• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A ceramic composition comprising si metal powder, frit particles with a fluid temperature comprised between 1185ºC and 1300ºC and a liquid part, to obtain metallic effects on ceramic supports after a firing cycle at temperatures between 1000ºC and 1280º c. This composition prevents the sedimentation or disintegration of the metallic particles when they are in a liquid suspension as well as their oxidation after cooking. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2638840A1
    申请号:ES201630359
    申请日:2016-03-23
    公开日:2017-10-24
    发明作者:Óscar RUIZ VEGA；Francisco Sanmiguel Roche
    申请人:Torrecid SA；
    IPC主号:
    专利说明:

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    CERAMIC COMPOSITION WITH METAL EFFECT AND PROCEDURE OF
    APPLICATION
    DESCRIPTION
    The present invention is framed in the field of ceramic compositions that provide metal effects on ceramic supports once they have undergone a cooking cycle at temperatures between 1000 ° C and 1280 ° C.
    STATE OF THE TECHNIQUE
    The obtaining of metallic effects in ceramic products for flooring and cladding constitutes a typology of product of great interest due to the aesthetic possibilities it offers.
    In this sense in the prior art prior to the present invention there are formulations of inks based on precious metals (Au, Ag, Pd, Pt, Ti, etc.) that allow obtaining the golden, silver and luster metallic effects. These inks are applied by various printing technologies such as screen printing, as described in US6355714B1, or inkjet, as disclosed in patent application WO2014037597A1. However, these types of compositions, in addition to their high price that prevents mass production, only develop the metallic effect when applied on ceramic products of third fire, that is, on glazed ceramic supports that have been previously cooked. In addition, cooking is limited to temperatures below 1000 ° C.
    In the state of the art, the development of metal effects is also addressed without the use of precious metals, as is the case of the ES2161193 patent which describes a enamel formulation for monocoction based on a P2O5 content between 7% and 27%. However, these enamels have a high coefficient of thermal dilatation, which easily causes defects such as cracks or curvatures after cooking as well as low chemical resistance.
    For its part, the international patent application WO2006136610A2 discloses materials for application on ceramic supports based on particles of atomized powder of Fe, Ni, Co, Cu or mixture thereof, with a particle size preferably between 50 micrometers and 150 micrometers. These materials are usually applied in liquid suspension (water or glycols) along with materials usually
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    used in ceramics, the metal powder being found in a concentration between 35% and 95% with respect to the total solids. However, these metallic powders are characterized by having a high density, around 7 g / cm3 or more, which causes that, when combined with the commonly used ceramic materials, which have a density of less than 3 g / cm3, they are produced disintegrations once the liquid suspension is prepared and, therefore, the sedimentation of the metal powders. Also the need to use metal powders in atomized form increases the cost and reduces the possibilities of application. Finally, the international patent application WO2006136610A2 also protects the use of nitrogen atmosphere in the cooling phase of the cooking process to avoid the tendency of metal powders to oxidize and therefore not to obtain the metallic effect, increasing the complexity of the process .
    Within the state of the art the patent application ES2235650 is also framed where ceramic formulations with metallic effect are protected based on any metal or mixture of metals or alloy of stainless metals with a melting point greater than 1100 ° C and a particle size lower than 100 micrometers, the Cr-Ni base Fe alloys being especially suitable for the purposes of said invention. However, metals or mixtures of metals or alloys of stainless metals have several limitations. One is the ease of oxidation as a result of its reactivity with the enamel and the cooking process. The other is again a high density that causes sedimentation when applied in liquid suspension. If the metals are also mixed with ceramic materials such as frits or clays, a separation due to their different density is produced, preventing its correct application through the techniques commonly used in the production of ceramic tiles (airbrush, bell, filera, etc.).
    EXPLANATION OF THE INVENTION
    Throughout the invention and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. In addition, the word "understand" includes the case "consists of". For those skilled in the art, other objects, advantages and characteristics of the invention will be derived partly from the description and partly from the practice of the invention.
    The present invention is a ceramic composition for obtaining metallic effects on ceramic supports after a cooking cycle at temperatures between 1000 ° C and 1280 ° C, comprising Si powder, frit particles with a flow temperature
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    between 1185 ° C and 1300 ° C that prevents the reactivity of the Si powder during cooking, and a liquid part.
    The use of Si metal powder in this ceramic composition prevents sedimentation or disintegration of metal particles when they are in a liquid suspension, because the density of Si metal powder is less than 3 g / cm3 and therefore similar to ceramic materials. Other metals have densities greater than 3 g / cm3 (around 7 g / cm3) so that they settle or disintegrate from ceramic materials when they are in aqueous suspension.
    The use of frit particles with a flow temperature between 1185 ° C and 1300 ° C prevents the reaction of oxidation of Si with ceramic materials, for example a ceramic enamel, during cooking and, therefore, does not occur the oxidation of the metal, achieving the desired metallic effect on the ceramic support.
    The term "ceramic support" as used in the present invention refers to any flat or embossed surface consisting of a mixture of clays and / or ceramic materials (frits, silicates, feldspars, oxides, etc.) formed by means of usual techniques in the ceramic sector such as press, laminate or extrusion, among others, which can be enameled or unglazed as well as raw or subjected to a cooking cycle.
    Thus, the present invention comprises Si metal powder with a particle size between 45 micrometers and 500 micrometers, preferably between 75 micrometers and 250 micrometers, a frit or mixture of frits with a flow temperature between 1185 ° C and 1300 ° C and a liquid part.
    According to the present invention, the Si powder content is between 10% and 45% by weight, preferably between 15% and 30%, with respect to the total solid part, that is, the sum of Si powder and fried or fried. On the other hand, in the ceramic composition object of the invention, the content of the fried or fried mixture is between 55% and 90% by weight, preferably between 70% and 85%, with respect to the total solid part, that is, the sum of Si powder and the mixture of fried or fried. Likewise, the fried or fried mixture has a particle size between 10 micrometers and 500 micrometers, preferably between 45 micrometers and 250 micrometers.
    Additionally, the composition of the frit or mixture of frits comprises SiO2 in a weight percentage between 50% and 65%, Al2O3 in a weight percentage between 15% and 25%,
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    Na2O in a weight percentage between 2% and 8%, K2O in a weight percentage between 2% and 8%, CaO in a weight percentage between 6% and 15% and MgO in a weight percentage between 1% and 4 %.
    The liquid part according to the present invention is formed by solvents and additives that are selected according to the deposition technique of the ceramic composition. In this sense the solvents are selected from the group comprising water, low polarity solvents, medium polarity solvents and high polarity solvents. On the other hand, the additives are selected from the group comprising dispersing agents, binding agents, thickeners, anti-settling agents, leveling agents, wetting agents, crosslinking agents, antifoaming agents, coalescing agents or mixing thereof.
    One aspect of the present invention includes that the liquid part is a ceramic enamel or slip, that is, it consists of a suspension of water, additives and components commonly used in this type of compositions (frits, clays, feldspars, silicates, oxides, pigments , carbonates, nitrates, etc.).
    The present invention contemplates a method of applying the ceramic composition comprising the following steps:
    1st. The Si powder, the fried or fried mixture and the liquid part are mixed to achieve a homogeneous and stable ceramic composition.
    2nd. The ceramic composition is applied on a ceramic support with a weight between 75 g / m2 and 1000 g / m2, preferably between 300 g / m2 and 650 g / m2.
    3rd. The ceramic support set and ceramic composition applied are subjected to a cooking cycle at a maximum temperature between 1,000 ° C and 1280 ° C.
    4th. The ceramic piece resulting from cooking is subjected to a polishing or roughing of the surface.
    The application method according to the present invention is carried out on a raw or cooked ceramic support, that is, it has been subjected to a cooking thereof prior to the application of the ceramic composition objective of the invention. Also the ceramic support can be enameled and / or decorated.
    In accordance with the present invention, the application of the ceramic composition is carried out by means of the techniques commonly used in the ceramic sector. Examples of
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    These techniques, by way of example but not limited to, include airbrush, file, bell, screenprint, flexograph and gravure. In short, the ceramic composition object of the invention works in any of the existing cooking and ceramic support typologies such as monocoction, bicoction, porcelain, porous, stoneware, third fire and fourth fire.
    A preferred embodiment of the present invention is a ceramic composition comprising:
    • 15% - 30% Si powder with a particle size between 75 micrometers and 250 micrometers.
    • 70% - 85% of a frit with a flow temperature between 1185 ° C and 1300 ° C and a particle size between 45 micrometers and 250 micrometers.
    • Liquid part formulated to achieve a suspension of the ceramic composition suitable for application by filler technique, with a viscosity between 30 and 40 seconds in a 4 mm Ford Cup.
    Then the ceramic composition is applied with a grammage of 500 g / m2 by means of the fillet technique on a ceramic support made of raw and decorated glazed porcelain. Subsequently, the ceramic support assembly with the application of the ceramic composition is subjected to a cooking cycle at a maximum temperature of 1195 ° C. Finally, a polishing of the surface of the ceramic piece resulting from cooking is done.
    Another preferred embodiment of the present invention is a ceramic composition comprising:
    • 15% - 30% Si powder with a particle size between 75 micrometers and 250 micrometers.
    • 70% - 85% of a frit with a flow temperature between 1185 ° C and 1300 ° C and a particle size between 45 micrometers and 250 micrometers.
    • Liquid part formulated to achieve a suspension of the ceramic composition suitable for application by airbrushing technique, with a viscosity between 20 and 30 seconds in a 4 mm Ford Cup.
    Then the ceramic composition is applied with a grammage of 400 g / m2 by means of the airbrush technique on a ceramic support of glazed and raw porous. Subsequently, the ceramic support assembly with the application of the ceramic composition is subjected to a cooking cycle at a maximum temperature of 1125 ° C.
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    Finally, a polishing of the surface of the ceramic piece resulting from cooking is done.
    Also the present invention contemplates another method of applying the ceramic composition comprising:
    1st. The Si powder, the fried or fried mixture and the liquid part are mixed to achieve a homogeneous and stable composition.
    2nd. The ceramic composition is subjected to drying to obtain flake, pellet or atomized particles.
    3rd. The ceramic composition in the form of scales, pellets or atomized is subjected to a process of forming by press, extrusion or rolling. For this, the flakes, pellets or atomized mix with the materials commonly used in the conformation of ceramic supports such as frits, clays, feldspars, oxides, pigments, etc.
    4th. The shaped ceramic piece is subjected to a cooking cycle at a maximum temperature between 1000 ° C and 1280 ° C.
    5th. The ceramic piece resulting from cooking is subjected to a polishing or roughing of the surface.
    EXAMPLES
    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 indicated herein.
    Example 1.
    A ceramic composition comprising (expressed as a percentage by weight of solids) was prepared:
    • 25% Si powder with a particle size between 75 micrometers and 250 micrometers.
    • 75% of a frit with a flow temperature between 1185 ° C and 1300 ° C and a particle size between 45 micrometers and 250 micrometers.
    • Solvents and additives selected to achieve a suspension of the ceramic composition suitable for application by filler technique, with a viscosity of between 30 and 40 seconds in a 4 mm Ford Cup.
    The resulting ceramic composition was applied by filler technique on a ceramic support of raw porcelain, enameled and decorated. The application weight
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    It was 500 g / m2. Then the resulting ceramic piece was subjected to a cooking cycle at a maximum temperature of 1195 ° C. Once cooked, a polishing was performed obtaining a ceramic tile with a metallic effect.
    Example 2
    A ceramic composition comprising (expressed as a percentage by weight of solids) was prepared:
    • 20% Si powder with a particle size between 75 micrometers and 250 micrometers.
    • 80% of a frit with a flow temperature between 1185 ° C and 1300 ° C and a particle size between 45 micrometers and 250 micrometers.
    • Solvents and additives selected to achieve a suspension of the ceramic composition suitable for application by airbrushing technique, with a viscosity of between 20 and 30 seconds in a 4 mm Ford Cup.
    The resulting ceramic composition was applied by airbrushing technique on a ceramic glazed porous ceramic support. The application weight was 400 g / m2. Then the resulting ceramic piece was subjected to a cooking cycle at a maximum temperature of 1125 ° C. Once cooked, a polishing was performed obtaining a ceramic tile with a metallic effect.
    Example 3
    A ceramic composition comprising (expressed as a percentage by weight of solids) was prepared:
    • 25% Si powder with a particle size between 75 micrometers and 250 micrometers.
    • 75% of a mixture of two frits with a flow temperature between 1185 ° C and 1300 ° C and a particle size between 45 micrometers and 250 micrometers.
    • Solvents and additives selected to achieve a suspension of the ceramic composition suitable for application by filler technique, with a viscosity of between 30 and 40 seconds in a 4 mm Ford Cup.
    The resulting ceramic composition was applied by filler technique on a ceramic support of raw porcelain, enameled and decorated. The application weight was 350 g / m2. Then the resulting ceramic piece was subjected to a cooking cycle at a maximum temperature of 1195 ° C. Once cooked, a polishing was performed obtaining a ceramic tile with a metallic effect.
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    Example 4
    A ceramic composition comprising (expressed as a percentage by total weight of the ceramic composition) was prepared:
    • 9% Si powder with a particle size between 60 micrometers and 500 micrometers.
    • 11% of a frit with a flow temperature between 1185 ° C and 1300 ° C and a particle size between 65 micrometers and 500 micrometers.
    • 80% of a ceramic slip for porcelain formulated to achieve a suspension of the ceramic composition suitable for obtaining scales.
    The mixture of the three components (Si powder, fried and liquid part in the form of ceramic slip) was subjected to a process of drying and obtaining scales with a particle size between 600 micrometers and 4000 micrometers. The scales obtained were subjected to a pressing process prior to mixing with the materials commonly used in the pressing of ceramic supports. Then the resulting ceramic piece was subjected to a cooking cycle with a maximum temperature of 1195 ° C. Finally, a polishing was performed obtaining a ceramic tile with a metallic effect.
    Example 5
    A ceramic composition comprising (expressed as a percentage by total weight of the ceramic composition) was prepared:
    • 9% Si powder with a particle size between 45 micrometers and 250 micrometers.
    • 11% of a frit with a flow temperature between 1185 ° C and 1300 ° C and a particle size between 45 micrometers and 300 micrometers.
    • 80% of a porcelain ceramic enamel formulated to achieve a suspension of the ceramic composition suitable for application by airbrushing technique, with a viscosity of between 20 and 30 seconds in a 4 mm Ford Cup.
    The resulting ceramic composition was applied by airbrushing technique on a ceramic support of raw and enameled porcelain. The application weight was 500 g / m2. Then the resulting ceramic piece was subjected to a cooking cycle at a maximum temperature of 1195 ° C. Once cooked, a polishing was performed obtaining a ceramic tile with a metallic effect.
    权利要求:
    Claims (14)
    [1]
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    1. A ceramic composition intended to obtain metallic effects on ceramic supports comprising:
    to. Si metal powder with a particle size between 45 micrometers and 500 micrometers, preferably between 75 micrometers and 250 micrometers.
    b. A frit or mixture of frits with a flow temperature between 1185 ° C and 1300 ° C.
    C. A liquid part.
    [2]
    2. The ceramic composition according to revindication 1 where the percentage by weight of Si powder is between 10% and 45%, preferably between 15% and 30%, with respect to the total solid part.
    [3]
    3. The ceramic composition according to revindication 1 where the percentage by weight of the fried or fried mixture is between 55% and 90%, preferably between 70% and 85%, with respect to the total solid part.
    [4]
    4. The ceramic composition according to revindication 1 where the fried or fried mixture has a particle size between 10 micrometers and 500 micrometers, preferably between 45 micrometers and 250 micrometers.
    [5]
    5. The ceramic composition according to revindication 1 where the composition of the fried or fried mixture comprises SiO2 in a weight percentage between 50% and 65%, Al2O3 in a weight percentage between 15% and 25%, Na2O in a percentage by weight between 2% and 8%, K2O in a weight percentage between 2% and 8%, CaO in a weight percentage between 6% and 15% and MgO in a weight percentage between 1% and 4%.
    [6]
    6. The ceramic composition according to revindication 1 where the liquid part comprises solvents and additives.
    [7]
    7. The ceramic composition according to revindication 6 where the solvents are selected from the group comprising water, low polarity solvents, medium polarity solvents and high polarity solvents.
    [8]
    8. The ceramic composition according to revindication 6 where the additives are selected from the group comprising dispersing agents, binding agents, thickening agents, anti-settling agents, leveling agents, wetting agents, crosslinking agents, anti-foaming agents, coalescing agents or mixing thereof.
    [9]
    9. The ceramic composition according to revindication 1 where the liquid part is an enamel or ceramic slip.
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    [10]
    10. A method of applying the ceramic composition according to claim 1 comprising the following steps:
    to. The Si powder, the fried or fried mixture and the liquid part are mixed to achieve a homogeneous and stable composition.
    b. The ceramic composition is applied on a ceramic support in a grammage between 75 g / m2 and 1000 g / m2, preferably between 300 g / m2 and 650 g / m2.
    C. The ceramic support set and ceramic composition applied are subjected to a cooking cycle at a maximum temperature between 1000 ° C and 1280 ° C.
    d. The ceramic piece resulting from cooking is subjected to a polishing or roughing of the surface.
    [11]
    11. The application method according to claim 10 wherein the ceramic support is raw or cooked.
    [12]
    12. The application method according to claim 10 wherein the ceramic support is enameled and / or decorated.
    [13]
    13. The application procedure according to claim 10 wherein the application is carried out by means of the techniques commonly used in the ceramic sector such as airbrush, file, bell, screenprint, flexograph and gravure, among others.
    [14]
    14. An application procedure according to claim 1 comprising the following steps:
    to. The Si powder, the fried or fried mixture and the liquid part are mixed to achieve a homogeneous and stable composition.
    b. The ceramic composition is subjected to drying to obtain particles of the flake, pellet or atomized type.
    C. The ceramic composition in the form of scales, pellets or atomized is subjected to a forming process by means of press, extrusion or laminate.
    d. The shaped ceramic piece is subjected to a cooking cycle at a maximum temperature between 1000 ° C and 1280 ° C.
    and. The ceramic piece resulting from cooking is subjected to a polishing or roughing of the surface.
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    同族专利:
    公开号 | 公开日
    EP3434654A4|2019-11-27|
    WO2017162896A1|2017-09-28|
    ES2638840B1|2018-08-06|
    EP3434654A1|2019-01-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3713854A|1971-09-08|1973-01-30|Corning Glass Works|Reduced silica-nucleated glassceramic articles|
    DE3503929A1|1985-02-06|1986-08-07|Reimbold & Strick GmbH & Co, 5000 Köln|CERAMIC COMPOSITIONS AND THEIR USE|
    GB9326526D0|1993-12-29|1994-03-02|Cookson Group Plc|Glaze for refractory materials|
    ES2301364B1|2006-05-24|2009-05-01|Fritta, S.L.|FORMULATION TO PRODUCE METAL EFFECTS.|
    PL2000443T3|2007-05-29|2013-01-31|Sa Minera Catalano Aragonesa|Metallic glaze composition|
    法律状态:
    2018-08-06| FG2A| Definitive protection|Ref document number: 2638840 Country of ref document: ES Kind code of ref document: B1 Effective date: 20180806 |
    优先权:
    申请号 | 申请日 | 专利标题
    ES201630359A|ES2638840B1|2016-03-23|2016-03-23|CERAMIC COMPOSITION WITH METAL EFFECT AND APPLICATION PROCEDURE|ES201630359A| ES2638840B1|2016-03-23|2016-03-23|CERAMIC COMPOSITION WITH METAL EFFECT AND APPLICATION PROCEDURE|
    PCT/ES2017/070119| WO2017162896A1|2016-03-23|2017-03-03|Ceramic composition with metallic effect and application method|
    EP17769502.0A| EP3434654A4|2016-03-23|2017-03-03|Ceramic composition with metallic effect and application method|
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