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    • 专利摘要:
    It is provided an inkjet ink comprising an iron oxide based red pigment; a liquid vehicle comprising a solvent having a boiling point equal to or higher than 200ºC selected from an ester, a glycol ester, a glycol ether ester, a fatty alcohol, and mixtures thereof, and at least one dispersant. It is also provided a process for the preparation of the inkjet ink, a process for the preparation of a constructive element by applying the inkjet ink, and the use of the inkjet ink for the decoration of constructive elements without being submitted to a firing process.
    公开号:ES2675214A2
    申请号:ES201890025
    申请日:2016-10-19
    公开日:2018-07-09
    发明作者:Juan Bautista VICENT PEÑA；Noelia ALBIOL RICO；David VALIENTE BORDANOVA；José Vicente AGRAMUNT LERMA；Antonio；Blasco Fuentes
    申请人:Innovaciones Tecn Aplicadas A Ceramicas Avanzadas S A U；Innovaciones Tecnicas Aplicadas A Ceramicas Avanzadas SAU；
    IPC主号:
    专利说明:

    DESCRIPTION

    Oil-based red inkjet ink comprising iron oxide pigments

    The present invention relates to the field of inks. In particular, the invention relates to an inkjet ink, a process for its preparation, and its use for decorating construction elements.

    BACKGROUND OF THE TECHNIQUE
     10
    The decoration in prefabricated elements whose surfaces are porous is achieved by various techniques, depending on the nature of the surface to be treated. For example, in the field of fiber cement, organic pigment inks cured by ultraviolet (UV) light or acrylic paints are commonly used. In the field of wood, 15 dyes, varnishes and paints are commonly used.

    The use of acrylic paints, suitable for outdoor use, restricts the possibilities of decoration due to limitations in its application. On the other hand, UV-curable organic pigment inks can be applied by inkjet printing. However, they have a bad behavior for outdoor use, and it is generally accepted that after two years they begin to lose their coloring characteristics.

    In the 2000-2010 decade, in the ceramic industry, 25 inkjet printing technology was developed with inorganic pigments applied to the tiles. This technique was a revolution in the industry, and in 2014 the degree of implementation was over 90% in Spain and Italy (major European manufacturers) and 64% worldwide.
     30
    The inkjet technology allows a great flexibility in the production, a greater regularity in the decoration process, a reduction of the consumption of pigments and the time necessary to make the change of model, the possibility of decorating the edges of the piece, and reducing the time elapsed since the idea of a new product design until manufacturing. 35

    In ceramic pieces, the cooking stage, after the inkjet decoration, allows to fix the pigments, which are integrated into the vitreous structure of the material. This guarantees good adhesion and pigment protection.
     5
    However, the application of inorganic pigment inks in porous support materials that are not going to be subsequently subjected to a cooking process has several drawbacks such as the incompatibility between the ink and the substrate, low opacity (which makes the substrate is partially visible and produces chromatic variability when the 10 properties of the substrate change), and solvent removal problems.

    Therefore, there is still a need for an improved inkjet ink useful for decorating support materials, in particular 15 porous support materials, which allows obtaining construction elements with the high quality, properties and performance required by the market. , without the need to be subjected to a cooking process.

    SUMMARY OF THE INVENTION 20

    The inventors have found an inkjet ink suitable for decorating construction elements that will not be subjected to any heat treatment after decoration, or that will be subjected to a heat treatment at a maximum temperature of 300 ° C. The ink of the invention 25 provides good outdoor strength compared to inks with organic pigments. The use of specific solvents in combination with dispersants and, optionally, rheological additives makes it possible to obtain an ink comprising a red pigment based on iron oxide that is stable and suitable for inkjet application on a substrate, in particular on a porous substrate.

    Therefore, a first aspect of the invention is the provision of an inkjet ink comprising:
    - a red pigment based on iron oxide; 35
    - a solvent or a mixture of solvents of a boiling point equal to or greater than 200 ° C, in particular equal to or greater than 250 ° C and equal to or less than 400 ° C, selected from an ester, an ester glycol, an ether ester of glycol, a fatty alcohol, or mixtures thereof,
    - at least one dispersant. 5

    The use of specific solvents of a boiling point equal to or greater than 200 ° C, in particular equal to or greater than 250 ° C and equal to or less than 400 ° C, that is, with relatively low vapor pressures, allows evaporation reduction of the solvent in the printheads, which prevents clogging of the inkjet nozzles, making the printing system more stable. The release of volatile organic compounds (VOCs) 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. In a second aspect, the invention relates to a process for the preparation of an inkjet ink as defined above comprising:  twenty a) mixing the ink components as defined above; b) add at least one dispersant and subject the mixture to a grinding process, dispersion or a mixture of both, until obtaining a homogeneous suspension with a viscosity of 10 to 200 cP at 40 ° C; 25 c) dilute the suspension with a solvent or solvent mixture; Y d) filter the suspension.In another aspect, the invention relates to the use of an inkjet ink as defined above for the decoration of a construction element that will not subsequently be subjected to a cooking process.In another aspect, the invention relates to a constructive element comprising: - a support material; 35 - a decorative coating formed by inkjet ink as defined above; Y - at least one protective cured polymeric coating formed by a curing composition at a temperature of up to 300 ° C.
     5
    DETAILED DESCRIPTION OF THE INVENTION

    All terms used in this application, unless otherwise indicated, should be understood in their common meaning as known in the art. Other terms used in the present application are defined below, which are applied uniformly throughout the report and in the claims, unless another definition indicating a broader definition is indicated.

    The term "naphthenic hydrocarbon" refers to an organic carbon and hydrogen compound with the general formula CnH2n containing one or more saturated cyclic structures.

    The term "fatty acid" refers to a linear, unbranched, saturated or unsaturated carboxylic acid containing between 6 and 24 carbon atoms, in particular 10 to 18 carbons.

    The terms "particle size" and "particle size distribution", as used herein, refer to the diameter regardless of the actual shape of the particles. The term "diameter," as used herein, is the diameter of an equivalent sphere that has the same diffraction pattern, when measured by laser diffraction, as the particle.

    As used herein, the term "primer" is the bottom layer applied to the support before printing. The primer guarantees a better adhesion of subsequent layers to the surface and provides additional protection for the material being decorated or painted. As used herein, the term "decorative coating" refers to a coating that has only an aesthetic effect, an informational effect or a functional effect. Examples of aesthetic effects include elements 35
    decorative that mimic the appearance of natural materials such as stone, wood, marble or synthetic materials such as concrete, cement, fabric or ceramics. Examples of information elements include graphic elements such as symbols, images, brands, logos, and signage. Examples of functional elements include light conducting elements, fluorescent elements, electricity conducting elements or, in general, any other element capable of providing additional functionality for the construction element.

    As used herein, the term "protective coating" refers to a coating that has only a protective effect and is cured by UV radiation, heat treatment or other techniques. The protective coating is applied after the decorative coating, making it the final layer.

    As used herein, the term "curing" refers to the hardening of non-solid polymers, which results from polymerization and / or crosslinking. With 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 "weight percent", "weight percentage 20" or "wt.%" Refers to the weight percentage of the ingredient by weight of the total composition.

    Inkjet ink
     25
    As mentioned above, the inkjet ink object of the invention comprises a red iron oxide pigment (Fe2O3); a solvent having a boiling point equal to or greater than 200 ° C, in particular equal to or greater than 250 ° C and equal to or less than 400 ° C, selected from a hydrocarbon, an ester, an ether, a glycol ester, an ester of glycol ether, a fatty alcohol, and mixtures thereof; and a dispersant.

    In a particular embodiment, optionally in combination with one or more characteristics of the particular embodiments defined above or subsequently, the inkjet ink has a viscosity of 4 to 40 cP at 40 ° C, and a
    solids content from 10% to 60% by weight with respect to the weight of the overall composition.

    The inorganic pigment of the inkjet ink object of the invention is the red iron oxide pigment (hereinafter referred to as Fe2O3), also known as CI Pigment Red 101, CI Pigment Red 102, CI (1975) No. 77491, No. INS 172 (ii), or inorganic red pigments containing at least 10 wt.% In Fe2O3 as hematite.

    Red iron oxide pigment has advantages over organic red pigments. It can be produced by economical preparation procedures, is environmentally friendly, light stable, easily dispersible, and is not altered by UV radiation.

    The use of the red iron oxide pigment has the advantage of providing the ink with greater stability against the action of solar radiation than that of inks formulated with organic pigments.

    In a particular embodiment, optionally in combination with one or more characteristics of the particular embodiments defined above or subsequently, the red iron oxide pigment is in an amount of 10% to 60% by weight, particularly 10% to 50% by weight, and more particularly from 15% to 30% by weight with respect to the total weight of the inkjet ink.
     25
    In a particular embodiment, optionally in combination with one or more characteristics of the particular embodiments defined above or subsequently, the solvent is selected from the group consisting of an ester derived from a fatty acid, benzoic acid, a polycarboxylic acid, or an acid containing hydroxyl; a glycol ester, a glycol ether ester, a fatty alcohol, and mixtures thereof.

    In a particular embodiment, optionally in combination with one or more characteristics of the particular embodiments defined above or subsequently, the ester is selected from the group consisting of fatty acid,
    benzoic acid, polycarboxylic acid, and esters of hydroxyl-containing acids. Examples of suitable fatty acids include: hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid (lauric), tridecanoic acid, tetradecanoic acid (myristic), pentadecanoic acid, hexadecanoic acid 5 (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic), 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 alcohols that form the esters include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, 2-ethylhexyl, caprilyl, nonyl, caprylic, undecyl, lauryl, tridecyl, isotridecyl, myristyl, cetyl alcohol, stearyl, oleyl (unsaturated), and arachidyl alcohols, and Guerbet C12 alcohol, Guerbet C14 alcohol, Guerbet C16 alcohol, Guerbet C18 alcohol, and Guerbet C20 alcohol.
     twenty
    Examples of polyalcohols that form the ester include ethylene glycol, propylene glycol, glycerol, neopentyl glycol (NP), trimethylolpropane (TMP), pentaerythritol (PE), sorbitol, xylitol, erythritol, galactitol, and mannitol.

    In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above or subsequently, the glycol ester is selected from the group that includes, but is not limited to, propylene glycol diacetate, propylene glycol octoate, and mixtures of the same.
     30
    In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above or below, the glycol ether ester is selected from the group that includes, but is not limited to, diethylene glycol n-butyl ether acetate, acetate of dipropylene glycol methyl ether, and mixtures thereof. 35

    In a particular embodiment, optionally in combination with one or more characteristics of the particular embodiments defined above or subsequently, the fatty alcohol is selected from the group comprising: C8-C24, especially C10-C20, fatty alcohols, such as decanol, 5 dodecanol , tetradecanol, pentadecanol, hexadecanol, octadecanol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, and mixtures thereof.

    The solvent has a low polarity. Particularly, the solvent has a solubility in water equal to or less than 10 g / 100 ml H2O at room temperature. The term "room temperature" refers to a temperature of 20-25 ° C.

    By using a low polarity solvent, an improved behavior is achieved in the print head. Thus, the solvent based inkjet inks of the invention do not contain water. In particular, problems arising from the incorporation of water in the printheads are avoided, so that the operation of the printheads is more reliable since they provide higher print quality and have a longer life.

    In a particular embodiment, optionally in combination with one or more characteristics of the particular embodiments defined above or subsequently, the solvent is in an amount of 25% to 90% by weight, preferably 40% to 75% by weight with respect to the Total weight of inkjet ink.

    The ink object of the invention may further comprise other solid components such as an additional inorganic pigment, an inorganic filler, and mixtures thereof.

    In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above or subsequently, the ink of the invention further comprises another pigment.
    inorganic in order to modify the chromaticity coordinates of the ink

    Examples of additional inorganic pigments include yttrium oxide and alumina (No. EINECS 234-443-8); cobalt orthophosphate (No. EINECS 236-655-6); manganese-alumina oxide (No. EINECS 269-061-0); 5-tin pink chrome sphene (No. EINECS 269-073-6); chrome alumina pink codindon (No. EINECS 269-083-0); pink alumina-chrome spinel (No. EINECS 269-230-9); iron-zirconium rose (No. EINECS 270-210-7); chrome-tin cassiterite (No. EINECS 269-104-3), antimony-nickel-titanium oxide yellow (No. EINECS 232-353-3); yellow antimony-lead pyrochloro (No. EINECS 232-10 382-1); Chromate and antimony titanate (No. EINECS 269-052-1); tungsten and chromium titanate (No. EINECS 269-054-2); yellow cassiterite vanadium and tin (nº EINECS 269-055-8); yellow zirconium-vanadium badeleyite (No. EINECS 269-063-1); praseodymium-zircon silicate (No. EINECS 269-075-7); manganese-antimony titanate (No. EINECS 270-185-2); Niobium chromium-15 titanate (No. EINECS 271-891-3); nickel-niobium titanate (No. EINECS 271-892-9); Zirconium Cadmium Silicate (No. EINECS 277-135-9); antimony titanate (No. EINECS 305-908-3); Cadmium-zircon encapsulated pigment (EINECS 310-077-5); iron oxyhydroxide yellow (No. EINECS 257-098-5), and mixtures thereof. Particularly, the amount of additional inorganic pigment 20 is 0.5% to 25% by weight, more particularly 1% to 15% by weight, based on the total weight of the ink.

    In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above or subsequently, the inkjet ink further comprises an inorganic filler. In particular, the inorganic filler 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, 30 barium carbonate, sodium feldspar, potassium feldspar, nepheline, calcium silicate, mullite, wollastonite, and talc. In particular, the amount of the inorganic filler is 0.5% to 25% by weight, more particularly 1% to 20% by weight, based on the total weight of the ink.
     35
    The use of the filler has the advantage of increasing the opacity of the ink and therefore the performance of the color coating is improved, while reducing the percentage of organic components, such as solvents.
     5
    In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above or subsequently, the ink further comprises a rheological modifier. In particular, the rheological modifier is selected from: high molecular weight polyamides such as Crayvallac Extra (Total), polyesters such as Thixatrol UV 1104 (Elementis Specialties), poly (ester-amides) such as SYLVACLEAR C75V (Arizona Chemicals ), hydrocarbon-based polymers such as Oppanol B200 (BASF), trihydroxystearin, organo-clays such as stearalkonium hectorite, organo-silicas such as oxide with polysiloxanes, organically modified montmorillonite, organically modified aluminum and magnesium silicate, natural polysaccharides or derivatives thereof such as carboxymethyl cellulose, and stearate salts. In a more particular embodiment, the rheological modifier is a stearate salt selected from the group containing: lithium, aluminum, calcium, ammonium, magnesium, potassium, sodium and zinc stearate. In particular, the amount of the rheological modifier is 0.1% to 5% by weight, preferably 0.2% to 2.5%, based on the total weight of the ink.

    Other examples of natural polysaccharides or derivatives thereof are alginic acid, pectin, xanthan gum, hyaluronic acid, chondroitin sulfate, a natural gum or a derivative thereof, such as gum arabic, guar gum, cationic guar gum. , and karaya gum, chitosan or a derivative thereof such as carboxymethylchitosan, and N-hydroxy-dicarboxyethyl-chitosan, cellulose or a derivative thereof such as cellulose gum, cationic hydroxyethyl cellulose, a cellulose ether, and cetyl-30 hydroxyethylcellulose , starch, modified potato starch, dextrins and cyclodextrins.

    The rheology modifier has the advantage of reducing sedimentation and facilitates redispersion by agitation. Particularly, in the case of 35
    sedimentation, redispersed ink is able to pass through a 1.5 µm sieve without leaving any residue, this indicates that the dispersion is adequate and that the ink can be used in inkjet printers with printheads 30 µm nozzle
     5
    The particles in the inkjet inks should be small enough to allow free flow of the ink through the inkjet device, to obtain maximum color intensity, and to reduce sedimentation.

    In a particular embodiment of the ink object of the invention, the particles 10 of the solid components comprised in the ink, namely the red iron oxide pigment and, optionally, the additional inorganic pigment, the inorganic filler, or a combination thereof, have a particle size distribution in which D90 is equal to or less than 0.9 µm, in particular from 0.25 µm to 0.60 µm, more particularly, from 0.25 µm to 0.45 µm. In particular, the ink of the invention is capable of passing through a sieve with a 1 µm mesh without leaving any residue.

    For volume-based particle size distributions, D50 is the median value, that is, the particle diameter that divides the distribution 20 into two halves, one of them above and the other below this average diameter. D90 is the diameter for which ninety percent of the distribution has a smaller particle size and ten percent has a larger particle size.
     25
    The particle size can be determined, for example, by laser light scattering using a particle size analyzer, such as the Mastersizer ™ apparatus available from Malvern Instruments Ltd. In the case of the ink composition of the present invention, the Particle size was determined by adding 3 drops of the dispersion in 100 ml of 30 isopropyl laurate. Then, the sample was homogenized and manual measurement was performed.

    The ink object of the invention may further comprise other additives normally used in the preparation of inks, such as dispersants,
    surfactants, defoamers, buffers for pH control, bactericides, fungicides, and preservatives. Appropriate additives and their amounts can easily be determined by those skilled in the art. In general, the amount of these other additives in the ink is 0.05% to 20% by weight, particularly 2% to 15% by weight with respect to the total weight 5 of the inkjet ink.

    In addition to providing optimum rheological behavior of the ink, the rheological modifier, optionally together with at least one of the additional additives mentioned above, allows to achieve a high content of solids with low viscosities, as well as preventing degradation of the ink with time.

    In a particular embodiment, optionally in combination with one or more characteristics of the particular embodiments defined above or subsequently, the at least one additive is a dispersant.

    Suitable dispersants include: propylene oxide (PO) homo-polymer, ethylene oxide (EO) / PO random co-polymer, EO / PO block co-polymer, phosphate ester, copolymer alkylammonium alkyl salt with 20 acid groups, polycarboxylic acid alkanolammonium salt, polyamine amide and polyester acid salt, polyester / polyamide copolymer, polyamide and acid ester salts, unsaturated carboxylic acid, acidic polyether, poly (12-hydroxystearic acid) copolymer -polyethyleneimine, copolymer of poly (ricinoleic acid) -polyethyleneimine, 12-hydroxystearic acid, products of reaction of homopolymer of N, N'-diemthyl-1,3-propanediamine, homopolymer of poly (12-hydroxystearic acid), homopolymer of poly (ricinoleic acid), macromolecular polymer salt with acid groups, fatty derivative copolymer, polycarboxylic acid polymer, polyurethane block copolymer, saturated polyol ester, poly ester unsaturated ol, 30 PIBSA alkanolamide, ethoxylated aryl phenol, alkyl aryl sulphonate, modified polyacrylate polymer, acrylic block copolymer, polymerized fatty acid ester, alkylethoxylates, nonylphenol ethoxylates, ethoxylates tributylphenol, ethoxylates triethylstyl alkylstyl of ethylene oxide-propylene oxide, polyethylene glycol esters of fatty acids, 35
    fatty acid polyglycerol esters, fatty acid polyglycerol ester ethoxylates, trihydroxystearin, sorbitan ester ethoxylates, wax emulsifiers, secondary alkyl sulphonates, olefin sulphonates, alkyl sulfates, alkyl ether sulfates, alkyl ether sulfates aryl, polyglycol ether sulfates, sulphosuccinic acid esters, 5 fatty alkyl amine sulfosuccinamates, alkyl phosphoric acid esters, alkyl polyethylene glycol ether phosphoric acid esters, alkyl phosphonic acids, alkyl polyethylene glycol ether carboxylic acid, fatty acid condensates (fatty acid isethionates, methyl taurides, sarcosine and sarkoside), alkyl sulfonates, Ca-salts, vinyl ether alkoxylates (PO-EO block polymers), allyl ether alkoxylates (PO-EO polymers -block), and allyl polyoxyalkylene sulfates.

    The dispersions obtained have a physicochemical stability suitable for use in an inkjet printer. Therefore, there is no significant variation in viscosity or density over time. The variation in density and viscosity over a period of 1 month must be less than 8% and 4 cP respectively. In addition, sedimentation is insignificant and does not affect the subsequent use of the inks.
     twenty
    Procedure for preparing an inkjet ink

    As mentioned above, the invention also relates to a process for the preparation of inkjet ink as defined above, comprising a) mixing of the ink components; b) adding a dispersant and subjecting the mixture to a milling process, a dispersion process or a mixture thereof, until a homogeneous suspension with a viscosity of 10 to 200 cP at 40 ° C is obtained; c) dilution of the suspension with a solvent or solvent mixture; and d) suspension filtration. 30

    In a particular embodiment, optionally in combination with one or more characteristics of the particular embodiments defined above or later, in step b) of the above process the mixture is subjected to a milling process until a homogeneous suspension having
    particles with a maximum diameter of less than 0.9 µm.

    In a particular embodiment, optionally in combination with one or more characteristics of the particular embodiments defined above or subsequently, the inkjet ink has a viscosity of 4 to 40 cP at 40 ° C, and a solids content of 10% to 60% with respect to the weight of the overall composition.

    Inkjet ink can be prepared as follows. First, the different components are mixed using a suitable dispersion system, such as a ball mill, basket mill, or a stirrer, until a homogeneous mixture is obtained. Then, the mixture is subjected to a grinding and / or dispersion process, in order to achieve a homogeneous suspension, in particular with a viscosity of 10 to 200 cP (at 40 ° C) and, more particularly, with particle sizes specified. The milling and / or dispersion process can be carried out with a microball mill, such as a Netzsch mill, LabStar type, with ZrO2 microspheres doped with yttrium oxide or cerium oxide 0.2 to 5 mm in diameter and with a load of 50% to 98% of the volume of the grinding chamber. During the milling and / or dispersion process the viscosity is controlled, for example with a Brookfield rotation viscometer as LVDV, and the particle size distribution is measured, for example using a particle size meter by Malvern Mastersizer laser diffraction 2000. Subsequently filtration of the concentrate is carried out through filter media such as fiberglass or polypropylene of different pore sizes, the suspension 25 is diluted with one or more solvents to obtain the final ink with the necessary rheological behavior. In particular, the inkjet ink obtained has a viscosity of 4 to 40 cP (at 40 ° C) and a solids content of 10% to 60% by weight.

    Preparation of a construction element 30

    As mentioned above, the inkjet ink object of the invention can be used for decorating construction elements not subjected to a cooking process.
     35
    The use of the inkjet ink object of the invention has the advantage of using red iron oxide pigment which provides the decorative element with a decorative coating with a durability, when used outdoors, which is superior to that of the construction elements decorated with inks containing organic pigments. 5

    The inkjet ink object of the invention can be applied on a support material by digital printing, in particular by inkjet printing. Then, a protective polymeric coating comprising a curable polymer at a temperature of up to 300 ° C and, optionally, a solvent, can be applied on the printed support material in order to fix the ink to the support, at the same time as proportional both support and ink protection.

    Support material 15

    There is no limitation on the type of support material. The support material can be porous, such as wood, cement fiber, concrete, ceramic, plaster, and plasterboard (such as Pladur®).
     twenty
    In a particular embodiment of the constructive element object of the invention, optionally in combination with one or more characteristics of the particular embodiments defined above or subsequently, the support material is porous.
     25
    In a particular embodiment, optionally in combination with one or more features of the particular embodiments defined above or subsequently, 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 or later, the support material is selected from the group containing a wooden slat, a cement fiber slat, a brick, a concrete slab, and a concrete paver.

    In another particular embodiment, optionally in combination with one or more 35
    characteristics of the particular embodiments defined above or subsequently, the support material has a porosity greater than 1% in volume measured by mercury porosimetry (cf. Giesche, H. "mercury porosimetry: a. general (practical) overview", of particles and characterization of particle systems, 2006, vol. 23, no 1, p. 9-19). 5

    In another particular embodiment, optionally in combination with one or more features of the particular embodiments defined above or subsequently, the construction element object of the invention further comprises a lower primer coating between the support material 10 and the decorative coating.

    Primer Composition

    The purpose of the primer is to obtain a better development of the range of 15 colors, facilitate the adhesion of the decorative coating and the protective coating, hide the color of the substrate, improve the uniformity of the surface (reducing the variability), improve the porosity, and / or increase the wettability of the ink so that the ink solvent drains properly (avoiding the defect known as "pooling"). twenty

    For the purpose of the invention, any primer composition known in the art can be used. As an example, the primer may 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. Commercial primer compositions such as polyester / acrylic primer composition can be used from BASF Corporation as U28AW031 Smoke. The primer composition may further comprise a crosslinking agent, opacifying agents (fillers), and a solvent. 30

    In a particular embodiment, the amount of crosslinking agent is 0.1 to 10% by weight, particularly 3 to 7% by weight, preferably 5% by weight. The crosslinking agent interacts with the protective polymeric coating to improve the adhesion of the coating. 35

    Examples of crosslinking agents include, but are not limited to: poly (hexamethylene diisocyanate), m-tolylidene diisocyanate, hexamethylene diisocyanate, ethylene diisocyanate, 1,2-diisocyanopropane, 1,3-diisocyanopropane, 1,4-butylene diisocyanate , lysine diisocyanate, 2,4-toluene diisocyanate of 5 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 provides good adhesion to the surface to be decorated and / or coated, in particular for the protective coating and / or inkjet ink.

    The primer composition can be applied by conventional methods such as by spray or roller coating. fifteen

    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 or subsequently, the lower primer layer comprises at least one opacifying agent. The presence 20 of the opacifying agent has the advantage that whiteness increases and therefore the color performance of the decorative coating is improved.

    In another particular embodiment, optionally in combination with one or more characteristics of the particular embodiments defined above or subsequently, the opacifying agent is selected from: calcium carbonate (CaCO3), aluminum oxide (Al2O3) and titanium dioxide (TiO2) . In particular, the opacifying agent is TiO2.

    Inkjet 30 printing method

    The inkjet ink object of the invention can be applied on a support by digital printing such as inkjet printing. Digital printing refers to methods of printing a digitally based image directly to a variety of media. The 35 inkjet printing method
    Ink includes the steps of: a) feeding an inkjet printhead with a colored ink comprising an inorganic pigment and at least one solvent; and b) inkjet ink firing by means of the printhead on a support material, optionally previously coated with a primer. 5

    The invention also relates to a process for the preparation of the constructive element object of the invention by applying inkjet ink as defined above by digital printing on a support, and subsequently applying a coating comprising a curable polymer 10 and , optionally, a solvent, to form a polymeric protective 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 or subsequently, the digital printing is done by inkjet printing. Particularly, inkjet printing is done with a single pass printer. The use of single-pass inkjet printers has the advantage of reducing the cost of the process compared to the current cost for decorating certain substrates such as cement fiber.

    In a particular embodiment, the process of the invention further comprises an additional step of applying a primer composition on the substrate prior to the application of inkjet ink. 25

    Protective polymeric coating

    The protective polymeric coating is formed by a composition comprising a curable polymer and, optionally, a solvent. Curing 30 of the protective polymeric coating is carried out in the absence of any cooking process, that is, at a temperature of up to 300 ° C. The solvent of the coating composition can be removed by volatilization during the curing process.
     35
    The polymeric protective coating allows the inorganic ink to be fixed to the porous support material. In addition, it provides the protection of the ink and the construction element as a whole, providing resistance to wear and hardness. Therefore, depending on the specific components, the polymeric coating can provide protection against various factors such as surface abrasion, scratches, and chemical attack. In addition, it can provide the desired final appearance of the product, including, for example, a matt, glossy or satin finish. The properties of the protective coating can be adjusted depending on the final application of the construction element (coating or 10 indoor or outdoor flooring, pedestrian traffic level).

    The polymeric protective coating has adequate adhesion with the entire substrate and / or the primer if present. In a particular embodiment, the adhesion of the polymeric protective coating is from 0 to 15 3, particularly from 0 to 2, according to the adhesion measurement test defined in the UNE-EN ISO 2409 standard. This standard classifies the Adhesion level in five categories, category 0 being the best result.
     twenty
    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 UV irradiation, as is known to those skilled in the art. In this sense, the irradiation is applied until a complete cure of the coating.

    Examples of curable protective coating compositions can be found in US4393187 (eg, line 55, column 9, 30 line 9, column 11) and US5571570 (line 64, column 2, line 28, column 5).

    As an example, the coating composition comprises: (a) from 35% to 65% by weight of an aliphatic acrylate urethane primer having a
    molecular weight from 500 to 2000 and formed by the reaction of (i) a multifunctional acrylate with a molecular weight of 190-500 and containing at least three polymerizable unsaturated groups per molecule, with (ii) an aliphatic urethane based on a polymer of allyl carbominocyclo diisocyanate with alkanopolyol 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 110 to 500 with an aliphatic based urethane in a polyether and having a molecular weight of 800 to 2,200; (c) from 10% to 55% by weight of one third of multifunctional acrylate having a molecular weight between 170 and 10 1000 and containing at least two polymerizable unsaturated groups per molecule; and (d) a photopolymerization initiator or sensitizer.

    As indicated above, the coating composition may also comprise a suitable solvent. Examples of such solvents include, but are not limited to: ester solvents, such as ethyl acetate and butyl acetate, ketone solvents such as acetone, methyl isobutyl ketone, and methyl ethyl ketone; alcohols such as butyl alcohol; and aromatic solvents such as toluene and xylene. The amount of solvent included will vary according to the particular application in question. Particularly, the amount of solvent is from 0% to 95% by weight, preferably from 40% to 60% by weight with respect to the entire composition of the coating.

    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 of which confers a specific property such as hardness, gloss, wear resistance , self-cleaning, or bactericidal.
     30
    Throughout the description and claims the word "comprises" and variations of the word, are not intended to exclude other technical characteristics, additives, components or steps. On the other hand, the word "comprises" covers the case of "consisting of".
     35
    The following examples are provided by way of illustration, and are not intended to be limiting of the present invention. In addition, the present invention covers all possible combinations of particular and preferred embodiments described herein.
     5
    EXAMPLES

    Example 1 - Preparation of a red iron oxide pigment ink

    A red ink was prepared with the following composition: 10

     Component  wt.%
     Iron oxide (C.I. red pigment 101)  fifteen
     DISPERPLAST 1150 (BYK)  5
     MASSOCARE PHS (MASSÓ)  10
     2-ethylhexyl stearate  70

    First, all components except half of the 2-ethylhexyl stearate used in the final composition were mixed, dispersed and ground to achieve a homogeneous suspension having a particle size distribution with a D90 of less than 0.9 μm in diameter . The milling process was carried out with a microball mill (Netzsch LabStar) containing ZrO2 pearls doped with 1 mm yttrium. During the grinding process, particle size distribution was controlled using the laser diffraction technique (Malvern Mastersizer 2000). To carry out the measurement, 20 drops of dispersion were added to 100 ml of isopropyl laurate.

    Subsequently, the suspension was diluted using the remaining 2-ethylhexyl stearate to obtain the final ink with the required rheological behavior, particularly the viscosity was 15 cP (Brookfiled LVDV) and the solids content was 15% by weight. Finally, the ink was filtered through a 1.5 μm polypropylene filter.

    Example 2 - Preparation of a red iron oxide pigment ink
     30
    A red ink was prepared with the following composition:

     Component  % in weigh
     Iron oxide (C.I. red pigment 101)  fifteen
     DISPERPLAST 1150 (BYK)  5
     Isopropyl laurate  21.5
     2-ethylhexyl palmitate  21.5
     2-ethylhexyl stearate  12
     Exxsol D140  9
     2-Hexildodecan-1-ol  10

    First, all components except isopropyl laurate were mixed, dispersed and ground, in order to achieve a homogeneous suspension with a viscosity of 150 cP and a particle size distribution with a D90 of less than 0, 9 µm in diameter. The milling process was carried out with a microball mill (Netzsch LabStar) containing ZrO2 microbeads doped with yttrium oxide of 1 mm in diameter. During grinding, the particle size distribution was measured by laser diffraction (Malvern Mastersizer 2000). To carry out the measurement, 3 drops of dispersion were added to 100 ml of isopropyl laurate.

    Subsequently, the suspension was diluted using isopropyl laurate to obtain the final ink with the required rheological behavior, in particular the viscosity was 25 cP (Brookfiled LVDV) and the solid content was 15% by weight. The ink was finally filtered through a 1.5 µm polypropylene filter.
     twenty
    Example 3 - Preparation of a red iron oxide pigment ink

    A red ink was prepared with the following composition:

     Component  % in weigh
     Iron oxide (C.I. red pigment 101)  twenty
     MASSOCARE PHS (MASSÓ)  10
     TEGO Dispers 656 (EVONIK)  5
     Isopropyl laurate  24.7
     Glyceryl tricaprate / tricaprilato  2. 3
     Exxsol D140  9
     2-Hexildecan-1-ol  5.3

    First, all components except isopropyl laurate were mixed, dispersed and ground, in order to achieve a homogeneous suspension with a D90 of less than 0.9 µm. The milling process was carried out with a microball mill (Netzsch LabStar) containing 5 ZrO2 microbeads doped with yttrium oxide of 1 mm in diameter. During grinding, the particle size distribution was measured by laser diffraction (Malvern Mastersizer 2000). To carry out the measurement, 3 drops of dispersion were added to 100 ml of isopropyl laurate.
     10
    Subsequently, the suspension was diluted using isopropyl laurate to obtain the final ink with the required rheological behavior, in particular the viscosity was 27 cP (Brookfiled LVDV) and the solid content was 20% by weight. The ink was finally filtered through a 1.5 µm polypropylene filter. fifteen

    Example 4 - Preparation of a red iron oxide pigment ink with additional pigment

    A red ink was prepared with the following composition: 20

     Component  % in weigh
     Iron oxide (C.I. red pigment 101)  fifteen
     Pink chrome tin tin (No. EINECS 269-073-6)  fifteen
     DISPERPLAST 1150 (BYK)  10
     Isopropyl Laurate  26
     2-ethylhexyl stearate  12
     Glyceryl tricaprate / tricaprilato  10
     Triethylene glycol-di- (2-ethylhexanoate)  5
     2-Hexildecan-1-ol  7

    First, all components except isopropyl laurate were mixed, dispersed and ground, in order to achieve a homogeneous suspension with a D90 of less than 0.9 µm. The milling process was carried out with a microball mill (Netzsch LabStar) containing 5 ZrO2 microbeads doped with yttrium oxide of 1 mm in diameter. During grinding, the particle size distribution was measured by laser diffraction (Malvern Mastersizer 2000). To carry out the measurement, 3 drops of dispersion were added to 100 ml of isopropyl laurate.
     10
    Subsequently, the suspension was diluted using isopropyl laurate to obtain the final ink with the required rheological behavior, in particular the viscosity was 24 cP (Brookfiled LVDV) and the solid content was 30% by weight. The ink was finally filtered through a 1.5 µm polypropylene filter. fifteen

    Example 5 - Preparation of a red iron oxide pigment ink with filler

    A red ink was prepared with the following composition: 20

     Component  % in weigh
     Iron oxide (C.I. red pigment 101)  twenty
     Titanium dioxide  10
     MASSOCARE PHS (MASSÓ)  9.5
     SOLDOC PG-280 (IQL)  5
     Pentaerythrityl tetraisoestearate  10
     Triethylene glycol-di- (2-ethylhexanoate)  7.5
     Nytex 8120  27.5
     2-Octildodecan-1-ol  10.5

    First, all components except Nytex 8120 were mixed, dispersed and ground, in order to achieve a homogeneous suspension with a D90 of less than 0.9 µm. The milling process took 25
    out with a microball mill (Netzsch LabStar) containing ZrO2 microbeads doped with yttrium oxide of 1 mm in diameter. During grinding, the particle size distribution was measured by laser diffraction (Malvern Mastersizer 2000). To carry out the measurement, 3 drops of dispersion were added to 100 ml of isopropyl laurate. 5

    Subsequently, the suspension was diluted using Nytex 8120 to obtain the final ink with the required rheological behavior, in particular the viscosity was 26 cP (Brookfiled LVDV) and the solid content was 30% by weight. The ink was finally filtered through a 10 1.5 µm polypropylene filter.

    Example 6 - Preparation of a red iron oxide pigment ink

    A red ink was prepared with the following composition:

     Component  % in weigh
     Iron oxide (C.I. red pigment 101)  twenty
     Pyrogenic amorphous silica  one
     DISPERPLAST 1150 (BYK)  12.5
     Isopropyl laurate  49.5
     Glyceryl tricaprate / tricaprilato  5
     Triethylene glycol-di- (2-ethylhexanoate)  3
     Exxsol D140  9

    First, all components except 50% of the isopropyl laurate were mixed, dispersed and ground, in order to achieve a homogeneous suspension with a D90 of less than 0.9 µm. The grinding process was carried out with a microball mill (Netzsch LabStar) containing ZrO2 microbeads doped with yttrium oxide of 1 mm in diameter. During grinding, the particle size distribution was measured by laser diffraction (Malvern Mastersizer 2000). To carry out the measurement, 3 drops of dispersion were added to 100 ml of isopropyl laurate.

    Subsequently, the suspension was diluted using the remaining isopropyl laurate to obtain the final ink with the required rheological behavior, in particular the viscosity was 25 cP (Brookfiled LVDV) and the solid content was 21% by weight. The ink was finally filtered through a 1.5 µm polypropylene filter. 5

    Example 7 - Preparation of a decorative fiber cement building element

    A low density density fiber cement board (1200 to 10 1500 g / m3) 1.2 m wide, 2.4 m long and 6 mm thick, manufactured by the Hatschek process, was decorated. The procedure followed was as follows:

    First, a primer (Bona Prime Classic, a monocomponent dispersion of water-based acrylate marketed by 15 Bona) was sprayed onto the airless spray fiber cement board in order to form a uniform layer that would provide whiteness to the surface and to enhance the adhesion of the back layers.

    A layer of ink was then applied by jet printing of 20 ink in order to introduce a decorative element, in particular a wood effect. Digital printing was done with a single pass printer with piezoelectric DOD (Drop on Demand) heads. Four different inks were used to obtain a decorative layer that mimics wood, in particular blue ink (CIS-BU4301 from the Esmalglass-Itaca group), red ink 25 (Example 2), yellow ink (CIS-YE5308 from the Esmalglass group) Itaca), and a black ink (CIS-BK6304 of the Esmalglass-Itaca group).

    Subsequently, 30 g / m2 of a protective coating was applied by roller on the ink layer. The protective coating consisted of a 100% solid UV curable resin (Uvinol 850, a solvent-free UV-cured epoxy acrylate sealant and protective layer marketed by Tikkurila Coatings). A 238 mm diameter applicator roller coated with ethylene propylene diene monomer (EPDM) of a hardness of 40 shores was used. Once applied on the layer of 35
    ink, the protective layer was cured by ultraviolet light with two mercury lamps of 120 W each.
    权利要求:
    Claims (15)
    [1]

    1. An inkjet ink comprising:
    - a red pigment based on iron oxide;
    - a solvent of a boiling point equal to or greater than 200 ° C 5 selected from the group consisting of an ester, a glycol ester, a glycol ether ester, a fatty alcohol, and mixtures thereof,
    - at least one dispersant.

    [2]
    2. The ink according to claim 1, wherein the ester is selected from the group consisting of fatty acid, benzoic acid, polycarboxylic acid and esters of hydroxyl-containing acids.

    [3]
    3. The ink according to any of claims 1 or 2, wherein the solvent has a water solubility equal to or less than 10 g / 100 ml H2O at room temperature.

    [4]
    4. The ink according to any one of claims 1 to 3, wherein the red iron oxide pigment is in an amount of 10% to 60% by weight, particularly 10% to 50%, and more particularly of the 15% to 30% 20 by weight, based on the total weight of inkjet ink.

    [5]
    5. The ink according to any of claims 1 to 4, wherein the solvent is in an amount of 25% to 90% by weight, particularly 40% to 75% by weight, based on the total weight of the ink inkjet 25

    [6]
    6. The ink according to any of claims 1 to 5, further comprising another inorganic pigment in an amount of 0.5% to 25% by weight, particularly 1% to 15% by weight, based on the total weight of the ink. 30

    [7]
    7. The ink according to any of claims 1 to 6, further comprising an inorganic filler in an amount of 0.5% to 25% by weight, particularly 1% to 20% by weight, based on the total weight of the ink. 5

    [8]
    8. The ink according to claim 7, wherein the inorganic filler 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, 10 magnesium calcium carbonate, barium carbonate, sodium feldspar, potassium feldspar, nepheline, calcium silicate and talc.

    [9]
    9. The ink according to any of claims 1 to 8, further comprising a rheological modifier in an amount of 0.1% to 5% by weight, preferably 0.2% to 2.5% by weight, with respect to the total weight of the ink.

    [10]
    10. The ink according to claim 9, wherein the rheological modifier is selected from:
    - a high molecular weight polyamide, a polyester, a poly (ester-amide) and a hydrocarbon-based polymer,
    - trihydroxystearin,
    - an organo-clay, organo-silica, organically modified montmorillonite, organically modified magnesium aluminum silicate, 25
    - a natural polysaccharide or a derivative thereof; Y
    - a stearate salt.

    [11]
    11. The ink according to claim 10, wherein the rheological modifier is a stearate salt selected from the group consisting of lithium, aluminum, calcium, ammonium, magnesium, potassium, sodium and zinc stearate.

    [12]
    12. The ink according to any of claims 1 to 11, wherein the solid components comprised in the ink, such as the red iron oxide pigment and, optionally, the inorganic filler, and the additional inorganic pigment, have a particle size distribution 5 wherein D90 is less than 0.9 µm, particularly 0.25 µm to 0.60 µm, more particularly 0.25 µm to 0.45 µm.

    [13]
    13. A process for preparing an inkjet ink as defined in any one of claims 1 to 12, the method comprising the following steps:
    a) mixing the ink components as defined in any one of claims 1 to 12;
    b) add at least one dispersant and subject the mixture to a grinding process or to a dispersion process, or a mixture thereof, until a homogeneous suspension with a viscosity of 10 to 200 cP is obtained at 40 ° C;
    c) dilute the suspension with a solvent or solvent mixture; Y
    d) filter the suspension.
     twenty
    [14]
    14. Use of an inkjet ink as defined in any of claims 1 to 12, for decorating a construction element that is not subsequently subjected to a cooking process.

    [15]
    15. A constructive element comprising: 25
    - a support material;
    - a decorative coating formed by inkjet ink as defined in any one of claims 1 to 12; Y
    - at least one cured protective polymeric coating formed with a composition that cures at a temperature of up to 300 ° C. 30
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    同族专利:
    公开号 | 公开日
    ES2675214R1|2018-10-30|
    WO2017067979A1|2017-04-27|
    ES2675214B1|2019-08-13|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4393187A|1982-06-23|1983-07-12|Congoleum Corporation|Stain resistant, abrasion resistant polyurethane coating composition, substrate coated therewith and production thereof|
    US5571570A|1994-04-22|1996-11-05|Red Spot Paint And Varnish Co., Inc.|UV curable blend compositions and processes|
    US8221536B2|2006-11-09|2012-07-17|Sun Chemical Corp.|Cosmetic comprising multi-colored lustrous pearlescent pigments|
    CN101891984B|2010-03-04|2012-08-29|珠海保税区天然宝杰数码科技材料有限公司|Printing ink combination, printing ink and method for forming image on ceramic surface|
    JP2013531621A|2010-05-10|2013-08-08|サジティス・インコーポレイテッド|Alkyl ketal esters as dispersants and slip agents for particulate solids, methods for their preparation and use|
    JP5662715B2|2010-06-29|2015-02-04|理想科学工業株式会社|Oil-based inkjet ink|
    KR101556224B1|2011-11-22|2015-09-30|디아이씨 가부시끼가이샤|Curing accelerator for oxidative polymerization type unsaturated resins, printing ink and coating material|
    TWI461491B|2012-12-28|2014-11-21|Ind Tech Res Inst|Dispersion, inkjet ink, and manufacturing the inkjet ink|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    EP15382515|2015-10-20|
    EP15382515|2015-10-20|
    PCT/EP2016/075085|WO2017067979A1|2015-10-20|2016-10-19|Red oil-based inkjet ink comprising iron oxide pigments|
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