EP0806299A2 - 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
EP0806299A2
EP0806299A2 EP97106976A EP97106976A EP0806299A2 EP 0806299 A2 EP0806299 A2 EP 0806299A2 EP 97106976 A EP97106976 A EP 97106976A EP 97106976 A EP97106976 A EP 97106976A EP 0806299 A2 EP0806299 A2 EP 0806299A2
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EP
European Patent Office
Prior art keywords
recording material
ink
material according
weight
layer
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
EP97106976A
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German (de)
French (fr)
Other versions
EP0806299A3 (en
EP0806299B1 (en
Inventor
Gerhard Dr. Dipl.-Ing. Dransmann
Horst Dipl.-Ing. Westfal
Claudia Dr. Dipl.-Chem. Jünger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Felix Schoeller Jr Foto und Spezialpapiere GmbH
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Felix Schoeller Jr Foto und Spezialpapiere GmbH
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • 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
    • B41M5/506—Intermediate layers
    • 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
    • B41M5/5218—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
    • B41M5/5245—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
    • 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • 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

Definitions

  • the invention relates to a recording material for the ink jet printing process (ink jet printing process).
  • the color printing technology associated with the general spread of electronic media has become very important in recent years.
  • the aim of this technology is to adapt the image quality of the color printouts to the level of silver salt photography.
  • thermo dye transfer system thermal dye transfer system
  • ink jet process Ink-Jet
  • electrophotography electrophotography
  • droplets of a recording liquid are applied to the surface of the recording material using various techniques.
  • a recording liquid ink
  • an ink jet is ejected from the nozzle, which dissolves into microscopic drops due to the surface tension.
  • the drops are charged electrically and placed on the base or deflected into a reservoir by means of downstream deflection plates which are controlled by the digital signals.
  • the image signal triggers a mechanical impulse that ejects the drop.
  • the first drop-on-demand printers used the piezoelectric Effect to cause the drops to be ejected.
  • the method is largely replaced by thermal ink jet, also called bubble jet.
  • the image signal activates a heating element, which creates a vapor bubble in the aqueous ink.
  • the resulting vapor pressure expels the drop.
  • the recording material (image receiving material) used for such recording systems generally consists of a support and an ink-receiving layer and, if appropriate, further auxiliary layers.
  • a polyester resin, diacetate or paper can be used as the carrier.
  • the ink-receiving layers are mostly hydrophilic coatings which are particularly well suited for the absorption of aqueous inks.
  • the ink-receiving layers usually consist of a pigment / binder mixture.
  • the pigments serve to retain the dyes from the recording liquid on the surface of the sheet.
  • Natural or synthetic polymers are used as binders, for example gelatin, starch, pectin, casein, carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone and the like.
  • cationic substances are often used in the ink receiving layer to fix the ink dyes.
  • recording materials the backing of which is paper, and the ink-receiving layer contains a water-soluble binder, tend to have such problems as insufficient water resistance or cockle of the material.
  • a recording material is known from Japanese Patent Application Laid-Open No. 61-041585, which has a polyvinyl alcohol / polyvinylpyrrolidone mixture and, in addition to the above-mentioned lack of water resistance, is characterized by poor wet rub resistance.
  • a recording material is known from Japanese laid-open publication JP 06-297831, which has a porous layer with a pseudoboehmite / polyvinyl alcohol mixture. This enables fast drying times.
  • a disadvantage is the high layer application quantity (35-45 g / m 2 ) required here for rapid absorption of even large amounts of ink.
  • the object of the present invention is therefore to provide a recording material which does not have the disadvantages mentioned above, in particular has very good water resistance, very high resolution and color density.
  • a recording material comprising a support and a receiving layer, an upper layer being arranged on the receiving layer and containing an inorganic pigment which has fine pores and has cationic charge centers.
  • Aluminum oxides, pyrrogenic aluminum hydroxides and aluminum oxide hydrates are particularly well suited for this purpose, but in particular the ⁇ -aluminum oxide monohydrate or the metahydroxide ⁇ -AlO (OH) (boehmite) with a pore radius distribution between 10 to 35 ⁇ .
  • a finely divided silica such as pyrrogenic silica can be used in the top layer.
  • the amount of finely divided silica can vary between 30 and 70% by weight, based on the total amount of the pigment.
  • a polyvinyl alcohol is used as a binder in the top layer.
  • a partially saponified polyvinyl alcohol with a degree of saponification between 70 and 90 mol% is particularly suitable.
  • Cationically modified binders such as, for example, a cationic polyvinyl alcohol or cationically modified starch, are also very suitable.
  • other water-soluble polymers can also be used as binders.
  • the amount of the binder can be 20 to 90% by weight. The quantitative range is preferably 40 to 90% by weight, but in particular 50 to 80% by weight (based on the dried layer).
  • the quantitative ratio of inorganic pigment and / or filler particles to binder can be 1: 0.4 to 1: 100, but in particular 1: 2 to 1: 100.
  • the top layer additionally contains at least one cationic polymer such as, for example, a cationically modified polyvinyl alcohol, a cationically modified starch, a cationically modified polystyrene, a cationically modified polyvinylpyrrolidone and similar polymers. Quaternary, hydroxy or amino functional acrylate homo- and / or acrylate copolymers are particularly suitable.
  • the amount of the cationic polymer is 1 to 30% by weight, in particular 5 to 20% by weight, based on the dried one Layer.
  • the top layer may contain an additional cationic dye-fixing agent, for example a quaternary polyammonium salt from the group of polyvinylbenzyltrimethyl, polydiallyldimethyl, polymethacryloxyethyldimethylhydroxyethyl, polyhydroxypropyldimethylammonium chlorides.
  • an additional cationic dye-fixing agent for example a quaternary polyammonium salt from the group of polyvinylbenzyltrimethyl, polydiallyldimethyl, polymethacryloxyethyldimethylhydroxyethyl, polyhydroxypropyldimethylammonium chlorides.
  • other dye-fixing agents such as cationic cationic polyamines, cationic polyacrylamides, cationic polyethyleneimines can also be used.
  • the amount of the dye-fixing agent can be up to 5% by weight, in particular from 0.5 to 3% by weight.
  • the ink-receiving layer can contain binders, color-fixing compounds, hardening agents and other auxiliaries.
  • binders polyvinyl alcohol, modified polyvinyl alcohol, cationically modified polystyrene, carboxymethyl cellulose, polyvinyl pyrrolidone, polyvinyl acetate, starch, gelatin or mixtures thereof can be used as binders.
  • gelatin is used in the ink-receiving layer.
  • a pork rind gelatin with a gel strength of 200 to 300 bloom (measured according to BS 757, 1975) has proven to be particularly advantageous, but a bovine bone gelatin can also be used.
  • a further binder in another embodiment of the invention, up to 20% by weight (based on the total binder) of a further binder can additionally be present.
  • the additional binder is a modified polyvinyl alcohol, carboxymethyl cellulose or polyvinyl pyrrolidone. Particularly good results are achieved if, in addition to the binder and the dye-fixing agents which can be used in an amount of up to 5% by weight Means additionally a cationic polymer is used.
  • the cationic polymer can be a quaternary, hydroxy or amino functional acrylate homo- and / or acrylate copolymer. However, other cationic polymers such as a cationic polystyrene or a cationically modified starch can also be used.
  • the quantitative ratio cat. Polymer / binder in the receiving layer is 1: 2 to 1:20.
  • a plastic film (film) or preferably an uncoated or coated base paper can be used as the carrier.
  • Paper that is coated on both sides with synthetic resin and has a weight per unit area of 50 to 250 g / m 2 is particularly suitable.
  • Polyolefins or polyester, for example, can be used as the synthetic resin.
  • the application amount of the synthetic resin coating, which may also contain pigments, dyes and other auxiliaries, is at least 5 g / m 2 .
  • a polyethylene-coated paper is used.
  • a coated base paper, in particular a barite-coated paper, is also suitable as a carrier.
  • the back of the recording material can also have a functional layer, for example an anticurl and / or antistatic layer.
  • Both the ink absorption and the top layer are applied from an aqueous dispersion (coating composition) and dried.
  • the coating composition can be applied to the carrier using all customary application and metering methods, such as, for example, roller application, engraving or nipping methods and air brushes or roller doctor metering.
  • the application amount of the ink-receiving layer is 1.0 to 20 g / m 2 , preferably 8 to 14 g / m 2 .
  • the application amount of the top layer is 0.5 to 5.0 g / m 2 , preferably 1.0 to 4.0 g / m 2 .
  • Tables 1 and 2 below show some of the many possible embodiments of the invention: Table 1 Components of the ink-receiving layer A A1 A2 A3 A4 A5 A6 A7 Gelatin, 264 Bloom 91.8 81.8 73.6 73.4 82.6 - - Polyvinyl alcohol, degree of saponification: 98 mol% - - 8.2 - 9.2 31.6 41.0 Polyvinylpyrrolidone, Molgew .: 630,000 daltons - - - 18.4 - 31.6 41.0 Vinyl acetate / butyl acrylate cop. - - - - - 31.6 - Aminomethyl methacrylate 5.0 15.0 15.0 5.0 5.0 - 15.0 quat.
  • the quantities are expressed in% by weight and relate to dried layers.
  • the front side of a base paper neutrally sized with alkyl ketene dimer and coated on both sides with polyethylene 1) of 80 g / m 2 basis weight was first coated with an ink absorption layer according to A1 (Tab. 1) and then with an upper layer according to B1, B2, B6, B7 and B8 ( Tab. 2).
  • corresponding aqueous coating compositions were first prepared, which were then applied to the substrate to be coated using a roller doctor blade and dried.
  • the order weights were: 1) The front of the base paper was covered with an LDPE ( low-density polyethylene ”) coated (19 g / m 2 ).
  • the back of the base paper was coated with a mixture of LDPE and HDPE (high-density polyethylene).
  • the application weight was 20 g / m 2 .
  • the recording material obtained was in a so-called. Thermal Jet "process printed and then analyzed.
  • the front of the base paper from Example 1 was first provided with an ink-receiving layer in accordance with A2 (Table 1) and then with an upper layer in accordance with B2, B6 and B8 (Table 2).
  • the order weights were: Ink receiving layer 12 g / m 2
  • a base paper provided with a baryta layer on the front (basis weight: 80 g / m 2 ) was first provided with an ink absorption layer in accordance with A7 and then with an upper layer in accordance with B9.
  • the barite layer contained 85% by weight of BaSO 4 and 15% by weight of gelatin.
  • test conditions were as in Example 1.
  • the base paper from Example 1 was coated with an ink absorption layer according to A2 (12 g / m 2 ) and then provided with an upper layer according to B6 (4 g / m 2 ), but without boehmite with a narrow pore radius distribution, instead with aluminum hydroxide with a pore radius distribution of 28 to 1000 ⁇ (V1a) and 20 to 140 ⁇ (V1b).
  • the base paper from Example 1 was only coated with an ink receiving layer in accordance with A2 and A6 without and with the addition of aluminum hydroxide.
  • the quantities are expressed in% by weight and relate to dried layers.
  • the recording material obtained in the comparative examples was in a so-called. Thermal Jet "process printed and then analyzed. The results are summarized in Table 4.
  • the recording material was printed using an HP Deskjet 550 C ink jet printer from Hewlett Packard, which works on the bubble jet principle (thermal jet).
  • the density measurements were made using a Original Reflection Densitometer SOS-45 "carried out. The measurements were carried out for the basic colors cyan, magenta, yellow and black.
  • the recording material was immersed in water to investigate the water resistance.
  • the density (%) remaining in a 25 ° C water bath after 60 s is used as a measure of the water stability.
  • the gloss values were measured using the RL3 laboratory reflectometer from Dr. Long according to DIN 67530.
  • the drying behavior of the recording material is determined as follows:
  • a bar is printed on a sheet of paper with black ink (pure black) and placed on paper after a waiting time of 120 seconds (20 sheets).
  • the color transfer is taken as a measure of drying.
  • the drying time can be ⁇ 120, 120-240 and> 240 seconds.
  • the recording materials produced according to the invention are distinguished by better water resistance, shorter drying times and better bleed behavior. Even if the water resistance and drying times of the papers produced according to V1a and V1b are also good, the bleed behavior is unsatisfactory. With regard to the gloss, too, the values in Example 2.2 are higher than in the corresponding Comparative Examples V1a and V1b.

Landscapes

  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)
  • Paper (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Particle Formation And Scattering Control In Inkjet Printers (AREA)

Abstract

Recording material for ink jet printing, with a base (A), a colour receiving layer (B) and an upper layer (C) containing inorganic pigment and/or filler particles (I) with microporous cationic charge centres.

Description

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

Die mit der allgemeinen Verbreitung der elektronischen Medien in Verbindung stehende Technologie zur Herstellung von Farbausdrucken hat in den letzten Jahren sehr an Bedeutung gewonnen. Ziel dieser Technologie ist die Anpassung der Bildqualität der Farbausdrucke an das Niveau der Silbersalzfotografie.The color printing technology associated with the general spread of electronic media has become very important in recent years. The aim of this technology is to adapt the image quality of the color printouts to the level of silver salt photography.

Es gibt verschiedene Aufzeichnungssysteme wie das thermische Farbstoffübertragungssystem (dye diffusion thermal transfer), Tintenstrahlverfahren (Ink-Jet) oder die Elektrofotografie.There are various recording systems such as the thermal dye transfer system (dye diffusion thermal transfer), ink jet process (Ink-Jet) or electrophotography.

Bei dem Ink-Jet-Verfahren werden Tröpfchen einer Aufzeichnungsflüssigkeit (Tinte) auf die Oberfläche des Aufzeichnungsmaterials mittels unterschiedlicher Techniken aufgetragen. Bei der Tropfenerzeugung gibt es grundsätzlich zwei Verfahrensvarianten. Beim kontinuierlichen Prozeß wird ein Tintenstrahl aus der Düse ausgestoßen, der sich aufgrund der Oberflächenspannung in mikroskopisch kleine Tropfen auflöst. Die Tropfen werden elektrisch aufgeladen und durch nachgeschaltete Ablenkplatten, die durch die digitalen Signale gesteuert werden, auf die Unterlage plaziert oder in ein Reservoir abgelenkt.
Bei der sog.

Figure imgb0001
drop-on-demand"-Methode löst das Bildsignal einen mechanischen Impuls aus, der den Tropfen ausstößt. Die ersten
Figure imgb0001
drop-on-demand"-Drucker benutzten den piezoelektrischen Effekt, um das Ausstoßen der Tropfen zu bewirken. Heute ist die Methode weitgehend durch Thermal Ink Jet, auch Bubble Jet genannt, ersetzt. Hierbei aktiviert das Bildsignal ein Heizelement, wodurch eine Dampfblase in der wässrigen Tinte entsteht. Der resultierende Dampfdruck stößt den Tropfen aus.In the ink-jet method, droplets of a recording liquid (ink) are applied to the surface of the recording material using various techniques. There are basically two process variants for drop generation. In the continuous process, an ink jet is ejected from the nozzle, which dissolves into microscopic drops due to the surface tension. The drops are charged electrically and placed on the base or deflected into a reservoir by means of downstream deflection plates which are controlled by the digital signals.
With the so-called
Figure imgb0001
drop-on-demand "method, the image signal triggers a mechanical impulse that ejects the drop. The first
Figure imgb0001
drop-on-demand printers used the piezoelectric Effect to cause the drops to be ejected. Today, the method is largely replaced by thermal ink jet, also called bubble jet. The image signal activates a heating element, which creates a vapor bubble in the aqueous ink. The resulting vapor pressure expels the drop.

An die Ink-Jet-Bildempfangsmaterialien werden hohe Anforderungen gestellt. Das mittels Ink-Jet-Verfahren erzeugte Bild soll verfügen über:

  • hohe Auflösung,
  • hohe Farbdichte,
  • genügend Farbabstufungen,
  • gute Wischfestigkeit,
  • gute Wasserfestigkeit.
  • gute Naßriebfestigkeit
High demands are placed on the ink jet image receiving materials. The image created using the ink jet process should have:
  • high resolution,
  • high color density,
  • enough color gradations,
  • good smudge resistance,
  • good water resistance.
  • good wet rub resistance

Um dies zu erreichen, müssen folgende Grundbedingungen erfüllt werden:

  • die Tinte muß vom Aufzeichnungsmaterial rasch absorbiert werden,
  • die aufgespritzten Tintentröpfchen müssen in möglichst exakter Weise (kreisförmig) und genau begrenzt auseinanderlaufen,
  • die Tintendiffusion in dem Aufzeichnungsmaterial darf nicht zu hoch sein, damit der Durchmesser der Tintenpunkte nicht mehr als unbedingt erforderlich vergrößert wird,
  • ein Tintenpunkt soll beim Überlappen mit einem vorher aufgebrachten Tintenpunkt diesen nicht beeinträchtigen oder verwischen,
  • das Aufzeichnungsmaterial muß eine Oberfläche aufweisen, die eine hohe visuelle Reflexionsdichte und eine hohe Brillanz der Farben ermöglicht,
  • das Aufzeichnungsmaterial soll eine hohe Formbeständigkeit aufweisen, ohne daß es sich nach dem Druckvorgang dehnt.
To achieve this, the following basic conditions must be met:
  • the ink must be quickly absorbed by the recording material,
  • the sprayed-on ink droplets must diverge as precisely as possible (circular) and precisely delimited,
  • the ink diffusion in the recording material must not be too high so that the diameter of the ink dots is not increased more than is absolutely necessary,
  • an ink dot should not affect or blur an overlapped ink dot,
  • the recording material must have a surface which enables a high visual reflection density and a high brilliance of the colors,
  • the recording material should have a high dimensional stability without stretching after the printing process.

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

Die zunehmende Verbesserung der Leistungsfähigkeit von Tintenstrahlaufzeichnungsvorrichtungen, die hohe Aufzeichnungsgeschwindigkeiten ermöglichen, wirkt sich bei Erfüllung der oben genannten Anforderungen erschwerend aus.The increasing improvement in the performance of ink jet recording devices which enable high recording speeds has made it difficult to meet the above requirements.

Das für derartige Aufzeichnungssysteme verwendete Aufzeichnungsmaterial (Bildempfangsmaterial) besteht in der Regel aus einem Träger und einer Tintenaufnahmeschicht sowie gegebenenfalls weiteren Hilfsschichten.
Als Träger kann beispielsweise ein Polyesterharz, Diacetat oder Papier verwendet werden.The recording material (image receiving material) used for such recording systems generally consists of a support and an ink-receiving layer and, if appropriate, further auxiliary layers.
For example, a polyester resin, diacetate or paper can be used as the carrier.

Bei den Tintenaufnahmeschichten handelt es sich meistens um hydrophile Beschichtungen, die besonders gut für die Aufnahme der wäßrigen Tinten geeignet sind.
Die Tintenaufnahmeschichten bestehen in der Regel aus einer Pigment/Bindemittel-Mischung. Die Pigmente dienen, neben der Erhöhung des Weißgrades des Materials, zur Retention der Farbstoffe aus der Aufzeichnungsflüssigkeit an die Oberfläche des Blattes. Als Bindemittel werden natürliche oder synthetische Polymere eingesetzt, beispielsweise Gelatine, Stärke, Pektin, Kasein, Carboxymethylcellulose, Polyvinylalkohol, Polyvinylpyrrolidon und ähnliche.
Oft werden in der Tintenaufnahmeschicht zusätzlich kationische Substanzen zur Fixierung der Tintenfarbstoffe eingesetzt.The ink-receiving layers are mostly hydrophilic coatings which are particularly well suited for the absorption of aqueous inks.
The ink-receiving layers usually consist of a pigment / binder mixture. In addition to increasing the whiteness of the material, the pigments serve to retain the dyes from the recording liquid on the surface of the sheet. Natural or synthetic polymers are used as binders, for example gelatin, starch, pectin, casein, carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone and the like.
In addition, cationic substances are often used in the ink receiving layer to fix the ink dyes.

Oft neigen Aufzeichnungsmaterialien, deren Träger ein Papier ist und die Tintenaufnahmeschicht ein wasserlösliches Bindemittel enthält zu solchen Problemen wie unzureichende Wasserfestigkeit oder Kräuseln (Cockle) des Materials. So ist beispielsweise aus der japanischen Offenlegungsschrift JP 61-041585 ein Aufzeichnungsmaterial bekannt, das eine Polyvinylalkohol/Polyvinylpyrrolidon-Mischung aufweist und sich neben der oben erwähnten mangelnden Wasserfestigkeit durch eine schlechte Naßriebfestigkeit auszeichnet.Often, recording materials, the backing of which is paper, and the ink-receiving layer contains a water-soluble binder, tend to have such problems as insufficient water resistance or cockle of the material. For example, a recording material is known from Japanese Patent Application Laid-Open No. 61-041585, which has a polyvinyl alcohol / polyvinylpyrrolidone mixture and, in addition to the above-mentioned lack of water resistance, is characterized by poor wet rub resistance.

Eine gute Wasserfestigkeit soll durch eine Schicht erreicht werden, in der neben einem Vinylpolymer ein (Meth)acrylpolymer und wasserlösliche Cellulose-Verbindungen enthalten sind (EP 0 672 537). Nachteilig an diesem Aufzeichnungsmaterial ist seine unbefriedigende Trocknungszeit.Good water resistance should be achieved by a layer which, in addition to a vinyl polymer, contains a (meth) acrylic polymer and water-soluble cellulose compounds (EP 0 672 537). A disadvantage of this recording material is its unsatisfactory drying time.

Aus der japanischen Offenlegungsschrift JP 06-297831 ist ein Aufzeichnungsmaterial bekannt, das eine poröse Schicht mit einer Pseudoboehmit/Polyvinylalkohol-Mischung aufweist. Dadurch werden schnelle Trocknungszeiten erreicht. Als Nachteil ist jedoch die hier für eine schnelle Aufnahme auch größerer Tintenmengen erforderliche hohe Schichtauftragsmenge (35-45 g/m2) anzusehen.A recording material is known from Japanese laid-open publication JP 06-297831, which has a porous layer with a pseudoboehmite / polyvinyl alcohol mixture. This enables fast drying times. A disadvantage, however, is the high layer application quantity (35-45 g / m 2 ) required here for rapid absorption of even large amounts of ink.

Bisher ist also kein Aufzeichnungsmaterial bekannt, das alle diese Anforderungen in zufriedenstellender Weise erfüllt.So far, no recording material is known that satisfies all of these requirements in a satisfactory manner.

Aufgabe der vorliegenden Erfindung ist es daher, ein Aufzeichnungsmaterial zur Verfügung zu stellen, das die oben erwähnten Nachteile nicht aufweist, insbesondere eine sehr gute Wasserfestigkeit, eine sehr hohe Auflösung und Farbdensität besitzt.The object of the present invention is therefore to provide a recording material which does not have the disadvantages mentioned above, in particular has very good water resistance, very high resolution and color density.

Die Aufgabe wird durch ein einen Träger und eine Empfangsschicht enthaltendes Aufzeichnungsmaterial gelöst, wobei auf der Empfangsschicht eine Oberschicht angeordnet ist, die ein feinporöses, kationische Ladungszentren aufweisendes anorganisches Pigment enhält.
Für diesen Zweck besonders gut geeignet sind Aluminiumoxide, pyrrogene Aluminiumhydroxide und Aluminiumoxidhydrate, insbesondere jedoch das α-Aluminiumoxid Monohydrat oder das Metahydroxid γ-AlO(OH) (Böhmit) mit einer Porenradiusverteilung zwischen 10 bis 35 Å. In einer besonderen Ausgestaltung der Erfindung kann in der Oberschicht eine feinteilige Kieselsäure wie pyrrogene Kieselsäure eingesetzt werden. Die Menge der feinteiligen Kieselsäure kann variieren zwischen 30 und 70 Gew.%, bezogen auf die Gesamtmenge des Pigments.The object is achieved by a recording material comprising a support and a receiving layer, an upper layer being arranged on the receiving layer and containing an inorganic pigment which has fine pores and has cationic charge centers.
Aluminum oxides, pyrrogenic aluminum hydroxides and aluminum oxide hydrates are particularly well suited for this purpose, but in particular the α-aluminum oxide monohydrate or the metahydroxide γ-AlO (OH) (boehmite) with a pore radius distribution between 10 to 35 Å. In a special embodiment of the invention, a finely divided silica such as pyrrogenic silica can be used in the top layer. The amount of finely divided silica can vary between 30 and 70% by weight, based on the total amount of the pigment.

In einer bevorzugten Ausführungsform der Erfindung wird in der Oberschicht ein Polyvinylalkohol als Bindemittel eingesetzt. Besonders gut geeignet ist ein teilverseifter Polyvinylalkohol mit einem Verseifungsgrad zwischen 70 und 90 Mol%. Ebenfalls gut geeignet sind kationisch modifizierte Bindemittel, wie beispielsweise ein kationischer Polyvinylalkohol oder kationisch modifizierte Stärke. Aber auch andere wasserlöslichen Polymere können als Bindemittel eingesetzt werden. Die Menge des Bindemittels kann 20 bis 90 Gew.% betragen. Bevorzugt wird der Mengenbereich 40 bis 90 Gew.%, insbesondere jedoch 50 bis 80 Gew.% (bezogen auf die getrocknete Schicht).In a preferred embodiment of the invention, a polyvinyl alcohol is used as a binder in the top layer. A partially saponified polyvinyl alcohol with a degree of saponification between 70 and 90 mol% is particularly suitable. Cationically modified binders, such as, for example, a cationic polyvinyl alcohol or cationically modified starch, are also very suitable. However, other water-soluble polymers can also be used as binders. The amount of the binder can be 20 to 90% by weight. The quantitative range is preferably 40 to 90% by weight, but in particular 50 to 80% by weight (based on the dried layer).

Das Mengenverhältnis anorganische Pigment-und/oder Füllstoffpartikeln zu Bindemittel kann 1:0,4 bis 1:100, insbesondere jedoch 1:2 bis 1:100 betragen.The quantitative ratio of inorganic pigment and / or filler particles to binder can be 1: 0.4 to 1: 100, but in particular 1: 2 to 1: 100.

In einer besonderen Ausgestaltung der Erfindung enthält die Oberschicht zusätztlich mindestens ein kationisches Polymer wie beispielsweise einen kationisch modifizierten Polyvinylalkohol, eine kationisch modifizierte Stärke, ein kationisch modifiziertes Polystyrol, ein kationisch modifiziertes Polyvinylpyrrolidon und ähnliche Polymere. Besonders geeignet sind quaternäre, hydroxy- oder aminofunktionelle Acrylat-Homo- und/oder Acrylat-Copolymere. Die Menge des kationischen Polymers beträgt 1 bis 30 Gew.%, insbesondere 5 bis 20 Gew.%, bezogen auf die getrocknete Schicht. Neben dem oben erwähnten kationischen Polymer kann die Oberschicht ein zusätzliches kationisches farbstoffixierendes Mittel enthalten, beispielsweise ein quaternäres Polyammoniumsalz aus der Gruppe der Polyvinylbenzyltrimethyl-, Polydiallyldimethyl-, Polymethacryloxyethyldimethylhydroxyethyl-, Polyhydroxypropyldimethylammoniumchloride. Aber auch andere farbstoffixierende Mittel wie kationische kationische Polyamine, kationische Polyacrylamide, kationische Polyethylenimine können eingesetzt werden. Die Menge des farbstoffixierenden Mittels kann bis 5 Gew.%, insbesondere von 0.5 bis 3 Gew.% betragen.In a special embodiment of the invention, the top layer additionally contains at least one cationic polymer such as, for example, a cationically modified polyvinyl alcohol, a cationically modified starch, a cationically modified polystyrene, a cationically modified polyvinylpyrrolidone and similar polymers. Quaternary, hydroxy or amino functional acrylate homo- and / or acrylate copolymers are particularly suitable. The amount of the cationic polymer is 1 to 30% by weight, in particular 5 to 20% by weight, based on the dried one Layer. In addition to the above-mentioned cationic polymer, the top layer may contain an additional cationic dye-fixing agent, for example a quaternary polyammonium salt from the group of polyvinylbenzyltrimethyl, polydiallyldimethyl, polymethacryloxyethyldimethylhydroxyethyl, polyhydroxypropyldimethylammonium chlorides. However, other dye-fixing agents such as cationic cationic polyamines, cationic polyacrylamides, cationic polyethyleneimines can also be used. The amount of the dye-fixing agent can be up to 5% by weight, in particular from 0.5 to 3% by weight.

Die Tintenaufnahmeschicht kann Bindemittel, farbfixierende Verbindungen, Härtungsmittel und andere Hilfsmittel enthalten. Als Bindemittel können beispielsweise Polyvinylalkohol, modifizierter Polyvinylalkohol, kationisch modifiziertes Polystyrol, Carboxymethylcellulose, Polyvinylpyrrolidon, Polyvinylacetat, Stärke, Gelatine oder Mischungen davon eingesetzt werden.In einer bevorzugten Ausgestaltung der Erfindung wird in der Tintenaufnahmeschicht Gelatine eingesetzt. Als besonders vorteilhaft erwies sich eine Schweineschwartengelatine mit einer Gallertfestigkeit von 200 bis 300 Bloom (gemessen nach BS 757, 1975 ), aber auch eine Rinderknochengelatine kann eingesetzt werden. In einer anderen Ausgestaltung der Erfindung können zusätzlich bis 20 Gew.% ( bezogen auf den gesamten Binder ) eines weiteren Binders enthalten sein. Bei dem zusätzlichen Binder handelt es sich um einen modifizierten Polyvinylalkohol, Carboxymethylcellulose oder Polyvinylpyrrolidon. Besonders gute Ergebnisse werden erreicht, wenn neben dem Bindemittel und den in einer Menge bis 5 Gew.% einsetzbaren farbstoffixierenden Mitteln zusätzlich ein kationisches Polymer eingesetzt wird. Das kationische Polymer kann ein quaternäres, hydroxy- oder aminofunktionelles Acrylat-Homo- und/oder Acrylat-Copolymer sein. Aber auch andere kationische Polymere wie beispielsweise ein kationisches Polystyrol oder eine kationisch modifizierte Stärke können verwendet werden. Das Mengenverhältnis kat. Polymer/Bindemittel in der Empfangsschicht beträgt 1:2 bis 1:20.The ink-receiving layer can contain binders, color-fixing compounds, hardening agents and other auxiliaries. For example, polyvinyl alcohol, modified polyvinyl alcohol, cationically modified polystyrene, carboxymethyl cellulose, polyvinyl pyrrolidone, polyvinyl acetate, starch, gelatin or mixtures thereof can be used as binders. In a preferred embodiment of the invention, gelatin is used in the ink-receiving layer. A pork rind gelatin with a gel strength of 200 to 300 bloom (measured according to BS 757, 1975) has proven to be particularly advantageous, but a bovine bone gelatin can also be used. In another embodiment of the invention, up to 20% by weight (based on the total binder) of a further binder can additionally be present. The additional binder is a modified polyvinyl alcohol, carboxymethyl cellulose or polyvinyl pyrrolidone. Particularly good results are achieved if, in addition to the binder and the dye-fixing agents which can be used in an amount of up to 5% by weight Means additionally a cationic polymer is used. The cationic polymer can be a quaternary, hydroxy or amino functional acrylate homo- and / or acrylate copolymer. However, other cationic polymers such as a cationic polystyrene or a cationically modified starch can also be used. The quantitative ratio cat. Polymer / binder in the receiving layer is 1: 2 to 1:20.

In dem erfindungsgemäßen Aufzeichnungsmaterial kann als Träger eine Kunststoffolie (-film) oder vorzugsweise ein unbeschichtetes oder beschichtetes Basispapier verwendet werden. Besonders gut geeignet ist ein beidseitig mit Kunstharz beschichtetes Papier mit einem Flächengewicht von 50 bis 250 g/m2. Als Kunstharz können beispielsweise Polyolefine oder Polyester eingesetzt werden. Die Auftragsmenge der Kunstharzbeschichtung, in der zusätzlich noch Pigmente, Farbstoffe und andere Hilfsstoffe enthalten sein können, beträgt mindestens 5 g/m2. In einer besonderen Ausgestaltung der Erfindung wird ein polyethylenbeschichtetes Papier eingesetzt. Als Träger geeignet ist aber auch ein gestrichenes Basispapier, insbesondere ein barytbeschichtetes Papier.In the recording material according to the invention, a plastic film (film) or preferably an uncoated or coated base paper can be used as the carrier. Paper that is coated on both sides with synthetic resin and has a weight per unit area of 50 to 250 g / m 2 is particularly suitable. Polyolefins or polyester, for example, can be used as the synthetic resin. The application amount of the synthetic resin coating, which may also contain pigments, dyes and other auxiliaries, is at least 5 g / m 2 . In a special embodiment of the invention, a polyethylene-coated paper is used. A coated base paper, in particular a barite-coated paper, is also suitable as a carrier.

Die Rückseite des Aufzeichnungsmaterials kann auch eine Funktionsschicht aufweisen, beispielsweise eine Anticurl- und/oder Antistatik-Schicht.The back of the recording material can also have a functional layer, for example an anticurl and / or antistatic layer.

Sowohl die Tintenaufnahme- als auch die Oberschicht werden aus einer wäßrigen Dispersion (Beschichtungsmasse) aufgetragen und getrocknet.
Die Beschichtungsmasse kann mit allen gebräuchlichen Auftrags- und Dosierverfahren, wie beispielsweise Walzenauftrag-, Gravur oder Nipp-Verfahren und Luftbürsten oder Rollrakeldosierung auf den Träger aufgetragen werden.Both the ink absorption and the top layer are applied from an aqueous dispersion (coating composition) and dried.
The coating composition can be applied to the carrier using all customary application and metering methods, such as, for example, roller application, engraving or nipping methods and air brushes or roller doctor metering.

Die Auftragsmenge der Tintenaufnahmeschicht beträgt 1,0 bis 20 g/m2, vorzugsweise 8 bis 14 g/m2. Die Auftragsmenge der Oberschicht beträgt 0,5 bis 5,0 g/m2, vorzugsweise 1,0 bis 4,0 g/m2.The application amount of the ink-receiving layer is 1.0 to 20 g / m 2 , preferably 8 to 14 g / m 2 . The application amount of the top layer is 0.5 to 5.0 g / m 2 , preferably 1.0 to 4.0 g / m 2 .

In den folgenden Tabellen 1 und 2 sind einige der vielen möglichen Ausführungsformen der Erfindung dargestellt: Tabelle 1 Bestandteile der Tintenaufnahmeschicht A A1 A2 A3 A4 A5 A6 A7 Gelatine, 264 Bloom 91,8 81,8 73,6 73,4 82,6 - - Polyvinylalkohol, Verseifungsgrad: 98 Mol% - - 8,2 - 9,2 31,6 41,0 Polyvinylpyrrolidon, Molgew.: 630 000 Dalton - - - 18,4 - 31,6 41,0 Vinylacetat/Butylacrylat-Cop. - - - - - 31,6 - Aminomethylmethacrylat 5,0 15,0 15,0 5,0 5,0 - 15,0 quat. Polyammoniumsalz 3,0 3,0 3,0 3,0 3,0 5,2 3,0 TAF/Formaldehyd 0,2 0,2 0,2 0,2 0,2 - - Tabelle 2 Bestandteile der Oberschicht B B1 B2 B3 B4 B5 B6 B7 B8 B9 B10 Polyvinylalkohol, Verseifungsgrad: 88 Mol% 65 - - - 80 - - - 36 - Polyvinylalkohol, Verseifungsgrad: 74 Mol% - 75 - - - 62 72 65 36 - Kat. Polyvinylalkohol - - 65 - - - - - - 72 Polyvinylpyrrolidon - - - 65 - - - - - - Al-Hydroxid, 10-30 A - - - 30 - - - - - - Boehmit, 10-35 A 30 20 30 - 15 20 20 10 10 20 Kieselsäure - - - - - - - 10 - - Aminomethylmethacrylat - - - - - 15 - 10 - 5 Hydroxyacrylat-Terpolymer - - - - - - 5 - 15 - Quat. Polyammoniumsalz 5 5 5 5 5 3 3 5 3 3 Tables 1 and 2 below show some of the many possible embodiments of the invention: Table 1 Components of the ink-receiving layer A A1 A2 A3 A4 A5 A6 A7 Gelatin, 264 Bloom 91.8 81.8 73.6 73.4 82.6 - - Polyvinyl alcohol, degree of saponification: 98 mol% - - 8.2 - 9.2 31.6 41.0 Polyvinylpyrrolidone, Molgew .: 630,000 daltons - - - 18.4 - 31.6 41.0 Vinyl acetate / butyl acrylate cop. - - - - - 31.6 - Aminomethyl methacrylate 5.0 15.0 15.0 5.0 5.0 - 15.0 quat. Polyammonium salt 3.0 3.0 3.0 3.0 3.0 5.2 3.0 TAF / formaldehyde 0.2 0.2 0.2 0.2 0.2 - - Components of the upper layer B B1 B2 B3 B4 B5 B6 B7 B8 B9 B10 Polyvinyl alcohol, degree of saponification: 88 mol% 65 - - - 80 - - - 36 - Polyvinyl alcohol, degree of saponification: 74 mol% - 75 - - - 62 72 65 36 - Cat. Polyvinyl alcohol - - 65 - - - - - - 72 Polyvinyl pyrrolidone - - - 65 - - - - - - Al hydroxide, 10-30 A. - - - 30th - - - - - - Boehmite, 10-35 A 30th 20th 30th - 15 20th 20th 10th 10th 20th Silica - - - - - - - 10th - - Aminomethyl methacrylate - - - - - 15 - 10th - 5 Hydroxyacrylate terpolymer - - - - - - 5 - 15 - Quat. Polyammonium salt 5 5 5 5 5 3rd 3rd 5 3rd 3rd

Die Mengenangaben sind in Gew.% ausgedrückt und beziehen sich auf getrocknete Schichten.The quantities are expressed in% by weight and relate to dried layers.

Die Erfindung soll mit Hilfe einiger ausgewählten Beispiele näher erläutert werden.The invention will be explained in more detail with the aid of a few selected examples.

Beispiel 1example 1

Die Vorderseite eines mit Alkylketendimer neutral geleimten und beidseitig mit Polyethylen beschichteten Basispapiers1) von 80 g/m2 Flächengewicht wurde erst mit einer Tintenaufnahmeschicht gemäß A1 (Tab. 1) und danach mit einer Oberschicht gemäß B1, B2, B6, B7 und B8 (Tab.2) versehen. Hierzu wurden zuerst entsprechende wäßrige Beschichtungsmassen hergestellt, die dann mit Hilfe eines Rollrakels auf das zu beschichtende Trägermaterial aufgetragen und getrocknet wurden. Die Auftragsgewichte betrugen:
1) Die Vorderseite des Basispapiers wurde mit einem LDPE (

Figure imgb0001
low-density polyethylen") beschichtet (19 g/m2).The front side of a base paper neutrally sized with alkyl ketene dimer and coated on both sides with polyethylene 1) of 80 g / m 2 basis weight was first coated with an ink absorption layer according to A1 (Tab. 1) and then with an upper layer according to B1, B2, B6, B7 and B8 ( Tab. 2). For this purpose, corresponding aqueous coating compositions were first prepared, which were then applied to the substrate to be coated using a roller doctor blade and dried. The order weights were:
1) The front of the base paper was covered with an LDPE (
Figure imgb0001
low-density polyethylene ") coated (19 g / m 2 ).

Standard-Drahtrakel/GrößeStandard wire squeegee / size TintenaufnahmeschichtInk receiving layer 10 g/m2 10 g / m 2 100100 OberschichtUpper class B1B1 2 g/m2 2 g / m 2 3535 B2B2 3 g/m2 3 g / m 2 4040 B6B6 4 g/m2 4 g / m 2 4545 B7B7 4 g/m2 4 g / m 2 4545 B8B8 4 g/m2 4 g / m 2 4545 BeispieleExamples 1.11.1 1.21.2 1.31.3 1.41.4 1.51.5 A1 + B1A1 + B1 A1 + B2A1 + B2 A1 + B6A1 + B6 A1 + B7A1 + B7 A1 + B8A1 + B8

Sonstige Versuchsbedingungen:Other test conditions:

MaschinengeschwindigkeitMachine speed
: 100 m/min: 100 m / min
Trocknungstemperatur (Luft)Drying temperature (air)
: 100°C: 100 ° C
TrocknungszeitDrying time
: 2-4 min: 2-4 min

Die Beschichtung enthielt außerdem:

  • 0,95 Gew.% optischer Aufheller,
  • 10 Gew.% Titandioxid,
  • 4 Gew.% Gleitmittel,
  • 10,8 Gew.% eines Pigmentkonzentrates (10 % Ultramarin, 90 % LDPE).
The 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 pigment concentrate (10% ultramarine, 90% LDPE).

Die Rückseite des Basispapiers wurde mit einer Mischung aus LDPE und HDPE (high-density polyethylen) beschichtet. Das Auftragsgewicht betrug 2o g/m2.The back of the base paper was coated with a mixture of LDPE and HDPE (high-density polyethylene). The application weight was 20 g / m 2 .

Das erhaltene Aufzeichnungsmaterial wurde in einem sog.

Figure imgb0001
Thermal Jet"-Verfahren bedruckt und anschließend analysiert.The recording material obtained was in a so-called.
Figure imgb0001
Thermal Jet "process printed and then analyzed.

Die Prüfergebnisse sind in Tabelle 3 zusammengestellt.The test results are summarized in Table 3.

Beispiel 2Example 2

Die Vorderseite des Basispapiers aus Beispiel 1 wurde erst mit einer Tintenaufnahmeschicht gemäß A2 (Tabelle 1) und anschließend mit einer Oberschicht gemäß B2, B6 und B8 (Tab. 2) versehen. Die Auftragsgewichte betrugen: Tintenaufnahmeschicht 12 g/m2 Oberschicht B2 4 g/m2 B6 5 g/m2 B8 2 g/m2 Beispiele 2.1 2.2 2.3 A2 + B2 A2 + B6 A2 + B8 The front of the base paper from Example 1 was first provided with an ink-receiving layer in accordance with A2 (Table 1) and then with an upper layer in accordance with B2, B6 and B8 (Table 2). The order weights were: Ink receiving layer 12 g / m 2 Upper class B2 4 g / m 2 B6 5 g / m 2 B8 2 g / m 2 Examples 2.1 2.2 2.3 A2 + B2 A2 + B6 A2 + B8

Versuchsbedingungen sind wie im Beispiel 1.Test conditions are as in Example 1.

Die Prüfergebnisse sind in Tabelle 3 zusammengestellt.The test results are summarized in Table 3.

Beispiel 3Example 3

Ein auf der Vorderseite mit Barytschicht versehene Basispapier (Flächengewicht: 80 g/m2) wurde erst mit einer Tintenaufnahmeschicht gemäß A7 und anschließend mit einer Oberschicht gemäß B9 versehen.A base paper provided with a baryta layer on the front (basis weight: 80 g / m 2 ) was first provided with an ink absorption layer in accordance with A7 and then with an upper layer in accordance with B9.

Die Barytschicht enthielt 85 Gew.% BaSO4 und 15 Gew.% Gelatine.The barite layer contained 85% by weight of BaSO 4 and 15% by weight of gelatin.

Die Versuchsbedingungen waren wie im Beispiel 1.The test conditions were as in Example 1.

Die Prüfergebnisse sind in Tabelle 3 zusammengestellt.The test results are summarized in Table 3.

Vergleichsbeispiel V1Comparative Example V1

Das Basispapier aus Beispiel 1 wurde mit einer Tintenaufnahmeschicht gemäß A2 beschichtet (12 g/m2) und anschließend mit einer Oberschicht gemäß B6 versehen (4 g/m2), jedoch ohne Boehmit mit enger Porenradiusverteilung, statt dessen mit Aluminiumhydroxid mit einer Porenradiusverteilung von 28 bis 1000 Å(V1a) und 20 bis 140 Å(V1b).The base paper from Example 1 was coated with an ink absorption layer according to A2 (12 g / m 2 ) and then provided with an upper layer according to B6 (4 g / m 2 ), but without boehmite with a narrow pore radius distribution, instead with aluminum hydroxide with a pore radius distribution of 28 to 1000 Å (V1a) and 20 to 140 Å (V1b).

Vergleichsbeispiel V2Comparative example V2

Das Basispapier aus Beispiel 1 wurde nur mit einer Tintenaufnahmeschicht gemäß A2 und A6 beschichtet ohne und mit Zugabe von Aluminiumhydroxid beschichtet. Bestandteile V2a V2b V2c Gelatine, 264 Bloom 81,80 - - Polyvinylalkohol, Verseifungsgrad: 98 Mol% - 31,60 21,60 Polyvinylpyrrolidon, - 31,60 21,60 Molgewicht: 630000 Dalton Vinylacetat/Butylacrylat-Cop. - 31,60 21,60 Aminomethylmethacrylat 15,00 - - quat. Polyammoniumsalz 3,00 5,20 5,20 Al-Hydroxid, 20-140 A - - 30,00 TAF/Formaldehyd 0,20 - - Auftrag, g/m2 15 15 15 The base paper from Example 1 was only coated with an ink receiving layer in accordance with A2 and A6 without and with the addition of aluminum hydroxide. Components V2a V2b V2c Gelatin, 264 Bloom 81.80 - - Polyvinyl alcohol, degree of saponification: 98 mol% - 31.60 21.60 Polyvinyl pyrrolidone, - 31.60 21.60 Molecular Weight: 630000 Daltons Vinyl acetate / butyl acrylate cop. - 31.60 21.60 Aminomethyl methacrylate 15.00 - - quat. Polyammonium salt 3.00 5.20 5.20 Al hydroxide, 20-140 A. - - 30.00 TAF / formaldehyde 0.20 - - Order, g / m2 15 15 15

Die Mengenangaben sind in Gew.% ausgedrückt und beziehen sich auf getrocknete Schichten.The quantities are expressed in% by weight and relate to dried layers.

Vergleichsbeispiel V3Comparative Example V3

Als Vergleich diente ein handelsübliches Aufzeichnungsmaterial: Folex Folie BG-32 WOA commercially available recording material was used for comparison: Folex film BG-32 WO

Das in den Vergleichsbeispielen erhaltene Aufzeichnungsmaterial wurde in einem sog.

Figure imgb0001
Thermal Jet"-Verfahren bedruckt und anschließend analysiert. Die Ergebnisse sind in Tabelle 4 zusammengestellt.The recording material obtained in the comparative examples was in a so-called.
Figure imgb0001
Thermal Jet "process printed and then analyzed. The results are summarized in Table 4.

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

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

Bei den erhaltenen Druckbildern wurden Farbdensität, Wasserfestigkeit, Trocknungszeit, Glanz und Bleed untersucht.Color density, water resistance, drying time, gloss and bleed were examined in the print images obtained.

Die Densitätsmessungen wurden mit Hilfe eines

Figure imgb0001
Original Reflection Densitometer SOS-45" durchgeführt. Die Messungen erfolgten für die Grundfarben Cyan, Magenta, Gelb und Schwarz.The density measurements were made using a
Figure imgb0001
Original Reflection Densitometer SOS-45 "carried out. The measurements were carried out for the basic colors cyan, magenta, yellow and black.

Für die Untersuchung der Wasserfestigkeit wurde das Aufzeichnungsmaterial in Wasser getaucht. Die nach 60 s im Wasserbad 25°C verbliebene Densität (%) wird als Maß für die Wasserstabilität herangezogen.The recording material was immersed in water to investigate the water resistance. The density (%) remaining in a 25 ° C water bath after 60 s is used as a measure of the water stability.

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

Die Messung der Glanzwerte erfolgte mit dem Labor Reflektometer RL3 der Fa. Dr. Lange nach DIN 67530.The gloss values were measured using the RL3 laboratory reflectometer from Dr. Long according to DIN 67530.

Das Trocknungsverhalten des Aufzeichnungsmaterials wird folgendermaßen ermittelt:The drying behavior of the recording material is determined as follows:

Auf ein Blatt Papier wird mit schwarzer Tinte (reines Schwarz) ein Balken ausgedruckt und nach einer Wartezeit von 120 Sekunden Papier (20 Blatt) aufgelegt. Der Farbtransfer wird als Maß für Trocknung genommen. Die Trocknungszeit kann <120, 120-240 und >240 Sekunden betragen.A bar is printed on a sheet of paper with black ink (pure black) and placed on paper after a waiting time of 120 seconds (20 sheets). The color transfer is taken as a measure of drying. The drying time can be <120, 120-240 and> 240 seconds.

Wie aus den Tabellen ersichtlich zeichnen sich die erfindungsgemäß hergestellten Aufzeichnungsmaterialien durch eine bessere Wasserfestigkeit, kürzere Trocknungszeiten sowie ein besseres Bleed-Verhalten aus. Auch wenn die Wasserfestigkeiten und Trocknungszeiten der nach V1a und V1b hergestellten Papiere ebenfalls gut sind, so ist das Bleed-Verhalten unbefriedigend. Auch hinsichtlich des Glanzes liegen die Werte bei Beispiel 2.2 höher als bei den entsprechenden Vergleichsbeispielen V1a und V1b. Tabellle 3 Prüfungsergebnisse - Beispiele 1 bis3 Beispiel Farbdensität Wasserfestigkeit % Trocknungszeit sek Glanz Bleed Note cyan magenta gelb schwarz 1.1 1,8 1,8 1,6 2,0 97 180 78 1 1.2 2,0 1,9 1,8 2,1 92 160 81 2 1.3 2,1 2,2 1,7 2,2 98 130 80 1 1.4 1,9 1,9 1,8 2,0 94 170 83 2 1.5 1,8 2,0 1,9 1,7 90 180 35 2 2.1 1,9 1,8 1,7 2,0 95 140 80 1 2.2 2,0 2,3 1,9 2,3 100 <120 81 1 2.3 1,8 1,9 1,9 1,9 92 180 62 2 3 1,8 1,6 1,5 1,7 100 <120 50 2 Tabelle 4 Prüfungsergebnisse - Vergleichsbeispiele V1 bis V3 Beispiel Farbdensität Wasserfestigkeit % Trocknungszeit sek Glanz Bleed Note cyan magenta gelb schwarz V1a 1,7 1,6 1,6 1,7 96 120 29 3 V1b 1,9 2,1 1,8 2,2 96 140 70 2 V2a 1,6 1,6 1,6 2,0 35 >240 80 3 V2b 1,4 1,6 1,6 1,8 35 >240 80 4 V2c 1,5 1,7 1,6 1,7 80 210 58 3 V3 1,6 1,5 1,6 1,7 42 >240 68 3 As can be seen from the tables, the recording materials produced according to the invention are distinguished by better water resistance, shorter drying times and better bleed behavior. Even if the water resistance and drying times of the papers produced according to V1a and V1b are also good, the bleed behavior is unsatisfactory. With regard to the gloss, too, the values in Example 2.2 are higher than in the corresponding Comparative Examples V1a and V1b. Table 3 Exam Results - Examples 1 through 3 example Color density Water resistance% Drying time sec shine Bleed note cyan magenta yellow black 1.1 1.8 1.8 1.6 2.0 97 180 78 1 1.2 2.0 1.9 1.8 2.1 92 160 81 2nd 1.3 2.1 2.2 1.7 2.2 98 130 80 1 1.4 1.9 1.9 1.8 2.0 94 170 83 2nd 1.5 1.8 2.0 1.9 1.7 90 180 35 2nd 2.1 1.9 1.8 1.7 2.0 95 140 80 1 2.2 2.0 2.3 1.9 2.3 100 <120 81 1 2.3 1.8 1.9 1.9 1.9 92 180 62 2nd 3rd 1.8 1.6 1.5 1.7 100 <120 50 2nd Test results - comparative examples V1 to V3 example Color density Water resistance% Drying time sec shine Bleed note cyan magenta yellow black V1a 1.7 1.6 1.6 1.7 96 120 29 3rd V1b 1.9 2.1 1.8 2.2 96 140 70 2nd V2a 1.6 1.6 1.6 2.0 35 > 240 80 3rd V2b 1.4 1.6 1.6 1.8 35 > 240 80 4th V2c 1.5 1.7 1.6 1.7 80 210 58 3rd V3 1.6 1.5 1.6 1.7 42 > 240 68 3rd

Claims (11)

Aufzeichnungsmaterial für Tintenstrahl-Druckverfahren mit einem Träger und einer Farbempfangsschicht, dadurch gekennzeichnet, daß auf der Farbempfangsschicht eine Oberschicht angeordnet ist, die feinporöse, kationische Ladungszentren aufweisende anorganische Pigment- und/oder Füllstoffpartikeln enthält.Recording material for inkjet printing processes with a support and an ink-receiving layer, characterized in that an upper layer is arranged on the ink-receiving layer, which contains fine-pored, inorganic pigment and / or filler particles with charge centers. Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, daß die anorganische Pigment- und/oder Füllstoffpartikeln eine Porenradiusverteilung von 10 bis 35 Å aufweisen.Recording material according to claim 1, characterized in that the inorganic pigment and / or filler particles have a pore radius distribution of 10 to 35 Å. Aufzeichnungsmaterial nach Anspruch 1 und 2, dadurch gekennzeichnet, daß die anorganischen Pigment- und/oder Füllstoffpartikeln ein Aluminiumhydroxid sind.Recording material according to claim 1 and 2, characterized in that the inorganic pigment and / or filler particles are an aluminum hydroxide. Aufzeichnungsmaterial nach Anspruch 3, dadurch gekennzeichnet, daß das Aluminiumhydroxid ein Böhmit ist.Recording material according to claim 3, characterized in that the aluminum hydroxide is a boehmite. Aufzeichnungsmaterial nach Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß die anorganischen Pigment- und/oder Füllstoffpartikeln ein pyrrogenes Aluminiumoxid sind.Recording material according to claims 1 to 4, characterized in that the inorganic pigment and / or filler particles are a pyrrogenic aluminum oxide. Aufzeichnungsmaterial nach Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß die Oberschicht mindestens ein kationisches Polymer enthält.Recording material according to claims 1 to 5, characterized in that the top layer contains at least one cationic polymer. Aufzeichnungsmaterial nach Ansprüchen 1 bis 6, dadurch gekennzeichnet, daß die Menge des kationischen Polymers in der Oberschicht 1 bis 30 Gew.%, insbesondere 5 bis 20 Gew.% beträgt.Recording material according to Claims 1 to 6, characterized in that the amount of the cationic polymer in the top layer is 1 to 30% by weight, in particular 5 to 20% by weight. Aufzeichnungsmaterial nach Ansprüchen 1 bis 7, dadurch gekennzeichnet, daß die Oberschicht ein farbstoffixierendes Mittel in einer Menge von 0,5 bis 3,0 Gew.% enthält.Recording material according to Claims 1 to 7, characterized in that the top layer contains a dye-fixing agent in an amount of 0.5 to 3.0% by weight. Aufzeichnungsmaterial nach Ansprüchen 1 bis 8, dadurch gekennzeichnet, daß die Oberschicht ein farbstoffixierendes Mittel in einer Menge von 0,5 bis 5,0 Gew.% enthält.Recording material according to Claims 1 to 8, characterized in that the top layer contains a dye-fixing agent in an amount of 0.5 to 5.0% by weight. Aufzeichnungsmaterial nach Ansprüchen 1 bis 9, dadurch gekennzeichnet, daß der Träger ein polyolefinbeschichtetes Papier ist.Recording material according to claims 1 to 9, characterized in that the carrier is a polyolefin-coated paper. Aufzeichnungsmaterial nach Ansprüchen 1 bis 10, dadurch gekennzeichnet, daß der Träger ein barythbeschichtetes Papier ist.Recording material according to claims 1 to 10, characterized in that the carrier is a barely coated paper.
EP97106976A 1996-05-09 1997-04-26 Recording material for the ink jet printing process Expired - Lifetime EP0806299B1 (en)

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US6183844B1 (en) 1998-12-16 2001-02-06 Hewlett-Packard Company Inkjet printing medium comprising multiple coatings
EP1048480A1 (en) * 1999-04-30 2000-11-02 Felix Schoeller jr Foto- und Spezialpapiere GmbH & Co. KG Ink jet recording material with pigmented layers
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EP1120281A1 (en) * 2000-01-28 2001-08-01 Oji Paper Company Limited Ink jet recording material
EP1138513A1 (en) * 2000-03-30 2001-10-04 Nippon Paper Industries Co., Ltd. Multilayer ink-receiver sheet for ink-jet printing
WO2002053391A1 (en) 2000-12-28 2002-07-11 Fuji Photo Film B.V. Ink jet recording medium
EP1226965B2 (en) † 2001-01-26 2010-12-08 Eastman Kodak Company Ink jet recording element and printing method
WO2003016068A1 (en) 2001-08-15 2003-02-27 Fuji Photo Film B.V. Ink jet recording medium
WO2004050379A1 (en) 2002-12-04 2004-06-17 Fuji Photo Film B.V. Ink-jet recording medium
WO2004054813A1 (en) 2002-12-13 2004-07-01 Fuji Photo Film B.V. Ink-jet recording medium
WO2005032834A1 (en) 2003-10-03 2005-04-14 Fuji Photo Film B.V. Recording medium
WO2005032835A1 (en) 2003-10-03 2005-04-14 Fuji Photo Film B.V. Recording medium
EP1738918A1 (en) 2005-06-29 2007-01-03 Mitsubishi HiTec Paper Flensburg GmbH Ink-jet recording medium
US8377521B2 (en) 2005-06-29 2013-02-19 Mitsubishi Hitec Paper Flensburgh Gmbh Ink jet recording material
EP2617580A1 (en) 2012-01-17 2013-07-24 Mitsubishi HiTec Paper Europe GmbH Ink jet recording material
WO2013186367A1 (en) * 2012-06-15 2013-12-19 Schoeller Technocell Gmbh & Co. Kg Receiving layer for digital printing methods having nanofibrillated cellulose
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US5911855A (en) 1999-06-15
DE19618607A1 (en) 1997-11-20
DE19618607C2 (en) 1999-07-08
ATE207816T1 (en) 2001-11-15
DE59705136D1 (en) 2001-12-06
JPH10100532A (en) 1998-04-21
DK0806299T3 (en) 2002-02-18
PT806299E (en) 2002-04-29
ES2166931T3 (en) 2002-05-01
EP0806299A3 (en) 1998-04-08
JP4024902B2 (en) 2007-12-19
EP0806299B1 (en) 2001-10-31

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