EP1761394B1 - Milieu reactif fusible - Google Patents

Milieu reactif fusible Download PDF

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Publication number
EP1761394B1
EP1761394B1 EP05762630A EP05762630A EP1761394B1 EP 1761394 B1 EP1761394 B1 EP 1761394B1 EP 05762630 A EP05762630 A EP 05762630A EP 05762630 A EP05762630 A EP 05762630A EP 1761394 B1 EP1761394 B1 EP 1761394B1
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EP
European Patent Office
Prior art keywords
layer
fusible
polymer
ink
functional
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EP05762630A
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German (de)
English (en)
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EP1761394A1 (fr
Inventor
Lawrence Paul Demejo
Xiaoru Wang
Gregory Edward Missell
Allan Wexler
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Eastman Kodak Co
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Eastman Kodak Co
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Priority claimed from US10/881,264 external-priority patent/US7655286B2/en
Priority claimed from US10/881,127 external-priority patent/US7648745B2/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of EP1761394A1 publication Critical patent/EP1761394A1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0027—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials

Definitions

  • the present invention relates to an inkjet recording element and a printing method using the element. More specifically, the invention relates to a porous media in which the top layer comprises fusible particles of a polymer having functional groups that crosslink with a crosslinking agent external to the particles when the layer is fused.
  • ink droplets are ejected from a nozzle at high speed towards a recording element or medium to produce an image on the medium.
  • the ink droplets, or recording liquid generally comprise a recording agent, such as a dye or pigment, and a large amount of solvent
  • the solvent, or carrier liquid typically is made up of water, an organic material such as a monohydric alcohol, a polyhydric alcohol or mixtures thereof.
  • An inkjet recording element typically comprises a support having on at least one surface thereof at least one ink-receiving layer.
  • the ink-receiving layer is typically either a porous layer that imbibes the ink via capillary action, or a polymer layer that swells to absorb the ink.
  • Transparent swellable hydrophilic polymer layers do not scatter light and therefore afford optimal image density and gamut, but may take an undesirably long time to dry.
  • Porous ink-receiving layers are usually composed of inorganic or organic particles bonded together by a binder.
  • porous coatings allow a fast "drying" of the ink and produce a smear-resistant image.
  • porous layers by virtue of the large number of air-particle interfaces, scatter light that may result in lower densities of printed images.
  • inkjet prints prepared by printing onto inkjet recording elements are subject to environmental degradation They are specially vulnerable to damage resulting from contact with water and atmospheric gases such as ozone.
  • the damage resulting from the post-imaging contact with water can take the form of water spots resulting from deglossing of the top coat, dye smearing due to unwanted dye diffusion, and even gross dissolution of the image recording layer.
  • Ozone can bleach inkjet dyes resulting in loss of density.
  • inkjet prints are often laminated. However, lamination is expensive, as it requires a separate roll of material.
  • Inkjet elements having a fusible porous upper layer are known in the art. Fusing the upper layer after printing the image has the advantage of providing a protective overcoat for water and stain resistance and reducing light scatter for improved image quality.
  • U.S. Patents 4,785,313 and 4,832,984 relate to an inkjet recording element comprising a support having thereon a porous fusible, ink-transporting layer and a swellable polymeric ink-retaining layer, wherein the ink-retaining layer is non-porous.
  • EP 858, 905A1 relates to an inkjet recording element having a porous fusible ink-transporting outermost layer formed by heat sintering thermoplastic particles, and an underlying porous layer to absorb and retain the ink applied to the outermost layer to form an image.
  • the underlying porous ink-retaining layer is constituted mainly of refractory pigments. After imaging, the outermost layer is made non-porous.
  • EP 1,188,573 A2 relates to a recording material comprising in order: a sheet-like paper substrate, at least one pigment layer coated thereon, and at least one sealing layer coated thereon. Also disclosed is an optional dye-trapping layer present between the pigment layer and the sealing layer.
  • U.S. Patent 6,497,480 to Wexler discloses inkjet media comprising both a fusible ink-transporting layer and a dye-trapping layer.
  • a base layer and/or a porous under the fusible layer may be employed to absorb ink carrier-liquid fiuid.
  • Protective overcoats and crosslinked overcoats for recording elements are also known in the art.
  • U.S. Patent 6,436,617 relates to protective overcoats for photographic image elements comprising water-dispersible latex particles, which particles comprise an epoxy material and a thermoplastic acid polymer, a water-soluble hydrophilic polymer and a hydrophobically modified associative thickener.
  • the hydrophilic polymer is substantially washed out during photographic processing facilitating the coalescence of the hydrophobic materials. Another driving force for this coalescence is the elevated temperature drying associated with photoprocessing.
  • U.S. Patent 6,548,182 relates to an inkjet recording material wherein the coating comprises a water-soluble polymer having a plurality of carboxyl groups and a water-soluble oxazoline group as a crosslinking agent.
  • an inkjet recording element comprising a support having in order thereon:
  • the optional dye-trapping layer and/or the support may optionally function as a liquid-absorbing sump layer to some extent, either alone or in combination with the optional ink carrier-liquid receptive layer.
  • the fusible particles are substantially spherical and monodisperse.
  • the UPA monodispersity which is defined as the weight average molecular weight divided by the number average molecular weight of the polymers in the bead, is less than 1.3, preferably less than 1.1, as measured by a Microtrac Ultra Fine Particle Analyzer (Leeds and Northrup) at a 50% median value.
  • Dp UPA monodispersity
  • a porous inkjet recording element is obtained that when printed with an inkjet ink, and subsequently fused, has improved water resistance and stain resistance and high print density.
  • Inkjet media made in accordance with the present invention may exhibit advantageous properties.
  • the crosslinking reaction may improve gloss durability.
  • Another advantage is that the invention allows the use of lower Tg polymers in the fusible beads, which in turn allows relatively lower fusing temperatures.
  • thermoplastic polymer as used herein is meant that the polymer flows upon appplication of heat, prior to crosslinking.
  • the polymeric particles can start at a lower Tg than polymeric particles that are not later crosslinked. After fusing, its Tg will increase due to the crosslinking, for example, from 50°C to 100°C.
  • the Tg of the fusible particles can optionally exist in unprinted inkjet media below the blocking temperature before fusing and, after fusing, gain the desired anti-blocking properties. This can facilitate fusing, as will be discussed below.
  • Another embodiment of the invention relates to an inkjet printing method comprising the steps of A) providing an inkjet printer is responsive to digital data signals; B) loading the inkjet printer with the inkjet recording element described above; C) loading the inkjet printer with preferably a dye-based inkjet ink composition; D) printing on the herein-described inkjet recording element using the inkjet ink composition in response to the digital data signals; and (E) fusing at least the fusible, porous top layer such that the layer is non-porous.
  • the uppermost layer can function as either an ink-transporting layer for a dye-based ink or an ink-trapping layer for a pigment-based ink. In the case of the uppermost layer being used as an ink-transporting layer, an underlying dye-trapping layer is also fused.
  • the term "ink-transporting layer” is used herein to mean that, in use, most (more than 50% by weight), preferably at least about 75% by weight, more preferably substantially all, of the dye colorant in the printed inkjet ink passes through and out of the ink-transporting layer.
  • dye-trapping layer is used herein to mean that, in use, most (more than 50% by weight), preferably at least about 75% by weight, more preferably substantially all, of the dye colorant in the printed inkjet ink is retained in the dye-trapping layer.
  • pigment-trapping layer or “ink-trapping layer” is used herein to mean that, in use, most (more than 50% by weight), preferably at least about 75% by weight, more preferably substantially all, of the pigment colorant in the inkjet ink remains in the pigment-trapping layer.
  • the fusible, polymeric particles employed in the uppermost layer of the invention may have a particle size conducive to forming a porous layer.
  • the average particle size of the fusible, polymeric particles suitably ranges from about 5 to about 10,000 nm.
  • the fusible, polymeric particles in said fusible, porous top layer range in size from about 50 to 5,000 nm, more preferably 0.2 to about 2 ⁇ m, most preferably 0.2 to 1 ⁇ m.
  • the fusible, polymeric particles in the ink-transporting layer comprise polyacrylate.
  • the fusible, polymeric particles comprise a polyacrylate polymer or copolymer (for example, acrylic beads) comprising one or more monomeric units derived from an alkyl acrylate or alkyl methacrylate monomer, wherein the alkyl group has 1 to 6 carbon atoms.
  • the fusible particles in the uppermost layer comprises a polymer having reactive functional groups.
  • the weight average molecular weight of the polymer can range from 5,000 to 1,000,000, and the glass transition temperature thereof preferably ranges from -50°C to 120°C.
  • the Tg of the polymer particles is above about 20°C and less than 120°C, more preferably above 50°C and below 90°C and most preferably below 80°C.
  • the polymer particles and the multifunctional chemical may be the reaction products of monomers comprising one or more non-reactive monomers and one or more reactive functional monomers.
  • complementary reactive functional monomeric unit on the multifunctional compound will complementarily react with reactive functionalities on the bead polymer.
  • Such reactive functional monomers may include monomers containing one or more of the following groups: cyanate, oxazoline, epoxy, acid, acid anhydride, hydroxyl, phenol, acetoacetoxy, thiol, and/or amine functionalities, and the like. Mixtures of multifunctional polymers and/or mixtures of polymer particles may be employed.
  • the polymer particles may comprise 0.1 to 50 mole percent of reactive monomeric units, more preferably 1 to 50 mole percent, most preferably less than 30 mole percent Too much crosslinking can result in undesirable brittleness.
  • the polymer particles may comprise 50 to 99.9 mole percent of non-reactive monomeric units.
  • the multifunctional compounds comprise.0.1 to 100 mole percent of complementary reactive monomeric units, more preferably 1 to 50 mole percent.
  • the multifunctional compounds may comprise 0 to 99.9 mole percent of non-reactive monomeric units.
  • the "functional group equivalent weight” (also referred to as the weight per functional group equivalent) is defined as the grams of solid containing one gram-equivalent of functional group ("g/equivalent").
  • the g/equivalent ratio of the functional groups on the polymer particles to the complementary reactive functional groups on the multifunctional compound in the inkjet recording element of the invention ranges from 1.0/0.1 to 1.0/5.0 and more preferably from 1.0/0.2 to 1.0/2.0.
  • the fusing and concurrent crosslinking should be sufficient. Under fusing can result in a tacky surface and, if the fusible, porous layer remains porous, the inkjet element will not be water and stain resistant, as well as not have the desired anti-blocking properties.
  • the functional group equivalent weight of the multifunctional compound is about 50 to 10,000, preferably from about 100 to 5,000, most preferably from about 100 to 2,000.
  • an epoxy-multifunctional compound can be a copolymer based on réelleichlorohydrin containing epoxy monomeric units which will react with amine, carboxylic acidic, hydroxyl, anhydride or the like reactive functionalities in the polymeric particles (or vice versa).
  • oxazoline-multifunctional compounds comprise monomeric units derived from monomers such as 2-vinyl-2-oxazoline and 2-isopropenyl-2-oxazolino.
  • multifunctional compounds with protic-type reactive functionalities include oligomers derived from acid-functional monomers such as methacrylic acid or hydroxy-functional monomers such as hydroxyalkyl (meth)acrylates, for example, hydroxyethyl (meth)acrylate.
  • epoxy-functional reactive groups in the multifunctional compound can react with carboxylic (--COOH), alcohol (--OH), primary amine (-NH 2 ) groups or thiol groups (--SH) in the polymer particles (or vice versa), for examples, polymer particles made from polymers comprising monomeric units derived from methacrylic acid (MAA), hydroxyalkylmethacrylates such as hydroxyethylmethacrylate (HEMA),or aminoalkyl methacrylates such as aminopropylmethacrylate, all common and commercially available monomers.
  • a catalyst such as 4-dimethylaminopyridine may be used to speed the reaction at room temperature, as will be understood by the skilled chemist.
  • oxazoline functional groups in a multifunctional compound can similarly react with carboxylic acids, acid anhydrides, amines, phenols and thiols in the polymer particles (or vice versa).
  • a multifunctional compound containing repeat units having at least one ring-opening group, an epoxide or an oxazoline reacts with polymer particles containing repeat units having a protic group, such as a carboxylic acid containing monomer.
  • protic reactive monomers include acrylic, methacrylic, itaconic, crotonic, fumaric and maleic acids, and anhydrides thereof
  • Suitable copolymerizable monomers for making the polymeric particles and/or the multifunctional compound include conventional vinyl monomers such as acrylates and methacrylates of the general formula: where R 2 is as defined above and R 5 is a straight chain or branched aliphatic, cycloaliphatic or aromatic group having up to 20 carbon atoms which is unsubstituted or substituted.
  • Useful or suitable copolymerizable monomers include, for example: methyl, ethyl, propel, isopropyl, butyl, ethoxyethyl, methoxyethyl, ethoxypropyl, phenyl, benzyl, cyclohexyl, hexafluoroisopropyl, or n-octyl-acrylates and -methacrylates, as well as, for example, styrene, alpha-methylstyrene, 1-hexene, vinyl chloride, etc.
  • the polymer particles are synthesized in a manner known per se from the corresponding monomers by an emulsion polymerization reaction customary to the person skilled in the art.
  • Emulsion polymerization initiators for the polymer particles include water-soluble initiators capable of generating ion radicals (such as potassium or ammonium persulfate) or free-radical-generating polymerization initiators of the type illustrated by acetyl peroxide, lauroyl peroxide, decanoyl peroxide, caprylyl peroxide, benzoyl peroxide, tertiary butyl peroxypivalate, sodium percarbonate, tertiary butyl peroctoate, and azobis-isobutyronitrile (AIBN).
  • water-soluble initiators capable of generating ion radicals (such as potassium or ammonium persulfate) or free-radical-generating polymerization initiators of the type illustrated by acetyl peroxide, lauroyl peroxid
  • Ultraviolet free-radical initiators illustrated by diethoxyacetophenone can also be used.
  • a polymer can be formed by: (1) mixing the monomers together; (2) adding a polymerization initiator; (3) subjecting the monomer/initiator mixture to a source of ultraviolet or actinic radiation and/or elevated temperature and polymerising the mixture. This polymer can then be dissolved in an appropriate solvent and the resulting solution dispersed in water with appropriate dispersing agents and sheared in a homogenizer to generate a crude emulsion. Rotary evaporation, at a temperature and vacuum condition appropriate for efficient removal of the solvent, yields a dispersion of polymer particles in water. Other method for generating aqueous dispersions of polymer particles for use in the invention can also be invoked.
  • the multifunctional compound has an oxazoline group represented by the following formula: wherein R 1 through R 5 are selected so to provide a branched or unbranched vinyl oxazoline compound, for example, by selecting R 1 in (I) to be a branched or unbranched vinyl group according to formula (II): wherein R 8 is selected from the group consisting of hydrogen, a branched or linear C 1 -C 20 alkyl moiety, a C 3 -C 20 cycloalkyl moiety, a C 6 -C 20 aryl moiety, and a C 7 -C 20 alkylaryl moiety.
  • R 1 is such a vinyl group
  • R 2 to R 5 are the same or different and are selected from hydrogen, a branched or linear C 1 -C 20 alkyl moiety, a C 3 -C 20 cycloalkyl moiety, a C 6 -C 20 aryl moiety and a C 7 -C 20 alkyaryl moiety.
  • oxazoline-functional unit derived from the monomer, will provide a polymer with a moiety that is reactive to complementary reactive functionalities such as -COOH, -NH, -SH and -OH (or vice versa).
  • complementary reactive functionalities such as -COOH, -NH, -SH and -OH (or vice versa).
  • Examples of a multifunctional compound having an oxazoline group include polymers containing an oxazoline group as obtained by homopolymerizing an addition-polymerizable oxazoline monomer or copolymerizing said monomer with a monomer copolymerizable therewith.
  • Examples of the addition-polymerizable oxazoline include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-4-ethyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-bopropenyl-5-ethyl-2-oxazoline, and 2-isopropenyl-4,5-dimethyl-2-oxazoline. These may be used either alone respectively or in combinations with each other.
  • the monomer 2-isopropenyl-2oxazoline for example, a non-limiting example of a vinyl oxazoline, is represented by the following structure:
  • a ring-opening reactive group in a multifunctional compound is provided by an epoxy-functionality polymer.
  • the preferred epoxy-multifunctional compound is based on an oxirane-containing monomer such as epichlorohydrin, glycidyl methacrylate, allyl glycidyl ether, 4-vinyl-1-cyclohexene-1,2-epoxide, and the like, although other epoxy-containing monomers may be used.
  • epoxy-multifunctional compound examples include the phenol, 4,4'-(1-methylethylidene)bis-, polymer with (chloromethyl)oxirane available from Crompton Corporation, Middlebury, Connecticut, under the trademark WTTCOBOND XW and the 2,2-bis(p-glycidyloxyphenyl)propane condensation product with 2,2 bis(p-hydroxyphenyl)propane and similar isomers available from Shell Corporation, Houston, Texas, under the trademark EPON 1001F.
  • Blended mixtures of epoxy oligomers or polymers with other oligomers or polymers can also be utilized such as the commercially available polyhydroxyalcan polyglycidylether mixture available from Esprix Technologies, Sarasota, Florida, under the trademark CR-5L.
  • the polymeric particles are intended to flow and crosslink when fused, for example, in a heated fuser nip, thereby achieving inkjet surface coatings and media with the excellent image-quality and print-durability performance.
  • the uppermost fusible, porous ink-transporting or ink-trapping layer of fusible polymeric particles optionally may, in addition, contain a film-forming hydrophobic binder.
  • a film-forming hydrophobic binder useful in the invention can be any film forming hydrophobic polymer capable of being dispersed in water. In a preferred embodiment of the invention, however, there is no binder. If a binder is used, it preferably should be used in a minor amount.
  • the particle-to-binder ratio of the particles and optional binder employed in the fusible, porous ink-transporting layer can range between about 100:0 and 60:40, preferably between about 100:0 and about 90:10. In general, a layer having particle-to-binder ratios outside the range stated will usually not be sufficiently porous to provide good image quality.
  • the fusible, porous ink-transporting layer or ink-trapping uppermost layer is usually present in an amount from about 1g/m 2 to about 50 g/m 2 . In a preferred embodiment, the fusible, porous ink-transporting layer is present in an amount from about 1 g/m 2 to about 10 g/m 2 .
  • a fusible dye-trapping layer under an ink-transporting layer receives the ink from the uppermost ink-transporting layer, preferably retains substantially all the dye, and allows for the passage of the ink carrier liquid to the optional underlying porous carrier-liquid-receptive layer and/or the optionally porous support.
  • the air-particle interfaces present in the original porous structure of the image layer are eliminated, and a non-scattering, substantially continuous layer forms which contains the printed image. It is an important feature of the invention that the fusible, porous ink-transporting layer and, if present, the underlying dye-trapping layer be transformable into a non-scattering layer as this significantly raises image density.
  • the fusible, polymeric particles employed in the dye-trapping layer typically range from about 0.1 ⁇ m to 10 ⁇ m, although smaller particles are possible.
  • the particles employed in the dye-trapping layer may be formed from any polymer that is fusible, i.e., capable of being converted from discrete particles into a substantially continuous layer through the application of heat and/or pressure.
  • the fusible, polymeric particles in the dye-trapping layer comprise the ester derivative of a natural polymer, such as cellulose acetate butyrate, a condensation polymer, such as a polyester or a polyurethane or an addition polymer, for example, a styrenic polymer, a vinyl polymer, an ethylene-vinyl chloride copolymer, a polyacrylate, poly(vinyl acetate), poly(vinylidene chloride), or a vinyl acetate-vinyl chloride copolymer, and the like.
  • a natural polymer such as cellulose acetate butyrate
  • a condensation polymer such as a polyester or a polyurethane or an addition polymer
  • a styrenic polymer such as a vinyl polymer, an ethylene-vinyl chloride copolymer, a polyacrylate, poly(vinyl acetate), poly(vinylidene chloride), or a vinyl acetate-vinyl
  • the binder employed in the dye-trapping layer can be any film-forming polymer that serves to bind together the fusible polymeric particles.
  • the binder is a hydrophobic film-forming binder derived from an aqueous dispersion of an acrylic polymer or polyurethane.
  • a dye mordant is preferably employed in the dye-trapping layer.
  • a dye mordant can be any material that is effectively substantive to the inkjet dyes.
  • the dye mordant removes dyes from the ink received from the porous ink-transporting layer and fixes the dye within the dye-trapping layer.
  • mordants include cationic lattices such as disclosed in U.S. 6,297,296 and references cited therein, cationic polymers such as disclosed in U.S. 5,342,688 , and multivalent ions as disclosed in U.S. 5,916,673 .
  • mordants include polymeric quaternary ammonium compounds, or basic polymers, such as poly(dimethylaminoethyl)-methacrylate, polyalkylenepolyamines, and products of the condensation thereof with dicyanodiamide, amine-epichlorohydrin polycondensates. Further, lecithins and phospholipid compounds can also be used.
  • mordant examples include the following: vinylbenzyl trimethyl ammonium chloride/ethylene glycol dimethacrylate; poly(diallyl dimethyl ammonium chloride); poly(2-N,N,N-trimethylammonium)ethyl methacrylate methosulfate; poly(3-N,N,N-trimethyl-ammonium)propyl: methacrylate chloride; a copolymer of vinylpyrrolidinone and vinyl(N-methylimidazolium chloride; and hydroxyethylcellulose derivatized with 3-N,N,N-trimethylammonium)propyl chloride.
  • the cationic mordant is a quaternary ammonium compound.
  • both the binder and the polymer comprising the fusible particles should be either uncharged or the same charge as the mordant. Colloidal instability and unwanted aggregation could result if the polymer particles or the binder had a charge opposite from that of the mordant.
  • the fusible particles in the dye-trapping layer may range from about 95 to about 60 parts by weight
  • the binder may range from about 40 to about 5 parts by weight
  • the dye mordant may range from about 2 parts to about 40 parts by weight.
  • the dye-trapping layer comprises about 80 parts by weight fusible particles, about 10 parts by weight binder, and about 10 parts by weight dye mordant.
  • the dye-trapping layer is present in an amount from about 1g/m 2 to about 50 g/m 2 , more preferably in an amount from about 1g/m 2 to about 10 g/m 2 .
  • the optional porous ink-carrier-liquid receptive layer receives the ink carrier liquid after the ink has passed through the porous uppermost layer (the ink-transporting or pigment-trapping layer) and through the optional porous dye-trapping layer for removing dye from a dye-based ink.
  • the ink-carrier-liquid receptive layer can be any conventional porous structure.
  • the ink carrier-liquid receptive layer is present in an amount from about 1g/m 2 to about 50 g/m 2 , preferably from about 10 g/m 2 to about 45 g/m 2 .
  • the thickness of this layer may depend on whether a porous or non-porous support is used.
  • the base ink porous ink-carrier-liquid receptive layer will have a thickness of about 1 ⁇ m to about 50 ⁇ m, and the porous ink-transporting layer residing thereon will usually have a thickness of about 2 ⁇ m to about 50 ⁇ m.
  • the ink-carrier-liquid receptive layer is a continuous, co-extensive porous layer that contains organic or inorganic particles.
  • organic particles which may be used include core/shell particles such as those disclosed in U.S. Patent No 6,492,006 and homogeneous particles such as those disclosed in U.S. Patent No. 6,475,602 .
  • organic particles that may be used in this layer include acrylic resins, styrenic resins, cellulose derivatives, polyvinyl resins, ethylene-allyl copolymers and polycondensation polymers such as polyesters.
  • inorganic particles examples include silica, alumina, titanium dioxide, clay, calcium carbonate, calcium metasilicate, barium sulfate, or zinc oxide.
  • the porous ink-carrier liquid receptive layer comprises from about 20 % by weight to about 100 % by weight of particles and from about 0 % to about 80% by weight of a polymeric binder, preferably from about 80 % by weight to about 95 % by weight of particles and from about 20% by weight to about 5% by weight of a polymeric binder.
  • the polymeric binder may be a hydrophilic polymer such as poly(vinyl alcohol), poly(vinyl pyrrolidone), gelatin, cellulose ethers, poly(oxazolines), poly(vinylacetamides), partially hydrolyzed poly(vinyl acetate/vinyl alcohol), poly(acrylic acid), poly(acrylamide), poly(alkylene oxide), sulfonated or phosphated polyesters and polystyrenes, casein, zein, albumin, chitin, chitosan, dextran, pectin, collagen derivatives, collodian, agar-agar, arrowroot, guar, carrageenan, tragacanth, xanthan or rhamsan.
  • hydrophilic polymer such as poly(vinyl alcohol), poly(vinyl pyrrolidone), gelatin, cellulose ethers, poly(oxazolines), poly(vinylacetamides), partially hydrolyzed poly(vin
  • the hydrophilic polymer is poly(vinyl alcohol), hydroxypropyl cellulose, hydroxypropyl methyl cellulose, a poly(alkylene oxide), poly(vinyl pyrrolidinone), poly(vinyl acetate) or copolymers thereof or gelatin.
  • Suitable porous materials for an ink carrier-liquid receptive layer include, for example, silica or alumina in a polymeric binder.
  • the ink carrier-liquid receptive layer is porous fumed alumina in a crosslinked poly(vinyl alcohol) binder.
  • crosslinkers which act upon the binder discussed above may be added in small quantities. Such an additive improves the cohesive strength of the layer.
  • Crosslinkers such as carbodiimides, polyfunctional aziridines, aldehydes, isocyanates, epoxides, polyvalent metal cations, vinyl sulfones, pyridinium, pyridylium dication ether, methoxyalkyl melamines, triazines, dioxane derivatives, chrom alum, zirconium sulfate and the like may be used.
  • the crosslinker is an aldehyde, an acetal or a ketal, such as 2,3-dihydroxy-1,4-dioxane.
  • the porous ink-carrier-liquid receptive layer can also comprise an open-pore polyolefin, open-pore polyester or open-pore membrane.
  • An open-pore membrane can be formed in accordance with the known technique of phase inversion. Examples of a porous ink-receiving layers comprising an open-pore membrane are disclosed in U.S. Patent No. 6,497,941 and U.S. Patent No. 6,503,607 .
  • the ink carrier-liquid receptive layer is a continuous, co-extensive porous calcium-metasilicate-containing base layer comprising calcium-metasilicate needles, and optionally organic and/or inorganic particles in a polymeric binder, the length of the calcium metasilicate being from 1 ⁇ m to 50 ⁇ m.
  • the calcium metasilicate may comprise essentially all of the particles in the layer, in a preferred embodiment, the ratio of the calcium metasilicate to the organic or inorganic particles is from 90:10 to 25:75.
  • the calcium metasilicate is preferably present in an amount of at least 25 weight percent, based on the total dry weight of the pore-forming particles, including inorganic and/or organic particles present.
  • the presence of the calcium metasilicate has been found to significantly help in preventing or minimizing cracking of particulate coatings upon drying and in enhancing the porous structure.
  • Examples of calcium metasilicate that can be used in the invention include VANSIL TM acicular Wollastonite. Such a material can also be represented by the commonly used formula for calcium metasilicate or CaSiO 3 .
  • VANSIL TM WG for example, is a high aspect ratio, long needle grade of Wollastonite.
  • Other useful grades depending on the particular inkjet recording system, include VANSIL TM HR- 1500 and HR-325, which are all commercially available from R.T. Vanderbilt Co., Inc., Norwalk, Conn. (website:www.rtvanderbilt.com).
  • the needles can vary in length from 1 ⁇ m to 50 ⁇ m, with the preferred length of less than 30 ⁇ m, more preferably less than 10 ⁇ m, most preferably about 2 to 9.0 ⁇ m.
  • the average aspect ratio is suitably at least 5:1, preferably 8:1 to 20:1, more preferably about 10:1 to 16:1, most preferably at least about 12:1.
  • the average length of the calcium metasilicate needles is suitably from 10 ⁇ m to 50 ⁇ m.
  • the density of calcium metasilicate is typically about 2.9 g/cm 3 .
  • the surface area (N 2 B.E.T.) is, for example, 1 to 4 m 2 /g.
  • the calcium metasilicate needles may be treated or surface modified, for example, subjected to silane treatment.
  • the calcium-metasilicate-containing base layer is a porous layer that contains organic or inorganic particles.
  • organic particles that may be used in this layer include polymer beads, including but not limited to acrylic resins such as methyl methacrylate, styrenic resins, cellulose derivatives, polyvinyl resins, ethylene-allyl copolymers and polycondensation polymers such as polyesters. Hollow styrene or acrylic beads are preferred organic particles for certain applications.
  • organic particles which may be used include core/shell particles such as those disclosed in U.S. Patent No. 6,492,006 and homogeneous particles such as those disclosed in U.S. Patent No. 6,475,602 .
  • inorganic particles examples include silica, alumina, titanium dioxide, clay, calcium carbonate, barium sulfate, or zinc oxide.
  • the average primary particle size of the organic or inorganic particles is about 0.3 ⁇ m (300 nm) to about 5 ⁇ m, preferably 0.5 ⁇ m (500 nm) to less than 1.0 ⁇ m.
  • a plurality of inorganic particles such as alumina may agglomerate into larger secondary particles.
  • any polymeric binder may be used in the metasilicate-containing base layer.
  • good results have been obtained with gelatin, polyurethanes, vinyl acetate-ethylene copolymers, ethylene-vinyl chloride copolymers, vinyl acetate-vinyl chloride-ethylene terpolymers, acrylic polymer, and polyvinyl alcohol or derivatives thereof.
  • the binder is a water-soluble hydrophilic polymer, most preferably polyvinyl alcohol or the like.
  • the porous calcium-metasilicate-containing base layer comprises between 75% by weight and 95% by weight of particles and between about 5% and 25% by weight of a polymeric binder, preferably from about 82% by weight to about 92% by weight of particles and from about 18% by weight to about 8% by weight of a polymeric binder, most preferably about 10% by weight of binder.
  • the calcium-metasilicate-containing layer comprises at least 25 percent by weight of calcium-metasilicate particles (in the form of needles).
  • the ratio of the needles to other organic or inorganic is about 30:70 to 70:30, preferably about 40:60 to 50:40, more preferably about 45:55 to 55:45.
  • the calcium-metasilicate-containing layer is typically at least 10 ⁇ m in thickness (dried), more preferably at least 15 ⁇ m or 20 depending on the presence of other ink-liquid-carrier absorbing layers, preferably about 30 to 60 ⁇ m
  • the calcium-metasilicate-containing layer is 30 to 70 ⁇ m thick, preferably at least 35 ⁇ m.
  • the calcium-metasilicate-containing layer may be 20 ⁇ m to 60 ⁇ m thick, preferably at least 25 ⁇ m.
  • the support used in the inkjet recording element of the invention may be opaque, translucent, or transparent.
  • the support is an open-structure paper support as used in the Examples below.
  • the thickness of the support employed in the invention can be from about 12 to about 500 ⁇ m, preferably from about 75 to about 300 ⁇ m.
  • the surface of the support may be corona-discharge-treated prior to applying the base layer or solvent-absorbing layer to the support.
  • the inkjet recording element may come in contact with other image recording articles or the drive or transport mechanisms of image recording devices, additives such as surfactants, lubricants, matte particles and the like may be added to the element to the extent that they do not degrade the properties of interest.
  • the layers described above, including the ink-carrier-liquid receptive layer, the pigment-trapping layer, the dye-trapping, layer; and the ink-transporting layer may be coated by conventional coating means onto a support material commonly used in this art.
  • Coating methods may include, but are not limited to, wound wire rod coating, air-knife coating, slot coating, slide hopper coating, gravure, curtain coating and the like. Some of these methods allow for simultaneous coatings of all three layers, which is preferred from a manufacturing economic perspective.
  • the fusible, porous uppermost layer (the ink-transporting or ink-trapping layer) is heat and/or pressure fused to form a substantially continuous overcoat layer on the surface.
  • the optional dye-trapping layer if present, is also fused at the same time.
  • these layers are rendered non-light scattering. Fusing may be accomplished in any manner that is effective for the intended purpose.
  • a description of a fusing method employing a fusing belt can be found in U.S. 5,258,256
  • a description of a fusing method employing a fusing roller can be found in U.S. 4,913,991 . If a fusing roller is used, it is advantageously facilitated by the low Tg reactive polymer particles of the present invention.
  • fusing is accomplished by contacting the surface of the element with a heat-fusing member, such as a fusing roller or fusing belt.
  • a heat-fusing member such as a fusing roller or fusing belt.
  • fusing can be accomplished by passing the element through a pair of heated rollers, heated to a temperature of about 60 °C to about 160 °C, using a pressure of 5 to about 15 MPa at a transport rate of about 0.005 ms -1 to about 0.5 ms -1 .
  • lower initial Tg for the fusible polymeric particles can be an advantage for fusing at relatively lower temperatures and/or lower pressures, for example less than about 149°C (300°F), instead of 177°C (350°F) as required for some prior art fusible polymeric particles of a cellulose ester.
  • a higher Tg for the top layer of the inkjet element is obtained so that blocking problems are avoided.
  • a further advantage of inkjet media that can be made in accordance with the present invention is that, since less heat may be required to fuse the element, the inkjet element can be released from the fusing element when relatively hot without deformation and without lowering gloss or adversely affecting a smooth surface. This facilitates the use of a fuser roller as compared to a belt fuser that may otherwise be needed to provide longer contact so that the inkjet element has sufficient time to cool before release.
  • Dye-based inkjet inks or pigmented inkjet inks preferably used to image the recording elements of the present invention are well known in the art.
  • the ink compositions used in inkjet printing typically are liquid compositions comprising a solvent or carrier liquid, dyes or pigments, humectants, organic solvents, detergents, thickeners, preservatives, and the like.
  • the solvent or carrier liquid can be solely water or can be water mixed with other water-miscible solvents such as polyhydric alcohols.
  • Inks in which organic materials such as polyhydric alcohols are the predominant carrier or solvent liquid may also be used. Particularly useful are mixed solvents of water and polyhydric alcohols.
  • the dyes used in such compositions are typically water-soluble direct or acid type dyes.
  • Such liquid compositions have been described extensively in the prior art including, for example, U.S. Patents 4,381,946 ; 4,239,543 and 4,781,758 .
  • Polymer particle dispersions P-1 to P-7 were prepared as follows. Unless otherwise indicated, the particle size and the monodispersity were measured by a Microtrac® Ultra Fine Particle Analyzer (Leeds and Northrup) at a 50%medianvalue.
  • the polymer particle dispersions were prepared by an emulsion polymerization technique.
  • Part (A) was first charged to a 1L3-neck flask equipped with a nitrogen inlet, mechanical stirrer and condenser. The flask was immersed in a constant temperature bath at 80°C and purged with nitrogen for 20 min.
  • Part (B) was added to the mixture. Agitation was maintained all the time during the feeding of the monomer emulsion. The addition time of the monomer emulsion (B) was two hours.
  • the polymerization was continued for 30 min after the addition of the monomer emulsion.
  • the mixture was cooled to room temperature and filtered.
  • the final solids were about 22% and the final particle size was about 820 nm.
  • the monodispersity was 1.02 as determined by UPA.
  • the polymer particle dispersions were prepared by an emulsion polymerization technique.
  • the polymer particle dispersions were prepared the same way as the above samples except that butyl acrylate was replaced with butyl methacrylate and there was no mercaptan acid in the recipe. Since mercaptan acid is a chain transfer agent that controls molecular weight, its absence results in a higher molecular weight than previous examples.
  • the final solids were about 22% by weight, and the final particle size was about 820 nm.
  • the monodispersity was 1.03 as determined by UPA.
  • Such particle dispersions can be reacted, in a fusible top layer, with multifunctional compounds having epoxy or oxazoline complementary reactive functionalities.
  • the polymer particle dispersions were prepared the same way as for the P-1 and P-2 samples except that the monomer composition was: ethyl methacrylate 55.25 g, hydroxyethyl methacrylate 3.25 g, and butyl methacrylate 6.5 g.
  • the final solids were about 22% by weight, and the final particle size was about 820 nm.
  • the monodispersity was 1.02 as determined by UPA.
  • the polymer particle dispersions were prepared the same way as the above P-1 and P-2 samples except that the monomer composition was: ethyl methacrylate 54.2 g, and dimethyl aminoethyl methacrylate 10.8 g.
  • the final solids were about 22% by weight, and the final particle size was about 820 nm.
  • the monodispersity was 1.03 as determined by UPA.
  • Such particle dispersions can be reacted, in a fusible top layer, with multifunctional compounds having acetoacetoxy complementary reactive functionalities.
  • the polymer particle dispersions were prepared the same way as the above P-1 and P-2 samples except that the monomer composition was: ethyl methacrylate 54.2 g and acetoacetoxylethyl methacrylate 10.8 g.
  • the final solids were about 22% by weight, and the final particle size was about 520 nm.
  • the monodispersity was 1.04 as determined by UPA.
  • Such particle dispersions can be reacted, in a fusible top layer, with multifunctional compounds having amino complementary reactive functionalities.
  • the polymer particles were prepared the same way as above P-1 and P-2 samples except the monomer composition was: ethyl methacrylate 45.5 g, methyl methacrylate 13.0 g and methacrylic acid 6.5 g; and also with chain transfer agent butyl mercaptan 0.65 g.
  • the final solids were about 22% by weight, and the final particle size was about 820 nm.
  • the monodispersity was 1.03 as determined by UPA.
  • the polymer particle dispersions were prepared the same way as above P-1 and P-2 samples except the monomer composition was: ethyl methacrylate 59.6 g and glycidyl methacrylate 5.4 g.
  • the final solids were about 22% by weight, and the final particle size was about 380 nm.
  • the monodispersity was 1.10 as determined by UPA.
  • Such particle dispersions can be reacted, in a fusible top layer, with multifunctional compounds having carboxylic acid complementary reactive functionalities.
  • a 25% solids aqueous solution was made containing calcium metasilicate (HR325 Wollastonite® from R.T. Vanderbilt Company Inc., Norwalk, Connecticut), plastic pigment latex (HS3000 NA TM high-Tg acrylic hollow beads (1 ⁇ ), from Dow Chemical, Marietta, Georgia), and polyvinyl alcohol (GH17 Gohsenol® from Nippon Gohsei, Osaka, Japan) at a dry weight ratio of 45/45/10. This was then coated and dried at a dry laydown of 26.9 g/m 2 (2.5 g/ft 2 ) on Domtar Quantum® 80 paper using a hopper coater.
  • calcium metasilicate HR325 Wollastonite® from R.T. Vanderbilt Company Inc., Norwalk, Connecticut
  • plastic pigment latex HS3000 NA TM high-Tg acrylic hollow beads (1 ⁇ )
  • Dow Chemical Marietta, Georgia
  • polyvinyl alcohol GH17 Gohsenol® from Nippon Go
  • a polymeric particle dispersion comprised of ethyl methacrylate and methacrylic acid, at the ratio of 95 to 5 (Polymer Particle Dispersion P-1) was diluted to make an 18% aqueous dispersion. This was then coated over the coating of Example 1 at a dry laydown of 8.6 g/m 2 (0.8 g/ft 2 ) and dried.
  • a polymeric particle dispersion comprised of ethyl methacrylate and methacrylic acid, at the ratio of 95 to 5 (Polymer Particle Dispersion P-1) was combined with an oxazoline multifunctional oligomeric copolymer (WS-500 TM from Esprix Technologies, Sarasota, Florida) so that the gram/equivalent acid functionality was equal to the gram/equivalent oxazoline functionality and diluted to an 18% aqueous dispersion. This was then coated over Example I at a dry laydown of 8.6 g/m 2 (0.8 g/sq ft) and dried.
  • a polymeric particle dispersion comprised of ethyl methacrylate and methacrylic acid, at the ratio of 95 to 5 (Polymer Particle Dispersion P-1) was combined with a polyhydroxyalcan polyglycidylether multifunctional polymer (CR-5L TM from Esprix Technologies) so that the gram/equivalent acid functionality was equal to the gram/equivalent polyhydroxyalcan polyglycidylether functionality and diluted to an 18% aqueous dispersion. This was then coated over Example 1 at a dry laydown of 8.6 g/m 2 (0.8 g/sqft) and dried.
  • a polymeric particle dispersion comprised of ethyl methacrylate and methacrylic acid, at the ratio of 95 to 5 (Polymer Particle Dispersion P-1) was combined with an epoxy-functional polymer (Witcobond® XW Epoxide from Crompton Corporation, Middlebury, Connecticut) so that the gram/equivalent acid functionality was equal to the gram/equivalent epoxy functionality and diluted to an 18% aqueous dispersion This was then coated over Example 1 at a dry laydown of 8.6 g/m 2 (0.8 g/ft 2 ) and dried.
  • a polymeric particle dispersion comprised of ethyl methacrylate, butyl acrylate, and methacrylic acid, at the ratio of 70 to 15 to 15 (Polymer Particle Dispersion P-2) was combined with an oxazoline functional copolymer (WS-500 TM from Esprix Technologies) so that the gram/equivalent acid functionality was equal to the gram/equivalent oxazoline functionality and diluted to an 18% aqueous dispersion. This was then coated over Example 1 at a dry laydown of 8.6 g/m 2 (0.8 g/ft 2 ) and dried.
  • a polymeric particle dispersion comprised of ethyl methacrylate, butyl acrylate, and methacrylic acid, at the ratio of 70 to 15 to 15 (Polymer Particle Dispersion P-1) was combined and a polyhydroxyalcan polyglycidylether multifunctional polymer (CR-5L TM from Esprix Technologies) so that the gram/equivalent acid functionality was equal to the gram/equivalent polyhydroxyalcan polyglycidylether functionality and diluted to an 18% aqueous dispersion. This was then coated over Example 1 at a dry laydown of 8.6 g/m 2 (0.8 g/ft 2 ) and dried.
  • a polymeric particle dispersion comprised of ethyl methacrylate, butyl acrylate, and methacrylic acid, at the ratio of 70 to 15 to 15 (Polymer Particle Dispersion P-2) was diluted to a 18% aqueous dispersion. This was then coated over Example 1 at a dry laydown of 8.6 g/m 2 (0.8g/ft 2 ) and died.
  • a polymeric particle dispersion comprised of ethyl methacrylate, methyl methacrylate, and methacrylic acid, at the ratio of 85 to 5 to 10 (Polymer Particle Dispersion P-7) was diluted to a 18% aqueous dispersion. This was then coated over Example 1 at a dry laydown of 8.6 g/m 2 (0.8g/ft 2 ) and dried.
  • a polymeric particle dispersion comprised of ethyl methacrylate, methyl methacrylate, and methacrylic acid, at the ratio of 85 to 5 to 10 (Polymer Particle Dispersion P-7) was combined with an epoxy-multifunctional polymer (Witcobond® XW Epoxide from Crompton Corp.) so that the gram/equivalent acid functionality was equal to the gram/equivalent epoxy functionality and diluted to an 18% aqueous dispersion. This was then coated over Example 1 at a dry laydown of 8.6 g/m 2 (0.8 g/ft 2 ) and dried.
  • a polymeric particle dispersion comprised of ethyl methacrylate, butyl methacrylate, and methacrylic acid, at the ratio of 85 to 10 to 5 (Polymer Particle Dispersion P-3) was combined with a polyhydroxyalcan polyglycidylether multifunctional polymer (CR-5L TM from Esprix Technologies) so that the gram/equivalent functionality was equal to the gram/equivalent polyhydroxyalcan polyglycidylether functionality and diluted to an 18% aqueous dispersion. This was then coated over Example 1 at a dry laydown of 8.6 g/m 2 (0.8 g/ft 2 ) and dried.
  • a polymeric particle dispersion comprised of ethyl methacrylate, butyl methacrylate, and methacrylic acid, at the ratio of 85 to 10 to 5 (Polymer Particle Dispersion P-3) was diluted to an 18% aqueous dispersion. This was then coated over Example 1 at a dry laydown of 8.6 g/m 2 (0.8 g/ft 2 ) and dried.
  • a polymeric particle dispersion comprised of ethyl methacrylate, butyl methacrylate, and hydroxylethyl methacrylate, at the ratio of 85 to 10 to 5 (polymer Particle Dispersion P-4) was diluted to an 18% aqueous dispersion. This was then coated over Example 1 at a dry laydown of 8.6 g/m 2 (0.8 g/ft 2 ) and dried.
  • a polymeric particle dispersion comprised of ethyl methacrylate, butyl methacrylate, and hydroxylethyl methacrylate, at the ratio of 85 to 10 to 5 (Polymer Particle Dispersion P-4) was combined with a polyhydroxyalcan polyglycidylether multifunctional polymer (CR-5L TM from Esprix Technologies) so that the gram/equivalent hydroxy functionality was equal to the gram/equivalent polyhydroxyalcan polyglycidylether functionality and diluted to an 18% aqueous dispersion. This was then coated over Example 1 at a dry laydown of 8.6 g/m 2 (0.8 g/ft 2 ) and dried.
  • Each example was then printed with a CANON i550 TM inkjet printer with KODAK TM pigmented inks, with a test target comprised of 1 cm 2 color patches, a set of each of the primary and secondary colors. Each patch was printed at 100% density.
  • the printed elements were allowed to dry for 1 hour and then were fused in a heated nip at 150°C and 4.2 kg/cm 2 against a sol-gel coated polyimide belt at 76 cm/min.
  • a drop of water, coffee, and fruit punch (Hawaiian Punch TM contains Red Dye #40 and Blue Dye #1) were placed on the color patches and a white non printed area and allowed to set for 10 minutes and then blotted off.
  • Each area where a drop was placed was visually inspected for any stain, water marks, and deformations to the surfaces. If any stain, watermark, or deformation was detected it was a fail grading. If no stain, watermark or deformation was seen it was a pass grade.
  • a polymeric particle dispersion comprised of ethyl methacrylate and methyl methacrylate, at the ratio of 83 to 17, the mordant divinylbenzene-co-N-vinylbenzyl-N,N,N-trimethylammonium chloride, and poly(vinyl alcohol) were diluted at the dry weight ratio of 80/10/10 to make an 18% aqueous dispersion. This was then coated over Example 1 at a dry laydown of 8.6 g/m 2 (0.8 g/sqft) and dried.
  • a polymeric particle dispersion comprised of ethyl methacrylate and methacrylic acid, at the ratio of 95 to 5 (polymer Particle Dispersion P-1) was diluted to make an 18% aqueous solution. This was then coated over Example 2 at a dry laydown of 8.6 g/m 2 (0.8g/sq ft) and dried.
  • a polymeric particle dispersion comprised of ethyl methacrylate and methacrylic acid, at the ratio of 95 to 5 (Polymer Particle Dispersion P-1) and an oxazoline functional copolymer (WS-500 TM from Esprix Technologies, Sarasota, Florida), were combined so that the gram/equivalent acid functionality was equal to the gram/equivalent oxazoline functionality, to make an 18% aqueous solution.
  • a polymeric particle dispersion comprised of ethyl methacrylate and methacrylic acid, at the ratio of 95 to 5 (Polymer Particle P-1) was combined with a polyhydroxyalcan polyglycidylether functional polymer (CR-5L TM from Esprix Technologies) so that the gram/equivalent acid functionality was equal to the gram/equivalent polyhydroxyalcan polyglycidylether functionality, to make an 18% aqueous solution.
  • This was then coated over Examples 15 at a dry laydown of 8.6 g/m 2 (0.8 g/sq ft) and dried.
  • a polymeric particle dispersion comprised of ethyl methacrylate, butyl methacrylate, and hydroxyethyl methacrylate, at the ratio of 85 to 10 to 5 (Polymer Particle Dispersion P-4) was diluted to an 18% aqueous solution. This was then coated over Example 15 at a dry laydown of 8.6 g/m 2 (0.8g/sq ft) and dried.
  • a polymeric particle dispersion comprised of ethyl methacrylate, butyl methacrylate, and hydroxyethyl methacrylate, at the ratio of 85 to 10 to 5 (Polymer Particle Dispersion P-4) was combined with a polyhydroxyalcan polyglycidylether functional polymer (CR-5L TM from Esprix Technologies) so that the gram/equivalent hydroxy functionality was equal to the gram/equivalent polyhydroxyalcan polyglycidylether functionality, to make an 18% aqueous solution. This was then coated over Example 15 at a dry laydown of 8.6 g/m 2 (0.8g/sq ft) and died.
  • Each example was then printed with a CANON i550 TM inkjet printer with CANON TM dye-based inks, with a test target comprised of 1 cm 2 color patches, a set of each of the primary and secondary colors. Each patch was printed at 100% density.
  • the printed elements were allowed to dry for 1 hour and then were fused in a heated nip at 150°C and 4.2 kg/cm 2 against a sol-gel coated polyimide belt at 76 cm/min.
  • a drop of water, coffee, and fruit punch (Hawaiian Punch TM , contains Red Dye #40 and Blue Dye #1) were placed on the color patches and a white non printed area and allowed to set for 10 minutes and then blotted off.
  • Each area where a drop was placed was visually inspected for any stain, watermarks, and deformations to the surfaces. If any stain, watermark, or deformation was detected it was assigned a fail grading. If no stain, watermark or deformation was seen it was assigned a pass grade.

Landscapes

  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)

Claims (9)

  1. Elément d'enregistrement par jet d'encre comprenant un support ayant, dans l'ordre, de :
    a) une couche superficielle, poreuse et fusible, comprenant (i) des particules polymères fusibles qui contiennent un polymère thermoplastique ayant des groupes fonctionnels réactifs, dans laquelle les particules polymères fusibles contiennent un polymère ou copolymère de polyacrylate ayant un ou plusieurs motifs monomères dérivés d'un monomère d'acrylate ou de méthacrylate d'alkyle, où le groupe alkyle contient 1 à 6 atomes de carbone, dans laquelle les particules polymères fusibles ont une monodiversité définie comme étant le poids moléculaire moyen pondéral divisé par le poids moléculaire moyen en nombre des polymères dans la bille à une valeur médiane de 50 % inférieure à 1,3, et (ii) en plus des particules polymères fusibles, un composé multifonctionnel ayant des groupes fonctionnels réactifs complémentaires capables de réticuler les groupes fonctionnels réactifs sur le polymère thermoplastique lorsqu'ils subissent une fusion, et (iii) en plus des particules polymères fusibles et du composé multifonctionnel, éventuellement un liant ;
    dans laquelle le polymère thermoplastique dans les particules polymères fusibles dans la couche superficielle de transport d'encre comprennent des motifs monomères ayant des fonctions réactives choisies dans le groupe constitué des fonctions oxazoline, époxy, acide, acide anhydride, acétoacétoxy, amine primaire ou secondaire, hydroxyle, phénol, thiol et isocyanate, et dans laquelle le composé multifonctionnel a des fonctions réactives complémentaires choisies dans le groupe constitué des fonctions oxazoline, époxy, acide, acide-anhydride, acétoacétoxy, amine primaire ou secondaire, hydroxyle, phénol, thiol et isocyanate ;
    b) une couche facultative de piégeage de colorants comprenant des particules polymères fusibles, un mordant pour les colorants et un liant hydrophile facultatif ; et
    c) une couche facultative réceptrice d'un liquide véhiculeur d'encre.
  2. Elément d'enregistrement selon la revendication 1, dans lequel la couche réceptrice de liquide véhiculeur d'encre est présente entre le support et la couche superficielle.
  3. Elément d'enregistrement selon la revendication 1, dans lequel le poids moléculaire moyen pondéral du polymère thermoplastique varie de 5 000 à 1 000 000 et la température de transition vitreuse est supérieure à 20 °C et inférieure à 100°C.
  4. Elément d'enregistrement selon la revendication 1, dans lequel le polymère thermoplastique dans les particules polymères fusibles dans la couche superficielle comprend des motifs monomères ayant des fonctions réactives choisies dans le groupe constitué des fonctions acide et hydroxyle, et dans lequel le composé multifonctionnel a des fonctions oxazoline, lesdites fonctions réactives complémentaires étant choisies dans le même groupe.
  5. Elément selon la revendication 1, dans lequel le composé multifonctionnel comprend 5 à 50 pourcent de motifs monomères ayant des fonctions réactives complémentaires choisies dans le groupe constitué des groupes époxy et oxazoline.
  6. Elément d'enregistrement selon la revendication 1, dans lequel le composé multifonctionnel est un polymère à groupe fonctionnel époxy, et le polymère thermoplastique est un polymère à groupe fonctionnel acide, à groupe fonctionnel hydroxy, à groupe fonctionnel amine ou à groupe fonctionnel acide-anhydride.
  7. Elément d'enregistrement selon la revendication 1, dans lequel le composé multifonctionnel est un polymère à groupe fonctionnel oxazoline, et le polymère thermoplastique est un polymère à groupe fonctionnel acide, à groupe fonctionnel acide-anhydride, à groupe fonctionnel phénol ou à groupe fonctionnel thiol.
  8. Elément d'enregistrement selon la revendication 1, dans lequel la couche fusible de piégeage de colorants est présente sous la couche superficielle poreuse et dans lequel la couche superficielle poreuse est capable de fonctionner comme une couche de transport d'encre.
  9. Procédé d'impression par jet d'encre comprenant les étapes de :
    A) fourniture d'une imprimante à jet d'encre sensible aux signaux de données numériques ;
    B) chargement dans l'imprimante de l'élément d'enregistrement par jet d'encre selon la revendication 1 ;
    C) chargement dans l'imprimante d'une composition d'encre pour impression par jet d'encre ;
    D) impression sur l'élément d'enregistrement par jet d'encre en utilisant la composition d'encre pour impression par jet d'encre en réponse aux signaux de données numériques ; et
    E) fusion au moins de la couche superficielle poreuse fusible, de telle sorte que la couche soit non-poreuse.
EP05762630A 2004-06-30 2005-06-13 Milieu reactif fusible Expired - Fee Related EP1761394B1 (fr)

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US10/881,264 US7655286B2 (en) 2004-06-30 2004-06-30 Fusible reactive media comprising mordant
US10/881,127 US7648745B2 (en) 2004-06-30 2004-06-30 Fusible reactive media
PCT/US2005/020733 WO2006011979A1 (fr) 2004-06-30 2005-06-13 Milieu reactif fusible

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Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4239543A (en) 1979-02-09 1980-12-16 Gould Inc. Non-crusting jet ink and method of making same
JPS56118471A (en) 1980-02-25 1981-09-17 Konishiroku Photo Ind Co Ltd Ink composition for ink jet recording
US4781758A (en) 1987-10-22 1988-11-01 International Business Machines Corporation Ink composition for drop-on-demand ink jet
JP2000052647A (ja) 1998-08-04 2000-02-22 Esprit Chemical Co インクジェット記録材料用コ―ティング剤およびインクジェット記録材料
US6503607B1 (en) 2000-07-27 2003-01-07 Eastman Kodak Company Ink jet recording element
US6497941B1 (en) 2000-07-27 2002-12-24 Eastman Kodak Company Ink jet recording element
GB2366748A (en) * 2000-09-15 2002-03-20 Ilford Imaging Uk Ltd Recording material and method
US6436617B1 (en) 2000-10-30 2002-08-20 Eastman Kodak Company Protective epoxy overcoat for imaging elements
JP2003071991A (ja) * 2001-09-05 2003-03-12 Teijin Dupont Films Japan Ltd 耐候性に優れた、インク受像層易接着性ポリエステルフィルム
DE60307193T2 (de) * 2002-09-30 2007-06-28 Eastman Kodak Company Tintenstrahlaufzeichnungselement und Druckverfahren
JP2004174981A (ja) * 2002-11-28 2004-06-24 Konica Minolta Holdings Inc インクジェット記録媒体とそれを用いた画像形成方法

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EP1761394A1 (fr) 2007-03-14
JP4726897B2 (ja) 2011-07-20
JP2008504984A (ja) 2008-02-21
WO2006011979A1 (fr) 2006-02-02
DE602005011438D1 (de) 2009-01-15

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