants) may be added to further improve the colloidal stability of the composition or to modify the interaction of the ink with the printing substrate, such as printing paper , or with the ink print head. Various anionic, cationic and nonionic dispersing agents may be used in conjunction with the ink composition of the present invention, and these may be used undiluted or in the form of an aqueous solution.
[22] In one embodiment, the composition comprises at least one dispersing agent, for example at least one polymeric dispersing agent. In one embodiment, the at least one polymeric dispersing agent can be provided in the form of aqueous dispersions of polymer particles, which can be formed, for example, by dispersing polymer particles in an aqueous medium using dispersing agents or forming polymer particles by polymerization in an aqueous medium. In one embodiment, the composition comprises at least one polymeric dispersing agent, such as anionic or nonionic dispersants. The nonionic dispersing agents may be chosen from block copolymers of polyoxyethylene / polyoxypropylene. Anionic dispersing agents may be selected from styrene-acrylic resins and methacrylic resins, such as styrene-methacrylic acid copolymers, styrene-methacrylic acid-methacrylate ester copolymers, styrene-α-methylstyrene-methacrylic acid copolymers copolymers of styrene-α-methylstyrene-methacrylic acid-methacrylate ester; styrene-maleic acid copolymers; copolymers of styrene-maleic anhydride. "Anionic dispersing agents" also include salts and esters thereof. In one embodiment, the at least one dispersing agent is selected from styrene-maleic acid copolymers and styrene-maleic anhydride copolymers.
[23] In one embodiment, the composition comprises at least one non-active surfactant among ethoxylated siloxanes, succinic acid esters and succinic acid salts. Suitable succinic acid esters include alkylsulfosuccinic acid esters (eg, dialkylsulfosuccinic acid esters), sulfosuccinates, alkylsulfosuccinates and salts thereof, for example Aerosol® IB-45 / Aerosol surfactants. ® TR-70 (sulfosuccinates available from Cytec Industries).
[24] In one embodiment, the composition comprises at least one polyurethane. In one embodiment, the at least one polyurethane may be provided in the form of an aqueous dispersion of a polymer comprising urethane groups and optionally urea groups. The at least one polyurethane may incorporate hydrophilic functionality, for example to maintain a stable dispersion of the polymer in water. In one embodiment, the at least one polyurethane is ionically self-stabilized, the polymer being mainly stabilized in the dispersion by an incorporated ionic functionality, and for example an anionic functionality such as neutralized acid groups to form polyurethane dispersions. -stabilized anionically. One embodiment provides a self-stabilized polyurethane dispersion comprising the at least one polyurethane having ionic functionality, e.g. anionic functionality, incorporated by the use of acid groups having chain extending agents.
[25] The at least one polyurethane can be prepared by a multistage process in which an isocyanate prepolymer (N = C = O, NCO) is initially formed and the chain is then extended in the aqueous phase, optionally presence of a polyfunctional group. The isocyanate prepolymer may also be formed by a one or more step process. The reaction components may include diisocyanates, polyols and isocyanate-reactive compounds containing ionic groups. In one embodiment, the respective molar amounts of these components are selected on the basis of the ratio A: B, where A is the molar amount of isocyanate groups and B is the sum of the molar amount of the hydroxyl groups and the molar amount. functional groups that can react with isocyanates in an addition reaction. In one embodiment, the reaction is carried out at a temperature in the range of 20 ° C to 180 ° C, for example 50 to 150 ° C, at atmospheric pressure. The reaction times required may range from a few minutes to a few hours, for example from 1 minute to 24 hours. One skilled in the art of polyurethane chemistry will know how the reaction time is influenced by many parameters such as temperature, the concentration of monomers and the reactivity of the monomers. To accelerate the reaction of the diisocyanates, it is possible to use the usual catalysts such as dibutyltin dilaurate, tin octoate (II) or diazabicyclo [2.2.2] octane.
[26] In one embodiment, anionic polyurethane is prepared from the reaction components in a water-miscible solvent at a temperature below 100 ° C at atmospheric pressure. In one embodiment, the reaction components are selected so that the ratio A: B is in the range of 0.5: 1 to 2: 1, for example 0.8: 1 to 1.5: 1, or from 0.9: 1 to 1.2: 1. In one embodiment, the ratio A: B is in the range of 0.9: 1 to 1: 0.9, for example about 1: 1. In one embodiment, an isocyanate group-bearing prepolymer is first prepared between diisocyanates and polyols in a water-miscible solvent. These prepolymers can then see their extended chain in the presence of water by reacting the isocyanate groups with amines bearing ionic groups and more than two amino groups which are isocyanate-reactive or amines bearing ionic groups and two isocyanate-reactive amino groups. . It is possible to add enough water to form a dispersion in which water is the coherent phase. The solvent can then be removed, for example distilled.
[27] In another embodiment, an isocyanate-containing prepolymer is first prepared from diisocyanates, polyols and isocyanate-reactive compounds containing ionic groups. In one embodiment, the reaction components are selected such that the ratio A: B is greater than 1: 3, for example 1.05: 1.5. The prepolymer is first dispersed in water and is then crosslinked by reacting the isocyanate groups with amines carrying more than two amino groups which are isocyanate-reactive, or whose chain is extended using amines having more than two amino groups. isocyanate reactants. In both processes, the isocyanate groups are hydrolyzed to form amine groups that react with remaining isocyanate groups of the prepolymers to extend the chains.
[28] Suitable examples of diisocyanates for reacting with the isocyanate-reactive compound containing ionic groups (or groups that can be rendered ionic, for example by neutralization) may include those containing isocyanate groups linked to aromatic, cycloaliphatic or aliphatic . In one embodiment, the isocyanate is a cycloaliphatic or aliphatic isocyanate. Examples of suitable cycloaliphatic or aromatic diisocyanates include cyclohexane-1,3- and 1,4-diisocyanate; 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate or IPDI); bis (4-isocyanatocyclohexyl) methane; 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane; 1-isocyanato-2-isocyanatomethylcyclopentane; bis (4-isocyanatocyclohexyl) methane; 2,4'-diisocyanato-dicyclohexylmethane; bis- {4-isocyanato-3-methyl-cyclohexyl) methane, α, α, α'-α-tetramethyl-1,3-and / or -1,4-xylylene diisocyanate; 1-isocyanato-1-methyl-4 (3) -isocyanatomethylcyclohexane; and 2,4- and / or 2,6-hexahydrotoluylene diisocyanate. Suitable examples of aliphatic diisocyanates include those containing linear or branched aliphatic groups having from 4 to 12 carbon atoms, for example from 4 to 8 carbon atoms or 6 carbon atoms, which include 1,4-tetramethylene diisocyanate; 1,6-hexamethylene diisocyanate; 2,2,4-trimethyl-1,6-hexamethylene diisocyanate; and 1,12-dodecamethylene diisocyanate.
[29] Isocyanate-reactive compounds containing acidic groups, such as carboxylic acid groups, carboxylate groups, sulfonic acid groups, sulfonate groups, phosphoric acid groups and phosphonate groups, may be incorporated chemically into the polyurethane to form provide hydrophilicity and allow the polyurethane to be stably dispersed in an aqueous medium. Suitable compounds for incorporating carboxyl groups are described in US Pat. Nos. 3,479,310, 4,408,814 and 4,408,008. The acid salts are formed by neutralizing the corresponding acid groups before, during or after the formation of the isocyanate prepolymer. for example, after the formation of the isocyanate prepolymer. Neutralizing agents suitable for converting carboxylic acid groups to carboxylate salt groups are also described in the foregoing US patents. As used herein, the term "neutralizing agents" is meant to encompass all types of agents that are useful for converting carboxylic acid groups to hydrophilic carboxylate salt groups.
[30] In one embodiment, isocyanate-reactive compounds containing a carboxylic group are hydroxycarboxylic acid compounds having the formula (HO) * Z (COOH) v, wherein Z represents a linear or branched hydrocarbon radical containing 1 to 12 carbon atoms, x is 1 or 2 (eg x is 2) and y is 1 to 3, for example, y is 1 or 2 or y is 1. Examples of hydroxycarboxylic acids include citric acid In one embodiment, the hydroxycarboxylic acids are those of the formula mentioned above wherein x is 2 and y is 1. Dihydroxyalkanoic acids are described in US Pat. 054. In one embodiment, the dihydroxyalkanoic acids are α, α-dimethylolalkanoic acids having the formula Z'-C (CH 2 OH) 2 COOH, wherein Z 'is hydrogen or an alkyl group containing 1 to 8 atoms In a mode of realization, the acid is α, α-dimethylolpropionic acid (DMPA) in which Z 'is methyl in the formula above.
[31] In one embodiment, the acidic groups are incorporated in the isocyanate-reactive compound in an amount sufficient to provide an ionic group content of at least about 6, eg, at least about 7 milligrams of KOH / grams of polyurethane resin solids. In one embodiment, the upper limit for the acid group content is about 100, for example about 80, about 70, about 40 or about 35 milligrams per 1 gram of polyurethane resin solids. In one embodiment, the at least one polyurethane has an acid number in the range of from about 6 to about 100 mg KOH / g polyurethane, for example from about 6 to about 80, from about 6 to about about 70, from about 6 to about 40, or from about 6 to about 35 mg KOH / g polyurethane, or from about 24 to about 60 mg KOH / g polyurethane. This ionic group content is equivalent to an acid number for polyurethane resin solids.
[32] In one embodiment, the higher molecular weight polyols are those containing at least two hydroxy groups and having a molecular weight in the range of about 400 to about 6000, e.g. 3,000 or about 1,000 to about 2,500. Molecular weights are number average molecular weights (Mn) and are determined by end group analysis (OH number, hydroxyl analysis). Examples of such high molecular weight compounds include polyester polyols, polyether polyols, polyhydroxypolycarbonates, polyhydroxypolyacetals, polyhydroxypolyacrylates, polyhydroxypolyesteramides, polyhydroxypolyolefins, polyhydroxypolyalkylsiloxanes and polyhydroxypolythioethers. A combination of the polyols can also be used in the polyurethane. In one embodiment, polyester polyols or polyether polyols are used.
[33] Suitable examples of polyester polyols include the reaction products of polyhydric alcohols, such as dihydric alcohols to which trihydric alcohols may be added, and polybasic carboxylic acids, such as dibasic carboxylic acids. The corresponding carboxylic acid anhydrides or polycarboxylic acid esters of lower alcohols or mixtures thereof can also be used. The polycarboxylic acid component may be aliphatic, cycloaliphatic, aromatic and / or heterocyclic, and may be substituted, for example, with halogen and / or unsaturated atoms. Specific examples include succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, acid anhydride phthalic anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, tetrachlorophthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride, glutaric acid anhydride, maleic acid, maleic anhydride, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, which can be mixed with monomeric fatty acids, dimethyl terephthalates and bis-glycol terephthalate. Suitable examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, neopentyl glycol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3- propanediol, 2,2,4-trimethyl-1,3-pentanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, glycerine and trimethylolpropane. The polyesters may also contain a portion of the carboxyl end groups. It is also possible to use lactone polyesters, such as ε-caprolactone, or hydroxycarboxylic acids, such as ω-hydroxycaproic acid.
[34] Suitable examples of hydroxyl-containing polycarbonates include products obtained from the reaction of diols (such as propanediol, butanediol, or hexanediol), diethylene glycol, triethylene glycol or tetraethylene glycol with phosgene, diaryl carbonates such as diphenylcarbonate, or with cyclic carbonates such as ethylene or propylene carbonate. Polyester carbonates obtained from the abovementioned polyesters or polylactones can also be used with phosgene, diaryl carbonates or cyclic carbonates.
[35] Suitable examples of polyetherpolyols include those obtained by the reaction of starting compounds which contain reactive hydrogen atoms with alkylene oxides such as ethylene oxide, propylene oxide, oxide and the like. butylene, styrene oxide, tetrahydrofuran, epichlorohydrin or mixtures of these alkylene oxides. In one embodiment, the polyethers contain not more than about 10% by weight of ethylene oxide units; for example, polyethers can be obtained without the addition of ethylene oxide. Suitable starting compounds containing reactive hydrogen atoms include the polyhydric alcohols established to prepare the polyester polyols and, in addition, water, methanol, ethanol, 1,2,6-hexane triol, 1, 2,4-butane triol, methylmethylethane, pentaerythritol, mannitol, sorbitol, methylglycoside, sucrose, phenol, isononylphenol, resorcinol, hydroquinone, 1,1,1- or 1,1, 2-tris (hydroxylphenyl) ethane.
[36] In one embodiment, polyethers obtained by the reaction of starting compounds containing amino compounds can also be used. Examples of such polyethers as well as suitable polyhydroxypolyacetals, polyhydroxypolyacrylates, polyhydroxypolyesteramides, polyhydroxypolyamides and polyhydroxypolythioethers include those described in US Pat. No. 4,701,080.
[37] Suitable examples of polymethylacrylates containing hydroxyl groups include those prepared by addition polymerization, such as cationic, anionic and radical polymerization, and the like, for example, α-ω diols. An example of these types of diols are those prepared by "living" or "control" or chain transfer polymerization processes for the placement of a hydroxyl group at or near the termini of the polymer. US Pat. Nos. 6,248,839 and 5,990,245 describe exemplary protocols for the preparation of such terminal diols.
[38] In one embodiment, the high molecular weight polyols that are reacted to form the prepolymer are present in the polyurethanes in an amount of at least about 5% by weight, for example at least 10% by weight, based on the weight of the polyurethane. In one embodiment, the maximum amount of these polyols is about 90%, for example in the range of about 50 to 90%, or about 75 to 90% by weight, based on the weight of the polyurethane.
[39] Other optional compounds may be used to prepare the isocyanate prepolymer. These include at least difunctional isocyanate-reactive molecular weight compounds having an average molecular weight of up to about 400. Examples include dihydric and higher functionality alcohols, which have been described previously for the preparation of polyester polyols and polyether polyols. Further, in addition to the difunctional components mentioned above used in the isocyanate polyaddition reaction, it is also possible to use monofunctional portions and even small portions of trifunctional and higher functional components. For example, trimethylolpropane or 4-isocyanantomethyl-1,8-octamethylene diisocyanate may be used to provide a slight branching of the isocyanate prepolymer or polyurethane. In one embodiment, the isocyanate prepolymers are substantially linear, and this can be achieved by maintaining the average functionality of the prepolymer starting components at 2: 1 or below.
[40] Other optional compounds also include isocyanate-reactive compounds containing lateral or terminal hydrophilic ethylene oxide units. These may have a content of hydrophilic ethylene oxide units of up to about 10%, for example up to about 8%, in the range of about 1 to about 6%, or in the range of about 1 to about 6%. from about 2 to about 6% by weight, based on the weight of the polyurethane. In one embodiment, up to about 75% of the chemically incorporated and acceptable hydrophilic ethylene oxide units may be replaced by known nonionic external emulsifiers including, for example, alkaryl types (such as polyoxyethylene nonylphenyl ether). or polyoxyethylene octylphenyl ether), alkyl ether types (such as polyoxyethylene lauryl ether or polyoxyethylene oleyl ether), alkyl ester types (such as polyoxyethylene laurate, polyoxyethylene oleate or polyoxyethylene stearate) and benzylated types of polyoxyethylene phenyl ether. The isocyanate-reactive compounds for incorporation of lateral or terminal hydrophilic ethylene oxide units may contain one or two isocyanate-reactive groups, for example hydroxy groups. Examples include those described in US Patents 3,905,929, 3,920,598 and 4,190,566. Examples of hydrophilic components include monohydroxy polyethers having terminal hydrophilic chains containing ethylene oxide units. These hydrophilic components can be produced as described in the previous patents by alkoxylation of a monofunctional starting element, such as methanol or n-butanol, using ethylene oxide and optionally another alkylene oxide, such as than propylene oxide.
[41] Other optional compounds also include isocyanate-reactive compounds containing self-condensation moieties. The content of these compounds depends on the desired level of self-condensation required to provide the desired resin properties. For example, 3-amino-1-triethoxysilylpropane reacts with isocyanates through the amino group and self-condenses through the silyl group when poured into water. Non-condensable silanes with isocyanate-reactive groups can also be used in place of or in association with isocyanate-reactive compounds containing self-condensation moieties. US Patents 5,760,123 and 6,046,295 disclose methods of using such optional silane-containing compounds.
[42] Any process condition may be used for the preparation of isocyanate prepolymers, including those described in the previously mentioned patents. In one embodiment, the final isocyanate prepolymer has a free isocyanate content in the range of about 1 to about 20%, for example from about 1 to about 10% by weight, based on the weight of the solids. of prepolymer.
[43] As mentioned above, aqueous polyurethane dispersions are typically prepared by extending the isocyanate prepolymer chain. Examples of chain extenders include polyamine chain extenders which may optionally be partially or completely blocked, and include those described in US Pat. Nos. 4,269,748 and 4,829,122 which also disclose the preparation of aqueous polyurethane dispersions by mixing isocyanate prepolymers with at least partially blocked diamine or hydrazine chain extenders in the absence of water, and then adding the mixture to water. In contact with water, the blocking agent is released and the resulting unblocked polyamine reacts with the isocyanate prepolymer to form the polyurethane. Suitable examples of blocked amines and hydrazines include the reaction products of polyamines with ketones and aldehydes to form ketimines and aldimines, and the reaction of hydrazine with ketones and aldehydes to form ketazines, aldazines , ketone hydrazones and aldehyde hydrazones. The at least partially blocked polyamines contain at most one primary or secondary amino group and at least one blocked primary or secondary amino group that releases a free primary or secondary amino group in the presence of water. Suitable examples of polyamines for preparing the at least partially blocked polyamines have an average functionality (i.e., the number of amine nitrogens per molecule) of 2 to 6, for example 2 to 4 and 2 to 3. The desired functionalities can be achieved by using polyamine mixtures containing primary or secondary amino groups. The polyamines may be aromatic, aliphatic or alicyclic amines and may contain from 1 to 30, for example from 2 to 15, or from 2 to 10 carbon atoms. These polyamines may contain additional substituents provided that they are not as reactive with isocyanate groups as primary or secondary amines. These same polyamines may be partially or totally blocked polyamines. Specific examples of polyamines include 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophorone diamine or IPDA), bis- (4-aminocyclohexyl) methane, bis- (4-amino) 3-methylcyclohexyl) methane, 1,6-diaminohexane, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine. Hydrazine can also be used. The chain extender may also include an ionic group, for example an anionic group, such as a carboxylic acid group. The chain extender may be a diamine having at least one carboxylic acid group, including, for example, H 2 N -CH 2 CH 2 -NH-CH 2 CH 2 -COOH.
[44] In one embodiment, the amount of chain extender to be used depends on the number of terminal isocyanate groups in the prepolymer. In one embodiment, the ratio of terminal isocyanate groups of the prepolymer to the isocyanate-reactive groups of the chain extender is from about 1: 0.6 to about 1: 1.1, for example about 1: 0.8 to about 1: 0.98, on an equivalent basis. Any isocyanate groups whose chain is not extended by an amine will react with water, which acts as a diamine chain extender. The chain extension can take place before the addition of water to the process, or can take place by combining the isocyanate prepolymer, chain extender, water and other optional components with stirring.
[45] Other monomers and / or oligomers that will not chemically participate in the polyurethane synthesis steps may be added. The addition can be anywhere in the synthesis cycle as long as there is no interference in the polyurethane synthesis. An example of a compatible oligomer / monomer is a styrene-allylic alcohol, abbreviated SM.
[46] Polyurethane dispersions can be characterized by various techniques known in the art. For example, thermogravimetric (TGA) analyzes can be used to characterize the thermal transitions of polyurethanes. Initial Tg is a characteristic of a polyurethane. In one embodiment, the at least one polyurethane has a Tg less than about -30 ° C. Standard thermogravimetric techniques are used to determine these glass transition temperatures. In addition, molecular weight is also a characteristic of polyurethane and is usually reported as weight average molecular weight, Mw. In one embodiment, the molecular weight Mw, for the at least one polyurethane, is at least 10,000 g / mol or at least 20,000 g / mol, for example at least 30 g / mol as a molecular weight, Mw, in the range of 10,000 to 150,000 g / mol or 20,000 to 150,000 g / mol. Polyurethane binders are not limited to the Gaussian molecular weight distribution, but may have other distributions such as bimodal distributions.
[47] In one embodiment, the at least one polyurethane is provided as dispersions in water or in the aqueous solution of polyurethane preparation. In one embodiment, the particle size of the polyurethane in the dispersion is in the range of about 30 to about 100,000 nm, for example, about 30 to about 350 nm, about 40 to about 250 nm, or about 50 and about 200 nm.
[48] In one embodiment, a sufficient amount of the acidic groups of the polyurethane is neutralized so that, when combined with the optional hydrophilic ethylene oxide units and optional external emulsifiers, the resulting polyurethane will remain stably dispersed in the aqueous medium. Generally, at least about 75%, for example at least about 90% of the acidic groups are neutralized for corresponding carboxylate salt groups. Suitable neutralizing agents for converting the acid groups into salt groups before, during or after incorporation into the isocyanate prepolymers include tertiary amines, alkali metal cations and ammonia. Examples of such neutralizing agents include those described in US Pat. Nos. 4,501,852 and 4,701,480. Examples of neutralizing agents include trialkyl-substituted tertiary amines, such as triethylamine, tripropylamine, dimethylcyclohexylamine and dimethylethylamine.
[49] Neutralization can occur at any point in the process. A typical procedure involves at least some neutralization of the prepolymer, the chain of which is then extended in water in the presence of an additional neutralizing agent. Additional details of the preparation of polyurethane dispersions can be found in the previously incorporated references. As noted above, the at least one polyurethane comprises a polyurethane having ionic functionality, for example anionic functionality, which is prepared using a chain extender having a carboxylic acid group. During neutralization, it is believed that the dispersed particles of these polyurethane dispersions would have the ionic groups on the outer surface of the particles and would therefore be self-stabilizing (i.e. they do not require surfactants and / or dispersing agents added to remain dispersed).
[50] In one embodiment, the final product is a stable aqueous dispersion of polyurethane particles having a solids content of up to about 60% by weight, for example from about 15 to about 60% by weight, or from about 30 to about 45% by weight. It is always possible to dilute the dispersions to any desired minimum solids content. Suitable aqueous polyurethane dispersions are commercially available from numerous commercial sources, for example, under the trade name Luphen®, including Luphen® D 200A, Luphen® D 259 U and Luphen® D 207 E polyurethane dispersions, available from BASF.
[51] The amount of polyurethane used in the inkjet ink compositions disclosed herein can be varied but is typically in an amount effective to provide the desired image quality (e.g., durability) without adversely affecting detrimental to the performance of the inkjet ink composition, such as printability. In one embodiment, the at least one polyurethane is present in an amount in the range of about 0.1% to about 10% based on the total weight of the inkjet ink composition, e.g. from about 0.1% to about 3%, from about 0.5% to about 3%, or from about 0.5% to about 2% based on the total weight of the composition. Similarly, the relative amounts of the at least one polyurethane and the modified pigment can be modified. In one embodiment, the modified pigment and the at least one polyurethane are present in a weight ratio in the range of about 10/1 to about 1/2, e.g., about 10/1 to about 1, about 5/1 to about 2/1, about 4/1 to about 2/1, or about 3/1 to about 2/1.
[52] In one embodiment, the ink jet ink composition comprises a modified pigment comprising a pigment having at least one attached organic group and a polyurethane dispersion. Various organic groups are described in more detail below. In one embodiment, the organic group comprises at least one geminal bisphosphonic acid group, partial esters thereof, or salts thereof. In another embodiment, the organic group comprises at least one carboxylic acid group, for example a benzenecarboxylic acid group (-CeHfl-COOH group), a benzene-dicarboxylic acid group, a benzene-tricarboxylic acid group. In one embodiment, the at least one polyurethane is: i) the reaction product of a polyester polyol, such as a polybutylene adipate, and a mixture, particularly about a 1: 1 mixture of toluene diisocyanate (TDI) and hexamethylene diisocyanate (HDI), further reacted with a chain extender comprising at least two amine groups and a carboxylic acid group, for example one of the formula H 2 N -CH 2 CH 2 -NH-CH 2 CH 2 -COOH, or ii) the reaction product of a polyether polyol, such as polybutylene glycol, toluene diisocyanate (TDI) and a chain extender comprising at least two alcohol groups and a carboxylic acid group, for example one of the formula HO- CH2-CH (CH3) (COOH) -CH 2 OH. Suitable Type I polyurethane dispersions can be prepared using the method described in US Pat. No. 5,756,170, and suitable Type II polyurethane dispersions can be prepared using, for example, the methods disclosed in US Pat. 891 580. In one embodiment, the at least one polyurethane is of type I.
Modified Carbon Blacks [53] In one embodiment, the carbon blacks are modified / processed to render them self-dispersible. For example, the carbon black may be an oxidized carbon black, for example having an oxygen content greater than or equal to 3%, which may be determined by methods known in the art (e.g., elemental analysis).
[54] Generally, oxidized blacks have a surface having oxygen-containing ionic or ionizable groups such as one or more of phenols, lactones, carbonyls, carboxyls (eg, carboxylic acids), anhydrides, and the like. , ethers and quinones. The extent of oxidation of carbon black can determine the surface concentration of such ionic or ionizable groups. The carbon blacks described herein can be oxidized by various oxidizing agents known in the art. Examples of oxidizing agents for carbon blacks include oxygen gas, ozone, NO 2 (including mixed NO 2 and air), peroxides such as hydrogen peroxide, persulfates such as sodium, potassium and ammonium persulfate, hypohalites such as sodium hypochlorite, halites, halides or perhalates (such as sodium chlorite, sodium chlorate or sodium perchlorate), oxidizing acids such as nitric acid and transition metal-containing oxidants such as permanganate salts, osmium tetroxide, chromium oxides, ceric ammonium nitrates and mixtures thereof, e.g. gaseous oxidants such as oxygen and ozone. In one embodiment, the carbon blacks described herein are oxidized via ozone oxidation.
[55] In one embodiment, the carbon black is a modified carbon black having at least one attached organic group. In one embodiment, an "attached" organic 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 occur. will not remove the attached group of pigment (eg, carbon black). In another embodiment, the organic group is attached to the pigment (e.g., carbon black) if the organic group can not be removed after repeated washing (e.g., 2, 3, 4, 5 or more washes) with a solvent or solvent mixture that can dissolve the organic starting material but can not disperse the treated pigment. In yet another embodiment, "attached" refers to a bond such as a covalent bond, e.g. a pigment (e.g., carbon black) bonded or covalently bonded to the organic group.
[56] The organic group may be an aliphatic group, a cyclic organic group or an organic compound having an aliphatic moiety and a cyclic moiety. In one embodiment, the organic group is attached through a diazonium salt derived from a primary amine capable of forming, even transiently, a diazonium salt. Other attachment methods are described below. The organic group may be substituted or unsubstituted, branched or unbranched. Aliphatic groups include, for example, groups derived from alkanes, alkenes, alcohols, ethers, aldehydes, ketones, carboxylic acids and carbohydrates. Cyclic organic groups include, but are not limited to, alicyclic hydrocarbon groups (e.g., cycloalkyls, cycloalkenyls), heterocyclic hydrocarbon groups (e.g. pyrrolidinyl, pyrrolinyl, piperidinyl, morpholinyl, and the like), aryl groups (e.g., phenyl, naphthyl, anthracenyl), and heteroaryl (imidazolyl, pyrazolyl, pyridinyl, thienyl, thiazolyl, furyl, indolyl and triazolyl, such as 1,2,4-triazolyl and 1,2,3-triazolyl) .
[57] In one embodiment, the at least one attached organic group comprises at least one ionic group, one ionizable group, or mixtures of an ionic group and an ionizable group. An ionic group may be anionic or cationic and may be associated with a counter-ion of the opposite charge, including inorganic or organic counter-ions, such as Na +, K +, Li +, NH4 +, N R1 /, acetate, NO3 '. , S042 ', R'SO3', R'OSCV, OH 'or Cl', where R 'is hydrogen or an organic group, such as a substituted or unsubstituted aryl or alkyl group. An ionizable group is a group capable of forming an ionic group in the use medium. Anionic groups are negatively charged ionic groups that can be generated from groups having 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 include -COO ', -SO3', -SO3 -HPO3 '; -0P032 'or -P032', and specific examples of an anionizable group may include -COOH, -SO3H, -PO3H2, -R'SH or -ROH, where R 'is hydrogen or an organic group, such as an aryl or substituted or unsubstituted alkyl group. Also, specific examples of cationic or cationizable groups include alkyls or arylamines, which can be protonated in an acidic medium to form ammonium groups -NR'2H +, where R 'represents an organic group, such as an aryl or alkyl group substituted or unsubstituted. Organic ionic groups include those described in US Patent 5,698,016.
[58] For example, the attached group may be an organic group such as a benzenecarboxylic acid group (-C6H4-COOH group), a benzene-dicarboxylic acid group, a benzene-tricarboxylic acid group, a benzene acid group, sulfonic acid (a -C6H4-S03H group), or salts thereof. In one embodiment, a surface modification for introducing ionic or ionizable groups onto a pigment surface, such as chlorination and sulfonylation, may also be used.
[59] In one embodiment, the organic group can be attached directly (bonding to a native carbon black atom) or indirectly via an intermediate or spacer group. In one embodiment, the intermediate or spacer group is selected from substituted and unsubstituted C1-C12 alkyl, C5-C20 aryl, C8-C24 alkylaryl and aralkyl, where "alkyl" may optionally be interrupted by a heteroatom-containing group. selected from N, O and S, and "aryl" includes cyclic carbon atoms optionally substituted with a group containing a heteroatom selected from N, O and S. Typically, the attached group resides on the surface of the pigment.
[60] The organic group may be substituted or unsubstituted. In one embodiment, the organic group is substituted with at least one functional group selected from esters, amides, ethers, carboxyls, aryls, alkyls, halides, sulfonates, sulfates, phosphonates, phosphates, carboxylates, OR ", COR", CO2R ", OCOR", CN, NR "2, SO2, CO, SO3, SO3H, SO2, OS03, SO3NR", R "IMSO2, NR" (COR "), NR "CO, CONR" 2, NO 2, NO 3, CONR ", NR" CO 2, O 2 CNR ", NR" COON ", S, NR", SO 2 C 2 H 4, arylene as defined above, alkylene as defined above, wherein R ", which may be the same or different, represents an organic group such as hydrogen, aryl and alkyl, as defined herein.
[61] Further examples of representative organic groups are described in US Patents 5,513,111; 5,630,868; 5,707,432, 5,955,232; 5,922,118; 5,900,029; 5,895,522; 5,885,335; 5,851,280; 5,837,045; 5,713,988; and 5,803,959; PCT publication WO 96/18688; and PCT publication WO 96/18690.
[62] In one embodiment, the organic group contains a 5-membered heteroaromatic group comprising at least two cyclic heteroatoms, such as those described in PCT Pub. WO 2011/143 533. In one embodiment, for example, the organic group may have the formula (Ib) or (11b): R2
N-N) r -N x (Ib), X * (Mb),
For Ib, X can be O, N (Ra), or S; and R1 may be H, C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C20 cycloalkyl, C3-C20 cycloalkenyl, C1-C20 heterocycloalkyl, C1-C20 heterocycloalkenyl, aryl, heteroaryl, halo, cyano, ORb, COORb, OC (O) Rb, C (O) Rb, C (O) NRbRc, SO3Rc, NRbRc, or N + (RbRcRd) Y, where each of Ra, Rb, Rc, and Ra , independently, may be H, C1-C10 alkyl, C3-C20 cycloalkyl, C1-C20 heterocycloalkyl, aryl or heteroaryl, and Y may be an anion. In general, Y can be any suitable anion, such as chloride, bromide, iodide, sulfate, nitrate, phosphate, citrate, methanesulfonate, trifluoroacetate, acetate, malate, tosylate, tartrate, fumurate, glutamate, glucuronate, lactate , glutarate or maleate. For Mb, X is O, N (Ra), or S; and each of R1 and R2, independently, is H, C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C20 cycloalkyl, C3-C20 cycloalkenyl, C1-C20 heterocycloalkyl, heterocycloalkenyl, and the like. C1-C20, aryl, heteroaryl, halo, cyano, ORb, COORb, OC (O) Rb, C (O) Rb, C (O) NRbRc, SO3Rc, NRbRc, or l T (RbRcRd) Y, each of Ra Wherein Rb, Rc, and Rd independently are H, C1-C10 alkyl, C3-C20 cycloalkyl, C1-C20 heterocycloalkyl, aryl or heteroaryl, and Y being an anion; as long as at least one of Ri and R2 is not H.
[63] In one embodiment, the at least one organic group comprises at least one group selected from carboxylic acids, sulfonic acids, phosphonic acids (e.g., bisphosphonic acids), hydroxyls, amines and esters. , amides and salts thereof.
[64] In one embodiment, the at least one organic group comprises the formula - [R (A)] -, wherein: R is attached to the carbon black and is selected from arylene, heteroarylene and alkylene, and A is selected from carboxylic acids, sulfonic acids, phosphonic acids, hydroxyls, amines, esters, amides and salts thereof.
[65] In one embodiment, the at least one organic group comprises the formula - [R (A)] -, wherein: R is attached to the carbon black and is selected from arylene, heteroarylene and alkylene, and A is selected from hydrogen, alkyls, aryls, heteroaryls, alkylene oxides (e.g., ethylene oxide or propylene oxide), carboxylic acid esters and glycols.
[66] In one embodiment, the at least one organic group comprises the formula - [R (A)] -, wherein: R is attached to the carbon black and is selected from arylene, heteroarylene and alkylene, and A is selected from polymers.
[67] Arylene, heteroarylene and alkylene may be unsubstituted or substituted, for example, with one or more of the functional groups listed above. Examples of arylenes include phenylene, naphthylene and biphenylene, and examples of heteroarylenes include phenylene, naphthylene and biphenylene having a cyclic carbon substituted with one or more oxygen or nitrogen atoms. In one embodiment, arylene is C5-C20 arylene. The heteroarylenes may be arylene as defined herein wherein one or more cyclic carbon atoms are replaced by a heteroatom, for example N, O and S. The heteroatom may be linked to other groups in addition to being a heteroatom. cyclic atom. Examples of arylenes include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, and examples of heteroarylenes include pyridinyl, imidazolyl, pyrazolyl, thienyl, thiazolyl, furyl, triazinyl, and the like. , indolyl, benzothiadiazolyl and benzothiazolyl. Alkylenes can be branched or unbranched. The alkylene may be C1-C12 alkylene, such as methylene, ethylene, propylene or butylene, optionally interrupted by a heteroatom.
[68] In one embodiment, R is substituted R and includes arylene, heteroarylene and alkylene substituted with at least one spacer group that is bonded to A. In one embodiment, a substituted R includes R'- Sp, wherein R is selected from arylene, heteroarylene, and alkylene, as defined above, and Sp is a spacer group selected from the functional groups listed above capable of binding both R 'and A. In another embodiment, Sp is selected from -CO2-, -O2C-, -CO-, -OSO2-, -SO3-, -SO2-, -SO2C2H4-O-, -SO2C2H4S-, -SO2C2H4NR-, -O-, -S-, -NR "-, -NR" CO-, -CON R "-, -NR" COr, -O2CNR "-, -NR" CONR "-, -N (COR") CO-, -CON ( COR ") -, -NR" COCH (CH2CO2R ") - and cyclic imides therefrom, -NR" COCH2CH (CO2R) - and cyclic imides therefrom, -CH (CH2CO2R ") CONR" - and cyclic imides in from, -CH (CO 2 R ") CH 2 CONR" and cyclic imides therefrom, (including phthalimide and maleimides thereof), sulfonamide groups (including -SO2NR "- and -NR" SOr) groups, arylene groups and alkylene groups. R'1, which may be the same or different, is defined as above, or is hydrogen or an organic group such as a substituted or unsubstituted aryl or alkyl group, for example C5-C20 aryl groups and substituted and unsubstituted C 1 -C 6 alkyl groups. In one embodiment, Sp is selected from -CO2-, -O2C-, -O-, -NR "-, -NR" CO-, -CONR'1-, -SO2NR "-, -SO2CH2CH2NR" -, - S02CH2CH2O-, or -SO2CH2CH2S-, where R "is defined as above, for example selected from H and C1-C6 alkyl groups.
[69] In another embodiment, Sp is derived from a compound having a reactive group selected from a carboxylic acid or an ester, an acid chloride, a sulfonyl chloride, an acyl azide, an isocyanate, a ketone, an aldehyde, an anhydride, an amide, an imide, an imine, an α, β-unsaturated ketone, an aldehyde or a sulphone, an alkyl halide, an epoxide, an alkyl sulphonate or a sulphate such as (2-sulfatoethyl) sulfone group, an amine, hydrazine, alcohol, thiol, hydrazide, oxime, triazene, carbanion, aromatic compound, salts or derivatives thereof, or any combination thereof them. Examples of such compounds include amino-functionalized aromatic compounds, such as 4-aminobenzylamine (4-ABA), 3-aminobenzylamine (3-ABA), 2-aminobenzylamine (2-ABA), 2-aminophenylethylamine, 4-aminophenyl (2-sulfatoethyl) -sulfone, (APSES), p-aminobenzoic acid (PABA), 4-aminophthalic acid (4-APA) and 5-aminobenzene-1,2-acid, 3-tricarboxylic.
[70] In one embodiment, the at least one organic group is capable of binding to calcium (e.g., having defined calcium index values), including the organic groups described in PCT Pub. WO 2007/053 564. For example, the organic group comprises at least one geminal bisphosphonic acid group, partial esters thereof or salts thereof, for example a group of formula -CQ (P03H2) 2, partial esters thereof or salts thereof, wherein Q is attached to the geminal position and may be H, R, OR, SR or NR2, where R ", which may be the same or different, is defined as above, or may be H, a saturated or unsaturated, branched or unbranched C1-C18 alkyl group, a saturated or unsaturated, branched or unbranched C1-C18 alkyl group, an aralkyl group, an alkaryl group or a group In addition, U.S. Patents 5,672,198, 5,922,118, 6,042,643 and 6,641,656 disclose modified pigments having various attached groups, including phosphonic acid groups.
[71] Other organic groups capable of binding calcium include: at least one hydroxamic acid group or a salt thereof (e.g., at least one group having the formula -N (OH) -CO- or a salt of it); at least one heteroaryl group having at least one OH group or a salt thereof (for example a nitrogen-containing heteroaryl group, such as a pyridinyl group or a quinolinyl group, and the organic group is a hydroxy pyridinyl group or a quinolinyl hydroxy group, wherein the hydroxy group is in a position on the heteroaryl group such that it is geometrically close to the heteroatom, as ortho to the heteroatom, or a heteroaryl having two OH groups in the ortho position one relative to each other); at least one phosphonic acid group or a salt thereof and at least one second ionic, tonable or basic group (a basic group is a Lewis base, such as an OH group or an amino group which may be geminal to the phosphonic acid group) ); at least one heteroaryl group having at least one carboxylic acid group or a salt thereof (for example, at least two or three carboxylic acid groups, such as at least two carboxylic acid groups which are ortho or meta-one, report to the other); an aryl group having at least one nitroso group and at least one OH group (for example, ortho to each other), or a salt thereof; an azoarene group having at least two OH groups, at least two NH 2 groups, or at least one OH group and at least one NH 2 group (for example, at least two OH groups, at least two NH 2 groups or at least one OH group and at least one NH 2 group) and has the formula Ar 1 N = N-Ar 2, wherein 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 (for example, the OH and / or NH 2 groups are located in positions ortho to the azo group). Other groups are described in WO 2007/053564.
[72] In one embodiment, the attached organic group comprises a polymer. In one embodiment, the polymer comprises at least one nonionic group. Examples include alkylene oxide groups of about 1 to about 12 carbon atoms and polyols, such as -CH 2 -CH 2 -O-, -CH (CH 3) -CH 2 -O-, a CH 2 -CH (CH 3) -O-, -CH 2 CH 2 CH 2 -0-, or combinations thereof. These nonionic groups may further comprise at least one ionic or ionizable group as described herein.
[73] The attached polymers, which may be homopolymers or copolymers, may also be derived from monomers selected from acrylic acid and methacrylic acid, acrylate esters, methacrylate esters, acrylamides and methacrylamides , acrylonitriles, cyanoacrylate esters, maleate and fumarate diesters, virtylpyridines, vinyl N-alkylpyrroles, vinyl acetate, vinyl oxazoles, vinyl thiazoles, vinyl pyrimidines, vinyl imidazoles, ketones vinyl ethers, vinyl ethers and styrenes. Vinyl ethers include those which can be prepared by cationic polymerization, such as those having the general structure CH 2 = CH (OR), wherein R is an alkyl, aralkyl, alkaryl or aryl group or is a group comprising one or more oxide groups alkylene. Vinyl ketones include those in which the β-carbon atom of the alkyl group does not carry a hydrogen atom, such as vinyl ketones in which both β-carbons bear a C 1 -C 4 alkyl group, a halogen, etc. or a vinyl phenyl ketone wherein the phenyl group may be substituted with 1 to 5 C 1 -C 6 alkyl groups and / or halogen atoms. Styrenes include those in which the vinyl group is substituted by a C1-C6 alkyl group, such as the α-carbon atom, and / or those in which the phenyl group is substituted with 1 to 5 substituents including a C1-alkyl group. -C 5, alkenyl (including vinyl) or alkynyl (including acetylenyl), phenyl, haloalkyl and functional groups such as C 1 -C 6 alkoxy, halogen, nitro, carboxy, sulfonate , C 1 -C 6 alkoxycarbinyl, hydroxy (including those protected by a C 1 -C 6 acyl group) and cyano groups. Specific examples include methyl acrylate (MA), methyl methacrylate (MMA), ethyl acrylate (EA), ethyl methacrylate (EMA), butyl acrylate (BA) 2-ethylhexyl acrylate (EHA), acrylonitrile (AN), methacrylonitrile, styrene and derivatives thereof.
[74] The polymer can be prepared by cationic or anionic polymerization of one or more polymerizable monomers. For example, polyvinyl ethers can be prepared by cationic polymerization of monomers, such as those having the general structure CH 2 = CH (OR), wherein R is alkyl, aralkyl, alkaryl or aryl or is a group comprising one or several alkylene oxides. Other cationically or anionically polymerizable monomers may also be included.
[75] The polymer can also be prepared by polycondensation techniques. For example, the polymer may be a polyester or polyurethane having a functional group as described above. Examples of suitable methods for polyurethanes include a solution process which comprises the preparation of an isocyanate-terminated prepolymer in a low-boiling solvent (such as acetone) unreactive with an isocyanate group. of a hydrophilic group such as a diamine or a polyol therein, performing a phase change by dilution with water, and distilling off a solvent to obtain a polyurethane dispersion. Another suitable method comprises preparing an isocyanate group-terminated prepolymer having an introduced hydrophilic group, a dispersion in water, and an amine chain extension.
[76] Polyurethanes can be prepared by the prepolymer process, and a polyhydroxy compound having a low molecular weight can then be used at that time. Examples of the low molecular weight polyhydroxy compound include polyester diols such as glycol and alkylene oxide, trihydric alcohol such as glycerine, trimethylolethane and trimethylolpropane.
[77] In one embodiment, the polymer has a low acid number. In one embodiment, the polymer may be an acid group-containing polymer having an acid number of less than or equal to about 200, as less than or equal to about 150, less than or equal to about 110, less than or equal to about 100 In another embodiment, the acid value of the polymer is greater than or equal to about 30. Thus, the polymer may be an acid group-containing polymer having an acid number of about 30 to about 200, as from about 30 to about 110, from about 110 to about 150, or from about 150 to about 200.
[78] In one embodiment, the carbon black is modified with at least one organic group by a diazonium treatment, as detailed, for example, in the following patents: U.S. Patents 5,554,739; 5,630,868; 5,672,198; 5,707,432; 5,851,280; 5,885,335; 5,895,522; 5,900,029; 5,922,118; 6,042,643, 6,534,569; 6,398,858 and 6,494,943 (high shear conditions), 6,372,820; 6,368,239; 6,350,519; 6,337,358; 6,103,380; 7,173,078; 7,056,962; 6,942,724; 6,929,889; 6,911,073; 6,478,863; 6,472,471; and WO 2011/143 533. In one embodiment, the linkage is provided by a diazonium reaction wherein the at least one organic group has a diazonium salt substituent. In another embodiment, the direct bond may be formed using the diazonium and stable free radical processes described, for example, in US Patents 6,068,688; 6,337,358; 6,368,239; 551393; 6,852,158, who use the. 08. reacting at least one radical with at least one particle, wherein a radical is generated from the interaction of at least one transition metal compound with at least one organohalogen compound in the presence of one or more particles capable of capturing radicals, and the like. In yet another embodiment, the at least one carbon black can be modified (e.g., to attach functional groups) using the methods of US Pat. Nos. 5,837,045, 6,660,075 and WO 2009/048,564 (US Pat. with organic compounds containing a double bond CC or a triple bond activated by at least one substituent) or publications US 2004/017 1725, 6 664 312, 6 831194 (reaction with an anhydride component), US 6,936,097, the US publications 2001/003 6994, 2003/0 101 901 (reaction with organic groups having a group -N = NN-), Canadian Patent 2,351,162, European Patent 1,394,221 and PCT Publications WO 01/51566 (reaction between at least one electrophile and at least one nucleophile), WO 04/63 289, WO 2010/141 071 (reaction with H2N-AY, where A is a heteroatom) and WO 99/23174.
[79] In one embodiment, the carbon black is attached to the organic group through an OC- bond, the -OC- bond forming one or more of phenolate, naphtholate, ester and ether linkages where the carbon atom of the -OC- bond, and substituents thereof, are not native to the carbon black before modification. In one embodiment, carbon black is attached to the organic group via phenolate or naphtholate linkages wherein the aromatic groups of phenolate or naphtholate are native to carbon black. In one embodiment, these linkages can be obtained via a Mitsunobu reaction, as described in PCT / US 2013/39381, wherein a first reagent comprising a protonated nucleophile having a pKa <15 is reacted with a second reagent comprising an organic group containing a hydroxyl. The carbon black may be attached to the first or second reagent.
[80] Other methods for preparing modified pigments, including those having attached polymeric groups, have also been described, for example, in PCT publication WO 01/51566, which discloses methods of making a modified pigment by reacting a first chemical group and a second chemical group to form a pigment having a third chemical group attached. PCT Publication WO 2007/053 563 discloses modified dyes having at least one attached polymeric group comprising a polymer having at least one functional group having defined calcium index values. Specific embodiments of the organic groups are described, including organic groups comprising at least one geminal bisphosphonic acid group, partial esters thereof, or salts thereof.
[81] Other methods for the preparation of polymer modified pigment products have also been developed. For example, US Patents 7,056,962, 6,478,863, 6,432,194, 6,336,965, US 2006/0189717, and PCT Publication WO 2008/091653, describe methods for attaching polymers to pigments by means of use of a diazonium salt. US Patents 7,173,078, 6,916,367, 6,911,073, 6,723,783, 6,699,319, 6,472,471 and 6,110,994, describe methods for preparing a polymer modified pigment by reacting a polymer and a pigment having a reactive group attached. Modified pigments having attached polymer groups have also been disclosed in US 2008/0177003, using a polymer in the form of a melt.
[82] Polymer-modified pigments can also be prepared by polymerizing monomers from a pigment. For example, polymer-modified pigments can be prepared by free-radical polymerization, controlled polymerization processes such as atom transfer radical polymerization (ATRP), stable radical polymerization (SFR), additive chain transfer polymerization, and the like. reversible fragmentation (RAFT), ionic polymerizations (anionic or cationic), such as group transfer polymerization (GTP), and condensation polymerization. Similarly, polymer-modified pigments can be prepared using the methods described, for example, in US Pat. Nos. 6,372,820, 6,350,519; 551393; or 6,368,239 or in PCT Publications 2006/086599 and 2006/086660. For modified pigments comprising the polymer-coated pigment, these modified pigments can be prepared using any method known in the art, such as those described in US Pat. Nos. 5,085,698, 5,998,501, 6,074,467, 6,852,777 and US Pat. and 7,074,843, and in international patent applications WO 2004/111140, WO2005 / 061087 and WO 2006/064193.
[83] Surface grafting of carbon black with polymers and prepolymers is described by N. Tsubokawa, in Prog. Polym. Sci., 17, 417, 1992, and J.
Polym. Sci. Polym. Chem. Ed. Vol. 20, 1943-1946 (1982). Polymers having hydroxyl or amino terminal groups may be grafted onto surface carboxyl groups of carbon black, as described by N. Tsubokawa in Reactive &amp; Functional Polymers 27 (1995), 75-81.
[84] Modified pigments having at least one attached polymeric group may further comprise a second organic group, which is different from the polymeric groups described above. These include, for example, the groups described in US Pat. No. 5,630,868. For example, the modified pigment may further comprise a second organic group attached which may comprise at least one ionic group, at least one ionizable group, or a mixture of these. In one embodiment, the ionic or ionizable group is an anionic or anionizable group. Any of the ionic or ionizable groups, for example the anionic or anionizable groups, described above for the pigment of the modified pigment of the present invention may be the second organic group. In addition, the second organic group may be a polymer group comprising a polymer. Any of the polymer groups described above may also be used as the second organic group attached.
[85] The amount of attached organic groups can be varied, depending on the desired use of the modified carbon black and the fixed group type. For example, the total amount of organic group may be from about 0.01 to about 10 micromoles of groups / m 2 of pigment surface, as measured by nitrogen adsorption (BET method), including about 0.5 at about 5 micromoles / m2, from about 1 to about 3 micromoles / m2, or from about 2 to about 2.5 micromoles / m2. Additional attached organic groups, which differ from those described for the various embodiments of the present invention, may also be present.
Dispersions and additives for ink ink [86] The ink jet ink composition can be formed with a minimum of additional components (additives and / or co-solvents) and processing steps. However, suitable additives may also be incorporated into these inkjet ink compositions to impart a number of desired properties while maintaining the stability of the compositions. For example, surfactants may be added to further improve the colloidal stability of the composition. Other additives are well known in the art and include humectants, biocides and fungicides, pH control agents, drying accelerators, penetrants, and the like. The amount of additive varies depending on various factors, but they are generally present in an amount in the range of 0% to 40%, for example 0.1% to 40%, based on the weight of the composition of the composition. inkjet ink. In addition, the inkjet ink compositions of the present invention may further incorporate dyes to alter color balance and adjust optical density. These dyes include food dyes, dyes FD &amp; C, acid dyes, direct dyes, reactive dyes, phthalocyanine sulphonic acid derivatives, including copper phthalocyanine derivatives, sodium salts, ammonium salts, potassium salts and salts of lithium. Additional details on the dispersions and inkjet ink compositions are provided below.
[87] In one embodiment, the ink jet ink composition further comprises a liquid vehicle, for example an aqueous or non-aqueous vehicle. In one embodiment, the liquid vehicle is an aqueous liquid vehicle, for example, the vehicle contains water as an aqueous solution. In one embodiment, the aqueous solution contains water alone or mixtures of water with water-miscible solvents such as alcohols or any solvent, co-solvent and / or water-miscible humectant. described here. In one embodiment, the inkjet ink composition contains more than 40% by weight or more than 50% by weight of water.
[88] It is also possible to add humectants and water-soluble organic compounds to the ink jet ink composition of the present invention, for example to prevent clogging of the nozzle as well as to ensure penetration of paper (penetrating agents), improved drying (drying accelerators), and anti-blistering properties. Specific examples of humectants and other water-soluble compounds that can be used include low molecular weight glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and dipropylene glycol; diols containing about 2 to about 40 carbon atoms, such as 1,3-pentanediol, 1,4-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 2,6-hexanediol, neopentyl glycol (2,2-dimethyl-1,3-propanediol), 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2,6-hexanetriol, poly (ethylene-co-propylene) glycol, and the like, and their reaction products with alkylene oxides, including ethylene oxides including ethylene oxide and propylene oxide; triol derivatives containing from about 3 to 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, as well as 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-propynl-ol (propargyl) alcohol 2-butene-1-ol, 3-butene-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; cellulosolves 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; urea and urea derivatives; internal salts such as betaine, and the like; thio (sulfur) derivatives of the aforementioned 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, propylcarboxylethanolamine, propylcarboxypropanolamine, and the like; reaction products of the abovementioned materials with alkylene oxides; and mixtures thereof. Additional examples include saccharides such as maltitol, sorbitol, gluconolactone and maltose; polyhydric alcohols such as trimethylolpropane and trimethylolethane; N-methyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidinone; sulfoxide derivatives containing about 2 to about 40 carbon atoms, including dialkyl sulfides (symmetrical and asymmetric sulfoxides) such as dimethylsulfoxide, methylethylsulfoxide, alkylphenylsulfoxides, and the like; and sulfone derivatives (symmetrical and asymmetric sulfones) containing from 2 to 40 carbon atoms, such as dimethylsulfone, methylethylsulfone, sulfolane (tetramethylenesulfone, cyclic sulfone), dialkylsulfones, alkylphenylsulfones, dimethylsulfone, methylethylsulfone, diethylsulfone, ethylpropylsulfone, methylphenylsulfone, methylsulfolane, dimethylsulfolane, and the like. Such materials can be used alone or in combination.
[89] Biocides and / or fungicides may also be added to the inkjet ink composition of the present invention. Biocides are important in preventing bacterial growth, since bacteria are often larger than ink nozzles and can cause clogging and other printing problems. Examples of useful biocides include, but are not limited to, benzoate or sorbate salts and isothiazolinones.
[90] In one embodiment, the ink jet ink composition comprises a co-solvent. In one embodiment, the cosolvent is soluble or miscible with water at concentrations of at least 10% by weight, and is also chemically stable under aqueous hydrolysis conditions (eg, reaction with water). water under thermal aging conditions including, for example, hydrolysis of esters and lactones). In one embodiment, the cosolvent has a dielectric constant lower than that of water, such as a dielectric constant in the range of about 10 to about 78 to 20 ° C. Examples of suitable cosolvents include low molecular weight glycols (such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and the like). 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-propynl-ol alcohol (propargyl), 2-butene-1-ol, 3-butene-2-ol, 3-butyn-2-ol and cyclopropanol); diols containing from about 2 to about 40 carbon atoms (such as 1,3-pentanediol, 1,4-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,6-hexanediol , 1,5-hexanediol, 2,6-hexanediol, neopentyl glycol (2,2-dimethyl-1,3-propanediol), 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol , 1,6-hexanediol, 1,2,6-hexanetriol and poly (ethylene-co-propylene) glycol, as well as their reaction products with alkylene oxides, including ethylene oxides, and 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 oxide, propylene oxide, and mixtures thereof); polyols (such as pentaerythritol); amides (such as dimethylformaldehyde and dimethylacetamide); ketones or keto-alcohols (such as acetone and diacetone alcohol); ethers (such as tetrahydrofuran and dioxane); lactams (such as 2-pyrrolidone, N-methyl-2-pyrrolidone and ε-caprolactam); urea or urea derivatives (such as di- (2-hydroxyethyl) -5,5-dimethylhydantoin (dantacol) and 1,3-dimethyl-2-imidazolidinone); internal salts (such as betaine); and hydroxyamide derivatives (such as acetylethanolamine, acetylpropanolamine, propylcarboxylethanolamine and propylcarboxypropanolamine, as well as their reaction products with alkylene oxides). Additional examples include saccharides (such as maltitol, sorbitol, gluconolactone, and maltose); sulfoxide derivatives (symmetrical and asymmetric) containing from about 2 to about 40 carbon atoms (such as dimethylsulfoxide, methylethylsulfoxide and alkylphenylsulfoxides); and sulfone derivatives (symmetrical or asymmetric) containing from about 2 to about 40 carbon atoms (such as dimethylsulfone, methylethylsulfone, sulfolane (tetramethylenesulfone, cyclic sulfone), dialkylsulfones, alkylphenylsulfones, dimethylsulfone, methylethylsulfone, diethylsulfone, ethylpropylsulfone, methylphenylsulfone, methylsulfolane and dimethylsulfolane). These co-solvents can be used alone or in combination.
[91] The amount of cosolvent may vary depending on various factors, including co-solvent properties (solubility and / or dielectric constant), the type of pigment modified and the desired performance of the ink composition for resulting inkjet. The optional cosolvent may be used in amounts of less than or equal to about 40% by weight based on the total weight of the inkjet ink composition, including less than or equal to about 30% and less than or equal to about 30% by weight. equal to about 20%. In addition, when used, the amount of the optional cosolvent is greater than or equal to about 2% by weight based on the total weight of the inkjet ink composition, including greater than or equal to about 5% and greater than or equal to about 10% by weight.
[92] Additives for controlling or regulating the pH of the ink jet ink composition (pH control agents) can also be used. Examples of suitable pH regulators include various amines such as diethanolamine and triethanolamine, as well as various hydroxide reagents. A hydroxide reagent is any reagent that includes an OH- ion, such as a salt having a hydroxide counterion. Examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, and tetramethylammonium hydroxide. Other hydroxide salts, as well as mixtures of hydroxide reactants, can also be used. In addition, other alkaline reagents can also be used which generate OH- ions in an aqueous medium. Examples include carbonates such as sodium carbonate, bicarbonates such as sodium bicarbonate, and alkoxides such as sodium methoxide and sodium ethoxide. Buffers can also be added.
[93] In one embodiment, the ink jet ink composition comprises the at least one polyurethane in an amount in the range of 0.1 to 1% by weight, the carbon black described in an amount in the range of 2 to 3% by weight, the composition of which has a pH in the range of 9 to 10. The carbon black may be modified with a benzenecarboxylic acid group (-C6H4-COOH group), a benzene acid group -dicarboxylic acid, a benzene-tricarboxylic acid group, a benzenesulfonic acid (a -C6H4-SO3H group), or salts thereof. The surfactants may be chosen from Silwet® L-7602 surfactant, an ethylenateoxide siloxane (Momentive Performance Materials) and Aerosol® IB-45 / Aerosol® TR-70 surfactants (sulfosuccinates available from Cytec Industries). Dispersing agents can be chosen from Joncryl® 683 styrene acrylic (BASF), SMA® 1440 styrene-maleic anhydride copolymer (Cray Valley) and Pluronic® F38 ethylene oxide / propylene oxide block copolymer ( BASF). The composition may comprise at least one co-solvent selected from trimethylolpropane and / or other co-solvents described herein. The polyurethane may be selected from anionically self-stabilizing polyurethane based on poly (propylene glycol), having an acid number in the range of 24 to 60 mg KOH / g polyurethane and a molecular weight (Mw) in the range of 20,000 to 150,000 g / mole, for example Luphen® polyurethanes (BASF).
EXAMPLES
Comparisons of Polymer Additives: Examples 1 to 4 and Comparative Examples 1 to 3 [94] The effect of various types of polymer additives on optical density (OD) was examined in Examples 1 to 4. Different inks were prepared according to the formula in Table 1, which lists the components in percent by weight.
Table 1
[95] Surfactant S7602 is Silwet® L-7602 surfactant, a siloxane ethoxylateoxide marketed by Momentive Performance Materials. The L259 durability additive is an aqueous dispersion of Luphen® D 259 U polyurethane available from BASF. The carbon black 1 is derived from a base carbon black prepared according to US Pat. No. 9,388,300 (Example G), having an OAN of 179 ml / 100 g and an STSA of 194 m2 / g-carbon black. The base material was then functionalized with 5-aminobenzene-1,2,3-tricarboxylic acid to form the self-dispersed carbon black 1, as described in US Pat. No. 7,972,428.
[96] The polymeric additives for Examples 1-4 are respectively: J819 = Joncryl® 819 styrene acrylic resin (BASF); JE684 = Joncryl® Acrylic Styrene Resin ECO 684 (BASF); SMA-EF40 = Flake SMA® EF-40, a styrene-maleic anhydride copolymer (Cray Valley); and PF38 = Pluronic® F38 block copolymer (polyoxyethylene / polyoxypropylene) (BASF). The inks of Examples 1 to 4 were compared to a control sample containing no polymeric additive and to three comparative examples: NaOH neutralized polyacrylic acid (Aldrich); Polyvinylpyrrolidone, molecular weight 10,000 (Scientific Polymer Products); and Z3700 = Zetasperse® pigment dispersion additive (Air Products).
[97] Ink extracts (75 μι) were obtained with a # 16 wire wound laboratory rod on Staples copy paper and Xerox 4200 paper. Optical density (OD) was analyzed using a X-rite 530 spectrophotometer with the following settings: illumination at D65, Standard Observer 2 degrees, DIN density standard, white base set to Abs, and no filter. For each paper, the OD value of Table 2 was indicated as an average of at least 5 measurements taken at different locations of the print images.
Table 2
[98] A performance of OD that is 0.05 units lower than that of the control was considered undesirable. Better or equal performance can be observed for the inks of Examples 1 to 4 compared with those of Comparative Examples 1 to 3. From Table 2, it can be seen that the inks containing the polymeric additive types of the invention were more effective at improving OD than others. Without wishing to be bound by any theory, certain polymer additives (such as those of Comparative Examples 1 to 3) may add too much stability to the pigment, which may lead to decreased performance of the OD.
Comparisons of Carbon Black: Example 5 and Comparative Examples 4 to 6 [99] In the following examples, inks containing carbon blacks of different OAN and STSA values are compared. Duplicates were made and OD values were obtained as described for Examples 1-4. Table 3 lists the ink formulations and the relative amounts of the ink components (% by weight), as well as the values. of resulting OD. For all inks, the solvent was 2-pyrrolidone, the surfactant was Silwet® L-7602 (Momentive Performance Materials) surfactant, the dispersant was SMA® EF-40 (Cray Valley) flake, and Durability additive was the aqueous dispersion of Luphen® D 259 U polyurethane (BASF).
[100] The carbon black 1 is as described in Examples 1 to 4. The carbon black 2 is a self-dispersed carbon black functionalized with 5-aminobenzene-1,2,3-tricarboxylic acid. in the same way as carbon black 1. Carbon black 3 is a self-dispersed pigment functionalized with 4-aminobenzoic acid. Carbon black 4 is a self-dispersed carbon black functionalized with bisphosphonate groups, and can be prepared as described in US Pat. No. 8,858,695.
Table 3
[101] Table 3 shows that carbon black containing ink satisfying OAN parameters> 170 ml / 100 g and STSA in the range of 160 to 220 m 2 / g (i.e. carbon black 1) provides the best performance values of OD versus inks containing those outside these parameters. we
Comparison of Surfactants: Examples 5 and 6 and Comparative Examples 7 to 12 [102] These examples demonstrate the effect of surfactant on OD values. Table 4 below lists ink formulations containing different types of surfactants in which the relative amounts of the ink components are provided in% by weight. For all inks, the solvent was 2-pyrrolidone, the dispersing agent was SMA® EF-40 flake (Cray Valley), the durability additive was Luphen® D 259 U aqueous polyurethane dispersion (BASF) and the pigment was carbon black 1 as described in Examples 1 to 5.
Table 4
[103] The ink of Example 5 is described above in the carbon black comparisons. For the rest of the inks, the various surfactants are as follows. IB45 / TR70 = Aerosol® IB-45 and TR70 surfactants, both of which are sulfosuccinate surfactants (Cytec); S465 and S440 = surfynol® surfactants 465 and 440, which are ethoxylated acetylenic diols (Air Products); octyl-2-pyrr. n-octyl-2-pyrrolidone; T 15-S-5 and T 15-S-7 = Tergitol ™ 15-S-5 and 15-S-7 surfactants, which are secondary alcohol ethoxyates (Dow); and D607 = Dynol® 607 surfactant, which is an ethoxylated acetylenic diol (Air Products). The surfactant was added in amounts to target a surface tension range of 32 to 39 dynes / cm, as measured by a Kruss K-11 digital tensiometer using a Du Nouy platinum ring. The actual amounts added reflect the different efficiencies of the surfactants in lowering the surface tension of the aqueous inks.
[104] An OD of more than 1.3 and 1.10 was considered acceptable on Staples and Xerox papers, respectively. From Table 4 it can be seen that inks containing the ethoxylated siloxane (Example 5) and the sulfosuccinate surfactant (Example 6) produced the best OD values when compared to other types. of surfactants, as shown in Comparative Examples 7 to 12.
[105] The use of the terms "one" and "one" and "the" must be interpreted to cover both the singular and the plural unless otherwise clearly indicated or contradicted by the context. The terms "including", "having", "including" and "containing" are to be interpreted as open terms (ie, "including, but not limited to") unless otherwise indicated. The indication of ranges of values of the present invention is merely intended to serve as an abbreviated process for individually referring to each separate value within the range, unless otherwise indicated herein, and each separate value is incorporated in the description as if it were indicated individually. All of the methods described herein can be carried out in any suitable order unless otherwise indicated in this document or otherwise clearly contradicted by the context. The use of any example and all examples, or example language element (eg "such as") provided in this document, is intended merely to further illuminate the invention and does not constitute a limitation of the invention, unless otherwise indicated.

权利要求:
Claims (49)
[1" id="c-fr-0001]
An ink jet ink composition comprising: (a) a carbon black having the following properties: OAN> 170 ml / 100 g; and STSA in the range of 160 to 220 m2 / g; (b) at least one dispersing agent selected from polyoxyethylene / polyoxypropylene block copolymers, styrene-acrylic resins, styrene-methacrylic resins, maleic-styrene acid copolymers, and maleic anhydride-styrene copolymers; (c) at least one surfactant selected from ethoxylated siloxanes, succinic acid esters, and succinic acid salts; and (d) at least one polyurethane.
[2" id="c-fr-0002]
The composition of claim 1, wherein an STSA / BET specific surface area of the carbon black is in the range of 0.7 to 1.
[3" id="c-fr-0003]
The composition of claim 1 or 2, wherein ΓΟΑΝ carbon black is in the range of 170 to 220 ml / 100 g.
[4" id="c-fr-0004]
The composition of claim 1 or 2, wherein the OAN of the carbon black is in the range of 170 to 210 ml / 100 g.
[5" id="c-fr-0005]
The composition of any one of claims 1 to 4, wherein the carbon black has a BET surface area in the range of 190 to 275 m2 / g.
[6" id="c-fr-0006]
The composition of any one of claims 1 to 5, wherein the BET specific surface area is in the range of 200 to 270 m2 / g.
[7" id="c-fr-0007]
The composition of any one of claims 1 to 5, wherein the BET specific surface area is in the range of 200 to 260 m2 / g.
[8" id="c-fr-0008]
The composition of any one of claims 1 to 7, wherein the carbon black has a COAN of at least 120 ml / 100 g.
[9" id="c-fr-0009]
The composition of any one of claims 1 to 7, wherein the carbon black has a COAN of at least 130 ml / 100 g.
[10" id="c-fr-0010]
The composition of any one of claims 1 to 9, wherein the carbon black has an OAN / COAN ratio in the range of 1.3 to 1.5.
[11" id="c-fr-0011]
11. Composition according to any one of claims 1 to 10, wherein the carbon black is a furnace black.
[12" id="c-fr-0012]
The composition of any one of claims 1 to 11, wherein the at least one polymeric dispersant is selected from styrene-methacrylic resins.
[13" id="c-fr-0013]
The composition of claim 12, wherein the styrene-methacrylic resins are selected from styrene-methacrylic acid copolymers, styrene-methacrylic acid-methacrylate ester copolymers, styrene-α-methylstyrene-methacrylic acid copolymers, and copolymers of styrene-α-methylstyrene-methacrylic acid-acid methacrylate ester, and salts thereof.
[14" id="c-fr-0014]
The composition according to any one of claims 1 to 11, wherein the at least one polymeric dispersing agent is selected from styrene-maleic acid copolymers and styrene-maleic anhydride copolymers.
[15" id="c-fr-0015]
The composition of any one of claims 1 to 11, wherein the at least one polymeric dispersing agent is selected from polyoxyethylene / polyoxypropylene block copolymers.
[16" id="c-fr-0016]
The composition of any one of claims 1 to 11, wherein the at least one polymeric dispersing agent is selected from styrene-acrylic resins.
[17" id="c-fr-0017]
17. A composition according to any one of claims 1 to 16, wherein the at least one active agent is selected from succinic acid esters and salts thereof.
[18" id="c-fr-0018]
18. The composition of claim 17, wherein the succinic acid esters are selected from alkylsulfosuccinic acid esters, alkylsulfosuccinates, and salts thereof.
[19" id="c-fr-0019]
19. A composition according to any one of claims 1 to 18, wherein the carbon black is modified with at least one attached organic group.
[20" id="c-fr-0020]
20. The composition of claim 19, wherein the at least one attached organic group is selected from carboxylic acids, sulfonic acids, phosphonic acids, hydroxyls, amines, esters, amides and salts thereof .
[21" id="c-fr-0021]
21. The composition of claim 19, wherein the at least one attached organic group is selected from carboxylic acids.
[22" id="c-fr-0022]
22. The composition of claim 19, wherein the at least one attached organic group is selected from benzenecarboxylic acid, benzenedicarboxylic acid, benzenetricarboxylic acid, benzenesulfonic acid and salts. of these.
[23" id="c-fr-0023]
23. Composition according to any one of claims 1 to 22, wherein the carbon black is an oxidized carbon black.
[24" id="c-fr-0024]
24. The composition of claim 23, wherein the oxidized carbon black has a surface comprising at least one group selected from phenols, lactones, carbonyls, carboxyls, anhydrides, ethers and quinones.
[25" id="c-fr-0025]
25. A composition according to any one of claims 1 to 24, wherein the carbon black has an average volume in the range of 0.1 to 0.18 μm.
[26" id="c-fr-0026]
26. A composition according to any one of claims 1 to 25, wherein the carbon black has a 010 in the range of 0.05 to 0.1 μm.
[27" id="c-fr-0027]
27. A composition according to any one of claims 1 to 25, wherein the carbon black has a D10 in the range of 0.06 to 0.1 μm.
[28" id="c-fr-0028]
28. A composition according to any one of claims 1 to 25, wherein the carbon black has a D10 in the range of 0.07 to 0.1 μm.
[29" id="c-fr-0029]
29. A composition according to any one of claims 1 to 28, wherein the carbon black has a D50 in the range of 0.1 to 0.16 μm.
[30" id="c-fr-0030]
30. A composition according to any one of claims 1 to 29, wherein the carbon black has a D90 in the range of 0.18 to 0.25 μm.
[31" id="c-fr-0031]
31. A composition according to any one of claims 1 to 29, wherein the carbon black has a D90 in the range of 0.15 to 0.24 μm.
[32" id="c-fr-0032]
32. A composition according to any one of claims 1 to 29, wherein the carbon black has a D90 in the range of 0.18 to 0.24 μm.
[33" id="c-fr-0033]
33. Composition according to one of claims 1 to 32, wherein the at least one polyurethane is prepared from a polyester polyol, a polyether polyol, a polyhydroxypolycarbonate, a polyhydroxypolyacetal, a polyhydroxypolyacrylate, a polyhydroxypolyesteramide, a polyhydroxypolyolefin, a polyhydroxypolydialkylsiloxane or a polyhydroxypolythioether.
[34" id="c-fr-0034]
34. Composition according to any one of claims 1 to 32, wherein the at least one polyurethane is prepared from a polyester polyol or a polyether polyol.
[35" id="c-fr-0035]
The composition of any one of claims 1 to 34, wherein the at least one polyurethane is present in an amount in the range of about 0.1 to about 10.0% by weight based on the total weight of the composition.
[36" id="c-fr-0036]
The composition of any one of claims 1 to 34, wherein the at least one polyurethane is present in an amount in the range of about 0.1 to about 3% by weight based on the total weight of the composition .
[37" id="c-fr-0037]
The composition of any one of claims 1 to 34, wherein the at least one polyurethane is present in an amount in the range of about 0.5 to about 3% by weight based on the total weight of the composition .
[38" id="c-fr-0038]
The composition of any one of claims 1 to 34, wherein the at least one polyurethane is present in an amount in the range of about 0.5 to about 2% by weight based on the total weight of the composition .
[39" id="c-fr-0039]
39. A composition according to any one of claims 1 to 38, wherein the carbon black and the at least one polyurethane are present in a weight ratio in the range of about 10/1 to about 1/2.
[40" id="c-fr-0040]
40. A composition according to any one of claims 1 to 38, wherein the carbon black and the at least one polyurethane are present in a weight ratio in the range of about 10/1 to about 1/1.
[41" id="c-fr-0041]
41. The composition of any one of claims 1 to 38, wherein the carbon black and the at least one polyurethane are present in a weight ratio in the range of about 5: 1 to about 2: 1.
[42" id="c-fr-0042]
42. The composition of any one of claims 1 to 38, wherein the carbon black and the at least one polyurethane are present in a weight ratio in the range of about 4: 1 to about 2: 1.
[43" id="c-fr-0043]
43. A composition according to any one of claims 1 to 38, wherein the carbon black and the at least one polyurethane are present in a weight ratio of about 3/1 to about 2/1.
[44" id="c-fr-0044]
44. A composition according to any one of claims 1 to 43, wherein the at least one polyurethane is anionically self-stabilizing and has: i) an acid number in the range of about 6 to about 70 mg KOH / polyurethane; and ii) a weight percent of polyol in the range of about 50% to about 90%.
[45" id="c-fr-0045]
45. The composition of any one of claims 1 to 44, wherein the at least one polyurethane has a molecular weight, Mw, in the range of about 10,000 to about 150,000 g / mol.
[46" id="c-fr-0046]
46. The composition of any one of claims 1 to 44, wherein the at least one polyurethane has a molecular weight, Mw, in the range of about 20,000 to about 150,000 g / mol.
[47" id="c-fr-0047]
47. Composition according to any one of claims 1 to 46, in which the at least one polyurethane is a polyurethane based on polypropylene glycol.
[48" id="c-fr-0048]
48. The composition of any one of claims 1 to 47, wherein the ink jet ink composition further comprises a liquid vehicle.
[49" id="c-fr-0049]
49. The composition of any one of claims 1 to 47, wherein the inkjet ink composition further comprises an aqueous liquid vehicle.

类似技术:

---

公开号 | 公开日 | 专利标题

---

FR2993261B1|2019-06-21|HIGHLY STRUCTURED CARBON BLACK

---

FR3043684A1|2017-05-19|

---

US9056991B2|2015-06-16|Polymeric pigment systems and methods

---

EP2201072B1|2018-11-14|Self-dispersed pigments and methods for making and using the same

---

WO2008055244A2|2008-05-08|Modified pigments and methods for making and using the same

---

FR3003259A1|2014-09-19|HEART-ENVELOPE POLYMERIC MATERIALS

---

FR3058151A1|2018-05-04|POLYMERS FOR INKS FOR INK JET PRINTERS

---

US8888264B2|2014-11-18|Method of preparing dispersions

---

JP5187679B2|2013-04-24|Hydrophilic resin-dispersed carbon black and method for producing aqueous dispersion thereof

---

FR3066496A1|2018-11-23|INK COMPOSITION FOR INK JET

---

FR3070689A1|2019-03-08|INK COMPOSITIONS FOR INK JET

同族专利:

---

公开号 | 公开日

---

JP6869241B2|2021-05-12|

---

GB201809921D0|2018-08-01|

---

WO2017087635A1|2017-05-26|

---

US10106696B2|2018-10-23|

---

JP2020172645A|2020-10-22|

---

IT201600116293A1|2018-05-17|

---

CN108431142A|2018-08-21|

---

DE112016005281T5|2018-08-09|

---

JP2018538390A|2018-12-27|

---

US20170137650A1|2017-05-18|

---

GB2559938A|2018-08-22|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

DE1495745C3|1963-09-19|1978-06-01|Bayer Ag, 5090 Leverkusen|Process for the production of aqueous, emulsifier-free polyurethane latices|

---

US3412054A|1966-10-31|1968-11-19|Union Carbide Corp|Water-dilutable polyurethanes|

---

DE2314513C3|1973-03-23|1980-08-28|Bayer Ag, 5090 Leverkusen|Process for the preparation of aqueous polyurethane dispersions|

---

DE2314512C3|1973-03-23|1980-10-09|Bayer Ag, 5090 Leverkusen|Thermoplastic, nonionic, water dispersible substantially linear polyurethane elastomers|

---

US4108814A|1974-09-28|1978-08-22|Bayer Aktiengesellschaft|Aqueous polyurethane dispersions from solvent-free prepolymers using sulfonate diols|

---

DE2555534C3|1975-12-10|1981-01-08|Bayer Ag, 5090 Leverkusen|Polyurethanes dispersible in water|

---

DE2725589A1|1977-06-07|1978-12-21|Bayer Ag|PROCESS FOR THE PRODUCTION OF Aqueous POLYURETHANE DISPERSIONS AND SOLUTIONS|

---

DE2811148A1|1978-03-15|1979-09-20|Bayer Ag|PROCESS FOR THE PRODUCTION OF Aqueous POLYURETHANE DISPERSIONS AND SOLUTIONS|

---

US4408008A|1981-07-24|1983-10-04|Mobay Chemical Corporation|Stable, colloidal, aqueous dispersions of cross-linked urea-urethane polymers and their method of production|

---

US4501852A|1983-06-20|1985-02-26|Mobay Chemical Corporation|Stable, aqueous dispersions of polyurethane-ureas|

---

US4701480A|1985-09-23|1987-10-20|Mobay Corporation|Stable, aqueous dispersions of polyurethane-ureas|

---

US5085698A|1990-04-11|1992-02-04|E. I. Du Pont De Nemours And Company|Aqueous pigmented inks for ink jet printers|

---

DE4308079A1|1993-03-13|1994-09-15|Basf Ag|Use of aqueous polyurethane dispersions as a composite film adhesive|

---

DE4314111A1|1993-04-29|1994-11-03|Goldschmidt Ag Th|alpha, omega-polymethacrylate diols, process for their preparation and their use for the production of polymers, in particular polyurethanes and polyesters|

---

US5554686A|1993-08-20|1996-09-10|Minnesota Mining And Manufacturing Company|Room temperature curable silane-terminated polyurethane dispersions|

---

DE4413562A1|1994-04-19|1995-10-26|Herberts Gmbh|Aqueous dispersion of polyurethanes containing siloxane bridges, their production and use in coating compositions|

---

IL116376A|1994-12-15|2001-03-19|Cabot Corp|Aqueous ink jet ink compositions containing modified carbon products|

---

IL116379A|1994-12-15|2003-12-10|Cabot Corp|Aqueous inks and coatings containing modified carbon products|

---

IL116378A|1994-12-15|2003-05-29|Cabot Corp|Non-aqueous coating or ink composition with improved optical properties containing modified carbon product and method of preparation of the composition|

---

US5571311A|1994-12-15|1996-11-05|Cabot Corporation|Ink jet ink formulations containing carbon black products|

---

IL154538A|1994-12-15|2009-12-24|Cabot Corp|Reaction of carbon black with diazonium salts, resultant carbon black products and their uses|

---

US5554739A|1994-12-15|1996-09-10|Cabot Corporation|Process for preparing carbon materials with diazonium salts and resultant carbon products|

---

DE19514583A1|1995-04-20|1997-02-13|Basf Ag|Polyurethane-coated packaging films|

---

US6110994A|1996-06-14|2000-08-29|Cabot Corporation|Polymeric products containing modified carbon products and methods of making and using the same|

---

US5698016A|1996-06-14|1997-12-16|Cabot Corporation|Compositions of modified carbon products and amphiphilic ions and methods of using the same|

---

US5707432A|1996-06-14|1998-01-13|Cabot Corporation|Modified carbon products and inks and coatings containing modified carbon products|

---

JP4697757B2|1996-06-14|2011-06-08|キャボットコーポレイション|Modified colored pigments and ink jet inks containing them|

---

US5837045A|1996-06-17|1998-11-17|Cabot Corporation|Colored pigment and aqueous compositions containing same|

---

CN1222584C|1996-09-13|2005-10-12|大日本油墨化学工业株式会社|Method for producing ink jet ink|

---

US5998501A|1997-02-07|1999-12-07|Kao Corporation|Process for producing aqueous ink for inkjet printing|

---

DE19705470A1|1997-02-13|1998-08-27|Goldschmidt Ag Th|Polymethacrylic acid-polyalkylene oxide block copolymers, process for their preparation and their use as dispersants|

---

US5955232A|1997-07-22|1999-09-21|Cabot Corporation|Toners containing positively chargeable modified pigments|

---

US5895522A|1997-08-12|1999-04-20|Cabot Corporation|Modified carbon products with leaving groups and inks and coatings containing modified carbon products|

---

JP2001521972A|1997-10-31|2001-11-13|キャボットコーポレイション|Particles having bonded stable free radicals, polymerized modified particles, and method for producing the same|

---

US6068688A|1997-11-12|2000-05-30|Cabot Corporation|Particle having an attached stable free radical and methods of making the same|

---

US6472471B2|1997-12-16|2002-10-29|Cabot Corporation|Polymeric products containing modified carbon products and methods of making and using the same|

---

DE69901944T3|1998-04-03|2009-05-14|Cabot Corp., Boston|MODIFIED PIGMENTS WITH IMPROVED DISPERSING PROPERTIES|

---

US6368239B1|1998-06-03|2002-04-09|Cabot Corporation|Methods of making a particle having an attached stable free radical|

---

US6103380A|1998-06-03|2000-08-15|Cabot Corporation|Particle having an attached halide group and methods of making the same|

---

WO2000039226A1|1998-12-28|2000-07-06|Kao Corporation|Water-based ink for ink-jet recording|

---

DE60002564T2|1999-03-05|2004-04-08|Cabot Corp., Boston|METHOD FOR PRODUCING COLORED PIGMENTS|

---

JP5344780B2|1999-05-06|2013-11-20|キャボットコーポレイション|Polymerized modified particles and method for producing the same|

---

CN101255284B|1999-10-28|2013-09-11|卡伯特公司|Ink jet inks, inks, and other compositions containing colored pigments|

---

WO2001051566A1|2000-01-07|2001-07-19|Cabot Corporation|Polymers and other groups attached to pigments and subsequent reactions|

---

AT442398T|2000-01-25|2009-09-15|Cabot Corp|POLYMERS CONTAINING MODIFIED PIGMENTS AND ITS MANUFACTURE|

---

US6660075B2|2000-03-16|2003-12-09|Degussa Ag|Carbon black|

---

DE10012784A1|2000-03-16|2001-09-27|Degussa|soot|

---

CA2351162A1|2000-06-22|2001-12-22|Degussa Ag|Printed media coating|

---

AU7308501A|2000-07-06|2002-01-21|Cabot Corp|Modified pigment products, dispersions thereof, and compositions comprising the same|

---

US20040171725A1|2001-06-01|2004-09-02|Richardson Benny R.|Substrates with modified carbon surfaces in composites|

---

JP4277490B2|2001-08-27|2009-06-10|セイコーエプソン株式会社|Microencapsulated pigment and method for producing the same, aqueous dispersion, and inkjet recording ink|

---

US6758891B2|2001-10-09|2004-07-06|Degussa Ag|Carbon-containing material|

---

US6641656B2|2001-10-17|2003-11-04|Cabot Corporation|Dispersions comprising modified pigments|

---

AU2003226020A1|2002-03-27|2003-10-13|Cabot Corporation|Method for attachment of one or more organic groups onto a particle|

---

US7173078B2|2002-04-12|2007-02-06|Cabot Corporation|Process for preparing modified pigments|

---

US6699319B2|2002-05-06|2004-03-02|Cabot Corporation|Process for preparing modified pigments|

---

US6833026B2|2002-05-10|2004-12-21|Cabot Corporation|Modified pigments and process for preparing modified pigments|

---

DE10238149A1|2002-08-15|2004-02-26|Degussa Ag|Modified carbon material, used as filler, UV stabilizer or conductive pigment in e.g. rubber, plastics, ink, toner, coating, paper, bitumen, concrete or tire mix, or as reducing agent in metallurgy, is modified with diarylazo compound|

---

US6831194B2|2002-08-28|2004-12-14|Columbian Chemicals Company|Surface modification of carbonaceous materials by introduction of gamma keto carboxyl containing functional groups|

---

US20040138503A1|2003-01-13|2004-07-15|Bollepalli Srinivas|Surface modification of carbonaceous materials with TRI substituted aminoalkyl substituents|

---

US6942724B2|2003-04-16|2005-09-13|Cabot Corporation|Modified organic colorants and dispersions, and methods for their preparation|

---

US6936097B2|2003-04-16|2005-08-30|Cabot Corporation|Modified organic colorants and dispersions, and methods for their preparation|

---

US20050090599A1|2003-06-06|2005-04-28|Spinelli Harry J.|Aqueous ionically stabilized dispersions|

---

GB0329601D0|2003-12-20|2004-01-28|Avecia Ltd|Process|

---

JP2005255959A|2004-03-15|2005-09-22|Seiko Epson Corp|Ink composition, and ink cartridge, recording device, recording method and recorded matter|

---

US7829057B2|2004-05-04|2010-11-09|Cabot Corporation|Carbon black and multi-stage process for making same|

---

US20070104636A1|2004-05-04|2007-05-10|Kutsovsky Yakov E|Carbon black and multi-stage process for making same|

---

GB0427747D0|2004-12-18|2005-01-19|Avecia Ltd|Process|

---

JP2008530306A|2005-02-11|2008-08-07|カーネギー メロン ユニバーシティ|Modified carbon particles|

---

US20060211791A1|2005-02-11|2006-09-21|Burns Elizabeth G|Inkjet inks comprising modified pigments having attached polymeric groups|

---

KR101298330B1|2005-08-31|2013-08-20|캐보트 코포레이션|Process for preparing modified pigments|

---

AU2006308951A1|2005-10-31|2007-05-10|Cabot Corporation|Modified colorants and inkjet ink compositions comprising modified colorants|

---

GB0620089D0|2006-10-11|2006-11-22|Fujifilm Imaging Colorants Ltd|Process, composition and ink|

---

EP2111430A2|2007-01-24|2009-10-28|Cabot Corporation|Process to form modified pigments|

---

US20090095200A1|2007-10-10|2009-04-16|Belmont James A|Modified colored pigments|

---

JP2010018741A|2008-07-11|2010-01-28|Dainippon Toryo Co Ltd|Aqueous ink composition|

---

US8580024B2|2009-06-04|2013-11-12|Cabot Corporation|Inkjet ink compositions comprising modified pigments|

---

WO2011143533A2|2010-05-14|2011-11-17|Cabot Corporation|Modified pigments|

---

EP2598587B1|2010-07-30|2018-12-19|Cabot Corporation|Polymeric pigment systems and methods|

---

JP5950080B2|2012-01-13|2016-07-13|セイコーエプソン株式会社|Ink for inkjet recording|

---

CN104619788B|2012-07-13|2018-04-03|卡博特公司|Super-normal structure black|

---

BR112015021129A2|2013-03-05|2017-07-18|Cabot Corp|aqueous pigment dispersions|

---

JP6293119B2|2013-03-28|2018-03-14|日本化薬株式会社|Ink composition, ink set, ink jet recording method, and colored body|

---

JP2016141733A|2015-02-02|2016-08-08|富士ゼロックス株式会社|Aqueous ink, recording apparatus, and recording method|CN110317496A|2018-03-28|2019-10-11|精工爱普生株式会社|Aqueous jet composition|

---

CN110964349B|2018-09-30|2021-08-17|山东欧铂新材料有限公司|Oxidation modified carbon black and preparation method thereof|

---

CN110616015A|2019-09-17|2019-12-27|湖州市南浔联谊喷涂厂|Acid rain resistant steel structure anticorrosive paint and preparation method thereof|

---

CN111117372A|2019-12-28|2020-05-08|东来涂料技术（上海）股份有限公司|Reactive color paste and preparation method thereof|

法律状态:
2017-10-18| PLFP| Fee payment|Year of fee payment: 2 |

---

2018-10-17| PLFP| Fee payment|Year of fee payment: 3 |

---

2019-10-29| PLFP| Fee payment|Year of fee payment: 4 |

---

2020-10-23| PLFP| Fee payment|Year of fee payment: 5 |

---

2021-10-25| PLFP| Fee payment|Year of fee payment: 6 |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201562256905P| true| 2015-11-18|2015-11-18|

---