ES2471691A1

ES2471691A1 - Curing hardened polymer paste with stoned base (Machine-translation by Google Translate, not legally binding)

Info

Publication number: ES2471691A1
Application number: ES201232010A
Authority: ES
Inventors: Alfonso Jos� CORTES IZURDIAGA; Mar�a Sonia FLORES RODR�GUEZ; Francisco Javier CARO HIDALGO; Mar�a Lourdes S�NCHEZ BAJO
Original assignee: Fundacion Centro Tecnologico Andaluz de La Piedra
Current assignee: Fundacion Centro Tecnologico Andaluz de La Piedra
Priority date: 2012-12-21
Filing date: 2012-12-21
Publication date: 2014-06-26
Anticipated expiration: 2032-12-21
Also published as: ES2471691B1

Abstract

Curing hardened polymer paste with stoned base. The object of the present invention is related to the formulation of a hardenable thixotropic paste composed of aggregates, other inorganic fillers and a polymeric binder. The thixotropic properties will be induced through additives included in the formulation of the polymer that will act as a binder. Since aggregates, including calcium carbonate, do not have plastic properties and their liquid solutions are not thixotropic, it is a technological challenge to artificially contribute thixotropy through specific polymer formulations and additives, so that a new stone can be generated plastic. The main innovation of the sturdy polymer paste with stone base derives from the large number of manufacturing processes and products that are applicable. Many limitations of form can be overcome, so that the possibilities of obtaining special volumes are enormous. In addition, the stony polymeric paste will open the field to manufacturing processes in which neither natural nor artificial stone has been able to enter, such as extrusion or forming of complex volumes. (Machine-translation by Google Translate, not legally binding)

Description

PASTA POLIM�RICA ENDURECIBLE CON BASE P�TREA HARMFUL POLYMER PASTE WITH BASE PENDAR

CAMPO TÉCNICO TECHNICAL FIELD

El objeto de la presente invención, tal y como se expresa en el enunciado de esta memoria descriptiva, est� relacionado con la formulación de una pasta tixotr�pica endurecible compuesta por áridos, otras cargas inorgánicas y un ligante polim�rico. Las propiedades tixotr�picas estarán inducidas a través de aditivos incluidos en la propia formulación del pol�mero que actuar� como ligante. The object of the present invention, as expressed in the statement of this specification, is related to the formulation of a hardenable thixotropic paste composed of aggregates, other inorganic fillers and a polymeric binder. The thixotropic properties will be induced through additives included in the formulation of the polymer itself that will act as a binder.

ANTECEDENTES DE LA INVENCIÓN BACKGROUND OF THE INVENTION

La evolución de la Ciencia de los Materiales ha sido sorprendente en los últimos años. Se han desarrollado nuevos materiales y aplicaciones que en un pasado reciente eran completamente impensables. El avance en el conocimiento de los pol�meros ha sido una de las bases fundamentales para esto. Como respuesta a este entorno, la tradicional industria de la piedra se encuentra ahora en la transición hacia una ‘piedra del futuro’, una piedra competitiva frente a otros materiales, que conserva su carácter emblemático pero añade valores tecnológicos y sensoriales completamente nuevos. The evolution of Materials Science has been surprising in recent years. New materials and applications have been developed that in the recent past were completely unthinkable. The advance in the knowledge of polymers has been one of the fundamental bases for this. In response to this environment, the traditional stone industry is now in the transition to a ‘stone of the future’, a competitive stone against other materials, which retains its emblematic character but adds completely new technological and sensory values.

En el mercado actual existe una amplia gama de materiales artificiales que contienen triturado o micronizado de piedra natural como su principal materia prima y que se han impuesto en el mercado en los últimos años a través de aplicaciones específicas, siendo el referente el caso de las encimeras de cocina. Estos materiales se conocen de manera genérica como piedra aglomerada, ya que est�n compuestos por un porcentaje mayoritario de piedra pulverulenta y una cantidad minoritaria de pol�mero que actúa como ligante. La piedra aglomerada presenta la ventaja frente a la piedra natural de poder ser fabricada en planchas, o bloques que posteriormente se cortan en planchas, del tamaño y color deseados, as� como con unas propiedades más adecuadas para el uso comercial general. In the current market there is a wide range of artificial materials that contain crushed or micronized natural stone as their main raw material and that have been imposed on the market in recent years through specific applications, being the case the countertops Cooking These materials are generically known as agglomerated stone, since they are composed of a majority percentage of pulverulent stone and a minor amount of polymer that acts as a binder. The agglomerated stone has the advantage over the natural stone of being able to be manufactured in plates, or blocks that are subsequently cut into plates, of the desired size and color, as well as with properties more suitable for general commercial use.

Sin embargo, no todos los procesos de fabricación, tales como extrusi�n However, not all manufacturing processes, such as extrusion

o conformado, son aplicables en su elaboración. Esto es debido fundamentalmente a que las masas con la piedra triturada y los pol�meros no tienen propiedades plásticas. Materiales como las arcillas s� disponen de este tipo de propiedades de manera natural, de modo que una vez mezcladas con agua pueden modelarse con facilidad y mantienen su forma tras un proceso de cocción. Aplica, en este caso, una propiedad denominada tixotrop�a, que supone que una masa fluida es capaz de disminuir su viscosidad y fluir bajo esfuerzos de cizalla y, una vez cesados estos esfuerzos, dejar de fluir y conservar su forma. La tixotrop�a aparece en productos tan cotidianos como la pasta de dientes. or conformed, they are applicable in its elaboration. This is mainly due to the fact that the masses with the crushed stone and the polymers have no plastic properties. Materials such as clays do have these types of properties naturally, so that once mixed with water they can be easily modeled and maintain their shape after a cooking process. It applies, in this case, a property called thixotropy, which assumes that a fluid mass is able to decrease its viscosity and flow under shear stresses and, once these efforts have ceased, stop flowing and retain its shape. Thixotropy appears in everyday products such as toothpaste.

Puesto que los áridos, entre ellos el carbonato cálcico, no poseen propiedades plásticas y sus disoluciones líquidas no son tixotr�picas, se plantea como reto tecnológico el aportar artificialmente la tixotrop�a a través de formulaciones específicas de pol�mero y aditivos, de modo que pueda generarse una nueva piedra plástica. Since aggregates, including calcium carbonate, do not have plastic properties and their liquid solutions are not thixotropic, it is considered as a technological challenge to artificially contribute thixotropy through specific polymer formulations and additives, so that a new plastic stone can be generated.

Existe una oportunidad de innovación total en el desarrollo de la piedra plástica, sobre todo derivada de la gran cantidad de procesos de fabricación y productos que sería posible aplicar. Cualquier limitación de forma se superaría, de modo que las posibilidades de obtener volúmenes especiales con la nueva piedra plástica serían infinitas. As�, la principal ventaja de la Piedra Plástica ser� que abrir� el campo a procesos de fabricación en los que la piedra ni natural ni artificial ha podido entrar, aportando dos grandes ventajas técnicas: por un lado la fabricación de productos con ilimitadas formas y, por otro lado, la capacidad de contemplar procesos de fabricación más económicos que permitan producir a costes mucho menores que en la actualidad. There is an opportunity for total innovation in the development of plastic stone, especially derived from the large number of manufacturing processes and products that would be possible to apply. Any limitation of form would be overcome, so that the possibilities of obtaining special volumes with the new plastic stone would be endless. Thus, the main advantage of the Plastic Stone will be that it will open the field to manufacturing processes in which the natural or artificial stone has been able to enter, providing two great technical advantages: on the one hand the manufacture of products with unlimited forms and, on the other hand, the ability to contemplate cheaper manufacturing processes that allow them to produce at much lower costs than at present.

DESCRIPCI�N DE LA INVENCIÓN DESCRIPTION OF THE INVENTION

La presente invención se refiere a la formulación de una pasta tixotr�pica endurecible compuesta por áridos, otras cargas inorgánicas y un ligante polim�rico debidamente acondicionado. The present invention relates to the formulation of a hardenable thixotropic paste composed of aggregates, other inorganic fillers and a properly conditioned polymeric binder.

Los áridos y las cargas inorgánicas pueden ser sólidos de distinta naturaleza y granulometr�a. En función de la curva granulom�trica de la mezcla de sólidos con la que se quiera elaborar la pasta, ser� necesario adicionar una mayor o menor cantidad de ligante polim�rico. Las proporciones de áridos inorgánicos en la pasta polim�rica endurecible con base p�trea pueden oscilar entre 65 y 95% en peso. Aggregates and inorganic fillers can be solids of different nature and granulometry. Depending on the granulometric curve of the solids mixture with which the paste is to be made, it will be necessary to add a greater or lesser amount of polymeric binder. The proportions of inorganic aggregates in the hardenable polymer paste with a stone base can range between 65 and 95% by weight.

El ligante polim�rico es una resina termoestable líquida, como por ejemplo poli�ster, epoxy o poliuretano. Este tipo de resinas tienen la característica de que endurecen por reacción química cuando se las mezcla con un reactivo adecuado (denominado genéricamente como endurecedor). Las proporciones de ligante polim�rico en la pasta polim�rica endurecible con base p�trea pueden oscilar entre 10 y 35% en peso. The polymeric binder is a liquid thermosetting resin, such as polyester, epoxy or polyurethane. These types of resins have the characteristic that they harden by chemical reaction when mixed with a suitable reagent (generically referred to as a hardener). The proportions of polymeric binder in the hardenable polymeric paste with a stone base can range between 10 and 35% by weight.

Las propiedades tixotr�picas est�n inducidas a través de aditivos denominados agentes tixotropantes incluidos en la propia formulación del ligante. Los agentes tixotropantes est�n constituidos por partículas extremadamente pequeñas (sílice, arcillas organof�licas, etc.) con alta tendencia a flocular, originando un alto retículo tridimensional en la disolución a la que se adicionan aumentando considerablemente la viscosidad. Esta estructura flocular es fácilmente rompible por altas tasas de cizallamiento, sin bien, cuando ceden estas tasas de cizallamiento vuelven a aparecer las interacciones entre las partículas, de modo que la disolución alcanza de nuevo su consistencia. Las proporciones de agentes tixotropantes en la pasta polim�rica endurecible con base p�trea pueden oscilar entre 0,1 y 2% en peso. The thixotropic properties are induced through additives called thixotropic agents included in the binder formulation itself. The thixotropants are made up of extremely small particles (silica, organophilic clays, etc.) with a high tendency to flocculate, causing a high three-dimensional lattice in the solution to which they are added, considerably increasing the viscosity. This flocular structure is easily breakable by high shear rates, however, when these shear rates yield, the interactions between the particles reappear, so that the solution reaches its consistency again. The proportions of thixotropic agents in the hardened polymeric paste with a stone base can range between 0.1 and 2% by weight.

La formulación del ligante polim�rico también considera la inclusión de aditivos en pequeñas proporciones que puedan mejorar las interacciones entre los otros componentes, fundamentalmente entre los áridos de naturaleza inorgánica y el ligante de naturaleza orgánica. Estos aditivos son denominados genéricamente como agentes de acoplamiento y son compuestos de tipo organomet�lico. Las proporciones de agentes de acoplamiento, o aditivos para mejorar las interacciones entre la mezcla de áridos y el ligante polim�rico, en la pasta polim�rica endurecible con base p�trea pueden oscilar entre 0 y 2% en peso. The polymeric binder formulation also considers the inclusion of additives in small proportions that can improve interactions between the other components, primarily between aggregates of inorganic nature and the binder of organic nature. These additives are generically referred to as coupling agents and are organomethyl type compounds. The proportions of coupling agents, or additives to improve the interactions between the mixture of aggregates and the polymeric binder, in the hardenable polymeric paste with a stone base can range between 0 and 2% by weight.

Los pasos para obtener la pasta polim�rica en base p�trea son los siguientes: The steps to obtain the polymeric paste in stone base are the following:

--: Inicialmente se prepara el ligante polim�rico, adicion�ndole el agente tixotr�pico en una proporción establecida y bajo unas condiciones de agitaci�n apropiadas. Tanto el tipo de agente tixotr�pico como su cantidad con respecto al ligante polim�rico se seleccionan en base a las propiedades finales fluidas que se deseen obtener en la pasta polim�rica. Existe una gran variedad de agentes tixotr�picos comerciales, que se diferencian en las condiciones de mezcla y en las propiedades finales que son capaces de aportar al fluido. Mediante la agitaci�n se consigue que el ligante adquiera las propiedades fluido dinámicas deseadas. Initially, the polymeric binder is prepared, adding the thixotropic agent in an established proportion and under appropriate agitation conditions. Both the type of thixotropic agent and its amount with respect to the polymeric binder are selected based on the fluid final properties that are desired to be obtained in the polymer paste. There is a great variety of commercial thixotropic agents, which differ in the mixing conditions and in the final properties that are capable of contributing to the fluid. By agitation, the binder is able to acquire the desired dynamic fluid properties.

--: En un segundo paso, se adicionan al ligante los agentes de acoplamiento y los aditivos que se considere necesarios. Una parafina, por ejemplo, puede ser interesante para evitar el desprendimiento de volátiles. In a second step, coupling agents and additives deemed necessary are added to the binder. A paraffin, for example, may be interesting to prevent the release of volatiles.

--: En el tercer paso, al ligante polim�rico elaborado en los pasos 5 anteriores se le añade el agente endurecedor en las proporciones adecuadas. In the third step, the hardening agent is added in the appropriate proportions to the polymeric binder made in steps 5 above.

--: Finalmente, puede adicionarse el ligante ya preparado a la mezcla de áridos. Es recomendable hacerlo de este modo y no al revés (adicionar la mezcla de áridos sobre el ligante polim�rico). Es preferible que este paso se haga poco a poco y agitando, de modo que la mezcla vaya tomando Finally, the binder already prepared can be added to the aggregate mixture. It is advisable to do it this way and not vice versa (add the mixture of aggregates on the polymeric binder). It is preferable that this step is done little by little and stirring, so that the mixture is taken

10 consistencia paulatinamente. Se trata de una operación muy similar al amasado que se realiza en panadería. La pasta as� preparada puede posteriormente modelarse a mano, o bien, elaborarse a través de un proceso industrial de deformación plástica (extrusi�n, conformado, etc.). 10 consistency gradually. It is an operation very similar to the kneading that is done in bakery. The paste thus prepared can then be modeled by hand, or it can be made through an industrial process of plastic deformation (extrusion, forming, etc.).

15 Una vez realizado el conformado, la pasta polim�rica endurecer� por reacción química del ligante polim�rico con su endurecedor. Puede acelerarse este proceso de endurecido si se aplica una temperatura superior a la ambiental. 15 After forming, the polymeric paste will harden by chemical reaction of the polymeric binder with its hardener. This hardening process can be accelerated if a temperature higher than the ambient temperature is applied.

Claims

1�.- Polymeric paste in stone base, which allows to create suspensions with plastic characteristics from any type of aggregates and other inorganic charges 5 regardless of their nature, characterized in that

It has the following composition (weight percent):

--: Mezcla de áridos inorgánicos de distinta naturaleza y granulometr�a: 65–95%. Mixture of inorganic aggregates of different nature and granulometry: 65–95%.

--: Ligante polim�rico, consistente en una resina líquida termoestable, o 10 producto similar que endurece por reacción química: 10-35%. Polymeric binder, consisting of a thermosetting liquid resin, or similar product that hardens by chemical reaction: 10-35%.

--: Agente tixotropante: 0,1-2%. Thixotropic agent: 0.1-2%.

--: Agente de acoplamiento, o aditivo en pequeñas proporciones para mejorar las interacciones entre la mezcla de áridos y el ligante polim�rico: 02%. Coupling agent, or additive in small proportions to improve interactions between the aggregate mixture and the polymeric binder: 02%.

2�.-Any product obtained by modeling and subsequent hardening of a composition according to claim 1.

SPANISH OFFICE OF THE PATENTS AND BRAND

Application No.: 201232010

SPAIN

Date of submission of the application: 21.12.2012

Priority Date:

REPORT ON THE STATE OF THE TECHNIQUE

51 Int. Cl.: C04B26 / 10 (2006.01)

RELEVANT DOCUMENTS

Categor�a Category: 56 Documentos citados Reivindicaciones afectadas 56 Documents cited Claims Affected

X X: WO 2004043873 A1 (UNIV SOUTHERN QUEENSLAND et al.) 27.05.2004, 1,2 WO 2004043873 A1 (UNIV SOUTHERN QUEENSLAND et al.) 27.05.2004, 1.2

p�gina 3, línea 10 – página 4, línea 16; página 7, líneas 21-26. page 3, line 10 - page 4, line 16; page 7, lines 21-26.

X X: GB 2237578 A (DART IND INC) 08.05.1991, 1,2 GB 2237578 A (DART IND INC) 08.05.1991, 1.2

p�gina 2, líneas 10-27; página 19, líneas 18-23; ejemplos. page 2, lines 10-27; page 19, lines 18-23; examples.

X X: EP 1447198 A2 (OPERA LAB FIORENTINI S P A) 18.08.2004, 1,2 EP 1447198 A2 (OPERA LAB FIORENTINI S P A) 18.08.2004, 1.2

p�rrafo [0033]. paragraph [0033].

X X: WO 2005014256 A1 (COSENTINO SA et al.) 17.02.2005, 1,2 WO 2005014256 A1 (COSENTINO SA et al.) 02.17.2005, 1.2

p�rrafos [0014],[0020]-[0022],[0024]. paragraphs [0014], [0020] - [0022], [0024].

Categor�a de los documentos citados X: de particular relevancia Y: de particular relevancia combinado con otro/s de la misma categoría A: refleja el estado de la técnica O: referido a divulgación no escrita P: publicado entre la fecha de prioridad y la de presentación de la solicitud E: documento anterior, pero publicado después de la fecha de presentación de la solicitud Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the submission of the application E: previous document, but published after the date of submission of the application

El presente informe ha sido realizado • para todas las reivindicaciones • para las reivindicaciones n�: This report has been prepared • for all claims • for claims no:

Fecha de realización del informe 19.03.2014 Date of realization of the report 19.03.2014: Examinador M. C. Bautista Sanz Página 1/4 Examiner M. C. Bautista Sanz Page 1/4

REPORT OF THE STATE OF THE TECHNIQUE

Application number: 201232010

Minimum documentation sought (classification system followed by classification symbols) C04B Electronic databases consulted during the search (name of the database and, if possible, terms of

search used) INVENES, EPODOC, WPI, BD Full text (WO, EP, US, GB, AU, CA)

State of the Art Report Page 2/4

WRITTEN OPINION

Application number: 201232010

Date of Completion of Written Opinion: 03.19.2014

Declaraci�n Statement

Novedad (Art. 6.1 LP 11/1986) Novelty (Art. 6.1 LP 11/1986): Reivindicaciones Reivindicaciones 1,2 SI NO Claims Claims 1.2 IF NOT

Actividad inventiva (Art. 8.1 LP11/1986) Inventive activity (Art. 8.1 LP11 / 1986): Reivindicaciones Reivindicaciones 1,2 SI NO Claims Claims 1.2 IF NOT

The application is considered to comply with the industrial application requirement. This requirement was evaluated during the formal and technical examination phase of the application (Article 31.2 Law 11/1986).

Opinion Base.-

This opinion has been made on the basis of the patent application as published.

State of the Art Report Page 3/4

WRITTEN OPINION

Application number: 201232010

1. Documents considered.-

The documents belonging to the state of the art taken into consideration for the realization of this opinion are listed below.

Documento Document: Número Publicación o Identificación Fecha Publicación Publication or Identification Number publication date

D01 D01: WO 2004043873 A1 (UNIV SOUTHERN QUEENSLAND et al.) 27.05.2004 WO 2004043873 A1 (UNIV SOUTHERN QUEENSLAND et al.) 05/27/2004

D02 D02: GB 2237578 A (DART IND INC) 08.05.1991 GB 2237578 A (DART IND INC) 08.05.1991

D03 D03: EP 1447198 A2 (OPERA LAB FIORENTINI S P A) 18.08.2004 EP 1447198 A2 (OPERA LAB FIORENTINI S P A) 18.08.2004

D04 D04: WO 2005014256 A1 (COSENTINO SA et al.) 17.02.2005 WO 2005014256 A1 (COSENTINO SA et al.) 02.17.2005

2. Statement motivated according to articles 29.6 and 29.7 of the Regulations for the execution of Law 11/1986, of March 20, on Patents on novelty and inventive activity; quotes and explanations in support of this statement

The object of the invention is a polymeric paste of stone base formed by inorganic aggregates in a majority proportion (65-95%), a polymeric binder (10-35%) and a thixotropic agent (0, 1-2%) to increase the fluidity of the dough and improve the product obtained from it (artificial stones).

Document D01 discloses a stone-based formulation formed by a resin of the polyester, epoxy or polyurethane type in a percentage between 25 and 30%, light inorganic aggregates (20-25%) and heavy (40-60 %) as well as a thixotropic agent (pyrogenic silica) in a proportion of 0.5 to 1% (page 3, line 10-page 4, line 16). The thixotropic agent is added to keep the light aggregates in suspension with the resin and thus achieve a homogeneous distribution within what is known as "polymer concrete" (page 7, lines 21-26).

Document D02 discloses an artificial stone molding composition, simulating marble, onyx or granite, which is formed by a polyester resin (10-25%), inorganic fillers (alumina, calcium carbonate, calcium sulfate, etc. . (5080%), a thixotropic agent (organo-clay, pyrogenic silica) in small quantities (0.35%, 0.60%) and an ethnically unsaturated monomer (10-25%) (page 2, lines 10-27; page 19, lines 18-23; Examples).

Documents D03 and D04 disclose stone-based polymer compositions to obtain products that look like stone or rock consisting of inorganic aggregates in a majority proportion and a polymeric binder (polyester in D03, polyester, epoxy or polyurethane, among others in D04) with small proportions of a thixotropic agent (pyrogenic silica or clays). See D03: paragraph [0033] and D04: paragraphs [0014], [0020] - [0022], [0024].

In view of what is disclosed in documents D01 to D04 independently considered, the invention, as defined, in claims 1 and 2 does not meet the requirement of novelty (Art. 6.1. Law 11/1986 on Patents).

State of the Art Report Page 4/4