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EP0764546B1 - Recording material for the ink-jet printing process - Google Patents

Recording material for the ink-jet printing process Download PDF

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Publication number
EP0764546B1
EP0764546B1 EP96114450A EP96114450A EP0764546B1 EP 0764546 B1 EP0764546 B1 EP 0764546B1 EP 96114450 A EP96114450 A EP 96114450A EP 96114450 A EP96114450 A EP 96114450A EP 0764546 B1 EP0764546 B1 EP 0764546B1
Authority
EP
European Patent Office
Prior art keywords
gelatin
recording material
ink
pigment
modified
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
EP96114450A
Other languages
German (de)
French (fr)
Other versions
EP0764546A1 (en
Inventor
Horst Westfal
Andreas Diekmann
Sonja Lönker
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
Original Assignee
Felix Schoeller Jr Foto und Spezialpapiere GmbH
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Filing date
Publication date
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Publication of EP0764546A1 publication Critical patent/EP0764546A1/en
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Publication of EP0764546B1 publication Critical patent/EP0764546B1/en
Anticipated expiration legal-status Critical
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
    • 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
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof
    • Y10T428/257—Iron oxide or aluminum oxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y10T428/31768—Natural source-type polyamide [e.g., casein, gelatin, etc.]
    • Y10T428/31772—Next to cellulosic
    • Y10T428/31775—Paper

Definitions

  • the invention relates to a recording material for the multicolored inkjet printing process.
  • droplets become one Recording liquid on the surface of the Carrier material using different techniques applied.
  • a recording material for the multicolored ink jet Printing process generally consists of a carrier and a receiving layer arranged thereon.
  • a carrier materials such as paper and foils are suitable.
  • the Reception layer usually consists of one Binder / pigment mixture.
  • the pigments increase the whiteness of the substrate and lead to better retention of the dyes on the Surface of the sheet.
  • a high pigment concentration leads to great porosity (DE-PS 30 24 205) and thus good smudge resistance, but at the same time Dyes from the ink to the inside of the Recording material and thus the Color density of the image deteriorated.
  • Binders for the receiving layers are, for example Gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, starch and acrylates.
  • DE-PS 22 34 823 describes a gelatin-coated paper for ink jet printing.
  • the gelatin coating is said to improve the smudge resistance and increase the dissolving power. It is disadvantageous that the symbols applied are not sufficiently smudge-proof in the desired short time, but only after more than 10 seconds. Another disadvantage is the long drying time, which is usually more than 15 minutes for gelatin layers.
  • Japanese laid-open patent publication JP 61-261 089 describes a as a binder in the receiving layer Mixture of polyvinyl alcohol, polyvinyl pyrolidone and a cationic resin. This mixture is said to fast drying and high image sharpness guarantee. The wet rub resistance is with this Binder mixture bad.
  • US 4 946 741 discloses an ink receiving layer, which is a carbonyl-modified gelatin with a Residual content of free amino groups of up to 50 mol% and a polyalkylene oxide is mandatory as a further binder contains.
  • EP 0 636 489 A1 describes a Recording medium for the ink jet process, which in addition to one in the ink receiving layer acidic or basic digested gelatin Contains aluminum oxide hydrate, creating a thick Ink receiving layer is commercially available.
  • the EP 0 298 424 A2 discloses an ink jet recording material, which in the Ink absorption layer to improve the Ink absorption is a mixture of silica and colloidal alumina and optionally Contains binders such as polyvinyl alcohol.
  • the object of the present invention is therefore to produce a recording material for the ink jet printing process which does not have the stated disadvantages and which is particularly simple Layer structure, high ink absorption capacity, in combination with high color density and good smudge resistance.
  • the recording material should, if possible, be used for all types of printers and inks.
  • a recording material which consists of a support and a gelatin and pigment-containing ink-receiving layer, the ink-receiving layer containing a carbonyl-modified gelatin with a residual content of free amino groups of up to 50 mol% as the sole binder.
  • a gelatin modified with maleic or phthalic anhydride but in particular a gelatin modified with succinic anhydride, can be used.
  • An acid digested pork rind gelatin is particularly preferred.
  • the residual content of free amino groups in the gelatin according to the invention is 1 to 50 mol%, preferably 2 to 30 mol% and in a particularly preferred embodiment 2 to 20 mol%.
  • the proportion of gelatin is between 95% by weight and 30% by weight, in a preferred form between 90% by weight and 70% by weight, based on the solids content of the ink-receiving layer. It was surprising that the use of a gelatin without a combination with another binder resulted in such a short drying time and high color density, especially since the use of gelatin alone according to the prior art did not lead to the expectation of corresponding results.
  • a colloidal aluminum-modified silica is used as the pigment.
  • the proportion of the pigment is between 5% by weight and 70% by weight, in a preferred form between 10% by weight and 30% by weight, based on the solids content.
  • inorganic and organic pigments can also be used as the pigment, such as CaCO 3 , TiO 2 , BaSO 4 , polymethyl methacrylate and polystyrene.
  • a dye-fixing agent used with a cationic dicyandiamide copolymer as special proved suitable.
  • constituents of the receiving layer can be hardening agents (Chrome alum, TAF / formaldehyde), wetting agents, dye-fixing agents and other auxiliaries.
  • the application quantity of the receiving layer is 1 g to 15 G. In a preferred form, it is 2 g to 7 g.
  • the aqueous coating composition can vary in the following amounts by weight: % By weight gelatin 28.50 - 90.25 aluminum modified silica 3.04 - 44.27 Auxiliaries 0.00 - 10.00 water Rest up to 100.0
  • the coating composition can be used with all common Application and dosing processes, such as roller application, engraving or nipping method and air brush or Roller doctor dosage can be applied.
  • the carrier material is preferably paper coated on both sides with synthetic resin and having a weight per unit area of 50 to 250 g / m 2 .
  • Polyolefins or polyester, for example, are used as the synthetic resin.
  • the application amount of the synthetic resin coating is at least 5 g / m 2 and pigments, dyes and other auxiliaries can also be contained in this coating.
  • An uncoated or coated base paper is also suitable as a carrier material.
  • the front of a polyethylene-coated base paper was coated with the following coating compositions: Components B1 B2 B3 B4 B5 B6 Demineralized water 10.70 10.70 7.55 4.35 13.20 8.70 modif. gelatin 20% 66.50 66.50 76.00 85.50 68.00 66.50 Al-modif. Silica 30% 19.00 19.00 12.65 6.35 11.35 19.00 Cat. Dicyandiamide cop.
  • the back of the base paper was coated with an LDPE ("low density" polyethylene) with an optical brightener content of 0.6% by weight.
  • the application weight was 22 g / m 2 .
  • the application weight was 19 g / m 2 .
  • the gelatin with a gel strength of 220 g Bloom is a normal, acid-digested bone gelatin.
  • the gelatin with a gel strength of 280 g Bloom is a normal, unmodified pork rind gelatin.
  • the test conditions are comparable to those of Examples B1-B6.
  • the recording material was printed with a commercially available ink jet color printer from Hewlett Packard, HP 550C, and the corresponding inks.
  • the printed images were examined for smear resistance, color density, image sharpness (color gradient), color transfer and gloss. The results are summarized in Tables 3-5.
  • the color density was measured using a Gretag densitometer measured in the colors cyan, magenta, yellow and black.
  • the print image was used to check the color transfer covered with a PTS base paper and using for 24 hours a 10 kg weight. Then the Fab transfer from the ink receiving layer to the PTS base paper assessed visually with grades 1-5. Note 1 means no color transfer, grade 5 means very strong Color transfer It also specifies the colors that are involved in the transfer.
  • the gloss measurement was carried out with a Three-angle gloss meter from Dr. Long with one Measuring angle of 60 °.

Landscapes

  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Paper (AREA)
  • Duplication Or Marking (AREA)
  • Ink Jet (AREA)

Abstract

A recording material for ink jet printing, comprises a base(A) and a pigment-contg. ink-absorbing layer (B) contg. a carbonyl gp.-modified gelatin (I) with a residual content of up to 50 mole% free amino gps. Pref. (I) is succinic acid-modified gelatin, esp. pref. acid-degraded pig-skin gelatin. Pref. pigment comprises colloidal aluminium-modified silica, in a (pigment):(gelatin) ratio of (1:0.4)-(1:20). Layer (B) contains a cationic dicyandiamide copolymer.

Description

Die Erfindung betrifft ein Aufzeichnungsmaterial für das mehrfarbige Tintenstrahl-Druckverfahren (Ink Jet Verfahren).The invention relates to a recording material for the multicolored inkjet printing process.

Bei dem Ink Jet Verfahren werden Tröpfchen einer Aufzeichnungsflüssigkeit auf die Oberfläche des Trägermaterials mittels unterschiedlicher Techniken aufgetragen.In the ink jet process, droplets become one Recording liquid on the surface of the Carrier material using different techniques applied.

Bei der Tropfenerzeugung gibt es grundsätzlich zwei Verfahrensvarianten.
Bei der Methode der kontinuierlichen Tropfenerzeugung wird unter Hochdruck ein permanenter Tröpfchenstrom aus der Düse getrieben. Die nicht für den Bildaufbau benötigten Tropfen werden durch verschiedene Prinzipien wieder dem Tintenvorratsbehälter zugeführt.
Bei der Drop-On-Demand Methode wird nur an den zu bebildernden Stellen auf Abruf ein Tintentröpfchen erzeugt.There are basically two process variants for drop generation.
With the method of continuous drop generation, a permanent stream of droplets is driven out of the nozzle under high pressure. The drops that are not required for image formation are fed back into the ink reservoir by various principles.
With the drop-on-demand method, an ink droplet is only generated at the locations to be imaged.

Durch eine digitale elektronische Steuerung ist es möglich, Bilder mit sehr hoher Auflösung direkt aus elektronischen Daten zu drucken.Through digital electronic control it is possible to take pictures with very high resolution directly to print electronic data.

An das Aufzeichnungsmaterial werden große Anforderungen gestellt. Zu den wichtigsten Anforderungen gehören:

  • hohe Auflösung,
  • hohe Farbdichte,
  • hohe Lichtstabilität,
  • gute Wischfestigkeit,
  • gute Wasserfestigkeit,
  • gute Naßriebfestigkeit,
  • hohe Tintenabsorptionsfähigkeit und
  • universelle Einsatzmöglichkeit.
    • Great demands are made of the recording material. The main requirements include:
  • high resolution,
  • high color density,
  • high light stability,
  • good smudge resistance,
  • good water resistance,
  • good wet rub resistance,
  • high ink absorbency and
  • universal application.

    • Diese Forderungen widersprechen sich teilweise. Durch die Vielzahl der eingesetzten Ink Jet Drucker und der unterschiedlichen Tinten lassen sich Eigenschaften wie Wischfestigkeit und Farbdichte nur sehr schwer in Einklang bringen. Ebenso stehen die Forderungen nach hoher Auflösung und Wischfestigkeit im Widerspruch.These demands partially contradict each other. Through the Large number of ink jet printers and different inks can have properties like Smudge resistance and color density are very difficult Bring in line. The demands are also inferior high resolution and smudge resistance in contradiction.

    Ein Aufzeichnungsmaterial für das mehrfarbige Ink Jet Druckverfahren besteht im allgemeinen aus einem Träger und einer darauf angeordneten Empfangsschicht. Als Träger eignen sich Materialien wie Papier und Folien. Die Empfangsschicht besteht in der Regel aus einem Bindemittel/Pigment Gemisch.A recording material for the multicolored ink jet Printing process generally consists of a carrier and a receiving layer arranged thereon. As a carrier materials such as paper and foils are suitable. The Reception layer usually consists of one Binder / pigment mixture.

    Die Pigmente erhöhen den Weißgrad des Trägermaterials und führen zu einer besseren Retention der Farbstoffe an der Oberfläche des Blattes. Eine hohe Pigmentkonzentration führt zu großer Porosität (DE-PS 30 24 205) und damit zu einer guten Wischfestigkeit.Gleichzeitig werden aber auch Farbstoffe aus der Tinte in das Innere des Aufzeichnungsmaterials hereingezogen und damit die Farbdichte des Bildes verschlechtert.The pigments increase the whiteness of the substrate and lead to better retention of the dyes on the Surface of the sheet. A high pigment concentration leads to great porosity (DE-PS 30 24 205) and thus good smudge resistance, but at the same time Dyes from the ink to the inside of the Recording material and thus the Color density of the image deteriorated.

    Bindemittel für die Empfangsschichten sind beispielsweise Gelatine, Polyvinylalkohol, Polyvinylpyrrolidon, Stärke und Acrylate. Binders for the receiving layers are, for example Gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, starch and acrylates.

    Die DE-PS 22 34 823 beschreibt ein mit Gelatine überzogenes Papier für den Ink Jet Druck. Durch den Gelatineüberzug soll die Wischfestigkeit verbessert und das Auflösevermögen erhöht werden. Nachteilig ist, daß die aufgetragenen Bildzeichen nicht in der gewünschten kurzen Zeit, sondern erst nach mehr als 10 Sekunden ausreichend wischfest sind.
    Ein weiterer Nachteil ist die lange Trockenzeit, die bei Gelatineschichten in der Regel mehr als 15 Minuten beträgt.    DE-PS 22 34 823 describes a gelatin-coated paper for ink jet printing. The gelatin coating is said to improve the smudge resistance and increase the dissolving power. It is disadvantageous that the symbols applied are not sufficiently smudge-proof in the desired short time, but only after more than 10 seconds.
    Another disadvantage is the long drying time, which is usually more than 15 minutes for gelatin layers.

    Die japanische Offenlegungsschrift JP 61-261 089 beschreibt als Bindemittel in der Empfangsschicht eine Mischung aus Polyvinylalkohol, Polyvinylpyrolidon und einem kationischem Harz. Diese Mischung soll eine schnelle Trocknung und eine hohe Bildschärfe gewährleisten. Die Naßriebfestigkeit ist aber bei dieser Bindemittelmischung schlecht.Japanese laid-open patent publication JP 61-261 089 describes a as a binder in the receiving layer Mixture of polyvinyl alcohol, polyvinyl pyrolidone and a cationic resin. This mixture is said to fast drying and high image sharpness guarantee. The wet rub resistance is with this Binder mixture bad.

    Die US 4 946 741 offenbart eine Tintenaufnahmeschicht, die eine carbonylgruppenmodifizierte Gelatine mit einem Restgehalt an freien Aminogruppen von bis zu 50 Mol.% und zwingend als weiteres Bindemittel ein Polyalkylenoxid enthält. Die EP 0 636 489 A1 beschreibt ein Aufzeichnungsmedium für das Tintenstrahlverfahren, welches in der Tintenaufnahmeschicht zusätzlich zu einer sauer oder basisch aufgeschlossenen Gelatine ein Alumiumoxidhydrat enthält, wodurch eine dicke Tintenaufnahmeschicht wirtschaftlich erhältlich ist. Die EP 0 298 424 A2 offenbart ein Ink-Jet-Aufzeichnungsmaterial, welches in der Tintenaufnahmeschicht zur Verbesserung der Tintenabsorption eine Mischung aus Kieselsäure und kolloidalem Aluminiumoxid sowie gegebenenfalls ein Bindemittel wie Polyvinylalkohol enthält.US 4 946 741 discloses an ink receiving layer, which is a carbonyl-modified gelatin with a Residual content of free amino groups of up to 50 mol% and a polyalkylene oxide is mandatory as a further binder contains. EP 0 636 489 A1 describes a Recording medium for the ink jet process, which in addition to one in the ink receiving layer acidic or basic digested gelatin Contains aluminum oxide hydrate, creating a thick Ink receiving layer is commercially available. The EP 0 298 424 A2 discloses an ink jet recording material, which in the Ink absorption layer to improve the Ink absorption is a mixture of silica and colloidal alumina and optionally Contains binders such as polyvinyl alcohol.

    Aufgabe der vorliegenden Erfindung ist es daher, ein Aufzeichnungsmaterial für das Ink Jet Druckverfahren herzustellen, das die angegebenen Nachteile nicht aufweist und sich insbesondere durch einfachen
    Schichtaufbau, hohe Tintenabsorptionsfähigkeit, in Kombination mit hoher Farbdichte und guter wischfestigkeit auszeichnet.
    Außerdem soll das Aufzeichnungsmaterial möglichst für alle Drucker- und Tintentypen einsetzbar sein.    The object of the present invention is therefore to produce a recording material for the ink jet printing process which does not have the stated disadvantages and which is particularly simple
    Layer structure, high ink absorption capacity, in combination with high color density and good smudge resistance.
    In addition, the recording material should, if possible, be used for all types of printers and inks.

    Diese Aufgabe wird durch ein Aufzeichnungsmaterial gelöst, das aus einem Träger und einer gelatine- und pigmenthaltigen Tintenaufnahmeschicht besteht, wobei die Tintenaufnahmeschicht eine carbonylmodifizierte Gelatine mit einem Restgehalt an freien Aminogruppen von bis zu 50 Mol.% als alleiniges Bindemittel enthält.
    In einer bevorzugten Form der Erfindung kann eine mit Maleinsäure- oder Phthalsäureanhydrid modifizierte Gelatine, insbesondere aber eine mit Bernsteinsäureanhydrid modifizierte Gelatine eingesetzt werden. Besonders bevorzugt ist eine sauer aufgeschlossene Schweineschwartengelatine. Der Restgehalt an freien Aminogruppen in der erfindungsgemäßen Gelatine beträgt 1 bis 50 Mol.%, vorzugsweise 2 bis 30 Mol.% und in einer besonders bevorzugten Ausführungsform 2 bis 20 Mol.%.    This object is achieved by a recording material which consists of a support and a gelatin and pigment-containing ink-receiving layer, the ink-receiving layer containing a carbonyl-modified gelatin with a residual content of free amino groups of up to 50 mol% as the sole binder.
    In a preferred form of the invention, a gelatin modified with maleic or phthalic anhydride, but in particular a gelatin modified with succinic anhydride, can be used. An acid digested pork rind gelatin is particularly preferred. The residual content of free amino groups in the gelatin according to the invention is 1 to 50 mol%, preferably 2 to 30 mol% and in a particularly preferred embodiment 2 to 20 mol%.

    Der Anteil der Gelatine liegt zwischen 95 Gew.% und 30 Gew.%, in einer bevorzugten Form zwischen 90 Gew.% und 70 Gew.% bezogen auf den Feststoffgehalt der Tintenaufnahmeschicht.
    Es war überraschend, daß der Einsatz einer Gelatine ohne Kombination mit einem anderen Bindemittel eine so kurze Trockenzeit und hohe Farbdichte ergab, zumal der alleinige Einsatz von Gelatine nach dem bisherigen Stand der Technik keine entsprechenden Ergebnisse erwarten lies.    The proportion of gelatin is between 95% by weight and 30% by weight, in a preferred form between 90% by weight and 70% by weight, based on the solids content of the ink-receiving layer.
    It was surprising that the use of a gelatin without a combination with another binder resulted in such a short drying time and high color density, especially since the use of gelatin alone according to the prior art did not lead to the expectation of corresponding results.

    In einer bevorzugten Ausführung der Erfindung wird als Pigment eine kolloidale aluminiummodifizierte Kieselsäure eingesetzt.
    Der Anteil des Pigments liegt zwischen 5 Gew.% und 70 Gew.%, in einer bevorzugten Form zwischen 10 Gew.% und 30 Gew.%, bezogen auf den Feststoffgehalt.    In a preferred embodiment of the invention, a colloidal aluminum-modified silica is used as the pigment.
    The proportion of the pigment is between 5% by weight and 70% by weight, in a preferred form between 10% by weight and 30% by weight, based on the solids content.

    Als Pigment können neben der modifizierten Kieselsäure auch andere anorganische und organische Pigmente eingesetzt werden, wie CaCO3 , TiO2 , BaSO4 , Polymethylmethacrylat und Polystyrol.In addition to the modified silica, other inorganic and organic pigments can also be used as the pigment, such as CaCO 3 , TiO 2 , BaSO 4 , polymethyl methacrylate and polystyrene.

    In einer weiteren Ausgestaltung der Erfindung wird ein farbstoffixierendes Mittel eingesetzt, wobei sich ein kationisches Dicyandiamid-Copolymer als besonders geeignet erwies.In a further embodiment of the invention, a dye-fixing agent used, with a cationic dicyandiamide copolymer as special proved suitable.

    Weitere Bestandandteile der Empfangsschicht können Härtungsmittel (Chromalaun, TAF/Formaldehyd), Netzmittel, farbstoffixierende Mittel und andere Hilfsstoffe sein.Other constituents of the receiving layer can be hardening agents (Chrome alum, TAF / formaldehyde), wetting agents, dye-fixing agents and other auxiliaries.

    Die Auftragsmenge der Empfangsschicht beträgt 1 g bis 15 g. In einer bevorzugten Form beträgt sie 2 g bis 7 g.The application quantity of the receiving layer is 1 g to 15 G. In a preferred form, it is 2 g to 7 g.

    Die wäßrige Beschichtungsmasse kann in folgenden Gewichtsmengen variieren: Gew.% Gelatine 28,50 - 90,25 aluminiummodifizierte Kieselsäure 3,04 - 44,27 Hilfsstoffe 0,00 - 10,00 Wasser Rest bis 100,0 The aqueous coating composition can vary in the following amounts by weight: % By weight gelatin 28.50 - 90.25 aluminum modified silica 3.04 - 44.27 Auxiliaries 0.00 - 10.00 water Rest up to 100.0

    Die Beschichtungsmasse kann mit allen gebräuchlichen Auftrags- und Dosierverfahren, wie Walzenauftrag-, Gravur oder Nipp-Verfahren und Luftbürsten- oder Rollrakeldosierung aufgetragen werden.The coating composition can be used with all common Application and dosing processes, such as roller application, engraving or nipping method and air brush or Roller doctor dosage can be applied.

    Bei dem Trägermaterial handelt es sich vorzugsweise um ein beidseitig mit Kunstharz beschichtetes Papier mit einem Flächengewicht von 50 bis 250 g/m2. Als Kunstharz werden beispielsweise Polyolefine oder Polyester eingesetzt. Die Auftragsmenge der Kunstharzbeschichtung beträgt mindestens 5g/m2 und es können zusätzlich noch Pigmente, Farbstoffe und andere Hilfsstoffe in dieser Beschichtung enthalten sein. Als Trägermaterial geeignet ist aber auch ein unbeschichtetes oder gestrichenes Basispapier. The carrier material is preferably paper coated on both sides with synthetic resin and having a weight per unit area of 50 to 250 g / m 2 . Polyolefins or polyester, for example, are used as the synthetic resin. The application amount of the synthetic resin coating is at least 5 g / m 2 and pigments, dyes and other auxiliaries can also be contained in this coating. An uncoated or coated base paper is also suitable as a carrier material.

    Die nachfolgenden Beispiele sollen die Erfindung näher erläutern, alle Angaben sind auf das Gewicht bezogen.The following examples are intended to illustrate the invention explain, all information is based on weight.

    Beispiele:Examples:

    Die Vorderseite eines polyethylenbeschichteten Basispapieres wurde mit folgenden Beschichtungsmassen beschichtet: Bestandteile B1 B2 B3 B4 B5 B6 Wasser entmineralisiert 10,70 10,70 7,55 4,35 13,20 8,70 modif. Gelatine 20%ig 66,50 66,50 76,00 85,50 68,00 66,50 Al-modif. Kieselsäure 30%ig 19,00 19,00 12,65 6,35 11,35 19,00 Kat. Dicyandiamid-Cop. 30%ig - - - - - 2,00 Netzmittel 10%ig in Wasser 0,80 0,80 0,80 0,80 0,80 0,80 Butanol 3,00 3,00 3,00 3,00 3,00 3,00 Zitronensäure 10%ig in Wasser - - - - 0,35 - Chromalaun 10%ig in Wasser - - - - 1,65 - TAF/ Formaldehyd 2%ig - - - - 1,65 - Auftrag g/m2 4,60 11,20 4,60 4,60 5,00 4,60 The front of a polyethylene-coated base paper was coated with the following coating compositions: Components B1 B2 B3 B4 B5 B6 Demineralized water 10.70 10.70 7.55 4.35 13.20 8.70 modif. gelatin 20% 66.50 66.50 76.00 85.50 68.00 66.50 Al-modif. Silica 30% 19.00 19.00 12.65 6.35 11.35 19.00 Cat. Dicyandiamide cop. 30% - - - - - 2.00 Wetting agent 10% in water 0.80 0.80 0.80 0.80 0.80 0.80 Butanol 3.00 3.00 3.00 3.00 3.00 3.00 Citric acid 10% in water - - - - 0.35 - Chromalun 10% in water - - - - 1.65 - TAF / formaldehyde 2% - - - - 1.65 - Order g / m 2 4.60 11.20 4.60 4.60 5.00 4.60

    Versuchsbedingungen:

    • Trocknungstemperatur: 100°C
    • Trocknungszeit : 25 - 60 Sekunden
    • Rakel : " 40"
    Test conditions:
    • Drying temperature: 100 ° C
    • Drying time: 25 - 60 seconds
    • Squeegee: "40"

    Als Unterlage diente ein beidseitig polyethylenbeschichtetes Basispapier mit einem Flächengewicht von 150 g/m2. Die Rückseite des Basispapieres wurde mit einem LDPE ("low density"-Polyethylen), mit einem Gehalt an optischem Aufheller von 0,6 Gew.%, beschichtet. Das Auftragsgewicht betrug 22 g/m2.A base paper with a polyethylene coating on both sides and a basis weight of 150 g / m 2 served as the base . The back of the base paper was coated with an LDPE ("low density" polyethylene) with an optical brightener content of 0.6% by weight. The application weight was 22 g / m 2 .

    Die Vorderseite wurde ebenfalls mit einem LDPE beschichtet. Die Vorderseitenbeschichtung enthielt außerdem:

    • 0,95 Gew.% optischer Aufheller,
    • 10 Gew.% Titandioxid,
    • 4 Gew.% Gleitmittel,
    • 10,8 Gew.% eines Blaumasterbatches (10% Ultramarin, 90% LDPE).
    The front was also coated with an LDPE. The front coating also contained:
    • 0.95% by weight optical brightener,
    • 10% by weight of titanium dioxide,
    • 4% by weight of lubricant,
    • 10.8% by weight of a blue masterbatch (10% ultramarine, 90% LDPE).

    Das Auftragsgewicht betrug 19 g/m2.The application weight was 19 g / m 2 .

    Die Vorderseite des polyethylenbeschichteten Trägermaterials wies folgende kolorimetrische Werte auf:

  • L = 93,45
  • a = -0,35
  • b = -4,10
    • The front of the polyethylene-coated carrier material had the following colorimetric values:
  • L = 93.45
  • a = -0.35
  • b = -4.10

    • Vergleichsbeispiele V1Comparative Examples V1

    BestandteileComponents V1aV1a V1bV1b V1cV1c Wasser entmineralisiertDemineralized water 17,0017.00 15,6515.65 4,354.35 Gelatine 220 g Bloom 20%igGelatin 220 g Bloom 20% 66,5066.50 -- 85,5085.50 Gelatine 280 g Bloom 20%igGelatin 280 g Bloom 20% -- 70,0070.00 -- Al-modif. Kieselsäure 30%igAl-modif. Silicic acid 30% -- -- 6,356.35 Netzmittel 10%igWetting agent 10% 0,500.50 0,500.50 0,500.50 Alkohol/Wasser Gemisch 50%igAlcohol / water mixture 50% 10,0010.00 10,0010.00 3,003.00 Zitronensäure 10%igCitric acid 10% 0,350.35 0,350.35 -- Chromalaun 10%igChromalun 10% 1,751.75 1,751.75 -- TAF/Formaldehyd 2%igTAF / formaldehyde 2% 1,751.75 1,751.75 -- Kat. Dicyandiamid-Cop. 30%igCat. Dicyandiamide cop. 30% 2,352.35 -- -- Auftrag g/m2 Order g / m 2 4,504.50 4,004.00 4,704.70

    Bei der Gelatine mit einer Gallertfestigkeit von 220 g Bloom handelt es sich um eine normale, sauer aufgeschlossene Knochengelatine.
    Die Gelatine mit einer Gallertfestigkeit von 280 g Bloom ist eine normale, nicht modifizierte SchweineschwartenGelatine.
    Die Versuchsbedingungen sind vergleichbar mit denen der Beispiele B1 - B6.     The gelatin with a gel strength of 220 g Bloom is a normal, acid-digested bone gelatin.
    The gelatin with a gel strength of 280 g Bloom is a normal, unmodified pork rind gelatin.
    The test conditions are comparable to those of Examples B1-B6.

    Vergleichsbeispiel V2Comparative example V2

    Als weiterer Vergleich diente ein handelsübliches Ink Jet Papier der Firma Hewlett Packard mit einer glänzenden Oberfläche.A commercial ink jet served as a further comparison Hewlett Packard paper with a glossy finish Surface.

    Prüfung des gemäß Beispiel B1 - B6 und Vergleichsbeispiel V1a - V1c, V2 erhaltenen Aufzeichnungsmaterials.Testing of according to example B1-B6 and comparative example V1a - V1c, V2 recording material obtained.

    Das Aufzeichnungsmaterial wurde mit einem handelsüblichen Ink Jet Farbdrucker der Firma Hewlett Packard, HP 550C, und den entsprechenden Tinten bedruckt.
    Die Druckbilder wurden auf Wischfestigkeit, Farbdensität, Bildschärfe (Farbverlauf), Farbtransfer und Glanz untersucht.
    Die Ergebnisse sind in Tabelle 3 - 5 zusammengefaßt.    The recording material was printed with a commercially available ink jet color printer from Hewlett Packard, HP 550C, and the corresponding inks.
    The printed images were examined for smear resistance, color density, image sharpness (color gradient), color transfer and gloss.
    The results are summarized in Tables 3-5.

    1. Wischfestigkeit:1. Smudge resistance:

    Die Wischfestigkeit wurde durch Abreiben des Druckbildes mit einem weißen Lappen geprüft. Diese Prüfung wurde für jede Farbe einzeln durchgeführt.

  • "+" - keine Farbreste an dem Lappen zu erkennen
  • "-" - Farbreste erkennbar.
    • The smear resistance was checked by rubbing the printed image with a white cloth. This test was carried out individually for each color.
  • "+" - no paint residue on the rag
  • "-" - color remains recognizable.

    • 2. Farbdensität:2. Color density:

    Die Farbdensität wurde mit einem Gretag Densitometer an den Farben Cyan, Magenta, Gelb und Schwarz gemessen. The color density was measured using a Gretag densitometer measured in the colors cyan, magenta, yellow and black.

    3. Bildschärfe:3. Sharpness:

    Die Bildschärfe wurde visuell mit den Noten 1-5 (sehr gut - schlecht) beurteilt.The sharpness of the image was visually rated 1-5 (very good - bad) judged.

    4. Farbtransfer:4. Color transfer:

    Zur Prüfung des Farbtransfers wurde das Druckbild mit einem PTS Basispapier abgedeckt und für 24 Stunden mit einem 10 kg Gewicht belastet. Anschließend wurde der Fabtransfer von der Tintenempfangsschicht auf das PTS-Basispapier visuell mit den Noten 1-5 beurteilt. Note 1 bedeutet kein Farbübertrag, Note 5 bedeutet sehr starker Farbübertrag. Außerdem werden die Farben angegeben, die an dem Transfer beteiligt sind.The print image was used to check the color transfer covered with a PTS base paper and using for 24 hours a 10 kg weight. Then the Fab transfer from the ink receiving layer to the PTS base paper assessed visually with grades 1-5. Note 1 means no color transfer, grade 5 means very strong Color transfer It also specifies the colors that are involved in the transfer.

    5. Glanz:5. Shine:

    Die Glanzmessung erfolgte mit einem Dreiwinkelglanzmessgerät der Firma Dr. Lange mit einem Meßwinkel von 60°. The gloss measurement was carried out with a Three-angle gloss meter from Dr. Long with one Measuring angle of 60 °.

    Ergebnisse der Prüfung auf Wischfestkeit der Beispiele B1 - B6 und der Vergleichsbeispiele V1 - V2.Results of the test for smear resistance of the examples B1 - B6 and comparative examples V1 - V2.

    CyanCyan Magentamagenta Gelbyellow Schwarzblack B1B1 ++ ++ ++ ++ B2B2 ++ ++ ++ ++ B3B3 ++ ++ -- ++ B4B4 ++ ++ ++ ++ B5B5 ++ ++ ++ ++ B6B6 ++ ++ ++ ++ V1aV1a -- -- -- ++ V1bV1b -- -- -- -- V1cV1c -- -- -- -- V2V2 -- -- -- -- + = gut+ = good - = schlecht- = bad

    Ergebnisse der Densitätsmessungen der Beispiele B1 - B6 und der Vergleichsbeispiele V1 - V2.Results of the density measurements of Examples B1-B6 and the comparative examples V1-V2.

    CyanCyan Magentamagenta Gelbyellow Schwarzblack B1B1 2,092.09 1,251.25 1,411.41 1,931.93 B2B2 2,072.07 1,211.21 1,391.39 1,901.90 B3B3 2,062.06 1,241.24 1,411.41 1,891.89 B4B4 2,062.06 1,241.24 1,371.37 1,901.90 B5B5 2,062.06 1,231.23 1,381.38 1,911.91 B6B6 2,072.07 1,251.25 1,411.41 1,901.90 V1aV1a 2,032.03 1,181.18 1,291.29 1,861.86 V1bV1b 1,941.94 1,171.17 1,311.31 1,791.79 V1cV1c 2,002.00 1,211.21 1,331.33 1,801.80 V2V2 2,102.10 1,411.41 1,391.39 1,911.91

    Ergebnisse der Prüfungen auf Bildschärfe, Farbtransfer und Glanz der Beispiele B1 - B6 und der Vergleichsbeispiele V1 - V2.Results of tests for sharpness, color transfer and gloss of Examples B1 - B6 and Comparative examples V1 - V2.

    BildschärfeSharpness FarbtransferColor transfer Glanz 60Gloss 60 B1B1 22nd 11 72,072.0 B2B2 22nd 11 80,680.6 B3B3 22nd 11 67,567.5 B4B4 22nd 3 MC3 MC 68,568.5 B5B5 22nd 2 MC2 MC 70,170.1 B6B6 22nd 11 68,068.0 V1aV1a 44th 4 C,M,G,MC4 C, M, G, MC 72,172.1 V1bV1b 22nd 5 C,M,G,MC5 C, M, G, MC 71,571.5 V1cV1c 44th 4 C,M,G,MC4 C, M, G, MC 68,868.8 V2V2 22nd 11 79,979.9 C Cyan wird abgegebenC Cyan is released M Margenta wird abgegebenM Margenta is handed over G Gelb wird abgegebenG Yellow is released MC Mischfarben werden abgegebenMC mixed colors are given

    Die Beispiele zeigen, daß die Wischfestigkeit, Bildschärfe und Farbdensität gegenüber denThe examples show that the smudge resistance, Sharpness and color density compared to the

    Vergleichsbeispielen verbessert werden konnte, der Farbtransfer konnte sogar ganz erheblich verbessert werden.Comparative examples could be improved, the Color transfer could even be improved considerably become.

    Claims (6)

    1. Recording material for the ink jet printing process, consisting of a support and a gelatin-containing and pigment-containing ink receiving layer, characterized in that the ink receiving layer comprises, as single binding agent, a carbonyl group-modified gelatin with a residual content of free amino groups of up to 50 mol%.
    2. Recording material according to claim 1, characterized in that the gelatin is a succinic anhydride-modified gelatin.
    3. Recording material according to claims 1 and 2, characterized in that the modified gelatin is an acid digested pig's skin gelatin.
    4. Recording material according to claims 1 to 3, characterized in that the pigment consists of colloidal, aluminium-modified silicic acid.
    5. Recording material according to claims 1 to 4, characterized in that the pigment to gelatin ratio is 1:0.4 to 1:20.
    6. Recording material according to claims 1 to 5, characterized in that the ink receiving layer comprises a cationic dicyandiamide-copolymer.
    EP96114450A 1995-09-21 1996-09-10 Recording material for the ink-jet printing process Expired - Lifetime EP0764546B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE19535072 1995-09-21
    DE19535072A DE19535072C3 (en) 1995-09-21 1995-09-21 Recording material for the ink-jet printing process

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    JPH1086508A (en) * 1996-09-19 1998-04-07 Konica Corp Ink jet recording sheet
    DE19721238C2 (en) * 1997-05-21 2000-08-03 Stoess & Co Gelatine Recording paper for inkjet printers
    WO1998052765A1 (en) * 1997-05-23 1998-11-26 Nashua Corporation Glossy ink jet paper
    EP1124693B1 (en) * 1998-10-02 2004-12-08 Cabot Corporation Silica dispersion, coating composition and recording medium
    US6492005B1 (en) * 1999-03-09 2002-12-10 Konica Corporation Ink jet recording sheet
    JP2002067475A (en) * 2000-08-23 2002-03-05 Mitsubishi Paper Mills Ltd Ink-jet recording materials
    DE10361247A1 (en) * 2003-12-22 2005-07-28 Deutsche Gelatine-Fabriken Stoess Ag Chitosan and its use as a color fixing agent in ink-jet recording materials
    US20070059652A1 (en) * 2005-09-15 2007-03-15 Kitchin Jonathan P Repositionable glossy photo media
    US20070059472A1 (en) * 2005-09-15 2007-03-15 3M Innovative Properties Company Repositionable photo media and photographs
    US20080003383A1 (en) * 2005-09-15 2008-01-03 3M Innovative Properties Company Repositionable photo paper
    US20070059631A1 (en) * 2005-09-15 2007-03-15 Kitchin Jonathan P Repositionable glossy photo media
    US20070059613A1 (en) * 2005-09-15 2007-03-15 Kitchin Jonathan P Repositionable photo card
    US20070089832A1 (en) * 2005-09-15 2007-04-26 Kitchin Jonathan P Repositionable matte photo media

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    EP0298424A2 (en) * 1987-07-07 1989-01-11 Asahi Glass Company Ltd. Carrier medium for a coloring matter

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    JPS62263084A (en) * 1986-05-09 1987-11-16 Honshu Paper Co Ltd Transparent sheet for ink jet recording
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    DK0764546T3 (en) 2000-08-28
    EP0764546A1 (en) 1997-03-26
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    DE19535072C2 (en) 1997-12-11
    ES2147879T3 (en) 2000-10-01
    JPH09226232A (en) 1997-09-02
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    ATE192085T1 (en) 2000-05-15
    DE59605029D1 (en) 2000-05-31

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    Owner name: FELIX *SCHOELLER JR FOTO- UND SPEZIALPAPIERE G.M.B

    Effective date: 20050930