WO2015003736A1 - Encre céramique pour impression par jet d'encre - Google Patents

Encre céramique pour impression par jet d'encre Download PDF

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Publication number
WO2015003736A1
WO2015003736A1 PCT/EP2013/064387 EP2013064387W WO2015003736A1 WO 2015003736 A1 WO2015003736 A1 WO 2015003736A1 EP 2013064387 W EP2013064387 W EP 2013064387W WO 2015003736 A1 WO2015003736 A1 WO 2015003736A1
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WO
WIPO (PCT)
Prior art keywords
glass frit
composition
μιη
pigment
present
Prior art date
Application number
PCT/EP2013/064387
Other languages
English (en)
Inventor
Tri Ratna TULADHAR
Domenico DI LONARDO
Fabio Enzo FENZI
Original Assignee
Fenzi Spa
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
Application filed by Fenzi Spa filed Critical Fenzi Spa
Priority to PCT/EP2013/064387 priority Critical patent/WO2015003736A1/fr
Publication of WO2015003736A1 publication Critical patent/WO2015003736A1/fr

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Classifications

    • 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
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • 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
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • 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
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • 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
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • 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
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • 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
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/29—Mixtures
    • 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
    • C03C2217/45—Inorganic continuous phases
    • C03C2217/452—Glass
    • 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
    • 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
    • C03C2217/70—Properties of coatings
    • C03C2217/72—Decorative coatings
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/119—Deposition methods from solutions or suspensions by printing

Definitions

  • the present invention relates to a ceramic inkjet ink and the manufacturing method thereof for printing on ceramic substrate such as glass. Further, the present invention relates to a glass frit composition and the manufacturing method thereof. Furthermore, the present invention relates to an inkjet process.
  • inorganic ceramic paints containing glass frit and inorganic pigments
  • silk-screen, roller coating, curtain coating and spray Typical paint viscosities for such applications are in
  • viscosity (less than 50 mPa.s) in order to eject drop.
  • the high solid concentration and particle size in the ink is also an issue in terms of nozzle blockage and reliable jetting.
  • typical drop on demand inkjet printhead require ink bulk viscosity of 6-20 mPa.s, a surface tension of 20-40 mN/m, a highly stable
  • particle/pigment size which is commonly less than 1 ⁇ and a solid content below 20 wt . %.
  • viscosity and surface tension which comprises particles with an average size distribution of more than 1 ⁇ and with a solid content higher than 20 wt. % which does not incur the drawback of nozzle blockage and therefore provides a
  • the ceramic inkjet ink composition according to the present invention comprises:
  • zinc oxide and/or bismuth oxide based glass frit composition comprising 20-60 wt . % S1O 2 , 3-30 wt % B 2 0 3 , 10-40 wt. % ZnO and/or 10-70 wt . % Bi 2 0 3 of the total weight of the (zinc oxide and/or bismuth oxide based) glass frit composition wherein the glass frit has the form of particles having an average size distribution in the range from 1.2 ⁇ to 3 ⁇ ;
  • the ceramic inkjet ink composition according to the present invention has suitable properties for inkjet printing.
  • the ceramic inkjet ink composition according to the present invention can be used for printing on any substrate, in any printing conditions.
  • the substrate can be for example glass, ceramic tiles.
  • the ceramic inkjet ink composition according to the present invention can be used in commercial drop on demand inkjet devices.
  • the ceramic inkjet ink composition comprises ' a glass frit composition'.
  • the ceramic inkjet ink comprises advantageously one glass frit composition, or the ceramic inkjet ink can comprise more than one glass frit composition, such as two, three, or four different glass frit compositions. Accordingly, the ceramic inkjet ink composition can comprise 'one or more glass frit composition'.
  • the glass frit composition is based on zinc oxide, or on bismuth oxide, or on zinc oxide and bismuth oxide.
  • the glass frit composition respectively comprises an amount of zinc oxide in weight percent of the total weight of the glass frit composition, or an amount of bismuth oxide in weight percent of the total weight of the glass frit composition, or an amount of zinc oxide and an amount of bismuth oxide in weight percent of the total weight of the glass frit composition.
  • the glass frit composition has the form of particles.
  • the shape of the particles can be any shape.
  • the size of the particle is defined by their "average particle size distribution”.
  • the term "average particle size distribution” is to be understood as defining the relative amount, typically by mass, of particles present according to size.
  • the average particle size distribution is also designated as D 90 (defining the distribution of the size (or diameter) of 90 percent of the particles) .
  • the glass frit composition is a glass frit which has the form of particles having an average size distribution in the range from 1.2 ⁇ to 3 ⁇ , more advantageously from 1.2 ⁇ to 2.5 ⁇ , even more advantageously from from 1.2 ⁇ to 2.0 ⁇ , yet more advantageously from 1.5 ⁇ to 2.0 ⁇ , most advantageously at about 1.7 ⁇ (e.g. 1.7 ⁇ +/- 0.25 ⁇ ) .
  • most of the particle size, or dimensions are within the above-mentioned range.
  • the term "about” is to be understood as within the boundaries of experimental error, i.e. +/- a certain value, such as 1% to 15% of the given parameter.
  • the glass frit composition comprises 20-70 wt . % of one glass frit composition, advantageously 20-60 wt . %, more advantageously 30-60 wt . %, most advantageously 45-60 wt . % .
  • the glass frit composition of the present invention is a zinc oxide and/or bismuth oxide based glass frit composition.
  • the glass frit composition according to the present invention comprises 20- 60 wt. % Si0 2 , 3-30 wt % B 2 0 3 and 10-40 wt . % ZnO, or 10-70 wt. % Bi 2 0 3 , or 10-40 wt . % ZnO and 10-70 wt . % Bi 2 0 3 , of the total weight of the zinc oxide and/or bismuth oxide based glass frit composition.
  • the glass frit composition can have the following formulations:
  • Formulation 1 bismuth based
  • oxides such as K 2 0, CaO, ZnO, MgO, BaO, P 2 05, ZrO, A1 2 0 3 can be present in an amount of less than 10 wt . % .
  • Formulation 2 zinc based
  • oxides such as MgO, BaO, A1 2 0 3 , P 2 0 5 ,
  • ZrO.can be present in an amount of less than 10 wt. %.
  • the glass frit composition used in the ceramic inkjet ink composition is the glass frit composition described hereafter.
  • the pigment can be any inorganic colour pigment.
  • the inorganic pigments powder is produced by high temperature calcination.
  • the pigments can be oxides of metals such as cobalt, iron, nickel, copper, titanium dioxide for different colours.
  • inorganic pigments used in the formulations can be Cobalt chromite Blue green Spinel (Shepherd Blue 211, Shepherd Blue 30C527), Cobalt Aluminate Blue Spinel
  • These pigments are heat resistant inorganic pigments, chemically inert and stable to ultraviolet light. They have high durability and hiding power.
  • the pigment type, size and its particle interaction can be adjusted during formulation to meet the final tempered colour of the ink as well as fulfil the requirement of hiding power (optical property used to describe the light- scattering efficiency of a white pigment) and opacity
  • the term “carrier” is to be understood as a liquid or organic solvent, such as at least one organic solvent, such as at least two organic solvents.
  • the carrier is a mixture of two or more different organic solvents which are low volatility solvents to prevent ink drying in the nozzle and prevent nozzle blockage. They can also be high volatile solvent to enhance drying post landing and prevent ink bleed/spread .
  • solvents can be alcohols, such as Methyl alcohol, Ethyl alcohol, propyl alcohols, butyl alcohols.
  • Glycol Methyl glycol (MG) , Ethyl glycol, propyl glycol, Butyl glycol (BG) , and/or glycol ether, such as Methoxy propanol (PM) , Ethoxy propanol (EP) , Diacetone propanol (DAA) , Methoxy butanol, Dipropylene glycol monomethyl ether (DPM) , Tripropylene glycol methyl ether (TPM) , propylene glycol mono methyl ether (PM) , di or tri Propylene glycol mono propyl ether (DPnP, TPnP) , Butyl diglycol (BDG) and/or esters such as Methyl acetate, Ethyl acetate (ETAC) , Propyl acetate ( IPAC) , Butyl acetate (BUAC) , Methoxy propyl acetate (PMA) , Ethyl-3-ethoxy-propan
  • the carrier can also be mixtures of short chain alkane waxes with a low melting point of 40-100°C. It is solid at room temperature.
  • Example of such carrier could be low melting paraffin wax.
  • the inkjet ink composition according to the present invention is a wax based inkjet ink.
  • the carrier is a mixture of alkanes with short chains, i.e.
  • n-alkanes linear alkanes
  • n-alkanes linear alkanes
  • the n-alkanes have at least 10 carbon atoms, preferably 12 carbon atoms, more preferably 14 carbon atoms.
  • the carrier is a mixture of alkanes with short chains, such as a C 10 -C25 chain, more advantageously a C10-C22 chain, even more advantageously a Cio-Cis chain, most advantageously a C 12 -C18 chain.
  • the mixture of alkanes can comprise at least two, at least three, at least four, at least five, at least six, at least seven, at least eight, at least nine, or at least ten (or more) different n-alkanes.
  • the ceramic ink composition of the present invention can comprise additives in an amount up to
  • the ceramic ink composition of the present invention can comprise 0-10 wt . % of one or more additives to meet jetting and substrate requirements.
  • the additives can be chosen from the group consisting of
  • rheology additives surfactants, ant i-sett ling/stat ic agents, dispersant, flow and levelling agent,
  • the glass frit According to the present invention, the glass frit
  • composition and the pigment form a solid content in the range 20-70 wt%, such as 30 to 60 wt%, preferably 40 to 60 wt%, more preferably 40 to 50 wt% of the total weight of the composition.
  • the remaining portion (in wt . %) of the total weight of the composition is the carrier and additives.
  • the glass frit According to the present invention, the glass frit
  • composition and the pigment form a solid content having an average particle size distribution in the range of 1.2 ⁇ to 3 ⁇ , advantageously 1.2 ⁇ to 2.5 ⁇ , more advantageously 1.5 ⁇ to 2.0 ⁇ .
  • the ceramic inkjet ink composition according to the present invention has accordingly an average particle size
  • the ink properties are tightly controlled and optimised to meet printhead and in-flight conditions in order to generate reliable drops, namely:
  • the apparent zero shear viscosity of the ink can be significantly higher than 20 mPa.s at room temperature, - a surface tension of 20-40 mN/m (process and substrate dependent ) ,
  • the ink properties of the ceramic inkjet ink composition according to the present invention are such, that at jetting, the following is prevented: drop
  • the ceramic inkjet ink composition according to the present invention is tuned with appropriate
  • resins/additives to give good grip after drying the ink on the substrate at temperature equal to or above 150°C, for manual handling.
  • the ceramic inkjet ink composition according to the present invention has a high chemical resistance, e.g. resistance to acid, base, UV resistance, a high
  • glass frit composition comprising:
  • the glass frit composition comprises 20-60 wt . % Si0 2 and/or - 30-70 wt. % Bi 2 0 3 ,
  • the glass frit composition comprises 20-60 wt . % Si0 2 and
  • the glass frit comprises 20-60 wt . % S1O 2 and
  • the glass frit According to the present invention, the glass frit
  • composition has the form of particles having an average size distribution equal to or below 3 ⁇ , advantageously equal to or below 2 ⁇ .
  • the particles have preferably an average size distribution in the range from 1.2 ⁇ to 3 ⁇ , more
  • the glass frit particles may as well be advantageous for the glass frit particles to have an average size distribution of at least 1.2 ⁇ , more
  • the particle of the glass frit can have any value with the above range, such as about 1.2 ⁇ , about 1.3 ⁇ , about 1.4 ⁇ , about 1.5 ⁇ , about 1.6 ⁇ , about 1.7 ⁇ , about 1.8 ⁇ , about 1.9 ⁇ , about 2.0 ⁇ , about 2.1 ⁇ , about 2.2 ⁇ , about 2.3 ⁇ , about 2.4 ⁇ , about 2.5 ⁇ , about 2.6 ⁇ , about 2.7 ⁇ , about 2.8 ⁇ , about 2.9 ⁇ , about 3.0 ⁇ .
  • the composition of the frit can be fine-tuned during frit preparation to meet the final substrate requirements after tempering (thermal treatment) : frit glass transition temperature is reached to melt the composition material and fuse on to the ceramic surfaces.
  • the glass frit according to the present invention has a high chemical resistance, e.g. resistance to acid, base, UV resistance, a high mechanical resistance, e.g.
  • the ceramic inkjet ink composition consists of components a) , b) and c) .
  • the glass frit composition consists of the above mentioned components.
  • Yet another aspect of the present invention is a method for the manufacture of a glass frit having a composition
  • step 5) reducing the size of the milled frit obtained in step 4) by wet milling to obtain a frit wherein the particles have an average particle size distribution equal to or below 3 ⁇ .
  • step 2 of the method according to the present invention occurs at the glass transition temperature of the glass frit
  • the frit stability and particle size is maintained through multiple grinding steps (steps 4) and 5)) to reduce the particle size below 3 micron: Milling is carried out in two stages: first, dry Milling followed by wet milling: The dried quenched frit is initially milled dry.
  • An example of such unit used in our application is fluidised jet mill. Commercial fluidised jet mill and ultra fine grinding system is used where milling is achieved by particle to particle impact along the gas stream and at the centre of the chamber. The frit is milled to achieve the final size around 7
  • milling is to be understood as a process of grinding materials. Dry milling is a milling process occurring without solvent. Wet milling occurs with additives.
  • jet milling is to be understood as a process of using highly compressed air or other gasses, usually in a vortex motion, to impact fine particles against each other in a chamber.
  • the concentrated premixed jet milled frit is milled in commercial high speed mill with special grinding chamber components such as zirconia, silicon nitrite and/or silicon carbide .
  • the milling can be carried in batch in multipass operation until the desired particle size is obtained.
  • the final composition is well dispersed frit paste with final particle size equal to, or below 3 ⁇ .
  • the definitions and preferences described for the ceramic inkjet ink composition according to the present invention are applicable to the glass frit composition and the method for the manufacture of the glass frit composition according to the present invention.
  • Still another aspect of the present invention relates to a method for the manufacture of an inkjet ink comprising the steps of :
  • step iii) in order to obtain a mixture having 30 to 60 wt. % of solid content of the total weight of the mixture; v) filtering the mixture obtained in step iv) and thereby providing an inkjet ink having a viscosity of 6-20 mPa.s at the jetting temperature and jetting
  • additives can be added in steps iii) and/or iv) , such as 0-2 wt . % of surfactant, and/or 0-10 wt . % of dispersants, and/or
  • wt . % of one or more additives chosen from the group consisting of deaerating agents, defoaming agents, flow and leveling agents, rheology modifiers.
  • the wt . % given for the additives is to be referred to the total weight of the ceramic inkjet ink mixture frit/pigment/carrier/eventual additives.
  • the additives are commercially available product or specifically tailored to the formulations.
  • additives examples include one or more compound of the following list:
  • polydimethylsiloxane BYK-301, BYK-302, BYK 306, BYK 337, BYK 341
  • polyether modified polydimethylsiloxane BYK-307, BYK 333
  • solution of a polyester-modified polydimethylsiloxane BYK-310, BYK-3163 solution of polyester-modified
  • Disperbyk 194, Tego Dispers 7502, Tego Dispers 752W) block- copolymer with pigment affinic groups (Disperbyk 2155), solution of alkylol ammonium salt of a higher molecular weight acidic polymer (Anti-terra-250 ) , structured acrylate copolymer with pigment affinic groups (Disperbyk 2010
  • polyvinylpyrrolidone PVP K-15, PVP K-30, PVP K-60
  • polymeric hyperdispersant Solsperse J930
  • - deaerating/defoaming agents Silicone free (BYK 051, BYK 052, BYK 053, BYK 054, BYK 055, BYK 057, BYK 1752, BYK-A 535), emulsion of hydrophobic solids, emulsifiers and foam destroying polysiloxanes (BYK-610), Fluoro modified silicone defoamer (Dynoadd F-470), non-silicone anionic (Dynoadd F- 603), organo-modified polysiloxane (Tego Airex 900,
  • the amount of glass frit is 20-70 wt %, preferably 20-60wt. % of the total weight of the mixture frit/pigment/carrier/eventual additives
  • the amount of inorganic pigment is 0-30 wt % of the total weight of the mixture frit/pigment/carrier/eventual additives
  • the carrier is 20-60 wt . % of the total weight of the mixture
  • frit /pigment/carrier/eventual additives frit /pigment/carrier/eventual additives .
  • the pigment paste in step i) is prepared by reducing the size of pigment
  • particles to an average size distribution equal to or below 1 ⁇ , preferably equal to or below 0.5 ⁇ , by milling and grinding in the presence of a dispersant and a carrier.
  • pigmented particle should be ideally below 1 ⁇ , preferably below 0.5 ⁇ .
  • the pigment size is reduced to an average size distribution equal to or below 1 ⁇ by milling and grinding in the presence of dispersant and carrier.
  • the pigment inter- medium paste must have defined particle size with a narrow particle size distribution and should be very stable.
  • the concentrated pigment paste (50-80 wt . % of the pigment paste) is then prepared using bead/ball mill resulting in a well dispersed pigment with a size less than 1 ⁇ .
  • the mechanical grinding in agitator bead mills produce particles in sub-micron range with a narrow particle size
  • Improper choice of the additive and milling process results in unstable pigments resulting in hard sedimentation in a matter of days .
  • the most suitable additives for each pigment are determined through a series of dosage ladder tests.
  • the selection of effective additives, optimum dosage and the milling process conditions are based on meeting criteria such as good affinity to pigments, excellent wetting and stabilising of particle during milling, reduction of inter particle
  • the compatibility of the additive with the medium is also evaluated throughout the final drying and tempering stages to prevent any aggregation or flocculation .
  • Pigment paste is prepared in two stages: (A) the primary mixing is done with a standard mixer to achieve homogenous mixture of the pigment, solvent, dispersant and other additives. The resultant pre-mix is then subjected to (B) secondary grinding in a ball/bead mill or a roller mill. Dispersants prevent the fine pigment particles from re- aggregating during the grinding stage.
  • the pigment paste comprises 50-80 wt . % pigment, 3-10 or 3-20 wt . % dispersant and 10-50 wt . % carrier.
  • the glass frit in step ii) is the glass frit manufactured in the method according to the present invention.
  • additives can be added with the carrier in step iv) .
  • Another aspect of the present invention is a jetting process comprising :
  • the present invention or the inkjet ink obtainable by the method according to the present invention, onto a substrate such as a ceramic, preferably glass;
  • substrate such as ceramic, preferably glass.
  • the present invention relates to the use of the inkjet ink composition according to the present invention or the inkjet ink obtainable by the method according to the present invention for inkjet printing onto a substrate such as a ceramic, preferably glass.
  • the properties of the ceramic inkjet inks according to the present invention are the following.
  • the viscosity is 6-20 mPa.s at the jetting temperature and conditions (printhead channel flow rate, print frequency and drop speed) .
  • the jetting temperature is 5-60°C.
  • a Newtonian fluid (no change in viscosity over the range of shear rates) is preferable for most applications.
  • the ink rheology is deliberately tailored to achieve
  • Static surface tension is 20-40 mN/m to meet the printhead and substrate requirements.
  • the specific additives are incorporated to adjust the dynamic properties of the ink to give uniform distribution of the particles during drying, thus preventing particle migration towards the edges or to the centre.
  • Another aspect of the present invention relates to a method for the manufacture of hot melt inkjet printing comprising of paraffin wax as the main carrier.
  • the frit and pigments are milled and stabilised in the molten paraffin with a combination of dispersants.
  • the carrier could also be a mixture of paraffin wax and aliphatic and /or aromatic solvents at different proportions. An example of such mixture could be paraffin wax and kerosene.
  • the ink is solid at room temperature and is heated to change its phase to liquid prior to entering the printhead.
  • the printhead ejects hot melt above the ink melting temperature.
  • the jetting temperature of the wax based ink can be above the wax melting temperature of 40-100°C depending on the type of wax.
  • Ceramic inkjet inks according to the present invention .
  • compositions have the same mixing protocol: (a) with non optimized additives;
  • Viscosity profile of ceramic inkjet black 1 and black 2 (higher thixotropic behavior) at the jetting condition.
  • Effective control of ink properties to prevent particle migration during drying (a) particle migration towards edges; (b) pigment distribution during drying.
  • Example 1 pigment compositions for wet milling Recipe 1 : Black pigment paste 1
  • Dispersant Disperbyk 180 4%
  • Dispersant Disperbyk 180 8%
  • Dispersant Disperbyk 180 8%
  • inkjet medium components (as specified in the above example) are milled in a bead/ball mill mixer.
  • the components are vigorously shaken in an enclosed ceramic container containing ziroconia grinding beads resulting in well dispersed pigment paste and with a final particle size below 1 ⁇ .
  • the three components are initially mixed in a high shear mixer and then milled in horizontal high speed mill with Zirconia grinding chamber in multi-pass operations for fixed time. This resulted in a highly stable frit with no or minimal sedimentation with particle size up to 3 lm.
  • the figure 1 shows the frit size profile as a result of jet milling and wet milling.
  • Example 3 Ceramic inkjet ink composition according to the present invention and method for the manufacture thereof.
  • the composition of the ceramic inkjet inks according to the present invention is the following:
  • Frit (Bismuth /Zn or hybrid based) : 20-60 wt . %
  • Inorganic pigment 0-30 wt . %
  • Carrier (two or more) : 20-60 wt . %
  • Additives Surfactants 0-2 wt . %, dispersants 0-5 wt . %, other additives 0-5 wt . %, such as
  • the manufacture process of such ink is the following:
  • top up carrier (which could be one or combination of other organic solvents) with additives such as surfactant, thixotropic additives, flow and levelling additives) and further mix for a fixed time.
  • additives such as surfactant, thixotropic additives, flow and levelling additives
  • the final ink is filtered without clogging the filter and without significantly changes in the solid content.
  • Example 4 Black ceramic inkjet inks according to the present invention.
  • Butyl acetate Inkjet Black 2 (with thixotropic additives)
  • the figure 2 shows the photographs of the sets of final ink et inks .
  • Example 5 Jetting samples
  • the figure 3 shows the photograph of the image of final tempered samples.
  • Printing on the glass was performed in single pass and multipass (several layers) in order to achieve sufficient thickness to meet the final requirements such as optical density after high temperature heat treatment or tempering at temperature above 500°C.
  • Example 6 Influence of choice of additive and mixing step on ink properties.
  • Non-optimised mixing steps results in non-homogeneous mixing between frits and pigments and hence sedimentations of pigments (figure 4) .
  • Additives are tailored to specific pigments. Non-optimisation of additives results in non-homogeneous mixing between frits and pigments and hence sedimentation and flocculation (figure 5).
  • the properties of the ceramic inkjet inks according to the present invention are the following.
  • the viscosity is 6-20 mPa.s at the jetting temperature and conditions (printhead channel flow rate, print frequency and drop speed) .
  • the jetting temperature is 5-60°C.
  • the jetting temperature of wax based ink is above the wax melting temperature in the range of 40-100°C.
  • a Newtonian fluid (no change in viscosity over the range of shear rates) is preferable for most applications
  • the ink rheology is deliberately tailored to achieve
  • Static surface tension is 20-40 mN/m to meet the printhead and substrate requirements.

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

Abstract

La présente invention porte sur une encre céramique pour l'impression par jet d'encre appropriée pour l'impression sur des substrats en céramique tels que du verre, comprenant : a) 20 à 70 % en poids d'une composition de fritte de verre qui est une composition de fritte de verre à base d'oxyde de zinc et/ou d'oxyde de bismuth comprenant 20 à 60 % en poids de SiO2, 3 à 30 % en poids de B2O3, 10 à 40 % en poids de ZnO et/ou 10 à 70 % en poids de Bi2O3 par rapport au poids total de la composition de fritte de verre à base d'oxyde de zinc et/ou d'oxyde de bismuth, la fritte de verre ayant la forme de particules ayant une distribution granulométrique dans la plage de 1,2 μm à 3 μm; b) 0 à 30 % en poids de pigment; c) 20 à 70 % en poids d'un véhicule. L'invention porte également sur son procédé de fabrication. En outre, la présente invention porte sur une composition de fritte de verre et sur son procédé de fabrication. En outre, la présente invention porte sur un procédé d'impression par jet d'encre.
PCT/EP2013/064387 2013-07-08 2013-07-08 Encre céramique pour impression par jet d'encre WO2015003736A1 (fr)

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Cited By (12)

* Cited by examiner, † Cited by third party
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WO2016008848A1 (fr) * 2014-07-14 2016-01-21 Schott Ag Encre céramique pour imprimante à jet d'encre destinée à du verre peu dilatable et/ou une vitrocéramique peu dilatable et son utilisation
CN107141888A (zh) * 2017-05-15 2017-09-08 广州市美科材料技术有限公司 一种钢化玻璃喷墨打印墨水的无机熔块及其配制而成的汽车钢化玻璃喷墨打印墨水
JP2019156935A (ja) * 2018-03-09 2019-09-19 御国色素株式会社 インク及び被印字体の製造方法
ES2745546A1 (es) * 2018-08-31 2020-03-02 Tecglass Sl Tintas de inyeccion ceramicas digitales para vidrio y procedimiento para obtener las mismas
WO2020043930A1 (fr) * 2018-08-31 2020-03-05 Tecglass Sl Encres d'injection céramiques numériques pour le verre et procédé d'obtention de ces dernières
JP2020041116A (ja) * 2018-09-12 2020-03-19 御国色素株式会社 印刷用インク及びその製造方法並びにプリンタ
ES2759973A1 (es) * 2018-11-12 2020-05-12 Torrecid Sa Composicion de tinta para decoracion de vajilla
CN112074491A (zh) * 2018-05-15 2020-12-11 尤罗科拉公司 用于在矿物基材上喷墨打印的矿物油墨
CN112708310A (zh) * 2020-12-29 2021-04-27 深圳市国瓷永丰源瓷业有限公司 用于陶瓷油墨喷涂的水性介质及油墨、方法、陶瓷制品
IT202000014053A1 (it) * 2020-06-12 2021-12-12 Skf Ab Sistema e metodo per l’identificazione di un componente meccanico, in particolare un anello di cuscinetto di rotolamento
EP4166616A1 (fr) 2021-10-18 2023-04-19 Schott Ag Encre d'impression pour céramique, en particulier pour une impression à jet d'encre, destiné à la fabrication d'un revêtement sur une plaque en vitrocéramique et plaque en vitrocéramique revêtue
IT202200000488A1 (it) * 2022-01-13 2023-07-13 Sicer S P A Veicolo per inchiostri digitali ceramici

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WO2007036942A2 (fr) * 2005-09-28 2007-04-05 Dip Tech. Ltd. Encre a effet de gravure pour impression sur des surfaces en ceramique
US20080090034A1 (en) * 2006-09-18 2008-04-17 Harrison Daniel J Colored glass frit
US20090188555A1 (en) * 2008-01-30 2009-07-30 Imelda Castillo Conductive Inks With Metallo-Organic Modifiers
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

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Publication number Priority date Publication date Assignee Title
WO2007036942A2 (fr) * 2005-09-28 2007-04-05 Dip Tech. Ltd. Encre a effet de gravure pour impression sur des surfaces en ceramique
US20080090034A1 (en) * 2006-09-18 2008-04-17 Harrison Daniel J Colored glass frit
US20090188555A1 (en) * 2008-01-30 2009-07-30 Imelda Castillo Conductive Inks With Metallo-Organic Modifiers
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

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016008848A1 (fr) * 2014-07-14 2016-01-21 Schott Ag Encre céramique pour imprimante à jet d'encre destinée à du verre peu dilatable et/ou une vitrocéramique peu dilatable et son utilisation
CN107141888A (zh) * 2017-05-15 2017-09-08 广州市美科材料技术有限公司 一种钢化玻璃喷墨打印墨水的无机熔块及其配制而成的汽车钢化玻璃喷墨打印墨水
JP2019156935A (ja) * 2018-03-09 2019-09-19 御国色素株式会社 インク及び被印字体の製造方法
CN112074491A (zh) * 2018-05-15 2020-12-11 尤罗科拉公司 用于在矿物基材上喷墨打印的矿物油墨
WO2020043930A1 (fr) * 2018-08-31 2020-03-05 Tecglass Sl Encres d'injection céramiques numériques pour le verre et procédé d'obtention de ces dernières
EP3845614A4 (fr) * 2018-08-31 2021-12-29 Tecglass SL Encres d'injection céramiques numériques pour le verre et procédé d'obtention de ces dernières
US11993723B2 (en) 2018-08-31 2024-05-28 Tecglass Sl Digital ceramic inkjet inks for glass and method for obtaining same
WO2020043929A1 (fr) * 2018-08-31 2020-03-05 Tecglass Sl Encres d'injection céramiques numériques pour le verre et procédé d'obtention de ces dernières
ES2745546A1 (es) * 2018-08-31 2020-03-02 Tecglass Sl Tintas de inyeccion ceramicas digitales para vidrio y procedimiento para obtener las mismas
US11866595B2 (en) 2018-08-31 2024-01-09 Tecglass Sl Digital ceramic inject inks for glass and procedure to obtain the same
EP3845615A4 (fr) * 2018-08-31 2022-05-18 Tecglass SL Encres d'injection céramiques numériques pour le verre et procédé d'obtention de ces dernières
JP2020041116A (ja) * 2018-09-12 2020-03-19 御国色素株式会社 印刷用インク及びその製造方法並びにプリンタ
CN110894380A (zh) * 2018-09-12 2020-03-20 广州精陶机电设备有限公司 一种打印墨水及其制备方法和打印机
WO2020099704A1 (fr) * 2018-11-12 2020-05-22 Torrecid, S.A Composition d'encre pour décoration de vaisselle de table
ES2759973A1 (es) * 2018-11-12 2020-05-12 Torrecid Sa Composicion de tinta para decoracion de vajilla
IT202000014053A1 (it) * 2020-06-12 2021-12-12 Skf Ab Sistema e metodo per l’identificazione di un componente meccanico, in particolare un anello di cuscinetto di rotolamento
CN112708310A (zh) * 2020-12-29 2021-04-27 深圳市国瓷永丰源瓷业有限公司 用于陶瓷油墨喷涂的水性介质及油墨、方法、陶瓷制品
EP4166616A1 (fr) 2021-10-18 2023-04-19 Schott Ag Encre d'impression pour céramique, en particulier pour une impression à jet d'encre, destiné à la fabrication d'un revêtement sur une plaque en vitrocéramique et plaque en vitrocéramique revêtue
DE102021126968A1 (de) 2021-10-18 2023-04-20 Schott Ag Keramische Druckfarbe, insbesondere für einen Tintenstrahldruck, zur Herstellung einer Beschichtung auf einer Glaskeramik und beschichtete Glaskeramikplatte
IT202200000488A1 (it) * 2022-01-13 2023-07-13 Sicer S P A Veicolo per inchiostri digitali ceramici
WO2023135568A1 (fr) * 2022-01-13 2023-07-20 Sicer S.P.A. Véhicule pour encres céramiques numériques

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