EP1370421B1 - Sheeny ink jet printing material - Google Patents

Sheeny ink jet printing material Download PDF

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Publication number
EP1370421B1
EP1370421B1 EP02727392A EP02727392A EP1370421B1 EP 1370421 B1 EP1370421 B1 EP 1370421B1 EP 02727392 A EP02727392 A EP 02727392A EP 02727392 A EP02727392 A EP 02727392A EP 1370421 B1 EP1370421 B1 EP 1370421B1
Authority
EP
European Patent Office
Prior art keywords
recording material
coating
ink
meth
cationic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02727392A
Other languages
German (de)
French (fr)
Other versions
EP1370421A1 (en
Inventor
Ulrich Heckes
André Becker
Kirsten Barth
Hans-Joachim Zorn
Olaf Friederichs
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M Real Zanders GmbH
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M Real Zanders GmbH
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Publication of EP1370421A1 publication Critical patent/EP1370421A1/en
Application granted granted Critical
Publication of EP1370421B1 publication Critical patent/EP1370421B1/en
Anticipated expiration legal-status Critical
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/506—Intermediate layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/508—Supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2942—Plural coatings
    • Y10T428/2949—Glass, ceramic or metal oxide in coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y10T428/31768—Natural source-type polyamide [e.g., casein, gelatin, etc.]
    • Y10T428/31772—Next to cellulosic
    • Y10T428/31775—Paper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

  • the present invention relates to a satin-glossy ink recording material, and a process for the production thereof, and the use of the ink jet recording ink jet recording material of the present invention, and a printed ink jet recording material.
  • the ink jet recording material should have certain surface properties depending on the desired use, and these should be achieved without adversely affecting the above-mentioned ink jet recording properties.
  • the common method for surface treatment is z. B. calendering, whereby the surface is smoothed and the coating layer is solidified.
  • DE-A 31 51 471 describes a process for producing an ink jet recording material in which a plurality of coating layers of an inorganic pigment and an aqueous binder composition is applied to a substrate and then the coating color is dried.
  • the thus prepared and dried recording material of a further surface treatment either in a gloss calender or a supercalender.
  • the recording material is exposed at a relatively high pressure of 200 N / mm and a temperature of about 70 ° C, whereas in the gloss calender, the pressure is 90 N / mm and the temperature is about 150 ° C.
  • DE-A 31 51 471 contains no Information on the gloss or surface smoothness of the thus prepared ink jet recording material.
  • US-A-4,770,934 relates to an ink jet recording material in which an ink recording layer containing a pigment such as e.g. B. a synthetic silica having a specific surface area of at least 100 m 2 / g and a binder is applied, and this surface layer is then formed in a cast-iron method.
  • a pigment such as e.g. B. a synthetic silica having a specific surface area of at least 100 m 2 / g and a binder
  • two different casting process namely the direct method (wet process), in which directly after the application of the coating color, the wet ink is dried by contact with a heated polished metal cylinder, in particular with chrome surface, under pressure.
  • the rewet process may be used, in which the coating is first dried and then, before being brought into contact with the hot polished metal cylinder and pressure, the already dried coating color layer is moistened again. Both procedures usually lead to a very high surface gloss. Due to the coating compositions used in US Pat. No
  • EP-A-0 732 219 a two-layer ink recording material is known.
  • an ink recording layer containing a pigment and a binder, and thereon a surface layer comprising cationic ultrafine particles having a particle diameter in the range of 1 nm to 500 nm.
  • the surface layer in this case has a gloss of at least 45% at a viewing angle of 75 °.
  • the recording material described in EP-A 0 732 219 already has these gloss values without any special surface treatment. The gloss can still be improved by a cast-iron process.
  • the above-mentioned direct and indirect methods and the gel method are mentioned.
  • the wet bar by passing the coated substrate through a coagulation or gelation bath and then brought into contact with the heated cylinder.
  • the ink recording material described in EP-A-0 732 219 has excellent ink-jet recording properties, it is only suitable for applications where high gloss is desired due to the inherent high gloss even when no cast-coat method is used.
  • EP 0 879 709 B1 describes another cast coating process for producing a glossy ink jet recording sheet.
  • To achieve a glossy surface it is necessary to use very fine silica particles.
  • It is essential that the coating layer after application to the substrate sheet and before drying on the highly polished surface of the metal cylinder has a very high water content.
  • the water content of the coating layer falls below a critical value, the mirror-finished surface of the metal cylinder can not be transferred to the ink-jet recording material. This results in surface defects that are inhomogeneously distributed throughout the paper and that cause inhomogeneously low gloss and smoothness values.
  • DE-A 2 310 891 describes a further process for the surface treatment of a paper.
  • This document deals with the problem, very smooth high gloss coatings that are comparable with those known from the cast coating processes described above.
  • an aqueous composition of a binder which is substantially free of pigments, is applied to form a surface layer.
  • the wet coating is passed through a heating zone and brought to a temperature which is above the film-forming temperature of the binder, so that a polymer film is formed.
  • the substrate is then brought into contact with a heated, polished roller.
  • DE-A 2 310 891 relates to the application of a protective plastic coating on already printed substrates. That is, the plastic coating should just have no porosity and is thus completely unsuitable for inkjet printing.
  • Another object of the present invention is to provide a method; with which an ink recording material having the above-mentioned requirements can be produced.
  • an ink recording material containing a substrate having at least on one side of the substrate an ink receiving layer containing a pigment and a binder and thereon a surface layer, the surface layer containing cationic inorganic particles, a binder and a release agent and the surface layer has a gloss value in the Range from 5 to 35 measured according to DIN 54502 R '(75 °) (measuring angle 75 °) and a surface smoothness according to the Parker Print Surf method (PPS) according to DIN ISO 8791-4 of less than 2.5 ⁇ m.
  • PPS Parker Print Surf method
  • the substrate coated with the coating color is not contacted with a heated metal cylinder either directly in the wet state, nor is the substrate coated with the coating color dried and then remoistened before it is brought into contact with the metal cylinder.
  • no gel method is performed in which the wet coating is coagulated or gelled before contacting the metal cylinder.
  • an aqueous Wiederweuchtungssch added, which in particular also contains a release agent to prevent adhesion of the coated substrate web to the metal cylinder during the molding and drying process.
  • the method of the present invention achieves significantly lower gloss values in comparison with the classical cast-coat method, without substantially reducing the smoothness of the recording material.
  • Another procedural advantage of the present invention is that the method can be carried out on existing cast coating equipment, and the reduced gloss is produced by the novel procedure without z.
  • the key advantage of the method of the invention is that it provides a satin-matt ink recording material having excellent ink receptivity properties.
  • the partial drying of the recording material in step c) of the method according to the invention is carried out such that the recording material has a residual moisture content of 14 to less than 20 wt .-%, preferably 16 to less than 20 wt .-% and particularly preferably 16 to 18 Wt .-% water, based on the total weight of the recording material is dried.
  • This can be z. B. by hot air drying at 30 ° C to 80 ° C, preferably at 40 ° C to 60 ° C for 3 to 60 seconds, preferably 10 to 30 seconds.
  • an infrared drying with comparable drying performance can be used.
  • the recording material is pressed against the heated cylinder with a nip roll having a line pressure of 400 to 800 N / cm, preferably 500 to 750 N / cm.
  • the surface temperature of the cylinder is preferably 90 ° C to 120 ° C, more preferably 100 ° C to 115 ° C.
  • the metal cylinder may be any cylinder commonly used in the casting process, in particular a cylinder with a polished chrome surface.
  • an aqueous coating composition for forming the ink-receiving layer is applied to at least one side of a planar substrate.
  • the aqueous coating composition for forming the ink-receiving layer, and thus the ink-receiving layer itself contains a pigment and a binder.
  • pigments suitable for the ink-receiving layer include inorganic pigments such as e.g. For example, silica, alumina, alumina hydrate, aluminum silicate, magnesium silicate, magnesium carbonate, talc, clay, hydrotalcite, calcium carbonate, titanium dioxide and zinc oxide as well as plastic pigments such as polyethylene, polystyrene and polyacrylate. These pigments can be used either singly or in combination. Particularly preferred are pigments, selected from silicic acid, alumina, alumina hydrate and magnesium carbonate. The particle size of these pigments can be in the range between 0.1 to 20 microns.
  • binders are water-soluble resins such.
  • latices acrylic polymers such.
  • polymers of acrylic acid esters or methacrylic acid esters and copolymers of these monomers with other monomers latices of carboxyl-modified conjugated diene copolymers and latexes of vinyl copolymers such.
  • B. ethylene vinyl acetate copolymers are used.
  • These binders can be used either singly or in combination.
  • the ratio of binder to pigment in the ink-receiving layer is preferably 2: 1 to 1:10, more preferably 1: 1 to 1: 5.
  • the aqueous coating composition for forming the ink-receiving layer, and thus the ink-receiving layer itself, may also contain additional components such as e.g. Crosslinking agents such as melamine resins, glyoxal and isocyanates, surfactants, antifoaming agents, antioxidants, optical brighteners, UV absorbers, viscosity adjusting agents for pH adjustment, etc.
  • Crosslinking agents such as melamine resins, glyoxal and isocyanates, surfactants, antifoaming agents, antioxidants, optical brighteners, UV absorbers, viscosity adjusting agents for pH adjustment, etc.
  • the ink-receiving layer can be applied either as a single layer or as a multi-layer, wherein the individual layers can be both identical and different.
  • the ink receiving layer preferably has a basis weight of 5 - 20 g / m 2 based on dry weight.
  • the recording material it is preferable to dry the recording material after applying the ink receiving layer and before applying the surface layer.
  • wet-on-wet application of the surface layer to a non or partially dried ink receptive layer is also possible.
  • a commercially available substrate having a pre-coat satisfying the above-defined criteria for the ink receiving layer may also be used as the starting material for applying the surface layer.
  • the surface layer is also applied to the already applied ink receiving layer with an aqueous coating.
  • the aqueous coating composition for forming the surface layer comprises cationic inorganic particles, a binder and a release agent.
  • the cationic particles for the surface layer are selected from alumina, alumina hydrate or silicic acid whose surface has been cationized.
  • alumina ⁇ -, ⁇ -, ⁇ - and ⁇ -alumina can be used.
  • Suitable alumina hydrates are gibbsite, bayerite, northeast rimite, crystalline boehmite, diaspore and pseudoboehmite.
  • cationic silicas include silicas exposed to a surface treatment with a compound containing cationic metal oxides or metal atoms, or silicas exposed to a surface treatment with an organic compound containing both amino groups or quaternary ammonium groups and functional groups containing the silanol groups on the surface with the silica react like As aminoethoxysilane or Aminoalkylglycidilether included.
  • the cationic particles have an average particle diameter in the range from 1 to 1000 nm, preferably 10 to 500 nm.
  • the ink jet recording material has at least a two-layer coating, wherein the surface layer is to provide the desired surface properties and the combination of surface layer and ink receiving layer should provide the desired ink absorption properties.
  • the ink recording material has a high ink receiving capacity as well as a high recording speed.
  • the color pigments of the inks are preferably fixed in the surface or near the surface to provide high color density and color brilliance.
  • the liquid and volatile carrier fluid of the ink is absorbed as quickly as possible from the ink recording material and separated from the ink dyes, so that no bleeding takes place and sharp contours are always generated in the printed image. In order to achieve this, especially the cationic particles in the surface layer are important.
  • the cationic particles in the surface layer create sufficient porosity of the surface layer that allows rapid ink pickup. Due to the cationic character of the particles, the ink dyes, which are often anionic, are at least partially fixed directly in the surface layer while the carrier fluid of the ink is rapidly transported into the ink receiving layer below the surface layer. Thus, it is ensured that already a substantial part of the ink dyes in the the uppermost layer of the recording material is fixed, even if a part of the ink dyes is held in the underlying ink-receiving layer. In any case, it is ensured that the ink dyes are fixed near the surface. Furthermore, the inventive structure of the ink recording material allows a very fast removal of the fluid carrier of the ink, whereby very high ink absorption rates and short drying times can be achieved.
  • the cationic particles have an average particle diameter in the range of 1 to 1000 nm, preferably 10 to 500 nm.
  • optimum ink recording properties as well as surface properties can be achieved.
  • a particular advantage of these preferred particle sizes is that the transparency of the surface layer can be increased so that the ink jet image has excellent color brilliance.
  • binder for the surface layer the same binders as described above in connection with the ink receiving layer come into consideration.
  • a particularly preferred binder is polyurethanes.
  • the ratio of cationic inorganic particles to binder in the surface layer is preferably within a range of 50: 1 to 1: 2.
  • finely divided organic resins may still be present in the surface layer. This increases the porosity of the surface layer.
  • the particles of the organic resins preferably have a diameter in the range of 0.05 ⁇ m to 2 ⁇ m.
  • Examples of fine particles of organic resins include latices of acrylic polymers such as e.g. B. polymers of acrylic esters or methacrylic esters and copolymers of these monomers with other monomers, latexes of carboxyl-modified conjugated diene polymers, latexes of vinylic copolymers such as.
  • Example ethylene vinyl acetate copolymers, finely divided polyvinyl chloride, finely divided polyethylene, finely divided copolymers of vinyl pyrrolidone and styrene and finely divided copolymers of vinyl alcohol and styrene.
  • Another essential component of the surface layer is a release agent to ensure that in the execution of the method according to the invention during the contacting of the partially dried recording material with the heated metal cylinder, the stroke is uniformly and completely formed without the line peels off and / or on the Metal cylinder adheres.
  • Suitable release agents are oleic acid, rapeseed oil, metal stearates, ammonium stearates, polyethylenes, ethoxylated polyethylenes, waxes, metal and ammonium salts of aliphatic acids, ketene dimers, fatty acid surfactants, sulfonated and sulfated oils, fatty acid triglycerides and fatty acid amides, with oleic acid and rapeseed oil being particularly preferred are.
  • the release agents can be used alone or in combination.
  • the total amount of release agent in the aqueous coating composition for forming the surface layer is preferably 1-10% by weight, based on the total mass of the solids in the coating composition.
  • either the aqueous coating composition for forming the ink-receiving layer or the aqueous coating composition for forming the surface layer or both coating compositions contains a cationic compound which is not a pigment. It is particularly advantageous if at least the surface layer contains such a cationic compound in order to improve the fixation of the usually anionic color pigments of the ink in the surface layer and thus to improve the wet strength of the inkjet printing.
  • Suitable cationic compounds are: polyallylamine and its quaternary ammonium salts, polyamine sulfone and its quaternary ammonium salts, polyvinylamine and its quaternary ammonium salts, chitosan and its acetates, polymers of monomers selected from the group consisting of dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) - acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylaminostyrene, copolymers of vinylpyrrolidone with a quaternary salt of an aminoalkyl (meth) acrylate and a copolymer of (meth) acrylamide with a quaternary salt of aminomethyl (meth) acrylamide.
  • the pH of the coating color in the acidic range.
  • the pH is preferably in the range of 2.5 to 5.0.
  • paper can be used inter alia. It is preferred if the substrate itself is porous, that is, has a liquid receptivity, provides the desired dimensional stability for the recording material, and exhibits sufficiently good adhesion to the receptive layer. Therefore, paper is particularly preferable as a substrate.
  • the basis weight of the paper substrate is preferably 40 to 300 g / m 2 .
  • the ink recording material of the present invention which can be prepared by the method of the present invention has a surface which has a gloss value in the range of 5% to 35% measured to DIN 54502 R '(75 °) (75 ° measurement angle) and Parker surface smoothness -Print surf method (PPS) according to DIN ISO 8791-4 of less than 2.5 microns.
  • the gloss value is 5 to less than 30%, in particular 10% to less than 30%, very particularly preferably 12% to 25% and the surface smoothness is less than 2.2 ⁇ m. Consequently
  • a satin-matt ink recording material having excellent ink-receiving properties and high smoothness is provided.
  • a particular advantage of the ink recording material according to the invention lies in the extremely short drying time close to zero of the applied ink jet printing image.
  • a coating color according to the composition shown in Table 1 with a solids content of 27 wt .-% was applied by means of an inking roll on the pre-coated paper web at a web speed of 30 m / min. With an air brush, excess coating color was removed so that a quantity of 11 g / m 2 (in the dried state) remains on the paper web.
  • the coated paper web When passing through a hot air drying at 50 ° C for 20 seconds, the coated paper web is dried to a residual moisture of 16 wt .-% water, based on the total weight of the paper web, and immediately then into the nip, consisting of an elastic pressure roller and a highly polished Chrome cylinder is formed, without rewetting led.
  • the line pressure of the roll / chrome cylinder pair was 625 N / cm and the temperature of the chrome cylinder surface was 110 ° C.
  • the ink jet recording material showed excellent printability in ink jet printing and had a surface gloss of 19% at 75 ° viewing angle, measured according to DIN 54502.

Landscapes

  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)
  • Soft Magnetic Materials (AREA)
  • Glass Compositions (AREA)
  • Particle Formation And Scattering Control In Inkjet Printers (AREA)

Abstract

The invention relates to a method for producing an ink jet printing material involving: a) the application of an aqueous coating slip containing a pigment and a binding agent to at least one surface of a substrate in order to form at least one ink jet receiving layer; b) the application of an aqueous coating slip containing cationic inorganic particles, a binding agent and a release agent onto the ink jet receiving layer(s) in order to form a surface layer; c) the partial drying of the printing material to a total wetness of 14 to less than 20 wt. % water with regard to the total weight of the printing material, and d); bringing the partially dried printing material into contact with a heated metal cylinder without rewetting the line. This results in obtaining an ink jet printing material containing a substrate, an ink jet receiving layer, which is located on at least one side of the substrate and which contains a pigment and a binding agent, and a surface layer situated thereon, whereby the surface layer contains cationic, inorganic particles, a binding agent, and a release agent, and the surface layer has a degree of gloss ranging from 5 to 35 when measured in accordance with DIN 54502 R'(75 DEG ) (angle of measurement 75 DEG ) and a surface smoothness of less than 2.5 mu m according to the Parker-Print-Surf (PPS) and in accordance with DIN-ISO 8791-4.

Description

Die vorliegende Erfindung betrifft ein seidenglänzendes Tintenaufzeichnungsmaterial sowie ein Verfahren zu dessen Herstellung und die Verwendung des erfindungsgemäßen Tintenstrahlaufzeichnungsmaterials für den Tintenstrahldruck sowie ein bedrucktes Tintenstrahlaufzeichnungsmaterial.The present invention relates to a satin-glossy ink recording material, and a process for the production thereof, and the use of the ink jet recording ink jet recording material of the present invention, and a printed ink jet recording material.

Aufgrund der zahlreichen guten Eigenschaften wie der Möglichkeit, mit hoher Geschwindigkeit zu drucken, des niedrigen Geräuschpegels während des Druckvorgangs, der großen Vielfalt der aufgezeichneten Muster, der Einfachheit beim Mehrfarbendruck, die hohe Qualität des Druckbildes, die sogar mit fotographischen Verfahren konkurrieren kann und dergleichen hat der Tintenstrahldruck in den vergangenen Jahren auf verschiedenen Gebieten eine wichtige Stellung eingenommen. Dementsprechend wurde in den vergangenen Jahren starke Anstrengungen unternommen, um Aufzeichnungsmaterialien für den Tintenstrahldruck mit verbesserten Eigenschaften zur Verfügung zu stellen. Dies spiegelt sich in einer nahezu unüberschaubaren Menge an Veröffentlichungen über Tintenstrahlaufzeichnungsmaterial in der Fach- und Patentliteratur wieder. Im folgenden sollen einige wichtige Eigenschaften für Tintenstrahlaufzeichnungsmaterialien zusammengefasst werden:

  • 1. Hohe Tintenaufnahmekapazität
  • 2. Schnelles Trocknen des aufgebrachten Tintenstrahlbildes
  • 3. Hohe optische Dichte der aufgebrachten Tintentropfen
  • 4. Klare Abgegrenztheit der aufgebrachten Tintenstrahltropfen
  • 5. Gleichmäßigkeit der Farbstärke und Farbdichte des aufgebrachten Tintenstrahldrucks
  • 6. Kein Ausbluten des aufgebrachten Tintenstrahlbildes
  • 7. Gute Wasser- und Feuchtigkeitsfestigkeit und Lichtechtheit des aufgebrachten Tintenstrahlbildes und
  • 8. Dimensionsstabilität des Aufzeichnungsmaterials nach dem Bedrucken, insbesondere Vermeiden des Auftretens von Wellen oder anderen Dimensionsänderungen.
Because of the many good features such as the ability to print at high speed, the low noise level during printing, the wide variety of recorded patterns, the ease of multi-color printing, the high quality of the printed image, which can even compete with photographic processes and the like In recent years, inkjet printing has occupied an important position in various fields. Accordingly, in recent years, great efforts have been made to provide recording materials for ink-jet printing having improved properties. This is reflected in an almost unmanageable amount of publications on inkjet recording material in the technical and patent literature. The following are some important properties for ink jet recording materials:
  • 1. High ink absorption capacity
  • 2. Quick drying of the applied ink jet image
  • 3. High optical density of applied ink drops
  • 4. Clear demarcation of the applied ink jet drops
  • 5. Uniformity of color strength and color density of the applied ink jet printing
  • 6. No bleeding of the applied ink jet image
  • 7. Good water and moisture resistance and light fastness of the applied ink jet image and
  • 8. Dimensional stability of the recording material after printing, especially avoiding the appearance of undulations or other dimensional changes.

Darüber hinaus sollte das Tintenstrahlaufzeichnungsmaterial je nach der gewünschten Verwendung bestimmte Oberflächeneigenschaften aufweisen, wobei diese erreicht werden sollen, ohne die oben angegebenen Tintenstrahlaufzeichnungseigenschaften negativ zu beeinflussen.Moreover, the ink jet recording material should have certain surface properties depending on the desired use, and these should be achieved without adversely affecting the above-mentioned ink jet recording properties.

Verschiedene Verfahren zur Ausbildung einer bestimmten Oberflächenqualität sind in der Papierherstellung seit langem bekannt. Dabei ist aber zu beachten, dass durch die Oberflächenbehandlung die Tintenaufnahmeeigenschaft nicht verschlechtert wird, bzw. dass das Aufzeichnungsmaterial so aufgebaut ist, dass die nachfolgende Oberflächenbehandlung zu keiner Verschlechterung der Tintenaufnahmeeigenschaften führt.Various methods for forming a certain surface quality have long been known in papermaking. It should be noted, however, that the surface treatment does not deteriorate the ink-receiving property or that the recording material is constructed so that the subsequent surface treatment does not result in deterioration of ink-receiving properties.

Das gängige Verfahren zur Oberflächenbehandlung ist z. B. das Kalandrieren, wodurch die Oberfläche geglättet und die Überzugsschicht verfestigt wird.The common method for surface treatment is z. B. calendering, whereby the surface is smoothed and the coating layer is solidified.

So beschreibt DE-A 31 51 471 ein Verfahren zur Herstellung eines Tintenstrahlaufzeichnungsmaterials, bei dem auf ein Substrat mehrere Überzugsschichten aus einem anorganischen Pigment und einer wässrigen Binderzusammensetzung aufgebracht wird und danach die Streichfarbe getrocknet wird. Nach der Lehre von DE-A 31 51 471 ist es bevorzugt, das so hergestellte und getrocknete Aufzeichnungsmaterial einer weiteren Oberflächenbehandlung entweder in einem Glanzkalander oder einem Superkalander zu unterziehen. Im Falle des Superkalanders wird das Aufzeichnungsmaterial bei einem relativ hohen Druck von 200 N/mm und einer Temperatur von etwa 70°C ausgesetzt, während beim Glanzkalander der Druck 90 N/mm und die Temperatur etwa 150°C beträgt. Die DE-A 31 51 471 enthält aber keinerlei Angaben über den Glanz oder die Oberflächenglätte des so hergestellten Tintenstrahlaufzeichnungsmaterials.Thus, DE-A 31 51 471 describes a process for producing an ink jet recording material in which a plurality of coating layers of an inorganic pigment and an aqueous binder composition is applied to a substrate and then the coating color is dried. According to the teaching of DE-A 31 51 471 it is preferred to subject the thus prepared and dried recording material of a further surface treatment either in a gloss calender or a supercalender. In the case of the supercalender, the recording material is exposed at a relatively high pressure of 200 N / mm and a temperature of about 70 ° C, whereas in the gloss calender, the pressure is 90 N / mm and the temperature is about 150 ° C. However, DE-A 31 51 471 contains no Information on the gloss or surface smoothness of the thus prepared ink jet recording material.

US-A-4,770,934 betrifft ein Tintenstrahlaufzeichnungsmaterial, bei dem eine Tintenaufzeichnungsschicht enthaltend ein Pigment wie z. B. eine synthetische Kieselsäure mit einer spezifischen Oberfläche von wenigstens 100 m2/g und ein Bindemittel aufgetragen wird, und diese Oberflächenschicht dann in einem Gussstrichverfahren ausgebildet wird. Hierbei können zwei unterschiedliche Gussstrichverfahren, nämlich die direkte Methode (wet process), bei der direkt nach dem Aufbringen der Streichfarbe die feuchte Farbe durch Kontakt mit einem beheizten polierten Metallzylinder, insbesondere mit Chromoberfläche, unter Druck getrocknet wird. Alternativ kann das indirekte Verfahren (rewet process) verwendet werden, bei dem der Strich zuerst getrocknet wird und dann vor Inkontaktbringen mit dem heißen polierten Metallzylinder und Druck die bereits getrocknete Streichfarbenschicht wieder angefeuchtet wird. Beide Verfahrensweisen führen in der Regel zu einem sehr hohen Oberflächenglanz. Aufgrund der in US-A 4,770,934 verwendeten Streichfarbenzusammensetzungen werden hier allerdings nur mittlere Glanzbereiche zwischen 20 und 50 % bei einem Betrachtungswinkel von 75° erreicht.US-A-4,770,934 relates to an ink jet recording material in which an ink recording layer containing a pigment such as e.g. B. a synthetic silica having a specific surface area of at least 100 m 2 / g and a binder is applied, and this surface layer is then formed in a cast-iron method. In this case, two different casting process, namely the direct method (wet process), in which directly after the application of the coating color, the wet ink is dried by contact with a heated polished metal cylinder, in particular with chrome surface, under pressure. Alternatively, the rewet process may be used, in which the coating is first dried and then, before being brought into contact with the hot polished metal cylinder and pressure, the already dried coating color layer is moistened again. Both procedures usually lead to a very high surface gloss. Due to the coating compositions used in US Pat. No. 4,770,934, however, only average gloss ranges of between 20 and 50% are achieved here at a viewing angle of 75 °.

Aus EP-A 0 732 219 ist ein zweischichtiges Tintenaufzeichnungsmaterial bekannt. Hierbei wird auf ein Substrat zuerst eine Tintenaufzeichnungsschicht enthaltend ein Pigment und ein Bindemittel aufgebracht und darauf eine Oberflächenschicht, die kationische ultrafeine Teilchen mit einem Teilchendurchmesser im Bereich von 1 nm bis 500 nm aufweist. Die Oberflächenschicht hat hierbei einen Glanz von wenigstens 45% bei einem Blickwinkel von 75°. Das in EP-A 0 732 219 beschriebene Aufzeichnungsmaterial weist diese Glanzwerte bereits ohne besondere Oberflächenbehandlung auf. Der Glanz kann aber noch durch ein Gussstrichverfahren verbessert werden. Hierbei sind die oben genannten direkten und indirekten Verfahren sowie das Gelverfahren genannt. Beim Gelverfahren wird der nasse Strich durch ein Durchleiten des beschichteten Substrats durch ein Koagulierungs- oder Gelierungsbad geliert und anschließend mit dem beheizten Zylinder in Kontakt gebracht. Das in EP-A 0 732 219 beschriebene Tintenaufzeichnungsmaterial weist zwar hervorragende Tintenaufzeichnungseigenschaften auf, ist aber aufgrund des inhärent auftretenden hohen Glanzes, selbst wenn kein Gussstrichverfahren angewendet wird, nur für Anwendungen geeignet, bei denen ein hoher Glanz erwünscht wird.From EP-A-0 732 219 a two-layer ink recording material is known. Here, on a substrate is first applied an ink recording layer containing a pigment and a binder, and thereon a surface layer comprising cationic ultrafine particles having a particle diameter in the range of 1 nm to 500 nm. The surface layer in this case has a gloss of at least 45% at a viewing angle of 75 °. The recording material described in EP-A 0 732 219 already has these gloss values without any special surface treatment. The gloss can still be improved by a cast-iron process. Here, the above-mentioned direct and indirect methods and the gel method are mentioned. In the gel process, the wet bar by passing the coated substrate through a coagulation or gelation bath and then brought into contact with the heated cylinder. While the ink recording material described in EP-A-0 732 219 has excellent ink-jet recording properties, it is only suitable for applications where high gloss is desired due to the inherent high gloss even when no cast-coat method is used.

Aus DE-A 197 44 724 ist ein spezielles Gussstrichverfahren bekannt, bei dem die Oberflächen des Chromzylinders, mit dem das befeuchtete Aufzeichnungsmaterial unter Druck in Kontakt gebracht wird, um die Streichfarbe zu trocknen, z. B. durch Sandstrahlen modifiziert wird. Hierbei wird die Glätte des Papiers reduziert, indem die Oberflächenstruktur des Zylinders, die bestimmte Vertiefungen aufweist, auf der Oberfläche des Papiers abgebildet wird. Hierdurch reduziert sich ebenfalls der Glanz.From DE-A 197 44 724 a special cast-coating method is known in which the surfaces of the chrome cylinder, with which the moistened recording material is brought into contact under pressure to dry the coating color, for. B. is modified by sandblasting. Here, the smoothness of the paper is reduced by the surface structure of the cylinder, which has certain wells, is imaged on the surface of the paper. This also reduces the gloss.

In EP 0 879 709 B1 wird ein weiteres Gussstrichverfahren zur Herstellung eines glänzenden Tintenstrahlaufzeichnungsblattes beschrieben. Zur Erzielung einer glänzenden Oberfläche ist es notwendig sehr feine Siliziumdioxidteilchen einzusetzen. Dabei ist es essentiell, daß die Beschichtungsschicht nach Aufbringung auf das Substratblatt und vor Trocknung an der hochglanzpolierten Oberfläche des Metallzylinders einen sehr hohen Wassergehalt hat. Wenn der Wassergehalt der Beschichtungsschicht unter einen kritischen Wert fällt kann die hochglanzpolierte Oberfläche des Metallzylinders nicht auf das Tintenstrahlaufzeichnungsmaterial übertragen werden. Dies resultiert in Oberflächendefekten, die inhomogen über das gesamte Papier verteilt sind und die inhomogene niedrige Glanz- und Glättewerte bedingen.EP 0 879 709 B1 describes another cast coating process for producing a glossy ink jet recording sheet. To achieve a glossy surface, it is necessary to use very fine silica particles. It is essential that the coating layer after application to the substrate sheet and before drying on the highly polished surface of the metal cylinder has a very high water content. When the water content of the coating layer falls below a critical value, the mirror-finished surface of the metal cylinder can not be transferred to the ink-jet recording material. This results in surface defects that are inhomogeneously distributed throughout the paper and that cause inhomogeneously low gloss and smoothness values.

In DE-A 2 310 891 ist ein weiteres Verfahren zur Oberflächenbehandlung eines Papiers beschrieben. Diese Druckschrift setzt sich mit dem Problem auseinander, sehr glatte hochglänzende Überzüge, die vergleichbar sind mit denen, die aus den oben beschriebenen Gussstrichverfahren bekannt sind, herzustellen. Hierzu wird eine wässrige Zusammensetzung eines Bindemittels, die im wesentlichen frei von Pigmenten ist, zur Ausbildung einer Oberflächenschicht aufgebracht. Danach wird die feuchte Beschichtung durch eine Erhitzungszone geführt und auf eine Temperatur gebracht, die oberhalb der Filmbildungstemperatur des Bindemittels liegt, so dass ein Polymerfilm ausgebildet wird. Nach der Filmbildung wird dann das Substrat mit einer erhitzten polierten Walze in Kontakt gebracht. Obwohl keine Glanzwerte angegeben sind, ist davon auszugehen, insbesondere da beabsichtigt ist, die Glanzwerte von Gussstrichverfahren zu reproduzieren, insbesondere da im Wesentlichen keine Pigmente in der Oberflächenschicht vorhanden sind, dass auch hier ein sehr hoher Glanz im Bereich oberhalb von 45 % bei 75° Betrachtungswinkel erreicht wird. Darüber hinaus betrifft die DE-A 2 310 891 das Aufbringen eines schützenden Kunststoffüberzugs auf bereits bedruckte Substrate. Das heißt, der Kunststoffüberzug soll gerade keine Porosität aufweisen und ist damit vollkommen ungeeignet für den Tintenstrahldruck.DE-A 2 310 891 describes a further process for the surface treatment of a paper. This document deals with the problem, very smooth high gloss coatings that are comparable with those known from the cast coating processes described above. For this purpose, an aqueous composition of a binder, which is substantially free of pigments, is applied to form a surface layer. Thereafter, the wet coating is passed through a heating zone and brought to a temperature which is above the film-forming temperature of the binder, so that a polymer film is formed. After film formation, the substrate is then brought into contact with a heated, polished roller. Although no gloss values are given, it is to be expected, in particular because it is intended to reproduce the gloss values of cast-coat processes, in particular because there are essentially no pigments in the surface layer, that also here a very high gloss in the range above 45% at 75 ° Viewing angle is achieved. In addition, DE-A 2 310 891 relates to the application of a protective plastic coating on already printed substrates. That is, the plastic coating should just have no porosity and is thus completely unsuitable for inkjet printing.

Aufgabe der vorliegenden Erfindung ist es daher, ein Tintenaufzeichnungsmaterial bereitzustellen, das hervorragende Tintenaufnahmeeigenschaften aufweist, und das auch für Anwendungen eingesetzt werden kann, bei denen hoher Glanz unerwünscht ist, und das trotz mittlerer Glanzwerte eine niedrige Oberflächenrauhheit aufweist.It is therefore an object of the present invention to provide an ink-jet recording material which has excellent ink-receptive properties, and which can also be used in applications where high gloss is undesirable and which has low surface roughness despite medium gloss values.

Eine weitere Aufgabe der vorliegenden Erfindung ist es, ein Verfahren bereitzustellen; mit dem ein Tintenaufzeichnungsmaterial mit den oben angegebenen Erfordernissen hergestellt werden kann.Another object of the present invention is to provide a method; with which an ink recording material having the above-mentioned requirements can be produced.

Diese Aufgabe wird durch ein Verfahren zur Herstellung eines Tintenstrahlaufzeichnungsmaterials umfassend:

  • a) Auftragen einer wässrigen Streichmasse enthaltend ein Pigment und ein Bindemittel auf mindestens eine Oberfläche eines Substrats zur Ausbildung mindestens einer Tintenaufnahmeschicht,
  • b) Auftragen einer wässrigen Streichmasse enthaltend kationische anorganische Teilchen, ein Bindemittel und ein Trennmittel auf die Tintenaufnahmeschicht(en) zur Ausbildung einer Oberflächenschicht,
  • c) partielles Trocknen des Aufzeichnungsmaterials und
  • d) Inkontaktbringen des partiell getrockneten Aufzeichnungsmaterials mit einem beheizten Metallzylinder ohne Wiederbefeuchtung des Strichs
gelöst.This object is achieved by a method for producing an ink jet recording material comprising:
  • a) applying an aqueous coating slip comprising a pigment and a binder to at least one surface of a substrate to form at least one ink receiving layer,
  • b) applying an aqueous coating slip comprising cationic inorganic particles, a binder and a release agent to the ink receiving layer (s) to form a surface layer,
  • c) partial drying of the recording material and
  • d) contacting the partially dried recording material with a heated metal cylinder without remoistening the stroke
solved.

Dadurch entsteht ein Tintenaufzeichnungsmaterial enthaltend ein Substrat, das mindestens auf einer Seite des Substrats eine Tintenaufnahmeschicht, die ein Pigment und ein Bindemittel enthält, und darauf eine Oberflächenschicht, wobei die Oberflächenschicht kationische anorganische Teilchen, ein Bindemittel und ein Trennmittel enthält und die Oberflächenschicht einen Glanzwert im Bereich von 5 bis 35 gemessen nach DIN 54502 R'(75°) (Messwinkel 75°) und eine Oberflächenglätte nach dem Parker-Print-Surf-Verfahren (PPS) nach DIN-ISO 8791-4 von kleiner 2,5 µm aufweist.This results in an ink recording material containing a substrate having at least on one side of the substrate an ink receiving layer containing a pigment and a binder and thereon a surface layer, the surface layer containing cationic inorganic particles, a binder and a release agent and the surface layer has a gloss value in the Range from 5 to 35 measured according to DIN 54502 R '(75 °) (measuring angle 75 °) and a surface smoothness according to the Parker Print Surf method (PPS) according to DIN ISO 8791-4 of less than 2.5 μm.

Für die vorliegende Erfindung ist es wesentlich, dass kein Gussstrichverfahren im klassischen Sinne verwendet wird. Das heißt, das mit der Streichfarbe beschichtete Substrat wird weder direkt im feuchten Zustand mit einem beheizten Metallzylinder in Kontakt gebracht, noch wird das mit der Streichfarbe beschichtete Substrat getrocknet und dann wiederbefeuchtet, bevor es mit dem Metallzylinder in Kontakt gebracht wird. Auch wird keine Gelmethode durchgeführt, bei der der feuchte Strich vor Inkontaktbringen mit dem Metallzylinder koaguliert oder geliert wird.For the present invention, it is essential that no cast-iron method is used in the classical sense. That is, the substrate coated with the coating color is not contacted with a heated metal cylinder either directly in the wet state, nor is the substrate coated with the coating color dried and then remoistened before it is brought into contact with the metal cylinder. Also, no gel method is performed in which the wet coating is coagulated or gelled before contacting the metal cylinder.

Der Erfolg des erfindungsgemäßen Verfahrens war insbesondere deshalb so überraschend, da der Fachmann erwarten würde, dass bei einem partiellen Trocknen ohne nachträgliches Wiederbefeuchten des Striches sich der Strich nicht gleichmäßig ausformt, sondern bei Inberührung mit der beheizten Walze sich ablöst und auf der Walze haften bleibt. Dies würde unweigerlich zu einem Zusammenbruch des Herstellungsverfahrens wie auch zu einer völlig unakzeptablen Papierqualität führen. Bisher ist die Fachwelt davon ausgegangen, dass bei einer Trocknung in jedem Fall eine Wiederbefeuchtung des Strichs notwendig ist, um eine gleichmäßige Ausformung des Strichs bei Kontakt mit dem Metallzylinder zu gewährleisten. Hierzu wird bei dem bekannten "Rewet-Verfahren" in dem Schlitz zwischen Andruckwalze und Metallzylinder ein wässriges Wiederbefeuchtungsmittel zugesetzt, das insbesondere auch ein Trennmittel enthält, um ein Anhaften der beschichteten Substratbahn an dem Metallzylinder während des Ausform- und Trockenprozesses zu verhindern.The success of the process according to the invention was so surprising, in particular, since the person skilled in the art would expect that in the case of partial drying without subsequent rewetting of the coating, the coating will not be uniform, but will detach when in contact with the heated roll and adhere to the roll. This would inevitably lead to a collapse of the manufacturing process as well as to a completely unacceptable paper quality. So far, the art has assumed that in any case a rewet of the line is necessary for drying to ensure uniform formation of the line in contact with the metal cylinder. For this purpose, in the known "Rewet method" in the slot between pressure roller and metal cylinder, an aqueous Wiederweuchtungsmittel added, which in particular also contains a release agent to prevent adhesion of the coated substrate web to the metal cylinder during the molding and drying process.

Weiterhin wurde überraschenderweise festgestellt, dass durch das Verfahren der vorliegenden Erfindung deutlich niedrigere Glanzwerte im Vergleich zu dem klassischen Gussstrichverfahren erreicht werden, ohne dass dadurch die Glätte des Aufzeichnungsmaterials wesentlich reduziert wird.Furthermore, it has surprisingly been found that the method of the present invention achieves significantly lower gloss values in comparison with the classical cast-coat method, without substantially reducing the smoothness of the recording material.

Ein weiterer verfahrenstechnischer Vorteil der vorliegenden Erfindung liegt darin, dass das Verfahren auf bereits vorhandenen Gussstrichanlagen durchgeführt werden kann, und der reduzierte Glanz durch die erfindungsgemäße Verfahrensweise erzeugt wird, ohne dass z. B. der polierte Metallzylinder durch einen oberflächenmodifizierten Metallzylinder, wie DE-A 197 55 724 lehrt, ausgetauscht werden muss.Another procedural advantage of the present invention is that the method can be carried out on existing cast coating equipment, and the reduced gloss is produced by the novel procedure without z. B. the polished metal cylinder by a surface-modified metal cylinder, as DE-A 197 55 724 teaches, must be replaced.

Der entscheidende Vorteil des erfindungsgemäßen Verfahrens liegt aber darin, dass hierdurch ein seidenmattes Tintenaufzeichnungsmaterial mit hervorragender Tintenaufnahmeeigenschaften bereitgestellt wird.However, the key advantage of the method of the invention is that it provides a satin-matt ink recording material having excellent ink receptivity properties.

Gemäß einer bevorzugten Ausführungsform wird die teilweise Trocknung des Aufzeichnungsmaterials in Schritt c) des erfindungsgemäßen Verfahrens so durchgeführt, dass das Aufzeichnungsmaterial eine Restfeuchte von 14 bis kleiner 20 Gew.-%, vorzugsweise 16 bis kleiner 20 Gew.-% und besonders bevorzugt 16 bis 18 Gew.-% Wasser, bezogen auf das Gesamtgewicht des Aufzeichnungsmaterials getrocknet wird. Dies kann z. B. durch Heißlufttrocknen bei 30°C bis 80°C, vorzugsweise bei 40°C bis 60°C für 3 bis 60 Sekunden, vorzugsweise 10 bis 30 Sekunden erfolgen. Alternativ kann auch eine Infrarottrocknung mit vergleichbarer Trocknungsleistung verwendet werden.According to a preferred embodiment, the partial drying of the recording material in step c) of the method according to the invention is carried out such that the recording material has a residual moisture content of 14 to less than 20 wt .-%, preferably 16 to less than 20 wt .-% and particularly preferably 16 to 18 Wt .-% water, based on the total weight of the recording material is dried. This can be z. B. by hot air drying at 30 ° C to 80 ° C, preferably at 40 ° C to 60 ° C for 3 to 60 seconds, preferably 10 to 30 seconds. Alternatively, an infrared drying with comparable drying performance can be used.

Weiterhin ist es bevorzugt, dass das Aufzeichnungsmaterial mit einer Anpresswalze mit einem Liniendruck von 400 bis 800 N/cm, vorzugsweise 500 bis 750 N/cm an den beheizten Zylinder angedrückt wird. Die Oberflächentemperatur des Zylinders beträgt dabei vorzugsweise 90°C bis 120°C, besonders bevorzugt 100°C bis 115°C.
Bei dem Metallzylinder kann es sich um jeden üblicherweise im Gussstrichverfahren eingesetzten Zylinder handeln, insbesondere um einen Zylinder mit polierter Chromoberfläche.Furthermore, it is preferred that the recording material is pressed against the heated cylinder with a nip roll having a line pressure of 400 to 800 N / cm, preferably 500 to 750 N / cm. The surface temperature of the cylinder is preferably 90 ° C to 120 ° C, more preferably 100 ° C to 115 ° C.
The metal cylinder may be any cylinder commonly used in the casting process, in particular a cylinder with a polished chrome surface.

Bei dem erfindungsgemäßen Verfahren wird in einem ersten Verfahrensschritt eine wässrige Streichmasse zur Ausbildung der Tintenaufnahmeschicht auf mindestens einer Seite eines flächigen Substrats aufgebracht. Die wässrige Streichmasse zur Ausbildung der Tintenaufnahmeschicht und somit die Tintenaufnahmeschicht selbst enthält ein Pigment und ein Bindemittel. Beispiele für Pigmente, die für die Tintenaufzeichnungsschicht geeignet sind, beinhalten anorganische Pigmente wie z. B. Kieselsäure, Aluminiumoxid, Aluminiumoxidhydrat, Aluminiumsilicat, Magnesiumsilicat, Magnesiumcarbonat, Talk, Clay, Hydrotalcid, Calciumcarbonat, Titandioxid und Zinkoxid wie auch Kunststoffpigmente wie Polyethylen, Polystyrol und Polyacrylat. Diese Pigmente können entweder einzeln oder in Kombination verwendet werden. Besonders bevorzugt sind Pigmente, ausgewählt aus Kieselsäure, Aluminiumoxid, Aluminiumoxidhydrat und Magnesiumcarbonat. Die Teilchengröße dieser Pigmente kann im Bereich zwischen 0,1 bis 20 µm liegen.In the method according to the invention, in a first method step, an aqueous coating composition for forming the ink-receiving layer is applied to at least one side of a planar substrate. The aqueous coating composition for forming the ink-receiving layer, and thus the ink-receiving layer itself, contains a pigment and a binder. Examples of pigments suitable for the ink-receiving layer include inorganic pigments such as e.g. For example, silica, alumina, alumina hydrate, aluminum silicate, magnesium silicate, magnesium carbonate, talc, clay, hydrotalcite, calcium carbonate, titanium dioxide and zinc oxide as well as plastic pigments such as polyethylene, polystyrene and polyacrylate. These pigments can be used either singly or in combination. Particularly preferred are pigments, selected from silicic acid, alumina, alumina hydrate and magnesium carbonate. The particle size of these pigments can be in the range between 0.1 to 20 microns.

Als Bindemittel sind wasserlösliche Harze wie z. B. Polyvinylalkohol, Stärke, kationisierte Stärke, Kasein, Gelatine, Acrylharze, Urethanharze, Natriumalginat, Polyvinylpyrrilidon. Carboxymethylcellulose und Hydroxyethylcellulose geeignet. Weiterhin können Latices acrylische Polymere wie z. B. Polymere von Acrylsäureester oder Methacrylsäureester und Copolymere dieser Monomere mit anderen Monomeren, Latices von carboxylmodifizierten konjugierten Diencopolymeren und Latices von Vinylcopolymeren wie z. B. Ethylenvinylacetatcopolymeren verwendet werden. Diese Binder können entweder einzeln oder in Kombination eingesetzt werden. Das Verhältnis von Bindemittel zu Pigment in der Tintenaufzeichnungsschicht beträgt vorzugsweise 2:1 bis 1:10, besonders bevorzugt 1:1 bis 1:5.As binders are water-soluble resins such. As polyvinyl alcohol, starch, cationized starch, casein, gelatin, acrylic resins, urethane resins, sodium alginate, polyvinylpyrrilidone. Carboxymethylcellulose and hydroxyethylcellulose. Furthermore, latices acrylic polymers such. As polymers of acrylic acid esters or methacrylic acid esters and copolymers of these monomers with other monomers, latices of carboxyl-modified conjugated diene copolymers and latexes of vinyl copolymers such. B. ethylene vinyl acetate copolymers are used. These binders can be used either singly or in combination. The ratio of binder to pigment in the ink-receiving layer is preferably 2: 1 to 1:10, more preferably 1: 1 to 1: 5.

Innerhalb der oben angegebenen Bereiche erhält man eine optimale Balance zwischen Festigkeit der Tintenaufzeichnungsschicht und Tintenaufnahmekapazität.Within the ranges given above, an optimum balance is achieved between the strength of the ink-receiving layer and the ink-receiving capacity.

Die wässrige Streichmasse zur Ausbildung der Tintenaufnahmeschicht und somit die Tintenaufnahmeschicht selbst kann auch zusätzliche Bestandteile wie z. B. Vernetzungsmittel wie Melaminharze, Glyoxal und Isocyanate, oberflächenaktive Mittel, Antischaummittel, Antioxidantien, optische Aufheller, UV-Absorptionsmittel, Uiskositätsmodifizierungsmittel zur pH-Wert-Einstellung usw. beinhalten.The aqueous coating composition for forming the ink-receiving layer, and thus the ink-receiving layer itself, may also contain additional components such as e.g. Crosslinking agents such as melamine resins, glyoxal and isocyanates, surfactants, antifoaming agents, antioxidants, optical brighteners, UV absorbers, viscosity adjusting agents for pH adjustment, etc.

Die Tintenaufnahmeschicht kann entweder als Einzelschicht oder als Mehrfachschicht aufgebracht werden, wobei die einzelnen Schichten sowohl identisch als auch unterschiedlich sein können. Die Tintenaufnahmeschicht weist vorzugsweise ein Flächengewicht von 5 - 20 g/m2 bezogen auf Trockengewicht auf.The ink-receiving layer can be applied either as a single layer or as a multi-layer, wherein the individual layers can be both identical and different. The ink receiving layer preferably has a basis weight of 5 - 20 g / m 2 based on dry weight.

Es ist bevorzugt, das Aufzeichnungsmaterial nach Aufbringen der Tintenaufnahmeschicht und vor Aufbringen der Oberflächenschicht zu trocknen. Ein Nass-auf-Nass-Auftrag der Oberflächenschicht auf eine nicht oder nur teilweise getrocknete Tintenaufnahmeschicht ist aber ebenfalls möglich. Darüber hinaus kann auch ein im Handel erhältliches Substrat, das einen Vorstrich aufweist, der die oben definierten Kriterien für die Tintenaufnahmeschicht erfüllt, als Ausgangsmaterial für das Aufbringen der 0berflächenschicht verwendet werden.It is preferable to dry the recording material after applying the ink receiving layer and before applying the surface layer. However, wet-on-wet application of the surface layer to a non or partially dried ink receptive layer is also possible. In addition, a commercially available substrate having a pre-coat satisfying the above-defined criteria for the ink receiving layer may also be used as the starting material for applying the surface layer.

Die Oberflächenschicht wird ebenfalls mit einer wässrigen Streichmasse auf die bereits aufgetragene Tintenaufnahmeschicht aufgebracht.The surface layer is also applied to the already applied ink receiving layer with an aqueous coating.

Ein wesentliches Merkmal der vorliegenden Erfindung ist, dass die wässrige Streichmasse zur Ausbildung der Oberflächenschicht kationische anorganische Teilchen, ein Bindemittel und ein Trennmittel aufweist.An essential feature of the present invention is that the aqueous coating composition for forming the surface layer comprises cationic inorganic particles, a binder and a release agent.

Gemäß einer bevorzugten Ausführungsform sind die kationischen Teilchen für die Oberflächenschicht ausgewählt aus Aluminiumoxid, Aluminiumoxidhydrat oder Kieselsäure, deren Oberfläche kationisiert wurde. Als geeignetes Aluminiumoxid kann α-,β-,γ- und δ-Aluminiumoxid verwendet werden. Geeignete Aluminiumoxidhydrate sind Gibbsit, Bayerit, Nordostrandit, kristalliner Böhmit, Diaspor und Pseudoböhmit. Beispiele kationischer Kieselsäuren beinhalten Kieselsäuren, die einer Oberflächenbehandlung mit einer Verbindung, die kationische Metalloxide oder Metallatome enthalten ausgesetzt werden, oder Kieselsäuren, die einer Oberflächenbehandlung mit einer organischen Verbindung ausgesetzt werden, die sowohl Aminogruppen oder quartäre Ammoniumgruppen als auch funktionelle Gruppen, die mit den Silanolgruppen auf der Oberfläche mit der Kieselsäure reagieren wie z. B. Aminoethoxysilan oder Aminoalkylglycidilether enthalten.According to a preferred embodiment, the cationic particles for the surface layer are selected from alumina, alumina hydrate or silicic acid whose surface has been cationized. As suitable alumina, α-, β-, γ- and δ-alumina can be used. Suitable alumina hydrates are gibbsite, bayerite, northeast rimite, crystalline boehmite, diaspore and pseudoboehmite. Examples of cationic silicas include silicas exposed to a surface treatment with a compound containing cationic metal oxides or metal atoms, or silicas exposed to a surface treatment with an organic compound containing both amino groups or quaternary ammonium groups and functional groups containing the silanol groups on the surface with the silica react like As aminoethoxysilane or Aminoalkylglycidilether included.

Besonders bevorzugt ist es, wenn die kationischen Teilchen einen mittleren Teilchendurchmesser im Bereich von 1 bis 1.000 nm, vorzugsweise 10 bis 500 nm aufweisen.It is particularly preferred if the cationic particles have an average particle diameter in the range from 1 to 1000 nm, preferably 10 to 500 nm.

Ein wesentliches Merkmal der vorliegenden Erfindung ist, dass das Tintenstrahlaufzeichnungsmaterial einen zumindest zweischichtigen Strich aufweist, wobei die Oberflächenschicht die gewünschten Oberflächeneigenschaften bereitstellen soll und die Kombination von Oberflächenschicht und Tintenaufnahmeschicht die gewünschten Tintenaufnahmeeigenschaften zur Verfügung stellen sollen. Hierbei ist es insbesondere wichtig, dass das Tintenaufzeichnungsmaterial eine hohe Tintenaufnahmekapazität als auch eine hohe Aufnahmegeschwindigkeit aufweist. Weiterhin ist es wesentlich, dass die Farbpigmente der Tinten vorzugsweise in der Oberfläche oder nahe der Oberfläche fixiert werden, um eine hohe Farbdichte und Farbbrillianz bereitzustellen. Weiterhin ist es wichtig, dass der flüssige und flüchtige Trägerfluid der Tinte möglichst schnell von dem Tintenaufzeichnungsmaterial aufgenommen wird und von den Tintenfarbstoffen separiert wird, so dass kein Ausbluten stattfindet und stets scharfe Konturen im Druckbild erzeugt werden. Um dies zu erreichen, sind insbesondere die kationischen Teilchen in der Oberflächenschicht wichtig.An essential feature of the present invention is that the ink jet recording material has at least a two-layer coating, wherein the surface layer is to provide the desired surface properties and the combination of surface layer and ink receiving layer should provide the desired ink absorption properties. Here, it is particularly important that the ink recording material has a high ink receiving capacity as well as a high recording speed. Furthermore, it is essential that the color pigments of the inks are preferably fixed in the surface or near the surface to provide high color density and color brilliance. Furthermore, it is important that the liquid and volatile carrier fluid of the ink is absorbed as quickly as possible from the ink recording material and separated from the ink dyes, so that no bleeding takes place and sharp contours are always generated in the printed image. In order to achieve this, especially the cationic particles in the surface layer are important.

Durch die kationischen Teilchen in der Oberflächenschicht wird eine ausreichende Porosität der Oberflächenschicht erzeugt, die eine schnelle Aufnahme der Tinte ermöglicht. Aufgrund des kationischen Charakters der Teilchen, werden die Tintenfarbstoffe, die häufig anionisch sind, zumindest teilweise unmittelbar in der Oberflächenschicht fixiert, während das Trägerfluid der Tinte schnell in die unter der Oberflächenschicht gelegenen Tintenaufnahmeschicht transportiert wird. Somit wird sichergestellt, dass bereits ein wesentlicher Teil der Tintenfarbstoffe in der obersten Schicht des Aufzeichnungsmaterials fixiert wird, auch wenn ein Teil der Tintenfarbstoffe in der darunter liegenden Tintenaufnahmeschicht festgehalten wird. In jedem Fall wird sichergestellt, dass die Tintenfarbstoffe oberflächennah fixiert werden. Weiterhin ermöglicht die erfindungsgemäße Struktur des Tintenaufzeichnungsmaterials einen sehr schnellen Abtransport des fluiden Trägers der Tinte, wodurch sehr hohe Tintenaufnahmegeschwindigkeiten und kurze Trocknungszeiten erreicht werden.The cationic particles in the surface layer create sufficient porosity of the surface layer that allows rapid ink pickup. Due to the cationic character of the particles, the ink dyes, which are often anionic, are at least partially fixed directly in the surface layer while the carrier fluid of the ink is rapidly transported into the ink receiving layer below the surface layer. Thus, it is ensured that already a substantial part of the ink dyes in the the uppermost layer of the recording material is fixed, even if a part of the ink dyes is held in the underlying ink-receiving layer. In any case, it is ensured that the ink dyes are fixed near the surface. Furthermore, the inventive structure of the ink recording material allows a very fast removal of the fluid carrier of the ink, whereby very high ink absorption rates and short drying times can be achieved.

Gemäß einer bevorzugten Ausführungsform der vorliegenden Erfindung haben die kationischen Teilchen einen mittleren Teilchendurchmesser im Bereich von 1 bis 1.000 nm, vorzugsweise 10 bis 500 nm. Bei dieser besonders bevorzugten Ausführungsform der vorliegenden Erfindung können optimale Tintenaufzeichnungseigenschaften wie auch Oberflächeneigenschaften erreicht werden. Ein besonderer Vorteil dieser bevorzugten Teilchengrößen liegt darin, dass die Transparenz der Oberflächenschicht gesteigert werden kann, so dass das Tintenstrahldruckbild eine hervorragende Farbbrillianz aufweist.According to a preferred embodiment of the present invention, the cationic particles have an average particle diameter in the range of 1 to 1000 nm, preferably 10 to 500 nm. In this particularly preferred embodiment of the present invention, optimum ink recording properties as well as surface properties can be achieved. A particular advantage of these preferred particle sizes is that the transparency of the surface layer can be increased so that the ink jet image has excellent color brilliance.

Als Bindemittel für die Oberflächenschicht kommen dieselben Bindemittel, die weiter oben im Zusammenhang mit der Tintenaufnahmeschicht beschrieben wurden, in Betracht. Ein besonders bevorzugtes Bindemittel sind Polyurethane.As the binder for the surface layer, the same binders as described above in connection with the ink receiving layer come into consideration. A particularly preferred binder is polyurethanes.

Das Verhältnis von kationischen anorganischen Teilchen zu Bindemittel in der Oberflächenschicht liegt vorzugsweise innerhalb eines Bereichs von 50:1 bis 1:2. Zusätzlich zu den anorganischen Teilchen können noch feinteilige organische Harze in der Oberflächenschicht vorhanden sein. Dadurch wird die Porosität der Oberflächenschicht gesteigert. Die Teilchen der organischen Harze haben vorzugsweise einen Durchmesser im Bereich von 0,05 µm bis 2 µm. Beispiele feiner Teilchen organischer Harze beinhalten Latices von Acrylpolymeren wie z. B. Polymeren von Acrylestern oder Methacrylestern und Copolymere dieser Monomere mit anderen Monomeren, Latices von carboxylmodifizierten konjugierten Dienpolymeren, Latices von Vinylcopolymeren wie z. B. Ethylenvinylacetat-Copolymere, feinteiliges Polyvinylchlorid, feinteiliges Polyethylen, feinteilige Copolymere aus Vinylpyrrolidon und Styrol und feinteilige Copolymere aus Vinylalkohol und Styrol.The ratio of cationic inorganic particles to binder in the surface layer is preferably within a range of 50: 1 to 1: 2. In addition to the inorganic particles, finely divided organic resins may still be present in the surface layer. This increases the porosity of the surface layer. The particles of the organic resins preferably have a diameter in the range of 0.05 μm to 2 μm. Examples of fine particles of organic resins include latices of acrylic polymers such as e.g. B. polymers of acrylic esters or methacrylic esters and copolymers of these monomers with other monomers, latexes of carboxyl-modified conjugated diene polymers, latexes of vinylic copolymers such as. Example, ethylene vinyl acetate copolymers, finely divided polyvinyl chloride, finely divided polyethylene, finely divided copolymers of vinyl pyrrolidone and styrene and finely divided copolymers of vinyl alcohol and styrene.

Ein weiterer wesentlicher Bestandteil der Oberflächenschicht ist ein Trennmittel, um sicherzustellen, dass bei der Ausführung des erfindungsgemäßen Verfahrens während dem Inkontaktbringen des partiell getrockneten Aufzeichnungsmaterials mit dem beheizten Metallzylinder der Strich gleichmäßig und vollständig ausgebildet wird, ohne dass sich der Strich ablöst und/oder an dem Metallzylinder anhaftet. Geeignete Trennmittel sind Ölsäure, Rapsöl, Metallstearate, Ammoniumstearate, Polyethylene, ethoxylierte Polyethylene, Wachse, Metall- und Ammoniumsalze von aliphatischen Säuren, Ketendimere, oberflächenaktive Mittel auf Grundlage von Fettsäuren, sulfonierte und sulfatierte Öle, Fettsäuretriglyceride und Fettsäureamide, wobei Ölsäure und Rapsöl besonders bevorzugt sind. Die Trennmittel können allein oder in Kombination eingesetzt werden. Die Gesamtmenge an Trennmittel in der wässrigen Streichmasse zur Ausbildung der Oberflächenschicht beträgt vorzugsweise 1 - 10 Gew.-% bezogen auf die Gesamtmasse der Feststoffe in der Streichmasse.Another essential component of the surface layer is a release agent to ensure that in the execution of the method according to the invention during the contacting of the partially dried recording material with the heated metal cylinder, the stroke is uniformly and completely formed without the line peels off and / or on the Metal cylinder adheres. Suitable release agents are oleic acid, rapeseed oil, metal stearates, ammonium stearates, polyethylenes, ethoxylated polyethylenes, waxes, metal and ammonium salts of aliphatic acids, ketene dimers, fatty acid surfactants, sulfonated and sulfated oils, fatty acid triglycerides and fatty acid amides, with oleic acid and rapeseed oil being particularly preferred are. The release agents can be used alone or in combination. The total amount of release agent in the aqueous coating composition for forming the surface layer is preferably 1-10% by weight, based on the total mass of the solids in the coating composition.

Gemäß einer besonders bevorzugten Ausführungsform enthält entweder die wässrige Streichmasse zur Ausbildung der Tintenaufnahmeschicht oder die wässrige Streichmasse zur Ausbildung der Oberflächenschicht oder beide Streichmassen eine kationische Verbindung, die kein Pigment ist. Es ist besonders vorteilhaft, wenn zumindest die Oberflächenschicht eine solche kationische Verbindung enthält, um die Fixierung der in der Regel anionischen Farbpigmente der Tinte in der Oberflächenschicht zu verbessern und somit die Nassfestigkeit des Tintenstrahldrucks zu verbessern.According to a particularly preferred embodiment, either the aqueous coating composition for forming the ink-receiving layer or the aqueous coating composition for forming the surface layer or both coating compositions contains a cationic compound which is not a pigment. It is particularly advantageous if at least the surface layer contains such a cationic compound in order to improve the fixation of the usually anionic color pigments of the ink in the surface layer and thus to improve the wet strength of the inkjet printing.

Als kationische Verbindungen kommen in Betracht: Polyallylamin und dessen quartäre Ammoniumsalze, Polyaminsulfon und dessen quartäre Ammoniumsalze, Polyvinylamin und dessen quartäre Ammoniumsalze, Chitosan und dessen Acetate, Polymere von Monomeren ausgewählt aus der Gruppe bestehend aus Dimethylaminoethyl(meth)acrylat, Diethylaminoethyl(meth)-acrylat, Methylethylaminoethyl(meth)acrylat, Dimethylaminostyrol, Diethylaminostyrol, Copolymere von Vinylpyrrolidon mit einem quartären Salz eines Aminoalkyl(meth)acrylats und einem Copolymer von (Meth)acrylamid mit einem quartären Salz von Aminomethyl(meth)acrylamid.Suitable cationic compounds are: polyallylamine and its quaternary ammonium salts, polyamine sulfone and its quaternary ammonium salts, polyvinylamine and its quaternary ammonium salts, chitosan and its acetates, polymers of monomers selected from the group consisting of dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) - acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylaminostyrene, copolymers of vinylpyrrolidone with a quaternary salt of an aminoalkyl (meth) acrylate and a copolymer of (meth) acrylamide with a quaternary salt of aminomethyl (meth) acrylamide.

Um den kationischen Charakter der Streichmasse insbesondere bei Anwesenheit einer kationischen Verbindung zu gewährleisten ist es vorteilhaft, den pH-Wert der Streichfarbe im sauren Bereich einzustellen. Der pH-Wert liegt vorzugsweise im Bereich von 2,5 bis 5,0.In order to ensure the cationic character of the coating composition, in particular in the presence of a cationic compound, it is advantageous to adjust the pH of the coating color in the acidic range. The pH is preferably in the range of 2.5 to 5.0.

Als Substrat kann unter anderem Papier verwendet werden. Es ist bevorzugt, wenn das Substrat selbst porös ist, das heißt, eine Aufnahmefähigkeit für Flüssigkeiten aufweist, die gewünschte Dimensionsstabilität für das Aufzeichnungsmaterial bereitstellt und eine ausreichend gute Adhäsion zu der Aufnahmeschicht zeigt. Daher ist Papier als Substrat besonders bevorzugt. Das Flächengewicht des Papiersubstrats beträgt vorzugsweise 40 bis 300 g/m2.As a substrate, paper can be used inter alia. It is preferred if the substrate itself is porous, that is, has a liquid receptivity, provides the desired dimensional stability for the recording material, and exhibits sufficiently good adhesion to the receptive layer. Therefore, paper is particularly preferable as a substrate. The basis weight of the paper substrate is preferably 40 to 300 g / m 2 .

Das erfindungsgemäße Tintenaufzeichnungsmaterial, das mit dem erfindungsgemäßen Verfahren hergestellt werden kann, hat eine Oberfläche, die einen Glanzwert im Bereich von 5 % bis 35 %, gemessen nach DIN 54502 R'(75°) (Messwinkel 75°) und eine Oberflächenglätte nach dem Parker-Print-Surf-Verfahren (PPS) nach DIN ISO 8791-4 von kleiner 2,5 µm auf. Gemäß einer bevorzugten Ausführungsform beträgt der Glanzwert 5 bis kleiner 30 %, insbesondere 10 % bis kleiner 30 %, ganz besonders bevorzugt 12 % bis 25 % und die Oberflächenglätte ist kleiner 2,2 µm. Somit wird ein seidenmattes Tintenaufzeichnungsmaterial mit hervorragenden Tintenaufnahmeeigenschaften und hoher Glätte bereitgestellt.
Ein besonderer Vorteil des erfindungsgemäßen Tintenaufzeichnungsmaterials liegt in der extrem kurzen Trocknungszeit nahe null des aufgebrachten Tintenstrahldruckbilds.The ink recording material of the present invention which can be prepared by the method of the present invention has a surface which has a gloss value in the range of 5% to 35% measured to DIN 54502 R '(75 °) (75 ° measurement angle) and Parker surface smoothness -Print surf method (PPS) according to DIN ISO 8791-4 of less than 2.5 microns. According to a preferred embodiment, the gloss value is 5 to less than 30%, in particular 10% to less than 30%, very particularly preferably 12% to 25% and the surface smoothness is less than 2.2 μm. Consequently For example, a satin-matt ink recording material having excellent ink-receiving properties and high smoothness is provided.
A particular advantage of the ink recording material according to the invention lies in the extremely short drying time close to zero of the applied ink jet printing image.

Die vorliegende Erfindung wird nun anhand eines Beispiels näher erläutert.The present invention will now be explained in more detail by way of example.

Beispielexample

Auf ein vorgefertigtes Basispapier, das aus einem Rohpapier mit einem Flächengewicht von 150 g/m2 besteht und mit einem Strich versehen ist, der Kieselsäure, Polyvinylalkohol und Polydiallyldimethylammoniumchlorid (bezogen auf die Trockenmasse) enthält und mit einem Flächengewicht von 10 g/m2 aufgebracht wurde, wurde eine Streichfarbe gemäß der in Tabelle 1 angegebenen Zusammensetzung mit einem Feststoffgehalt von 27 Gew.-% mittels einer Farbauftragswalze auf die vorgestrichene Papierbahn mit einer Bahngeschwindigkeit von 30 m/min aufgetragen. Mit einer Luftbürste wurde soviel Streichfarbenüberschuss entfernt, dass eine Strichmenge von 11 g/m2 (im getrockneten Zustand) auf der Papierbahn verbleibt.On a prefabricated base paper, which consists of a base paper with a basis weight of 150 g / m 2 and is provided with a bar containing silica, polyvinyl alcohol and polydiallyldimethylammonium chloride (based on the dry matter) and applied with a basis weight of 10 g / m 2 was applied, a coating color according to the composition shown in Table 1 with a solids content of 27 wt .-% was applied by means of an inking roll on the pre-coated paper web at a web speed of 30 m / min. With an air brush, excess coating color was removed so that a quantity of 11 g / m 2 (in the dried state) remains on the paper web.

Beim Durchlauf durch eine Heißlufttrocknung bei 50°C für 20 Sekunden wird die gestrichene Papierbahn auf eine Restfeuchte von 16 Gew.-% Wasser, bezogen auf das Gesamtgewicht der Papierbahn, getrocknet und sofort anschließend in den Walzenspalt, der aus einer elastischen Anpresswalze und einem hochglanzpolierten Chromzylinder gebildet wird, ohne Wiederbefeuchtung geführt.When passing through a hot air drying at 50 ° C for 20 seconds, the coated paper web is dried to a residual moisture of 16 wt .-% water, based on the total weight of the paper web, and immediately then into the nip, consisting of an elastic pressure roller and a highly polished Chrome cylinder is formed, without rewetting led.

Der Liniendruck des Walzen/Chromzylinder-Paars betrug 625 N/cm und die Temperatur der Chromzylinderoberfläche betrug 110°C.The line pressure of the roll / chrome cylinder pair was 625 N / cm and the temperature of the chrome cylinder surface was 110 ° C.

Das Tintenstrahlaufzeichnungsmaterial zeigte hervorragende Bedruckbarkeit im Tintenstrahldruck und wies einen Oberflächenglanz von 19 % bei 75° Betrachtungswinkel, gemessen nach DIN 54502 auf. Die Oberflächenglätte nach dem Parker-Print-Surf-Verfahren, gemessen nach DIN ISO 8791-4 betrug 1,95 µm. Tabelle 1 Rohstoff Prozentanteile bezogen auf Trockensubstanz Ameisensäure 0,7 kationische Substanz1 0,7 Antischaummittel2 0,2 Böhmit3 71,5 Glycerin 1,7 Polyurethan4 17,8 Vernetzungsmittel5 1,7 Ölsäure 5,0 Rapsöl 0,7 1 = Polydiallyldimethylammoniumchlorid von INDULOR Chemie 2 = Antifoam FG 116 von HARCORS Chemicals 3 = Disperal 140 HT von CONDEA Chemie 4 = Neorez SB-80-SE von AVECIA 5 = Ucarlink XL-29 SE von UNION CARBIDE pH = 4,0 The ink jet recording material showed excellent printability in ink jet printing and had a surface gloss of 19% at 75 ° viewing angle, measured according to DIN 54502. The surface smoothness according to the Parker Print Surf method, measured according to DIN ISO 8791-4, was 1.95 μm. Table 1 raw material Percentages based on dry matter formic acid 0.7 cationic substance 1 0.7 Antifoam 2 0.2 Boehmite 3 71.5 glycerin 1.7 Polyurethane 4 17.8 Crosslinking agent 5 1.7 oleic acid 5.0 rapeseed oil 0.7 1 = polydiallyldimethylammonium chloride from INDULOR Chemie 2 = Antifoam FG 116 from HARCORS Chemicals 3 = Disperal 140 HT from CONDEA Chemie 4 = Neorez SB-80-SE from AVECIA 5 = Ucarlink XL-29 SE from UNION CARBIDE pH = 4.0

Claims (28)

  1. An inkjet recording material comprising a substrate and, at least on one side of the substrate, an ink acceptance coating which contains a pigment and a binder, and a surface coating thereon, the surface coating containing cationic inorganic particles, a binder and a release agent and the surface coating having a gloss value in the range from 5 to 35 percent, measured according to DIN 54502 R' (75°) (measuring angle 75°), and a surface smoothness, according to the Parker-Print-Surf method (PPS) according to DIN-ISO 8791-4, of less than 2.5 µm.
  2. The recording material as claimed in claim 1, characterized in that either the surface coating or the ink acceptance coating or both coatings contains or contain a cationic compound which is not a pigment.
  3. The recording material as claimed in claim 2, characterized in that the cationic compound is selected from polyallylamine and the quaternary salts thereof, polyamine sulfone and the quaternary salts thereof, polyvinylamine and the quaternary salts thereof, chitosan and the acetates thereof, polymers of monomers selected from the group consisting of dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, methylethylaminoethyl (meth)acrylate, dimethylaminostyrene, diethylaminostyrene, copolymers of vinylpyrrolidone with a quaternary salt of an aminoalkyl (meth)-acrylate and a copolymer of (meth)acrylamide with a quaternary salt of aminomethyl (meth)acrylamide.
  4. The recording material as claimed in any of the preceding claims, characterized in that the cationic particles are selected from alumina, aluminum oxide hydrate or silica, the surface of which has been converted into cationic form.
  5. The recording material as claimed in any of the preceding claims, characterized in that the cationic particles have a mean particle diameter in the range from 1 to 1000 nm, preferably 10 to 500 nm.
  6. The recording material as claimed in any of the preceding claims, characterized in that the surface coating additionally contains organic pigments obtained from a thermoplastic resin.
  7. The recording material as claimed in any of the preceding claims, characterized in that the gloss value is 10 to 30 percent, particularly preferably 12 to 25 percent.
  8. The recording material as claimed in any of the preceding claims, characterized in that the release agent is selected from oleic acid, rapeseed oil, metal stearates, ammonium stearates, polyethylenes, ethoxylated polyethylenes, waxes, metal salts and ammonium salts of aliphatic acids, ketene dimers, surface-active agents based on fatty acids, sulfonated and sulfated oils, fatty acid triglycerides, fatty acid amides and combinations thereof.
  9. The recording material as claimed in any of the preceding claims, characterized in that the pigment in the ink acceptance coating is selected from silica, alumina, aluminum oxide hydrate and basic magnesium carbonate.
  10. The recording material as claimed in any of the preceding claims, characterized in that the substrate is paper.
  11. The recording material as claimed in any of the preceding claims, characterized in that the basis weight of the ink acceptance coating is 5 to 20 g/m2 and the basis weight of the surface coating is 5 to 20 g/m2, based in each case on the dry weight.
  12. A process for the production of an inkjet recording material, comprising:
    a) application of an aqueous coating slip comprising a pigment and a binder to at least one surface of a substrate for the formation of at least one ink acceptance coating;
    b) application of an aqueous coating slip comprising cationic inorganic particles, a binder and a release agent to the ink acceptance coating(s) for the formation of a surface coating;
    c) partial drying of the recording material; and
    d) bringing the partially dried recording material into contact with a heated metal cylinder without remoistening of the coating.
  13. The process as claimed in claim 12, characterized in that the recording material is dried to a moisture content of 14 to 20 percent by weight, preferably 16 to 20 percent by weight, of water, based on the total weight of the recording material.
  14. The process as claimed in either of claims 12 and 13, characterized in that the recording material is pressed against the heated cylinder by means of a pressure roll with a nip pressure of 400 to 800 N/cm, preferably 500 to 750 N/cm.
  15. The process as claimed in any of claims 12 to 14, characterized in that the heated cylinder is a polished chromium cylinder.
  16. The process as claimed in any of claims 12 to 15, characterized in that either the aqueous coating slip for the formation of the ink acceptance coating or the aqueous coating slip for the formation of the surface coating or both coating slips contains or contain a cationic compound which is not a pigment.
  17. The process as claimed in claim 16, characterized in that the cationic compound is selected from polyallylamine and the quaternary ammonium salts thereof, polyamine sulfone and the quaternary ammonium salts thereof, polyvinylamine and the quaternary ammonium salts thereof, chitosan and the acetates thereof, polymers of monomers selected from the group consisting of dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)-acrylate, methylethylaminoethyl (meth)acrylate, dimethylaminostyrene, diethylaminostyrene, copolymers of vinylpyrrolidone with a quaternary salt of an aminoalkyl (meth)acrylate and a copolymer of (meth)acrylamide with a quaternary salt of aminomethyl (meth)acrylamide.
  18. The process as claimed in any of claims 12 to 17, characterized in that the cationic particles are selected from alumina, aluminum oxide hydrate or silica, the surface of which has been converted into cationic form.
  19. The process as claimed in any of claims 12 to 18, characterized in that the cationic particles have a mean particle diameter in the range from 1 to 1000 nm, preferably 10 to 500 nm.
  20. The process as claimed in any of claims 12 to 19, characterized in that the aqueous coating slip for the formation of the surface coating additionally contains organic pigments obtained from a thermoplastic resin.
  21. The process as claimed in any of claims 12 to 20, characterized in that the release agent is selected from oleic acid, rapeseed oil, metal stearates, ammonium stearates, polyethylenes, ethoxylated polyethylenes, waxes, metal salts and ammonium salts of aliphatic acids, ketene dimers, surface-active agents based on fatty acids, sulfonated and sulfated oils, fatty acid triglycerides, fatty acid amides and combinations thereof.
  22. The process as claimed in any of claims 12 to 21, characterized in that the pigment in the aqueous coating slip for the formation of the ink acceptance coating is selected from silica, alumina, aluminum oxide hydrate and magnesium carbonate.
  23. The process as claimed in any of claims 12 to 22, characterized in that the substrate is paper.
  24. The process as claimed in any of claims 12 to 23, characterized in that the aqueous coating slip for the formation of the ink acceptance coating is applied in an amount to give a basis weight of the ink acceptance coating in the dry state of 5 to 20 g/m2 and the aqueous coating slip for the formation of the surface coating is applied in an amount to give a basis weight of the surface coating in the dried state of 5 to 20 g/m2.
  25. The process as claimed in any of claims 12 to 24, characterized in that the ink recording coating is dried before application of the surface coating.
  26. An inkjet recording material obtainable by a process as claimed in any of claims 12 to 25.
  27. The use of the inkjet recording material as claimed in any of claims 1 to 11 and 26 for printing on by means of an inkjet printer.
  28. The inkjet recording material as claimed in any of claims 1 to 11 and 26, which has a printed image produced by means of an inkjet printer.
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DE2001112327 DE10112327A1 (en) 2001-03-13 2001-03-13 Satin gloss inkjet recording material
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PCT/EP2002/002633 WO2002072359A1 (en) 2001-03-13 2002-03-09 Sheeny ink jet printing material

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DE50205703D1 (en) 2006-04-13
WO2002072359A1 (en) 2002-09-19
CA2440326A1 (en) 2002-09-19
CN1228505C (en) 2005-11-23
CN1496310A (en) 2004-05-12
ATE316472T1 (en) 2006-02-15
DE10112327A1 (en) 2002-10-02
US20040146726A1 (en) 2004-07-29
JP2004522630A (en) 2004-07-29
HK1065983A1 (en) 2005-03-11

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