(19)
(11)EP 3 152 270 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
29.07.2020 Bulletin 2020/31

(21)Application number: 14893875.6

(22)Date of filing:  04.06.2014
(51)International Patent Classification (IPC): 
C09D 11/30(2014.01)
B41M 5/00(2006.01)
C09D 11/38(2014.01)
B41J 2/01(2006.01)
C09D 11/322(2014.01)
(86)International application number:
PCT/US2014/040851
(87)International publication number:
WO 2015/187148 (10.12.2015 Gazette  2015/49)

(54)

PIGMENT-BASED INKJET INKS

PIGMENTBASIERTE TINTENSTRAHLTINTEN

ENCRES À BASE DE PIGMENT POUR L'IMPRESSION PAR JET D'ENCRE


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(43)Date of publication of application:
12.04.2017 Bulletin 2017/15

(73)Proprietor: Hewlett-Packard Development Company, L.P.
Spring TX 77389 (US)

(72)Inventors:
  • CHAFFINS, Sterling
    Corvallis, Oregon 97330-4239 (US)
  • DEKAM, Kevin P.
    Corvallis, Oregon 97330-4239 (US)
  • BHATT, Jayprakash C.
    Corvallis, Oregon 97330-4239 (US)
  • DEARDURFF, Larrie
    Corvallis, Oregon 97330-4239 (US)
  • RUUD, Cory J.
    Corvallis, Oregon 97330-4239 (US)
  • THORNBERRY, Matthew
    Corvallis, Oregon 97330-4239 (US)

(74)Representative: Beccarelli, Sandra Béatrice Yvonne 
IP Section Hewlett-Packard Limited Long Down Avenue Stoke Gifford
Bristol BS34 8QZ
Bristol BS34 8QZ (GB)


(56)References cited: : 
EP-A1- 2 025 726
WO-A2-2008/048869
US-A1- 2004 252 169
US-A1- 2013 063 518
WO-A1-2013/015813
US-A- 5 837 044
US-A1- 2005 039 634
US-A1- 2013 079 442
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    BACKGROUND



    [0001] There are several reasons that inkjet printing has become a popular way of recording images on various media surfaces, particularly paper. Some of these reasons include low printer noise, capability of high-speed recording, and multi-color recording. Additionally, these advantages can be obtained at a relatively low price to consumers. Though there has been great improvement in inkjet printing, accompanying this improvement are increased demands by consumers, e.g., higher speeds, higher resolution, full color image formation, increased stability, large format printing, etc.

    [0002] A few characteristics of inkjet printing systems that are desirable to achieve relate to nozzle health, short term and sustained decap performance, kogation, color gamut, durability, ink efficiency, to name a few. Accordingly, investigations continue into developing ink formulations that can be printed accurately and with acceptable durability without excessive clogging.

    [0003] US 2013/063518 relates to a pigment particle that has a yellow hue. The pigment particle has a specific structure and has a maximum absorption wavelength of an absorption spectrum in a wavelength region of 200 nm or more and 800 nm or less is present in a range of 340 nm or more and 360 nm or less. The application also describes the ink composition comprising it and further containing a 1,2-alkanediol

    [0004] EP 2 025 726 describes an aqueous ink for an inkjet, comprising a pigment and two a water-soluble organic solvent. one comprising at least one of a diglycerol and a polyglycerol; and the other comprising a polyethylene glycol mono-alkyl ether represented by formula RO(CH2CH2O)nH wherein R represents an alkyl group having from 4 to 6 carbon atoms, and n represents an integer from 4 to 6.

    [0005] US 2013/079442 relates to A blue ink for postage printing, which contains a blue pigment, a black dye, and an aqueous carrier, wherein the weight ratio of blue pigment to black dye is in the range of 50:1 to 2:1. The blue pigment is a copper phthalocyanine pigment or an anthraquinone pigment, and the black dye is an azo dye.

    DETAILED DESCRIPTION



    [0006] The present disclosure is drawn to pigment-based inkjet inks with certain co-solvents or classes of co-solvents, and a blend of two surfactants that, in combination, can be formulated to provide inks suitable for high speed printing with improved decap performance (such as, for example, would be desirable in wide or large format printers that utilize a page wide printhead bar assembly). In further detail, the pigment-based inkjet inks can include water, from 2 wt% to 9 wt% pigment solids, from 0.05 wt% to 2 wt% of an acetylenic diol non-ionic surfactant, from 0.05 wt% to 2 wt% of a second surfactant, and from 5 wt% to 50 wt% of an organic solvent system comprising triethylene glycol and a cyclic amide, wherein the cyclic amide comprises a cyclic diamide. The second surfactant can be one of the following: a polysorbate having at least 50 wt% lipophilic oleic acid groups and having an HLB value of less than 15; or a C12-C18 polyoxyethylene glycol ether having an ethylene oxide number less than 20; or a perfluoropolyether including a polyethylene glycol primary alcohol or diol. In a related example, a method of inkjet printing can include jetting the inkjet ink described above onto a media substrate.

    [0007] In another example, a method of making a pigment-based inkjet ink can include preparing a liquid vehicle including water, organic solvent, surfactant, and a polymeric binder; and slowly adding pigment particles to disperse and suspend the pigment particles within the liquid vehicle. In this manner, substantially all of the pigments are dispersed effectively the liquid vehicle, e.g., >99wt%. The pigment-based inkjet ink after preparation can comprise water; from 2 wt% to 9 wt% pigment solids; from 0.05 wt% to 2 wt% of an acetylenic diol non-ionic surfactant; from 0.05 wt% to 2 wt% of a second surfactant, said second surfactant being a polysorbate having an HLB value of less than 15, or a C12-C18 polyoxyethylene glycol ether having an ethylene oxide number less than 20, or a perfluoropolyether including a polyethylene glycol primary alcohol or diol; from 5 wt% to 50 wt% of an organic solvent system comprising triethylene glycol and a cyclic amide, wherein the cyclic amide comprises a cyclic diamide; and 0.1 wt% to 3 wt% polymeric binder.

    [0008] Though the inkjet ink in each of these embodiments can be fired from a variety of different types of inkjet architecture, it is noteworthy to point out that these inks can be fired very rapidly with improved decap performance, and thus are suitable for printing from printhead bars such as a page wide printhead assembly or other print bars. Since these types of printheads are typically designed to have a width that is at or about the width of the print media being printed to, no side to side carriage motion occurs. Instead, the media sheet or roll moves beneath the laterally stationary page wide printhead assembly or bar. Thus, inkjet inks that can be printed rapidly with high print quality and long decap performance can be highly advantageous for fast printing processes. That being stated, there is no requirement that the inkjet inks of the present disclosure be printed from this specific type of printhead assembly. These inkjet inks are, however, suitable for use in page wide printhead assemblies that may not be serviced or spit from unused nozzles as frequently as carriage type printhead assemblies.
    thus, solving decap problems with frequent spitting is not a good option. Hence, to maintain a low frequency of spitting on paper, good sustained decap performance is beneficial when printing from a laterally stationary print bar. In accordance with this, the inkjet ink formulations described herein can provide excellent sustained decap performance (spitting frequency of 10s for 10min or more) to enable high speed and high quality printing.

    [0009] The speeds that can be printed from page wide and other printers can be very fast. Certain high speed scanning printers with inks such as those described herein can be printed at ranges from 20 inches per second (ips) to 60 ips. Other page wide printers can be adapted to print at ranges such as 2 ips to 15 ips, 2 ips to 20 ips, or 2 ips to 30 ips. Thus, a range of speeds suitable for the present inks can be from 2 ips to 60 ips.

    [0010] With this background in mind, in accordance with the examples described herein, various details are provided herein which are applicable to the inkjet ink, method of printing, method of making, etc., of the present disclosure.

    [0011] In accordance with embodiments of the present disclosure, the liquid vehicle includes certain surfactants in combination, as well as certain organic co-solvents in combination, as will be described in greater detail hereinafter. Other ingredients that can be present include water, other co-solvents, other surfactants, biocides, sequestering agents, plasticizers, binders, etc.

    [0012] In further detail with respect to the surfactant, there are two (or more) different surfactants present in the inkjet ink formulations of the present disclosure. The first surfactant that is present is an acetylenic diol non-ionic surfactant, typically present at from 0.05 wt% to 2 wt% based on the ink as a whole. An example of an acetylenic diol non-ionic surfactant is Surfynol® 104 (2,4,7,9-tetramethyl-5-decyne-4,7-diol). The second surfactant can be one of three types of surfactants, namely a polysorbate having at least 50% lipophilic oleic acid groups and having an HLB value of less than 15; or a C12-C18 polyoxyethylene glycol ether having an ethylene oxide number less than 20; or a perfluoropolyether including a polyethylene glycol primary alcohol or diol.

    [0013] Polysorbate surfactants, generally, include Polysorbate 20 (or polyoxyethylene 20 sorbitan monolaurate), Polysorbate 40 (or polyoxyethylene 20 sorbitan monopalmitate), Polysorbate 60 (or polyoxyethylene 20 sorbitan monostearate), Polysorbate 80 (or polyoxyethylene 20 sorbitan monooleate), or the like. However, not all of these polysorbates have at least 50 wt% lipophilic oleic acid groups and having an HLB value of less than 15. Brand names for these polysorbate surfactants include those sold under the tradename Tween® or Alkest®. Regarding the nomenclature of these polysorbates, the number "20" following "polyoxyethylene" refers to the total number of oxyethylene - (CH2CH2O)- groups found in the molecule. The number 20, 40, 60, or 80 following "polysorbate" is related to the type of fatty acid associated with the polyoxyethylene sorbitan portion. Monolaurate is indicated by 20, monopalmitate is indicated by 40, monostearate by 60 and monooleate by 80. Polysorbate 20, Polysorbate 60, and Polysorbate 80 are shown by example below, as follows:







    [0014] Other polysorbates can likewise be used, including Polysorbate 85, or Tween® 85, which is polyethylene glycol sorbitan trioleate; or Polysorbate 81, or Tween® 81, which is a polyoxyethylene (5) sorbitan monooleate. Tween® 85 and Tween® 81 are oleyl type compounds and include 70 wt% oleic acid. Polyoxyethylene sorbitan dioleate can also be used.

    [0015] The second surfactant can alternative be a polyoxyethylene glycol ether, including those having the base structure, as follows:

            CH3(CH2)n(CH2CH2O)mH

    where m can be less than 20, and n can be from about 8 to 20 (note that there are Brij® surfactants and other polyoxyethylene glycol ether surfactants that fall outside of these ranges, but those within the ranges of m=less than 20 and n=8-20 are listed as being particularly beneficial in the inkjet inks of the present disclosure). In one particular example, the polyoxyethylene glycol ether can have a tolerance of up to 1 "cis" unsaturated (oleyl) group, e.g., 0 or 1 "cis" group (which would reduce the total number of hydrogen atoms by 2 at the double bond along the alkyl chain portion of the formula). Thus, oleyl type surfactants are included in this definition, even though they do not strictly fit within the above structural formulation, as the formulation is provided merely for convenience. Examples surfactants, their type, and their relative n and m values are provided in Table 1, as follows:
    Table 1
    Surfactant Trade NameTypenm
    Brij® S10 Stearyl 18 10
    Brij® S5 Stearyl 18 5
    Brij® S15 Stearyl 18 15
    Brij® S20 Stearyl 18 20
    Brij® S2/93 Stearyl 18 2
    Brij® S7 Stearyl 18 7
    Brij® 98/O20 Oleyl 18 20
    Brij® O10 Oleyl 18 10
    Brij® O2 Oleyl 18 2
    Brij® O3 Oleyl 18 3
    Brij® O5 Oleyl 18 5
    Brij® C2 Cetyl 16 2
    Brij® C7 Cetyl 16 7
    Brij® C10 Cetyl 16 10
    Brij® C20 Cetyl 16 20
    Brij® L4/30 Lauryl 12 4
    Brij® L9 Lauryl 12 9
    Brij® L15 Lauryl 12 15
    Synperonic® 91-2.5 Decyl 10 2
    Synperonic® 91-10 Decyl 10 10
    Synperonic® 13-12 Tridecyl 13 12


    [0016] In yet another alternative example, the second surfactant can be a perfluoropolyether with a primary alcohol or diol. Examples include Fluorolink® D (HOCH2CF2O(CF2CF2O)p(CF2O)qCF2CH2OH); Fluorolink® E (HO(CH2CH2O)nCH2CF2O(CF2CF2O)p(CF2O)qCF2CH2(OCH2CH2)nOH); Fluorolink® C10 (HOOCCF2O(CF2CF2O)p(CF2O)qCF2COOH); or Fluorolink® T (HOCH2CH(OH)CH2OCH2CF2O(CF2CF2O)p(CF2O)qCF2CH2OCH2CH(OH) CH2OH), for example. In these examples, p + q can be 20 to 200, or from 40 to 180. Also, p/q can be 0.25 to 5, or can be from 0.5 to 2. n can be from 1 to 6, or from 1 to 4, or from 1 to 2.

    [0017] In the inkjet inks described herein, suitable co-solvents for use include water and water soluble organic co-solvents. Any of a number of solvents can be used, but in accordance with examples of the present disclosure, certain organic co-solvents are used to provide some of the benefits described herein. Triethylene glycol is one such solvent. Triethylene glycol provides the benefit of acting as a humectants providing improved short term decap performance. Additionally, the presence of a cyclic amide can provide certain benefits, including short term and sustained decap, and these solvents can work well with the surfactants described herein. In one example, there can be two cyclic amides present. For example, a combination of 2-pyrrolidinone and Dantocol [di(2-hydroxyethyl)-5, 5-dimethylhydantoin] can be particularly effective together. Benefits provided by this combination of cyclic amides include assistance with nozzle health and trajectory at certain concentrations and ratios. It is noted that in one example, the presence of triethylene glycol, Dantocol, and 2-pyrrolidinone strongly interact with one another, so formulations that utilize all three tend to perform better with respect to short term decap, sustained decap, and trajectory than systems without all three solvents.

    [0018] Examples of water soluble organic co-solvents that may additionally be used include, but are not limited to, aliphatic alcohols, aromatic alcohols, diols, triols, glycol ethers, poly(glycol) ethers, lactams, formamides, acetamides, long chain alcohols, ethylene glycol, propylene glycol, diethylene glycols, triethylene glycols, glycerine, dipropylene glycols, glycol butyl ethers, polyethylene glycols, polypropylene glycols, amides, ethers, carboxylic acids, esters, organosulfides, organosulfoxides, sulfones, alcohol derivatives, carbitol, butyl carbitol, cellosolve, ether derivatives, amino alcohols, and ketones. For example, co-solvents can include primary aliphatic alcohols of 30 carbons or less, primary aromatic alcohols of 30 carbons or less, secondary aliphatic alcohols of 30 carbons or less, secondary aromatic alcohols of 30 carbons or less, 1,2-diols of 30 carbons or less, 1,3-diols of 30 carbons or less, 1,5-diols of 30 carbons or less, ethylene glycol alkyl ethers, propylene glycol alkyl ethers, poly(ethylene glycol) alkyl ethers, higher homologs of poly(ethylene glycol) alkyl ethers, poly(propylene glycol) alkyl ethers, higher homologs of poly(propylene glycol) alkyl ethers, lactams, substituted formamides, unsubstituted formamides, substituted acetamides, and unsubstituted acetamides. Specific examples of certain co-solvents that may likewise be used include, but are not limited to, 1,5-pentanediol, Liponic ethoxylated glycerol 1 (EG-1), Liponic ethoxylated glycerol 7 (EG-7), 2-methyl-2,4-pentanediol, 2-methyl-1,3-propanediol, 2-ethyl-2-hydroxymethyl-1,3-propanediol, diethylene glycol, 3-methoxybutanol, propylene glycol monobutyl ether, 1,3-dimethyl-2-imidazolidinone, and derivatives thereof. Co-solvents can be added to reduce the rate of evaporation of water in the inkjet ink to minimize clogging or provide other improved properties related to viscosity, pH, surface tension, optical density, gamut, durability, decap, and print quality, for example. The water soluble organic co-solvent system total concentration can range from about 5 wt% to about 50 wt%, or from 10 wt% to 40 wt%. Each organic co-solvent alone can be typically present at from about 0.1 wt% to about 20 wt% of the inkjet ink composition. This being said, the solvents may be present in the inkjet ink composition at any concentration that is effective for use.

    [0019] In another aspect of the present disclosure, various biocides can be used to inhibit growth of undesirable microorganisms. Several non-limiting examples of suitable biocides include benzoate salts, sorbate salts, and commercial products such as Nuosept®, Ucarcide®, Vancide®, Proxel GXL, Anticide® B20 or M20, Kordex® MLX for example. Typically, such biocides comprise less than about 5 wt% of the inkjet ink composition and often from about 0.05 wt% to about 2 wt%.

    [0020] Other known additives can also be included, as known in the art.

    [0021] The ink vehicle or liquid vehicle described herein can provide pigment-based inkjet inks with improved decap performance. For example, many similar inkjet inks that have been commercially available deliver short term decap performance of only 0-2 seconds, or there are others which deliver short term decap performance for longer periods, but that is typically a 2nd drop short term decap. In accordance with the present disclosure, inkjet inks can be prepared with a short term 1st drop decap of 0-8 seconds, which is very good short term decap performance as recognized in the thermal inkjet arts. Likewise, sustained decap performance with many commercially available inkjet inks is also relatively poor, even at typical spitting frequencies of 5 seconds for 10 minutes. The inkjet inks of the present disclosure can be formulated to have sustained decap performance exceeding this, e.g., 5 second for 10 minutes or 10 seconds for 10 minutes.

    [0022] In order to improve durability further, a binder can be included in the inkjet inks of the present disclosure as well. Though the addition of a binder can improve durability, too much binder can significantly impact decap performance negatively. Thus, a balance between decap performance and durability can be considered when adding binder to the formulations of the present disclosure.

    [0023] An exemplary binder that can be included in the inkjet ink is a Hydran™ RW-7500 or Hydran™ RW-7581 from DIC, which are polyurethane binders obtained by reacting a polyol containing a vinyl polymer having two hydroxyl groups at one end and at least one polyol. Other suitable binders that can be used include other water-dispersible or water soluble polymers. Examples of polymer classes include acrylics, styrenics, polyethylenes, polypropylenes, polyesters, polyamides, (other) polyurethanes, polyureas, polyethers, polycarbonates, polyacid anhydrides, and copolymers and/or combinations thereof. Such polymer particles can be iono-meric, film-forming, non-film-forming, fusible, or heavily crosslinked, and can have a wide range of molecular weights and glass transition temperatures.

    [0024] Examples of useful polymeric binders include styrene-acrylic copolymers sold under the trade names Joncryl® (S.C. Johnson Co.), Ucar™ (Dow Chemical Co.), Jonrez® (MeadWestvaco Corp.), and Vancryl® (Air Products and Chemicals, Inc.); sulfonated polyesters sold under the trade name Eastman AQ® (Eastman Chemical Co.); polyethylene or polypropylene resin emulsions and polyurethanes (such as the Witcobonds® from Witco); polyacrylic type polymers such as polyacrylic acid and styrene-acrylic methacrylic acid copolymers (such as as Joncryl® 70 from S.C. Johnson Co., TruDot™ IJ-4655 from MeadWestvaco Corp., and Vancryl® 68S from Air Products and Chemicals, Inc. These polymers can be used because they are compatible in typical aqueous-based inkjet ink compositions, and because they render printed images that are highly durable towards physical abrasion. Binders are normally included in the inkjet inks of the present disclosure at from 0.1 wt% to 3 wt%, but more typically from 0.5 wt% to 2 wt%, based on the polymer solids content.

    [0025] The pigments that can be used in accordance with embodiments of the present disclosure include both self-dispersed pigments as well as conventionally dispersed pigments, e.g., pigments dispersed by a separate dispersing agent that is not covalently attached to the surface. If self-dispersed, a dispersant is typically prepared in a precursor form, and then the precursor is attached to the pigment to chemically modify the surface of the pigment. In one example, the dispersant can be attached to the pigment using various precursor materials, such as para-aminobenzoic acids, isophthalic acids, tricarboxylic acids, carboxylic groups, sulfonylic groups, phosphates, oligomers, polymers, and isomers thereof, for example. Other precursors can also be used to attach to the pigment, as would be known by those skilled in the art.

    [0026] The formulations of the present disclosure can be effective for use with both black and colored pigments. Specifically, if black is used, the black pigment can be any commercially available black pigment that provides acceptable optical density and print characteristics. Such black pigments can be manufactured by a variety of known methods such as channel methods, contact methods, furnace methods, acetylene methods, or thermal methods, and are commercially available from such vendors as Cabot Corporation, Columbian Chemicals Company, Evonik, Mitsubishi, and E.I. DuPont de Nemours and Company. For example, commercially available carbon black pigments include Color Black FW 200, Color Black FW 2V, Color Black FW1, Color Black FW 18, Color Black FW S160, Color Black FW S170, Printex® including 95, 85, 75, 55, 45, 300, 35, 25, 200, 12, and Special Blacks including, 4A, 4, 5, 6, 550, 350, 250; BP1100, BP900, BP800, M1100, M900, M800, Monarch® 1400, Monarch® 1300, Monarch® 1100, Monarch® 1000, Monarch® 900, Monarch® 880, and Monarch® 700; Cab-O-Jet® 200 and Cab-O-Jet® 300; Raven® 2500 Ultra, Raven® 2000, Raven® 7000, Raven® 5750, Raven® 5250, Raven® 5000, and Raven® 3500; 45 B, and combinations thereof.

    [0027] If colored pigments are used, any of a number of pigments can be selected for inclusion in the inkjet inks of the present disclosure, such as cyan, magenta, yellow, blue, orange, green, pink, etc. Suitable organic pigments include, for example, azo pigments including diazo pigments and monoazo pigments, polycyclic pigments (e.g., phthalocyanine pigments such as phthalocyanine blues and phthalocyanine greens, perylene pigments, perynone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, pyranthrone pigments, and quinophthalone pigments), insoluble dye chelates (e.g., basic dye type chelates and acidic dye type chelate), nitropigments, nitroso pigments, anthanthrone pigments such as Pigment Red 168, and the like. Representative examples of phthalocyanine blues and greens include copper phthalocyanine blue, copper phthalocyanine green and derivatives thereof (Pigment Blue 15 and Pigment Green 36). Representative examples of quinacridones include Pigment Orange 48, Pigment Orange 49, Pigment Red 282, Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209, Pigment Violet 19 and Pigment Violet 42. Representative examples of anthraquinones include Pigment Red 43, Pigment Red 194, Pigment Red 177, Pigment Red 216 and Pigment Red 226. Representative examples of perylenes include Pigment Red 123, Pigment Red 149, Pigment Red 179, Pigment Red 190, Pigment Red 189 and Pigment Red 224. Representative examples of thioindigoids include Pigment Red 86, Pigment Red 87, Pigment Red 88, Pigment Red 181, Pigment Red 198, Pigment Violet 36, and Pigment Violet 38. Pigment 150 is another example of an azo pigment. Representative examples of heterocyclic yellows include Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow 65, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 90, Pigment Yellow 110, Pigment Yellow 117, Pigment Yellow 120, Pigment Yellow 128, Pigment Yellow 138, Pigment Yellow 150, Pigment Yellow 151, Pigment Yellow 155, and Pigment Yellow 213. Such pigments are commercially available in powder, press cake, or dispersion form from a number of sources. In one example, pigment blends or dispersions from various manufacturers can be used.

    [0028] Typically, the pigments of the present disclosure can be from about 5 nm to about 10 µm in size, and in one aspect, the pigments can be from 10 nm to about 500 nm in size, although sizes outside this range can be used if the pigment can remain dispersed and provide adequate printing properties.

    [0029] In further detail regarding the pigments, with inks generally, colorants used to improve color gamut on the hue-saturation plane are often dyes rather than pigments. However, dye based inks can have poor durability (e.g. water fastness, light fastness, and air/ozone fastness). Inkjet ink formulations prepared in accordance with the present disclosure, even without the presence of dyes, can have acceptable color gamut, while at the same time providing acceptable decap performance and improved durability compared to dye-based inks.

    [0030] It is noted that, as used in this disclosure, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "an inkjet ink" includes one or more of such inks, and reference to "the pigment" includes reference to one or more amounts of pigments.

    [0031] As used herein, "liquid vehicle" or "ink vehicle" refers to the liquid fluid in which colorant is dispersed or dissolved to form an ink. Liquid vehicles are well known in the art, and a wide variety of ink vehicles may be used in accordance with embodiments of the present disclosure. Such liquid vehicles may include a mixture of a variety of different agents, including without limitation, surfactants, organic co-solvents, buffers, biocides, viscosity modifiers, sequestering agents, stabilizing agents, and/or water. The liquid vehicle can also carry other additives such as latex particulates, binders, or other polymers, in some embodiments. It is noted that though the liquid vehicles of the present disclosure can include many of these ingredients, the present technology relates more specifically to the use of certain specific organic co-solvents and/or surfactants as set forth herein.

    [0032] As used herein, "ink" or "inkjet ink" refers to a single liquid vehicle that contains at least one pigment, and in accordance with embodiments of the present disclosure, the inks can also include certain more specific classes of solvents and/or surfactants. In one example, the inkjet ink can be a thermal inkjet ink.

    [0033] As used herein, "pigment" refers to a colorant particle which is typically substantially insoluble in the liquid vehicle in which it is used. Pigments can be conventionally dispersed using a separate dispersing agent, or can be self-dispersed, having a dispersing agent attached to the surface of the pigment.

    [0034] As used herein, "self-dispersed" generally refers to pigments that have been functionalized with a dispersing agent, such as by chemical attachment of the dispersing agent to the surface of the pigment. The dispersing agent can be a small molecule or a polymer or an oligomer. The dispersing agent can be attached to such pigments to terminate an outer surface of the pigment with a charge, thereby creating a repulsive nature that reduces agglomeration of pigment particles within the liquid vehicle.

    [0035] As used herein, the term "about" is used to provide flexibility to a numerical range endpoint by providing that a given value may be "a little above" or "a little below" the endpoint. The degree of flexibility of this term can be dictated by the particular variable and would be within the knowledge of those skilled in the art to determine based on experience and the associated description herein.

    [0036] As used herein, a plurality of items, structural elements, compositional elements, and/or materials may be presented in a common list for convenience. However, these lists should be construed as though each member of the list is individually identified as a separate and unique member. Thus, no individual member of such list should be construed as a de facto equivalent of any other member of the same list solely based on their presentation in a common group without indications to the contrary.

    [0037] Concentrations, amounts, and other numerical data may be expressed or presented herein in a range format. It is to be understood that such a range format is used merely for convenience and brevity and thus should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. As an illustration, a numerical range of "about 1 wt% to about 5 wt%" should be interpreted to include not only the explicitly recited values of about 1 wt% to about 5 wt%, but also include individual values and sub-ranges within the indicated range. Thus, included in this numerical range are individual values such as 2, 3.5, and 4 and sub-ranges such as from 1-3, from 2-4, and from 3-5, etc. This same principle applies to ranges reciting only one numerical value. Furthermore, such an interpretation should apply regardless of the breadth of the range or the characteristics being described.

    EXAMPLES



    [0038] The following examples illustrate the embodiments of the disclosure that are presently best known. However, it is to be understood that the following are only exemplary or illustrative of the application of the principles of the present technology. Numerous modifications and alternative compositions and methods may be devised by those skilled in the art without departing from the spirit and scope of the present disclosure. The appended claims are intended to cover such modifications and arrangements.

    Example 1 - Formulations



    [0039] Multiple inkjet ink formulations were prepared in accordance with the following general formulation shown in Table 2, with the specific "Second Surfactant" as set forth in Table 3. Thus, 23 formulations were prepared (i.e. Formulation A through Formulation W), as follows:
    Table 2
    INGREDIENTTYPEWT%
    2-Pyrrolidinone Co-Solvent 7.5
    Triethylene Glycol Co-Solvent 10
    Dantocol Co-Solvent 4
    Surfynol 104 (Acetylenic Diol Non-Ionic Surfactant) Surfactant 0.3
    Second Surfactant (Polysorbate, or Polyoxyethylene Glycol Ether, or Perfluoropolyether) Surfactant 0.1 to 1**
    Proxel GXL (1,2-Benzisothiazolin-3-one) Biocide 0.1
    Kordek MLX (Methylisothiazolone) Biocide 0.14
    Hydran™ RW 7500 Binder 1
    Pigment Red 282 Pigment Dispersion 3.1 solids
    Pigment Red 15 Pigment Dispersion 1.3 solids
    **Surfactant concentration for the Second Surfactant was based on the equimolar concentration using Brij® S10 is at 0.3 wt% as a benchmark.
    Table 3
    IDSURFACTANTCLASSPROPERTIES
    A Fluorolink® D Perfluoropolyether Primary alcohol
    B Fluorolink® E Perfluoropolyether PEG-primary alcohol
    C Fluorolink® C10 Perfluoropolyether Acid
    D Flouorolink T Perfluoropolyether Diol (opened epoxy)
    E Brij® S10 (control) PEG ether Stearyl (C18); EO 10; HLB 12
    F Brij® 93 (veg) PEG ether Oleyl (C18); EO 10; HLB 4
    G Brij® 98 (veg) or (Brij® 020) PEG ether Oleyl (C18); EO 20; HLB 15
    H Brij® 30 PEG ether Lauryl (C12); EO 4; HLB 9
    I Brij® C10 PEG ether Cetyl (C16); EO 10; HLB 12
    J Brij® C2 PEG ether Cetyl (C16); EO 2; HLB 5
    K Brij® C20 PEG ether Cetyl (C16); EO 20; HLB 15
    L Brij® CS20 PEG ether Cetyl (C16); Steryl (C18); EO 20; HLB 16
    M Brij® L23 PEG ether Lauryl (C12); EO 23; HLB 17
    N Brij® 010 PEG ether Oleyl (C18); EO10; HLB 12
    O Brij® S100 PEG ether Stearyl (C18); EO 100; HLB 18
    P Brij® S20 PEG ether Stearyl (C18); EO 20; HLB 15
    Q Brij® S721 PEG ether Stearyl (C18); EO21; HLB 16
    R Synperonic® 13/12 PEG ether Tridecanol (C13); EO 12; HLB 15
    S Tween® 20 Polysorbate Lauryl (C12); HLB 16.7; 1228 Mw
    T Tween® 60 Polysorbate Stearyl (C18); HLB 14.9; 1309 Mw
    U Tween® 80 Polysorbate Oleyl (C18); HLB 15; 1310 Mw
    V Tween® 81 Polysorbate Oleyl (C18); HLB 10; Oleic Acid 70 wt%
    W Tween® 85 Polysorbate Oleyl (C18); HLB 11; Oleic Acid 70 wt%

    Example 2 - Ink Evaluation of Decap, Gamut, and Durability



    [0040] Each of the 23 inks prepared were evaluated for decap performance (short term and sustained decap), gamut, and durability. For each of these tests, an HP Inkjet Printer known commercially available OfficeJet Pro 8000 was used, and the ink lines, boxes, or other markings were printed on HP Multipurpose media.

    [0041] Decap can be evaluated two different ways. Short Term Decap (ST) performance is verified by first warming up the printer bar, and then, after a printing delay for some (decap) time, several lines were printed and the line quality is judged by image analysis for line darkness, width, and offset relative to a reference (top half of the printhead). More specifically, approximately 50 lines were printed. Typically, line recovery occurs immediately or in the first few lines, but this varies from ink to ink. That being stated, Sustained Decap (SOP) is a more difficult problem to solve. In evaluating SOP, the printing bar is warmed up along the entire printhead width and a reference line was printed. With SOP evaluation of the present example, a variable printing delay was followed by printing 15 or more additional lines. The exact delay and number of lines printed being dependent on the expected printer use. Though SOP values are not present in Table 4, these values are often acceptable when the corresponding ST decap is acceptable, though this is not always the case for every ink.

    [0042] Gamut was determined by printing varying blocks of colors on print media and then assessing the values with a Gretag-Macbeth spectrophotometer. Performance was judged based on saturation at a fixed ink limit (ng/300th).

    [0043] Durability was determined by printing an area fill plot on one side, followed by pulling the media back into the printer with a duplexer used for two sided printing. Star wheels can damage the print, and thus, each printed image was analyzed to quantify the amount of damage caused by the star wheels.

    [0044] Data for three tests is provided herein (Short Term Decap, Gamut, and Durabiltiy), and a grade scale ranging from 1 to 5 (with 1 being poor performance and 5 being excellent performance) was used, and the results are shown in Table 4 below:
    Table 4
    IDDECAP (ST)GAMUTDURABILITY
    A 2 4 3
    B 3 5 1
    C 1 2 1
    D 3 3 5
    E 3 3 3
    F 4 3 2
    G 2 4 4
    H 5 3 3
    I 3 4 1
    J 4 5 5
    K 1 4 3
    L 1 5 3
    M 1 4 4
    N 4 5 2
    O 1 2 1
    P 2 4 2
    Q 1 4 1
    R 3 5 1
    S 4 2 2
    T 2 4 3
    U 1 4 3
    V 3 5 5
    W 4 5 2


    [0045] While the present technology has been described with reference to certain examples, those skilled in the art will appreciate that various modifications, changes, omissions, and substitutions can be made without departing from the spirit of the disclosure. It is therefore intended that the disclosure be limited only by the scope of the appended claims.


    Claims

    1. A pigment-based inkjet ink, comprising:

    water;

    from 2 wt% to 9 wt% pigment solids;

    from 0.05 wt% to 2 wt% of an acetylenic diol non-ionic surfactant;

    from 0.05 wt% to 2 wt% of a second surfactant, said second surfactant being:

    a polysorbate having an HLB value of less than 15, or

    a C12-C18 polyoxyethylene glycol ether having an ethylene oxide number less than 20, or

    a perfluoropolyether including a polyethylene glycol primary alcohol or diol; and

    from 5 wt% to 50 wt% of an organic solvent system comprising triethylene glycol and a cyclic amide, wherein the cyclic amide comprises a cyclic diamide.


     
    2. The pigment-based inkjet ink of claim 1, wherein the acetylenic diol non-ionic surfactant is a 2,4,7,9-tetramethyl-5-decyne-4,7-diol surfactant or derivative thereof.
     
    3. The pigment-based inkjet ink of claim 1, wherein the second surfactant is the polysorbate.
     
    4. The pigment-based inkjet ink of claim 3, wherein the polysorbate includes at least 50 wt% lipophilic oleic acid.
     
    5. The pigment-based inkjet ink of claim 1, wherein the second surfactant is the C12-C18 polyoxyethylene glycol ether.
     
    6. The pigment-based inkjet ink of claim 5, wherein the C12-C18 polyoxyethylene glycol ether is oleyl with a single cis unsaturated group.
     
    7. The pigment-based inkjet ink of claim 1, wherein the second surfactant is the perfluoropolyether.
     
    8. The pigment-based inkjet ink of claim 1, wherein the cyclic amide comprises 2-pyrrolidinone and di-(2-hydroxyethyl)-5,5-dimethylhydantoin.
     
    9. The pigment-based inkjet ink of claim 1, wherein the pigment solids comprise two different pigments collectively in the range of 2 wt% to 9 wt%.
     
    10. The pigment-based inkjet ink of claim 1, wherein the inkjet ink is devoid of dye.
     
    11. The pigment-based inkjet ink of claim 1, further comprising from 0.1 wt% to 3 wt% polymeric binder.
     
    12. A method of inkjet printing, comprising jetting an inkjet ink onto a media substrate, said inkjet ink comprising water; from 2 wt% to 9 wt% pigment solids; from 0.05 wt% to 2 wt% of an acetylenic diol non-ionic surfactant; from 0.05 wt% to 2 wt% of a second surfactant selected from a polysorbate having an HLB value of less than 15, a C12-C18 polyoxyethylene glycol ether having an EO value less than 20, or a perfluoropolyether including a polyethylene glycol primary alcohol or diol; and from 5 wt% to 50 wt% of an organic solvent system comprising triethylene glycol and a cyclic amide, wherein the cyclic amide comprises a cyclic diamide.
     
    13. The method of claim 12, wherein the step of jetting is from a page wide, laterally stationary, printhead assembly bar at a speed ranging from 2 inches per second to 60 inches per second.
     
    14. A method of making a pigment-based inkjet ink, comprising:

    preparing a liquid vehicle including water, organic solvent, surfactant, and a polymeric binder; and

    slowly adding pigment particles to disperse and suspend the pigment particles within the liquid vehicle,

    wherein the pigment-based inkjet ink after preparation comprises water; from 2 wt% to 9 wt% pigment solids; from 0.05 wt% to 2 wt% of an acetylenic diol non-ionic surfactant; from 0.05 wt% to 2 wt% of a second surfactant, said second surfactant being a polysorbate having an HLB value of less than 15, or a C12-C18 polyoxyethylene glycol ether having an ethylene oxide number less than 20, or a perfluoropolyether including a polyethylene glycol primary alcohol or diol; from 5 wt% to 50 wt% of an organic solvent system comprising triethylene glycol and a cyclic amide, wherein the cyclic amide comprises a cyclic diamide; and 0.1 wt% to 3 wt% polymeric binder.


     


    Ansprüche

    1. Tintenstrahltinte auf Pigmentbasis, Folgendes umfassend:

    Wasser;

    von 2 Gew.-% bis 9 Gew.-% Pigmentfeststoffe;

    von 0,05 Gew.-% bis 2 Gew.-% eines nichtionischen Acetylendiol-Tensids;

    von 0,05 Gew.-% bis 2 Gew.-% eines zweiten Tensids, wobei es sich bei dem zweiten Tensid um Folgendes handelt:

    ein Polysorbat mit einem HLB-Wert unter 15 oder

    ein C12-C18-Polyoxyethylenglycolether mit einer Ethylenoxidzahl unter 20 oder

    ein Perfluorpolyether mit einem Polyethylenglycol-Primäralkohol oder -diol; und

    von 5 Gew.-% bis 50 Gew.-% eines organischen Lösungsmittelsystems, umfassend Triethylenglycol und ein cyclisches Amid, wobei das cyclische Amid ein cyclisches Diamid umfasst.


     
    2. Tintenstrahltinte auf Pigmentbasis nach Anspruch 1, wobei das nichtionische Acetylendiol-Tensid ein 2,4,7,9-Tetramethyl-5-decin-4,7-diol-Tensid oder ein Derivat davon ist.
     
    3. Tintenstrahltinte auf Pigmentbasis nach Anspruch 1, wobei das zweite Tensid das Polysorbat ist.
     
    4. Tintenstrahltinte auf Pigmentbasis nach Anspruch 3, wobei das Polysorbat mindestens 50 Gew.-% lipophile Ölsäure enthält.
     
    5. Tintenstrahltinte auf Pigmentbasis nach Anspruch 1, wobei das zweite Tensid der C12-C18-Polyoxyethylenglycolether ist.
     
    6. Tintenstrahltinte auf Pigmentbasis nach Anspruch 5, wobei der C12-C18-Polyoxyethylenglycolether Oleyl mit einer einzelnen ungesättigten cis-Gruppe ist.
     
    7. Tintenstrahltinte auf Pigmentbasis nach Anspruch 1, wobei das zweite Tensid der Perfluorpolyether ist.
     
    8. Tintenstrahltinte auf Pigmentbasis nach Anspruch 1, wobei das cyclische Amid 2-Pyrrolidinon und Di-(2-hydroxyethyl)-5,5-dimethylhydantoin umfasst.
     
    9. Tintenstrahltinte auf Pigmentbasis nach Anspruch 1, wobei die Pigmentfeststoffe zwei verschiedene Pigmente, die gemeinsam im Bereich von 2 Gew.-% bis 9 Gew.-% liegen, umfassen.
     
    10. Tintenstrahltinte auf Pigmentbasis nach Anspruch 1, wobei die Tintenstrahltinte frei von Farbstoff ist.
     
    11. Tintenstrahltinte auf Pigmentbasis nach Anspruch 1, ferner von 0,1 Gew.-% bis 3 Gew.-% Polymerbindemittel umfassend.
     
    12. Verfahren zum Tintenstrahldrucken, umfassend das Ausstoßen einer Tintenstrahltinte auf ein Mediensubstrat, wobei die Tintenstrahltinte Folgendes umfasst: Wasser; von 2 Gew.-% bis 9 Gew.-% Pigmentfeststoffe; von 0,05 Gew.-% bis 2 Gew.-% eines nichtionischen Acetylendiol-Tensids; von 0,05 Gew.-% bis 2 Gew.-% eines zweiten Tensids, ausgewählt aus einem Polysorbat mit einem HLB-Wert unter 15, einem C12-C18-Polyoxyethylenglycolether mit einer EO-Zahl unter 20 oder einem Perfluorpolyether mit einem Polyethylenglycol-Primäralkohol oder -diol; und von 5 Gew.-% bis 50 Gew.-% eines organischen Lösungsmittelsystems, umfassend Triethylenglycol und ein cyclisches Amid, wobei das cyclische Amid ein cyclisches Diamid umfasst.
     
    13. Verfahren nach Anspruch 12, wobei der Schritt des Ausstoßens von einer seitenweiten, seitlich stationären Druckkopfanordnungsleiste mit einer Geschwindigkeit im Bereich von 2 Zoll pro Sekunde bis 60 Zoll pro Sekunde erfolgt.
     
    14. Verfahren zur Herstellung einer Tintenstrahltinte auf Pigmentbasis, Folgendes umfassend:

    Herstellen eines flüssigen Trägermittels, das Wasser, organisches Lösungsmittel, Tensid und ein Polymerbindemittel enthält; und

    langsames Hinzufügen von Pigmentpartikeln zum Dispergieren und Suspendieren der Pigmentpartikel in dem flüssigen Grägermittel,

    wobei die Tintenstrahltinte auf Pigmentbasis nach der Herstellung Folgendes umfasst: Wasser; von 2 Gew.-% bis 9 Gew.-% Pigmentfeststoffe; von 0,05 Gew.-% bis 2 Gew.-% eines nichtionischen Acetylendiol-Tensids; von 0,05 Gew.-% bis 2 Gew.-% eines zweiten Tensids, wobei es sich bei dem zweiten Tensid um ein Polysorbat mit einem HLB-Wert unter 15 oder ein C12-C18-Polyoxyethylenglycolether mit einer Ethylenoxidzahl unter 20 oder ein Perfluorpolyether mit einem Polyethylenglycol-Primäralkohol oder -diol handelt; von 5 Gew.-% bis 50 Gew.-% eines organischen Lösungsmittelsystems, umfassend Triethylenglycol und ein cyclisches Amid, wobei das cyclische Amid ein cyclisches Diamid umfasst; und 0,1 Gew.-% bis 3 Gew.-% Polymerbindemittel.


     


    Revendications

    1. Encre pour jet d'encre à base de pigments, comprenant :

    de l'eau ;

    de 2 % à 9 % en poids de pigments solides ;

    de 0,05 % à 2 % en poids de tensioactif non ionique à base de diol acétylénique ;

    de 0,05 % en poids à 2 % en poids d'un second tensioactif, ledit second tensioactif étant :

    un polysorbate ayant une valeur de HLB inférieure à 15, ou

    un éther de polyoxyéthylène glycol en C12 à C18 ayant un indice d'oxyde d'éthylène inférieur à 20, ou

    un perfluoropolyéther comportant un alcool ou diol primaire de polyéthylène glycol ; et

    de 5 % en poids à 50 % en poids d'un système de solvant organique comprenant du triéthylène glycol et un amide cyclique, l'amide cyclique comprenant un diamide cyclique.


     
    2. Encre pour jet d'encre à base de pigments selon la revendication 1, dans laquelle le tensioactif non ionique à base de diol acétylénique est un tensioactif à base de 2,4,7,9-tétraméthyl-5-décyne-4,7-diol ou d'un dérivé de celui-ci.
     
    3. Encre pour jet d'encre à base de pigments selon la revendication 1, dans laquelle le second tensioactif est le polysorbate.
     
    4. Encre pour jet d'encre à base de pigments selon la revendication 3, dans laquelle le polysorbate comporte au moins 50 % en poids d'acide oléique lipophile.
     
    5. Encre pour jet d'encre à base de pigments selon la revendication 1, dans laquelle le second tensioactif est l'éther de polyoxyéthylène glycol en C12 à C18.
     
    6. Encre pour jet d'encre à base de pigments selon la revendication 5, dans laquelle l'éther de polyoxyéthylène glycol en C12 à C18 est un oléyle avec un groupe cis insaturé unique.
     
    7. Encre pour jet d'encre à base de pigments selon la revendication 1, dans laquelle le second tensioactif est le perfluoropolyéther.
     
    8. Encre pour jet d'encre à base de pigments selon la revendication 1, dans laquelle l'amide cyclique comprend de la 2-pyrrolidinone et de la di-(2-hydroxyéthyl)-5,5-diméthylhydantoïne.
     
    9. Encre pour jet d'encre à base de pigments selon la revendication 1, dans laquelle les solides de pigment comprennent deux pigments différents collectivement dans la plage de 2 % en poids à 9 % en poids.
     
    10. Encre pour jet d'encre à base de pigments selon la revendication 1, dans laquelle l'encre pour jet d'encre est dépourvue de colorant.
     
    11. Encre pour jet d'encre à base de pigments selon la revendication 1, comprenant en outre de 0,1 % en poids à 3 % en poids de liant polymère.
     
    12. Procédé d'impression à jet d'encre, comprenant le jet d'une encre pour jet d'encre sur un substrat de support, ladite encre pour jet d'encre comprenant de l'eau ; de 2 % à 9 % en poids de pigments solides ; de 0,05 % à 2 % en poids de tensioactif non ionique à base de diol acétylénique ; de 0,05 % en poids à 2 % en poids d'un second tensioactif choisi parmi un polysorbate ayant une valeur de HLB inférieure à 15, un éther de polyoxyéthylène glycol en C12 à C18 ayant une valeur d'EO inférieure à 20, ou un perfluoropolyéther comportant un alcool ou diol primaire de polyéthylène glycol ; et de 5 % en poids à 50 % en poids d'un système de solvant organique comprenant du triéthylène glycol et un amide cyclique, l'amide cyclique comprenant un diamide cyclique.
     
    13. Procédé selon la revendication 12, dans lequel l'étape de jet s'effectue à partir d'une barre d'ensemble tête d'impression à largeur de page, latéralement immobile, à une vitesse dans la plage de 2 pouces par seconde à 60 pouces par seconde.
     
    14. Procédé de fabrication d'une encre pour jet d'encre à base de pigments, comprenant :

    la préparation d'un véhicule liquide comportant de l'eau, un solvant organique, un tensioactif et un liant polymère ; et

    l'ajout progressif de particules de pigment pour disperser et suspendre les particules de pigment dans le véhicule liquide, l'encre pour jet d'encre à base de pigments après préparation comprenant de l'eau ;

    de 2 % à 9 % en poids de pigments solides ; de 0,05 % à 2 % en poids de tensioactif non ionique à base de diol acétylénique ; de 0,05 % en poids à 2 % en poids d'un second tensioactif, ledit second tensioactif étant un polysorbate ayant une valeur de HLB inférieure à 15, ou un éther de polyoxyéthylène glycol en C12 à C18 ayant un indice d'oxyde d'éthylène inférieur à 20, ou un perfluoropolyéther comportant un alcool ou diol primaire de polyéthylène glycol ; de 5 % en poids à 50 % en poids d'un système de solvant organique comprenant du triéthylène glycol et un amide cyclique, l'amide cyclique comprenant un diamide cyclique ; et 0,1 % en poids à 3 % en poids de liant polymère.


     






    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description