US20050020730A1 - Inkjet ink - Google Patents

Inkjet ink Download PDF

Info

Publication number
US20050020730A1
US20050020730A1 US10/843,133 US84313304A US2005020730A1 US 20050020730 A1 US20050020730 A1 US 20050020730A1 US 84313304 A US84313304 A US 84313304A US 2005020730 A1 US2005020730 A1 US 2005020730A1
Authority
US
United States
Prior art keywords
polymer
soluble
inkjet ink
ink
ink set
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/843,133
Inventor
Jose Valentini
Dean Fake
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
E I du Pont de Nemours and Co
Original Assignee
E I du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US47179803P priority Critical
Application filed by E I du Pont de Nemours and Co filed Critical E I du Pont de Nemours and Co
Priority to US10/843,133 priority patent/US20050020730A1/en
Assigned to E. I. DU PONT DE NEMOURS AND COMPANY reassignment E. I. DU PONT DE NEMOURS AND COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FAKE, DEAN M., VALENTINI, JOSE E.
Publication of US20050020730A1 publication Critical patent/US20050020730A1/en
Application status is Abandoned legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • C09D11/32Inkjet printing inks characterised by colouring agents
    • C09D11/324Inkjet printing inks characterised by colouring agents containing carbon black
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • C09D11/40Ink-sets specially adapted for multi-colour inkjet printing

Abstract

This invention pertains to an ink for inkjet printing, in particular to an aqueous ink comprising a self-dispersing pigment colorant and certain soluble polymers which enhance print quality without compromising jetting performance.

Description

    CROSS-REFERENCE TO RELATED APPLICATION
  • This application claims priority under 35 U.S.C. §119 from U.S. Provisional Application Ser. No. 60/471,798 (filed May 19, 2003), which is incorporated by reference herein as if fully set forth.
  • BACKGROUND OF THE INVENTION
  • This invention pertains to an inkjet ink, in particular to an aqueous inkjet ink comprising self-dispersible pigment and certain soluble polymers to improve print quality.
  • Inkjet printing is a non-impact printing process in which droplets of ink are deposited on print media, such as paper, to form the desired image. The droplets are ejected from a printhead in response to electrical signals generated by a microprocessor.
  • Both dyes and pigments have been used as colorants for inkjet inks. While dyes are typically easier to formulate compared to pigments, they tend to fade quickly and are more prone to rub off. Inks comprising pigments dispersed in aqueous media are advantageously superior to inks using water-soluble dyes in water-fastness and light-fastness of printed images.
  • Pigments suitable for aqueous inkjet inks are in general well-known in the art. Traditionally, pigments were stabilized by dispersing agents, such as polymeric dispersants or surfactants, to produce a stable dispersion of the pigment in the vehicle. More recently though, so-called “self-dispersible” or “self-dispersing” pigments (hereafter “SDP”) have been developed. As the name would imply, SDPs are dispersible in water without dispersants.
  • SDPs are often advantageous over traditional dispersant stabilized pigments from the standpoint of greater stability and lower viscosity at the same pigment loading. This can provide greater formulation latitude in final ink.
  • Prints made with SDP ink, however, tend to be susceptible to rub off and smear. EP-A-1114851 demonstrates (Comparative Example 2 in Table 3) the problem of poor smear resistance in an SDP inkjet ink (therein referred to as rubbing/scratching resistance). There is taught the combination of SDP and dispersant stabilized pigment to improve image properties. EP-A-1158030 likewise demonstrates (Example 9 in Table 1) the problem of poor smear resistance with SDP inkjet ink (therein is referred to as highlighter resistance).
  • Addition of polymer binder to improve print properties is often proposed. Ink with SDP and polymer are disclosed, for example, in U.S. Pat. No. 5,571,311, U.S. Pat. No. 5,630,868, U.S. Pat. No. 5,672,198, U.S. Pat. No. 6,057,384, U.S. Pat. No. 6,103,780, U.S. Pat. No. 6,329,446, US20020147252, EP-A-1304364, EP-A-1146090 and EP-A-0894835.
  • All of the above-identified publications are incorporated by reference herein for all purposes as if fully set forth.
  • SDP ink, like any inkjet ink, must exhibit good jetting performance {jetability}. Favorable jetability characteristics include stable drop volume and direction, and little or no kogation. Additives to the ink formulation to improve print quality should not come at the expense of jetability.
  • A need still exists for improved inkjet ink formulations of SDPs that provide good print quality and good jetability.
  • SUMMARY OF THE INVENTION
  • It has now been found that the addition of a soluble structured polymer binder to an aqueous ink comprising SDP colorant allows improved fastness of the printed image without compromising jetting performance. In contrast, addition of soluble unstructured (random) polymer is detrimental to jetting performance.
  • Further, it has been found that the jetting performance of an ink comprising a SDP and a dispersed polymer binder can be improved by addition of a soluble structured polymer.
  • In accordance with these findings, the present invention pertains to an aqueous inkjet ink composition comprising:
      • (a) an SDP colorant;
      • (b) an aqueous vehicle; and
      • (c) a soluble structured polymer.
  • The ink jet ink may optionally contain other additives and adjuvants well-known to those of ordinary skill in the relevant art. One such optional additive is a dispersed polymer binder. Preferably, the SDP colorant is a carbon black SDP colorant.
  • The present invention also pertains to an inkjet ink set for color printing, comprising at least three differently colored inks (such as CMY), and preferably at least four differently colored inks (such as CMYK), wherein at least one of the inks is an aqueous inkjet ink as set forth above.
  • The present invention still further pertains to a method for inkjet printing comprising the step of jetting an ink onto a substrate, wherein the ink is the aqueous inkjet ink as set forth above.
  • The present invention still further pertains to a method for inkjet printing comprising the step of jetting an inkjet ink set onto a substrate, wherein the inkjet ink set is as set forth above.
  • These and other features and advantages of the present invention will be more readily understood by those of ordinary skill in the art from a reading of the following detailed description. It is to be appreciated that certain features of the invention which are, for clarity, described above and below in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. In addition, references in the singular may also include the plural (for example, “a” and “an” may refer to one, or one or more) unless the context specifically states otherwise.
  • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • According to the present invention, there is provided an inkjet ink comprising an SDP colorant, an aqueous vehicle and a certain soluble polymer. The prescribed soluble polymer is a “structured polymer” which, when present at the proper levels in the ink formulation, enhance print quality without sacrificing jetting performance. The ink may optionally comprise a dispersed polymer binder to further enhance print quality. Also, the ink may optionally contain other additives and adjuvants well-known in the relevant art.
  • Herein, reference to enhanced or improved “print quality” generally means some aspect of fastness (resistance to color removal) is increased, including, for example, rub fastness (finger rub), water fastness (water drop) and smear fastness (higher pen stroke)
  • Colorant
  • The colorant in the inks of present invention comprises a pigment. By definition, pigments do not form (to a significant degree) a solution in the aqueous vehicle and must be dispersed.
  • The pigment colorants of the present invention are more specifically self-dispersing pigments. SDPs are surface modified with dispersibility imparting groups to allow stable dispersion without separate dispersant. For dispersion in an aqueous vehicle, the surface modification involves addition of hydrophilic groups and most typically ionizable hydrophilic groups. See, for example, U.S. Pat. No. 5,554,739, U.S. Pat. No. 5,571,311, U.S. Pat. No. 5,609,671, U.S. Pat. No. 5,672,198, U.S. Pat. No. 5,698,016, U.S. Pat. No. 5,707,432, U.S. Pat. No. 5,718,746, U.S. Pat. No. 5,747,562, U.S. Pat. No. 5,749,950, U.S. Pat. No. 5,803,959, U.S. Pat. No. 5,837,045, U.S. Pat. No. 5,846,307, U.S. Pat. No. 5,851,280, U.S. Pat. No. 5,861,447, U.S. Pat. No. 5,885,335, U.S. Pat. No. 5,895,522, U.S. Pat. No. 5,922,118, U.S. Pat. No. 5,928,419, U.S. Pat. No. 5,976,233, U.S. Pat. No. 6,057,384, U.S. Pat. No. 6,099,632, U.S. Pat. No. 6,123,759, U.S. Pat. No. 6,153,001, U.S. Pat. No. 6,221,141, U.S. Pat. No. 6,221,142, U.S. Pat. No. 6,221,143, U.S. Pat. No. 6,277,183, U.S. Pat. No. 6,281,267, U.S. Pat. No. 6,329,446, U.S. Pat. No. 6,332,919, U.S. Pat. No. 6,375,317, US2001/0035110, EP-A-1086997, EP-A-1114851, EP-A-1158030, EP-A-1167471, EP-A-1122286, WO01/10963, WO01/25340 and WO01/94476, the disclosures of which are incorporated by reference herein for all purposes as if fully set forth.
  • The SDP colorant can be further defined by its ionic character. Anionic SDP yields, in an aqueous medium, particles with anionic surface charge. Conversely, cationic SDP yields, in an aqueous medium, particles with cationic surface charge. Particle surface charge can be imparted, for example, by attaching groups with anionic or cationic moieties to the particle surface. The SDP of the present invention are preferably, although not necessarily, anionic.
  • Anionic moieties attached to the anionic SDP surface can be any suitable anionic moiety but are preferably (I) or (II):
    —CO2Z  (I)
    —SO3Z  (II)
    wherein Z is selected from the group consisting of conjugate acids of organic bases; alkali metal ions; “onium” ions such as ammonium, phosphonium and sulfonium ions; and substituted “onium” ions such as tetraalkylammonium, tetraalkyl phosphonium and trialkyl sulfonium ions; or any other suitable cationic counterion. Useful anionic moieties also include phosphates and phosphonates. Most preferred are type I (“carboxylate”) anionic moieties.
  • Also preferred is a degree of functionalization wherein the density of anionic groups is less than about 3.5 μmoles per square meter of pigment surface (3.5 μmol/m2), and more preferably less than about 3.0 μmol/m2. Degrees of functionaliztion of less than about 1.8 μmol/m2, and even less than about 1.5 μmol/m2, are also suitable and may be preferred for certain specific types of SDPs. As used above and otherwise herein, “degree of functionalization” refers to the amount of hydrophilic groups present on the surface of the SDP per unit surface area, measured in accordance with the method described further herein.
  • Carboxylated anionic SDP species include those described, for example, in previously incorporated U.S. Pat. No. 5,571,311, U.S. Pat. No. 5,609,671 and WO01/94476; and, sulfonated (type II) SDPs include those described, for example, in previously incorporated U.S. Pat. No. 5,571,331, U.S. Pat. No. 5,928,419 and EP-A-1,146,090.
  • It is desirable to use small colorant particles for maximum color strength and good jetting. The particle size may generally be in the range of from about 0.005 micron to about 15 microns, is typically in the range of from about 0.005 to about 1 micron, is preferably from about 0.005 to about 0.5 micron, and is more preferably in the range of from about 0.01 to about 0.3 micron.
  • The levels of SDPs employed in the instant inks are those levels that are typically needed to impart the desired optical density to the printed image. Typically, SDP levels are in the range of about 0.01 to about 10% by weight of the ink.
  • The SDPs may be black, such as those based on carbon black, or may be colored pigments such as those based on PB 15:3 and 15:4 cyan, PR 122 and 123 magenta, and PY 128 and 74 yellow.
  • The SDPs may be prepared by grafting a functional group or a molecule containing a functional group onto the surface of the pigment, or by physical treatment (such as vacuum plasma), or by chemical treatment (for example, oxidation with ozone, hypochlorous acid or the like). A single type or a plurality of types of hydrophilic functional groups may be bonded to one pigment particle. The type and degree of functionalization may be properly determined by taking into consideration, for example, dispersion stability in ink, color density, and drying properties at the front end of an ink jet head. Further details may be found by reference to the numerous publications incorporated above.
  • In one preferred embodiment, the hydrophilic functional group(s) on the SDP are primarily carboxyl groups, or a combination of carboxyl and hydroxyl groups; even more preferably the hydrophilic functional groups on the SDP are directly attached and are primarily carboxyl groups, or a combination of carboxyl and hydroxyl.
  • Preferred pigments in which the hydrophilic functional group(s) are directly attached may be produced, for example, by a method described in previously incorporated WO01/94476. Carbon black treated by the method described in this publication has a high surface-active hydrogen content that is neutralized with base to provide very stable dispersions in water. Application of this method to colored pigments is also possible.
  • In a preferred embodiment, the colorant in the ink of the present invention comprises only SDP. If other pigment colorant is present as dispersant-stabilized pigment, the dispersant is preferably a structured polymer such as those referenced herein. Furthermore, when dispersant-stabilized pigment with structured polymer is present, the structured dispersant and the soluble structured polymer for the SDP are preferably the same polymer.
  • Aqueous Vehicle “Aqueous vehicle” refers to water or a mixture of water and at least one water-soluble organic solvent (co-solvent). Selection of a suitable mixture depends on requirements of the specific application, such as desired surface tension and viscosity, the selected colorant, drying time of the ink, and the type of substrate onto which the ink will be printed. Representative examples of water-soluble organic solvents that may be selected are disclosed in U.S. Pat. No. 5,085,698 (the disclosure of which is incorporated by reference herein for all purposes as if fully set forth).
  • If a mixture of water and a water-soluble solvent is used, the aqueous vehicle typically will contain about 30% to about 95% water with the balance (i.e., about 70% to about 5%) being the water-soluble solvent. Preferred compositions contain about 60% to about 95% water, based on the total weight of the aqueous vehicle.
  • The amount of aqueous vehicle in the ink is typically in the range of about 70% to about 99.8%, and preferably about 80% to about 99.8%, based on total weight of the ink.
  • The aqueous vehicle can be made to be fast penetrating (rapid drying) by including surfactants or penetrating agents such as glycol ethers and 1,2-alkanediols. Glycol ethers include ethylene glycol monobutyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-isopropyl ether. 1,2-Alkanediols are preferably 1,2-C4-6 alkanediols, most preferably 1,2-hexanediol. Suitable surfactants include ethoxylated acetylene diols (e.g. Surfynols® series from Air Products), ethoxylated primary (e.g. Neodol® series from Shell) and secondary (e.g. Tergitol® series from Union Carbide) alcohols, sulfosuccinates (e.g. Aerosol® series from Cytec), organosilicones (e.g. Silwet® series from Witco) and fluoro surfactants (e.g. Zonyl® series from DuPont).
  • The amount of glycol ether(s) and 1,2-alkanediol(s) added must be properly determined, but is typically in the range of from about 1 to about 15% by weight and more typically about 2 to about 10% by weight, based on the total weight of the ink. Surfactants may be used, typically in the amount of about 0.01 to about 5% and preferably about 0.2 to about 2%, based on the total weight of the ink.
  • Soluble Polymer Binder
  • The ink contains at least one soluble polymer binder. Soluble means dissolved in the aqueous vehicle. The soluble polymer is furthermore a structured polymer. The term “structured polymer” means a polymer having a block, branched or graft structure. Especially preferred are AB or BAB block copolymers such as those disclosed in U.S. Pat. No. 5,085,698, ABC block copolymers such as those disclosed in disclosed in U.S. Pat. No. 5,519,085, and graft polymers such as those disclosed in U.S. Pat. No. 5,231,131. The disclosures of these three publications are incorporated by reference herein for all purposes as if fully set forth.
  • Preferably the number average molecular weight (Mn) is in the range of about 1,000 to about 20,000, more preferably about 1,000 to about 10,000, and most preferably about 2,000 to about 6,000. These soluble polymers are preferably comprised of ionic monomers, preferably anionic monomers with ionizable acid groups. The preferred acid content is between about 0.65 and about 6 milliequivalents per gram of polymer, and the most preferred being between about 0.90 and about 1.75 milliequivalents per gram of polymer. All polymers may also contain monomers that have hydrophilic groups including, but not limited to, hydroxyls, amides and ethers. Preferably anionic polymers are used with anionic SDP and cationic polymers are used with cationic SDP.
  • In a particularly preferred embodiment, the soluble binder polymer is comprised substantially of monomers of (meth)acrylic acid and/or derivatives thereof, and the preferred Mn is between about 4000 to about 6000.
  • In one preferred embodiment, the soluble structured polymer is linear.
  • The soluble structured polymer is advantageously used at levels, based on the final weight of ink, of at least about 0.3% and preferably at least about 0.6%. Upper limits are dictated by ink viscosity or other physical limitations, but generally no more than about 3% soluble polymer is present in the ink, and more commonly no more than about 2% is present, based on the total weight of the ink.
  • Also relevant is the weight ratio of pigment to soluble structured polymer binder (P/B). The P/B is preferably between about 0.5 and about 20, more preferably between about 2 and about 10.
  • Dispersed Polymer Binders
  • Inks may optionally comprise a dispersed polymer binder. These are polymers that are in a heterogeneous dispersed phase rather than dissolved in the vehicle, and are sometimes also referred to as an “emulsion polymer” or a “latex”. The polymers can be any chemical class suitable for binding inks to substrate and include, for example, acrylics, styrene-acrylics and polyurethanes.
  • Particularly preferred are polyurethane dispersion binders such as those disclosed in US20030184629, the disclosure of which is incorporated by reference for all purposes as if fully set forth.
  • Other Ingredients
  • Other ingredients may be formulated into the inkjet ink, to the extent that such other ingredients do not interfere with the stability and jetablity of the ink, which may be readily determined by routine experimentation. Such other ingredients are in a general sense well known in the art.
  • Biocides may be used to inhibit growth of microorganisms.
  • Inclusion of sequestering (or chelating) agents such as ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid (IDA), ethylenediamine-di(o-hydroxyphenylacetic acid) (EDDHA), nitrilotriacetic acid (NTA), dihydroxyethylglycine (DHEG), trans-1,2-cyclohexanediaminetetraacetic acid (CyDTA), dethylenetriamine-N,N,N′,N″, N″-pentaacetic acid (DTPA), and glycoletherdiamine-N,N,N′,N′-tetraacetic acid (GEDTA), and salts thereof, may be advantageous, for example, to eliminate deleterious effects of heavy metal impurities.
  • Ink Properties
  • Jet velocity, separation length of the droplets, drop size and stream stability are greatly affected by the surface tension and the viscosity of the ink. Pigmented ink jet inks typically have a surface tension in the range of about 20 dyne/cm to about 70 dyne/cm at 25° C. Viscosity can be as high as 30 cP at 25° C., but is typically somewhat lower. The ink has physical properties compatible with a wide range of ejecting conditions, i.e., driving frequency of the piezo element, or ejection conditions for a thermal head, for either a drop-on-demand device or a continuous device, and the shape and size of the nozzle. The inks should have excellent storage stability for long periods so as not clog to a significant extent in an ink jet apparatus. Further, the ink should not corrode parts of the ink jet printing device it comes in contact with, and it should be essentially odorless and nontoxic.
  • Although not restricted to any particular viscosity range or printhead, the inventive ink set is particularly suited to lower viscosity applications such as those required by thermal printheads. Thus the viscosity (at 25° C.) of the inventive inks and fixer can be less than about 7 cps, is preferably less than about 5 cps, and most advantageously is less than about 3.5 cps. Thermal inkjet acutators rely on instaneous heating/bubble formation to eject ink drops and this mechanism of drop formation generally requires inks of lower viscosity.
  • Substrate
  • The instant invention is particularly advantageous for printing on plain paper such as common electrophotographic copier paper.
  • Ink Sets
  • The ink sets in accordance with the present invention comprises at least three differently colored inks (such as CMY), and preferably at least four differently colored inks (such as CMYK), wherein at least one of the inks is an aqueous inkjet ink comprising:
      • (a) an SDP colorant;
      • (b) an aqueous vehicle; and
      • (c) a soluble structured polymer
        as set forth above.
  • As indicated above, preferably the ink set comprises at least 4 different colored inks (CMYK), wherein the black (K) ink comprises:
      • (a) a black SDP colorant;
      • (b) an aqueous vehicle; and
      • (c) a soluble structured polymer
        as set forth above.
  • The other inks of the ink set are preferably also aqueous inks, and may contain dyes, pigments or combinations thereof as the colorant. Such other inks are, in a general sense, well known to those of ordinary skill in the art.
  • EXAMPLES
  • Dispersion 1
  • Carbon black (S-160 from Degussa, surface area 150 m2/g) was oxidized with ozone according to the process described in WO01/94476 and neutralized with LiOH. After recovery, a 16.6 weight percent dispersion of self-dispersing carbon black pigment in water was obtained with a viscosity of 3.5 cps (25° C.). The median particle size was 110 nm and the acid number (degree of functionalization) was 3.3 μmol/m2. The degree of functionalization, as measured, was slightly above the target level of <3.0 μmol/m2.
  • The degree of functionalization (acid value) of this SDP (and others in these examples made by the process according to WO01/94476) was determined by the equivalent moles of base required to neutralize the treated pigment to a pH of 7. As the surface hydrophilic groups are substantially all acidic, the acid value also equals the degree of functionalization.
  • Equivalent moles of base can be determined by titration or, in the case of inorganic bases such as alkali metal hydroxides, by atomic absorption (AA) or Inductive Coupled Plasma (ICP) analysis. Moles of base per gram of SDP is obtained and converted to μmol/m2 by dividing by the surface area of the pigment and adjusting the units appropriately. For accuracy, the neutralized sample must be free of contaminants, such as free acids or salts, which would interfere with the measurement.
  • Dispersion 2
  • Carbon black (FW-18 from Degussa, surface area 260 m2/g) was oxidized with ozone according to the process described in WO01/94476. After recovery, a 17 weight percent dispersion of self-dispersing carbon black pigment in water was obtained with a viscosity of 6.4 cps (25° C.). The median particle size was 90 nm and the acid number (degree of functionalization) was less than 2.8 μmol/m2.
  • Polymer 1 (Soluble Structured Polymer)
  • Polymer 1 is a block copolymer consisting of benzyl methacrylate//methacrylic acid/ethyltriethyleneglycol methacrylate (BzMA//MAA/ETEGMA, mole ratio 13//13/7.5). It was prepared in a manner similar to “polymer 2” described in U.S. Pat. No. 6,087,416 (incorporated by reference herein for all purposes as if fully set forth), except the amount of ETEGMA was slightly lower. Number average molecular weight was about 5,000 and weight average molecular weight was about 5,000 g/mol.
  • Polymer 2 (Soluble Random Polymer, Comparative)
  • Polymer 2 is a random copolymer consisting of benzyl methacrylate, hydroxyethylmethacrylate, ethyltriethyleneglycolmethatcrylate and methacrylic acid (BzMA/HEMA/ETEGMA/MAA, weight ratio 60/20/10/10) was made by the same technique as Polymer 1 except all monomers were co-added, in proper proprotion, to make a random polymer. The number average molecular weight was about 5,000 and weight average molecular weight was about 5,000 g/mol.
  • Polymer 3 (Soluble Structured Polymer)
  • Polymer 3 is a block copolymer consisting of benzyl methacrylate//methacrylic acid/ethyltriethyleneglycol methacrylate (BzMA//MAA/ETEGMA weight ratio 40/50/10). It was prepared by the same technique as Polymer 1 above. The number average molecular weight was about 2000-2500 and weight average molecular weight was about 2500 g/mol.
  • Polymer 4 (Soluble Structured Polymer)
  • Polymer 5 is a block copolymer of methacrylic acid//benzyl methacrylate//ethyltriethyleneglycol methacrylate (MAA//BzMA//ETEGMA, mole ratio 13//15//4). It was prepared in a manner similar to “preparation 4” described in previously incorporated U.S. Pat. No. 5,519,085, except the BzMA ratio is higher. The number average molecular weight was about 5,000 and weight average molecular weight was about 5,000 g/mol.
  • Polyurethane Dispersion (PUD) Binders
  • PUD 1 is a polyurethane with polyol component which is a polyester diol. The acid number was 25 and the median particle diameter was 0.018 microns. It was used as a water dispersion with 26% by weight solids.
  • PUD 2 is a polyurethane with a polyol component which is a polycarbonate polyester diol. The acid number was 25 and the median particle diameter was 0.036 microns. It was used as a water dispersion with 40% by weight solids.
  • Preparation of Inks
  • Inks with soluble structured polymer (Ex1-5) and comparative inks with random soluble polymer (C1-3) were prepared according to the following recipes.
    Composition, (weight %)
    C1 C2 C3 Ex 1 Ex 2 Ex 3 Ex 4 Ex 5
    Dispersion 1 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0
    (pigment)
    Polymer 1 8.0 0.4 0.2
    Polymer 2 8.0 0.4 0.2
    Polymer 3 1.33 0.67
    Glycerol 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0
    Ethylene 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0
    Glycol
    Surfonyl ® 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0
    485
    Liponic 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0
    EG-1
    (Lipo Co.)
    H2O bal. bal. bal. bal. bal. bal. bal. bal.
    Properties
    Viscosity 4.84 2.20 2.10 10.20 2.34 2.24 2.18 2.10
    (cps @25 C.)
    PH 9.04 7.78 7.56 8.31 7.64 7.50 7.09 7.12
    Surface tension 43.50 40.69 39.89 43.79 41.17 40.32 43.67 42.82
    (Dyne/cm)
  • Inks comprising PUD binder with soluble structured polymer and comparative inks with PUD binder alone were prepared according to the following recipes.
    Composition, (weight %)
    C6 C7 Ex6 Ex7
    Dispersion 2 (pigment) 4 4 4 4
    PUD 1 (solids basis) 0.29 0.29
    PUD 2 (solids basis) 0.29 0.29
    Polymer 4 0.29 0.29
    Glycerol 13.0 13.0 13.0 13.0
    Ethylene Glycol 4.0 4.0 4.0 4.0
    Surfynol ® 485 1.0 1.0 1.0 1.0
    Liponic EG-1 (Lipo Co.) 4.0 4.0 4.0 4.0
    H2O bal. bal. bal. bal.
    Properties
    Viscosity (cps @25 C.) 3.08 2.98 2.98 3.0
    PH 7.53 7.37 7.33 7.45
    Surface tension 40.71 39.84 41.49 40.13
    (Dyne/cm)

    Substrate
  • The following papers were used as substrate in print tests: Hammermill Copy Plus, Xerox 4024 and Hewlett Packard office paper.
  • Drop Weight Test
  • An HP51645A thermal inkjet pen was filled with the ink to be tested and a driver controlled by a computer fired 22 selected nozzles at a frequency of 12 kHz for burst of 0.08 milliseconds. The ink drops are collected and weighed, and a weight per drop fired (drop weight) is calculated. The process of firing and weighing drops is repeated, using the same 22 nozzles, until the ink volume in the cartridge (about 25 gm) has been depleted. The drop weight as a function of amount of ink jetted can be plotted if changes occur during the course of the test. Most preferably, from the standpoint of providing good color density, the drop weight remains constant throughout the test.
  • Kogation Test
  • Kogation is a measure of the amount of residue left on the nozzles and/or resistors of a thermal ink jet pen after the pen has been used in the Drop Weight test. After prying open the nozzle plate to expose the resistors and nozzle chambers, the used resistors nozzles are observed with a microscope and rated as follows.
      • Good—No significant amount of residue—Clean resistors
      • Fair—Small amount of residue—Partially covered resistors
      • Poor—Significant amount of residue—Covered resistors
        Most preferably, from the standpoint of long pen life, there is no residue.
    Results for Inks with Soluble Structured Polymer Compared to Inks with Random Soluble Polymer.
  • Comparative Drop wt. Inventive Drop wt.
    Example P/B (ng) Kogation Example P/B (ng) Kogation
    C1 0.5 12 fair Ex 1 0.5 17 good
    C2 10 14 fair Ex 2 10 24 fair
    C3 20 18 poor Ex 3 20 25 good
    Ex 4 3 29 good
    Ex 5 6 28 good
  • For an ink with equivalent formulation as the above, but without any soluble binder (“no added polymer” case), the drop weight was 25-28 nanograms and the kogation rating was good. Adding soluble random polymer (Examples C1-C3) causes a decrease in the kogation rating and a reduction in drop volume. The inventive examples with soluble structured polymer (Examples E1-E5) show good kogation ratings and, generally, a drop weight similar to the “no added polymer” case. The lower drop weight of Ex. 1 may be explained by the relatively higher viscosity. Higher levels of soluble polymer increase ink viscosity and many inkjet pens are designed for lower viscosity ink.
  • The added soluble structured polymer (binder) improves the fastness of the ink on the printed page, especially at P/B (pigment to binder) ratios greater than about 20 and more effectively at ratios greater than 10. In particular, rub fastness (resistance to rub-off from fingers) and water fastness (resistance to bleed on contact with a water drop) are improved.
  • Results for Inks Containing Polyurethane Dispersion Binder
  • Comparative Drop Wt. Inventive Drop Wt.
    example ng Kogation example ng Kogation
    C6 22 fair Ex 6 30 good
    C7  15* poor Ex 7 23 good

    *lost jetting, stopped after 5 ml
  • In the above examples, inks with PUD alone (C6 and C7) are improved by addition of soluble structured polymer (Ex 6-7). The Kogation is better and the drop volume is higher. Furthermore, benefits in fastness of the ink on the printed page from both the soluble structured polymer and the PUD are realized. Thus the rub fastness, water fastness and smear fastness (resistance to bleed from a highlighter pen stroke) are all improved. Polymer 4 is also advantageously employed in an ink without PUD.
  • Ink Containing a Graft Copolymer as the Soluble Structure Polymer
  • Polymer 5, a soluble, grafted polymer was prepared as follows. First a macromonomer of ethoxytriethyleneglycol methacrylate-co-methacrylic acid, was made by reaction of portions 1-3.
    Parts by Weight
    Portion 1
    Isopropanol 124
    Acetone 126
    Methanol 115
    Portion 2
    Methacrylic acid monomer (MAA) 215
    Ethoxytriethyleneglycol methacrylate monomer 31
    (ETEG MA)
    Methanol 40
    Portion 3
    Bis(borondifluorodiphenyl 0.197
    glyoximato) Cobaltate (II),
    2,2′-azobis(2,4-dimethylvaleronitrile), (Vazo ® 7.151
    52 from DuPont Co., Wilmington, DE)
    Acetone 90
  • Portion 1 mixture was charged into a 2 liter flask equipped with a thermometer, stirrer, addition funnels, reflux condenser and a means of maintaining a nitrogen blanket over the reactants. The mixture was heated to reflux temperature and refluxed for about 20 minutes. Portion 2 solution was added over 240 minutes. Portion 3 was fed to the reactor over 270 min. simultaneously with portion 2 while the reaction mixture was held at reflux temperature at about 62° C. Reflux was continued for another 2 hours and the solution was cooled to room temperature. The resulting solution of macromonomer was a clear thin polymer solution and had a solid content of about 33%. The macromonomer contained 12.5 weight % of ethoxytriethyleneglycol methacrylate and 87.5% of methacrylic acid and had a weight average molecular weight of approximately 1600 and a number average molecular weight of 800 as measured by Gel Permeation Chromatography (GPC) on a methylated macromonomer sample using polymethyl methacrylate as the standard.
  • The macromonomer was then copolymerized with phenoxyethyl acrylate and ethoxytriethyleneglycol methacrylate to create the graft block structure. The following synthesis illustrates the preparation of a block copolymer, phenoxyethylacrylate-co-ethoxytriethyleneglycol methacrylate//g-ethoxytriethyleneglycol methacrylate-co methacrylic acid, 50/20//4/26 by weight, from a macromonomer.
    Parts Weight
    Portion 4
    Macromonomer solution from above 469
    2-Pyrrolidone 73
    Portion 5
    Phenoxylethyl acrylate (POEA) 250
    Ethoxytriethyleneglycol methacrylate 96
    (ETEGMA)
    Isopropylalcohol 6
    Portion 6
    t-butyl peroxypivalate 15.8
    isopropanol 90.4
    Portion 7
    2-Pyrrolidone 403
  • The Portion 4 mixture was charged into a 3 L flask equipped with a thermometer, stirrer, addition funnels, reflux condenser and a means of maintaining a nitrogen blanket over the reaction mixture. The mixture was heated to reflux temperature and refluxed for about 10 minutes. At time zero, 16.7% of portion 6 solution was added. Subsequently, portion 5 and 80% of the remaining portion 6 were simultaneously added over 240 minutes while the reaction mixture was held at the reflux temperature of about 65° C. The reaction was held at reflux for another hour, and then, the remainder of portion 6 solution was added. The mixture was heated to 120° C. distilling and about 360 g of volatiles were collected. Approximately 30 g of portion 6 was added when the temperature reached 90° C. to thin the polymer solution. When the mixture reached 120° C. the heating was stopped and the remainder of portion 6 was added. The reaction was then cooled to room temperature. Subsequently, the polymer was neutralized with lithium hydroxide and the mixture was adjusted with water to provide a solution with a solids content of about 20%.
  • Polymer 5 thus produced was a graft polymer of POEA/ETEGMA-g-ETEGMA/MAA having an approximate overall composition of 50.4% POEA, 23.3% ETEGMA and 26.3% MM by weight, and a number average molecular weight of about 4000 and a weight average molecular weight of about 13600 g/mol.
  • Ink 8 with soluble grafted polymer 5 was prepared according to the following recipe.
    Composition (weight %)
    E8 E9 E10
    Dispersion 2 (pigment basis) 4.5 5 5
    Polymer 5 (solids basis) 0.75 0.5 0.83
    Glycerol 9 26.4 26.4
    Ethylene Glycol 6
    BYK348 (surfactant) 0.1
    1-2 Hexanediol 5
    Ethylenediaminetetra 0.01
    acetate, sodium salt
    Water Bal. Bal. Bal.
    Properties
    Viscosity (cps @25 C) 2.78 3.18 3.48
    PH 6.78 7.5 7.4
    Surface tension 25.8 63.3 54.7
    (Dyne/cm)
  • As with the previous inventive inks, the soluble structured polymer in Inks E8-10 provides enhanced rub fastness and water fastness without detrimental effect on jetting performance.

Claims (21)

1. An aqueous inkjet ink composition comprising:
(a) an SDP colorant;
(b) an aqueous vehicle; and
(c) a soluble structured polymer.
2. The ink of claim 1, wherein the soluble structured polymer is present at a P/B ratio of between about 0.5 to about 20.
3. The ink of claim 1, wherein the soluble polymer is a substantially linear, anionic polymer having a number average molecular weight in the range of about 1,000 to about 20,000.
4. The ink of claim 1, wherein the substantially linear soluble polymer is a block copolymer.
5. The ink of claim 1, further comprising a dispersed polymer binder.
6. The ink of claim 1, wherein the dispersed polymer binder is a polyurethane.
7. The ink of claim 1, wherein the self-dispersing pigment is a self-dispersing carbon black pigment comprising anionic hydrophilic moieties.
8. The ink of claim 7, wherein the anionic hydrophillic moieties on the self-dispersing carbon black pigment are primarily carboxyl groups directly attached to the pigment surface.
9. An inkjet ink set for color printing, comprising at least three differently colored inks, at least one of which is cyan, at least one of which is magenta and at least one of which is yellow, wherein at least one of the inks is an aqueous inkjet ink composition comprising:
(a) an SDP colorant;
(b) an aqueous vehicle; and
(c) a soluble structured polymer.
10. The inkjet ink set of claim 9, wherein the soluble structured polymer is present at a P/B ratio of between about 0.5 to about 20.
11. The inkjet ink set of claim 9, wherein the soluble polymer is a substantially linear, anionic polymer having a number average molecular weight in the range of about 1,000 to about 20,000.
12. The inkjet ink set of claim 9, wherein the substantially linear soluble polymer is a block copolymer.
13. The inkjet ink set of claim 9, further comprising a dispersed polymer binder.
14. The inkjet ink set of claim 9, wherein the dispersed polymer binder is a polyurethane.
15. An inkjet ink set for color printing, comprising at least four differently colored inks, at least one of which is cyan, at least one of which is magenta, at least one of which is yellow, and at least one of which is black, wherein at least one of the inks is a black ink comprising:
(a) an SDP colorant;
(b) an aqueous vehicle; and
(c) a soluble structured polymer,
wherein the SDP colorant is a self-dispersing carbon black pigment comprising anionic hydrophilic moieties.
16. The inkjet ink set of claim 15, wherein the anionic hydrophillic moieties on the self-dispersing carbon black pigment are primarily carboxyl groups directly attached to the pigment surface.
17. The inkjet ink set of claim 15, wherein the soluble structured polymer is present at a P/B ratio of between about 0.5 to about 20.
18. The inkjet ink set of claim 15, wherein the soluble polymer is a substantially linear, anionic polymer having a number average molecular weight in the range of about 1,000 to about 20,000.
19. The inkjet ink set of claim 15, wherein the substantially linear soluble polymer is a block copolymer.
20. The inkjet ink set of claim 15, further comprising a dispersed polymer binder.
21. The inkjet ink set of claim 15, wherein the dispersed polymer binder is a polyurethane.
US10/843,133 2003-05-19 2004-05-11 Inkjet ink Abandoned US20050020730A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US47179803P true 2003-05-19 2003-05-19
US10/843,133 US20050020730A1 (en) 2003-05-19 2004-05-11 Inkjet ink

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/843,133 US20050020730A1 (en) 2003-05-19 2004-05-11 Inkjet ink
US11/891,087 US8710116B2 (en) 2003-05-19 2007-08-08 Inkjet ink

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/891,087 Continuation US8710116B2 (en) 2003-05-19 2007-08-08 Inkjet ink

Publications (1)

Publication Number Publication Date
US20050020730A1 true US20050020730A1 (en) 2005-01-27

Family

ID=33476888

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/843,133 Abandoned US20050020730A1 (en) 2003-05-19 2004-05-11 Inkjet ink
US11/891,087 Active 2026-07-29 US8710116B2 (en) 2003-05-19 2007-08-08 Inkjet ink

Family Applications After (1)

Application Number Title Priority Date Filing Date
US11/891,087 Active 2026-07-29 US8710116B2 (en) 2003-05-19 2007-08-08 Inkjet ink

Country Status (6)

Country Link
US (2) US20050020730A1 (en)
EP (1) EP1625186B1 (en)
JP (1) JP5276268B2 (en)
AT (1) AT437924T (en)
DE (2) DE202004021559U1 (en)
WO (1) WO2004104119A1 (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040059021A1 (en) * 2002-09-24 2004-03-25 Mayuko Okada Ink for ink-jet recording
US20050032930A1 (en) * 2003-07-02 2005-02-10 Christian Jackson Inkjet ink
US20050137282A1 (en) * 2003-12-19 2005-06-23 Cagle Phillip C. Liquid vehicle systems for improving latex ink-jet ink frequency response
US20050176849A1 (en) * 2004-02-09 2005-08-11 Haixin Yang Ink jet printable thick film compositions and processes
US20050176848A1 (en) * 2004-02-09 2005-08-11 Xiaohe Chen Ink compositions for ink-jet printing
US20080206465A1 (en) * 2007-02-28 2008-08-28 Han-Adebekun Gang C Aqueous inkjet ink composition
US20090020037A1 (en) * 2007-04-20 2009-01-22 Christian Jackson Ink jet ink
US20100081740A1 (en) * 2008-09-29 2010-04-01 Christian Jackson Aqueous inkjet ink comprising self-dispersing pigment
US20100092669A1 (en) * 2008-10-14 2010-04-15 Irving Mark E Inkjet printing system, ink, and process
US20100273931A1 (en) * 2007-12-04 2010-10-28 E.I. Du Pont De Nemours And Company Decarboxylating block copolymers
WO2012087542A2 (en) 2010-12-20 2012-06-28 Eastman Kodak Company Inkjet ink composition with jetting aid
WO2012016125A3 (en) * 2010-07-30 2012-07-05 Cabot Corporation Polymeric pigment systems and methods
US9133355B2 (en) 2011-03-30 2015-09-15 Hewlett-Packard Development Company, L.P. Aqueous ink compositions and method of preparing same

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7172276B2 (en) * 2004-12-10 2007-02-06 Xerox Corporation Heterogeneous low energy gel ink composition
JP5414151B2 (en) * 2007-01-10 2014-02-12 キヤノン株式会社 Aqueous ink jet recording method and an ink cartridge
JP5546108B2 (en) * 2008-04-28 2014-07-09 キヤノン株式会社 The method of manufacturing an ink jet recording pigment ink
JP2011523964A (en) * 2008-05-23 2011-08-25 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company Inkjet ink and a self-dispersing pigment and a polyurethane ink additive
WO2011008810A1 (en) 2009-07-15 2011-01-20 E. I. Du Pont De Nemours And Company Crosslinking pigment dispersion based on diblock polymeric dispersants
WO2011008813A1 (en) * 2009-07-15 2011-01-20 E. I. Du Pont De Nemours And Company An aqueous ink jet ink comprising a crosslinking pigment dispersion based on diblock polymeric dispersants
US8591021B2 (en) 2009-07-15 2013-11-26 E I Du Pont De Nemours And Company Method of printing using ink jet inks comprising a crosslinking pigment dispersion based on diblock polymeric dispersants
EP2456832A1 (en) * 2009-07-24 2012-05-30 E. I. du Pont de Nemours and Company Self-dispersing pigment dispersions and ink jet inks containing them
US20130005851A1 (en) * 2011-06-30 2013-01-03 Xiaorong Cai Aqueous Pigmented Black Inks Having a Unique Dispersant Mixture
JP2013060563A (en) * 2011-09-15 2013-04-04 Ricoh Co Ltd Inkjet recording ink, cartridge, inkjet recording apparatus, image forming method, and image-recorded matter
JP5846545B2 (en) * 2011-12-08 2016-01-20 株式会社リコー Jet recording ink
JP2013159644A (en) * 2012-02-01 2013-08-19 Ricoh Co Ltd Inkjet ink and method for producing the same
JP5999306B2 (en) * 2012-03-06 2016-09-28 セイコーエプソン株式会社 Water-based ink for inkjet recording
JP6064471B2 (en) * 2012-09-13 2017-01-25 株式会社リコー Jet recording ink, ink cartridge, inkjet recording apparatus, an image forming method, an image forming material
JP2014172963A (en) * 2013-03-07 2014-09-22 Ricoh Co Ltd Ink for inkjet recording, ink cartridge, inkjet recording method, inkjet recording device and ink printed matter
EP3152272A4 (en) 2014-06-04 2017-06-07 Hewlett-Packard Development Company, L.P. Magenta inks
WO2015187144A1 (en) 2014-06-04 2015-12-10 Hewlett-Packard Development Company, L.P. Pigment-based inkjet inks
JP2017066314A (en) * 2015-09-30 2017-04-06 ブラザー工業株式会社 Aqueous ink for inkjet recording and ink cartridge

Citations (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5085698A (en) * 1990-04-11 1992-02-04 E. I. Du Pont De Nemours And Company Aqueous pigmented inks for ink jet printers
US5554739A (en) * 1994-12-15 1996-09-10 Cabot Corporation Process for preparing carbon materials with diazonium salts and resultant carbon products
US5571311A (en) * 1994-12-15 1996-11-05 Cabot Corporation Ink jet ink formulations containing carbon black products
US5609671A (en) * 1994-06-20 1997-03-11 Orient Chemical Industries, Ltd. Water-based pigment ink and process for producing the same
US5630868A (en) * 1994-12-15 1997-05-20 Cabot Corporation Ink jet ink formulations containing modified carbon products
US5672198A (en) * 1994-12-15 1997-09-30 Cabot Corporation Aqueous inks and coatings containing modified carbon products
US5698016A (en) * 1996-06-14 1997-12-16 Cabot Corporation Compositions of modified carbon products and amphiphilic ions and methods of using the same
US5707432A (en) * 1996-06-14 1998-01-13 Cabot Corporation Modified carbon products and inks and coatings containing modified carbon products
US5718746A (en) * 1995-03-20 1998-02-17 Orient Chemical Industries, Ltd. Process of producing aqueous pigment ink
US5747562A (en) * 1996-06-14 1998-05-05 Cabot Corporation Ink and coating compositions containing silicon-treated carbon black
US5837045A (en) * 1996-06-17 1998-11-17 Cabot Corporation Colored pigment and aqueous compositions containing same
US5846307A (en) * 1996-04-19 1998-12-08 Orient Chemical Industries, Ltd. Aqueous pigment ink composition
US5851280A (en) * 1994-12-15 1998-12-22 Cabot Corporation Reaction of carbon black with diazonium salts, resultant carbon black products and their uses
US5861447A (en) * 1996-07-19 1999-01-19 Orient Chemical Industries, Ltd. Aqueous pigment ink composition
US5895522A (en) * 1997-08-12 1999-04-20 Cabot Corporation Modified carbon products with leaving groups and inks and coatings containing modified carbon products
US5922118A (en) * 1996-06-14 1999-07-13 Cabot Corporation Modified colored pigments and ink jet inks, inks, and coatings containing modified colored pigments
US5928419A (en) * 1996-10-07 1999-07-27 Toyo Ink Manufacturing Co., Ltd. Surface-treated organic pigment and process for the production thereof
US5976233A (en) * 1996-11-13 1999-11-02 Canon Kabushiki Kaisha Water-based pigment ink, and ink-jet recording method and instruments using the same
US6057384A (en) * 1997-10-31 2000-05-02 Hewlett-Packard Company Latex polymer blends for improving the permanence of ink-jet inks
US6087416A (en) * 1998-07-22 2000-07-11 E.I. Du Pont De Nemours And Company Aqueous pigmented ink jet inks for printing on vinyls
US6099632A (en) * 1997-07-24 2000-08-08 Orient Chemical Industries, Ltd. Aqueous pigment ink composition
US6103780A (en) * 1998-04-16 2000-08-15 Westvaco Corporation Ink jet inks
US6123759A (en) * 1996-12-26 2000-09-26 Mitsubishi Chemical Corporation Carbon black, process for producing the same, and aqueous dispersion and water-base ink both containing the same
US6153001A (en) * 1997-12-18 2000-11-28 Fuji Xerox Co., Ltd. Ink jet recording ink, method for producing the same, and ink jet recording method
US6221142B1 (en) * 1999-06-18 2001-04-24 Hewlett-Packard Company Superior waterfastness and bleed control with specifically treated pigments for ink-jet printing
US6221143B1 (en) * 1999-03-12 2001-04-24 Cabot Corporation Cationic pigments and aqueous compositions containing same
US6221141B1 (en) * 1998-06-23 2001-04-24 Canon Kabushiki Kaisha Ink, ink-jet recording process, recording unit, ink cartridge and ink-jet recording apparatus
US6277183B1 (en) * 1998-10-08 2001-08-21 Cabot Corporation Ink compositions containing metal oxides
US6281267B2 (en) * 1998-10-29 2001-08-28 Hewlett-Packard Company Ink to ink bleed and halo control using specific polymers in ink-jet printing inks
US20010035110A1 (en) * 2000-01-06 2001-11-01 Seiko Epson Corporation Ink composition capable of realizing images possessing excellent color development and fixation
US6329446B1 (en) * 1997-06-05 2001-12-11 Xerox Corporation Ink composition
US6332919B2 (en) * 1998-03-20 2001-12-25 Canon Kabushiki Kaisha Ink, ink set, ink cartridge, recording unit, image recording apparatus and image recording method
US6368397B1 (en) * 1999-01-13 2002-04-09 Fuji Xerox Co., Ltd. Ink for ink jet printing
US6375317B1 (en) * 1998-10-27 2002-04-23 Canon Kabushiki Kaisha Ink, ink-jet recording process, recording unit, ink cartridge and ink-jet recording apparatus
US6379443B1 (en) * 1999-03-12 2002-04-30 Seiko Epson Corporation Ink jet recording method and ink composition for use in said method
US20020147252A1 (en) * 2001-02-02 2002-10-10 Adams Curtis E. Ink compositions comprising salts with polyvalent ions
US20030008080A1 (en) * 1998-11-06 2003-01-09 Takatsugu Doi Ink jet recording liquid and ink jet recording method
US6511534B1 (en) * 1999-09-17 2003-01-28 Canon Kabushiki Kaisha Ink, ink set, ink cartridge, printing unit, image printing apparatus, ink-jet printing method, and coloring material
US20030184629A1 (en) * 2002-01-16 2003-10-02 Valentini Jose E. Smear resistant inkjet inks
US20040092622A1 (en) * 2002-07-01 2004-05-13 Pearlstine Kathryn Amy Inkjet ink with reduced bronzing
US20040201658A1 (en) * 2003-01-16 2004-10-14 Christian Jackson Inkjet ink set and method of using same
USH2113H1 (en) * 1999-08-16 2005-01-04 Xerox Corporation Ink compositions
US7001936B2 (en) * 2003-07-16 2006-02-21 Lexmark International, Inc. Pigmented inkjet ink
US7029109B2 (en) * 2001-08-22 2006-04-18 Canon Kabushiki Kaisha Ink, ink set, ink jet recording method, ink jet recording apparatus, recording unit and ink cartridge

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5231131A (en) 1991-12-24 1993-07-27 E. I. Du Pont De Nemours And Company Aqueous graft copolymer pigment dispersants
DE69325401T2 (en) 1992-02-20 1999-11-25 Du Pont Triblock polymer water dispersions containing dispersant
DE4408947C2 (en) 1994-03-16 1997-03-13 Balzers Hochvakuum Vacuum treatment plant
US6040358A (en) * 1996-12-27 2000-03-21 E. I. Du Pont De Nemours And Company Ink jet inks containing linear polymer additives
US5912280A (en) * 1996-12-27 1999-06-15 E. I. Du Pont De Nemours And Company Ink jet inks containing emulsion-polymer additives to improve water-fastness
JPH11269418A (en) * 1997-12-29 1999-10-05 E I Du Pont De Nemours & Co Water-base ink jet ink composition containing block copolymer dispersant
JP4250249B2 (en) * 1998-04-01 2009-04-08 キヤノン株式会社 Inkjet ink, ink cartridge, recording unit, an ink set, an image recording method and image recording apparatus
US6229446B1 (en) * 1998-09-02 2001-05-08 David Lloyd-Jones Alarm apparatus
DE60042091D1 (en) 1999-06-09 2009-06-04 Seiko Epson Corp Inkjet printing ink with fungicide
JP2003506554A (en) 1999-08-09 2003-02-18 キャボット コーポレイション High or ink composition having a pigment modified with a low degree of processing
ES2277812T3 (en) 1999-09-17 2007-08-01 Canon Kabushiki Kaisha Ink, ink set and image printing process to improve the density of an image printed by ink jet.
AU7740800A (en) 1999-10-01 2001-05-10 Cabot Corporation Modified pigments having steric and amphiphilic groups
US6460989B1 (en) * 1999-11-12 2002-10-08 Canon Kabushiki Kaisha Ink set, formation of colored area on recording medium, and ink-jet recording apparatus
JP3915369B2 (en) * 2000-04-05 2007-05-16 富士ゼロックス株式会社 An ink-jet recording method and an inkjet recording ink
JP2002020673A (en) 2000-04-10 2002-01-23 Seiko Epson Corp Method for manufacturing pigment dispersion, pigment dispersion obtained thereby, ink jet recording ink using the same, and recording method and recorded matter therewith
DE60122824T2 (en) 2000-05-23 2007-10-11 Kao Corp. Ink water-based composition
US6852156B2 (en) 2000-06-05 2005-02-08 E.I. Du Pont De Nemours And Company Self-dispersing pigment and process of making and use of same
US6547381B2 (en) 2000-06-23 2003-04-15 Canon Kabushiki Kaisha Ink, image recording process, ink cartridge, recording unit, ink set, crust-preventing method and image forming apparatus
JP3595805B2 (en) * 2001-08-07 2004-12-02 キヤノン株式会社 Stimuli-responsive composition, and an image forming method and apparatus using the composition
JP4100986B2 (en) * 2001-08-22 2008-06-11 キヤノン株式会社 Ink, ink cartridge, recording unit, ink jet recording method, method for stabilizing ink-jet recording apparatus and ink discharge
US6742869B2 (en) * 2001-10-04 2004-06-01 E. I. Du Pont De Nemours And Company Method and system for printing with an inkjet printer to simulate screen printing
US6726757B2 (en) 2001-10-19 2004-04-27 Hewlett-Packard Development Company, L.P. Ink additives to improve decel
JP3891571B2 (en) * 2002-06-14 2007-03-14 キヤノン株式会社 Functional composition, image forming method and image forming apparatus using the same
JP2004204112A (en) * 2002-12-26 2004-07-22 Canon Finetech Inc Ink for inkjet printer and recording method
EP1454969B1 (en) * 2003-03-06 2006-08-02 Kao Corporation Ink set

Patent Citations (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5085698A (en) * 1990-04-11 1992-02-04 E. I. Du Pont De Nemours And Company Aqueous pigmented inks for ink jet printers
US5609671A (en) * 1994-06-20 1997-03-11 Orient Chemical Industries, Ltd. Water-based pigment ink and process for producing the same
US5554739A (en) * 1994-12-15 1996-09-10 Cabot Corporation Process for preparing carbon materials with diazonium salts and resultant carbon products
US5571311A (en) * 1994-12-15 1996-11-05 Cabot Corporation Ink jet ink formulations containing carbon black products
US5630868A (en) * 1994-12-15 1997-05-20 Cabot Corporation Ink jet ink formulations containing modified carbon products
US5672198A (en) * 1994-12-15 1997-09-30 Cabot Corporation Aqueous inks and coatings containing modified carbon products
US5851280A (en) * 1994-12-15 1998-12-22 Cabot Corporation Reaction of carbon black with diazonium salts, resultant carbon black products and their uses
US5718746A (en) * 1995-03-20 1998-02-17 Orient Chemical Industries, Ltd. Process of producing aqueous pigment ink
US5846307A (en) * 1996-04-19 1998-12-08 Orient Chemical Industries, Ltd. Aqueous pigment ink composition
US5707432A (en) * 1996-06-14 1998-01-13 Cabot Corporation Modified carbon products and inks and coatings containing modified carbon products
US5749950A (en) * 1996-06-14 1998-05-12 Cabot Corporation Ink and coating compositions containing silicon-treated carbon black
US5803959A (en) * 1996-06-14 1998-09-08 Cabot Corporation Modified carbon products and ink jet inks, inks and coatings containing modified carbon products
US5922118A (en) * 1996-06-14 1999-07-13 Cabot Corporation Modified colored pigments and ink jet inks, inks, and coatings containing modified colored pigments
US5747562A (en) * 1996-06-14 1998-05-05 Cabot Corporation Ink and coating compositions containing silicon-treated carbon black
US5885335A (en) * 1996-06-14 1999-03-23 Cabot Corporation Modified carbon products and inks and coatings containing modified carbon products
US5698016A (en) * 1996-06-14 1997-12-16 Cabot Corporation Compositions of modified carbon products and amphiphilic ions and methods of using the same
US5837045A (en) * 1996-06-17 1998-11-17 Cabot Corporation Colored pigment and aqueous compositions containing same
US5861447A (en) * 1996-07-19 1999-01-19 Orient Chemical Industries, Ltd. Aqueous pigment ink composition
US5928419A (en) * 1996-10-07 1999-07-27 Toyo Ink Manufacturing Co., Ltd. Surface-treated organic pigment and process for the production thereof
US5976233A (en) * 1996-11-13 1999-11-02 Canon Kabushiki Kaisha Water-based pigment ink, and ink-jet recording method and instruments using the same
US6123759A (en) * 1996-12-26 2000-09-26 Mitsubishi Chemical Corporation Carbon black, process for producing the same, and aqueous dispersion and water-base ink both containing the same
US6329446B1 (en) * 1997-06-05 2001-12-11 Xerox Corporation Ink composition
US6099632A (en) * 1997-07-24 2000-08-08 Orient Chemical Industries, Ltd. Aqueous pigment ink composition
US5895522A (en) * 1997-08-12 1999-04-20 Cabot Corporation Modified carbon products with leaving groups and inks and coatings containing modified carbon products
US6057384A (en) * 1997-10-31 2000-05-02 Hewlett-Packard Company Latex polymer blends for improving the permanence of ink-jet inks
US6153001A (en) * 1997-12-18 2000-11-28 Fuji Xerox Co., Ltd. Ink jet recording ink, method for producing the same, and ink jet recording method
US6332919B2 (en) * 1998-03-20 2001-12-25 Canon Kabushiki Kaisha Ink, ink set, ink cartridge, recording unit, image recording apparatus and image recording method
US6103780A (en) * 1998-04-16 2000-08-15 Westvaco Corporation Ink jet inks
US6221141B1 (en) * 1998-06-23 2001-04-24 Canon Kabushiki Kaisha Ink, ink-jet recording process, recording unit, ink cartridge and ink-jet recording apparatus
US6087416A (en) * 1998-07-22 2000-07-11 E.I. Du Pont De Nemours And Company Aqueous pigmented ink jet inks for printing on vinyls
US6277183B1 (en) * 1998-10-08 2001-08-21 Cabot Corporation Ink compositions containing metal oxides
US6375317B1 (en) * 1998-10-27 2002-04-23 Canon Kabushiki Kaisha Ink, ink-jet recording process, recording unit, ink cartridge and ink-jet recording apparatus
US6281267B2 (en) * 1998-10-29 2001-08-28 Hewlett-Packard Company Ink to ink bleed and halo control using specific polymers in ink-jet printing inks
US6620229B2 (en) * 1998-11-06 2003-09-16 Fuji Xerox Co., Ltd. Ink jet recording liquid and ink jet recording method
US20030008080A1 (en) * 1998-11-06 2003-01-09 Takatsugu Doi Ink jet recording liquid and ink jet recording method
US6368397B1 (en) * 1999-01-13 2002-04-09 Fuji Xerox Co., Ltd. Ink for ink jet printing
US6379443B1 (en) * 1999-03-12 2002-04-30 Seiko Epson Corporation Ink jet recording method and ink composition for use in said method
US6221143B1 (en) * 1999-03-12 2001-04-24 Cabot Corporation Cationic pigments and aqueous compositions containing same
US6221142B1 (en) * 1999-06-18 2001-04-24 Hewlett-Packard Company Superior waterfastness and bleed control with specifically treated pigments for ink-jet printing
USH2113H1 (en) * 1999-08-16 2005-01-04 Xerox Corporation Ink compositions
US6511534B1 (en) * 1999-09-17 2003-01-28 Canon Kabushiki Kaisha Ink, ink set, ink cartridge, printing unit, image printing apparatus, ink-jet printing method, and coloring material
US20010035110A1 (en) * 2000-01-06 2001-11-01 Seiko Epson Corporation Ink composition capable of realizing images possessing excellent color development and fixation
US20020147252A1 (en) * 2001-02-02 2002-10-10 Adams Curtis E. Ink compositions comprising salts with polyvalent ions
US7029109B2 (en) * 2001-08-22 2006-04-18 Canon Kabushiki Kaisha Ink, ink set, ink jet recording method, ink jet recording apparatus, recording unit and ink cartridge
US20030184629A1 (en) * 2002-01-16 2003-10-02 Valentini Jose E. Smear resistant inkjet inks
US20040092622A1 (en) * 2002-07-01 2004-05-13 Pearlstine Kathryn Amy Inkjet ink with reduced bronzing
US20040201658A1 (en) * 2003-01-16 2004-10-14 Christian Jackson Inkjet ink set and method of using same
US7001936B2 (en) * 2003-07-16 2006-02-21 Lexmark International, Inc. Pigmented inkjet ink

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040059021A1 (en) * 2002-09-24 2004-03-25 Mayuko Okada Ink for ink-jet recording
US7414083B2 (en) * 2002-09-24 2008-08-19 Brother Kogyo Kabushiki Kaisha Ink for ink-jet recording
US20050032930A1 (en) * 2003-07-02 2005-02-10 Christian Jackson Inkjet ink
US20050137282A1 (en) * 2003-12-19 2005-06-23 Cagle Phillip C. Liquid vehicle systems for improving latex ink-jet ink frequency response
US20050176849A1 (en) * 2004-02-09 2005-08-11 Haixin Yang Ink jet printable thick film compositions and processes
US7683107B2 (en) * 2004-02-09 2010-03-23 E.I. Du Pont De Nemours And Company Ink jet printable thick film compositions and processes
US20050176848A1 (en) * 2004-02-09 2005-08-11 Xiaohe Chen Ink compositions for ink-jet printing
US8492456B2 (en) * 2004-02-09 2013-07-23 Hewlett-Packard Development Company, L.P. Ink compositions for ink-jet printing
US20080206465A1 (en) * 2007-02-28 2008-08-28 Han-Adebekun Gang C Aqueous inkjet ink composition
WO2008106145A1 (en) * 2007-02-28 2008-09-04 Eastman Kodak Company Aqueous inkjet ink composition
US7771523B2 (en) 2007-04-20 2010-08-10 E.I. Du Pont De Nemours And Company Ink jet ink
US20090020037A1 (en) * 2007-04-20 2009-01-22 Christian Jackson Ink jet ink
US8362106B2 (en) 2007-12-04 2013-01-29 E I Du Pont De Nemours And Company Decarboxylating block copolymers
US20100273931A1 (en) * 2007-12-04 2010-10-28 E.I. Du Pont De Nemours And Company Decarboxylating block copolymers
US20100081740A1 (en) * 2008-09-29 2010-04-01 Christian Jackson Aqueous inkjet ink comprising self-dispersing pigment
US8263182B2 (en) 2008-10-14 2012-09-11 Eastman Kodak Company Inkjet printing system, ink, and process
US20100092669A1 (en) * 2008-10-14 2010-04-15 Irving Mark E Inkjet printing system, ink, and process
WO2012016125A3 (en) * 2010-07-30 2012-07-05 Cabot Corporation Polymeric pigment systems and methods
US9056991B2 (en) 2010-07-30 2015-06-16 Cabot Corporation Polymeric pigment systems and methods
WO2012087542A2 (en) 2010-12-20 2012-06-28 Eastman Kodak Company Inkjet ink composition with jetting aid
US9133355B2 (en) 2011-03-30 2015-09-15 Hewlett-Packard Development Company, L.P. Aqueous ink compositions and method of preparing same

Also Published As

Publication number Publication date
DE602004022283D1 (en) 2009-09-10
JP5276268B2 (en) 2013-08-28
WO2004104119A1 (en) 2004-12-02
JP2007505203A (en) 2007-03-08
AT437924T (en) 2009-08-15
EP1625186A1 (en) 2006-02-15
US20080017067A1 (en) 2008-01-24
US8710116B2 (en) 2014-04-29
EP1625186B1 (en) 2009-07-29
DE202004021559U1 (en) 2009-01-02

Similar Documents

Publication Publication Date Title
US6500248B1 (en) Ink composition for ink-jet recording and method of ink-jet recording
EP1728835B1 (en) Water color ink, set of reaction liquid and water color ink and image forming method
US7276110B2 (en) Cyan ink and ink set
EP1457536B1 (en) Ink composition
EP0851014B1 (en) Ink jet inks containing hydrosols as polymer additives
EP0718383B1 (en) Ink jet ink compositions and printing processes
US7399351B2 (en) Pigmented inkjet ink and ink set
JP4551622B2 (en) Water-based ink
DE69917384T2 (en) Aqueous pigmented inkjet inks for printing on vinyl surfaces
EP0826751B1 (en) Aqueous dispersions containing graft copolymers as the dispersant
CN1930253B (en) Ink-jet ink, method for ink-jet recording
US6932465B2 (en) Reaction solution, set of reaction solution and ink, ink jet recording apparatus and image recording method
JP3430512B2 (en) The aqueous ink composition and a recording method using the
US9028600B2 (en) Inkjet ink, inkjet recording method, and inkjet recording device
KR100947295B1 (en) Ink for recording, and ink cartridge, ink recorded matter, inkjet recording apparatus and inkjet recording method using the same
US7985784B2 (en) Ink set, and recording method and recorded material using the same
US20020044185A1 (en) Ink-jet printing method
US20060100311A1 (en) Aqueous ink, ink-jet recording method, ink cartridge, recording unit, ink-jet recording apparatus and image forming method
JP3874336B2 (en) Recording liquid, ink-jet recording method and recording apparatus using the same
US5205861A (en) Aqueous ink jet inks containing alkylene oxide condensates of certain nitrogen heterocyclic compounds as cosolvents
EP1631635B1 (en) Aqueous ionically stabilized dispersions
JP5376810B2 (en) The ink composition, ink set, and an image forming method
KR100980746B1 (en) Pigment dispersion, recording ink, ink cartridge, ink-jet recording method and ink-jet recording apparatus
US5997623A (en) Ink jet inks comprising anti-curl agents and printing processes
US5958121A (en) Ink compositions and multicolor thermal ink jet printing process for the production of high quality images

Legal Events

Date Code Title Description
AS Assignment

Owner name: E. I. DU PONT DE NEMOURS AND COMPANY, DELAWARE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:VALENTINI, JOSE E.;FAKE, DEAN M.;REEL/FRAME:015425/0972

Effective date: 20040910