EP0786552A2 - Recording medium for the ink-jet recording method - Google Patents

Recording medium for the ink-jet recording method Download PDF

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Publication number
EP0786552A2
EP0786552A2 EP97100087A EP97100087A EP0786552A2 EP 0786552 A2 EP0786552 A2 EP 0786552A2 EP 97100087 A EP97100087 A EP 97100087A EP 97100087 A EP97100087 A EP 97100087A EP 0786552 A2 EP0786552 A2 EP 0786552A2
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EP
European Patent Office
Prior art keywords
ink
weight
recording material
material according
polyvinyl alcohol
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
EP97100087A
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German (de)
French (fr)
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EP0786552A3 (en
EP0786552B1 (en
Inventor
Wolfgang Storbeck
Gerhard Dr. Dransmann
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Felix Schoeller Jr Foto und Spezialpapiere GmbH
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Felix Schoeller Jr Foto und Spezialpapiere GmbH
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/02—Chemical or chemomechanical or chemothermomechanical pulp
    • D21H11/04—Kraft or sulfate pulp
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/508—Supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • B41M5/529—Macromolecular coatings characterised by the use of fluorine- or silicon-containing organic compounds
    • 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

Definitions

  • the invention relates to a recording material for the ink jet printing process (ink jet process).
  • the ink jet process is one of the electronic printing processes. It is possible to assemble pictures, texts and graphics on the computer and print them out directly as a screen hardcopy.
  • droplets of a recording liquid are applied to the surface of the carrier material using various techniques.
  • 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.
  • the receiving material consists of a carrier material, an ink receiving layer and optionally further auxiliary layers. Both the carrier material and the ink-receiving layer layer must be coordinated with one another to solve these problems.
  • Ink-jet printers for the production of photo-like prints use inks with a high proportion of water as a solvent.
  • the ink consumption of these printers is greater than that of conventional ink jet printers.
  • foils were used as receiving materials because they are characterized by high dimensional stability when wetted with water.
  • the high water content that penetrates through the ink absorption layer into the paper base causes a ripple in the transverse direction (print cockle). This ripple leads to contact with the print head and results in a deterioration of the print image.
  • the head contact can damage the receiving material.
  • GB 2 210 812 A1 describes a receiving material consisting of a paper base and an ink receiving layer.
  • the paper contains calcium carbonate as a pigment; high demands are made of paper sizing.
  • a Fourdrinier paper machine is proposed for producing the base.
  • the ink absorption layer consists of calcium carbonate and a binder made of cationic vinyl acetate copolymer and a polyvinyl alcohol with silanol groups.
  • the receiving material is characterized by good water resistance and sharpness.
  • JP 06-262845 A describes a receiving material consisting of a paper support and an ink receiving layer.
  • the paper backing contains hardwood pulp and a glue of starch and alkyl ketene dimer.
  • the disadvantage here is the occurrence of a waviness of the carrier material due to the sole use of short fiber pulp.
  • a recording material consisting of a paper support and a pigment and Binder-containing layer, wherein the paper consists of a mixture of softwood sulfate and eucalyptus pulp, has a wet elongation in the transverse direction ⁇ 3.0, a tear length ratio longitudinal / transverse ⁇ 2, a bending stiffness ratio longitudinal / transverse ⁇ 2 and a density ⁇ 0.8.
  • the paper carrier according to the invention can be produced on the machines customary in the paper industry, in particular on a Yankee paper machine.
  • the softwood sulfate pulp is pine sulfate pulp.
  • the proportion of softwood sulfate pulp is 5% to 80%, in particular 10% to 40% of the total pulp.
  • This composition has proven to be advantageous for achieving high dimensional stability.
  • inorganic pigments such as calcium carbonate, clay, titanium dioxide and silicates can be added.
  • the orientation of the fibers in the longitudinal and transverse directions must be chosen so that there is a longitudinal / transverse ratio ⁇ 2.0 for the tear length and the bending stiffness. All compounds customary in the paper industry can be used as sizing and wet strength agents.
  • the paper can be both acid and neutral sized.
  • the moisture expansion across the fennel must be ⁇ 3.0%, in a preferred embodiment ⁇ 2.0%.
  • the density of the paper must be ⁇ 0.8, in a preferred embodiment ⁇ 0.7.
  • the basis weight of the paper according to the invention is 60 g / m 2 to 220 g / m 2 . In a preferred embodiment, the weight per unit area is 80 g / m 2 to 160 g / m 2 .
  • the receiving layer of the receiving material according to the invention contains silica as a pigment or a mixture of silica with other pigments such as aluminum oxide, calcium carbonate, magnesium carbonate, titanium dioxide and silica gel.
  • a mixture of a polyvinyl alcohol with silanol groups, a cationic polyvinyl alcohol, a cationic polyacrylate, a polyvinyl alcohol mixed with boric acid and a cationic polymer based on an acrylic acid ester is used as the binder.
  • This mixture of binders achieves high water resistance, high color densities and good light stability. Leakage of the colors at the edges of color areas in mixed colors with a magenta component is avoided.
  • dye-fixing agents such as poly-dadmac, dyes, optical brighteners and alcohols.
  • the proportion of the cationic polyvinyl alcohol in the ink-receiving layer can be 5% by weight to 20% by weight, in particular 10% by weight to 15% by weight, based on the dried layer.
  • the proportion of the polyvinyl alcohol with silanol groups in the ink-receiving layer can be 5% by weight to 20% by weight, in particular 10% by weight to 15% by weight, based on the dried layer.
  • the proportion of the polyvinyl alcohol with boric acid in the ink receiving layer can be 5% by weight to 20% by weight, in particular 10% by weight to 15% by weight, based on the dried layer.
  • the proportion of the cationic polyacrylate in the ink-receiving layer can be 2% by weight to 20% by weight, in particular 5% by weight to 10% by weight, based on the dried layer.
  • the proportion of pigment or pigment mixture in the ink-receiving layer can be 30% by weight to 70% by weight, in particular 50% by weight to 60% by weight, based on the dried layer.
  • the coating weight of the ink receiving layer is between 2 g / m 2 and 16g / m 2, in particular between 4 g / m 2 and 12g / m 2.
  • Table 2 composition a b c d amorphous silicon dioxide 18%, commercially available 20.00 25.00 28.00 35.00 amorphous silicon dioxide 18%, commercially available 20.00 25.00 28.00 35.00 Polydadmac 40%, 4.00 4.00 4.00 4.00 cationic acrylate 20%, commercially available 7.00 14.00 8.00 7.00 cationic acrylic acid ester 20%, commercially available 15.00 10.00 10.00 8.00 Polyvinyl alcohol with boric acid 10%, commercially available 15.00 15.00 cationic polyvinyl alcohol 20%, commercially available 19.00 7.00 8.00 5.00 Polyvinyl alcohol with 8% silanol groups, commercially available 14.00 6.00 Order g / m2 7.20 9.40 8.80 10.30
  • the paper 1 produced according to the invention was coated with the coating compositions a to d produced according to the invention (example 1a, 1b, 1c, 1d).
  • Paper 2 produced according to the invention was coated with coating composition a produced according to the invention (Example 2a).
  • the paper 3 produced according to the invention was coated with the coating composition d produced according to the invention (example 3d).
  • This paper support was provided with an ink-receiving layer which, as a binder, contained a mixture of a vinyl acetate, butyl acrylate, Versatic acid copolymer and a polyvinyl alcohol.
  • a silica was used as the pigment.
  • Other additives were defoamers, dyes and ink fixing aids.
  • Comparative example V2 was a commercially available paper from Hoffmann and Engelmann type HRC 600/1.
  • a paper support and an ink-receiving layer were prepared according to Example 6 of GB 2 210 812.
  • the color density was measured using a Gretag Densitometer type 186D on the colors cyan, magenta, yellow and black. Using a computer program, the colors cyan, magenta, yellow and black are printed in a calculated target density. The actual density was measured with a Gretag Densitometer type 186D.
  • the printed papers are placed in warm water at 25 ° C for 1 minute and dried. The color density is measured before and after washing. The remaining color density is given in percent.
  • the field distance is the distance between two colored areas and should be 1mm.
  • the actual distance is determined with a microscope with a measuring device.
  • the field distance is a measure of the image sharpness or point distance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Paper (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

In ink jet printing material, consisting of a paper base and an ink-receptive coating containing pigment and binder, the paper contains a mixture of softwood sulphate and eucalyptus pulp and has a wet elongation < 3.0 in the transverse direction, a tearing length ratio < 2 and flexural stiffness ratio < 2 in the machine/transverse directions and a density < 0.8 m<3>/kg.

Description

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

Das Ink-Jet-Verfahren gehört zu den elektronischen Druckverfahren. Hierbei ist es möglich, Bilder, Texte und Graphiken am Rechner zusammenzusetzen und als Bildschirmhardcopy direkt auszudrucken.The ink jet process is one of the electronic printing processes. It is possible to assemble pictures, texts and graphics on the computer and print them out directly as a screen hardcopy.

Bei dem Ink-Jet-Verfahren werden Tröpfchen einer Aufzeichnungsflüssigkeit auf die Oberfläche des Trägermaterials mittels unterschiedlicher Techniken aufgetragen. 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.In the ink jet process, droplets of a recording liquid are applied to the surface of the carrier material using various techniques. 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.

Bei der DropOn-Demand Methode wird nur an den zu bebildernden Stellen auf Abruf ein Tintentröpfchen erzeugt. Durch eine digitale elektronische Steuerung, wie bei dem Hertz Verfahren, ist es möglich, Bilder mit sehr hoher Auflösung direkt aus elektronischen Daten zu erzeugen.With the DropOn-Demand method, an ink droplet is only generated at the locations to be imaged. With a digital electronic control, as with the Hertz process, it is possible to generate images with very high resolution directly from electronic data.

Das Ink-Jet-Aufzeichnungsverfahren wird zur Herstellung von Farbgraphiken, Vollfarbkopien und auch für Textdrucke eingesetzt, es umfaßt also ein sehr breites Anwendungsfeld. An das Aufzeichnungsmaterial werden unterschiedliche Anforderungen gestellt wie

  • Punktgröße
  • Lichtstabilität
  • Farbverlaufen (Bleed)
  • Wasserfestigkeit
  • Densität
  • Dimensionsstabilität.
The ink jet recording process is used for the production of color graphics, full color copies and also for text printing, so it covers a very wide field of application. Different requirements are placed on the recording material such as
  • Dot size
  • Light stability
  • Bleeding
  • Water resistance
  • Density
  • Dimensional stability.

Das Empfangsmaterial besteht aus einem Trägermaterial, einer Tintenempfangsschicht und gegebenenfalls weiteren Hilfsschichten. Sowohl Trägermaterial als auch Tintenaufnahmeschichtschicht müssen zur Lösung dieser Probleme aufeinander abgestimmt sein.The receiving material consists of a carrier material, an ink receiving layer and optionally further auxiliary layers. Both the carrier material and the ink-receiving layer layer must be coordinated with one another to solve these problems.

Ink-Jet-Drucker zur Herstellung fotoähnlicher Drucke benutzen Tinten mit einem hohen Anteil Wasser als Lösungsmittel. Außerdem ist der Tintenauftrag dieser Drucker gößer als bei herkömmlichen Ink-Jet-Druckern. Als Empfangsmaterialien wurden anfangs Folien eingesetzt, da diese sich durch hohe Dimensionsstabilität bei Benetzung mit Wasser auszeichnen. Bei Benutzung herkömmlicher Ink-Jet-Papiere tritt durch den hohen Wassergehalt, der durch die Tintenaufnahmeschicht in die Papierunterlage eindringt, eine Welligkeit in Querrichtung (print cockle) auf. Diese Welligkeit führt zu einem Kontakt mit dem Druckkopf und hat eine Verschlechterung des Druckbilds zur Folge. Außerdem kann der Kopfkontakt zu einer Beschädigung des Empfangsmaterials führen.Ink-jet printers for the production of photo-like prints use inks with a high proportion of water as a solvent. In addition, the ink consumption of these printers is greater than that of conventional ink jet printers. Initially, foils were used as receiving materials because they are characterized by high dimensional stability when wetted with water. When using conventional ink jet papers, the high water content that penetrates through the ink absorption layer into the paper base causes a ripple in the transverse direction (print cockle). This ripple leads to contact with the print head and results in a deterioration of the print image. In addition, the head contact can damage the receiving material.

Es ist daher notwendig, für die Herstellung fotoähnlicher Ink-Jet-Drucke ein Empfangsmaterial einzusetzen, bei dem der Papierkern eine hohe Dimensionsstabilität aufweist und somit in der Lage ist, eine große Wassermenge aufzunehmen und die Empfangsschicht die angeführten Anforderungen an die Bild- und Textqualität erfüllt.It is therefore necessary to use a receiving material for the production of photo-like ink-jet prints in which the paper core has a high dimensional stability and is therefore able to absorb a large amount of water and the receiving layer fulfills the stated requirements for image and text quality .

Die GB 2 210 812 A1 beschreibt ein Empfangsmaterial, besthend aus einer Papierunterlage und einer Tintenaufnahmeschicht. Das Papier enthält Calciumcarbonat als Pigment; an die Papierleimung werden hohe Anforderungen gestellt. Zur Herstellung der Unterlage wird eine Fourdrinier Papiermaschine vorgeschlagen. Die Tintenaufnahmeschicht besteht aus Calciumcarbonat und einem Bindemittel aus kationischem Vinylacetat-Copolymer und einem Polyvinylalkohol mit Silanolgruppen. Das Empfangsmaterial zeichnet sich durch gute Wasserfestigkeit und Bildschärfe aus.GB 2 210 812 A1 describes a receiving material consisting of a paper base and an ink receiving layer. The paper contains calcium carbonate as a pigment; high demands are made of paper sizing. A Fourdrinier paper machine is proposed for producing the base. The ink absorption layer consists of calcium carbonate and a binder made of cationic vinyl acetate copolymer and a polyvinyl alcohol with silanol groups. The receiving material is characterized by good water resistance and sharpness.

Nachteilig ist allerdings das Auftreten einer Welligkeit bei hoher Wasseraufnahme und eine Abnahme der Farbdichte bei höheren AuftragsgewichtenHowever, the disadvantages are the appearance of a ripple with high water absorption and a decrease in color density with higher application weights

Die JP 06-262845 A beschreibt ein Empfangsmaterial, bestehend aus einem Papierträger und einer Tintenaufnahmeschicht. Der Papierträger enthält Laubholz-Zellstoff und eine Leimung aus Stärke und Alkylketen-Dimer. Nachteilig ist auch hier das Auftreten einer Welligkeit des Trägermaterials durch den alleinigen Einsatz von Kurzfaserzellstoff.JP 06-262845 A describes a receiving material consisting of a paper support and an ink receiving layer. The paper backing contains hardwood pulp and a glue of starch and alkyl ketene dimer. The disadvantage here is the occurrence of a waviness of the carrier material due to the sole use of short fiber pulp.

Aufgabe der Erfindung ist es, ein Aufzeichnungsmaterial für das Ink-Jet-Druckverfahren zur Verfügung zu stellen, das sich auszeichnet durch:

  • hohe Farbdichte,
  • gute Wasserfestigkeit,
  • geringes Farbverlaufen,
  • Bildschärfe und
  • Dimensionsstabilität.
The object of the invention is to provide a recording material for the ink jet printing process, which is characterized by:
  • high color density,
  • good water resistance,
  • slight color gradient,
  • Sharpness and
  • Dimensional stability.

Diese Aufgabe wird durch ein Aufzeichnungsmaterial gelöst, das aus einem Papierträger und einer pigment- und bindemittelhaltigen Schicht besteht, wobei das Papier aus einer Mischung von Nadelholzsulfat- und Eukalyptuszellstoff besteht, eine Feuchtdehnung in Querrichtung < 3,0, ein Reißlängenverhältnis längs/quer < 2,ein Biegesteifigkeitsverhältnis längs/quer < 2 und eine Dichte < 0,8 aufweist.This object is achieved by a recording material consisting of a paper support and a pigment and Binder-containing layer, wherein the paper consists of a mixture of softwood sulfate and eucalyptus pulp, has a wet elongation in the transverse direction <3.0, a tear length ratio longitudinal / transverse <2, a bending stiffness ratio longitudinal / transverse <2 and a density <0.8.

Der erfindungsgemäße Papierträger kann auf den in der Papierindustrie üblichen Maschinen, insbesondere auf einer Yankee Papiermaschine, hergestellt werden. In einer bevorzugten Form handelt es sich bei dem Nadelholzsulfatzellstoff um Kiefernsulfatzellstoff.The paper carrier according to the invention can be produced on the machines customary in the paper industry, in particular on a Yankee paper machine. In a preferred form, the softwood sulfate pulp is pine sulfate pulp.

Der Anteil des Nadelholzsulfatzellstoffs betägt 5% bis 80%, insbesondere 10% bis 40% vom Gesamtzellstoff. Diese Zusammensetzung hat sich als Vorteilhaft zur Erreichung einer hohen Dimensionsstabilität erwiesen. Zur Erhöhung der Weiße und Opazität können anorganische Pigmente wie Calciumcarbonat, Clay, Titandioxid und Silikate zugegeben werden. Die Ausrichtung der Fasern in Längs- und Querrichtung muß so gewählt werden, daß sich bei der Reißlänge und der Biegesteifigkeit ein Verhältnis längs/quer < 2,0 ergiebt. Als Leimungs- und Naßfestmittel können alle in der Papierindustrie üblichen Verbindungen eingesetzt werden. Das Papier kann sowohl sauer als auch neutral geleimt sein.The proportion of softwood sulfate pulp is 5% to 80%, in particular 10% to 40% of the total pulp. This composition has proven to be advantageous for achieving high dimensional stability. To increase whiteness and opacity, inorganic pigments such as calcium carbonate, clay, titanium dioxide and silicates can be added. The orientation of the fibers in the longitudinal and transverse directions must be chosen so that there is a longitudinal / transverse ratio <2.0 for the tear length and the bending stiffness. All compounds customary in the paper industry can be used as sizing and wet strength agents. The paper can be both acid and neutral sized.

Die Feuchtdehnung quer nach Fenchel muß < 3,0%, in einer bevorzugten Ausführung <2,0% sein. Die Dichte des Papies muß < o,8, in einer bevorzugten Ausführung < 0,7 sein. Das Flächengewicht des erfindungsgemäßen Papieres beträgt 60g/m2 bis 220g/m2. In einer bevorzugten Ausführung beträgt das Flächengewicht 80g/m2 bis 160g/m2.The moisture expansion across the fennel must be <3.0%, in a preferred embodiment <2.0%. The density of the paper must be <0.8, in a preferred embodiment <0.7. The basis weight of the paper according to the invention is 60 g / m 2 to 220 g / m 2 . In a preferred embodiment, the weight per unit area is 80 g / m 2 to 160 g / m 2 .

Die Empfangsschicht des erfindungsgemäßen Empfangsmaterials enthält als Pigment Kieselsäure oder eine Mischung von Kieselsäure mit anderen Pigmenten wie Aluminiumoxid, Calciumcarbonat, Magnesiumcarbonat, Titandioxid und Kieselgel.The receiving layer of the receiving material according to the invention contains silica as a pigment or a mixture of silica with other pigments such as aluminum oxide, calcium carbonate, magnesium carbonate, titanium dioxide and silica gel.

Als Bindemittel wird ein Gemisch aus einem Polyvinylalkohol mit Silanolgruppen, einem kationischem Polyvinylalkohol, einem kationischen Polyacrylat, einem mit Borsäure versetzten Polyvinylalkohol und einem kationischen Polymer auf Basis eines Acrylsäureesters verwendet.A mixture of a polyvinyl alcohol with silanol groups, a cationic polyvinyl alcohol, a cationic polyacrylate, a polyvinyl alcohol mixed with boric acid and a cationic polymer based on an acrylic acid ester is used as the binder.

Durch diese Bindemittelmischung erreicht man eine hohe Wasserfestigkeit, hohe Farbdichten und eine gute Lichtstabilität. Vermieden wird ein Auslaufen der Farben an den Rändern von Farbflächen bei Mischfarben mit einem Magentaanteil.This mixture of binders achieves high water resistance, high color densities and good light stability. Leakage of the colors at the edges of color areas in mixed colors with a magenta component is avoided.

Weitere Bestandteile der Tintenaufnahmeschicht können farbstoffixierende Mittel wie Poly-Dadmac, Farbstoffe, optische Aufheller und Alkohole sein.Other constituents of the ink-receiving layer can be dye-fixing agents such as poly-dadmac, dyes, optical brighteners and alcohols.

Der Anteil des kationischen Polyvinylalkohols in der Tintenaufnahmeschicht kann 5 Gew.% bis 20 Gew.%, insbesondere 10 Gew.% bis 15 Gew.%, bezogen auf die getrocknete Schicht, betragen. Der Anteil des Polyvinylalkohols mit Silanolgruppen in der Tintenaufnahmeschicht kann 5 Gew.% bis 20 Gew.%, insbesondere 10 Gew.% bis 15 Gew.%, bezogen auf die getrocknete Schicht, betragen. Der Anteil des Polyvinylalkohols mit Borsäure in der Tintenaufnahmeschicht kann 5 Gew.% bis 20 Gew.%, insbesondere 10 Gew.% bis 15 Gew.%, bezogen auf die getrocknete Schicht, betragen. Der Anteil des kationischen Polyacrylats in der Tintenaufnahmeschicht kann 2 Gew.% bis 20 Gew.%, insbesondere 5 Gew.% bis 10 Gew.%, bezogen auf die getrocknete Schicht, betragen. Der Anteil des Pigments oder des Pigmentgemisches in der Tintenaufnahmeschicht kann 30 Gew.% bis 70 Gew.%, insbesondere 50 Gew.% bis 60 Gew.%, bezogen auf die getrocknete Schicht, betragen. Das Auftragsgewicht der Tintenaufnahmeschicht liegt zwischen 2g/m2 und 16g/m2, insbesondere zwischen 4g/m2 und 12g/m2.The proportion of the cationic polyvinyl alcohol in the ink-receiving layer can be 5% by weight to 20% by weight, in particular 10% by weight to 15% by weight, based on the dried layer. The proportion of the polyvinyl alcohol with silanol groups in the ink-receiving layer can be 5% by weight to 20% by weight, in particular 10% by weight to 15% by weight, based on the dried layer. The proportion of the polyvinyl alcohol with boric acid in the ink receiving layer can be 5% by weight to 20% by weight, in particular 10% by weight to 15% by weight, based on the dried layer. The proportion of the cationic polyacrylate in the ink-receiving layer can be 2% by weight to 20% by weight, in particular 5% by weight to 10% by weight, based on the dried layer. Of the The proportion of pigment or pigment mixture in the ink-receiving layer can be 30% by weight to 70% by weight, in particular 50% by weight to 60% by weight, based on the dried layer. The coating weight of the ink receiving layer is between 2 g / m 2 and 16g / m 2, in particular between 4 g / m 2 and 12g / m 2.

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

Der erfindungsgemäße Papierträger wurde wie folgt hergestellt:

Nadelholzsulfatzellstoff
250,0 kg
Eukalyptuszellstoff
1250,0 kg
Wasser
14 m3
Füllstoff
408,6 kg
kationische Stärke
12 kg
The paper carrier according to the invention was produced as follows:
Softwood sulfate pulp
250.0 kg
Eucalyptus pulp
1250.0 kg
water
14 m 3
filler
408.6 kg
cationic strength
12 kg

Mittels Dosierpumpen wurden Leimungs- und Naßfestmittel kontinuierlich zum Dünnstoff zugegeben:

Leimungsmittel
300,0 ml/min.
Naßfestmittel 4,0%
1600,0 ml/min.
Sizing and wet strength agents were continuously added to the thin material by means of metering pumps:
Sizing agents
300.0 ml / min.
Wet strength agent 4.0%
1600.0 ml / min.

Mit dieser Rezeptur wurden Papiere mit unterschiedlichen Flächengewichten gefertigt:

Beispiel 1
80 g/m2
Beispiel 2
100 g/m2
Beispiel 3
120 g/m2
This recipe was used to produce papers with different basis weights:
example 1
80 g / m 2
Example 2
100 g / m 2
Example 3
120 g / m 2

An diesen Papieren wurden folgende Prüfungen durchgeführt:

  • 1. Feuchtdehnung quer nach Fenchel
  • 2. Zugfestigkeit nach DIN 53112, Verhältnis längs/quer
  • 3. Biegesteifigkeit nach DIN 53121, Verhältnis längs/quer
  • 4. Glätte nach Bekk
The following tests were carried out on these papers:
  • 1. Moisture stretch across the fennel
  • 2. Tensile strength according to DIN 53112, ratio longitudinal / transverse
  • 3. Bending rigidity according to DIN 53121, ratio longitudinal / transverse
  • 4. Smoothness according to Bekk

Ergebnisse der PapierprüfungenResults of the paper tests

Tabelle 1Table 1 PrüfartTest type 11 22nd 33rd FeuchtdehnungWet expansion 1,871.87 2,042.04 1,951.95 Zugfestigkeittensile strenght 1,821.82 1,891.89 1,801.80 BiegesteifigkeitBending stiffness 1,881.88 1,931.93 1,771.77 Glättesmoothness 126126 210210 110110 Dichtedensity 0,750.75 0,690.69 0,650.65

Herstellung der erfindungsgemäßen Beschichtungsmasse. Tabelle 2 Zusammensetzung a b c d amorphes Siliciumdioxid 18%, handelsüblich 20,00 25,00 28,00 35,00 amorphes Siliciumdioxid 18%, handelsüblich 20,00 25,00 28,00 35,00 Polydadmac 40%, 4,00 4,00 4,00 4,00 kationisches Acrylat 20%, handelsüblich 7,00 14,00 8,00 7,00 kationischer Acrylsäureester 20%, handelsüblich 15,00 10,00 10,00 8,00 Polyvinylalkohol mit Borsäure 10%, handelsüblich 15,00 15,00 kationischer Polyvinylalkohol 20%, handelsüblich 19,00 7,00 8,00 5,00 Polyvinylalkohol mit Silanolgruppen 8%, handelsüblich 14,00 6,00 Auftrag g/m2 7,20 9,40 8,80 10,30 Production of the coating composition according to the invention. Table 2 composition a b c d amorphous silicon dioxide 18%, commercially available 20.00 25.00 28.00 35.00 amorphous silicon dioxide 18%, commercially available 20.00 25.00 28.00 35.00 Polydadmac 40%, 4.00 4.00 4.00 4.00 cationic acrylate 20%, commercially available 7.00 14.00 8.00 7.00 cationic acrylic acid ester 20%, commercially available 15.00 10.00 10.00 8.00 Polyvinyl alcohol with boric acid 10%, commercially available 15.00 15.00 cationic polyvinyl alcohol 20%, commercially available 19.00 7.00 8.00 5.00 Polyvinyl alcohol with 8% silanol groups, commercially available 14.00 6.00 Order g / m2 7.20 9.40 8.80 10.30

Als Lösungsmittel diente in allen Fällen Wasser.Water was used as the solvent in all cases.

Alle Angaben in Gew.%, bezogen auf die getrocknete Schicht.All data in% by weight, based on the dried layer.

Das erfindungsgemäß hergestellte Papier 1 wurde mit den erfindungsgemäß hergestellten Beschichtungsmassen a bis d beschichtet, (Beispiel 1a, 1b, 1c, 1d).The paper 1 produced according to the invention was coated with the coating compositions a to d produced according to the invention (example 1a, 1b, 1c, 1d).

Das erfindungsgemäß hergestellte Papier 2 wurde mit der erfindungsgemäß hergestellten Beschichtungsmasse a beschichtet, (Beispiel 2a).Paper 2 produced according to the invention was coated with coating composition a produced according to the invention (Example 2a).

Das erfindungsgemäß hergestellte Papier 3 wurde mit der erfindungsgemäß hergestellten Beschichtungsmasse d beschichtet, (Beispiel 3d).The paper 3 produced according to the invention was coated with the coating composition d produced according to the invention (example 3d).

Vergleichsbeispiel V1Comparative Example V1

Vergleichsbeispiel V1 war ein Papierträger mit einem Flächengewicht von 100g/m2, mit einem Anteil an Nadelholzsulfatzellstoff von 31% und einem Eukalyptuszellstoffanteil von 69%. Der FÜllstoffanteil lag bei 25 Gew.%. Das Papier war neutal geleimt, es wurden folgende Prüfwerte ermittelt:

Dichte
0,95
Feuchtdehnung
3,9%
Steifigkeit l/q
2,4
Zugfestigkeit l/q
2,3
Glätte (Bekk)
90 Sekunden
Comparative example V1 was a paper support with a basis weight of 100 g / m 2 , with a proportion of softwood sulphate pulp of 31% and a proportion of eucalyptus pulp of 69%. The filler content was 25% by weight. The paper was glued neutrally, the following test values were determined:
density
0.95
Wet expansion
3.9%
Stiffness l / q
2.4
Tensile strength l / q
2.3
Smoothness (Bekk)
90 seconds

Dieser Papierträger wurde mit einer Tintenaufnahmeschicht versehen, die als Bindemittel ein Gemisch aus einem Vinylacetat, Butylacrylat, Versatic-Säure Copolymer und einem Polyvinylalkohol enthielt. Als Pigment diente eine Kieselsäure. Weitere Zusätze waren Entschäumer, Farbstoffe und Tintenfixierhilfsmittel.This paper support was provided with an ink-receiving layer which, as a binder, contained a mixture of a vinyl acetate, butyl acrylate, Versatic acid copolymer and a polyvinyl alcohol. A silica was used as the pigment. Other additives were defoamers, dyes and ink fixing aids.

Vergleichsbeispiel V2Comparative example V2

Vergleichsbeispiel V2 war ein im Handel erhältliches Papier der Firma Hoffmann und Engelmann Typ HRC 600/1.Comparative example V2 was a commercially available paper from Hoffmann and Engelmann type HRC 600/1.

Vergleichsbeispiel V3Comparative Example V3

Ein Papierträger und eine Tintenaufnahmeschicht wurden nach Beispiel 6 der Offenlegungsschrift GB 2 210 812 hergestellt.A paper support and an ink-receiving layer were prepared according to Example 6 of GB 2 210 812.

Prüfung des gemäß Beispiel B 3.1 bis B 3.6 und der Vergleichsbeispiele V1 und V2.Testing of according to example B 3.1 to B 3.6 and comparative examples V1 and V2.

1. Farbdensität und 50% Densität1. Color density and 50% density

Die Farbdensität wurde mit einem Gretag Densitometer Typ 186D an den Farben Cyan, Magenta, Gelb und Schwarz gemessen. Mittel eines Computerprogramms werden die Farben Cyan, Magenta, Gelb und Schwarz in einer berechneten Solldensität aufgedruckt. Die tatsächliche Densität wurde mit einem Gretag Densitometer Typ 186D gemessen.The color density was measured using a Gretag Densitometer type 186D on the colors cyan, magenta, yellow and black. Using a computer program, the colors cyan, magenta, yellow and black are printed in a calculated target density. The actual density was measured with a Gretag Densitometer type 186D.

2. Wasserfestigkeit2. Water resistance

Die bedruckten Papiere werden für 1 Minute in 25°C warmes Wasser gelegt und getrocknet. Die Farbdichte wird vor und nach der Wässerung gemessen. Andegeben wird die verbliebene Farbdichte in Prozent.The printed papers are placed in warm water at 25 ° C for 1 minute and dried. The color density is measured before and after washing. The remaining color density is given in percent.

3. Verlaufen (Bleed)3. Bleed

Das Ineinanderlaufen der Tinten an den Rändern von zusammenliegenden Farbflächen wurde visuell mit den Noten 1 bis 6 (sehr gut bis sehr schlecht) beurteilt.The running together of the inks at the edges of color areas lying together was assessed visually with the marks 1 to 6 (very good to very bad).

4. Feldabstand4. Field distance

Der Feldabstand ist der Abstand zwischen zwei Farbflächen und soll 1mm betragen. Der tatsächliche Abstand wir mit einem Mikroskop mit Meßeinrichtung bestimmt. Der Feldabstand ist ein Maß für die Bildschärfe bzw. Punktabstand.The field distance is the distance between two colored areas and should be 1mm. The actual distance is determined with a microscope with a measuring device. The field distance is a measure of the image sharpness or point distance.

5. Dimensionsstabilität5. Dimensional stability

Zur Bestimmung der Dimensionsstabilität legt man das zu prüfende Papier auf ein ebene Unterlage. Die Planlage des Papiers wird mit den Noten 1 bis 12 (sehr gut bis sehr schlecht) beurteilt.To determine the dimensional stability, place the paper to be tested on a flat surface. The flatness of the paper is assessed with grades 1 to 12 (very good to very bad).

Ergebnisse der Prüfungen der BeispieleResults of the tests of the examples

FarbdensitätColor density EmpfangsmaterialReceiving material CyanCyan Magentamagenta Gelbyellow Schwarzblack B 1aB 1a 2,192.19 1,221.22 1,631.63 2,212.21 B 1bB 1b 2,152.15 1,221.22 1,581.58 2,192.19 B 1cB 1c 2,142.14 1,221.22 1,591.59 2,162.16 B 1dB 1d 2,142.14 1,221.22 1,621.62 2,252.25 B 2aB 2a 2,172.17 1,221.22 1,611.61 2,202.20 B 3dB 3d 2,132.13 1,241.24 1,631.63 2,242.24 50% Densität50% density EmpfangsmaterialReceiving material CyanCyan Magentamagenta Gelbyellow Schwarzblack B 1aB 1a 0,860.86 0,460.46 0,690.69 0,980.98 B 1bB 1b 0,920.92 0,470.47 0,690.69 0,990.99 B 1cB 1c 0,900.90 0,460.46 0,670.67 0,940.94 B 1dB 1d 0,920.92 0,460.46 0,700.70 1,011.01 B 2aB 2a 0,900.90 0,450.45 0,680.68 0,990.99 B 3dB 3d 0,880.88 0,470.47 0,710.71 0,940.94 Wasserfestigkeit in ProzentWater resistance in percent EmpfangsmaterialReceiving material CyanCyan Magentamagenta Gelbyellow Schwarzblack B 1aB 1a 98,698.6 81,181.1 98,298.2 98,198.1 B 1bB 1b 102,3102.3 81,181.1 95,595.5 99,199.1 B 1cB 1c 99,599.5 81,981.9 98,198.1 97,297.2 B 1dB 1d 97,397.3 84,484.4 98,198.1 97,797.7 B 2aB 2a 98,598.5 83,383.3 97,197.1 98,598.5 B 3dB 3d 99,499.4 82,182.1 97,597.5 97,897.8 Feldabstand, Verlaufen, DimensionsstabilitätField distance, gradient, dimensional stability EmpfangsmaterialReceiving material FeldabstandField distance BleedBleed WelligkeitRipple B 1aB 1a 0,900.90 Note 2Grade 2 Note 2Grade 2 B 1bB 1b 0,850.85 Note 2Grade 2 Note 2Grade 2 B 1cB 1c 0,900.90 Note 2Grade 2 Note 2Grade 2 B 1dB 1d 0,900.90 Note2Note2 Note 2Grade 2 B 2aB 2a 0,850.85 Note2Note2 Note 2Grade 2 B 3dB 3d 0,900.90 Note2Note2 Note 1Note 1 Ergebnisse der Prüfungen der Vergleichsbeispiele V1 und V2Results of the tests of comparative examples V1 and V2 Prüfungexam V1V1 V2V2 V3V3 FarbdichteColor density CyanCyan 1,991.99 2,202.20 2,112.11 Magentamagenta 1,001.00 1,101.10 1,121.12 Gelbyellow 1,421.42 1,631.63 1,611.61 Schwarzblack 1,791.79 2,182.18 2,122.12   50% Farbdichte50% color density CyanCyan 0,760.76 0,870.87 0,810.81 Magentamagenta 0,390.39 0,390.39 0,410.41 Gelbyellow 0,550.55 0,560.56 0,570.57 Schwarzblack 0,870.87 0,900.90 0,880.88   WasserfestigkeitWater resistance CyanCyan 98,9098.90 96,3096.30 98,1098.10 Magentamagenta 98,0098.00 99,6099.60 99,2099.20 Gelbyellow 99,1099.10 98,6098.60 98,5098.50 Schwarzblack 98,0098.00 97,6097.60 97,7097.70   VerlaufenGet lost Note 4Grade 4 Note 3Note 3 Note 2Grade 2   Dimensionsstab.Dimension rod. Note 8Note 8 Note 7Note 7 Note 7Note 7   FeldabstandField distance 0,750.75 0,810.81 0,810.81

Die Beispiele zeigen, daß bei hohen Farbdichten, guten Wasserfestigkeits- und Verlaufungungseigenschaften eine sehr gute Dimensionsstabilität des Empfangsmaterials erreicht werden konnte.The examples show that with high color densities, good water resistance and leveling properties, a very good dimensional stability of the receiving material could be achieved.

Claims (9)

Aufzeichnungsmaterial für das Ink-Jet-Druckverfahren, bestehend aus einem Papierträger und einer Pigment und Bindemittel enthaltenden Tintenaufnahmeschicht, dadurch gekennzeichnet, daß das Papier eine Mischung von Nadelholzsulfat- und Eukalyptuszellstoff enthält, eine Feuchtdehnung in Querrichtung < 3,0 ein Reißlängenverhältnis längs/quer < 2, ein Biegesteifigkeitsverhältnis länds/quer < 2 und eine Dichte < 0,8 m3/kg aufweistRecording material for the ink jet printing process, consisting of a paper support and an ink-receiving layer containing pigment and binder, characterized in that the paper contains a mixture of softwood sulphate and eucalyptus pulp, a moisture expansion in the transverse direction <3.0 and a tear length ratio longitudinal / transverse < 2, a bending stiffness ratio land / cross <2 and a density <0.8 m 3 / kg Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, daß der Anteil des Nadelholzsulfatzellstoffs 10 bis 40% vom Gesamtzellstoff beträgt.Recording material according to claim 1, characterized in that the proportion of the softwood sulfate pulp is 10 to 40% of the total pulp. Aufzeichnungsmaterial nach Anspruch 1 und 2, dadurch gekennzeichnet, daß die Tintenaufnahmeschicht einen Polyvinylalkohol mit Silanolgruppen und/oder einen Polyvinylalkohol mit Borsäure als Bindemittel der Tintenaufnahmeschicht enthält.Recording material according to claims 1 and 2, characterized in that the ink-receiving layer contains a polyvinyl alcohol with silanol groups and / or a polyvinyl alcohol with boric acid as a binder of the ink-receiving layer. Aufzeichnungsmaterial nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß die Tintenaufnahmeschicht ein kationisches Polyacrylat enthält.Recording material according to claims 1 to 3, characterized in that the ink-receiving layer contains a cationic polyacrylate. Aufzeichnungsmaterial nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß die Tintenaufnahmeschicht einen kationischen Polyvinylalkohol enthält.Recording material according to claims 1 to 4, characterized in that the ink-receiving layer contains a cationic polyvinyl alcohol. Aufzeichnungsmaterial nach Anspruch 1 bis 5, dadurch gekennzeichnet, daß der Anteil des Polyvinylalkohols mit Silanolgruppen 5 bis 20 Gew.% und in einer besonderen Ausführung 10 bis 15 Gew.%, bezogen auf die getrocknete Schicht, beträgt.Recording material according to Claims 1 to 5, characterized in that the proportion of polyvinyl alcohol with silanol groups is 5 to 20% by weight and in a special embodiment 10 to 15% by weight, based on the dried layer. Aufzeichnungsmaterial nach Anspruch 1 bis 6, dadurch gekennzeichnet, daß der Anteil des Polyvinylalkohols mit Borsäure 5 bis 20 Gew.% und in einer besonderen Ausführung 10 bis 15 Gew.%, bezogen auf die getrocknete Schicht, beträgt.Recording material according to Claims 1 to 6, characterized in that the proportion of polyvinyl alcohol with boric acid is 5 to 20% by weight and in a special embodiment 10 to 15% by weight, based on the dried layer. Aufzeichnungsmaterial nach Anspruch 1 bis 7, dadurch gekennzeichnet, daß der Anteil des kationischen Polyvinylalkohols 5 bis 20 Gew.% und in einer besonderen Ausführung 10 bis 15 Gew.%, bezogen auf die getrocknete Schicht, beträgt.Recording material according to Claims 1 to 7, characterized in that the proportion of the cationic polyvinyl alcohol is 5 to 20% by weight and in a special embodiment 10 to 15% by weight, based on the dried layer. Aufzeichnungsmaterial nach Anspruch 1 bis 8 dadurch gekennzeichnet, daß der Anteil des kationischen Acrylats 2 bis 20 Gew.% und in einer besonderen Ausführung 5 bis 10 Gew%., bezogen auf die getrocknete Schicht, beträgt.Recording material according to Claims 1 to 8, characterized in that the proportion of the cationic acrylate is 2 to 20% by weight and in a special embodiment 5 to 10% by weight, based on the dried layer.
EP97100087A 1996-01-26 1997-01-04 Recording medium for the ink-jet recording method Revoked EP0786552B1 (en)

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CN100392182C (en) * 2000-06-27 2008-06-04 日本制纸股份有限公司 Coated paper for printing
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DE59707178D1 (en) 2002-06-13
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ES2176529T3 (en) 2002-12-01
DK0786552T3 (en) 2002-08-26

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