EP0812697B1 - Recording material for ink-jet printing process - Google Patents

Recording material for ink-jet printing process Download PDF

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Publication number
EP0812697B1
EP0812697B1 EP97109444A EP97109444A EP0812697B1 EP 0812697 B1 EP0812697 B1 EP 0812697B1 EP 97109444 A EP97109444 A EP 97109444A EP 97109444 A EP97109444 A EP 97109444A EP 0812697 B1 EP0812697 B1 EP 0812697B1
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EP
European Patent Office
Prior art keywords
recording material
layer
ink
material according
colour
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EP97109444A
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German (de)
French (fr)
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EP0812697A1 (en
Inventor
Debabrata Dr. Mukherjee
Clifford M. Dr. Kaufmann
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Schoeller Technical Papers Inc
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Schoeller Technical Papers Inc
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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
    • B41M5/52—Macromolecular coatings
    • B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B41M5/5272—Polyesters; Polycarbonates
    • 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
    • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B41M5/5281—Polyurethanes or polyureas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/529—Macromolecular coatings characterised by the use of fluorine- or silicon-containing organic compounds

Definitions

  • 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.
  • 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) for ink jet printing processes usually consists of a carrier and a color receiving layer and optionally further Auxiliary layers.
  • a polyester resin, Diacetate film or paper can be used.
  • JP-OS 61-35277 describes a recording material for the inkjet printing process, which is based on a transparent Polyester carrier one ink-permeable and one underneath has lying ink-absorbing PVA layer.
  • the ink-permeable Layer is one from an aqueous solution natural or synthetic polymer, for example one Sodium alginate, applied layer by drying forms a large number of microcracks.
  • the recording material has, due to the large number of microcracks, undefined Size required for quick drainage of the ink liquid poor surface quality and a low gloss.
  • JP-OS 61-35278 a recording material is also known which has a microporous ink-permeable layer lying on an ink-receiving layer, which additionally contains a powder layer (for example SiO 2 ) on its surface.
  • a powder layer for example SiO 2
  • the ink-receiving layers are mostly hydrophilic coatings that are particularly good for inclusion of the aqueous inks are suitable.
  • the ink receiving layers usually consist of a pigment / binder mixture.
  • the pigments serve, in addition to increasing the degree of whiteness of the material, for the retention of the dyes from the Recording liquid to the surface of the sheet.
  • Binders are used natural or synthetic polymers, for example gelatin, starch, pectin, casein, Carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone and similar. Often, additional in the ink receiving layer cationic substances for fixing the ink dyes used.
  • a recording material from aforementioned type which is characterized in that at least a microporous membrane layer between the ink receiving layer and the carrier layer is arranged.
  • Such a membrane can preferably have an average pore diameter of 0.001 and 100 ⁇ m, or preferably between 0.01 and 10 ⁇ m can be used to get a high gloss achieve.
  • the color receiving layer can either be a mono layer or be a multiple layer. You can binders, color-fixing cationic compounds, pigments, fillers and others Auxiliaries such as dispersing aids, Contain hardening agents, defoamers or pH regulators.
  • Water-soluble polymers such as gelatin, Polyvinyl alcohol, polyacrylamide, sodium alginite, polyvinyl pyrrolidone, Casein, starch or sodium polyacrylate are used become. Also suitable as binders in organic Solvent-soluble polymers such as polyvinyl butyral, polyvinyl chloride, Polyvinyl acetate, polyacrylonitrile, polymethyl methacrylate, Melamine resin, polyurethane and the like.
  • silica, talc, kaolin, calcium carbonate (CaCO 3 ), aluminum silicate, aluminum oxide (Al 2 0 3 ), zeolite or titanium dioxide (Ti0 2 ) can be used as pigments or fillers.
  • Compounds include, for example, quaternary ammonium polymers such as quaternary polyhydroxyammonium salt, quaternary Polyammonium methacrylate salt or polydiallyldimethylammonium salt.
  • the ink receiving layer is made from an aqueous dispersion (Coating compound) applied and dried.
  • the coating composition can be applied to the carrier using all customary application and metering methods, such as roller application, engraving or nipping methods and air brushes or roller doctor metering.
  • the application amount of the receiving layer is 0.1 to 20 g / m 2 , preferably between 1 to 14 g / m 2 .
  • the membrane layer is preferably made of a dissolved polymer from the group of polyether sulfones, polysulfones, cellulose acetate, Polypropylene, polyamide, polyvinylidene fluoride, cellulose esters, Polycarbonates, polytetrafluoroethylene, polyvinyl chloride or formed from acrylic polymers. For example is by phase inversion or by evaporation of a solvent manufactured.
  • Pore formers in the form of LiCl or LiNO 3 as well as organic substances (e.g. polyvinylpyrrolidone) or swelling agents can be added to the casting solutions.
  • Pigments e.g. Ti0 2
  • fillers can also be used.
  • the Structure of the membrane fixed e.g. B. by immersion of the sol film into a precipitant.
  • suitable crosslinking agents such as aldehydes, polyamines, Polyisocyanates, or improved by gamma radiation become.
  • the casting solution can be applied to the carrier by means of nozzles or doctor blades.
  • the application weight of the membrane layer is 0.1 to 75 g / m 2 , in particular 0.5 to 50 g / m 2 .
  • the ink receiving layer can be made thin, assuming will that in this case the ink liquid will pass through quickly the ink receiving layer can migrate through, even if this the average pore diameter required for high gloss having.
  • the ink liquid occurs after the Wander through the color receiving layer semi-permeably through the Membrane layer and is taken up by the carrier layer. Since the membrane layer only in the direction of the support layer is permeable to the ink liquid, can also here short flow times and thus drying times Reach the ink receiving layer. A decrease in the ink liquid in the color receiving layer is not possible because of the selective direction of passage of the membrane layer.
  • a plastic film or an uncoated or coated base paper with a basis weight of 50 to 250 g / m 2 can be used as the carrier layer for the recording material.
  • the back of the recording material can also have a functional layer, for example an anticurl and / or antistatic layer, the application amount of which can be 0.1 to 25 g / m 2 .
  • a membrane layer can also be used as a color receiving layer become.
  • By appropriate modification of the membrane surface in particular by hydrophilizing the membrane surface, high resolution and good Achieve color gradation.
  • the thickness of the membrane layer is 0.1 to 75 ⁇ m, in particular 0.5 to 50 ⁇ m, but preferably 0.5 to 5 ⁇ m, for one Color of the ink receiving layer between 0.1 and 20 microns.
  • Embodiments of the invention are in the following examples explains:
  • the front of a neutral sized base paper with a basis weight of 100 g / m 2 was coated with a casting solution of cellulose acetate (25% by weight), acetone (45% by weight) and formamide (30% by weight) at room temperature. After pouring the solution and an evaporation time of about 25 s, the layer was gelled by immersion in water. The coated paper was then dried to remove the rest of the solvent. The application weight of the membrane layer produced was 15 g / m 2 . In a further operation, the paper provided with the membrane layer was coated with an aqueous coating composition in order to produce a dye-receiving layer.
  • the receiving layer has the following composition: Polyvinyl alcohol (degree of saponification: 98 mol%) 31.6% by weight Polyvinyl pyrrolidone (Mol. 630,000 daltons) 31.6% by weight Vinyl acetate / butyl acrylate cop. 31.6% by weight quat. Polyammonium salt 5.2% by weight
  • the application weight of the receiving layer was 10 g / m 2 .
  • the amounts in% by weight relate to the dried layer.
  • the recording paper obtained was printed in a so-called " thermal jet " process and then analyzed.
  • the back of the recording paper produced according to Example 1 was additionally coated with an anti-curl layer.
  • an aqueous gelatin solution with a gelatin content of 7% by weight was prepared, containing 0.5% by weight of saponin and 0.6% by weight of a curing agent combination of 1,3,5-triacryloyl-hexahydro-s-triazine and Formaldehyde (1: 0.2) was added.
  • This gelatin solution was poured onto the back of the recording paper in a known manner in such a quantity that an anti-curl layer with an application weight of 5 g / m 2 resulted after customary solidification with subsequent drying.
  • the recording paper consisting of the anti-curl layer, paper support, membrane layer and ink-receiving layer was printed as in Example 1 and analyzed for its properties.
  • the front of a neutral sized base paper with a basis weight of 120 g / m 2 was coated with the following receiving layer: Polyvinyl alcohol (degree of saponification: 98 mol%) 41.0% by weight Polyvinyl pyrrolidone (Mol. 630,000 daltons) 41.0% by weight Aminomethyl methacrylate 15.0% by weight quat. Polyammonium salt 3.0% by weight
  • the application weight of the receiving layer was 9 g / m 2 .
  • the amounts in% by weight relate to the dried layer.
  • the paper provided with the receiving layer was coated with a casting solution composed of polyamide (10% by weight), dimethylacetamide (85% by weight) and TiO 2 (5% by weight). After partial evaporation of the solvent, the mixture was coagulated in water. The application weight of the membrane layer was 1 g / m 2 .
  • V1a V1b Polyvinyl alcohol 41.0% by weight 36.0% by weight Polyvinyl pyrrolidone 41.0% by weight 36.0% by weight Aminomethyl methacrylate 15.0% by weight 5.0% by weight quat. Polyammonium salt 3.0% by weight 3.0% by weight Colloidal silica - 20.0% by weight
  • the front of a base paper with a basis weight of 100 g / m 2 was coated with LDPE ( low density polyethylene ) in a quantity of 20 g / m 2 and the back with a mixture of LDPE and HDPE ( high density polyethylene ) in a quantity of 20 g / m 2 coated.
  • a receiving layer according to Example 1 was applied in an amount of 10 g / m 2 to the polyethylene-coated paper.
  • the recording material obtained was printed as in Example 1 and analyzed for its properties.
  • the recording material was printed using an HP DESKJET® 550 C ink jet printer from HEWLETT PACKARD, which works on the bubble jet principle ( Themal Jet ).
  • the density measurements were made using the densitometer "XRITE® 428" carried out. The measurements were made for the Basic colors cyan, magenta, yellow and black with 100% saturation.
  • the gloss values were measured with the laboratory reflectometer RL3 of the FA. DR. LANGE according to DIN 67530 with a measuring angle of 60 °.
  • the drying behavior of the recording material becomes as follows determined:
  • a bar is printed out 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 (very good), 120-240 and> 240 (bad) seconds.

Landscapes

  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)
  • Laminated Bodies (AREA)
  • Duplication Or Marking (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

Recording material (I) for ink jet printing, containing (A)an ink-receiving layer and (B) a base layer, with (C) at least one microporous membrane layer between (A) and (B) and/or on the outside of (A). Also claimed is a process for the production of (I).

Description

Die Erfindung betrifft ein Aufzeichnungsmaterial für das Tintenstrahl-Druckverfahren, das wenigstens folgende Schichten umfaßt:

  • eine Farbempfangsschicht, auf die ein Tintenstrahl auftrifft und durch die die Tintenflüssigkeit unter Zurücklassung des Tintentfarbstoffes bis zu der Schichtgrenze der Farbempfangsschicht hindurchtritt,
  • und eine Trägerschicht, die einen Überschuß an Tintenflüssigkeit aufzunehmen vermag.
The invention relates to a recording material for the inkjet printing process, which comprises at least the following layers:
  • an ink-receiving layer on which an ink jet strikes and through which the ink liquid passes, leaving the ink dye as far as the layer boundary of the ink-receiving layer,
  • and a support layer capable of absorbing excess ink liquid.

Beim 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. In the ink jet process, droplets become a recording liquid (Ink) on the surface of the recording material applied using different techniques. At There are basically two process variants for drop generation. In the continuous process, an ink jet is used ejected from the nozzle due to the surface tension dissolves into microscopic drops. The drops are electrically charged and by baffles controlled by the digital signals placed on the pad or distracted into a reservoir.

Bei der sog. "drop-on-demand"-Methode löst das Bildsignal einen mechanischen Impuls aus, der den Tropfen ausstößt. Die ersten "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 so-called " drop-on-demand " method, 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. 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 eine

  • hohe Auflösung,
  • hohe Farbdichte,
  • 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 a
  • high resolution,
  • high color density,
  • 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 (kurze Trocknungszeiten),
  • 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 absorbed quickly by the recording material (short drying times),
  • 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. B. means setting the Smudge resistance that an ink drop does not or only slightly diverges and thereby the clarity of the resulting Image is disadvantaged.

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, the high recording speeds enable, affects the fulfillment of the above requirements aggravating.

Das Aufzeichnungsmaterial (Bildempfangsmaterial) für Tintenstrahl-Druckverfahren besteht in der Regel aus einem Träger und einer Farbempfangsschicht sowie gegebenenfalls weiteren Hilfsschichten. Als Träger kann beispielsweise ein Polyesterharz-, Diacetat-Folie oder Papier verwendet werden.The recording material (image receiving material) for ink jet printing processes usually consists of a carrier and a color receiving layer and optionally further Auxiliary layers. A polyester resin, Diacetate film or paper can be used.

Die JP-OS 61-35277 beschreibt ein Aufzeichnungsmaterial für das Tintenstrahl-Druckverfahren, das auf einem transparenten Polyesterträger eine tintendurchlässige und eine darunter liegende tintenaufnehmende PVA-Schicht aufweist. Die tintendurchlässige Schicht ist eine aus einer wäßrigen Lösung eines natürlichen oder synthetischen Polymers, beispielsweise eines Natriumalginats, aufgetragene Schicht, die durch Trocknung eine Vielzahl Mikrorisse bildet. Das Aufzeichnungsmaterial weist, bedingt durch die Vielzahl von Mikrorissen undefinierter Größe, die für eine schnelle Abführung der Tintenflüssigkeit verantwortlich sind, eine schlechte Oberflächenqualität und einen niedrigen Glanz auf.JP-OS 61-35277 describes a recording material for the inkjet printing process, which is based on a transparent Polyester carrier one ink-permeable and one underneath has lying ink-absorbing PVA layer. The ink-permeable Layer is one from an aqueous solution natural or synthetic polymer, for example one Sodium alginate, applied layer by drying forms a large number of microcracks. The recording material has, due to the large number of microcracks, undefined Size required for quick drainage of the ink liquid poor surface quality and a low gloss.

Aus der JP-OS 61-35278 ist weiterhin ein Aufzeichnungsmaterial bekannt, welches eine auf einer Tintenaufnahmeschicht liegende mikroporöse tintendurchlässige Schicht aufweist, die auf ihrer Oberfläche zusätzlich eine Pulverschicht (z.B. Si02) enthält. Aus der genannten Schrift geht jedoch nicht hervor, welche Funktionen und welchen Vorteil die Plazierung eine derartige Membran in dem beschichteten Aufbau des Aufzeichnungsmaterials hat.From JP-OS 61-35278 a recording material is also known which has a microporous ink-permeable layer lying on an ink-receiving layer, which additionally contains a powder layer (for example SiO 2 ) on its surface. However, it is not clear from the cited document what functions and what advantages the placement of such a membrane has in the coated structure of the recording material.

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/BindemittelMischung. 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 that are particularly good for inclusion of the aqueous inks are suitable. The ink receiving layers usually consist of a pigment / binder mixture. The pigments serve, in addition to increasing the degree of whiteness of the material, for the retention of the dyes from the Recording liquid to the surface of the sheet. As Binders are used natural or synthetic polymers, for example gelatin, starch, pectin, casein, Carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone and similar. Often, additional in the ink receiving layer cationic substances for fixing the ink dyes used.

Während Ink-Jet-Papiere, die mit hydrophilen, wasserlösliche Polymeren (z. B. Gelatine, Polyvinylalkohol) enthaltenden Empfangsschichten versehen sind, eine hohe Bildauflösung aufweisen, ist die Schaffung eines hohen Glanzes bei diesen Papieren ein großes Problem. Um einen hohen Glanz (>70% bei 60°) der Aufzeichnungspapiere zu erreichen, wird das Basispapier zuerst mit wasserlöslichen Polymeren wie beispielsweise Polyethylen extrusionsbeschichtet und anschließend mit einer Empfangsschicht versehen. Dies hat jedoch schlechte Trocknungszeiten zur Folge.While ink jet papers are made with hydrophilic, water soluble Containing polymers (e.g. gelatin, polyvinyl alcohol) Receiving layers are provided, have a high image resolution, is the creation of a high gloss on these papers a big problem. For a high gloss (> 70% at To reach 60 °) of the recording paper, the base paper first with water-soluble polymers such as Polyethylene extrusion coated and then with a Provide receiving layer. However, this has poor drying times result.

Eines der Erfordernisse in bezug auf eine Farbempfangsschicht ist, daß die Tintenflüssigkeit durch die Farbempfangsschicht hindurch viskos und damit schnell fließt. Ein solches Fließen ist um Größenordnungen schneller als ein diffundierendes Fließen und führt daher zu einem raschen Abtrocknen der Tintenflüssigkeit auf der Farbempfangsschicht. Nach dem Hagen-Poiseuilleschen Gesetz ist die Flüssigkeitsmenge pro Zeiteinheit, die durch eine Porenanordnung fließt, mit der vierten Potenz des mittleren Durchmessers der Poren proportional. Daher geht der größte Teil des Flusses der Flüssigkeit durch Poren mit großem Radius.One of the requirements for a color receiving layer is that the ink liquid passes through the color receiving layer viscous and therefore flows quickly. Such a flow is orders of magnitude faster than a diffusing one Flow and therefore leads to a quick drying of the ink liquid on the ink receiving layer. After the Hagen-Poiseuilleschen Law is the amount of liquid per unit of time, which flows through a pore arrangement, with the fourth Potency of the average diameter of the pores proportional. Therefore goes through most of the flow of the liquid Pores with a large radius.

Jedoch hat eine Porendurchmesser-Verteilung, bei der der Mittelwert zu größeren Poren verschoben ist, eine Verringerung des erwünschten Glanzes des Aufzeichnungsmaterials zur Folge. Erst wenn eine mittlere Porengröße in der Größenordnung 0,1 bis 1 um bei der Farbempfangsschicht erreicht ist, führt dies zu einem hochglänzenden Produkt.However, it has a pore diameter distribution where the mean is shifted to larger pores, a reduction the desired gloss of the recording material. Only when an average pore size in the order of 0.1 to 1 µm in the ink receiving layer, this leads to a high-gloss product.

Es stellt sich daher die Aufgabe, ein Aufzeichnungsmaterial anzugeben, das gleichzeitig einen hohen Glanz und eine hohe Abtrocknungsgeschwindigkeit für die Tintenflüssigkeit aufweist, sowie hohe Farbdichte und gute Auflösung zeigt.It is therefore the task of a recording material indicate that at the same time a high gloss and a high Has drying speed for the ink liquid, as well as high color density and good resolution.

Diese Aufgabe wird gelöst durch ein Aufzeichnungsmaterial der vorgenannten Art, das dadurch gekennzeichnet ist, daß wenigstens eine mikroporöse Membranschicht zwischen der Farbempfangsschicht und der Trägerschicht angeordnet ist.This object is achieved by a recording material from aforementioned type, which is characterized in that at least a microporous membrane layer between the ink receiving layer and the carrier layer is arranged.

Eine solche Membran kann vorzugsweise mit einem mittleren Porendurchmesser von 0,001 und 100 µm, bzw. vorzugsweise zwischen 0,01 und 10µm verwendet werden, um einen hohen Glanz zu erzielen.Such a membrane can preferably have an average pore diameter of 0.001 and 100 µm, or preferably between 0.01 and 10µm can be used to get a high gloss achieve.

Die Farbempfangsschicht kann entweder eine Mono-Schicht oder eine Mehrfach-Schicht sein. Sie kann Bindemittel, farbfixierende kationische Verbindungen, Pigmente, Füllstoffe und andere Hilfsmittel wie beispielsweise Dispergierhilfsmittel, Härtungsmittel, Entschäumer oder pH-Regler enthalten.The color receiving layer can either be a mono layer or be a multiple layer. You can binders, color-fixing cationic compounds, pigments, fillers and others Auxiliaries such as dispersing aids, Contain hardening agents, defoamers or pH regulators.

Als Bindemittel können wasserlösliche Polymere wie Gelatine, Polyvinylalkohol, Polyacrylamid, Natriumalginit, Polyvinylpyrrolidon, Kasein, Stärke oder Natrium-Polyacrylat eingesetzt werden. Auch eignen sich als Bindemittel in organischen Lösungsmitteln lösliche Polymere wie Polyvinylbutyral, Polyvinylchlorid, Polyvinylacetat, Polyacrylnitril, Polymethylmethacrylat, Melaminharz, Polyurethan und ähnliche.Water-soluble polymers such as gelatin, Polyvinyl alcohol, polyacrylamide, sodium alginite, polyvinyl pyrrolidone, Casein, starch or sodium polyacrylate are used become. Also suitable as binders in organic Solvent-soluble polymers such as polyvinyl butyral, polyvinyl chloride, Polyvinyl acetate, polyacrylonitrile, polymethyl methacrylate, Melamine resin, polyurethane and the like.

Als Pigmente bzw. Füllstoffe können beispielsweise Kieselsäure, Talcum, Kaolin, Calciumcarbonat (CaCO3), Al-Silikat, Aluminiumoxid (Al203), Zeolith oder Titandioxid (Ti02) verwendet werden.For example, silica, talc, kaolin, calcium carbonate (CaCO 3 ), aluminum silicate, aluminum oxide (Al 2 0 3 ), zeolite or titanium dioxide (Ti0 2 ) can be used as pigments or fillers.

Zu den verschiedenen einsetzbaren kationischen farbstoffixierenden Verbindungen gehören beispielsweise quaternäre Ammoniumpolymere wie quaternäres Polyhydroxyammonium-Salz, quaternäres Polyammoniummethacrylat-Salz oder Polydiallyldimethylammonium-Salz.To the various cationic dye fixers that can be used Compounds include, for example, quaternary ammonium polymers such as quaternary polyhydroxyammonium salt, quaternary Polyammonium methacrylate salt or polydiallyldimethylammonium salt.

Die Farbempfangsschicht wird aus einer wäßrigen Dispersion (Beschichtungsmasse) aufgetragen und getrocknet.The ink receiving layer is made from an aqueous dispersion (Coating compound) applied and dried.

Die Beschichtungsmasse kann mit allen gebräuchlichen Auftrags- und Dosierverfahren, wie beispielsweise WalzenauftragGravur- oder Nipp-Verfahren und Luftbürsten oder Rollrakeldosierung auf den Träger aufgetragen werden. Die Auftragsmenge der Empfangsschicht beträgt 0,1 bis 20 g/m2, vorzugsweise zwischen 1 bis 14 g/m2.The coating composition can be applied to the carrier using all customary application and metering methods, such as roller application, engraving or nipping methods and air brushes or roller doctor metering. The application amount of the receiving layer is 0.1 to 20 g / m 2 , preferably between 1 to 14 g / m 2 .

Die Membranschicht kann beispielsweise aus einer Gießlösung eines hydrophoben oder hydrophilen Polymers in einem geeigneten Lösungsmittel auf einer der genannten Schichten gebildet werden. Die Stufen der Membranschicht-Bildung können wie folgt beschrieben werden:

  • 1. Aufbringen einer Polymerlösung;
  • 2. Verdunsten des Hauptteils des Lösungsmittels;
  • 3. Gelieren des Polymers;
  • 4. Kapillaren-Bildung und Immobilisierung;
  • 5. Verdunsten des Restes des Lösungsmittels.
    • The membrane layer can be formed, for example, from a casting solution of a hydrophobic or hydrophilic polymer in a suitable solvent on one of the layers mentioned. The stages of membrane layer formation can be described as follows:
  • 1. Application of a polymer solution;
  • 2. Evaporation of the main part of the solvent;
  • 3. gelation of the polymer;
  • 4. capillary formation and immobilization;
  • 5. Evaporation of the rest of the solvent.

    • Vorzugsweise wird die Membranschicht aus einem gelösten Polymer aus der Gruppe Polyethersulfone, Polysulfone, Celluloseacetat, Polypropylen, Polyamid, Polyvinylidenfluorid, Cellulose-Estern, Polycarbonate, Polytetrafluorethylen, Polyvinylchlorid oder aus Acryl-Polymeren gebildet. Beispielsweise wird durch Phaseninversion oder durch Abdampfen eines Lösungsmittels hergestellt.The membrane layer is preferably made of a dissolved polymer from the group of polyether sulfones, polysulfones, cellulose acetate, Polypropylene, polyamide, polyvinylidene fluoride, cellulose esters, Polycarbonates, polytetrafluoroethylene, polyvinyl chloride or formed from acrylic polymers. For example is by phase inversion or by evaporation of a solvent manufactured.

    Den Gießlösungen können Porenbildner in Form von LiCl oder LiNO3 sowie organische Substanzen (z. B. Polyvinylpyrrolidon) oder Quellmittel zugesetzt werden. Aber auch Pigmente (z. B. Ti02) und/oder Füllstoffe können eingesetzt werden.Pore formers in the form of LiCl or LiNO 3 as well as organic substances (e.g. polyvinylpyrrolidone) or swelling agents can be added to the casting solutions. Pigments (e.g. Ti0 2 ) and / or fillers can also be used.

    Vor dem vollständigen Verdampfen des Lösungsmittels wird die Struktur der Membran fixiert (Koagulation), z. B. durch Eintauchen des Solfilmes in ein Fällungsmittel. Dieser Vorgang kann durch geeignete Vernetzungsmittel, wie Aldehyde, Polyamine, Polyisocyanate, oder durch gamma-Bestrahlung verbessert werden.Before the solvent has completely evaporated, the Structure of the membrane fixed (coagulation), e.g. B. by immersion of the sol film into a precipitant. This process by suitable crosslinking agents, such as aldehydes, polyamines, Polyisocyanates, or improved by gamma radiation become.

    Die Gießlösung kann mittels Düsen oder Rakeln auf den Träger aufgebracht werden. Das Auftragsgewicht der Membranschicht beträgt 0,1 bis 75 g/m2, insbesondere 0,5 bis 50 g/m2.The casting solution can be applied to the carrier by means of nozzles or doctor blades. The application weight of the membrane layer is 0.1 to 75 g / m 2 , in particular 0.5 to 50 g / m 2 .

    Durch die Verwendung von Membranschicht kann die Farbempfangsschicht dünn gemacht werden, wobei davon ausgegangen wird, daß in diesem Falle die Tintenflüssigkeit schnell durch die Farbempfangsschicht hindurchwandern kann, auch wenn diese die für einen hohen Glanz erforderlichen mittleren Porendurchmesser aufweist. Die Tintenflüssigkeit tritt nach dem Durchwandern der Farbempfangsschicht semipermeabel durch die Membranschicht hindurch und wird von der Trägerschicht aufgenommen. Da die Membranschicht nur in Richtung Trägerschicht für die Tintenflüssigkeit durchlässig ist, lassen sich auch hier kurze Durchflußzeiten und damit Abtrocknungszeiten der Farbempfangsschicht erreichen. Ein Zurückgehen der Tintenflüssigkeit in die Farbempfangsschicht ist nicht möglich wegen der selektiven Durchlaßrichtung der Membranschicht.By using a membrane layer, the ink receiving layer can be made thin, assuming will that in this case the ink liquid will pass through quickly the ink receiving layer can migrate through, even if this the average pore diameter required for high gloss having. The ink liquid occurs after the Wander through the color receiving layer semi-permeably through the Membrane layer and is taken up by the carrier layer. Since the membrane layer only in the direction of the support layer is permeable to the ink liquid, can also here short flow times and thus drying times Reach the ink receiving layer. A decrease in the ink liquid in the color receiving layer is not possible because of the selective direction of passage of the membrane layer.

    Als Trägerschicht für das Aufzeichnungsmaterial kann eine Kunststoffolie oder ein unbeschichtetes oder beschichtetes Basispapier mit einem Flächengewicht von 50 bis 250 g/m2 verwendet werden.A plastic film or an uncoated or coated base paper with a basis weight of 50 to 250 g / m 2 can be used as the carrier layer for the recording material.

    Die Rückseite des Aufzeichnungsmaterials kann auch noch eine Funktionsschicht aufweisen, beispielsweise eine Anticurlund/oder Antistatikschicht, deren Auftragsmenge 0,1 bis 25 g/m2 betragen kann.The back of the recording material can also have a functional layer, for example an anticurl and / or antistatic layer, the application amount of which can be 0.1 to 25 g / m 2 .

    Eine Membranschicht kann auch als Farbempfangsschicht eingesetzt werden. Durch entsprechende Modifikation der Membranoberfläche, insbesondere durch Hydrophilierung der Membranoberfläche, lassen sich eine hohe Auflösung und eine gute Farbabstufung erreichen.A membrane layer can also be used as a color receiving layer become. By appropriate modification of the membrane surface, in particular by hydrophilizing the membrane surface, high resolution and good Achieve color gradation.

    Die Dicke der Membranschicht beträgt 0,1 bis 75 µm, insbesondere 0,5 bis 50 µm, vorzugsweise jedoch 0,5 bis 5 µm, bei einer Dicke der Farbempfangsschicht zwischen 0,1 und 20 µm.The thickness of the membrane layer is 0.1 to 75 μm, in particular 0.5 to 50 µm, but preferably 0.5 to 5 µm, for one Color of the ink receiving layer between 0.1 and 20 microns.

    Ausführungsbeispiele der Erfindung sind in den folgenden Beispielen erläutert:Embodiments of the invention are in the following examples explains:

    Beispiel 1example 1

    Die Vorderseite eines neutral geleimten Rohpapiers mit einem Flächengewicht von 100 g/m2 wurde mit einer Gießlösung aus Celluloseacetat (25 Gew.%), Aceton (45 Gew.%) und Formamid (30 Gew.%) bei Zimmertemperatur beschichtet. Nach dem Gießen der Lösung und einer Verdampfungszeit von etwa 25 s folgte die Gelierung der Schicht durch eintauchen in Wasser. Anschließend wurde das beschichtete Papier getrocknet, um den Rest des Lösungsmittels zu entfernen. Das Auftragsgewicht der erzeugten Membranschicht betrug 15 g/m2. In einem weiteren Arbeitsgang wurde das mit der Membran-Schicht versehene Papier mit einer wäßrigen Beschichtungsmasse zwecks Erzeugung einer Farbstoffempfangsschicht beschichtet. Die Empfangsschicht hat eine folgende Zusammensetzung: Polyvinylalkohol (Verseifungsgrad: 98 Mol%) 31,6 Gew.% Polyvinylpyrrolidon (Molgew. 630 000 Dalton) 31,6 Gew.% Vinylacetat/Butylacrylat-Cop. 31,6 Gew.% quat. Polyammoniumsalz 5,2 Gew.% The front of a neutral sized base paper with a basis weight of 100 g / m 2 was coated with a casting solution of cellulose acetate (25% by weight), acetone (45% by weight) and formamide (30% by weight) at room temperature. After pouring the solution and an evaporation time of about 25 s, the layer was gelled by immersion in water. The coated paper was then dried to remove the rest of the solvent. The application weight of the membrane layer produced was 15 g / m 2 . In a further operation, the paper provided with the membrane layer was coated with an aqueous coating composition in order to produce a dye-receiving layer. The receiving layer has the following composition: Polyvinyl alcohol (degree of saponification: 98 mol%) 31.6% by weight Polyvinyl pyrrolidone (Mol. 630,000 daltons) 31.6% by weight Vinyl acetate / butyl acrylate cop. 31.6% by weight quat. Polyammonium salt 5.2% by weight

    Das Auftragsgewicht der Empfangsschicht betrug 10 g/m2. Die Mengenangaben in Gew.% beziehen sich auf die getrocknete Schicht. Das erhaltene Aufzeichnungspapier wurde in einem sogenannten "Thermal-Jet"-Verfahren bedruckt und anschließend analysiert.The application weight of the receiving layer was 10 g / m 2 . The amounts in% by weight relate to the dried layer. The recording paper obtained was printed in a so-called " thermal jet " process and then analyzed.

    Die Prüfergebnisse sind in Tabelle 1 zusammengestellt.The test results are summarized in Table 1.

    Beispiel 2Example 2

    Die Rückseite des nach Beispiel 1 hergestellten Aufzeichnungspapiers wurde zusätzlich mit einer Anti-Curl-Schicht überzogen. Zu dem Zweck wurde eine wäßrige Gelatinelösung mit einem Gelatinegehalt von 7 Gew.% hergestellt, die mit 0,5 Gew.% Saponin und 0,6 Gew.% einer HärtungsmittelKombination von 1,3,5-Triacryloyl-Hexahydro-s-Triazin und Formaldehyd (1:0,2) versetzt wurde. Diese Gelatinelösung wurde in bekannter Weise in solcher Menge auf die Rückseite des Aufzeichnungspapiers gegossen, daß nach üblicher Erstarrung mit anschließender Trocknung eine Anti-Curl-Schicht mit einem Auftragsgewicht von 5 g/m2 resultierte. Das aus Anti-Curl-Schicht, Papierträger, Membranschicht und Farbempfangsschicht bestehende Aufzeichnungspapier wurde wie in Beispiel 1 bedruckt und hinsichtlich seiner Eigenschaften analysiert.The back of the recording paper produced according to Example 1 was additionally coated with an anti-curl layer. For this purpose, an aqueous gelatin solution with a gelatin content of 7% by weight was prepared, containing 0.5% by weight of saponin and 0.6% by weight of a curing agent combination of 1,3,5-triacryloyl-hexahydro-s-triazine and Formaldehyde (1: 0.2) was added. This gelatin solution was poured onto the back of the recording paper in a known manner in such a quantity that an anti-curl layer with an application weight of 5 g / m 2 resulted after customary solidification with subsequent drying. The recording paper consisting of the anti-curl layer, paper support, membrane layer and ink-receiving layer was printed as in Example 1 and analyzed for its properties.

    Beispiel 3Example 3

    Die Vorderseite eines neutralgeleimten Rohpapiers mit einem Flächengewicht von 120 g/m2 wurde mit folgender Empfangsschicht beschichtet: Polyvinylalkohol (Verseifungsgrad: 98 Mol%) 41,0 Gew.% Polyvinylpyrrolidon (Molgew. 630 000 Dalton) 41,0 Gew.% Aminomethylmethacrylat 15,0 Gew.% quat. Polyammoniumsalz 3,0 Gew.% The front of a neutral sized base paper with a basis weight of 120 g / m 2 was coated with the following receiving layer: Polyvinyl alcohol (degree of saponification: 98 mol%) 41.0% by weight Polyvinyl pyrrolidone (Mol. 630,000 daltons) 41.0% by weight Aminomethyl methacrylate 15.0% by weight quat. Polyammonium salt 3.0% by weight

    Das Auftragsgewicht der Empfangsschicht betrug 9 g/m2. Die Mengenangaben in Gew.% beziehen sich auf die getrocknete Schicht.The application weight of the receiving layer was 9 g / m 2 . The amounts in% by weight relate to the dried layer.

    Das mit der Empfangsschicht versehene Papier wurde in einem weiteren Arbeitsgang mit einer Gießlösung aus Polyamid (10 Gew.%), Dimethylacetamid (85 Gew.%) und Ti02 (5 Gew.%) beschichtet. Nach teilweisem Verdampfen des Lösungsmittels wurde in Wasser koaguliert. Das Auftragsgewicht der Membranschicht betrug 1 g/m2.In a further operation, the paper provided with the receiving layer was coated with a casting solution composed of polyamide (10% by weight), dimethylacetamide (85% by weight) and TiO 2 (5% by weight). After partial evaporation of the solvent, the mixture was coagulated in water. The application weight of the membrane layer was 1 g / m 2 .

    Beispiel 4Example 4

    Auf die Vorderseite eines Basispapiers mit einem Flächengewicht von 80 g/m2 wurde eine Gießlösung aus Natrium-Polysulfon (40 Gew.%), Dimethylformamid (48 Gew.%) und Chloroform (12 Gew.%) zu einem Solfilm von 50 µm Dicke vergossen. Die Verdunstungszeit betrug 3 min, danach folgte der Koagulationsschritt. Nach einer für diese Membran-Art notwendigen thermischen Behandlung wurde auf die Membranschicht eine Farbempfangsschicht gemäß Beispiel 3 aufgetragen.On the front of a base paper with a basis weight of 80 g / m 2 , a casting solution of sodium polysulfone (40 wt.%), Dimethylformamide (48 wt.%) And chloroform (12 wt.%) To a sol film of 50 microns thick shed. The evaporation time was 3 minutes, followed by the coagulation step. After a thermal treatment necessary for this type of membrane, a color-receiving layer according to Example 3 was applied to the membrane layer.

    Vergleichsbeispiel 1Comparative Example 1

    Die Vorderseite eines neutral geleimten Rohpapiers mit einem Flächengewicht von 100 g/m2 wurde mit folgenden Empfangsschichten beschichtet: V1a V1b Polyvinylalkohol 41,0 Gew.% 36,0 Gew.% Polyvinylpyrrolidon 41,0 Gew.% 36,0 Gew.% Aminomethylmethacrylat 15,0 Gew.% 5,0 Gew.% quat. Polyammoniumsalz 3,0 Gew.% 3,0 Gew.% Kolloidale Kieselsäure - 20,0 Gew.% The front of a neutral sized base paper with a basis weight of 100 g / m 2 was coated with the following receiving layers: V1a V1b Polyvinyl alcohol 41.0% by weight 36.0% by weight Polyvinyl pyrrolidone 41.0% by weight 36.0% by weight Aminomethyl methacrylate 15.0% by weight 5.0% by weight quat. Polyammonium salt 3.0% by weight 3.0% by weight Colloidal silica - 20.0% by weight

    Vergleichsbeispiel 2Comparative Example 2

    Die Vorderseite eines Rohpapiers mit einem Flächengewicht von 100 g/m2 wurde mit LDPE (low density polyethylene) in einer Auftragsmenge von 20 g/m2 und die Rückseite mit einer Mischung aus LDPE und HDPE (high density polyethylene) in einer Auftragsmenge von 20 g/m2 beschichtet. Auf das polyethylenbeschichtete Papier wurde eine Empfangsschicht gemäß Beispiel 1 in einer Menge von 10 g/m2 aufgetragen. Das erhaltene Aufzeichnungsmaterial wurde wie im Beispiel 1 bedruckt und hinsichtlich seiner Eigenschaften analysiert.The front of a base paper with a basis weight of 100 g / m 2 was coated with LDPE ( low density polyethylene ) in a quantity of 20 g / m 2 and the back with a mixture of LDPE and HDPE ( high density polyethylene ) in a quantity of 20 g / m 2 coated. A receiving layer according to Example 1 was applied in an amount of 10 g / m 2 to the polyethylene-coated paper. The recording material obtained was printed as in Example 1 and analyzed for its properties.

    Prüfung des gemäß den Beispielen und Vergleichsbeispielen erhaltenen AufzeichnungmaterialsExamination of that obtained according to the examples and comparative examples Recording material

    Das Aufzeichnungsmaterial wurde mit Hilfe eines nach dem Bubble-Jet-Prinzip (Themal 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 ( Themal Jet ).

    Bei den erhaltenen Druckbildern wurden Farbdensität, Trocknungszeit, Glanz und sog. "Bleed" untersucht.In the print images obtained, color density, Drying time, gloss and so-called "bleed" examined.

    Die Densitätsmessungen wurden mit Hilfe des Densitometers "XRITE® 428" durchgeführt. Die Messungen erfolgten für die Grundfarben Cyan, Magenta, Gelb und Schwarz bei 100 % Sättigung.The density measurements were made using the densitometer "XRITE® 428" carried out. The measurements were made for the Basic colors cyan, magenta, yellow and black with 100% saturation.

    Das Ineinanderlaufen der Tinten an den Rändern von zusammenliegenden Farbflächen (Bleed) wurde visuell mit den Noten 1-6 (sehr gut bis sehr schlecht) beurteilt.The blending 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 bei einem Meßwinkel von 60°.The gloss values were measured with the laboratory reflectometer RL3 of the FA. DR. LANGE according to DIN 67530 with a measuring angle of 60 °.

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

    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 (sehr gut), 120-240 und >240 (schlecht) Sekunden betragen. Prüfergebnisse Beispiel Farbdensität Trocknungszeit (s) Glanz (%) Bleed Note cyan magenta gelb schwarz 1 1,8 1,8 1,6 2,0 <120 90 1 2 1,8 1,8 1,6 2,0 <120 90 1 3 2,0 1,9 1,8 2,1 <120 85 1 4 2,0 1,9 1,9 2,2 <120 90 1 V1a 2,0 1,9 1,8 2,1 200 75 2 V1b 2,1 2,0 1,9 2,2 180 70 2 V2 1,8 1,7 1,6 1,9 >240 80 2 A bar is printed out 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 (very good), 120-240 and> 240 (bad) seconds. Test results example Color density Drying time (s) Shine (%) Bleed note cyan magenta yellow black 1 1.8 1.8 1.6 2.0 <120 90 1 2nd 1.8 1.8 1.6 2.0 <120 90 1 3rd 2.0 1.9 1.8 2.1 <120 85 1 4th 2.0 1.9 1.9 2.2 <120 90 1 V1a 2.0 1.9 1.8 2.1 200 75 2nd V1b 2.1 2.0 1.9 2.2 180 70 2nd V2 1.8 1.7 1.6 1.9 > 240 80 2nd

    Claims (11)

    1. A recording material for ink-jet printing, comprising a colour-receiving layer and a carrier layer, characterized in that at least one microporous membrane layer is disposed between the colour-receiving layer and the carrier layer.
    2. A recording material according to claim 1, characterized in that the pore size of the membrane layer is between 0.01 and 10 µm.
    3. A recording material according to claims 1 and 2, characterized in that the thickness of the membrane layer is between 0.1 and 75 µm, preferably between 0.5 and 50 µm.
    4. A recording material according to claims 1 to 3, characterized in that the membrane layer is formed of a pouring solution of a hydrophobic or hydrophilic polymer.
    5. A recording material according to claim 4, characterized in that the membrane layer consists of a polymer selected from the group comprising polyether sulphones, polysulphones, cellulose acetate, polypropylene, polyamide, polyvinylidene fluoride, cellulose esters, polycarbonates, polytetrafluoroethylene, polyvinyl chloride or of acrylic polymers.
    6. A recording material according to one of the foregoing claims, characterized in that a solvent for the membrane layer is selected from the group comprising N-methylpyrrolidone, dimethylformamide, dimethylacetamide, chloroform, butanol, dimethylsulphoxide, propylene carbonate and tetrahydrofuran.
    7. A recording material according to one of the foregoing claims, characterized in that water-soluble polymers such as gelatine, polyvinyl alcohol, polyacrylamide, sodium alginate, polyvinyl pyrrolidone, casein, starch or sodium polyacrylate are used as binders for the colour-receiving layer.
    8. A recording material according to one of the foregoing claims, characterised in that polymers soluble in organic solvents, such as polyvinyl butyral, polyvinyl chloride, polyvinyl acetate, polyacrylonitrile, polymethyl methacrylate, melamine resin, or polyurethane, are used as binders for the colour-receiving layer.
    9. A recording material according to one of the foregoing claims, characterised in that the membrane layer includes a filler and/or a pigment.
    10. A recording material according to one of the foregoing claims, characterised in that a membrane layer takes the place of a colour-receiving layer.
    11. A method for producing a recording material for ink-jet printing, characterised by
      application of a membrane matrix of a solution of a hydrophilic and/or hydrophobic polymer in a suitable solvent to a carrier layer;
      treatment of the membrane matrix with a suitable coagulant and conversion of the matrix to a substantially non-swollen state;
      application of a colour-receiving layer of an aqueous solution that contains a hydrophilic and/or hydrophobic binder, colour-fixing agent and optionally other auxiliary substances.
    EP97109444A 1996-06-12 1997-06-11 Recording material for ink-jet printing process Expired - Lifetime EP0812697B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE19623432A DE19623432C2 (en) 1996-06-12 1996-06-12 Recording material for the inkjet printing process and process for the production thereof
    DE19623432 1996-06-12

    Publications (2)

    Publication Number Publication Date
    EP0812697A1 EP0812697A1 (en) 1997-12-17
    EP0812697B1 true EP0812697B1 (en) 1999-10-13

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    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP97109444A Expired - Lifetime EP0812697B1 (en) 1996-06-12 1997-06-11 Recording material for ink-jet printing process

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    US (1) US6534123B1 (en)
    EP (1) EP0812697B1 (en)
    JP (1) JPH10114146A (en)
    AT (1) ATE185518T1 (en)
    DE (2) DE19623432C2 (en)
    DK (1) DK0812697T3 (en)
    ES (1) ES2140164T3 (en)
    GR (1) GR3031831T3 (en)

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    EP1020300A1 (en) * 1999-01-13 2000-07-19 Azon Corporation Ink jet media prepared from water-based formulation
    US6225381B1 (en) * 1999-04-09 2001-05-01 Alliedsignal Inc. Photographic quality inkjet printable coating
    US20020037395A1 (en) * 2000-07-21 2002-03-28 Qiping Zhong Ink jet recording medium
    US20020182376A1 (en) * 2001-03-27 2002-12-05 Debabrata Mukherjee Novel universal ink jet recording medium
    US6951671B2 (en) * 2001-04-20 2005-10-04 P. H. Glatfelter Company Ink jet printable heat transfer paper
    AU2003285828A1 (en) * 2002-12-04 2004-06-23 Fuji Photo Film B.V. Ink-jet recording medium
    US20050041084A1 (en) * 2003-02-03 2005-02-24 Deba Mukherjee Quick drying, waterfast inkjet recording media
    WO2005016655A1 (en) * 2003-08-13 2005-02-24 Fuji Photo Film B.V. Ink-jet recording medium
    GB0406981D0 (en) * 2004-03-27 2004-04-28 Eastman Kodak Co Ink receiving material
    GB0406976D0 (en) * 2004-03-27 2004-04-28 Eastman Kodak Co Ink-jet receiver
    EP1924341A1 (en) * 2005-08-05 2008-05-28 FUJIFILM Manufacturing Europe B.V. Porous membrane and recording medium comprising same
    WO2007018421A1 (en) * 2005-08-05 2007-02-15 Fujifilm Manufacturing Europe B.V. Porous membrane and recording medium comprising same
    EP1924344A1 (en) 2005-08-05 2008-05-28 FUJIFILM Manufacturing Europe B.V. Porous membrane and recording medium comprising same
    WO2007018425A1 (en) * 2005-08-05 2007-02-15 Fujifilm Manufacturing Europe B.V. Porous membrane and recording medium comprising same
    WO2007018424A1 (en) * 2005-08-05 2007-02-15 Fujifilm Manufacturing Europe B.V. Porous membrane and recording medium comprising same
    JP5341514B2 (en) 2005-08-05 2013-11-13 フジフィルム マニュファクチャリング ユーロプ ビー．ブイ． Porous membrane and recording medium and method for preparing them
    WO2008016301A1 (en) * 2006-08-04 2008-02-07 Fujifilm Manufacturing Europe B.V. Porous membranes and recording media comprising same
    ATE474022T1 (en) * 2006-08-04 2010-07-15 Fujifilm Mfg Europe Bv COMPOSITIONS FOR POROUS MEMBRANES AND RECORDING MEDIA
    ATE502691T1 (en) * 2006-08-04 2011-04-15 Fujifilm Mfg Europe Bv POROUS MEMBRANE AND METHOD FOR PRODUCING

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    Also Published As

    Publication number Publication date
    DE59700545D1 (en) 1999-11-18
    DE19623432C2 (en) 2003-05-22
    DE19623432A1 (en) 1997-12-18
    US6534123B1 (en) 2003-03-18
    GR3031831T3 (en) 2000-02-29
    DK0812697T3 (en) 2000-04-25
    ATE185518T1 (en) 1999-10-15
    ES2140164T3 (en) 2000-02-16
    EP0812697A1 (en) 1997-12-17
    JPH10114146A (en) 1998-05-06

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