EP1466217A1 - Ceramic toner for electro-photographic printing - Google Patents

Ceramic toner for electro-photographic printing

Info

Publication number
EP1466217A1
EP1466217A1 EP02791827A EP02791827A EP1466217A1 EP 1466217 A1 EP1466217 A1 EP 1466217A1 EP 02791827 A EP02791827 A EP 02791827A EP 02791827 A EP02791827 A EP 02791827A EP 1466217 A1 EP1466217 A1 EP 1466217A1
Authority
EP
European Patent Office
Prior art keywords
ceramic
weight
glass
toner according
toner
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.)
Withdrawn
Application number
EP02791827A
Other languages
German (de)
French (fr)
Inventor
Bernd Schultheis
Cora Krause
Inka Henze
Harry Engelmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Schott AG
Carl Zeiss AG
Schott Glaswerke AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE2002100412 external-priority patent/DE10200412A1/en
Priority claimed from DE20200229U external-priority patent/DE20200229U1/en
Application filed by Schott AG, Carl Zeiss AG, Schott Glaswerke AG filed Critical Schott AG
Publication of EP1466217A1 publication Critical patent/EP1466217A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09708—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0902—Inorganic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/26—Printing on other surfaces than ordinary paper
    • B41M1/34—Printing on other surfaces than ordinary paper on glass or ceramic surfaces
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
    • C03C2217/485—Pigments

Definitions

  • the invention relates to a ceramic toner which can be transferred by means of electrophotographic printing to a glass, glass ceramic or ceramic substrate with high temperature resistance and can be baked in a subsequent temperature process and which, in addition to glass flow particles, also contains color pigment particles.
  • WO 98/39272 and EP 0 647 885 B1 show, ceramic color compositions are used for decorating ceramic and glass products which are applied to a paper support as a transfer agent in the electrophotographic reproduction process.
  • the paper backing is coated with gum arabic, poly vinyl acetate or wax.
  • the coloring substances copied onto the paper backing are applied to the glassy or ceramic
  • the paper carrier burns. This in-direct printing process is cumbersome and a completely residue-free burning of the paper carrier is not always guaranteed. These residues often lead to rejects.
  • the ceramic colors specified in these publications are specially designed for the decoration of ceramic articles. The colors cannot be used on special glass, glass ceramics and glasses with low thermal expansion.
  • the toner has:> 30 to 80% by weight, in particular 45 to 60% by weight, of a special glass frit,
  • This toner has a composition of a glass frit and inorganic pigments, which is especially tailored to the printing of glass, glass ceramic or ceramic. This overcomes the disadvantageous liability problems in the prior art when printing on special glasses.
  • the toner can in particular have a thermoplastic plastic matrix that melts homogeneously on the substrate in the temperature range from 100 ° C. to 400 ° C. and in the temperature range from 300 ° C. to 500 ° C. evaporates and / or burns out almost completely.
  • the toner can have flow aids, with the aid of which the wetting of the printable
  • Substrates can be controlled.
  • the plastic matrix as a carrier of the inorganic glass frits and pigments can be selected by the choice of melting, decomposition and / or vaporization.
  • the temperature of the plastic used must be adapted to the burn-in process so that the plastic melts homogeneously onto the substrate before it burns out and then evaporates and / or decomposes and does not hinder the melting together of the glass flux and color pigment particles.
  • the toner image can be transferred directly to the substrate in electrophotographic printing
  • the percentages by weight refer in particular to the total weight of the toner, in particular in the case of one-component toner.
  • the carrier is not taken into account in the weight composition information.
  • 3 to 25% by weight of toner are used in commercially available two-component toners.
  • the rest (75 to 97% by weight) make up the carrier.
  • the percentage by weight is
  • the flow in the total two-component toner is between 3 and 8% by weight (10% by weight • 30% by weight or 80% by weight • 10% by weight).
  • the pigment content is accordingly in the range between 0 and 2% by weight.
  • the proportion of binder resin is between 3 and 5% by weight.
  • toner is transferred indirectly.
  • a transfer agent for example paper coated with gum arabic, is then used.
  • the toner has no coloring pigments, so that the proportion of the glass frit is in the range between 50 to 70% by weight and the proportion of the plastic matrix is in the range between 30 and 50% by weight.
  • the plastic matrix has toner resins based on acrylate, in particular styrene acrylate, polymethyl methacrylate. These substances are easy to process and have good adhesion to the substrate. In addition, these substances burn without residue.
  • the influence of the depolymerization, the melting, the evaporation and / ⁇ o or decomposition temperature can be achieved by choosing different polymers for the plastic matrix. Suitable materials are polyvinyl alcohol, polyoxymethylene, styrene copolymers, polyvinylidene fluoride, polyvinyl butyral, polyester (unsaturated and / or saturated or mixtures thereof), polycarbonate, polyvinylpyrrolidone, vinylimidazole copolymers and polyether.
  • the toner can additionally contain charge control substances and / or oxidizing agents in a known manner to improve the image transfer or to decompose the organic without residues.
  • the added oxidants accelerate the thermal decomposition of the plastic matrix.
  • the toner is additionally coated with additives to improve the wetting when the toner melts on the generally relatively polar and smooth, unlike paper, non-absorbent surface.
  • additives to improve the wetting when the toner melts on the generally relatively polar and smooth, unlike paper, non-absorbent surface.
  • the polarity of the toners between non-polar, hydrophobic, neutral, polar, hydrophilic, and thus the wetting of the substrates can be controlled via a suitable choice of known additives.
  • Known flow aids such as aerosils and transfer aids can be used to improve the quality of the print.
  • the proportion of such auxiliaries is between 0 and 1.0% by weight, typically between 0.2 and 0.5% by weight.
  • peroxides or azo compounds can be added to the toner, but these have decomposition temperatures> 150 ° C., so that the decomposition does not start during the melting phase (fixing phase).
  • inorganic additives are also possible, for example catalytically active pigments, which accelerate the decomposition of the organic plastic matrix. Examples of this are so-called perovskites of the general form ABO 3 , for example LaMnO 3 , LaCoO 3 , La ⁇ Sr / , Co Mn ⁇ 5 O 3 + e .
  • perovskites of the general form ABO 3 for example LaMnO 3 , LaCoO 3 , La ⁇ Sr / , Co Mn ⁇ 5 O 3 + e .
  • the table below shows exemplary embodiments of glass compositions (frits or rivers) which are particularly suitable for a ceramic toner. The percentages by weight relate in each case to the composition of the glass frit.
  • Glass compositions 1 to 6 are particularly suitable for glass and glass ceramics.
  • glass composition 1 Special exemplary embodiments for glass composition 1 are:
  • glass composition 2 Special exemplary embodiments for glass composition 2 are:
  • Glass composition 7 is particularly suitable for glass ceramics in secondary firing.
  • Glass composition 8 to 10 is particularly suitable for glass.
  • Glass composition 11 to 12 is particularly suitable for ceramics. Earthenware. Bone china and porcelain.
  • composition ranges 1 and 2 properties of these glass frits are specified which relate in particular to the special requirements for the direct printing of glass ceramics with an expansion coefficient of less than 2x60 6 K 1 (in the temperature range from 20 to 700 ° C). Mixtures of the above glass frits are also conceivable depending on the application.
  • these glass frits are particularly suitable in combination with appropriate inorganic pigments for the electrophotographic printing of special glass plates, such as soda lime glass or
  • Borosilicate glass (if necessary, each previously coated, for example, with SiO 2 and / or with TiO 2 or with one of the above-mentioned glass frits, for example for the use of oven front panes, oven inner panes, refrigerator shelves, counter glass etc., as well as for direct printing on glass ceramics with low expansion, for example for applications such as glass-ceramic cooktops or grilling surfaces or fireplace viewing panes, but can also be used to print directly on ceramic surfaces such as tiles or sanitary objects. Requirements regarding abrasion resistance, adhesion and chemical resistance are taken into account with the glass frit composition according to the table.
  • Color pigments typically include inorganic compounds, such as metal oxides, mixed phases metal oxide pigments or CIC pigments (complex inorganic color pigments), inclusion pigments, metal powders or flakes, metal colloids, pearlescent or luster pigments based on mica or glassy or SiO 2 - or Al 2 O 3 platelets, fluorescent pigments, magnetic pigments, anti-corrosive pigments, transparent pigments, sintered pigments and / or mixtures of pigments with glass frits, pigments for four-color sets, etc. or mixtures of the above-mentioned variants, which are already considered sufficient in the literature (eg "Ullmann's Encyclopedia of Industrial Chemistry ", vol. A20, 1 992, VCH Publishers, Inc.).
  • the pigments can be based on a wide variety of crystal structures (rutile, spinel,
  • the typical size of the glass flow particles and the inorganic pigments is in the range from 0.5 to 25 ⁇ m (D50 vol.), In particular in the range from 1 to
  • Examples of grinding processes for the production of such particles are counter-jet grinding, grinding in ball, annular gap or pin mills.
  • the glass flow particles as well as the pigments are typically only partially from the plastic matrix due to the manufacturing process of the toner, i.e. incompletely encased, and usually have an irregular shape. This is due in particular to the fact that the inorganic constituents (glass flux and pigments) have different fracture toughnesses compared to the organic plastic matrix and preferentially break open at the grain boundaries during the grinding process of the toner. Additional additives or flow aids that are added later accumulate on the surface of the plastic matrix or on the exposed flux and / or pigment particles.

Abstract

The invention relates to a ceramic toner which is transferable to a high-temperature resistant glass, glass ceramic or ceramic substrate by means of electrophotographic printing and which can be fired in a subsequent temperature process, containing colour pigment particles in addition to special glass flow particles. According to the invention, said ceramic toner is provided with a thermoplastic synthetic matrix which melts in a homogeneous manner on the substrate within a temperature range of 100 DEG C - 400 DEG C and which, within the temperature range of 300 DEG C -500 DEG C, vaporises in an almost residue-free manner and/or decomposes in order to obtain a toner which can be transferred especially in a direct printing mode and which has almost no synthetic matrix residue after firing.

Description

Keramischer Toner für elektrofotographischen DruckCeramic toner for electrophotographic printing
Die Erfindung betrifft einen keramischen Toner, der mittels elektrofotographischem Druck auf ein Glas-, Glaskeramik- oder Keramik-Substrat hoher Temperaturbeständigkeit übertragbar und in einem anschließenden Temperatur- prozess einbrennbar ist und der neben Glasfluss-Partikel auch Farbpigment-Partikel enthält.The invention relates to a ceramic toner which can be transferred by means of electrophotographic printing to a glass, glass ceramic or ceramic substrate with high temperature resistance and can be baked in a subsequent temperature process and which, in addition to glass flow particles, also contains color pigment particles.
Wie die DE 44 13 168 A1 , die WO 98/39272 und die EP 0 647 885 B1 zeigen, werden keramische Farbzusammensetzungen zum Dekorieren von Keramik- und Glaserzeugnissen verwendet, die im elektrofotographischen Reproduktionsverfahren auf einen Papierträger als Transfermittel aufgetragen werden. Der Papierträger ist mit Gummi-Arabicum, Poly vinylacetat oder Wachs beschichtet. Die auf den Papierträger kopierten, färbenden Substanzen werden nach dem Aufbringen auf dem zu bedruckenden Gegenstand in die glasige oder kera- As DE 44 13 168 A1, WO 98/39272 and EP 0 647 885 B1 show, ceramic color compositions are used for decorating ceramic and glass products which are applied to a paper support as a transfer agent in the electrophotographic reproduction process. The paper backing is coated with gum arabic, poly vinyl acetate or wax. The coloring substances copied onto the paper backing are applied to the glassy or ceramic
mische Oberfläche eingebrannt. Dabei verbrennt der Papierträger. Dieses in-direkte Druckverfahren ist umständlich und ein vollständig rückstandloses Verbrennen des Papierträgers ist nicht immer gewährleistet. Diese Rückstände führen oft zu Ausschussware. Die in diesen Druckschriften angegebenen kera-mischen Farben sind speziell für die Dekoration von keramischen Artikeln konzipiert. Auf Spezialglas, Glaskeramiken und Gläsern mit niedrigen ther-mischen Ausdehnungen lassen sich die Farben nicht verwenden.mixed surface baked. The paper carrier burns. This in-direct printing process is cumbersome and a completely residue-free burning of the paper carrier is not always guaranteed. These residues often lead to rejects. The ceramic colors specified in these publications are specially designed for the decoration of ceramic articles. The colors cannot be used on special glass, glass ceramics and glasses with low thermal expansion.
Es ist Aufgabe der Erfindung, einen Toner der eingangs erwähnten Art zu schaffen, der im elektrofotographischen Direktdruck auf Glas-, Glaskeramik- und Keramik-Substraten verwendet werden kann, der auf die besonderen Gebrauchsanforderungen dieser Anwendungen abgestimmt ist und dessen Träger- Stoffe beim Einbrennen des Tonerbildes nahezu rückstandslos ausbrennt und dabei ein homogenes Zusammenfließen der Glasfluss- und Farbpigment-Partikel nicht behindert und für die Substrate eine gute, homogene Benetzung gewähr-leistet.It is an object of the invention to provide a toner of the type mentioned at the outset which can be used in direct electrophotographic printing on glass, glass ceramic and ceramic substrates, which is matched to the particular use requirements of these applications and whose carrier substances when baking the The toner image burns out almost without residue and does not hinder a homogeneous flow of the glass flux and color pigment particles and ensures good, homogeneous wetting for the substrates.
Diese Aufgabe wird nach der Erfindung dadurch gelöst, dass der Toner auf-weist: > 30 bis 80 Gew. %, insbesondere 45 bis 60 Gew.%, einer speziellen Glasfritte,This object is achieved according to the invention in that the toner has:> 30 to 80% by weight, in particular 45 to 60% by weight, of a special glass frit,
0 bis < 20 Gew. %, insbesondere > 5 bis < 20 Gew. % anorgani-sche Pigmente und 20 bis 60 Gew. %, insbesondere > 30 bis 50 Gew. % einer Kunststoff- Matrix. Dieser Toner weist eine Zusammensetzung einer Glasfritte und anorganischen Pigmenten auf, die besonders auf die Bedruckung von Glas, Glaskeramik oder Keramik abestimmt ist. Hierdurch werden die im Stand der Technik nachteiligen Haftungsprobleme bei Bedruckung von Spezialgläsern überwunden. Der Toner kann insbesondere eine thermoplastische Kunststoff- Matrix aufweisen, die im Temperaturbereich von 100° C bis 400° C homogen auf das Substrat aufschmilzt und im Temperaturbereich ab 300° C bis 500° C nahezu rückstandslos verdampft und/oder ausbrennt. Weiterhin kann der Toner o Fließhilfsstoffe aufweisen, mit deren Hilfe die Benetzung der zu bedruckenden0 to <20% by weight, in particular> 5 to <20% by weight of inorganic pigments and 20 to 60% by weight, in particular> 30 to 50% by weight of a plastic matrix. This toner has a composition of a glass frit and inorganic pigments, which is especially tailored to the printing of glass, glass ceramic or ceramic. This overcomes the disadvantageous liability problems in the prior art when printing on special glasses. The toner can in particular have a thermoplastic plastic matrix that melts homogeneously on the substrate in the temperature range from 100 ° C. to 400 ° C. and in the temperature range from 300 ° C. to 500 ° C. evaporates and / or burns out almost completely. Furthermore, the toner can have flow aids, with the aid of which the wetting of the printable
Substrate gesteuert werden kann.Substrates can be controlled.
Die Lösung der Aufgabe stellt eine Abkehr von der Entwicklungsrichtung dar. Es ist das Verdienst des Erfinders, erkannt zu haben, dass gerade die Erniedrigung 5 des Pigmentanteils zu Gunsten der Glasfritte zu verbesserten Druckergebnissen führt.The solution to the problem is to turn away from the direction of development. It is thanks to the inventor that he recognized that the lowering of the pigment content 5 in favor of the glass frit leads to improved printing results.
Die Kunststoff-Matrix als Träger der anorganischen Glasfritten und Pigmente kann durch die Auswahl der Schmelz-, der Zersetzungs- und/oder Verdamp-The plastic matrix as a carrier of the inorganic glass frits and pigments can be selected by the choice of melting, decomposition and / or vaporization.
D fungstemperatur des verwendeten Kunststoffes so an den Einbrennvorgang an- gepasst werden, dass der Kunststoff vor dem Ausbrennen homogen auf das Substrat aufschmilzt und dann verdampft und/oder sich zersetzt und dabei das Zusammenschmelzen der Glasfluss- und Farbpigment-Partikel nicht behindert. Das Tonerbild kann im elektrofotographischen Druck direkt auf das Substrat übertragenThe temperature of the plastic used must be adapted to the burn-in process so that the plastic melts homogeneously onto the substrate before it burns out and then evaporates and / or decomposes and does not hinder the melting together of the glass flux and color pigment particles. The toner image can be transferred directly to the substrate in electrophotographic printing
5 werden, wobei ein rückstandsfreies Entfernen des Trägermaterials beim5, with a residue-free removal of the carrier material during
Einbrennvorgang gewährleistet ist.Burning process is guaranteed.
An dieser Stelle wird ausdrücklich darauf verwiesen, dass sich die Gew. %- Angaben insbesondere bei Einkomponententoner auf das Gesamtgewicht des ) Toners beziehen. Bei sogenanntem Zwei-Komponententoner, d.h. Toner mit magnetischen Carriern, wird der Carrier nicht bei den Gewichtszusammensetzungsangaben berücksichtigt. Üblicherweise werden bei handelsüblichen Zwei- Komponenten-Tonern 3 bis 25 Gew. % Toner verwendet. Der Rest (75 bis 97 Gew. %) macht den Carrier aus. Zur Verdeutlichung: wird beispielsweise Zwei-Komponententoner verwendet, der ιo 10 Gew. % Toner und 90 Gew. % Carrier enthält, so ist der Gew. %-Anteil anAt this point, reference is expressly made to the fact that the percentages by weight refer in particular to the total weight of the toner, in particular in the case of one-component toner. In the case of so-called two-component toners, ie toners with magnetic carriers, the carrier is not taken into account in the weight composition information. Usually 3 to 25% by weight of toner are used in commercially available two-component toners. The rest (75 to 97% by weight) make up the carrier. To clarify: if, for example, two-component toner is used which contains 10% by weight of toner and 90% by weight of carrier, the percentage by weight is
Fluss in dem Gesamt-Zwei-Komponententoner erfindungsgemäß in den Gren-zen zwischen 3 bis 8 Gew. % (10 Gew. % • 30 Gew. % bzw. 80 Gew. % • 10 Gew. %) belegen. Der Pigmentanteil liegt dementsprechend im Bereich zwischen 0 und 2 Gew. %. Der Bindemittelharzanteil liegt im Bereich zwischen 3 und 5 Gew. %.According to the invention, the flow in the total two-component toner is between 3 and 8% by weight (10% by weight • 30% by weight or 80% by weight • 10% by weight). The pigment content is accordingly in the range between 0 and 2% by weight. The proportion of binder resin is between 3 and 5% by weight.
I 5I 5
Denkbar ist auch, dass der Toner mittelbar übertragen wird. Hierbei wird dann ein Transfermittel, beispielsweise ein mit Gummi-Arabicum beschichtetes Papier verwendet.It is also conceivable that the toner is transferred indirectly. A transfer agent, for example paper coated with gum arabic, is then used.
:o In weiteren Ausgestaltungen besitzt der Toner keine farbgebenden Pigmente, so dass der Anteil der Glasfritte im Bereich zwischen 50 bis 70 Gew. % und der Anteil der Kunststoff-Matrix im Bereich zwischen 30 und 50 Gew. % liegt.: o In further configurations, the toner has no coloring pigments, so that the proportion of the glass frit is in the range between 50 to 70% by weight and the proportion of the plastic matrix is in the range between 30 and 50% by weight.
Die Kunststoff-Matrix weist nach einer Ausgestaltung Tonerharze auf Acrylat- i5 Basis, insbesondere Styrolacrylat, Polymethylmetacrylat auf. Diese Stoffe sind einfach zu verarbeiten und weisen eine gute Haftung auf dem Substrat auf. Außerdem verbrennen diese Stoffe rückstandsfrei.According to one embodiment, the plastic matrix has toner resins based on acrylate, in particular styrene acrylate, polymethyl methacrylate. These substances are easy to process and have good adhesion to the substrate. In addition, these substances burn without residue.
Die Beeinflussung der Depolymerisation, der Schmelz-, der Verdampfungs- und/ ιo oder Zersetzungstemperatur kann durch Wahl verschiedener Polymere für die Kunststoff-Matrix erreicht werden. Als geeignete Materialien haben sich Polyvinylalkohol, Polyoxymethylen, Styrolcopolymere, Polyvinylidenfluorid, Polyvinylbutyral, Polyester (ungesättigte und/oder gesättigte oder Mischungen davon), Polycarbonat,Polyvinylpyrrolidon, Vinylimidazol-Copolymere sowie Polyether erwiesen.The influence of the depolymerization, the melting, the evaporation and / ιo or decomposition temperature can be achieved by choosing different polymers for the plastic matrix. Suitable materials are polyvinyl alcohol, polyoxymethylene, styrene copolymers, polyvinylidene fluoride, polyvinyl butyral, polyester (unsaturated and / or saturated or mixtures thereof), polycarbonate, polyvinylpyrrolidone, vinylimidazole copolymers and polyether.
Dabei kann der Toner in bekannter Weise zur Verbesserung der Bildübertragung bzw. zum rückstandsfreien Zersetzen der Organik zusätzlich Ladungssteuer-stoffe und/oder Oxidationsmittel enthalten . Die beigefügten Oxidationsmittel beschleunigen die thermische Zersetzung der Kunststoff-Matrix.The toner can additionally contain charge control substances and / or oxidizing agents in a known manner to improve the image transfer or to decompose the organic without residues. The added oxidants accelerate the thermal decomposition of the plastic matrix.
Zur Verbesserung der Benetzung beim Aufschmelzen des Toners auf der in der Regel relativ polaren und glatten, im Gegensatz zu Papier nicht saugfähigen Oberfläche, ist der Toner zusätzlich mit Additiven beschichtet. Über eine geeignete Wahl bekannter Additive kann die Polarität der Toner zwischen un-polar, hydrophob, neutral, polar, hydrophil, und damit die Benetzung der Substrate gesteuert werden. Es kann dabei auf bekannte Fließhilfsstoffe, wie Aerosile und Übertragungshilfsmittel zurückgegriffen werden, um die Qualität des Druckes zu verbessern. Der Anteil derartiger Hilfsstoffe beträgt zwischen 0 und 1 ,0 Gew. %, typisch zwischen 0,2 und 0,5 Gew. %.The toner is additionally coated with additives to improve the wetting when the toner melts on the generally relatively polar and smooth, unlike paper, non-absorbent surface. The polarity of the toners between non-polar, hydrophobic, neutral, polar, hydrophilic, and thus the wetting of the substrates, can be controlled via a suitable choice of known additives. Known flow aids such as aerosils and transfer aids can be used to improve the quality of the print. The proportion of such auxiliaries is between 0 and 1.0% by weight, typically between 0.2 and 0.5% by weight.
Zum Abbau der Polymere (Depolymerisation) können dem Toner Peroxide oder Azoverbindungen beigegeben werden, die jedoch Zersetzungstemperaturen > 150° C aufweisen, damit die Zersetzung nicht schon während der Auf- schmelzphase (Fixierungsphase) einsetzt. Weiterhin sind auch anorganische Zuschlagsstoffe möglich, z.B. katalytisch wirkende Pigmente, die die Zersetzung der organischen Kunststoff-Matrix beschleunigen. Beispiele dafür sind soge-nannte Perowskite der allgemeinen Form ABO3, z.B. LaMnO3, LaCoO3, LaσSr/,Co Mn<5O3+e. Die nachstehende Tabelle zeigt Ausführungsbeispiele von Glaszusammenset- zungen (Fritten oder auch Flüsse), die sich besonders für einen keramischen Toner eignen. Die Gew. %-Angaben beziehen sich jeweils auf die Zusammen-setzung der Glasfritte.To break down the polymers (depolymerization), peroxides or azo compounds can be added to the toner, but these have decomposition temperatures> 150 ° C., so that the decomposition does not start during the melting phase (fixing phase). In addition, inorganic additives are also possible, for example catalytically active pigments, which accelerate the decomposition of the organic plastic matrix. Examples of this are so-called perovskites of the general form ABO 3 , for example LaMnO 3 , LaCoO 3 , La σ Sr / , Co Mn <5 O 3 + e . The table below shows exemplary embodiments of glass compositions (frits or rivers) which are particularly suitable for a ceramic toner. The percentages by weight relate in each case to the composition of the glass frit.
Die Glaszusammensetzungen 1 bis 6 sind besonders geeignet für Glas und Glaskeramiken.Glass compositions 1 to 6 are particularly suitable for glass and glass ceramics.
Spezielle Ausführungsbeispiele für Glaszusammensetzung 1 sind: Special exemplary embodiments for glass composition 1 are:
Spezielle Ausführungsbeispiele für Glaszusammensetzung 2 sind:Special exemplary embodiments for glass composition 2 are:
Glaszusammensetzung 7 ist besonders geeignet für Glaskeramik im Sekundärbrand. Glass composition 7 is particularly suitable for glass ceramics in secondary firing.
Glaszusammensetzung 8 bis 10 ist besonders geeignet für Glas.Glass composition 8 to 10 is particularly suitable for glass.
Glaszusammensetzung 11 bis 12 ist besonders geeignet für Keramik. Steingut. Bone China und Porzellan. Glass composition 11 to 12 is particularly suitable for ceramics. Earthenware. Bone china and porcelain.
Dabei sind zumindest bei den Zusammensetzungsbereichen 1 und 2 Eigen-schaften dieser Glasfritten angegeben, die insbesondere auf die besonderen Anforderungen für die Direktbedruckung von Glaskeramik mit einem Ausdeh-nungskoeffizienten von kleiner als 2x606 K 1 (im Temperaturbereich von 20 bis 700° C) abgestimmt sind. Mischungen der o.g. Glasfritten sind je nach Anwendungsfall ebenfalls denkbar.At least in the composition ranges 1 and 2 properties of these glass frits are specified which relate in particular to the special requirements for the direct printing of glass ceramics with an expansion coefficient of less than 2x60 6 K 1 (in the temperature range from 20 to 700 ° C). Mixtures of the above glass frits are also conceivable depending on the application.
Aufgrund der Eigenschaften dieser Glasfritten eignen sich diese daher besonders in Verbindung mit entsprechenden anorganischen Pigmenten zur elektrofotogra- fischen Bedruckung von Spezialglasplatten, wie beispielsweise Kalknatronglas oderDue to the properties of these glass frits, they are particularly suitable in combination with appropriate inorganic pigments for the electrophotographic printing of special glass plates, such as soda lime glass or
Borosilikatglas (gegebenenfalls jeweils zuvor beispielsweise mit SiO2 und/oder mit TiO2 oder mit einer der o.g. Glasfritten beschichtet, beispielsweise für die Anwendungen Ofenvorsatzscheiben, Backofen-Innenscheiben, Kühlschrankeinlegeböden, Thekenglas etc., sowie für die Direktbedruckung von Glaskeramik mit niedriger Ausdehnung, z.B. für die Anwendungen Glaskeramik- Kochflächen bzw. -Grillflächen oder Kaminsichtscheiben. Aber auch Keramik- Oberflächen, wie beispielsweise Fliesen oder Sanitärobjekte, lassen sich damit direkt bedrucken. Anforderungen hinsichtlich Abriebsbeständigkeit, Haftung und chemische Beständigkeit werden jeweils mit der Glasfrittenzusammensetzung gemäß der Tabelle besonders berücksichtigt.Borosilicate glass (if necessary, each previously coated, for example, with SiO 2 and / or with TiO 2 or with one of the above-mentioned glass frits, for example for the use of oven front panes, oven inner panes, refrigerator shelves, counter glass etc., as well as for direct printing on glass ceramics with low expansion, for example for applications such as glass-ceramic cooktops or grilling surfaces or fireplace viewing panes, but can also be used to print directly on ceramic surfaces such as tiles or sanitary objects. Requirements regarding abrasion resistance, adhesion and chemical resistance are taken into account with the glass frit composition according to the table.
Als Farbpigmente kommen typischerweise anorganische Verbindungen, wie beispielsweise Metalloxide, Mischphasen Metalloxid-Pigmente oder CIC-Pigmente (complex inorganic colour pigments), Einschlusspigmente, Metallpulver oder - flakes, Metallkolloide, Perlglanz- oder Lüsterpigmente auf Basis von Glimmer- oder glasigen oder SiO2- oder AI2O3-Plättchen, fluoreszierende Pigmente, mag-netische Pigmente, antikorrosive Pigmente, transparente Pigmente, eingesinterte Pigmente und/oder Mischungen von Pigmenten mit Glasfritten, Pigmente für Vierfarbsatz, usw. oder Mischungen der oben genannten Varianten in Betracht, die bereits hinreichend in der Literatur (z.B. "Ullmann's Encyclopedia of Industrial Chemistry", Vol. A20, 1 992, VCH Publishers, Inc.) beschrieben sind. Die Pigmente können auf unterschiedlichsten Kristallstrukturen basieren (Rutil, Spinell,Color pigments typically include inorganic compounds, such as metal oxides, mixed phases metal oxide pigments or CIC pigments (complex inorganic color pigments), inclusion pigments, metal powders or flakes, metal colloids, pearlescent or luster pigments based on mica or glassy or SiO 2 - or Al 2 O 3 platelets, fluorescent pigments, magnetic pigments, anti-corrosive pigments, transparent pigments, sintered pigments and / or mixtures of pigments with glass frits, pigments for four-color sets, etc. or mixtures of the above-mentioned variants, which are already considered sufficient in the literature (eg "Ullmann's Encyclopedia of Industrial Chemistry ", vol. A20, 1 992, VCH Publishers, Inc.). The pigments can be based on a wide variety of crystal structures (rutile, spinel,
Zirkon, Baddeleyit, Cassiterit, Korund, Garnet, Sphen, Pyrochlore, Olivin, Phenacit, Periklas, Sulfide, Perowskite ...) .Zircon, Baddeleyite, Cassiterite, Corundum, Garnet, Sphen, Pyrochlore, Olivine, Phenacite, Periclase, Sulfide, Perovskite ...).
Die typische Größe der Glasfluss-Partikel und der anorganischen Pigmente liegt dabei im Bereich von 0,5 bis 25 μm (D50 Vol.), insbesondere im Bereich von 1 bisThe typical size of the glass flow particles and the inorganic pigments is in the range from 0.5 to 25 μm (D50 vol.), In particular in the range from 1 to
10 μm. Beispiele für Mahlverfahren zur Herstellung derartiger Partikel sind Gegenstrahlmahlungen, Mahlungen in Kugel-, Ringspalt- oder Stiftmühlen.10 μm. Examples of grinding processes for the production of such particles are counter-jet grinding, grinding in ball, annular gap or pin mills.
Die Glasflussteilchen sowie die Pigmente sind aufgrund des Herstellprozesses des Toners von der Kunststoff-Matrix typischerweise nur teilweise, d.h. un-vollständig eingehüllt, und weisen in der Regel eine unregelmäßige Form auf. Dies liegt insbesondere daran, dass die anorganischen Bestandteile (Glasfluss und Pigmente) gegenüber der organischen Kunststoffmatrix unterschiedliche Bruchzähigkeiten aufweisen und beim Mahlprozess des Toners bevorzugt an den Korngrenzen aufbrechen. Zusatzadditive bzw. Fließhilfsstoffe, die später zugegeben werden, lagern sich an die Oberfläche der Kunststoffmatrix bzw. an die der frei liegenden Fluss- und/oder Pigmentteilchen an. The glass flow particles as well as the pigments are typically only partially from the plastic matrix due to the manufacturing process of the toner, i.e. incompletely encased, and usually have an irregular shape. This is due in particular to the fact that the inorganic constituents (glass flux and pigments) have different fracture toughnesses compared to the organic plastic matrix and preferentially break open at the grain boundaries during the grinding process of the toner. Additional additives or flow aids that are added later accumulate on the surface of the plastic matrix or on the exposed flux and / or pigment particles.

Claims

10A n s p r ü c h e1 5 10 Claims 1 5
1 . Keramischer Toner, der mittels elektrofotographischem Druckverfahren auf ein Glas-, Glaskeramik- oder Keramik-Substrat hoher Temperaturbeständigkeit übertragbar und in einem anschließenden Temperatur-prozess einbrennbar ist und der neben Glasfluss-Partikel auch Farb-pigment-Partikel1 . Ceramic toner that can be transferred to a glass, glass ceramic or ceramic substrate with high temperature resistance using an electrophotographic printing process and that can be burned in a subsequent temperature process, and which, in addition to glass flow particles, also contains color pigment particles
20 enthält, dadurch gekennzeichnet, dass er aufweist:20 contains, characterized in that it comprises:
> 30 bis 80 Gew. %, insbesondere 45 bis 60 Gew. %, einer speziellen> 30 to 80% by weight, in particular 45 to 60% by weight, of a special one
Glasfritte, undGlass frit, and
>5 0 bis < 20 Gew. %, insbesondere 5 bis < 20 Gew. % anorganische Pigmente und 20 bis 60 Gew. %, insbesondere > 30 bis 50 Gew. % einer Kunststoff-Matrix.> 50 to <20% by weight, in particular 5 to <20% by weight of inorganic pigments and 20 to 60% by weight, in particular> 30 to 50% by weight of a plastic matrix.
2. Keramischer Toner nach Anspruch 1 , ιo dadurch gekennzeichnet, dass der Glasfluss folgende Zusammensetzung aufweist: o2. Ceramic toner according to claim 1, characterized in that the glass flow has the following composition: O
3. Keramischer Toner nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Toner eine thermoplastische Kunststoff-Matrix aufweist, die im Temperaturbereich von 100° C bis 400° C homogen auf das Substrat aufschmilzt und im Temperaturbereich ab 300° C bis 500° C nahezu rückstandslos verdampft und/oder ausbrennt.3. Ceramic toner according to claim 1 or 2, characterized in that the toner has a thermoplastic plastic matrix which melts homogeneously on the substrate in the temperature range from 100 ° C to 400 ° C and in the temperature range from 300 ° C to 500 ° C evaporates and / or burns out almost completely.
4. Keramischer Toner nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Kunststoff-Matrix Tonerharze auf Acrylat-Basis, insbesondere Styrolacrylat, Polymethylmethacelat enthält.4. Ceramic toner according to one of claims 1 to 3, characterized in that the plastic matrix contains toner resins based on acrylate, in particular styrene acrylate, polymethyl methacelate.
5. Keramischer Toner nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Kunststoff-Matrix Polymere, beispielsweise Polyvinylalkohol, Polyoxymethylen, Styrolcopolymere, Polyvinylidenfluorid, Polyvinyl-butyral, Polyester (ungesättigte und/oder gesättigte oder Mischungen davon), Polycarbonat, Polyvinylpyrrolidon, Vinylimidazol-Copolymere und/oder Polyether enthält.5. Ceramic toner according to one of claims 1 to 4, characterized in that the plastic matrix polymers, for example polyvinyl alcohol, polyoxymethylene, styrene copolymers, polyvinylidene fluoride, polyvinyl butyral, polyester (unsaturated and / or saturated or mixtures thereof), polycarbonate, polyvinyl pyrrolidone , Vinylimidazole copolymers and / or polyethers.
6. Keramischer Toner nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass er als Zusatzadditive Ladungssteuerstoffe und/oder Oxidationsmittel enthält, zusätzlich Fließhilfsstoffe, wie Aerosile, enthält. 6. Ceramic toner according to one of claims 1 to 5, characterized in that it contains charge control agents and / or oxidizing agents as additional additives, additionally contains flow aids, such as aerosils.
7. Keramischer Toner nach einem der Ansprüche 1 bis 6, o dadurch gekennzeichnet, dass er zusätzlich mit Fließhilfsstoffen, wie Aerosile, beschichtetest.7. Ceramic toner according to one of claims 1 to 6, characterized in that it is additionally coated with flow aids, such as aerosils.
8. Keramischer Toner nach Anspruch 6 oder 7, dadurch gekennzeichnet,8. Ceramic toner according to claim 6 or 7, characterized in that
5 dass die Zuastzadditive und die Fließhilfsstoffe in einer Menge von jeweils5 that the additives and the flow aids in an amount of each
0 bis 1 ,0 Gew. %, insbesondere 0,2 bis 0,5 Gew. %, zugesetzt sind.0 to 1.0% by weight, in particular 0.2 to 0.5% by weight, are added.
9. Keramischer Toner nach einer der Ansprüche 1 und 8, dadurch gekennzeichnet, o dass die Partikelgröße der Glasfritte und der Pigmente im Bereich 0,5 bis 25 μm (D50 Vol.), insbesondere im Bereich von 1 bis 1 0 μm liegt.9. Ceramic toner according to one of claims 1 and 8, characterized in that the particle size of the glass frit and the pigments is in the range from 0.5 to 25 μm (D50 vol.), In particular in the range from 1 to 10 μm.
10. Keramischer Toner nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet,10. Ceramic toner according to one of claims 1 to 9, characterized in
5 dass die Tonerteilchen eine unregelmäßige Form aufweisen und nur teilweise von der Kunststoff-Matrix eingehüllt sind.5 that the toner particles have an irregular shape and are only partially enveloped by the plastic matrix.
1 1 . Keramischer Toner nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet,1 1. Ceramic toner according to one of claims 1 to 10, characterized in that
3 dass er zum Abbau der Polymere Peroxide und/oder Azoverbindungen mit3 that it uses peroxides and / or azo compounds to degrade the polymers
Zersetzungstemperaturen > 1 50° C aufweist. Has decomposition temperatures> 1 50 ° C.
1 2. Keramischer Toner nach einem der Ansprüche 1 bis 1 1 , o dadurch gekennzeichnet, dass der Toner auf ein Transfermittel aufbringbar ist.1 2. Ceramic toner according to one of claims 1 to 1 1, o characterized in that the toner can be applied to a transfer agent.
1 3. Keramischer Toner nach Anspruch 1 2, dadurch gekennzeichnet,1 3. Ceramic toner according to claim 1 2, characterized in
5 dass das Transfermittel ein mit Gummi-Arabicum beschichteter Träger, beispielsweise ein Papier oder eine Folie ist. 5 that the transfer agent is a carrier coated with gum arabic, for example a paper or a film.
EP02791827A 2002-01-08 2002-12-14 Ceramic toner for electro-photographic printing Withdrawn EP1466217A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE2002100412 DE10200412A1 (en) 2002-01-08 2002-01-08 A ceramic toner transferable to a high temperature resistant glass, glass or ceramic substrate by electrophotographic printing useful for the decoration of ceramic and glass products
DE20200229U DE20200229U1 (en) 2002-01-08 2002-01-08 Ceramic toner for electrophotographic printing
DE10200412 2002-01-08
DE20200229U 2002-01-08
PCT/EP2002/014262 WO2003058351A1 (en) 2002-01-08 2002-12-14 Ceramic toner for electro-photographic printing

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CA2472951A1 (en) 2003-07-17
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