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WO2024030383A1 - Compositions d'encre résistantes à l'oxydation et procédés d'utilisation - Google Patents

Compositions d'encre résistantes à l'oxydation et procédés d'utilisation Download PDF

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Publication number
WO2024030383A1
WO2024030383A1 PCT/US2023/029132 US2023029132W WO2024030383A1 WO 2024030383 A1 WO2024030383 A1 WO 2024030383A1 US 2023029132 W US2023029132 W US 2023029132W WO 2024030383 A1 WO2024030383 A1 WO 2024030383A1
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WO
WIPO (PCT)
Prior art keywords
ink composition
ink
oxidizing
pigment
solvent
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.)
Ceased
Application number
PCT/US2023/029132
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English (en)
Inventor
Nadeepuram K. Ranganathan
Barry Brucker
Ramesh Subbaraman
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.)
Independent Ink Inc
Original Assignee
Independent Ink Inc
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 claimed from US17/980,523 external-priority patent/US11773279B2/en
Application filed by Independent Ink Inc filed Critical Independent Ink Inc
Publication of WO2024030383A1 publication Critical patent/WO2024030383A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0023—Digital printing methods characterised by the inks used

Definitions

  • the subject of this patent application relates generally to printing, and more particularly to ink compositions and methods for printing on oxidizing and alkaline substrates or surfaces.
  • laundry tablets for example, contain percarbonate, or more particularly percarbonate salt, or other such active ingredient or readily oxidizing agent that renders such substrates alkaline or relatively high pH and are configured to release oxygen upon wetting for higher performance in washing and stain removal, and so any ink to be applied to the tablet would have to be stable in the presence of an oxidizing agent or not oxidize or decompose and also be non-staining and readily dissolve along with the tablet itself in a washing machine or dishwasher, for example, during normal use.
  • inkjet inks are typically waterborne or water-based inks with water wettable reactants, or constituents that react when wet, which in turn means that such inks, or the water in them, would liberate oxygen that then reacts with the other materials of the tablet or other substrate or surface and produces oxidation or instability of the ink, whether at the point of printing or more gradually over time.
  • high demand or high duty cycle and attendant ink heat management, color or color intensity or general image resolution, regulatory or environmental, and other such requirements must be met notwithstanding the threshold challenge of printing on an oxidizing and alkaline substrate or surface.
  • an ink composition for the purpose of reliably printing on alkaline and readily oxidizing surfaces, comprises one or more pigments, one or more solvents for adjusting viscosity, surface tension, and/or heat tolerance, and water, the pigments “loaded” in the ink sufficiently to meet the relevant coIor and optical density requirements for the ink while such ink composition still also meets the duty cycle requirements of the application for then being jetted or otherwise applied to the oxidizing and alkaline substrate or surface.
  • inventive subject matter provides many exemplary embodiments of the inventive subject matter. Although each embodiment represents a single combination of inventive elements, the inventive subject matter is considered to include all possible combinations of the disclosed elements. Thus, if one embodiment comprises elements A, B, and C, and a second embodiment comprises elements B and D, then the inventive subject matter is also considered to include other remaining combinations of A, B, C, or D, even if not explicitly disclosed.
  • oxidation-resistant ink compositions generally comprising one or more pigments, one or more solvents, and water and methods of their use in printing or otherwise applying such ink to a readily oxidizing and alkaline substrate or surface.
  • These three ingredients or groups of ingredients may be combined in various proportions depending on the application to arrive at new and useful ink compositions according to aspects of the present invention.
  • an “effective amount” or “effective concentration” of any such ingredient or additive of any particular ink composition refers to the minimal percentage of a substance used in an ink composition of the present invention to achieve the desired effect.
  • an effective amount of pigment refers to the minimal percentage of pigment required to achieve the desired coIorand optical density for the particular application and substrate
  • an effective amount of solvent refers to the minimal percentage of such solvent to achieve the desired ink application or jetting and/or heat management effect in the particular context.
  • the new and novel ink composition according to aspects of the present invention for reliably printing on alkaline and readily oxidizing surfaces is also capable of performing at high duty cycle and so under attendant elevated temperatures, in the cartridge in the inkjet context, by managing the heat within the ink itself or controlling its upper temperature limit and thereby enabling larger volumes of ink through the cartridge or larger numbers of prints by the cartridge without a failure.
  • Tl J thermal inkjet
  • CM continuous inkjet
  • DOD drop-on-demand
  • PZT piezo inkjet
  • LCP large character printing
  • MEMS micro-electro-mechanical systems
  • fundamental aspects of the present invention relate to printing and long-term retention of precise, on-demand, and sequentially counted images of defined color and density at high rates on readily oxidizing surfaces made of water-activated percarbonate, carbonate, and bicarbonate salts in overwhelming quantity with inks of water-based formulae.
  • an objective of such an oxidation-resistant inkjet ink according to aspects of the present invention is that the ink once printed on such a tablet would be relatively stable in the presence of the percarbonate or other oxidizing agent or nascent oxygen donors (the ink and the colorants in it would not oxidize).
  • any such ink must be stable in an alkaline (high pH) environment with water wettable reactants.
  • Some pigments are known to be non-oxidizing or oxidation-resistant and thus stable in an alkaline environment, but what is not known and has not been previously achieved is employing such pigment dispersions in inkjet inks, or inks for use in non-contact printing systems, particularly on said oxidizing and alkaline surfaces with high duty cycle printing systems, which objective, among others, has been met by ink compositions according to aspects of the present invention, including but not limited to those specific compositions disclosed herein, and the methods of their use.
  • the ink compositions of the present invention generally comprise a colorant which might be a pigment or combination thereof, i.e., a pigment or a mixture or dispersion of pigments.
  • the said pigments are solid particles which are not soluble in water or the cosolvents specified in the exemplary ink compositions.
  • the terms “pigment” and “colorant” are used interchangeably throughout. Any colorant in the form of a solid particle or the like that may be suspended somewhat homogeneously in the ink to achieve the targeted color and optical density may be used in the present invention.
  • the pigments must be finely divided, all in the sub-micron range of particle size, preferably all particles below 0.5 microns (500 nanometers), substantially homogeneously dispersed in water with or without the aid of surfactants, wherein during normal use the particles do not settle by gravity or other forces, even in the long term, and the particles do not agglomerate inherently or in the presence of formulation ingredients, even in the long term.
  • pigments must be capable of withstanding nascent oxidation, caused by wetting oxygen-releasing chemicals such as percarbonate, carbonate, and/or bicarbonate salts often found in detergents and soaps, in an alkaline environment (i.e., from the detergent tablet).
  • Suitable colorants may include, but are not limited to, Pigment Yellow 155, Pigment Blue 15.3 (cyan), and Pigment Red 122 (magenta). Any such colorants may be supplied as solid particles or liquid suspensions or dispersions, though are typically in aqueous form, and of course other colors of the colorants may be employed alone or in combination to achieve a desired final ink color, in any case the weight or mass percentages for all such pigments are shown throughout based on the amount of actual pigment in the finished formulation, with all water in the case of a dispersion included in the weight percentage for water, rather than reflecting the weight percentage for the total amount of pigment dispersion “as presented” in the market.
  • the total colorant represented as weight or mass percent in the finished formula of the actual pigment particles or solids, not including any aqueous component, might be present in an ink composition according to aspects of the present invention in the range of about one percent (1%) to about ten percent (10%) by weight, more preferably in the range of about one-and-a-half percent (1 .5%) to about seven percent (7%) by weight, and even more preferably in the range of about two percent (2%) to about five percent (5%) by weight.
  • the effective concentration of the colorant may depend on the percentage by weight of the colorant required in the ink composition to produce the desired color and optical density.
  • pigments or resulting pigment dispersions beneficially have oxidation resistance due to each pigment particle being encapsulated or coated in whole or in part by a polymer as through a chemical bond, such as achieved by physically and chemically bonding the pigment particle to a polymer, drying the joined entity and crushing it into a powder having sub-micron particle size, and then dispersing and suspending the powder of preferably uniform and narrow particle size distribution within the liquid or aqueous ink composition base.
  • Such pigment dispersion-based ink compositions as disclosed herein thus meet the challenge of image color and resolution requirements while also meeting the oxidation-resistance and anti-kogation or high demand or duty cycle and thus the ink heat management requirements of some applications.
  • Solvents suitable for the ink compositions of the present invention may comprise several types of solvents, most of which are organic, though this is not necessarily required in all applications or commercial contexts.
  • Organic solvents suitable for the ink compositions of the present invention may include solvents used as additives to modify the properties of the ink composition, such as to adjust viscosity and to improve moisture retention and heat tolerance. Examples of such solvents include, but are not limited to, alcohols, amines, esters, glycol ethers, ketones, polyols, and keto-pyrroles.
  • an ink composition according to aspects of the present invention particularly suited for higher duty cycle or other heat management requirements, a combination of the polyols 1 ,3-propanediol, 1 ,2-hexanediol, and propylene glycol was employed as a humectant or ingredient providing the benefit of retaining or preserving moisture and also serving as a heat management or anti-kogation agent in terms of enabling the ink to control its upper temperature limit or manage how or the limit to which it takes on heat.
  • the heat tolerance or anti-kogation capacity of the ink, or the ink’s ability to mitigate against or prevent the gradual degradation or burning or charring of the printhead of an inkjet printer, such as through the particular mechanism of the polymer cladding the electrical resistor in the thermal inkjet nozzle under sustained heat, is a necessary performance requirement in some commercial relatively high duty cycle applications in order to prevent print quality degradation or premature failure of the printhead.
  • 1 ,3- propanediol and 1 ,2-hexanediol were together found to be sufficient in all respects in terms of the ink performance, in both single use cartridges containing on the order of 30-50 ml_ of ink to bulk systems supplying 1 ,000 mL or more of ink to the printhead, though even in bulk printing contexts the amount of ink effectively metered to the printhead being in the range of roughly 10-20 mL, for example.
  • 1,3-propanediol and 1 ,2-hexanediol were employed as heat management or anti-kogation ingredients as noted above, though as noted below propylene glycol in the ink formulation serves this purpose as well.
  • 1,3-propanediol is an organic compound with the formula CH 2 (CH 2 OH) 2 having a heat tolerance capacity but that is alone insufficient, at least in appropriate quantities in the finished ink composition, to address kogation or heat tolerance of the ink satisfactorily.
  • the exemplary ink compositions also include 1 ,2-hexanediol, a chemical commonly used as a preservative or emollient, with the chemical formula CeHi4O 2 , as a further anti-kogation agent or means of preventing scale formation on heated surfaces, which compound was found to also work well in the context of a pigment dispersion-based inkjet ink.
  • the 1 ,3-propanediol alone might be present in an ink composition according to aspects of the present invention in the range of about one percent (1 %) to about fifteen percent (15%) by weight, more preferably in the range of about two percent (2%) to about ten percent (10%) by weight, and even more preferably in the range of about three percent (3%) to about seven percent (7%) by weight.
  • the 1 ,2- hexanediol alone might be present in an ink composition according to aspects of the present invention in the range of about one percent (1 %) to about fifteen percent (15%) by weight, more preferably in the range of about two percent (2%) to about ten percent (10%) by weight, and even more preferably in the range of about three percent (3%) to about seven percent (7%) by weight.
  • aspects of the present invention relate to an ink composition having an effective amount of 1 ,3-propanediol and/or 1 ,2-hexanediol to cooperate in helping to prevent or mitigate against kogation at relatively high print rates or duty cycles, wherein a scale preventer is necessary over and above other more common high heat capacity solvents that also provide anti-kogation to a secondary or lesser extent.
  • propylene glycol in relatively high concentration was substituted for 1 ,3-propanediol and 1 ,2-hexanediol in the formulation to yield a relatively higher viscosity ink. More particularly, the amount of propylene glycol in the finished formulation was significantly increased as compared to other formulations, with 1 ,3-propanediol and 1 ,2-hexanediol removed altogether, though not necessarily so.
  • Propylene glycol also referred to as propane-1 ,2-diol, is a viscous, colorless liquid having the chemical formula CHSCH(OH)CH2OH and so containing two alcohol groups, and is thus classed as a diol, and is miscible with a broad range of solvents, including water.
  • the propylene glycol alone, represented as weight or mass percent in the finished formula, might be present in an ink composition according to aspects of the present invention in the range of about twenty percent (20%) to about sixty percent (60%) by weight, more preferably in the range of about thirty percent (30%) to about fifty-eight percent (58%) by weight, and even more preferably in the range of about forty percent (40%) to about fifty-five percent (55%) by weight.
  • solvents may be included with the propylene glycol as well, including but not limited to glycerin, hydroxy propyl cellulose (“HPC”), and/or hydroxy propyl methyl cellulose (“HPMC”), in such quantities as appropriate to the application or commercial context, such as to adjust the ink viscosity to suit a particular printhead, for example.
  • HPC hydroxy propyl cellulose
  • HPMC hydroxy propyl methyl cellulose
  • HPC and HPMC as water-soluble polymers provide a different means of adjusting the viscoelasticity of the resulting inks as may be required or beneficial in some printing contexts for clean drop breakoff (to prevent build-up of ink on the faceplate of the printhead) and image acuity, as such non-volatiles rapidly increase the resistance to flow as compared to water and other evaporating ingredients, such as alcohols and lower polyols, and any case HPS and HPMC would thus only be employed to increase viscosity in relatively high viscosity ink printing applications (e.g., piezoelectric (“PZT”) printheads and contact printing technologies such as pad or transfer printing, in any case HPC and/or HPMC typically being present in the ink in the range of about a hundredth percent (0.01 %) to about five percent (5%).
  • PZT piezoelectric
  • Polyols may generally be added to various ink compositions of the present invention for their humectant property and as further providing for heat stability or capacity, as already noted above regarding 1 ,3-propanediol and 1,2-hexanediol in the exemplary formulations.
  • Humectants may play an important role in any ink formulation in preventing crusting at the nozzles in addition to heat management.
  • Relatively fast drying inks of the type described in the various inventive embodiments of the present invention might be more susceptible to nozzle crusting than slower drying inks of the prior art, i.e., conventional aqueous ink compositions for thermal inkjet printing systems.
  • Polyols suitably employed in the ink compositions of the present invention may include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerin, glycerol, propanediol, butanediol, pentanediol, hexanediol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, and derivatives thereof.
  • one or more polyol might be present in an ink composition according to aspects of the present invention, represented as weight or mass percent in the finished formula, in the range of about one percent (1 %) to about twenty percent (20%) by weight, more preferably in the range of about three percent (3%) to about fifteen percent (15%) by weight, and even more preferably in the range of about five percent (5%) to about twelve percent (12%) by weight.
  • one or more polyol might be present in an ink composition according to aspects of the present invention, represented as weight or mass percent in the finished formula, in the range of about twenty percent (20%) to about sixty percent (60%) by weight, more preferably in the range of about twenty-five percent (25%) to about fifty-eight percent (58%) by weight, and even more preferably in the range of about thirty percent (30%) to about fifty-five percent (55%) by weight.
  • any such exemplary ink formulation according to aspects of the present invention involving anti-kogation or heat management solvents, or solvents or agents with relatively higher specific heat or heat capacity represented as weight or mass percent in the finished formula, as including but not limited to 1 ,3-propanediol and/or 1 ,2-hexanediol, as well as other solvents such as the polyols or humectants discussed immediately above, particularly propylene glycol and/or other glycols as in the exemplary formulations provided herein, might be present in an ink composition according to aspects of the present invention in the range of about ten percent (10%) to about sixty percent (60%) by weight, more preferably in the range of about twelve percent (12%) to about fifty-eight percent (58%) by weight, and even more preferably in the range of about thirteen percent (13%) to about fifty- five percent (55%) by weight.
  • the effective concentration of such solvents may depend on the percentage by weight of such solvents required in the ink composition to produce the desired heat tolerance, which in turn would depend on the particular printing system, and specifically the typical or sustained temperatures in use and other factors, such as the effective concentration or particle or solids quantity and size or density of the particular pigment dispersion.
  • piezo or piezoelectric (“PZT”) printheads whether or not a heater or heating element is provided and/or employed, heat is generated by long periods of high frequency mechanical vibration of the piezoelectric crystal and its surroundings particularly at high duty cycles of marking large amounts of continuously produced laundry products or the like (long and/or high frequency operation).
  • the quantity of heat generated is referenced by the rise in the observed temperature of the overall cartridge, especially in close vicinity of the piezoelectric crystal of the printhead, and this is the mechanism governing the absorption of heat by the ink, or the need thereof, which heat is the product of the mass of ink times the specific heat of the ink and the numerical rise in temperature of the mass of ink.
  • the heat capacity of the ink via its components, namely, the high boiling point co-solvents, such as the indicated polyols (e.g., propylene glycol).
  • Tuning the ink via the weight percent of such components provides the control or time taken to heat the ink to a range where rheological properties are out of range for the ink to respond synchronously to the driving mechanism, thereby reducing the rate at which the ink heats up. That is, the effective ink harmonic is substantially in sync with the printhead harmonic via the “tuning” of the ink, which waveform tuning is particularly applicable in the piezo context.
  • Alcohol may typically be employed as a secondary solvent in various ink compositions of the present invention, if at all, to modify the drying property of the resulting ink.
  • Alcohols suitable for the ink compositions of the present invention may include, but are not limited to, methanol, ethanol, isopropyl alcohol, n-propyl alcohol, tert-butanol, n-pentanol, benzyl alcohol, and derivatives thereof.
  • isopropyl alcohol may be added to an ink composition of the present invention to increase the drying rate.
  • An effective concentration of alcohol may be empirically determined relative to the desired end use application to balance between the problem of crusting at the nozzles and achieving the desired drying rate.
  • one or more alcohols might be present in an ink composition according to aspects of the present invention, represented as weight or mass percent in the finished formula, in the range of about a half percent (0.5%) to about twenty percent (20%) by weight, more preferably in the range of about three-quarter percent (0.75%) to about eighteen percent (18%) by weight, and even more preferably in the range of about one percent (1 %) to about fifteen percent (15%) by weight.
  • the alcohol(s) represented as weight or mass percent in the finished formula may be in the range of about a half percent (0.5%) to about five percent (5%) by weight, more preferably in the range of about three-quarter percent (0.75%) to about four percent (4%) by weight, and even more preferably in the range of about one percent (1 %) to about three percent (3%) by weight, and in another piezoelectric (“PZT”) printhead context with related ink viscosity requirement, for example, the alcohol(s) represented as weight or mass percent in the finished formula may be in the range of about three percent (3%) to about twenty percent (20%) by weight, more preferably in the range of about five percent (5%) to about fifteen percent (15%) by weight, and even more preferably in the range of about eight percent (8%) to about twelve percent (12%) by weight.
  • Tl J thermal inkjet
  • PZT piezoelectric
  • an antimicrobial additive may be included in an exemplary ink composition according to aspects of the present invention, including but not limited to Proxel GXLTM antimicrobial solution manufactured by Arch Chemicals, Inc., which broad spectrum biocide may be employed for the preservation of industrial water-based products such as the instant ink compositions against spoilage from bacteria, yeasts and fungi.
  • one or more surfactants or wetting agents may be added to an exemplary ink composition according to aspects of the present invention, including but not limited to DOSS-70 or sodium dioctyl sulfosuccinate 70%, an anionic surfactant manufactured by Expo, DynolTM 604, an ultra low-VOC, low-foam, non-ionic wetting agent and surfactant manufactured by Evonik, and ZonylTM FSO-100, an ethoxylated, non-ionic fluoro-surfactant that reduces plasticizer migration manufactured by Chemours. Any and all such surfactants, fluoro-surfactants, and anitmicrobials may be incorporated in an ink composition according to aspects of the present invention without departing from its spirit and scope.
  • Various mixtures of the aforementioned solvents may be selected at an effective concentration in terms of percentage by weight for a particular ink formulation or composition and a particular printing application, including substrate and printing system, according to aspects of the present invention, thereby providing balance of the desired properties, as will be appreciated by those skilled in the art.
  • Important properties for selecting appropriate solvents for an oxidation-resistant pigment dispersion-based inkjet ink to print on a wide range of oxidizing and alkaline substrates include one or more of the following: substantial solubility with water; desirable evaporating rate; substantial miscibility with water; relatively low toxicity; relatively low viscosity; and relatively high heat tolerance.
  • exemplary formulations should not be construed in any way as limitations on the present invention, but should be understood merely as illustrative of the principles of the invention and instructive of at least one preferred ink composition based on current materials and data.
  • the following ink formulations may be made using conventional ink mixing equipment.
  • each of Examples #1-A to 1-D and 2-A such exemplary, non-limiting green and blue ink compositions according to aspects of the present invention are suitable for jetting in an industrial thermal inkjet system such as the FlexCodeTM printer available from Independent Ink, Inc. employing single use cartridges or bulk printing cartridges such as from Hewlett-Packard or Funai/Lexmark and/or bulk feed systems or components such as bags and valves.
  • an industrial thermal inkjet system such as the FlexCodeTM printer available from Independent Ink, Inc. employing single use cartridges or bulk printing cartridges such as from Hewlett-Packard or Funai/Lexmark and/or bulk feed systems or components such as bags and valves.
  • Table 1 Low to high duty cycle TIJ green ink
  • Table 2 Low to high duty cycle TIJ blue ink
  • Example #1-A through 1-D yielding a green ink (nominally PMS Green 2423U), Pigment Yellow 155 and Pigment Blue 15.3 pigments or pigment dispersions were employed. And in Example #2-A yielding a blue ink (nominally PMS Blue 2145U), Pigment Red 122 and Pigment Blue 15.3 pigments or pigment dispersions were employed.
  • a green ink nominally PMS Green 2423U
  • a blue ink nominally PMS Blue 2145U
  • Pigment Red 122 and Pigment Blue 15.3 pigments or pigment dispersions were employed.
  • the resulting viscosity of the ink may be in the range of 1 .5 - 4.0 cPs at 25°C, and the resulting surface tension of the ink may be in the range of 20 - 40 Dynes per cm.
  • such exemplary, non-limiting green and blue ink compositions according to aspects of the present invention are suitable for jetting in an industrial piezoelectric inkjet system such as the FlexPrintTM IL 500 printer available from Independent Ink, Inc. employing a Ricoh piezoelectric printhead such as the GH2220 printhead.
  • a piezo printing system may involve in addition to the printer and printhead, a bulk ink container, preferably a constant level second ink container, a damper which suppresses surges and rarities, and a set of tubes that connect the various components for supplying or circulating the ink in the system.
  • Table 4 Low to high duty cycle blue piezo inkjet ink
  • the ethanol, 2-propanol, methanol, and methyl isobutyl ketone in the above exemplary ink composition formulations may be supplied together in a single solution as A-1 200-proof ethanol or any other such supplied solution as appropriate, whether now known or later developed.
  • any such exemplary ink compositions according to aspects of the present invention for printing in a piezo inkjet printer or system other co-solvents may be employed instead of or in addition to the co-solvents as noted above, with the w/w percentages adjusted accordingly, for the primary purpose of raising and maintaining viscosity or adjusting viscosity and/or surface tension for stable or optimum jetting and image quality, including but not limited to propylene glycol, 1 ,3-propanediol, 1 ,2-hexanediol, isopropyl alcohol, and ethanol, such as in exemplary ink compositions for use in inkjet printers and systems as set forth herein by way of illustration and not limitation.
  • Example #3-A a green ink (nominally PMS Green 2423U), Pigment Yellow 155 and Pigment Blue 15.3 pigments or pigment dispersions were employed. And in Example #4-A yielding a blue ink (nominally PMS Blue 279U), Pigment Blue 15.3 and Pigment Red 122 pigments or pigment dispersions were employed.
  • a blue ink nominally PMS Blue 279U
  • Pigment Blue 15.3 and Pigment Red 122 pigments or pigment dispersions were employed.
  • the resulting viscosity of the ink may be in the range of 6.5 - 12.0 cPs at 25°C, and the resulting surface tension of the ink may be in the range of 20 - 50 Dynes per cm.
  • the weight or mass percentages are for the finished formula and thus those represented for the pigments are the amounts of actual pigment or the mass of particles in suspension, with all water in the case of a pigment liquid suspension or dispersion included in the weight percentage for deionized (“DI”) water.
  • DI deionized
  • oxidation-resistant ink compositions may again be employed in a single use cartridge or an industrial or bulk inkjet cartridge, including but not limited to those cartridges available from Hewlett-Packard and Funai/Lexmark, along with any related printhead and inkjet system now known or later developed, such as the FlexCodeTM printer available from Independent Ink, Inc., in the illustrative thermal inkjet context, and the FlexPrintTM IL-500 printer and related Ricoh GH2220 printhead in the piezoelectric inkjet context, and in any case whether or not in combination with a bulk feed cartridge or related bulk feed system in a manner known in the art, here with the unique capability of the ink compositions of the present invention of printing on a variety of oxidizing and alkaline substrates or surfaces such as laundry detergent tablets or the like containing percarbonates or other readily oxidizing agent or other fabric care product, bath and bar soap, and other contexts having an oxidating and alkaline surface
  • a piezoelectric printhead such as available from Ricoh, Epson, Toshiba, Konica, and Xaar and related single-use or bulk feed cartridge or system may be employed along with any suitable printer or printing system now known or later developed in conjunction with ink compositions according to aspects of the present invention. It will be further appreciated that a variety of other industrial contexts, both in terms of the particular inkjet, piezo, or other printing system and the substrate or surface to be printed on, are possible according to aspects of the present invention, the exemplary applications being understood as merely illustrative of features and aspects of the invention and non-limiting.
  • Example 1 Example 1
  • This example demonstrates preparing and printing of a nominally green inkjet ink.
  • the ink was mixed using conventional ink mixing equipment and techniques such that the weight percentages of the components in the resulting ink were 71.39% deionized water, 5.39% 1 ,3-propanediol, 5.55% 1 ,2-hexanediol, 5.22% polyethylene glycol 600, 2.82% isopropyl alcohol (propan-2-ol), 6.60% propylene glycol, 0.08% Proxel GXL biocide, 0.16% Expo Doss 70 surfactant, 2.12% Pigment Yellow 155 pigment, and 0.67% Pigment Blue 15.3 pigment (Formulation 1-A in Table 1).
  • the ink At ambient conditions of 25°C and one atmosphere, the ink’s viscosity measured 2.7 cPs and its surface tension measured 33 Dynes per cm.
  • the ink was then loaded in a FlexCodeTM industrial thermal inkjet system from Independent Ink, Inc. employing a Funai Claron 1.0 bulk feed cartridge.
  • the printer was configured for printing a 100 mm long text and graphic image on test stock containing percarbonate salt, to simulate laundry detergent tablets and other such oxidizing and alkaline substrates, at a nominal rate of about 20 prints per second. Specifically, over a period of roughly fifteen hours, approximately 1 ,000,000 prints were laid down with sufficient image quality in the range of 300-350 dpi and having a Pantone color of PMS Green 2423U.
  • This example demonstrates preparing and printing of a nominally blue inkjet ink.
  • the ink was mixed using conventional ink mixing equipment and techniques such that the weight percentages of the components in the resulting ink were 70.15% deionized water, 5.36% 1 ,3-propanediol, 5.53% 1 ,2-hexanediol, 5.20% polyethylene glycol 600, 2.81% isopropyl alcohol (propan-2-ol), 6.40% propylene glycol, 0.08% Proxel GXL biocide, 3.00% Pigment Blue 15.3 pigment, and 1.35% Pigment Red 122 pigment (Formulation 2-A in Table 2).
  • the ink At ambient conditions of 25°C and one atmosphere, the ink’s viscosity measured 3.6 cPs and its surface tension measured 26 Dynes per cm.
  • the ink was then loaded in a FlexCodeTM industrial thermal inkjet system from Independent Ink, Inc. employing a Funai Claron 1.0 bulk feed cartridge.
  • the printer was configured for printing a 100 mm long text and graphic image on test stock containing percarbonate salt, to simulate laundry detergent tablets and other such oxidizing and alkaline substrates, at a nominal rate of about 20 prints per second. Specifically, over a period of roughly sixteen hours, approximately 1 ,100,000 prints were laid down with sufficient image quality in the range of 300-350 dpi and having a Pantone color of PMS Blue 279U.
  • This example demonstrates preparing and printing of a nominally green inkjet ink.
  • the ink was mixed using conventional ink mixing equipment and techniques such that the weight percentages of the components in the resulting ink were 32.76% deionized water, 54.58% propylene glycol, 9.27% A-1 200 proof ethanol, 2.59% Pigment Yellow 155 pigment, and 0.80% Pigment Blue 15.3 pigment (Formulation 3-A in Table 3).
  • the ink At ambient conditions of 25°C and one atmosphere, the ink’s viscosity measured 8.5 cPs and its surface tension measured 35 Dynes per cm.
  • the ink was then loaded in a FlexPrintTM IL 500 industrial inkjet system from Independent Ink, Inc.
  • the printer was configured for printing a 100 mm long text and graphic image on test stock containing percarbonate salt, to simulate laundry detergent tablets and other such oxidizing substrates, at a nominal rate of about 20 prints per second. Specifically, over a period of roughly fifteen hours, approximately 1 ,000,000 prints were laid down with sufficient image quality in the range of 350-400 dpi and having a Pantone color of PMS Green 2423U.
  • the numbers expressing quantities of components or ingredients, properties such as dimensions, weight, concentration, reaction conditions, and so forth, used to describe and claim certain embodiments of the inventive subject matter are to be understood as being modified in some instances by terms such as “about,” “approximately,” or “roughly.” Accordingly, in some embodiments, the numerical parameters set forth in the written description and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

L'invention concerne des compositions d'encre et des procédés d'utilisation pour une impression fiable sur des surfaces alcalines et à oxydation facile faisant appel à un ou plusieurs pigments, à un ou plusieurs solvants destinés à ajuster la viscosité, la tension de surface et/ou la tolérance à la chaleur, et à de l'eau, les pigments étant "chargés" dans l'encre en quantité suffisante pour satisfaire les exigences de couleur et de densité optique pertinentes pour l'encre tandis qu'une telle composition d'encre satisfait également les exigences de cycle de service de l'application.
PCT/US2023/029132 2022-08-01 2023-07-31 Compositions d'encre résistantes à l'oxydation et procédés d'utilisation Ceased WO2024030383A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US202263394105P 2022-08-01 2022-08-01
US63/394,105 2022-08-01
US17/980,523 US11773279B2 (en) 2021-07-14 2022-11-03 Oxidation-resistant ink compositions and methods of use
US17/980,523 2022-11-03

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WO2024030383A1 true WO2024030383A1 (fr) 2024-02-08

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010009892A1 (en) * 1999-12-16 2001-07-26 Bonsall Judith Maria Process for preparing granular detergent compositions
US20100215812A1 (en) * 2007-07-05 2010-08-26 Sheskey Paul J In situ, liquid-activated film coated tablets and a process for making the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010009892A1 (en) * 1999-12-16 2001-07-26 Bonsall Judith Maria Process for preparing granular detergent compositions
US20100215812A1 (en) * 2007-07-05 2010-08-26 Sheskey Paul J In situ, liquid-activated film coated tablets and a process for making the same

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