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WO2001070508A2 - Preparation d'images emettrices de lumiere, tres reflechissantes, et/ou d'apparence metallique sur une surface de substrat - Google Patents

Preparation d'images emettrices de lumiere, tres reflechissantes, et/ou d'apparence metallique sur une surface de substrat Download PDF

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Publication number
WO2001070508A2
WO2001070508A2 PCT/US2001/008816 US0108816W WO0170508A2 WO 2001070508 A2 WO2001070508 A2 WO 2001070508A2 US 0108816 W US0108816 W US 0108816W WO 0170508 A2 WO0170508 A2 WO 0170508A2
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WO
WIPO (PCT)
Prior art keywords
acid
substrate
poly
opaque coating
polybase
Prior art date
Application number
PCT/US2001/008816
Other languages
English (en)
Other versions
WO2001070508A3 (fr
Inventor
Asutosh Nigam
Original Assignee
Sri International
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
Application filed by Sri International filed Critical Sri International
Priority to DE60102081T priority Critical patent/DE60102081T2/de
Priority to JP2001568739A priority patent/JP2003527984A/ja
Priority to AT01918836T priority patent/ATE259719T1/de
Priority to CA002403469A priority patent/CA2403469A1/fr
Priority to EP01918836A priority patent/EP1274586B1/fr
Priority to AU2001245864A priority patent/AU2001245864A1/en
Publication of WO2001070508A2 publication Critical patent/WO2001070508A2/fr
Publication of WO2001070508A3 publication Critical patent/WO2001070508A3/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0029—Formation of a transparent pattern using a liquid marking fluid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44F—SPECIAL DESIGNS OR PICTURES
    • B44F1/00—Designs or pictures characterised by special or unusual light effects
    • B44F1/08—Designs or pictures characterised by special or unusual light effects characterised by colour effects
    • B44F1/10—Changing, amusing, or secret pictures
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/001—Special chemical aspects of printing textile materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06Q—DECORATING TEXTILES
    • D06Q1/00—Decorating textiles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • 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
    • B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
    • 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
    • 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
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the present invention relates generally to compositions and methods for preparing images on substrates, and more particularly relates to compositions and methods for the preparation of light-emitting, highly reflective, and/or metallic-looking images on glossy, light emitting, reflective or luminescent substrates.
  • the invention also relates to substrates having light-emitting, highly reflective and/or metallic looking images thereon.
  • U.S. Patent No. 5,656,331 to Kline describes a printed substrate having a metallic finish where the metallic appearance is achieved by applying a first layer having the desired final color pattern, a second layer comprising a moire dispersion pattern and a third coating of water pearl.
  • Complex thermal processing methods have also been used.
  • U.S. Patent No. 5,564,843 to Kawaguchi describes a method of producing a reflective image by printing the image on the surface of a film using a thermal print head and then affixing the film onto a reflective surface.
  • the present invention features a novel process for producing a light-emitting, glossy, reflective or metallic-looking image utilizing opaque coating compositions on a reflective, glossy, or luminescent substrate wherein the original surface of the substrate is initially masked but, after contact with a recording liquid, becomes transparent, revealing the glossy, reflective or luminescent substrate through the contacted, coated area.
  • the opaque coating compositions are composed of a mixture of a polyacid and a polybase and may be used to treat a substrate either during or after manufacture. Substrates treated with the present opaque coating compositions can be used to yield high quality light-emitting, glossy, reflective, or metallic-looking images.
  • It is a primary object of the invention to provide a method for producing a light- emitting, glossy, reflective or metallic-looking image comprising the steps of applying an opaque coating composition to the surface of a light emitting, glossy, reflective or luminescent substrate and contacting the coated substrate with a recording liquid, wherein the opaque coating comprises a mixture of a polyacid and a polybase.
  • Another object of the invention is to provide opaque coatings for the treatment of glossy, reflective or luminescent substrates, which provide a light-emitting, reflective, glossy, or metallic-looking image when contacted with a recording liquid.
  • a further object of the invention is to provide an opaquely coated reflective or luminescent substrate wherein the opaque coating provides a light-emitting, reflective, glossy, or metallic-looking image when contacted with a recording liquid.
  • a process for producing a light-emitting, reflective, glossy, or metallic-looking image comprising the steps of (1) applying an opaque coating composition to the surface of a substrate wherein the surface is selected from the group consisting of glossy surfaces, reflective surfaces and luminescent surfaces and (2) contacting the coated substrate with a recording liquid, wherein the opaque coating composition is such that it becomes transparent upon contact with a recording liquid.
  • a substrate having a surface selected from the group consisting of glossy surfaces, reflective surfaces and luminescent surfaces, coated with an opaque coating composition that becomes transparent upon contact with a recording liquid.
  • a process is provided for producing a light-emitting, glossy, reflective or metallic-looking image comprising the steps of (1) forming a preselected image or color scheme on top of the surface of a substrate having a surface selected from the group consisting of reflective surfaces and luminescent surfaces, (2) applying an opaque coating composition on top of the preselected image or color scheme, and (3) applying a recording liquid to the coated substrate, wherein the opaque coating composition becomes transparent upon contact.
  • a substrate having a surface selected from the group consisting of reflective surfaces, glossy surfaces, and luminescent surfaces, having a preselected image or color scheme on the surface and additionally coated with an opaque coating composition that becomes transparent upon contact with a recording liquid.
  • Aqueous based ink refers to ink composed of an aqueous carrier medium and a colorant, such as dye or pigment dispersions.
  • An aqueous carrier medium is composed of water or a mixture of water and one or more water-soluble organic solvents. Exemplary aqueous based ink compositions are described in detail below.
  • Colorant as used herein is meant to encompass dyes, pigments, stains, and the like compatible for use with the opaque coating compositions of the invention.
  • coating as used herein to refer to the application of an opaque coating composition of the invention to a substrate, is intended to include application of a coating to a substrate surface with the composition.
  • organic solvent is used herein in its conventional sense to refer to a liquid organic compound, typically a monomeric organic material in the form of a liquid, preferably a relatively non- viscous liquid, the molecular structure of which contains hydrogen atoms, carbon atoms, and optionally other atoms as well, and which is capable of dissolving solids, gases or liquids.
  • fluid resistance is used herein to describe the resistance of a printed substrate to penetration by a fluid, with the term “water resistance” specifically referring to resistance of a substrate to penetration by water.
  • luminescence is meant light emitted by radiative dissipation from an electronically excited state of a molecule.
  • fluorescence is used to signify luminescence between states of identical multiplicity, typically between the lowest excited singlet state and the singlet ground state of the molecule.
  • phosphorescence is used to signify luminescence between states of differing multiplicity, typically between the lowest excited triplet state and the singlet ground state.
  • transparent is used herein to signify a material capable of transmitting light so that objects or images can be seen as if there were no intervening material.
  • “Textile” or “textile substrate” as used herein refers to any cellulose-based or non- cellulose based textile material suitable for use as a printing substrate in connection with the coatings and/or methods of the invention. In general, where appropriate, the textile substrate has been sized, internally and/or externally, prior to application of the compositions of the invention.
  • treated textile substrate coated textile substrate
  • treated textile substrate treated textile substrate
  • coated textile substrate treated textile substrate
  • coated textile substrate coated textile substrate
  • coated textile substrate coated textile substrate
  • the opaque coating composition is applied to the substrate in a separate coating operation prior to image formation, typically in amounts ranging from fifty (50) to five hundred (500) pounds per ton of substrate.
  • recording liquid is used herein to signify any ink, aqueous or solvent based, ink-gel, gel, or solution that is capable of rendering the opaque coating composition transparent or of increasing the amount of light capable of being emitted through the opaque coating composition.
  • opaque is used herein to signify a material that is not transparent or is only slightly translucent, so that images either cannot be seen through it at all or cannot be seen as if there were no intervening material.
  • the opaque coating may or may not contain a color component.
  • alkyl refers to a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, «-propyl, isopropyl, n- butyl, isobutyl, t-butyl. octyl, decyl, tetradecyl.
  • lower alkyl intends an alkyl group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
  • alkylene refers to a difunctional, branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, including without limitation methylene, ethylene, ethane- 1,1-diyl, propane-2,2-diyl, propane- 1,3-diyl, butane- 1, 3 -diyl, and the like.
  • “Lower alkylene” refers to an alkylene group of 1 to 6 carbon atoms.
  • alkenyl refers to a branched or unbranched hydrocarbon group of 2 to 24 carbon atoms containing at least one carbon-carbon double bond, such as ethenyl, o-propenyl, isopropenyl, /?-butenyl, isobutenyl, t-butenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl and the like.
  • Preferred alkenyl groups herein contain 2 to 12 carbon atoms and 2 to 3 carbon-carbon double bonds.
  • cycloalkenyl intends a cyclic alkenyl group of 3 to 8, preferably 5 or 6, carbon atoms.
  • alkenylene refers to a difunctional branched or unbranched hydrocarbon chain containing from 2 to 24 carbon atoms and at least one carbon-carbon double bond.
  • alkoxy intends an alkyl group bound through a single, terminal ether linkage; that is, an “alkoxy” group may be defined as -OR where R is alkyl as defined above.
  • a "lower alkoxy” group intends an alkoxy group containing 1 to 6 carbon atoms.
  • aryl refers to an aromatic species containing 1 to 3 aromatic rings, either fused or linked, and either unsubstituted or substituted with 1 or more substituents typically selected from the group consisting of lower alkyl, halogen, -NH 2 and - NO 2 . Preferred aryl substituents contain 1 aromatic ring or 2 fused or linked aromatic rings.
  • Halo or “halogen” refers to fluoro, chloro, bromo or iodo, and usually relates to halo substitution for a hydrogen atom in an organic compound.
  • poly- as in “polyacid” or “polybase” is intended to mean that the compound so designated has two or more acidic groups or two or more basic groups, respectively.
  • polyacid herein encompasses a diacid
  • polybase herein encompasses a dibase.
  • polymer is used herein in its conventional sense to refer to a compound having two or more monomer units, and is intended to include homopolymers as well as copolymers.
  • monomer is used herein to refer to compounds that are not polymeric.
  • the present invention is based upon the discovery that an opaque coating composition comprising a mixture of a polyacid and a polybase is effective in masking the original surface of a glossy, reflective or luminescent substrate when coated or printed thereon, but upon contact with a solution or ink, e.g., upon printing, becomes more transparent, thereby increasing the amount of light reflected or emitted from the substrate's surface, revealing the glossy, reflective or luminescent substrate through the contacted area.
  • Any conventional printing method may be used to form the image, e.g., printing, such as, ink-jet printing, including drop-on-demand and continuous printing, off-set printing, gravure printing, flexographic printing; brush stenciling; spray painting, etc. All that is required is that a recording liquid be contacted with the opaque coating composition to form the image.
  • the method is even adaptable to non-mechanical imaging methods, e.g., drawing, handwriting and painting with aqueous inks, markers, or pens.
  • the coated substrates react rapidly with a number of colorants. Because colorants react quickly with the opaque coating, the recording liquid contacted, treated substrates are fast drying and do not require a separate curing step. This fast-drying characteristic provides for images that are "non-sticky," thus allowing the printed substrate to be handled immediately after formation. Processes for producing light-emitting, reflective or metallic- looking images using opaque coating compositions, the opaque coating compositions themselves, substrates coated with the opaque coatings, described herein, and other features of the invention are described in greater detail below.
  • the invention features a method for producing a light-emitting, glossy, reflective or metallic-looking image on a substrate surface by first applying to a glossy, reflective or luminescent substrate surface an opaque coating composition comprising a mixture of a polyacid and a polybase and then contacting the treated substrate with a recording liquid, e.g., applying an ink or solution.
  • the recording liquid comprised an ink that contains a colorant having ionizable, nucleophilic or otherwise reactive groups capable of reacting with the opaque coating agent in the opaque coating composition.
  • Non-ionizable colorants such as dispersed pigment type ink are also suitable.
  • the substrate may be comprised of a material that inherently provides a light-emitting, reflective, glossy, or luminescent surface, or a substrate that does not have these characteristics may be used so long as it is coated or treated with a light-emitting, reflective, glossy, or luminescent material to provide the desired surface.
  • the substrates may be flexible or rigid, porous or nonporous, and cellulosic or non-cellulosic.
  • Suitable substrates with which the present compositions and methods can be used include, but are not limited to, paper, polymeric substrates, textiles, inorganic substrates, metallic sheets, laminates, foil laminated polymer sheets, metallized polymer sheets, and the like.
  • specific substrates include, for example: polymeric films, sheets, coatings, and solid blocks, comprised of, for example, polyesters (including "MYLAR " flexible film), vinyl polymers, polysulfones, polyurethanes, polyacrylates, polyimides, or the like; metallic films, sheets, coatings, foils and solid blocks, comprised of, for example, aluminum, brass, copper, or the like; inorganic substrates in the form of films, sheets, coatings, objects, and solid blocks, comprised, of, for example, glass, metal oxides, silicon-containing ceramics, and the like; textiles having a reflective or luminescent surface; and laminates such as a paper/polymeric film, polymeric film/metal foil laminate, or paper/metal
  • any substrate having a light emitting, reflective, glossy, or luminescent surface can be used in conjunction with the invention to produce a glossy, reflective , light emitting, or metallic-looking image when contacted with a recording liquid.
  • the substrate When the substrate is not itself, light-emitting, reflective, glossy, or luminescent, it must be treated to provide a light-emitting, reflective, glossy, or luminescent surface.
  • a layer of a metallic foil or reflective polymeric film can be laminated to the substrate, or the substrate surface may be coated or treated with reflective or luminescent materials, e.g., luminescent dyes from the fluorescein, rhodamine, pyrene and porphyrin families. After such a treatment, the light-emitting, reflective, or luminescent surface may be coated with a transparent coating that does not interfere with the opaque coating composition.
  • the substrate is comprised of a paper/foil laminate or a polymer film that has been metallized by sputtering or other processes.
  • the paper layer may be formed from any convenient type of printing paper stock of desired weight.
  • the paper substrate is preferably in the form of a flat or sheet structure of variable dimensions. "Paper” is meant to encompass printing paper (e.g., inkjet printing or conventional printing paper such as gravure, litho, etc.), writing paper, drawing paper, and the like, as well as board materials such as cardboard, poster board, Bristol board, and the like.
  • a reflective layer is applied to the paper portion of the substrate by using a suitable coating method such as spraying, to deposit a metal-containing coating onto the paper surface, or by adhering a metallicized sheet such as thin metal foil to the paper surface. While the foil or coating may be applied only in selected areas, it is preferred in most cases to have the entire surface of the paper covered with the reflective layer. Papers with preapplied foil coverings forming paper foils are also available commercially and may be used herein. These commercial paper/foil laminates are available in a range of thicknesses and weights, such that foil papers with any desired degree of flexibility or stiffness can be selected. Those skilled in the art will be readily able to select the appropriate type of paper, foil or paper/foil laminate for use with the desired type and weight of final product to be produced.
  • the substrate is a reflective or glossy textile or a textile that has been treated with a luminescent material.
  • the opaque coating compositions and printing methods of the invention can be used with any textile substrate amenable to use with such coating compositions and methods so long as the textile has a light-emitting, reflective or luminescent surface.
  • Suitable textile substrates for use with the present invention include textiles having natural, synthetic, cellulose-based, or non-cellulose-based fibers or any combination thereof. Exemplary textile substrates include, but are not limited to.
  • textiles having hydroxy group-containing fibers such as natural or regenerated cellulosic fibers (cotton, rayon, and the like); nitrogen group-containing fibers such as polyacrylonitrile; natural or synthetic polyamides (including wool, silk, or nylon); and/or fibers having acid-modified polyester and polyamide groups.
  • the substrates may be additionally pre-treated or after-treated with resins or other substances compatible with the coating compositions and methods of the invention, and may be finished or unfinished.
  • the textile substrate may also be sized prior to application of the opaque coating composition.
  • the present coating compositions may be incorporated into an external sizing process, so that sizing and coating is conducted in a single step.
  • the fibers of the textile substrate may be in any suitable form compatible with the selected image forming process, e.g., loose yarns, or fabrics. Fabrics are a convenient and preferred form.
  • the fibers may be blended with other fibers that are susceptible to treatment with the opaque coating composition of the invention, or with fibers that may prove less susceptible to such treatment.
  • the opaque coating composition is then applied to the light-emitting, reflective, glossy, or luminescent surface.
  • the opaque coating composition may be applied in any conventional manner, e.g.. using a Meyer rod, slot die, roller, knife, dipping, painting, spraying, etc. Generally, coating is accomplished by dip coating, reverse roll coating, extrusion coating, or the like. If the substrate is a paper or thin polymeric film and the coating composition is applied on-machine, in order to achieve acceptable manufacture speeds of about 100 to 2000 feet per minute, preferably 100-1000 feet per minute, it is recommended that the weight of the substrate, e.g., sized paper, be greater than about 30 grams per square meter.
  • the opaque coating compositions are composed of an opaque coating agent that comprises a mixture of a polyacid and a polybase.
  • the coating composition can include components such as film-forming binders, pigments, and other additives.
  • the opaque coating compositions can be readily prepared from commercially available starting materials and/or reagents, are compatible with additional binders or additives, can be used with a variety of substrates, are compatible with a variety of printing methods, including conventional and digital printing methods (particularly ink-jet printing, including drop-on-demand printing and continuous printing), and can also be used with existing commercial manufacturing methods and equipment, including, for example, paper production processes and equipment.
  • the opaque coating composition is inexpensive to prepare, and relatively small amounts are required to provide a coated substrate suitable herein.
  • the opaque coating compositions are also easy to handle due to their solubility in water, and do not require the use of large volumes of organic solvents.
  • the opaque coating agent typically represents approximately 5% to 95%, preferably about 10% to 95%, of the opaque coating composition, based upon total solids weight of the composition after drying.
  • the polyacid and polybase which together represent the "opaque coating agent," may be either monomeric or polymeric. That is, the opaque coating agent may be composed of any suitable combination of: 1) a monomeric polyacid and a monomeric polybase; 2) a polymeric polyacid and a polymeric polybase; 3) a polymeric polyacid and a monomeric polybase; and/or 4) a monomeric polyacid and a polymeric polybase.
  • the opaque coating agent may also be comprised of more than one different type of polyacid or polybase and compositions comprised of, for example, a monomeric polyacid, a monomeric polybase, and a polymeric polybase or a monomeric poly acid, a polymeric polyacid, and a monomeric and/or polymeric polybase and the like are also possible.
  • compositions comprised of, for example, a monomeric polyacid, a monomeric polybase, and a polymeric polybase or a monomeric poly acid, a polymeric polyacid, and a monomeric and/or polymeric polybase and the like are also possible.
  • the selection of these combinations for use as the opaque coating agent in the present compositions will vary according to a variety of factors such as the nature of the substrate to be treated, the colorant to be used in printing on the treated substrate, etc.
  • the relative ratios of the polyacid and polybase within the mixture will also vary according to such factors, but typically the ratio of base to acid is in the range of approximately 0.5: 1
  • the pH of the coating composition having a polyacid/polybase opaque coating agent is generally in the range of about 6- 12, preferably at least about 7.5- 10.
  • the pH is maintained by the addition of appropriate bases such ammonia, primary, secondary, and tertiary alkyl amines, ethanolamines, diamine, and the like.
  • monomeric polyacids will contain two or more carboxylic, sulfonic and/or phosphonic acid groups.
  • Exemplary monomeric polyacids have the structural formula (I)
  • R is selected from the group consisting of alkyl, alkenyl, aryl of 1 to 3 rings which may be fused or linked, and 5- and 6-membered heterocyclic rings having from 1 to 3 heteroatoms selected from N, S and O;
  • L is an alkylene or alkenylene chain containing 1 to 8 carbon atoms;
  • x is 0 or 1 ;
  • y is an integer in the range of 2 to 10 inclusive; and
  • z is 1 , 2 or
  • preferred monomeric polyacids include, but are not necessarily limited to, oxalic acid, maleic acid, succinic acid, methylsuccinic acid, malonic acid, adipic acid, glutaric acid, fumaric acid, dihydroxyfumaric acid, malic acid, mesaconic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-, 1,3- and 1,4- cyclohexane dicarboxylic acids, 1,2,3-cyclohexane tricarboxylic acid, 1,2,4-cyclohexane tricarboxylic acid, 1 ,3,5-cyclohexane tricarboxylic acid, 1.2- and 1,3-cyclopentane dicarboxylic acids, citric acid, tartaric acid, dihydroxyterephthalic acid, 1,2,3-, 1,2,4- and 1,2,5-benzene tricarboxylic acids, tricarballylic acid, 1,
  • R 1 and R 2 are hydrogen, alkyl, alkoxy, or hydroxyl-substituted alkoxy, and R, L, x, y and z are as defined with respect to the monomeric polyacid.
  • monomeric polybases include, but are not limited to, ethylenediamine, 1,2-propane diamine, 1,3-propanediamine.
  • 1,2,3-triaminopropane cis-1,2- cyclohexanediamine, tr ⁇ r ⁇ -l,2-cyclohexanediamine, l,3-bis(aminomethyl)cyclohexane, -, m- and /3-phenylenediamine, tetramethyl o-, m- and / 3-phenylenediamine, hexamethylenediamine, hexamethylenetetraamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, pentamethyl diethylenetriamine, tris(2- aminoethyl)amine, 1,1,4,7,10,10-hexamefhyl triethylenetetramine, tetramethyl-/?- phenylenediamine, tetramethylethylenediamine, triethylenetetraamine, 4,4'-bipyridyl, and combinations thereof
  • the polymeric polyacids contain carboxylic, sulfonic and/or phosphonic acid groups, but most preferably contain carboxylic acid groups.
  • Examples of polymeric polyacids include, without limitation, poly(acrylic acid), poly(acrylonitrile-acrylic acid), poly(styrene-acrylic acid), poly(butadiene-acrylonitrile acrylic acid), poly(butylacrylate- acrylic acid), poly(ethyl acrylate-acrylic acid), poly(methacrylate-acrylic acid), poly(methyl methacrylate-acrylic acid), poly(methyl methacrylate-styrene-acrylic acid), poly(vinyl pyrrolidone-acrylic acid), poly(styrene-co-maleic acid), poly(methyl methacrylate-styrene- co-maleic), poly(ethylene-propylene-acrylic acid), poly(propylene-acrylic acid), alginic acid, phytic acid, and combinations thereof.
  • the polymeric polybases comprise nitrogenous polymers that may have pendant primary, secondary or tertiary amine groups and/or nitrogenous moieties in the backbone, i.e., -NH- or -NX- groups, where X is typically alkyl of 2 to 8 carbon atoms, lower acyl, or - (CH 2 ) m R 3 wherein m is an integer in the range of 1 to 10 and R 3 is hydroxyl or -OR 4 wherein R 4 is C ] -C 4 alkyl.
  • the basic polymer may be a copolymer containing first monomer units having the structure -CH 2 -CH 2 -NH-, second monomer units having the structure -CH 2 -CH 2 -NX- wherein X is as defined above, and optionally third monomer units having the structure -CH 2 -CH(COOH)-.
  • Exemplary polymeric polybases include, but are not limited to, polyethyleneimine, polyvinylpyridine, polyallylamine (including N-alkylated and N,N-dialkylated polyallylamines), polyvinylaziridine, polyimidazole, polylysine, chitosan, poly(amino and alkylated amino)ethylenes, ethoxylated polyethyleneimine, propoxylated polyethyleneimine, polyvinylpyrrolidone, dimefhylaminoacrylate, polyvinylpyrrolidone diethylaminoacrylate, vinyl pyrrolidone-dimethylaminopropyl methacrylamide copolymer and combinations thereof.
  • the opaque coating composition preferably includes a film-forming binder, i.e., a substance that provides for improved strength of a substrate upon application thereto.
  • a film-forming binder i.e., a substance that provides for improved strength of a substrate upon application thereto.
  • Film-forming binders used in connection with the compositions of the invention include any film-forming binders that are compatible with the selected opaque coating agent and other components of the coating composition.
  • Exemplary film-forming binders include, but are not necessarily limited to: polysaccharides and derivatives thereof, e.g., starches, cellulosic polymers, dextran and the like; polypeptides (e.g., collagen and gelatin); and synthetic polymers, particularly synthetic vinyl polymers such as poly(vinyl alcohol), poly(vinyl phosphate), poly(vinyl pyrrolidone).
  • vinyl-pyrrolidone-vinyl acetate copolymers vinyl acetate-acrylic acid copolymers, vinyl alcohol-vinyl acetate copolymers, vinyl pyrrolidone-styrene copolymers, and poly(vinyl amine), synthetic acrylate polymers and copolymers such as poly(acrylic acid-co-methacrylate), poly(vinyl-co-acrylate), poly(vinylpyrrolidone-co-dimethylaminopropyl-methacrylamide), and the like, and water- soluble or water-dispersible polyesters such as sulfopolyesters (e.g., as available from Eastek).
  • Polysaccharide binders represent one category of suitable film-forming binders for use herein. Suitable starches may be any of a variety of natural, converted, and synthetically modified starches. Exemplary starches include, but are not necessarily limited to, starch (e.g., SLS-280 (St.
  • cationic starches e.g., Cato-72 (National Starch), hydroxyalkylstarch, wherein the alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from about 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl, or the like (e.g., hydroxypropyl starch #02382 (PolySciences, Inc.), hydroxyethyl starch #06733 (PolySciences, Inc.), Penford Gum 270 and 280 (Penford), and Film-Kote (National Starch)), starch blends (see, e.g., U.S.
  • ASA alkyl or alkenyl succinic anhydride
  • OSA 1- octenyl succinic anhydride
  • the film-forming binder can also be a synthetically produced polysaccharide, such as a cationic polysaccharide esterified by a dicarboxylic acid anhydride (see, e.g., U.S. Pat. No. 5,647,898).
  • Additional saccharide binders include cellulosic materials such as alkyl celluloses, aryl celluloses, hydroxy alkyl celluloses, alkyl hydroxy alkyl celluloses, hydroxy alkyl celluloses, dihydroxyalkyl cellulose, dihydroxyalkyl cellulose, hydroxy alkyl hydroxy alkyl cellulose, halodeoxycellulose, amino deoxycellulose, dialkylammonium halide hydroxy alkyl cellulose, hydroxyalkyl trialkyl ammonium halide hydroxyalkyl cellulose, dialkyl amino alkyl cellulose, carboxy alkyl cellulose salts, cellulose sulfate salts, carboxyalkylhydroxyalkyl cellulose and the like).
  • cellulosic materials such as alkyl celluloses, aryl celluloses, hydroxy alkyl celluloses, alkyl hydroxy alkyl celluloses, hydroxy alkyl celluloses, dihydroxyalkyl cellulose, dihydroxyalkyl cellulose
  • Still additional film-forming binders of this type include dextran (e.g., dialkyl aminoalkyl dextran, amino dextran, and the like), carrageenan, Karaya gum, xanthan, guar and guar derivatives, (e.g., carboxyalkyl hydroxyalkyl guar, cationic guar, and the like), and gelatin.
  • Additional exemplary film-forming binders include resins (e.g., such as formaldehyde resins such as melamine-formaldehyde resin, urea-formaldehyde resin, alkylated urea-formaldehyde resin, and the like), ionic polymers (e.g., poly(2-acrylamide-2- methyl propane sulfonic acid, poly(N,N-dimethyl-3,5-dimethylene piperidinium chloride, poly(methylene-guanidine), and the like), maleic anhydride and maleic acid-containing polymers (e.g., styrene-maleic anhydride copolymers, vinyl alkyl ether-maleic anhydride copolymers, alkylene-maleic anhydride copolymers, butadiene-maleic acid copolymers, vinylalkylether-maleic acid copolymers, alkyl vinyl ether-maleic acid esters, and the like), acrylamide-containing poly
  • any of the above exemplary film-forming binders can be used in any effective relative amounts, although typically the film-forming binder, if present, represents approximately 1 wt.% to 50 wt.%, preferably 1 wt.% to 25 wt.%, most preferably 1 wt.% to 15 wt.% of the opaque coating composition, after drying on a substrate. Starches and latexes are of particular interest because of their availability and applicability to a variety of substrates.
  • Additional components of the opaque coating composition may be present, and include, but are not necessarily limited to, inorganic fillers, anti-curl agents, surfactants, plasticizers, humectants, UN absorbers, optical brighteners, light fastness enhancers, polymeric dispersants, dye mordants and leveling agents, as are commonly known in the art.
  • Preferred additives are optical brighteners, which generally represents approximately 0.0 wt.% to 2.0 wt.% of the coating composition after drying on a substrate. Illustrative examples of such additives are provided in U.S. Patent ⁇ os. 5,279,885 and 5,537,137.
  • the opaque coating compositions may also include a crosslinking agent such as zirconium acetate, ammonium zirconium carbonate, or the like, for intramolecular and/or intermolecular crosslinking of the opaque coating agent, and/or a chelating agent such as boric acid.
  • a crosslinking agent such as zirconium acetate, ammonium zirconium carbonate, or the like, for intramolecular and/or intermolecular crosslinking of the opaque coating agent, and/or a chelating agent such as boric acid.
  • Colorants e.g., pigments, dyes, or other colorants, may also be present in the opaque coating composition.
  • the opaque coating composition can be prepared in an organic solvent, it is preferably provided in an aqueous liquid vehicle wherein small amounts of a water-soluble organic solvent may be present.
  • the aqueous liquid vehicle will generally be water, although other inorganic compounds which are either water-soluble or water miscible may be included as well. It may on occasion be necessary to add a solubilizing compound during preparation of the coating composition so that the components dissolve in the aqueous liquid vehicle, e.g., an inorganic base such as ammonia and/or an organic amine.
  • Suitable organic amines include lower alkyl-substituted amines such as methylamine, dimethylamine, ethylamine, and trimethylamine, as well as ethanolamine, diethanolamine, triethanolamine, and substituted ethanolamines, typically lower alkyl-substituted ethanolamines such as N-methyl and N,N-dimethyl ethanolamines, and morpholine.
  • Such compounds are also useful for bringing the pH into the desired range for basic formulations as discussed in the preceding section, and, if present, will generally represent not more than about 20 wt.%) of the composition, and in most cases will represent not more than about 10 wt.% of the composition.
  • C. IMAGE FORMATION Once an opaquely coated, reflective, glossy, or luminescent substrate is produced, the opaquely coated substrate is contacted with an ink or other solution to render the coating transparent; in a preferred embodiment, an image forming step using an aqueous or solvent based ink is employed to impart desired colors and form a light-emitting, reflective, glossy,or metallic-looking image.
  • the image forming step may employ any of a variety of printing techniques, including inkjet printing, laserjet printing, flexographic printing, gravure printing and the like, or may employ the use of a writing instrument such as a pen, marker, gel pen, rollerball pen, ballpoint pen, and the like.
  • the image forming process involves applying, in an imagewise pattern, a recording liquid to a coated substrate of the invention.
  • Inkjet printing processes suitable for the method of the invention are well known in the art; see, for example, U.S. Patent Nos. 4,601,777; 4,251,824; 4,410,899; 4,412.224; and 4,532,530.
  • Thermal ink transfer printers that use dye sublimation process can also form the light-emitting, reflective or metallic-looking images.
  • Hot melt type inkjet printers such as Tektronix inkjet printers that use inks formed of low melting solids are also suitable.
  • the light-emitting, reflective or metallic-looking images can also be produced using a variety of other printing and imaging processes, such as offset printing, printing with pen plotters, drawing, handwriting, painting with ink pens, brush stenciling, spray painting, and the like.
  • inks are used in the formation of the image on the treated substrates of the invention.
  • the ink may be any suitable ink containing a colorant, e.g., a pigment, dye, or stain, having one or more reactive groups suitable for reacting, either covalently or ionically, with a colorant-reactive component of the opaque coating agent present on the treated substrate.
  • a colorant e.g., a pigment, dye, or stain
  • Aqueous and solvent-based, dye sublimation, or hot melt inks are all acceptable. The selection of the specific ink and colorant will vary with the colorant- reactive component of the image-enhancing agent.
  • preferred colorants for use in forming an image on a substrate treated with the present image-enhancing compositions are those containing one or more ionizable, nucleophilic or otherwise reactive moieties.
  • Particularly preferred colorants contained in the inks useful with the invention are thus dyes containing acidic groups (e.g., carboxylate, phosphonate, sulfonate or thiosulfonate moieties), basic groups (e.g., unsubstituted amines or amines substituted with 1 or 2 alkyl, typically lower alkyl, groups), and/or nucleophilic or otherwise reactive moieties (e.g., hydroxyl, sulfhydryl, cyano or halo).
  • acidic groups e.g., carboxylate, phosphonate, sulfonate or thiosulfonate moieties
  • basic groups e.g., unsubstituted amines or amines substituted with 1 or 2 alky
  • the selection of the ink will depend upon the requirements of the specific application, such as desired surface tension, viscosity, drying time, and the like. If aqueous ink is selected, the aqueous liquid vehicle of inks suitable for use in the invention will generally be water, although other nonorganic compounds which are either water-soluble or water miscible may be included as well.
  • the colorant may be dissolved, dispersed or suspended in the aqueous liquid vehicle, and is present in an amount effective to provide the dried ink with the desired color and color intensity.
  • the dye is contained in a carrier medium composed of ink and a water-soluble organic solvent.
  • representative solvents include polyols such as polyethylene alcohol, diethylene glycol, propylene glycol, and the like. Additional solvents are simple alcohols such as ethanol, isopropanol and benzyl alcohol, and glycol ethers, e.g., ethylene glycol monomethyl ether, diethylene glycol monoethyl ether.
  • Representative examples of water-soluble organic solvents are described in U.S. Patent 5,085,698 and U.S. Patent No. 5,441,561.
  • Suitable water soluble organic solvents include, but are not limited to, C,. 5 -alkanols, e.g.
  • alkylene glycols or thioglycols containing a C 2 -C 6 alkylene group e.g., ethylene glycol, propylene glycol, butylene glycol, pentylene glycol and hexylene glycol
  • poly(alkylene-glycol)s and poly(alkylene- thioglycol)s e.g., diethylene glycol, thiodiglycol, polyethylene glycol and polypropylene glycol
  • lower alkyl glycol and polyglycol ethers e.g., 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)-thanol, 2-(2-butoxyethoxy)ethanol, 3-butoxypropan-l -ol, -[2-(2-methoxyethoxyethoxy
  • Water insoluble organic solvents may also be used. Suitable water insoluble organic solvents include, but are not limited to, aromatic hydrocarbons, e.g., toluene, xylene, naphthalene, tetrahydronaphthalene and methyl naphthalene; chlorinated aromatic hydrocarbons, e.g., chlorobenzene, fluorobenzene, chloronaphthalene and bromonaphthalene; esters, e.g., butyl acetate, ethyl acetate, methyl benzoate, ethyl benzoate, benzyl benzoate, butyl benzoate, phenylethyl acetate, butyl lactate, benzyl lactate, diethyleneglycol dipropionate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di(2-ethylhexyl)phthalate; alcohols having six or more carbon atoms,
  • suitable colorants include, but are not limited to, the following: Dispersol Blue Grains (Zeneca, Inc.), Duasyn Acid Blue (Hoechst Celanese), Duasyn Direct Turquoise Blue (Hoechst Celanese), Phthalocyanine blue (C.I. 74160), Diane blue (C.I. 21180), Pro-jet Cyan 1 (Zeneca, Inc.), Pro-jet Fast Cyan 2 (Zeneca, Inc.), Milori blue (an inorganic pigment equivalent to ultramarine) as cyan colorants; Dispersol Red D-B Grains (Zeneca, Inc.), Brilliant carmine 6B (C.I.
  • Pro-jet magenta 1 (Zeneca, Inc.), Pro-jet Fast magenta 2 (Zeneca, Inc.), Brilliant Red F3B-SF (Hoechst Celanese), Red 3B-SF (Hoechst Celanese), Acid Rhodamine (Hoechst Celanese), Quinacridone magenta (C.I. Pigment Red 122) and Thioindigo magenta (C.I. 73310) as magenta colorants; Dispersol Yellow D-7G 200 Grains (Zeneca, Inc.), Brilliant yellow (Hoechst Celanese), Pro-jet yellow 1 (Zeneca, Inc.). Pro-jet Fast Yellow 2 (Zeneca, Inc.), benzidine yellow (C.I.
  • Specific and preferred black colorants include Acid Black 48 (Aldrich), Direct Black 58756 A (Crompton & Knowles), BPI Molecular Catalytic Gray (Brain Power), Fasday Cool Gray (Hunter Delator), Dispersol Navy XF Grains (Zeneca, Inc.), Dispersol Black CR-N Grains (Zeneca, Inc.), Dispersol Black XF Grains (Zeneca, Inc.), Disperse Black (BASF), Color Black FW18 (Degussa), Color Black FW200 (Degussa), Hostafine Black TS (Hoechst Celanese), Hostafine Black T (Hoechst Celanese), Duasyn Direct Black (Hoechst Celanese), Pro-jet Black 1 (Zeneca, Inc.) and Pro-jet Fast Black 2 (Zeneca, Inc.).
  • Other suitable colorants are disclosed in U.S. Patent Nos. 4,761,180, 4,836,851, 4,994,110 and 5,098,474.
  • the light-emitting, reflective or metallic- looking image is produced by having the image or color scheme printed on the reflective or luminescent layer prior to the coating with the opaque coating composition.
  • the light- emitting, reflective or metallic-looking image is generated by contacting the coated substrate with an aqueous solution that may optionally contain a dye or colorant, as discussed above.
  • aqueous solution may optionally contain a dye or colorant, as discussed above.
  • Embodiments of this type have utility as art or craft materials.
  • the coated substrates of the invention may be used as "magic" papers and the like for children, wherein a hidden image appears on contact with a solution.
  • Joncryl 62 Joncryl 62 , arcrylic polymer (SC Johnson);
  • Epomine 1050 Epomine 1050 , polyethylene imine (Nippon Shokubai, Co Ltd.);
  • Acusol 445 Acusol 445 , acrylate copolymer (Rohm & Haas Co.)
  • Alcosperse 409 Alcosperse 409 ,polyacrylic acid (Alco Chemical);
  • Surfynol SE-F Surfynol SE-F , surfacant (Air Product);
  • Silica Aerosil MOX 170 , fumed silica (Degussa).
  • the above given general procedure can also be used as two component system and components can be mixed prior to use.
  • the following components were obtained by blended the listed constituents for 10 minutes at 4000 rpm in a high shear mixer. Each component was then labeled and stored in a separate vial.
  • Component A Component B J Joonnccrryyll 6622 6 622..55gg Lupasol SKA 20.0g
  • Alcosperse 409 10.0g Liquor Ammonia 30. Og
  • Example 1 The procedure of Example 1 was repeated using the following using a coating solution containing the following components:
  • Example 1 The procedure of Example 1 was repeated using a coating solution containing the following components:
  • Example 1 The procedure of Example 1 was repeated using a coating solution containing the following components:
  • Table 1 summarizes exemplary opaque coating compositions in accordance with the invention.
  • Each of the representative formulations was prepared using the methods described in Example 1 and used to coat metallized sheets, which were then printed on using an aqueous ink and an inkjet printer. The resulting images so prepared were found to have the metallic-looking appearance described herein.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Paints Or Removers (AREA)
  • Electroluminescent Light Sources (AREA)
  • Illuminated Signs And Luminous Advertising (AREA)
  • Printing Methods (AREA)
  • Laminated Bodies (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Chemically Coating (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

L'invention concerne des caractéristiques et des compositions permettant de produire une image d'apparence métallique sur un substrat qui possède une surface réfléchissante ou luminescente. Le procédé utilise une composition de revêtement opaque contenant un agent de revêtement opaque, constitué d'un mélange de polyacide et de polybase. Lorsqu'on l'applique sur un substrat émetteur de lumière, réfléchissant ou luminescent, la composition de revêtement opaque masque au moins partiellement la surface dudit substrat, et devient de plus en plus translucide ou transparente au contact d'un liquide d'enregistrement, tel que l'encre, ce qui révèle une surface émettrice de lumière, réfléchissante ou luminescente.
PCT/US2001/008816 2000-03-20 2001-03-19 Preparation d'images emettrices de lumiere, tres reflechissantes, et/ou d'apparence metallique sur une surface de substrat WO2001070508A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE60102081T DE60102081T2 (de) 2000-03-20 2001-03-19 Verfahren zur herstellung von licht-emittierenden, hochreflektierenden und/oder metallischen bildern auf der oberfläche eines trägers
JP2001568739A JP2003527984A (ja) 2000-03-20 2001-03-19 基板表面上での、光放射性画像、高度な反射画像および／または金属様画像の調製
AT01918836T ATE259719T1 (de) 2000-03-20 2001-03-19 Verfahren zur herstellung von licht-emittierenden,hochreflektierenden und/oder metallischen bildern auf der oberfläche eines trägers
CA002403469A CA2403469A1 (fr) 2000-03-20 2001-03-19 Preparation d'images emettrices de lumiere, tres reflechissantes, et/ou d'apparence metallique sur une surface de substrat
EP01918836A EP1274586B1 (fr) 2000-03-20 2001-03-19 Preparation d'images emettrices de lumiere, tres reflechissantes, et/ou d'apparence metallique sur une surface de substrat
AU2001245864A AU2001245864A1 (en) 2000-03-20 2001-03-19 Preparation of light-emitting, highly reflective and/or metallic-looking images on a substrate surface

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US19084000P 2000-03-20 2000-03-20
US60/190,840 2000-03-20

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US7217504B2 (en) 2004-09-03 2007-05-15 Eastman Kodak Company Method of imaging
WO2008068051A1 (fr) * 2006-12-07 2008-06-12 Agfa-Gevaert Précurseur de support d'informations et support d'informations fabriqué avec celui-ci
WO2008068053A1 (fr) * 2006-12-07 2008-06-12 Agfa-Gevaert Précurseur de support d'informations et support d'informations fabriqué avec celui-ci

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KR101291666B1 (ko) * 2008-10-15 2013-08-01 (주)엘지하우시스 불투명 코팅층을 포함하는 벽지 및 그 제조방법

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GB1604488A (en) * 1978-03-01 1981-12-09 Rhone Poulenc Syst Method of making a transparency or photographic negative from a record material
US4299880A (en) * 1979-11-15 1981-11-10 Minnesota Mining And Manufacturing Company Demand and timed renewing imaging media
DE3129745C2 (de) * 1981-07-28 1985-01-17 Hoechst Ag, 6230 Frankfurt Offenporig-mikroporös ausgebildeter Formkörper mit inhärenter latenter Strukturumwandelbarkeit
JPS62244690A (ja) * 1986-04-18 1987-10-26 Canon Inc 被記録材
JP2514194B2 (ja) * 1986-12-26 1996-07-10 日本製紙株式会社 インクジエツト記録用シ−ト
JPH0832478B2 (ja) * 1987-01-16 1996-03-29 株式会社クラレ インク用記録媒体
FR2644803B1 (fr) * 1989-03-22 1993-10-29 Arjomari Prioux Nouveau support avec couche pouvant etre rendue transparente pour document de securite
JP3737840B2 (ja) * 1995-07-04 2006-01-25 富士写真フイルム株式会社 記録用シートの製造方法
JP3574236B2 (ja) * 1995-10-06 2004-10-06 セイコーエプソン株式会社 インク受容層を有する記録媒体
JPH09226233A (ja) * 1995-12-21 1997-09-02 Daicel Chem Ind Ltd インクジェット記録用シート
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7217504B2 (en) 2004-09-03 2007-05-15 Eastman Kodak Company Method of imaging
WO2008068051A1 (fr) * 2006-12-07 2008-06-12 Agfa-Gevaert Précurseur de support d'informations et support d'informations fabriqué avec celui-ci
WO2008068053A1 (fr) * 2006-12-07 2008-06-12 Agfa-Gevaert Précurseur de support d'informations et support d'informations fabriqué avec celui-ci

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EP1274586A2 (fr) 2003-01-15
ATE259719T1 (de) 2004-03-15
EP1274586B1 (fr) 2004-02-18
DE60102081T2 (de) 2004-10-21
AU2001245864A1 (en) 2001-10-03

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