EP0701902A1 - Farbstoffbildempfangselement - Google Patents

Farbstoffbildempfangselement Download PDF

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Publication number
EP0701902A1
EP0701902A1 EP94202686A EP94202686A EP0701902A1 EP 0701902 A1 EP0701902 A1 EP 0701902A1 EP 94202686 A EP94202686 A EP 94202686A EP 94202686 A EP94202686 A EP 94202686A EP 0701902 A1 EP0701902 A1 EP 0701902A1
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EP
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Prior art keywords
image
ink image
ink
gelatin
receiving element
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Granted
Application number
EP94202686A
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English (en)
French (fr)
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EP0701902B1 (de
Inventor
Leo c/o Agfa-Gevaert N.V. Vermeulen
Diane c/o Agfa-Gevaert N.V. Vertruyen
Guido C/O Agfa-Gevaert N.V. Desie
Daniel C/O Agfa-Gevaert N.V. Timmerman
Ronny c/o Agfa-Gevaert N.V. De Clercq
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Agfa Gevaert NV
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Agfa Gevaert NV
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Priority to EP19940202686 priority Critical patent/EP0701902B1/de
Priority to DE1994607288 priority patent/DE69407288T2/de
Priority to JP26077995A priority patent/JP3639013B2/ja
Publication of EP0701902A1 publication Critical patent/EP0701902A1/de
Application granted granted Critical
Publication of EP0701902B1 publication Critical patent/EP0701902B1/de
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    • 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
    • B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose

Definitions

  • This invention relates to an all-round image-receiving element in that it is suited for use in impact as well as in nonimpact type printing and can be written on with pencil.
  • thermo(photo)graphic printing in which thermoplastic resin-containing toner particles are transferred from electrostatic charge patterns to a receiving material and fixed thereon by heat.
  • ink is applied by means of a pen-plotter or ink jet.
  • Still another transfer printing technique applies a thermal printer or impact printer (e.g. type writer) to transfer bodily and imagewise coloured waxy strata of a transfer ribbon onto a receiving element (ref. e.g. US-P 5,292,593).
  • a thermal printer or impact printer e.g. type writer
  • a receiving element e.g. US-P 5,292,593
  • High speed printing requires the fast touch-dryness of each successive print in order to avoid smudging on mutual contact of the fresh prints. So, it is particularly important that the ink-image receiving layer has a high ink absorbing speed (short ink drying time), and that the deposited ink (aqueous or mainly organic) will not feather, not smear and/or not offset immediately after its application on the printing stock in contact with a next superposed sheet.
  • Water-based inks are commonly applied in ink-jet printing and organic inks are applied in offset printing which is a method derived from lithography in that on a printing machine the printing plate is first moistened with water by means of a roller and then guided towards an inking roller wherefrom greasy or oily ink is imagewise transferred (offset) on the paper printing stock.
  • Ink receiving materials especially for use in high quality ink jet printing should have an ink image-receiving layer as thin as possible combined with a high ink absorbance, so that absorbed ink dots will not spread and give rise to sharp high density images without blotting.
  • the ink image-receiving layer must be readily wetted so that there is no "puddling", i.e. coalescence of adjacent ink dots, and on the other hand the ink-absorbing properties of the ink image-receiving layer should be such that the deposited ink image has a good water-fastness, i.e. becomes waterproof.
  • ink-receiving material in sheet form may not show any curl or may not tend to stick to other sheets when stacked before or after being printed even at high printing speed.
  • ink image-receiving layers suited for use in combination with water-based inks preferably comprise a protein, e.g. gelatin, albumin or casein, polysaccharide, cellulose or cellulose derivative, polyvinyl alcohol or copolymer of vinyl alcohols.
  • the image-receiving layer containing these polymers may contain a hydrophylic silica gel and a white toner.
  • An improvement in optical density and reduction in drying time can be obtained by using particulate material in the polymeric binder.
  • particulate material such as kaolin, talc, bariet, and TiO2 applied in starch and polyvinyl alcohol (PVA) as binder are used for said purposes.
  • the drafting film more particularly contains (A) gelatin, (B) one or more silica matting agents, (C) an opacifying agent, (D) an epoxysilane compound, (E) a polyurethane and (F) a hardening agent.
  • the writability by pencil on said drafting film comes mainly from crystalline silica that gives the image-receiving layer a mild abrasive power to ensure good uptake of pencil graphite.
  • the opacity of the drafting film comes preferably from titanium dioxide particles of the anatase crystal modification.
  • the image-receiving layers of the drafting material according to said EP-A are coated from aqueous medium.
  • the use of organic solvents in the coating of imaging layers is frequently undesirable from ecological viewpoint and objectionable for reasons of flammability and odour problems.
  • a recording sheet suitable for use in both ink jet and electrophotographic imaging processes but having no drafting film properties is described e.g. in US-P 5,254,403.
  • an ink image-receiving element which element comprises a sheetlike or weblike support coated with an ink image-receiving layer containing gelatin as binding agent together with water-insoluble particulate organic material, called matting agent, partially protruding therefrom, characterized in that said layer contains (1) gelatin, (2) a water-soluble alkali metal carboxymethyl cellulose and (3) an organic polymeric particulate matting agent in such an amount that said ingredients (1), (2) and (3) together represent at least 75 % of the total weight of said layer, wherein the coverage of gelatin in said layer is in the range of 0.5 to 10 g/m2, the alkali metal carboxymethyl cellulose expressed as ratio by weight with respect to gelatin is present in said layer in the range of 1/20 to 5/1, said particulate polymeric organic matting agent has an average particle size in the range of 1 to 15 ⁇ m, and said matting agent is composed of an essentially organic polymeric composition having a glass transition value (Tg) of at least 25 °C,
  • the average thickness of the ink image-receiving layer having partially protruding matting agent particles is preferably in the range of 2 to 15 ⁇ m.
  • the coverage of gelatin in said layer is preferably in the range of 1.0 to 5.0 g/m2
  • the ratio by weight of said alkali metal carboxymethyl cellulose to gelatin is preferably in the range of 1/10 to 2/1
  • the ratio by weight of said matting agent to gelatin is preferably in the range of 1/2 to 5/1.
  • any type of commercial gelatin may be used.
  • Commercial gelatin is a mixture of proteins of varying molecular weight from 15,000 to 250,000. Poorly degraded (by hydrolysis) commercial gelatins having an average molecular weight above 55,000 are preferred.
  • gelatin can be prepared advantageously starting from a so-called lime-treated collagen-containing pig skin, bone or cattle hide material. As with all types of gelatin, swelling in water is at minimum at the isoelectric point. It is advantageous for improving the take up of aqueous ink in the coated and dry ink image-receiving layer that the pH of the applied ink is substantially different from the pH at the isoelectric point of the gelatin present in the image-receiving layer.
  • Gelatin gels are distinguished by their gel strength.
  • An ink image receiving layer having good mechanical strength contains preferably gelatin having a gel strength of at least 200 g determined according to British Standard Institution BS 757:1975 "Methods for Sampling and Testing Gelatin".
  • Gelatins preferred for use in the present ink image-receiving layers are characterized by a viscosity of at least 20 mPa.s when such viscosity is measured at 36 °C at pH 6 for a 10 % by weight aqueous solution at a shear rate of 1000s ⁇ 1.
  • the gelatin may be hardened to some degree thereby providing an improved cohesivity and resistance to abrasion together with a reduced bleeding or feathering of aqueous inks and improved water-fastness.
  • aldhyde hardeners such as formaldehyde, glyoxal and glutaraldehyde, s-triazines, e.g. 2,4-dichloro-6-hydroxy-s-triazine in the form of water-soluble sodium salt, active olefins, e.g. bis(vinylsulphonyl) compounds, and carbamoyl pyridinium salts.
  • Water-soluble carboxymethyl cellulose is normally applied as sodium salt.
  • Types of sodium carboxymethyl cellulose preferred for use according to the present invention have a substitution degree (DS) in the range of 0.5 to 1.3, more preferably in the range of 0.75 to 0.90.
  • the substitution degree (DS) relates to the average number of hydroxyl groups (maximum 3) in pyranose rings of the cellulose that have been transformed into -O-CH2-COONa groups.
  • Such water-soluble sodium carboxymethyl cellulose is mainly responsible for an improved take up of aqueous inks and shortens drying time of aqueous ink images.
  • Sodium carboxymetyl cellulose is obtained by reaction of alkali-cellulose with Cl-CH2-COONa, and contains normally from 50 to 600 linked pyranose rings of which the sodium atom of the -CH2ONa group on part or all of said rings has been substituted by -CH2-COONa.
  • the -CH2-COONa content of the carboxymethyl cellulose may be determined by titration with a strong acid transforming the -COONa groups into carboxylic acid groups and may be expressed as mg NaOH per gram of sodium carboxymethyl cellulose polymer corresponding with the equivalent amount of acid used in the transformation of -CH2-COONa groups into free acid groups. From the measured -CH2-COONa content compared with the -CH2-COONa content of a fully substituted cellulose the substitution degree can be easily calculated.
  • the water-insoluble polymeric matting agent particles protruding partially from the recording layer provide a rapid touch-dryness of the aqueous and non-aqueous inks and prevents sticking of stacking printed sheets immediately after their ink reception, preventing thereby smearing of printed parts. Further said matting agent provides for a strong adherence of oleophilic inks used in impact printing and provides for a strong heat-fixing of toner images obtained by electro(photo)graphic imaging with triboelectrically charged toner particles containing heat-softenable thermoplastic resin.
  • the organic matting agent is present in the ink-receiving layer in the form of single particles having an average particle size of 1-15 ⁇ m, but preferably of 3-10 ⁇ m.
  • the use of said particles in the indicated percentage by weight of said matting agent to gelatin gives a certain surface roughness to the ink-receiving layer and capillarity enhancing its ink absorption capacity.
  • the surface roughness of the present ink image-receiving layers is preferably in the range of 0.5 to 3.0 ⁇ m being Ra-values determined by means of a PERTH-O-METER (tradename) according to ANSI norm ASME B 46.1-1985.
  • Preferred particulate organic polymeric matting agent material for use in the image-receiving layer of the ink image-receiving material according to the present invention is in the form of polymer beads the glass transition temperature of which is at least 25 °C and more preferably above 40 °C.
  • the preparation of said matting agents may proceed by addition polymerization of ⁇ , ⁇ -ethylenically unsaturated monomers applying common polymerization initiator substances in a liquid medium serving as dispersion medium for the formed polymer that is obtained as a latex.
  • the polymer beads may consist of a homopolymer or copolymer and may be a graft polymer comprising a core and envelope of different polymers. The latter type of graft polymer is preferred for the structure of the polymer beads has at its surface micro-cavities formed by grafted dangling polymer chains which cavities provide a good ink retention.
  • suitable matting agents are in the form of polymethylmethacrylate or polystyrene beads, e.g. prepared by suspension polymerisation. These particles are known matting agents or spacer beads in photographic silver halide emulsion materials (ref. e.g. US-P 5,057,407).
  • the glass transition temperature (Tg) of polymethylmethacrylate and polystyrene is 105 °C and 100 °C respectively whereby these polymers have at room temperature a hardness sufficient to act as mild abrasive material for pencil.
  • Tg glass transition temperature
  • Still other suitable organic polymeric matting agents can be prepared according to techniques described in published European patent applications (EP-A) 0 466 982 and 0 584 407.
  • the matting agents prepared according to the lastmentioned EP-A are alkali-soluble.
  • Preferred organic matting agents providing rapid touch dryness of ink images and making the ink image-receiving layer writable on with pencil are prepared according to US-P 4,287,299 and 4,614,708. According to the method described therein finely divided solid spherical polymer beads having an average particle size between about 0.5 and about 15 ⁇ m can be produced, said beads having a glass transition temperature of at least 40°C. Said method disclosed in said US-P documents comprises the steps of :
  • the size of the beads is determined by the nature of the graft-polymerizable polymer, but can also be controlled by reaction temperature, and adjustment of other reaction parameters e.g. the concentration of the ⁇ , ⁇ -ethylenically unsaturated monomer(s) and especially the proportion between the volumes of water and of the water-miscible solvent, e.g. alcohol, in the aqueous solvent mixture.
  • Polymer beads with an average size in the range of 0.5 to 15 ⁇ m can be prepared in this way.
  • the reaction medium mainly consists of a homogeneous solution at room temperature, in the solvent mixture, of the graft-polymerizable polymer, the water-soluble free radical-forming polymerization initiator, and at least one ⁇ , ⁇ -ethylenically unsaturated monomer.
  • the dissolved initiator decomposes and forms free radicals, which then enter into reaction with the dissolved graft-polymerizable polymer either via a labile hydrogen atom or via a reactive position and thus form living molecules, which while remaining dissolved in the aqueous solvent mixture, encounter either reactive monomers or already growing polymer chains of such monomers, thus forming a graft polymer.
  • Polymer beads are thus formed, which are composed of a nucleus and an envelope.
  • the nucleus of the beads consists of a bundle of intertwisted polymer chains obtained by polymerization of the monomer(s) which is (are) insoluble in the aqueous solvent mixture, and of a small proportion of some polymer chains obtained by copolymerization of the monomer(s) and the initial dissolved polymer, said polymer chains being intertwisted with polymer chains grafted by one end to the core of the polymer beads and thus forming an envelope for the polymer beads.
  • the enveloping polymer acts by sterical hindering as dispersion stabilizer in aqueous medium.
  • the enveloping polymer contains preferably hydrophilic groups, e.g. carboxylic acid or carboxylic anhydride groups that provide good adherence to the gelatin matrix of the ink image-receiving layer.
  • Suitable ⁇ , ⁇ -ethylenically unsaturated monomers for use in the preparation of the nucleus of said polymer beads are e.g. styrene, vinyltoluene and substituted vinyltoluene e.g. vinyl benzyl chloride and the homologues thereof, chlorostyrene, alkyl methacrylates e.g. methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and the higher methacrylates, e.g. stearyl methacrylate; substituted alkyl methacrylates e.g.
  • vinylidene chloride, vinyl chloride, acrylonitrile, and methacrylonitrile are not solvents for their own polymers and can thus not be used for the formation of homopolymers. Nevertheless they can be combined with one or more suitable monomers complying with the requirements set forth to form copolymers that are soluble in the latter monomers.
  • Particularly suitable graft-polymerizable polymers for use in the preparation of the envelope of the polymeric matting agents in the form of enveloped-core micro-beads are e.g. polyethylene oxide, low molecular weight polyvinyl alcohol, polyvinyl pyrrolidone, co(vinyl alcohol/vinyl acetate) containing 12 mol % of vinyl acetate units and the same copolymer containing 40 mol % of vinyl acetate units, sodium or potassium salts of co(acrylic acid/styrene) containing 40 to 60 mol % of acrylic acid, co(vinyl acetate/crotonic acid), the reaction products of copoly (styrene/maleic anhydride), of copoly(vinyl acetate/maleic anhydride), of copoly (ethylene/maleic anhydride), or of copoly (N-vinyl pyrrolidone/maleic anhydride) with hydroxyalkyl or aminoalkyl
  • the weight ratio of the graft-polymerizable core polymer to said monomer(s) is generally comprised between 1.5 : 100 and 8 : 100. Optimum proportions for obtaining a given average particle size can be easily determined by making some simple tests.
  • Polymer beads obtained with the above co(styrene/maleic acid monosodium salt) through graft-polymerization on polymerized methyl methacrylate (core-polymer) are particularly suited for use in a coating composition for preparing an aqueous ink image-receiving layer of an image-receiving material according to the present invention.
  • a characteristic of polymer bead dispersions prepared according to said US-P 4,614,708 is that it contains discrete solid polymer which are stabilized sterically as a result of the stable arrangement in space of the grafted polymer chains (envelope) around the nuclei of the beads .
  • the presence of ionic groups in the grafted polymer provides for a certain solvation in aqueous medium. This solvation has a stabilizing effect supplemental to the steric stabilization of the grafted polymer chains of the bead-envelope.
  • the ink image-receiving layer may contain other kinds of ingredients that improve one or more of the properties aimed at such as good ink reception (wetting), good ink absorption, rapid touch-dryness and good writing on capability with pencil.
  • Ingredients that improve one or more of said properties are e.g. other hydrophilic binding agents than gelatin and CMC such as (1) hydroxyethyl cellulose; (2) hydroxypropyl cellulose; (3) hydroxyethylmethyl cellulose; (4) hydroxypropyl methyl cellulose; (5) hydroxybutylmethyl cellulose; (6) methyl cellulose; (7) sodium carboxymethylhydroxethyl cellulose; (8) water soluble ethylhydroxyethyl cellulose; (9) cellulose sulfate; (10) polyvinyl alcohol; (11) polyvinyl acetate; (12) polyvinylacetal; (13) polyvinyl pyrrolidone; (14) polyacrylamide; (15) acrylamide/acrylic acid copolymer; (16) styrene/acrylic acid copolymer; (17) ethylene-vinylacetate copolymer; (18) vinylmethyl ether/maleic acid copolymer; (19) poly(2-acrylamido-2-methyl propane s
  • wetting power for aqueous inks is improved in particular with surfactants that may be any of the cationic, anionic, amphoteric, and nonionic type.
  • alkali metal salts of fatty acids are alkali metal salts of fatty acids (soaps), N-alkylamino acid salts, alkylether carboxylic acid salts, acylated peptides, alkylsulfonic acid salts, alkylbenzene and alkylnaphthalene sulfonic acid salts, sulfosuccinic acid salts, olefin sulfonic acid salts, N-acylsulfonic acid salts, sulfonated oils, alkylsulfonic acid salts, alkylether sulfonic acid salts, alkylallylethersulfonic acid salts, alkylamidesulfonic acid salts, alkylphosphoric acid salts, alkyletherphosphoric acid salts, alkylallyletherphosphoric acid salts, alkyl and alkylallylpolyoxyethylene ethers, alkylallylformaldehyde condensed acid
  • fluoro C2-C10 alkylcarboxylic acids disodium N-perfluorooctanesulfonyl glutamate, sodium 3-(fluoro-C6-C11alkylaxy)-1-C3-C4 alkyl sulfonates, sodium 3-( ⁇ -fluoro-C6-C8 alkanoyl-N-ethylamino)-1-propane sulfonates, N-[3-(perfluorooctanesulfonamide)-propyl]-N,N-dimethyl-N-carboxymethylene ammonium betaine, fluoro-C11-C20 alkylcarboxylic acids, perfluoro C7-C13 alkyl carboxylic acids, perfluorooctane sulfonic acid diethanolamide, Li K and Na perfluoro C4-C12 alkyl sulfonates, N-propyl-N-(2-hydroxyethyl)
  • These surfactants are commercially available from DuPont and 3M.
  • the concentration of surfactant(s) in an ink image-receiving layer for aqueous ink reception is typically in the range of 0.1 to 2 percent by weight, preferably in the range of 0.4 to 1.5 percent by weight on the total dry weight of that layer.
  • ingredients are applied for improving water-fastness of the ink image and for preventing bleeding of the obtained images.
  • These ingredients may be a reactive component that form a substance improving water-fastness with a reactive component contained in the ink as described e.g. in US-P 4,694,302, wherein the formation in situ of a water-insoluble salt, e.g. aluminium salt, of carboxymethylcellulose has been mentioned.
  • the ink image-receiving layer contains basic or onium type mordants such as polymers containing ammonium groups. Examples of such polymers are described in US P 4,371,582, US P 4,575,465, US P 4,649,064, GB-P 1,221,131, GB-P 1,221,195, GB-P 2,210,071 and EP 423 829.
  • the ink receiving layer itself may be opacified with a whitening agent.
  • TiO2 (rutile or anatase) pigment is used preferably in an amount sufficient to produce a transmission density to white light of at least 0.05, and preferably 0.3 or higher.
  • the coverage of the whitener can range from 0.1 to 10 g/m2, and is preferably from 1 to 3 g/m2.
  • a slurry of the whitener may be added by batchwise addition or by in-line injection just prior to coating the image-receiving layer on its support.
  • opacifying pigments being inorganic particulate materials that may have a porous character or form porous conglomerates are e.g. colloidal particles of silica, talc, clay, koalin, diatomaceous earth, calcium carbonate, magnesium carbonate, aluminium hydroxide, aluminium oxide, zinc oxide, barium sulfate, calcium sulfate, zinc sulfide, aluminium silicate, calcium silicate and lithopone.
  • the specific surface area of these inorganic particulate materials may vary from 10 to 200 m2/g (BET specific surface), and oil absorption may be 150 ml/100 g or more as described for silica particles in US-P 5,213,873.
  • the ink acceptance of inks containing polar solvents may be improved by compounds acting as plasticizers for gelatin such as ethylene glycol, dietylene glycol, propylene glycol, polyethylene glycol, glycerol monomethylether, glycerol monochlorohydrin, ethylene carbonate, propylene carbonate, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, urea phosphate, triphenylphosphate, glycerolmonostearate, propylene glycol monostearate, tetramethylene sulfone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, and polymer latices with low Tg-value such as polyethylacrylate, polymethylacrylate, etc.
  • compounds acting as plasticizers for gelatin such as ethylene glycol, dietylene glycol, propylene glycol, polyethylene glycol, glycerol monomethylether,
  • the ink image-receiving layer of the material of the present invention may comprise still other additives e.g. compounds absorbing ultra-violet radiation, e.g.optical brightening agents and antistatic agents.
  • additives e.g. compounds absorbing ultra-violet radiation, e.g.optical brightening agents and antistatic agents.
  • said layer or an adjacent layer in water-permeable relationship therewith may contain physical development nuclei.
  • Preferred physical development nuclei are colloidal noble metal particles, e.g. silver particles, colloidal heavy metal sulfide particles such as colloidal palladium sulfide, nickel sulfide and mixed silver-nickel sulfide.
  • said nuclei are formed in situ with reactants contained in the ink-receiving material.
  • the ink-receiving layer may contain the physical development nuclei in operative contact with physical development accelerators, examples of which are thioether compounds described e.g. in published German patent application (DE-OS) 1,124,354, US-P 4,013,471; 4,072,526 and published European patent allication (EP-A) 0,026,520.
  • physical development accelerators examples of which are thioether compounds described e.g. in published German patent application (DE-OS) 1,124,354, US-P 4,013,471; 4,072,526 and published European patent allication (EP-A) 0,026,520.
  • an ink image receiving layer for ink jet printing contains physical development nuclei and a reducing agent for a reducible metal contained in the ink.
  • the present ink receiving material may be adapted to serve as receiving material for reactive inks, e.g. contains physical development nuclei and a reducing agent whereby in the receiving layer a metal image, e.g. silver image, is formed by catalyzed reduction of a reducible metal salt deposited by ink jet.
  • the ink image-receiving layers may be single or double-side coated on all kinds of support materials being transparent, translucent or opaque, e.g. metal, glass, resin and paper supports.
  • Particularly useful transparent supports are the resin supports applied in the manufacture of photographic films, e.g. made of cellulose ester such as cellulose acetate, polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polyesters containing in their structure hydrophilic moieties derived e.g. from sulfo-isophthalic acid and polyoxyalkylene diols, further polyamides, polycarbonates, polyimides, polyolefins, e.g. polypropylene, polyalkylmethacrylates, polyvinylchloride, poly(vinylacetals), polyethers and polysulfonamides.
  • cellulose ester such as cellulose acetate
  • polyesters such as polyethylene terephthalate, polyethylene naphthalate
  • polyesters containing in their structure hydrophilic moieties derived e.g. from sulfo-isophthalic acid and polyoxyalkylene diols, further polyamides, polycarbonates
  • Polyester film supports and especially supports made of poly (ethyleneterephthalate) are preferred because of their excellent dimensional stability.
  • a subbing layer is normally present to improve the bonding of the gelatin-containing image-receiving layer to the support.
  • Useful subbing layers for this purpose are well known from the production of photographic silver halide emulsion materials as described e.g. in Research Disclosure November 1989, item 307105 and include, for example, polymers of vinylidene chloride such as vinylidene chloride/acrylonitrile/acrylic acid terpolymers or vinylidene chloride/methyl acrylate/itaconic acid terpolymers.
  • Common opaque supports are paper supports in which the paper may be coated with a resin layer, e.g. polyolefin resin layer, preferably polyethylene-coated paper.
  • a resin layer e.g. polyolefin resin layer, preferably polyethylene-coated paper.
  • high-quality opacified resin supports are used, e.g. whitener-loaded polyesters or resin supports having internal light-scattering voids, e.g. obtained by extrusion of blends of poly (ethylenenterephthalate) and polypropylene, so-called synthetic paper or paper-like film [ref. e.g. (PCT) WO 94/06849].
  • the inks used to image the image-recording elements of the present invention may be of various types and are not neccesarily restricted to water-based inks since rapid touch dryness on the present ink image-receiving materials can be obtained likewise with common offset inks which are oil-based.
  • the ink compositions used in ink-jet printing are typically liquid compositions comprising a solvent or carrier liquid, dyes or pigments, humectants, organic solvents, detergents, thickeners, preservatives, etc.
  • the solvent or carrier liquid is predominantly water, although ink in which organic materials such as polyhydric alcohols are used as carrier liquid, can be used.
  • the dyes used in such ink-jet ink compositions are typically water-soluble direct dyes or acid type dyes (anionic dyes).
  • Such liquid ink compositions have been extensively described in e.g. US P 4,381,946, US P 4,781,758, and US P 4,994,110.
  • the image-receiving material according to the present invention is suited for the production of identification documents, so-called I.D. cards in the form of laminar articles in which image information is protected against mechanical damage and counterfeiting or forgery.
  • I.D. cards as security document, e.g. to establish a person's authorization to conduct certain activities (e.g. driver's licence) or to have access to certain areas or to engage in particular commercial actions, it is important that forgery of the I.D. card by alteration of certain of its data and/or photograph is made impossible.
  • a laminar article according to the present invention comprises the above defined image-receiving layer incorporating an image, e.g. a black-and-white and/or dye image obtained by a diffusion transfer technique, enveloped between a resin support, e.g. vinyl chloride polymer support and a resin cover sheet fixed to the image-receiving layer by lamination using pressure and heat.
  • an image e.g. a black-and-white and/or dye image obtained by a diffusion transfer technique
  • the cover sheet may be any hydrophobic thermoplastic resin sheet, e.g. made of polyester resin such as polyethylene terephthalate, a polycarbonate of a bis-phenol, a polyolefin e.g. polyethylene or polypropylene, or a vinyl chloride polymer as defined herein.
  • the cover sheet is a polyethylene terephthalate sheet being coated with a resinous melt-adhesive layer, e.g. a polyethylene or polypropylene layer.
  • the lamination of the imaged image-receiving material with said resin cover sheet proceeds preferably by heat-sealing between flat steel plates or roller laminator under a pressure of e.g. 10 to 15 kg/cm2 at a temperature in the range of 120 to 150°C, e.g. at 135°C Cooling of the just laminated article proceeds under pressure to avoid distortion.
  • the laminate may contain the image-receiving layer over the whole area of the support or in a part thereof, e.g. leaving free the edge area as described in US-P 4,425,421.
  • the image-receiving layer is coated onto an opaque polyvinyl chloride having a thickness of only 0.050 to 0.300 mm.
  • a sheet of that thickness can receive printed data by means of a mechanical printing process, e.g. offset or intaglio printing.
  • the image receiving layer can be coated on a support containing itself and/or an associated coating security marks.
  • the security mark may be in the form of a watermark.
  • Security marks that can be printed on the support or subbing layer are finger prints, printed patterns known from here notes, e.g. guilloches, coded information, e.g. magnetic binary code information, signature or other printed personal data that may be applied with nacreous pigment inks, or ultra-violet legible printing inks as described e.g. in GB-P 1,518,946 and US-P 4,105,333, or by applying marks containing liquid crystals as described e.g. in European patent (EP) 0 400 220.
  • EP European patent
  • nacreous pigments by which is meant light-interference pigments changing colour by viewing in transmission or reflection, infra-red absorbing markings, magnetic dots or stripes and electronic microcircuits either or not combined with ultra-violet radiation absorbing markings hidden from visibility and/or holograms as described e.g. in DE-OS 2,639,952, GB-P 1,502,460 and 1,572,442 and US-P 3,668,795.
  • the holographic patterns may be obtained in silver halide emulsion layers, normally Lippmann emulsions, especially designed for that purpose and can either or not be combined with a photograph in the laminate.
  • the resin sheet used as support of the laminate has to possess a thickness required for an identification card to be inserted in a slot of an electronic identification apparatus
  • several sheets of matted polyvinyl chloride are stacked and laminated so as to reach a final thickness of e.g. 0.68 mm to 0.84 mm.
  • a polyethylene terephthalate film having a thickness of 100 ⁇ m was double-side subbed for improving adherence to a gelatin-containing layer and double-side coated with one of the following aqueous coating compositions 1 to 12 (see TABLE 1 hereinafter).
  • the coating proceeded at 36 °C.
  • the coated layer was chilled at 5 °C for 20 s and finally dried at 35 °C for 120 s at relative humidity (RH) conditions of 30 %.
  • the basic ingredients of these coating compositions were water, dissolved gelatin and sodium carboxymethyl cellulose (CMC) and dispersed polymer beads (PB) prepared according to Example 1 of US-P 4,614,708, wherein the reaction conditions were adapted in such a way that polymethyl methacrylate beads grafted with co(styrene/maleic acid monosodium salt chains were obtained having an average size by volume of 3.3 ⁇ m for the beads used in EXAMPLES 1, 2, 3, 4, 6, 8 and 10, and of 4.5 ⁇ m in EXAMPLE 7.
  • the beads of EXAMPLE 5 and of EXAMPLES 9 and 11 had an average particle size by volume of 6.2 ⁇ m. Particle size measurements were carried out by means of the COULTER (registered trade mark) NANO-SIZER.
  • Example 4 the coating composition contained polyvinylpyrrolidone [LUVISKOL K90 (tradename of BASF, Germany)], having an average molecular weight of 630,000 and applied at a coverage of 1.30 g/m2.
  • the gelatin used in each coating compositions had a gel strength of 250.
  • the sodium carboxymethyl cellulose (CMC) used had a DS value in the range of 6.5 - 8.5 and a 2 % aqueous solution thereof had a viscosity at 25 °C of 25 - 40 mPa.s.
  • CMC carboxymethyl cellulose
  • Such type of CMC is commercially available under the tradename WALOCEL CRT 30 PA/GA sold by Wolf-Walsrode, Germany.
  • each coating composition contained 0.25 parts of di-isooctylsulfosuccinate (wetting agent), and 0.17 parts of formaldehyde on a totality of 1000 parts by volume of coating composition ready for coating.
  • the image-receiving elements containing said coating compositions 1 to 12 before use in ink jet printing were first conditioned for at least 2 hours at 25°C and 30% relative humidity (RH), and then a test image was applied thereon by ink jet.
  • the application of the ink proceeded with a Hewlett-Packard DeskJet 500C (tradename) multicolour printer operating with aqueous coloured inks cyan, magenta and yellow.
  • the ink absorbency was evaluated as follows : an ink jet print in the form of several solid area (blocks) applied with colored inks (yellow, magenta and cyan) and black ink was made on the image receiving materials, but so that there was a large lapse of time between successiveively numbered blocks of the applied inks. Immediately after finishing a print, the inked side was put into contact with a conventional paper for use in dry toner electrophotography. The thus obtained sandwich was conducted through the nip of a roller pair with constant pressure. After peeling off the image receiving material the optical density of the blocks on the paper substrate was measured with a Macbeth TR-1224 (tradename) optical densitometer.
  • the block number corresponding with a reflection density smaller than a given comparison density was determined for each color.
  • a mean value for yellow, magenta, cyan and black is given in Table 1, wherein a smaller value corresponds with a faster drying of the ink whereby risk of image smearing and ink-offset on a next stacked-on printing sheet becomes less. The smaller that value the faster the ink absorption proceeds and consequently the more rapid touch dryness is obtained avoiding image smearing.
  • the ink-receiving layers of the image receiving materials according to the present invention show much smaller drying times than the ink-receiving layers of the image -receiving materials of comparative NON-INVENTION EXAMPLES 9 to 12) especially with respect to the ink absorbency and rapid touch dryness.
  • the ink-receiving layers of the image receiving materials 1 to 12 were also used in an electrophotographic laser printing machine HEWLETT PACKARD LaserJet III (tradename) to form thereon a toner image using a commercial thermoplastic resinous toner containing carbon black.
  • a transparent pressure-adhesive tape (SCOTCH BRAND TAPE) commercially available from 3M Co.
  • U.S.A was sticked to a conditioned (2 hours storage at 22 °C and 30 % relative humidity) image-receiving material being used for transferring thereon an electrophotographically produced "dry" toner image representing different line patterns and solid area of transferred and heat-fixed toner.
  • the tape was pressed by finger nail onto the toner-imaged material for a few seconds and then teared off abruptly in the direction of the image plane, i.e. horizontally.
  • the optical density of toner transferred to the tape was measured and compared with toner transfer onto a commercially available transparent toner receptor film material [TRANSPAREX T787 (tradename of Agfa-Gevaert N.V. Belgium)] having a rating "good” corresponding with practically no torn-off toner.
  • the image-receiving materials of Invention Examples 1 to 8 had the same rating, whereas the image-receiving materials of Non-invention Examples 9, 11 and 12 were rated "bad".
  • the take up of pencil was determined by measuring optical density which for the Invention materials 1 to 8 was above 1.0 measured with MACBETH TR-1224 (tradename) densitometer and was assessed to be good.
  • An aluminium offset printing plate prepared by the silver complex diffusion reversal (DTR) process as described in Example 1 of US-P 3,989,522 was mounted on a commercial offset printing apparatus A.
  • B. Dick 350 CD (tradename) in which the plate was wet with a lithographic graphic preparation as described in said Example and used in offset printing with a fatty printing ink as described in Example 1 of US-P 3,989,522.
  • Said fatty printing ink is a conventional offset printing ink described in the book "Printing Ink Technology" by E. A. Apps, Leonard Hill [Books] Limited, Edenstreet, London, N.W.
  • Offset printing with said fatty ink did not result in ink-offsetting on successiveively printed sheets of double-side coated printing stock having the composition as defined in present Invention Examples 1 to 8, whereas stain formed by ink-offsetting was found on the rear sides of the Non-invention materials 9, 11 and 12.
  • a polyethylene terephthalate sheet having a thickness of 100 ⁇ m previously being coated at one side with a polyethylene sheet of 75 ⁇ m was laid and laminated with the polyethylene in contact with the imaged image-receiving layer.
  • a hot roll laminator was used for pressing the layers together at a temperature of 110 °C.
  • the image contained in the thus obtained laminate was protected against forgery and could not be peeled apart without destroying the DTR-image contained therein.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Paper (AREA)
  • Ink Jet (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Printing Methods (AREA)
EP19940202686 1994-09-19 1994-09-19 Farbstoffbildempfangselement Expired - Lifetime EP0701902B1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP19940202686 EP0701902B1 (de) 1994-09-19 1994-09-19 Farbstoffbildempfangselement
DE1994607288 DE69407288T2 (de) 1994-09-19 1994-09-19 Farbstoffbildempfangselement
JP26077995A JP3639013B2 (ja) 1994-09-19 1995-09-12 インク像受容材料

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19940202686 EP0701902B1 (de) 1994-09-19 1994-09-19 Farbstoffbildempfangselement

Publications (2)

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EP0701902A1 true EP0701902A1 (de) 1996-03-20
EP0701902B1 EP0701902B1 (de) 1997-12-10

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DE (1) DE69407288T2 (de)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0856414A3 (de) * 1997-01-31 1998-08-26 Konica Corporation Aufzeichnungsblatt für Tintenstrahldruck und Aufzeichnungsverfahren
EP0992846A1 (de) * 1998-10-08 2000-04-12 Agfa-Gevaert N.V. Verfahren zur Herstellung eines Druckvorbereitungs-Bildes durch Tintenstrahlaufaufzeichnung
US6248161B1 (en) 1999-01-11 2001-06-19 Hewlett-Packard Company Preparation of permanent color inks from water-soluble colorants using specific phosphonium salts
EP1138509A3 (de) * 2000-03-28 2001-11-14 Mitsubishi Paper Mills Limited Tintenstrahlaufzeichnungsmaterial und Tintenstrahlaufzeichnungsverfahren
EP1060901A3 (de) * 1999-06-18 2002-01-30 Eastman Kodak Company Bildaufzeichnungselement für Tintenstrahltinte
US6460957B1 (en) 1998-08-10 2002-10-08 Agfa-Gevaert Use of an ink jet image as prepress intermediate
WO2003106520A1 (en) * 2002-06-12 2003-12-24 Meadwestvaco Corporation Cationic core-shell particles with acid-swellable shells
EP1849618A1 (de) 2006-04-27 2007-10-31 FUJIFILM Manufacturing Europe B.V. Quervernetzte Polymerblätter und ihre Herstellungsverfahren
CN117551382A (zh) * 2024-01-11 2024-02-13 富维薄膜（山东）有限公司 一种涂布料及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008238737A (ja) * 2007-03-28 2008-10-09 Fujifilm Corp 感熱転写受像シート及びその製造方法
JP5580571B2 (ja) * 2009-11-05 2014-08-27 三菱製紙株式会社 インクジェット記録材料の製造方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994020303A2 (en) * 1993-03-02 1994-09-15 Mitsubishi Paper Mills Limited Ink jet recording sheet

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994020303A2 (en) * 1993-03-02 1994-09-15 Mitsubishi Paper Mills Limited Ink jet recording sheet

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0856414A3 (de) * 1997-01-31 1998-08-26 Konica Corporation Aufzeichnungsblatt für Tintenstrahldruck und Aufzeichnungsverfahren
US6153305A (en) * 1997-01-31 2000-11-28 Konica Corporation Recording sheet for ink-jet recording and ink jet recording method
US6460957B1 (en) 1998-08-10 2002-10-08 Agfa-Gevaert Use of an ink jet image as prepress intermediate
EP0992846A1 (de) * 1998-10-08 2000-04-12 Agfa-Gevaert N.V. Verfahren zur Herstellung eines Druckvorbereitungs-Bildes durch Tintenstrahlaufaufzeichnung
US6248161B1 (en) 1999-01-11 2001-06-19 Hewlett-Packard Company Preparation of permanent color inks from water-soluble colorants using specific phosphonium salts
EP1060901A3 (de) * 1999-06-18 2002-01-30 Eastman Kodak Company Bildaufzeichnungselement für Tintenstrahltinte
EP1138509A3 (de) * 2000-03-28 2001-11-14 Mitsubishi Paper Mills Limited Tintenstrahlaufzeichnungsmaterial und Tintenstrahlaufzeichnungsverfahren
US6589635B2 (en) 2000-03-28 2003-07-08 Mitsubishi Paper Mills, Limited Ink-jet recording material and ink-jet recording method
WO2003106520A1 (en) * 2002-06-12 2003-12-24 Meadwestvaco Corporation Cationic core-shell particles with acid-swellable shells
EP1849618A1 (de) 2006-04-27 2007-10-31 FUJIFILM Manufacturing Europe B.V. Quervernetzte Polymerblätter und ihre Herstellungsverfahren
CN117551382A (zh) * 2024-01-11 2024-02-13 富维薄膜（山东）有限公司 一种涂布料及其制备方法
CN117551382B (zh) * 2024-01-11 2024-04-02 富维薄膜（山东）有限公司 一种涂布料及其制备方法

Also Published As

Publication number Publication date
DE69407288T2 (de) 1998-07-09
DE69407288D1 (de) 1998-01-22
JP3639013B2 (ja) 2005-04-13
JPH08156398A (ja) 1996-06-18
EP0701902B1 (de) 1997-12-10

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