EP0445327A1 - Recording medium for ink-jet printing - Google Patents

Recording medium for ink-jet printing Download PDF

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Publication number
EP0445327A1
EP0445327A1 EP19900104332 EP90104332A EP0445327A1 EP 0445327 A1 EP0445327 A1 EP 0445327A1 EP 19900104332 EP19900104332 EP 19900104332 EP 90104332 A EP90104332 A EP 90104332A EP 0445327 A1 EP0445327 A1 EP 0445327A1
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EP
European Patent Office
Prior art keywords
recording material
ink
material according
receiving layer
copolymer
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
EP19900104332
Other languages
German (de)
French (fr)
Other versions
EP0445327B1 (en
Inventor
Reiner Dipl.-Chem. Dr. Jahn
Horst Dipl.-Ing. Westfal
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.)
Felex Schoeller Jr and GmbH and Co KG
Original Assignee
Felix Schoeller Jr Foto und Spezialpapiere GmbH
Felex Schoeller Jr and GmbH and Co KG
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Application filed by Felix Schoeller Jr Foto und Spezialpapiere GmbH, Felex Schoeller Jr and GmbH and Co KG filed Critical Felix Schoeller Jr Foto und Spezialpapiere GmbH
Priority to EP90104332A priority Critical patent/EP0445327B1/en
Priority to DE59006369T priority patent/DE59006369D1/en
Priority to JP3036085A priority patent/JP2693278B2/en
Priority to US07/665,601 priority patent/US5141599A/en
Publication of EP0445327A1 publication Critical patent/EP0445327A1/en
Application granted granted 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
    • B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
    • 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.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31899—Addition polymer of hydrocarbon[s] only
    • 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]
    • Y10T428/31971—Of carbohydrate
    • 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]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31993—Of paper

Definitions

  • the invention relates to a recording material with a glossy surface for the ink jet recording process (ink jet printing).
  • droplets of a recording liquid are applied to the recording material using various techniques.
  • Hertz process which, by means of a digital electronic control of fine ink droplets which are pressed out of special nozzles, allows the printing of images with very high resolution directly from electronic data.
  • a recording material for multicolored ink jet printing usually consists of a support and an ink receiving layer arranged thereon.
  • the carrier can be a film made of polyester resin, diacetate resin or paper etc. be.
  • the ink-receiving layers basically consist of a pigment / binder mixture.
  • the pigments serve to retain the dyes from the recording liquid on the surface of the sheet.
  • a high pigment concentration leads to high porosity of the layer (DE-PS 30 24 205).
  • This coating is intended to improve the smudge resistance and increase the resolving power.
  • a disadvantage of this recording material is above all that the sprayed-on symbols do not appear in the desired short time, but only after more than 10 seconds. are sufficiently smudge-proof. Another disadvantage is that the ink droplets do not diverge sufficiently and quickly enough.
  • DE-OS 30 16 766 claims a recording material which is intended to ensure a high density and resolution of the printed image by applying a coating of a water-soluble polymer to a paper carrier which has a defined water absorption capacity due to an internal sizing.
  • a disadvantage of this recording material is the fact that, in order to achieve the desired color density, the material must also be smoothed in a separate operation after application of the ink receiving layer, e.g. by using a glossy or super calender.
  • JP 58-193 185 two layers are applied to a support.
  • the top layer made of polyvinyl alcohol is said to provide good smudge resistance, that is, quick ink absorption.
  • the lower layer which contains synthetic silica, is said to ensure a high color density.
  • a disadvantage of this recording material in addition to the unsatisfactory color density, are the several work steps: two layers are applied separately and finally smoothed using a calender.
  • the object of the present invention is to produce a recording material for ink jet processes which does not have the stated disadvantages and which is distinguished in particular by the high color density of the printed images in combination with a quickly attainable smudge resistance of the sprayed-on characters.
  • Another object of the invention is to provide a recording material with a glossy surface to provide, the production of which requires as little effort as possible and saves additional smoothing operations.
  • an ink-receiving layer is applied to a polyolefin-coated base paper, which contains a mixture of gelatin and starch with a grain size below 20 ⁇ m.
  • the starch is rice and / or wheat starch type B.
  • the ratio is preferably in the range from 1: 1 to 10: 1.
  • the ink-receiving layer additionally contains a polar group-containing copolymer, e.g. an acrylate copolymer containing carboxyl groups, metal-bonded carboxyl groups and / or nitrile groups, or a carboxylated vinylidene chloride copolymer and others.
  • a polar group-containing copolymer e.g. an acrylate copolymer containing carboxyl groups, metal-bonded carboxyl groups and / or nitrile groups, or a carboxylated vinylidene chloride copolymer and others.
  • the amount of the copolymer containing polar groups in the mixture is 0.5 to 35% by weight, preferably 4 to 10% by weight.
  • the ink-receiving layer can contain all other usual additives, such as inorganic or organic pigments (polymethyl methacrylate, polystyrene, urea-formaldehyde condensation products, silicic acid, CaCOs, Ti0 2 , BaS0 4, etc.), hardening agents (chrome alum, TAF / formaldehyde ), Wetting agents (eg saponin), shading dyes, antistatic agents and other auxiliaries.
  • inorganic or organic pigments polymethyl methacrylate, polystyrene, urea-formaldehyde condensation products, silicic acid, CaCOs, Ti0 2 , BaS0 4, etc.
  • hardening agents chrome alum, TAF / formaldehyde
  • Wetting agents eg saponin
  • shading dyes eg., antistatic agents and other auxiliaries.
  • the application amount of the ink-receiving layer is 0.5 to 10 g / m 2 , preferably 2 to 7 g / m 2.
  • the ink-receiving layer solution can be applied to the carrier using all customary application and metering methods, such as roller application, engraving or nipping processes as well as air brush or roller doctor metering.
  • the polyolefin used to coat the base paper is preferably low density polyethylene (LDPE) and / or high density polyethylene (HDPE). However, other polyolefins such as LLDPE or polypropylene can also be used.
  • the application amount of the polyolefin coating, which may additionally contain pigments and other substances, is at least 5 g / m 2.
  • the gloss of the recording material according to the invention does not require additional post-treatments, e.g. by means of a glossy calender, and is obviously achieved through the interaction of the PE-coated base and the ink-receiving layer.
  • the very good color density is achieved even without pigmentation of the ink receiving layer.
  • a layer support according to Example 1 was coated with the following coating compositions:
  • a layer support according to Example 1 was coated with the following coating compositions:
  • a layer support according to Example 1 was coated with the following coating compositions:
  • the recording material obtained in the comparative examples was printed in a continuous ink jet process and then analyzed.
  • the results are summarized in Table 5.
  • the recording material obtained was printed with the aid of an Excelerator 4/1120 inkjet printer from Stork X-cel, which works according to the Hertz inkjet printing principle, using the inks developed by Stork.
  • the density measurements were made before and after a 24-hour exposure of the images using a xenon lamp.
  • the device used for this was an original reflection densitometer SOS-45.
  • the measurements were carried out in the color gradations F1 - F11 for the basic colors cyan, magenta, yellow and black, the values for F1, F5 and F11 being given in the tables.
  • the smear resistance was judged by the degree of so-called "knocking off” of the ink from the surface of the material.
  • the test was carried out individually for all four primary colors. "+” was used to denote the smudge resistance of such a recording material, in which all the colors "hit” immediately away from the sheet surface, ie penetrate into the interior of the layer.
  • the designation “o” means that three primary colors immediately penetrate into the interior of the sheet and the fourth basic color only after a few seconds "-” was used to denote poor smudge resistance of the material, ie no or only weak "striking away" of almost all colors was observed.
  • the water resistance and the abrasion resistance were examined. For that was the sample of the recording material is heated in water and rubbed at 5 ° C intervals with the finger. The temperature at which the white background of the recording material shows through was taken as a measure of the water resistance and abrasion resistance.
  • the gloss of the recording material was determined using a three-angle gloss meter according to Dr. Long at a measurement angle of 60 0 measured.
  • Tables 1-5 show that the recording material produced in accordance with the invention achieves print images with high values of color density and at the same time quickly achievable smudge resistance.
  • the images printed on the recording material produced according to the invention also have better values than the comparison material with regard to water and abrasion resistance.

Abstract

A description is given of a recording medium for ink-jet printing which consists of a polyolefin-coated backing paper and an ink absorption layer applied to the front of the latter and containing a mixture of gelatine and rice starch.

Description

Die Erfindung betrifft ein Aufzeichnungsmaterial mit glänzender Oberfläche für das Tintenstrahlaufzeichnungsverfahren (ink jet printing).The invention relates to a recording material with a glossy surface for the ink jet recording process (ink jet printing).

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

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

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

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

Um dies zu erreichen, müssen folgende Grundbedingungen erfüllt werden:

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

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

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

Ein Aufzeichnungsmaterial für den mehrfarbigen ink jet-Druck besteht in der Regel aus einem Träger und einer darauf angeordneten Tintenaufnahmeschicht. Der Träger kann eine Folie aus Polyesterharz, Diacetatharz oder Papier u.a. sein.A recording material for multicolored ink jet printing usually consists of a support and an ink receiving layer arranged thereon. The carrier can be a film made of polyester resin, diacetate resin or paper etc. be.

Die Tintenaufnahmeschichten bestehen grundsätzlich aus einer Pigment/Bindemittel-Mischung.The ink-receiving layers basically consist of a pigment / binder mixture.

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. Es ist bekannt, für die ink-jet-Aufzeichnungsmaterialien ein mit Gelatineüberzug versehenes Papier zu verwenden (DE-PS 22 34 823) . Durch diese Beschichtung soll die Wischfestigkeit verbessert und das Auflösungsvermögen erhöht werden. Nachteilig an diesem Aufzeichnungsmaterial ist vor allem, daß die aufgespritzten Bildzeichen nicht in der gewünschten kurzen Zeit, sondern erst nach mehr als 10 sek. ausreichend wischfest sind. Nachteilig ist ferner, daß die Tintentröpfchen nicht ausreichend und schnell genug auseinanderlaufen.In addition to increasing the whiteness of the material, the pigments serve to retain the dyes from the recording liquid on the surface of the sheet. A high pigment concentration leads to high porosity of the layer (DE-PS 30 24 205). Although this achieves good smudge resistance, at the same time pigments from the ink are drawn into the interior of the recording material, which worsens the color density of the image. It is known to use a paper provided with a gelatin coating for the ink-jet recording materials (DE-PS 22 34 823). This coating is intended to improve the smudge resistance and increase the resolving power. A disadvantage of this recording material is above all that the sprayed-on symbols do not appear in the desired short time, but only after more than 10 seconds. are sufficiently smudge-proof. Another disadvantage is that the ink droplets do not diverge sufficiently and quickly enough.

In der DE-OS 30 16 766 wird ein Aufzeichnungsmaterial beansprucht, welches durch Aufbringen eines Überzuges aus einem wasserlöslichen Polymer auf einen Papierträger, der durch eine Innenleimung eine definierte Wasserabsorptionsfähigkeit aufweist, eine hohe Dichte und Auflösung des gedruckten Bildes gewährleisten soll. Nachteilig an diesem Aufzeichnungsmaterial ist die Tatsache, daß zur Erzielung der angestrebten Farbdichte, das Material nach Aufbringen der Tintenaufnahmeschicht zusätzlich in einem gesonderten Arbeitsgang geglättet werden muß, z.B. durch Anwendung eines Glanz- oder Superkalanders.DE-OS 30 16 766 claims a recording material which is intended to ensure a high density and resolution of the printed image by applying a coating of a water-soluble polymer to a paper carrier which has a defined water absorption capacity due to an internal sizing. A disadvantage of this recording material is the fact that, in order to achieve the desired color density, the material must also be smoothed in a separate operation after application of the ink receiving layer, e.g. by using a glossy or super calender.

In der japanischen Schrift JP 58-193 185 werden auf einen Träger zwei Schichten aufgetragen. Die obere aus Polyvinylalkohol bestehende Schicht soll für eine gute Wischfestigkeit, also schnelle Tintenabsorption, sorgen.In JP 58-193 185, two layers are applied to a support. The top layer made of polyvinyl alcohol is said to provide good smudge resistance, that is, quick ink absorption.

Die untere Schicht, die eine synthetische Kieselsäure enthält, soll eine hohe Farbdichte gewährleisten. Nachteilig an diesem Aufzeichungsmaterial sind neben der unbefriedigenden Farbdichte die mehreren Arbeitsgänge: zwei Schichten werden gesondert aufgetragen und zum Schluß mit Hilfe eines Kalanders geglättet.The lower layer, which contains synthetic silica, is said to ensure a high color density. A disadvantage of this recording material, in addition to the unsatisfactory color density, are the several work steps: two layers are applied separately and finally smoothed using a calender.

Aufgabe der vorliegenden Erfindung ist es, ein Aufzeichnungsmaterial für ink jet-Verfahren herzustellen, das die angegebenen Nachteile nicht aufweist und sich insbesondere durch hohe Farbdichte der Druckbilder in Kombination mit einer schnell erreichbaren Wischfestigkeit der aufgespritzten Zeichen auszeichnet.The object of the present invention is to produce a recording material for ink jet processes which does not have the stated disadvantages and which is distinguished in particular by the high color density of the printed images in combination with a quickly attainable smudge resistance of the sprayed-on characters.

Eine weitere Aufgabe der Erfindung besteht darin, ein Aufzeichnungsmaterial mit glänzender Oberfläche bereitzustellen, dessen Herstellung möglichst wenig Aufwand erfordert und zusätzliche Glättungsarbeitsgänge erspart.Another object of the invention is to provide a recording material with a glossy surface to provide, the production of which requires as little effort as possible and saves additional smoothing operations.

Diese Aufgabe wird dadurch gelöst, daß auf ein polyolefinbeschichtetes Basispapier eine Tintenaufnahmeschicht aufgetragen wird, die eine Mischung aus Gelatine und Stärke mit einer Korngröße unter 20 um enthält. Bei der Stärke handelt es sich um Reis- und/oder Weizenstärke Typ B. Das Mengenverhältnis liegt vorzugsweise im Bereich von 1:1 bis 10:1.This object is achieved in that an ink-receiving layer is applied to a polyolefin-coated base paper, which contains a mixture of gelatin and starch with a grain size below 20 µm. The starch is rice and / or wheat starch type B. The ratio is preferably in the range from 1: 1 to 10: 1.

In einer bevorzugten Form enthält die Tintenaufnahmeschicht zusätzlich ein polare Gruppen enthaltendes Copolymer, wie z.B. ein Carboxylgruppen, metallgebundene Carboxylgruppen und/oder Nitrilgruppen enthaltendes Acrylat-Copolymer, oder ein carboxyliertes Vinylidenchlorid-Copolymer und andere.In a preferred form, the ink-receiving layer additionally contains a polar group-containing copolymer, e.g. an acrylate copolymer containing carboxyl groups, metal-bonded carboxyl groups and / or nitrile groups, or a carboxylated vinylidene chloride copolymer and others.

In einer weiteren bevorzugten Form beträgt die Menge des polare Gruppen enthaltenden Copolymers in der Mischung 0,5 bis 35 Gew.-%, vorzugsweise 4 bis 10 Gew.-%.In a further preferred form, the amount of the copolymer containing polar groups in the mixture is 0.5 to 35% by weight, preferably 4 to 10% by weight.

Die Tintenaufnahmeschicht kann alle sonst üblichen weiteren Zusätze enthalten, wie z.B. anorganische oder organische Pigmente (Polymethylmethacrylat, Polystyrol, Harnstoff-Formaldehyd-Kondensationsprodukte, Kieselsäure, CaCOs, Ti02, BaS04. u.ä.), Härtungsmittel (Chromalaun, TAF/Formaldehyd), Netzmittel (z.B. Saponin), Nuancierfarbstoffe, Antistatika und andere Hilfsstoffe.The ink-receiving layer can contain all other usual additives, such as inorganic or organic pigments (polymethyl methacrylate, polystyrene, urea-formaldehyde condensation products, silicic acid, CaCOs, Ti0 2 , BaS0 4, etc.), hardening agents (chrome alum, TAF / formaldehyde ), Wetting agents (eg saponin), shading dyes, antistatic agents and other auxiliaries.

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

Das zur Beschichtung des Basispapiers verwendete Polyolefin ist vorzugsweise Polyethylen niedriger Dichte (LDPE) und/oder Polyethylen hoher Dichte (HDPE). Aber auch andere Polyolefine, wie z.B. LLDPE oder Polypropylen können verwendet werden. Die Auftragsmenge der Polyolefinbeschichtung, die zusätzlich Pigmente und andere Stoffe enthalten kann, beträgt wenigstens 5 g/m2. The polyolefin used to coat the base paper is preferably low density polyethylene (LDPE) and / or high density polyethylene (HDPE). However, other polyolefins such as LLDPE or polypropylene can also be used. The application amount of the polyolefin coating, which may additionally contain pigments and other substances, is at least 5 g / m 2.

Es war überraschend, daß eine Kombination der Bindemittel d.h. von mindestens Gelatine und Stärke eine so ausgezeichnete Druckbildqualität ergab, da die Einzelkomponenten keine entsprechend guten Ergebnisse lieferten.It was surprising that a combination of the binders i.e. of at least gelatin and starch resulted in such an excellent print image quality since the individual components did not give correspondingly good results.

Der Glanz des erfindungsgemäßen Aufzeichnungsmaterials erfordert keine zusätzlichen Nachbehandlungen, z.B. mittels eines Glanzkalanders, und wird offensichtlich über das Zusammenwirken der PEbeschichteten Unterlage und der Tintenaufnahmeschicht erreicht.The gloss of the recording material according to the invention does not require additional post-treatments, e.g. by means of a glossy calender, and is obviously achieved through the interaction of the PE-coated base and the ink-receiving layer.

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

Darüber hinaus war auch eine gute Wasserfestigkeit und Abriebfestigkeit der Druckbilder gegeben.In addition, the water resistance and abrasion resistance of the printed images were good.

Die folgenden Beispiele sollen die Erfindung näher erläutern, jedoch nicht einschränken.The following examples are intended to illustrate the invention but not to limit it.

BeispieleExamples Beispiel 1 .Example 1 .

Die Vorderseite eines polyethylenbeschichteten Basispapiers 1) wurde mit den folgenden Beschichtungsmassen beschichtet (Tab. 1):

Figure imgb0001
The front of a polyethylene-coated base paper 1 ) was coated with the following coating compositions (Tab. 1):
Figure imgb0001

Sonstige Versuchsbedingungen:

  • - Maschinengeschwindigkeit : 100 m/min.
  • - Trocknungstemperatur : 100° C
  • - Trocknungszeit : 1 - 2 Minuten
Other test conditions:
  • - machine speed: 100 m / min.
  • - Drying temperature: 100 ° C
  • - Drying time: 1-2 minutes

1) Als Unterlage diente ein beidseitig polyethylenbeschichtetes Basispapier mit einem Flächengewicht von 175 g/m2.1) A base paper with a polyethylene coating on both sides and a basis weight of 175 g / m 2 was used.

Die Rückseite des Basispapiers wurde mit klarem Polyethylen, welches eine Mischung aus LDPE und HDPE ist (35 % HDPE mit einer Dichte d = 0,959 g/cm3, MFI = 8; 40 % HDPE mit d = 0,950 g/cm3, MFI = 7; 25 % LDPE mit d = 0,923 g/cm3, MFI = 4,4), in einer Auftragsmenge von 31 g/m2 beschichtet.The back of the base paper was covered with clear polyethylene, which is a mixture of LDPE and HDPE (35% HDPE with a density d = 0.995 g / cm 3 , MFI = 8; 40% HDPE with d = 0.950 g / cm 3 , MFI = 7; 25% LDPE with d = 0.923 g / cm 3 , MFI = 4.4), coated in an application amount of 31 g / m 2 .

Die Vorderseite wurde mit pigmentiertem Polyethylengemisch, (24,7 % HDPE mit d = 0,959 g/cm3, MFI = 8; 19,8 % LDPE mit d = 0,934 g/cm3, MFI = 3; 33,6 % LDPE mit d = 0,915 g/cm3, MFI = 8; 20,7 % Ti02-Masterbatch mit 50 % Ti02, MFI - 20 0,2 % Ultramarinblau-Masterbatch mit 10 % Pigment, MFI - 5 1,0 % Kobaltviolett-Masterbatch mit 40 % Pigment, MFI - 12), in einer Auftragsmenge von 29 g/m2 beschichtet.The front was covered with pigmented polyethylene mixture, (24.7% HDPE with d = 0.959 g / cm 3 , MFI = 8; 19.8% LDPE with d = 0.934 g / cm 3 , MFI = 3 ; 33.6% LDPE with d = 0.915 g / cm 3 , MFI = 8; 20.7% Ti0 2 masterbatch with 50% Ti0 2 , MFI - 20 0.2% ultramarine blue masterbatch with 10% pigment, MFI - 5 1.0% cobalt violet - Masterbatch with 40% pigment, MFI - 12), coated in a quantity of 29 g / m 2 .

Die colorimetrischen Werte des so beschichteten Trägers waren: L = 96, a = + 0,4, b = - 0,3. 2) Die Polyethylenbeschichtung der Vorderseite wurde eingefärbt, so daß die Vorderseite folgende colorimetrische Werte aufwies: L = 87,5, a = - 0,7, b = + 6,1.The colorimetric values of the support coated in this way were: L = 96, a = + 0.4, b = - 0.3. 2) The polyethylene coating of the front was colored so that the front had the following colorimetric values: L = 87.5, a = - 0.7, b = + 6.1.

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

Beispiel 2Example 2

Ein Schichtträger gemäß Beispiel 1 wurde mit den folgenden Beschichtungsmassen beschichtet:

Figure imgb0002
A layer support according to Example 1 was coated with the following coating compositions:
Figure imgb0002

Sonstige Versuchsbedingungen waren wie im Beispiel 1.Other test conditions were as in Example 1.

Die Ergebnisse der Untersuchung der anschließend erhaltenen Druckbilder sind in Tabelle 2 aufgeführt.The results of the examination of the print images subsequently obtained are shown in Table 2.

Beispiel 3Example 3

Ein Schichtträger gemäß Beispiel 1 wurde mit den folgenden Beschichtungsmassen beschichtet:

Figure imgb0003
A layer support according to Example 1 was coated with the following coating compositions:
Figure imgb0003

Sonstige Versuchsbedingungen waren wie im Beispiel 1.Other test conditions were as in Example 1.

Die Ergebnisse der Untersuchung der anschließend erhaltenen Druckbilder sind in Tabelle 3 zusammengestellt.The results of the examination of the print images subsequently obtained are summarized in Table 3.

Beispiel 4Example 4

Ein Schichtträger gemäß Beispiel 1 wurde mit den folgenden Beschichtungsmassen beschichtet:

Figure imgb0004
A layer support according to Example 1 was coated with the following coating compositions:
Figure imgb0004

Sonstige Versuchsbedingungen waren wie im Beispiel 1.Other test conditions were as in Example 1.

Die Ergebnisse der Untersuchung der anschließend erhaltenen Druckbilder sind in Tabelle 4 zusammengestellt.The results of the examination of the print images subsequently obtained are summarized in Table 4.

VergleichsbeispieleComparative examples

  • V 1. Die Durchführung erfolgte wie im Beispiel 1. Als Bindemittel wurde Gelatine (Fa. Koepff, 220 Bloom) allein verwendet.V 1. The procedure was as in Example 1. Gelatin (Koepff, 220 Bloom) was used alone as the binder.
  • V 2. Die Durchführung erfolgte wie im Beispiel 1. Als Bindemittel wurde eine Mischung aus Gelatine und kationischer Stärke (Emcoat C, Emsland-Stärke GmbH) eingesetzt.V 2. The procedure was as in Example 1. A mixture of gelatin and cationic starch (Emcoat C, Emsland-Starch GmbH) was used as the binder.
  • V 3. Für die Tintenaufnahmeschicht wurde ein carboxyliertes Vinylidenchlorid-Copolymer (Geon 660x14, BFGoodrich Comp.) als Bindemittel verwendet. Sonstige Versuchsbedingungen waren wie in Beispiel 1.V 3. A carboxylated vinylidene chloride copolymer (Geon 660x14, BFGoodrich Comp.) Was used as the binder for the ink-receiving layer. Other test conditions were as in Example 1.

Die Tintenaufnahmeschichten gemäß Vergleichsbeispiel V 1 bis V 3 wurden aus wäßrigem Milieu in folgender Zusammensetzung aufgetragen:

Figure imgb0005
The ink-receiving layers according to Comparative Example V 1 to V 3 were applied from an aqueous medium in the following composition:
Figure imgb0005

Das in den Vergleichsbeispielen erhaltene Aufzeichnungsmaterial wurde in einem kontinuierlichen ink jet-Verfahren bedruckt und anschließend analysiert. Die Ergebnisse sind in Tabelle 5 zusammengestellt.The recording material obtained in the comparative examples was printed in a continuous ink jet process and then analyzed. The results are summarized in Table 5.

Prüfung des gemäß Beispiel 1 - 4 und Vergleichsbeispiel V 1 - V 3 erhaltenen AufzeichnungsmaterialsExamination of the recording material obtained according to Examples 1-4 and Comparative Example V1-3

Das erhaltene Aufzeichungsmaterial wurde mit Hilfe eines nach dem Hertz-Tintenstrahldruck-Prinzip arbeitenden Excelerator 4/1120-Tintenstrahldrucker der Fa. Stork X-cel unter Verwendung der von der Fa. Stork entwickelten Tinten bedruckt.The recording material obtained was printed with the aid of an Excelerator 4/1120 inkjet printer from Stork X-cel, which works according to the Hertz inkjet printing principle, using the inks developed by Stork.

Bei den erhaltenen Druckbildern wurden Farbdensität, Wischfestigkeit, Wasserfestigkeit und Glanz untersucht.Color density, smudge resistance, water resistance and gloss were examined in the print images obtained.

Die Densitätsmessungen erfolgten vor und nach einer 24 h-Belichtung der Bilder mittels Xenon-Lampe. Das hierzu verwendete Gerät war ein Original Reflection Densitometer SOS-45. Die Messungen erfolgten in den Farbabstufungen F1 - F11 für die Grundfarben Cyan, Magenta, Gelb und Schwarz, wobei in den Tabellen die Werte für F1, F5 und F11 angegeben sind.The density measurements were made before and after a 24-hour exposure of the images using a xenon lamp. The device used for this was an original reflection densitometer SOS-45. The measurements were carried out in the color gradations F1 - F11 for the basic colors cyan, magenta, yellow and black, the values for F1, F5 and F11 being given in the tables.

Die Wischfestigkeit wurde nach dem Grad des sog. "Wegschlagens" der Druckfarbe von der Oberfläche des Materials beurteilt. Der Test wurde für alle vier Grundfarben einzeln durchgeführt. Mit " + wurde die Wischfestigkeit eines solchen Aufzeichnungsmaterials bezeichnet, bei dem alle Farben gleichermaßen sofort von der Blattoberfläche "wegschlagen", d.h. in das Schichtinnere penetrieren. Die Bezeichnung "o" bedeutet, daß drei Grundfarben sofort von der Blattoberfläche in das Schichtinnere penetrieren und die vierte Grundfarbe erst nach Ablauf von einigen Sekunden. Mit "-" wurde eine schlechte Wischfestigkeit des Materials bezeichnet, d.h. es wird keines oder nur schwaches "Wegschlagen" fast aller Farben beobachtet.The smear resistance was judged by the degree of so-called "knocking off" of the ink from the surface of the material. The test was carried out individually for all four primary colors. "+" Was used to denote the smudge resistance of such a recording material, in which all the colors "hit" immediately away from the sheet surface, ie penetrate into the interior of the layer. The designation "o" means that three primary colors immediately penetrate into the interior of the sheet and the fourth basic color only after a few seconds "-" was used to denote poor smudge resistance of the material, ie no or only weak "striking away" of almost all colors was observed.

In einem weiteren Test wurden die Wasserfestigkeit und die Abriebfestigkeit untersucht. Hierfür wurde das Aufzeichnungsmaterialmuster in Wasser erhitzt und in Abständen von 5°C mit dem Finger gerieben. Die Temperatur, bei der der weiße Untergrund des Aufzeichnungsmaterials durchscheint, wurde als Maß für die Wasserfestigkeit und Abriebfestigkeit genommen.In another test, the water resistance and the abrasion resistance were examined. For that was the sample of the recording material is heated in water and rubbed at 5 ° C intervals with the finger. The temperature at which the white background of the recording material shows through was taken as a measure of the water resistance and abrasion resistance.

Der Glanz des Aufzeichnungsmaterials wurde mit einem Dreiwinkel-Glanzmeßgerät nach Dr. Lange bei einem Meßwinkel von 600 gemessen.The gloss of the recording material was determined using a three-angle gloss meter according to Dr. Long at a measurement angle of 60 0 measured.

Die in den Tabellen 1 - 5 aufgeführten Ergebnisse zeigen, daß mit dem erfindungsgemäß hergestellten Aufzeichnungsmaterial Druckbilder mit hohen Werten der Farbdensität bei gleichzeitig schnell erreichbarer Wischfestigkeit erzielt werden. Auch hinsichtlich der Wasser- und Abriebfestigkeit weisen die auf erfindungsgemäß hergestelltem Aufzeichnungsmaterial gedruckten Bilder bessere Werte als das Vergleichsmaterial auf.

Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
 The results listed in Tables 1-5 show that the recording material produced in accordance with the invention achieves print images with high values of color density and at the same time quickly achievable smudge resistance. The images printed on the recording material produced according to the invention also have better values than the comparison material with regard to water and abrasion resistance.
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010

Claims (12)

1. Aufzeichnungsmaterial mit glänzender Oberfläche für das Tintenstrahlaufzeichnungsverfahren bestehend aus einem Träger und einer darauf angeordneten ein proteinhaltiges Bindemittel enthaltenden Tintenaufnahmeschicht, dadurch gekennzeichnet, daß auf ein polyolefinbeschichtetes Basispapier eine Tintenaufnahmeschicht aufgetragen wird, die eine Mischung aus Gelatine und Stärke mit einer Korngröße unter 20 um enthält.1. Recording material with a glossy surface for the ink jet recording process consisting of a support and an ink-receiving layer containing a protein-containing binder arranged thereon, characterized in that a on a polyolefin-coated base paper Ink receiving layer is applied, which contains a mixture of gelatin and starch with a grain size below 20 microns. 2. Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, daß die Stärke eine Reis- und/oder Weizenstärke Typ B ist und daß das Mengenverhältnis Gelatine zu Stärke in der Mischung 1:1 bis 10:1 beträgt.2. Recording material according to claim 1, characterized in that the starch is a rice and / or wheat starch type B and that the quantitative ratio of gelatin to starch in the mixture is 1: 1 to 10: 1. 3. Aufzeichnungsmaterial nach Anspruch 1 und 2, dadurch gekennzeichnet, daß die Tintenaufnahmeschicht zusätzlich ein polare Gruppen enthaltendes Copolymer enthält.3. Recording material according to claim 1 and 2, characterized in that the ink-receiving layer additionally contains a copolymer containing polar groups. 4. Aufzeichnungsmaterial nach Anspruch 3, dadurch gekennzeichnet, daß das Copolymer ein carboxyliertes Vinylidenchlorid-Copolymer ist.4. Recording material according to claim 3, characterized in that the copolymer is a carboxylated vinylidene chloride copolymer. 5. Aufzeichnungsmaterial nach Anspruch 3, dadurch gekennzeichnet, daß das Copolymer ein Carboxylgruppen, metallgebundene Carboxylgruppen und/oder Nitrilgruppen enthaltendes Acrylat-Copolymer ist.5. Recording material according to claim 3, characterized in that the copolymer is a carboxyl group, metal-bonded carboxyl group and / or nitrile group-containing acrylate copolymer. 6. Aufzeichnungsmaterial nach Anspruch 3 bis 5, dadurch gekennzeichnet, daß die Menge des polare Gruppen enthaltenden Copolymers in der Tintenaufnahmeschicht 0,5 bis 35 Gew.-%, vorzugsweise 4 bis 10 Gew.-% beträgt.6. Recording material according to claim 3 to 5, characterized in that the amount of the copolymer containing polar groups in the ink receiving layer is 0.5 to 35 wt .-%, preferably 4 to 10 wt .-%. 7. Aufzeichnungsmaterial nach Anspruch 1 bis 6, dadurch gekennzeichnet, daß die Tintenaufnahmeschicht zusätzlich organische und/oder anorganische Pigmente enthält.7. Recording material according to claim 1 to 6, characterized in that the ink-receiving layer additionally contains organic and / or inorganic pigments. 8. Aufzeichnungsmaterial nach Anspruch 7, dadurch gekennzeichnet, daß das organische Pigment ein reaktive Methylolgruppen enthaltendes Harnstoff-Formaldehyd-Kondensationsprodukt ist.8. Recording material according to claim 7, characterized in that the organic pigment is a reactive methylol group-containing urea-formaldehyde condensation product. 9. Aufzeichnungsmaterial nach Anspruch 1 bis 8, dadurch gekennzeichnet, daß die Tintenaufnahmeschicht andere Zusätze wie Härtungsmittel, Netzmittel, Nuancierfarbstoffe, Antistatika und andere Hilfsstoffe enthält.9. Recording material according to claim 1 to 8, characterized in that the ink-receiving layer contains other additives such as curing agents, wetting agents, shading dyes, antistatic agents and other auxiliaries. 10. Aufzeichnungsmaterial nach Anspruch 1 bis 9, dadurch gekennzeichnet, daß die Auftragsmenge der Tintenaufnahmeschicht 0,5 bis 10 g/m2, vorzugsweise 2 bis 7 g/m2 beträgt.10. Recording material according to claim 1 to 9, characterized in that the application amount of the ink-receiving layer is 0.5 to 10 g / m 2 , preferably 2 to 7 g / m 2 . 11. Aufzeichnungsmaterial nach Anspruch 1 bis 10, dadurch gekennzeichnet, daß für die Polyolefinbeschichtung eine Mischung aus LDPE und HDPE verwendet wird.11. Recording material according to claim 1 to 10, characterized in that a mixture of LDPE and HDPE is used for the polyolefin coating. 12. Aufzeichnungsmaterial nach Anspruch 1 bis 11, dadurch gekennzeichnet, daß die Auftragsmenge der Polyolefinbeschichtung wenigstens 5 g/m2, vorzugsweise 15 bis 35 g/m2 beträgt.12. Recording material according to claim 1 to 11, characterized in that the application amount of the polyolefin coating is at least 5 g / m 2 , preferably 15 to 35 g / m 2 .
EP90104332A 1990-03-07 1990-03-07 Recording medium for ink-jet printing Expired - Lifetime EP0445327B1 (en)

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EP90104332A EP0445327B1 (en) 1990-03-07 1990-03-07 Recording medium for ink-jet printing
DE59006369T DE59006369D1 (en) 1990-03-07 1990-03-07 Recording material for the inkjet printing process.
JP3036085A JP2693278B2 (en) 1990-03-07 1991-03-01 Recording material with glossy surface for inkjet recording method
US07/665,601 US5141599A (en) 1990-03-07 1991-03-05 Receiving material for ink-jet printing

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Also Published As

Publication number Publication date
DE59006369D1 (en) 1994-08-11
JPH04216990A (en) 1992-08-07
JP2693278B2 (en) 1997-12-24
EP0445327B1 (en) 1994-07-06
US5141599A (en) 1992-08-25

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