EP0455343B1 - Révélateur liquide comportant des matériaux porteurs liquides durcissables - Google Patents

Révélateur liquide comportant des matériaux porteurs liquides durcissables Download PDF

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Publication number
EP0455343B1
EP0455343B1 EP19910302757 EP91302757A EP0455343B1 EP 0455343 B1 EP0455343 B1 EP 0455343B1 EP 19910302757 EP19910302757 EP 19910302757 EP 91302757 A EP91302757 A EP 91302757A EP 0455343 B1 EP0455343 B1 EP 0455343B1
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Prior art keywords
liquid
developer
image
curable
liquid developer
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EP19910302757
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German (de)
English (en)
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EP0455343A1 (fr
Inventor
Ian D. Morrison
Bing R. Hsieh
Jerry H. Taylor
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Xerox Corp
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Xerox Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G17/00—Electrographic processes using patterns other than charge patterns, e.g. an electric conductivity pattern; Processes involving a migration, e.g. photoelectrophoresis, photoelectrosolography; Processes involving a selective transfer, e.g. electrophoto-adhesive processes; Apparatus essentially involving a single such process
    • G03G17/04—Electrographic processes using patterns other than charge patterns, e.g. an electric conductivity pattern; Processes involving a migration, e.g. photoelectrophoresis, photoelectrosolography; Processes involving a selective transfer, e.g. electrophoto-adhesive processes; Apparatus essentially involving a single such process using photoelectrophoresis
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G03G9/125—Developers with toner particles in liquid developer mixtures characterised by the liquid
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G03G9/13—Developers with toner particles in liquid developer mixtures characterised by polymer components
    • G03G9/131—Developers with toner particles in liquid developer mixtures characterised by polymer components obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention is directed to liquid developer compositions suitable for the development of electrostatic latent images. More specifically, the present invention is directed to liquid developers having curable liquid vehicles.
  • Curable inks are known in the printing industry.
  • U.S. Patent 4,680,368 (Nakamoto et al.),discloses an ultraviolet curable ink composition comprising a polyurethane polymethacrylate obtained by reacting a polyisocyanate compound of the formula wherein R 1 is a hydrogen atom or a methyl group, and n is an integer of from 1 to 20, with a hydroxyl group containing methacrylate and having in one molecule at least two methacryloyl groups and at least two urethane bonds, a radical polymerizable low molecular weight compound, and a photopolymerization initiator.
  • U.S. Patent 4,443,495 discloses a heat curable conductive ink which comprises (1) an ethylenically unsaturated member of the group consisting of (a) a liquid ethylenically unsaturated monomer, oligomer, or prepolymer of the formula wherein R is H or CH 3 , R 1 is an organic moiety and n is at least 2, (b) a polythiol in combination with (a), a polythiol in combination with a liquid ethylenically unsaturated monomer, oligomer, or prepolymer of the formula wherein R 2 is H or CH 3 , R 3 is an organic moiety and n is at least 2, and (d) mixtures of (a), (b), and (c); (2) a thermal initiator; and (3) an electrically conductive material. Heating of the composition in a desired pattern on a substrate results in a printed electric circuit.
  • U.S. Patent 4,751,102 discloses a radiation curable ink composition comprising pigment and a photohardenable composition, wherein the photohardenable composition comprises a free radical addition polymerizable or crosslinkable compound and an ionic dye reactive counter ion compound which is capable of absorbing actinic radiation and producing free radicals which initiate free radical polymerization or crosslinking of the polymerizable or crosslinkable compound.
  • U.S. Patent 4,334,970 discloses a photosensitive resin system that is essentially solvent free and contains an ester produced from an unsaturated organic acid and a polyhydroxyl containing material, a photoinitiator, a carbonyl initiator, a monomer capable of reacting with an acrylic monomer, and an unsaturated hydroxyl containing polymer hydrocarbon.
  • U.S. Patent 3,661,614, U.S. Patent 4,003,868, and U.S. Patent 4,215,167 also disclose ultraviolet curable printing inks.
  • U.S. Patent 4,399,209 discloses a transfer imaging system wherein images are formed by imagewise exposing a layer comprising a chromogenic material and pressure rupturable capsules containing, as an internal phase, a photosensitive composition.
  • a coated composition containing the chromogenic material and the encapsulated photosensitive composition is exposed to actinic radiation and the capsules are subsequently ruptured in the presence of a developer, the image-forming reaction between the chromogenic material and the developer discriminately occurs in the exposed or unexposed areas and produces a detectable image. This result is accomplished by controlling whether the chromogenic material can transfer from the imaging sheet to the developer sheet.
  • the photosensitive composition has a viscosity that changes upon exposure to actinic radiation such that upon exposure there is a change in the viscosity of the internal phase in the exposed areas which imagewise determines whether the chromogenic material is accessible to the developer.
  • the photosensitive composition may be a radiation curable composition which, upon exposure to light, increases in viscosity and immobilizes the chromogenic material, thereby preventing it from transferring to the developer sheet and reacting with the developer material.
  • the chromogenic material can be encapsulated with a substance which is depolymerized or otherwise decreased in molecular weight upon exposure, resulting in a decrease in viscosity which renders the chromogenic material accessible or transferrable to the developer in the exposed areas.
  • liquid developers and liquid development processes for the development of electrostatic latent images are also known.
  • the liquid developers generally comprise a liquid vehicle and colored toner particles, and frequently also contain a charge control agent.
  • the colored toner particles become charged, and upon contacting the electrostatic latent image with the liquid developer, the particles migrate through the liquid vehicle toward the charged image, thereby effecting development. Any residual liquid vehicle remaining on the image subsequent to development is evaporated or absorbed into the receiving sheet.
  • liquid developers employ hydrocarbon liquid vehicles, most commonly high boiling aliphatic hydrocarbons that are relatively high in resistivity and nontoxic. Developers and processes of this type are disclosed in, for example, U.S. Patent 4,476,210, U.S. Patent 2,877,133, U.S.
  • Patent 2,890,174 U.S. Patent 2,899,335, U.S. Patent 2,892,709, U.S. Patent 2,913,353, U.S. Patent 3,729,419, U.S. Patent 3,841,893, U.S. Patent 3,968,044, U.S. Patent 4,794,651, U.S. Patent 4,762,764, U.S. Patent 4,830,945, U.S. Patent 4,686,936, U.S. Patent 4,766,049, U.S. Patent 4,707,429, U.S. Patent 4,780,388, U.S. Patent 3,976,808, U S. Patent 4,877,698, U.S. Patent 4,880,720, and U.S. Patent 4,880,432.
  • colored photosensitive toner particles are suspended in an insulating carrier liquid.
  • the suspension is placed between at least two electrodes subjected to a potential difference and exposed to a light image.
  • the imaging suspension is placed on a transparent electrically conductive support in the form of a thin film and exposure is made through the transparent support while a second biased electrode is rolled across the suspension.
  • the particles bear an initial charge once suspended in the liquid carrier which causes them to be attracted to the transparent base electrode upon application of the potential difference.
  • the particles change polarity by exchanging charge with the base electrode so that the exposed particles migrate to the second or roller electrode, thereby forming images on each of the electrodes by particle subtraction, each image being complementary one to the other.
  • Both polychromatic and monochromatic images can be formed by the process; when polychromatic images are prepared, the liquid developer can contain toner particles of more than one color.
  • Liquid developers containing curable resins in a liquid vehicle such as an aliphatic hydrocarbon are also known, as disclosed, for example, in "Ultra-Violet Curable Liquid Immersion Development Toner," C.C. Chow, Xerox Disclosure Journal , Vol. 1, No. 5 (1976), Japanese Patent 62-115 171, Japanese Patent 62-018 575, Japanese Patent 62-018 574, Japanese Patent 61-156 264, Japanese Patent 61-156 263, Japanese Patent 61-156 262, Japanese Patent 61-156 261, Japanese Patent 61-060 714, Japanese Patent 63-155 055, and Japanese Patent 62-098 364.
  • Patent 4,764,447, Japanese Patent 62-007 718, Japanese Patent 62-007 717, Japanese Patent 62-007 716, Japanese Patent 62-004 714, Japanese Patent 61-020 056, and Japanese Patent 60-249 156 disclose processes for polymerizing monomers in a hydrocarbon liquid vehicle to form dispersions of polymer particles suitable for use as liquid developers. Further, Japanese Patent 62-014168 discloses an encapsulated toner contained in a liquid vehicle. The capsule core can be cured by heat, and the monomers or oligomers become fixed to paper when images developed with the developer are cured.
  • liquid developer compositions that produce prints with little or substantially no odor.
  • a need also remains for liquid developer compositions that reduce or substantially eliminate the emission or carryout of solvent vapors from copiers and printers employing liquid development processes.
  • liquid developer compositions that have curable liquid vehicles and that enable generation of high quality images.
  • liquid developers and liquid development techniques that reduce or eliminate the need to dispose of solvents from a copier or printer employing liquid development.
  • liquid developers and liquid development processes that enable formation of images with excellent fix to a substrate.
  • a need remains for liquid developers and liquid development processes that enable simplified containment and capture procedures for reducing or eliminating solvent emissions for copiers or printers employing liquid development.
  • the present invention also provides a liquid electrophoretic developer which comprises a substantial amount of a curable liquid vehicle having a resistivity of no less than about 5 ⁇ 10 9 ohm-cm and a viscosity of no more than about 20 centipoise, a charge control agent, and colored particles capable of becoming charged and migrating through the liquid vehicle to develop an electrostatic latent image.
  • the liquid vehicle may have a viscosity of no more than about 3 centipoise and/or a resistivity of no less than about 10 10 ohm-cm.
  • the present invention further provides a liquid developer which comprises a colorant and a substantial amount of a curable liquid vehicle having a resistivity of from about 10 8 to about 10 11 ohm-cm and a viscosity of from about 25 to about 500 centipoise. More specifically, in this aspect of the invention, the liquid vehicle may have a viscosity of from about 30 to about 300 centipoise and/or a resistivity of from about 2 X 10 9 to about 10 10 ohm-cm.
  • a liquid photoelectrophoretic developer which comprises a substantial amount of a curable liquid vehicle having a resistivity of no less than about 5 ⁇ 10 9 ohm-cm and a viscosity of no more than about 20 centipoise and photosensitive colored particles. More specifically, in this aspect of the invention, the liquid vehicle may have a viscosity of no more than about 3 centipoise and/or a resistivity of no less than about 10 10 ohm-cm.
  • the developer may contain photosensitive colored particles of at least two different colours.
  • the present invention also provides a process which comprises generating an electrostatic latent image, developing the image with an electrophoretic liquid developer which comprises a substantial amount of a curable liquid vehicle having a viscosity of no more than about 20 centipoise and a resistivity of no less than about 5 ⁇ 10 9 ohm-cm, a charge control additive, and colored particles capable of becoming charged and migrating through the liquid vehicle, and curing the liquid vehicle remaining on the developed image subsequent to development.
  • Curing can take place at any time before or after transfer of the developed image to a substrate. Transfer to a substrate is optional, and imaging and development may take place on the substrate as, for example, when direct marking imaging techniques are employed.
  • the present invention further provides a process which comprises generating an electrostatic latent image on an imaging member, providing an applicator having raised areas and depressed areas, applying to the depressed areas of the applicator a liquid developer comprising a colorant and a substantial amount of a curable liquid vehicle having a resistivity of from about 10 8 to about 10 11 ohm-cm and a viscosity of from about 25 to about 500 centipoise, contacting the raised portions of the applicator with the imaging member to cause the image to attract the developer from the depressed portions of the applicator onto the latent image, thereby developing the image, and curing the liquid vehicle remaining on the developed image.
  • a process which comprises placing a liquid developer comprising a substantial amount of a curable liquid vehicle having a resistivity of no less than about 5 ⁇ 10 9 ohm-cm and a viscosity of no more than about 20 centipoise and photosensitive colored particles between at least two electrodes, exposing the developer between the electrodes to a light image while applying a potential between the electrodes, thereby causing the formation of an image by deposition of the suspended particles in imagewise configuration on the electrodes, and curing the liquid vehicle remaining on the developed image.
  • the liquid vehicle in a developer according to the present invention can be any suitable liquid having the desired resistivity and viscosity characteristics and capable of becoming cured to form a solid.
  • the liquid vehicle When the liquid developer is intended for use in electrophoretic development or photoelectrophoretic development systems, the liquid vehicle must be capable of permitting the colored toner particles of the developer to migrate through the vehicle to develop electrostatic latent images.
  • the liquid vehicle is sufficiently high in resistivity to enhance the development of particles over that of free ions, typically having a resistivity of more than about 5 ⁇ 10 9 ohm-cm and preferably more than about 10 10 ohm-cm as measured by determining the average current flowing across a 1.5 millimeter gap at 5 hertz and 5 volts square wave applied potential.
  • the liquid vehicle is sufficiently low in viscosity to permit the toner particles to migrate toward the electrostatic latent image with sufficient rapidity to enable development of the image within the desired development time.
  • the liquid vehicle has a viscosity of no more than about 20 centipoise at the operating temperature of the copier or printer, and preferably no more than about 3 centipoise at the machine operating temperature.
  • the liquid developer When the liquid developer is intended for use in a polarizable liquid development system, the liquid developer is applied to an applicator such as a gravure roll and brought near an electrostatic latent image.
  • the charged image polarizes the liquid developer in the depressions in the applicator, thereby drawing the developer from the depressions and causing it to flow to the image bearing member to develop the image.
  • the liquid vehicle of the liquid developer is somewhat more viscous than is the situation with electrophoretic development, since particle migration within the developer is generally not necessary and since the liquid developer must be sufficiently viscous to remain in the depressions in the applicator prior to development.
  • liquid developers for use in polar development systems typically have a viscosity of from about 25 to about 500 centipoise at the operating temperature of the copier or printer, and preferably from about 30 to about 300 centipoise at the machine operating temperature.
  • liquid developers intended for use in polarizable liquid development systems typically have a resistivity lower than liquid developers employed in electrophoretic or photoelectrophoretic development systems to enable the developer to become polarized upon entering proximity with the electrostatic latent image.
  • Liquid developers in accordance with the present invention generally have resistivities that are significantly higher than the resistivities of typical printing inks, for which resistivities generally are substantially less than about 10 9 ohm-cm.
  • liquid developers for polarizable liquid development systems have a resistivity of from about 10 8 to about 10 11 ohm-cm, and preferably from about 2 ⁇ 10 9 to about 10 10 ohm-cm.
  • Typical liquids suitable as the curable liquid vehicle include ethylenically unsaturated compounds, including monomers, dimers, or oligomers having one or more ethylenically unsaturated groups such as vinyl or allyl groups, and polymers having terminal or pendant ethylenic unsaturation.
  • suitable curable liquids include, but are not limited to, acrylate and methacrylate monomers or polymers containing acrylic or methacrylic group(s) of the general structure wherein R 1 is H or CH 3 .
  • the active group can be attached to an aliphatic or aromatic group with from 1 to about 20 carbon atoms and preferably from about 8 to about 12 carbon atoms, to an aliphatic or aromatic siloxane chain or ring with from 1 to about 20 dimethyl siloxane units, to a combination of the aforementioned groups, or to a polymer chain.
  • Examples of such compounds include n-dodecyl acrylate, n-lauryl acrylate, methacryloxypropylpenta-methyldisiloxane, methylbis(trimethylsioxy)-silylpropylgylcerolmethacrylate, bis(methacrylowybutyl)tetramethyldisiloxane, 2-phenoxyethyl acrylate, polyethylene glycol diacrylate, ethyoxylated bisphenol A diacrylate, pentaerythritol triacrylate, poly(acryloxypropylmethyl)siloxane, siloxane, methacrylate terminated polystyrene, polybutyldiene diacrylate, and the like.
  • curable liquids believed to be suitable include acrylic and methacrylic esters of polyhydric alcohols such as trimethylolpropane, pentaerythritol, and the like, and acrylate or methacrylate terminated epoxy resins, acrylate or methacrylate terminated polyesters, and the like.
  • Another polymerizable material is the reaction product of epoxidized soy bean oil and acrylic or methacrylic acid as described in U.S. Patent 4,215,167, as well as the urethane and amine derivatives described therein.
  • radiation curable substances include acrylate prepolymers derived from the partial reaction of pentaerythritol with acrylic acid or acrylic acid esters, including those available from Richardson Company, Melrose Park, IL. Further, isocyanate modified acrylate, methacrylate and itaconic acid esters of polyhydric alcohols as disclosed in U.S. Patent 3,783,151, U.S. Patent 3,759,809, and U.S. Patent 3,825,479 are believed to be suitable.
  • Radiation curable compositions based on these isocyanate modified esters including reactive diluents such as tetraethylene glycol diacrylate as well as photoinitiators such as chlorinated resins, chlorinated paraffins, and amine photoinitiation synergists are commercially available from Sun Chemical Corporation under the trade name of Suncure.
  • reactive diluents such as tetraethylene glycol diacrylate
  • photoinitiators such as chlorinated resins, chlorinated paraffins, and amine photoinitiation synergists
  • mixtures of pentaerythritol acrylate and halogenated aromatic, alicyclic, or aliphatic photoinitiators as described in U.S. Patent 3,661,614, as well as other halogenated resins that can be crosslinked by ultraviolet radiation. Additionally, materials believed to be suitable are disclosed in U.S. Patent 4,399,209.
  • epoxy monomers or epoxy containing polymers having one or a plurality of epoxy functional groups such as those resins which result from the reaction of bisphenol A (4,4'-isopropylidenediphenol) and epichlorohydrin, or by the reaction of low molecular weight phenol-formaldehyde resins (Novolak resins) with epichlorohydrin, alone or in combination with an epoxy containing compound as a reactive diluent.
  • Reactive diluents such as phenyl glycidyl ether, 4-vinylcyclohexene dioxide, limonene dioxide, 1,2-cyclohexane oxide, glycidyl acrylate, glycidyl methacrylate, styrene oxide, allyl glycidyl ether, and the like may be used as viscosity modifying agents.
  • the range of these compounds can be extended to include polymeric materials containing terminal or pendant epoxy groups. Examples of these compounds are vinyl copolymers containing glycidyl acrylate or methacrylate as one of the comonomers.
  • epoxy-siloxane resins examples include epoxy-siloxane resins, epoxy-polyurethanes, and epoxy-polyesters.
  • suitable epoxy resins are described in Encyclopedia of Polymer Science and Technology , 2nd edition, Wiley Interscience, New York, pages 322 to 382 (1986) and in Methoden Der Organischen Chemie , Vol. E20 part 3, Georg Thiame Verlag Stuttgart, New York, pages 1891 to 1994 ( 1987).
  • Examples of such materials include decyl vinyl ether, dodecyl vinyl ether, hexadecyl vinyl ether, 4-chlorobutylvinyl ether, cyclohexyl vinyl ether, 1,4-cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, octanediol divinyl ether, decanediol divinyl ether.
  • Further examples of vinyl ether monomers and polymers are shown in "Synthesis, Characterization, and Properties of Novel Aromatic Bispropenyl Ether" by J.V. Crivello and D.A.
  • styrene and indene monomers or oligomers are H, alkyl, or aromatic groups
  • X is an electron donating group such as alkyl, alkoxy, N, N-dialkylamine groups and the like.
  • the styrenic and indenic groups shown above can be attached to a polymer chain.
  • Examples of such materials include butyl-styrene, p-ethoxy styrene, p-butoxy styrene, p-octoxy styrene, o-allyloxystyrene, divinyl benzene, 1,4-bis(p-vinylbenzeneoxy) butane, 1,8-bis(p-vinylbenzeneoxy)octane, and the like.
  • Further examples of styrene and indene monomers are disclosed in Vinyl and Related Polymers , by C.E. Schildknecht, Wiley and Sons, 1952, chapters 1, 2, and 3, and Cationic Polymerization of Olefins: A Critical Inventory , by J.P. Kennedy, Wiley and Sons, 1975, pages 228-330.
  • Typical examples include diethyl ketene acetal, di-butyl ketene acetal, diphenyl ketene acetal, 2-methylene-1,3-dioxepane, 4-phenyl-2-methylene-1,3-dioxepane, 4,6-dimethyl-2-methylene-1,3-dioxane, 2-methylene-1,3-dioxe-5-pene, 4-vinyl-2-methylene-1,3-dioxzlane, and the like. Further examples are disclosed in "Ring-Opening Polymerization" by W.J. Bailey in Comprehensive Polymer Science , Vol. 3, pages 283 to 320 ( 1989).
  • linear or branched aliphatic ⁇ -olefins such as 1-dodecene, 5-methyl-1-heptene, 2,5-dimethyl-1,5-hexadiene, and the like
  • alicyclic olefins and diolefins such as d-limonene, 1,4-dimethylenecyclohexane, 1-methylene-4-vinylcyclohexane, and the like
  • conjugated polyenes such as 2-phenyl-1,3-butadiene, myrcene, allocimene, 1-vinylcyclohexene, ethylbenzofulvene, and the like
  • bicyclic olefins such as ⁇ -pinene, ⁇ -pinene, 2-methylene-norbornane, and the like are all suitable carrier liquids.
  • these classes of olefins are disclosed in Cationic Polymerization of Olefins: A
  • Liquid 1,2-polybutadiene resins of the formula -[CH 2 -CH-(CH CH 2 )] n - with a molecular weight between about 200 and about 3000, and preferably between about 200 and 1000, are also suitable.
  • a thiol compound is generally present as the comonomers with the olefin monomers. Typical examples include trithiol trimethylolethane tris( ⁇ -mercaptopropionate), tetrathiol pentaerythritol tetrakis(thiogylcolate), dimonene dimercaptane, and the like.
  • curable liquid materials include those that contain moieties such as cinnamic groups of the formula fumaric or maleic groups of the formula or maleimido groups of the formula These functional groups can be present within either a monomer or a polymer comprising the liquid.
  • Specific examples include citrial, cinnamyl acetate, cinnamaldehyde, 4-vinylphenyl cinnamates, 4-vinylphenyl, 4-nitrocinnamate, 4-isopropenylphenyl cinnamate, poly[1-(cinnamoyloxy-methylphenyl)ethylene], poly ⁇ 1-(cinnamoyloxymethylphenyl)ethylene-co-1-[(4-nitrophenoxy)methylphenyl]ethylene ⁇ , 3-(2-furyl)acrolein), fumaric acid diethylester, fumaric acid dihexyl ester, maleic acid dibutylester, maleic acid diphenyl ester, N-phenyl maleinide, N-(4-butylphenyl) maleimide, m-phenylenediamine bis(maleimide), and N, N'-1, 3 phenylenedimaleimide, and polyfunctional maleimide polymer MP-2000 from Kennedy and
  • monomers, dimers, or oligomers containing a multiplicity of one or more suitable functional groups can also be employed as the curable liquid.
  • the curable liquid can contain a crosslinking agent.
  • Crosslinking agents generally are monomers, dimers, or oligomers containing a multiplicity of functional groups, such as two styrene functionalities, a styrene functionality and an acrylate functionality, or the like.
  • the curable liquid can consist entirely of these multifunctional monomers, dimers, or oligomers, can contain no crosslinking agent at all, and can contain both monofunctional monomers, dimers, or oligomers and multifunctional monomers or oligomers.
  • the presence of a crosslinking agent is preferred to provide improved film forming characteristics, faster curing, and improved adhesion of the cured image to the substrate.
  • the crosslinking agent is present in an effective amount, typically from about 1 to about 100 percent by weight of the curable liquid and preferably from about 10 to about 50 percent by weight of the curable liquid.
  • Liquid developers in accordance with the present invention can also contain an initiator to initiate curing of the liquid vehicle.
  • the initiator can be added before or after development of the image. Any suitable initiator can be employed: examples of the types of initiators suitable include thermal initiators, radiation sensitive initiators such as ultraviolet initiators, infrared initiators, visible light initiators, or the like, initiators sensitive to electron beam radiation, ion beam radiation, gamma radiation, or the like. In addition, combinations of initiators from one or more class of initiators can be employed. Radical photoinitiators and radical thermal initiators are well known, as is electron beam curing; these materials and processes are disclosed in, for example, "Radiation Curing of Coatings," G.A. Senich and R.E.
  • initiators include those that generate radicals by direct photofragmentation, including benzoin ethers such as benzoin isobutyl ether, benzoin isopropyl ether, benzoin methyl ether and the like, acetophenone derivatives such as 2,2-dimethoxy-2-phenylacetophenone, dimethoxyacetophenone, 4-(2-hydroxyethoxy)phenyl-(2-propyl)ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2,2-trichloroacetophenone, 2,4,6-trimethylbenzoyldiphenylphospine oxide, and the like; initiators that form radicals by bimolecular hydrogen transfer, such as the photoexcited triplet state of diphenyl ketone or benzophenone, diphenoxybenzophenone, bis(N,N-di
  • Suitable initiators include alpha-alkoxy phenyl ketones, O-acylated alpha-oximinoketones, polycyclic quinones, xanthones, thioxanthones, halogenated compounds such as chlorosulfonyl and chloromethyl polynuclear aromatic compounds, chlorosulfonyl and chloromethyl heterocyclic compounds, chlorosulfonyl and chloromethyl benzophenones and fluorenones, haloalkanes, alpha-halo alpha-phenylacetophenones, photoreducible dye-reducing agent redox couples, halogenated paraffins such as brominated or chlorinated paraffin, benzoin alkyl esters, cationic diborate anion complexes, anionic di-iodonium ion compounds, and anionic dye-pyrrilium compounds.
  • halogenated compounds such as chlorosulfonyl and chloromethyl polynuclear aromatic compounds,
  • the initiator is present in the curable liquid in an effective amount, generally from about 0.1 to about 10 percent by weight of the liquid, and preferably from about 0.1 to about 3 percent by weight of the liquid.
  • autoxidizer which is generally a compound capable of consuming oxygen in a free radical chain process.
  • autoxidizers include N,N-dialkylaninines, particularly those substituted in one or more of the ortho, meta, or para positions with groups such as methyl, ethyl, isopropyl, t-butyl, 3,4-tetramethylene, phenyl, trifluoromethyl, acetyl, ethoxycarbonyl, carboxy, carboxylate, trimethylsilylmethyl, trimethylsilyl, triethylsilyl, trimethylgermanyl, triethylgermanyl, trimethylstannyl, triethylstannyl, n-butoxy, n-pentyloxy, phenoxy, hydroxy, acetyl-oxy, methylthio, ethylthio, isopropyl
  • a UV sensitizer which could impart electron transfer, and exciplex-induced bond cleavage processes during radiation curing can, if desired, be included in a liquid developer in accordance with the present invention.
  • Typical photosensitizers include anthrecene, perylene, phenothiazine, thioxanthone, benzophenone, fluorenone, and the like.
  • the sensitizer is present in an effective amount, typically from about 0.1 to about 5 pecent by weight, of the curable liquid.
  • a liquid developer in accordance with the present invention can also include a charge control agent.
  • a charge control agent would generally be present in electrophoretic liquid developers and photoelectrophoretic liquid developers to impart to the particles contained in the liquid a charge sufficient to enable them to migrate through the liquid vehicle to develop an image.
  • Suitable charge control agents for liquid developers include the lithium, cadmium, calcium, manganese, magnesium and zinc salts of heptanoic acid; the barium, aluminum, cobalt, manganese, zinc, cerium and zirconium salts of 2-ethyl hexanoic acid, (these are known as metal octoates); the barium, aluminum, zinc, copper, lead and iron salts of stearic acid; the calcium, copper, manganese, nickel, zinc and iron salts of naphthenic acid; and ammonium lauryl sulfate, sodium dihexyl sulfosuccinate, sodium dioctyl sulfosuccinate, aluminum diisopropyl salicylate, aluminum resinate, aluminum salt of 3,5 di-t-butyl gamma resorcylic acid.
  • charge control agents include lecithin (Fisher Inc.); OLOA 1200, a polyisobutylene succinimide available from Chevron Chemical Company; basic barium petronate (Witco Inc.); zirconium octoate (Nuodex); aluminum stearate; salts of calcium, manganese, magnesium and zinc with heptanoic acid; salts of barium, aluminum, cobalt, manganese, zinc, cerium, and zirconium octoates; salts of barium, aluminum, zinc, copper, lead, and iron with stearic acid; iron naphthenate; and the like, as well as mixtures thereof.
  • the charge control additive may be present in an amount of from about 0.001 to about 3 percent by weight, and preferably from about 0.01 to about 0.8 percent by weight of the developer composition.
  • Other additives such as charge adjuvants added to improve charging characteristics of the developer, may be added to the developers.
  • Charge adjuvants such as stearates, metallic soap additives, polybutylene succinimides, and the like are described in references such as U.S. Patent 4,707,429, U.S. Patent 4,702,984, and U.S. Patent 4,702,985.
  • the curable liquid component is present in a large amount and generally constitutes that percentage by weight of the developer not accounted for by the solid components although (as described later) a non-curable liquid component, for example a release agent, may also be present.
  • the total amount of liquid vehicle present is at least 80 percent by weight of the developer and contains at least 80 percent by weight of curable liquid.
  • a liquid developer in accordance with the present invention can contain any kind of colored toner particle typically used in conventional liquid developers and compatible with the liquid vehicle.
  • the toner particles can consist solely of pigment particles dispersed in the liquid vehicle. Since the liquid vehicle is cured to a solid before, or after transfer, the pigment particles can become affixed to the print substrate by the cured liquid vehicle, and no additional polymeric component is required in the developer for fixing purposes. If desired, however, a polymeric component can be present in the developer. That is, in certain embodiments of the invention, the colored particles are pigment particles and the developer also contains a polymer.
  • the polymer can be soluble in the liquid vehicle, and can include polymers such as poly(2-ethyl hexylmethacrylate); poly(isobutylene-co-isoprenes), such as Kalene 800, available from Hardman Company, N.J.; polyvinyl toluene-based copolymers, including vinyl toluene acrylic copolymers such as Pliolite OMS, Pliolite AC, Pliolite AC-L, Pliolite FSA, Pliolite FSB, Pliolite FSD, Pliolite FSE, Pliolite VT, Pliolite VT-L, Pliolite VTAC, and Pliolite VTAC-L, available from the Goodyear Tire and Rubber Company, Neocryl S-1002 and EX519, available from Polyvinyl Chemistry Industries, Parapol 900, Parapol 1300, and Parapol 2200, available from Exxon Company, and the like; block copolymers such as poly(sty
  • the polymer can be insoluble in the liquid vehicle, and can be present either as separate particles or as an encapsulating shell around the pigment particles. That is, in certain embodiments of the invention, the colored particles comprise pigment particles and a polymer.
  • suitable polymers in this instance include ethylene-vinyl acetate copolymers such as the Elvax I resins available from E.I. Du Pont de Nemours & Company, copolymers of ethylene and an ⁇ , ⁇ -ethylenically unsaturated acid selected from acrylic or methacrylic acid, where the acid moiety is present in an amount of from 0.1 to 20 percent by weight, such as the Nucrel II resins available from E.I.
  • Du Pont de Nemours & Company polybutyl terephthalates, ethylene ethyl acrylate copolymers such as those available as Bakelite DPD 6169, DPDA 6182 Natural, and DTDA 9169 Natural from Union Carbide Company, ethylene vinyl acetate resins such as DQDA 6479 Natural 7 and DQDA 6832 Natural 7 avalable from Union Carbide Company, methacrylate resins such as polybutyl methacrylate, polyethyl methacrylate, and polymethyl methacrylate, available under the trade name Elvacite from E.I Du Pont de Nemours & Company, and others as disclosed in, for example, British Patent 2,169,416 and U.S. Patent 4,794,651.
  • the polymer can be partially soluble in the liquid vehicle, or soluble in the vehicle at elevated temperatures of, for example, over 75°C and insoluble at ambient temperatures of, for example, from about 10°C to about 65°C.
  • suitable polymers in this instance include polyolefins and halogenated polyolefins, such as chlorinated polypropylenes and poly- ⁇ -olefins, including polyhexadecenes, polyoctadecenes, and the like.
  • Suitable pigment materials include carbon blacks such as Microlith® CT, available from BASF, Printex® 140 V, available from Degussa, Raven® 5250 and Raven® 5720, available from Columbian Chemicals Company, and Mogul-L, Black Pearls L, and the Regal carbon blacks from Cabot Corporation.
  • Pigment materials may be colored, and may include magenta pigments such as Hostaperm Pink E (Hoechst Celanese Corporation) and Lithol Scarlet (BASF), yellow pigments such as Diarylide Yellow (Dominion Color Company), cyan pigments such as Sudan Blue OS (BASF), and the like.
  • any pigment material is suitable provided that it consists of small particles and that it either combines well with any polymeric material also included in the developer composition or is suitable in itself as a toner particle in that it is of the desired particle size and, in the electrophoretic and photoelectrophoretic embodiments of the present invention, is capable of becoming charged and migrating through the liquid vehicle to develop an image.
  • the pigment particles are present in an amount sufficient to enable development of a colored image, typically from about 5 to about 100 percent by weight of the solids content of the developer.
  • Polymeric components of the solids portion of the developers, when present, are present in any amount up to about 95 percent by weight of the solids component of the liquid developer.
  • photosensitive pigments suitable for use in photoelectrophoretic liquid developers in accordance with the present invention are disclosed in, for example, U.S. Patent 3,384,488. This patent also discloses additional materials, such as charge transfer materials, that can be contained in photoelectrophoretic liquid developers in accordance with the present invention.
  • the pigment can be a "flushed" pigment.
  • Flushed pigments generally are those pigments that are sold in a form readily suitable for dispersion into organic media. Pigments often are manufactured by an aqueous precipitation reaction, and the product is collected in a water-wet pigment cake by filtration. The cake is then dried to obtain a dry pigment powder. Flushed pigments, however, are not dried to powder; instead, the filter cake is mixed with an organic solvent such as mineral oils, litho oils, or gloss ink varnishes, until a phase transfer occurs in which the pigment spontaneously transfers from the aqueous phase to the organic phase as a result of stirring.
  • an organic solvent such as mineral oils, litho oils, or gloss ink varnishes
  • flushed pigments for developers in accordance with the present invention results in advantages such as a reduced need for mixing and processing of the liquid developer during formulation to obtain desirable pigment particle sizes, since the particles are already small in the organic dispersion.
  • the organic pigment dispersion can be mixed readily with a variety of vehicles.
  • Particularly preferred for developers in accordance with the present invention are flushed pigments in curable liquid media, such as alkyds, polyesters, or the like.
  • a liquid developer in accordance with the present invention can be prepared from flushed pigments by simple mixing of the flushed pigment with the liquid vehicle and the other developer ingredients.
  • flushed pigments suitable for the present invention include Alkyd Based, Sunset II, Quantum Set II, Polyversyl, and Valuset II flushes from Sun Chemical Corporation, and the like. Further information regarding flushed pigments is disclosed in, for example, U.S. Patent 4,794,066.
  • liquid developers in accordance with the present invention can contain toner particles comprising dyed silica particles.
  • the developer can contain a dye instead of pigment particles.
  • the particles can be colored with a dye instead of with a pigment.
  • Suitable dyes include Orasol Blue 2GLN, Red G, Yellow 2GLN, Blue GN, Blue BLN, Black CN, Brown CR, all available from Ciba-Geigy, Inc., Mississauga, Ontario, Morfast Blue 100, Red 101, Red 104, Yellow 102, Black 101, Black 108, all available from Morton Chemical Company, Ajax, Ontario, Bismark Brown R, available from Aldrich, Neolan Blue, available from Ciba-Geigy, Savinyl Yellow RLS, Black RLS, Red 3GLS, Pink GBLS, all available from Sandoz Company, Mississauga, Ontario, and the like. Dyes generally are present in an amount of from about 5 to about 30 percent by weight of the toner particle, although other amounts may be present.
  • Liquid developers in accordance with the present invention can also contain various polymers added to modify the viscosity of the developer or to modify the mechanical properties of the developed or cured image such as adhesion or cohesion.
  • the developer when the liquid developer is intended for use in polarizable liquid development processes, the developer can also include viscosity controlling agents.
  • suitable viscosity controlling agents include thickeners such as alkylated polyvinyl pyrrolidones, such as Ganex V216, available from GAF; polyisobutylenes such as Vistanex, available from Exxon Corporation, Kalene 800, available from Hardman Company, New Jersey, ECA 4600, available from Paramins, Ontario, and the like; Kraton G-1701, a block copolymer of polystyrene-b-hydrogenated butadiene available from Shell Chemical Company, Polypale Ester 10, a glycol rosin ester available from Hercules Powder Company; and other similar thickeners.
  • thickeners such as alkylated polyvinyl pyrrolidones, such as Ganex V216, available from GAF; polyisobutylenes such as Vistanex, available from Exxon Corporation, Kalene 800, available from Hardman Company, New Jersey, ECA 4600, available from Paramins, Ontario, and the like; Kraton G-1701,
  • additives such as pigments, including silica pigments such as Aerosil 200, Aerosil 300, and the like available from Degussa, Bentone 500, a treated montmorillonite clay available from NL Products, and the like can be included to achieve the desired developer viscosity.
  • Additives are present in any effective amount, typically from about 1 to about 40 percent by weight in the case of thickeners and from about 0.5 to about 5 percent by weight in the case of pigments and other particulate additives.
  • liquid developers in accordance with the present invention intended for use in polarizable liquid development processes can also contain conductivity enhancing agents.
  • the developers can contain additives such as quaternary ammonium compounds as disclosed in, for example, U.S. Patent 4,059,444.
  • the liquid developers can contain a small amount of a release agent.
  • Images prepared with the developers can be cured before or after transfer of the image to a printing substrate.
  • the images can be partially cured prior to transfer, followed by additional curing subsequent to transfer.
  • the image is desirable for the image to be released easily from the imaging member and also to adhere to the substrate, such as paper, transparency material, or the like.
  • the substrate such as paper, transparency material, or the like.
  • suitable release agents include noncurable liquids typically employed as liquid vehicles for liquid developers, such as high purity aliphatic hydrocarbons with, for example, from about 7 to about 25 carbon atoms and preferably with a viscosity of less than 2 centipoise, such as Norpar® 12, Norpar® 13, and Norpar® 15, available from Exxon Corporation, isoparaffinic hydrocarbons such as Isopar® G, H, K, L, M, and V, available from Exxon Corporation, Amsco® 460 Solvent, Amsco® OMS, available from American Mineral Spirits Company, Soltrol®, available from Phillips Petroleum Company, Pagasol®, available from Mobil Oil Corporation, Shellsol®, available from Shell Oil Company, and the like, as well as mixtures thereof.
  • noncurable liquids typically employed as liquid vehicles for liquid developers such as high purity aliphatic hydrocarbons with, for example, from about 7 to about 25 carbon atoms and preferably with a viscosity of less than 2 centipoise, such as Nor
  • the release agent can be present in any amount of up to about 20 percent by weight of the liquid. Curing or partial curing of an image developed with a developer containing a noncurable release agent results in a coherent image that is readily released from the smooth imaging member but that still adheres readily to the substrate, particularly porous substrates such as paper or fabric. The non-curing portion of the liquid is then absorbed into the substrate, particularly when this portion is a high molecular weight hydrocarbon, such as Magiesol 60 or Isopar® V, or a silicone oil.
  • the release agent functionality may also be obtained by using siloxane or fluorocarbon containing components in the curable vehicle.
  • the liquid vehicle can either contain a siloxane or fluorocarbon release agent as an additive, or, if the selected siloxane or fluorocarbon release agent is of suitable viscosity and resisitivity, the liquid vehicle can contain a major portion (up to 100 percent) of the siloxane or fluorocarbon release agent.
  • siloxane materials include polydimethylsiloxanes terminated with 4-vinylcyclohexene oxide, such as the UV9300 and UV9305 silicone epoxy polymers from GE.
  • Liquid developers in accordance with the present invention generally can be prepared by any method suitable for the type of toner particles selected.
  • the developer can be prepared by mixing the ingredients, followed by grinding the mixture in an attritor in the presence of the selected liquid vehicle.
  • the toner ingredients comprise colored silica particles
  • the developer can be prepared by heating and mixing the ingredients, followed by grinding the mixture in an attritor until homogeneity of the mixture has been achieved.
  • Colored silica particles can be prepared by the processes described in, for example, U.S. Patent 4,566,908, U.S. Patent 4,576,888, and U.S. Patent 4,877,451.
  • the polymer can be dispersed by heating the mixture, grinding the mixture in an attritor at elevated temperatures, and grinding while the mixture cools.
  • Methods of preparing various kinds of liquid developers are disclosed in several of the documents previously mentioned, including U.S. Patent 4,476,210, U.S. Patent 4,794,651, U.S. Patent 4,877,698, U.S. Patent 4,880,720, and U.S. Patent 4,880,432.
  • the charge control agent can be added to the mixture either during mixing of the other ingredients or after the developer has been prepared.
  • the initiator that enables curing of the liquid vehicle can either be added with the other developer ingredients or at a later time, including immediately before use of the developer.
  • the liquid developer contains little or no initiator during the development step, and the initiator is added to the developed image. This can be accomplished in any suitable manner, such as by spraying the developed image with the initiator, by incorporating the initiator into the substrate on which the final image will be contained, by applying the initiator as an undercoat or an overcoat, or the like.
  • the liquid developer can contain little or no crosslinking agent during the development step, and the crosslinking agent can be added to the developed image in any suitable manner.
  • liquid electrophoretic developers and polarizable liquid developers in accordance with the present invention, images are developed by generating an electrostatic latent image and contacting the latent image with the liquid developer, thereby causing the image to be developed.
  • a liquid electrophoretic developer When a liquid electrophoretic developer is employed, the process entails generating an electrostatic latent image and contacting the latent image with the developer comprising a liquid vehicle and charged toner particles, thereby causing the charged particles to migrate through the liquid and develop the image.
  • Developers and processes of this type are disclosed in, for example, U.S. Patent 4,804,601, U.S. Patent 4,476,210, U.S. Patent 2,877,133, U.S. Patent 2,890,174, U.S.
  • the process entails generating an electrostatic latent image on an imaging member, applying the liquid developer to an applicator, and bringing the applicator into sufficient proximity with the latent image to cause the image to attract the developer onto the imaging member, thereby developing the image.
  • Developers and processes of this type are disclosed in, for example, U.S. Patent 4,047,943, U.S. Patent 4,059,444, U.S. Patent 4,822,710, U.S. Patent 4,804,601, U.S. Patent 4,766,049, U.S. Patent 4,686,936, U.S.
  • any suitable means can be employed to generate the image.
  • a photosensitive imaging member can be exposed by incident light or by laser to generate a latent image on the member, followed by development of the image and transfer to a substrate such as paper, transparency material, cloth, or the like.
  • an image can be generated on a dielectric imaging member by electrographic or ionographic processes as disclosed, for example, in U.S. Patent 3,564,556, U.S. Patent 3,611,419, U.S. Patent 4,240,084, U.S. Patent 4,569, 584, U.S.
  • transferred images can be fused to the substrate by any suitable means, such as by heat, pressure, exposure to solvent vapor or to sensitizing radiation such as ultraviolet light or the like as well as combinations thereof.
  • liquid developers in accordance with the present invention can be employed to develop electrographic images wherein an electrostatic image is generated directly onto a substrate by electrographic or ionographic processes and then developed, with no subsequent transfer of the developed image to an additional substrate.
  • the photoelectrophoretic liquid developers of the present invention can be employed in photoelectrophoretic development processes, which generally entail placing a suspension of electrically photosensitive particles in a fluid between two electrodes, at least one of which is generally a substantially transparent plate. Exposure of the suspension to a light image while a field is applied between the electrodes causes the formation of an image by deposition of the suspended particles in imagewise configuration on the electrode.
  • both electrodes are transparent plates.
  • both electrodes are transparent plates.
  • Patent 4,023,968 one electrode is a transparent conductive support and the other is a generally cylindrically shaped biased electrode that is rolled across the first electrode upon which has been placed the suspension of photosensitive particles.
  • Multicolor images can be made by, among other methods, employing a developer containing photosensitive particles of all desired colors and sequentially exposing the suspension to light images through color filters.
  • Photoelectrophoretic processes are described in detail in, for example, U.S. Patent 4,043,655, U.S. Patent 4,023,968, U.S. Patent 4,066,452, U.S. Patent 3,383,993, U.S. Patent 3,384,566, U.S. Patent 3,384,565, and U.S. Patent 3,384,488.
  • Photoelectrophoretic liquid developers in accordance with the present invention can be prepared by preparing any of the liquid photoelectrophoretic developers disclosed in these patents with the exception that the liquid vehicle is replaced with a curable liquid having the desired resistivity and viscosity characteristics.
  • the image is cured, causing residual liquid vehicle on the image to solidify. Curing can take place before transfer, or after transfer. In situations such as electrographic imaging wherein the image is developed directly on the substrate and no transfer occurs, the image is cured subsequent to development.
  • the developed image can be partially cured prior to transfer; partial curing can impart tacky surface characteristics to the developed image, which can enhance transfer to a substrate.
  • curing subsequent to transfer can greatly enhance adhesion of the image to the substrate, since the liquid vehicle can penetrate the substrate, particularly when the substrate is porous such as cloth or paper, and curing results in the image being tightly bound to the fibers of the substrate.
  • curing subsequent to transfer can greatly enhance adhesion to the substrate, whether the substrate is smooth or porous, when the substrate has reactive sites, either naturally occurring as in cellulose or clays, or added as a precoating, with which reactive species in the liquid developer can react.
  • Curing can be by any suitable means, and generally is determined at least in part by the nature of the initiator selected.
  • a photoinitiator is selected, curing is effected by exposure of the image to radiation in the wavelength to which the initiator is sensitive, such as ultraviolet light.
  • suitable ultraviolet lamps include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, xenon lamps, mercury xenon lamps, arc lamps, gallium lamps, lasers, and the like.
  • a thermal initiator is selected, the image is heated to a temperature at which the initiator can initiate curing of the liquid vehicle and maintained at that temperature for a period sufficient to cure the image.
  • Electron beam curing can be initiated by any suitable electron beam apparatus.
  • Examples include scanned beam apparatuses, in which electrons are generated nearly as a point source and the narrow beam is scanned electromagnetically over the desired area, such as those available from High Voltage Engineering Corporation, Radiation Dynamics, Inc. (a subsidiary of Monsanto Company), Polymer Physik of Germany, or the like, and linear-filament apparatuses or curtain processor apparatuses, in which electrons are emitted from a line-source filament and accelerated perpendicular to the filament in a continuous linear curtain, such as those available from Energy Sciences, Inc. under the trade name Electrocurtain. Ion beam curing can be initiated by any suitable means, such as a corotron.
  • Liquid developers of the present invention exhibit several advantages over liquid developers having noncurable liquid vehicles.
  • the copies or prints prepared with liquid developers having noncurable liquid vehicles frequently exhibit an objectionable odor caused by residual liquid vehicle remaining in the paper.
  • Copies or prints prepared with liquid developers of the present invention exhibit little or no odor, since any liquid vehicle remaining on the print substrate after transfer is cured to a solid state.
  • copiers or printers employing liquid development processes frequently emit solvent vapors from the drying of the noncurable liquid vehicle of the developer. Costly and complex solvent capture systems are necessary to reduce solvent emissions of these solvents. Since the hydrocarbon liquid vehicles frequently employed in conventional liquid developers tend to be chemically unreactive, vapors from these hydrocarbons can be captured only by physical or mechanical means.
  • the curable liquid vehicles of developers in accordance with the present invention are more chemically reactive than noncurable liquid hydrocarbons, and solvent emissions from copiers or printers employing these developers can be captured by simple, inexpensive chemical means such as by the presence of a catalyst that cures the liquid or by light exposure.
  • waste disposal of used developer from copiers and printers employing conventional liquid developers constitutes an additional expense and inconvenience, since the liquid vehicle must be disposed of by acceptable organic solvent disposal procedures.
  • Liquid developers in accordance with the present invention can be cured to a solid, so that unused developer in the machine can be cured and disposed of as a solid. Additionally the major portion of the liquid in curable liquid developers will be carried out in the cured solid image.
  • Copies or prints prepared from liquid developers in accordance with the present invention also exhibit excellent fix to a substrate, particularly when the developed image is cured after it has been transferred to the substrate.
  • the uncured liquid vehicle in the developed image penetrates the substrate, and subsequent curing results in the image becoming intimately bound to the paper or fabric fibers or to the substrate surface.
  • An electrophoretic liquid developer curable by ultraviolet radiation was prepared by first preparing a concentrated developer as described generally by Trout in U.S. Patent 4,707,429, column 11, Example 3, and then diluting the concentrate with UV curable monomers. Specifically, 35 parts by weight of Nucrel 699, a copolymer of ethylene (91 percent) and methacrylic acid (9 percent) with a Melt Index at 190°C of 100 and an Acid Number of 60, available from E.I.
  • the average particle size by area was monitored during milling with a Horiba CAPA-500 centrifugal particle analyzer (the particle sizing procedure is described in U.S. Patent 4,707,429, column 4, lines 60 to 67).
  • the average particle size was less than 10 microns
  • the ingredients were cooled to room temperature while milling was continued.
  • the steel balls were removed after the mixture had reached room temperature.
  • Basic Barium Petronate an oil-soluble petroleum sulfonate, available from Sonneborn Division of Witco Chemical Corporation, New York, NY, was then added (96 milligrams per gram of solids) to the mixture as a charge director. Subsequently, the concentrate mixture prepared according to the process of U.S.
  • Patent 4,707,429 was diluted to 2% by weight solids with a one-to-one mixture by weight of decyl vinyl ether (Decave, available from International Flavors & Fragrances, Inc., New York, NY) and 1,4,-bis[(vinyloxy)methyl)]-cyclohexane (Rapi-Cure CHVE, available from GAF Corporation, Wayne, NJ).
  • the resistivity of the developer was measured (at 5 volts, 5 hertz) as 4.3 x 10 10 ohm-cm.
  • the Isopar® L from the concentrate remained in the liquid developer as a release agent.
  • an electrostatic image was created on a sheet of dielectric coated paper (Versatec® 4011 electrographic paper, available from Versatec, Santa Clara, CA) by (1) lightly gluing a 4 inch by 5 inch piece of the dielectric paper, coated side out, to a 4 inch by 5 inch by 0.5 inch aluminum block; (2) grounding the aluminum plate to a high voltage power supply, model 206 Pacific Precision Instruments, Concord, CA; (3) setting the power supply to + 500 volts and attaching the power supply lead to a bundle of resistive carbon fibers, Celion Celect 675, Celanese, Chatam, NJ held in a thin plastic tube; and (4) writing an image on the dielectric paper with the charged fiber bundle used as a pencil.
  • the electrostatic image was developed into a visible image by (1) mounting the aluminum plate with the attached imagewise charged dielectric paper over a second aluminum plate so that the gap between the plates was 1 millimeter; (2) attaching the power supply ground to the image-holding plate and attaching the power supply lead with + 100 volt potential applied to the opposite aluminum electrode (this electrical bias suppresses background development on the charged dielectric paper); (3) pouring approximately 5 milliliters of the electrophoretic liquid developer between the two plates allowing the excess to drain out; and (4) separating the aluminum plates. A dark image with little background development corresponding to the written image was clearly visible.
  • the developed image was cured by (1) making a 0.67 percent by weight solution of bis(tert-butylphenyl) iodinum hexafluoroarsenate prepared by the method described by Crivello and Lam, Macromolecules , 10(6) 1307 ( 1977), the disclosure of which is totally incorporated herein by reference, in a 2 to 1 mixture of decyl vinyl ether (Decave) and 1,4,-bis[(vinyloxy)methyl)]-cyclohexane (Rapi-Cure CHVE) and heating the solution to 90°C for 15 minutes; (2) spraying this initiator solution over the toned image with a Crown Spra-tool, Crown Industrial Products Company, Hebron, IL; and (3) passing the oversprayed toned image through a Hanovia UV-6 cure station, Hanovia, Newark, NJ, with the UV lamp set to 300 watts and the conveyor traveling at 20 feet per minute.
  • the image was dry to the touch after curing and withstood the abrasion of
  • a UV curable electrophoretic liquid developer was prepared as described in Example I except that the Sterling carbon black was replaced by Copper Phthalocyanine, a cyan pigment available from BASF, Holland, MI.
  • An electrostatic image was created on dielectric paper by the procedure described in Example I, and the electrostatic image was developed with this cyan liquid developer by the procedure described in Example I except the background bias was set to + 50 volts.
  • the developed image was cured to a cyan solid by the procedure described in Example I.
  • the cured image was dry to the touch and withstood the abrasion of rubbing with a finger.
  • the resistivity of the developer (at 5 volts, 5 hertz) was 6.8 x 10 10 ohm-cm.
  • a UV curable electrophoretic liquid developer was prepared as described in Example I except that the Sterling carbon black was replaced by Diarlylide Yellow, a yellow pigment available from Sun Chemical, Cincinnati, OH.
  • An electrostatic image was created on dielectric paper by the procedure described in Example I, and the electrostatic image was developed with this yellow liquid developer by the procedure described in Example I.
  • the developed image cured to a yellow solid by the procedure described in Example I.
  • the image was dry to the touch and withstood the abrasion of rubbing with a finger.
  • the resistivity of the developer (at 5 volts, 5 hertz) was 4.1 x 10 10 ohm-cm.
  • a UV curable electrophoretic liquid developer was prepared by charging a 4 ounce glass bottle with 10 grams of Hostaperm Pink CM29701 pigment, available from BASF, Holland, MI, 90 grams of decyl vinyl ether (Decave), and 100 grams of 1/8 inch stainless steel shots and rolling the dispersion overnight. Five grams of the resulting concentrate was then diluted with 45 grams of decyl vinyl ether (Decave) and 50 grams of 1,4,-bis[(vinyloxy)methyl)]-cyclohexane (Rapi-Cure CHVE). Subsequently, one gram of a 0.1 percent by weight solution of a charge director, Basic Barium Petronate, in dodecane was added to the diluted concentrate to form a developer.
  • a charge director Basic Barium Petronate
  • the resistivity of the developer (at 5 volts, 5 hertz) was 2.0 x 10 11 ohm-cm.
  • An electrostatic image was created by the procedure described in Example I except that the power supply was set to deliver -500 volts to the coated surface of the dielectric paper.
  • the electrostatic image was developed with this developer composition by the procedure described in Example I except the background bias was set to -100 volts.
  • the developed image was cured to a magenta solid by the procedure described in Example I.
  • a second electrostatic image was created under the same conditions and developed with the same developer except the bias voltage was set to -150 volts.
  • This magenta image was cured to a magenta solid by the procedure described in Example I. The image was dry to the touch and withstood the abrasion of rubbing with a finger.
  • a UV curable electrophoretic liquid developer was prepared by the procedure described in Example IV except that 2 grams of the 0.1 percent by weight solution of Basic Barium Petronate in dodecane was used. The resistivity of the developer (at 5 volts, 5 hertz) was 1.1 x 10 11 ohm-cm.
  • An electrostatic image was created and developed with this developer composition as described in Example IV with the background bias voltage set to -100 volts, and the visible image was cured to a magenta solid by the procedure described in Example I. The image was dry to the touch and withstood the abrasion of rubbing with a finger
  • a UV curable liquid developer for polarizable liquid development was prepared by (a) making a 30 percent by weight solution of styrene-butylmethacrylate (equal molar) copolymer with a molecular weight of about 50,000 in butanediol divinylether (Rapi-Cure BDVE, available from GAF, Linden NJ); (b) combining equal parts by weight of this polymer solution and the Hostaperm Pink dispersion described in Example IV; (c) preparing a UV initiator, di(isobutylphenyl)iodinum hexafluoroarsenate as described by Crivello and Lam, Macromolecules .
  • An electrostatic image was created on a sheet of dielectric paper as described in Example I except that the potential applied to the carbon fibers was -400 volts.
  • the electrostatic image was then developed into a visible image by applying the polarizable liquid developer to the electrostatic image with a Pamarco Hand Proofer, Pamarco, Inc., Roselle, NJ using a 150Q gravure and a 0.095 inch by 20 millimeter by 7 millimeter polyurethane doctor blade.
  • the visible magenta image was cured by passing it through a Hanovia UV-6 cure station with the UV lamp set to 300 watts and the conveyor traveling at 20 feet per minute. The image was dry to the touch and withstood the abrasion of rubbing with a finger.
  • a UV curable liquid developer for polarizable liquid development was prepared by (a) making a 40 percent by weight solution of styrene-butylmethacrylate (equal molar) copolymer with a molecular weight of about 50,000 in butanediol divinylether (Rapi-Cure BDVE); (b) milling 37.5 grams of Mogul L carbon black, available from Cabot Corporation, Boston, MA and 170 grams of decyl vinyl ether (Decave) in an 01S Attritor at ambient temperature for 2 hours and then adding an additional 42.5 grams of decyl vinyl ether; and (c) combining 50 parts by weight of the carbon black dispersion with 10 parts by weight of decyl vinyl ether, 40 parts by weight of the polymer solution, and 0.2 parts by weight of di(isobutylphenyl)iodinum hexafluoroarsenate.
  • the viscosity of the polarizable developer thus formed was 145 cent
  • Example VI An electrostatic image was created, the electrostatic image was developed, and the developed image was cured as described in Example VI.
  • the resulting black cured image was dry to the touch and withstood the abrasion of rubbing with a finger.
  • Example VII was repeated except that the butanediol divinyl ether used was from BASF Corporation, Parsippany, NJ.
  • the resistivity of the developer was the same but the viscosity was 160 centipoise.
  • An electrostatic image was written and the image developed and cured as described in Example VI. The resulting black cured image was dry to the touch and withstood the abrasion of rubbing with a finger.
  • a curable photoelectrophoretic developer is prepared by adding about 7 percent by weight of Locarno Red X-1686, 1-(4'-methyl-5'-chloroazobenzene-2'-sulfonic acid)-2-hydroxy-3-napthoic acid, C.I. No. 15865, available from American Cyanamide to a one-to-one mixture of decyl vinyl ether (Decave) and 1,4,-bis[(vinyloxy)methyl)]-cyclohexane (Rapi-Cure CHVE) and grinding the resulting mixture in a ball mill for about 48 hours to reduce the particle size to an average diameter of less than 1 micron.
  • Locarno Red X-1686 1-(4'-methyl-5'-chloroazobenzene-2'-sulfonic acid)-2-hydroxy-3-napthoic acid
  • C.I. No. 15865 available from American Cyanamide
  • Decave decyl vinyl ether
  • Rapi-Cure CHVE 1,4,
  • a photoelectrophoretic imaging appartus of the general type schematically illustrated in Figure 1a of U.S. Patent 3,384,488, is used to test the developer with the developer coated on the NESA glass substrate through which exposure is made.
  • the NESA glass surface is connected in series with a switch, a potential source, and the conductive center of a roller having a coating of baryta paper on its surface.
  • the roller is approximately 2.5 inches in diameter and is moved across the plate surface at about 1.5 centimeters per second.
  • the plate employed is roughly 3 inches square and is exposed with a light intensity of about 1800 foot-candles.
  • a positive potential of about 2500 volts is imposed on the core of the roller.
  • the gap between the baryta paper surface and the NESA glass surface is about 1 mil. Exposure is made with a 3200°K lamp through a 0.30 neutral density step wedge filter to measure the sensitivity of the suspension to white light and then Wratton filters 29, 61 and 47b are individually superimposed over the light source in separate runs to measure the sensitivity of the suspension to red, green, and blue light, respectively.
  • the images on the baryta paper are overcoated with the initiator solution and cured to a solid as described in Example I.
  • Example II Twenty parts by weight of the concentrated electrophoretic liquid developer described in Example I (prior to dilution to a 2 percent solids solution with decyl vinyl ether and 1,4,-bis[(vinyloxy)methyl)]-cyclohexane was mixed with 40 parts by weight of a 30 percent by weight solution of styrene-butylmethacrylate (equal molar) coploymer with a molecular weight of about 50,000 in decyl vinyl ether (Decave) and with 40 parts by weight of 1.4.bis[(vinyloxy)methyl)]-cyclohexane (Rapi-Cure CHVE).
  • the resistivity of this developer was 1.8x10 11 ohm-cm which is within the range of resistivities for developers used in electrophoretic development processes as described herein.
  • the viscosity was 50 centipoise which is outside the range of viscosities for developers used in electrophoretic development processes as described herein.
  • Example I To an electrophoretic developer prepared as described in Example I was added 0.02 percent by weight UV9310C, a di (-p-dodecylphenyl) iodonium hexafluoroantimonate available from GE. This additive decreased the resistivity from 2.8 x 10 10 ohm-cm, which is within the range of resistivities for developers used in electrophoretic development processes as described herein, to 2.5 x 10 9 , which is outside this range.
  • An electrostatic image was created and an attempt was made to develop the electrostatic image into a visible image as described in Example I. No image, however, was formed. The low resistivity of this liquid developer resulted in the electrostatic image being destroyed before the toner particles could develop a visible image.
  • Example VII To 43.5 parts by weight of the carbon black in decyl vinyl ether dispersion prepared in Example VII was added 21.7 parts more of decyl vinyl ether and 34.8 parts of 1,4,-bis[(vinyloxy)methyl)]-cyclohexane.
  • the resistivity of this developer was 2.6 x 10 10 and was within the range of resistivities for liquid developers used in polarizable liquid development processes as described herein, but the viscosity of the developer was 20 centipoise, which was outside the range of viscosities for liquid developers used in polarizable liquid development processes as described herein.
  • An electrostatic image was created on dielectric paper and an attempt was made to develop the image as described in Example VI. The low viscosity of the developer, however, resulted in the developer covering the dielectric paper, and the image was nearly impossible to see and unacceptable in that it was difficult to distinguish the image from the background.
  • developers in accordance with the invention and as described above offers various advantages, including the reduction or substantial elimination of solvent vapor emissions from copiers or printers employing these liquid developers, the reduction or substantial elimination of solvent vapor emissions from documents prepared by liquid development processes employing these liquid developers, and the reduction of solvent disposal from liquid development apparatuses.

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  • General Physics & Mathematics (AREA)
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  • Liquid Developers In Electrophotography (AREA)

Claims (11)

  1. Développateur liquide comprenant un colorant et une quantité importante d'une véhicule liquide durcissable possédant une viscosité qui ne dépasse pas environ 50 mPa (centipoise) et une résistivité qui n'est pas inférieur à environ 108 ohm-cm, dans lequel au moins environ 80 pour cent en poids du composant liquide du développateur comprennent un liquide durcissable.
  2. Développateur liquide selon la revendication 1, dans lequel le véhicule liquide durcissable possède une viscosité ne dépassant pas environ 20 mPa (centipoise) et une résistivité non inférieure à environ 5 X 109 ohm-cm, un agent de contrôle de charge, et dans lequel le dit colorant comprend des particules colorées aptes à devenir chargées et à migrer à travers le véhicule liquide pour développer une image latente électrostatique.
  3. Développateur liquide selon la revendication 1 ou 2, dans lequel le véhicule liquide durcissable est choisi dans le groupe constitué des monoacrylates, des monométhacrylates, des époxydes, des vinyléthers, des styrènes, des indènes, des acétals vinyliques et de leurs mélanges.
  4. Développateur liquide selon la revendication 1, dans lequel le véhicule liquide durcissable possède une viscosité d'environ 25 à environ 500 mPa (centipoise) et une résistivité d'environ 108 à environ 1011 ohm-cm.
  5. Développateur liquide selon la revendication 1 ou 4, dans lequel le véhicule liquide durcissable comprend des molécules possédant des fragments choisis dans le groupe constitué des groupes cinnamique, fumarique, maléique, maléimido, et de leurs mélanges.
  6. Développateur liquide selon la revendication 1, dans lequel le véhicule liquide durcissable possède une viscosité ne dépassant pas environ 20 mPa (centipoise) et une résistivité qui n'est pas inférieure à environ 5 X 109 ohm-cm, et dans lequel ledit colorant comprend des particules colorées photosensibles.
  7. Développateur liquide selon l'une quelconque des revendications précédentes, dans lequel le développateur contient également un initiateur.
  8. Développateur liquide selon l'une quelconque des revendications précédentes, dans lequel le développateur contient un agent de libération en une quantité pouvant atteindre environ 20 pour cent en poids du véhicule liquide.
  9. Procédé de formation d'images, qui comprend les étapes consistant à générer une image latente électrostatique, mettre l'image latente en contact avec un développateur liquide selon l'une quelconque des revendications 1 à 3 ou des revendications 7 ou 8 lorsqu'annexées à l'une quelconque des revendications 1 à 3, et durcir le véhicule liquide demeurant sur l'image développée après le développement.
  10. Procédé de formation d'images selon la revendication 9, dans lequel le développateur liquide est un développateur liquide selon l'une quelconque des revendications 1, 4 ou 5 ou des revendications 7 ou 8 lorsqu'annexées à l'une quelconque des revendications 1, 4 ou 5 ; et dans lequel le procédé comprend en outre les étapes consistant à :
    a. réaliser un applicateur possédant des zones surélevées et des zones enfoncées ;
    b. appliquer aux zones enfoncées de l'applicateur le développateur liquide ;
    c. mettre les parties surélevées de l'applicateur en contact avec un élément de formation d'image, permettant ainsi à l'image latente d'attirer le développateur depuis les parties enfoncées de l'applicateur jusque sur l'image latente, avec pour effet de développer l'image latente ; et
    d. durcir le véhicule liquide demeurant sur l'image développée.
  11. Procédé de formation d'images selon la revendication 9, dans lequel le développateur liquide est un développateur liquide selon l'une quelconque des revendications 1 ou 6 ou des revendications 7 ou 8 lorsqu'annexées à l'une quelconque des revendications 1 ou 6 ; et dans lequel le procédé comprend en outre les étapes consistant à :
    a. placer ledit développateur liquide entre au moins deux électrodes ;
    b. exposer le développateur situé entre les électrodes à une image lumineuse tout en appliquant un potentiel entre les électrodes, avec pour effet d'entraîner la formation d'une image par déposition des particules en suspension, en une configuration conforme à l'image, sur les électrodes ; puis
    c. durcir le véhicule liquide demeurant sur l'image développée.
EP19910302757 1990-03-30 1991-03-28 Révélateur liquide comportant des matériaux porteurs liquides durcissables Expired - Lifetime EP0455343B1 (fr)

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US501585 1990-03-30

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EP0455343B1 true EP0455343B1 (fr) 1997-04-23

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JPH0772669A (ja) * 1993-06-16 1995-03-17 Fuji Xerox Co Ltd 静電写真用液体現像剤
JP4815074B2 (ja) * 2001-08-08 2011-11-16 株式会社リコー 電子写真液体現像剤及び画像形成方法
JP4025090B2 (ja) * 2002-02-18 2007-12-19 サカタインクス株式会社 光硬化型液体現像剤
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EP1416332A1 (fr) * 2002-11-01 2004-05-06 Seiko Epson Corporation Appareil de formation d'images utilisant toner liquide avec commande de densité d'image
JP2005352363A (ja) * 2004-06-14 2005-12-22 Ricoh Co Ltd 液体現像剤、液体現像剤収容器、および画像形成方法、画像形成装置
US7208257B2 (en) * 2004-06-25 2007-04-24 Xerox Corporation Electron beam curable toners and processes thereof
DE102004032922A1 (de) * 2004-07-07 2006-02-02 OCé PRINTING SYSTEMS GMBH Vorrichtung und Verfahren zur Entwicklung von zuvor auf einem Potentialbildträger erzeugten die zu druckenden Bilder enthaltenden Potentialbildern bei einer elektrografischen Druck- oder Kopiereinrichtung
US8158321B2 (en) * 2005-07-27 2012-04-17 Hewlett-Packard Development Company, L.P. Method and apparatus for liquid electrostatic printing
EP1973003A1 (fr) 2007-03-20 2008-09-24 AEG Elektrofotografie GmbH Composition de révélateur liquide et son procédé de préparation
JP5549241B2 (ja) * 2009-06-17 2014-07-16 株式会社リコー 光硬化型液体現像剤、現像装置及び画像形成装置。
EP2348363B1 (fr) 2010-01-25 2012-08-29 Ricoh Company, Ltd. Développeur liquide photodurcissable, procédé de production associé, dispositif de développement et appareil de formation d'images
JP5966500B2 (ja) 2011-05-02 2016-08-10 株式会社リコー シリコーン化合物、該シリコーン化合物を用いた光硬化型液体インク及びその製造方法
US9098004B2 (en) 2012-12-27 2015-08-04 Kao Corporation Liquid developer
US20160062258A1 (en) * 2013-07-05 2016-03-03 Hewlett-Packard Indigo B.V. Electrophotographic printing
WO2015079979A1 (fr) * 2013-11-28 2015-06-04 キヤノン株式会社 Révélateur liquide durcissable par rayons ultraviolets
JP6505037B2 (ja) * 2015-05-27 2019-04-24 キヤノン株式会社 紫外線硬化型液体現像剤
US9891546B2 (en) 2015-05-27 2018-02-13 Canon Kabushiki Kaisha Ultraviolet-curable liquid developer
WO2016190410A1 (fr) * 2015-05-27 2016-12-01 キヤノン株式会社 Matière imprimée et procédé de formation d'image
JP6468947B2 (ja) 2015-05-27 2019-02-13 キヤノン株式会社 紫外線硬化型液体現像剤及びその製造方法
JP6504917B2 (ja) * 2015-05-27 2019-04-24 キヤノン株式会社 硬化型液体現像剤の製造方法
US9891547B2 (en) 2015-05-27 2018-02-13 Canon Kabushiki Kaisha Ultraviolet-curable liquid developer
JP6501615B2 (ja) * 2015-05-27 2019-04-17 キヤノン株式会社 液体現像剤及び該液体現像剤の製造方法
US9857716B2 (en) 2015-05-27 2018-01-02 Canon Kabushiki Kaisha Curable liquid developer and image-forming method using curable liquid developer
JP6516565B2 (ja) * 2015-05-27 2019-05-22 キヤノン株式会社 硬化型液体現像剤
JP6505036B2 (ja) * 2015-05-27 2019-04-24 キヤノン株式会社 紫外線硬化型液体現像剤
EP3151067A1 (fr) 2015-09-30 2017-04-05 Canon Kabushiki Kaisha Révélateur liquide durcissable
JP2017068246A (ja) * 2015-09-30 2017-04-06 キヤノン株式会社 硬化型液体現像剤
NL2016696B1 (en) 2016-04-29 2017-11-20 Xeikon Mfg Nv Digital printing apparatus and process using liquid toner.
WO2018092902A1 (fr) * 2016-11-21 2018-05-24 キヤノン株式会社 Révélateur liquide pouvant durcir
WO2019088246A1 (fr) * 2017-11-06 2019-05-09 キヤノン株式会社 Révélateur liquide durcissable et procédé de formation d'image utilisant ledit révélateur liquide durcissable

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US8931412B2 (en) 2004-03-01 2015-01-13 OCé PRINTING SYSTEMS GMBH Method for printing of a recording

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JP3442406B2 (ja) 2003-09-02
JPH06236078A (ja) 1994-08-23
EP0455343A1 (fr) 1991-11-06
DE69125748D1 (de) 1997-05-28
DE69125748T2 (de) 1997-11-13

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