WO2024017818A1 - Vehicle for ceramic inkjet inks - Google Patents

Vehicle for ceramic inkjet inks Download PDF

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Publication number
WO2024017818A1
WO2024017818A1 PCT/EP2023/069758 EP2023069758W WO2024017818A1 WO 2024017818 A1 WO2024017818 A1 WO 2024017818A1 EP 2023069758 W EP2023069758 W EP 2023069758W WO 2024017818 A1 WO2024017818 A1 WO 2024017818A1
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WO
WIPO (PCT)
Prior art keywords
ceramic
vehicle
mixtures
chosen
water
Prior art date
Application number
PCT/EP2023/069758
Other languages
French (fr)
Inventor
Alice TOMBINI
Marco BIETTI
Stefano Crespi
Tamara Verzotti
Simona Esposito
Original Assignee
Lamberti Spa
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Filing date
Publication date
Application filed by Lamberti Spa filed Critical Lamberti Spa
Publication of WO2024017818A1 publication Critical patent/WO2024017818A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/4505—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application
    • C04B41/4535—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application applied as a solution, emulsion, dispersion or suspension
    • C04B41/4539—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application applied as a solution, emulsion, dispersion or suspension as a emulsion, dispersion or suspension
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/007—Digital printing on surfaces other than ordinary paper on glass, ceramic, tiles, concrete, stones, etc.

Definitions

  • the present invention relates to a water-compatible solvent-based vehicle for ceramic inkjet inks comprising a polar solvent, a carboxylic ester and a hyperdispersant.
  • the present invention also relates to ceramic inkjet inks containing said vehicle and to a method for decorating green or fired ceramic bodies comprising the use of said ceramic inkjet inks.
  • Ceramic manufactured products such as wall tiles and floor tiles, are made of a ceramic body that confers form and mechanical properties to the object; the ceramic body generally has some porosity and poor aesthetic qualities.
  • Said ceramic body which is defined “green” or, alternatively, "fired”, if previously fired, is then usually coated with a ceramic layer, called ceramic glaze.
  • the ceramic glaze is completely sintered by firing, in such a way to gain suitable superficial aesthetic qualities and, in the meantime, to become a fluid-proof barrier.
  • the ceramic glaze has usually no porosity and it is generally resistant to abrasion and to the attack of chemical agents such as acids, bases, dyes.
  • the aesthetic finishing of the ceramic material can be completed by a decoration phase that is by the application of sinterable and variously coloured ceramic materials, which are applied according to a preset drawing (decor).
  • the decor can be applied either on green or fired ceramic body, on which the glaze was previously set, or, in the so called third firing decorations, after the firing, on the sintered glaze.
  • inkjet digital printing has become the reference technology for the decoration of ceramic articles, in particular plates and tiles for floors and coverings.
  • Digital printing and decoration by inkjet technique is widely used in multiple sectors and it is well known, both referring to the printing equipments and also to the inks used.
  • inks constituted by solutions of metallic cations and, more often, inks based on dispersions of inorganic pigments in a suitable liquid vehicle.
  • Suitable liquid vehicle for pigment dispersions may be both organic based or water based.
  • the organic vehicle present in the ceramic inkjet ink can be a polar organic vehicle, a substantially apolar organic vehicle or a mixture thereof.
  • Aromatic and aliphatic hydrocarbons are used as apolar components, both cyclical and open chain, or even mixtures of the same.
  • apolar vehicles are isoparrafins or their mixtures, such as the solvents sold by EXXON MOBIL with the trade name ISOPAR®, or dearomatised aliphatic hydrocarbons or their mixtures, such as EXXSOL® produced by EXXON MOBIL and HYDROSEAL® and SPIRDANE® from TOTAL.
  • the polar component of vehicle can be made up of one or several of the fol lowing products: glycols, poly-glycols, glycol ethers, glycol esters, phenols, alkyl-phenols, terpenic alcohols, terpenic oils and vinylpyrridilone copolymers.
  • esterified fatty acids have gradually replaced the glycol ethers for the production of inks.
  • a problem of common hydrophobic ester and aliphatic solvent-based ceramic inkjet inks is that these hydrophobic inks create water-repellent area on the substrates, which make difficult to apply water-based glazes after the decoration.
  • water-based vehicle can dissolve the salts of redox active metals, such as iron, which have corrosive properties. As a result, these metal ions can interact with and degrade exposed metallic printer components.
  • Another object of the invention is to provide a vehicle which allows the preparation of ceramic inkjet inks for decorating ceramic substrates that limits the phenomenon of water-repellency of the applications of glaze after the ceramic decoration proper.
  • Another object of the present invention is to provide a vehicle for ceramic inkjet inks, which avoids clogging and corrosion of the print heads and has high lubricating power during dispensing of the inks, considerably reducing wear and tear and the risk of breakage of the print heads.
  • a water-compatible solvent-based vehicle comprising a polar solvent, a specific carboxylic ester and a hyperdispersant.
  • ceramic pigment relates to inorganic compounds, both dyeing and non-dyeing, adapted to obtain technical and/or special aesthetic effects on the ceramic manufactured article.
  • the expression "ceramic inkjet ink” includes any kind of inkjet ink commonly used in the ceramic field, such as common inkjet inks, but also inkjet inks for special effect, such as gloss and matt inks, luster inks, inks with sinking effects, anti-slip inks, metallic inks and the like.
  • all the particle dimension parameters i.e. Dvio, Dv 5 o, Dv 90 and Dvioo, are calculated from volume-based distributions.
  • a water- compatible solventbased vehicle for ceramic inkjet inks comprising: a) from 30 to 70 by weight (wt%) of a polar solvent chosen among glycols, glycol ethers, glycol esters and mixtures thereof; b) from 20 to 55 wt% of an ester chosen in the group consisting of diesters of C2-C8 dicarboxylic acids or anhydrides thereof with C1-C4 alcohols, glyceryl triacetate and mixtures thereof; c) from 1.0 to 14 wt% of a hyperdispersant.
  • a polar solvent chosen among glycols, glycol ethers, glycol esters and mixtures thereof
  • an ester chosen in the group consisting of diesters of C2-C8 dicarboxylic acids or anhydrides thereof with C1-C4 alcohols, glyceryl triacetate and mixtures thereof
  • c) from 1.0 to 14 wt% of a hyperdispersant comprising: a) from 30 to 70 by weight
  • the invention is a method of decorating green or fired ceramic substrates by inkjet printing, comprising the following steps: i. preparing one or more inkjet ceramic inks by dispersing from 10 to 60 wt% of ceramic pigments in said water-compatible solvent-based vehicle; ii. decorating the glazed green or fired substrate surface by means of an inkjet printer with the one or more of the inks of point (i); iii. firing the obtained decorated substrate at a temperature comprised between 750 and 1350 °C.
  • water-compatible means the vehicle can incorporate at least 10 wt%, preferably at least 15 wt%, more preferably at least 20 wt%, of water, based on the weight of the vehicle, without becoming cloudy.
  • the vehicle of the invention is also solvent-based.
  • solvent-based means a vehicle which is substantially free of water or which contains a minor amount of water. This minor amount of water in the vehicle medium can be ascribed to different sources, forexample residual moisture which can be present in the non-aqueous fluids after the production process and water from the other ingredients, for example from the dispersant, which can be provided in the form of a water solution.
  • the solvent-based vehicle may contain up to 20 wt% of water, preferably up to 15 wt%, more preferably up to 10 wt%, based on the total vehicle weight.
  • the water- compatible solvent-based vehicle for ceramic inkjet inks comprises: a) from 35 to 65 wt% of said polar solvent; b) from 25 to 50 wt% of said ester; c) from 1.5 to 10 wt% of a hyperdispersant.
  • the glycol is chosen among mono-, di-, tri- and tetra-C2-C5 glycols and mixture thereof. More preferably among mono-, di-, tri- and tetra-C2-C3 glycols and mixture thereof.
  • suitable glycols are monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, monopropylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, monobutylene glycol, dibutylene glycol, tributylene glycol, tetrabutylene glycol and mixtures thereof.
  • the glycol ether is chosen among C1-C4 monoalkyl or dialkyl ethers of mono-, di-, tri- and tetra-C2-C5 glycols and mixture thereof. More preferably among C1-C4 monoalkyl or dialkyl ethers of mono-, di-, tri- and tetra-C2-C3 glycols and mixtures thereof.
  • glycol ethers examples include diethylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, dipropylene glycol dimethyl ether and mixtures thereof.
  • glycol esters ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and mixtures thereof.
  • the polar solvent is preferably chosen among glycols, glycol ethers and mixtures thereof. Most preferably, the polar solvents are chosen among mono-, di- and tri-C2-C3 glycols, monomethyl or monoethyl ethers of mono-, di- and tri-C2-Cs glycols and mixtures thereof.
  • Examples of aliphatic and aromatic dicarboxylic acids or their anhydrides suitable for the preparation of the esters b) are oxalic acid, adipic acid, phthalic acid, phthalic anhydride, maleic anhydride, maleic acid, fumaric acid, malonic acid, succinic acid, glutaric acid and mixtures thereof.
  • C1-C4 alcohols examples include methanol, ethanol, n-propanol, isopropanol, n- butanol, isobutanol and mixtures thereof.
  • ester b) are dimethyl oxalate, diethyl oxalate, dimethyl adipate, diethyl adipate, di-isopropyl adipate, dimethyl malonate, diethyl malonate, di-isopropyl malonate, dimethyl glutarate, diethyl glutarate, dimethyl succinate, diethyl succinate and mixtures thereof.
  • the ester b) is chosen in the group consisting of diesters of C2-C6 dicarboxylic acids or anhydrides thereof with C1-C3 alcohols, glyceryl triacetate, and mixtures thereof. More preferably, the ester b) is chosen in the group consisting of diesters of malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid with ethanol or methanol, glyceryl triacetate, and mixtures thereof.
  • the hyperdispersant helps to reduce the particle sizes of inorganic metal oxide pigments and to stabilize the particles of the dense ceramic pigments in inkjet inks to avoid their settling and plugging of ink jet nozzles.
  • Hyperdispersants are polymers with two- component structures: an anchoring group, which provides strong adsorption on the pigment surface, and polymeric chains, providing steric stabilisation so as to hold the particles apart and prevent flocculation.
  • the content of the hyperdispersant in the vehicle of the invention is between 1.0 and 14 wt%, , preferably from 1.5 to 10 wt% .
  • hyperdispersant or any combination of hyperdispersants commonly used in the field to disperse inkjet ceramic pigments in medium and high polarity vehicle are suitable for the preparation of the solvent-based vehicle of the invention.
  • suitable hyperdispersant are Fluijet® or Envipol® (from Lamberti), Solsperse® (from Lubrizol), Disperbyk® (from Byk) and Tego® (from Evonik), Atlox® and Zephrym® (from Croda).
  • hyperdispersants include, but are not limited to, Fluijet 1730, Fluijet 1725, Envipol 5130, Disperbyk 190, Disperbyk 2010, Disperbyk 2015, Disperbyk 199, Disperbyk 180, Solsperse W32O, Solsperse 44000, Solsperse 55000, Atlox 4913 and Zephrym PD 3315.
  • the water-compatible solvent-based vehicle of the invention has a viscosity at 35°C a shear rate of 100 sec-1 below 17 mPa*s, preferably from 4 to 15 mPa*s, more preferably from 5 to 13 mPa*s.
  • the water- compatible solvent-based vehicle for ceramic inkjet inks may be prepared by simply mixing in any order under mechanical stirring, the ingredients a) to c). Preferably, they are mixed in the order from a) to c).
  • the water- compatible solvent-based vehicle of the invention can be used to prepare ceramic inkjet inks, which contain from 10 to 60 wt% of ceramic pigments, preferably from 15 to 50 wt%, based on the total weight of the ink.
  • the content of the solvent-based vehicle is from 30 to 80 wt%, preferably from 45 to 80 wt%, based on the total weight of the ink.
  • the inorganic ceramic pigment of the inkjet ink of the present invention exhibit a Dv50 between 0.1 and 1.0
  • the ink according to the invention may be used with any type of ceramic component, while remaining within the scope of the present invention.
  • ceramic pigments such as, for example, zirconates and silicates of Cr, Sn, Ni, Pr, Fe, Co and oxides thereof, and ceramic pigments selected from ZrPr, ZrPrSi, ZrFeSi, TiCrSb, CoAIZn, ZrVaSi, FeCrCoNi, CrCaSnSi, CoSi, and FeCrZn.
  • the ink of the invention may further comprise other ceramic components such as a frit or else a vitreous material able to promote the fusibility of the ink during firing and its consolidation on the surface of the ceramic product to be decorated.
  • the ink may comprise other ceramic raw materials, for example, but not limited to, clays, kaolins, feldspars, silica, zirconates, aluminates, silicate oxides, and other minerals in general.
  • the ink of the invention may comprise one or more additives for regulating physical and rheological properties, including, but not limited to, surfactants, deaerators/defoamers, rheology modifiers, flow and leveling agents, anti-settling agents, preservatives, etc.
  • surfactant examples include anionic surfactants, cationic, non-ionic, amphoteric and zwitterionic surfactants.
  • Exemplary anionic surfactant are soaps, ethoxy carboxylated, ester carboxylated, amide carboxylated, ester sulphonates, phosphate esters, alcohol sulphates, alcohol ether sulphates, sulphated alkanolamide ethoxylates, sulphated oils and glycerides, nonylphenol ether sulphates, paraffin sulphonates, alkyl benzene sulphonates, fatty acid and ester sulphonates, alkyl naphtalene sulphonates, olefin sulphonates, petroleum sulphonates, lignin sulphonates and derivatives, sulphosuccinates and sulphosuccinamates, amide sulphonates.
  • Non-ionic surfactant can be selected between acetylenic surfactants, alcohol ethoxylates, alkanolamides, amine oxides, phosphine oxides, sulphoxides, mono/poly saccharides derivatives, ethoxylated alkanolamides, ethoxylated long-chain amines, ethylene oxide/propylene oxide copolymers, fatty acid ethoxylates, sorbitan derivatives, ethylene glycol, propylene glycol, glycerol and polyglyceryl esters plus their ethoxylated derivatives, alkyl amines, alkyl imidazolines, ethoxylated oils and fats, alkyl phenol ethoxylates.
  • the surfactants are preferably used in a concentration within the range of 0.1 to 2 wt%, preferably of 0.1 to 1.5 wt%, based on the total weight of the ink.
  • the ceramic inkjet ink compositions of the present invention can further comprise from 0.1 to 5 wt%, preferably from 0.2 to 2.0 wt%, of an anti-settling agent. These substances are used to prevent settling of the pigments in the ink.
  • suitable anti-settling agents are pyrogenic silica, modified ureas and waxes, polymeric fatty esters, polyamides, derivatives of aromatic hydrocarbons and polyether modified polydimethyl siloxanes.
  • Exemplary brand names of suitable anti-settling agent are Anti-Terra® (from Byk), Terrablend (from Coatex) and TEGO® and AEROSIL® (from Evonik Operation).
  • the ceramic inkjet ink of the invention can also comprise from 0.01 to 1 % by weight, based on the total weight of the ink, of at least one defoamer such as modified silicones, polydimethyl siloxanes, mineral oil derivatives and fatty derivatives.
  • defoamer such as modified silicones, polydimethyl siloxanes, mineral oil derivatives and fatty derivatives.
  • the ceramic inkjet ink of the invention can be prepared by milling a commercial ceramic inorganic pigment having average particle size between 1.0 and 10.0
  • the inorganic ceramic pigment and the liquid organic vehicle may be mixed in any order, the mixture then being subjected to milling with beads having diameters from 0.1 to 0.5 mm to reduce the particles of the pigment to an appropriate size.
  • the viscosity at room temperature and shear rate of 200 sec -1 of the ceramic inkjet ink is between 18 and 40 mPa*s.
  • the ceramic substrates decorated with the ink according to the present invention can be tiles, kitchenware and sanitary ceramics.
  • the tiles can be for example unfired tiles, fired tiles, tiles made of stoneware, porcelain stoneware, porous single-firing ceramic, double-fired ceramic, clinker, third-firing and fourth-firing.
  • the kitchenware can be unfired kitchenware and fired kitchenware and comprises household items.
  • Sanitary ceramics comprise for example sanitary fixtures, sinks and washbasins, washtubs, shower trays.
  • the term "ceramic substrate” does not include a glassy material such as for example glass-ceramics.
  • TEG T riethylene glycol
  • TPG Tripropylene Glycol
  • DEG Diethylene Glycol
  • MEG Monoethylene glycol
  • TPM Tripropylene Glycol Methyl Ether
  • MDM E Mixture of Dimethyl Esters of Adipic, Glutaric and Succinic Acids
  • Triacetin Glyceryl Triacetate
  • TPnB Tripropylene Glycol n-Butyl Ether
  • EHCT Esteril 2-EHCT (from Lamberti S.p.A.);
  • DISP1 FLUIJET 1725, 100% active matter (from Lamberti S.p.A.);
  • DISP2 ENVIPOL 5130, about 42 wt% active matter in water (from Lamberti S.p.A.);
  • DISP3 Fluijet 987 (from Lamberti S.p.A.);
  • the viscosity (mPa*s) of the vehicles and of the inkjet inks was determined with a Anton Paar Physica MCR301 rheometer at 35 and 45 °C and shear rate of 100 sec -1 .
  • the compatibility of the vehicle with water was determined by adding water drop by drop to 5 g of vehicle until it become cloudy. The results are reported as % by weight of added water, based on the weight of the vehicle + water.
  • the weight loss was determined with a HPS 200T Thermobalance (Dini Argeo s.r.l.) set at 70 °C.
  • the particle size parameters of the pigment after milling were measured with a Mastersizer 2000 (Malvern Pananlytical).
  • the water-compatible solvent-based vehicles of the invention were prepared according to the recipes of Tables 1-3 (in grams) by first mixing the polar solvents a), then adding under stirring the diesters b) and, finally, the hyperdispersants. The resulting mixtures were homogenized under stirring for 5 min.
  • the water-compatible solvent-based vehicles of the invention show a good viscosity comparable with the viscosity of vehicles of the prior art. Moreover, they show an excellent compatibility with water.
  • the vehicles of the Examples were used to prepare inkjet inks with different pigment/vehicle ratio (see Tables 4-6).
  • Tables 4-6 report the viscosity (mPa*s) at 35 °C and 45 °C as soon as prepared and after aging at 50 °C for 2 weeks and the Dvio, Dv 5 o, Dv?o and Dvioo (
  • Table 4
  • Comparative The inkjet inks of the invention show good stability, even after aging.
  • the ink based on water-compatible solvent-based vehicle of the invention show a reduced weight loss at 70 °C compared to the water-based vehicle and it shows a weight loss comparable to solvent-based vehicles.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The present invention relates to a water-compatible solvent-based vehicle for ceramic inkjet inks comprising a polar solvent, a carboxylic ester and a hyperdispersant. The present invention also relates to ceramic inkjet inks containing said vehicle and to a method for decorating green or fired ceramic bodies comprising the use of said ceramic inkjet inks.

Description

VEHICLE FOR CERAMIC INKJET INKS
FIELD OF THE INVENTION
The present invention relates to a water-compatible solvent-based vehicle for ceramic inkjet inks comprising a polar solvent, a carboxylic ester and a hyperdispersant.
The present invention also relates to ceramic inkjet inks containing said vehicle and to a method for decorating green or fired ceramic bodies comprising the use of said ceramic inkjet inks.
BACKGROUND OF THE ART
Most traditional ceramic manufactured products, such as wall tiles and floor tiles, are made of a ceramic body that confers form and mechanical properties to the object; the ceramic body generally has some porosity and poor aesthetic qualities.
Said ceramic body, which is defined "green" or, alternatively, "fired", if previously fired, is then usually coated with a ceramic layer, called ceramic glaze. The ceramic glaze is completely sintered by firing, in such a way to gain suitable superficial aesthetic qualities and, in the meantime, to become a fluid-proof barrier. As a matter of fact, after firing, the ceramic glaze has usually no porosity and it is generally resistant to abrasion and to the attack of chemical agents such as acids, bases, dyes.
The aesthetic finishing of the ceramic material can be completed by a decoration phase that is by the application of sinterable and variously coloured ceramic materials, which are applied according to a preset drawing (decor).
The decor can be applied either on green or fired ceramic body, on which the glaze was previously set, or, in the so called third firing decorations, after the firing, on the sintered glaze.
In the last two decades, inkjet digital printing has become the reference technology for the decoration of ceramic articles, in particular plates and tiles for floors and coverings.
Digital printing and decoration by inkjet technique is widely used in multiple sectors and it is well known, both referring to the printing equipments and also to the inks used.
Peculiarly, in ceramic applications, the thermal treatment, which is required once the substrate has been printed, makes the conventional inks, that are used in the other applications, such as graphic arts and textile industry, unsuitable for use. Two kind of inks for inkjet printing of ceramics are known: inks constituted by solutions of metallic cations and, more often, inks based on dispersions of inorganic pigments in a suitable liquid vehicle.
Suitable liquid vehicle for pigment dispersions may be both organic based or water based. The organic vehicle present in the ceramic inkjet ink can be a polar organic vehicle, a substantially apolar organic vehicle or a mixture thereof.
Aromatic and aliphatic hydrocarbons are used as apolar components, both cyclical and open chain, or even mixtures of the same. Examples of apolar vehicles are isoparrafins or their mixtures, such as the solvents sold by EXXON MOBIL with the trade name ISOPAR®, or dearomatised aliphatic hydrocarbons or their mixtures, such as EXXSOL® produced by EXXON MOBIL and HYDROSEAL® and SPIRDANE® from TOTAL.
The polar component of vehicle can be made up of one or several of the fol lowing products: glycols, poly-glycols, glycol ethers, glycol esters, phenols, alkyl-phenols, terpenic alcohols, terpenic oils and vinylpyrridilone copolymers. In the last years, esterified fatty acids have gradually replaced the glycol ethers for the production of inks.
A problem of common hydrophobic ester and aliphatic solvent-based ceramic inkjet inks is that these hydrophobic inks create water-repellent area on the substrates, which make difficult to apply water-based glazes after the decoration.
Water has been proposed as partial replacement of organic vehicles.
However, by using water-based vehicle in inkjet apparatuses, there is a possibility that, given that water is eva porable at a relatively low temperature, the solids dispersed therein can clog the minuscule nozzles of the printing heads with consequent deterioration of printing quality as well as damage to the head itself.
Moreover, water-based vehicle can dissolve the salts of redox active metals, such as iron, which have corrosive properties. As a result, these metal ions can interact with and degrade exposed metallic printer components.
As a consequence, there is still the industrial need for improved vehicle for ceramic inkjet inks which allows to overcome at least some of the above mentioned problems.
Therefore, it is an object of the invention to provide a vehicle which allows the preparation of ceramic inkjet inks for decorating ceramic substrates that limits the phenomenon of water-repellency of the applications of glaze after the ceramic decoration proper. Another object of the present invention is to provide a vehicle for ceramic inkjet inks, which avoids clogging and corrosion of the print heads and has high lubricating power during dispensing of the inks, considerably reducing wear and tear and the risk of breakage of the print heads.
Surprisingly, these objects can be achieved by a water-compatible solvent-based vehicle comprising a polar solvent, a specific carboxylic ester and a hyperdispersant.
As far as the Applicant knows, no one has previously described the water-compatible solvent-based vehicle of the present disclosure and its advantageous properties.
Within the scope of the present disclosure, the expression "ceramic pigment" relates to inorganic compounds, both dyeing and non-dyeing, adapted to obtain technical and/or special aesthetic effects on the ceramic manufactured article.
In the present invention, the expression "ceramic inkjet ink" includes any kind of inkjet ink commonly used in the ceramic field, such as common inkjet inks, but also inkjet inks for special effect, such as gloss and matt inks, luster inks, inks with sinking effects, anti-slip inks, metallic inks and the like.
In the present invention, all the particle dimension parameters, i.e. Dvio, Dv5o, Dv90 and Dvioo, are calculated from volume-based distributions.
In the present invention, all the percentage by weight, unless otherwise specified, are based on the total weight of the vehicles or of the inks.
DESCRIPTION OF THE INVENTION
It is therefore a fundamental object of the present invention a water- compatible solventbased vehicle for ceramic inkjet inks comprising: a) from 30 to 70 by weight (wt%) of a polar solvent chosen among glycols, glycol ethers, glycol esters and mixtures thereof; b) from 20 to 55 wt% of an ester chosen in the group consisting of diesters of C2-C8 dicarboxylic acids or anhydrides thereof with C1-C4 alcohols, glyceryl triacetate and mixtures thereof; c) from 1.0 to 14 wt% of a hyperdispersant.
It is further object of the present invention a ceramic inkjet ink useful for the decoration of green or fired ceramic substrates comprising from 10 to 60 wt% of ceramic pigments, which are dispersed in said water-compatible solvent-based vehicle. According to a further aspect, the invention is a method of decorating green or fired ceramic substrates by inkjet printing, comprising the following steps: i. preparing one or more inkjet ceramic inks by dispersing from 10 to 60 wt% of ceramic pigments in said water-compatible solvent-based vehicle; ii. decorating the glazed green or fired substrate surface by means of an inkjet printer with the one or more of the inks of point (i); iii. firing the obtained decorated substrate at a temperature comprised between 750 and 1350 °C.
DETAILED DESCRIPTION OF THE INVENTION
The definition "water-compatible" means the vehicle can incorporate at least 10 wt%, preferably at least 15 wt%, more preferably at least 20 wt%, of water, based on the weight of the vehicle, without becoming cloudy.
The vehicle of the invention is also solvent-based. As referred to herein, "solvent-based" means a vehicle which is substantially free of water or which contains a minor amount of water. This minor amount of water in the vehicle medium can be ascribed to different sources, forexample residual moisture which can be present in the non-aqueous fluids after the production process and water from the other ingredients, for example from the dispersant, which can be provided in the form of a water solution. The solvent-based vehicle may contain up to 20 wt% of water, preferably up to 15 wt%, more preferably up to 10 wt%, based on the total vehicle weight.
Preferably, the water- compatible solvent-based vehicle for ceramic inkjet inks comprises: a) from 35 to 65 wt% of said polar solvent; b) from 25 to 50 wt% of said ester; c) from 1.5 to 10 wt% of a hyperdispersant.
Preferably, the glycol is chosen among mono-, di-, tri- and tetra-C2-C5 glycols and mixture thereof. More preferably among mono-, di-, tri- and tetra-C2-C3 glycols and mixture thereof. Example of suitable glycols are monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, monopropylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, monobutylene glycol, dibutylene glycol, tributylene glycol, tetrabutylene glycol and mixtures thereof.
Preferably the glycol ether is chosen among C1-C4 monoalkyl or dialkyl ethers of mono-, di-, tri- and tetra-C2-C5 glycols and mixture thereof. More preferably among C1-C4 monoalkyl or dialkyl ethers of mono-, di-, tri- and tetra-C2-C3 glycols and mixtures thereof. Examples of suitable glycol ethers includes diethylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, dipropylene glycol dimethyl ether and mixtures thereof.
Examples of glycol esters ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and mixtures thereof.
The polar solvent is preferably chosen among glycols, glycol ethers and mixtures thereof. Most preferably, the polar solvents are chosen among mono-, di- and tri-C2-C3 glycols, monomethyl or monoethyl ethers of mono-, di- and tri-C2-Cs glycols and mixtures thereof. Examples of aliphatic and aromatic dicarboxylic acids or their anhydrides suitable for the preparation of the esters b) are oxalic acid, adipic acid, phthalic acid, phthalic anhydride, maleic anhydride, maleic acid, fumaric acid, malonic acid, succinic acid, glutaric acid and mixtures thereof.
Examples of suitable C1-C4 alcohols are methanol, ethanol, n-propanol, isopropanol, n- butanol, isobutanol and mixtures thereof.
Specific examples of ester b) are dimethyl oxalate, diethyl oxalate, dimethyl adipate, diethyl adipate, di-isopropyl adipate, dimethyl malonate, diethyl malonate, di-isopropyl malonate, dimethyl glutarate, diethyl glutarate, dimethyl succinate, diethyl succinate and mixtures thereof.
Preferably, the ester b) is chosen in the group consisting of diesters of C2-C6 dicarboxylic acids or anhydrides thereof with C1-C3 alcohols, glyceryl triacetate, and mixtures thereof. More preferably, the ester b) is chosen in the group consisting of diesters of malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid with ethanol or methanol, glyceryl triacetate, and mixtures thereof.
The hyperdispersant helps to reduce the particle sizes of inorganic metal oxide pigments and to stabilize the particles of the dense ceramic pigments in inkjet inks to avoid their settling and plugging of ink jet nozzles. Hyperdispersants are polymers with two- component structures: an anchoring group, which provides strong adsorption on the pigment surface, and polymeric chains, providing steric stabilisation so as to hold the particles apart and prevent flocculation. The content of the hyperdispersant in the vehicle of the invention is between 1.0 and 14 wt%, , preferably from 1.5 to 10 wt% .
Any hyperdispersant or any combination of hyperdispersants commonly used in the field to disperse inkjet ceramic pigments in medium and high polarity vehicle are suitable for the preparation of the solvent-based vehicle of the invention. Exemplary brand names of suitable hyperdispersant are Fluijet® or Envipol® (from Lamberti), Solsperse® (from Lubrizol), Disperbyk® (from Byk) and Tego® (from Evonik), Atlox® and Zephrym® (from Croda). Specific examples of suitable hyperdispersants include, but are not limited to, Fluijet 1730, Fluijet 1725, Envipol 5130, Disperbyk 190, Disperbyk 2010, Disperbyk 2015, Disperbyk 199, Disperbyk 180, Solsperse W32O, Solsperse 44000, Solsperse 55000, Atlox 4913 and Zephrym PD 3315.
Usually, the water-compatible solvent-based vehicle of the invention has a viscosity at 35°C a shear rate of 100 sec-1 below 17 mPa*s, preferably from 4 to 15 mPa*s, more preferably from 5 to 13 mPa*s.
The water- compatible solvent-based vehicle for ceramic inkjet inks may be prepared by simply mixing in any order under mechanical stirring, the ingredients a) to c). Preferably, they are mixed in the order from a) to c).
The water- compatible solvent-based vehicle of the invention can be used to prepare ceramic inkjet inks, which contain from 10 to 60 wt% of ceramic pigments, preferably from 15 to 50 wt%, based on the total weight of the ink.
Usually, the content of the solvent-based vehicle is from 30 to 80 wt%, preferably from 45 to 80 wt%, based on the total weight of the ink.
Usually, the inorganic ceramic pigment of the inkjet ink of the present invention exhibit a Dv50 between 0.1 and 1.0 |im, preferably from 0.1 to 0.8 pm and more preferably from 0.1 to 0.6 pm, as measured by a laser diffraction particle size analyzer.
It is emphasized that the ink according to the invention may be used with any type of ceramic component, while remaining within the scope of the present invention. Any of the recognized classes of pigments used in ceramic decoration (ceramic pigments) may be used such as, for example, zirconates and silicates of Cr, Sn, Ni, Pr, Fe, Co and oxides thereof, and ceramic pigments selected from ZrPr, ZrPrSi, ZrFeSi, TiCrSb, CoAIZn, ZrVaSi, FeCrCoNi, CrCaSnSi, CoSi, and FeCrZn.
The ink of the invention may further comprise other ceramic components such as a frit or else a vitreous material able to promote the fusibility of the ink during firing and its consolidation on the surface of the ceramic product to be decorated. Moreover, the ink may comprise other ceramic raw materials, for example, but not limited to, clays, kaolins, feldspars, silica, zirconates, aluminates, silicate oxides, and other minerals in general.
The ink of the invention may comprise one or more additives for regulating physical and rheological properties, including, but not limited to, surfactants, deaerators/defoamers, rheology modifiers, flow and leveling agents, anti-settling agents, preservatives, etc.
Examples of surfactant include anionic surfactants, cationic, non-ionic, amphoteric and zwitterionic surfactants.
Exemplary anionic surfactant are soaps, ethoxy carboxylated, ester carboxylated, amide carboxylated, ester sulphonates, phosphate esters, alcohol sulphates, alcohol ether sulphates, sulphated alkanolamide ethoxylates, sulphated oils and glycerides, nonylphenol ether sulphates, paraffin sulphonates, alkyl benzene sulphonates, fatty acid and ester sulphonates, alkyl naphtalene sulphonates, olefin sulphonates, petroleum sulphonates, lignin sulphonates and derivatives, sulphosuccinates and sulphosuccinamates, amide sulphonates.
Non-ionic surfactant can be selected between acetylenic surfactants, alcohol ethoxylates, alkanolamides, amine oxides, phosphine oxides, sulphoxides, mono/poly saccharides derivatives, ethoxylated alkanolamides, ethoxylated long-chain amines, ethylene oxide/propylene oxide copolymers, fatty acid ethoxylates, sorbitan derivatives, ethylene glycol, propylene glycol, glycerol and polyglyceryl esters plus their ethoxylated derivatives, alkyl amines, alkyl imidazolines, ethoxylated oils and fats, alkyl phenol ethoxylates.
In the present invention, the surfactants are preferably used in a concentration within the range of 0.1 to 2 wt%, preferably of 0.1 to 1.5 wt%, based on the total weight of the ink.
The ceramic inkjet ink compositions of the present invention can further comprise from 0.1 to 5 wt%, preferably from 0.2 to 2.0 wt%, of an anti-settling agent. These substances are used to prevent settling of the pigments in the ink. Examples of suitable anti-settling agents are pyrogenic silica, modified ureas and waxes, polymeric fatty esters, polyamides, derivatives of aromatic hydrocarbons and polyether modified polydimethyl siloxanes. Exemplary brand names of suitable anti-settling agent are Anti-Terra® (from Byk), Terrablend (from Coatex) and TEGO® and AEROSIL® (from Evonik Operation).
The ceramic inkjet ink of the invention can also comprise from 0.01 to 1 % by weight, based on the total weight of the ink, of at least one defoamer such as modified silicones, polydimethyl siloxanes, mineral oil derivatives and fatty derivatives.
The ceramic inkjet ink of the invention can be prepared by milling a commercial ceramic inorganic pigment having average particle size between 1.0 and 10.0 |im, in the presence of the water- compatible solvent-based vehicle of the invention.
The inorganic ceramic pigment and the liquid organic vehicle may be mixed in any order, the mixture then being subjected to milling with beads having diameters from 0.1 to 0.5 mm to reduce the particles of the pigment to an appropriate size.
Usually, the viscosity at room temperature and shear rate of 200 sec-1 of the ceramic inkjet ink is between 18 and 40 mPa*s.
Another aspect of the invention relates to a method to decorate green or fired ceramic substrates by inkjet printing using the inkjet ceramic ink according to the present invention. The ceramic substrates decorated with the ink according to the present invention can be tiles, kitchenware and sanitary ceramics. Specifically, the tiles can be for example unfired tiles, fired tiles, tiles made of stoneware, porcelain stoneware, porous single-firing ceramic, double-fired ceramic, clinker, third-firing and fourth-firing. The kitchenware can be unfired kitchenware and fired kitchenware and comprises household items. Sanitary ceramics comprise for example sanitary fixtures, sinks and washbasins, washtubs, shower trays.
In the context of the present invention, the term "ceramic substrate" does not include a glassy material such as for example glass-ceramics.
The invention is further illustrated by the following examples wherein all references are to parts by weight unless otherwise specified.
EXAMPLES
In the Examples the following ingredients were used:
TEG = T riethylene glycol;
TPG = Tripropylene Glycol; DEG = Diethylene Glycol;
MEG = Monoethylene glycol;
TPM = Tripropylene Glycol Methyl Ether;
MDM E = Mixture of Dimethyl Esters of Adipic, Glutaric and Succinic Acids;
DMS = Dimethyl Succinate;
Triacetin = Glyceryl Triacetate;
TPnB = Tripropylene Glycol n-Butyl Ether;
EHCT = Esteril 2-EHCT (from Lamberti S.p.A.);
SL191 = Augeo SL191 (from Solvay S.A.);
DISP1 = FLUIJET 1725, 100% active matter (from Lamberti S.p.A.);
DISP2 = ENVIPOL 5130, about 42 wt% active matter in water (from Lamberti S.p.A.);
DISP3 =Fluijet 987 (from Lamberti S.p.A.);
Pigment = Yellow ICD 1O/A128, Dvso = 4 pm (from Inco Industria Colori S.p.A.);
Characterization Methods
The viscosity (mPa*s) of the vehicles and of the inkjet inks was determined with a Anton Paar Physica MCR301 rheometer at 35 and 45 °C and shear rate of 100 sec-1.
The compatibility of the vehicle with water was determined by adding water drop by drop to 5 g of vehicle until it become cloudy. The results are reported as % by weight of added water, based on the weight of the vehicle + water.
The weight loss was determined with a HPS 200T Thermobalance (Dini Argeo s.r.l.) set at 70 °C.
The particle size parameters of the pigment after milling (Dv10, Dv50, Dv90 and Dv100) were measured with a Mastersizer 2000 (Malvern Pananlytical).
Examples 1-18
The water-compatible solvent-based vehicles of the invention were prepared according to the recipes of Tables 1-3 (in grams) by first mixing the polar solvents a), then adding under stirring the diesters b) and, finally, the hyperdispersants. The resulting mixtures were homogenized under stirring for 5 min.
The comparative Examples were prepared following the same procedure. Table 1
Figure imgf000011_0001
* Comparative
Table 2
Figure imgf000011_0002
Table 3
Figure imgf000012_0001
Comparative
The water-compatible solvent-based vehicles of the invention show a good viscosity comparable with the viscosity of vehicles of the prior art. Moreover, they show an excellent compatibility with water.
Inks
The vehicles of the Examples were used to prepare inkjet inks with different pigment/vehicle ratio (see Tables 4-6). The inks were prepared by adding under moderate to high shear rate stirring the pigment to the vehicles of the Examples (in the quantity necessary to process 1.0 kg of total ink), The obtained slurries were homogenized for 10-15 min. Then, the slurries were transferred in a Netzsch Labstar laboratory bead mill (Agitator Speed = 2800 rpm and Pump Speed = 110 rpm) and milled for about 90 - 120 min.
Tables 4-6 report the viscosity (mPa*s) at 35 °C and 45 °C as soon as prepared and after aging at 50 °C for 2 weeks and the Dvio, Dv5o, Dv?o and Dvioo (|-Lm) of the pigment particles after milling. Table 4
Figure imgf000013_0001
Table 5
Figure imgf000013_0002
* Comparative
Table d
Figure imgf000013_0003
Comparative The inkjet inks of the invention show good stability, even after aging.
In order to further highlight the stability of the ceramic inkjet inks containing the vehicles of the invention, weight loss tests were carried out at 70 °C. Table 7 reports the results obtained, as a percentage of residual weight.
Table 7
Figure imgf000014_0001
* Comparative
The ink based on water-compatible solvent-based vehicle of the invention show a reduced weight loss at 70 °C compared to the water-based vehicle and it shows a weight loss comparable to solvent-based vehicles.

Claims

1) A water- compatible solvent-based vehicle for ceramic inkjet inks comprising: a) from 30 to 70 % by weight (wt%) of a polar solvent chosen among glycols, glycol ethers, glycol esters and mixtures thereof; b) from 20 to 55 wt% of an ester chosen in the group consisting of diesters of C2-C8 dicarboxylic acids or anhydrides thereof with C1-C4 alcohols, glyceryl triacetate and mixtures thereof; c) from 1.0 to 14 wt% of a hyperdispersant.
2) The vehicle of claim 1), comprising: a) from 35 to 65 wt% of said polar solvent; b) from 25 to 50 wt% of said ester; c) from 1.5 to 10 wt% of a hyperdispersant.
3) The vehicle of claim 1), further comprising up to 20 wt% of water.
4) The vehicle of claim 1), wherein the polar solvent a) is chosen among glycols, glycol ethers and mixtures thereof.
5) The vehicle of claim 1), wherein the ester b) is chosen in is chosen in the group consisting of diesters of C2-C6 dicarboxylic acids or anhydrides thereof with C1-C3 alcohols, glyceryl triacetate, and mixtures thereof.
6) The vehicle of claim 5), wherein the ester b) is chosen in the group consisting of diesters of malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid with ethanol or methanol, glyceryl triacetate, and mixtures thereof.
7) A ceramic inkjet ink comprising from 10% to 60% by weight of ceramic pigments which are dispersed in a water- compatible solvent-based vehicle for ceramic inkjet inks comprising: a) from 30 to 70 wt% of a polar solvent chosen among glycols, glycol ethers, glycol esters and mixtures thereof; b) from 20 to 55 wt% of an ester chosen in the group consisting of diesters of C2-C8 dicarboxylic acids or anhydrides thereof with C1-C4 alcohols, glyceryl triacetate and mixtures thereof; c) from 1.0 to 14 wt% of a hyperdispersant.
8) Ceramic inkjet ink according to claim 8), comprising from 10 to 60 wt% of the pigment and from 30 to 80 wt% of said vehicle. ) A method of decorating green or fired ceramic substrates by inkjet printing, comprising the following steps: i. preparing one or more inkjet ceramic inks by dispersing from 10 to 60 parts by weight of ceramic pigments in a water-compatible solvent-based vehicle for ceramic inkjet inks comprising: a) from 30 to 70 wt% of a polar solvent chosen among glycols, glycol ethers, glycol esters and mixtures thereof; b) from 20 to 55 wt% of an ester chosen in the group consisting of diesters of C2-C8 dicarboxylic acids or anhydrides thereof with C1-C4 alcohols, glyceryl triacetate and mixtures thereof; c) from 1.0 to 14 wt% of a hyperdispersant; ii. decorating the glazed green or fired substrate surface by means of a inkjet printer with the one or more of the inks of point (i); iii. firing the obtained decorated substrate at a temperature comprised between 750 and 1350 °C.
PCT/EP2023/069758 2022-07-21 2023-07-17 Vehicle for ceramic inkjet inks WO2024017818A1 (en)

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