US20020187310A1 - Compositions and methods for printing on specialty media - Google Patents

Compositions and methods for printing on specialty media Download PDF

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US20020187310A1
US20020187310A1 US09859864 US85986401A US2002187310A1 US 20020187310 A1 US20020187310 A1 US 20020187310A1 US 09859864 US09859864 US 09859864 US 85986401 A US85986401 A US 85986401A US 2002187310 A1 US2002187310 A1 US 2002187310A1
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alcohol
acetate
polyvinyl
ink
graft copolymer
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US09859864
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Alexey Kabalnov
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Hewlett-Packard Development Co LP
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HP Inc
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0011Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
    • B41M5/0017Application of ink-fixing material, e.g. mordant, precipitating agent, on the substrate prior to printing, e.g. by ink-jet printing, coating or spraying
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41JTYPEWRITERS; SELECTIVE PRINTING MECHANISMS, e.g. INK-JET PRINTERS, THERMAL PRINTERS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01Ink jet
    • B41J2/21Ink jet for multi-colour printing
    • B41J2/2107Ink jet for multi-colour printing characterised by the ink properties
    • B41J2/2114Ejecting transparent or white coloured liquids, e.g. processing liquids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/021Block or graft polymers containing only sequences of polymers of C08C or C08F
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/54Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S524/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S524/906Multipackage compositions
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers

Abstract

Compositions and methods for printing on specialty media are disclosed. The methods comprise the steps of providing a fixing fluid, providing a dye- or pigment-based ink-jet ink containing an effective amount of a polyvinyl(alcohol-acetate) species, jetting the fixing fluid onto the specialty media forming a coated substrate, and jetting the ink-jet ink onto the coated substrate. Additionally, a gelled printed image on a substrate is disclosed comprising a fixing fluid containing a fixing agent and an aqueous ink-jet ink containing a polyvinyl(alcohol-acetate) species. In both the method and with respect to the image, the polyvinyl(alcohol-acetate) species used can be a known species, or one of a number of new graft copolymers containing a polyvinyl(alcohol-acetate) polymer as one of the constituents of the copolymer.

Description

    FIELD OF THE INVENTION
  • The present invention is drawn to compositions and methods for printing on specialty media. [0001]
  • BACKGROUND OF THE INVENTION
  • In recent years, computer printer technology has evolved to a point where very high resolution images can be transferred to various media. One particular type of printing involves the placement of small drops of a fluid ink onto a surface in response to a digital signal. Typically, the fluid ink is placed or jetted onto the surface without physical contact between the printing device and the surface. The specific method for which the ink is deposited onto the printing surface varies from system to system. However, two major methods include continuous ink deposit and drop-on-demand ink deposit. [0002]
  • With regard to continuous printing systems, inks used are typically based on solvents including methyl ethyl ketone and/or ethanol. Essentially, continuous printing systems function as a stream of ink droplets are ejected and directed by a printer nozzle. The ink droplets are directed additionally with the assistance of an electrostatic charging device in close proximity to the nozzle. If the ink is not used on the desired printing surface, the ink is recycled for later use. With regard to drop-on-demand printing systems, the ink-jet inks are typically based upon water and glycols. Essentially, with these systems, ink droplets are propelled from a nozzle by heat or by a pressure wave. Additionally, all of the ink droplets are used to form the printed image and are ejected when needed. [0003]
  • There are several reasons that ink-jet printing has become a popular way of recording images on surfaces, particularly paper. Some of these reasons include low printer noise, capability of high speed recording, multi-color recording, and potential versatility. Additionally, these advantages can be provided at a relatively low price. However, though there has been great improvement in ink-jet printing, accompanying this improvement are increased printing demands, e.g., higher speed, higher resolution, full color image formation, new applications, etc. [0004]
  • Papers used for ink-jet printing have typically included high-quality and wood-free papers designed to have high ink absorptivity or papers having a coated porous surface. These papers are functionally good for ink-jet printing because the inks may be absorbed readily and dry quickly. However, such papers often do not allow for a crisp or sharp image. Additionally, there are many potential substrates that do not provide avenues for absorption, and thus, typical ink-jet inks can puddle on those surfaces. For example, non-porous plastic is such a substrate. [0005]
  • Polyvinyl alcohol-acetate is a commercially available polymer produced by partial hydrolysis of polyvinyl acetate. However, there are various specific structures that can be formed based on several variables. For example, different chain length and degree of hydrolysis can effect the properties of the structure. Specifically, the solubility of polyvinyl(alcohol-acetate) in water is dependent, in part, upon the degree of hydrolysis that the polyvinyl acetate has undergone. To illustrate this, a fully hydrolyzed product is typically soluble only in hot water and tends to have a high degree of crystallinity in the dry state. On the other hand, a polyvinyl(alcohol-acetate) polymer that is about 88% hydrolyzed is water-soluble at room temperature. Non-hydrolyzed polyvinyl acetate is not water-soluble. [0006]
  • Polyvinyl(alcohol-acetate) has been widely used in making photo paper and special papers for ink-jet applications. However, its use as an ink-jet ink component has been very limited. The problems associated with the use of polyvinyl(alcohol-acetate) in ink-jet inks include poor long term and short term nozzle reliability due to increased viscosity and nozzle plugging. [0007]
  • One property of polyvinyl(alcohol-acetate) is that it can be gelled in presence of some chemicals, such as borax, boric acid, or copper sulfate. However, this property has not been known to be used for ink-jet applications. Though the formation of plasticized gels can be desirable when printing on certain types of media, e.g., specialty media including non-porous plastics, the difficulties associated with jetting are problematic. [0008]
  • Thus, it would be desirable to provide compositions and methods for printing on specialty media such that good pen reliability could be maintained, and yet also provide good gelation properties once printed on a substrate. [0009]
  • SUMMARY OF THE INVENTION
  • The present invention is drawn to compositions and methods for printing ink-jet inks onto various substrates, particularly on smooth non-porous substrates. Specifically, a method of printing on specialty media is disclosed comprising providing a fixing fluid containing a fixing agent, providing a dye- or pigment-based ink-jet ink containing an effective amount of a polyvinyl(alcohol-acetate) species, jetting the fixing fluid onto the specialty media forming a coated substrate, and jetting the ink-jet ink onto the coated substrate. The step of allowing the ink-jet ink and the fixing fluid containing the fixing agent to gel on the surface of the substrate is also a preferred step of the present invention. [0010]
  • Additionally, a gelled printed image on a substrate is disclosed comprising (a) a fixing fluid containing an effective amount of a fixing agent, printed in contact with (b) an aqueous ink-jet ink comprising a low molecular weight humectant, an effective amount of a polyvinyl(alcohol-acetate) species, and an effective amount of a dye or pigment, such that the fixing agent and the ink-jet ink interact to form a gel on the substrate surface. For both the method and the gelled printed image, various polyvinyl(alcohol-acetate) species can be used including known polyvinyl(alcohol-acetate) polymers as well as some new graft copolymers disclosed herein. [0011]
  • Turning to the various novel compositions for use in ink-jet inks, a graft copolymer for ink-jet ink formulations is disclosed comprising glycerol having from 2 to 3 polyvinyl(alcohol-acetate) chains attached thereto, wherein the polyvinyl(alcohol-acetate) chains have a weight average molecular weight from about 300 to 10,000. Additionally, a graft copolymer for ink-jet ink formulations is disclosed comprising a polyvinyl(alcohol-acetate) polymer having a weight average molecular weight from about 300 to 10,000, and a polyethylene glycol chain having a weight average molecular weight from about 300 to 10,000, wherein the polyethylene glycol is attached by etherification to from 5% to 30% of the alcohol groups of the polyvinyl(alcohol-acetate). Further, a graft copolymer for ink-jet ink formulations is disclosed comprising a low molecular weight styrene-maleic acid ester copolymer having a weight average molecular weight from about 1,000 to 10,000; a polyvinyl(alcohol-acetate) chain attached thereto, wherein the polyvinyl(alcohol-acetate) has a weight average molecular weight from about 1,000 to 10,000. [0012]
  • DETAILED DESCRIPTION OF THE INVENTION
  • Before the present invention is disclosed and described, it is to be understood that this invention is not limited to the particular process steps and materials disclosed herein because such process steps and materials may vary somewhat. It is also to be understood that the terminology used herein is used for the purpose of describing particular embodiments only. The terms are not intended to be limiting because the scope of the present invention is intended to be limited only by the appended claims and equivalents thereof. [0013]
  • It must be noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the content clearly dictates otherwise. [0014]
  • The term “species,” when used in connection with polyvinyl(alcohol-acetate)s, includes partially and fully hydrolyzed polyvinyl(alcohol-acetate) polymers, as well as graft copolymers containing at least one polyvinyl(alcohol-acetate). [0015]
  • “Graft copolymer” includes copolymers where polyvinyl(alcohol-acetate) has been grafted into a second polymer or a second polymer has been grafted into the polyvinyl(alcohol-acetate). Additionally, more than two polymers can be present, as long as at least one is a polyvinyl(alcohol-acetate) polymer. [0016]
  • “Specialty media” includes substrates that are relatively smooth, and have difficulty absorbing conventional ink-jet inks. For example, plastics such as polyethylene, polyvinyl chloride and polystyrene, non-porous and low-porous coated papers, glasses, metals, and rubbers are examples of specialty media. [0017]
  • “Gelling” shall be defined as a state of consistency wherein an ink-jet ink (with or without a fixing agent) exhibits substantial increase in viscosity properties such that puddling on the surface of a substrate is minimized. [0018]
  • “Hydrolyzed” with respect to polyvinyl(alcohol-acetate), refers to the number of hydroxy groups or acetate groups that are present on the polymer. [0019]
  • “Humectant” can include any substance used as a wetting or moistening agent. The use of low molecular weight humectants that do not interfere with gelation are preferred. [0020]
  • “Fixing agent” or “fixer” shall be defined as any substance that, when combined with any polyvinyl(alcohol-acetate) species, causes some gelation to occur. For example, borax (sodium tetraborate), boric acid, and copper sulfate are good fixers for use with various polyvinyl(alcohol-acetate) species. [0021]
  • “Fixing fluid” or “fixer fluid” include any fluid(s) that contains a fixing agent in a functional concentration such that gelation will occur when in contact with an effective amount of a polyvinyl(alcohol-acetate) species. [0022]
  • “Image” is defined as any marking on a substrate. [0023]
  • A “surfactant” is a compound that contains a hydrophilic and a hydrophobic segment. Thus, when a surfactant is added to water or some other solvent, the surface tension of the system can be reduced. In general, surfactants can be used for several purposes including wetting, emulsifying, dispersing, foaming, scouring, or lubricating a system. [0024]
  • For purposes of the present invention, “low molecular weight,” when describing humectants, includes molecular weight from about 100 to 1,000. [0025]
  • Polyvinyl alcohol-acetate [PV(Al-Ac)] can be modified to form a gel by the addition of small amount of certain complexing agents, e.g., boric acid or borax. Because of these gelation properties, it is possible to use polyvinyl(alcohol-acetate)s for certain ink-jet ink applications. However, one of the main practical challenges involved in using polyvinyl(alcohol-acetate) in ink-jet inks stems from issues of reliability. To illustrate, ink-jet inks in general require humectants to be present in the formulation. Humectants are typically high-boiling water-miscible organic compounds, such as polyols, amides, or polyethers. Specific examples include diethylene glycol, tetraethylene glycol, trimethylolpropane, glycerol, and 2-pyrrolidinone. Thus, when water evaporates from a printhead, humectants will not evaporate with the water creating a soft plug at the nozzles. At the same time, without the presence of one or more humectant, inks containing polyvinyl(alcohol-acetate) tend to crust. Additionally, by adding one or more humectant to a polyvinyl(alcohol-acetate)-containing ink-jet ink, interference with gelation properties can occur, making any gel formed less rigid. To solve this problems, appropriate selection of one or more humectant that will not interfere with the polyvinyl(alcohol-acetate) gelation is preferred. [0026]
  • With this in mind, the present invention is drawn to compositions and methods for ink-jet printing, particularly on specialty media. Specifically, a method of printing on specialty media is disclosed comprising providing a fixing fluid containing a fixing agent, providing a dye-based ink-jet ink containing an effective amount of a polyvinyl(alcohol-acetate) species, jetting the fixing fluid onto the specialty media forming a coated substrate, and jetting the ink-jet ink onto the coated substrate. The step of allowing the ink-jet ink and the fixing agent to gel is also a preferred step of the present invention. The gelling is effectuated as the fixing agent of the fixing fluid and the polyvinyl(alcohol-acetate) of the ink-jet ink contact one another and are allowed to react. Though the preferred embodiment provides that the fixing fluid be printed first, one skilled in the art would recognize that the ink-jet ink could be printed prior to the application of the fixing fluids for some applications. [0027]
  • Additionally, a gelled printed image on a substrate is disclosed which can be prepared by the methods described above, or other equivalent methods. The gelled printed image comprises at least two fluids printed in layers or in series, in either order. For example, one of the layers is provided as a fixing fluid containing an effective amount of a fixing agent is printed on a substrate. The other layer is provided as an aqueous ink-jet ink comprising a low molecular weight humectant, an effective amount of a polyvinyl(alcohol-acetate) species, and an effective amount of a dye is printed such that contact occurs with the fixing fluid. Thus, the image on the substrate, prior to drying, can form a gel. [0028]
  • The fixing fluid, in order to provide appropriate gelling characteristics described above, must contain a fixing agent that interacts with a polyvinyl(alcohol-acetate) species to form a gel of appropriate consistency. The fixing agent can be suspended or dissolved in an appropriate fixing fluid as described. Examples of such fixing agents include the use of borax (sodium tetraborate), boric acid, and/or copper sulfate. Additionally, other optional ingredients can be present including certain humectants, wetting agents, surfactants, dyes, pigments, and combinations thereof, provided they do not substantially interfere with gelation. [0029]
  • With respect to the ink-jet ink, it is preferred that a humectant be present in order to prevent crusting and other known problems that occur when the humectant component is omitted. However, the humectant should be selected so that it does not interfere substantially with the gelation properties of the polyvinyl(alcohol-acetate)/fixing agent combination (once contact occurs). Appropriate humectants include low molecular weight polymers such as polyethylene glycol, glycereth including glycereth-7 and glycereth-1 (such as those sold under the tradenames LEG™-7 and LEG™-1 respectively), tetraethylene glycol, urea, tetramethylurea, betaine, betaine hydrochloride, and combinations thereof. [0030]
  • As state previously, the polyvinyl(alcohol-acetate) species can be a partially hydrolyzed or fully hydrolyzed known polymer, or can be one of the new graft copolymers disclosed herein, i.e., a polyvinyl(alcohol-acetate)/second polymer graft copolymer. With respect to the degree of hydrolysis, a polyvinyl(alcohol-acetate) polymer that is hydrolyzed at from 70% to 100% is preferred. More specifically, from about 75% to 90% hydrolysis is more preferred, and about 88% is most preferred. No matter what polyvinyl(alcohol-acetate) species is used, an effective amount of a surfactant can be added to improve drying and reliability characteristics with respect to either the ink-jet ink formulations or the fixing fluid formulations. [0031]
  • Appropriate surfactants that can be added to the ink-jet ink composition in order to improve drytime and spreading include TRITONS™ (ethoxylated octylphenols), IGEPALS™ (alkyl phenoxypoly(ethleneoxy)ethanols), SILWETS™ (silicone glycol copolymers including polyalkylene oxide-modified polydimethylsiloxanes), SURFYNOLS™ (ethoxlyated tetramethyl decyndiols), TERGITOLS™ (including ethoxylated trimethylnonanols), BRIJS™ (polyoxyethylene ethers), PLURONICS™ (ethylene oxide/propylene oxide copolymers), FLUORADS™ and ZONYLS™ (fluorosurfactants), and NEODOLS™ (nonionic ethoxylated surfactants). [0032]
  • Turning now to the novel graft copolymers disclosed herein, several compositions are disclosed. Though these graft copolymers are functional with the methods and in preparing the images described, their use is not limited to these specific applications. [0033]
  • First, a graft copolymer for ink-jet ink formulations is disclosed comprising glycerol having from 2 to 3 polyvinyl(alcohol-acetate) chains attached thereto, wherein the polyvinyl(alcohol-acetate) chains have a weight average molecular weight from about 300 to 10,000. With this graft copolymer, the polyvinyl(alcohol-acetate) can be fully or partially hydrolyzed, though it is preferred that the polymer be partially hydrolyzed with respect to the methods and images described herein. There are essentially three preferred varieties of this specific embodiment of graft copolymer. In one variety, three polyvinyl(alcohol-acetate) chains can be etherified to a glycerol molecule. Second, two polyvinyl(alcohol-acetate) chains can be etherified to a glycerol molecule. In a third variety, two polyvinyl(alcohol-acetate) chains and one polyethylene oxide chain can be etherified to a glycerol molecule. [0034]
  • Next, a graft copolymer for ink-jet ink formulations is disclosed comprising a polyvinyl(alcohol-acetate) having a weight average molecular weight from about 300 to 10,000, and a polyethylene glycol chain having a weight average molecular weight from about 300 to 10,000, wherein the polyethylene glycol is attached by etherification to from 5% to 30% of the alcohol groups of the polyvinyl(alcohol-acetate). Again, the polyvinyl(alcohol-acetate) polymer can be partially or fully hydrolyzed, though an 88% hydrolyzed polymer is preferred. [0035]
  • Additionally, a graft copolymer for ink-jet ink formulations is disclosed comprising a low molecular weight styrene-maleic acid ester copolymer having a weight average molecular weight from about 1,000 to 10,000, and a polyvinyl(alcohol-acetate) chain attached thereto, wherein the polyvinyl(alcohol-acetate) has a weight average molecular weight from about 1,000 to 10,000. In this embodiment, the the polyvinyl(alcohol-acetate) can be fully or partially hydrolyzed, though partial hydrolysis of about 88% is preferred. Additionally, in a preferred embodiment, there is one polyvinyl(alcohol-acetate) unit per each maleic acid unit. [0036]
  • Specific examples of graft copolymers that are functional with the present invention are described as follows. First, glycerol etherified with three polyvinyl alcohol-acetate 88% hydrolyzed chains is functional. Each side-chain can be of different or similar sizes. For example, three chains having molecular weights of 500 Mw, 1,000 Mw, and 2,000 Mw, respectively, exemplify good polymers for use. However, any polyvinyl(alcohol-acetate) structures at from 300 Mw to 10,000 Mw can be used. Second, glycerol etherified with two 88% hydrolyzed chains of polyvinyl alcohol-acetates and one polyethylene glycol chain (or two polyethylene glycol chains and one polyvinyl alcohol-acetate chain) can be functional. Again, from 300 Mw to 10,000 Mw for either the polyvinyl(alcohol-acetate) or the polyethylene glycol provides a functional range for use. Third, a partially hydrolyzed polyvinyl alcohol acetate (88% hydrolysis) randomly graft-etherified with polyethylene glycol is also functional. The degree of etherification can be varied from 5% to 30%. In other words, from 5% to 30% of the alcohol groups on the polyvinyl(alcohol-acetate) can tether a side chain of polyethylene glycol. Fourth, a low-molecular weight styrene-maleic acid anhydride co-polymer can be opened with polyvinyl alcohol-acetate (88% hydrolysis), and along the backbone, polyvinyl alcohol-acetate chains can be added to the opened ester.[0037]
  • EXAMPLES
  • The following examples illustrate the preferred embodiments of the invention that are presently best known. However, other embodiments may be practiced which are also within the scope of the present invention. [0038]
  • Example 1 Viscosity and Gelation Capability of Various Polyvinyl(Alcohol-Acetate) Compositions
  • Four different amounts of polyvinyl(alcohol-acetate) were dissolved in two different ink vehicles: one being water/LEG-7 mixture 8:2 w/w; the other being water/LEG-7 mixture 7:3 w/w. The polyvinyl(alcohol-acetate) used was Fluka 15,000 at 88% hydrolysis. The viscosity and gelation results are shown below in Tables 1a and 1b. The gelation was evaluated by mixing the polymer solution described above with 7.5% borax solution in water at 1:1 w/w mixing ratio. [0039]
    TABLE 1a
    Concentration of Viscosity
    pv(al-ac) present in water:LEG-7 Gelation at
    LEG-7:water mixture 8:2 w/w 7.5% Borax
    1%  3.0 cPf No
    3%  5.5 cPf No
    5% 10.0 cPf Yes
    7% 20.0 cPf Yes
  • [0040]
    TABLE 1b
    Concentration of Viscosity
    pv(al-ac) present in Water:LEG-7 Gelation at
    LEG-7:water mixture 7:3 w/w 7.5% Borax
    1%  3.0 cPf No
    3%  6.5 cPf No
    5% 14.0 cPf Yes
    7% 28.0 cPf Yes
  • Example 2
  • A study was conducted to determine whether or not various humectants interfered with the gelation that normally occurs between polyvinyl(alcohol-acetate) and borax in water. Specifically, 10% by weight of a humectant and 5% by weight of 88% polyvinyl(alcohol-acetate) were admixed in water. The various humectants tested at the above ratios are listed in Table 2 below, followed by a characterization as to whether the humectant substantially interfered with gelation, when mixed with 7.5% borax solution in water at 1:1 w/w mixing ratio. Thus, characterizations stating “No” are examples of good humectants for use with the present invention. [0041]
    TABLE 2
    HUMECTANT TESTED INTERFERENCE OBSERVERD
    LEG ™-7 No
    Glycerol Yes
    Urea No
    Betaine No
    Diethylene Glycol Yes
    Isopropyl Alcohol Yes
    2-Butanol Yes
    Polyethylene glycol-400 No
    Tetraethylene glycol No
    2-Pyrrolidone Yes
  • Example 3 Preparation of a Fixing Fluid
  • A fixing fluid was prepared which contained a fixing agent, i.e., borax. This fixing fluid comprised the ingredients described in Table 3 below. [0042]
    TABLE 3
    Component Weight Percentage
    2-pyrrolidone 7.5%
    1,5-pentanediol 8.0%
    Trimethylolpropane 7.5%
    Borax (fixing agent) 7.5%
    Surfynol ™ 465 0.2%
    Water balance
  • The fixing fluid described above in Table 3 provides a composition that can be jetted from an ink-jet pen with good reliability. Additionally, the borax component acts as the active ingredient that is capable of forming a gel after contact with a polyvinyl(alcohol-acetate) species. [0043]
  • Example 4 Preparation of Ink-Jet Ink Composition for Use With a Fixing Fluid
  • An ink-jet ink composition was prepared which contained partially hydrolyzed polyvinyl(alcohol-acetate). This ink-jet ink composition comprised the ingredients described in Table 4 below. [0044]
    TABLE 4
    Component Weight Percentage
    LEG ™-7 (Liponic)  20%
    Polyvinyl (alcohol-acetate) 3.0%
    88% hydrolyzed, M = 15,000
    CI Acid Red-52, Lithium salt 0.1%
    Surfynol ™ 465 0.2%
    Water balance
  • Example 5 Preparation of Ink-Jet Ink Composition for Use With a Fixing Fluid
  • An ink-jet ink composition was prepared which contained partially hydrolyzed polyvinyl(alcohol-acetate). This ink-jet ink composition comprised the ingredients described in Table 5 below. [0045]
    TABLE 5
    Component Weight Percentage
    Polyvinyl (alcohol-acetate), 5.0%
    88% hydrolyzed, M = 15,000
    CI Acid Red-52, Lithium salt 0.1%
    Surfynol ™ 465 0.2%
    Water balance
  • Example 6 Preparation of Ink-Jet Ink Composition for Use With a Fixing Fluid
  • An inkjet ink composition was prepared which contained partially hydrolyzed polyvinyl(alcohol-acetate). This ink-jet ink composition comprised the ingredients described in Table 6 below. [0046]
    TABLE 6
    Component Weight Percentage
    Polyvinyl (alcohol-acetate), 7.0%
    88% hydrolyzed, M = 15,000
    CI Acid Red-52, Lithium salt 0.1%
    Surfynol ™ 465 0.2%
    Water balance
  • Example 7 Printability of Ink-Jet Inks of Examples 4-6
  • Various printing tests were conducted using an HP 2000C printer. The inks of Examples 4-6 were placed in specially designed pens, based on the construction of HP C4800A black pen, i.e., the geometry of the firing chamber was modified to allow the firing of inks having a higher viscosity. The fixing fluid of Example 3 was deposited from an unmodified HP C4802A pen. The drop volume was set at around 32 pL for the HP C4800A pen (ink-jet ink) and around 8 pL for the HP C4802A pen (fixer). Nozzle diagnostics for each of the ink-jet inks were conducted at an increasing frequency of firing, i.e., up to 11 kHz. No firing chamber refill problems were observed up to the 11 kHz firing frequency tested. [0047]
  • Example 8 Fixing Fluid and Ink-jet Ink Deposition
  • Various printing tests were conducted using a HP 2000C printer. First, a rectangular block of the fixing agent-containing fixing fluid described in Example 3 was printed onto a substrate. Immediately thereafter, the inks of Examples 4-6 were printed directly on top of the fixing agent-containing fixing fluid. This was repeated in the same location three times, i.e., fixing fluid, ink-jet ink, fixing fluid, ink-jet ink, fixing fluid, ink-jet ink. The ratio of the number of fixing agent-containing fixing fluid drops to ink-jet ink drops per unit area tested were 0%, 25%, 75%, and 100%. Accordingly, fixer flux to ink flux ratio by volume was 0%, 6.25%, 18.75%, and 25%, respectively. [0048]
  • The substrates tested included Hammermill DP paper and HP premium transparency film plastic sheets. For the plastic sheets, the reverse non-porous side of the sheet was used. With respect to the inks of Examples 4-6, a substantial immobilization of the ink to the surface of the paper was seen when the fixing agent-containing fixing fluid was present. The best immobilization was seen at a 75% fixing agent-containing fixing fluid to ink-jet ink ratio (by the number of drops). The same effect of immobilization was seen on the plastic sheet. Particularly with the plastic substrate, when no fixing fluid was applied, the inks on plastic pulled into irregular puddles. [0049]
  • Example 9 Synthesis of Polyvinyl(Alcohol-Acetate) Having Polyethylene Oxide Chains Grafted Thereto
  • Two grams of a poly(vinyl-acetate) polymer were provided having a weight average molecular weight of about 12,800 Mw. The polyvinyl(alcohol-acetate) was dissolved in 100 ml of toluene in a 250 ml flask equipped with a condenser and a mechanical stirrer. At 40° C., 0.1 ml of aqueous 40% NaOH was added to the solution to initiate hydrolysis. After several minutes, to stop the hydrolysis, the system was extracted with water. The toluene solution of the polymer was then reacted with ethylene oxide gas at room temperature in presence of aluminum chloride. After bubbling the ethylene oxide through the toluene solution for 2 hours, the reaction was stopped and the mixture was extracted with water to remove any non-grafted ethylene oxide homopolymers. The hydrolysis of the acetate groups was completed by again adding 1 ml of aqueous NaOH and heating the mixture to 40° C. The hydrolysis proceeded with the precipitation of polyvinyl(alcohol-acetate) having poly(ethylene oxide) chains grafted thereto. After standing for about one-half hour, the mixture was filtered and washed several times with MeOH. The polymer was then washed with MeOH in a Soxhlet extractor to extract sodium acetate and NaOH. [0050]
  • Example 10 Synthesis of Styrene-Maleic Anhydride Ester of Polyvinyl(Alcohol-Acetate)
  • About 38 grams of Poly(styrene-co-maleic anhydride) which is cumene terminated, has 75% styrene repeat units, and an average weight average moleculare weight of 1,900 Mw was melted in a nitrogen atmosphere. The melt was then mixed with 900 grams of 80% hydrolyzed polyvinyl(alcohol-acetate) (Mw=9,000 to 10,000). This provided a mixing ratio of about one polyvinyl(alcohol-acetate) polymer chain per each maleic anhydride repeat unit. Mechanical mixing occurred for about 24 hours, and the product was dissolved in water and neutralized by sodium hydroxide to a pH of 7. This process produced about 900 grams of a styrene-maleic anhydride ester of polyvinyl(alcohol-acetate). [0051]
  • While the invention has been described with reference to certain preferred embodiments, those skilled in the art will appreciate that various modifications, changes, omissions, and substitutions can be made without departing from the spirit of the invention. It is therefore intended that the invention be limited only by the scope of the appended claims.[0052]

Claims (33)

    What is claimed is:
  1. 1. A method for printing on specialty media comprising:
    a) providing a fixing fluid containing a fixing agent;
    b) providing a dye- or pigment-based ink-jet ink containing an effective amount of a polyvinyl(alcohol-acetate) species;
    c) jetting the fixing fluid onto a specialty media substrate thereby forming a coated substrate; and
    d) jetting the ink-jet ink onto the coated substrate.
  2. 2. A method as in claim 1 further comprising the step of allowing the polyvinyl(alcohol-acetate) of the ink-jet ink and the fixing agent of the fixing fluid to gel on the substrate.
  3. 3. A method as in claim 1 wherein the fixing agent is selected from the group consisting of borax, boric acid, copper sulfate, and combinations thereof.
  4. 4. A method as in claim 1 wherein the fixing fluid comprises components selected from the group consisting of humectants, wetting agents, surfactants, water and combinations thereof.
  5. 5. A method as in claim 1 wherein the dye- or pigment-based ink-jet ink comprises a humectant that does not interfere with gelation.
  6. 6. A method as in claim 5 wherein the humectant is selected from the group consisting of low molecular weight polyethylene glycol, glycereth- 1, glycereth-7, tetraethylene glycol, urea, tetramethylurea, betaine, betaine hydrochloride, and combinations thereof.
  7. 7. A method as in claim 1 wherein the polyvinyl(alcohol-acetate) species is hydrolyzed at from 70% to 100%.
  8. 8. A method as in claim 7 wherein the polyvinyl(alcohol-acetate) species is hydrolyzed at from 75% to 90%.
  9. 9. A method as in claim 7 wherein the polyvinyl(alcohol-acetate) species is hydrolyzed at about 88%.
  10. 10. A method as in claim 1 wherein the polyvinyl(alcohol-acetate) species is a graft copolymer of polyvinyl(alcohol-acetate) and a second polymer.
  11. 11. A gelled printed image on a substrate comprising:
    a) a fixing fluid containing an effective amount of a fixing agent, printed in contact with,
    b) an aqueous ink-jet ink comprising:
    i) a low molecular weight humectant,
    ii) an effective amount of a polyvinyl(alcohol-acetate) species, and
    iii) an effective amount of a dye or pigment, such that said fixing agent and said polyvinyl(alcohol-acetate) interact to form a gel on said substrate.
  12. 12. An image as in claim 11 wherein the fixing agent is selected from the group consisting of borax, boric acid, copper sulfate, and combinations thereof.
  13. 13. An image as in claim 11 wherein the fixing fluid comprises components selected from the group consisting of humectants, drying agents, surfactants, and combinations thereof.
  14. 14. An image as in claim 11 wherein the low molecular weight humectant of the ink-jet ink does not substantially interfere with gelation.
  15. 15. An image as in claim 14 wherein the low molecular weight humectant is selected from the group consisting of low molecular weight polyethylene glycol, glycereth-1, glycereth-7, tetraethylene glycol, urea, tetramethylurea, betaine, betaine hydrochloride, and combinations thereof.
  16. 16. An image as in claim 11 wherein the polyvinyl(alcohol-acetate) is hydrolyzed at from 70% to 100%.
  17. 17. An image as in claim 16 wherein the polyvinyl(alcohol-acetate) is hydrolyzed at from 75% to 90%.
  18. 18. An image as in claim 16 wherein the polyvinyl(alcohol-acetate) is hydrolyzed at about 88%.
  19. 19. An image as in claim 11 wherein the ink-jet ink comprises an effective amount of a surfactant.
  20. 20. An image as in claim 11 wherein the polyvinyl(alcohol-acetate) species is a graft copolymer of polyvinyl(alcohol-acetate) and a second polymer.
  21. 21. A graft copolymer for ink-jet ink formulations comprising glycerol having from 2 to 3 polyvinyl(alcohol-acetate) chains attached thereto, wherein the polyvinyl(alcohol-acetate) chains have a weight average molecular weight from about 300 to 10,000.
  22. 22. A graft copolymer as in claim 21 wherein the polyvinyl(alcohol-acetate) is partially hydrolyzed.
  23. 23. A graft copolymer as in claim 22 wherein the polyvinyl(alcohol-acetate) is about 88% hydrolyzed.
  24. 24. A graft copolymer as in claim 21 having three polyvinyl(alcohol-acetate) chains etherified to the glycerol.
  25. 25. A graft copolymer as in claim 21 having two polyvinyl(alcohol-acetate) chains etherified to the glycerol.
  26. 26. A graft copolymer as in claim 25 further comprising one polyethylene glycol chain etherified to the glycerol.
  27. 27. A graft copolymer for ink-jet ink formulations comprising:
    a) a polyvinyl(alcohol-acetate) having a weight average molecular weight from about 300 to 10,000; and
    b) a polyethylene glycol chain having a weight average molecular weight from about 300 to 10,000, wherein the polyethylene glycol is attached by etherification to from 5% to 30% of the alcohol groups of the polyvinyl(alcohol-acetate).
  28. 28. A graft copolymer as in claim 27 wherein the polyvinyl(alcohol-acetate) is partially hydrolyzed.
  29. 29. A graft copolymer as in claim 27 wherein the polyvinyl(alcohol-acetate) is about 88% hydrolyzed.
  30. 30. A graft copolymer for ink-jet ink formulations comprising:
    a) a low molecular weight styrene-maleic acid ester copolymer having a weight average molecular weight from about 1,000 to 10,000;
    b) a polyvinyl(alcohol-acetate) chain attached thereto, wherein the polyvinyl(alcohol-acetate) has a weight average molecular weight from about 1,000 to 10,000.
  31. 31. A graft copolymer as in claim 30 wherein the polyvinyl(alcohol-acetate) is partially hydrolyzed.
  32. 32. A graft copolymer as in claim 31 wherein the polyvinyl(alcohol-acetate) is about 88% hydrolyzed.
  33. 33. A graft copolymer as in claim 30 wherein there is one polyvinyl(alcohol-acetate) unit per each maleic acid unit.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110200799A1 (en) * 2005-03-31 2011-08-18 Seiko Epson Corporation Treatment liquid for plastic film, primer liquid for printing, ink composition, and method for ink jet recording using them
US20150361285A1 (en) * 2014-06-14 2015-12-17 Xerox Corporation Aqueous Ink Composition

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7129284B2 (en) * 2002-12-03 2006-10-31 Hewlett-Packard Development Company, L.P. Fluorosurfactant packages for use in inkjet printing and methods of controlling puddling in inkjet pens
US7122077B2 (en) 2003-03-28 2006-10-17 E. I. Du Pont De Nemours And Company Inkjet ink set and method of using same
US7622513B2 (en) * 2004-12-01 2009-11-24 Hewlett-Packard Development Company, L.P. Inkjet printing system that provides improved mottle
JP4710337B2 (en) * 2005-02-03 2011-06-29 セイコーエプソン株式会社 Fixing accelerator composition for ink-jet printing, jet printing set, and ink-jet printing process
JP2007217821A (en) * 2006-02-16 2007-08-30 Seiko Epson Corp Fixation promoting composition for ink-jet printing comprising fluorescent agent, ink-jet printing set and method for ink-jet printing
US9410010B2 (en) 2007-12-10 2016-08-09 E I Du Pont De Nemours And Company Urea-terminated polyurethane dispersants
JP5152650B2 (en) * 2008-04-22 2013-02-27 株式会社リコー Image quality improvement treatment liquid, the image quality improvement processing method, an image forming method and image forming apparatus
WO2009143441A1 (en) 2008-05-23 2009-11-26 E. I. Du Pont De Nemours And Company Urea-terminated polyurethane dispersants
EP2845882A3 (en) 2008-10-29 2015-11-18 Fujifilm Corporation Dye, Photoelectric Conversion Element and Photoelectrochemical Cell
JP2013500851A (en) 2009-07-30 2013-01-10 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company Process for the preparation of the dispersion
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US20130231439A1 (en) 2010-12-15 2013-09-05 E.I. Du Pont De Nemours And Company Method of preparing encapsulated pigment dispersions
US8912249B2 (en) 2011-04-25 2014-12-16 E I Du Pont De Nemours And Company Method of preparing encapsulated pigment dispersions which include polyurethane dispersions
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JP5553094B2 (en) * 2012-08-22 2014-07-16 セイコーエプソン株式会社 Recording method and recorded matter
JP5972811B2 (en) 2013-02-22 2016-08-17 富士フイルム株式会社 Photoelectric conversion elements, the manufacturing method and the dye-sensitized solar cell of the photoelectric conversion element
JP2015120777A (en) * 2013-12-20 2015-07-02 株式会社パイロットコーポレーション Aqueous ink composition for ballpoint pen and ballpoint pen containing the same
US20180030295A1 (en) * 2015-04-27 2018-02-01 Hewlett-Packard Development Company, L.P. Fluid sets for inkjet imaging
US9376582B1 (en) 2015-07-30 2016-06-28 Eastman Kodak Company Printing on water-impermeable substrates with water-based inks
US9573349B1 (en) 2015-07-30 2017-02-21 Eastman Kodak Company Multilayered structure with water-impermeable substrate

Citations (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4547405A (en) * 1984-12-13 1985-10-15 Polaroid Corporation Ink jet transparency
US5096489A (en) * 1989-08-25 1992-03-17 Ciba-Geigy Corporation Light-stabilized ink compositions
US5213873A (en) * 1989-10-20 1993-05-25 Oji Paper Co., Ltd. Aqueous ink-jet recording sheet
US5270103A (en) * 1990-11-21 1993-12-14 Xerox Corporation Coated receiver sheets
US5352503A (en) * 1992-09-21 1994-10-04 Rexham Graphics Inc. Recording paper for ink jet recording processes
US5476540A (en) * 1994-10-05 1995-12-19 Hewlett Packard Corporation Gel-forming inks for use in the alleviation of bleed
US5494759A (en) * 1993-07-03 1996-02-27 Felix Schoeller Jr. Foto-Und Spezialpapiere Gmbh & Co. Kg Ink jet printing material
US5518821A (en) * 1993-07-06 1996-05-21 Canon Kabushiki Kaisha Recording medium and ink-jet recording method employing the same
US5569529A (en) * 1993-07-03 1996-10-29 Felix Schoeller Jr. Foto-Und Spezial-Papiere Gmbh & Co. Kg Ink jet printing material
US5570120A (en) * 1993-07-16 1996-10-29 Canon Kabushiki Kaisha Ink-jet recording method and color image forming method
US5609993A (en) * 1991-04-17 1997-03-11 Nippon Paint Co., Ltd. Process for producing lithographic printing plate, photosensitive plate and aqueous ink composition therefor
US5635297A (en) * 1992-12-10 1997-06-03 Mitsubishi Paper Mills Limited Ink jet recording sheet
US5662997A (en) * 1994-05-23 1997-09-02 Seiko Epson Corporation Ink jet recording film comprising cation-modified polyvinyl alcohol and recording method using the same
US5789070A (en) * 1996-12-11 1998-08-04 Eastman Kodak Company Inkjet ink image recording elements with cationically modified cellulose ether layers
US5853899A (en) * 1996-11-04 1998-12-29 Rexam Graphics Inc. Aqueous ink receptive ink jet receiving medium yielding a water resistant ink jet print
US5861230A (en) * 1997-04-21 1999-01-19 Polaroid Corporation Process for the polymerization of 4-vinyl pyridine monomers
US5888253A (en) * 1994-07-21 1999-03-30 Canon Kabushiki Kaisha Textile-printing method, printed textile obtained thereby, and ink
US5912280A (en) * 1996-12-27 1999-06-15 E. I. Du Pont De Nemours And Company Ink jet inks containing emulsion-polymer additives to improve water-fastness
US5985425A (en) * 1997-03-31 1999-11-16 Somar Corporation Ink-jet recording film of improved ink fixing comprising a combination of silica powders
US6001463A (en) * 1996-12-26 1999-12-14 Fuji Photo Film Co., Ltd. Image recording medium and image recording process
US6013354A (en) * 1997-07-31 2000-01-11 Somar Corporation Ink-jet recording film
US6129785A (en) * 1997-06-13 2000-10-10 Consolidated Papers, Inc. Low pH coating composition for ink jet recording medium and method
US6140406A (en) * 1996-06-28 2000-10-31 Consolidated Papers, Inc. High solids interactive coating composition, ink jet recording medium, and method
US6146712A (en) * 1997-11-26 2000-11-14 Oji Paper Co., Ltd. Ink-jet recording sheet and process for producing the same
US6153310A (en) * 1997-10-14 2000-11-28 Nisshinbo Industries, Inc. Ink jet recording sheet
US6165606A (en) * 1997-02-06 2000-12-26 Konica Corporation Ink jet recording paper and ink jet recording method
US6214099B1 (en) * 1998-03-31 2001-04-10 Minolta Co., Ltd. Liquid composition and ink set, and an image forming method using said composition and set
US6214417B1 (en) * 1997-07-12 2001-04-10 Seiren Co., Ltd. Cloth for ink-jet printing, method of fabricating same, and method of ink-jet printing same
US6248805B1 (en) * 1997-10-31 2001-06-19 Hewlett-Packard Company Ink-jet printing ink compositions having magnetic properties and specific core/shell binder
US6270214B1 (en) * 1998-04-29 2001-08-07 Xerox Corporation Ink jet printing process with improved image fixation
US6395459B1 (en) * 2000-09-29 2002-05-28 Eastman Kodak Company Method of forming a protective overcoat for imaged elements and related articles
US6548571B1 (en) * 1999-08-30 2003-04-15 Xerox Corporation Ink compositions and processes
US6620470B2 (en) * 2000-08-31 2003-09-16 Konica Corporation Ink jet recording media

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1015849A (en) * 1964-09-28 1966-01-05 Borden Co Plasticised alkoxylated polyvinyl alcohol compositions
US4072529A (en) 1975-08-20 1978-02-07 The Dow Chemical Company Gelled photopolymer composition and methods of making them
DE69406731T2 (en) 1993-07-30 1998-03-26 Canon Kk Recording element, the ink jet recording method using the same, and thus obtained dispersion and pressure process for the preparation of the recording element using the dispersion
JPH07238243A (en) * 1994-03-01 1995-09-12 Seiko Instr Inc Recording ink
JPH0880633A (en) 1994-09-14 1996-03-26 Matsushita Electric Ind Co Ltd Image forming device
JP3591969B2 (en) 1995-03-15 2004-11-24 キヤノン株式会社 Ink-jet recording medium and a color ink jet recording method using the same
US6372818B1 (en) 1995-08-31 2002-04-16 Canon Kabushiki Kaisha Water-based ink for ink-jet, and ink-jet recording method and instruments using the same
DE69727928D1 (en) 1996-05-23 2004-04-08 Novartis Ag Shelf stable hydrogel
US5683793A (en) 1996-06-03 1997-11-04 Xerox Corporation Ink jet transparencies
DE19628341C2 (en) 1996-07-13 1998-09-17 Sihl Gmbh Recording material for ink-jet method with an aqueous ink, and use for making water and light resistant records on this material
JP3640369B2 (en) 1997-09-04 2005-04-20 株式会社リコー Image recording method and image recording apparatus and image recording promoting liquid
DE69824996T2 (en) * 1997-09-05 2004-12-16 Seiko Epson Corp. The ink composition for forming an image having excellent storage stability
US6020397A (en) 1997-10-10 2000-02-01 Westvaco Corporation Two-component ink jet ink system
US6261353B1 (en) 1998-05-29 2001-07-17 Fuji Xerox Co., Ltd Recording material and image forming method using the same
JP3707966B2 (en) 1998-10-26 2005-10-19 三菱製紙株式会社 Ink jet recording sheet and a method of manufacturing the same
US6488753B1 (en) 1999-03-10 2002-12-03 Seiko Epson Corporation Aqueous pigment dispersion water-base ink composition and recording method using the ink composition
JP2000301821A (en) 1999-04-23 2000-10-31 Canon Inc Method for forming image
JP2001046954A (en) 1999-08-17 2001-02-20 Fuji Photo Film Co Ltd Formation of dry coating film
US6406138B1 (en) 2000-04-20 2002-06-18 Hewlett-Packard Company Polymer systems for high quality inkjet printing
US6482883B1 (en) 2000-05-10 2002-11-19 Kanzaki Specialty Papers, Inc. Ink jet recording material demonstrating a balance of properties including improved imaging performance and good water resistance

Patent Citations (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4547405A (en) * 1984-12-13 1985-10-15 Polaroid Corporation Ink jet transparency
US5096489A (en) * 1989-08-25 1992-03-17 Ciba-Geigy Corporation Light-stabilized ink compositions
US5213873A (en) * 1989-10-20 1993-05-25 Oji Paper Co., Ltd. Aqueous ink-jet recording sheet
US5270103A (en) * 1990-11-21 1993-12-14 Xerox Corporation Coated receiver sheets
US5609993A (en) * 1991-04-17 1997-03-11 Nippon Paint Co., Ltd. Process for producing lithographic printing plate, photosensitive plate and aqueous ink composition therefor
US5352503A (en) * 1992-09-21 1994-10-04 Rexham Graphics Inc. Recording paper for ink jet recording processes
US5635297A (en) * 1992-12-10 1997-06-03 Mitsubishi Paper Mills Limited Ink jet recording sheet
US5494759A (en) * 1993-07-03 1996-02-27 Felix Schoeller Jr. Foto-Und Spezialpapiere Gmbh & Co. Kg Ink jet printing material
US5569529A (en) * 1993-07-03 1996-10-29 Felix Schoeller Jr. Foto-Und Spezial-Papiere Gmbh & Co. Kg Ink jet printing material
US5518821A (en) * 1993-07-06 1996-05-21 Canon Kabushiki Kaisha Recording medium and ink-jet recording method employing the same
US5570120A (en) * 1993-07-16 1996-10-29 Canon Kabushiki Kaisha Ink-jet recording method and color image forming method
US5662997A (en) * 1994-05-23 1997-09-02 Seiko Epson Corporation Ink jet recording film comprising cation-modified polyvinyl alcohol and recording method using the same
US5888253A (en) * 1994-07-21 1999-03-30 Canon Kabushiki Kaisha Textile-printing method, printed textile obtained thereby, and ink
US5476540A (en) * 1994-10-05 1995-12-19 Hewlett Packard Corporation Gel-forming inks for use in the alleviation of bleed
US6140406A (en) * 1996-06-28 2000-10-31 Consolidated Papers, Inc. High solids interactive coating composition, ink jet recording medium, and method
US5853899A (en) * 1996-11-04 1998-12-29 Rexam Graphics Inc. Aqueous ink receptive ink jet receiving medium yielding a water resistant ink jet print
US5789070A (en) * 1996-12-11 1998-08-04 Eastman Kodak Company Inkjet ink image recording elements with cationically modified cellulose ether layers
US6001463A (en) * 1996-12-26 1999-12-14 Fuji Photo Film Co., Ltd. Image recording medium and image recording process
US5912280A (en) * 1996-12-27 1999-06-15 E. I. Du Pont De Nemours And Company Ink jet inks containing emulsion-polymer additives to improve water-fastness
US6165606A (en) * 1997-02-06 2000-12-26 Konica Corporation Ink jet recording paper and ink jet recording method
US5985425A (en) * 1997-03-31 1999-11-16 Somar Corporation Ink-jet recording film of improved ink fixing comprising a combination of silica powders
US5861230A (en) * 1997-04-21 1999-01-19 Polaroid Corporation Process for the polymerization of 4-vinyl pyridine monomers
US6129785A (en) * 1997-06-13 2000-10-10 Consolidated Papers, Inc. Low pH coating composition for ink jet recording medium and method
US6214417B1 (en) * 1997-07-12 2001-04-10 Seiren Co., Ltd. Cloth for ink-jet printing, method of fabricating same, and method of ink-jet printing same
US6013354A (en) * 1997-07-31 2000-01-11 Somar Corporation Ink-jet recording film
US6153310A (en) * 1997-10-14 2000-11-28 Nisshinbo Industries, Inc. Ink jet recording sheet
US6248805B1 (en) * 1997-10-31 2001-06-19 Hewlett-Packard Company Ink-jet printing ink compositions having magnetic properties and specific core/shell binder
US6146712A (en) * 1997-11-26 2000-11-14 Oji Paper Co., Ltd. Ink-jet recording sheet and process for producing the same
US6214099B1 (en) * 1998-03-31 2001-04-10 Minolta Co., Ltd. Liquid composition and ink set, and an image forming method using said composition and set
US6270214B1 (en) * 1998-04-29 2001-08-07 Xerox Corporation Ink jet printing process with improved image fixation
US6548571B1 (en) * 1999-08-30 2003-04-15 Xerox Corporation Ink compositions and processes
US6620470B2 (en) * 2000-08-31 2003-09-16 Konica Corporation Ink jet recording media
US6395459B1 (en) * 2000-09-29 2002-05-28 Eastman Kodak Company Method of forming a protective overcoat for imaged elements and related articles

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110200799A1 (en) * 2005-03-31 2011-08-18 Seiko Epson Corporation Treatment liquid for plastic film, primer liquid for printing, ink composition, and method for ink jet recording using them
US20110200798A1 (en) * 2005-03-31 2011-08-18 Seiko Epson Corporation Treatment liquid for plastic film, primer liquid for printing, ink composition, and method for ink jet recording using them
US9079418B2 (en) 2005-03-31 2015-07-14 Seiko Epson Corporation Treatment liquid for plastic film, primer liquid for printing, ink composition, and method for ink jet recording using them
US9254676B2 (en) 2005-03-31 2016-02-09 Seiko Epson Corporation Treatment liquid for plastic film, primer liquid for printing, ink composition, and method for ink jet recording using them
US20150361285A1 (en) * 2014-06-14 2015-12-17 Xerox Corporation Aqueous Ink Composition
US9371464B2 (en) * 2014-06-14 2016-06-21 Xerox Corporation Aqueous ink composition

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US20090225127A1 (en) 2009-09-10 application
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US8076394B2 (en) 2011-12-13 grant
EP1258510A1 (en) 2002-11-20 application

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