EP1375179B1 - Ink jet recording element and printing method - Google Patents

Ink jet recording element and printing method Download PDF

Info

Publication number
EP1375179B1
EP1375179B1 EP20030076863 EP03076863A EP1375179B1 EP 1375179 B1 EP1375179 B1 EP 1375179B1 EP 20030076863 EP20030076863 EP 20030076863 EP 03076863 A EP03076863 A EP 03076863A EP 1375179 B1 EP1375179 B1 EP 1375179B1
Authority
EP
European Patent Office
Prior art keywords
recording element
ink jet
metal hydroxide
ink
jet recording
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
EP20030076863
Other languages
German (de)
French (fr)
Other versions
EP1375179A2 (en
EP1375179A3 (en
Inventor
Krishamohan c/o Eastman Kodak Company Sharma
Christine c/o Eastman Kodak Com. Landry-Coltrain
Joseph F. C/O Eastman Kodak Company Bringley
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US10/180,182 external-priority patent/US7138162B2/en
Priority claimed from US10/180,187 external-priority patent/US6984033B2/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of EP1375179A2 publication Critical patent/EP1375179A2/en
Publication of EP1375179A3 publication Critical patent/EP1375179A3/en
Application granted granted Critical
Publication of EP1375179B1 publication Critical patent/EP1375179B1/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5218Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays

Definitions

  • the present invention relates to an ink jet recording element containing a stabilizer and a printing method using the element.
  • 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.
  • EPA 1174279A teaches the use of zinc oxide in ink jet recording elements to improve light stability. However, there is problem with such elements in that they do not provide protection against environmental gasses such as ozone.
  • EPA 988993A and EPA 893270A disclose the use of aluminum hydrate and aluminum hydroxides in ink jet recording elements. However, there is a problem with these elements in that they do not provide good image stability.
  • Still another object of the invention is to provide a printing method using the above-described element.
  • 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.
  • the metal hydroxide salt described above is located in the image-receiving layer.
  • M can be two different metal ions such as zinc and tin.
  • the metal hydroxide salt described above is in a particulate form.
  • a is greater than 0.5 and b is less than 1.5.
  • 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 salt described above is less than aout 5 ⁇ m, preferably less than 1 ⁇ m.
  • M 2+ hydroxide salts can be synthesized from a variety of synthetic routes, such as addition of base to metal salts, reacting a metal salt with a metal oxide or through ion exchange. Some of the M 2+ hydroxide salts form layered structures and are commonly referred to as hydroxy double salts. However, M 2+ hydroxides can also exist as polycationic nanoparticles. It is possible to control particle size, shape and structure of M 2+ hydroxide salts using appropriate anions or metal ions or synthetic routes.
  • M 2+ useful in the invention include zinc, magnesium, barium, calcium, tin, nickel, cobalt and copper.
  • M 2+ hydroxide salts include zinc hydroxy double salts such as Zn 5 (OH) 8 (A p- ), wherein A p- is Cl, Br, nitrate, acetate or propionate.
  • 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 ink 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 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 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 (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.
  • the results are shown in Table 1.
  • Inorganic particles of Al 2 O 3 , SiO 2 , ZnO, Zn(OH) 2 , laponite and montmorillonite were purchased from commercial sources as fine particles or as colloidal particulate dispersions and were used to evaluate the stability of ink jet dyes in comparison with the materials employed in the present invention. The particulates were then coated and tested as described above.
  • a coating composition was prepared from 70.0 wt. % of an aqueous colloidal suspension (15.8 wt. % solids) of Zn 5 (OH) 8 (CH 3 COO) 2 •2H 2 O, 2.0 wt. % poly(vinyl alcohol) (Gohsenol® GH-17 from Nippon Gohsei Co.), and 28.0 wt. % water.
  • the relative proportion of Zn 5 (OH) 8 (CH 3 COO) 2 •2H 2 O to PVA is therefore 85/15 by weight.
  • the solution was coated onto a base support comprised of a polyethylene resin coated photographic paper stock, which had been previously subjected to corona discharge treatment, using a calibrated coating knife, and dried to remove substantially all solvent components to form the ink receiving layer.
  • This element was prepared the same as Element 1 except that the coating composition was 73.5 wt. % of an aqueous colloidal suspension (15.0 wt. % solids) of Zn 5 (OH) 8 (Cl) 2 •2H 2 O, 2.0 wt. % poly(vinyl alcohol) (Gohsenol® GH-17 from Nippon Gohsei Co.), and 24.5 wt. % water. (The relative proportion of Zn 5 (OH) 8 (Cl) 2 •2H 2 O to PVA is therefore 85/15 by weight).
  • This element was prepared the same as Element 1 except that the coating composition was 14.8wt. % Zn 5 (OH) 8 (NO 3 ) 2 •2H 2 O, 0.83 wt. % poly(vinyl alcohol) (Gohsenol® GH-23 from Nippon Gohsei Co.), 1.48 wt. % Dowfac 2A1 ® surfactant, and 82.9 wt. % water (The relative proportion of Zn 5 (OH) 8 (NO 3 ) 2 •2H 2 O to PVA is therefore 95/5 by weight).
  • This element was prepared the same as Element 1 except that the coating composition was 14.0 wt. % of an aqueous colloidal suspension of Zn 5 (OH) 8 (CH 3 COO) 2 •2H 2 O (15.8 wt. % solids), and 22.0 wt. % silica (a 40 wt. % aqueous colloidal suspension of Nalco2329® (75 nm silicon dioxide particles) from Nalco Chemical Co.), 2.0 wt. % poly(vinyl alcohol) (Gohsenol® GH-17 from Nippon Gohsei Co.), and 62.0 wt. % water.
  • the coating composition was 14.0 wt. % of an aqueous colloidal suspension of Zn 5 (OH) 8 (CH 3 COO) 2 •2H 2 O (15.8 wt. % solids), and 22.0 wt. % silica (a 40 wt. % aqueous colloidal suspension of Nalco2329
  • This element was prepared the same as Element 1 except that the coating composition was 14.0 wt. % of an aqueous colloidal suspension of Zn 5 (OH) 8 (CH 3 COO) 2 •2H 2 O (15.8 wt. % solids), 22 wt. % fumed alumina (40 wt. % alumina in water, Cab-O-Sperse® PG003 from Cabot Corporation), 2.0 wt. % poly(vinyl alcohol) (Gohsenol® GH-17 from Nippon Gohsei Co.), and 62.0 wt. % water.
  • the coating composition was 14.0 wt. % of an aqueous colloidal suspension of Zn 5 (OH) 8 (CH 3 COO) 2 •2H 2 O (15.8 wt. % solids), 22 wt. % fumed alumina (40 wt. % alumina in water, Cab-O-Sperse® PG003 from Cabot Corporation),
  • This element was prepared the same as Element 1 except that the coating composition was 14.5 wt. % of an aqueous colloidal suspension of Zn 5 (OH) 8 (Cl) 2 •2H 2 O (15.0 wt. % solids), 22.0 wt. % silica (a 40 wt. % aqueous colloidal suspension of Nalco2329® (75 nm silicon dioxide particles) from Nalco Chemical Co.), 2.0 wt. % poly(vinyl alcohol) (Gohsenol® GH-17 from Nippon Gohsei Co.), and 61.5 wt. % water.
  • the coating composition was 14.5 wt. % of an aqueous colloidal suspension of Zn 5 (OH) 8 (Cl) 2 •2H 2 O (15.0 wt. % solids), 22.0 wt. % silica (a 40 wt. % aqueous colloidal suspension of Nalco2329® (75 nm silicon dioxide
  • This element was prepared the same as Element 1 except that the coating composition was 14.5 wt. % of an aqueous colloidal suspension of Zn 5 (OH) 8 (Cl) 2 •2H 2 O (15.0 wt. % solids), 22.0 wt. % fumed alumina (40 wt. % alumina in water, Cab-O-Sperse® PG003 from Cabot Corporation), 2.0 wt. % poly(vinyl alcohol) (Gohsenol® GH-17 from Nippon Gohsei Co.), and 61.5 wt. % water.
  • the coating composition was 14.5 wt. % of an aqueous colloidal suspension of Zn 5 (OH) 8 (Cl) 2 •2H 2 O (15.0 wt. % solids), 22.0 wt. % fumed alumina (40 wt. % alumina in water, Cab-O-Sperse® PG003 from Cabot Corporation), 2.0 wt
  • This element was prepared the same as Element 1 except that the coating composition was 34.0 wt. % of silica (a 40 wt. % aqueous colloidal suspension of Nalco2329® (75 nm silicon dioxide particles) from Nalco Chemical Co.), 2.4 wt. % poly(vinyl alcohol), (Gohsenol® GH-23 from Nippon Gohsei Co.), and 63.6 wt. % water. (The relative proportions of silica to PVA are 85/15).
  • This element was prepared the same as Element 1 except that the coating composition was 34.0 wt. % of a fumed alumina solution (40 wt. % alumina in water, Cab-O-Sperse® PG003 from Cabot Corporation), 2.4 wt. % poly(vinyl alcohol), (Gohsenol® GH-23 from Nippon Gohsei Co.), and 63.6 wt. % water. (The relative proportions of alumina to PVA are 85/15).
  • the above elements were printed using a Lexmark Z51 ink jet printer and a cyan inkjet ink, prepared using a standard formulation with a copper phthalocyanine dye (Clariant Direct Turquoise Blue FRL-SF), and a magenta ink, prepared using a standard formulation with Dye 6 from U.S. Patent 6,001,161.
  • the red channel density (cyan) patches and green channel density (magenta) patches at D-max (the highest density setting) were read using an X-Rite ® 820 densitometer.
  • the printed elements were then subjected to 1 day exposure to a nitrogen flow containing 5 ppm ozone, in the dark.

Description

  • The present invention relates to an ink jet recording element containing a stabilizer and a printing method using the element.
  • In a typical ink jet recording or printing system, 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.
  • An important characteristic of ink jet recording elements is their need to dry quickly after printing. To this end, 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. For example, a porous recording element can be manufactured by coating in which a particulate-containing coating is applied to a support and is dried.
  • When a porous recording element is printed with dye-based inks, the dye molecules penetrate the coating layers. However, there is a problem with such porous recording elements in that the optical densities of images printed thereon are lower than one would like. The lower optical densities are believed to be due to optical scatter which occurs when the dye molecules penetrate too far into the porous layer. Another problem with a porous recording element is that atmospheric gases or other pollutant gases readily penetrate the element and lower the optical density of the printed image causing it to fade.
  • EPA 1174279A teaches the use of zinc oxide in ink jet recording elements to improve light stability. However, there is problem with such elements in that they do not provide protection against environmental gasses such as ozone.
  • EPA 988993A and EPA 893270A disclose the use of aluminum hydrate and aluminum hydroxides in ink jet recording elements. However, there is a problem with these elements in that they do not provide good image stability.
  • It is an object of this invention to provide an ink jet recording element that, when printed with dye-based inks, provides superior optical densities, good image quality, image stability and has an excellent dry time.
  • Still another object of the invention is to provide a printing method using the above-described element.
  • These and other objects are achieved in accordance with the invention which comprises an ink jet recording element containing a metal hydroxide salt,

            (M2+)(OH)a(Ap-)b•xH2O;

    wherein:
    • M2+ is at least one metal ion having a 2+ oxidation state;
    • A is an organic or inorganic anion;
    • p is 1 or 2; and
    • x is equal to or greater than 0; and
    • a and b comprise rational numbers as follows: 0 < a < 2 and 0 < b < 2 so that the charge of M2+ is balanced.
  • By use of the invention, 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:
    • A) providing an ink jet printer that is responsive to digital data signals;
    • B) loading the printer with an ink jet recording element as described above;
    • C) loading the printer with an ink jet ink composition; and
    • D) printing on the ink jet recording element using the ink jet ink composition in response to the digital data signals.
  • In a preferred embodiment of the invention, the metal hydroxide salt described above is located in the image-receiving layer. In another preferred embodiment, M can be two different metal ions such as zinc and tin. In another preferred embodiment, the metal hydroxide salt described above is in a particulate form. In another preferred embodiment, a is greater than 0.5 and b is less than 1.5.
  • In yet still another preferred embodiment of the invention, Ap- is an organic anion such as R-COO-, R-O-, R-SO3 -, R-OSO3 - or R-O-PO3 - where R is an alkyl or aryl group. In another preferred embodiment, Ap- is an inorganic anionic such as I-, Cl-, Br-, F-, ClO4 -, NO3 -, CO3 2- or SO4 2-. The particle size of the salt described above is less than aout 5 µm, preferably less than 1 µm.
  • M2+ hydroxide salts can be synthesized from a variety of synthetic routes, such as addition of base to metal salts, reacting a metal salt with a metal oxide or through ion exchange. Some of the M2+ hydroxide salts form layered structures and are commonly referred to as hydroxy double salts. However, M2+ hydroxides can also exist as polycationic nanoparticles. It is possible to control particle size, shape and structure of M2+ hydroxide salts using appropriate anions or metal ions or synthetic routes.
  • Examples of M2+ useful in the invention include zinc, magnesium, barium, calcium, tin, nickel, cobalt and copper.
  • Specific examples of M2+ hydroxide salts include zinc hydroxy double salts such as Zn5(OH)8(Ap-), wherein Ap- is Cl, Br, nitrate, acetate or propionate.
  • In a preferred embodiment of the invention, 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. In another preferred embodiment, 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. In still another preferred embodiment of the invention, the hydrophilic polymer is poly(vinyl alcohol), hydroxypropyl cellulose, hydroxypropyl methyl cellulose, or a poly(alkylene oxide). In yet still another preferred embodiment, the hydrophilic binder is poly(vinyl alcohol).
  • In addition to the image-receiving layer, 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. Patents 5,853,965; 5,866,282; 5,874,205; 5,888,643; 5,888,681; 5,888,683; and 5,888,714. These 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 µm, preferably from 75 to 300 µm. Antioxidants, antistatic agents, plasticizers and other known additives may be incorporated into the support, if desired.
  • In order to improve the adhesion of the ink-receiving layer to the support, 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.
  • In order to impart mechanical durability to an ink jet recording element, 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.
  • To improve colorant fade, UV absorbers, radical quenchers or antioxidants 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. In order to obtain adequate coatability, 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 ink 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.
  • 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 following examples are provided to illustrate the invention.
  • Example 1 Dye Stability Evaluation Tests
  • The dye used for testing was a magenta colored ink jet dye having the structure shown below. To assess dye stability on a given substrate, a measured amount of the ink jet dye and solid particulates or aqueous colloidal dispersions of solid particulates (typically 10%-20.0% by weight solids) were added to a known amount of water such that the concentration of the dye was 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 (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. The results are shown in Table 1.
    Figure imgb0001
  • Comparative Coatings C-1 to C-6 (Non-metal 2+ hydroxide salts)
  • Inorganic particles of Al2O3, SiO2, ZnO, Zn(OH)2, laponite and montmorillonite were purchased from commercial sources as fine particles or as colloidal particulate dispersions and were used to evaluate the stability of ink jet dyes in comparison with the materials employed in the present invention. The particulates were then coated and tested as described above.
  • Inventive Coatings I-1 to I-7
  • I-1. 81.5 g of ZnO (1.0 mol) (J.T. Baker Co.) was suspended in 100 ml of distilled deionized water. To this suspension, 148.5 g of Zn(NO3)2•6H2O (0.5 mol) dissolved in 500 mL of distilled deionized water was added rapidly (within 5-10 min.). The resultant suspension was stirred vigorously for five days at 60°C. The final product, Zn5(OH)8(NO3)2•2H2O, was filtered and washed with copious amounts of distilled water and air dried. The final product was dispersed in distilled water and used for evaluating the stability of ink jet dyes as described above.
  • I-2. 162.8 g of ZnO (2.0 mol) (J.T. Baker Co.) was suspended in 200 ml of distilled deionized water. To this suspension, 219.5 g of Zn(CH3COO)2•6H2O (1.0 mol) dissolved in 500 mL of distilled deionized water was added rapidly (within 5-10 min). The resultant suspension was stirred vigorously 36 h at 60°C. The final product, Zn5(OH)8(CH3COO)2•2H2O.was filtered and washed with copious amounts of distilled water and air dried. The final product was dispersed in distilled water and used for evaluating the stability of ink jet dyes as described above.
  • I-3. 40.6 g of ZnO ( 0.5 mol), (Alfa Aesar Co.), 325 mesh powder, was suspended in 50 ml of distilled deionized water. To this suspension, 35.5 g of ZnCl2 (0.26 mol) dissolved in 250 mL of distilled deionized water was added rapidly (within 5-10 min.). The resultant suspension was stirred vigorously for two days at room temperature. The final product, Zn5(OH)8(Cl)2•2H2O, was filtered and washed with copious amounts of distilled water and air dried. The final product was dispersed in distilled water and used for evaluating the stability of ink jet dyes as described above.
  • I-4. 40.6 g of ZnO ( 0.5 mol), (Alfa Aesar Co.), 325 mesh powder, was suspended in 50 ml of distilled deionized water. A separate solution was made by dissolving 70.0 g of Zn(NO3)2 (0.0235 ml) and 4.5 g of Co(NO3)2 (0.0015 mol) in 250 mL of distilled deionized water. The mixed metal nitrate solution was filtered and then added rapidly to this suspension of ZnO. The final reaction mixture was vigorously stirred for two days at room temperature. The product, (Zn5-x, Cox)(OH)8(NO3)2•2H2O: was filtered and washed with copious amounts of distilled water and air dried. The final product was dispersed in distilled water and used for evaluating the stability of ink jet dyes as described above.
  • I-5. 20.35 g of ZnO ( 0.25 mol), (JT Baker Co.) was suspended in 50 ml of distilled deionized water. To this suspension, 23.1 g of zinc sulfate mono hydrate (0.128 mol) dissolved in 125 mL of distilled deionized water was added rapidly (within 5-10 min.). The resultant suspension, 3Zn(OH)2•ZnSO4•4H2O, was stirred vigorously for two days at room temperature. The final product was dispersed in distilled water and used for evaluating the stability of ink jet dyes as described above.
  • I-6. Fine particles of [Zn5(OH)8(NO3)2]•xH2O (5.0 g, 0.008 mol) were suspended in 200 ml of distilled water. To this suspension 4.0 g of 1-napthalene sulfonic acid sodium salt ( 0.017 mol) was added while vigorously stirring the suspension at 60°C. The stirring was continued for 2 days and the final product, Zn5(OH)8(napthalene sulfonate)y was filtered and washed with copious amounts of acetone and air dried. The final product was dispersed in distilled water and used for evaluating the stability of ink jet dyes as described above.
  • I-7. Fine particles of [Zn5(OH)8(NO3)2]•xH2O (5.0 g, 0.008 mol) were suspended in to 200 ml of distilled water. To this suspension 2.5 g of salicylic acid (0.0018 mol) was added at room temperature and the reaction mixture was stirred for 2 days. The final product of this reaction is a physical mixture of hydroxy double salt containing nitrate and salicylate anions, [Zn5(OH)8(salicylate)y]x[Zn5(OH)8(NO3)]1-x. The final product was dispersed in distilled water and used for evaluating the stability of ink jet dyes as described above. Table 1
    Coating Particle Fade Time
    C-1 Al2O3 18 hours
    C-2 SiO2 18 hours
    C-3 ZnO 2 days
    C-4 Zn(OH)2 5 days
    C-5 Laponite 4 days
    C-6 Montmorillonite 18 hours
    I-1 Zn5(OH)8(NO3)2•2H2O 7 days
    I-2 Zn5(OH)8(CH3COO)2•2H2O > 14 days
    I-3 Zn5(OH)8(Cl)2•2H2O 6 days
    I-4 (Zn5-x, Cox) (OH)8(NO3)2•2H2O 2 days
    I-5 3Zn(OH)2•ZnSO4•4H2O 2 days
    I-6 [Zn5(OH)8(1-naphthalene sulfonate)y]•xH2O > 14 days
    I-7 [Zn5(OH)8(Salicylate)y]x [Zn5(OH)8(NO3)]1-x > 14 days
  • The above results show that the salts employed in the elements of the present invention provide superior image stability to ink jet dyes against fade changes as compared to the control elements.
  • Example 2 Element 1
  • A coating composition was prepared from 70.0 wt. % of an aqueous colloidal suspension (15.8 wt. % solids) of Zn5(OH)8(CH3COO)2•2H2O, 2.0 wt. % poly(vinyl alcohol) (Gohsenol® GH-17 from Nippon Gohsei Co.), and 28.0 wt. % water. The relative proportion of Zn5(OH)8(CH3COO)2•2H2O to PVA is therefore 85/15 by weight. The solution was coated onto a base support comprised of a polyethylene resin coated photographic paper stock, which had been previously subjected to corona discharge treatment, using a calibrated coating knife, and dried to remove substantially all solvent components to form the ink receiving layer.
  • Element 2
  • This element was prepared the same as Element 1 except that the coating composition was 73.5 wt. % of an aqueous colloidal suspension (15.0 wt. % solids) of Zn5(OH)8(Cl)2•2H2O, 2.0 wt. % poly(vinyl alcohol) (Gohsenol® GH-17 from Nippon Gohsei Co.), and 24.5 wt. % water. (The relative proportion of Zn5(OH)8(Cl)2•2H2O to PVA is therefore 85/15 by weight).
  • Element 3
  • This element was prepared the same as Element 1 except that the coating composition was 14.8wt. % Zn5(OH)8(NO3)2•2H2O, 0.83 wt. % poly(vinyl alcohol) (Gohsenol® GH-23 from Nippon Gohsei Co.), 1.48 wt. % Dowfac 2A1 ® surfactant, and 82.9 wt. % water (The relative proportion of Zn5(OH)8(NO3)2•2H2O to PVA is therefore 95/5 by weight).
  • Element 4
  • This element was prepared the same as Element 1 except that the coating composition was 14.0 wt. % of an aqueous colloidal suspension of Zn5(OH)8(CH3COO)2•2H2O (15.8 wt. % solids), and 22.0 wt. % silica (a 40 wt. % aqueous colloidal suspension of Nalco2329® (75 nm silicon dioxide particles) from Nalco Chemical Co.), 2.0 wt. % poly(vinyl alcohol) (Gohsenol® GH-17 from Nippon Gohsei Co.), and 62.0 wt. % water. (The relative proportion of Zn5(OH)8(CH3COO)2•2H2O to silica is 20/80 and that of (Zn5(OH)8(CH3COO)2•2H2O-silica) particles to PVA is therefore 85/15 by weight).
  • Element 5
  • This element was prepared the same as Element 1 except that the coating composition was 14.0 wt. % of an aqueous colloidal suspension of Zn5(OH)8(CH3COO)2•2H2O (15.8 wt. % solids), 22 wt. % fumed alumina (40 wt. % alumina in water, Cab-O-Sperse® PG003 from Cabot Corporation), 2.0 wt. % poly(vinyl alcohol) (Gohsenol® GH-17 from Nippon Gohsei Co.), and 62.0 wt. % water. (The relative proportion of Zn5(OH)8(CH3COO)2•2H2O to alumina is 20/80 and that of (Zn5(OH)8(CH3COO)2•2H2O-alumina) particles to PVA is therefore 85/15 by weight)).
  • Element 6
  • This element was prepared the same as Element 1 except that the coating composition was 14.5 wt. % of an aqueous colloidal suspension of Zn5(OH)8(Cl)2•2H2O (15.0 wt. % solids), 22.0 wt. % silica (a 40 wt. % aqueous colloidal suspension of Nalco2329® (75 nm silicon dioxide particles) from Nalco Chemical Co.), 2.0 wt. % poly(vinyl alcohol) (Gohsenol® GH-17 from Nippon Gohsei Co.), and 61.5 wt. % water. (The relative proportion of Zn5(OH)8(Cl)2•2H2O to silica is 20/80 and that of (Zn5(OH)8(Cl)2•2H2O -silica) particles to PVA is therefore 85/15 by weight).
  • Element 7
  • This element was prepared the same as Element 1 except that the coating composition was 14.5 wt. % of an aqueous colloidal suspension of Zn5(OH)8(Cl)2•2H2O (15.0 wt. % solids), 22.0 wt. % fumed alumina (40 wt. % alumina in water, Cab-O-Sperse® PG003 from Cabot Corporation), 2.0 wt. % poly(vinyl alcohol) (Gohsenol® GH-17 from Nippon Gohsei Co.), and 61.5 wt. % water. (The relative proportion of Zn5(OH)8(Cl)2•2H2O to alumina is 20/80 and that of (Zn5(OH)8(Cl)2•2H2O -alumina) particles to PVA is therefore 85/15 by weight)
  • Comparative Element C-1 (Non-metal 2+ hydroxide salt)
  • This element was prepared the same as Element 1 except that the coating composition was 34.0 wt. % of silica (a 40 wt. % aqueous colloidal suspension of Nalco2329® (75 nm silicon dioxide particles) from Nalco Chemical Co.), 2.4 wt. % poly(vinyl alcohol), (Gohsenol® GH-23 from Nippon Gohsei Co.), and 63.6 wt. % water. (The relative proportions of silica to PVA are 85/15).
  • Comparative Element C-2 (Non-metal 2+ hydroxide salt)
  • This element was prepared the same as Element 1 except that the coating composition was 34.0 wt. % of a fumed alumina solution (40 wt. % alumina in water, Cab-O-Sperse® PG003 from Cabot Corporation), 2.4 wt. % poly(vinyl alcohol), (Gohsenol® GH-23 from Nippon Gohsei Co.), and 63.6 wt. % water. (The relative proportions of alumina to PVA are 85/15).
  • Printing and dye stability testing
  • The above elements were printed using a Lexmark Z51 ink jet printer and a cyan inkjet ink, prepared using a standard formulation with a copper phthalocyanine dye (Clariant Direct Turquoise Blue FRL-SF), and a magenta ink, prepared using a standard formulation with Dye 6 from U.S. Patent 6,001,161. The red channel density (cyan) patches and green channel density (magenta) patches at D-max (the highest density setting) were read using an X-Rite ® 820 densitometer. The printed elements were then subjected to 1 day exposure to a nitrogen flow containing 5 ppm ozone, in the dark. The density of each patch was read after the exposure test using an X-Rite ® 820 densitometer. The % dye retention was calculated as the ratio of the density after the exposure test to the density before the exposure test. The results for cyan and magenta D-max are reported in Table 2. Table 2
    Element Material % dye retention magenta D-max % dye retention cyan D-max
    C-1 SiO2 14 85
    C-2 Al2O3 25 93
    1 Zn5(OH)8(CH3COO)2•2H2O 100 100
    2 Zn5(OH)8(Cl)2•2H2O 42 81
    3 Zn5(OH)8(NO3)2•2H2O 100 100
    4 Zn5(OH)8(CH3COO)2•2H2O /silica 45 73
    5 Zn5(OH)8(CH3COO)2•2H2O/alumina 33 73
    6 Zn5(OH)8(Cl)2•2H2O /silica 68 92
    7 Zn5(OH)8(Cl)2•2H2O /alumina 10 37
  • The above results show that the elements of the invention had better dye retention than the control elements.

Claims (10)

  1. An ink jet recording element comprising a support having thereon an image-receiving layer, said ink jet recording element containing a metal hydroxide salt,

            (M2+)(OH)a(Ap-)b•xH2O;

    wherein:
    M2+ is at least one metal ion having a 2+ oxidation state;
    A is an organic or inorganic anion;
    p is 1 or 2; and
    x is equal to or greater than 0; and
    a and b comprise rational numbers as follows: 0 < a < 2 and 0 < b < 2 so that the charge of M2+ is balanced.
  2. The recording element of Claim 1 wherein said metal hydroxide salt is present in said image-receiving layer.
  3. The recording element of Claim 1 wherein M2+ is zinc, magnesium, barium, calcium, tin, nickel, cobalt or copper.
  4. The recording element of Claim 1 wherein said metal hydroxide salts is a zinc hydroxy double salt.
  5. The recording element of Claim 3 wherein Ap- is an organic anion R-COO-, R-O-, R-SO3 -, R-OSO3 - or R-O-PO3 - where R is an alkyl or aryl group.
  6. The recording element of Claim 1 wherein Ap- is an inorganic anion I-, Cl-, Br-, F-, ClO4 -, NO3 -, CO3 2- or SO4 2-.
  7. The recording element of Claim 1 wherein said metal hydroxide salt is in particulate form.
  8. The recordang element of Claim 1 wherein said metal hydroxide salt is prepared from an aqueous dispersion having a pH between 3 and 10.
  9. The recording element of Claim 1 wherein M is Zn.
  10. An ink jet printing method comprising the steps of:
    A) providing an ink jet printer that is responsive to digital data signals;
    B) loading said printer with the ink jet recording element of Claim 1;
    C) loading said printer with an ink jet ink composition; and
    D) printing on said inkjet recording element using said ink jet ink composition in response to said digital data signals.
EP20030076863 2002-06-26 2003-06-16 Ink jet recording element and printing method Expired - Fee Related EP1375179B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US180187 1988-04-11
US180182 2002-06-26
US10/180,182 US7138162B2 (en) 2002-06-26 2002-06-26 Ink jet recording element
US10/180,187 US6984033B2 (en) 2002-06-26 2002-06-26 Ink jet printing method

Publications (3)

Publication Number Publication Date
EP1375179A2 EP1375179A2 (en) 2004-01-02
EP1375179A3 EP1375179A3 (en) 2005-07-20
EP1375179B1 true EP1375179B1 (en) 2006-08-02

Family

ID=29718499

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20030076863 Expired - Fee Related EP1375179B1 (en) 2002-06-26 2003-06-16 Ink jet recording element and printing method

Country Status (3)

Country Link
EP (1) EP1375179B1 (en)
JP (1) JP4261256B2 (en)
DE (1) DE60307187T2 (en)

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5770691A (en) * 1980-10-22 1982-05-01 Mitsubishi Paper Mills Ltd Recording sheet
US5244861A (en) 1992-01-17 1993-09-14 Eastman Kodak Company Receiving element for use in thermal dye transfer
JPH0732725A (en) * 1993-07-16 1995-02-03 Fuji Photo Film Co Ltd Ink jet recording paper
US5888643A (en) 1997-05-23 1999-03-30 Eastman Kodak Company Controlling bending stiffness in photographic paper
US5853965A (en) 1997-05-23 1998-12-29 Eastman Kodak Company Photographic element with bonding layer on oriented sheet
US5874205A (en) 1997-05-23 1999-02-23 Eastman Kodak Company Photographic element with indicia on oriented polymer back sheet
US5866282A (en) 1997-05-23 1999-02-02 Eastman Kodak Company Composite photographic material with laminated biaxially oriented polyolefin sheets
DE69800515T2 (en) 1997-07-23 2001-06-28 Mitsubishi Paper Mills Ltd Ink jet recording sheet
US6945646B2 (en) 1998-09-25 2005-09-20 Canon Kabushiki Kaisha Recording medium
JP3891546B2 (en) * 2000-07-19 2007-03-14 日本製紙株式会社 Inkjet recording medium

Also Published As

Publication number Publication date
DE60307187D1 (en) 2006-09-14
EP1375179A2 (en) 2004-01-02
DE60307187T2 (en) 2007-06-28
EP1375179A3 (en) 2005-07-20
JP2004025880A (en) 2004-01-29
JP4261256B2 (en) 2009-04-30

Similar Documents

Publication Publication Date Title
US20050014000A1 (en) Cationic shelled particle
KR20020097027A (en) Ink jet recording sheet
EP1680280B1 (en) Ink jet media with core shell particles
US20040201664A1 (en) Ink jet printing method
US6984033B2 (en) Ink jet printing method
EP1375179B1 (en) Ink jet recording element and printing method
US7122231B2 (en) Ink jet recording element
US7138162B2 (en) Ink jet recording element
JP2000211239A (en) Recording medium containing near infrared ray absorption compound and image forming method employing the medium
EP1375177B1 (en) Ink jet recording element and printing method
EP1375178B1 (en) Ink jet recording element and priting method
EP1375180B1 (en) Ink jet recording element and printing method
US6565205B2 (en) Ink jet printing method
US6991835B2 (en) Ink jet recording element
US7105215B2 (en) Ink jet recording element
US20040201663A1 (en) Ink jet printing method
EP1319518B1 (en) Ink jet recording element and printing method
US20030137574A1 (en) Ink jet printing method
US20040001924A1 (en) Ink jet printing method
EP1319517A1 (en) Ink jet recording element and printing method
US7901748B2 (en) Ink jet recording element
EP1170146B1 (en) Ink jet printing method
JPH11301100A (en) Manufacture of ink jet recording material
EP1238815A2 (en) Ink jet recording element and printing method

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

17P Request for examination filed

Effective date: 20051205

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

AKX Designation fees paid

Designated state(s): DE FR GB

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60307187

Country of ref document: DE

Date of ref document: 20060914

Kind code of ref document: P

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20070503

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20090605

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20090507

Year of fee payment: 7

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20100616

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20110228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100616

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20130628

Year of fee payment: 11

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60307187

Country of ref document: DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60307187

Country of ref document: DE

Effective date: 20150101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150101