WO2006092450A1 - Acrylate-based polymeric composition for coating architectural surfaces, which has been improved with the inclusion of suitable solvents - Google Patents

Acrylate-based polymeric composition for coating architectural surfaces, which has been improved with the inclusion of suitable solvents Download PDF

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Publication number
WO2006092450A1
WO2006092450A1 PCT/ES2005/000089 ES2005000089W WO2006092450A1 WO 2006092450 A1 WO2006092450 A1 WO 2006092450A1 ES 2005000089 W ES2005000089 W ES 2005000089W WO 2006092450 A1 WO2006092450 A1 WO 2006092450A1
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WIPO (PCT)
Prior art keywords
composition according
composition
weight
acrylate
ethyl
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Application number
PCT/ES2005/000089
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Spanish (es)
French (fr)
Inventor
Juan CARDA CASTELLÓ
Manuel Llavata Gimeno
Original Assignee
Mediterranea De Investigacion Cientifica, S.L.
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Priority to PCT/ES2005/000089 priority Critical patent/WO2006092450A1/en
Publication of WO2006092450A1 publication Critical patent/WO2006092450A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating 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
    • C04B41/48—Macromolecular compounds
    • C04B41/483—Polyacrylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • Polymeric acrylate-based composition for improved architectural surface coating by including suitable solvents are suitable solvents.
  • the present invention relates to a composition for the protection of architectural substrates comprising acrylic derivatives and a mixture of solvents which allows the application of said composition at the construction site.
  • Patent DE 111690 (25.03.96) of Bernd Neumann "Coating a protective layer for hard surfaces against atmospheric corrosion, mechanical stresses and chemical products, preparation and use procedure” is related to a coating of a protective layer or an impregnation for hard surfaces, especially lacquered surfaces of stone, ceramics, glass, metal, wood and plastic, as protection against atmospheric corrosion, stresses mechanical or chemical products applied, as well as to facilitate the elimination of possible stains or unwanted paints (graffiti) in impregnations or protective coatings.
  • These protective coatings or impregnations are composed of an active principle consisting of at least one natural and / or synthetic wax, at least one polymer or precursor and optionally pyrogenic silicic acid, a liquid carrier consisting of at least one organic liquid and / or water and optionally one or more conventional additives from the group of surfactants, levelers, dispersers, emulsifiers, stabilizers, protective colloids, fillers, flavorings, preservatives, dermal protectors, matting agents, pigments, dyes and / or color shades .
  • Penetration treatment for porous substrates describes a penetrating treatment composition, which contains high levels of one or more acrylate or alkyl methacrylate monomers of long chain together with one or several self-oxidizing compounds that function as initiators of the polymerization and one or several metal dryers that can communicate long-term hydrorepelence to the porous substrates.
  • Suitable alkyl acrylates and methacrylates include decyl acrylate and methacrylate, lauryl acrylate and methacrylate, stearyl acrylate and methacrylate, lauryl and stearyl acrylate and methacrylate, dodecyl and pentadelate acrylate and methacrylate, and similar cetyl and eicosyl methacrylate and mixtures thereof.
  • JW Knapczyk in Journal of Coating Tecnoloy, 60 (756), 63 72, 1988, describes the formation of films, among others pentaerythritol triacrylate and hexanediol diacrylate.
  • Patent DE 4021502 (05.07.90) by Bernhard Dotzauer et al. To Basf Aktiengesellschaft "Concrete stone covered with copolymer films” describes the way in which a concrete stone is coated in a simple way and that it becomes very dirty at high temperature; In addition, the coating has to develop its effect as quickly as possible. For this, it uses a copolymer formed by an acrylic ester of alkanols with 1 to 8 carbon atoms, methacrylic ester of alkanols with 1 to 8 carbon atoms and / or vinylaromatic monomers (preferably at least two monomers).
  • Non-removable dirt resistant coatings describes a sealant coating to permanently protect the flooring material, which can be applied during The manufacture or preparation of the dirt-resistant architectural substrate, particularly hydrophobic fouling agents, and que_prppqrcjona.a brjllo raised to the architectural substrate.
  • the sealer coating composition comprising a polymer comprising, (a) 20% or less by weight of (meth) acrylate whose homopolymers have a glass transition temperature less than 20 0 C; (b) styrene; (c) methyl methacrylate; and (d) an ethylenically unsaturated carboxylic acid.
  • a process for permanently sealing a substrate comprising coating the substrate with a sealant coating composition.
  • Patent DE 4310005 (27.03.93) "Stabilization and protective impregnation of polymer solution for porous construction materials" of Dr. Maurizio Ragnetti and others for Degussa Aktiengesellschaft, claims the protection of construction materials by means of compounds that should allow impregnation with high penetration depth and a hydrophobic function, specifically a prepolymer based on an (meth) acrylic ester, of an ethylenically unsaturated monomer, which carries an epoxy function, and possibly of an ethylenically unsaturated alkoxysilane group, where the (meth) acrylic ester from 48 to 98% by weight and the epoxy monomer from 0.5 to 50% by weight.
  • composition for the protection against stains of polished ceramic tiles of stoneware and other similar architectural substrates comprising: (a) a liquid polymer obtained by polymerization of a mixture containing hexanediol diacrylate and tri / Pentaerythritol tetraacrylate or its derivatives, (b) an acrylic monomer such as ethyl acrylate and, optionally, (c) a photoinitiator such as benzophenone, using an aliphatic alcoholic acid such as methanol as solvent of the mixture.
  • Said composition has the disadvantage that the evaporation of the solvent is too fast.
  • the present invention aims to overcome the problems associated with the techniques currently in use by seeking to provide a coating composition that can be applied to the architectural substrate in the same place where the work is performed, which is permanent and resistant to dirt, particularly to the agents hydrophobic foulers. It is also an object of the present invention to provide a method for providing an improved resistance against dirt to an architectural substrate.
  • the present invention relates to a composition for the protection against stains of architectural surfaces comprising: a) between 18 and 30% by weight of a liquid polymer obtained by polymerization of an acrylate; and b) between 1 and 20% by weight of an acrylic monomer; characterized in that it comprises between 60 and 80% by weight of a solvent that is selected from the group consisting of a linear aliphatic hydrocarbon of between 5 and 8 carbon atoms, a compound of formula I
  • R 1 COR 2 wherein R 1 and R 2 are each independently methyl, ethyl or propyl; a compound of formula Il
  • surface means any porous surface preferably used terrazzo, marble, a natural stone, brick, pavers, concrete, crockery or porcelain.
  • stain protection refers to the ability of a material to prevent permanent discoloration by the usual domestic and industrial agents and whose discolorations are not removable by conventional cleaning techniques or treatment with water-based cleaning agents or in organic solvents
  • the strongest fouling agents include coal asphalt / tar, shoe polish, mustard, ketchup, coffee, lipstick, tobacco and other types of cigarettes, neozone, chocolate syrup and the like.
  • Coal tar / tar is the most intense of these fouling agents.
  • the resistance to fouling by asphalt / coal tar is usually indicative of the resistance to fouling by other less intense fouling agents. [Standard UNE-EN ISO10545-13. 5501033, "Stain resistance (ceramic tiles)"].
  • the compounds used as solvents are selected from the group consisting of hexane, 2-butanone, ethylene glycol acetate, ethyl glycol, propylene glycol or mixtures thereof.
  • said liquid polymer (a) is that obtained by polymerization of an acrylate that is selected from the group formed by the pentaerythritol tri / tetraacrylate (PETIA):
  • R 2 CH 2 (CH 2 J- (CH 2 R 2 where R 1 represents H or the acrylate or methacrylate radial: CH 2 CHOOO OR CH 2 C (CH 3 ) COO and R 2 represents the acrylate or methacrylate radial:
  • the tri / tetraacrylate ratio of hexanediol pentaerythritokdiacrylate preferably ranges between 40:60 by weight and 60:40 by weight.
  • the polymer can be substituted by the one commercially available from the firm CHEMICALS (UCB Qu ⁇ mica Ibérica, S.A.) under the registered trademark UVERCRYL® 29203.
  • said acrylic monomer is an alkyl diacrylate, preferably - • ethyl diacrylate;
  • the composition may comprise a surface additive, preferably polyester-modified polydimethyloxy copolymer; an antifoam, preferably alkylbenzene modified with methoxypropyl acetate; a photoinitiator, preferably benzophenone, isopropylthioxanthone or mixtures thereof.
  • a surface additive preferably polyester-modified polydimethyloxy copolymer
  • an antifoam preferably alkylbenzene modified with methoxypropyl acetate
  • a photoinitiator preferably benzophenone, isopropylthioxanthone or mixtures thereof.
  • the proportion of said surface additive is between 0.01 and 0.3% by weight with respect to the total weight of the composition.
  • the proportion of said antifoam is between 0.01 and 1.5% by weight with respect to the total weight of the composition.
  • the proportion of said photoinitiator is between 0.1 and 3% by weight with respect to the total weight of the composition.
  • the present invention relates to a method for permanently sealing an architectural surface, preferably in the same place where the architectural surface is installed, which comprises the following correlative steps:
  • the process according to the present invention does not require a stage of elimination of the residual polymer, since the longer evaporation time of the product allows the total in situ absorption of the composition.
  • the present invention relates to the use of a composition Ia protection of an architectural surface against stains.
  • said surface is terrazzo, marble, a natural stone, brick, pavers, concrete, earthenware or porcelain
  • mixtures according to the present invention have a much longer evaporation time than those of known products (mixture 1) allowing their application on very porous or irregular surfaces, without losing efficiency in the final result. It also allows its direct application on site, since there is sufficient time between the application of the composition and the evaporation of the solvent so that the composition is completely absorbed and a homogeneous protective layer is formed along the entire surface.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to a protective coating composition for architectural surfaces, such as terrazzo, marble, natural stone, brick, paving stones, concrete, earthenware or porcelain, which seals the surface pores of said surfaces and renders same resistant to dirt. The inventive composition comprises a liquid polymer which is obtained by polymerisation of a mixture containing hexanediol diacrylate and pentaerytritol tri/tetraacrylate or the derivatives thereof, an acrylic monomer (ethyl diacrylate) and a solvent or a mixture of same, with a longer evaporation time than known products, such that the composition is absorbed completely and forms a uniform protective layer over the entire surface. Suitable solvents include hexane, 2-butanone, acetate of ethylene glycol, ethyl glycol, propylene glycol or mixtures thereof. The sealing method comprises the application of the composition, followed by exposure to ultraviolet radiation. The use of the above-mentioned solvents in the composition dispenses with the need for a step comprising the elimination of any residual polymer from the surface to be treated.

Description

Composición polimérica a base de acrilatos para el recubrimiento de superficies arquitectónicas mejorada mediante la inclusión de disolventes adecuados.Polymeric acrylate-based composition for improved architectural surface coating by including suitable solvents.
Campo de Ia técnicaField of the technique
La presente invención se refiere a una composición para Ia protección sustratos arquitectónicos que comprende derivados acrílicos y una mezcla de disolventes Ia cual permite Ia aplicación de dicha composición en el lugar de construcción.The present invention relates to a composition for the protection of architectural substrates comprising acrylic derivatives and a mixture of solvents which allows the application of said composition at the construction site.
IntroducciónIntroduction
En Ia actualidad existe Ia necesidad de un producto para Ia protección de superficies arquitectónicas contra las manchas, apto para su aplicación en el mismo lugar de construcción.At present there is a need for a product for the protection of architectural surfaces against stains, suitable for application in the same place of construction.
Para evitar el ensuciamiento de las superficies, existen hasta ahora soluciones que pasan por aplicar una serie de productos, generalmente de naturaleza orgánica, después de que Ia pieza es cocida y pulida, permitiendo el cubrir los poros abiertos por dichos productos.To avoid dirtying the surfaces, there are so far solutions that apply to apply a series of products, usually of an organic nature, after the piece is cooked and polished, allowing the pores opened by said products to be covered.
La naturaleza de estos productos suele ser ceras, parafinas, siliconas, etc., los cuales precisan un mantenimiento posterior, ya que sufren un proceso de degradación con el tiempo, requiriendo este mantenimiento el de sucesivas aplicaciones al cabo de intervalos de tiempo de unos seis meses como máximo. Además, el grado de efectividad de Ia protección contra las manchas no Io es al 100% con los productos " "que séf aplican" hasta ahoraTAdicionalmente, muchos de estos productos se aplican en las cadenas de producción de las superficies, bien sean cerámica, piedra, mármol u otro tipo de superficie.The nature of these products is usually waxes, paraffins, silicones, etc., which require subsequent maintenance, since they undergo a degradation process over time, requiring this maintenance that of successive applications after time intervals of about six maximum months In addition, the degree of effectiveness of the protection against stains is not 100% with the products "" that apply " until now. Traditionally, many of these products are applied in the production chains of the surfaces, whether ceramic, stone , marble or other type of surface.
Estado de Ia técnica La patente DE 111690 (25.03.96) de Bernd Neumann "Recubrimiento de una capa protectora para superficies duras contra Ia corrosión atmosférica, los esfuerzos mecánicos y los productos químicos, procedimiento de preparación y utilización" esta relacionada con un recubrimiento de una capa protectora o una impregnación para superficies duras, en especial superficies lacadas de piedra, cerámica, vidrio, metal, madera y plástico, como protección frente a Ia corrosión atmosférica, los esfuerzos mecánicos o los productos químicos aplicados, así como para facilitar Ia eliminación de posibles manchas o pinturas indeseadas (graffiti) en las impregnaciones o recubrimientos protectores. Estos recubrimientos protectores o impregnaciones están compuestos por un principio activo que consta como mínimo de una cera natural y/o sintética, como mínimo un polímero o precursor y opcionalmente ácido silícico pirógeno, un portador liquido que consta como mínimo de un liquido orgánico y/o agua y opcionalmente uno o varios aditivos convencionales del grupo de los agentes tensioactivos, niveladores, dispersores, emulsionantes, estabilizadores, coloides protectores, agentes de relleno, aromatizantes, conservantes, protectores dérmicos, agentes de mateado, pigmentos, colorantes y/o matizantes de color.State of the art Patent DE 111690 (25.03.96) of Bernd Neumann "Coating a protective layer for hard surfaces against atmospheric corrosion, mechanical stresses and chemical products, preparation and use procedure" is related to a coating of a protective layer or an impregnation for hard surfaces, especially lacquered surfaces of stone, ceramics, glass, metal, wood and plastic, as protection against atmospheric corrosion, stresses mechanical or chemical products applied, as well as to facilitate the elimination of possible stains or unwanted paints (graffiti) in impregnations or protective coatings. These protective coatings or impregnations are composed of an active principle consisting of at least one natural and / or synthetic wax, at least one polymer or precursor and optionally pyrogenic silicic acid, a liquid carrier consisting of at least one organic liquid and / or water and optionally one or more conventional additives from the group of surfactants, levelers, dispersers, emulsifiers, stabilizers, protective colloids, fillers, flavorings, preservatives, dermal protectors, matting agents, pigments, dyes and / or color shades .
La patente US 115856 (2.11.87) de Albert Barry Smith "Proceso para tapar poros de Ia superficie de un sólido poroso" en Ia que el sólido poroso (un material tal como el mármol, travertino, piedra caliza o caliza) se somete a un tratamiento con un disolvente industrial para quitar brillo o manchas; se hace un bruñido de Ia superficie con un abrasivo tal como el diamante industrial, se enjuaga Ia superficie para extraer el detritus, se extrae el agua con una solución orgánica, se frota Ia superficie con un paño pegajoso para extraer Ia gravilla, se aplica una mezcla de poliuretano curado en humedad, p.e. de fórmula C3H7NO2 que obtura los poros, y finalmente Ia superficie tratada se seca naturalmente. La superficie sellada es resistente al agua, calor, climatología y agentes químicos y se puede aplicar a Ia piedra natural o artículos hechos de este material.US Patent 115856 (2.11.87) of Albert Barry Smith "Process for covering pores of the surface of a porous solid" in which the porous solid (a material such as marble, travertine, limestone or limestone) is subjected to a treatment with an industrial solvent to remove shine or stains; The surface is polished with an abrasive such as the industrial diamond, the surface is rinsed to extract the detritus, the water is extracted with an organic solution, the surface is rubbed with a sticky cloth to extract the gravel, a Moisture-cured polyurethane mixture, eg of formula C 3 H 7 NO 2 that clogs the pores, and finally the treated surface dries naturally. The sealed surface is resistant to water, heat, weather and chemical agents and can be applied to natural stone or articles made of this material.
La patente US 155660 (12.02.88) de Donald Bruce Larson para Rohn and Haas Company "Tratamiento de penetración para substratos porosos", describe una composición de tratamiento penetrante, que contiene altos niveles de uno o varios monómeros de acrilato o metacrilato de alquilo de cadena larga junto con uno o varios compuestos autooxidantes que funcionan como iniciadores de Ia polimerización y uno o varios secativos metálicos que puede comunicar hidrorrepelencia a largo plazo a los sustratos porosos. Entre los acrilatos y metacrilatos de alquilo adecuados están el acrilato y metacrilato de decilo, el acrilato y metacrilato de laurilo, el acrilato y metacrilato de esterarilo, el acrilato y metacrilato de laurilo y estearilo, el acrilato y metacrilato de dodecilo y pentadecilo, el acrilato y metacrilato de cetilo y eicosilo similares y sus mezclas. J.W. Knapczyk, en Journal of Coating Tecnoloy, 60(756), 63 72, 1988, describe la formación de películas, entre otros de triacrilato de pentaeritritol y de diacrilato de hexanodiol.US Patent 155660 (12.02.88) of Donald Bruce Larson for Rohn and Haas Company "Penetration treatment for porous substrates" describes a penetrating treatment composition, which contains high levels of one or more acrylate or alkyl methacrylate monomers of long chain together with one or several self-oxidizing compounds that function as initiators of the polymerization and one or several metal dryers that can communicate long-term hydrorepelence to the porous substrates. Suitable alkyl acrylates and methacrylates include decyl acrylate and methacrylate, lauryl acrylate and methacrylate, stearyl acrylate and methacrylate, lauryl and stearyl acrylate and methacrylate, dodecyl and pentadelate acrylate and methacrylate, and similar cetyl and eicosyl methacrylate and mixtures thereof. JW Knapczyk, in Journal of Coating Tecnoloy, 60 (756), 63 72, 1988, describes the formation of films, among others pentaerythritol triacrylate and hexanediol diacrylate.
La patente DE 4021502 (05.07.90) de Bernhard Dotzauer y otros para Basf Aktiengesellschaft "Piedra de hormigón recubierta de películas copolímeras", describe Ia manera de que una piedra de hormigón esté recubierta de manera sencilla y que se ensucia poco a temperatura elevada; además el recubrimiento tiene que desarrollar su efecto Io más rápidamente posible. Para ello utiliza un copolímero formado por un éster acrílico de alcanoles con 1 a 8 átomos de carbono, éster metacrílico de alcanoles con 1 a 8 átomos de carbono y/o monómeros vinilaromáticos (preferentemente al menos dos monómeros).Patent DE 4021502 (05.07.90) by Bernhard Dotzauer et al. To Basf Aktiengesellschaft "Concrete stone covered with copolymer films" describes the way in which a concrete stone is coated in a simple way and that it becomes very dirty at high temperature; In addition, the coating has to develop its effect as quickly as possible. For this, it uses a copolymer formed by an acrylic ester of alkanols with 1 to 8 carbon atoms, methacrylic ester of alkanols with 1 to 8 carbon atoms and / or vinylaromatic monomers (preferably at least two monomers).
La patente US 713717 (11.06.91) "Composiciones de revestimiento de acrilato o metacrilato que comprenden ceras" de George, W. Frost para "Minnesota Mining and Manufacturing Company", describe composiciones de acrilato o metacrilato para el revestimiento de superficies porosas, en las que Ia composición comprende entre un 90 y un 99.9% de acrilato y/o metacrilato, y entre un 0.1 y un 5% de cera. La cera en estas composiciones es soluble en los monómeros de acrilato y metacrilato cuando los monómeros se encuentran en estado liquido. La cera es incompatible con el revestimiento endurecido formado a partir de Ia polimerización de los monómeros de acrilato y/o metacrilato. Las composiciones se secan para suministrar una superficie no áspera en periodos de tiempo sorprendentemente cortos comparados con las composiciones de acrilato metacrilato, constituidas de forma similar.US 713717 (11.06.91) "Acrylate or methacrylate coating compositions comprising waxes" by George, W. Frost for "Minnesota Mining and Manufacturing Company", describes acrylate or methacrylate compositions for coating porous surfaces, in those that the composition comprises between 90 and 99.9% of acrylate and / or methacrylate, and between 0.1 and 5% of wax. The wax in these compositions is soluble in the acrylate and methacrylate monomers when the monomers are in a liquid state. The wax is incompatible with the hardened coating formed from the polymerization of the acrylate and / or methacrylate monomers. The compositions are dried to provide a non-rough surface in surprisingly short periods of time compared to similarly formed methacrylate acrylate compositions.
La-patente US 859174 (27.03.92) de Harrison Scott Killam y Karl John Hartman para Rohm and Haas Company "Recubrimientos no eliminables resistentes a Ia suciedad", describe un recubrimiento sellante para proteger permanentemente el material para suelos, que se puede aplicar durante Ia fabricación o preparación del sustrato arquitectónico resistente a Ia suciedad, particularmente a los agentes ensuciadores hidrófobos, y que_prppqrcjona.un brjllo elevado al sustrato arquitectónico. La composición de recubrimiento sellante comprende un polímero que comprende, (a) un 20% o menos en peso de monómeros de (met)acrilato cuyos homopolímeros tienen una temperatura de transición vitrea menor de 20 0C; (b) estireno; (c) metacrilato de metilo; y (d) un ácido carboxílico etilénicamente insaturado. Se proporciona un procedimiento para sellar permanentemente un sustrato que comprende recubrir el sustrato con una composición de recubrimiento sellante.US Patent 859174 (27.03.92) of Harrison Scott Killam and Karl John Hartman for Rohm and Haas Company "Non-removable dirt resistant coatings", describes a sealant coating to permanently protect the flooring material, which can be applied during The manufacture or preparation of the dirt-resistant architectural substrate, particularly hydrophobic fouling agents, and que_prppqrcjona.a brjllo raised to the architectural substrate. The sealer coating composition comprising a polymer comprising, (a) 20% or less by weight of (meth) acrylate whose homopolymers have a glass transition temperature less than 20 0 C; (b) styrene; (c) methyl methacrylate; and (d) an ethylenically unsaturated carboxylic acid. A process for permanently sealing a substrate comprising coating the substrate with a sealant coating composition.
La patente DE 4310005 (27.03.93) "Impregnación estabilizadora y protectora de solución de polímeros para materiales de construcción porosos" del Dr. Maurizio Ragnetti y otros para Degussa Aktiengesellschaft, reivindica Ia protección de materiales de construcción mediante compuestos que deben permitir una impregnación con alta profundidad de penetración y una función hidrofóbica, concretamente un prepolimero a base de un éster (met)acrílico, de un monómero no saturado etilénicamente, que porta una función epoxídica, y eventualmente de un grupo alcoxisilano no saturado etilénicamente, donde se encuentra presente el éster (met)acrílico desde 48 hasta 98% en peso y el monómero epoxídico desde 0,5 hasta 50% en peso.Patent DE 4310005 (27.03.93) "Stabilization and protective impregnation of polymer solution for porous construction materials" of Dr. Maurizio Ragnetti and others for Degussa Aktiengesellschaft, claims the protection of construction materials by means of compounds that should allow impregnation with high penetration depth and a hydrophobic function, specifically a prepolymer based on an (meth) acrylic ester, of an ethylenically unsaturated monomer, which carries an epoxy function, and possibly of an ethylenically unsaturated alkoxysilane group, where the (meth) acrylic ester from 48 to 98% by weight and the epoxy monomer from 0.5 to 50% by weight.
En Ia solicitud de patente ES200202443 se describe una composición para Ia protección contra las manchas de baldosas cerámicas pulidas de gres y otros sustratos arquitectónico similares que comprende: (a) un polímero líquido obtenido por polimerización de una mezcla que contiene diacrilato de hexanodiol y tri/tetraacrilato de pentaeritritol o sus derivados, (b) un monómero acrílico tal como el acrilato de etilo y, opcionalmente, (c) un fotoiniciador tal como Ia benzofenona, utilizando como disolvente de Ia mezcla un alcohólico alifático tal como el metanol. Dicha composición presenta Ia desventaja de que Ia evaporación del disolvente es demasiado rápida. Esto crea un serio problema en su aplicación sobre superficies muy irregulares o en su aplicación directa en obra, ya que no hay tiempo suficiente entre Ia aplicación de Ia — composición y Ia evaporación-del-disolvente-como para-que se forme una capa protectora homogénea a Io largo de toda Ia superficie. Por Io tanto, existe Ia necesidad de encontrar un disolvente que retarde el tiempo de evaporación pero que al mismo tiempo sea capaz de producir una mezcla suficientemente homogénea y estable.In the patent application ES200202443 a composition is described for the protection against stains of polished ceramic tiles of stoneware and other similar architectural substrates comprising: (a) a liquid polymer obtained by polymerization of a mixture containing hexanediol diacrylate and tri / Pentaerythritol tetraacrylate or its derivatives, (b) an acrylic monomer such as ethyl acrylate and, optionally, (c) a photoinitiator such as benzophenone, using an aliphatic alcoholic acid such as methanol as solvent of the mixture. Said composition has the disadvantage that the evaporation of the solvent is too fast. This creates a serious problem in its application on very irregular surfaces or in its direct application on site, since there is not enough time between the application of the - composition and the evaporation-of-the-solvent-like-so that a protective layer is formed homogeneous along the entire surface. Therefore, there is a need to find a solvent that retards evaporation time but at the same time is capable of producing a sufficiently homogeneous and stable mixture.
Descripción de Ia invenciónDescription of the invention
La presente invención pretende superar los problemas asociados con las técnicas actualmente en uso buscando proporcionar una composición de recubrimiento que se pueda aplicar sobre el sustrato arquitectónico en el mismo lugar en el que se realiza Ia obra, que sea permanente y resistente a Ia suciedad, particularmente a los agentes ensuciadores hidrófobos. También es un objeto de Ia presente invención proporcionar un procedimiento para proporcionar una resistencia mejorada contra Ia suciedad a un sustrato arquitectónico.The present invention aims to overcome the problems associated with the techniques currently in use by seeking to provide a coating composition that can be applied to the architectural substrate in the same place where the work is performed, which is permanent and resistant to dirt, particularly to the agents hydrophobic foulers. It is also an object of the present invention to provide a method for providing an improved resistance against dirt to an architectural substrate.
Por Io tanto, de acuerdo con un primer aspecto esencial, Ia presente invención se refiere a una composición para Ia protección contra las manchas de superficies arquitectónicas que comprende: a) entre 18 y un 30 % en peso de un polímero líquido obtenido por polimerización de un acrilato; y b) entre 1 y un 20 % en peso de un monómero acrílico; caracterizada porque comprende entre un 60 y un 80% en peso de un disolvente que se selecciona del grupo formado por un hidrocarburo alifático lineal de entre 5 y 8 átomos de carbono, un compuesto de fórmula ITherefore, in accordance with a first essential aspect, the present invention relates to a composition for the protection against stains of architectural surfaces comprising: a) between 18 and 30% by weight of a liquid polymer obtained by polymerization of an acrylate; and b) between 1 and 20% by weight of an acrylic monomer; characterized in that it comprises between 60 and 80% by weight of a solvent that is selected from the group consisting of a linear aliphatic hydrocarbon of between 5 and 8 carbon atoms, a compound of formula I
R1COR2 en donde R1 y R2 son cada uno de forma independiente metilo, etilo o propilo; un compuesto de fórmula IlR 1 COR 2 wherein R 1 and R 2 are each independently methyl, ethyl or propyl; a compound of formula Il
R3O(CHR5) (CHR6)OR4 en donde R3 y R4 son cada uno de forma independiente metilo, etilo o acetato y R5 y R6 son cada uno de forma independiente metilo o hidrógeno; o mezclas de los mismos.R 3 O (CHR 5 ) (CHR 6 ) OR 4 wherein R 3 and R 4 are each independently methyl, ethyl or acetate and R 5 and R 6 are each independently methyl or hydrogen; or mixtures thereof.
En Ia presente descripción se entiende como "superficie" cualquier superficie porosa usada preferentemente terrazo, mármol, una piedra natural, ladrillo, adoquines, hormigón, loza o porcelana.In this description "surface" means any porous surface preferably used terrazzo, marble, a natural stone, brick, pavers, concrete, crockery or porcelain.
El término "protección contra las manchas" se refiere a Ia capacidad de un material para prevenir Ia decoloración permanente por los agentes domésticos e industriales habituales y cuyas decoloraciones no son eliminables mediante técnicas de limpieza convencionales o tratamiento con agentes de limpieza basados en agua o en disolventes orgánicos. Los agentes ensuciadores más fuertes incluyen asfalto/alquitrán de hulla, betún de zapato, mostaza, ketchup, café, lápiz de labios, tabaco y otros tipos de cigarrillos, neozono, jarabe de chocolate y similares. El asfalto/alquitrán de hulla es el más intenso de estos agentes ensuciadores. La resistencia al ensuciamiento por asfalto/alquitrán de hulla habitualmente es indicativa de Ia resistencia al ensuciamiento mediante otros agentes ensuciadores menos intensos. [Norma UNE-EN ISO10545-13. 5501033, "Resistencia a las manchas (baldosas cerámicas)"].The term "stain protection" refers to the ability of a material to prevent permanent discoloration by the usual domestic and industrial agents and whose discolorations are not removable by conventional cleaning techniques or treatment with water-based cleaning agents or in organic solvents The strongest fouling agents include coal asphalt / tar, shoe polish, mustard, ketchup, coffee, lipstick, tobacco and other types of cigarettes, neozone, chocolate syrup and the like. Coal tar / tar is the most intense of these fouling agents. The resistance to fouling by asphalt / coal tar is usually indicative of the resistance to fouling by other less intense fouling agents. [Standard UNE-EN ISO10545-13. 5501033, "Stain resistance (ceramic tiles)"].
Preferiblemente, los compuestos que se utilizan como disolventes se seleccionan del grupo formado por el hexano, Ia 2-butanona, el acetato de etilenglicol, el etilglicol, el propilenglicol o mezclas de los mismosPreferably, the compounds used as solvents are selected from the group consisting of hexane, 2-butanone, ethylene glycol acetate, ethyl glycol, propylene glycol or mixtures thereof.
De acuerdo con una realización preferida según Ia presente invención, dicho polímero líquido (a) es el obtenido por polimerización de un acrilato que se selecciona del grupo formado por el tri/tetraacrilato de pentaeritritol (PETIA):In accordance with a preferred embodiment according to the present invention, said liquid polymer (a) is that obtained by polymerization of an acrylate that is selected from the group formed by the pentaerythritol tri / tetraacrylate (PETIA):
RiCH2C(CH2R2)3 el del diacrilato de hexanodiol (HDDA):RiCH 2 C (CH 2 R 2 ) 3 that of hexanediol diacrylate (HDDA):
R2CH2(CH2J-(CH2R2 donde R1 representa H o el radial acrilato o metacrilato: CH2CHOOO O CH2C(CH3)COO y R2 representa el radial acrilato o metacrilato:R 2 CH 2 (CH 2 J- (CH 2 R 2 where R 1 represents H or the acrylate or methacrylate radial: CH 2 CHOOO OR CH 2 C (CH 3 ) COO and R 2 represents the acrylate or methacrylate radial:
CH2CHCOO O CH2C(CH3)COO; o mezclas de los mismos.CH 2 CHCOO OR CH 2 C (CH 3 ) COO; or mixtures thereof.
La proporción tri/tetraacrilato de pentaeritritokdiacrilato de hexanodiol preferiblemente varía entre un 40:60 en peso y 60:40 en peso. El polímero puede ser sustituido por el que se dispone comercialmente de Ia firma CHEMICALS (UCB Química Ibérica, S.A.) bajo Ia marca registrada UVERCRYL® 29203.The tri / tetraacrylate ratio of hexanediol pentaerythritokdiacrylate preferably ranges between 40:60 by weight and 60:40 by weight. The polymer can be substituted by the one commercially available from the firm CHEMICALS (UCB Química Ibérica, S.A.) under the registered trademark UVERCRYL® 29203.
Preferiblemente, dicho monómero acrílico es un diacrilato de alquilo, preferentemente - • el diacrilato-de-etilo;Preferably, said acrylic monomer is an alkyl diacrylate, preferably - • ethyl diacrylate;
(CH2CHCOO)2CH3CH3; el dimetacrilato de etilo:(CH 2 CHCOO) 2 CH 3 CH 3 ; ethyl dimethacrylate:
(CH2C(CH3)COO)2CH3CH3 o mezclas de los mismos.(CH 2 C (CH 3 ) COO) 2 CH 3 CH 3 or mixtures thereof.
Como sustancias complementarias, Ia composición puede comprender un aditivo superficial, preferiblemente copolímero polidimetilxiloxano modificado con poliéster; un antiespumante, preferiblemente alquilbenceno modificado con acetato de metoxipropilo; un fotoiniciador, preferiblemente benzofenona, isopropiltioxantona o mezclas de los mismos. Opcionalmente, Ia proporción de dicho aditivo superficial es de entre un 0,01 y un 0,3% en peso con respecto al peso total de Ia composición. Opcionalmente, Ia proporción de dicho antiespumante es de entre un 0,01 y un 1 ,5% en peso con respecto al peso total de Ia composición. Opcionalmente, Ia proporción de dicho fotoiniciador es de entre un 0,1 y un 3% en peso con respecto al peso total de Ia composición.As complementary substances, the composition may comprise a surface additive, preferably polyester-modified polydimethyloxy copolymer; an antifoam, preferably alkylbenzene modified with methoxypropyl acetate; a photoinitiator, preferably benzophenone, isopropylthioxanthone or mixtures thereof. Optionally, the proportion of said surface additive is between 0.01 and 0.3% by weight with respect to the total weight of the composition. Optionally, the proportion of said antifoam is between 0.01 and 1.5% by weight with respect to the total weight of the composition. Optionally, the proportion of said photoinitiator is between 0.1 and 3% by weight with respect to the total weight of the composition.
De acuerdo con un segundo aspecto esencial, Ia presente invención se refiere a un procedimiento para sellar permanentemente una superficie arquitectónica, preferiblemente en el mismo lugar en el que se instala Ia superficie arquitectónica, que comprende las siguientes etapas correlativas:According to a second essential aspect, the present invention relates to a method for permanently sealing an architectural surface, preferably in the same place where the architectural surface is installed, which comprises the following correlative steps:
• aplicación de una composición arquitectónica según cualquiera de las reivindicaciones 1-14 sobre Ia superficie arquitectónica; y• application of an architectural composition according to any of claims 1-14 on the architectural surface; Y
• aplicación de radiación ultravioleta sobre dicha superficie arquitectónica;• application of ultraviolet radiation on said architectural surface;
El procedimiento según Ia presente invención no requiere una etapa de eliminación del polímero residual, ya que el mayor tiempo de evaporación del producto permite Ia total absorción in situ de Ia composición.The process according to the present invention does not require a stage of elimination of the residual polymer, since the longer evaporation time of the product allows the total in situ absorption of the composition.
De acuerdo con un tercer aspecto esencial, Ia presente invención se refiere al uso una composición Ia protección de una superficie arquitectónica contra las manchas. Preferiblemente, dicha superficie es terrazo, mármol, una piedra natural, ladrillo, adoquines, hormigón, loza o porcelanaAccording to a third essential aspect, the present invention relates to the use of a composition Ia protection of an architectural surface against stains. Preferably, said surface is terrazzo, marble, a natural stone, brick, pavers, concrete, earthenware or porcelain
EjemplosExamples
A continuación se dan una serie de ejemplos, no limitativos, que muestran las principales ventajas de Ia presente invención.A series of non-limiting examples are given below, which show the main advantages of the present invention.
Ejemplo 1Example 1
El presente ejemplo se ha realizado con el fin de mostrar Ia mejora obtenida en Ia aplicación directa en obra de una composición según Ia presente invención. Se han preparado tres muestras en las que solo se ha variado el disolvente y se ha medido el tiempo tardado en que se evapore sustancialmente todo el disolvente. Los resultados se muestran en Ia tabla 1 :The present example has been carried out in order to show the improvement obtained in the direct application on site of a composition according to the present invention. Three samples have been prepared in which only the solvent has been varied and the time taken for substantially all of the solvent to evaporate has been measured. The results are shown in table 1:
Figure imgf000008_0001
Figure imgf000009_0001
Figure imgf000008_0001
Figure imgf000009_0001
Tabla 1Table 1
Como puede observarse, las mezclas según Ia presente invención (mezclas 2 y 3) tienen un tiempo de evaporación muy superiores a los de productos conocidos (mezcla 1) permitiendo su aplicación sobre superficies muy porosas o irregulares, sin perder eficacia en el resultado final. También permite su aplicación directa en obra, ya que hay tiempo suficiente entre Ia aplicación de Ia composición y Ia evaporación del disolvente como para que Ia composición sea completamente absorbida y se forme una capa protectora homogénea a Io largo de toda Ia superficie. As can be seen, the mixtures according to the present invention (mixtures 2 and 3) have a much longer evaporation time than those of known products (mixture 1) allowing their application on very porous or irregular surfaces, without losing efficiency in the final result. It also allows its direct application on site, since there is sufficient time between the application of the composition and the evaporation of the solvent so that the composition is completely absorbed and a homogeneous protective layer is formed along the entire surface.

Claims

REIVINDICACIONES 1. Una composición para Ia protección contra las manchas de superficies arquitectónicas que comprende: a) entre 18 y un 30 % en peso de un polímero líquido obtenido por polimerización de un acrilato; y b) entre 1 y un 20 % en peso de un monómero acrílico; caracterizada porque comprende entre un 60 y un 80% en peso de un disolvente que se selecciona del grupo formado por un hidrocarburo alifático lineal de entre 5 y 8 átomos de carbono, un compuesto de fórmula ICLAIMS 1. A composition for the protection against stains of architectural surfaces comprising: a) between 18 and 30% by weight of a liquid polymer obtained by polymerization of an acrylate; and b) between 1 and 20% by weight of an acrylic monomer; characterized in that it comprises between 60 and 80% by weight of a solvent that is selected from the group consisting of a linear aliphatic hydrocarbon of between 5 and 8 carbon atoms, a compound of formula I
R1COR2 en donde Ri y R2 son cada uno de forma independiente metilo, etilo o propilo; un compuesto de fórmula IlR 1 COR 2 where Ri and R 2 are each independently methyl, ethyl or propyl; a compound of formula Il
R3O(CHR5) (CHR6)OR4 en donde R3 y R4 son cada uno de forma independiente metilo, etilo o acetato y R5 yR 3 O (CHR 5 ) (CHR 6 ) OR 4 wherein R 3 and R 4 are each independently methyl, ethyl or acetate and R 5 and
R6 son cada uno de forma independiente metilo o hidrógeno; o mezclas de los mismos.R 6 are each independently methyl or hydrogen; or mixtures thereof.
2.- Una composición según Ia reivindicación 1 , caracterizada porque dicho hidrocarburo alifático lineal es hexano.2. A composition according to claim 1, characterized in that said linear aliphatic hydrocarbon is hexane.
3.- Una composición según cualquiera de las reivindicaciones anteriores, caracterizada porque dicho compuesto de fórmula I es 2-butanona.3. A composition according to any of the preceding claims, characterized in that said compound of formula I is 2-butanone.
4.- Una composición según cualquiera de las reivindicaciones anteriores, caracterizada porque dicho compuesto de fórmula Il se selecciona del grupo formado por el acetato de etilenglicol, el etilglicol, el propilenglicol o mezclas de los mismos.4. A composition according to any of the preceding claims, characterized in that said compound of formula Il is selected from the group consisting of ethylene glycol acetate, ethyl glycol, propylene glycol or mixtures thereof.
5. Una composición según cualquiera de las reivindicaciones anteriores, caracterizada porque dicho polímero líquido (a) es el obtenido por polimerización de un acrilato que se selecciona del grupo formado por el tri/tetraacrilato de pentaeritritol:
Figure imgf000010_0001
el del diacrilato de hexanodiol:5. A composition according to any of the preceding claims, characterized in that said liquid polymer (a) is that obtained by polymerization of an acrylate which is selected from the group formed by the pentaerythritol tri / tetraacrylate:
Figure imgf000010_0001
hexanediol diacrylate:
R2CM2(CH2)4CH2R2 donde Ri representa H o el radial acrilato o metacrilato:R2CM2 (CH2) 4 CH2R2 where Ri represents H or the acrylate or methacrylate radial:
CH2CHOOO O CH2C(CH3)COO y R2 representa el radial acrilato o metacrilato:CH 2 CHOOO OR CH 2 C (CH 3 ) COO and R 2 represents the radial acrylate or methacrylate:
CH2CHCOO O CH2C(CH3)COO; o mezclas de los mismos.CH 2 CHCOO OR CH 2 C (CH 3 ) COO; or mixtures thereof.
6.- Una composición según Ia reivindicación 5, caracterizada porque Ia proporción tri/tetraacrilato de pentaeritritohdiacrilato de hexanodiol varía entre un 40:60 en peso y 60:40 en peso.6. A composition according to claim 5, characterized in that the tri / tetraacrylate ratio of hexanediol pentaerythrityl diacrylate varies between 40:60 by weight and 60:40 by weight.
7. Una composición según cualquiera de las reivindicaciones anteriores, caracterizada porque dicho monómero acrílico (b) es un diacrilato de alquilo.7. A composition according to any of the preceding claims, characterized in that said acrylic monomer (b) is an alkyl diacrylate.
8.- Una composición según Ia reivindicación 7, caracterizada porque dicho diacrilato de alquilo se selecciona del grupo formado por el diacrilato de etilo:8. A composition according to claim 7, characterized in that said alkyl diacrylate is selected from the group formed by ethyl diacrylate:
(CH2CHCOO)2CH3CH3; el dimetacrilato de etilo:(CH 2 CHCOO) 2 CH 3 CH 3 ; ethyl dimethacrylate:
(CH2C(CH3)COO)2CH3CH3 o mezclas de los mismos.(CH 2 C (CH 3 ) COO) 2 CH 3 CH 3 or mixtures thereof.
9.- Una composición según cualquiera de las reivindicaciones anteriores, caracterizada porque además comprende un aditivo superficial, preferiblemente copolímero polidimetilxiloxano modificado con poliéster.9. A composition according to any of the preceding claims, characterized in that it further comprises a surface additive, preferably polyester-modified polydimethyloxy copolymer.
10.- Una composición según Ia reivindicación 9, caracterizada porque Ia proporción de dicho aditivo superficial es de entre un 0,01 y un 0,3% en peso con respecto al peso total de Ia composición.10. A composition according to claim 9, characterized in that the proportion of said surface additive is between 0.01 and 0.3% by weight with respect to the total weight of the composition.
11.- Una composición según cualquiera de las reivindicaciones anteriores, caracterizada porque además comprende un antiespumante, preferiblemente alquilbenceno modificado con acetato de metoxipropilo.11. A composition according to any of the preceding claims, characterized in that it further comprises an antifoam, preferably alkylbenzene modified with methoxypropyl acetate.
12.- Una composición según Ia reivindicación 11 , caracterizada porque Ia proporción de dicho antiespumante es de entre un 0,01 y un 1 ,5% en peso con respecto al peso total de Ia composición. 12. A composition according to claim 11, characterized in that the proportion of said antifoam is between 0.01 and 1.5% by weight with respect to the total weight of the composition.
13.- Una composición según cualquiera de las reivindicaciones anteriores, caracterizada porque además comprende un fotoiniciador, preferiblemente benzofenona, isopropiltioxantona o mezclas de los mismos.13. A composition according to any of the preceding claims, characterized in that it further comprises a photoinitiator, preferably benzophenone, isopropylthioxanthone or mixtures thereof.
14.- Una composición según Ia reivindicación 13, caracterizada porque Ia proporción de dicho fotoiniciador es de entre un 0,1 y un 3% en peso con respecto al peso total de Ia composición.14. A composition according to claim 13, characterized in that the proportion of said photoinitiator is between 0.1 and 3% by weight with respect to the total weight of the composition.
15. Procedimiento para sellar permanentemente una superficie arquitectónica caracterizado por comprender las siguientes etapas correlativas:15. Procedure to permanently seal an architectural surface characterized by comprising the following correlative stages:
• aplicación de una composición arquitectónica según cualquiera de las reivindicaciones 1-14 sobre Ia superficie arquitectónica; y• application of an architectural composition according to any of claims 1-14 on the architectural surface; Y
• aplicación de radiación ultravioleta sobre dicha superficie arquitectónica.• application of ultraviolet radiation on said architectural surface.
16- Procedimiento según Ia reivindicación 15, caracterizado porque dicho procedimiento se realiza después de situar dicha superficie arquitectónica en Ia construcción.16- Procedure according to claim 15, characterized in that said procedure is performed after placing said architectural surface in the construction.
17. Uso una composición según las reivindicaciones 1 a 16 para Ia protección de una superficie arquitectónica contra Ia suciedad.17. Use a composition according to claims 1 to 16 for the protection of an architectural surface against dirt.
18.- Uso según Ia reivindicación 17 en donde dicha superficie arquitectónica se selecciona del grupo formado por terrazo, mármol, una piedra natural, ladrillo, adoquines, hormigón, loza o porcelana. 18. Use according to claim 17 wherein said architectural surface is selected from the group consisting of terrazzo, marble, a natural stone, brick, pavers, concrete, earthenware or porcelain.
PCT/ES2005/000089 2005-02-25 2005-02-25 Acrylate-based polymeric composition for coating architectural surfaces, which has been improved with the inclusion of suitable solvents WO2006092450A1 (en)

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Publication number Priority date Publication date Assignee Title
ES2387430A1 (en) * 2011-02-25 2012-09-21 Quimigama, S.L. Stone protector (Machine-translation by Google Translate, not legally binding)
CN111826036A (en) * 2020-05-29 2020-10-27 安徽老石人石业有限公司 Preparation method of stone protective agent for wet environment of subway station

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