EP0631880B1 - Recording sheet for ink jet printing process - Google Patents

Recording sheet for ink jet printing process Download PDF

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Publication number
EP0631880B1
EP0631880B1 EP19940105767 EP94105767A EP0631880B1 EP 0631880 B1 EP0631880 B1 EP 0631880B1 EP 19940105767 EP19940105767 EP 19940105767 EP 94105767 A EP94105767 A EP 94105767A EP 0631880 B1 EP0631880 B1 EP 0631880B1
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EP
European Patent Office
Prior art keywords
recording sheet
sheet according
receiving layer
ink
amount
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
EP19940105767
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German (de)
French (fr)
Other versions
EP0631880A1 (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 as well as a coating material for production an ink receiving layer for the ink jet process.
  • ink jet recording systems printing processes are carried out by using ink droplets using different inkjet methods, like electrostatic attraction process, Blistering process, formed and on a recording material to be brought.
  • Another group of recording materials are those with an ink-receiving layer of papers.
  • the ink receiving layers basically consist of one Pigment / binder mixture.
  • the pigments serve, besides the increase the degree of whiteness of the material, for retention of the dyes from the recording liquid on the surface of the Leaf.
  • a high pigment concentration leads to high porosity the layer (DE-PS 30 24 205). This will make it a good one Smudge resistance is achieved, but at the same time also pigments from the ink to the inside of the recording material pulled in, which worsens the color density of the image.
  • JP 61-261 089 a proposed transparent material for "over head" projectors, which in addition to a polyvinyl alcohol / polyvinyl pyrrolidone mixture additionally contains a cationic conductive resin. This does have good smudge resistance and water resistance, but did not achieve sufficient wet friction.
  • EP-A-275100 discloses an ink recording material whose recording layer is polyvinyl alcohol, Contains chitosan and an aldehyde. This does make one high water resistance and transparency, but none sufficient wet friction resistance achieved.
  • the object of the present invention is therefore a recording material to propose for the ink jet printing process which meets the requirements mentioned above, in particular but in addition to high color density and sharpness, good water resistance and wet rub resistance guaranteed.
  • a recording material which consists of a support and an ink-receiving layer disposed thereon consists of a mixture of polyvinyl alcohol, polyvinyl pyrrolidone homopolymer and / or vinyl pyrrolidone copolymer as a binder and a contains water-soluble substance containing aldehyde groups, the Quantity ratio of polyvinyl alcohol to vinyl pyrrolidone homopolymer and / or copolymer is 10: 1 to 4: 1.
  • the water-soluble substance containing aldehyde groups can be a Melamine formaldehyde condensation product containing free CHO groups of at least 0.05 mol.%. But also a multi-value one Aldehyde such as oxalaldehyde can be used here.
  • the quantitative ratio of the water-soluble substance to that in the ink-receiving layer contained polyvinyl alcohol-containing binders, which is a blend of polyvinyl alcohol, polyvinyl pyrrolidone homopolymer and / or polyvinylpyrrolidone copolymer 1: 1 to 1:40. In a preferred embodiment, the ratio is 1: 1.5 to 1:27.
  • the polyvinylpyrrolidone copolymer a vinyl pyrrolidone / vinyl acetate or a Vinyl pyrrolidone / styrene copolymer.
  • the amount of the water-soluble substance containing aldehyde groups in the ink receiving layer is 2 to 15% by weight, particularly 3 to 10% by weight.
  • the amount of the 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 contain other additives, such as B. white pigments, colored pigments, dyes, Dispersing aids, wetting agents, curing agents and optical Brightener included.
  • the pigments used in the ink-receiving layer include: silica, clay, zeolite and other inorganic Pigments.
  • in the ink-receiving layer contain an amorphous silica, which a pore volume of 1.0 - 2.5 ml / g with a particle size of ⁇ 5 ⁇ m.
  • the amount of pigment in the ink-receiving layer is 10 to 80% by weight, in particular 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 / m 2 , preferably 2 to 8 g / m 2 .
  • 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 TiO 2 , CaCO 3 and SiO 2 .
  • the back of the base paper has a layer on it modified hydrophilic colloidal binder such as starch Contains starch, polyvinyl alcohol, gelatin. Particularly preferred becomes an oxidized potato starch.
  • the back layer can contain up to 60% by weight of fillers (e.g. clay, zeolite, CaCO 3 ), pigments and other additives.
  • fillers e.g. clay, zeolite, CaCO 3
  • the front side of a base paper of neutral weight with alkyl ketene dimer and containing 20% by weight CaCO 3 in the mass of 80 g / m 2 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% by weight CaCO 3 .
  • the application weight of this back layer was 4 g / m 2 .
  • 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 / m 2 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 made with a receiving layer provided that 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 / m 2 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 created using a bubble jet principle (Thermal Jet) working inkjet printer HP Deskjet 550 C from Hewlett Packard printed.
  • a bubble jet principle Thermal Jet working inkjet printer HP Deskjet 550 C from Hewlett Packard printed.
  • the density measurements were carried out using an "Original Reflection Densitometer SOS-45". The measurements were made for the Basic colors cyan, magenta, yellow and black.
  • the recording material was used for the investigation of the water resistance submerged in water. The one remaining in the water bath after 60 s Density (%) is used as a measure of water stability used.
  • the image sharpness is determined with the help of a thread counter. It are field distances between a red and a green or read two black fields (maximum value 1mm).
  • the colored ones Fields (composed of the primary colors) have 200% Ink coverage. They therefore serve as test fields for Fixing large amounts 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 as well as a coating material for production 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.With ink jet recording systems, printing processes are carried out by using ink droplets using different inkjet methods, like electrostatic attraction process, Blistering process, formed and on a recording material to be brought.

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.Some of these are contradictory claims, e.g. B. means that the smudge resistance is set too quickly, that an ink drop does not diverge, or only slightly and thereby disadvantages the clarity of the resulting image becomes.

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. Based on the demands made on the recording material Nevertheless, ways are searched which lead to an image with high color density with the highest possible smudge resistance to lead.

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 as a recording material for ink jet printing Use paper in which the color liquids in between the paper fibers or between fibers and filler Spaces can be absorbed.

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

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 one Pigment / binder mixture. The pigments serve, besides the increase the degree of whiteness of the material, for retention of the dyes from the recording liquid on the surface of the Leaf. A high pigment concentration leads to high porosity the layer (DE-PS 30 24 205). This will make it a good one Smudge resistance is achieved, but at the same time also pigments from the ink to the inside of the recording material pulled in, 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 a recording material with a receiving layer To produce polyvinyl alcohol and polyvinyl pyrrolidone. The Mixing ratio of both components PVA: PVP is 3: 1 up to 1: 5. A disadvantage of this material is the lack of it 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. In Japanese laid-open patent publication JP 61-261 089 a proposed transparent material for "over head" projectors, which in addition to a polyvinyl alcohol / polyvinyl pyrrolidone mixture additionally contains a cationic conductive resin. This does have good smudge resistance and water resistance, but did not achieve sufficient wet friction.

Die EP-A-275100 offenbart ein Tintenaufzeichnungsmaterial, dessen Aufzeichnungsschicht Polyvinylalkohol, Chitosan und ein Aldehyd enthält. Dadurch wird zwar eine hohe Wasserfestigkeit und Transparenz, aber keine ausreichende Naßreibfestigkeit erreicht. EP-A-275100 discloses an ink recording material whose recording layer is polyvinyl alcohol, Contains chitosan and an aldehyde. This does make one high water resistance and transparency, but none sufficient wet friction resistance achieved.

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 a recording material to propose for the ink jet printing process which meets the requirements mentioned above, in particular but in addition to high color density and sharpness, good water resistance and wet rub resistance guaranteed.

Gelöst wird diese Aufgabe durch ein Aufzeichnungsmaterial, welches aus einem Träger und einer darauf angeordneten Tintenaufnahmeschicht besteht, die eine Mischung aus Polyvinylalkohol, Polyvinylpyrrolidon-Homopolymer und/oder Vinylpyrrolidon-Copolymer als Bindemittel und eine wasserlösliche, Aldehydgruppen enthaltende Substanz enthält, wobei das Mengenverhältnis Polyvinylalkohol zu Vinylpyrrolidon-Homopolymer und/oder -Copolymer 10 : 1 bis 4 : 1 beträgt.This task is solved by a recording material which consists of a support and an ink-receiving layer disposed thereon consists of a mixture of polyvinyl alcohol, polyvinyl pyrrolidone homopolymer and / or vinyl pyrrolidone copolymer as a binder and a contains water-soluble substance containing aldehyde groups, the Quantity ratio of polyvinyl alcohol to vinyl pyrrolidone homopolymer and / or copolymer is 10: 1 to 4: 1.

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 containing free CHO groups of at least 0.05 mol.%. But also a multi-value one Aldehyde such as oxalaldehyde can be used here.

Das Mengenverhältnis der wasserlöslichen Substanz zum in der Tintenaufnahmeschicht enthaltenen polyvinylalkoholhaltigen 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 that in the ink-receiving layer contained polyvinyl alcohol-containing binders, which is a blend of polyvinyl alcohol, polyvinyl pyrrolidone homopolymer and / or polyvinylpyrrolidone copolymer 1: 1 to 1:40. In a preferred embodiment, the ratio is 1: 1.5 to 1:27.

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 a vinyl pyrrolidone / vinyl acetate or a Vinyl pyrrolidone / 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, particularly 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 the 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 contain other additives, such as B. white pigments, colored pigments, dyes, Dispersing aids, wetting agents, curing agents and optical Brightener included.

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.%.The pigments used in the ink-receiving layer include: silica, clay, zeolite and other inorganic Pigments. In a preferred embodiment of the invention, in the ink-receiving layer contain an amorphous silica, which a pore volume of 1.0 - 2.5 ml / g with a particle size of ≤ 5 µm. The amount of pigment in the ink-receiving layer is 10 to 80% by weight, in particular 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 / m 2 , preferably 2 to 8 g / m 2 . 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 TiO 2 , CaCO 3 and SiO 2 .

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 on it modified hydrophilic colloidal binder such as starch Contains starch, polyvinyl alcohol, gelatin. Particularly preferred becomes an oxidized potato starch.

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, CaCO 3 ), pigments and other additives.

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

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 The front side of a base paper of neutral weight with alkyl ketene dimer and containing 20% by weight CaCO 3 in the mass of 80 g / m 2 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 / m 2 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

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% by weight CaCO 3 . The application weight of this back layer was 4 g / m 2 .

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 in a so-called. "Thermal Jet" process printed 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 / m 2 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 made with a receiving layer provided that 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 / m 2 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 AufzeichnungsmaterialsTesting the according to the examples and comparative examples recording material obtained

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 created using a bubble jet principle (Thermal Jet) working inkjet printer HP Deskjet 550 C from Hewlett Packard printed.

Bei den erhaltenen Druckbildern wurden Farbdensität, Bildschärfe, Wasserfestigkeit und Naßreibfestigkeit untersucht.Color density, image sharpness, Water resistance and wet friction resistance 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 made 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 used for the investigation of the water resistance submerged in water. The one remaining in the water bath after 60 s Density (%) is used as a measure of water stability used.

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. It are field distances between a red and a green or read two black fields (maximum value 1mm). The colored ones Fields (composed of the primary colors) have 200% Ink coverage. They therefore serve as test fields for Fixing large amounts 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). Eigenschaften des bedruckten und gemäß Beispiel 1 hergestellten Aufzeichnungsmaterials Beispiel Farbidensität Bildschärfe (Feldabstand in mm) Wasserfestigkeit (cyan) % Naßreibfestigkeit (cyan) Note cyan magenta gelb schwarz rot/grün 1a 2,15 1,57 1,68 2,30 0,9 98,6 2 1b 2,01 1,43 1,55 2,06 0,9 98,0 2 1c 2,01 1,40 1,50 2,22 0,8 100,0 2 1d 1,99 1,38 1,47 2,21 0,9 100,0 2 1e 2,02 1,50 1,66 2,22 0,9 94,0 2 1f 1,90 1,37 1,45 2,11 0,9 98,6 1 1g 1,92 1,35 1,45 2,09 0,9 99,0 3 1h 1,98 1,38 1,52 2,02 1,0 100,0 1 Eigenschaften des bedruckten und gemäß Beispiel 2 hergestellten Aufzeichnungsmaterials Beispiel Farbidensität Bildschärfe (Feldabstand in mm) Wasserfestigkeit (cyan) % Naßreibfestigkeit (cyan) Note cyan magenta gelb schwarz rot/grün 2a 2,01 1,48 1,58 2,20 0,9 100,0 2 2b 1,94 1,40 1,52 2,11 0,8 97,0 1 2c 1,99 1,38 1,48 2,14 0,9 91,0 2 2d 2,10 1,54 1,65 2,14 0,8 90,0 3 Prüfung des gemäß Vergleichsbeispiel 1 und 2 hergestellten und des handelsüblichen Aufzeichnungsmaterials Beispiel Farbdensität Bildschärfe (Feldabstand in mm) Wasserfestigkeit (cyan) % Naßreibfestigkeit (cyan) Note cyan magenta gelb schwarz rot/grün V1 1,85 1,34 1,42 2,05 0,8 78,0 3 V2 1,90 1,35 1,45 2,09 0,8 87,2 4 HP 51 630 Z CX Jet Ser. 1,75 1,27 1,26 2,07 0,8 88,0 5 Canon LC101 1,65 1,21 1,26 1,79 0,8 92,0 5 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). Properties of the printed recording material produced according to Example 1 example Color density Sharpness (field distance in mm) Water resistance (cyan)% Wet rub resistance (cyan) grade cyan magenta yellow black Red Green 1a 2.15 1.57 1.68 2.30 0.9 98.6 2nd 1b 2.01 1.43 1.55 2.06 0.9 98.0 2nd 1c 2.01 1.40 1.50 2.22 0.8 100.0 2nd 1d 1.99 1.38 1.47 2.21 0.9 100.0 2nd 1e 2.02 1.50 1.66 2.22 0.9 94.0 2nd 1f 1.90 1.37 1.45 2.11 0.9 98.6 1 1g 1.92 1.35 1.45 2.09 0.9 99.0 3rd 1h 1.98 1.38 1.52 2.02 1.0 100.0 1 Properties of the printed recording material produced according to Example 2 example Color density Sharpness (field distance in mm) Water resistance (cyan)% Wet rub resistance (cyan) grade cyan magenta yellow black Red Green 2a 2.01 1.48 1.58 2.20 0.9 100.0 2nd 2 B 1.94 1.40 1.52 2.11 0.8 97.0 1 2c 1.99 1.38 1.48 2.14 0.9 91.0 2nd 2d 2.10 1.54 1.65 2.14 0.8 90.0 3rd Testing of the recording material produced according to Comparative Examples 1 and 2 and of the commercially available recording material example Color density Sharpness (field distance in mm) Water resistance (cyan)% Wet rub resistance (cyan) grade cyan magenta yellow black Red Green V1 1.85 1.34 1.42 2.05 0.8 78.0 3rd V2 1.90 1.35 1.45 2.09 0.8 87.2 4th HP 51 630 Z CX Jet Ser. 1.75 1.27 1.26 2.07 0.8 88.0 5 Canon LC101 1.65 1.21 1.26 1.79 0.8 92.0 5

Claims (17)

  1. Recording sheet for ink yet printing processes consisting of a support and a binder containing a polyvinyl alcohol and a receiving layer containing pigments, characterized in that the receiving layer contains a mixture of polyvinyl alcohol and vinylpyrrolidone homopolymer and/or vinylpyrrolidone copolymer as binder, a water soluble compound containing aldehyde groups, wherein the ratio of polyvinylalcohol to vinylpyrrolidone homopolymer and/or copolymer is 10:1 to 4:1.
  2. Recording sheet according to claim 1, characterized in that the water soluble compound containing aldehyde groups is a melamine formaldehyde condensation product.
  3. Recording sheet according to claim 1, characterized in that the water soluble compound containing aldehyde groups is a polyvalent aldehyde.
  4. Recording sheet according to claims 1 to 3, characterized in that the ratio of the water soluble compound containing aldehyde groups to the binder containing polyvinyl alcohol is 1:1.5 to 1:27.
  5. Recording sheet according to claims 1 to 4, characterized in that the amount of water soluble compound containing aldehyde groups in the ink receiving layer is between 2 to 15 wt%, particularly 3 to 10 wt%.
  6. Recording sheet according to claims 1 to 5, characterized in that the ink receiving layer contains a quaternary ammonium compound.
  7. 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 solution of sodium polyethene sulfonate.
  8. Recording sheet according to claims 6 and 7, characterized in that the quaternary ammonium compound is a polyamide salt, particularly a polydiallyl dimethyl ammonium chloride.
  9. Recording sheet according to claims 1 to 8, characterized in that the amount of quaternary ammonium compound does not exceed 10 wt%.
  10. Recording sheet according to claims 1 to 9, characterized in that the ink receiving layer may contain an amorphous silicic acid, a clay, a zeolite or other inorganic pigments.
  11. Recording sheet according to claim 10, characterized in that the amorphous silicic acid has a pore volume of 1.0 to 2.5 ml/g at a particle size of ≤ 5 µm.
  12. Recording sheet according to claims 1 to 11, characterized in that the amount of pigment in the ink receiving layer is 10 to 80 wt%, particularly 40 to 65 wt%.
  13. Recording sheet according to claims 1 to 12, characterized in that the amount of hydrophylic binder is 15 to 80 wt%, particularly 30 to 60 wt%.
  14. Recording sheet according to claims 1 to 13, characterized in that the ink receiving layer is applied to a support made of a sized raw paper in the amount of 0.5 to 15 g/m2, particularly 2 to 8 g/m2.
  15. Recording sheet according to claims 1 to 14, characterized in that the back side of the support includes a starch sizing in the amount of 2 to 7 g/m2, particularly 3 to 5 g/m2.
  16. Recording sheet according to claim 15, characterized in that the starch is an oxidized potato starch.
  17. Coating material containing pigments for the manufacture of an ink receiving layer for an ink yet recording sheet according to claims 1 to 16.
EP19940105767 1993-07-03 1994-04-14 Recording sheet for ink jet printing process Expired - Lifetime EP0631880B1 (en)

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DE4322179C2 (en) 1997-02-13
JP3731166B2 (en) 2006-01-05
JPH07304248A (en) 1995-11-21
DE59406174D1 (en) 1998-07-16
ES2119922T3 (en) 1998-10-16
DK0631880T3 (en) 1999-03-22
ATE167117T1 (en) 1998-06-15
US5569529A (en) 1996-10-29
EP0631880A1 (en) 1995-01-04
DE4322179A1 (en) 1995-01-12

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