WO2005052071A1 - Composition d'encre d'impression numerique - Google Patents

Composition d'encre d'impression numerique Download PDF

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Publication number
WO2005052071A1
WO2005052071A1 PCT/GB2004/004951 GB2004004951W WO2005052071A1 WO 2005052071 A1 WO2005052071 A1 WO 2005052071A1 GB 2004004951 W GB2004004951 W GB 2004004951W WO 2005052071 A1 WO2005052071 A1 WO 2005052071A1
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WO
WIPO (PCT)
Prior art keywords
composition according
dispersion
frit
poly
pigment
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Application number
PCT/GB2004/004951
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English (en)
Inventor
Peter Trenton Bishop
James Spencer Dalton
Detlef Rehorek
Abdurrahman Ugur Tezer
Alison Mary Wagland
Raimond Jozef Elisabeth Winkel
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Johnson Matthey Public Limited Company
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Publication of WO2005052071A1 publication Critical patent/WO2005052071A1/fr

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Classifications

    • 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents

Definitions

  • This invention relates to a composition suitable for application by an ink-jet print head, to a method of producing such a composition, and its use for the coating of substrates.
  • Inkjet printing as a printing or coating technique. It can produce high quality prints at high speed. As a non-contact method, it can be used to print on a wide range of substrates having different surface textures. The image to be printed is stored digitally, thus obviating the need for screens, engraving etc. In addition, images can be altered easily and rapidly, thus allowing for more variation in prints. No down time or cleaning between different designs is required. As the ink is only deposited where required, the technique minimises ink wastage and reduces cleaning requirements. The small size of the nozzles in a typical ink-jet print head place stringent demands on the physico-chemical properties of any ink used, however. Factors such as pigment particle size and ink viscosity, and the quality of pigment and frit dispersion, are important to prevent nozzle blockage.
  • compositions for application to substrates commonly include a powdered glass component or 'frit'. During subsequent heat treatment ("firing") the frit melts and bonds to the substrate.
  • the composition also contains an inorganic pigment, which does not itself melt during heat treatment, but is affixed to the substrate by, or incorporated with, the frit.
  • a combination of a frit and a pigment is often termed an enamel.
  • Enamels are widely used to decorate or produce coatings on ceramics such as tableware, where the composition may be applied by simple screen-printing methods, by applying decals comprising the enamels or by manual application for example, using dipping or a brush.
  • compositions applied by such techniques can vary within wide ranges without significantly affecting the final coating.
  • Compositions which do not contain a frit can only be affixed to substrates which at least partially melt during heat treatment, such as those already coated with a frit-containing composition, or by applying an over-layer of a frit-containing composition.
  • ink-jet ink formulations are soft materials and are available with a small particle size, in the order of tens to hundreds of nanometres. Such formulations are widely used for printing onto paper. It is less well known to use formulations containing harder, inorganic pigments.
  • WO 98/51749 discusses ink-jet compositions with low sedimentation rates, containing pigments of particle size less than 300 nm.
  • Patent GB 2268505 discusses continuous ink-jet printing of inks containing pigments of a size 0.2 - 2.0 ⁇ m. The pigments are suspended in a solvent, such as MEK and printed onto ceramic or glass substrates prior to firing.
  • US 6,332,943 discuss formulations containing organic and/or inorganic pigments stabilised with particular dispersants.
  • US 6,110,266 describes pigment preparations containing particles of inorganic materials of particles size 0.1-50 nm. There is little or no discussion of practicable ink-jet inks containing a frit component or metal particles, and we do not believe that such inks have been successfully prepared and printed.
  • a frit may be defined as "any fused substance or mixture quenched to a glass-like form" and is thus an amorphous material, as opposed to inorganic pigments which are very often crystalline and thus possess a primary particle size. Frits are also generally harder materials than inorganic pigments and as such, there is a danger that they could abrade the nozzles of an ink-jet printer. The other concern with frit (and indeed inorganic pigments) is that they are dense materials. Compared to organic pigments which have densities of the order of 1 g cm "3 , frits have densities in the order of 2-5 g cm "3 ' This means that compositions containing them may segregate more rapidly than conventional ink-jet inks. The properties of brittleness, hardness and high density combine to make frit a highly difficult material to formulate into an ink suitable for ink-jet printing. Similar problems apply to metal particles.
  • the present invention provides an improved composition which can be applied to a substrate by digital printing techniques and fixed thereto by heat treatment.
  • the prime interest of the Applicants is in inks formulated for ink-jet printing, successful trials have been carried out in producing inks according to the invention which have been successfully printed by bubble jet techniques, and it is contemplated that inks according to the invention will be suitable for other digital printing systems using liquid, thermoplastic or solid inks. The skilled person will determine necessary characteristics such as viscosity, drying characteristics etc.
  • a digital printing ink composition for example suitable for application by an ink-jet print head, comprises particles of at least one glass frit or metal, wherein the particles have a dioo size less than 2 ⁇ m, preferably less than 1 ⁇ m, more especially less than 0.7 ⁇ m, and a dispersion medium.
  • composition may be a concentrate, to be diluted before use, possibly with the addition of additional components, for application by an ink-jet printing head or by other systems.
  • the glass frit may be any suitable glass frit, for example a bismuth silicate frit, zinc borosilicate frit, lead silicate frits or other suitable frits. Mixtures of two or more glass frits are also suitable. In general, the particular frit chosen will depend upon the substrate and the firing profile, as is conventional.
  • the at least one glass frit or metal particles comprises between 1 and 70wt%, more preferably, between 20 and 50wt% of the composition.
  • a coating of glass frit, or a blend of glass frits or a blend of one or more glass frits with one or more colourless additives such as silica or alumina only from a frit/dispersion medium ink.
  • the composition further comprises at least one inorganic pigment. Suitable pigments will be known to those skilled in the art, are commercially available and include any refractory pigment.
  • Some non-limiting examples include copper chromite as a black, cobalt aluminium oxide and nickel chromium oxide.
  • the pigment may be simply a coloured frit, such as a blue frit, for example Johnson Matthey blue frit GK277B, and the invention thus encompasses such a coloured frit as the sole colouring agent in an ink composition, or in addition to a separate pigment. Frit and pigment may be combined in the form of an enamel, that is a sintered combination of frit and pigment. Further the ink composition may comprise a pigment, or conceivably a frit or frit component, that is fluorescent or luminescent.
  • Such pigments include: magnesium fluorogermanate red (Meldform Germanium Ltd), Lumilux green GDI 17, Lumilux blue CD 164, Lumilux red CD115 and Lumilux yellow/orange CD 130 (All Lumilux products available from Allied Signal or its distributors, e.g. Chemproha, Chemie Partner BV). Mixtures of two or more pigments, or pigments with metal particles are also suitable.
  • the at least one inorganic pigment comprises between 1 and 40wt% of the composition.
  • the particle size of the glass frit or metal particles, as well as any pigment used should be small.
  • the at least one glass frit and any pigment used have a d 10 o particle size of less than 2 ⁇ m, more preferably less than 1 ⁇ m, most especially less than 0.5 ⁇ m.
  • d 100 particle size is the particle size at which 100% of particles in a given sample are smaller, and may readily be achieved by sieving out oversize particles.
  • the medium comprises one or more of water, alcohols, glycol ethers, lactates, glycol ether acetates, aldehydes, ketones, aromatic hydrocarbons and oils. Mixtures of two or more solvents are also suitable. Some presently preferred examples include; diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether and 1-methoxy 2- propanol. These media are ideal for "drop-on-demand" piezoelectric or electrostatic printheads.
  • the composition may frirther comprises one or more synthetic or natural polymers.
  • Polymers may be used to alter the viscosity and viscoelastic nature of the compositions which influences the break-up of the jet and thus ink satellites and ligaments. Polymers may also be used to provide green strength to the applied composition prior to heat treatment. Suitable polymers include; poly(acrylates), poly(methacrylates), cellulose derivatives, poly(styrene-co- maleic anhydride) polymers both partially esterified and non-esterified, poly(vinylpyrrolidone), poly(styrenes), poly(vinylalcohols), poly(vinylbutyral) and poly(esters). Rosin-derived material such as hydrogenated rosins, rosin dimers, maleated rosin and rosin esters, may also be added.
  • the composition may further comprise one or more additives.
  • additives may include surfactants to modify the surface tension or wetting properties of the ink such as poly(siloxane) based wetting agents, defoamers, humectants, biocides, buffers, adhesion promoters, tackifiers and dyes.
  • the additives may also comprise "dispersing aids", such as, but not limited to those from the disperB YK, Solsperse or Dispex ranges, in particular Disperbyk 180 and Solsperse 40000, and/or rheology modifiers.
  • a method for producing a composition, according to the invention comprises forming a dispersion of a glass frit in a dispersion medium, comminuting the dispersion to reduce the particle size of the frit, and filtering the dispersion to remove oversized frit particles.
  • a dispersion of a glass frit in a dispersion medium
  • comminuting the dispersion to reduce the particle size of the frit
  • filtering the dispersion to remove oversized frit particles.
  • metal particles techniques are known for producing small particles by solution chemistry and other techniques.
  • the method further comprises forming a second dispersion of an inorganic pigment in a solvent, comminuting the dispersion to reduce the particle size of the inorganic pigment, filtering the second dispersion to remove oversized pigment particles, and combining the filtered second dispersion with the filtered frit dispersion.
  • both the frit and the pigment may be comminuted as a single dispersion, which is then filtered. This leads to a simpler process but is presently not preferred as the different physical properties of the frit and the pigment make achieving a uniform particle size for both problematic.
  • a method of producing a coating on a substrate comprises applying a composition as described hereinbefore to a substrate using a digital print technique such as an ink-jet printing head, and heat treating the substrate.
  • the substrate is a transfer medium, such as a gum or release paper, and the printed pattern in the form of a decal is transferred to the substrate before firing.
  • the substrate may be a ceramic such as bone china, porcelain or earthenware, a glass article or sheet or a metal, or similar substrate such an enamelled metal substrate or a glazed substrate such as a tile.
  • the substrate may be a plastics substrate, for example a glass fibre- reinforced printed circuit board substrate, in which case the heat treatment may be a temperature- or UV-initiated curing step.
  • the temperature and length of the heat treatment step will depend on the nature of the composition applied and the type of substrate. Typically, temperatures between 400 and 1300°C will be suitable.
  • Heat treatment may be by any suitable means for example, furnace heating, laser heating. The heat treatment conditions can be optimised by routine trial and error.
  • the coating may be a decorative coating such as a picture or pattern.
  • the method may be used to provide a functional coating.
  • functional coatings include security markings, including information tagging or information marking and barcodes, and, coatings on glass sheets to provide safety contrast bands to indicate the presence of glass sheets to pedestrians, barrier coatings or bands including UV barrier coatings, such as black obscuration bands for vehicle glass.
  • functional coatings such as conductive tracks may be produced, or a decorative coating in the case of gold.
  • Gold particle-containing inks may also comprise solubilised gold compounds which yield a gold film.
  • a bismuth silicate glass frit J5405F (440g, Johnson Matthey Glass, Maastricht) supplied with a d 0 of 15 microns, was stirred into a mixture of Dowanol DB (145g), poly(vinylpyrrolidone) (6g) and Disperbyk 180 (1 lg).
  • the mixture was dispersed in a Dispermat bead mill at a rate of 5000 rpm for 6 hours.
  • the milling media used was 0.8mm yttria stabilised zirconia beads.
  • the particle size attained was a d 9 o of ⁇ 2 microns.
  • a further 50g of Dowanol DB was used to clear the ink from the mill and then the mixture was further diluted with the addition of more medium to give a solids content of 49.3% by weight.
  • Dispersions as made in Examples 1 and 2 were filtered through a 3 micron polypropylene precision mesh in order to remove any larger particles.
  • the two dispersions were mixed together thoroughly at the ratio of 3 parts frit to 1 part pigment by weight to produce a black ink.
  • the ink had a viscosity of 9 Pas at a shear rate of 10s "1 as measured on a Bohlin CVOR rheometer at 23 °C.
  • the surface tension was 30.1 mNm "1 as measured on a Camtel CDA 100.
  • Ink prepared as in Example 3 was printed through a Trident Ultrajet II piezoelectric print head onto glass. The prints were further treated by heating in a furnace with a 10 minute ramp from room temperature to 700°C followed by a dwell at 700°C for 3 minutes and a return to room temperature over 10 minutes. The ink was well adhered to the glass and possessed a good opacity.
  • Example 5 A lead borosilicate frit 2160BF (440 g, Johnson Matthey Glass), supplied with a d 0 of 1.9 microns, was stirred into a mixture of Dowanol DB (165 g) and Solsperse 40000 (11 g). The mixture was dispersed in a Dispermat bead mill at a rate of 6000 rpm for 6 hours to obtain a particle size with d 90 of less than 1.5 microns. The milling media used was 0.8 mm yttria stabilised zirconia beads. The ink was removed from the mill and diluted to 50 weight % solids using Dowanol DB. The residue ink remaining in the mill was removed separately and not added to the main ink.
  • Dowanol DB 165 g
  • Solsperse 40000 11 g.
  • the mixture was dispersed in a Dispermat bead mill at a rate of 6000 rpm for 6 hours to obtain a particle size with d 90 of less than
  • a blue cobalt aluminate pigment (420 g), supplied with a d 90 of 1.9 microns, was stirred into a mixture of Dowanol DB (216 g), poly(vinylpyrrolidone) (8 g) and Disperbyk 180 (18 g).
  • the mixture was dispersed in a Dispermat bead mill at a rate of 5500 rpm for 2 hours to obtain a particle size with d 0 of 1.1 microns.
  • the milling media used was 0.8 mm yttria stabilised zirconia beads.
  • the ink was removed from the mill and diluted to 50 weight % solids using Dowanol DB. The residue ink remaining in the mill was removed separately and not added to the main ink.
  • Ink prepared as in example 3 was printed through a Spectra piezoelectric printhead. The prints were further treated by heating in a furnace to 580 °C. The ink was well adhered to the glass and possessed a good opacity.
  • a bismuth silicate glass frit J5405F (35.6 kg, Johnson Matthey Glass) supplied with a d 90 of 15 microns was stirred into a mixture of Dowanol DB (13.54 kg) and Disperbyk 180 (0.864 kg). The mixture was dispersed and milled on a Netzsch LMZ 10 for 8 hours. After 6 hours a further 2.66 kg of Dowanol DB/Disperbyk mixture (ratio 94 parts :6 parts) was added. The milling media used was 0.4-0.7 mm zirconox beads. The particle size obtained was a d 90 ⁇ 1.5 microns.
  • This 'inkjet concentrate' had a viscosity of 320 mPas at a shear stress of 50 Pa after an initial pre shear of 20 seconds at 50 Pa.
  • the 'inkjet concentrate' was diluted with a glycol ether or glycol ether acetate to attain a viscosity ⁇ 15 mPas required for inkjet printing through Spectra or Trident printheads.
  • Typical solids content was 40 — 55%
  • a copper chromite pigment (25 kg) supplied with a d 90 of 3.1 microns was stirred into a mixture of Dowanol DB (9.5 kg) and Disperbyk 180 (0.625 kg). The mixture was dispersed and milled on aNetzsch LMZ 10 for 5 hours. After 3 hours a further 2.66 kg of Dowanol DB/Disperbyk mixture (ratio 94 parts :6 parts) was added. The milling media used was 0.4-0.7 mm zirconox beads. The particle size obtained was a d 99 ⁇ 1.0 microns.
  • the 'inkjet concentrate' was diluted with a glycol ether or glycol ether acetate to attain a viscosity ⁇ 15 mPas required for inkjet printing through Spectra or Trident printheads.
  • Typical solids content was 40 - 55%
  • a Johnson Matthey frit J5405F was milled in Dowanol DB together with 0.46 wt% Disperbyk 180 to produce a first suspension.
  • a conventional copper chromite black pigment Black 1G, Shepherd Color Co. was milled in Dowanol DB, together with 2 wt% of Disperbyk 180, and mixed with the first suspension in an amount to yield a frit to pigment solids ratio of 3:1.
  • the mixed suspensions are diluted with Dowanol PMA and the other components listed below, and stirred for an hour using a high shear mixer.
  • the mixture was filtered through a 1 micron screen, and the viscosity adjusted to about 15 cP, to form an ink.
  • the ink was successfully printed onto glass sheet using a commercial ink-jet print head, and the glass sheet was fired.
  • a solution of silver nitrate (12.5 g - 25.0 g) in deionised water was prepared. This was added to a 2-10 wt% polyvinylpyrrolidone (Mol. Wt. 40,000 or 55,000) solution in Dowanol DE, Dowanol TM or a 50:50 mix of Dowanol PM and diethyleneglycol (50g). The solution was gently stiired for 24 hours to form a PVP-stabilised silver nanoparticle suspension. To 40g of this suspension up to 0.1 g of rhodium acetate was added as an adhesion improvement component. The inks produced have been successfully printed through Spectra and Trident printheads.
  • 1272464 was mixed with a solvent (a glycol ether, such as dipropyleneglycol monopropyl ether (Dowanol DPnP), dipropyleneglycol monobutyl ether (Dowanol DPnB) or diethyleneglycol monobutyl ether (Dowanol DB), or a ketone such as 3,3,5 trimythylcyclohexanone or menthone.) After stirring, the resulting gold particle suspension is filtered through a 1 micron filter mesh.
  • a glycol ether such as dipropyleneglycol monopropyl ether (Dowanol DPnP), dipropyleneglycol monobutyl ether (Dowanol DPnB) or diethyleneglycol monobutyl ether (Dowanol DB)
  • a ketone such as 3,3,5 trimythylcyclohexanone or menthone.
  • the suspension may contain additional components selected from one or more of rhodium ethylhexanoate for promotion of gold film formation, polyvinylpyrrolidone (MW 40,000) as a film former (preferably ininitially dissoled in the solvent) and a vanadium salt to improve adhesion.
  • polyvinylpyrrolidone MW 40,000
  • a vanadium salt to improve adhesion.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Wood Science & Technology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention a trait à une composition d'encre d'impression numérique comportant au moins une fritte de verre ou des particules métalliques ayant une taille de particule inférieure à 2 νm et un milieu de dispersion, comprenant de préférence également un pigment inorganique, et est appropriée pour un dépôt sur des substrats. Le revêtement d'encre peut être soumis à une cuisson pour produire un revêtement permanent.
PCT/GB2004/004951 2003-11-25 2004-11-24 Composition d'encre d'impression numerique WO2005052071A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0327340A GB0327340D0 (en) 2003-11-25 2003-11-25 Ink-jet composition
GB0327340.6 2003-11-25

Publications (1)

Publication Number Publication Date
WO2005052071A1 true WO2005052071A1 (fr) 2005-06-09

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Cited By (22)

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WO2008053235A1 (fr) * 2006-11-04 2008-05-08 Xennia Technology Limited Impression par jet d'encre
EP1975209A1 (fr) * 2007-03-27 2008-10-01 Mimaki Engineering Co., Ltd. Encre à basé de solvant pour impression à jet d'encre.
WO2008148901A1 (fr) * 2007-06-08 2008-12-11 Chimigraf Ibérica, Sl Procédé de fabrication d'une encre d'impression numérique et encre ainsi obtenue
WO2009029738A1 (fr) * 2007-08-31 2009-03-05 Ferro Corporation Structure de contact en couches pour des cellules solaires
WO2009067151A3 (fr) * 2007-11-20 2009-11-26 Corning Incorporated Pâtes contenant une fritte permettant de produire des motifs de fritte frittés sur des feuilles de verre
WO2009147676A1 (fr) * 2008-06-05 2009-12-10 Dip Tech. Ltd. Procede d’impression sur le cote interieur d’un verre stratifie et stratifies de verre ainsi formes
US7781493B2 (en) 2005-06-20 2010-08-24 Dow Global Technologies Inc. Protective coating for window glass
US7803221B2 (en) 2003-08-25 2010-09-28 DIP Tech LTd.. Ink for ceramic surfaces
US7939161B2 (en) 2006-12-19 2011-05-10 Dow Global Technologies Llc Encapsulated panel assemblies and methods for making same
US20130209769A1 (en) * 2012-02-09 2013-08-15 E I Du Pont De Nemours And Company Corona resistant structures and methods relating thereto
WO2013130332A3 (fr) * 2012-02-29 2013-11-28 Wki Holding Company, Inc. Procédé et système pour impression à jet d'encre d'images sur des surfaces à contours complexes d'articles en céramique et en verre tels que de la vaisselle
WO2014072553A1 (fr) * 2012-11-12 2014-05-15 Torrecid, S.A. Composition d'émail numérique pour injection d'encre
WO2014111606A1 (fr) * 2013-01-21 2014-07-24 Torrecid, S.A Émail numérique pour grammages supérieurs, sans emploi d'agents stabilisateurs
CN104011151A (zh) * 2012-04-24 2014-08-27 埃斯马尔格拉斯股份有限公司 数字釉墨
US8894872B2 (en) 2007-09-24 2014-11-25 Dip Tech Ltd. Etching compositions, methods and printing components
EP2808366A4 (fr) * 2012-01-26 2015-07-15 Hitachi Ind Equipment Sys Encre, base à imprimer, imprimante, procédé d'impression et procédé de production d'une base à imprimer
DE202015006002U1 (de) 2014-07-14 2015-09-22 Schott Ag Keramische Tintenstrahldrucktinte für niedrigausdehnendes Glas und/oder niedrigausdehnende Glaskeramik
EP2818523A4 (fr) * 2012-02-23 2015-10-14 Torrecid Sa Composition d'encre pour décoration de substrats non poreux
US9193880B2 (en) 2006-12-19 2015-11-24 Dow Global Technologies Llc Adhesion promotion additives and methods for improving coating compositions
WO2016110724A1 (fr) * 2015-01-07 2016-07-14 Fenzi Spa Composition de fritte de verre et encre pour impression jet d'encre sur céramique la comprenant
US10120111B2 (en) 2016-12-14 2018-11-06 Google Llc Thin ceramic imaging screen for camera systems
WO2019117697A1 (fr) * 2017-12-13 2019-06-20 Guzman Diaz Covarrubias Leonardo Verre décoré pour appareil électroménager et ligne blanche

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WO1996003466A1 (fr) * 1994-07-27 1996-02-08 Cookson Matthey Ceramics & Materials Limited Compositions de pates ou d'encres d'imprimerie
JPH09237570A (ja) * 1996-02-28 1997-09-09 Dainichiseika Color & Chem Mfg Co Ltd ブラックマトリックス用着色組成物、ブラックマトリックスの製造方法及び遮光性ブッラクマトリックスを付した発光型フラットパネルディスプレイパネル
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