EP0539678B1 - Recording material for the ink jet process - Google Patents

Recording material for the ink jet process Download PDF

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Publication number
EP0539678B1
EP0539678B1 EP92114117A EP92114117A EP0539678B1 EP 0539678 B1 EP0539678 B1 EP 0539678B1 EP 92114117 A EP92114117 A EP 92114117A EP 92114117 A EP92114117 A EP 92114117A EP 0539678 B1 EP0539678 B1 EP 0539678B1
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EP
European Patent Office
Prior art keywords
oxidized polyethylene
recording material
coating material
emulsified
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP92114117A
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German (de)
French (fr)
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EP0539678A1 (en
Inventor
Horst Dipl.-Ing. Westfal (Fh)
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Felex Schoeller Jr and GmbH and Co KG
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Felex Schoeller Jr and GmbH and Co KG
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Publication of EP0539678A1 publication Critical patent/EP0539678A1/en
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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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/506—Intermediate layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—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
    • B41M5/508—Supports
    • 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
    • B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • Y10T428/24901—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material including coloring matter
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/3179—Next to cellulosic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers

Definitions

  • the invention relates to a recording material for the ink jet process and a coating composition for producing an ink receiving layer for the ink jet process.
  • droplets of a recording liquid are applied to the recording material using various techniques.
  • Hertz process which, by means of a digital electronic control of fine ink droplets which are pressed out of special nozzles, allows the printing of images with very high resolution directly from electronic data.
  • a recording material for multicolored ink jet printing generally consists of a support and an ink receiving layer arranged thereon.
  • a plastic film (polyester resin, diacetate resin) or paper and the like can be used as the carrier. be used.
  • the ink-receiving layers basically consist of a pigment / binder mixture.
  • the pigments serve to retain the dyes from the recording liquid on the surface of the sheet.
  • a high pigment concentration leads to high porosity of the layer (DE-PS 30 24 205). Although this achieves good smudge resistance, at the same time pigments from the ink are drawn into the interior of the recording material, which worsens the color density of the image.
  • DE-OS 30 167 66 claims a recording material which is intended to ensure a high density and resolution of the printed image by applying a coating of a water-soluble polymer to a paper carrier which has a defined water absorption capacity due to an internal sizing.
  • a disadvantage of this recording material is the fact that the material has to be smoothed in a separate operation in order to achieve the desired color density after application of the ink-receiving layer, e.g. B. by using a gloss or super calender.
  • JP 58-193 185 two layers are applied to a support.
  • the top layer made of polyvinyl alcohol is said to ensure fast ink absorption.
  • the lower layer, which contains synthetic silica, is said to ensure a high color density.
  • the disadvantage of this is that several steps are required to produce this recording material, namely the separate application of two layers and the smoothing with the aid of a calender.
  • EP-A-445327 describes a recording material for the ink jet printing process in which the ink receiving layer contains a mixture of gelatin and rice starch.
  • the object of the present invention is to propose a recording material for the ink jet process which does not have the disadvantages mentioned above and which is distinguished in particular by a high color density and a high resolving power with at the same time quickly achievable wiping resistance of the ink droplets.
  • an ink receiving layer which contains a hydrophilic binder and an oxidized polyethylene is applied to a polyolefin-coated base paper, the oxidized polyethylene being present in the aqueous coating composition used for the ink receiving layer as a cationically emulsified oxidized polyethylene.
  • the hydrophilic binder is a protein-containing binder, in particular gelatin.
  • the oxidized polyethylene contained in the ink receiving layer is present in the coating composition used for this in a cationically emulsified form.
  • the oxidized polyethylene with compounds from the group of fatty amines, fatty amine acetates, quaternary ammonium compounds and the like. cationically emulsified.
  • the oxidized polyethylene is an oxidized polyethylene cationically emulsified with stearyl fatty amine acetate.
  • the amount of the cationically emulsified oxidized polyethylene in the aqueous coating composition is between 0.1 and 5% by weight, in particular between 1 and 4% by weight.
  • the amount of the binder in the ink-receiving layer is at least 50% by weight, preferably 70 to 99% by weight, based on the dry layer.
  • the ink-receiving layer can additionally contain white pigments, dyes, hardening agents, dispersing aids, wetting agents and the like. Contain auxiliaries.
  • the application amount of the ink-receiving layer is 0.5 to 10 g / m2, preferably 2 to 7 g / m2.
  • the coating composition for the ink-receiving layer can be applied to the carrier by all customary application and metering methods, such as e.g. Roller application, engraving or nipping processes as well as air brush or roller doctor metering.
  • the polyolefin used to coat the base paper is preferably low density polyethylene (LDPE) and / or high density polyethylene (HDPE). But also other polyolefins, such as. B. LLDPE or polypropylene can be used.
  • the application amount of the polyolefin coating, which may additionally contain pigments and other additives, is at least 5 g / m2.
  • the gloss of the recording material according to the invention does not require additional post-treatments, e.g. using a glossy calender.
  • the very good color density is achieved even without pigmentation of the ink receiving layer.
  • the print images also have good water resistance and abrasion resistance.
  • the front of a polyethylene-coated base paper according to Example 1 was coated with the following coating compositions: Components Composition,% by weight 2a 2 B Gelatin (220 Bloom) 20% in water 51.0 46.0 Oxidized 32% polyethylene stabilized in water with stearyl fatty amine acetate (Südranol 270, Süd Weg Emulsions-Chemie GmbH) 0.4 5.0 amphoteric silica 10.0 10.0 Wetting agent (Triton X100) 10% in water 0.5 0.5 Alcohol mixture IPA / BU / H2O 25: 25: 50 10.0 10.0 Citric acid 10% in water 0.3 0.3 Chromalun 10% in water 1.2 1.1 TAF / formaldehyde (1: 0.05) 2% in IPA / BU / H2O 1.2 1.1 Water, demineralized 25.4 26.0 Order quantity, g / m2 7 7
  • the ink-receiving layers according to V1 and V2 were applied from an aqueous medium in the following composition: Components Composition,% by weight V1 V2 Gelatin (220 Bloom) 20% in water 61.4 61.0 oxidized polyethylene 32% in water non-ionic emulsifier system (Südranol 340, Süd Weg Emulsions-Chemie GmbH) - 0.4 Wetting agent (Triton X100) 10% in water 0.5 0.5 Alcohol mixture IPA / BU / H2O 25: 25: 50 10.0 10.0 Citric acid 10% in water 0.3 0.3 Chromalun 10% in water 1.5 1.5 TAF / formaldehyde (1: 0.05) 2% in IPA / BU / H2O 1.5 1.5 Water, demineralized 24.8 24.8 Order quantity, g / m2 7 7
  • the recording material obtained according to the comparative examples was printed in a continuous ink jet process and then analyzed.
  • the results are summarized in Table 2.
  • the recording material was printed with the aid of an Excelerator 4/1120 inkjet printer from Stork X-cel, which works according to the Hertz inkjet printing principle, using the inks developed by Stork. Color density, abrasion resistance, water resistance and gloss were examined in the print images obtained.
  • the density measurements were carried out before and after a 24-hour exposure of the images using a xenon lamp.
  • the device used for this was an original reflection densitometer SOS-45.
  • the measurements were carried out in the color gradations F1 - F6 for the colors cyan, magenta, yellow and black, the values for F1 and F6 being given in the tables.
  • the smudge resistance was assessed according to the degree of so-called "knocking off” of the printing ink from the surface of the material. The test was carried out individually for all four primary colors. The designation “+” means that all colors immediately “strike away” from the leaf surface, ie penetrate into the layer interior. The designation “o” means that 3 primary colors immediately penetrate from the leaf surface into the layer interior and the fourth primary color only after a few seconds. "-” denotes a poor smudge resistance of the material, ie no or only weak penetration of almost all colors is observed.
  • the recording material sample was heated in water and rubbed with a finger at 5 ° C. intervals.
  • the temperature at which the white background of the recording material shows through was taken as a measure of the water resistance and abrasion resistance.
  • the gloss of the recording material was measured using a three-angle gloss meter according to Dr. Measured for a long time at a measuring angle of 60 ° C.

Landscapes

  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating Apparatus (AREA)
  • Paper (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to a recording material for the ink-jet process, having an ink receiving layer which contains a hydrophilic binder and an oxidised polyethylene, where the oxidised polyethylene is in the form of a cation-actively emulsified oxidised polyethylene in the aqueous coating composition used for the ink receiving layer.

Description

Die Erfindung betrifft ein Aufzeichnungsmaterial für das ink jet-Verfahren sowie eine Beschichtungsmasse zur Herstellung einer Tintenaufnahmeschicht für das ink jet-Verfahren.The invention relates to a recording material for the ink jet process and a coating composition for producing an ink receiving layer for the ink jet process.

Bei ink jet-Verfahren werden Tröpfchen einer Aufzeichnungsflüssigkeit (Tinte) nach verschiedenen Techniken auf das Aufzeichnungsmaterial aufgebracht.In ink jet processes, droplets of a recording liquid (ink) are applied to the recording material using various techniques.

Es gibt z.B. ein Verfahren (Hertz-Verfahren), welches durch eine digitale elektronische Steuerung feiner Tintentröpfchen, die aus speziellen Düsen ausgepreßt werden, das Drucken von Bildern mit sehr hoher Auflösung direkt aus elektronischen Daten erlaubt.There are e.g. a process (Hertz process) which, by means of a digital electronic control of fine ink droplets which are pressed out of special nozzles, allows the printing of images with very high resolution directly from electronic data.

Mit zunehmender Verbesserung der Funktionsweise von ink jet-Druckern werden an die Aufzeichnungsmaterialien immer höhere Anforderungen gestellt. Das mittels ink jet-Verfahren hergestellte Bild soll verfügen über

  • hohe Auflösung,
  • hohe Farbdichte,
  • genügend Farbabstufungen,
  • gute Wischfestigkeit.
As the functionality of ink jet printers improves, more and more demands are placed on the recording materials. The image created using the ink jet process is said to have
  • high resolution,
  • high color density,
  • enough color gradations,
  • good smudge resistance.

Um dies zu erreichen, müssen folgende Grundbedingungen erfüllt werden:

  • das Aufzeichnungsmaterial muß die Tinte möglichst schnell absorbieren,
  • die aufgespritzten Tintentröpfchen müssen in möglichst exakter Weise (kreisförmig) und genau begrenzt auseinanderlaufen,
  • die Tintendiffusion in dem Aufzeichnungsmaterial darf nicht zu hoch sein, damit der Durchmesser der Tintenpunkte nicht mehr als unbedingt erforderlich vergrößert wird,
  • das Aufzeichnungsmaterial muß eine glänzende Oberfläche aufweisen, um eine hohe visuelle Reflexionsdichte und eine große Brillianz der Farben zu erzielen.
To achieve this, the following basic conditions must be met:
  • the recording material must absorb the ink as quickly as possible,
  • the sprayed-on ink droplets must diverge as precisely as possible (circular) and precisely delimited,
  • the ink diffusion in the recording material must not be too high so that the diameter of the ink dots is not increased more than is absolutely necessary,
  • the recording material must have a glossy surface in order to achieve a high visual reflection density and a great brilliance of the colors.

Hierbei handelt es sich zum Teil um sich widersprechende Forderungen, z.B. bedeutet die zu schnelle Einstellung der Wischfestigkeit, daß ein Tintentropfen nicht oder nur wenig auseinanderläuft und dadurch die Klarheit des entstandenen Bildes benachteiligt wird.Some of these are contradictory claims, e.g. If the wiping resistance is set too quickly, this means that an ink drop does not diverge, or only slightly, and the clarity of the resulting image is thereby disadvantageous.

Ausgehend von den an das Aufzeichnungsmaterial gestellten Forderungen werden trotzdem Wege gesucht, die zu einem Bild mit möglichst hoher Farbdichte bei möglichst hoher Wischfestigkeit führen.Starting from the demands placed on the recording material, ways are nevertheless sought which lead to an image with the highest possible color density and the highest possible smudge resistance.

Ein Aufzeichnungsmaterial für den mehrfarbigen ink jet-Druck besteht in der Regel aus einem Träger und einer darauf angeordneten Tintenaufnahmeschicht.A recording material for multicolored ink jet printing generally consists of a support and an ink receiving layer arranged thereon.

Als Träger kann eine Kunststoffolie (Polyesterharz, Diacetatharz) oder Papier u.ä. verwendet werden.A plastic film (polyester resin, diacetate resin) or paper and the like can be used as the carrier. be used.

Die Tintenaufnahmeschichten bestehen grundsätzlich aus einer Pigment/Bindemittel-Mischung. Die Pigmente dienen, neben der Erhöhung des Weißgrades des Materials, zur Retention der Farbstoffe aus der Aufzeichnungsflüssigkeit an der Oberfläche des Blattes. Eine hohe Pigmentkonzentration führt zu großer Porosität der Schicht (DE-PS 30 24 205). Dadurch wird zwar eine gute Wischfestigkeit erreicht, gleichzeitig aber werden auch Pigmente aus der Tinte in das Innere des Aufzeichnungsmaterials hereingezogen, was die Farbdichte des Bildes verschlechtert.The ink-receiving layers basically consist of a pigment / binder mixture. In addition to increasing the whiteness of the material, the pigments serve to retain the dyes from the recording liquid on the surface of the sheet. A high pigment concentration leads to high porosity of the layer (DE-PS 30 24 205). Although this achieves good smudge resistance, at the same time pigments from the ink are drawn into the interior of the recording material, which worsens the color density of the image.

Es ist bekannt, für ein ink jet-Aufzeichnungsmaterial ein mit Gelatineüberzug versehenes Papier zu verwenden (DE-PS 22 34 823). Durch diese Beschichtung soll die Wischfestigkeit verbessert und das Auflösungsvermögen erhöht werden. Nachteilig an diesem Aufzeichnungsmaterial ist vor allem, daß die aufgespritzten Bildzeichen nicht in der gewünschten kurzen Zeit, sondern erst nach mehr als 10 sek. ausreichend wischfest sind. Nachteilig ist ferner, daß die Tintentröpfchen nicht ausreichend und schnell genug auseinanderlaufen.It is known to use a paper provided with a gelatin coating for an ink jet recording material (DE-PS 22 34 823). This coating is intended to improve the smudge resistance and increase the resolving power. A disadvantage of this recording material is above all that the sprayed-on symbols do not appear in the desired short time, but only after more than 10 seconds. are sufficiently smudge-proof. Another disadvantage is that the ink droplets do not diverge sufficiently and quickly enough.

In der DE-OS 30 167 66 wird ein Aufzeichnungsmaterial beansprucht, welches durch Aufbringen eines Überzuges aus einem wasserlöslichen Polymer auf einen Papierträger, der durch eine Innenleimung eine definierte Wasserabsorptionsfähigkeit aufweist, eine hohe Dichte und Auflösung des gedruckten Bildes gewährleisten soll.DE-OS 30 167 66 claims a recording material which is intended to ensure a high density and resolution of the printed image by applying a coating of a water-soluble polymer to a paper carrier which has a defined water absorption capacity due to an internal sizing.

Nachteilig an diesem Aufzeichnungsmaterial ist der Umstand, daß das Material zur Erzielung der angestrebten Farbdichte nach Aufbringen der Tintenaufnahmeschicht zusätzlich in einem gesonderten Arbeitsgang geglättet werden muß, z. B. durch Anwendung eines Glanz- oder Superkalanders.A disadvantage of this recording material is the fact that the material has to be smoothed in a separate operation in order to achieve the desired color density after application of the ink-receiving layer, e.g. B. by using a gloss or super calender.

In der japanischen Schrift JP 58-193 185 werden auf einen Träger zwei Schichten aufgetragen. Die obere aus Polyvinylalkohol bestehende Schicht soll für eine schnelle Tintenabsorption sorgen. Die untere eine synthetische Kieselsäure enthaltende Schicht soll eine hohe Farbdichte gewährleisten. Nachteilig ist daran, daß zur Herstellung dieses Aufzeichnungsmaterials mehrere Arbeitsgänge erforderlich sind, nämlich das gesonderte Auftragen zweier Schichten und das Glätten mit Hilfe eines Kalanders.In JP 58-193 185, two layers are applied to a support. The top layer made of polyvinyl alcohol is said to ensure fast ink absorption. The lower layer, which contains synthetic silica, is said to ensure a high color density. The disadvantage of this is that several steps are required to produce this recording material, namely the separate application of two layers and the smoothing with the aid of a calender.

Die EP-A-445327 beschreibt ein Aufzeichnungsmaterial für das Tintenstrahldruck-Verfahren, in dem die Tintenaufnahmeschicht eine Mischung aus Gelatine und Reisstärke enthält.EP-A-445327 describes a recording material for the ink jet printing process in which the ink receiving layer contains a mixture of gelatin and rice starch.

Aufgabe der vorliegenden Erfindung ist es, ein Aufzeichnungsmaterial für das ink jet-Verfahren vorzuschlagen, welches die oben erwähnten Nachteile nicht aufweist und sich insbesondere durch eine hohe Farbdichte und ein hohes Auflosevermögen bei gleichzeitig schnell erreichbarer Wischfestigkeit der Tintentröpfchen auszeichnet.The object of the present invention is to propose a recording material for the ink jet process which does not have the disadvantages mentioned above and which is distinguished in particular by a high color density and a high resolving power with at the same time quickly achievable wiping resistance of the ink droplets.

Aufgabe der Erfindung ist es ebenfalls, eine Beschichtungsmasse zur Herstellung einer Tintenaufnahmeschicht für ein ink jet-Aufzeichnungsmaterial bereitzustellen, die die Herstellung eines Aufzeichnungsmaterials ohne die oben erwähnten Nachteile ermöglicht.It is also an object of the invention to provide a coating composition for the production of an ink-receiving layer for an ink jet recording material which enables the production of a recording material without the disadvantages mentioned above.

Diese Aufgabe wird dadurch gelost, daß auf ein polyolefinbeschichtetes Basispapier eine Tintenaufnahmeschicht aufgetragen wird, die ein hydrophiles Bindemittel und ein oxydiertes Polyethylen enthält, wobei das oxydierte Polyethylen in der für die Tintenaufnahmeschicht verwendeten wäßrigen Beschichtungsmasse als ein kationaktiv emulgiertes oxydiertes Polyethylen vorliegt.This object is achieved in that an ink receiving layer which contains a hydrophilic binder and an oxidized polyethylene is applied to a polyolefin-coated base paper, the oxidized polyethylene being present in the aqueous coating composition used for the ink receiving layer as a cationically emulsified oxidized polyethylene.

Bei dem hydrophilen Bindemittel handelt es sich in einer bevorzugten Form der Erfindung um ein proteinhaltiges Bindemittel, insbesondere Gelatine.In a preferred form of the invention, the hydrophilic binder is a protein-containing binder, in particular gelatin.

Das in der Tintenaufnahmeschicht enthaltene oxydierte Polyethylen liegt in der hierfür verwendeten Beschichtungsmasse in einer kationaktiv emulgierten Form vor. Vorzugsweise ist das oxydierte Polyethylen mit Verbindungen aus der Gruppe der Fettamine, Fettaminacetate, der quartären Ammoniumverbindungen u.ä. kationaktiv emulgiert. Insbesondere ist das oxydierte Polyethylen ein mit Stearylfettaminacetat kationaktiv emulgiertes oxydiertes Polyethylen.The oxidized polyethylene contained in the ink receiving layer is present in the coating composition used for this in a cationically emulsified form. Preferably, the oxidized polyethylene with compounds from the group of fatty amines, fatty amine acetates, quaternary ammonium compounds and the like. cationically emulsified. In particular, the oxidized polyethylene is an oxidized polyethylene cationically emulsified with stearyl fatty amine acetate.

Die Menge des kationaktiv emulgierten oxydierten Polyethylens in der wäßrigen Beschichtungsmasse beträgt zwischen 0,1 und 5 Gew.-%, insbesondere zwischen 1 und 4 Gew.-%.The amount of the cationically emulsified oxidized polyethylene in the aqueous coating composition is between 0.1 and 5% by weight, in particular between 1 and 4% by weight.

Die Menge des Bindemittels in der Tintenaufnahmeschicht beträgt wenigstens 50 Gew.-%, vorzugsweise 70 bis 99 Gew.-%, bezogen auf die trockene Schicht.The amount of the binder in the ink-receiving layer is at least 50% by weight, preferably 70 to 99% by weight, based on the dry layer.

Die Tintenaufnahmeschicht kann zusätzlich Weißpigmente, Farbstoffe, Härtungsmittel, Dispergierhilfsmittel, Netzmittel u.ä. Hilfsstoffe enthalten.The ink-receiving layer can additionally contain white pigments, dyes, hardening agents, dispersing aids, wetting agents and the like. Contain auxiliaries.

Die Auftragsmenge der Tintenaufnahmeschicht beträgt 0,5 bis 10 g/m², vorzugsweise 2 bis 7 g/m². Die Beschichtungsmasse für die Tintenaufnahmeschicht kann mit allen gebräuchlichen Auftrags- und Dosierverfahren auf den Träger aufgetragen werden, wie z.B. Walzenauftrag-, Gravur- oder Nipp-Verfahren sowie Luftbürsten- oder Rollrakeldosierung.The application amount of the ink-receiving layer is 0.5 to 10 g / m², preferably 2 to 7 g / m². The coating composition for the ink-receiving layer can be applied to the carrier by all customary application and metering methods, such as e.g. Roller application, engraving or nipping processes as well as air brush or roller doctor metering.

Die Beschichtungsmasse wurde folgendermaßen hergestellt (Mengen wie in Beispiel 1 und 2):
Eine wäßrige Gelatinelösung mit einem Gelatinegehalt von 20 Gew.-% wurde unter Rühren in auf 45° C erwämtes Wasser zugegeben. Danach wurde unter Rühren eine kationaktiv stabilisierte 32 %ige wäßrige Emulsion eines oxydierten Polyethylens zugegeben. Die Mischung wurde mittels Natron-Lauge auf einen pH-Wert = 8,5 eingestellt.
Die Zugabe weiterer Komponenten erfolgte in der in Beispiel 1 und 2 angegebenen Reihenfolge, wobei zwischen den einzelnen Zugaben eine Rührzeit von ca. 3 bis 5 Minuten eingehalten werden soll. Nach Zugabe der letzten Komponente wurde die Mischung noch 30 Minuten bei 45° C weitergerührt und anschließend verarbeitet.The coating composition was produced as follows (amounts as in Examples 1 and 2):
An aqueous gelatin solution with a gelatin content of 20% by weight was added to water heated to 45 ° C. with stirring. Thereafter, a 32% aqueous emulsion of an oxidized polyethylene stabilized in a cationically active manner was added. The mixture was adjusted to pH = 8.5 using sodium hydroxide solution.
Further components were added in the order given in Examples 1 and 2, with a stirring time of about 3 to 5 minutes being maintained between the individual additions. After the last component had been added, the mixture was stirred at 45 ° C. for a further 30 minutes and then processed.

Das zur Beschichtung des Basispapiers verwendete Polyolefin ist vorzugsweise Polyethylen niedriger Dichte (LDPE) und/oder Polyethylen hoher Dichte (HDPE). Aber auch andere Polyolefine, wie z. B. LLDPE oder Polypropylen können verwendet werden. Die Auftragsmenge der Polyolefinbeschichtung, die zusätzlich Pigmente und andere Zusätze enthalten kann, beträgt wenigstens 5 g/m².The polyolefin used to coat the base paper is preferably low density polyethylene (LDPE) and / or high density polyethylene (HDPE). But also other polyolefins, such as. B. LLDPE or polypropylene can be used. The application amount of the polyolefin coating, which may additionally contain pigments and other additives, is at least 5 g / m².

Es war überraschend, daß eine Kombination des hydrophilen Bindemittels mit einem oxydierten Polyethylen, welches in der wäßrigen Beschichtungsmasse in Form einer kationaktiv eingestellten Emulsion vorlag, eine so ausgezeichnete Druckbildqualität lieferte. Es war überraschend, weil das hydrophile Bindemittel allein oder in Kombination mit einem oxydierten Polyethylen, dessen Emulsion nicht kationaktiv stabilisiert war, keine entsprechend guten Ergebnisse lieferte.It was surprising that a combination of the hydrophilic binder with an oxidized polyethylene, which was present in the aqueous coating composition in the form of a cationically adjusted emulsion, gave such an excellent print image quality. It was surprising because the hydrophilic binder alone or in combination with an oxidized polyethylene, the emulsion of which was not cationically stabilized, did not give correspondingly good results.

Der Glanz des erfindungsgemäßen Aufzeichnungsmaterials erfordert keine zusätzlichen Nachbehandlungen, z.B. mittels eines Glanzkalanders.The gloss of the recording material according to the invention does not require additional post-treatments, e.g. using a glossy calender.

Überraschenderweise wird die sehr gute Farbdichte auch ohne Pigmentierung der Tintenaufnahmeschicht erreicht.Surprisingly, the very good color density is achieved even without pigmentation of the ink receiving layer.

Darüber hinaus ist auch eine gute Wasserfestigkeit und Abriebfestigkeit der Druckbilder gegeben.In addition, the print images also have good water resistance and abrasion resistance.

Die folgenden Beispiele sollen die Erfindung näher erläutern.The following examples are intended to explain the invention in more detail.

Beispiel 1example 1

Figure imgb0001
Figure imgb0001
Figure imgb0002
Figure imgb0002

Das erhaltene Aufzeichnungsmaterial wurde in einem "continuous ink jet printing"-Verfahren bedruckt und anschließend analysiert. Die Ergebnisse sind in Tabelle 1 zusammengestellt.The recording material obtained was printed in a "continuous ink jet printing" process and then analyzed. The results are summarized in Table 1.

Beispiel 2Example 2

Die Vorderseite eines polyethylenbeschichteten Basispapiers gemäß Beispiel 1 wurde mit den folgenden Beschichtungsmassen beschichtet: Bestandteile Zusammensetzung, Gew.-% 2a 2b Gelatine (220 Bloom) 20%ig in Wasser 51,0 46,0 oxydiertes Polyethylen 32%ig in Wasser mit Stearylfettaminacetat stabilisiert (Südranol 270, Süddeutsche Emulsions-Chemie GmbH) 0,4 5,0 amphotere Kieselsäure 10,0 10,0 Netzmittel (Triton X100) 10%ig in Wasser 0,5 0,5 Alkohol-Mischung IPA/BU/H₂O 25 : 25 : 50 10,0 10,0 Zitronensäure 10%ig in Wasser 0,3 0,3 Chromalaun 10%ig in Wasser 1,2 1,1 TAF/Formaldehyd (1 : 0,05) 2%ig in IPA/BU/H₂O 1,2 1,1 Wasser, entmineralisiert 25,4 26,0 Auftragsmenge, g/m² 7 7 The front of a polyethylene-coated base paper according to Example 1 was coated with the following coating compositions: Components Composition,% by weight 2a 2 B Gelatin (220 Bloom) 20% in water 51.0 46.0 Oxidized 32% polyethylene stabilized in water with stearyl fatty amine acetate (Südranol 270, Süddeutsche Emulsions-Chemie GmbH) 0.4 5.0 amphoteric silica 10.0 10.0 Wetting agent (Triton X100) 10% in water 0.5 0.5 Alcohol mixture IPA / BU / H₂O 25: 25: 50 10.0 10.0 Citric acid 10% in water 0.3 0.3 Chromalun 10% in water 1.2 1.1 TAF / formaldehyde (1: 0.05) 2% in IPA / BU / H₂O 1.2 1.1 Water, demineralized 25.4 26.0 Order quantity, g / m² 7 7

Die sonstigen Versuchsbedingungen waren wie im Beispiel 1.The other test conditions were as in Example 1.

Die Prüfergebnisse sind in Tabelle 1 zusammengestellt.The test results are summarized in Table 1.

VergleichsbeispieleComparative examples

  • V1. Für die Beschichtungsmasse wurde als Bindemittel Gelatine allein verwendet. Auf den Zusatz von kationaktiv stabilisiertem oxydiertem Polyethylen wurde verzichtet.
    Die sonstigen Versuchsbedingungen waren wie im Beispiel 1.     V1. Gelatin alone was used as the binder for the coating composition. No cationically stabilized oxidized polyethylene was added.
    The other test conditions were as in Example 1.
  • V2. Für die Beschichtungsmasse wurde neben Gelatine ein nicht ionogen stabilisiertes oxydiertes Polyethylen verwendet.V2. In addition to gelatin, a non-ionically stabilized oxidized polyethylene was used for the coating composition.

Die sonstigen Versuchsbedingungen waren wie im Beispiel 1.The other test conditions were as in Example 1.

Die Tintenaufnahmeschichten gemäß V1 und V2 wurden aus wäßrigem Milieu in folgender Zusammensetzung aufgetragen: Bestandteile Zusammensetzung, Gew.-% V1 V2 Gelatine (220 Bloom) 20%ig in Wasser 61,4 61,0 oxydiertes Polyethylen 32%ig in Wasser nichtionoges Emulgatorensystem (Südranol 340, Süddeutsche Emulsions-Chemie GmbH) - 0,4 Netzmittel (Triton X100) 10%ig in Wasser 0,5 0,5 Alkohol-Mischung IPA/BU/H₂O 25 : 25 : 50 10,0 10,0 Zitronensäure 10%ig in Wasser 0,3 0,3 Chromalaun 10%ig in Wasser 1,5 1,5 TAF/Formaldehyd (1 : 0,05) 2%ig in IPA/BU/H₂O 1,5 1,5 Wasser, entmineralisiert 24,8 24,8 Auftragsmenge, g/m² 7 7 The ink-receiving layers according to V1 and V2 were applied from an aqueous medium in the following composition: Components Composition,% by weight V1 V2 Gelatin (220 Bloom) 20% in water 61.4 61.0 oxidized polyethylene 32% in water non-ionic emulsifier system (Südranol 340, Süddeutsche Emulsions-Chemie GmbH) - 0.4 Wetting agent (Triton X100) 10% in water 0.5 0.5 Alcohol mixture IPA / BU / H₂O 25: 25: 50 10.0 10.0 Citric acid 10% in water 0.3 0.3 Chromalun 10% in water 1.5 1.5 TAF / formaldehyde (1: 0.05) 2% in IPA / BU / H₂O 1.5 1.5 Water, demineralized 24.8 24.8 Order quantity, g / m² 7 7

Das gemäß den Vergleichsbeispielen erhaltene Aufzeichnungsmaterial wurde in einem kontinuierlichen ink jet-Verfahren bedruckt und anschließend analysiert. Die Ergebnisse sind in Tabelle 2 zusammengestellt.The recording material obtained according to the comparative examples was printed in a continuous ink jet process and then analyzed. The results are summarized in Table 2.

Prüfung des gemäß Beispiel 1 - 2 und Vergleichsbeispiel V1 - V2 hergestellten AufzeichnungsmaterialsExamination of the recording material produced according to Examples 1-2 and Comparative Example V1-V2

Das Aufzeichnungsmaterial wurde mit Hilfe eines nach dem Hertz-Tintenstrahldruck-Prinzip arbeitenden Excelerator 4/1120-Tintenstrahldruckers der Fa. Stork X-cel unter Verwendung der von der Fa. Stork entwickelten Tinten bedruckt. Bei den erhaltenen Druckbildern wurden Farbdensität, Abriebfestigkeit, Wasserfestigkeit und Glanz untersucht.The recording material was printed with the aid of an Excelerator 4/1120 inkjet printer from Stork X-cel, which works according to the Hertz inkjet printing principle, using the inks developed by Stork. Color density, abrasion resistance, water resistance and gloss were examined in the print images obtained.

Die Densitätsmessungen erfolgten vor und nach einer 24-h-Belichtung der Bilder mittels Xenon-Lampe. Das hierzu verwendete Gerät war ein Original Reflection Densitometer SOS-45. Die Messungen erfolgten in den Farbabstufungen F1 - F6 für die Farben Cyan, Magenta, Gelb und Schwarz, wobei in den Tabellen die Werte für F1 und F6 angegeben sind.The density measurements were carried out before and after a 24-hour exposure of the images using a xenon lamp. The device used for this was an original reflection densitometer SOS-45. The measurements were carried out in the color gradations F1 - F6 for the colors cyan, magenta, yellow and black, the values for F1 and F6 being given in the tables.

Die Wischfestigkeit wurde nach dem Grad des sog. "Wegschlagens" der Druckfarbe von der Oberfläche des Materials beurteilt. Der Test wurde für alle vier Grundfarben einzeln durchgeführt. Die Bezeichnung "+" bedeutet, daß alle Farben gleichermaßen sofort von der Blattoberfläche "wegschlagen", d.h. in das Schichtinnere penetrieren. Die Bezeichnung "o" bedeutet, daß 3 Grundfarben sofort von der Blattoberfläche in das Schichtinnere penetrieren und die vierte Grundfarbe erst nach Ablauf von einigen Sekunden. Mit "-" wurde eine schlechte Wischfestigkeit des Materials bezeichnet, d.h. es wird keines oder nur schwaches Penetrieren fast aller Farben beobachtet.The smudge resistance was assessed according to the degree of so-called "knocking off" of the printing ink from the surface of the material. The test was carried out individually for all four primary colors. The designation "+" means that all colors immediately "strike away" from the leaf surface, ie penetrate into the layer interior. The designation "o" means that 3 primary colors immediately penetrate from the leaf surface into the layer interior and the fourth primary color only after a few seconds. "-" denotes a poor smudge resistance of the material, ie no or only weak penetration of almost all colors is observed.

Für den Wasserfestigkeits- und Abriebfestigkeitstest wurde das Aufzeichnungsmaterialmuster in Wasser erhitzt und in Abständen von 5° C mit dem Finger gerieben. Die Temperatur, bei der der weiße Untergrund des Aufzeichnungsmaterials durchscheint, wurde als Maß der Wasserfestigkeit und Abriebfestigkeit genommen.For the water resistance and abrasion resistance test, the recording material sample was heated in water and rubbed with a finger at 5 ° C. intervals. The temperature at which the white background of the recording material shows through was taken as a measure of the water resistance and abrasion resistance.

Der Glanz des Aufzeichnungsmaterials wurde mit einem Dreiwinkel-Glanzmeßgerät nach Dr. Lange bei einem Meßwinkel von 60° C gemessen.The gloss of the recording material was measured using a three-angle gloss meter according to Dr. Measured for a long time at a measuring angle of 60 ° C.

Die in den Tabellen 1 und 2 zusammengestellten Ergebnisse zeigen, daß mit dem erfindungsgemäßen Aufzeichnungsmaterial Druckbilder mit hohen Werten der Farbdensität bei gleichzeitig schnell erreichbarer Wischfestigkeit erzielt werden. Aber auch hinsichtlich der Wasser- und Abriebfestigkeit und des Glanzes weisen die auf erfindungsgemäß erzeugtem Aufzeichnungsmaterial gedruckten Bilder bessere Werte als das Vergleichsmaterial auf.

Figure imgb0003
Figure imgb0004
 The results summarized in Tables 1 and 2 show that the recording material according to the invention achieves print images with high values of color density and at the same time quickly achievable smudge resistance. But also in terms of water and abrasion resistance and gloss, the images printed on the recording material produced according to the invention have better values than the comparison material.
Figure imgb0003
Figure imgb0004

Claims (20)

  1. Recording material for an ink jet process consisting of a carrier with a dried ink absorbing layer applied as an aqueous coating thereon, characterized in that the ink absorbing layer contains a hydrophilic binder and an oxidized polyethylene, said oxidized polyethylene being present in the ink absorbing layer aqueous coating as a cationic active emulsified oxidized polyethylene.
  2. Recording material of claim 1, characterized in that the carrier is a polyolefin coated base paper or a plastic foil.
  3. Recording material of claims 1 and 2, characterized in that hydrophilic binder is a protein containing binder.
  4. Recording material of claim 3, characterized in that hydrophilic binder is a gelatin.
  5. Recording material of claims 1 to 4, characterized in that the oxidized polyethylene is a cationic active oxidized polyethylene emulsified with compounds from the group consisting of fatty amines, fatty amino acetates and quaternary ammonium compounds.
  6. Recording material of claims 5, characterized in that the oxidized polyethylene is a cationic active oxidized polyethylene emulsified with stearyl fatty amino acetate.
  7. Recording material of claims 1 to 6, characterized in that the quantity of the cationic active, emulsified, oxidized polyethylene present in the coating is between 0.1 to 5 wt%.
  8. Recording material of claim 1, characterized in that the quantity of the binder in the ink absorbing layer is at least 50% by weight.
  9. Recording material of claims 1 to 8, characterized in that the ink absorbing layer additionally contains pigments, coloring agents, hardening agents, auxiliary dispersion agents, surface active agents and other auxiliary agents.
  10. Recording material of claims 1 to 9, characterized in that the carrier is a base paper coated with a polyolefin.
  11. Recording material of claims 1 to 10, characterized in that the amount of the polyolefin coating is at least 5 g /m², in particular 10 to 35 g/m².
  12. Coating material for the preparation of an ink absorbing layer or an ink jet process characterized in that the coating material contains a hydrophilic binder and a cationic active emulsified oxidized polyethylene.
  13. Coating material of claim 12, characterized in that the oxidized polyethylene is a cationic active oxidized polyethylene emulsified with compounds from the group consisting of fatty amines, fatty amino acetates and quaternary ammonium compounds.
  14. Coating material of claim 13, wherein the oxidized polyethylene is a cationic active, oxidized polyethylene emulsified with stearyl fatty amino acetate.
  15. Coating material of claims 12 to 14, characterized in that the amount of the cationic active emulsified oxidized polyethylene in the coating material is from 0.1 to 5% by weight.
  16. Coating material of claims 12 to 15, characterized in that the hydrophilic binder is a protein containing binder, in particular gelatin.
  17. Coating material of claims 12 to 16, characterized in that the amount of the binder in the coating material is at least 30% by weight.
  18. Coating material of claims 12 to 17, characterized in that the coating material contains additionally pigments, coloring agents, hardening agents, dispersion auxiliary agents, surfactants and other auxiliary agents.
  19. Coating material of claims 12 to 15, characterized in that it is applied on a polyolefin coated base paper, in particular a polyethylene coated base paper.
  20. Coating material of claims 12 to 18, characterized in that it is applied on a plastic foil.
EP92114117A 1991-10-26 1992-08-19 Recording material for the ink jet process Expired - Lifetime EP0539678B1 (en)

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DE4135388 1991-10-26
DE4135388A DE4135388A1 (en) 1991-10-26 1991-10-26 RECORD MATERIAL FOR INK JET PROCEDURE

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US6203153B1 (en) 1996-02-28 2001-03-20 Hewlett-Packard Company Method and apparatus for printing on gelatin coated media
US6270858B1 (en) 1996-11-15 2001-08-07 Fargo Electronics, Inc. Method of coating using an ink jet printable mixture
US6051306A (en) * 1996-11-15 2000-04-18 Fargo Electronics, Inc. Ink jet printable surface
US6153288A (en) * 1997-07-24 2000-11-28 Avery Dennison Corporation Ink-receptive compositions and coated products
JP4178493B2 (en) * 1999-11-30 2008-11-12 北越製紙株式会社 Inkjet recording sheet
US7037013B2 (en) * 2001-03-05 2006-05-02 Fargo Electronics, Inc. Ink-receptive card substrate
US6979141B2 (en) * 2001-03-05 2005-12-27 Fargo Electronics, Inc. Identification cards, protective coatings, films, and methods for forming the same
US6485609B1 (en) 2001-03-08 2002-11-26 Celanese International Corporation Ink jet printing paper incorporating amine functional poly(vinyl alcohol)
EP1412422A4 (en) 2001-07-25 2006-04-26 Avery Dennison Corp Synthetic paper skins and methods of their manufacture
US8956490B1 (en) 2007-06-25 2015-02-17 Assa Abloy Ab Identification card substrate surface protection using a laminated coating
JP6253243B2 (en) * 2013-04-16 2017-12-27 キヤノン株式会社 Recording apparatus and recording method

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