WO2022260506A1 - Ceramic coatings used in the construction industry, with biocidal properties - Google Patents

Ceramic coatings used in the construction industry, with biocidal properties Download PDF

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Publication number
WO2022260506A1
WO2022260506A1 PCT/MX2022/050046 MX2022050046W WO2022260506A1 WO 2022260506 A1 WO2022260506 A1 WO 2022260506A1 MX 2022050046 W MX2022050046 W MX 2022050046W WO 2022260506 A1 WO2022260506 A1 WO 2022260506A1
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WIPO (PCT)
Prior art keywords
ceramic
layer
ceramic coating
size
enamel
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PCT/MX2022/050046
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Spanish (es)
French (fr)
Inventor
Mauricio-Esteban MENDEZ-GONZALEZ
Jenny-Lorena MORALES-CASTILLO
Fernando-Raúl BLAITT-URIBE
Fernando-Andrés AGUILERA-MORA
Arturo-Adolfo BANDA-IBARRA
Shen YANG-HSIEH
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Grupo Lamosa S A B De C V
Nano Quantum Group Spa
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Application filed by Grupo Lamosa S A B De C V, Nano Quantum Group Spa filed Critical Grupo Lamosa S A B De C V
Publication of WO2022260506A1 publication Critical patent/WO2022260506A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • 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
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals

Definitions

  • the present invention is related to ceramic coatings or coatings, and more particularly with ceramic coatings or coatings whose surfaces have incorporated encapsulated copper nanoparticles that provide the ceramic coating or coating with biocidal properties capable of combating agents such as bacteria. , viruses, fungi and yeasts.
  • US Patent No. US9439439B2 describes a transparent glass cover for applications such as touch screen devices incorporating antimicrobial, antifungal and antiviral properties.
  • Antimicrobial glasses contain Cu or Cu20 nanoparticles on the glass surface.
  • Antimicrobial glasses may additionally have a fluorosilane or other coating on the surface to make the glasses easy to clean.
  • glass surfaces are disclosed having antibacterial or antimicrobial surfaces and a protective coating on the surface that do not inhibit the antibacterial or antimicrobial properties of the glass. The disclosure is further directed to methods of making such articles.
  • WO201 6028554 describes an improved antimicrobial product (including methods of making it) having a glass or glass-ceramic composition, a plurality of primary surfaces, and an antimicrobial structure on at least one of the primary surfaces .
  • the antimicrobial structure comprises a plurality of copper nanoparticles configured to self-passivate under lifetime conditions of the article.
  • Such antimicrobial articles may demonstrate antimicrobial efficacy as evidenced by log kill rates of 3 or greater in the EPA-approved dry test for copper-containing surfaces.
  • the protective layer of enamel incorporates copper nanoparticles with 0 valence encapsulated in a glassy material.
  • the tile has antibacterial properties that comply with ISO 22196 (Measurement of antibacterial activity in plastics and non-porous surfaces).
  • ISO 22196 Measurement of antibacterial activity in plastics and non-porous surfaces.
  • Escherichia coli ATCC 25922 Staphylococcus aureus ATCC 6538.
  • the tile has antiviral properties certified by TONA (The Ceramic Council of North America) with the ISO 21702 Standard (Measurement of antiviral activity in plastics and non-porous surfaces).
  • TONA The Ceramic Council of North America
  • ISO 21702 Standard Measurement of antiviral activity in plastics and non-porous surfaces.
  • Influenza A virus H3N2
  • SARS- CoV- 2 Human coronavirus 229E H3N2
  • SARS- CoV- 2 Human coronavirus 229E SARS- CoV- 2 Human coronavirus
  • the tile has antifungal properties certified by the INTA University of Chile, with the ISO 22196 Standard (Measurement of antibacterial activity in plastics and non-porous surfaces).
  • ISO 22196 Standard Measurement of antibacterial activity in plastics and non-porous surfaces.
  • the product being nCu encapsulated in glassy material, is highly safe for operators in all ceramic production processes.
  • the product being nCu encapsulated and/or embedded in glassy material, complies with the standards for vitrification of materials with heavy metals as an environmental solution, transforming this product into an eco-friendly one. It should be remembered that vitrification is the most secure scheme against sensitive products, and in the case of copper it is a higher level of environmental, operational, handling and control safety.
  • the capacity of copper in its metallic state and nanometric size allows its incorporation into ceramic surfaces, providing great surface capacity, generating catalysis in the enamel that allows an ionic release of copper that in very low doses provides a great biocidal capacity, this has productive advantages. , logistic, economic and environmental impact that cannot be achieved with other products.
  • a ceramic tile of the nature described above which is composed of a ceramic support, a slip layer, a base layer and a protective layer of enamel, wherein the protective layer of enamel incorporates copper nanoparticles in valence state 0 encapsulated in a glassy material.
  • bacteria Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 6538
  • virus Influenza A virus (H3N2), SARS-CoV- 2 Human coronavirus 229E
  • microorganisms Aspergillus niger ATCC 16404, Candida albicans ATCC 90028 - report date 02-15.
  • the present invention relates to a ceramic coating with biocidal properties.
  • the ceramic coating of the present invention comprises: a ceramic support body, which comprises extremely compact mass material, made up of several crystalline phases immersed in a glassy matrix, mainly composed of silica derivatives.
  • a layer called engobe which comprises a semi-porous layer that precedes the application of the enamel and has different functions such as uniforming the water absorption of successive applications, isolating the color of the support, uniforming the imperfections of the support, generating adherence to the support , establish a coefficient of expansion that allows to adequately regulate the planarity of the tiles, waterproof and opaque in a way that allows to minimize the effect of water stains resulting from the absorption of water from the support.
  • the slip layer has a typical thickness of 67 microns and is made up of alkali or alkaline earth metal aluminosilicates and zirconium silicate mainly; a layer called base or enamel which comprises a vitreous coating, on the support, the result of the fusion of powdered oxides through a heating process.
  • a layer called base or enamel which comprises a vitreous coating, on the support, the result of the fusion of powdered oxides through a heating process.
  • Its objective is to adapt the product to its intended use and provide certain aesthetic qualities.
  • the suitability of the product for use is related to the improvement of the surface properties provided by the glazed coating, such as impermeability, mechanical, chemical, optical, thermal properties, etc.
  • the enamels constitute an artistic expression where they combine a graphic, with elements of color, shapes and textures.
  • the base layer or enamel has a typical thickness of 67 microns and is made up of Alkaline or alkaline earth metal aluminosilicates which melt at temperatures higher than 1000°C to obtain the desired final finish.
  • a protective layer which comprises a layer of enamel applied to the surface of the base layer or enamel, and generates greater protection, avoiding the appearance of surface defects.
  • the ceramic coating is characterized in that: the protective layer has a thickness of between 6 to 200 microns, preferably 13 microns and contains copper nanoparticles in a 0 valence state, encapsulated in a glassy material, with a size of between 20 to 40nm preferred 25nm where the size distribution of the particle size shows a trend of values with a mean of 35nm with a standard deviation of 0.8nm, in an amount between 0.1 to 1,000RRM per m 2 ; homogeneously incorporated into the glassy material under a process of homogenization, casting and grinding.
  • the ceramic coating has the following certifications:
  • the present invention relates to a method for making a ceramic coating with biocidal properties, wherein the ceramic coating comprises a supporting ceramic body; A layer called enamel that consists of a vitreous layer that defines the functional and decorative properties of the ceramic coating; a layer called engobe which allows a good bond between the enamel and the ceramic body, and a protective layer which comprises a layer of enamel applied to the surface of the base layer or enamel, wherein said method comprises adding to the layer protective copper nanoparticles with 0 valence encapsulated in a glassy material, with a size between 20 to 40nm, preferably 25nm in an amount between 0.1 to 1,000PPM per m 2 during the enameling process, in the drop application thread inside of any known ceramic tile production process.
  • the size distribution of the size of the nanoparticles shows a trend of values with a mean of 35nm with a standard deviation of 0.8nm.
  • the nCu used is Cu in the metallic state, being eminently Cu°, which gives it the mechanical properties of Cu malleability, positive zeta potential collaborating with the interaction in SiO-type matrices, generating a synergy between the materials.
  • nCu is smaller than 50 nm in size (range of polyaggregated particles from 20 to 40 nm). Its interaction with silicates of average sizes of MESH 100 (approximately 150 microns), makes each silicate have interactions with several nCu at the same time.
  • the mechanism of viral inactivation on copper surfaces is complex and involves not only the direct action of the copper ion on multiple targets, but also the generation of destructive oxygen radicals, resulting in "metabolic suicide". These reactions they generate the enzymatic peroxidation of the envelope, damage of the membrane proteins and the nucleoproteins of the virus through hydroxyls. You do not need light to activate this mechanism.
  • nCu copper nanoparticles
  • the copper nanoparticles (nCu) in vitreous silicate material for ceramics produced were mixed, homogenized with the glaze material of the protective layer in a concentration lower than 1,000RRM per m 2 (standardized concentration).
  • enamels may have other additives such as pigments, metals as they are used in the industry
  • antiviral activity tests were carried out, following ISO 22196 standards, with the following viruses: Haemophilus influenza H1 N1 at 24 hours; and Coronavirus SARSII at 24 hours. In all of them it was observed that the ceramic with nanoparticles eliminates over 99.9% in relation to the “White” ceramic.
  • the ceramic coating and method for its production of the present invention is not limited to the modality described above and that experts in the field will be enabled, by the teachings established herein, to make changes in the ceramic coating and method for its production of the present invention, the scope of which will be established exclusively by the following claims.

Abstract

In a first aspect, the present invention relates to a ceramic coating or covering with biocidal properties and, in a second aspect, to a method for producing a ceramic covering with biocidal properties.

Description

REVESTIMIENTOS CERÁMICOS EMPLEADOS EN LA INDUSTRIA DE LA CONSTRUCCIÓN CON PROPIEDADES BIOCIDAS ANTECEDENTES DE LA INVENCION CERAMIC COATINGS USED IN THE CONSTRUCTION INDUSTRY WITH BIOCIDAL PROPERTIES BACKGROUND OF THE INVENTION
A. CAMPO DE LA INVENCION La presente invención está relacionada con revestimientos o recubrimientos cerámicos, y más particularmente con revestimientos o recubrimientos cerámicos cuyas superficies tienen incorporadas nanopartículas de cobre encapsuladas que le proporcionan al revestimiento o recubrimiento cerámico propiedades biocidas capaces de combatir agentes tales como bacterias, virus, hongos y levaduras. A. FIELD OF THE INVENTION The present invention is related to ceramic coatings or coatings, and more particularly with ceramic coatings or coatings whose surfaces have incorporated encapsulated copper nanoparticles that provide the ceramic coating or coating with biocidal properties capable of combating agents such as bacteria. , viruses, fungi and yeasts.
B. DESCRIPCION DEL ARTE RELACIONADO B. DESCRIPTION OF RELATED ART
Existe actualmente una gran necesidad de contar con superficies de contacto con seres humanos que se encuentren libres de virus y organismos patógenos, como respuesta a la necesidad actual del mundo en tener superficies que contribuyan a la reducción de enfermedades, especialmente durante la actual pandemia de Coronavirus. There is currently a great need to have surfaces in contact with humans that are free of viruses and pathogenic organisms, in response to the current need in the world to have surfaces that contribute to the reduction of diseases, especially during the current Coronavirus pandemic. .
Especialmente existe la necesidad de contar con pisos y recubrimientos para utilizarse en la industria de la construcción, con propiedades biocidas cuya superficie sea capaz de eliminar virus y organismos patógenos. A lo largo de los años, se han desarrollado métodos para proporcionar a superficies propiedades biocidas y superficies con propiedades biocidas, algunos de los cuales se describen de manera general a continuación. There is especially a need for floors and coatings to be used in the construction industry, with biocidal properties whose surface is capable of eliminating viruses and pathogenic organisms. Over the years, methods for providing surfaces with biocidal properties and surfaces with biocidal properties have been developed, some of which are described generally below.
La patente norteamericana No.US9439439B2 describe una cubierta de vidrio transparente para aplicaciones tales como dispositivos de pantalla táctil que incorporan propiedades antimicrobianas, antifúngicas y antivirales. Los vidrios antimicrobianos contienen nanopartículas de Cu o Cu20 en la superficie del vidrio. Los vidrios antimicrobianos pueden tener además un revestimiento de fluorosilano u otro revestimiento en la superficie para que los vidrios sean fáciles de limpiar. Además, se describen superficies de vidrio que tienen superficies antibacterianas o antimicrobianas y un revestimiento protector en la superficie que no inhiben las propiedades antibacterianas o antimicrobianas del vidrio. La divulgación se dirige además a métodos para fabricar tales artículos. La publicación de solicitud de patente internacional PCT No. WO201 6028554 describe un producto antimicrobiano mejorado (que incluye métodos para fabricarlo) que tiene una composición de vidrio o vitrocerámica, una pluralidad de superficies primarias y una estructura antimicrobiana en al menos una de las superficies primarias. La estructura antimicrobiana comprende una pluralidad de nanopartículas de cobre configuradas para autopasivarse en condiciones de vida útil del artículo. Dichos artículos antimicrobianos pueden demostrar eficacia antimicrobiana evidenciada por tasas de destrucción logarítmicas de 3 o más en la prueba seca aprobada por la EPA para superficies que contienen cobre. US Patent No. US9439439B2 describes a transparent glass cover for applications such as touch screen devices incorporating antimicrobial, antifungal and antiviral properties. Antimicrobial glasses contain Cu or Cu20 nanoparticles on the glass surface. Antimicrobial glasses may additionally have a fluorosilane or other coating on the surface to make the glasses easy to clean. In addition, glass surfaces are disclosed having antibacterial or antimicrobial surfaces and a protective coating on the surface that do not inhibit the antibacterial or antimicrobial properties of the glass. The disclosure is further directed to methods of making such articles. PCT International Patent Application Publication No. WO201 6028554 describes an improved antimicrobial product (including methods of making it) having a glass or glass-ceramic composition, a plurality of primary surfaces, and an antimicrobial structure on at least one of the primary surfaces . The antimicrobial structure comprises a plurality of copper nanoparticles configured to self-passivate under lifetime conditions of the article. Such antimicrobial articles may demonstrate antimicrobial efficacy as evidenced by log kill rates of 3 or greater in the EPA-approved dry test for copper-containing surfaces.
El artículo titulado “Glass-(nAg, nCu) Biocide Coatings on Ceramic Oxide Substrates” (Esteban-Tejeda, L., Malpartida, F., Díaz, L., Torrecillas, R., Rojo, F., & Moya, J. (2012). Glass-(nAg, nCu) Biocide Coatings on Ceramic Oxide Substrates. Píos ONE, 7(3), e33135. doi: 10.1371/journal. pone.0033135), describe la obtención de recubrimientos biocidas constituidos por una matriz vitrea de cal sodada que contiene nanopartículas de plata o cobre sobre sustratos cerámicos (a base de alúmina y zirconia). Ambos revestimientos vitreos muestran una alta actividad biocida frente a bacterias Gram2. The article entitled “Glass-(nAg, nCu) Biocide Coatings on Ceramic Oxide Substrates” (Esteban-Tejeda, L., Malpartida, F., Díaz, L., Torrecillas, R., Rojo, F., & Moya, J (2012). Glass-(nAg, nCu) Biocide Coatings on Ceramic Oxide Substrates. Píos ONE, 7(3), e33135. doi: 10.1371/journal. pone.0033135), describes obtaining biocidal coatings made up of a matrix soda lime vitreous containing silver or copper nanoparticles on ceramic substrates (alumina and zirconia based). Both glass coatings show a high biocidal activity against Gram2 bacteria.
El artículo titulado “Copper-containing glass ceramic with high antimicrobial efficacy” (Gross, T., Lahiri, J., Golas, A., Luo, J., Verrier, F., &The article entitled “Copper-containing glass ceramic with high antimicrobial efficacy” (Gross, T., Lahiri, J., Golas, A., Luo, J., Verrier, F., &
Kurzejewski, J. et al. (2019). Copper-containing glass ceramic with high antimicrobial efficacy. Nature Communications, 10(1). doi: 10.1038/s41467-019- 09946-9) describe un polvo de cobre-vitrocerámica como aditivo para superficies antimicrobianas; en donde su mecanismo se basa en la liberación controlada de iones de cobre (I) (Cu1 +) a partir de nanocristales de cuprita que se forman in situ en la fase lábil al agua de la vitrocerámica bifásica. Las pinturas de látex que contienen polvo de cobre-vitrocerámica muestran una reducción >99,9% en los recuentos de colonias de S. aureus, P. aeruginosa, K. aerogenes y E. Coli cuando se evalúan mediante el método de prueba de la EPA de EE. UU. para determinar la eficacia de las superficies de aleación de cobre como desinfectantes, acercándose el del cobre metálico de referencia. Kurzejewski, J. et al. (2019). Copper-containing glass ceramic with high antimicrobial efficacy. Nature Communications, 10(1). doi: 10.1038/s41467-019-09946-9) describes a copper-glass ceramic powder as an additive for antimicrobial surfaces; where its mechanism is based on the controlled release of copper ions (I) (Cu1 +) from cuprite nanocrystals that are formed in situ in the water-labile phase of the biphasic glass-ceramic. Latex paints containing copper-glass ceramic powder show >99.9% reduction in colony counts of S. aureus, P. aeruginosa, K. aerogenes, and E. coli when tested by the Latex Test Method. US EPA to determine the effectiveness of copper alloy surfaces as disinfectants, coming close to that of the reference metallic copper.
No obstante, ninguna de las publicaciones mencionadas describe o sugiere pisos y recubrimientos para utilizarse en la industria de la construcción. En vista de lo anterior, el solicitante desarrolló un revestimiento o recubrimiento cerámico con propiedades biocidas, el cual cuenta con las siguientes características: However, none of the mentioned publications describe or suggest flooring and coatings for use in the construction industry. In view of the foregoing, the applicant developed a ceramic lining or coating with biocidal properties, which has the following characteristics:
• Está compuesto por un soporte cerámico, una capa de engobe, una capa de base y una capa protectora de esmalte. • It is made up of a ceramic support, a layer of slip, a base layer and a protective layer of enamel.
• La capa protectora de esmalte incorpora nanopartículas de cobre con valencia 0 encapsuladas en un material vitreo. • The protective layer of enamel incorporates copper nanoparticles with 0 valence encapsulated in a glassy material.
• La baldosa tiene propiedades antibacteriales que cumplen con la norma ISO 22196 (Medición de actividad antibacterial en plásticos y en superficies no porosas). Para las siguientes bacterias: Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 6538. • The tile has antibacterial properties that comply with ISO 22196 (Measurement of antibacterial activity in plastics and non-porous surfaces). For the following bacteria: Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 6538.
• La baldosa tiene propiedades antivirales certificadas por por la TONA (El Consejo Cerámico de Norte América) con la Norma ISO 21702 (Medición de actividad antiviral en plásticos y en superficies no porosas). Para los siguientes virus: Influenza A virus (H3N2), SARS- CoV- 2 Human coronavirus 229E. • The tile has antiviral properties certified by TONA (The Ceramic Council of North America) with the ISO 21702 Standard (Measurement of antiviral activity in plastics and non-porous surfaces). For the following viruses: Influenza A virus (H3N2), SARS- CoV- 2 Human coronavirus 229E.
• La baldosa tiene propiedades antimicóticas certificadas por la Universidad INTA de Chile, con la Norma ISO 22196 (Medición de actividad antibacterial en plásticos y en superficies no porosas). Para los siguientes microorganismos: Aspergillus niger ATCC 16404, Candida albicans ATCC 90028 - fecha de informe 15-02. • The tile has antifungal properties certified by the INTA University of Chile, with the ISO 22196 Standard (Measurement of antibacterial activity in plastics and non-porous surfaces). For the following microorganisms: Aspergillus niger ATCC 16404, Candida albicans ATCC 90028 - report date 02-15.
Durante el desarrollo del recubrimiento cerámico, se realizaron ensayos en el proceso de fabricación añadiendo primeramente nano partículas de cobre en el esmalte en proceso en crudo antes de la cocción en el horno, este insumo fue agregado en diferentes porcentajes en el esmalte cerámico teniendo resultados negativos, ya que la superficie del cerámico luego de la cocción se dañaba con partículas grises y verdosas en la superficie, esto ocasionado por la oxidación del Cobre. During the development of the ceramic coating, tests were carried out in the manufacturing process by first adding copper nanoparticles to the glaze in the raw process before firing in the kiln. This input was added in different percentages to the ceramic glaze, with negative results. , since the surface of the ceramic after firing was damaged with gray and greenish particles on the surface, this caused by the oxidation of Copper.
Teniendo en cuenta lo sucedido en las pruebas anteriores donde las nano partículas se oxidaron al ser aplicadas en el esmalte líquido en el proceso, se decidió utilizar Nano partículas de Cobre de valencia “0” encapsuladas con un material vitreo de características similares al esmalte usado. Finalmente se realizaron los cálculos respectivos para definir el porcentaje de nano partícula de cobre encapsuladas que se aplicaron en el esmalte líquido en el cerámico que luego fue quemado, teniendo un resultado satisfactorio observándose que la superficie ya no se dañaba ya que las nano partículas de cobre no se oxidaron manteniendo su poder biocida. Taking into account what happened in the previous tests where the nanoparticles oxidized when applied to the liquid enamel in the process, it was decided to use “0” valence Copper Nanoparticles encapsulated with a vitreous material with characteristics similar to the enamel used. Finally, the respective calculations were made to define the percentage of encapsulated copper nanoparticles that were applied in the liquid enamel on the ceramic that was later burned, having a satisfactory result, observing that the surface was no longer damaged since the copper nanoparticles They did not oxidize, maintaining their biocide power.
El producto al ser nCu encapsulado en material vitreo, es altamente seguro para los operarios en todos los procesos de producción de las cerámicas. The product, being nCu encapsulated in glassy material, is highly safe for operators in all ceramic production processes.
Además, el producto al ser nCu encapsulado y/o embebido en material vitreo cumple con las normas de vitrificación de materiales con metales pesados como solución medioambiental, transformando a este producto en uno eco- amigable. Cabe recordar que la vitrificación es el esquema de mayor seguridad frente a productos sensibles, y en el caso del cobre es un nivel mayor de seguridad ambiental, de operaciones, manipulación y control. In addition, the product, being nCu encapsulated and/or embedded in glassy material, complies with the standards for vitrification of materials with heavy metals as an environmental solution, transforming this product into an eco-friendly one. It should be remembered that vitrification is the most secure scheme against sensitive products, and in the case of copper it is a higher level of environmental, operational, handling and control safety.
La capacidad del cobre en estado metálico y tamaño nanométñco permite su incorporación en las superficies cerámicas otorgando gran capacidad superficial, generando una catálisis en el esmalte que permite una liberación iónica de cobre que en muy bajas dosis otorgan una gran capacidad biocida, esto tiene ventajas productivas, logísticas, económicas y de impacto ambiental que con otros productos no es posible lograr. The capacity of copper in its metallic state and nanometric size allows its incorporation into ceramic surfaces, providing great surface capacity, generating catalysis in the enamel that allows an ionic release of copper that in very low doses provides a great biocidal capacity, this has productive advantages. , logistic, economic and environmental impact that cannot be achieved with other products.
SUMARIO DE LA INVENCION SUMMARY OF THE INVENTION
Es por lo tanto un objetivo principal de la presente invención el proporcionar una baldosa cerámica con propiedades biocidas. It is therefore a main objective of the present invention to provide a ceramic tile with biocidal properties.
Es aún un objetivo principal de la presente invención el proporcionar una baldosa cerámica de la naturaleza anteriormente descrita, la cual está compuesta por un soporte cerámico, una capa de engobe, una capa de base y una capa protectora de esmalte, en donde la capa protectora de esmalte incorpora nanopartículas de cobre en estado de valencia 0 encapsuladas en un material vitreo. It is still a main objective of the present invention to provide a ceramic tile of the nature described above, which is composed of a ceramic support, a slip layer, a base layer and a protective layer of enamel, wherein the protective layer of enamel incorporates copper nanoparticles in valence state 0 encapsulated in a glassy material.
Es un objetivo adicional de la presente invención, el proporcionar una baldosa cerámica de la naturaleza anteriormente descrita, la cual tiene propiedades antibacteriales, antivirales y antimicóticas certificadas para los siguientes organismos patógenos: bacterias: Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 6538; virus: Influenza A virus (H3N2), SARS- CoV- 2 Human coronavirus 229E; microorganismos: Aspergillus niger ATCC 16404, Candida albicans ATCC 90028 - fecha de informe 15-02. It is an additional objective of the present invention to provide a ceramic tile of the nature described above, which has certified antibacterial, antiviral and antifungal properties against the following pathogenic organisms: bacteria: Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 6538; virus: Influenza A virus (H3N2), SARS-CoV- 2 Human coronavirus 229E; microorganisms: Aspergillus niger ATCC 16404, Candida albicans ATCC 90028 - report date 02-15.
Estos y otros objetivos y ventajas de la presente invención se harán evidentes a las personas con conocimientos normales en el ramo mediante la siguiente descripción detallada de la invención. These and other objects and advantages of the present invention will become apparent to those of ordinary skill in the art from the following detailed description of the invention.
DESCRIPCION DETALLADA DE LA INVENCION. DETAILED DESCRIPTION OF THE INVENTION.
En un primer aspecto, la presente invención se refiere a un revestimiento o recubrimiento cerámico con propiedades biocidas. In a first aspect, the present invention relates to a ceramic coating with biocidal properties.
El recubrimiento cerámico de la presente invención comprende: un cuerpo cerámico de soporte, el cual comprende material de masa extremadamente compacta, constituida por varias fases cristalinas inmersas en una matriz vitrea, compuesta principalmente por derivados del Sílice. una capa denominada engobe, el cual comprende una capa semiporosa que precede a la aplicación del esmalte y tiene diferentes funciones como uniformizar la absorción de agua de las sucesivas aplicaciones, aislar el color del soporte, uniformizar las imperfecciones del soporte, generar una adherencia al soporte, establecer un coeficiente de dilatación que permita regular adecuadamente el planar de las baldosas, impermeabilizar y opacar de manera que permita minimizar el efecto de mancha de agua producto de la absorción de agua del soporte. La capa de engobe tiene un espesor típico de 67 mieras y está constituido por aluminosilicatos de metales alcalinos o alcalinotérreos y silicato de circonio principalmente; una capa denominada base o esmalte el cual comprende un recubrimiento vitreo, sobre el soporte, resultado de la fusión de óxidos en polvo a través de un proceso de calentamiento. Tiene el objetivo de adecuar el producto al uso que va destinado y proporcionarle cualidades estéticas determinadas. La adecuación del producto al uso está relacionada con la mejora de las propiedades superficiales que proporciona el recubrimiento vidriado, como la impermeabilidad, propiedades mecánicas, químicas, ópticas, térmicas, etc. En cuanto a las cualidades estéticas, los esmaltes constituyen una expresión artística donde conjugan una gráfica, con elementos de color, formas y texturas. La capa base o esmalte tiene un grosor típico de 67 mieras y está constituido por aluminosilicatos de metales alcalinos o alcalinotérreos los cuales funden a temperaturas mayores a 1000°C para obtener el acabado final deseado. una capa protectora: la cual comprende una capa de esmalte aplicada en la superficie de la capa de base o esmalte, y genera una mayor protección evitando la aparición de defectos superficiales. en donde el recubrimiento cerámico está caracterizado porque: la capa protectora tiene un espesor de entre 6 a 200 mieras, preferentemente 13 mieras y contiene nanopartículas de cobre en estado de valencia 0, encapsuladas en un material vitreo, con un tamaño de entre 20 a 40nm preferente de 25nm en donde el tamaño distribución del tamaño de partícula muestra una tendencia de valores con una media de 35nm con una derivación estándar de 0.8nm, en una cantidad de entre 0.1 a 1 .000RRM por m2; incorporadas de manera homogénea en el material vitreo bajo un proceso de homogenización, fundición y molienda. en donde el recubrimiento cerámico cuenta con las siguientes certificaciones: The ceramic coating of the present invention comprises: a ceramic support body, which comprises extremely compact mass material, made up of several crystalline phases immersed in a glassy matrix, mainly composed of silica derivatives. a layer called engobe, which comprises a semi-porous layer that precedes the application of the enamel and has different functions such as uniforming the water absorption of successive applications, isolating the color of the support, uniforming the imperfections of the support, generating adherence to the support , establish a coefficient of expansion that allows to adequately regulate the planarity of the tiles, waterproof and opaque in a way that allows to minimize the effect of water stains resulting from the absorption of water from the support. The slip layer has a typical thickness of 67 microns and is made up of alkali or alkaline earth metal aluminosilicates and zirconium silicate mainly; a layer called base or enamel which comprises a vitreous coating, on the support, the result of the fusion of powdered oxides through a heating process. Its objective is to adapt the product to its intended use and provide certain aesthetic qualities. The suitability of the product for use is related to the improvement of the surface properties provided by the glazed coating, such as impermeability, mechanical, chemical, optical, thermal properties, etc. Regarding the aesthetic qualities, the enamels constitute an artistic expression where they combine a graphic, with elements of color, shapes and textures. The base layer or enamel has a typical thickness of 67 microns and is made up of Alkaline or alkaline earth metal aluminosilicates which melt at temperatures higher than 1000°C to obtain the desired final finish. a protective layer: which comprises a layer of enamel applied to the surface of the base layer or enamel, and generates greater protection, avoiding the appearance of surface defects. wherein the ceramic coating is characterized in that: the protective layer has a thickness of between 6 to 200 microns, preferably 13 microns and contains copper nanoparticles in a 0 valence state, encapsulated in a glassy material, with a size of between 20 to 40nm preferred 25nm where the size distribution of the particle size shows a trend of values with a mean of 35nm with a standard deviation of 0.8nm, in an amount between 0.1 to 1,000RRM per m 2 ; homogeneously incorporated into the glassy material under a process of homogenization, casting and grinding. where the ceramic coating has the following certifications:
• Tiene propiedades antibacteriales que cumplen con la norma ISO 22196 (Medición de actividad antibacterial en plásticos y en superficies no porosas). Para las siguientes bacterias: Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 6538. • Has antibacterial properties that comply with ISO 22196 (Measurement of antibacterial activity in plastics and non-porous surfaces). For the following bacteria: Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 6538.
• Tiene propiedades antivirales certificadas por la TCNA (El Consejo Cerámico de Norte América) con la Norma ISO 21702 (Medición de actividad antiviral en plásticos y en superficies no porosas). Para los siguientes virus: Influenza A virus (H3N2), SARS- CoV- 2 Human coronavirus 229E. • It has antiviral properties certified by the TCNA (The Ceramic Council of North America) with the ISO 21702 Standard (Measurement of antiviral activity in plastics and non-porous surfaces). For the following viruses: Influenza A virus (H3N2), SARS- CoV- 2 Human coronavirus 229E.
• Tiene propiedades antimicóticas certificadas por la Universidad INTA de Chile, con la Norma ISO 22196 (Medición de actividad antibacterial en plásticos y en superficies no porosas). Para los siguientes microorganismos: Aspergillus niger ATCC 16404, Candida albicans ATCC 90028 - fecha de informe 15-02. • It has antifungal properties certified by the INTA University of Chile, with the ISO 22196 Standard (Measurement of antibacterial activity in plastics and non-porous surfaces). For the following microorganisms: Aspergillus niger ATCC 16404, Candida albicans ATCC 90028 - report date 02-15.
En un segundo aspecto, la presente invención se refiere a un método para elaborar un recubrimiento cerámico con propiedades biocidas, en donde el recubrimiento cerámico comprende un cuerpo cerámico de soporte; una capa denominada esmalte que consiste en una capa vitrea que define las propiedades funcionales y decorativas del recubrimiento cerámico; una capa denominada engobe el cual permite una buena unión entre el esmalte y el cuerpo cerámico, y una capa protectora la cual comprende una capa de esmalte aplicada en la superficie de la capa de base o esmalte, en donde dicho método comprende agregar a la capa protectora nanopartículas de cobre con valencia 0 encapsuladas en un material vitreo, con un tamaño de entre 20 a 40nm, preferentemente 25nm en una cantidad de entre 0.1 a 1.000PPM por m2 durante el proceso de esmaltado, en el subproceso de aplicación de gota dentro de cualquier proceso de producción conocido de recubrimientos cerámicos. In a second aspect, the present invention relates to a method for making a ceramic coating with biocidal properties, wherein the ceramic coating comprises a supporting ceramic body; A layer called enamel that consists of a vitreous layer that defines the functional and decorative properties of the ceramic coating; a layer called engobe which allows a good bond between the enamel and the ceramic body, and a protective layer which comprises a layer of enamel applied to the surface of the base layer or enamel, wherein said method comprises adding to the layer protective copper nanoparticles with 0 valence encapsulated in a glassy material, with a size between 20 to 40nm, preferably 25nm in an amount between 0.1 to 1,000PPM per m 2 during the enameling process, in the drop application thread inside of any known ceramic tile production process.
El tamaño distribución del tamaño de las nanopartículas muestra una tendencia de valores con una media de 35nm con una derivación estándar de 0.8nm. The size distribution of the size of the nanoparticles shows a trend of values with a mean of 35nm with a standard deviation of 0.8nm.
Las nanopartículas agregadas a la capa protectora cuentan con las siguientes características específicas:
Figure imgf000008_0001
The nanoparticles added to the protective layer have the following specific characteristics:
Figure imgf000008_0001
El nCu utilizado es de Cu en estado metálico siendo eminentemente Cu°, la que le confiere las propiedades mecánicas de maleabilidad del Cu, potencial zeta positivo colaborando con la interacción en matrices tipo SiO, generando de una sinergia entre los materiales. Al ser el nCu de tamaños menores a 50 nm (rango de las partículas poliagregadas de 20 a 40nm). Su interacción con silicatos de tamaños promedio de MESH 100 (aproximadamente 150 mieras), hace que cada silicato tenga interacciones con vahas nCu a la vez. Una vez unidos y estabilizados puede liberar Cu++, sin liberar nCu que está en esta matriz, siendo su acción a largo plazo y no se elimina posterior exposición a acción ambiental, ni exposición a agentes químicos, gracias a la protección otorgada por la matriz de silicatos The nCu used is Cu in the metallic state, being eminently Cu°, which gives it the mechanical properties of Cu malleability, positive zeta potential collaborating with the interaction in SiO-type matrices, generating a synergy between the materials. As the nCu is smaller than 50 nm in size (range of polyaggregated particles from 20 to 40 nm). Its interaction with silicates of average sizes of MESH 100 (approximately 150 microns), makes each silicate have interactions with several nCu at the same time. One time united and stabilized, it can release Cu++, without releasing nCu that is in this matrix, its action being long-term and subsequent exposure to environmental action or exposure to chemical agents is not eliminated, thanks to the protection provided by the silicate matrix
El mecanismo de la inactivación viral en las superficies de cobre es complejo e involucra no solo la acción directa del ion de cobre en múltiples objetivos, sino también la generación de radicales destructivos de oxígeno, lo que resulta en un "suicidio metabólico", Estas reacciones generan la Peroxidación enzimática de la envoltura, daño de las proteínas de membrana y las nucleoproteínas del virus mediante hidroxilos. No necesita luz para activar este mecanismo.
Figure imgf000009_0001
The mechanism of viral inactivation on copper surfaces is complex and involves not only the direct action of the copper ion on multiple targets, but also the generation of destructive oxygen radicals, resulting in "metabolic suicide". These reactions they generate the enzymatic peroxidation of the envelope, damage of the membrane proteins and the nucleoproteins of the virus through hydroxyls. You do not need light to activate this mechanism.
Figure imgf000009_0001
EXPERIMENTOS EXPERIMENTS
Las nanopartículas de cobre (nCu) en material vitreo de silicatos para cerámicas producidas, fueron mezcladas, homogenizadas con el material de esmaltado de la capa protectora en una concentración inferior a 1 .000RRM por m2 (concentración estandarizada). Cabe destacar que los esmaltes pueden tener otros aditivos como pigmentos, metales como son usados en la industriaThe copper nanoparticles (nCu) in vitreous silicate material for ceramics produced, were mixed, homogenized with the glaze material of the protective layer in a concentration lower than 1,000RRM per m 2 (standardized concentration). It should be noted that enamels may have other additives such as pigments, metals as they are used in the industry
Luego se aplicó en la cerámica y procesada de igual manera que la cerámica tradicional al esmaltar. Esta cerámica con nanopartículas fue cortada en probetas de 50 x 50 mm, siendo las probetas de ensayo activo. Junto a ellas se hicieron probetas “Blancos” que no contengan la cerámica con nanopartículas. Con estas probetas se ensayaron las pruebas de actividad antimicrobiológicas y virales en los distintos ensayos. It was then applied to the ceramic and processed in the same way as traditional ceramic when glazing. This ceramic with nanoparticles was cut into 50 x 50 mm specimens, the active test specimens being. Together with them, "White" test tubes were made that did not contain ceramic with nanoparticles. With these test tubes, the antimicrobial and viral activity tests were tested in the different tests.
Los ensayos de actividad antimicrobiológica siguieron las normas ISO 22196 con los siguientes microorganismos: Eschehchia coli ATCC 8739 (bacteria Gram (-) ) a 24 horas, Staphylococcus aureus ATCC 6538 (bacteria Gram (+) resistente a antibiótico) a 24 horas, Candida albicans ATCC 90028 (levadura de contagio humano) a 48 horas, y Aspergillus niger ATCC 16404 (hongo de contaminación alimentaria) a 24 horas. En todas ellas se observó que la cerámica con Biocer elimina sobre el 98 a 99.9% en relación a la cerámica “Blanco”. The antimicrobial activity tests followed the ISO 22196 standards with the following microorganisms: Eschechia coli ATCC 8739 (Gram (-) bacteria) at 24 hours, Staphylococcus aureus ATCC 6538 (Gram (+) bacteria resistant to antibiotics) at 24 hours, Candida albicans ATCC 90028 (human contagious yeast) at 48 hours, and Aspergillus niger ATCC 16404 (food contaminated fungus) at 24 hours. In all of them it was observed that the ceramic with Biocer eliminates about 98 to 99.9% in relation to the "White" ceramic.
Además se hicieron ensayos de actividad antiviral, siguiendo las normas ISO 22196, con los siguientes virus: Haemophilus influenza H1 N1 a 24 horas; y Coronavirus SARSII a 24 horas. En todas ellas se observó que la cerámica con nanopartículas elimina sobre el 99.9% en relación a la cerámica “Blanco”. In addition, antiviral activity tests were carried out, following ISO 22196 standards, with the following viruses: Haemophilus influenza H1 N1 at 24 hours; and Coronavirus SARSII at 24 hours. In all of them it was observed that the ceramic with nanoparticles eliminates over 99.9% in relation to the “White” ceramic.
Con estos ensayos queda declarado, que las cerámicas esmaltadas con esmaltes con nanopartículas son biocidas y autohigienizantes. With these tests it is declared that glazed ceramics with enamels with nanoparticles are biocidal and self-sanitizing.
Deberá finalmente entenderse que el revestimiento cerámico y método para su producción de la presente invención no se limita a la modalidad descrita anteriormente y que los expertos en el ramo quedarán capacitados, por las enseñanzas que aquí se establecen, para efectuar cambios en el revestimiento cerámico y método para su producción de la presente invención, cuyo alcance quedará establecido exclusivamente por las siguientes reivindicaciones. Finally, it should be understood that the ceramic coating and method for its production of the present invention is not limited to the modality described above and that experts in the field will be enabled, by the teachings established herein, to make changes in the ceramic coating and method for its production of the present invention, the scope of which will be established exclusively by the following claims.

Claims

REIVINDICACIONES
1. Un revestimiento cerámico con propiedades biocidas empleado en la industria de la construcción, que consiste en un cuerpo cerámico de soporte, una capa denominada base la cual comprende una capa vitrea que define las propiedades funcionales y decorativas del revestimiento cerámico, una capa denominada engobe, la cual permite la unión entre la capa base y el cuerpo cerámico de soporte, y una capa protectora la cual comprende una capa de esmalte aplicada en la superficie de la capa base, y genera una mayor protección evitando la aparición de defectos superficiales, en donde el revestimiento cerámico está caracterizado porque: la capa protectora tiene un espesor de entre 6 a 200 mieras y contiene nanopartículas de cobre con valencia 0 encapsuladas en un material vitreo, con un tamaño de entre 20 a 40nm en una cantidad de entre 0.1 a 1.000RRM por m2. 1. A ceramic coating with biocidal properties used in the construction industry, consisting of a ceramic support body, a layer called base which comprises a vitreous layer that defines the functional and decorative properties of the ceramic coating, a layer called engobe , which allows the union between the base layer and the supporting ceramic body, and a protective layer which comprises a layer of enamel applied to the surface of the base layer, and generates greater protection avoiding the appearance of surface defects, in where the ceramic coating is characterized because: the protective layer has a thickness between 6 to 200 microns and contains copper nanoparticles with valence 0 encapsulated in a glassy material, with a size between 20 to 40nm in an amount between 0.1 to 1,000 RRM per m 2 .
2. Un revestimiento cerámico de conformidad con la reivindicación 1, en donde las nanopartículas de cobre tienen un tamaño de 25nm. 2. A ceramic coating according to claim 1, wherein the copper nanoparticles have a size of 25nm.
3. Un revestimiento cerámico de conformidad con la reivindicación 1, en donde el tamaño distribución del tamaño de las nanopartículas muestra una tendencia de valores con una media de 35nm con una derivación estándar de 0.8nm. 3. A ceramic coating according to claim 1, wherein the size distribution of the size of the nanoparticles shows a trend of values with a mean of 35nm with a standard deviation of 0.8nm.
4. Un método para elaborar un revestimiento cerámico con propiedades biocidas empleado en la industria de la construcción que consiste en un cuerpo cerámico de soporte, una capa denominada engobe, la cual permite la unión entre el esmalte y el cuerpo cerámico de soporte, una capa denominada esmalte la cual comprende una capa vitrea que define las propiedades funcionales y decorativas del revestimiento cerámico y una capa protectora la cual comprende una capa de esmalte aplicada en la superficie de la capa de base o esmalte, y genera una mayor protección evitando la aparición de defectos superficiales, en donde dicho método comprende: proporcionar a la capa protectora un espesor de entre 6 a 200 mieras: y agregar a la capa protectora nanopartículas de cobre con valencia 0 encapsuladas en un material vitreo, con un tamaño de entre 20 a 40nm en una cantidad de entre 0.1 a 1.000PPM por m2 durante el proceso de esmaltado, en el subproceso de aplicación de gota dentro de cualquier proceso de producción conocido de recubrimientos cerámicos. 4. A method for making a ceramic coating with biocidal properties used in the construction industry consisting of a ceramic support body, a layer called engobe, which allows the union between the enamel and the ceramic support body, a layer called enamel which comprises a vitreous layer that defines the functional and decorative properties of the ceramic coating and a protective layer which comprises a layer of enamel applied to the surface of the base layer or enamel, and generates greater protection avoiding the appearance of surface defects, wherein said method comprises: providing the protective layer with a thickness of between 6 to 200 microns: and adding copper nanoparticles to the protective layer with valence 0 encapsulated in a glassy material, with a size between 20 to 40nm in an amount between 0.1 to 1,000PPM per m2 during the enameling process, in the drop application sub-process within any known production process of ceramic coatings .
5. Un método para elaborar un revestimiento cerámico de conformidad con la reivindicación 1, en donde las nanopartículas de cobre agregadas tienen un tamaño de 25nm. 5. A method for making a ceramic coating according to claim 1, wherein the added copper nanoparticles have a size of 25nm.
6. Un método para elaborar un revestimiento cerámico de conformidad con la reivindicación 1, en donde el tamaño distribución del tamaño de las nanopartículas muestra una tendencia de valores con una media de 35nm con una derivación estándar de 0.8nm. 6. A method for making a ceramic coating according to claim 1, wherein the size distribution of the size of the nanoparticles shows a trend of values with a mean of 35nm with a standard deviation of 0.8nm.
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WO2013128302A1 (en) * 2012-02-27 2013-09-06 Accord Comunicaciones Ltda. Process for manufacturing ceramic articles having antifungal, antibacterial and antimicrobial properties, and ceramic articles
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