ES2484591A1 - Use of luminous pigments in natural stone materials by adding these in the resins, commonly used, in the natural stone industry (Machine-translation by Google Translate, not legally binding) - Google Patents

Use of luminous pigments in natural stone materials by adding these in the resins, commonly used, in the natural stone industry (Machine-translation by Google Translate, not legally binding) Download PDF

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Publication number
ES2484591A1
ES2484591A1 ES201300164A ES201300164A ES2484591A1 ES 2484591 A1 ES2484591 A1 ES 2484591A1 ES 201300164 A ES201300164 A ES 201300164A ES 201300164 A ES201300164 A ES 201300164A ES 2484591 A1 ES2484591 A1 ES 2484591A1
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pigments
natural stone
resin
natural
luminous
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ES2484591B1 (en
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Armando José YÁÑEZ SOLER
Enrique AMAT GONZÁLEZ
Leopoldo Diez Canto
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Ganofita SL
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/48Macromolecular compounds

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Luminescent Compositions (AREA)

Abstract

The present invention refers to the inclusion of autoluminescent pigments, that is to say those that are capable of storing light and then emitting it in the dark, mixed in the resins used in natural stone materials in a percentage between 1 and 60% by weight. With this technique it is possible to increase the decorative and functional characteristics such as signaling. (Machine-translation by Google Translate, not legally binding)

Description

DESCRIPCiÓN Description

Se puede definir como Piedra natural a aquellas rocas que, después de un proceso de elaboración, son aptas para ser utilizadas como materiales nobles de construcción, elementos de ornamentación, arte funerario y escultórico, objetos artísticos variados, conservando su composición, textura y características físico-químicas. Las piedras naturales de mayor interés comercial son aquellas que por sus propiedades de vistosidad, físico-químicas, y aptitud para el pulido constituyen la materia prima de la llamada Industria de la Piedra Natural. Se distinguen tres grupos denominados genéricamente granitos, mármoles y pizarras, más el grupo de piedras traslúcidas como el Ónix o Alabastro. It can be defined as natural stone to those rocks that, after a process of elaboration, are suitable to be used as noble building materials, ornamentation elements, funerary and sculptural art, varied artistic objects, preserving their composition, texture and physical characteristics -chemistry. The natural stones of greater commercial interest are those that, due to their colorful, physical-chemical and polishing properties, constitute the raw material of the so-called Natural Stone Industry. There are three groups generically called granites, marbles and blackboards, plus the group of translucent stones such as Onyx or Alabaster.

Estado de la técnica State of the art

Esta invención tiene su aplicación dentro de la industria y fabricación de materiales pétreos, y la decoración de los mismos. This invention has its application within the industry and manufacture of stone materials, and their decoration.

Campo de la invención Field of the Invention

La invención de la presente aplicación se refiere a la incorporación sobre piedras naturales de pigmentos o materiales con propiedades luminiscentes o fluorescentes. Más específicamente, la invención se refiere a una piedra natural a la que se le aumenta su función decorativa incorporándole la propiedad de que pueda emitir luz, que previamente haya almacenado, o por desprender luz al ser irradiada con luz ultravioleta, mediante la incorporación de pigmentos luminosos en las resinas que comúnmente se emplean en la industria de la piedra natural. The invention of the present application relates to the incorporation on natural stones of pigments or materials with luminescent or fluorescent properties. More specifically, the invention relates to a natural stone to which its decorative function is enhanced by incorporating the property that it can emit light, which it has previously stored, or by releasing light when irradiated with ultraviolet light, by incorporating pigments luminous in the resins that are commonly used in the natural stone industry.

Objeto de la invención Object of the invention

Utilización de pigmentos luminosos imagen1en materiales pétreos naturales al añadir estos en las en la industria de la piedra natural. Use of luminous pigments image 1 in natural stone materials by adding these in the natural stone industry.

Más concretamente, y desde un punto de vista científico, el mármol se define como una piedra caliza metamórfica (recristalizada) compuesta principalmente por granos finos y cristalinos de calcita, dolomita o ambos, teniendo textura de mosaico o entrelazada que puede ser pulida, conteniendo a veces fósiles. More specifically, and from a scientific point of view, marble is defined as a metamorphic (recrystallized) limestone composed mainly of fine and crystalline grains of calcite, dolomite or both, having mosaic or interlaced texture that can be polished, containing Fossil times

Los mármoles, poseen una gran belleza estética y alta aceptación en el mercado de la
construcción y decoración, alguno de ellos con vistosos colores debido a impurezas metálicas.
The marbles, have a great aesthetic beauty and high acceptance in the market of the
construction and decoration, some of them with colorful colors due to metallic impurities.

Sin embargo, al ser productos de origen sedimentario, son materiales poco consolidados mecánicamente y presentan diversas heterogeneidades, fisuras, grietas y oquedades que, si bien resaltan su valor estético, constituyen zonas con elevado riesgo de rotura frente a esfuerzos mecánicos externos. Esto provoca que, durante el procesado y manipulación de las baldosas, en algunos casos más del 50% de las piezas se fracturen, convirtiéndose en materiales de desecho con un grado de reutilización muy pequeño. Con el fin de paliar este problema, las empresas del sector del mármol aplican recubrimientos basados en polímeros termoestables a dichas baldosas antes de realizar la etapa de pulido. Se pretende rellenar las fisuras y grietas con polímeros que tienen adecuadas propiedades adhesivas y consolidan mecánicamente las piezas de mármol, aumentando la resistencia a la flexión y al impacto. However, being products of sedimentary origin, they are poorly mechanically consolidated materials and have various heterogeneities, cracks, cracks and cavities that, although they highlight their aesthetic value, constitute areas with a high risk of breakage against external mechanical stresses. This causes that, during the processing and handling of the tiles, in some cases more than 50% of the pieces are fractured, becoming waste materials with a very small degree of reuse. In order to alleviate this problem, companies in the marble sector apply coatings based on thermosetting polymers to these tiles before performing the polishing stage. It is intended to fill the cracks and cracks with polymers that have adequate adhesive properties and mechanically consolidate the marble pieces, increasing resistance to bending and impact.

La patente en cuestión se refiere a la inclusión de pigmentos lumínicos como componentes en la formulación de la resina que se vaya a emplear en el tratamiento de las piedras naturales. Se trata de aportar un componente nuevo en la piedra natural para que sea capaz de emitir luz en la oscuridad. The patent in question refers to the inclusion of light pigments as components in the formulation of the resin to be used in the treatment of natural stones. It is about providing a new component in natural stone so that it is capable of emitting light in the dark.

Sobre la piedra se puede emplear la resinas no solo para rellenar las oquedades, fracturas o fisuras que tenga de forma natural sino que se pueden realizar reservas para la creación de diversos motivos artísticos o de señalización que se pretenda. A este respecto, se pueden realizar estos trabajos mediante ataque mecánico, ej. Fresado, y/o químico, mediante diversos ácidos. La resina formulada con los pigmentos o elementos luminiscentes, y los elementos resultantes tendrán una excelente incorporación en el mercado de la decoración, señalización, construcción, etc. On the stone you can use the resins not only to fill in the cavities, fractures or fissures that you have in a natural way but you can make reservations for the creation of various artistic or signaling motives that are intended. In this regard, these works can be performed by mechanical attack, eg. Milling, and / or chemical, by various acids. The resin formulated with the pigments or luminescent elements, and the resulting elements will have an excellent incorporation in the market of decoration, signage, construction, etc.

Otra forma importante de incorporar estos pigmentos con la resina es en el pegado de dos piezas de piedra del tipo translucido en forma de sándwich, como el Ónix, para aprovechar la transparencia de las mismas. Esta técnica permitiría el uso de los elementos resultantes en ventanas, tragaluces y objetos de iluminación y/o retroiluminación. Another important way to incorporate these pigments with the resin is by gluing two pieces of translucent sandwich-shaped stone, such as Onyx, to take advantage of their transparency. This technique would allow the use of the resulting elements in windows, skylights and lighting and / or backlight objects.

En el sector de la piedra natural, tradicionalmente, los polímeros utilizados han sido resinas de poliéster insaturado con peróxido de metil-etil-cetona como agente de entrecruzamiento. Posteriormente se incluyó la aplicación de los polímeros basados en resina epoxi. Un ejemplo de resina de consolidación son los basados en sistemas poliméricos sencillos compuestos por una resina epoxi típica basada en DGBA (éter diglicidílico de Bisfenol A) a la
que se le añaden diferentes endurecedores poliamínicos puros.
In the natural stone sector, traditionally, the polymers used have been polyester resins unsaturated with methyl ethyl ketone peroxide as a crosslinking agent. Subsequently the application of polymers based on epoxy resin was included. An example of consolidation resin are those based on simple polymeric systems composed of a typical epoxy resin based on DGBA (diglycidyl ether of Bisphenol A) at
that different pure polyamine hardeners are added.

Un ejemplo preferente sobre esta invención sería la inclusión de los pigmentos luminosos con un aglutinante resinoso curable por exposición a la radiación ultravioleta (UV). Preferiblemente, la resina es una composición que comprende una resina oligomérica clara y un componente sensible a la radiación UV. Preferiblemente, la resina oligomérica consta de monómeros que tienen uno o más grupos funcionales reticulables, tales como acrilato o metacrilato. En realizaciones específicas, los monómeros son acrilatos epoxídicos, acrilatos de poliuretano, acrilatos de políester y acrilatos acrílicos. El componente sensible a la radiación UVes un compuesto fotoiniciador que absorbe luz ultravioleta e inicia la polimerización de los monómeros. En realizaciones específicas, el compuesto fotoiniciador es una benzoína, un benzoín alquil éter, un bencilcetal, un derivado de acetofenona, una benzofenona, una cetona de Michler, un alfa-aciloxima éster, una tioxantona o un derivado de tioxantona, una quinona, antraquinona o un derivado, un peróxido orgánico, un compuesto orgánico de azufre, un compuesto metálico o un ion de un metal, un dicromato de un metal alcalino, un compuesto orgánico de fósforo, un clorosilano o un compuesto azoo A preferred example of this invention would be the inclusion of the luminous pigments with a resinous binder curable by exposure to ultraviolet (UV) radiation. Preferably, the resin is a composition comprising a clear oligomeric resin and a component sensitive to UV radiation. Preferably, the oligomeric resin consists of monomers having one or more crosslinkable functional groups, such as acrylate or methacrylate. In specific embodiments, the monomers are epoxy acrylates, polyurethane acrylates, polyester acrylates and acrylic acrylates. The UV radiation sensitive component is a photoinitiator compound that absorbs ultraviolet light and initiates polymerization of the monomers. In specific embodiments, the photoinitiator compound is a benzoin, a benzoyl alkyl ether, a benzyl acetal, a derivative of acetophenone, a benzophenone, a ketone of Michler, an alpha-acyloxyl ester, a thioxanthone or a derivative of thioxanthone, a quinone, anthraquinone or a derivative, an organic peroxide, an organic sulfur compound, a metal compound or an ion of a metal, an alkali metal dichromate, an organic phosphorus compound, a chlorosilane or an azo compound

Un campo de aplicación preferente emplean las resinas polimerizables de estireno, mediante el curado por radiación ultravioleta. A preferred field of use employs polymerizable styrene resins, by curing by ultraviolet radiation.

Los pigmentos que se pueden emplear en esta nueva técnica son de dos tipos principales, los pigmentos fosforescentes que son los que emiten luz o fosforescencia cuando son irradiados con luz ultravioleta, y los autoluminiscentes o fotoluminiscentes que son aquellos que tras ser irradiados con luz natural, luz artificial y/o luz ultravioleta son capaces de almacenar la energía lumínica para posteriormente emitirla durante horas. The pigments that can be used in this new technique are of two main types, the phosphorescent pigments that emit light or phosphorescence when irradiated with ultraviolet light, and the self-luminescent or photoluminescent ones which are those that after being irradiated with natural light, artificial light and / or ultraviolet light are capable of storing the light energy and then emitting it for hours.

Los pigmentos fosforescentes se encuentran en forma de polvos finos, y se desarrollaron en un principio con ayuda del elemento fósforo, aunque actualmente se puede usar conjuntamente con otros elementos metálicos como el cinc o el estroncio. Un ejemplo es el aluminato de estroncio o el sulfuro de cinc. Los pigmentos autoluminiscentes suelen contener fósforo al que se le añade diferentes aluminatos de tierras raras metálicas que contienen el elemento europio, en forma de óxido o sus sales. También se consiguen diferentes tonalidades añadiendo pequeñas cantidades de pigmentos inorgánicos, y lo mismo con diferentes colorantes empleados en la industria. Phosphorescent pigments are in the form of fine powders, and were initially developed with the help of the phosphorus element, although currently they can be used in conjunction with other metallic elements such as zinc or strontium. An example is strontium aluminate or zinc sulphide. The self-luminescent pigments usually contain phosphorus to which different metal rare earth aluminates containing the europium element are added, in the form of oxide or its salts. Different shades are also achieved by adding small amounts of inorganic pigments, and the same with different dyes used in the industry.

Realización preferente de la invención Preferred Embodiment of the Invention

A continuación se exponen dos ejemplos de aplicación, uno para relleno de grietas de
la piedra natural, y el segundo como relleno de huecos realizados sobre la misma piedra.
Below are two application examples, one for filling cracks of
the natural stone, and the second as a filling of holes made on the same stone.

El segundo ejemplo de aplicación de la patente es el uso de estos pigmentos luminosos sobre piedras naturales a las que se les ha realizado motivos con huecos y/o oquedades con fines artísticos o de señalización mediante el uso de procedimientos químicos, bien mediante reservas y ataque de ácido, o mediante procedimientos mecánicos usando fresas u otros elementos. El proceso es totalmente similar al descrito anteriormente para el relleno de las fisuras de las piedras naturales. The second example of patent application is the use of these luminous pigments on natural stones that have been made motifs with holes and / or cavities for artistic or signaling purposes through the use of chemical procedures, either through reservations and attack of acid, or by mechanical procedures using strawberries or other elements. The process is totally similar to the one described above for filling the fissures of natural stones.

Ambos elementos se mezclan por agitación mecánica hasta lograr una pasta uniforme y homogénea. A continuación se aplica mediante espátula la resina preparada sobre las piezas con el fin de rellenar las oquedades y fisuras. A continuación se introducen las piezas en un horno con ventilación y reflector de aluminio brillante donde se somete a la acción de la luz ultravioleta con ayuda de lámparas de mercurio de media o alta presión, y otra lámpara de Yoduro de Galio suministrando una energía de 80 a 160 watios/cm2. A continuación se pasa la pieza por un tren de pulido donde se obtiene lista la pieza para ser comercializada. Both elements are mixed by mechanical agitation until a uniform and homogeneous paste is achieved. The resin prepared on the pieces is then applied by spatula in order to fill the cavities and fissures. The pieces are then introduced in a ventilated oven with a bright aluminum reflector where it is subjected to the action of ultraviolet light with the help of medium or high pressure mercury lamps, and another Gallium Iodide lamp providing an energy of 80 at 160 watts / cm2. Then the piece is passed through a polishing train where the piece is ready to be marketed.

600 g de pigmento autoluminiscente basado en aluminatos de tierras metálicas raras que comprende el elemento europio. 600 g of self-luminescent pigment based on rare earth metal aluminates comprising the europium element.

4000 g de Resina, por ejemplo la denominada "Suco Pasta Lux", basada en resina de poliéster no saturada, derivada del estireno, capaz de reticular mediante lámparas de ultravioleta UV. 4000 g of Resin, for example the so-called "Suco Pasta Lux", based on unsaturated polyester resin, derived from styrene, capable of crosslinking by UV ultraviolet lamps.

En principio se realiza el corte de los bloques extraídos de la cantera a unas medidas y espesores adecuados. A continuación se realiza el proceso de calibrado de superficie de las piezas para eliminar irregularidades. Seguidamente se introducen las piezas en hornos de aire caliente para eliminar el sobrante de agua y su secado correspondiente. A continuación se realiza el proceso de relleno de huecos e imperfecciones superficiales mediante resinas o masillas con fines estéticos y mejora de las propiedades mecánicas. Es, en este momento, cuando se introducen los pigmentos lumínicos en la piedra natural mediante la adición a la resina que se emplea. En este caso usamos una resina. Este ejemplo se realiza concretamente sobre 10 metros cuadrados de Mármol marrón emperador y se emplea la fórmula siguiente: In principle, the blocks extracted from the quarry are cut to appropriate sizes and thicknesses. Next, the surface calibration process of the pieces is carried out to eliminate irregularities. The pieces are then introduced into hot air ovens to remove excess water and its corresponding drying. Next, the filling process of holes and surface imperfections is carried out by means of resins or putties for aesthetic purposes and improvement of the mechanical properties. It is, at this time, when the light pigments are introduced into the natural stone by adding to the resin that is used. In this case we use a resin. This example is done specifically on 10 square meters of Emperor Brown Marble and the following formula is used:

imagen2los pigmentos luminosos a una piedra natural en el proceso fabricación de piezas o losas de mármol. image2 Luminous pigments to a natural stone in the process of manufacturing pieces or marble slabs.


Con estos dos procedimientos se obtienen piezas que tras ser irradiadas con luz natural o luz ultravioleta son capaces de desprender luz en la oscuridad en el caso de emplear pigmentos autoluminiscentes, o de desprender luz cuando se irradian con la denominada luz negra. Son objetos o piezas de 'piedra natural donde se les ha añadido un alto valor artístico o de señalización.

With these two procedures, parts are obtained that, after being irradiated with natural light or ultraviolet light, are capable of releasing light in the dark in the case of using self-luminescent pigments, or of releasing light when they are irradiated with the so-called black light. They are objects or pieces of 'natural stone where a high artistic or signaling value has been added to them.

La proporción de los pigmentos respecto al peso de la resina empleada pueden variar. Un valor usual de referencia puede ser el 15% en peso de pigmento respecto a la resina empleada. Dependiendo del objeto y sus características que se quiere obtener, se puede usar concentraciones que pueden variar entre el 1 y el 60 por % del peso de los pigmentos luminosos frente al peso de la resina empleada. The proportion of the pigments with respect to the weight of the resin used may vary. A usual reference value may be 15% by weight of pigment with respect to the resin used. Depending on the object and its characteristics to be obtained, concentrations that can vary between 1 and 60% of the weight of the luminous pigments can be used versus the weight of the resin used.

La presente invención se ha expuesto y descrito aquí con lo que se considera que son las realizaciones más prácticas y preferentes. Se reconoce, sin embargo, que se pueden hacer variaciones de ella que están dentro del ámbito de la invención, y que un experto en la técnica idearía modificaciones después de leída la descripción. The present invention has been set forth and described herein with what is considered to be the most practical and preferred embodiments. It is recognized, however, that variations can be made therein that are within the scope of the invention, and that one skilled in the art would devise modifications after the description has been read.

Claims (4)

imagen1image 1 REIVINDICACIONES de aplicación de pigmentos luminosos a piedras naturales, caracterizado por la incorporación de pigmentos autoluminiscentes, en una proporción de entre el 1 y el 60 % en peso, a la resina que comúnmente se emplea en la industria para sellado de huecos y fisuras propias en el proceso de consolidación de la piedra natural. of application of luminous pigments to natural stones, characterized by the incorporation of self-luminescent pigments, in a proportion of between 1 and 60% by weight, to the resin that is commonly used in the industry for sealing gaps and own fissures in the natural stone consolidation process.
2. 2.
Procedimiento de de aplicación de pigmentos luminosos a piedras naturales, según reivindicación 1, caracterizado por emplear lámparas de ultravioleta en el proceso de curado de la resina a poli merizar. Method of applying luminous pigments to natural stones, according to claim 1, characterized by using ultraviolet lamps in the curing process of the resin to be polymerized.
3. 3.
Procedimiento de de aplicación de pigmentos luminosos a piedras naturales según reivindicación 1, caracterizado por la incorporación de pigmentos autolumínicos en la resina para rellenar huecos o figuras creadas artificialmente sobre la piedra natural por medios químicos, por ejemplo ataque de ácido, o por medios mecánicos, por ejemplo ataque por fresas. Method of applying luminous pigments to natural stones according to claim 1, characterized by the incorporation of autoluminal pigments in the resin to fill holes or artificially created figures on the natural stone by chemical means, for example acid attack, or by mechanical means, for example strawberry attack.
4. Four.
Procedimiento de de aplicación de pigmentos luminosos a piedras naturales según reivindicación 1, caracterizado por introducir el pigmento luminoso en la resina para pegado de piedras naturales, formando un sándwich, útiles sobre todo en caso de usar materiales con propiedades de transparencia, para su uso en elementos de iluminación, por ejemplo ónix o alabastro. Procedure for applying luminous pigments to natural stones according to claim 1, characterized by introducing the luminous pigment into the resin for bonding natural stones, forming a sandwich, useful especially in case of using materials with transparency properties, for use in lighting elements, for example onyx or alabaster.
ES201300164A 2013-02-07 2013-02-07 Use of luminous pigments in natural stone materials by adding these in the resins, commonly used, in the natural stone industry Expired - Fee Related ES2484591B1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2360039A (en) * 2000-03-07 2001-09-12 Magicmatch Ltd Filler compound
ES2282035A1 (en) * 2006-03-06 2007-10-01 Aidico, Asociacion De Industrias De La Construccion Instituto Tecnologico Epoxy and unsaturated polyester adhesives in aqueous emulsion for consolidating natural stones
DE102007055280A1 (en) * 2007-05-12 2008-11-13 Süleyman, Aydin Joint filling composition, e.g. for grouting between floor tiles, contains components providing phosphorescent pathway marking effect visible in the dark

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2360039A (en) * 2000-03-07 2001-09-12 Magicmatch Ltd Filler compound
ES2282035A1 (en) * 2006-03-06 2007-10-01 Aidico, Asociacion De Industrias De La Construccion Instituto Tecnologico Epoxy and unsaturated polyester adhesives in aqueous emulsion for consolidating natural stones
DE102007055280A1 (en) * 2007-05-12 2008-11-13 Süleyman, Aydin Joint filling composition, e.g. for grouting between floor tiles, contains components providing phosphorescent pathway marking effect visible in the dark

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BASE DE DATOS WPI EN EPOQUE, AN 2009-B51157, KR20080016211 (HANWHA L & CORP), 21.02.2008, resumen *

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