WO2016146816A2 - Inkjet ink and constructive element decorated by digital printing - Google Patents

Inkjet ink and constructive element decorated by digital printing Download PDF

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Publication number
WO2016146816A2
WO2016146816A2 PCT/EP2016/055970 EP2016055970W WO2016146816A2 WO 2016146816 A2 WO2016146816 A2 WO 2016146816A2 EP 2016055970 W EP2016055970 W EP 2016055970W WO 2016146816 A2 WO2016146816 A2 WO 2016146816A2
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WO
WIPO (PCT)
Prior art keywords
ink
ester
glycol
ether
fatty acid
Prior art date
Application number
PCT/EP2016/055970
Other languages
French (fr)
Other versions
WO2016146816A3 (en
Inventor
David VALIENTE BORDANOVA
Vicente Cantavella Soler
Vicente BAGÁN VARGAS
José Vicente AGRAMUNT LERMA
Jesús FERNÁNDEZ VALENZUELA
Original Assignee
Innovaciones Técnicas Aplicadas A Cerámicas Avanzadas, S.A.U.
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Application filed by Innovaciones Técnicas Aplicadas A Cerámicas Avanzadas, S.A.U. filed Critical Innovaciones Técnicas Aplicadas A Cerámicas Avanzadas, S.A.U.
Publication of WO2016146816A2 publication Critical patent/WO2016146816A2/en
Publication of WO2016146816A3 publication Critical patent/WO2016146816A3/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0054—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or film forming compositions cured by thermal means, e.g. infrared radiation, heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0045—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or film forming compositions cured by mechanical wave energy, e.g. ultrasonics, cured by electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams, or cured by magnetic or electric fields, e.g. electric discharge, plasma
    • 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
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • 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
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/70—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • C04B41/71—Coating or impregnation for obtaining at least two superposed coatings having different compositions at least one coating being an organic material
    • 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
    • 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
    • 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
    • B41M5/0011—Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
    • B41M5/0017—Application of ink-fixing material, e.g. mordant, precipitating agent, on the substrate prior to printing, e.g. by ink-jet printing, coating or spraying

Definitions

  • the present invention relates to the field of decorated constructive elements.
  • the invention relates to a colour inkjet ink, to a constructive element decorated by digital printing and to processes for its preparation.
  • Decoration in precast elements porous surfaces is achieved by several techniques, depending on the nature of the surface to be treated.
  • organic pigment inks cured by ultraviolet (UV) or acrylic paints are typically used for this purpose.
  • UV ultraviolet
  • acrylic paints suitable for outdoor use, restricts the decoration possibilities due to limitations on their application.
  • organic pigment UV-curable inks can be applied by ink jet printing. However, they have a bad behaviour for outdoor use, and it is generally accepted that after two years they begin to lose their colouring characteristics.
  • Inkjet technology allows great production flexibility, greater consistency in the decorating process, reducing the consumption of pigments, reducing the time required to change models, possibility of decorating to the edges of the piece, and reducing the time elapsed since the idea for a new product design to manufacturing.
  • firing stage after the inkjet decoration allows to fix pigments, which became integrated into the vitreous structure of the material. This guarantees good adhesion and protection of the pigment.
  • the ink of the invention provides good outdoors resistance compared to organic pigmented inks.
  • the use of some specific solvents in combination with some specific surfactants and polarity modifiers allows obtaining an inkjet ink comprising an inorganic pigment which is stable and suitable for its inkjet application on a porous substrate.
  • the constructive element comprises a porous support material a decorative coating and a protective coating.
  • the use of a protective coating curing at temperatures up to 300 °C allows fixing the ink to the support at the same time that provides protection to both the support and the ink.
  • the method is particularly useful for the decoration of constructive elements made of porous supports that would be destroyed at temperatures higher than 300 °C.
  • a colour inkjet ink comprising:
  • At least one polarity modifier selected from the group consisting of a glycol ether, a glycol ester, and a glycol ester ether in an amount such that provides the ink with an appropriate polarity value to make the ink compatible with a porous substrate.
  • the use of the specific solvents having a boiling point point equal to or higher than 200 °C, particularly equal to or higher than 250 °C and equal to or lower than 400 °C, namely with relatively low vapour pressures, allows reducing the evaporation of the solvent in the printheads, which prevents the clogging of inkjet nozzles, making the printing system more stable. Incidentally, the release of Volatile Organic Compounds (VOC) during the decoration process is also reduced.
  • the solvents used in this invention are not curable by UV radiation, and therefore, this ink cannot be used in UV-curable printing systems.
  • the use of the solvent, the surfactant and the polarity modifier allows increasing the compatibility of the ink with the porous support such that the ink is easily absorbed by the support an a decorative coating of high quality is provided.
  • a second aspect of the invention is the provision of a constructive element comprising a a) porous support material; b) a decorative coating formed by at least one colour inkjet ink as defined herein above and below; and c) at least one protective cured polymeric coating formed with a composition curing at a temperature of up to 300 °C.
  • the invention in a third aspect relates to a process for the preparation of the constructive element as defined herein above and below, the process comprising applying a colour inkjet ink as defined herein above and below on a porous support material by digital printing, particularly by inkjet printing; and forming a protective polymeric coating by applying a composition comprising a curable polymer and, optionally, a solvent, wherein the curing of the polymeric coating takes place at a temperature up to 300 °C.
  • the invention relates to the use of an inkjet ink as defined herein above and below for the decoration of constructive elements as defined above without being submitted to a firing process.
  • curing refers to the hardening of non-solid polymers, which results from polymerization and/or crosslinking.
  • free radical initiators curing can be initiated by UV light or by the action of heat or moisture.
  • the term "primer” is a preparatory coating put on support materials before printing. Priming ensures better adhesion of subsequent coating layers to the surface and provides additional protection for the material being decorated or painted.
  • the term "decorative coating” relates to a coating having merely an aesthetic effect, an informative effect or a functional effect.
  • Examples of aesthetic effects include decorative element mimicking the appearance of natural materials such as stone, wood, marble or synthetic materials such as concrete, cement, weaving or pottery.
  • Examples of information elements include graphical elements as symbols, images, marks, logotypes, and signposting.
  • Examples of functional elements include light conductor elements, fluorescent elements, electrically conductive elements or, in general, any other element capable of providing additional functionality to the construction element.
  • weight percent refers to the percentage by weight of the ingredient per weight of the overall composition. Support material
  • porous support materials include wood, fibre cement, concrete, ceramic, gypsum, and gypsum board (such as Pladur ® ). Particularly, the support material is wood, fibre cement, or concrete.
  • the support material is a modular element in the form of a plate or a board.
  • the support material is selected from the group consisting of a wood strip, a strip of fibre cement, a brick, a concrete slab, and a concrete paver.
  • the support material has a porosity greater than 1 vol% measured by mercury porosimetry (cf. Giesche, H. "Mercury porosimetry: a general (practical) overview", Particle & particle systems characterization, 2006, vol. 23, no 1 , p. 9-19).
  • the constructive element of the invention further comprising a primer coating between the support material and the decorative coating.
  • the colour inkjet ink comprising:
  • At least one inorganic pigment particularly an inorganic pigment having a colour such as blue, yellow, beige, orange, red, coral, pink, violet, green, brown, black, and grey;
  • 200 °C selected from the group consisting of a hydrocarbon, an ester, and a fatty alcohol
  • At least one polarity modifier selected from the group consisting of a glycol ether, a glycol ester, and a glycol ester ether in an amount such that provides the ink with an appropriate polarity value that makes the ink compatible with a porous substrate.
  • the amount of polarity modifier is from 0,5 wt.% to 20 wt.%, particularly from 2 wt.% to 15 wt.%, based on the total weight of the inkjet ink.
  • the specific combination of solvent, surfactant, and polarity modifier allows improving the compatibility of the ink and the porous support, namely the ink is better absorbed by the support.
  • the compatibility between the ink and the substrate is determined by measuring the expansion of the point formed when the ink droplet impinges on the substrate. Further expansion means less definition in the final ink design.
  • the ink of the invention allows forming points on porous substrates with a lower expansion than the inkjet inks of the prior art.
  • the ink having an appropriate polarity value that makes the ink compatible with a porous substrate means that the expansion of the point formed when a 12 pi ink droplet impinges on the substrate is from 40 to 45 ⁇ (the expansion of the point for inks of the prior art is from 55 to 60 ⁇ ).
  • the use of inorganic pigments provides to the ink a higher stability against the action of solar radiation than inks formulated with organic pigments.
  • the constructive element of the invention has a higher durability when used outdoors than constructive elements that cannot be submitted to a firing process decorated with organic pigment inks.
  • the inorganic pigment can be both crystalline and vitreous or a mixture thereof. Pigment particles in inkjet inks are sufficiently small to permit free flow of the ink through the inkjet-printing device, to get maximum colour strength and to reduce sedimentation.
  • the at least one inorganic colour pigment is in an amount from 5 wt.% to 70 wt.%, particularly from 10 wt.% to 60 wt.%, more particularly from 20 wt.% to 50 wt.%, based on the total weight of the inkjet ink.
  • inorganic blue pigments are, without being limited to, Cobalt- Alumina (EINECS No 310-193-6), Cobalt-Zinc-Alumina (EINECS No 269-049- 5), Cobalt-Silica (EINECS No. 269-093- 5), Cobalt-Zinc-Silica (EINECS No 270-208-6), Cobalt Oxide (EINECS No 215-157-2), and Vanadium-Zirconium Silicate (EINECS No 269-057-9).
  • Cobalt- Alumina EINECS No 310-193-6
  • Cobalt-Zinc-Alumina EINECS No 269-049- 5
  • Cobalt-Silica EINECS No. 269-093- 5
  • Cobalt-Zinc-Silica EINECS No 270-208-6
  • Cobalt Oxide EINECS No 215-157-2
  • Vanadium-Zirconium Silicate EINECS No 269-057-9
  • inorganic yellow, beige and orange pigments are, without being limited to, Antimony-Nickel Titanate (EINECS No 232-353-3), Pyrochlore Antimony-Lead (EINECS No 232-382-1 ), Chromium antimony Titanate (EINECS No 269-052-1 ) Chromium Tungsten titanate (EINECS No 269-054- 2), Tin-Vanadium Cassiterite (EINECS No 269-055-8), Zirconium Oxide- Vanadium (EINECS No.
  • inorganic red, coral, pink and violet pigments are, without being limited to, Yttrium-Alumina (Oxide EINECS No 234-443-8), orthophosphate Cobalt (EINECS No 236-655-6), Alumina-Manganese Oxide (EINECS No
  • EINECS n°215-168-2 Sphene Tin-Chromium
  • EINECS No 269-073-6 Sphene Tin-Chromium
  • Alumina-Chrome Oxide EINECS No 269-083-0
  • Chromium-Alumina Spinel EINECS No 269- 230-9
  • Zirconium-Iron Silicate EINECS No 270-210-7
  • Chromium-Tin Cassiterite EINECS No 269-104-3
  • Iron Oxide EINECS n°215-168-2).
  • inorganic green pigments are, without being limited to, Chromium Oxide (EINECS No 235-790-8), Titanate Cobalt (EINECS No 269-047-4) Chromium-Cobalt Spinel (EINECS No. 269-072- 0), Chromium-Cobalt Spinel (EINECS No 269-101 -7), Garnet (EINECS 271 -385-2), Iron-Chromium
  • inorganic brown pigments are, without being limited to,
  • Chromium-Zinc Spinel (EINECS No 234-637-2), Iron-Chromium-Zinc Spinel (EINECS No 269-050-0), Iron-Chromium-manganese-Zinc Spinel (EINECS No 269-058-4), Iron-Chromium Spinel (EINECS No 269-069-4), Iron-Titanium Spinel (EINECS No 269-064-7), Iron-Zinc Spinel (EINECS No 269-103-8), Iron-Chromium-Manganese Spinel (EINECS No 269-050-0), and Iron Oxide (EINECS n°215-168-2).
  • inorganic black, and grey pigments are, without being limited to, Chromium-Copper Spinel (EINECS No 269-053-7), Iron-Manganese Spinel (EINECS No 269-056-3), Iron-Chromium-Cobalt Spinel (EINECS No 269-060- 5), vanadium-antimony titanate (EINECS No 269-062-6), Cobalt-Tin Spinel (EINECS No 269-066-8), Iron-Cobalt Spinel (EINECS No. 269-102-2), Tin- Antimony Cassiterite (EINECS No 269-105-9), Iron-Chromium-Nickel Spinel (EINECS No 275-738-1 ), and Iron Oxide (EINECS n°235-442-5).
  • Chromium-Copper Spinel EINECS No 269-053-7
  • Iron-Manganese Spinel EINECS No 269-056-3
  • inorganic white pigments are, without being limited to, titanium dioxide, zirconium silicate, zirconium oxide, tin oxide, cerium oxide, zinc oxide, aluminium oxide, silica, kaolin, calcium carbonate, magnesium carbonate, calcium magnesium carbonate, barium carbonate, sodium feldspar, potassium feldspar, nepheline, calcium silicate, and talc.
  • the solvent has to be compatible with support heads and machines for the application of inkjet inks.
  • the solvent having a boiling point equal to or higher than 200 °C is selected from the group consisting of:
  • C10-C25 hydrocarbon is selected from C10-C25 n-alkanes, C10-C25 isoalkanes or C10-C25 naphthenic hydrocarbons, and mixtures thereof.
  • Suitable C10-C25 n-alkanes include decane, undecane, dodecane.
  • Suitable C10-C25 isoalkanes include 2-methyl-nonane.
  • Suitable C10-C25 naphthenic hydrocarbons include, 2-(5-ethyloctyl)-decahydronaphtalene.
  • Suitable fatty acids include hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic (lauric) acid, tridecanoic acid, tetradecanoic (myristic) acid, pentadecanoic acid, hexadecanoic (palmitic) acid, heptadecanoic acid, octadecanoic (stearic) acid, nonadecanoic acid, eicosanoic acid, oleic acid, linoleic acid, linolenic acid, and erucic acid.
  • Suitable polycarboxylic acids include succinic acid, glutaric acid, maleic acid, phthalic acid.
  • suitable hydroxyl-containing acids include tartaric acid, tartronic acid, lactic acid, citric acid, mucic acid, malic acid, hydroxy-butyric acid and glycolic acid.
  • Examples of the alcohol forming the ester include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, 2-ethylhexyl, caprylyl, nonyl, capryl, undecyl, lauryl, tridecyl, isotridecyl, myristyl, cetyl-alcohol, stearyl, oleil (unsatured), and arachidyl alcohols, and a C12-Guerbet alcohol, a C14-Guerbet alcohol, a C16- Guerbet alcohol, a C18-Guerbet alcohol, and a C20-Guerbet alcohol.
  • polyalcohols forming the ester include ethylene glycol, propylene glycol, glycerol, neopentyl glycol (NP), trimethylolpropane (TMP), pentaeritritol (PE), sorbitol, xylitol, erythitol, galactitol, and mannitol.
  • the fatty alcohol is selected from the group consisting of Cs-C2 4 , particularly C 10-C20, fatty alcohols, such as decanol, dodecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, and oleyl alcohol.
  • the solvent is a C10-C25 hydrocarbon.
  • the solvent is an ester selected from the group consisting of fatty acid, benzoic acid, polycarboxylic acid, and hydroxyl containing acid esters.
  • the solvent is a fatty alcohol.
  • the at least one solvent is in an amount from 25 wt.% to 90 wt.%, particularly from 40 wt.% to 75 wt.%, more particularly from 50 wt.% to 75 wt.%, based on the total weight of the inkjet ink.
  • the solvent has a solubility in water equal to or lower than 10 g/100 ml H 2 O and the surfactant is a non-ionic surfactant having a HLB (Hydrophilic-Lipophilic Balance) equal to or lower than 12 and is selected from the group consisting of a propylene oxide (PO) homo-polymer, a ethylene oxide (EO)/PO random co-polymer, a EO/PO block co-polymer, a fatty derivative copolymer, a saturated polyol ester, a unsaturated polyol ester, an acrylic block copolymer, a polymerized fatty acid ester, an alkyi ethoxylate, a fatty acid polyethyleneglycol ester, a fatty acid polypropyleneglycol esters, a fatty acid polyglycerol ester, a fatty acid polyglycerol ester ethoxylate, a
  • HLB Hydrophilic-Lipophilic
  • the solvent has a solubility in water higher than 10 g/100 ml H 2 O and the surfactant is either an ionic surfactant selected from the group consisting of a phospate ester, an alkyi phosphonic acid, an alkyi polyethyleneglycol ether phosphoric acid ester, and an alkyi phosphoric acid ester, or a non-ionic surfactant having a HLB higher than 12 and selected from the group consisting of a propylene oxide (PO) homo-polymer, a ethylene oxide (EO)/PO random co-polymer, a EO/PO block co-polymer, a fatty derivative copolymer, a saturated polyol ester, a unsaturated polyol ester, an acrylic block copolymer, a polymerized fatty acid ester, an alkyl ethoxylate, a fatty acid polyethyleneglycol ester, a fatty acid polyprop
  • polyethylene glycol ether carboxylic acid a fatty acid condensate such as fatty acid isethionates, methyl taurides, sarkosin and sarkoside, a vinyl ether alkoxylate (PO-EO-block polymers), an allyl ether alkoxylate (PO-EO-block polymers), polypropylene glycol, and a propoxylated fatty alcohol, or a mixture thereof.
  • a fatty acid condensate such as fatty acid isethionates, methyl taurides, sarkosin and sarkoside
  • PO-EO-block polymers vinyl ether alkoxylate
  • PO-EO-block polymers an allyl ether alkoxylate
  • polypropylene glycol polypropylene glycol
  • propoxylated fatty alcohol or a mixture thereof.
  • the at least one surfactant is in an amount from 0,5 wt.% to 20 wt.%, particularly from 2 wt.% to 15 wt.%, based on the total weight of the inkjet ink.
  • glycol ethers include, without being limited to, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol n- butyl ether, and tripropylene glycol n-butyl ether.
  • glycol esters include, without being limited to, propylene glycol diacetate, triethylene glycol-di-(2-ethylhexanoate), and propylene glycol octoate.
  • glycol ether esters include, without being limited to, diethylene glycol n-butyl ether acetate, and dipropylene glycol methyl ether acetate.
  • the polarity modifier is selected from the group consisting of dipropylene glycol
  • the polarity modifier selected from the group consisting of dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol n-butyl ether, and tripropylene glycol n-butyl ether, and triethylene glycol-di-(2-ethylhexanoate).
  • the at least one polarity modifier is in an amount from 0,5 wt.% to 20 wt.%, particularly from 2 wt.% to 15 wt.%, based on the total weight of the inkjet ink.
  • the at least one inorganic colour pigment is in an amount from 5 wt.% to 70 wt.%, particularly from 10 wt.% to 60 wt.%, more particularly from 20 wt.% to 50 wt.%, based on the total weight of the inkjet ink;
  • the at least one solvent is in an amount from 25 wt.% to 90 wt.%, particularly from 40 wt.% to 75 wt.%, more particularly from 50 wt.% to 75 wt.%, based on the total weight of the inkjet ink;
  • the at least one surfactant in an amount from 0,5 wt.% to 20 wt.%, particularly from 2 wt.% to 15 wt.%, based on the total weight of the inkjet ink;
  • the at least one polarity modifier is in an amount from 0,5 wt.% to 20 wt.%, particularly
  • the ink of the invention further comprises an inorganic opacifying agent.
  • the opacifying agent is selected from the group consisting of titanium dioxide, zirconium silicate, zirconium oxide, tin oxide, cerium oxide, zinc oxide, aluminium oxide, silica, kaolin, calcium carbonate, magnesium carbonate, calcium magnesium carbonate, barium carbonate, sodium feldspar, potassium feldspar, nepheline, calcium silicate, mullite, wollastonite, and talc.
  • the opacifying agent is selected from the group consisting of calcium carbonate, aluminium oxide, zirconium silicate and titanium dioxide.
  • the amount of opacifying agent is from 0.5 to 25 wt.%, more particularly from 1 to 20 wt.%, more particularly from 5 to 20 wt.%, based on the total weight of the ink.
  • the inkjet ink further comprises at least an additive which allows improving the rheological properties of the ink.
  • additives allow reaching a high solid content with low viscosities, as well as preventing degradation of the ink over time. Examples of such additives are, without being limited to dispersants, wetting agents,
  • the additives must be compatible with the pigments and solvents employed, and must be suitable for grinding.
  • the appropriate additives and their amounts can readily be determined by those skilled in the art.
  • the amount of additives in the ink is from 0.05 wt.% to 20 wt.%, particularly from 2 wt.% to 15 wt.%, based on the total weight of the inkjet ink.
  • the at least one additive is a dispersant.
  • dispersants are, without being limited to, polyamines and carboxyl terminated polyesters with formation of amidic and/or salt linkages such as the ones disclosed in US4224212, US4861380, US5700395,
  • the at least one dispersant can be in an amount from 0 wt.% to 20 wt.%, particularly from 2 wt.% to 15 wt.%, based on the total weight of the inkjet ink.
  • Particles in inkjet inks must be small enough to permit free flow of the ink through the inkjet-printing device, to get maximum colour strength, and to reduce sedimentation.
  • particles of solid components comprised in the ink namely the inorganic pigment and, optionally, opacifying agent have a particle size distribution wherein D 90 is equal to or lower than 0.9 ⁇ , particularly from 0.25 ⁇ to 0.60 ⁇ , more particularly, from 0.25 to 0.45.
  • the ink of the invention is able to pass through a sieve with a 1 ⁇ mesh without leaving any residue.
  • D 50 is the median value, namely the particle size diameter that splits the distribution with half above and half below this diameter.
  • D 90 describes the diameter where ninety percent of the distribution has a smaller particle size and ten percent has a larger particle size.
  • Particle size can be determined, for example, by laser light scattering using a particle size analyser, such as the MastersizerTM apparatus available from Malvern Instruments Ltd. In the case of the ink composition of the present invention, particle size was determined introducing 3 drops of dispersion in 100 ml of isopropyl laurate. Afterwards the sample was manually
  • a suitable dispersing system such as a ball mill, basket mill, or Cowles type agitator, until obtaining a homogeneous mixture.
  • a suitable dispersing system such as a ball mill, basket mill, or Cowles type agitator
  • the mixture is submitted to a grinding and/or dispersion process, in order to achieve a homogeneous suspension, particularly with a viscosity from 10 to 200 cP (at 40 °C), and specific particle sizes with a maximum particle diameter of less than 2 ⁇ .
  • the grinding and/or dispersion process can be carried out with a microballs mill, such as a Netzsch mill, LabStar type, with yttrium or cerium doped ZrO2 microspheres from 0.2 to 5 mm in diameter and with a load from 50% to 98% of the volume of the grinding chamber.
  • viscosity controls for instance with a rotational viscometer such as Brookfield LVDV
  • particle size distribution measures for instance particle analysis by laser diffraction with a Malvern Mastersizer 2000
  • the obtained colour inkjet ink has a viscosity from 4 to 40 cP (at 40 °C) and a solid content from 5 to 60 wt.%.
  • the obtained dispersions have a physicochemical stability suitable to be used in an inkjet printer, that is, without significant variations in viscosity and density over time, as well as a negligible sedimentation not affecting their later use.
  • the decorative coating on the support material of the constructive element of the invention is formed by at least one inkjet ink comprising an inorganic pigment, and at least one solvent.
  • the colour inkjet ink is applied on the support by digital printing such as inkjet printing.
  • Digital printing refers to methods of printing from a digital-based image directly to a variety of media.
  • the inkjet printing method includes the steps of: a) feeding an inkjet printhead with a colour inkjet ink comprising an inorganic pigment and at least one solvent; and b) jetting the colour inkjet ink with the inkjet printhead on a support material, optionally coated with a primer.
  • the invention also relates to a process for the
  • composition comprising a curable polymer and, optionally, a solvent, to form a protective polymeric coating that cures at a temperature of up to 300 °C.
  • the digital printing is made by inkjet printing.
  • inkjet printing is performed with a single- pass printer.
  • the use of the single-pass inkjet printers allows reducing the cost of the process compared to current cost for the decoration of certain substrates such as fibre cement.
  • the process of the invention further comprises an additional step of applying a primer composition on the substrate previously to the application of the colour inkjet ink.
  • the protective polymeric coating is formed with a composition comprising a curable polymer and, optionally, a solvent. Curing of the protective polymeric coating takes place in the absence of any firing process, namely at a temperature of up to 300 °C.
  • the solvent of the coating composition can be removed by volatilization during the curing process.
  • the protective polymeric coating allows fixing the inorganic ink to the porous support material. Additionally, it provides protection of the ink and of the constructive element as a whole by providing wear resistance and hardness. Thus, depending on the specific components, the polymeric coating can provide protection against several factors such as surface abrasion, scratch, and chemical attack. Additionally, it can provide the sought final appearance of the product, including for example a matte, bright or satin finish. Properties of the protective coating can be adjusted depending on the final application of the constructive element (indoor or outdoor siding or flooring, level of pedestrian traffic).
  • the protective polymeric coating has an appropriate adhesiveness with all of the substrate and/or the primer if present.
  • the protective polymeric coating exhibits adhesiveness from 0 to 3, particularly from 0 to 2, according to the adhesion measurement test defined in UNE-EN ISO 2409. This standard classifies the level of adhesion on five categories, being category 0 the best result.
  • the polymeric coating is UV curable.
  • the coating composition can be cured by irradiation with ultraviolet rays as is known to those skilled in the art. In this regard, the irradiation is applied until complete curing of the coating.
  • Example of a suitable curable protective coating compositions are such as the ones disclosed in US4393187 (Example, line 55, column 9, to line 9, column 1 1 ) and US5571570 (line 64, column 2, to line 28, column 5).
  • the coating composition comprises: (a) 35% to 65% by weight of a first acrylate aliphatic urethane having a molecular weight of 500 to 2000 and formed by the reaction of (i) a first multifunctional acrylate with a molecular weight of 190 to 500 and containing at least three polymerizable unsaturated groups per molecule, with (ii) an aliphatic urethane based on a polymer of allyl carbomonocycle diisocyanate with alkanepolyol polyacrylates; (b) 5% to 25% by weight of a second acrylated aliphatic urethane having a molecular weight of 1200 to 2600 and formed by the reaction of a second multifunctional acrylate with a molecular weight of 1 10 to 500 with an aliphatic urethane based on a polyether and having a molecular weight of 800 to 2200; (c) 10% to 55% by weight of a third multifunctional acrylate having a molecular weight
  • the coating composition can also comprise a suitable solvent.
  • suitable solvents include, without being limited to, ester solvents, such as ethyl acetate and butyl acetate, ketone solvents such as acetone, methyl isobutyl ketone, and methylethyl ketone; alcohols such as butyl alcohol; and aromatic solvents such as toluene and xylene.
  • ester solvents such as ethyl acetate and butyl acetate
  • ketone solvents such as acetone, methyl isobutyl ketone, and methylethyl ketone
  • alcohols such as butyl alcohol
  • aromatic solvents such as toluene and xylene.
  • the amount of solvent included will vary in accordance with the particular application at hand. Particularly, the amount of solvent is from 0% to 95%, more particularly from 40% to 60%, by weight of the entire coating composition.
  • the constructive element of the invention comprises additional coating layers each one conferring a specific property such as as hardness, gloss, wear resistance, self-cleaning, or bactericidal.
  • the coating composition can be applied by any conventional coating method known in the art such as curtain coating, roller coating, and spraying.
  • Primer composition The aim of the primer is to obtain a better colour gamut development, facilitate adhesion of the decorative layer and of the protective layer, hide the substrate colour, improve the smoothness of the surface (reducing variability), enhance porosity, and/or increase the wettability of the ink so that the solvent in the ink drains correctly (avoiding the defect known as "lack of drying").
  • any primer composition known in the art can be used.
  • the primer can comprise a polyurethane as a primary binder resin, a neutralizing agent such as an amine and, optionally, a third component such as an epoxy or an acrylic resin.
  • Primer compositions are commercially available, such as the polyester/acrylic primer composition from BASF Corporation as Smoke U28AW031 .
  • the primer composition can further comprise a crosslinking agent, opacifying agents (fillers), and a solvent system.
  • the amount of crosslinking agent is from 0.1 to 10 wt.%, particularly from 3 to 7 wt.%, more particularly of a 5%.
  • the crosslinking agent interacts with the protective polymeric coating improving the
  • crosslinking agents include, without being limited to,
  • diphenylmethane, 4,4'-diisocyanate 1,6-hexamethylene diisocyanate, p- phenylene diisocyanate; tetramethyl xylene diisocyanate, and m-xylene diisocyanate.
  • the primer affords good adhesion to the surface to be decorated and or coated, particularly to the protective coating and/or to the inkjet ink.
  • the primer composition can be applied by conventional methods such as by spraying or roller coating.
  • the primer coating comprises at least one opacifying agent.
  • the presence of the opacifying agent has the advantage that whiteness is increases and thus the performance of the decorative colour coating is improved.
  • the opacifying agent is selected from calcium carbonate (CaCOs), aluminium oxide (AI2O3), zirconium silicate (ZrSiO 4 ) and titanium dioxide (T1O2). Particularly, the opacifying agent is ZrSiO 4 or ⁇ 2.
  • Example2 and Example 3 were applied on a concrete substrate with an inkjet head having a print resolution of 360x360 dpi and a maximum drop of 84 pi. Chromaticity coordinates of the ink of Example 2 (without the presence of
  • An ink layer was applied by inkjet printing in order to introduce a decorative element, in particular a wood effect.
  • Digital printing was performed with a single-pass printer with DOD (Drop on Demand) piezoelectric printheads.
  • Four different inks were used to obtain an ink layer which imitates wood, particularly blue ink (ink of Example 1 ), red ink (CIS -RE3309 from Esmalglass-itaca group), yellow ink (CIS-YE5308 from Esmalglass-itaca group), and black ink (CIS-BK6304 from Esmalglass-itaca group).
  • the solid content of the inks was 25 wt.%.
  • each one of the other inks comprised an inorganic pigment (particularly, iron oxide for the red ink, praseodymium zirconate for the yellow ink and chromium-nickel-cobalt- iron-manganese spinel for the black ink), a polymeric dispersant (Solsperse 3000, 5 wt.%), a non-ionic surfactant (2 wt.%), an aliphatic isoparaffinic hydrocarbon (47 wt.%), a fatty alcohol (7 wt.%), polypropylene glycol (4 wt.%), a fatty acid ester (10 wt.%).
  • an inorganic pigment particularly, iron oxide for the red ink, praseodymium zirconate for the yellow ink and chromium-nickel-cobalt- iron-manganese spinel for the black ink
  • a polymeric dispersant Solsperse 3000, 5 wt.%)
  • a protective coating consisting of a 100% solids UV curable resin (Uvinol 850, a solvent-free, UV-curing, clear epoxy acrylate sealer and topcoat commercialized by Tikkurila Coatings) was applied by roller coating over the ink layer.
  • An applicator roller having an applicator roll 238 mm in diameter coated with 40 shores hardness ethylene propylene diene monomer (EPDM) was used.
  • EPDM hardness ethylene propylene diene monomer
  • Example 4 was repeated also with the inks of Examples 1 to 3, but first, a primer (Bona Prime Classic, a waterborne one-component acrylate dispersion commercialized by Bona) was sprayed onto the fibre cement plate by airless spraying in order to form a uniform layer providing whiteness to the surface and with the aim of promoting adhesion of the subsequent layers. In all the cases an excellent compatibility of the ink and the support treated with the primer was observed, which lead to well defined decorative element.
  • a primer “Bona Prime Classic, a waterborne one-component acrylate dispersion commercialized by Bona

Abstract

It is provided a colour inkjet ink comprising: i) at least one inorganic pigment, ii) at least one solvent having a boiling point equal to or higher than 200ºC selected from a hydrocarbon, an ester, and a fatty alcohol; iii) at least one surfactant, and iv) at least one polarity modifier selected from a glycol ether, a glycol ester, and a glycol ester ether. It is also provided a constructive element comprising a support material; a decorative coating formed by at least one colour inkjet ink as defined above; and a protective cured polymeric coating formed with a composition curing at a temperature of up to 300ºC. It is also provided a process for the preparation of the constructive element above, and the use of the colour inkjet ink for the decoration of constructive elements without being submitted to a firing process.

Description

Inkjet ink and constructive element decorated by digital printing
The present invention relates to the field of decorated constructive elements. In particular, the invention relates to a colour inkjet ink, to a constructive element decorated by digital printing and to processes for its preparation.
BACKGROUND ART
Decoration in precast elements porous surfaces is achieved by several techniques, depending on the nature of the surface to be treated. For example, in the field of fibre cement organic pigment inks cured by ultraviolet (UV) or acrylic paints are typically used for this purpose. In the field of wood stains, varnishes and paints are commonly used. The use of acrylic paints, suitable for outdoor use, restricts the decoration possibilities due to limitations on their application. On the other hand, organic pigment UV-curable inks can be applied by ink jet printing. However, they have a bad behaviour for outdoor use, and it is generally accepted that after two years they begin to lose their colouring characteristics.
In the decade 2000-2010, in the ceramic industry, inkjet printing technology using inorganic pigments applied on tiles was developed. This technique was a revolution in the industry, and in 2014 the degree of implementation was over 90% in Spain and Italy (leading European manufacturers) and 64% worldwide.
Inkjet technology allows great production flexibility, greater consistency in the decorating process, reducing the consumption of pigments, reducing the time required to change models, possibility of decorating to the edges of the piece, and reducing the time elapsed since the idea for a new product design to manufacturing.
In ceramic pieces, firing stage after the inkjet decoration allows to fix pigments, which became integrated into the vitreous structure of the material. This guarantees good adhesion and protection of the pigment.
Nevertheless, the application of inorganic pigment inks on porous support materials that are not being to be subsequently subjected to a firing process presents several drawbacks such as incompatibility between the ink and the substrate, high heterogeneity of the substrate, low opacity pigmented inks (which makes the substrate partially visible), lack of fixation to the substrate, and solvent removal problems.
Therefore, there is still a need for an improved inkjet ink and method for the inkjet decoration of porous support materials that allows obtaining constructive elements with the high demanding quality properties and performance required by the market without the need of being submitted to a firing process.
SUMMARY OF THE INVENTION
Inventors have found a colour inkjet ink suitable for decorating constructive elements which will not be subjected to any thermal treatment after
decoration, or that will be subsequently subjected to a thermal treatment at a maximum temperature of 300 °C. The ink of the invention provides good outdoors resistance compared to organic pigmented inks. The use of some specific solvents in combination with some specific surfactants and polarity modifiers allows obtaining an inkjet ink comprising an inorganic pigment which is stable and suitable for its inkjet application on a porous substrate.
Additionally, inventors have found a method to obtain a decorated constructive element that is not being to be subsequently subjected to a firing process with a good outdoors resistance. The constructive element comprises a porous support material a decorative coating and a protective coating.
Advantageously, the use of a protective coating curing at temperatures up to 300 °C allows fixing the ink to the support at the same time that provides protection to both the support and the ink. The method is particularly useful for the decoration of constructive elements made of porous supports that would be destroyed at temperatures higher than 300 °C.
Thus, a first aspect of the invention is the provision of a colour inkjet ink comprising:
i) at least one inorganic pigment,
ii) at least one solvent having a boiling point equal to or higher than 200 °C selected from the group consisting of a hydrocarbon, an ester, and a fatty alcohol;
at least one surfactant, and
at least one polarity modifier selected from the group consisting of a glycol ether, a glycol ester, and a glycol ester ether in an amount such that provides the ink with an appropriate polarity value to make the ink compatible with a porous substrate.
The use of the specific solvents having a boiling point point equal to or higher than 200 °C, particularly equal to or higher than 250 °C and equal to or lower than 400 °C, namely with relatively low vapour pressures, allows reducing the evaporation of the solvent in the printheads, which prevents the clogging of inkjet nozzles, making the printing system more stable. Incidentally, the release of Volatile Organic Compounds (VOC) during the decoration process is also reduced. The solvents used in this invention are not curable by UV radiation, and therefore, this ink cannot be used in UV-curable printing systems.
Additionally, the use of the solvent, the surfactant and the polarity modifier allows increasing the compatibility of the ink with the porous support such that the ink is easily absorbed by the support an a decorative coating of high quality is provided.
A second aspect of the invention is the provision of a constructive element comprising a a) porous support material; b) a decorative coating formed by at least one colour inkjet ink as defined herein above and below; and c) at least one protective cured polymeric coating formed with a composition curing at a temperature of up to 300 °C. In a third aspect the invention relates to a process for the preparation of the constructive element as defined herein above and below, the process comprising applying a colour inkjet ink as defined herein above and below on a porous support material by digital printing, particularly by inkjet printing; and forming a protective polymeric coating by applying a composition comprising a curable polymer and, optionally, a solvent, wherein the curing of the polymeric coating takes place at a temperature up to 300 °C. In another aspect the invention relates to the use of an inkjet ink as defined herein above and below for the decoration of constructive elements as defined above without being submitted to a firing process.
DETAILED DESCRIPTION OF THE INVENTION
All terms as used herein in this application, unless otherwise stated, shall be understood in their ordinary meaning as known in the art. Other more specific definitions terms as used in the present application are as set forth below and are intended to apply uniformly throughout the specification and claims unless an otherwise expressly set out definition provides a broader definition.
As used herein, the term "curing" refers to the hardening of non-solid polymers, which results from polymerization and/or crosslinking. By the appropriate choice of free radical initiators, curing can be initiated by UV light or by the action of heat or moisture.
As used herein, the term "primer" is a preparatory coating put on support materials before printing. Priming ensures better adhesion of subsequent coating layers to the surface and provides additional protection for the material being decorated or painted.
As used herein, the term "decorative coating" relates to a coating having merely an aesthetic effect, an informative effect or a functional effect.
Examples of aesthetic effects include decorative element mimicking the appearance of natural materials such as stone, wood, marble or synthetic materials such as concrete, cement, weaving or pottery. Examples of information elements include graphical elements as symbols, images, marks, logotypes, and signposting. Examples of functional elements include light conductor elements, fluorescent elements, electrically conductive elements or, in general, any other element capable of providing additional functionality to the construction element. As used herein, the term "weight percent", "percentage by weight" or "wt.%" refers to the percentage by weight of the ingredient per weight of the overall composition. Support material
Examples of porous support materials include wood, fibre cement, concrete, ceramic, gypsum, and gypsum board (such as Pladur®). Particularly, the support material is wood, fibre cement, or concrete.
In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above, the support material is a modular element in the form of a plate or a board. In another particular embodiment, optionally in combination with one or more features of the particular embodiments defined above, the support material is selected from the group consisting of a wood strip, a strip of fibre cement, a brick, a concrete slab, and a concrete paver.
In another particular embodiment, optionally in combination with one or more features of the particular embodiments defined above, the support material has a porosity greater than 1 vol% measured by mercury porosimetry (cf. Giesche, H. "Mercury porosimetry: a general (practical) overview", Particle & particle systems characterization, 2006, vol. 23, no 1 , p. 9-19).
In another particular embodiment, optionally in combination with one or more features of the particular embodiments defined above, the constructive element of the invention further comprising a primer coating between the support material and the decorative coating.
It has also been observed that the use of the combination of the specific solvent, surfactant and polarity modifier in the ink of the invention allows increasing the compatibility of the ink with the primer facilitating the adhesion of the decorative layer. Thus a decorative coating of higher quality is provided also when a primer is applied on the support.
Inorganic pigment inkjet ink As mentioned above, the colour inkjet ink comprising:
i) at least one inorganic pigment, particularly an inorganic pigment having a colour such as blue, yellow, beige, orange, red, coral, pink, violet, green, brown, black, and grey;
ii) at least one solvent having a boiling point equal to or higher than
200 °C selected from the group consisting of a hydrocarbon, an ester, and a fatty alcohol;
iii) at least one surfactant, and
iv) at least one polarity modifier selected from the group consisting of a glycol ether, a glycol ester, and a glycol ester ether in an amount such that provides the ink with an appropriate polarity value that makes the ink compatible with a porous substrate.
Particularly, the amount of polarity modifier is from 0,5 wt.% to 20 wt.%, particularly from 2 wt.% to 15 wt.%, based on the total weight of the inkjet ink.
Advantageously, the specific combination of solvent, surfactant, and polarity modifier allows improving the compatibility of the ink and the porous support, namely the ink is better absorbed by the support.
The compatibility between the ink and the substrate is determined by measuring the expansion of the point formed when the ink droplet impinges on the substrate. Further expansion means less definition in the final ink design. The ink of the invention allows forming points on porous substrates with a lower expansion than the inkjet inks of the prior art. Thus, the ink having an appropriate polarity value that makes the ink compatible with a porous substrate means that the expansion of the point formed when a 12 pi ink droplet impinges on the substrate is from 40 to 45 μιτι (the expansion of the point for inks of the prior art is from 55 to 60 μιτι).
Additionally, the use of inorganic pigments provides to the ink a higher stability against the action of solar radiation than inks formulated with organic pigments. As a consequence, the constructive element of the invention has a higher durability when used outdoors than constructive elements that cannot be submitted to a firing process decorated with organic pigment inks.
The inorganic pigment can be both crystalline and vitreous or a mixture thereof. Pigment particles in inkjet inks are sufficiently small to permit free flow of the ink through the inkjet-printing device, to get maximum colour strength and to reduce sedimentation.
In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above, the at least one inorganic colour pigment is in an amount from 5 wt.% to 70 wt.%, particularly from 10 wt.% to 60 wt.%, more particularly from 20 wt.% to 50 wt.%, based on the total weight of the inkjet ink.
Examples of inorganic blue pigments are, without being limited to, Cobalt- Alumina (EINECS No 310-193-6), Cobalt-Zinc-Alumina (EINECS No 269-049- 5), Cobalt-Silica (EINECS No. 269-093- 5), Cobalt-Zinc-Silica (EINECS No 270-208-6), Cobalt Oxide (EINECS No 215-157-2), and Vanadium-Zirconium Silicate (EINECS No 269-057-9). Examples of inorganic yellow, beige and orange pigments are, without being limited to, Antimony-Nickel Titanate (EINECS No 232-353-3), Pyrochlore Antimony-Lead (EINECS No 232-382-1 ), Chromium antimony Titanate (EINECS No 269-052-1 ) Chromium Tungsten titanate (EINECS No 269-054- 2), Tin-Vanadium Cassiterite (EINECS No 269-055-8), Zirconium Oxide- Vanadium (EINECS No. 269 -063-1 ), Zirconium-Praseodymium Silicate (EINECS No 269-075-7), Antimony-manganese titanate (EINECS No 270- 185-2), Chrome-niobium titanate (EINECS No 271 -891 -3), nickel-niobium titanate (EINECS No 271 -892-9), Zirconium-Cadmium Silicate (EINECS No 277-135-9), Antimony titanate (EINECS No 305-908-3), and Silicic acid zirconium salt cadmium pigment-encapsulated (EINECS No 310-077-5), and iron hydroxide (EINECS n°257-098-5).
Examples of inorganic red, coral, pink and violet pigments are, without being limited to, Yttrium-Alumina (Oxide EINECS No 234-443-8), orthophosphate Cobalt (EINECS No 236-655-6), Alumina-Manganese Oxide (EINECS No
269-061 -0), Sphene Tin-Chromium (EINECS No 269-073-6), Alumina-Chrome Oxide (EINECS No 269-083-0), Chromium-Alumina Spinel (EINECS No 269- 230-9), Zirconium-Iron Silicate (EINECS No 270-210-7), Chromium-Tin Cassiterite (EINECS No 269-104-3), and Iron Oxide (EINECS n°215-168-2).
Examples of inorganic green pigments are, without being limited to, Chromium Oxide (EINECS No 235-790-8), Titanate Cobalt (EINECS No 269-047-4) Chromium-Cobalt Spinel (EINECS No. 269-072- 0), Chromium-Cobalt Spinel (EINECS No 269-101 -7), Garnet (EINECS 271 -385-2), Iron-Chromium
Hematite (EINECS No 272-713-7), Copper Spinels (EINECS No. 305 -908-3), and Chrome Spinel (EINECS No 306-013-0).
Examples of inorganic brown pigments are, without being limited to,
Chromium-Zinc Spinel (EINECS No 234-637-2), Iron-Chromium-Zinc Spinel (EINECS No 269-050-0), Iron-Chromium-manganese-Zinc Spinel (EINECS No 269-058-4), Iron-Chromium Spinel (EINECS No 269-069-4), Iron-Titanium Spinel (EINECS No 269-064-7), Iron-Zinc Spinel (EINECS No 269-103-8), Iron-Chromium-Manganese Spinel (EINECS No 269-050-0), and Iron Oxide (EINECS n°215-168-2).
Examples of inorganic black, and grey pigments are, without being limited to, Chromium-Copper Spinel (EINECS No 269-053-7), Iron-Manganese Spinel (EINECS No 269-056-3), Iron-Chromium-Cobalt Spinel (EINECS No 269-060- 5), vanadium-antimony titanate (EINECS No 269-062-6), Cobalt-Tin Spinel (EINECS No 269-066-8), Iron-Cobalt Spinel (EINECS No. 269-102-2), Tin- Antimony Cassiterite (EINECS No 269-105-9), Iron-Chromium-Nickel Spinel (EINECS No 275-738-1 ), and Iron Oxide (EINECS n°235-442-5).
Examples of inorganic white pigments are, without being limited to, titanium dioxide, zirconium silicate, zirconium oxide, tin oxide, cerium oxide, zinc oxide, aluminium oxide, silica, kaolin, calcium carbonate, magnesium carbonate, calcium magnesium carbonate, barium carbonate, sodium feldspar, potassium feldspar, nepheline, calcium silicate, and talc.
The solvent has to be compatible with support heads and machines for the application of inkjet inks.
In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above or below, the solvent having a boiling point equal to or higher than 200 °C is selected from the group consisting of:
i) a C10-C25 hydrocarbon;
ii) an ester derived from a fatty acid, a benzoic acid, a polycarboxylic acid, or a hydroxyl containing acid; and iii) a fatty alcohol.
More particularly the C10-C25 hydrocarbon is selected from C10-C25 n-alkanes, C10-C25 isoalkanes or C10-C25 naphthenic hydrocarbons, and mixtures thereof. Suitable C10-C25 n-alkanes include decane, undecane, dodecane. Suitable C10-C25 isoalkanes include 2-methyl-nonane. Suitable C10-C25 naphthenic hydrocarbons include, 2-(5-ethyloctyl)-decahydronaphtalene.
Examples of suitable fatty acids include hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic (lauric) acid, tridecanoic acid, tetradecanoic (myristic) acid, pentadecanoic acid, hexadecanoic (palmitic) acid, heptadecanoic acid, octadecanoic (stearic) acid, nonadecanoic acid, eicosanoic acid, oleic acid, linoleic acid, linolenic acid, and erucic acid. Examples of suitable polycarboxylic acids include succinic acid, glutaric acid, maleic acid, phthalic acid. Examples of suitable hydroxyl-containing acids include tartaric acid, tartronic acid, lactic acid, citric acid, mucic acid, malic acid, hydroxy-butyric acid and glycolic acid.
Examples of the alcohol forming the ester include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, 2-ethylhexyl, caprylyl, nonyl, capryl, undecyl, lauryl, tridecyl, isotridecyl, myristyl, cetyl-alcohol, stearyl, oleil (unsatured), and arachidyl alcohols, and a C12-Guerbet alcohol, a C14-Guerbet alcohol, a C16- Guerbet alcohol, a C18-Guerbet alcohol, and a C20-Guerbet alcohol. Examples of polyalcohols forming the ester include ethylene glycol, propylene glycol, glycerol, neopentyl glycol (NP), trimethylolpropane (TMP), pentaeritritol (PE), sorbitol, xylitol, erythitol, galactitol, and mannitol.
Particularly, the fatty alcohol is selected from the group consisting of Cs-C24, particularly C 10-C20, fatty alcohols, such as decanol, dodecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, and oleyl alcohol.
In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above or below, the solvent is a C10-C25 hydrocarbon. In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above or below, the solvent is an ester selected from the group consisting of fatty acid, benzoic acid, polycarboxylic acid, and hydroxyl containing acid esters.
In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above or below, the solvent is a fatty alcohol. In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above, the at least one solvent is in an amount from 25 wt.% to 90 wt.%, particularly from 40 wt.% to 75 wt.%, more particularly from 50 wt.% to 75 wt.%, based on the total weight of the inkjet ink.
In a particular embodiment of the ink of the invention, the solvent has a solubility in water equal to or lower than 10 g/100 ml H2O and the surfactant is a non-ionic surfactant having a HLB (Hydrophilic-Lipophilic Balance) equal to or lower than 12 and is selected from the group consisting of a propylene oxide (PO) homo-polymer, a ethylene oxide (EO)/PO random co-polymer, a EO/PO block co-polymer, a fatty derivative copolymer, a saturated polyol ester, a unsaturated polyol ester, an acrylic block copolymer, a polymerized fatty acid ester, an alkyi ethoxylate, a fatty acid polyethyleneglycol ester, a fatty acid polypropyleneglycol esters, a fatty acid polyglycerol ester, a fatty acid polyglycerol ester ethoxylate, a sorbitan ester ethoxylate, an alkyi polyethylene glycol ether carboxylic acid, a fatty acid condensate such as fatty acid isethionates, methyl taurides, sarkosin and sarkoside, a vinyl ether alkoxylate (PO-EO-block polymers), an allyl ether alkoxylate (PO-EO-block polymers), polypropylene glycol, and a propoxylated fatty alcohol.
In another particular embodiment of the ink of the invention, the solvent has a solubility in water higher than 10 g/100 ml H2O and the surfactant is either an ionic surfactant selected from the group consisting of a phospate ester, an alkyi phosphonic acid, an alkyi polyethyleneglycol ether phosphoric acid ester, and an alkyi phosphoric acid ester, or a non-ionic surfactant having a HLB higher than 12 and selected from the group consisting of a propylene oxide (PO) homo-polymer, a ethylene oxide (EO)/PO random co-polymer, a EO/PO block co-polymer, a fatty derivative copolymer, a saturated polyol ester, a unsaturated polyol ester, an acrylic block copolymer, a polymerized fatty acid ester, an alkyl ethoxylate, a fatty acid polyethyleneglycol ester, a fatty acid polypropyleneglycol esters, a fatty acid polyglycerol ester, a fatty acid polyglycerol ester ethoxylate, a sorbitan ester ethoxylate, an alkyl
polyethylene glycol ether carboxylic acid, a fatty acid condensate such as fatty acid isethionates, methyl taurides, sarkosin and sarkoside, a vinyl ether alkoxylate (PO-EO-block polymers), an allyl ether alkoxylate (PO-EO-block polymers), polypropylene glycol, and a propoxylated fatty alcohol, or a mixture thereof.
In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above, the at least one surfactant is in an amount from 0,5 wt.% to 20 wt.%, particularly from 2 wt.% to 15 wt.%, based on the total weight of the inkjet ink.
Examples of glycol ethers include, without being limited to, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol n- butyl ether, and tripropylene glycol n-butyl ether.
Examples of glycol esters include, without being limited to, propylene glycol diacetate, triethylene glycol-di-(2-ethylhexanoate), and propylene glycol octoate. Examples of glycol ether esters include, without being limited to, diethylene glycol n-butyl ether acetate, and dipropylene glycol methyl ether acetate.
In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above or below, the polarity modifier is selected from the group consisting of dipropylene glycol
monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol n- butyl ether, tripropylene glycol n-butyl ether, propylene glycol diacetate, triethylene glycol-di-(2-ethylhexanoate), propylene glycol octoate, diethylene glycol n-butyl ether acetate, and dipropylene glycol methyl ether acetate.
Particularly, the polarity modifier selected from the group consisting of dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol n-butyl ether, and tripropylene glycol n-butyl ether, and triethylene glycol-di-(2-ethylhexanoate).
In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above, the at least one polarity modifier is in an amount from 0,5 wt.% to 20 wt.%, particularly from 2 wt.% to 15 wt.%, based on the total weight of the inkjet ink.
In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above, the at least one inorganic colour pigment is in an amount from 5 wt.% to 70 wt.%, particularly from 10 wt.% to 60 wt.%, more particularly from 20 wt.% to 50 wt.%, based on the total weight of the inkjet ink; the at least one solvent is in an amount from 25 wt.% to 90 wt.%, particularly from 40 wt.% to 75 wt.%, more particularly from 50 wt.% to 75 wt.%, based on the total weight of the inkjet ink; the at least one surfactant in an amount from 0,5 wt.% to 20 wt.%, particularly from 2 wt.% to 15 wt.%, based on the total weight of the inkjet ink; and the at least one polarity modifier is in an amount from 0,5 wt.% to 20 wt.%, particularly from 2 wt.% to 15 wt.%, based on the total weight of the inkjet ink. In another particular embodiment, optionally in combination with one or more features of the particular embodiments defined above, the ink of the invention further comprises an inorganic opacifying agent. Particularly, the opacifying agent is selected from the group consisting of titanium dioxide, zirconium silicate, zirconium oxide, tin oxide, cerium oxide, zinc oxide, aluminium oxide, silica, kaolin, calcium carbonate, magnesium carbonate, calcium magnesium carbonate, barium carbonate, sodium feldspar, potassium feldspar, nepheline, calcium silicate, mullite, wollastonite, and talc. More particularly, the opacifying agent is selected from the group consisting of calcium carbonate, aluminium oxide, zirconium silicate and titanium dioxide. Particularly, the amount of opacifying agent is from 0.5 to 25 wt.%, more particularly from 1 to 20 wt.%, more particularly from 5 to 20 wt.%, based on the total weight of the ink.
Advantageously, by the use of the opacifying agent the opacity of the ink is increased and thus the performance of the decorative colour coating is improved, while allowing reducing the percentage of organic components, such as the solvents. In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above, the inkjet ink further comprises at least an additive which allows improving the rheological properties of the ink. Apart from providing optimum rheological behaviour of the ink, additives allow reaching a high solid content with low viscosities, as well as preventing degradation of the ink over time. Examples of such additives are, without being limited to dispersants, wetting agents,
bactericides, anti-foaming agents, and rheology agents. The additives must be compatible with the pigments and solvents employed, and must be suitable for grinding. The appropriate additives and their amounts can readily be determined by those skilled in the art. Usually, the amount of additives in the ink is from 0.05 wt.% to 20 wt.%, particularly from 2 wt.% to 15 wt.%, based on the total weight of the inkjet ink. In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above, the at least one additive is a dispersant.
Examples of dispersants are, without being limited to, polyamines and carboxyl terminated polyesters with formation of amidic and/or salt linkages such as the ones disclosed in US4224212, US4861380, US5700395,
US6197877 and US7008988.
The at least one dispersant can be in an amount from 0 wt.% to 20 wt.%, particularly from 2 wt.% to 15 wt.%, based on the total weight of the inkjet ink.
Particles in inkjet inks must be small enough to permit free flow of the ink through the inkjet-printing device, to get maximum colour strength, and to reduce sedimentation.
In a particular embodiment of the ink of the invention, particles of solid components comprised in the ink, namely the inorganic pigment and, optionally, opacifying agent have a particle size distribution wherein D90 is equal to or lower than 0.9 μιτι, particularly from 0.25 μιτι to 0.60 μιτι, more particularly, from 0.25 to 0.45. Particularly, the ink of the invention is able to pass through a sieve with a 1 μιτι mesh without leaving any residue. For particle size distributions, using a volume base calculation, D50 is the median value, namely the particle size diameter that splits the distribution with half above and half below this diameter. D90 describes the diameter where ninety percent of the distribution has a smaller particle size and ten percent has a larger particle size.
Particle size can be determined, for example, by laser light scattering using a particle size analyser, such as the Mastersizer™ apparatus available from Malvern Instruments Ltd. In the case of the ink composition of the present invention, particle size was determined introducing 3 drops of dispersion in 100 ml of isopropyl laurate. Afterwards the sample was manually
homogeneized and measured.
The colour inkjet ink can be prepared as follows. First, the different
components are mixed using a suitable dispersing system, such as a ball mill, basket mill, or Cowles type agitator, until obtaining a homogeneous mixture. Then, the mixture is submitted to a grinding and/or dispersion process, in order to achieve a homogeneous suspension, particularly with a viscosity from 10 to 200 cP (at 40 °C), and specific particle sizes with a maximum particle diameter of less than 2 μιτι. The grinding and/or dispersion process can be carried out with a microballs mill, such as a Netzsch mill, LabStar type, with yttrium or cerium doped ZrO2 microspheres from 0.2 to 5 mm in diameter and with a load from 50% to 98% of the volume of the grinding chamber. During the grinding and/or dispersion process viscosity controls, for instance with a rotational viscometer such as Brookfield LVDV, and particle size distribution measures, for instance particle analysis by laser diffraction with a Malvern Mastersizer 2000, can be performed. Subsequently, filtration of the
concentrate through filter media such as fiberglass or polypropylene of different pore sizes, and dilution with one or more solvents is carried out to obtain the final ink with the required rheological behaviour. Particularly, the obtained colour inkjet ink has a viscosity from 4 to 40 cP (at 40 °C) and a solid content from 5 to 60 wt.%.
The obtained dispersions have a physicochemical stability suitable to be used in an inkjet printer, that is, without significant variations in viscosity and density over time, as well as a negligible sedimentation not affecting their later use. Inkjet Printing Method
As disclosed above, the decorative coating on the support material of the constructive element of the invention is formed by at least one inkjet ink comprising an inorganic pigment, and at least one solvent.
The colour inkjet ink is applied on the support by digital printing such as inkjet printing. Digital printing refers to methods of printing from a digital-based image directly to a variety of media. The inkjet printing method includes the steps of: a) feeding an inkjet printhead with a colour inkjet ink comprising an inorganic pigment and at least one solvent; and b) jetting the colour inkjet ink with the inkjet printhead on a support material, optionally coated with a primer.
As mentioned above, the invention also relates to a process for the
preparation of the constructive element of the invention by applying the colour inkjet ink as defined above by digital printing onto a support, and subsequently applying a composition comprising a curable polymer and, optionally, a solvent, to form a protective polymeric coating that cures at a temperature of up to 300 °C.
In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above, the digital printing is made by inkjet printing. Particularly, inkjet printing is performed with a single- pass printer. Advantageously, the use of the single-pass inkjet printers allows reducing the cost of the process compared to current cost for the decoration of certain substrates such as fibre cement.
In a particular embodiment, the process of the invention further comprises an additional step of applying a primer composition on the substrate previously to the application of the colour inkjet ink.
Protective polymeric coating
The protective polymeric coating is formed with a composition comprising a curable polymer and, optionally, a solvent. Curing of the protective polymeric coating takes place in the absence of any firing process, namely at a temperature of up to 300 °C. The solvent of the coating composition can be removed by volatilization during the curing process.
The protective polymeric coating allows fixing the inorganic ink to the porous support material. Additionally, it provides protection of the ink and of the constructive element as a whole by providing wear resistance and hardness. Thus, depending on the specific components, the polymeric coating can provide protection against several factors such as surface abrasion, scratch, and chemical attack. Additionally, it can provide the sought final appearance of the product, including for example a matte, bright or satin finish. Properties of the protective coating can be adjusted depending on the final application of the constructive element (indoor or outdoor siding or flooring, level of pedestrian traffic).
The protective polymeric coating has an appropriate adhesiveness with all of the substrate and/or the primer if present. In a particular embodiment, the protective polymeric coating exhibits adhesiveness from 0 to 3, particularly from 0 to 2, according to the adhesion measurement test defined in UNE-EN ISO 2409. This standard classifies the level of adhesion on five categories, being category 0 the best result.
In a particular embodiment of the constructive element of the invention, optionally in combination with one or more features of the particular embodiments defined above, the polymeric coating is UV curable. Thus, once applied, the coating composition can be cured by irradiation with ultraviolet rays as is known to those skilled in the art. In this regard, the irradiation is applied until complete curing of the coating.
Example of a suitable curable protective coating compositions are such as the ones disclosed in US4393187 (Example, line 55, column 9, to line 9, column 1 1 ) and US5571570 (line 64, column 2, to line 28, column 5).
As an instance the coating composition comprises: (a) 35% to 65% by weight of a first acrylate aliphatic urethane having a molecular weight of 500 to 2000 and formed by the reaction of (i) a first multifunctional acrylate with a molecular weight of 190 to 500 and containing at least three polymerizable unsaturated groups per molecule, with (ii) an aliphatic urethane based on a polymer of allyl carbomonocycle diisocyanate with alkanepolyol polyacrylates; (b) 5% to 25% by weight of a second acrylated aliphatic urethane having a molecular weight of 1200 to 2600 and formed by the reaction of a second multifunctional acrylate with a molecular weight of 1 10 to 500 with an aliphatic urethane based on a polyether and having a molecular weight of 800 to 2200; (c) 10% to 55% by weight of a third multifunctional acrylate having a molecular weight of between 170 and 1000 and containing at least two polymerizable unsaturated groups per molecule; and (d) a photopolymerization initiator or sensitizer. As stated above, the coating composition can also comprise a suitable solvent. Examples of such solvents include, without being limited to, ester solvents, such as ethyl acetate and butyl acetate, ketone solvents such as acetone, methyl isobutyl ketone, and methylethyl ketone; alcohols such as butyl alcohol; and aromatic solvents such as toluene and xylene. The amount of solvent included will vary in accordance with the particular application at hand. Particularly, the amount of solvent is from 0% to 95%, more particularly from 40% to 60%, by weight of the entire coating composition.
In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above, the constructive element of the invention comprises additional coating layers each one conferring a specific property such as as hardness, gloss, wear resistance, self-cleaning, or bactericidal. The coating composition can be applied by any conventional coating method known in the art such as curtain coating, roller coating, and spraying.
Primer composition The aim of the primer is to obtain a better colour gamut development, facilitate adhesion of the decorative layer and of the protective layer, hide the substrate colour, improve the smoothness of the surface (reducing variability), enhance porosity, and/or increase the wettability of the ink so that the solvent in the ink drains correctly (avoiding the defect known as "lack of drying").
For the purpose or the invention, any primer composition known in the art can be used. As an example, the primer can comprise a polyurethane as a primary binder resin, a neutralizing agent such as an amine and, optionally, a third component such as an epoxy or an acrylic resin. Primer compositions are commercially available, such as the polyester/acrylic primer composition from BASF Corporation as Smoke U28AW031 . The primer composition can further comprise a crosslinking agent, opacifying agents (fillers), and a solvent system.
In a particular embodiment, the amount of crosslinking agent is from 0.1 to 10 wt.%, particularly from 3 to 7 wt.%, more particularly of a 5%. The crosslinking agent interacts with the protective polymeric coating improving the
adhesiveness of the coating.
Examples of crosslinking agents include, without being limited to,
poly(hexamethylene-diisocyanate), m-tolylidene diisocyanate, hexamethylene diisocyanate, ethylene diisocyanate, 1 ,2-diisocyanatopropane,1 ,3- diisocyanatopropane,1 ,4-butylene diisocyanate, lysine diisocyanate, 2,4- toluene diisocyanate diphenylmethane, 2,6- toluene diisocyanate
diphenylmethane, 4,4'-diisocyanate; 1 ,6-hexamethylene diisocyanate, p- phenylene diisocyanate; tetramethyl xylene diisocyanate, and m-xylene diisocyanate.
The primer affords good adhesion to the surface to be decorated and or coated, particularly to the protective coating and/or to the inkjet ink. The primer composition can be applied by conventional methods such as by spraying or roller coating.
In a particular embodiment of the constructive element of the invention, optionally in combination with one or more features of the particular embodiments defined above, the primer coating comprises at least one opacifying agent. The presence of the opacifying agent has the advantage that whiteness is increases and thus the performance of the decorative colour coating is improved.
In another particular embodiment, optionally in combination with one or more features of the particular embodiments defined above, the opacifying agent is selected from calcium carbonate (CaCOs), aluminium oxide (AI2O3), zirconium silicate (ZrSiO4) and titanium dioxide (T1O2). Particularly, the opacifying agent is ZrSiO4 or ΤΊΟ2.
Throughout the description and claims the word "comprise" and variations of the word, are not intended to exclude other technical features, additives, components, or steps. Furthermore, the word "comprise" encompasses the case of "consisting of.
The following examples are provided by way of illustration, and they are not intended to be limiting of the present invention. Furthermore, the present invention covers all possible combinations of particular and preferred embodiments described herein.
EXAMPLES
Example 1 - Blue ink
Figure imgf000020_0001
Example 2- Blue ink
Component wt.%
Co-AI Pigment (EINECS No 310-193-6) 35
Poly(12-hydroxystearic acid) homopolymer 5
tripropylene glycol monomethyl ether 35
2-Hexyldodecan-1 -ol 10
EO/PO block copolymer containing 10% w/w EO, 3
Genapol PF80 (Clariant)
triethylene glycol-di-(2-ethylhexanoate) 12 Example 3- Blue ink
Figure imgf000021_0001
The ink of Example2 and Example 3 were applied on a concrete substrate with an inkjet head having a print resolution of 360x360 dpi and a maximum drop of 84 pi. Chromaticity coordinates of the ink of Example 2 (without the presence of
ZrSiO4) were L * = 39.7, a * = -1 .7, b * = -6.0, while chromaticity coordinates of the ink of Example 3 were L * = 42.1 , a * = - 2.4, b * = - 9.5. It is observed that an increased L * and a significant reduced b * were obtained by the addition of the inorganic opacifying agent.
Example 4 - Preparation of a decorated fibre cement constructive element
A low density fibre cement plate (1 .2-1 .5 kg / dm3) of 1 .2 m wide, 2.4 m long and 6 mm thick, manufactured by the Hatschek process, was decorated in the following way.
An ink layer was applied by inkjet printing in order to introduce a decorative element, in particular a wood effect. Digital printing was performed with a single-pass printer with DOD (Drop on Demand) piezoelectric printheads. Four different inks were used to obtain an ink layer which imitates wood, particularly blue ink (ink of Example 1 ), red ink (CIS -RE3309 from Esmalglass-itaca group), yellow ink (CIS-YE5308 from Esmalglass-itaca group), and black ink (CIS-BK6304 from Esmalglass-itaca group). The solid content of the inks was 25 wt.%. Apart from the ink of Example 1 which is a blue ink, each one of the other inks comprised an inorganic pigment (particularly, iron oxide for the red ink, praseodymium zirconate for the yellow ink and chromium-nickel-cobalt- iron-manganese spinel for the black ink), a polymeric dispersant (Solsperse 3000, 5 wt.%), a non-ionic surfactant (2 wt.%), an aliphatic isoparaffinic hydrocarbon (47 wt.%), a fatty alcohol (7 wt.%), polypropylene glycol (4 wt.%), a fatty acid ester (10 wt.%).
Subsequently, 30 g/m2 of a protective coating consisting of a 100% solids UV curable resin (Uvinol 850, a solvent-free, UV-curing, clear epoxy acrylate sealer and topcoat commercialized by Tikkurila Coatings) was applied by roller coating over the ink layer. An applicator roller having an applicator roll 238 mm in diameter coated with 40 shores hardness ethylene propylene diene monomer (EPDM) was used. Once applied onto the ink layer, the protective coating was cured by action of ultraviolet light with two mercury lamps 120 W each.
Similar constructive elements were obtained by using inks of Examples 2 and 3. In all the cases an excellent compatibility of the ink and the support was observed, which lead to well defined decorative element.
Example 5 - Preparation of a decorated fibre cement constructive element
Example 4 was repeated also with the inks of Examples 1 to 3, but first, a primer (Bona Prime Classic, a waterborne one-component acrylate dispersion commercialized by Bona) was sprayed onto the fibre cement plate by airless spraying in order to form a uniform layer providing whiteness to the surface and with the aim of promoting adhesion of the subsequent layers. In all the cases an excellent compatibility of the ink and the support treated with the primer was observed, which lead to well defined decorative element.
REFERENCES CITED IN THE APPLICATION
1 . UNE-EN ISO 2409
2. US4393187
3. US5571570 4. Giesche, H. "Mercury porosimetry: a general (practical) overview", Particle & particle systems characterization, 2006, vol. 23, no 1 , p. 9-19
5. US4224212
6. US4861380
7. US5700395
8. US6197877
9. US7008988

Claims

1 . A colour inkjet ink comprising:
i) at least one inorganic pigment,
ii) at least one solvent having a boiling point equal to or higher than 200 °C selected from the group consisting of a hydrocarbon, an ester, and a fatty alcohol;
iii) at least one surfactant, and
iv) at least one polarity modifier selected from the group consisting of a glycol ether, a glycol ester, and a glycol ester ether in an amount such that provides the ink with an appropriate polarity value to make the ink compatible with a porous substrate.
2. The ink according to claim 1 , wherein the at least one inorganic colour pigment is in an amount from 5 wt.% to 70 wt.% based on the total weight of the inkjet ink; the at least one solvent is in an amount from 25 wt.% to 90 wt.% based on the total weight of the inkjet ink; the at least one surfactant in an amount from 0,5 wt.% to 20 wt.% based on the total weight of the inkjet ink; and the at least one polarity modifier is in an amount from 0,5 wt.% to 20 wt.% based on the total weight of the inkjet ink.
3. The ink according to claims 1 or 2, wherein the solvent has a solubility in water equal to or lower than 10 g/100 ml H2O and the surfactant is a non-ionic surfactant having a HLB (Hydrophilic-Lipophilic Balance) equal to or lower than 12 and is selected from the group consisting of a propylene oxide (PO) homo-polymer, a ethylene oxide (EO)/PO random co-polymer, a EO/PO block co-polymer, a fatty derivative copolymer, a saturated polyol ester, a
unsaturated polyol ester, an acrylic block copolymer, a polymerized fatty acid ester, an alkyl ethoxylate, a ethylene oxide-propylene oxide block polymer, a fatty acid polyethyleneglycol ester, a fatty acid polyglycerol ester, a fatty acid polyglycerol ester ethoxylate, a sorbitan ester ethoxylate, an alkyl
polyethylene glycol ether carboxylic acid, a fatty acid condensate such as fatty acid isethionates, methyl taurides, sarkosin and sarkoside, a vinyl ether alkoxylate (PO-EO-block polymers), an allyl ether alkoxylate (PO-EO-block polymers), polypropylene glycol, and a propoxylated fatty alcohol.
4. The ink according to claims 1 or 2, wherein the solvent has a solubility in water higher than 10 g/100 ml H2O and the surfactant is either an ionic surfactant selected from the group consisting of a phosphate ester, an alkyl phosphonic acid, an alkyl polyethyleneglycol ether phosphoric acid ester, and an alkyl phosphoric acid ester, or a non-ionic surfactant having a HLB higher than 12 and selected from the group consisting of a propylene oxide (PO) homo-polymer, a ethylene oxide (EO)/PO random co-polymer, a EO/PO block co-polymer, a fatty derivative copolymer, a saturated polyol ester, a
unsaturated polyol ester, an acrylic block copolymer, a polymerized fatty acid ester, an alkyl ethoxylate, a fatty acid polyethyleneglycol ester, fatty acid polypropyleneglycol esters, a fatty acid polyglycerol ester, a fatty acid polyglycerol ester ethoxylate, a sorbitan ester ethoxylate, an alkyl
polyethylene glycol ether carboxylic acid, a fatty acid condensate such as fatty acid isethionates, methyl taurides, sarkosin and sarkoside, a vinyl ether alkoxylate (PO-EO-block polymers), an allyl ether alkoxylate (PO-EO-block polymers), polypropylene glycol, and a propoxylated fatty alcohol, or a mixture thereof.
5. The ink according to any one of claims 1 to 4, wherein the polarity modifier is selected from the group consisting of dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol diacetate, propylene glycol octoate, diethylene glycol n-butyl ether acetate, and dipropylene glycol methyl ether acetate.
6. The ink according to claim 5, wherein the polarity modifier is selected from the group consisting of dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol n-butyl ether, and tripropylene glycol n-butyl ether, and triethylene glycol-di-(2-ethylhexanoate.
7. The ink according to any one of claims 1 to 6, further comprising an inorganic opacifying agent.
8. The ink according to claim 7, wherein the opacifying agent is selected from the group consisting of titanium dioxide, zirconium silicate, zirconium oxide, tin oxide, cerium oxide, zinc oxide, aluminum oxide, silica, kaolin, calcium carbonate, magnesium carbonate, calcium magnesium carbonate, barium carbonate, sodium feldspar, potassium feldspar, nepheline, calcium silicate, mullite, wollastonite, and talc.
9. The ink according to claims 7 or 8, wherein the opacifying agent is in an amount from 0.5 to 25 wt.% based on the total weight of the ink.
10. A constructive element comprising:
- a porous support material;
- a decorative coating formed by at least one colour inkjet ink as defined in any one of claims 1 to 9; and
- at least one protective cured polymeric coating formed with a
composition curing at a temperature of up to 300 °C.
1 1 . The constructive element according to claim 10, wherein the protective polymeric coating exhibits an adhesiveness from 0 to 3 according to the adhesion measurement test defined in UNE-EN ISO 2409.
12. The constructive element according to claims 10 or 1 1 , wherein the polymeric coating is UV curable.
13. The constructive element according to any one of claims 10 to 12, further comprising a primer coating between the porous support material and the decorative coating.
14. A process for the preparation of the constructive element as defined in any one of claims 10 to 13, the process comprising:
- applying a colour inkjet ink as defined in any one of claims 1 to 9 onto a porous support; and
- forming a protective polymeric coating by applying a composition
comprising a curable polymer and, optionally, a solvent, wherein the curing of the polymeric coating takes place at a temperature of up to 300 °C.
15. Use of an inkjet ink as defined in any one of claims 1 to 9, for the decoration of constructive elements as defined in any one of claims 10 to 13.
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