WO2020099704A1 - Composition d'encre pour décoration de vaisselle de table - Google Patents

Composition d'encre pour décoration de vaisselle de table Download PDF

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Publication number
WO2020099704A1
WO2020099704A1 PCT/ES2019/070767 ES2019070767W WO2020099704A1 WO 2020099704 A1 WO2020099704 A1 WO 2020099704A1 ES 2019070767 W ES2019070767 W ES 2019070767W WO 2020099704 A1 WO2020099704 A1 WO 2020099704A1
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WIPO (PCT)
Prior art keywords
mixture
ink composition
tableware
composition according
ink
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/ES2019/070767
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English (en)
Spanish (es)
Inventor
Óscar RUIZ VEGA.
Francisco Alejandro TIRADO FRANCISCO.
Alejandro Forés Fernandes
Javier Navarro Verdú
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Torrecid SA
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Torrecid SA
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Filing date
Publication date
Application filed by Torrecid SA filed Critical Torrecid SA
Publication of WO2020099704A1 publication Critical patent/WO2020099704A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form

Definitions

  • the present invention is framed in the field of inkjet inks using technology called Drop-on-Demand (Drop-on-demand, which is free of Ni, Cd and Pb and provide chromatic effects in-glaze and on-glaze on tableware supports after a firing cycle at temperatures between 850 ° C and 1300 ° C.
  • Drop-on-Demand Drop-on-Demand
  • the decorated tableware sector is made up of different types of products such as porcelain, stoneware and bone-china.
  • two types of decorative applications are distinguished.
  • One is called an on-glaze, characterized in that the decoration is deposited on a previously enameled tableware support, and the support-enamel-decoration set is subjected to a firing cycle at temperatures between 850 ° C and 1000 ° C.
  • the second decorative application is called in-glaze, and although it is also applied on a previously enameled tableware support, the cooking of the support-enamel-decoration set is carried out at higher temperatures, between 1000 ° C and 1300 ° C.
  • current crockery decoration techniques focus on brush and screen printing. In the case of silk-screen decoration, it is made by direct printing on the surface of the tableware product to be decorated or, indirectly, by applying the decoration on a decal that is subsequently deposited on the tableware product to be decorated.
  • patent application US6063446 describes a tableware production process using a decoration coloring substance comprising a pigment and a glass flux. Said ink is subjected to a firing temperature of between 1000 ° C and 1200 ° C.
  • said patent application focuses on screen printing formulations and especially, as described in the examples, at a mean particle size D50 of 1.3 micrometers and decoration on decal (transfer pattern).
  • patent application US6063446 establishes three conditions in the composition of the coloring substance, that the pigment has an average particle size (expressed as D50) equal to or less than 2 microns, that the glass flux has a density equal to or less 2.6 g / cm3 and that said glass flux also has a hemisphere temperature of less than 930 ° C. Finally, it is important to indicate that it is essential to achieve a correct coupling between the baked enamel of the tableware support and the decoration, which will be determined by the coefficient of thermal expansion of the frit or frits present in the ink. However, the aforementioned patent application US6063446 does not make any reference to this data.
  • patent application CN 103224727 protects an enamel composition (it is called ink enamel although its function is only for enameling) based on water that contains 30-50% of a ceramic enamel, 15-25% of an organic solvent, 4-10% of a dispersing agent, 2-5% of a water reducing agent (chelating agent), 2-5% of resin, 0.3-0, 6% of an antifoaming agent, 0.1-0, 2% of a leveling agent, 0.1% -0.2% of a pH regulator (buffer), 2-5% of a viscosity regulator, 0.1 -0.3% of a preservative, and the rest, water.
  • an enamel composition it is called ink enamel although its function is only for enameling
  • the composition of the enamel is expressed, as usual, in the form of oxides in such a way that said enamel has a composition of 45-65 parts of Si02, 20-26 parts of AI203, 0.2-1 parts of K20 , 2-7 parts Na20, 0.2-1 parts CaO, 0.02-0 parts MgO, 0.1-0.3 parts Fe203, 0.05-0.2 parts Ti02 and 1- 3 parts of ZnO.
  • said water-based ink enamel has a viscosity of between 10 and 40 mPa-s.
  • the aforementioned application CN 103224727 has the function of enameling instead of decorating, since it does not describe the use of pigments or their content in ink enamel.
  • being a composition where the main solvent is water it requires the use of additional additives specific for aqueous media such as chelating agents (named in the application water reducing agent) and pH regulators.
  • CN application 103224727 also discloses organic solvents, but they are polar and compatible with water, specifically glycerol, to regulate viscosity, and alcohols, preferably ethylene glycol and propylene glycol. Since it is an enamel, it is known in the state of the art that the oxide composition of an enamel is preferably achieved by using isolated raw materials although it may also contain some frit.
  • patent application CN 103224727 does not indicate whether it contains frit or its content or composition.
  • the fact that it is a water-based composition together with the presence of Fe203 indicates that raw materials are used in the composition of the enamel.
  • frits in the decoration of tableware with decorative inks, it is necessary to use only frits, and with a certain composition, since their function is to act as a flux causing the integration of the pigment in the enamel of the tableware holder, an aspect that does not It is achieved using isolated raw materials.
  • isolated raw materials have two additional drawbacks: on the one hand, it is more complex and expensive to decrease the particle size by grinding to adjust it to that required by DoD printing technology, and on the other hand, it is also more difficult to stabilize it in the medium.
  • an inkjet enamel composition specifically for its application in the enameling of fully enameled natural stone ceramic tiles. Specifically, it protects two enamel compositions, one that is deposited on the surface of the ceramic substrate and a second that is deposited on the first. In both cases its composition is described in the form of isolated raw materials expressed in oxides, as usual in the formulation of enamels. Again these are compositions based on water, specifically 33% water. Furthermore, it contains specific components for aqueous media such as sodium tripolyphosphate, widely known in the state of the art for its chelating agent function, and cellulose ether, also known in the state of the art as a thickening agent.
  • aqueous media such as sodium tripolyphosphate, widely known in the state of the art for its chelating agent function
  • cellulose ether also known in the state of the art as a thickening agent.
  • CN application 107640980 does not describe the use of frits or pigments, both necessary for decorative inkjet tableware applications. Furthermore, it does not describe the viscosity as a function of the shear rate or derived from the transverse deformation with respect to time, fundamental data to define a DoD decoration ink.
  • the present invention is an ink composition intended for in-glaze and on-glaze decoration using Drop-on-Demand (DoD) inkjet technology that is free of Ni, Cd and Pb and provides color effects on tableware supports after they have been cooked through a cycle at temperatures between 850 ° C and 1300 ° C.
  • DoD Drop-on-Demand
  • the decorated tableware products obtained are characterized by passing the test of resistance to washing with a dishwasher according to the ASTM3565 standard.
  • frit refers to a mixture of inorganic compounds that has been subjected to a fusion and subsequent cooling process to obtain an amorphous glassy compound, that is, without a crystalline structure, and whose composition is expressed as oxide.
  • the ink composition comprises at least one frit in a percentage by weight, with respect to the total ink composition, comprised between 35% and 55%, free of Ni, Cd and Pb and with a coefficient of thermal expansion between 70 x10 7 ° C 1 and 85 x10 7 ° C 1 in the temperature range between 25 ° C and 500 ° C.
  • the measurement of the coefficient of thermal expansion (also known by the acronym CDT) is widely known to the person skilled in the art matter and is performed using a dilatometer (type BAHR Model DIL801 L THERMO ANALYSE or the like). For this, a piece of the ceramic material with dimensions 10 cm x 10 cm is prepared and fired at the heat treatment temperature according to the present invention.
  • the composition by weight, with respect to the total composition of the frit, of each of the frits present in the ink according to the invention comprises between 50% and 65% of Si02, between 5% and 22% of R20, between 0% and 12% of RO, between 0% and 8% of M02, between 7% and 11% of AI203 and between 10% and 18% of B203; where R20 represents at least one oxide selected from Li20, Na20 and K20 or a mixture thereof, where RO represents at least one oxide selected from ZnO, MgO, CaO and BaO or a mixture thereof and where M02 represents at least one oxide selected from Ti02 , Zr02 and Ce02 or a mixture of them.
  • the ink composition comprises at least one apolar solvent in a percentage by weight, with respect to the total of the ink composition, comprised between 25% and 40%.
  • apolar solvents according to the invention, by way of illustration but not limitation, are aliphatic hydrocarbons, aromatic hydrocarbons, petroleum distillates and aliphatic esters.
  • the ceramic pigments used in the ink composition according to the invention have a D50 particle size of between 100 nanometers and 500 nanometers. Outside of this range, ceramic pigments have been found to have ink instability problems causing ink to settle as well as block the DoD printhead exit holes.
  • Ceramic pigments according to the invention by way of example but not limitation are Fe203, CuO, CeO, Cr207, among others, as well as crystalline structures of the spinel, perovskite, zirconium silicate type, etc. doped with different cations such as Pr, La, V, Co, Cu, Fe, Cr, among others. Also, the pigments are free of Ni, Cd and Pb.
  • the ink according to the present invention also contemplates at least one dispersant in a percentage by weight, with respect to the total composition of the ink, comprised between 1% and 5% and is selected from the group comprising derivatives of carboxylic acids, acrylic copolymers, polymeric fatty esters, polymeric esters, acidic polyesters, polyamide salts, alkyl ammonium salts, acids polycarboxylic acids, polycarboxylic acid esters, polyamides, modified polyurethanes, phosphoric esters, polyacrylate salt, alkoxides, derivatives of non-ionic modified fatty acid, carboxylic acid salt, polyether phosphoric acid and polycarboxylic acid salt or mixture of the above.
  • the ink contains at least one thickener in a percentage by weight, with respect to the total composition of the ink, comprised between 1% and 5% and is selected from the group comprising acrylic resins, derived from cellulose and / or polyvinyl alcohols.
  • the tableware ink also contains at least one humectant in a percentage by weight, with respect to the total ink composition, comprised between 0.1% and 1% and is selected from the group that comprises a mixture of ethers with glycol of polyethylene-polypropylene with monobenzyl ether and C8-C10 alcohols, polyether polysiloxane copolymer, nonionic surfactants, polyether-modified polydimethylsiloxane, fluorinated derivatives, alkoxylated alcohols, copolymers of ethylene oxide and polyethylene and polydimethylsiloxanes modified with polyester.
  • the ink composition object of the present invention is characterized by having the following viscosity values at 22 ° C as a function of the shear rate:
  • the inks can be used to directly decorate any type of tableware holder.
  • the tableware support can be both enameled and raw, that is, without the enamel fired, as well as enameled and with previously fired enamel.
  • tableware holders by way of example but not limitation include bone-chine, fine-china, porcelain, stoneware, tableware for hotels (also known as hotelware in English), stoneware, etc.
  • the inks can be used to decorate tableware supports using decals.
  • This type of decoration is especially interesting for decorating crockery supports with high relief or curvature.
  • the decoration procedure consists of depositing the inks on the decal, which in turn is attached to a support. Once the decal is decorated, it is wetted and removed from the support to which it was attached. Finally, the decorated decal is deposited, either manually or with an automatic equipment that takes the decal and deposits it, in both cases on the previously enameled and cooked crockery support and the whole is subjected to a firing cycle at the appropriate temperature.
  • the following table shows the three compositions of the frits, expressed in percent by weight of the oxides according to the present invention with the aim of achieving the desired properties and a particle size necessary for the formulation of DoD inks, specifically with a D50 of 200 nm.
  • the thermal expansion coefficient (CDT) obtained in each of them is also indicated at a D50 particle size of 200 nm.
  • Example 1 In-glaze decoration of bone-china using decal.
  • the five inks thus obtained were applied by means of a DoD inkjet equipment on a decal. Subsequently, the decal decorated with the inks was placed on bone-china tableware support previously enameled and fired. Once the five inks had been applied, the tableware set with decorated decal was subjected to a firing cycle at a maximum temperature of 1150 ° C.
  • Example 2 In-glaze bone-china decoration.
  • Table 5 shows the composition of each ink expressed in percentages by weight of each of the components.
  • the five inks thus obtained were applied by means of a DoD inkjet equipment directly on a previously enameled bone-china tableware support. Once the five inks had been applied, the tableware set decorated with inks was subjected to a firing cycle at a maximum temperature of 1160 ° C. Finally the resulting tableware product was subjected to a dishwasher resistance test in accordance with ASTM-D-3565. The following table shows the result obtained for each ink composition.
  • Table 8 shows the composition of each ink expressed in percentages by weight of each of the components.
  • the five inks thus obtained were applied by means of a DoD inkjet equipment on a decal. Subsequently, the decal decorated with the inks was placed on bone-china tableware support previously enameled and fired. Once the five inks had been applied, the tableware set with decorated decal was subjected to a firing cycle at a maximum temperature of 860 ° C.
  • the five inks thus obtained were applied by means of a DoD inkjet equipment directly on a previously enameled bone-china tableware support. Once the five inks were applied, the tableware set decorated with inks underwent a firing cycle at a maximum temperature of 895 ° C. Finally the resulting tableware product was subjected to a dishwasher resistance test in accordance with ASTM-D-3565. The following table shows the result obtained for each ink composition.
  • Table 13 Example 5. In-glaze porcelain decoration using decal. Five different color ink compositions were prepared: black (K5), blue (B5), red (R5), yellow (Y5) and green (G5) according to the present invention. Table 14 shows the composition of each ink expressed in percentages by weight of each of the components.
  • the five inks thus obtained were applied by means of a DoD inkjet equipment on a decal. Subsequently, the decal decorated with the inks was deposited on a previously enameled and fired porcelain tableware support. Once applied the five inks, the set of dishes with decorated decal was subjected to a cooking cycle at a maximum temperature of 1170 ° C.
  • Example 6 In-glaze porcelain decoration.
  • Table 17 shows the composition of each ink expressed in percentages by weight of each of the components.
  • the five inks thus obtained were applied by means of a DoD inkjet equipment on a previously enameled porcelain tableware support. Once the five inks were applied, the tableware set decorated with inks was subjected to a firing cycle at a maximum temperature of 1250 ° C.
  • Example 7 On-glaze porcelain decoration using decal.
  • Table 20 shows the composition of each ink expressed in percentages by weight of each of the components.
  • the five inks thus obtained were applied by means of a DoD inkjet equipment on a decal. Subsequently, the decal decorated with the inks was deposited on a previously enameled and fired porcelain tableware support. Once the five inks were applied, the tableware set with decorated decal was subjected to a firing cycle at a maximum temperature of 925 ° C.
  • Table 22 Example 8. On-glaze porcelain decoration. Five different color ink compositions were prepared: black (K8), blue (B8), red (R8), yellow (Y8) and green (G8) according to the present invention. Table 28 shows the composition of each ink expressed in percentages by weight of each of the components.
  • the five inks thus obtained were applied by means of a DoD inkjet equipment on a previously enameled porcelain tableware support. Once the five inks had been applied, the tableware set decorated with inks underwent a firing cycle at a maximum temperature of 965 ° C. Finally the resulting tableware product was subjected to a dishwasher resistance test in accordance with ASTM-D-3565. The following table shows the result obtained for each ink composition.
  • free of Ni, Cd and Pb means that any component of the ink that can present said elements as impurities, must be purified until the content in said elements is below 100 ppm of the total solid content of the ink.

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

Abstract

La présente invention concerne une composition d'encre pour une technologie d'impression du type goutte à la demande (Drop-on- demand – Do D) qui produit des effets chromatiques en camaïeu et sur émail sur des supports de vaisselle de table émaillés après avoir été soumis à un cycle de cuisson à des températures comprises entre 850 °C et 1300 °C.
PCT/ES2019/070767 2018-11-12 2019-11-11 Composition d'encre pour décoration de vaisselle de table Ceased WO2020099704A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ESP201831085 2018-11-12
ES201831085A ES2759973A1 (es) 2018-11-12 2018-11-12 Composicion de tinta para decoracion de vajilla

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4166616A1 (fr) * 2021-10-18 2023-04-19 Schott Ag Encre d'impression pour céramique, en particulier pour une impression à jet d'encre, destiné à la fabrication d'un revêtement sur une plaque en vitrocéramique et plaque en vitrocéramique revêtue

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2912799B2 (es) * 2020-11-27 2022-10-19 Torrecid Sa Metodo para producir relieves en baldosas ceramicas y baldosas ceramicas con relieves fabricadas segun el metodo

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070084379A1 (en) * 2005-10-14 2007-04-19 Laszlo Balazs Ink composition for making glass and ceramic surfaces
WO2013124506A1 (fr) * 2012-02-23 2013-08-29 Torrecid, S.A. Composition d'encre pour décoration de substrats non poreux
US20150015638A1 (en) * 2013-07-15 2015-01-15 Dip-Tech Ltd. Ceramic inkjet inks
WO2015003736A1 (fr) * 2013-07-08 2015-01-15 Fenzi Spa Encre céramique pour impression par jet d'encre
WO2016110724A1 (fr) * 2015-01-07 2016-07-14 Fenzi Spa Composition de fritte de verre et encre pour impression jet d'encre sur céramique la comprenant
ES2597166A1 (es) * 2015-06-16 2017-01-16 Torrecid, S.A Composición cerámica para el recubrimiento de superficies metálicas, método y capa cerámica resultante
ES2676757T3 (es) * 2014-07-14 2018-07-24 Schott Ag Tinta cerámica para impresión por inyección para vidrio de expansión reducida y/o cerámica de vidrio de expansión reducida, y su empleo

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070084379A1 (en) * 2005-10-14 2007-04-19 Laszlo Balazs Ink composition for making glass and ceramic surfaces
WO2013124506A1 (fr) * 2012-02-23 2013-08-29 Torrecid, S.A. Composition d'encre pour décoration de substrats non poreux
WO2015003736A1 (fr) * 2013-07-08 2015-01-15 Fenzi Spa Encre céramique pour impression par jet d'encre
US20150015638A1 (en) * 2013-07-15 2015-01-15 Dip-Tech Ltd. Ceramic inkjet inks
ES2676757T3 (es) * 2014-07-14 2018-07-24 Schott Ag Tinta cerámica para impresión por inyección para vidrio de expansión reducida y/o cerámica de vidrio de expansión reducida, y su empleo
WO2016110724A1 (fr) * 2015-01-07 2016-07-14 Fenzi Spa Composition de fritte de verre et encre pour impression jet d'encre sur céramique la comprenant
ES2597166A1 (es) * 2015-06-16 2017-01-16 Torrecid, S.A Composición cerámica para el recubrimiento de superficies metálicas, método y capa cerámica resultante

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4166616A1 (fr) * 2021-10-18 2023-04-19 Schott Ag Encre d'impression pour céramique, en particulier pour une impression à jet d'encre, destiné à la fabrication d'un revêtement sur une plaque en vitrocéramique et plaque en vitrocéramique revêtue
US12209047B2 (en) 2021-10-18 2025-01-28 Schott Ag Ceramic printing ink, in particular for inkjet printing, for producing a coating on a glass ceramic, and coated glass ceramic panel

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