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
  • 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
  • B41M5/506—Intermediate 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
  • B41M5/52—Macromolecular coatings
  • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays

Definitions

• the present invention relates to an ink jet recording element and a printing method using the element containing core/shell particles which improve stability and optical density.
• 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 and an organic material such as a monohydric alcohol, a polyhydric alcohol or mixtures thereof.
• An ink jet recording element typically comprises a support having on at least one surface thereof an ink-receiving or image-receiving layer, and includes those intended for reflection viewing, which have an opaque support, and those intended for viewing by transmitted light, which have a transparent support.
• porous recording elements have been developed which provide nearly instantaneous drying as long as they have sufficient thickness and pore volume to effectively contain the liquid ink.
• a porous recording element can be manufactured by coating in which a particulate-containing coating is applied to a support and is dried.
• EP 1 016 543 relates to an ink jet recording element containing aluminum hydroxide in the form of boehmite.
• this element is not stable to light and exposure to atmospheric gases.
• EP 0 965 460A2 relates to an ink jet recording element containing aluminum hydrate having a boehmite structure and a non-coupling zirconium compound.
• a metal oxy(hydroxide) complex as described herein.
• U.S. Patent 5,372,884 relates to ink jet recording elements containing a cation-modified acicular or fibrous colloidal silica, wherein the cation-modifier is at least one hydrous metal oxide selected from the group consisting of hydrous aluminum oxide, hydrous zirconium oxide and hydrous tin oxide.
• the cation-modifier is at least one hydrous metal oxide selected from the group consisting of hydrous aluminum oxide, hydrous zirconium oxide and hydrous tin oxide.
• hydrous metal oxide selected from the group consisting of hydrous aluminum oxide, hydrous zirconium oxide and hydrous tin oxide.
• Still another object of the invention is to provide a printing method using the above-described element.
• an ink jet recording element comprising a support having thereon an image-receiving layer, the ink jet recording element containing core/shell particles wherein the shell of the particles consists of a metal(oxy)hydroxide complex, M n+ (O) a (OH) b (A p- ) c •xH 2 O, wherein M is at least one metal ion; n is 3 or 4; A is an organic or inorganic ion; p is 1, 2 or 3; and x is equal to or greater than 0; with the proviso that when n is 3, then a, b and c each comprise a rational number as follows: 0 ⁇ a ⁇ 1.5; 0 ⁇ b ⁇ 3; and 0 ⁇ pc ⁇ 3, so that the charge of the M 3+ metal ion is balanced; and when n is 4, then a, b and c each comprise a rational number as follows: 0 ⁇
• an ink jet recording element is obtained that, when printed with dye-based inks, provides superior optical densities, good image quality and has an excellent dry time.
• Another embodiment of the invention relates to an ink jet printing method comprising the steps of:
• the core/shell particles consist of a core particle having a negative charge upon its surface and having thereon a shell.
• Core particles useful in the invention include silica, zinc oxide, zirconium oxide, titanium dioxide, barium sulfate, and clay minerals such as montmorillonite.
• the core particles are negatively charged.
• the core particles consist of silica, such as silica gel, hydrous silica, fumed silica, colloidal silica, etc.
• the size of the core particles may be from 0.01 to 10 ⁇ m, preferably from 0.05 to 1.0 ⁇ m.
• the shell may comprise 0.1 to 50 % by weight, based upon the weight of the core particle, but is preferably from 3 to 40 % by weight of the core particle, preferably 10 to 30 % by weight.
• the shell may have a thickness of 0.005 to 0.500 ⁇ m, preferably 0.01 to 0.100 um thick.
• the core/shell particles described above are located in the image-receiving layer.
• M in the above formula is a Group IIIA, IIIB, IVA, IVB metal or a lanthanide group metal of the periodic chart, such as tin, titanium, zirconium, aluminum, silica, yttrium, cerium or lanthanum or mixtures thereof.
• n is 4; a, b and c each comprise a rational number as follows: 0 ⁇ a ⁇ 1; 1 ⁇ b ⁇ 4; and 1 ⁇ pc ⁇ 4, so that the charge of the M 4+ metal ion is balanced.
• a is 0, n is 4, and b+pc is 4.
• a is 0, n is 3, and b+pc is 3.
• a p- is an organic anion such as R-COO - , R-O - , R-SO 3 - , R-OSO 3 - or R-O-PO 3 - where R is an alkyl or aryl group.
• a p- is an inorganic anionic such as I - , Cl - , Br - , F - , ClO 4 - , NO 3 - , CO 3 2 - or SO 4 2- .
• the particle size of the complex described above is less than 1 ⁇ m, preferably less than.0.1 ⁇ m.
• Metal (oxy)hydroxide complexes employed herein as the shell material may be prepared by dissolving a metal salt in water and adjusting the concentration, pH, time and temperature to induce the precipitation of metal (oxy)hydroxide tetramers, polymers or particulates upon the core material.
• the conditions for precipitation vary depending upon the nature and concentrations of the counter ion(s) present and can be determined by one skilled in the art.
• soluble complexes suitable for preparation of the zirconium (oxy)hydroxide shell materials include, but are not limited to, ZrOCl 2 ⁇ 8H 2 O, and the halide, nitrate, acetate, sulfate, carbonate, propionate, acetylacetonate, citrate and benzoate salts; and hydroxy salts with any of the above anions. It is also possible to prepare the shell materials employed in the invention via the hydrolysis of organically soluble zirconium complexes such as zirconium alkoxides, e.g., zirconium propoxide, zirconium isopropoxide, zirconium ethoxide and related organometallic zirconium compounds.
• zirconium alkoxides e.g., zirconium propoxide, zirconium isopropoxide, zirconium ethoxide and related organometallic zirconium compounds.
• the hydrolyzed zirconium oxyhydroxides may exist as tetrameric zirconia units or as polymeric complexes of tetrameric zirconia, wherein zirconium cations are bridged by hydroxy and/or oxo groups.
• hydrolyzed zirconia salts are amorphous and may exist predominantly in the ⁇ form. However, depending upon the experimental conditions (solvents, pH, additives, aging and heating conditions), the hydrolyzed product may contain significant number of "oxo" bridges.
• oligomeric or polymeric units of metal complexes may be condensed via hydrolysis reactions to form larger particulates ranging in size from 3 nm to 500 nm.
• core/shell particulates ranging in size from 0.500 ⁇ m to 5.0 ⁇ m. Preferred particles sizes are in the range from 5 nm to 1000 nm. Calcination of amorphous metal (oxy)hydroxide leads to the formation of crystalline polymorphs of metal oxides.
• the image-receiving layer is porous and also contains a polymeric binder in an amount insufficient to alter the porosity of the porous receiving layer.
• the polymeric binder is 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, rhamsan and the like.
• the hydrophilic polymer is poly(vinyl alcohol), hydroxypropyl cellulose, hydroxypropyl methyl cellulose, or a poly(alkylene oxide).
• the hydrophilic binder is poly(vinyl alcohol).
• the recording element may also contain a base layer, next to the support, the function of which is to absorb the solvent from the ink.
• Materials useful for this layer include particles, polymeric binder and/or crosslinker.
• the support for the ink jet recording element used in the invention can be any of those usually used for ink jet receivers, such as resin-coated paper, paper, polyesters, or microporous materials such as polyethylene polymer-containing material sold by PPG Industries, Inc., Pittsburgh, Pennsylvania under the trade name of Teslin ®, Tyvek ® synthetic paper (DuPont Corp.), and OPPalyte® films (Mobil Chemical Co.) and other composite films listed in U.S. Patent 5,244,861.
• Opaque supports include plain paper, coated paper, synthetic paper, photographic paper support, melt-extrusion-coated paper, and laminated paper, such as biaxially oriented support laminates. Biaxially oriented support laminates are described in U.S.
• biaxially oriented supports include a paper base and a biaxially oriented polyolefin sheet, typically polypropylene, laminated to one or both sides of the paper base.
• Transparent supports include glass, cellulose derivatives, e.g., a cellulose ester, cellulose triacetate, cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate; polyesters, such as poly(ethylene terephthalate), poly(ethylene naphthalate), poly( 1 ,4-cyclohexanedimethylene terephthalate), poly(butylene terephthalate), and copolymers thereof; polyimides; polyamides; polycarbonates; polystyrene; polyolefins, such as polyethylene or polypropylene; polysulfones; polyacrylates; polyetherimides; and mixtures thereof.
• the papers listed above include a broad range of papers, from high end papers, such as photographic paper to low end papers, such as newsprint. In a preferred embodiment, polyethylene-coated paper is employed.
• the support used in the invention may have a thickness of from 50 to 500 ⁇ m, preferably from 75 to 300 ⁇ m.
• Antioxidants, antistatic agents, plasticizers and other known additives may be incorporated into the support, if desired.
• the surface of the support may be subjected to a corona-discharge treatment prior to applying the image-receiving layer.
• Coating compositions employed in the invention may be applied by any number of well known techniques, including dip-coating, wound-wire rod coating, doctor blade coating, gravure and reverse-roll coating, slide coating, bead coating, extrusion coating, curtain coating and the like.
• Known coating and drying methods are described in further detail in Research Disclosure no. 308119, published Dec. 1989, pages 1007 to 1008.
• Slide coating is preferred, in which the base layers and overcoat may be simultaneously applied. After coating, the layers are generally dried by simple evaporation, which may be accelerated by known techniques such as convection heating.
• 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, and the like may all be used.
• UV absorbers may also be added to the image-receiving layer as is well known in the art.
• Other additives include inorganic or organic particles, pH modifiers, adhesion promoters, rheology modifiers, surfactants, biocides, lubricants, dyes, optical brighteners, matte agents, antistatic agents, etc.
• additives known to those familiar with such art such as surfactants, defoamers, alcohol and the like may be used.
• a common level for coating aids is 0.01 to 0.30 % active coating aid based on the total solution weight.
• These coating aids can be nonionic, anionic, cationic or amphoteric. Specific elements are described in MCCUTCHEON's Volume 1: Emulsifiers and Detergents, 1995, North American Edition.
• the image-receiving layer employed in the invention can contain one or more mordanting species or polymers.
• the mordant polymer can be a soluble polymer, a charged molecule, or a crosslinked dispersed microparticle.
• the mordant can be non-ionic, cationic or anionic.
• the coating composition can be coated either from water or organic solvents, however water is preferred.
• the total solids content should be selected to yield a useful coating thickness in the most economical way, and for particulate coating formulations, solids contents from 10-40% are typical.
• the ink jet inks used to image the recording elements of the present invention are well-known in the art.
• the ink compositions used in ink jet 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 watersoluble 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, the disclosures of which are hereby incorporated by reference.
• the dye used for testing was a magenta colored ink jet dye having the structure shown below.
• a measured amount of the ink jet dye and solid particulates or aqueous colloidal dispersions of solid particulates were added to a known amount of water such that the concentration of the dye was about 10 -5 M.
• the solid dispersions containing dyes were carefully stirred and then spin coated onto a glass substrate at a speed of 1000-2000 rev/min.
• the spin coatings obtained were left in ambient atmosphere with fluorescent room lighting (about 0.5 Klux) kept on at all times during the measurement.
• the fade time was estimated by noting the time required for complete disappearance of magenta color as observed by the naked eye or by noting the time required for the optical absorption to decay to less than 0.03 of the original value.
• colloidal dispersions of silica particles were obtained from Nalco Chemical Company.
• Silica dispersion A had a mean particle size of 112 nm, a pH of 9.6, specific gravity of 1.3 g/ml, and a solids content of 41 %.
• Silica dispersion B had a mean particle size of 94 nm, a pH of 8.4, specific gravity of 1.3 g/ml, and a solids content of 40 %.
• the colloidal dispersions were used as received and coated and tested as described above.
• a ZrO(OH)acetate dispersion was obtained from MEI Corporation.
• the dispersion had 36.5 % solids, an average particle size of less than 10 nm, a pH of 3.8 and a specific gravity of 1.3 g/ml.
• Core/shell colloidal dispersions were prepared by the simultaneous addition of the silica and zirconium colloidal dispersions into a highly efficient mixing apparatus. The colloidal dispersions were introduced via calibrated peristaltic pumps at known flow rates. The mixing efficiencies and flow rates were varied to obtain stable core/shell colloidal dispersions. The details of the preparation and the characteristics of the dispersions are given below.
• the mixing efficiency was kept constant for each example and was about 25 tumovers/min.
• I-2 This was prepared in an identical manner to that of 1-1, except that the zirconium (oxy)hydroxy acetate colloid was added at a rate of 1.8 ml/min. The weight ratio of the resulting colloid was therefore 92.5 % silica and 7.5 % zirconium(oxy)hydroxy acetate. The resulting dispersion had a particle size of 210 nm and settled after standing, indicating that the dispersion was not colloidally stable. The resulting dispersion was then coated and tested as described above and the results shown in Table 1 below.
• I-3 This was prepared in an identical manner to that of I-1, except that the zirconium(oxy)hydroxy acetate colloid was added at a rate of 2.5 ml/min. The weight ratio of the resulting colloid was therefore 90.0 % silica and 10.0 % zirconium(oxy)hydroxy acetate. The resulting dispersion had a particle size of 145 nm and did not settle after standing, indicating that the dispersion was a stable colloid. The resulting dispersion was then coated and tested as described above and the results shown in Table 1 below.
• I-4 This was prepared in an identical manner to that of I-1, except that silica colloid B was substituted in place of colloid A, and the zirconium(oxy)hydroxy acetate colloid was added at a rate of 2.5 ml/min. The weight ratio of the resulting colloid was therefore 90.0 % silica and 10.0 % zirconium(oxy)hydroxy acetate. The resulting dispersion had a particle size of 151 nm and did not settle after standing, indicating that the dispersion was a stable colloid. The resulting dispersion was then coated and tested as described above and the results shown in Table 1 below.
• I-5 This was prepared in an identical manner to that of 1-1, except that the zirconium(oxy)hydroxy acetate colloid was added at a rate of 4.0 ml/min. The weight ratio of the resulting colloid was therefore 85.0 % silica and 15.0 % zirconium(oxy)hydroxy acetate The resulting dispersion had a particle size of 131 nm and did not settle after standing, indicating that the dispersion was a stable colloid. The resulting dispersion was then coated and tested as described above and the results shown in Table 1 below.
• I-6 This was prepared in an identical manner to that of 1-1, except that the zirconium(oxy)hydroxy acetate colloid was added at a rate of 5.6 ml/min. The weight ratio of the resulting colloid was therefore 80.0 % silica and 20.0 % zirconium(oxy)hydroxy acetate. The resulting dispersion had a particle size of 130 nm and did not settle after standing, indicating that the dispersion was a stable colloid. The resulting dispersion was then coated and tested as described above and the results shown in Table 1 below.
• I-7 This was prepared in an identical manner to that of I-1, except that the zirconium(oxy)hydroxy acetate colloid was added at a rate of 9.3 ml/min. The weight ratio of the resulting colloid was therefore 70.0 % silica and 30.0 % zirconium(oxy)hydroxy acetate. The resulting dispersion had a particle size of 138 nm and did not settle after standing, indicating that the dispersion was a stable colloid. The resulting dispersion was then coated and tested as described above and the results shown in Table 1 below.
• I-8 This was prepared in an identical manner to that of 1-1, except that silica colloid B was substituted in place of colloid A, and the zirconium(oxy)hydroxy acetate colloid was added at a rate of 9.3 ml/min. The weight ratio of the resulting colloid was therefore 70.0 % silica and 30.0 % zirconium(oxy)hydroxy acetate. The resulting dispersion had a particle size of 93 nm and did not settle after standing, indicating that the dispersion was a stable colloid. The resulting dispersion was then coated and tested as described above and the results shown in Table 1 below.
• I-9 This was prepared in an identical manner to that of I-1, except that silica colloid B was substituted in place of colloid A, and the zirconium(oxy)hydroxy acetate colloid was added at a rate of 14.5 ml/min. The weight ratio of the resulting colloid was therefore 60.0 % silica and 40.0 % zirconium(oxy)hydroxy acetate. The resulting dispersion had a particle size of 96 nm and did not settle after standing, indicating that the dispersion was a stable colloid. The resulting dispersion was then coated and tested as described above and the results shown in Table 1 below.
• colloidal silica dispersion B (median particle size 94 nm) was diluted by the addition of 2.0 ml distilled deionized water. 0.23 g of a 14 % (w/w) aqueous dispersion of Yttrium(oxy)hydroxy acetate (median particle size 15 nm) was then added slowly with vigorous stirring. The weight ratio of the resulting colloid was therefore 92.5 % silica and 7.5 % yttrium(oxy)hydroxy acetate. The resulting dispersion had a particle size of 146 nm and did not settle after standing, indicating that the dispersion was a stable colloid. The resulting dispersion was then coated and tested as described above arid the results shown in Table 1 below.
• 1.0 g of colloidal silica dispersion B (median particle size 94 nm) was diluted by the addition of 2.0 ml distilled deionized water. 1.0 g of a 14 % (w/w) aqueous dispersion of Yttrium(oxy)hydroxy acetate (median particle size 15 nm) was then added slowly with vigorous stirring. The weight ratio of the resulting colloid was therefore 74.0 % silica and 26.0 % yttrium(oxy)hydroxy acetate. The resulting dispersion had a particle size of 154 nm and did not settle after standing, indicating that the dispersion was a stable colloid.
• a coating solution for the base layer was prepared by combining fumed alumina (Cab-O-Sperse® PG003, Cabot Corp.), poly(vinyl alcohol) (Gohsenol® GH-17, Nippon Gohsei Co., Ltd.) and 2,3-dihydroxy-1,4-dioxane (Clariant Corp.) in a ratio of 89:9:2 to give an aqueous coating formulation of 30% solids by weight.
• the coating solution for the image-receiving layer was 1-4 described above and poly(vinyl alcohol) (Gohsenol® GH-23A, Nippon Gohsei Co.), and mordant polymeric particles of a copolymer of (vinylbenzyl)trimethylammonium chloride and divinylbenzene (87:13 molar ratio), and surfactant Zonyl® FSN (E. I. du Pont de Nemours and Co.) in a ratio of 73/2/20/5 to give an aqueous coating formulation of 10% solids by weight.
• poly(vinyl alcohol) Gohsenol® GH-23A, Nippon Gohsei Co.
• mordant polymeric particles of a copolymer of (vinylbenzyl)trimethylammonium chloride and divinylbenzene (87:13 molar ratio)
• surfactant Zonyl® FSN E. I. du Pont de Nemours and Co.
• the layers were simultaneously bead-coated at 40°C on polyethylene-coated paper base which had been previously subjected to corona discharge treatment.
• the image-receiving layer was coated on top of the base layer.
• the coating was then dried at 60°C by forced air to yield a two-layer recording element in which the thicknesses of the topmost and bottom layers were 2 ⁇ m and 40 ⁇ m, respectively.
• Element 2 of the invention was prepared the same as Element 1 except that the ratio of I-4, poly(vinyl alcohol) (Gohsenol® GH-23A, Nippon Gohsei Co.), mordant polymeric particles of a copolymer of (vinylbenzyl)trimethylammonium chloride and divinylbenzene (87:13 molar ratio), and surfactant Zonyl® FSN (E. I. du Pont de Nemours and Co.) was 67/2/26/5.
• poly(vinyl alcohol) Gohsenol® GH-23A, Nippon Gohsei Co.
• mordant polymeric particles of a copolymer of (vinylbenzyl)trimethylammonium chloride and divinylbenzene 87:13 molar ratio
• surfactant Zonyl® FSN E. I. du Pont de Nemours and Co.
• Comparative Elements C-1 to C-4 were prepared the same as Element 1 except that fumed alumina (Cab-O-Sperse® PG003, Cabot Corp.) was used in place of the core/shell material.
• fumed alumina Cab-O-Sperse® PG003, Cabot Corp
• poly(vinyl alcohol) Gohsenol® GH-23A, Nippon Gohsei Co.
• surfactant Zonyl® FSN E. I. du Pont de Nemours and Co.
• the dried coatings were visually evaluated for cracking defects.
• the dried coatings were measured for 60° specular glossiness using a Gardener® Gloss Meter. A gloss measurement of at least about 60 % is desirable.
• a piece of bond paper was placed over the printed image and rolled with a smooth, heavy weight. Then the bond paper was separated from the printed image. Ink transferred to the bond paper if the recording element was not dry.
• the length of the bar imaged on the bond paper was measured.
• the length of the bar imaged on the bond paper was measured and is proportional to the dry time. Dry times corresponding to a length of about 4 cm or less are acceptable.

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