WO1995006564A1 - Procede de production d'image a jet d'encre et element d'enregistrement - Google Patents

Procede de production d'image a jet d'encre et element d'enregistrement Download PDF

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Publication number
WO1995006564A1
WO1995006564A1 PCT/US1994/009644 US9409644W WO9506564A1 WO 1995006564 A1 WO1995006564 A1 WO 1995006564A1 US 9409644 W US9409644 W US 9409644W WO 9506564 A1 WO9506564 A1 WO 9506564A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
ink
adhesive
substrate
imaged
Prior art date
Application number
PCT/US1994/009644
Other languages
English (en)
Inventor
Douglas Allan Cahill
Richard Scott Himmelwright
Dene Harvey Taylor
Donald Armand Brault
Original Assignee
Rexham Graphics Incorporated
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US08/115,564 external-priority patent/US5766398A/en
Priority claimed from US08/115,561 external-priority patent/US5795425A/en
Application filed by Rexham Graphics Incorporated filed Critical Rexham Graphics Incorporated
Priority to JP7508191A priority Critical patent/JPH09503168A/ja
Priority to DE69422048T priority patent/DE69422048T2/de
Priority to DE0716633T priority patent/DE716633T1/de
Priority to AU76747/94A priority patent/AU7674794A/en
Priority to EP94927239A priority patent/EP0716633B1/fr
Publication of WO1995006564A1 publication Critical patent/WO1995006564A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17—Dry transfer
    • B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/506—Intermediate layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0027—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—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
    • 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
    • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B41M5/5272—Polyesters; Polycarbonates
    • 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
    • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B41M5/5281—Polyurethanes or polyureas

Definitions

  • This invention relates to ink jet printing processes for making images, and particularly, color images. More particularly, this invention relates to ink jet printing processes and the elements used therein for the production and protection of large size, full color images.
  • ink jet printing processes in the manufacture of multicolor images is well known in the art.
  • ink droplets are emitted from a nozzle and deposited on substrates, such as paper, to form an image.
  • substrates such as paper
  • rapid absorption of the ink into the substrate is required, but at the same time the ink colorant must be retained at or near the surface of the substrate with lateral ink migration limited to the resolution of the printer.
  • Ink jet printing and its use in making full color images is reviewed in general by Werner E.
  • the substrate e.g., paper
  • the substrate is coated with a formulation to meet the requirements discussed supra.
  • paper stock is extensively used as the substrate for ink jet printing, many other materials are used including plastic films and sheets, and the like.
  • transparencies typically a coated transparent plastic film or sheet is used as the substrate. Since aqueous based inks are the common type of ink used in ink jet printing processes, substrate coating formulations typically are hydrophilic and contain appropriate absorptive materials.
  • ink jet printing processes, inks and substrates are capable of producing high quality four color images in sizes ranging from office copy up to sizes useful for posters, displays and billboards.
  • application of ink jet printing has been limited largely to such uses as office copy and the like where environmental and abrasion damage to the finished ink image is unlikely.
  • the water sensitive ink jet image and underlying substrate must be protected from rain, sunlight, and other environmental contaminants and should likewise be protected from abrasion and graffiti to provide adequate useful life to the image displayed.
  • an image protective film and its method of use is disclosed in Yoshida, U.S. Patent 5,217,773; the film comprises a base layer, a release layer formed of a resin having no compatibility with the base layer and an adhesive layer formed of a thermoadhesive resin.
  • the film is superposed on an image surface of an object article such that the adhesive layer comes in contact with the image surface and thereafter heated.
  • the base layer is separated from the object article and the adhesive layer and the release layer remain on the object article to form a protective layer.
  • a substrate comprising: a) a support; and b) a first adhesive layer on a first surface of said support, by contacting said first surface of said substrate to said imaged ink receptive layer, and,
  • the first adhesive layer of the substrate is omitted and the ink receptive layer includes an adhesive which is activated to permanently adhere the imaged ink receptive layer to the substrate.
  • the substrate further comprises: c) a second adhesive layer on a second surface of said support opposite said first surface; and optionally, d) a removable cover sheet temporarily adhered to the second adhesive layer; and in performing step (B) the substrate is oriented so that the surface of the substrate bearing the second adhesive layer is away from the imaged ink receptive layer and either before or after step (C) , there is performed the additional step: D) removing the removable cover sheet, if present, from the adhesive layer and adhering the adhesive layer of the imaged laminate to a second substrate to form a mounted, imaged laminate.
  • the image transparent, ink receptive layer is receptive to aqueous ink jet inks and comprises a hydrophilic resin material and, optionally, an adhesive material.
  • Figure 1 is a cross section view illustrating details of the ink deposition step of the process of this invention and an ink receptive element used therein.
  • Figure 2 is a cross section view illustrating details of the imaged ink receptive element and the substrate.
  • Figures 3a and 3b are cross section views illustrating subsequent process steps of this invention using the element of figure 2.
  • Figure 4 is a cross section view illustrating details of an alternate embodiment of the imaged ink receptive element and the substrate.
  • Figures 5a and 5b are cross section views illustrating subsequent process steps of this invention using the element of figure 4.
  • the first process step (A) comprises imagewise depositing one or more ink images on an ink receptor element.
  • an ink jet device (11) traversing in a direction (19) across an ink receptor element, imagewise deposits ink droplets (17) on an image transparent, ink receptive layer (16) to form an imaged ink receptive layer (18).
  • the imaged ink receptor element (10) which is formed comprises; a temporary carrier layer (12), an image transparent, protective layer (14), and an image transparent imaged ink receptive layer (18) .
  • the ink jet device (11) which is used to generate an image on the imaged ink receptive layer (18) may be any of the conventional ink jet printers used to print a single color or a full color image as disclosed by Werner E. Haas in "Non- Impact Printing Technologies": Chapter 13, pages 379-384, supra. Additional ink jet devices include Hewlett Packard Desk Jet 500 and 500C printers; IBM Lexmark ® ink jet printers; Cannon Bubblejet ® printers; ENCAD Computer Corporation Novajet ® printers; and the like.
  • an imaged ink receptive layer (18) e.g., a four color subtractive color image consisting of yellow, magenta, cyan and black images in register.
  • the ink image typically is printed on the ink receptive layer (16) as a reverse or mirror image so that the completed protected ink image will possess correct orientation when applied to an opaque substrate.
  • the inks used in the ink imaging process of this invention are well known for this purpose.
  • the ink compositions used typically are liquid compositions comprising a solvent or carrier liquid, dyes or pigments, humectant, organic solvents, detergents, thickeners, preservatives, and the like.
  • the solvent or carrier liquid typically is water, although ink in which organic materials such as polyhydric alcohols as the predominant solvent or carrier also are used.
  • the dyes used in such compositions are typically water-soluble direct or acid type dyes.
  • Such liquid ink compositions have been extensively described in the prior art, e.g. , such as disclosed by P. Gender in "Materials Aspects For High Quality Color Thermal Ink Jet Printing" IS&T's 46th Annual Conference (1993), pages 175-177.
  • the imaged receptor element (10) is oriented to a substrate (20), comprising a support (22) and a first adhesive layer (24) applied to a first surface of the support, so that the surface of the adhesive layer (24) faces the surface of the imaged ink receptive layer (18)
  • the temporary carrier layer (12) of the ink receptor element (10) functions as a temporary support to the superposed layers during the process steps of this invention and may be any web or sheet material possessing suitable flexibility, dimensional stability and adherence properties to the protective layer (14).
  • the web or sheet material is a flexible polymeric film, e.g.
  • a foraminous material e.g., such as a paper sheet and the like.
  • the web or sheet may also be surface treated or coated with a material to enhance desired release characteristics, e.g., such as treatment with a silicone release agent and the like.
  • the protective layer (14) of the ink receptor element (10) is a polymeric film material which is resistant to scratching, abrasions and the like, and to environmental components and contaminants.
  • the protective layer (14) is permanently adhered to the image transparent, ink receptive layer (16) while being only temporarily adhered to the temporary carrier layer (12).
  • the protective layer (14) is visually transparent in at least one region within the visible spectral region and typically is transparent throughout the visible spectral region.
  • Polymeric materials which are useful in making this layer include polyvinyl chloride; polyvinylidene chloride; fluorinated polymers and copolymers; polyvinyl butyral; cellulose acetate propionate; cellulose acetate butyrate; polyesters; acrylics; fluorinated polymers; polyurethanes; styrene copolymers, e.g., such as styrene acrylonitrile; and combinations thereof.
  • This layer may contain components which strongly absorb ultraviolet radiation thereby reducing damage to underlying images by ambient ultraviolet light, e.g., such as 2-hydroxy-benzophenones; oxalanilides; aryl esters and the like; hindered amine light stabilizers, such as bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate and the like; and combinations thereof.
  • This layer may also contain components which provide protection from biological attack, such as, fungicides and bactericides, and the like.
  • the protective layer (14) may be provided with a matt surface. This matt surface can be obtained by including in the layer particles sufficiently large to give surface irregularities to the layer, or may be imparted or embossed by the surface characteristics of the temporary carrier layer (12). Particles of average diameter in the range of about 1 ⁇ m to about 15 ⁇ m are suitable.
  • the protective layer also may be provided with a graffiti-proof surface, typically, a perfluorinated polymer surface.
  • the protective layer (14) typically has a thickness in the range of about 0.5 ⁇ m to about 20 ⁇ m and preferably in the range of about 3 ⁇ m to about 10 ⁇ m. Such layers typically will withstand scribing with the point of a 4H pencil without breakthrough.
  • the image transparent, ink receptive layer (16) of the ink receptor element (10), is permanently adhered to the protective layer (14), and is a hydrophilic, aqueous ink sorptive, coating material.
  • the ink receptive layer (16) is visually transparent in at least one region within the visible spectral region and typically is transparent throughout the visible spectral region.
  • the visible spectral region of the ink receptive layer (16) typically is matched to that of the protective layer (14).
  • the image transparent, ink receptive layer (16) may be prepared from a wide variety of hydrophilic, aqueous ink sorptive, coating materials.
  • the ink receptive layer (16) typically is formulated to provide suitable ink receptivity tuned for a particular ink jet device (11) and related ink (17) used therein.
  • suitable formulations for the ink receptive layer (16) are disclosed in Desjarlais, U.S. Patent 4,775,594; Light, U.S. Patent 5,126,195; and Kruse, U.S. Patent 5,198,306.
  • the ink receptive layer (16) typically is comprised of at least one hydrophilic polymer or resin which also may be water soluble.
  • Suitable hydrophilic polymers or resins include polyvinyl alcohols, including substituted polyvinyl alcohols; polyvinyl pyrrolidones, including substituted polyvinyl pyrrolidones; vinyl pyrrolidone/vinyl acetate copolymer; vinyl acetate/acrylic copolymers; acrylic acid polymers and copolymers; acryla ide polymers and copolymers; cellulosic polymers and copolymers; styrene copolymers of allyl alcohol, acrylic acid, malaeic acid, esters or anhydride, and the like; alkylene oxide polymers and copolymers; gelatins and modified gelatins; polysaccharides; and the like.
  • Preferred hydrophilic polymers include polyvinyl pyrrolidone; substituted polyvinyl pyrrolidone; polyvinyl alcohol; substituted polyvinyl alcohol; vinyl pyrrolidone/vinyl acetate copolymer; vinyl acetate/acrylic copolymer; polyacrylic acid; polyacrylamides; hydroxyethylcellulose; carboxyethylcellulose; gelatin; and polysaccharides.
  • the ink receptive layer (16) may also contain other water insoluble or hydrophobic polymers or resins to impart a suitable degree of hydrophilicity and/or other desirable physical and chemical characteristics.
  • Suitable polymers or resins of this class include polymers and copolymers of styrene, acrylics, urethanes, and the like.
  • Preferred polymers and resins of this type include a styrenated acrylic copolymer; styrene/allyl alcohol copolymer; nitrocellulose; carboxylated resin; polyester resin; polyurethane resin; polyketone resin; polyvinyl butyral resin; or mixtures thereof.
  • the ink receptive layer (16) typically contains other added components such as a dye mordant, a surfactant, particulate materials, a colorant, an ultraviolet absorbing material, an organic acid, an optical brightener, and the like.
  • Dye mordants which may be used to fix the printed ink to the ink receptive layer (16) may be any conventional dye mordant, e.g. such as polymeric quaternary ammonium salts, polyvinyl pyrrolidone, and the like.
  • Surfactants which are used as coating aids for the ink receptive layer (16) may be any nonionic, anionic, or cationic surfactant. Particularly useful, are fluorosurfactants, alkylphenoxypolyglycidols, and the like.
  • the ink receptive layer may also contain particulate material.
  • Suitable particulate material includes inorganic particles such as silicas, chalk, calcium carbonate, magnesium carbonate, kaolin, calcined clay, pyrophylite, bentonite, zeolite, talc, synthetic aluminum and calcium silicates, diatomatious earth, anhydrous silicic acid powder, aluminum hydroxide, barite, barium sulfate, gypsum, calcium sulfate, and the like; and organic particles such as polymeric beads including beads of polymethylmethacrylate, copoly(methylmethacrylate/divinylbenzene) , polystyrene, copoly(vinyltoluene/t-butylstyrene/methacrylic acid) , polyethylene, and the like
  • the ink receptive layer (16) may also contain a colorant, e.g., a dye or pigment, provided the layer is visually transparent in at least one region within the visible spectral region and typically is transparent throughout the visible spectral region.
  • This layer may contain components which strongly absorb ultraviolet radiation thereby reducing damage to underlying images by ambient ultraviolet light, e.g., such as 2-hydroxybenzophenones; oxalanilides; aryl esters and the like; hindered amine light stabilizers, such as bis(2,2,6,6- tetramethyl-4-piperidinyl) sebacate and the like; and combinations thereof.
  • Organic acids which are used to adjust the pH and hydrophilicity in the ink receptive layer (16) typically are non-volatile organic acids such as a alkoxy acetic acid, a glycolic acid, a dibasic carboxylic acid and half esters thereof, a tribasic carboxylic acid and partial esters thereof, aromatic sulfonic acids, and mixtures thereof.
  • Preferred organic acids include glycolic acid, methoxy acetic acid, citric acid, malonic acid, tartaric acid, malic acid, aleic acid, fumaric acid, itaconic acid, succinic acid, oxalic acid, 5-sulfo-salicylic acid, p-toluenesulphonic acid, and mixtures thereof.
  • Optical brighteners which may be used to enhance the visual appearance of the imaged layer may be any conventional, compatible optical brightener, e.g., such as optical brighteners marketed by Ciba-Geigy under the trademark of Tinopal ® .
  • the first adhesive layer (24) of the substrate (20), functions to permanently adhere the imaged ink receptive layer (18) and the protective layer (14) of the imaged receptor element (10), to the substrate during the process of this invention.
  • the adhesive layer (24) may be chosen from a variety of conventional adhesive materials, e.g., such as thermally activated, pressure sensitive, photo-activated, or contact adhesives and the like.
  • the adhesive material will be a thermally activated adhesive material comprised of thermoplastic polyurethanes; polycaprolactone; acrylic copolymers; and combinations thereof.
  • thermally activated adhesive materials include Morthane ® CA- 116 urethane resin (a product of Morton International); Tone ® Polymer P767E biodegradable plastic resin (a product of Union Carbide); Elvax ® 240 Ethylene vinyl acetate (a product of Dupont Chemicals); and the like.
  • the support (22) of the substrate (20) typically functions as the final support for the protected imaged ink receptive layer (18) formed during the process steps of this invention.
  • the support (22) may be any surface upon which an ink jet image is desired. Typically, it is a web or sheet material possessing dimensional stability and adherence properties through the adhesive layer (24) to the imaged ink receptive layer (18) of the imaged ink receptor element (10).
  • the web or sheet material may be a flexible polymeric film, e.g., such as polyethylene terephthalate film and the like; a foraminous material, e.g., such as a paper sheet, textile fabrics, and the like; metal films or webs, e.g., such as aluminum, steel, tin-plate, and the like; or any composites or laminates thereof.
  • the support (22) may be a rigid or semi ⁇ rigid sheeting or plate, e.g., such as sheeting or plates of metal, glass, ceramic, plastic, cardboard, or any composites or laminates thereof.
  • the support (22) may vary in size from that of a photographic print, e.g., having an area of about 30 cm 2 or less, to that of vehicle sign or billboards, e.g., having an area of about 70 m 2 or greater. Since the thin protective (14) and ink receptive (16) layers are highly compliant, the support (22) also may vary in shape and surface topography, e.g., spherical, embossed, etc. When a transparency is to be produced by the process of this invention, the support (22) and first adhesive layer (24) are visually transparent in at least one region within the visible spectral region and typically is transparent throughout the visible spectral region.
  • This layer may also contain components which strongly absorb ultraviolet radiation thereby reducing damage to underlying images by ambient ultraviolet light, e.g., such as 2-hydroxybenzophenones; oxalanilides; aryl esters and the like; hindered amine light stabilizers, such as bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate and the like; and combinations thereof.
  • the web or sheet may also be surface treated or coated with a material to enhance desired surface characteristics, e.g. sub-coatings, electric discharge treatment, and the like.
  • the imaged ink receptor element (10) can be applied to most solids or foraminous materials, e.g., adhesive backed vinyl, static cling vinyl, and polyethylene terephthlate films; steel, glass, ceramic, and wood sheets and objects.
  • the substrate (20) may further have a second adhesive layer adhered to a second surface of the support (22) opposite the first surface, e.g., the reverse side; and optionally a removable cover sheet may be temporarily adhered to the second adhesive layer.
  • the adhesive material of the second adhesive layer may be any contact, thermal or pressure sensitive adhesive, such as described supra, and may be an integral part of the substrate (20) or it may be applied just prior to a mounting step.
  • a removable cover sheet is temporarily adhered to the adhesive surface(s) of the substrate (20) to protect against damage during storage or preliminary handling.
  • the removable cover sheet may be any conventional release cover sheet.
  • the ink imaging process of this invention comprises three process steps of which the initial process step (A) of producing an imaged receptor element (10) has been described, supra, by reference to Figure 1. The remaining steps of the process will now be described by reference to Figures 3a and 3b.
  • the second process step (B) comprises applying to the imaged ink receptive layer (18) of the ink receptor element (10), the surface of the first adhesive layer (24) of the substrate (20) .
  • the first adhesive layer (24) is contacted and permanently adhered to the imaged ink receptive layer (18) using an applied pressure (31) to the surfaces of the temporary carrier layer (12) and the support (22) to form an imaged laminate (30).
  • the applied pressure (31) must be sufficient to activate the adhesive to form a permanent bond between the layers.
  • the adhesive substrate (20) is typically applied to the imaged ink receptive layer (18) under an applied pressure (31) of atmospheric pressure or greater.
  • the applied pressure (31) may be about 0.07 kg/cm 2 (1 p.s.i.) to about 7 kg/cm 2 (100 p.s.i.) or greater.
  • applied pressure is intended to mean the absolute pressure which is applied to a unit area of the surface as conventionally derived from the geometry of the pressure means, e.g., the geometry of the laminating nip, in combination with a measurement means, e.g., a calibrated gauge pressure.
  • Suitable means that may be used to apply pressure include platen presses; counterpoised, double roll, laminating devices; vacuum laminating devices; scanning, single roll, laminating devices; hand-held, rollers and squeegees; and the like.
  • roll laminating devices are preferred since they readily minimize air entrapment between the adhesive layer (24) and the imaged ink receptive layer (18) during the application process step.
  • Vacuum may be applied with such devices to further eliminate air entrapment.
  • the adhesive layer (24) is a thermally activated adhesive. In this instance, heat is typically applied to the adhesive layer (24) prior to and/or concurrently with the application of the applied pressure (31). While the temperature used to activate the adhesive depends on the nature of the material, the adhesive substrate (20) is applied to the imaged ink receptive layer (18) at a temperature of about 80°C or greater and preferably about
  • the adhesive substrate (20) may be heated prior to its application by radiant or contact heaters and then applied while hot to the imaged ink receptive layer (18).
  • the pressure means itself may also function as a heater, e.g. , such as a hot roll laminator, or both prior and concurrent heating may be used in combination.
  • the adhesive layer (24) may also be a photo-activated adhesive.
  • the adhesive layer (24) typically is irradiated with actinic radiation either concurrently with or subsequent to the application of the applied pressure (31).
  • the support (22) and/or any intervening layer should be sufficiently transparent to the actinic radiation which activates the photo adhesive.
  • the applied pressure (31) may be just sufficient to bring the surface of the adhesive layer (24) into intimate contact with the surface of the imaged ink receptive layer (18).
  • the third process step (C) comprises removing the temporary carrier layer (12) from the surface of the protective layer (14) of the imaged laminate (30).
  • the temporary carrier layer (12) is peeled, using a peel force (41), from the surface of the protective layer (14) to form the completed protected ink image element (40).
  • the temporary carrier layer (12) is peeled with a peel force (41) directed at an angle of 90° or more from the surface of the protective layer (14).
  • the peel rate and the peel force (41) are not critical and preferred values will depend on the nature of the protective and carrier materials.
  • the temperature at which the temporary carrier layer (12) is peeled form the protective layer (14) will depend on the nature of the substrate, adhesive, protective and carrier materials used in the imaged laminate (30).
  • the temporary carrier layer (12) may be peeled at room temperature or, alternatively, the imaged laminate (30) may be heated to facilitate removal of the temporary carrier layer (12).
  • a thermally activated adhesive material is used to form the imaged laminate (30)
  • the temporary carrier layer (12) can be removed immediately after formation of the imaged laminate (30) (i.e., while still in a heated state from the application process step (B)) without delamination of the thermal first adhesive layer (24) or any of the other component layers.
  • the term "immediately” is intended to mean a time span of about 1 minute or less and preferably between about 1 second and about 20 seconds.
  • the laminate when a thermally activated adhesive material is used to form the imaged laminate (30), the laminate may be cooled and stored before removal of the temporary carrier layer (12).
  • the temporary carrier layer (12) can be removed at room temperature from the imaged laminate (30) without delamination of the first adhesive layer (24) or any of the other component layers.
  • the imaged laminate (30) may be reheated prior to removal of the temporary carrier layer (12).
  • the laminate typically is reheated to a temperature which is within about ⁇ 5°C of the temperature used to form the element in process step (B) .
  • the temporary carrier layer (12) may be kept adhered to the imaged laminate (30) during its intermediate storage and handling, and then removed just prior to use.
  • the adhesive substrate (20) further comprises a second adhesive layer adhered to a second surface of the support (22) opposite the first surface; and optionally, there is a removable cover sheet temporarily adhered to the second adhesive layer.
  • the process further comprises; either before or after step (C) , the added step (D) of removing the removable cover sheet, if present, from the second adhesive layer and adhering the second adhesive layer of the protected ink image element (40) to a second substrate to form a mounted, imaged laminate.
  • step (C) the added step of removing the removable cover sheet, if present, from the second adhesive layer and adhering the second adhesive layer of the protected ink image element (40) to a second substrate to form a mounted, imaged laminate.
  • This embodiment is particularly useful for preparing component protected image "tiles" and then mounting each tile to form a composite display image such as on a billboard or the like.
  • the mounting adhesive may be either permanent or temporary.
  • Ink receptor element (110) includes a temporary carrier layer 12 and a protective layer 14 as herein above described.
  • An image transparent, adhesive, ink receptive layer (116) is permanently adhered to the image transparent, protective layer (14), and provides a dual function of ink receptivity as well as an adhesive to the ink receptor element (110).
  • the material of the image transparent, adhesive, ink receptive layer (116) is a hydrophilic, aqueous ink sorptive, coating material as well as an adhesive which, when activated, functions to adhere the protected image to the substrate (122).
  • the adhesive, ink receptive layer (116) may be a blend of the necessary materials in a single layer, or it may be a composite of two or more individual layers wherein one layer would contain the major character of the ink receptive material and the other would contain the major character of an adhesive material and in part a shared character of the ink receptive material.
  • the adhesive, ink receptive layer (116) is visually transparent in at least one region within the visible spectral region and typically is transparent throughout the visible spectral region.
  • the visible spectral region of the adhesive, ink receptive layer (116) typically is matched to that of the protective layer (14) as stated earlier.
  • the image transparent, adhesive, ink receptive layer (116) may be prepared from a wide variety of hydrophilic, aqueous ink sorptive, coating materials again as herein above described.
  • the adhesive material of the image transparent, adhesive, ink receptive layer (116), becomes imaged layer (118) and functions to permanently adhere itself and protective layer (14) of the imaged receptor element (110), to substrate (122) during the process of this invention.
  • the adhesive material may be chosen from a variety of conventional adhesive materials, e.g., such as thermally activated, pressure sensitive, photo activated, or contact adhesives and the like, provided it is compatible with the components of the ink receptive material and that it contributes, at least in part, to ink receptivity.
  • compatible is intended to mean that the adhesive material may be dispersed within the image transparent, adhesive, ink receptive layer (16) without substantially altering the image transparency or ink receptivity of the layer.
  • the adhesive material will be a thermally activated, hydrophilic, adhesive material comprised of thermoplastic polyurethanes; polycaprolactone; acrylic copolymers; and combinations thereof.
  • thermally activated adhesive materials include Rovace ® HP-2931 vinyl acetate/acrylic copolymer (a product of Rohm & Haas Company); Morthane ® CA- 116 urethane resin (a product of Morton International); Tone ® Polymer P767E biodegradable plastic resin (a product of Union Carbide); Elvax ® 240 Ethylene vinyl acetate (a product of Dupont Chemicals); and the like.
  • preferred adhesive materials are vinyl acetate/acrylic copolymers.
  • preferred adhesive materials are polycaprolactones.
  • the layer typically has a thickness in the range of about 0.5 ⁇ m to about 10 ⁇ m.
  • the ink imaging process of this invention comprises three process steps of which the initial process step (A) of producing an imaged receptor element (110) is the same as was described above by reference to Figure 1. The remaining steps of the process may be described by reference to Figures 5a and 5b.
  • the second process step (B) comprises applying to the imaged layer (118) of the imaged receptor element (110), the surface of the substrate (122).
  • the substrate (122) is contacted and adhered to the imaged ink receptive layer (118) using an applied pressure (131) to the surfaces of the temporary carrier layer (12) and the substrate (122) to activate the adhesive and form an imaged laminate (130).
  • the application and adhering steps used are similar to the steps disclosed above in describing the process wherein the element used had no adhesive in the ink receptive layer. When only a pressure sensitive adhesive is used, the applied pressure (131) must be sufficient to activate the adhesive to form a permanent bond between the layers.
  • the third process step (C) again comprises removing the temporary carrier layer (12) from the surface of the protective layer (14) of the imaged laminate (130).
  • the temporary carrier layer (12) is peeled, using a peel force (41), from the surface of the protective layer (14) to form the completed protected element (140).
  • the substrate (122) may again further comprise an second adhesive layer adhered to a surface thereof and, optionally, a removable cover sheet temporarily adhered to the second adhesive layer.
  • the process further comprises; either before or after step (C) , the added step (D) of removing the removable cover sheet, if present, from the adhesive layer and adhering the adhesive layer of the protected ink image element (140) to a second substrate to form a mounted, imaged laminate.
  • Another embodiment of this invention comprises an added step wherein after step (C) , the image transparent, protective layer along with the image transparent, adhesive, imaged ink receptive layer are removed intact from the substrate.
  • the image transparent, protective layer along with the image transparent, adhesive, imaged ink receptive layer are removed from the substrate, they may be reapplied to the same substrate or to a second substrate.
  • These added steps allow for the complete removal of the adhered layers after a period of use, e.g., removal of a promotional display from a window.
  • the adhered layers may be partially or totally removed, realigned, and then reapplied to the substrate or another substrate, e.g., for display in another window.
  • Example 1 An ink receptor element was prepared as follows: An abrasion resistant coating solution was prepared from the following ingredients.
  • NeoRez ® R-9679 1) polyurethane 90.0 Tinuvin ® 1130 ⁇ ) UV absorber 5.0 Ethanol 5 . 0
  • NeoRez ® R-9679 is an aliphatic aqueous colloidal dispersion of a urethane polymer containing 37% by weight solids (specific gravity of solids is 1.16 and acid number of resin solids is 17.0), and is a product of Zeneca Resins, Inc., Wilmington, Massachusetts.
  • (2) - Tinuvin ® 1130 UV absorber a product of Ciba-Geigy, is the reaction product of polyethylene glycol 300 and the methyl ester of beta-(3-(2h-benzotriazole-2-yl)-4- hydroxy-5-tert-butylphenyl)propionic acid.
  • the Tinuvin ® 1130 was dissolved in the ethanol to form a 50% by weight solution.
  • the Tinuvin ® solution was stirred into the NeoRez ® R-9679 aqueous dispersion in a Lightnin ® mixer at slow speed and mixed for ten minutes.
  • the resulting dispersion was then coated on a 0.10 mm (-0.004 inch) thick, untreated, polyethylene terephthlate film (the temporary carrier layer) using a #16 meyer rod and dried at 240°F (115°C) for two minutes to form the image transparent, protective layer having a dry coating thickness of 3.6 ⁇ m.
  • the Tinuvin ® 1130 UV absorber in the protective layer blocks about 90% of the incident UV radiation having a wavelength between 310 and 380 nm.
  • An ink receptive coating solution was prepared from the following ingredients:
  • Amorphous silica (ave. particle size 15 ⁇ m) ⁇ 5) 0.067 Zonyl ® FSJ (6) fluorosurfactant 0.023
  • - Joncryl ® 61LV acrylic resin solution is, by weight, 35% Joncryl ® 678 acrylic resin, 51% water, 5% isopropanol, 1.5% ethylene glycol, and 7.5% Ammonia (28%); the resin has an acid number of 70 and a Tg of 95°C; and is a product of S.C. Johnson & Son, Inc., Racine, Wisconsin.
  • - PVP K-90 is polyvinylpyrrolidone which has a viscosity average molecular weight of 700,000 and is a product of GAF Chemicals Corporation, Wayne, New Jersey.
  • (5) - Amorphous silica is Syloid ® 620 and is a product of Davison Chemical Division of W.R. Grace & Co., Baltimore, Maryland.
  • (6) - Zonyl ® FSJ is an anionic fluorosurfactant and is a product of E.I. du Pont de Nemours & Co., Wilmington Delaware.
  • An adhesive substrate was made as follows: An adhesive layer coating solution was prepared from the following ingredients.
  • Amorphous silica (ave. particle size 3 ⁇ m) 0.04
  • Morton-Thiokol is a hydroxyl terminated polyurethane elastomer.
  • the coating solution was made by mixing the methyl ethyl ketone, toluene and urethane resin for 30 minutes with a high speed Lightnin ® mixer. Amorphous silica was then added and mixed for 5 minutes. The solution was coated onto a sheet of 0.0055 inch ( ⁇ 0.14 mm) thick static cling vinyl coated with an ink receptive layer and backed with a 10 pt. paper liner (Flexmark ® CV600 W, manufactured by Flexcon Co., Inc.) using a #12 meyer rod and dried at 240°F (115°C) for two minutes to give a dry coating thickness of 2.0 ⁇ m to form the adhesive layer of the adhesive substrate.
  • a 10 pt. paper liner Felexmark ® CV600 W, manufactured by Flexcon Co., Inc.
  • substrates were prepared in the same manner except the substrates were an adhesively backed sheet of 0.004 inch ( ⁇ 0.1 mm) thick untreated cast vinyl polymer having a removable release liner; a sheet of Rexcal ® 4000-000 white cast vinyl sheet (a product of Rexham Branded Products, Lancaster, South Carolina); a sheet of TYPAR ® spunbonded polypropylene fabric with an acrylic primed surface (a product of Eastern Banner Supply, Moorsesville, Indiana; and a corrugated cardboard paper product. Five 8.5 inch x 11 inch ( 21.6 cm x 27.9 cm) sheets were cut from the ink receptor element prepared supra.
  • a four color image was printed on the ink receptive layer of each sheet using an IBM Lexmark ® ink jet printer using the manufacturer's recommended inks and printing conditions. RH was maintained between 50% and 70%, and temperature was maintained between 65°F ( ⁇ 18.3°C) and 75°F ( ⁇ 23.8°C).
  • the laminating step was performed by first laying each adhesive substrate in such a way that the adhesive layer of the adhesive substrate and the ink imaged layer of each imaged receptor element were contacting each other. Each composite was then passed through the hot nip of an IT 6000 hot roll laminator at a speed of 2 feet/minute ( ⁇ 1.02 cm/second), at a temperature of 270°F ( ⁇ 132°C) and at a pressure of 100 psi ( ⁇ 7.0 kg/cm 2 ). As each laminated element exited from the hot nip, the polyethylene terephthlate, temporary carrier layer contiguous to the protective layer was stripped therefrom to form a protected ink image on each of the five substrates. The surface of each protected ink image produced could withstand scribing with a 4H pencil with no removal of the protective layer or image.
  • the protected ink image on the static cling vinyl can be used as a removable decal on a substrate, e.g., a window.
  • the protected ink image on the adhesive backed vinyl can be mounted by the adhesive backing to the surface of a substrate to form a mounted protected image, e.g., a poster, billboard, sign, and the like.
  • the protected ink image on the cast white vinyl sheet can be used as a back lighted display.
  • the protected ink image on the spunbonded polypropylene fabric can be used as a banner.
  • the protected ink image on the corrugated cardboard can be used in product packaging.
  • Example 2 An ink receptor element was prepared as described in Example 1 except that the ink receptive coating solution was prepared from the following ingredients: Ingredient Parts By Weight
  • - Polyvinyl alcohol is GOHSENAL ® T-330H a special grade of Polyvinyl alcohol wherein a 4% water solution at 20°C has a viscosity of 27-32 cps determined by the Hoeppler falling ball method; a hydrolysis of 99-100 mol % (dry basis); and a pH of 6-8.
  • (9) - Amorphous silica is IMSIL ® A-10 and is a product of Illinois Minerals Co., Cairo, Illinois.
  • (10) - Amorphous silica is Hi-Sil ® T-600 and is a product of PPG Industries.
  • An adhesive substrate was made as described in Example 1 except that the substrate was a sheet of cast coated 0.004 inch ( ⁇ 0.1 mm) thick adhesive backed vinyl sheet (Rexcal ® 4000-000).
  • a four color image was printed on the ink receptive layer of the ink receptor element using an IBM Lexmark ® ink jet printer using the manufacturer's recommended inks and printing conditions. RH was maintained between 50% and 70%, and temperature was maintained between 65°F ( ⁇ 18.3°C) and 75°F ( ⁇ 23.8°C) .
  • the laminating step was performed by first laying the adhesive substrate in such a way that the adhesive layer and the ink imaged layer of the imaged receptor element were contacting each other.
  • the composite was then passed through the hot nip of an IT 6000 hot roll laminator at a speed of 2 feet/minute ( ⁇ 1.02 cm/second), at a temperature of 250°F ( ⁇ 121°C) and at a pressure of 100 psi ( ⁇ 7.0 kg/cm 2 ).
  • the polyethylene terephthlate, temporary carrier layer contiguous to the protective layer was stripped therefrom to form a protected ink image on the substrate.
  • the surface of the protected ink image produced could withstand scribing with a 4H pencil with no removal of the protective layer or image.
  • Example 3 An ink receptor element was prepared as follows: An abrasion resistant coating solution was prepared as disclosed in example 1.
  • An adhesive, ink receptive coating solution was prepared from the following ingredients: Ingredient Parts By Weight Ethanol 30.841
  • (3) - Joncryl ® 61LV acrylic resin solution is, by weight, 35% Joncryl ® 678 acrylic resin, 51% water, 5% isopropanol, 1.5% ethylene glycol, and 7.5% Ammonia (28%); the resin has an acid number of 70 and a Tg of 95°C; and is a product of S.C. Johnson & Son, Inc., Racine, Wisconsin.
  • PVP K-90 is 2-Pyrrolidone methenyl homopolymer which has a viscosity average molecular weight of 700,000 and is a product of GAF Chemicals Corporation, Wayne eMs ⁇ y.
  • - Amorphous silica is Syloid ® 620 and is a product of Davison Chemical Division of W.R. Grace & Co., Baltimore, Maryland.
  • (6) - Zonyl ® FSJ is an anionic fluorosurfactant and is a product of E.I. du Pont de Nemours & Co., Wilmington Delaware.
  • - Rovace ® HP-2931 is a vinyl acetate/ acrylic copolymer aqueous emulsion containing 50% solids, and is a product of Rohm & Haas Company, Philadelphia, Pennsylvania.
  • the above ingredients were added in the order shown and mixed in a Lightnin ® mixer at medium speed until all ingredients were fully incorporated (about 1 hour).
  • the solution was overcoated onto the previously coated protective layer using a #38 meyer rod and dried at 240°F ( ⁇ 115°C) for two minutes to give a dry coating thickness of 9.1 ⁇ m to form the image transparent, adhesive, ink receptive layer of the ink receptor element.
  • the substrates used to demonstrate the process of this invention were; a sheet of 0.0055 inch ( ⁇ 0.14 mm) thick vinyl coated with an ink receptive layer and backed with a 10 pt. paper liner (Flexmark ® CV600 W, manufactured by Flexcon Co., Inc.); an adhesively backed sheet of 0.004 inch ( ⁇ 0.1 mm) thick untreated cast vinyl polymer having a removable release liner; a sheet of Rexcal ® 4000-000 white cast vinyl sheet (a product of Rexham Branded Products, Lancaster, South Carolina); a sheet of TYPAR ® spunbonded polypropylene fabric with an acrylic primed surface (a product of Eastern Banner Supply, Moorsesville, Indiana; a corrugated cardboard paper product; and an unfinished hardwood plank.
  • a sheet of 0.0055 inch ( ⁇ 0.14 mm) thick vinyl coated with an ink receptive layer and backed with a 10 pt. paper liner (Flexmark ® CV600 W, manufactured by Flexcon
  • the laminating step was performed by first laying each substrate in such a way that the substrate surface and the ink imaged layer of each imaged receptor element were contacting each other. Each composite was then passed through the hot nip of an IT 6000 hot roll laminator at a speed of 2 feet/minute ( ⁇ 1.02 cm/second), at a temperature of 250°F ( ⁇ 121°C) and at a pressure of 100 psi ( ⁇ 7.0 kg/cm 2 ). After each laminated element exited from the hot nip, it was held for 30 seconds and then the polyethylene terephthlate, temporary carrier layer contiguous to the protective layer was stripped therefrom to form a protected ink image on each of the three substrates.
  • each protected ink image produced could withstand scribing with a 4H pencil with no removal of the protective layer or image.
  • the protected ink image on the static cling vinyl can be used as a removable decal on a substrate, e.g., a window.
  • the protected ink image on the adhesive backed vinyl can be mounted by the adhesive backing to the surface of a substrate to form a mounted protected image, e.g., a poster, billboard, sign, and the like.
  • the protected ink image on the cast white vinyl sheet can be used as a back lighted display.
  • the protected ink image on the spunbonded polypropylene fabric can be used as a banner.
  • the protected ink image on the corrugated cardboard can be used in product packaging.
  • the protected ink image on the untreated hardwood can be used as a decorative decal on furniture or buildings.
  • Example 4 An ink receptor element was prepared as follows: An abrasion resistant coating solution was prepared and coated on a 0.10 mm (-0.004 inch) thick, untreated, polyethylene terephthlate film as described in Example 3. An ink receptive coating solution was prepared as in example 1 above. The solution was overcoated onto the previously coated protective layer using a #38 meyer rod and dried at 240 ⁇ F ( ⁇ 115°C) for two minutes to give a dry coating thickness of 8.1 ⁇ m to form the image transparent, ink receptive layer of the ink receptor element.
  • An adhesive layer coating solution was prepared from the following ingredients, ingredient par s 3y weight
  • Amorphous silica (ave. particle size 3 ⁇ m) 4.00
  • the coating solution was made by mixing the ingredients in the order shown with a high speed Lightnin* mixer and stirred for 1 hour.
  • the solution was overcoated onto the previously coated protective layer using a meyer rod and dried at 240 ⁇ F ( ⁇ 115 * C) for one minute to form the image transparent, adhesive layer of the ink receptor element.
  • An 8.5 inch x 11 inch ( 21.6 cm x 27.9 cm) sheet was cut from the ink receptor element prepared supra.
  • a color image was printed on the ink receptive layer of the sheet using an Hewlett-Packard Deskjet* 500C color printer using the manufacturer's recommended inks and printing conditions.
  • the laminating step was performed by first laying a sheet of an adhesively backed sheet of 0.004 inch ( ⁇ 0.1 mm) thick untreated cast vinyl polymer having a removable release liner in such a way that the vinyl polymer surface and the ink imaged layer of the imaged receptor element were contacting each other.
  • the composite was then passed through the hot nip of an IT 6000 hot roll laminator at a speed of 2 feet/minute ( ⁇ 1.02 cm/second), at a temperature of 250°F ( ⁇ 121°C) and at a pressure of 100 psi ( ⁇ 7.0 kg/cm 2 ).
  • the polyethylene terephthlate, temporary carrier layer contiguous to the protective layer was stripped therefrom to form a protected ink image on the vinyl polymer substrate.

Landscapes

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

Abstract

Nouveau procédé à trois étapes destiné à la production d'images multicolores protégées par impression à jet d'encre, aptes à être utilisées sur des affiches ou des panneaux d'affichage grand format et autres. Un élément (10) récepteur d'encre, utilisé selon ce procédé, comprend une couche de support temporaire (12), une couche protectrice (14), et une couche (18) réceptrice d'encre. Ce nouveau procédé de formation d'images consiste à: A) déposer une couche d'encre (17) formant une image sur la surface de l'élément récepteur d'encre (10) de façon que ladite couche à image (17) colle à la surface de la couche réceptrice (18); B) laminer et faire adhérer sous pression un substrat récepteur (20) à la couche à image (17) pour former un élément à image laminé (30); et C) enlever la couche de support temporaire (12) de la couche protectrice (14) de l'élément laminé (30) pour former un substrat protégé (40) présentant une image.
PCT/US1994/009644 1993-09-03 1994-09-02 Procede de production d'image a jet d'encre et element d'enregistrement WO1995006564A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP7508191A JPH09503168A (ja) 1993-09-03 1994-09-02 インクジェット描画の方法と記録要素
DE69422048T DE69422048T2 (de) 1993-09-03 1994-09-02 Tintenstrahlaufzeichnungsverfahren und aufzeichnungsmaterial
DE0716633T DE716633T1 (de) 1993-09-03 1994-09-02 Tintenstrahlaufzeichnungsverfahren und aufzeichnungsmaterial
AU76747/94A AU7674794A (en) 1993-09-03 1994-09-02 Ink jet imaging process and recording element
EP94927239A EP0716633B1 (fr) 1993-09-03 1994-09-02 Procede de production d'image a jet d'encre et element d'enregistrement

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US08/115,564 US5766398A (en) 1993-09-03 1993-09-03 Ink jet imaging process
US08/115,561 US5795425A (en) 1993-09-03 1993-09-03 Ink jet imaging process and recording element for use therein
US08/115,561 1993-09-03
US08/115,564 1993-09-03

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WO1995006564A1 true WO1995006564A1 (fr) 1995-03-09

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EP (1) EP0716633B1 (fr)
JP (1) JPH09503168A (fr)
AU (1) AU7674794A (fr)
DE (2) DE69422048T2 (fr)
WO (1) WO1995006564A1 (fr)

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US6824839B1 (en) 1995-08-25 2004-11-30 Avery Dennison Corporation Water-activated polymers and adhesive image transfer technique
WO1997028974A1 (fr) * 1996-02-12 1997-08-14 Zweckform Etikettiertechnik Gmbh Etiquette imprimee par transfert
WO1997030852A1 (fr) * 1996-02-21 1997-08-28 Minnesota Mining And Manufacturing Company Couche transparente de protection pour images
US5681660A (en) * 1996-02-21 1997-10-28 Minnesota Mining And Manufacturing Company Protective clear layer for images
CN1081994C (zh) * 1996-02-21 2002-04-03 美国3M公司 保护有图象底材的层和方法、以及含该层的复合材料
WO1997042040A1 (fr) * 1996-05-04 1997-11-13 Tullis Russell Brittains Decalcomania Papers Limited Decalcomanie
FR2750080A1 (fr) * 1996-06-21 1997-12-26 Dubuit Mach Film pour la decoration a chaud d'un objet en matiere synthetique thermoplastique
WO1998015411A1 (fr) * 1996-10-08 1998-04-16 Andries Cornelis Pasma Materiel et procede de preparation d'un article imprime
EP0865932A1 (fr) * 1997-03-18 1998-09-23 Eastman Kodak Company Document non-falsifiable
WO1999012743A1 (fr) * 1997-09-12 1999-03-18 Minnesota Mining And Manufacturing Company Procede de transfert d'image
EP1127710A1 (fr) * 1997-09-12 2001-08-29 Minnesota Mining And Manufacturing Company Méthode de transfert d'image
WO1999014057A1 (fr) * 1997-09-15 1999-03-25 Autotec Ag Procede permettant de marquer des objets
US6315855B1 (en) 1997-09-15 2001-11-13 Autotec Ag Process for identifying objects
EP0921013A1 (fr) * 1997-12-02 1999-06-09 Thomson-Csf Procédé de réalisation d'un document sécurisé et document sécurisé obtenu par ce procédé
FR2771675A1 (fr) * 1997-12-02 1999-06-04 Thomson Csf Procede de realisation d'un document securise et document securise obtenu par ce procede
US6299719B1 (en) 1997-12-02 2001-10-09 Thomson-Csf Method for the making of a secured document and secured document obtained by this method
WO1999029511A1 (fr) * 1997-12-08 1999-06-17 Imation Corp. Procede de transfert d'image pour images produites par jet d'encre
FR2776236A1 (fr) * 1998-03-20 1999-09-24 Adhetec Transfert a sec a froid, procede de fabrication et procede d'application
EP0962829A1 (fr) * 1998-06-05 1999-12-08 E.I. Du Pont De Nemours And Company Couche protectrice pour des épreuves en couleur
US6210844B1 (en) 1998-06-05 2001-04-03 E. I. Du Pont De Nemours And Company Protective layer for color proofs
WO2000000352A1 (fr) * 1998-06-30 2000-01-06 Hunt Graphics Europe Ltd. Stratifie imprimable
WO2000002735A1 (fr) * 1998-07-09 2000-01-20 3M Innovative Properties Company Procede de transfert de couches receptrices de jet d'encre, sur des substrats
WO2000016167A1 (fr) * 1998-09-11 2000-03-23 Imation Corp. Articles multicouches assembles par collage presentant une surface encree contre-collee a une deuxieme surface
WO2000016166A1 (fr) * 1998-09-11 2000-03-23 Imation Corp. Articles multicouches assembles par collage presentant une surface encree contre-collee a une deuxieme surface au moyen d'un adhesif photopolymerise
WO2000016165A1 (fr) * 1998-09-11 2000-03-23 Imation Corp. Articles multicouches possedant une surface contenant de l'encre, liee a une seconde surface comportant un adhesif thermoplastique de thermoscellage
ES2152169A1 (es) * 1998-11-11 2001-01-16 Cruz Molina Cristina De Procedimiento de obtencion de un cuerpo con imagenes impresas y cuerpo con tal procedimiento.
WO2000027630A1 (fr) * 1998-11-11 2000-05-18 Cruz Molina Ma Cristina De Procede d'obtention d'un corps sur lequel sont imprimees des images et corps ainsi obtenu
EP1016544A3 (fr) * 1998-12-28 2000-07-26 Canon Kabushiki Kaisha Milieu d'enregistrement, méthode de fabrication de ce milieu, et méthode de formation d'image à partir de celui-ci
EP1016544A2 (fr) * 1998-12-28 2000-07-05 Canon Kabushiki Kaisha Milieu d'enregistrement, méthode de fabrication de ce milieu, et méthode de formation d'image à partir de celui-ci
US6402316B1 (en) 1998-12-28 2002-06-11 Canon Kabushiki Kaisha Recording medium, production process of the recording medium, and image forming process using the recording medium
EP1043175A2 (fr) * 1999-04-09 2000-10-11 SJP Group Technologies Limited Feuille de transfert et procédé de fabrication
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US6974609B2 (en) 2000-02-08 2005-12-13 Engle Lori P Media for cold image transfer
US7005162B2 (en) 2000-02-08 2006-02-28 3M Innovative Properties Company Methods of fixing ink
US6764725B2 (en) 2000-02-08 2004-07-20 3M Innovative Properties Company Ink fixing materials and methods of fixing ink
GB2362852A (en) * 2000-03-27 2001-12-05 Hewlett Packard Co Photo-media printing using an opaque backing layer
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EP1157852A1 (fr) * 2000-05-17 2001-11-28 Du Pont De Nemours (Deutschland) Gmbh Feuille réceptrice d'encre et procédé pour son utilisation
WO2001087636A1 (fr) * 2000-05-17 2001-11-22 E. I. Du Pont De Nemours And Company Feuille receptrice d'encre et procede d'utilisation
US7097298B2 (en) 2000-05-17 2006-08-29 E. I. Du Pont De Nemours And Company Ink receptor sheet and it's process of use
EP1375185A1 (fr) * 2000-09-03 2004-01-02 Hewlett-Packard Indigo B.V. Impression d'images plastifiées
US7241355B1 (en) 2000-09-03 2007-07-10 Hewlett-Packard Development Company, L.P. Laminated image printing method
WO2002051649A3 (fr) * 2000-12-22 2003-07-24 Lamberti Spa Decalcomanie pour decorer des articles ceramiques ou en verre
WO2002051649A2 (fr) * 2000-12-22 2002-07-04 Lamberti Spa Decalcomanie pour decorer des articles ceramiques ou en verre
US6874421B2 (en) 2001-04-20 2005-04-05 3M Innovative Properties Company Ink jet transfer printing process
WO2004037556A1 (fr) * 2002-10-22 2004-05-06 3M Innovative Properties Company Procede d'impression par transfert a jet d'encre
US7625627B2 (en) 2005-12-30 2009-12-01 E.I. Du Pont De Nemours And Company Decorative polyvinyl butyral solar control laminates
US10160258B2 (en) 2008-10-23 2018-12-25 Mcc-Norwood, Llc Digitally printed heat transfer label and method of making a decorated article
EP2376289A2 (fr) * 2009-01-14 2011-10-19 Graphic Packaging International, Inc. Etiquette à transfert thermique par impression numérique et procédé de fabrication d'un article décoré
EP2376289A4 (fr) * 2009-01-14 2012-08-29 Graphic Packaging Int Inc Etiquette à transfert thermique par impression numérique et procédé de fabrication d'un article décoré
US10328668B1 (en) 2010-02-17 2019-06-25 Mcc-Norwood, Llc Heat transfer label assembly
CN103732416A (zh) * 2011-08-02 2014-04-16 3M创新有限公司 图形制品
US9308773B2 (en) 2011-08-02 2016-04-12 3M Innovative Properties Company Graphic article
EP3398789A3 (fr) * 2015-12-08 2018-11-21 Canon Finetech Nisca Inc. Matériau de transfert, matériau imprimé et procédé de fabrication d'un matériau imprimé

Also Published As

Publication number Publication date
DE69422048T2 (de) 2000-05-31
EP0716633A4 (fr) 1997-03-05
EP0716633A1 (fr) 1996-06-19
AU7674794A (en) 1995-03-22
DE716633T1 (de) 1996-11-28
DE69422048D1 (de) 2000-01-13
JPH09503168A (ja) 1997-03-31
EP0716633B1 (fr) 1999-12-08

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