EP0631880A1 - Recording sheet for ink jet printing process - Google Patents

Recording sheet for ink jet printing process Download PDF

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Publication number
EP0631880A1
EP0631880A1 EP19940105767 EP94105767A EP0631880A1 EP 0631880 A1 EP0631880 A1 EP 0631880A1 EP 19940105767 EP19940105767 EP 19940105767 EP 94105767 A EP94105767 A EP 94105767A EP 0631880 A1 EP0631880 A1 EP 0631880A1
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EP
European Patent Office
Prior art keywords
recording sheet
sheet according
ink
receiving layer
water
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.)
Granted
Application number
EP19940105767
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German (de)
French (fr)
Other versions
EP0631880B1 (en
Inventor
Dieter Dr. Dipl.-Chem. Becker
Gerhard Dr. Dr.-Ing. Dransmann
Jürgen Dipl.-Ing. Graumann (FH)
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Felix Schoeller Jr Foto und Spezialpapiere GmbH
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Felix Schoeller Jr Foto und Spezialpapiere GmbH
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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
    • 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
    • B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
    • 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
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • 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
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y10T428/277—Cellulosic substrate
    • 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
    • Y10T428/31928—Ester, halide or nitrile of addition polymer

Definitions

  • the invention relates to a recording material for the ink-jet printing process and a coating composition for producing an ink-receiving layer for the ink-jet process.
  • ink jet recording systems printing operations are carried out by forming ink droplets by various ink jet methods such as electrostatic attraction, bubble formation and applying them to a recording material.
  • Another group of recording materials are the papers provided with an ink-receiving layer.
  • 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.
  • Japanese patent application JP 61-261 089 proposes a transparent material for "overhead" projectors which, in addition to a polyvinyl alcohol / polyvinylpyrrolidone mixture, additionally contains a cationic conductive resin. Good wiping and water resistance is achieved, but not sufficient wet rub resistance.
  • the object of the present invention is therefore to propose a recording material for the ink-jet printing process which fulfills the requirements mentioned at the outset, but in particular, in addition to high color density and sharpness, ensures good water resistance and wet friction resistance.
  • a recording material which consists of a support and an ink receiving layer arranged thereon, which contains a polyvinyl alcohol, polyvinylpyrrolidone homopolymer and / or vinylpyrrolidone copolymer and a water-soluble substance containing aldehyde groups.
  • the water-soluble substance containing aldehyde groups can be a melamine-formaldehyde condensation product with a free CHO group content of at least 0.05 mol%.
  • a polyvalent aldehyde such as oxalaldehyde can also be used here.
  • the quantitative ratio of the water-soluble substance to the hydrophilic binder contained in the ink-receiving layer is 1: 1 to 1:40. In a preferred embodiment, the ratio is 1: 1.5 to 1:27.
  • the quantitative ratio of polyvinyl alcohol to polyvinyl pyrrolidone homopolymer and / or copolymer in the binder mixture is 10: 1 to 4: 1.
  • the polyvinylpyrrolidone copolymer is a vinylpyrrolidone / vinyl acetate or a vinylpyrrolidone / styrene copolymer.
  • the amount of the water-soluble substance containing aldehyde groups in the ink receiving layer is 2 to 15% by weight, in particular 3 to 10% by weight.
  • the amount of binder in the layer is 15 to 80% by weight, in particular 30 to 60% by weight.
  • the ink-receiving layer contains a quaternary ammonium compound with a certain cationicity, which can be determined using a PCD titration with a 1. 10 ⁇ 3 n solution of the polyethensulfonic acid sodium (PES solution) is determined.
  • the cationicity values determined by this method for the ammonium compounds according to the invention are 15 to 30 ml of PES solution, in particular 20 to 25 ml of PES solution.
  • Ammonium compounds include e.g. B. polyamine salts and polyamide amine compounds. Polydiallyldimethylammonium chloride has proven to be particularly advantageous.
  • the ink-receiving layer according to the invention can also other additives, such as. B. white pigments, colored pigments, dyes, dispersants, wetting agents, curing agents and optical brighteners.
  • Pigments used in the ink receptive layer include: silica, clay, zeolites and other inorganic pigments.
  • the ink-receiving layer contains an amorphous silica which has a pore volume of 1.0-2.5 ml / g with a particle size of ⁇ 5 ⁇ m.
  • the amount of the pigment in the ink receiving layer is 10 to 80% by weight, especially 40 to 65% by weight.
  • the ink-receiving layer is applied to the carrier from an aqueous dispersion using all customary application and metering methods.
  • the application amount of the ink-receiving layer is 0.5 to 15 g / m2, preferably 2 to 8 g / m2.
  • a plastic film, a coated or an uncoated base paper can be used as the carrier.
  • the base paper can be acidic or neutral sized. Preference is given to a base paper sized with diketene and containing 5 to 20% by weight of pigment and / or filler, such as TiO2, CaCO3 and SiO2.
  • the back of the base paper has a layer which contains a hydrophilic colloidal binder, such as starch, modified starch, polyvinyl alcohol, gelatin.
  • a hydrophilic colloidal binder such as starch, modified starch, polyvinyl alcohol, gelatin.
  • An oxidized potato starch is particularly preferred.
  • the back layer can contain up to 60% by weight of fillers (e.g. clay, zeolite, CaCO3), pigments and other additives.
  • fillers e.g. clay, zeolite, CaCO3
  • the front of a neutral sized with alkyl ketene dimer and 20 wt.% CaCO3 in the mass-containing base paper of 80 g / m2 basis weight was coated with an aqueous coating material and dried.
  • the ink-receiving layers obtained have the following composition: Components Composition,% by weight 1a 1b 1c 1d 1e 1f 1g 1h
  • Polyvinylpyrrolidone molecular weight 630,000 daltons 7.0 7.0 - - 7.0 7.0 7.0 7.0 7.0 Vinyl pyrrolidone / vinyl acetate cop.
  • the back of the base paper was provided with a layer consisting of oxidized potato starch and 20 wt .-% CaCO3.
  • the application weight of this back layer was 4 g / m2.
  • the front of the base paper from Example 1 was coated with an aqueous coating composition and dried.
  • the ink-receiving layer obtained has the following composition: Components Composition,% by weight 2a 2 B 2c 2d Polyvinyl alcohol saponification degree: 88 mol% 28.0 28.0 28.0 40.0 Polyvinylpyrrolidone molecular weight: 630,000 daltons 7.0 7.0 7.0 4.0 Amorphous silica A 50.0 50.0 58.0 52.0 Polyammonium salt with a cationicity of: 21.58 ml PES solution 10.0 5.0 2.0 2.0 Melamine formaldehyde condensation product 5.0 10.0 5.0 2.0 Order quantity, g / m2 4th 4th 4th 4th
  • Example 2 The back of the base paper was provided with a starch screed as in Example 1. The other test conditions were as in Example 1. The results of the examination of the print images subsequently obtained are summarized in Table 2.
  • Example 1b The procedure was as in Example 1b. Instead of the polydimethyldiallylammonium chloride, an amide derivative with a cationicity of 13.11 ml of PES solution was used.
  • the base paper from Example 1 was provided with a receiving layer in which the use of a water-soluble substance containing aldehyde groups was dispensed with.
  • the ink-receiving layers according to Comparative Examples V1 and V2 were applied from an aqueous medium and had the following compositions after drying: Components Composition,% by weight V1 V2 Polyvinyl alcohol saponification degree: 88 mol% 28.0 28.0 Polyvinylpyrrolidone molecular weight: 630,000 daltons 7.0 7.0 Amorphous silica A 56.5 56.5 Polyamidamine with a cationicity of: 13.11 ml PES solution 3.5 - Polydiallyldimethylammonium chloride (see Example 1) - 8.5 Melamine formaldehyde resin 5.0 - Application weight, g / m2 4th 4th
  • the recording material obtained in the comparative examples was printed in a so-called "thermal jet” process and then analyzed.
  • the results are summarized in Table 3.
  • two commercially available recording materials were used and analyzed.
  • the test results are summarized in Tab. 3.
  • the recording material was printed using an HP Deskjet 550 C ink jet printer from Hewlett Packard, which works on the bubble jet principle (thermal jet).
  • the density measurements were carried out using an "Original Reflection Densitometer SOS-45". The measurements were carried out for the basic colors cyan, magenta, yellow and black.
  • the recording material was immersed in water to investigate the water resistance.
  • the density (%) remaining in the water bath after 60 s is used as a measure of the water stability.
  • the image sharpness is determined with the help of a thread counter.
  • Field distances between a red and a green or two black fields are read (maximum value 1mm).
  • the colored fields (composed of the primary colors) have 200% ink coverage. They therefore serve as test fields for fixing large quantities of ink.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Laminated Bodies (AREA)
  • Paper (AREA)
  • Ink Jet (AREA)

Abstract

A recording sheet for ink-jet printing processes, comprising a support (carrier, base, substrate) and an ink take-up (absorption) layer containing a hydrophilic binder and a pigment, where the ink take-up layer contains a mixture of polyvinyl alcohol, vinylpyrrolidone homopolymer and/or vinylpyrrolidone copolymer as binder and a water-soluble substance containing aldehyde groups.

Description

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

Bei Ink-Jet-Aufzeichnungssystemen werden Bedruckvorgänge durchgeführt, indem Tintentröpfchen mittels verschiedener Tintenstrahlverfahren, wie elektrostatisches Anziehungsverfahren, Blasenbildungsverfahren, gebildet und auf ein Aufzeichnungsmaterial gebracht werden.In ink jet recording systems, printing operations are carried out by forming ink droplets by various ink jet methods such as electrostatic attraction, bubble formation and applying them to a recording material.

Für derartige Aufzeichnungsvorgange, die das Drucken von Bildern mit sehr hoher Auflösung direkt aus elektronischen Daten erlaubt, werden an die hierfür eingesetzten Bildempfangsmaterialien hohe Anforderungen gestellt. Das mittels Ink-Jet-Verfahren erzeugte Bild soll verfügen über

  • hohe Auflösung,
  • hohe Farbdichte,
  • genügend Farbabstufungen,
  • gute Wischfestigkeit,
  • gute Wasserfestigkeit.
For such recording processes that allow the printing of images with very high resolution directly from electronic data, high demands are placed on the image-receiving materials used for this purpose. The image created using the ink jet process is said to have
  • high resolution,
  • high color density,
  • enough color gradations,
  • good smudge resistance,
  • good water resistance.

Um dies zu erreichen, müssen folgende Grundbedingungen erfüllt werden:

  • die Tinte muß vom Aufzeichnungsmaterial rasch absorbiert werden,
  • 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,
  • ein Tintenpunkt soll beim überlappen mit einem vorher aufgebrachten Tintenpunkt diesen nicht beeinträchtigen oder verwischen,
  • das Aufzeichnungsmaterial muß eine Oberfläche aufweisen, die eine hohe visuelle Reflexionsdichte und eine hohe Brillanz der Farben ermöglicht,
  • das Aufzeichnungsmaterial soll eine hohe Formbeständigkeit aufweisen, ohne daß es sich nach dem Druckvorgang dehnt.
To achieve this, the following basic conditions must be met:
  • the ink must be quickly absorbed by the recording material,
  • 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,
  • an ink dot should not interfere with or blur an ink dot when it is overlapped,
  • the recording material must have a surface which enables a high visual reflection density and a high brilliance of the colors,
  • the recording material should have a high dimensional stability without stretching after the printing process.

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.These are partly contradictory claims, e.g. B. means that the wiping resistance is set too quickly that an ink drop does not diverge, or only slightly, and thereby the clarity of the resulting image is 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.

Es ist bekannt, als Aufzeichnungsmaterial für den Ink-Jet-Druck Papier zu verwenden, in dem die Farbflüssigkeiten in den zwischen den Papierfasern oder zwischen Fasern und Füllstoff gebildeten Räumen absorbiert werden können.It is known to use paper as a recording material for ink-jet printing, in which the color liquids can be absorbed in the spaces formed between the paper fibers or between fibers and filler.

Eine andere Gruppe von Aufzeichnungsmaterialien sind die mit einer Tintenaufnahmeschicht versehenen Papiere.Another group of recording materials are the papers provided with an ink-receiving layer.

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.

Aus der japanischen Offenlegungsschrift JP 61-041 585 ist bekannt, ein Aufzeichnungsmaterial mit einer Empfangsschicht aus Polyvinylalkohol und Polyvinylpyrrolidon herzustellen. Das Mischungsverhältnis beider Komponenten PVA : PVP beträgt 3 : 1 bis 1 : 5. Nachteilig an diesem Material ist jedoch die mangelnde Wasserfestigkeit und Naßreibfestigkeit des Materials.From Japanese published patent application JP 61-041 585 it is known to produce a recording material with a receiving layer made of polyvinyl alcohol and polyvinyl pyrrolidone. The mixing ratio of both components PVA: PVP is 3: 1 to 1: 5. A disadvantage of this material is the lack of water resistance and wet friction resistance of the material.

In der japanischen Offenlegungsschrift JP 61-261 089 wird ein transparentes Material für "over head"-Projektoren vorgeschlagen, welches neben einer Polyvinylalkohol/Polyvinylpyrrolidon-Mischung zusätzlich ein kationisches leitfähiges Harz enthält. Dadurch wird zwar eine gute Wischfestigkeit und Wasserfestigkeit, aber keine ausreichende Naßreibfestigkeit erreicht.Japanese patent application JP 61-261 089 proposes a transparent material for "overhead" projectors which, in addition to a polyvinyl alcohol / polyvinylpyrrolidone mixture, additionally contains a cationic conductive resin. Good wiping and water resistance is achieved, but not sufficient wet rub resistance.

Aufgabe der vorliegenden Erfindung ist es daher, ein Aufzeichnungsmaterial für das Ink-Jet-Druckverfahren vorzuschlagen, welches die eingangs erwähnten Anforderungen erfüllt, insbesondere aber neben hoher Farbdichte und Bildschärfe eine gute Wasserfestigkeit und Naßreibfestigkeit gewährleistet.The object of the present invention is therefore to propose a recording material for the ink-jet printing process which fulfills the requirements mentioned at the outset, but in particular, in addition to high color density and sharpness, ensures good water resistance and wet friction resistance.

Gelöst wird diese Aufgabe durch ein Aufzeichnungsmaterial, welches aus einem Träger und einer darauf angeordneten Tintenaufnahmeschicht besteht, die ein Polyvinylalkohol, Polyvinylpyrrolidon-Homopolymer und/oder Vinylpyrrolidon-Copolymer sowie eine wasserlösliche, Aldehydgruppen enthaltende Substanz enthält.This object is achieved by a recording material which consists of a support and an ink receiving layer arranged thereon, which contains a polyvinyl alcohol, polyvinylpyrrolidone homopolymer and / or vinylpyrrolidone copolymer and a water-soluble substance containing aldehyde groups.

Die wasserlösliche, Aldehydgruppen enthaltende Substanz kann ein Melamin-Formaldehyd-Kondensationsprodukt sein mit einem Gehalt an freien CHO-Gruppen von mindestens 0,05 mol-%. Aber auch ein mehrwertiges Aldehyd, wie Oxalaldehyd kann hier Verwendung finden.The water-soluble substance containing aldehyde groups can be a melamine-formaldehyde condensation product with a free CHO group content of at least 0.05 mol%. However, a polyvalent aldehyde such as oxalaldehyde can also be used here.

Das Mengenverhältnis der wasserlöslichen Substanz zum in der Tintenaufnahmeschicht enthaltenen hydrophilen Bindemittel, welches eine Mischung aus Polyvinylalkohol, Polyvinylpyrrolidon-Homopolymer und/oder Polyvinylpyrrolidon-Copolymer ist, beträgt 1 : 1 bis 1 : 40. In bevorzugter Ausführung beträgt das Verhältnis 1 : 1,5 bis 1 : 27.The quantitative ratio of the water-soluble substance to the hydrophilic binder contained in the ink-receiving layer, which is a mixture of polyvinyl alcohol, polyvinylpyrrolidone homopolymer and / or polyvinylpyrrolidone copolymer, is 1: 1 to 1:40. In a preferred embodiment, the ratio is 1: 1.5 to 1:27.

Das Mengenverhältnis Polyvinylalkohol zu Polyvinylpyrrolidon-Homopolymer und/oder Copolymer in der Bindemittel-Mischung beträgt 10 : 1 bis 4 : 1.The quantitative ratio of polyvinyl alcohol to polyvinyl pyrrolidone homopolymer and / or copolymer in the binder mixture is 10: 1 to 4: 1.

In einer besonderen Ausgestaltung der Erfindung ist das Polyvinylpyrrolidon-Copolymer ein Vinylpyrrolidon/Vinylacetat oder ein Vinylpyrrolidon/Styrol-Copolymer.In a special embodiment of the invention, the polyvinylpyrrolidone copolymer is a vinylpyrrolidone / vinyl acetate or a vinylpyrrolidone / styrene copolymer.

Die Menge der wasserlöslichen, Aldehydgruppen enthaltenden Substanz in der Tintenaufnahmeschicht beträgt 2 bis 15 Gew.%, insbesondere 3 bis 10 Gew.%.The amount of the water-soluble substance containing aldehyde groups in the ink receiving layer is 2 to 15% by weight, in particular 3 to 10% by weight.

Die Menge des Bindemittels in der Schicht beträgt 15 bis 80 Gew.%, insbesondere 30 bis 60 Gew.%.The amount of binder in the layer is 15 to 80% by weight, in particular 30 to 60% by weight.

In einer besonderen Ausgestaltung der Erfindung enthält die Tintenaufnahmeschicht eine quaternäre Ammonium-Verbindung mit einer bestimmten Kationizität, die mit Hilfe der sog. PCD-Titration mit einer 1 . 10⁻³ n Lösung des polyethensulfonsauren Natriums (PES-Lösung) ermittelt wird. Die nach dieser Methode ermittelten Werte der Kationizität für die erfindungsgemäßen Ammonium-Verbindungen betragen 15 bis 30 ml PES-Lösung, insbesondere 20 bis 25 ml PES-Lösung. Zu den quat. Ammonium-Verbindungen gehören z. B. Polyaminsalze und Polyamidamin-Verbindungen. Als besonders vorteilhaft hat sich das Polydiallyldimethylammoniumchlorid erwiesen.In a special embodiment of the invention, the ink-receiving layer contains a quaternary ammonium compound with a certain cationicity, which can be determined using a PCD titration with a 1. 10⁻³ n solution of the polyethensulfonic acid sodium (PES solution) is determined. The cationicity values determined by this method for the ammonium compounds according to the invention are 15 to 30 ml of PES solution, in particular 20 to 25 ml of PES solution. To the quat. Ammonium compounds include e.g. B. polyamine salts and polyamide amine compounds. Polydiallyldimethylammonium chloride has proven to be particularly advantageous.

Die erfindungsgemäße Tintenaufnahmeschicht kann auch andere Zusatzstoffe, wie z. B. Weißpigmente, Buntpigmente, Farbstoffe, Dispergierhilfsmittel, Netzmittel, Härtungsmittel und optische Aufheller enthalten.The ink-receiving layer according to the invention can also other additives, such as. B. white pigments, colored pigments, dyes, dispersants, wetting agents, curing agents and optical brighteners.

Zu den in der Tintenaufnahmeschicht Verwendung findenden Pigmenten gehören: Kieselsäure, Clay, Zeolithe und andere anorganische Pigmente. In einer bevorzugten Ausgestaltung der Erfindung ist in der Tintenaufnahmeschicht eine amorphe Kieselsäure enthalten, die ein Porenvolumen von 1,0 - 2,5 ml/g bei einer Teilchengröße von ≦ 5 µm aufweist. Die Menge des Pigments in der Tintenaufnahmeschicht beträgt 10 bis 80 Gew.%, insbesondere 40 bis 65 Gew.%.Pigments used in the ink receptive layer include: silica, clay, zeolites and other inorganic pigments. In a preferred embodiment of the invention, the ink-receiving layer contains an amorphous silica which has a pore volume of 1.0-2.5 ml / g with a particle size of ≦ 5 μm. The amount of the pigment in the ink receiving layer is 10 to 80% by weight, especially 40 to 65% by weight.

Die Tintenaufnahmeschicht wird aus einer wäßrigen Dispersion mit Hilfe aller gebräuchlichen Auftrags- und Dosierverfahren auf den Träger aufgetragen. Die Auftragsmenge der Tintenaufnahmeschicht beträgt 0,5 bis 15 g/m², vorzugsweise 2 bis 8 g/m². Als Träger kann eine Kunststoffolie, ein beschichtetes oder ein unbeschichtetes Basispapier eingesetzt werden. Das Basispapier kann ein sauer oder ein neutral geleimtes Papier sein. Bevorzugt wird ein mit Diketen geleimtes Basispapier, das 5 bis 20 Gew.% Pigment und/oder Füllstoff enthält, wie TiO₂, CaCO₃ und SiO₂.The ink-receiving layer is applied to the carrier from an aqueous dispersion using all customary application and metering methods. The application amount of the ink-receiving layer is 0.5 to 15 g / m², preferably 2 to 8 g / m². A plastic film, a coated or an uncoated base paper can be used as the carrier. The base paper can be acidic or neutral sized. Preference is given to a base paper sized with diketene and containing 5 to 20% by weight of pigment and / or filler, such as TiO₂, CaCO₃ and SiO₂.

In einer weiteren bevorzugten Ausgestaltung der Erfindung weist die Rückseite des Basispapiers eine Schicht auf, die ein hydrophiles kolloidales Bindemittel, wie Stärke, modifizierte Stärke, Polyvinylalkohol, Gelatine enthält. Insbesondere bevorzugt wird eine oxydierte Kartoffelstärke.In a further preferred embodiment of the invention, the back of the base paper has a layer which contains a hydrophilic colloidal binder, such as starch, modified starch, polyvinyl alcohol, gelatin. An oxidized potato starch is particularly preferred.

Die Rückseitenschicht kann bis 60 Gew.% Füllstoffe (z. B. Clay, Zeolith, CaCO₃), Pigmente und andere Zusatzstoffe enthalten.The back layer can contain up to 60% by weight of fillers (e.g. clay, zeolite, CaCO₃), pigments and other additives.

Die Erfindung soll mit Hilfe der nachfolgenden Beispiele näher erläutert werden.The following examples are intended to illustrate the invention.

Beispiel 1example 1

Die Vorderseite eines mit Alkylketendimer neutral geleimten und 20 Gew.% CaCO₃ in der Masse enthaltenden Rohpapiers von 80 g/m² Flächengewicht wurde mit einer wäßrigen Beschichtungsmasse beschichtet und getrocknet. Die erhaltenen Tintenaufnahmeschichten haben folgende Zusammensetzung: Bestandteile Zusammensetzung, Gew.% 1a 1b 1c 1d 1e 1f 1g 1h Polyvinylalkohol Verseifungsgrad:98Mol% 28,0 - - - - - - - Verseifungsgrad:88Mol% 28,0 28,0 28,0 28,0 28,0 28,0 28,0 Polyvinylpyrrolidon Molgewicht: 630 000 Dalton 7,0 7,0 - - 7,0 7,0 7,0 7,0 Vinylpyrrolidon/Vinylacetat-Cop. 70/30 - - 7,0 - - - - - Vinylpyrrolidon/Styrol-Cop. 50/50 - - - 7,0 - - - - Amorphe Kieselsäure A 56,6 56,6 56,6 56,6 - 56,6 56,6 56,6 B - - - - 56,5 - - - Polyammoniumsalz mit einer Kationizität von 21,58 ml PES-Lösung*) 3,5 3,5 3,5 3,5 3,5 - 3,5 3,5 24,37 ml " - - - - - 3,5 - - Melamin-Formaldehyd-Kondensationsprodukt 5,0 5,0 5,0 5,0 5,0 5,0 - 5,0 Oxalaldehyd - - - - - - 5,0 - Auftragsmenge, g/m² 4 4 4 4 4 4 4 6 A Teilchengröße: 3,2 µm, Porenvolumen 1,2 ml/g
B Teilchengröße: 3,0 µm, Porenvolumen 1,8 ml/g *) PES-Lösung: 1 . 10⁻³n Polyethensulfonsäure - Natrium The front of a neutral sized with alkyl ketene dimer and 20 wt.% CaCO₃ in the mass-containing base paper of 80 g / m² basis weight was coated with an aqueous coating material and dried. The ink-receiving layers obtained have the following composition: Components Composition,% by weight 1a 1b 1c 1d 1e 1f 1g 1h Polyvinyl alcohol Degree of saponification: 98 mol% 28.0 - - - - - - - Degree of saponification: 88 mol% 28.0 28.0 28.0 28.0 28.0 28.0 28.0 Polyvinylpyrrolidone molecular weight: 630,000 daltons 7.0 7.0 - - 7.0 7.0 7.0 7.0 Vinyl pyrrolidone / vinyl acetate cop. 70/30 - - 7.0 - - - - - Vinyl pyrrolidone / styrene cop. 50/50 - - - 7.0 - - - - Amorphous silica A 56.6 56.6 56.6 56.6 - 56.6 56.6 56.6 B - - - - 56.5 - - - Polyammonium salt with a cationicity of 21.58 ml PES solution *) 3.5 3.5 3.5 3.5 3.5 - 3.5 3.5 24.37 ml " - - - - - 3.5 - - Melamine formaldehyde condensation product 5.0 5.0 5.0 5.0 5.0 5.0 - 5.0 Oxalaldehyde - - - - - - 5.0 - Order quantity, g / m² 4th 4th 4th 4th 4th 4th 4th 6 A particle size: 3.2 µm, pore volume 1.2 ml / g
B particle size: 3.0 µm, pore volume 1.8 ml / g *) PES solution: 1. 10⁻³n polyethylene sulfonic acid - sodium

Die Rückseite des Basispapiers wurde mit einer Schicht versehen, die aus oxydierter Kartoffelstärke und 20 Gew.-% CaCO₃ besteht. Das Auftragsgewicht dieser Rückseitenschicht betrug 4 g/m².The back of the base paper was provided with a layer consisting of oxidized potato starch and 20 wt .-% CaCO₃. The application weight of this back layer was 4 g / m².

Sonstige Versuchsbedingungen:Other test conditions:

- Maschinengeschwindigkeit- machine speed 100 m/min100 m / min - Trocknungstemperatur- drying temperature 130° C130 ° C - Trocknungszeit- drying time 5 min.5 min.

Das erhaltene Aufzeichnungsblatt wurde in einem sog. "Thermal Jet"-Verfahren bedruckt und anschließend analysiert. Die Prüfergebnisse sind in Tab. 1 zusammengestellt.The recording sheet obtained was printed in a so-called "thermal jet" process and then analyzed. The test results are summarized in Tab. 1.

Beispiel 2Example 2

Die Vorderseite des Basispapiers aus Beispiel 1 wurde mit einer wäßrigen Beschichtungsmasse beschichtet und getrocknet. Die erhaltene Tintenaufnahmeschicht hat folgende Zusammensetzung: Bestandteile Zusammensetzung, Gew.-% 2a 2b 2c 2d Polyvinylalkohol Verseifungsgrad: 88 Mol.-% 28,0 28,0 28,0 40,0 Polyvinylpyrrolidon Molgewicht: 630 000 Daltons 7,0 7,0 7,0 4,0 Amorphe Kieselsäure A 50,0 50,0 58,0 52,0 Polyammoniumsalz mit einer Kationizität von: 21,58 ml PES-Lösung 10,0 5,0 2,0 2,0 Melamin-Formaldehyd-Kondensationsprodukt 5,0 10,0 5,0 2,0 Auftragsmenge, g/m² 4 4 4 4 The front of the base paper from Example 1 was coated with an aqueous coating composition and dried. The ink-receiving layer obtained has the following composition: Components Composition,% by weight 2a 2 B 2c 2d Polyvinyl alcohol saponification degree: 88 mol% 28.0 28.0 28.0 40.0 Polyvinylpyrrolidone molecular weight: 630,000 daltons 7.0 7.0 7.0 4.0 Amorphous silica A 50.0 50.0 58.0 52.0 Polyammonium salt with a cationicity of: 21.58 ml PES solution 10.0 5.0 2.0 2.0 Melamine formaldehyde condensation product 5.0 10.0 5.0 2.0 Order quantity, g / m² 4th 4th 4th 4th

Die Rückseite des Basispapiers wurde wie im Beispiel 1 mit einem Stärkestrich versehen.
Die sonstigen Versuchsbedingungen waren wie im Beispiel 1. Die Ergebnisse der Untersuchung der anschließend erhaltenen Druckbilder sind in Tabelle 2 zusammengestellt.The back of the base paper was provided with a starch screed as in Example 1.
The other test conditions were as in Example 1. The results of the examination of the print images subsequently obtained are summarized in Table 2.

Vergleichsbeispiel V 1Comparative Example V1

Die Durchführung erfolgte gemäß Beispiel 1 b.
Anstatt des Polydimethyldiallylammoniumchlorids wurde ein Amidderivat mit einer Kationizität von 13,11 ml PES-Lösung eingesetzt.The procedure was as in Example 1b.
Instead of the polydimethyldiallylammonium chloride, an amide derivative with a cationicity of 13.11 ml of PES solution was used.

Vergleichsbeispiel V 2Comparative Example V2

Das Basispapier aus Beispiel 1 wurde mit einer Empfangsschicht versehen, bei der auf den Einsatz einer wasserlöslichen, Aldehydgruppen enthaltenden Substanz verzichtet wurde.The base paper from Example 1 was provided with a receiving layer in which the use of a water-soluble substance containing aldehyde groups was dispensed with.

Die Tintenaufnahmeschichten gemäß den Vergleichsbeispielen V1 und V2 wurden aus wäßrigem Milieu aufgetragen und hatten nach der Trocknung folgende Zusammensetzungen: Bestandteile Zusammensetzung, Gew.-% V1 V2 Polyvinylalkohol Verseifungsgrad: 88 Mol.-% 28,0 28,0 Polyvinylpyrrolidon Molgewicht: 630 000 Daltons 7,0 7,0 Amorphe Kieselsäure A 56,5 56,5 Polyamidamin mit einer Kationizität von: 13,11 ml PES-Lösung 3,5 - Polydiallyldimethylammoniumchlorid (s. Bsp. 1) - 8,5 Melamin-Formaldehyd-Harz 5,0 - Auftragsgewicht, g/m² 4 4 The ink-receiving layers according to Comparative Examples V1 and V2 were applied from an aqueous medium and had the following compositions after drying: Components Composition,% by weight V1 V2 Polyvinyl alcohol saponification degree: 88 mol% 28.0 28.0 Polyvinylpyrrolidone molecular weight: 630,000 daltons 7.0 7.0 Amorphous silica A 56.5 56.5 Polyamidamine with a cationicity of: 13.11 ml PES solution 3.5 - Polydiallyldimethylammonium chloride (see Example 1) - 8.5 Melamine formaldehyde resin 5.0 - Application weight, g / m² 4th 4th

Das in den Vergleichsbeispielen erhaltene Aufzeichnungsmaterial wurde in einem sog. "Thermal jet"-Verfahren bedruckt und anschließend analysiert. Die Ergebnisse sind in Tabelle 3 zusammengestellt.
Zusätzlich zu den Vergleichsbeispielen wurden zwei handelsübliche Aufzeichnungsmaterialien herangezogen und analysiert. Die Prüfergebnisse sind in Tab. 3 zusammengestellt.The recording material obtained in the comparative examples was printed in a so-called "thermal jet" process and then analyzed. The results are summarized in Table 3.
In addition to the comparative examples, two commercially available recording materials were used and analyzed. The test results are summarized in Tab. 3.

Prüfung des gemäß den Beispielen und Vergleichsbeispielen erhaltenen AufzeichnungsmaterialsExamination of the recording material obtained according to the examples and comparative examples

Das Aufzeichnungsmaterial wurde mit Hilfe eines nach dem Bubble-Jet-Prinzip (Thermal Jet) arbeitenden Tintenstrahldruckers HP Deskjet 550 C der Fa. Hewlett Packard bedruckt.The recording material was printed using an HP Deskjet 550 C ink jet printer from Hewlett Packard, which works on the bubble jet principle (thermal jet).

Bei den erhaltenen Druckbildern wurden Farbdensität, Bildschärfe, Wasserfestigkeit und Naßreibfestigkeit untersucht.In the print images obtained, color density, image sharpness, water resistance and wet friction resistance were examined.

Die Densitätsmessungen wurden mit Hilfe eines "Original Reflection Densitometer SOS-45" durchgeführt. Die Messungen erfolgten für die Grundfarben Cyan, Magenta, Gelb und Schwarz.The density measurements were carried out using an "Original Reflection Densitometer SOS-45". The measurements were carried out for the basic colors cyan, magenta, yellow and black.

Für die Untersuchung der Wasserfestigkeit wurde das Aufzeichnungsmaterial in Wasser getaucht. Die nach 60 s im Wasserbad verbliebene Densität (%) wird als Maß für die Wasserstabilität herangezogen.The recording material was immersed in water to investigate the water resistance. The density (%) remaining in the water bath after 60 s is used as a measure of the water stability.

Die Bildschärfe wird mit Hilfe eines Fadenzählers ermittelt. Es werden Feldabstände zwischen einem roten und einem grünen bzw. zwei schwarzen Feldern abgelesen (Maximalwert 1mm). Die farbigen Felder (zusammengesetzt aus den Grundfarben) haben 200 % Farbdeckung (ink coverage). Sie dienen daher als Prüffelder zur Fixiering großer Tintenmengen.The image sharpness is determined with the help of a thread counter. Field distances between a red and a green or two black fields are read (maximum value 1mm). The colored fields (composed of the primary colors) have 200% ink coverage. They therefore serve as test fields for fixing large quantities of ink.

Zur Ermittlung der Naßreibfestigkeit wird ein mit einem feuchten Tuch bespanntes Gewicht (1 kg) fünfmal über einen mit 100 % der Farbe Schwarz oder Cyan bedruckten Probestreifen gezogen. Der Densitätsverlust wird benotet (Note 1 - 5).

Figure imgb0001
Figure imgb0002
Figure imgb0003
 To determine the wet friction resistance, a weight (1 kg) covered with a damp cloth is drawn five times over a test strip printed with 100% black or cyan color. The loss of density is graded (marks 1 - 5).
Figure imgb0001
Figure imgb0002
Figure imgb0003

Claims (17)

Aufzeichnungsblatt für Ink-Jet-Druckverfahren, bestehend aus einem Träger und einer ein hydrophiles Bindemittel und ein Pigment enthaltenden Tintenaufnahmeschicht, dadurch gekennzeichnet, daß die Tintenaufnahmeschicht eine Mischung aus Polyvinylalkohol, Vinylpyrrolidon-Homopolymer und/oder Vinylpyrrolidon-Copolymer als Bindemittel sowie eine wasserlösliche, Aldehydgruppen enthaltende Substanz enthält.Recording sheet for ink-jet printing process, consisting of a support and a hydrophilic binder and a pigment-containing ink receiving layer, characterized in that the ink receiving layer comprises a mixture of polyvinyl alcohol, vinylpyrrolidone homopolymer and / or vinylpyrrolidone copolymer and a water-soluble binder, aldehyde contains substance. Aufzeichnungsblatt nach Anspruch 1, dadurch gekennzeichnet, daß die wasserlösliche, Aldehydgruppen enthaltende Substanz ein Melamin-Formaldehyd-Kondensationsprodukt ist.A recording sheet according to claim 1, characterized in that the water-soluble aldehyde-containing substance is a melamine-formaldehyde condensation product. Aufzeichnungsblatt nach Anspruch 1, dadurch gekennzeichnet, daß die wasserlösliche, Aldehydgruppen enthaltende Substanz ein mehrwertiges Aldehyd ist.A recording sheet according to claim 1, characterized in that the water-soluble aldehyde-containing substance is a polyvalent aldehyde. Aufzeichnungsblatt nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß das Mengenverhältnis der wasserlöslichen, Aldehydgruppen enthaltenden Verbindung zum hydrophilen Bindemittel 1 : 1 bis 1 : 40, insbesondere 1 : 1,5 bis 1 : 27 beträgt.A recording sheet according to claim 1 to 3, characterized in that the quantitative ratio of water-soluble, aldehyde groups of the compound containing the hydrophilic binder 1: 1.5 to 1: 27 is 1 to 1: 40, in particular. 1 Aufzeichnungsblatt nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß die Menge der wasserlöslichen, Aldehydgruppen enthaltenden Substanz in der Tintenaufnahmeschicht zwischen 2 bis 15 Gew. %, insbesondere 3 bis 10 Gew.% beträgt.A recording sheet according to claim 1 to 4, characterized in that the amount of water-soluble aldehyde is of substance containing in the ink receiving layer is between 2 to 15 wt.%, In particular 3 to 10 wt.%. Aufzeichnungsblatt nach Anspruch 1 bis 5, dadurch gekennzeichnet, daß die Tintenaufnahmeschicht eine quaternäre Ammonium-Verbindung enthält.A recording sheet according to claim 1 to 5, characterized in that the ink receiving layer contains a quaternary ammonium compound. Aufzeichnungsblatt nach Anspruch 6, dadurch gekennzeichnet, daß die quaternäre Ammonium-Verbindung eine Kationizität von 15 bis 30 ml einer 1 x 10⁻³ n Lösung des polyethensulfonsauren Natriums aufweist.A recording sheet according to claim 6, characterized in that the quaternary ammonium compound has a cationicity of 15 to 30 ml of a 1 x 10⁻³ N solution of sodium polyethensulfonsauren. Aufzeichnungsblatt nach Anspruch 6 und 7, dadurch gekennzeichnet, daß die quaternäre Ammonium-Verbindung ein Polyaminsalz, insbesondere ein Polydiallyldimethylammoniumchlorid ist.A recording sheet according to claim 6 and 7, characterized in that the quaternary ammonium compound is a polyamine, particularly a polydiallyl dimethyl ammonium chloride is. Aufzeichnungsblatt nach Anspruch 1 bis 8, dadurch gekennzeichnet, daß die Menge der quaternären Ammonium-Verbindung höchstens 10 Gew.% beträgt.A recording sheet according to claim 1 to 8, characterized in that the amount of the quaternary ammonium compound is at most 10 wt.%. Aufzeichnungsblatt nach Anspruch 1 bis 9, dadurch gekennzeichnet, daß die Tintenaufnahmeschicht eine amorphe Kieselsäure, ein Clay, einen Zeolith oder andere anorganische Pigmente enthalten kann.A recording sheet according to claim 1 to 9, characterized in that the ink receiving layer may contain an amorphous silicic acid, a clay, a zeolite or other inorganic pigments. Aufzeichnungsblatt nach Anspruch 10, dadurch gekennzeichnet, daß die amorphe Kieselsäure ein Porenvolumen von 1,0 bis 2,5 ml/g bei einer Teilchengröße von ≦ 5 µm aufweist.A recording sheet according to claim 10, characterized in that the amorphous silica has a pore volume of 1.0 to 2.5 ml / g at a particle size of ≦ microns. 5 Aufzeichnungsblatt nach Anspruch 1 bis 11, dadurch gekennzeichnet, daß die Menge des Pigments in der Tintenaufnahmeschicht 10 bis 80 Gew.% , insbesondere 40 bis 65 Gew.%, beträgt.A recording sheet according to claim 1 to 11, characterized in that the amount of pigment in the ink receiving layer is 10 to 80 wt.%, In particular 40 to 65 wt.% Is. Aufzeichnungsblatt nach Anspruch 1 bis 12, dadurch gekennzeichnet, daß die Menge des hydrophilen Bindemittels 15 bis 80 Gew.%, insbesondere 30 bis 60 Gew.%, beträgt.A recording sheet according to claims 1 to 12, characterized in that the amount of the hydrophilic binder 15 to 80 wt.%, In particular 30 to 60 wt.% Is. Aufzeichnungsmaterial nach Anspruch 1 bis 13, dadurch gekenzeichnet, daß die Tintenaufnahmeschicht in einer Auftragsmenge von 0,5 bis 15 g/m², insbesondere 2 bis 8 g/m², auf einen Träger aus einem geleimten Rohpapier aufgetragen ist.Recording material according to Claims 1 to 13, characterized in that the ink- receiving layer is applied in an application amount of 0.5 to 15 g / m², in particular 2 to 8 g / m², to a support made from a sized base paper. Aufzeichnungsblatt nach Anspuch 1 bis 14, dadurch gekennzeichnet, daß die Rückseite des Trägers mit einem Stärke-Strich mit einem Auftragsgewicht von 2 bis 7 g/m², insbesondere 3 bis 5 g/m², versehen ist.A recording sheet according Anspuch 1 to 14, characterized in that the back of the support with a starch-stroke with a coating weight of 2 to 7 g / m², especially 3 is provided to 5 g / m². Aufzeichnungsblatt nach Anspruch 15, dadurch gekennzeichnet, daß die Stärke eine oxydierte Kartoffelstärke ist.A recording sheet according to claim 15, characterized in that the starch is a potato starch oxidized. Pigmenthaltige Beschichtungsmasse zur Herstellung einer Tintenaufnahmeschicht für ein Ink-Jet-Aufzeichnungsblatt der Ansprüche 1 bis 16.A pigment-containing coating composition for producing an ink-receiving layer for an ink-jet recording sheet as claimed in claims 1 to 16.
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WO1997022670A1 (en) * 1995-12-19 1997-06-26 Degussa Aktiengesellschaft Milled silicates and silicas used in ink jet printing
EP0795418A1 (en) * 1996-03-13 1997-09-17 Alusuisse Technology & Management AG Support with base coat for printing
EP0824077A2 (en) * 1996-08-12 1998-02-18 TOYO BOSEKI KABUSHIKI KAISHA Trading under the name of Toyobo Co., Ltd. Ink-receptive recording material
EP0824077A3 (en) * 1996-08-12 1999-06-02 TOYO BOSEKI KABUSHIKI KAISHA Trading under the name of Toyobo Co., Ltd. Ink-receptive recording material
US7235284B1 (en) 1997-03-20 2007-06-26 Ilford Imaging Switzerland Gmbh Recording sheets for ink jet printing
WO2009000768A1 (en) 2007-06-25 2008-12-31 Technocell Dekor Gmbh & Co. Kg Ink-jet-printable decorative paper
US8153211B2 (en) 2007-06-25 2012-04-10 Technocell Dekor Gmbh & Co. Kg Ink-jet-printable decorative paper
US8460767B2 (en) 2007-12-17 2013-06-11 Schoeller Technocell Gmbh & Co. Kg Compressible decorative paper impregnating agent which can be printed by the inkjet method
US8221895B2 (en) 2007-12-21 2012-07-17 Technocell Dekor Gmbh & Co. Kg Base paper for decorative coating materials

Also Published As

Publication number Publication date
ES2119922T3 (en) 1998-10-16
EP0631880B1 (en) 1998-06-10
DE4322179A1 (en) 1995-01-12
DE4322179C2 (en) 1997-02-13
DK0631880T3 (en) 1999-03-22
JPH07304248A (en) 1995-11-21
US5569529A (en) 1996-10-29
JP3731166B2 (en) 2006-01-05
ATE167117T1 (en) 1998-06-15
DE59406174D1 (en) 1998-07-16

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