EP0812697A1 - Recording material for ink-jet printing process - Google Patents

Recording material for ink-jet printing process Download PDF

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Publication number
EP0812697A1
EP0812697A1 EP97109444A EP97109444A EP0812697A1 EP 0812697 A1 EP0812697 A1 EP 0812697A1 EP 97109444 A EP97109444 A EP 97109444A EP 97109444 A EP97109444 A EP 97109444A EP 0812697 A1 EP0812697 A1 EP 0812697A1
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EP
European Patent Office
Prior art keywords
recording material
layer
ink
material according
receiving layer
Prior art date
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Granted
Application number
EP97109444A
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German (de)
French (fr)
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EP0812697B1 (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

  • 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 by means of downstream baffles, which are generated by the digital signals controlled, placed on the pad or distracted into a reservoir.
  • 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) for inkjet printing processes generally consists of a support and an ink-receiving layer and, if appropriate, further auxiliary layers.
  • a polyester resin, diacetate film 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. 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.
  • cationic substances are often used in the ink receiving layer to fix the ink dyes.
  • a recording material of the aforementioned type which is characterized in that at least one microporous membrane layer is arranged between the ink receiving layer and the carrier layer and / or on the outside of the ink receiving layer.
  • Such a membrane can preferably be of a medium size Capillary diameters 0.001 and 100 ⁇ m, or preferably between 0.01 and 10 ⁇ m, can be used to achieve a high gloss.
  • the color receiving layer can be either a mono-layer or a multi-layer. It can contain binders, color-fixing cationic compounds, pigments, fillers and other auxiliaries such as, for example, dispersing aids, curing agents, defoamers or pH regulators.
  • Water-soluble polymers such as gelatin, polyvinyl alcohol, polyacrylamide, sodium alginite, polyvinyl pyrrolidone, casein, starch or sodium polyacrylate can be used as binders.
  • binders are polymers which are soluble in organic solvents, such as polyvinyl butyral, polyvinyl chloride, polyvinyl acetate, polyacrylonitrile, polymethyl methacrylate, melamine resin, polyurethane and the like.
  • silica, talc, kaolin, CaCO 3 , Al silicate, Al 2 0 3 , zeolite or Ti0 2 can be used as pigments or fillers.
  • the various cationic dye-fixing compounds which can be used include, for example, quaternary ammonium polymers such as quaternary polyhydroxyammonium salt, quaternary polyammonium methacrylate salt or polydiallyldimethylammonium salt.
  • the ink receiving layer is applied from an aqueous dispersion (coating material) 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 quantity applied to the receiving layer is 0.1 to 20 g / m 2 , preferably between 1 to 14 g / m 2 .
  • the membrane layer is preferably formed from a dissolved polymer from the group consisting of polyether sulfones, polysulfones, cellulose acetate, polypropylene, polyamide, polyvinylidene fluoride, cellulose esters, polycarbonates, polytetrafluoroethylene, polyvinyl chloride or from acrylic polymers. For example, by inversion of phase or by evaporation of a solvent.
  • 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 is fixed (coagulation), e.g. B. by immersing the sol film in a precipitant.
  • coagulation e.g. B. by immersing the sol film in a precipitant.
  • suitable crosslinking agents such as aldehydes, polyamines, polyisocyanates, or by gamma radiation.
  • 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 that becomes that in this case the ink liquid can move quickly through the ink-receiving layer, even if it has the average pore diameter required for high gloss.
  • the ink liquid passes semi-permeably through the membrane layer after it has passed through the ink-receiving layer and is absorbed by the carrier layer. Since the membrane layer is permeable to the ink liquid only in the direction of the carrier layer, short flow times and thus drying times of the ink receiving layer can also be achieved here. A return of the ink liquid into 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.
  • a membrane layer can also be used as a color receiving layer.
  • the membrane layer can also be arranged as the uppermost layer on the ink receiving layer.
  • the membrane layer can form a transparent or opaque top layer and at the same time serves as a transport layer for the ink, while the color receiving layer serves as a fixing layer for the dye.
  • 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 a thickness of the ink receiving layer between 0.1 and 20 microns.
  • 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 test results are summarized in Tab. 1.
  • 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, 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 moved.
  • 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 Ti0 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.
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • a receiving layer according to Example 1 was applied in an amount of 10 g / m 2 .
  • 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 (thermal jet).
  • the density measurements were carried out using the "X RITE 428" densitometer. The measurements were carried out for the basic colors cyan, magenta, yellow and black with 100% saturation.
  • the gloss values were measured using the FA RL3 laboratory reflectometer. DR. LANGE according to DIN 67530 with a measuring angle of 60 °.
  • the drying behavior of the recording material is determined as follows: 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, bei dem eine Tinte benutzt wird, die aus einem Farbstoff und einer Tintenflüssigkeit besteht, wobei das Aufzeichnungsmaterial wenigstens folgende Schichten umfaßt:

  • eine Farbempfangsschicht, auf die der Tintenstrahl auftrifft und durch die die Tintenflüssigkeit unter Zurücklassung des Farbstoffes 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 ink jet printing process, using an ink consisting of a dye and an ink liquid, the recording material comprising at least the following layers:
  • an ink receiving layer on which the ink jet strikes and through which the ink liquid passes, leaving the dye, up to the layer boundary of the ink receiving layer,
  • and a support layer capable of absorbing excess ink liquid.

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.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 by means of downstream baffles, which are generated by the digital signals controlled, 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.These are partly contradictory claims, e.g. B. means that the wiping resistance is set too quickly that an ink drop does not diverge, or only slightly, and thereby the clarity of the resulting image is 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 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. 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 recording material (image-receiving material) for inkjet printing processes generally consists of a support and an ink-receiving layer and, if appropriate, further auxiliary layers. For example, a polyester resin, diacetate film 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. 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.

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 which have hydrophilic, water-soluble polymers (eg gelatin, polyvinyl alcohol) containing receiving layers have a high image resolution, the creation of a high gloss is a major problem with these papers. For a high gloss (> 70% at To reach 60 °) of the recording paper, the base paper is first extrusion-coated with water-soluble polymers such as polyethylene and then provided with a receiving layer. However, this results in poor drying times.

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 with respect to an ink-receiving layer is that the ink liquid flows through the ink-receiving layer viscously and therefore quickly. Such flow is orders of magnitude faster than diffusing flow and therefore leads to rapid drying of the ink liquid on the ink receiving layer. According to Hagen-Poiseuillean law, the amount of liquid per unit time that flows through a pore arrangement is proportional to the fourth power of the average diameter of the pores. Therefore, most of the flow of the liquid goes through large radius pores.

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 µm bei der Farbempfangsschicht erreicht ist, führt dies zu einem hochglänzenden Produkt.However, a pore diameter distribution with the mean shifted to larger pores results in a reduction in the desired gloss of the recording material. Only when an average pore size of the order of 0.1 to 1 µm is reached in the ink-receiving layer does this lead 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 specifying a recording material which at the same time has a high gloss and a high 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 und/oder auf der Außenseite der Farbempfangsschicht angeordnet ist.This object is achieved by a recording material of the aforementioned type, which is characterized in that at least one microporous membrane layer is arranged between the ink receiving layer and the carrier layer and / or on the outside of the ink receiving layer.

Eine solche Membran kann vorzugsweise mit einem mittleren Kapillardurchmesser 0,001 und l00 µm, bzw. vorzugsweise zwischen 0,01 und l0µm verwendet werden, um einen hohen Glanz zu erzielen.Such a membrane can preferably be of a medium size Capillary diameters 0.001 and 100 µm, or preferably between 0.01 and 10 µm, can be used to achieve a high gloss.

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 be either a mono-layer or a multi-layer. It can contain binders, color-fixing cationic compounds, pigments, fillers and other auxiliaries such as, for example, dispersing aids, curing 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. Als Pigmente bzw. Füllstoffe kann beispielsweise Kieselsäure, Talcum, Kaolin, CaCO3, Al-Silikat, Al203, Zeolith oder Ti02 verwendet werden.Water-soluble polymers such as gelatin, polyvinyl alcohol, polyacrylamide, sodium alginite, polyvinyl pyrrolidone, casein, starch or sodium polyacrylate can be used as binders. Also suitable as binders are polymers which are soluble in organic solvents, such as polyvinyl butyral, polyvinyl chloride, polyvinyl acetate, polyacrylonitrile, polymethyl methacrylate, melamine resin, polyurethane and the like. For example, silica, talc, kaolin, CaCO 3 , Al silicate, Al 2 0 3 , zeolite or 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.The various cationic dye-fixing compounds which can be used 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. 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. Die Auftragsmenge der Empfangsschicht beträgt 0,1 bis 20 g/m2, vorzugsweise zwischen l bis 14 g/m2.The ink receiving layer is applied from an aqueous dispersion (coating material) 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 quantity applied to 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 dar 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, for example, from a casting solution a hydrophobic or hydrophilic polymer can be formed 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, CelluloseEstern, Polycarbonate, Polytetrafluorethylen, Polyvinylchlorid oder aus Acryl-Polymeren gebildet. Beispielsweise wird durch Phaseninversion oder durch Abdampfen eines Lösungsmittels hergestellt.The membrane layer is preferably formed from a dissolved polymer from the group consisting of polyether sulfones, polysulfones, cellulose acetate, polypropylene, polyamide, polyvinylidene fluoride, cellulose esters, polycarbonates, polytetrafluoroethylene, polyvinyl chloride or from acrylic polymers. For example, by inversion of phase or by evaporation of a solvent.

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 evaporates completely, the structure of the membrane is fixed (coagulation), e.g. B. by immersing the sol film in a precipitant. This process can be improved by suitable crosslinking agents, such as aldehydes, polyamines, polyisocyanates, or by gamma radiation.

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 that becomes that in this case the ink liquid can move quickly through the ink-receiving layer, even if it has the average pore diameter required for high gloss. The ink liquid passes semi-permeably through the membrane layer after it has passed through the ink-receiving layer and is absorbed by the carrier layer. Since the membrane layer is permeable to the ink liquid only in the direction of the carrier layer, short flow times and thus drying times of the ink receiving layer can also be achieved here. A return of the ink liquid into 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 Anticurl- und/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. By appropriately modifying the membrane surface, in particular by hydrophilizing the membrane surface, high resolution and good color gradation can be achieved.

In einer weiteren Ausgestaltung der Erfindung kann die Membranschicht auch als oberste Schicht auf der Farbempfangsschicht angeordnet sein. Die Membranschicht kann eine transparente oder opake Oberschicht bilden und dient gleichzeitig als Transportschicht für die Tinte, während die Farbempfangsschicht als Fixierschicht für den Farbstoff dient. Die Dicke der Membranschicht beträgt 0,1 bis 75 µm, insbesondere 0,5 - 50 µm, vorzugsweise jedoch 0,5 bis 5 µm, bei einer Dicke der Farbempfangsschicht zwischen 0,1 und 20 µm.In a further embodiment of the invention, the membrane layer can also be arranged as the uppermost layer on the ink receiving layer. The membrane layer can form a transparent or opaque top layer and at the same time serves as a transport layer for the ink, while the color receiving layer serves as a fixing layer for the dye. 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 a thickness of the ink receiving layer between 0.1 and 20 microns.

Ausführungsbeispiele der Erfindung sind in den folgenden Beispielen erläutert:Exemplary embodiments of the invention are explained in the following examples:

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 sog. "Thermal-Jet"-Verfahren bedruckt und anschließend analysiert. Die Prüfergebnisse sind in Tab. 1 zusammengestellt.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 test results are summarized in Tab. 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 Härtungsmittel-Kombination 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, 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 moved. 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 l20 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 (l0 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 Ti0 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 polyethylen) in einer Auftragsmenge von 20 g/m2 und die Rückseite mit einer Mischung aus LDPE und HDPE (high density polyethylen) 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. On the polyethylene-coated paper, a receiving layer according to Example 1 was applied in an amount of 10 g / m 2 . The recording material obtained was printed as in Example 1 and analyzed for its properties.

Prüfung des gemäß den Beispielen und Vergleichsbeispielen erhaltenen Aufzeichnungsmaterials:Testing 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, Trocknungszeit, Glanz und sog. "Bleed" untersucht.In the print images obtained, color density, drying time, gloss and so-called "bleed" were examined.

Die Densitätsmessungen wurden mit Hilfe des Densitometer "X RITE 428" durchgeführt. Die Messungen erfolgten für die Grundfarben Cyan, Magenta, Gelb und Schwarz bei l00 % Sättigung.The density measurements were carried out using the "X RITE 428" densitometer. The measurements were carried out 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 using the FA RL3 laboratory reflectometer. DR. LANGE according to DIN 67530 with a measuring angle of 60 °.

Das Trocknungsverhalten des Aufzeichnungsmaterials wird folgendermaßen ermittelt:
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. Tabelle 1 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 The drying behavior of the recording material is determined as follows:
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. Table 1 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)

Aufzeichnungsmaterial für das Tintenstrahl-Druckverfahren, enthaltend eine Farbempfangsschicht und eine Trägerschicht, dadurch gekennzeichnet, daß wenigstens eine mikroporöse Membranschicht zwischen der Farbempfangsschicht und der Trägerschicht und/oder auf der Außenseite der Farbempfangsschicht angeordnet ist.Recording material for the inkjet printing process, comprising an ink receiving layer and a carrier layer, characterized in that at least one microporous membrane layer is arranged between the ink receiving layer and the carrier layer and / or on the outside of the ink receiving layer. Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, daß die Porengröße der Membranschicht zwischen 0,0l und 10 µm liegt.Recording material according to claim 1, characterized in that the pore size of the membrane layer is between 0.01 and 10 µm. Aufzeichnungsmaterial nach Anspruch 1 und 2, dadurch gekennzeichnet, daß die Dicke der Membranschicht zwischen 0,1 und 75 µm, vorzugsweise zwischen 0,5 und 50 µm, liegt.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. Aufzeichnungsmaterial nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß die Membranschicht aus einer Gießlösung eines hydrophoben oder hydrophilen Polymers gebildet ist.Recording material according to claims 1 to 3, characterized in that the membrane layer is formed from a casting solution of a hydrophobic or hydrophilic polymer. Aufzeichnungsmaterial nach Anspruch 4, dadurch gekennzeichnet, daß die Membranschicht aus einem Polymer aus der Gruppe der Polyethersulfone, Polysulfone, Celluloseacetat, Polypropylen, Polyamid, Polyvinylidenfluorid, Cellulose-Estern, Polycarbonate, Polytetrafluorethylen, Polyvinylchlorid oder aus Acryl-Polymeren besteht.Recording material according to claim 4, characterized in that the membrane layer consists of a polymer from the group of the polyether sulfones, polysulfones, cellulose acetate, polypropylene, polyamide, polyvinylidene fluoride, cellulose esters, polycarbonates, polytetrafluoroethylene, polyvinyl chloride or acrylic polymers. Aufzeichnungsmaterial nach einem der vohergehenden Ansprüche, dadurch gekennzeichnet, daß ein Lösungsmittel für die Membranschicht aus der Gruppe N-methylpyrrolidon, DimethylFormamid, Dimethyl-Acetamid, Chloroform, Butanol, DimethylSulfoxid, Propylen-Carbonat, Tetrahydrofuran gewählt ist.Recording material according to one of the preceding claims, characterized in that a solvent for the membrane layer is selected from the group consisting of N-methylpyrrolidone, dimethylformamide, dimethyl acetamide, chloroform, butanol, dimethyl sulfoxide, propylene carbonate and tetrahydrofuran. Aufzeichnungsmaterial nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß als Bindemittel für die Farbempfangsschicht wasserlösliche Polymere, wie Gelatine, Polyvinylalkohol, Polyacrylamid, Natriumalginit, Polyvinylpyrrolidon, Kasein, Stärke oder Natrium-Polyacrylat verwendet sind.Recording material according to one of the preceding claims, characterized in that water-soluble polymers such as gelatin, polyvinyl alcohol, polyacrylamide, sodium alginite, polyvinyl pyrrolidone, casein, starch or sodium polyacrylate are used as binders for the ink-receiving layer. Aufzeichnungsmaterial nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß als Bindemittel für die Farbempfangsschicht in organischen Lösungsmitteln lösliche Polymere, wie Polyvinylbutyral, Polyvinylchlorid, Polyvinylacetat, Polyacrylnitril, Polymethylmethacrylat, Melaminharz oder Polyurethan verwendet sind.Recording material according to one of the preceding claims, characterized in that polymers which are 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 ink-receiving layer. Aufzeichnungsmaterial nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Membranschicht einen Füllstoff und/oder ein Pigment enthält.Recording material according to one of the preceding claims, characterized in that the membrane layer contains a filler and / or a pigment. Aufzeichnungsmaterial nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß an die Stelle einer Farbempfangsschicht eine Membranschicht tritt.Recording material according to one of the preceding claims, characterized in that a membrane layer takes the place of a color receiving layer. Verfahren zur Herstellung eines Aufzeichnungsmaterials für das Tintenstrahl-Druckverfahren, gekennzeichnet durch: - Auftragen einer Membranmatrix aus einer Lösung eines hydrophilen und/oder hydrophoben Polymers in einem geeigneten Lösungsmittel auf eine Trägerschicht, - Behandlung der Membranmatrix mit einem geeigneten Koagulationsmittel und Umwandlung der Matrix in einen im wesentlichen nicht-gequollenen Zustand, - Auftragen einer Farbempfangsschicht aus einer wäßrigen, ein hydrophiles und/oder hydrophobes Bindemittel, farbfixierendes Mittel und gegebenenfalls andere Hilfsstoffe enthaltenden Lösung. Process for producing a recording material for the inkjet printing process, characterized by: Applying a membrane matrix from a solution of a hydrophilic and / or hydrophobic polymer in a suitable solvent to a support layer, Treatment of the membrane matrix with a suitable coagulant and transformation of the matrix into an essentially non-swollen state, - Application of a color receiving layer from an aqueous solution containing a hydrophilic and / or hydrophobic binder, color-fixing agent and optionally other auxiliaries.
EP97109444A 1996-06-12 1997-06-11 Recording material for ink-jet printing process Expired - Lifetime EP0812697B1 (en)

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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

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

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EP (1) EP0812697B1 (en)
JP (1) JPH10114146A (en)
AT (1) ATE185518T1 (en)
DE (2) DE19623432C2 (en)
DK (1) DK0812697T3 (en)
ES (1) ES2140164T3 (en)
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1020300A1 (en) * 1999-01-13 2000-07-19 Azon Corporation Ink jet media prepared from water-based formulation
WO2000061375A1 (en) * 1999-04-09 2000-10-19 Alliedsignal Inc. Photographic quality inkjet printable coatings
WO2002007984A2 (en) * 2000-07-21 2002-01-31 Skc America, Inc. Microporous ink jet recording material
WO2007018421A1 (en) * 2005-08-05 2007-02-15 Fujifilm Manufacturing Europe B.V. Porous membrane and recording medium comprising same
WO2007018422A1 (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
WO2007018425A1 (en) * 2005-08-05 2007-02-15 Fujifilm Manufacturing Europe B.V. Porous membrane and recording medium comprising same
US7910520B2 (en) 2005-08-05 2011-03-22 Fujifilm Manufacturing Europe B.V. Porous membrane and recording medium comprising same
US8093180B2 (en) 2005-08-05 2012-01-10 Fujifilm Manufacturing Europe B.V. Porous membrane and recording medium, as well as process for preparing same

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6135277A (en) * 1984-07-27 1986-02-19 Canon Inc Recording material
JPS6135278A (en) * 1984-07-27 1986-02-19 Canon Inc Recording material
EP0409440A1 (en) * 1989-07-21 1991-01-23 Imperial Chemical Industries Plc Inkable sheet
JPH07156536A (en) * 1993-12-07 1995-06-20 Dainippon Printing Co Ltd Image receiving sheet and recording method thereof
EP0685344A2 (en) * 1994-05-19 1995-12-06 Mitsubishi Paper Mills, Ltd. Ink jet recording sheet and process for its production

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3920875A (en) * 1969-07-11 1975-11-18 Tosho Suzuki Coated polymeric paper films and a method of producing the same
US4542059A (en) * 1982-08-23 1985-09-17 Canon Kabushiki Kaisha Recording medium
US4642247A (en) * 1984-06-29 1987-02-10 Canon Kabushiki Kaisha Recording medium
JP2683019B2 (en) * 1987-04-10 1997-11-26 キヤノン株式会社 Recording material and method for producing printed matter using the same
US5108607A (en) * 1987-05-20 1992-04-28 Gelman Sciences, Inc. Filtration membranes and method of making the same
US4894157A (en) * 1987-10-05 1990-01-16 Micron Separations, Inc. Process for producing supported celluosic membranes and products
JP2513902B2 (en) * 1989-06-02 1996-07-10 東レ株式会社 Surface porous film
EP0524626B1 (en) * 1991-07-26 1996-12-11 Asahi Glass Company Ltd. Recording sheet for an ink jet printer
DE59204608D1 (en) * 1992-06-20 1996-01-18 Celfa Ag Record carrier for the inclusion of coloring substances.
WO1995002447A1 (en) * 1993-07-16 1995-01-26 E.I. Du Pont De Nemours And Company Asymmetric membranes of polytetrafluoroethylene and their preparation
AU7157396A (en) * 1995-10-26 1997-05-15 Minnesota Mining And Manufacturing Company Ink-jet recording sheet
US5605750A (en) * 1995-12-29 1997-02-25 Eastman Kodak Company Microporous ink-jet recording elements
US5759639A (en) 1997-01-28 1998-06-02 Osmonics, Inc. Method of fabricating a membrane coated paper

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6135277A (en) * 1984-07-27 1986-02-19 Canon Inc Recording material
JPS6135278A (en) * 1984-07-27 1986-02-19 Canon Inc Recording material
EP0409440A1 (en) * 1989-07-21 1991-01-23 Imperial Chemical Industries Plc Inkable sheet
JPH07156536A (en) * 1993-12-07 1995-06-20 Dainippon Printing Co Ltd Image receiving sheet and recording method thereof
EP0685344A2 (en) * 1994-05-19 1995-12-06 Mitsubishi Paper Mills, Ltd. Ink jet recording sheet and process for its production

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 10, no. 191 (M - 495) 4 July 1986 (1986-07-04) *
PATENT ABSTRACTS OF JAPAN vol. 95, no. 9 31 October 1995 (1995-10-31) *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1020300A1 (en) * 1999-01-13 2000-07-19 Azon Corporation Ink jet media prepared from water-based formulation
WO2000061375A1 (en) * 1999-04-09 2000-10-19 Alliedsignal Inc. Photographic quality inkjet printable coatings
US6225381B1 (en) 1999-04-09 2001-05-01 Alliedsignal Inc. Photographic quality inkjet printable coating
US6534155B1 (en) 1999-04-09 2003-03-18 Honeywell International Inc. Photographic quality inkjet printable coatings
WO2002007984A2 (en) * 2000-07-21 2002-01-31 Skc America, Inc. Microporous ink jet recording material
WO2002007984A3 (en) * 2000-07-21 2002-05-23 Skc America Inc Microporous ink jet recording material
WO2007018421A1 (en) * 2005-08-05 2007-02-15 Fujifilm Manufacturing Europe B.V. Porous membrane and recording medium comprising same
WO2007018422A1 (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
WO2007018425A1 (en) * 2005-08-05 2007-02-15 Fujifilm Manufacturing Europe B.V. Porous membrane and recording medium comprising same
US7704573B2 (en) 2005-08-05 2010-04-27 Fujifilm Manufacturing Europe B.V. Porous membrane and recording medium comprising same
US7910520B2 (en) 2005-08-05 2011-03-22 Fujifilm Manufacturing Europe B.V. Porous membrane and recording medium comprising same
US8093180B2 (en) 2005-08-05 2012-01-10 Fujifilm Manufacturing Europe B.V. Porous membrane and recording medium, as well as process for preparing same

Also Published As

Publication number Publication date
DE59700545D1 (en) 1999-11-18
DE19623432C2 (en) 2003-05-22
DE19623432A1 (en) 1997-12-18
EP0812697B1 (en) 1999-10-13
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
JPH10114146A (en) 1998-05-06

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