WO2013044980A1 - Curable mixture - Google Patents

Curable mixture Download PDF

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Publication number
WO2013044980A1
WO2013044980A1 PCT/EP2011/067128 EP2011067128W WO2013044980A1 WO 2013044980 A1 WO2013044980 A1 WO 2013044980A1 EP 2011067128 W EP2011067128 W EP 2011067128W WO 2013044980 A1 WO2013044980 A1 WO 2013044980A1
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Prior art keywords
mixture
wt
fluoroorganic
water
silicon compound
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PCT/EP2011/067128
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French (fr)
Inventor
Ulf Kehrer
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Akzo Nobel Chemicals International B.V.
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Priority to PCT/EP2011/067128 priority Critical patent/WO2013044980A1/en
Publication of WO2013044980A1 publication Critical patent/WO2013044980A1/en

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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
    • C04B20/00Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10Coating or impregnating
    • C04B20/1051Organo-metallic compounds; Organo-silicon compounds, e.g. bentone
    • 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
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • 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
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04Portland cements
    • 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
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482Coating or impregnation materials
    • 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
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482Coating or impregnation materials
    • C04B2111/00508Cement paints
    • 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
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00586Roofing materials
    • C04B2111/00594Concrete roof tiles
    • 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
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00637Uses not provided for elsewhere in C04B2111/00 as glue or binder for uniting building or structural materials
    • 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
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00663Uses not provided for elsewhere in C04B2111/00 as filling material for cavities or the like
    • C04B2111/00672Pointing or jointing materials
    • 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
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20Resistance against chemical, physical or biological attack
    • C04B2111/203Oil-proof or grease-repellant materials
    • 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
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20Resistance against chemical, physical or biological attack
    • C04B2111/27Water resistance, e.g. waterproof or water-repellant materials
    • 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
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20Resistance against chemical, physical or biological attack
    • C04B2111/28Fire resistance, i.e. materials resistant to accidental fires or high temperatures
    • 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
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/60Flooring materials
    • 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
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/70Grouts, e.g. injection mixtures for cables for prestressed concrete
    • 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
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/72Repairing or restoring existing buildings or building materials
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/90Reuse, recycling or recovery technologies cross-cutting to different types of waste
    • Y02W30/91Use of waste materials as fillers for mortars or concrete
    • Y02W30/96Use of waste materials as fillers for mortars or concrete organic, e.g. rubber, polystyrene
    • Y02W30/97Vegetable refuse, e.g. rice husks, maize-ear refuse; cellulosic materials, e.g. paper

Abstract

The present invention relates to a curable mixture comprising - more than 25 wt.% of one or more mineral binders, based on the total amount of the curable mixture, - 0.001 to 8 wt.% of one or more fluoroorganic-substituted silicon compounds, which is adsorbed on a solid, based on the total amount of the curable mixture, and - optionally further added substances, as well as to the cured mixture, processes for the preparation of the curable and the cured mixture and their use. The cured mixture has excellent hydrophobic and oleophobic and therefore excellent dirt repellent, i.e. easy-to-clean properties.

Description

CURABLE MIXTURE

The present invention relates to a curable mixture and its preparation, a cured mixture and its preparation, as well as to the use of the curable mixture and to the use of a fluoroorganic-substituted silicon compound, which is adsorbed on a solid, in the curable mixture, wherein the cured mixture has excellent hydrophobic and oleophobic - and therefore excellent dirt-repellent, i.e. easy-to- clean - properties. Curable mixtures such as mineral setting materials, for instance hydraulically setting materials, e.g. cement bound materials, are widely used in the modern building and construction industry in numerous places. Non-limiting examples are concrete paving tiles for driveways, doorways, pavements, terraces, for grouts and any type of surface coatings such as plasters and renders.

A big problem is soiling of the surfaces of these materials, outdoors as well as indoors. They can be stained by various substances such as traffic and industry fumes, in particular soot, pollen, grassy flecks, oils, in particular motor oils, cosmetics and makeup, residues of meals and drinks such as Coca Cola, coffee, red wine or ketchup, as well as growth of microorganisms such as algae or fungi. All these stains are a big problem from an aesthetic point of view. Therefore, it is desirable to equip cured mixtures, in particular hydraulically set building and construction materials, which are used in such applications and which might be exposed to such stains, with hydrophobic and oleophobic - and thus dirt- repellent - properties. Such properties are also summarized under the term "easy-to-clean" or for short "ETC".

The skilled person understands dirt repellent properties to mean int. al. the property of the surface to prevent the penetration of aqueous as well as oily substances into the material and to facilitate the removal of these substances from the surfaces. Furthermore, paints, coating, lacquers, dusts as well as growths of various materials such as moss and algae can be removed easily. The testing of the staining properties is suitably carried out by measuring the water and oil repellency and/or according to DIN EN ISO 10545-14. Thus, materials having such easy-to-clean properties must be not only water-repellent, i.e. hydrophobic, but also oil-repellent, i.e. oleophobic.

It is known from the prior art that in particular inorganic substrate surfaces can be equipped with easy-to-clean properties by post-treatment of the cured surfaces with a fluoroorganic-substituted silicon compound. However, an additional working step is required for this operation, which is costly. Furthermore, if the substrate surface which is treated in this way is damaged e.g. by abrasion or cracks, the easy-to-clean properties deteriorate.

EP 1 262 464 discloses a grout powder for admixture with water to produce grouts. The grout powder comprises cement powder. At least one component, e.g. the cement powder or the quartz particles of the grout powder, is first treated on its surface with a fluorochemical compound, e.g. a silane. The manufacture of this grout powder comprising ingredients which are treated with a fluorochemical compound is complex and comprises - among others - the treatment of the cement-containing mixture with water, organic solvents, and the fluorochemical compound, followed by drying and homogenizing. The thus obtained pre-treated grout powder- after mixing with water, application, and curing - shows oil- and water-repellent properties. However, since at least one component of the grout powder has been pre-treated with a fluorochemical compound, such mortars show hydrophobic properties already upon addition of water and mixing therewith. Thus, the wettability of these mixtures is poor, leading to problems of homogenizing the mortar.

It was therefore the objective of the present invention to provide a curable mixture where the curable as well as the cured mixture can be obtained with as few as possible, preferably simple, working steps. Furthermore, the cured mixture must exhibit high compressive strengths and sufficient dirt-repellent properties of the surface, and in particular of abraded, damaged, and cracked surfaces, which have to be most durable.

Surprisingly, it was now found that the problem can be solved with a curable mixture comprising

- more than 25 wt.%, preferably more than 25 to 60 wt.%, most preferably 26 to 45 wt.%, of one or more mineral binders, based on the total of the curable mixture,

- 0.001 to 8 wt.% of one or more fluoroorganic-substituted silicon compounds which are adsorbed on a solid, based on the total of the curable mixture, and

- optionally further added substances.

The amounts of the added components are based on the total of the curable mixture and thus relate - unless specified otherwise - to the water-free part, i.e. generally to the dry proportion including the fluoroorganic-substituted silicon compounds which are adsorbed on a solid, of the respective components and are given in parts by weight, i.e. in wt.%. Furthermore, they sum up to 100 wt.%.

Surprisingly, it was found that the mixture according to the invention is suitable to provide the cured mixture with excellent hydrophobic as well as oleophobic - and thus easy-to-clean - properties, even with very small amounts of a fluoroorganic- substituted silicon compound. The mixture according to the invention is easy to manufacture and process further. Typically, it is in the form of a powder or granules. The fluoroorganic-substituted silicon compound which is adsorbed on a solid is distributed homogeneously in the curable mixture and is not very sensitive to traces of moisture which would enter during storage of the mixture. After the mixture is mixed with water and cured, the total mass of the cured mixture reveals excellent hydrophobic as well as oleophobic properties. This is most important when the surface becomes damaged by e.g. abrasion or cracks. Furthermore, it was found that despite the pronounced hydrophobic and oleophobic properties of the cured mixture, the curable mixture has a good wettability with water. Additionally, the adhesion of the cured mixture to the various surfaces is sufficiently high for at least most applications, which is contrary to what the skilled person in the art expects. Moreover, due to the high content of mineral binder, i.e. more than 25 wt% based on the water-free mixture, increased compressive strengths of the cured mixture can be obtained. This is of particular advantage for the production of mortars, which, in comparison to concrete, have a higher number of pores, in particular air pores.

The use of the fluoroorganic-substituted silicon compound according to the invention was found to have a benefit when compared to conventional silanes. Conventional silanes, i.e. silicon compound, often have an undesired liquefying effect on mortar preparations. The fluoroorganic-substituted compounds of the invention surprisingly do not influence the viscosity, especially any thixotropic behaviour, negatively. Therefore, the yield point of the curable mixture mixed with water is not or only slightly influenced by the addition of the fluoroorganic- substituted silicon compound.

Also claimed are processes to make the curable mixture of the invention. In one embodiment, the curable mixture is obtained by mixing a fluoroorganic- substituted silicon compound which is adsorbed on a solid with at least one component of the curable mixture. By doing so, it is possible to make one- component dry mortars, which easily can be stored and transported. On the building site, they only need to be mixed with water and applied in order to reveal the advantageous properties in the cured state. However, it is also possible to prepare two-component mortars comprising a dry part which is free of water comprising the fluoroorganic-substituted silicon compound which is adsorbed on a solid, and a liquid component comprising the water required to obtain the desired water/cement ratio. The thus obtained cured mixtures are obtained in an easy manner and show the advantageous easy-to-clean properties. In another embodiment, the curable mixture is made by a process wherein in a first step a component (i) comprising the mineral binder and a component (ii) comprising the fluoroorganyl-substituted silicon compound which is adsorbed on a solid are prepared. The further added substances are mixed with components (i) and/or (ii). In a second step the components (i) and (ii) are mixed with one another. With this process it is possible to make mortars of the invention from two or more components.

Claimed also is a process to make the cured mixture of the invention, comprising the step of mixing the curable mixture of the invention and/or the curable mixture prepared according to the processes of the invention with 1 to 120 wt.% water, based on 100 wt.% of curable, water-free mixture. Hence, the two or more components can be mixed together on the building site without the need to add further water. Alternatively, dry mortars can be mixed with water from e.g. a water pipe. Afterwards, the obtained mixture can be applied onto e.g. a substrate or processed into a form such as a precast form, and allowed to cure. The thus obtained cured mixture is obtained in an easy manner and shows the desired easy-to-clean properties.

The invention further provides the cured mixture having hydrophobic and oleophobic properties obtainable according to said processes of the invention.

The hydrophobic and oleophobic properties are determined as follows. In a first step a specimen consisting of the cured mixture having an even surface, e.g. a prism having the mass of 8 x 4 x 4 cm, is prepared without any form oil according to EN 12808-5. After one day, the prism is stripped. After a total of 28 days at standard conditions (23°C/ 50% RH), the contact angle of water (to determine the hydrophobicity) and of olive oil (to determine the oleophobicity), respectively, is measured. To this end a drop (ca. 0.2 ml) of the respective liquid is placed onto the surface of the mortar. Two minutes after the drop has been placed, the contact angle is measured optically using a contact angle measuring device with a camera (e.g. type DSA100 of Kruss). The analysis can be made with the device-specific software. The surface possesses hydrophobic (water drop) and oleophobic (olive oil drop) properties in accordance with the invention, respectively, when a contact angle of at least 60°, preferably at least 70°, in particular at least 80°, is measured.

With the processes of the invention it is possible to provide the curable mixture as well as the cured mixture in a surprisingly easy and economical manner, using known agitators in traditional containers and mixers.

The mixture made according these processes after curing possesses the mentioned, advantageous easy-to-clean properties not only on the surface, but in the total mass. Thus, they are mass-hydrophobized and mass-oleophobized.

It was surprising that the fluoroorganic-substituted silicon compound can - on the one hand - be absorbed on a solid to obtain a stable mixture with known processes and materials. On the other hand, it was not to be expected that the adsorbed fluoroorganic-substituted silicon compound in the curable mixture with such a high proportion of mineral binder is stable enough to be mixed into a stable composition, even more so since hydraulic binders have a strongly basic reaction upon contact with water. Additionally, it was particularly surprising to find that the fluoroorganic-substituted silicon compound adsorbed on the solid is hydrophilic enough - when the mixture containing the same is mixed with water - to desorb from the solid, followed by hydrolysis and further reactions, e.g. condensation.

In order to obtain in the cured mixture the desired easy-to-clean properties, the various complex processes and reactions need to occur at the right time. Based on conventional knowledge, it is expected that, in order to obtain the favoured modification of the total mass, i.e. mass modification, the fluoroorganic- substituted silicon compound needs to be distributed homogeneously. Also, it is expected that when the curable mixture is mixed with water, it is essential that the fluoroorganic-substituted silicon compound desorbs from the solid, i.e. carrier, at the right time and thus is released. This is based on the expectation that when the fluoroorganic-substituted silicon compound is adsorbed too strongly on the solid, the silicon compound hydrolyzes and condenses before desorption of the silicon compound occurs. This leads to hydrophobization and oleophobization of the solid the silicon compound is absorbed on, but not at all to the desired mass modification. Therefore, in order to obtain the desired easy-to-clean effect in the cured mixture, based on conventional knowledge, all of these processes need to occur and to be completed in the right order and well before the start of the setting of the curable mixture with its related solidification. The skilled person in the art does not expect this to be feasible.

Surprisingly, it was found that the kinetic of all these different processes are just right for the fluoroorganic-substituted compounds of the invention. Even the smallest amount of a fluoroorganic-substituted silicon compound already provides excellent easy-to-clean properties. Furthermore, it was found that the material properties, e.g. the interfacial tension, of the fluoroorganic-substituted silicon compound are different from those of other silicon compounds due to the fluorine substitution. Additionally, the high ionogenicity and alkalinity, as occurring in particular in aqueous curable mixtures on the basis of hydraulic setting binders, have a strong influence on the kinetics of said processes. Thus it was surprising and unexpected to the skilled person in the art that the superior easy-to-clean properties are obtained not only on the surface of the cured mineral-based mortar, but also on the inside of the set mixture.

The invention further pertains to the use of a fluoroorganic-substituted silicon compound which is adsorbed on a solid in a hydraulically curable mixture containing more than 25 to 60 wt.% of hydraulically setting binder, 20 to 74 wt.% of at least one added substance, and 0.001 to 8 wt.% of the fluoroorganic- substituted silicon compound which is adsorbed on a solid, and optionally 0 to 40 wt.% of further adjuvants, based on 100 wt.% of curable, water-free mixture. This mixture in cured form exhibits the desired easy-to-clean properties.

The use of the fluoroorganic-substituted silicon compound which is adsorbed on a solid surprisingly does not show any negative properties. It can be employed in the known formulations without the need to adapt the formulation to any great extent. Hence, e.g. the wettability, the mortar workability, the water demand to obtain the same consistency, and the hydration do not change at all or only marginally in comparison with the formulation without the fluoroorganic- substituted silicon compound.

The cited objective of the present invention can be achieved in a particularly surprising and advantageous manner by homogeneously admixing the fluoroorganic-substituted silicon compound which is already adsorbed on a solid with the dry mixture, e.g. a dry building material composition, or upon mixing water into the dry mixture. By doing so, the permanent easy-to-clean properties can be obtained throughout the manufactured substrate and the building material composition, respectively. Thus, fluoroorganic-substituted silicon compounds adsorbed on a solid and preferably in a free-flowing form can be stored, transported, and handled easily, e.g. for sacking, transporting, weighing, and dosing when making the curable mixture. They can therefore exert their desired effect in the building material composition, preferably in hydraulically setting mixtures, in particular cement-containing mixtures such as concrete and mortars, as homogeneously distributed components in connection with the mixing water and the prevailing alkaline pH-value, in which process hydrolysis of the added fluoroorganic-substituted silicon compound occurs, followed by reaction with the present components of the building material composition. The thus obtained and cured material reveals in advantageous manner the permanent and in particular the homogeneous easy-to-clean properties. The utilization of a fluoroorganic-substituted silicon compound which is adsorbed on a solid in the curable mixture according to the invention, the process to make the same, and its use yields various advantages. Hence, homogeneous mixtures, in particular dry mixtures, and preparations can be manufactured in an easy manner ex factory. When used at the building or construction site, they just have to be mixed with water. The cured mixtures obtained according to this embodiment also impart the advantageous easy-to-clean properties.

The curable mixture according to the invention which comprises the fluoroorganic-substituted silicon compound which is adsorbed on a solid possesses a good wettability and mortar workability when mixed with water. Hence, the hydrophobic and oleophobic properties are revealed only after the mixture has cured. When a monomer compound having alkoxy groups, e.g. fluoroalkoxy silane, is used, the silicon compound is typically in non-hydrolyzed and in monomer form, i.e. not more than about 10%, in particular not more than 5%, of the alkoxy groups of the silicon compound are hydrolyzed. As a result, the reactive groups, in particular the alkoxy groups, survive during the preparation and storage of the fluoroorganic-substituted silicon compound which is adsorbed on a solid, even when mixed with other solid mortar ingredients, as long as no water is added. After the addition of water and mixing therewith, the fluoroorganic-substituted silicon compound is believed to desorb from the solid and the alkoxy groups hydrolyze, in which process due to the subsequent reactions, e.g. condensation, the desired advantageous properties are achieved. The curable mixtures according to the invention are preferably concrete-related mixtures and mortars. The term concrete-related mixture is understood by the skilled person in the art to include dry concrete mixtures, optionally mixed with water, subsequently summarized as concrete. Concrete comprises aggregates with a diameter of 3 mm and larger and up to 64 mm. Mortars comprise aggregates which - in the context of mortars - are also known as fillers, with a diameter of 0.005 to 5 mm, in particular 0.001 to 3 mm. Mortars can be in the form of dry mortars, pasty mortars, and mortars with two or more components. In many cases dry mortars are preferred, in particular when all components, i.e. ingredients, are present in solid form. Hence, the dry mortars can be mixed ex factory and only water needs to be added on the building or construction site before application. Pasty mortars are often preferred when no hydraulically setting binders are present and when completely pre-mixed systems, including the total amount of required water, are desired. Mortars with two and more components include mortars comprising a solid, e.g. a powdery component and one or more liquid and/or high-viscous components. The liquid component typically comprises the liquid ingredients of the formulation.

In the context of the invention, mineral binders comprise a) a hydraulically setting binder, in particular a cement, activated blast furnace slag and/or silico- calcareous fly ash, b) a latent hydraulic binder, such as in particular pozzolane and/or metakaolin, which reacts hydraulically in combination with a calcium source such as calcium hydroxide and/or cement and/or c) a non-hydraulic binder which reacts under the influence of air and water, in particular calcium hydroxide, calcium oxide, quicklime, hydrated lime, magnesia cements, water glass and/or gypsum, by which is meant in this invention in particular calcium sulfate in the form of a- and/or β-semihydrate and/or anhydrite of form I, II and/or III.

Preferred hydraulically setting binder a) are cements, in particular Portland cement, Portland composite cement, blast furnace cement and blast furnace slag cement, pozzolane cement, i.e. cement with a proportion of pozzolane, for instance in accordance with EN 197-1 CEM I, II, III, IV, and V and/or calcium phosphate cement and/or aluminous cement such as high alumina cement, calcium alumina cement, sulfo-alumina cement and/or calcium sulfo-alumina cement. Preferred latent hydraulic binders b) are pozzolane, metakaolin, burnt shale, diatomaceous earth, moler, rice husk ash, air cooled slag, calcium metasilicate and/or volcanic slag, volcanic tuff, trass, fly ash, silica fume, microsilica, blastfurnace slag and/or silica dust.

Preferred non-hydraulic binders c) are gypsum, by which is meant in this invention in particular calcium sulfate in the form of a- and/or β-semihydrate and/or anhydrite of form I, II and/or III, calcium hydroxide, calcium oxide, lime such as quicklime and/or hydrated lime, magnesia cements and/or water glass.

The particularly preferred mineral binder is a hydraulically setting binder, e.g. cement, in particular Portland cement, Portland composite cement, blast furnace cement, calcium alumina cement, calcium sulfo-alumina cement, sulfo-alumina cement, which may contain some (i.e. up to 10% by weight of the binder) latent- hydraulic and/or non-hydraulic binder.

In a preferred embodiment, the curable mixture comprises a mineral binder which itself comprises at least one hydraulically setting binder. When several mineral binders are used, it is as a rule advantageous to employ less than 50 wt.%, in particular less than 30 wt.%, of latent hydraulic binder b) and/or non-hydraulic binder c), based on the sum of added mineral binders. For all embodiments, the curable mixture preferably comprises less than 10 wt.%, in particular less than 5 wt.%, of latent hydraulic binder b) and/or non-hydraulic binder c), based on the sum of added mineral binders.

In addition to the mineral binder, it is possible to add organic binders. They comprise film-forming, water-insoluble polymer binders in the form of an aqueous polymer dispersion or a water-redispersible polymer powder obtained by drying aqueous dispersions. The aqueous polymer dispersions, according to the invention also just named dispersions, are typically obtained by emulsion and/or suspension polymerization. These are well-established technologies known to the skilled person in the art.

In the context of the invention, water-insoluble polymer binders may be vinyl (co)polymers, polyurethanes, poly(meth)acrylates, polyesters, polyethers, as well as mixtures and hybrids thereof. In a preferred embodiment, water- insoluble polymer binders are aqueous polymer dispersions and water- redispersible polymer powders which may be obtained by drying the dispersions. The dispersions are typically obtained by emulsion and/or suspension polymerization and may contain vinyl (co)polymers, polyurethanes, poly(meth)acrylates, polyesters, polyethers, as well as mixtures and hybrids thereof. In a particularly preferred embodiment, the dispersions are based on (co)polymers of ethylenically unsaturated monomers preferably comprising monomers from the group of vinyl acetate, ethylene, acrylate, methacrylate, vinyl chloride, styrene, butadiene and/or C4-C12 vinyl ester monomers.

Such (co)polymers are preferably homo- or copolymerizates on the basis of vinyl acetate, ethylene-vinyl acetate, ethylene-vinyl acetate-vinyl versatate, ethylene-vinyl acetate-(meth)acrylate, ethylene-vinyl acetate-vinyl chloride, vinyl acetate-vinyl versatate, vinyl acetate-vinyl versatate-(meth)acrylate, vinyl versatate-(meth)acrylate, pure (meth)acrylate, styrene-acrylate and/or styrene- butadiene, wherein the vinyl versatate preferably is a C4- to C-12-vinyl ester, in particular a C9 -, C10 - and/or a Cn-vinyl ester, and the homo- or copolymerizates can contain about 0 - 50 wt.%, in particular about 0 - 30 wt.%, and quite especially preferably about 0 - 10 wt.% of further monomers, in particular monomers with functional groups.

In a preferred embodiment, the dispersions and the water-red ispersed polymer powders are film-forming at a temperature of 23° C or higher; preferably at 10° C or higher; in particular at 5° C or higher. It is worth mentioning that for aqueous systems the minimum film formation temperature (MFFT) is limited at around 0°C due to freezing of the water. Film-forming means that the (co)polymer is capable of forming a film determined according to DIN 53787.

The binders are stabilized with surfactants and/or water-soluble polymers in a known manner. Aqueous dispersions are typically free of organic solvents. The water-redispersible polymer powders are typically obtained by drying, in particular by spray drying of the aqueous dispersions, which are preferably stabilized with water-soluble polymers. When the water-redispersible polymer powders get into contact with water, they redisperse spontaneously or by at most slight stirring.

In one embodiment, the one or more fluoroorganic-substituted silicon compounds are the only silicon compounds in the curable mixture. In another embodiment, they are used in conjunction with non-fluoroorganic-substituted silicon compounds, e.g. with non-substituted organic silicon compounds, such as aminosilanes or alkoxysilanes, i.e. octyltriethoxysilane. The silicon compounds can be used in any ratio. However, it is noticed that the desired easy-to-clean properties can be obtained only if the fluoroorganic-substituted silicon compound is present in an amount as presented in the claims. Variation of said amount may be desired, depending on the formulation and the specific application. The skilled person in the art is well aware of how to adjust the formulation to achieve an optimized performance.

Fluoroorganic-substituted silicon compounds according the invention may be of various character. In one embodiment (i) they are compounds which are derived from the general formulae (I), (II), (III), (IV) and/or (V). They may contain cross- linkable structural elements which form aliphatic, cyclic and/or crosslinked structures. In a preferred embodiment, at least one structure corresponds in idealized form to the general formula (I)

(HO)[(HO)i-x(R2)xSi(A)0]a[Si(B)(R3)y(OH)1-yO]b[Si(C)(R5)u(OH)1-uO]c - [Si(D)(OH)0]dH (HX)e (I) wherein in formula (I) the structural elements are derived from alkoxy silanes of the general formulae (II), (III), (IV) and/or (V) and - A in formula (I) corresponds in the structural element to an amino residue H2N(CH2)f(NH)g(CH2)h(NH)m(R7)n- and is derived from the general formula (II)

H2N(CH2)f(NH)g(CH2)h(NH)m(R7)nS i(OR1 )3-x(R2)x (II), wherein f is an integer between 0 and 6, g=0 if f=0 and g=1 if f>0, h is an integer between 0 and 6, x=0 or 1 , m=0 or 1 and n=0 or 1 , with n+m=0 or 2 in formula (II), and R7 is a linear, branched or cyclic divalent alkyl group with 1 to 16 C- atoms, - B in formula (I) relates in the structural element to a fluoroalkyl residue R -Y- (CH2)k- derived from the general formula (III)

R -Y-(CH2)kSi(R3)y(OR1 )3-y (III), wherein R4 is a mono-, oligo- or perfluorinated alkyl group with 1 to 9 C-atoms or a mono-, oligo- or perfluorinated aryl group, Y is a CH2-, O- or S-group, R3 is a linear, branched or cyclic alkyl group with 1 to 8 C-atoms or an aryl group, k=0, 1 or 2 and y=0 or 1 , preferably R4 = F3C(CF2)r-, with r=0 to 18, preferably r=5, with Y being a CH2- or O-group, and preferably is k=1 with Y = -CH2-,

- C in formula (I) relates in the structural element to an alkyl residue R5-, derived from the general formula (IV)

R6-Si(R5)u(OR1 )3-u (IV), wherein R5 is a linear or branched alkyl group with 1 to 4 C-atoms, in particular methyl, and u=0 or 1 in formula (IV),

- D in formula (I) relates in the structural element to an alkyl residue R5-, derived from the general formula (V)

R6-Si(OR1)3 (V), wherein R6 of the aforesaid formula is a linear, branched or cyclic alkyl group with 1 to 8 C-atoms, and

R1 in the formulae (II), (III), (IV), (V) and/or (VI) independently is a linear, branched or cyclic alkyl group with 1 to 8 C-atoms or an aryl group, preferably R1 independently is methyl, ethyl or propyl; with R2, R3 and/or R5 in the aforementioned formula independently representing a linear or branched alkyl residue with 1 to 4 C-atoms, preferably methyl or ethyl, and

- in formula (I) HX represents an acid, wherein X is an inorganic or organic acid residue, with x, y, and u independent from one another being equal to 0 or 1 and a, b, c, d, and e are independent from one another and an integer with a>0, b>0, c>0, d>0, e>0, and (a+b+c+d) >2, preferably (a+b+c+d) >4, in particular (a+b+c+d) >10, with X comprising e.g. chloride, nitrate, formate or acetate.

In another embodiment (ii) the fluoroorganic-substituted silicon compounds according to the invention are organosiloxane co-condensates or block co- condensates or mixtures thereof, derived from at least two of the aforementioned alkoxy silanes of general formulae (II), (III), (IV), and (V), preferably of formulae (II) and (III) with a molar ratio of 1 :< 3.5 or with a, b, c, and d of the alkoxy silane of formulae (II), (III), (IV), and (V) with a molar ratio of 0.1 < [a/b+c+d], in particular 0,25 < [a/b+c+d] < 6000, and preferably 1 < [a/b+c+d] < 3 with a > 0, b > 0, c > 0, and d > 0. In yet another embodiment (iii) the fluoroorganic-substituted silicon compounds are in monomeric form of the general formula (VI)

R -Y-(CH2)kSi(R3)y(OR1)3-y (VI), wherein R4, Y, R1 , R3, k, and y have the meaning as stated above. In addition to this, they may be mixtures of two or more monomeric compounds of the general formula (VI).

In a preferred embodiment, the curable mixture according to the invention comprises as fluoroorganic-substituted silicon compound a fluoroalkylalkoxy- silane of the formula (VII)

F3C(CF2)x(C2H4)ySi(CH3)z(OR)3-z (VII) wherein each R is selected independently from the group consisting of methyl, ethyl, n-propyl, and i-propyl with x being an integer with a value of 0 to 16, y = 0 or 1 , and z = 0 or 1 , preferably y = 1 , and in particular y = 1 , z = 0 and x = 3, 4, 5, 6, 7, 8 or 10.

Preferred, but non-limiting examples of fluoroalkylalkoxysilane of formula (VII) are tridecafluor-1 , 1 ,2,2-tetrahydrooctyl-triethoxysilane and/or tridecafluor-1 , 1 ,2,2- tetrahydrooctyl-trimethoxysilane.

The fluoroorganic-substituted silicon compounds which are used according the invention are preferably selected from the group of fluoroorganic-substituted silanes and fluoroorganic-substituted siloxanes or mixtures thereof. They are preferably selected from the group of fluoroalkyl-substituted monomeric silanes and fluoroalkyl-substituted siloxanes or mixtures thereof. An example of a fluoroalkyl-substituted monomeric silane is 3,3,4,4,5,5,6,6,7,7,8,8,8-trideca- fluorooctyl-triethoxysilane.

Although a large number of different fluoroorganyl-substituted silicon compounds can be used, it is often preferred when the fluoroorganyl-substituted silicon compound does not contain a Si-H bond.

The fluoroorganic-substituted silicon compounds which are adsorbed on a solid can be extracted from the solid with a suitable solvent, e.g. methylene chloride. The obtained liquid extract can be analyzed by GC/MS and/or by NMR. For NMR investigations 29Si- and 19F-NMR in particular are useful. Where appropriate, also 1H- and/or 13C-NMR spectroscopy may be used. These methods are known to the skilled person. If the fluoroorganic-substituted silicon compound is located in the cured mixture, it can be analyzed according to the process disclosed in EP 0 741 293 A2.

In a preferred embodiment, the fluoroorganic-substituted silicon compound is selected from the group of fluoroorganic-substituted silanes and fluoroorganic- substituted siloxanes, in particular fluoroalkyl-substituted monosilanes and monosiloxanes, and mixtures thereof. The term mixture is understood to include mixtures of fluoroorganic-substituted silicon compounds with other non-fluorine substituted silicon compounds, in particular mixtures of fluoroorganic-substituted silicon compounds of formula (VII) and CrC 6-alkylalkoxysilanes with alkoxy groups being methoxy, ethoxy, and propoxy groups and as alkyl groups methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and hexadecyl groups are particularly preferred. When mixtures with non-fluorine substituted silicon compounds are introduced, the amount of fluoroorganic-substituted silicon compounds is preferably at least 25 wt.%, in particular at least 50 wt.%, and most preferably at least 75 wt.%, based on the total amount of silicon compound present. The solid, i.e. carrier, on which the fluoroorganyl-substituted silicon compound is adsorbed typically is an inorganic or organic carrier. Preferably, the carrier is free-flowing, can be dosed easily, stored over several months, and wets nicely upon contact with water. It was surprisingly found that these properties do not change at all, or at least not significantly, when adsorbing the fluoroorganyl- substituted silicon compound onto the carrier, i.e. solid. Furthermore, the fluoroorganic-substituted silicon compound which is adsorbed on a solid can be easily mixed with the mineral binder.

It is noted that EP-A-0 919 526 discloses building material compositions comprising a hydrophobic powder containing silicic acid as carrier and hydrophobic components that are liquid at 10°C. The hydrophobic components contain an organosilicon compound, solvent and/or water and emulsifier, with the powder containing 5-80 wt.% of organosilicon compound. The latter is preferably selected from specific alkylalkoxysilanes, organosilanes, and alkalisiliconates. The alkylalkoxysilanes may also be substituted with a halogen, with unsubstituted alkylalkoxysilanes being preferred. It is neither disclosed nor suggested that said mixture may be used for easy-to-clean applications.

In the context of this invention, the solid, i.e. the carrier or carrier material, on which the fluoroorganic-substituted silicon compound is adsorbed is preferably in the form of a powder or granule. According to the invention, the term powder includes granules. Organic carriers are preferably water-soluble polymers and inorganic carriers are an inert inorganic material, i.e. not a mineral binder.

In the context of this invention, the solid, i.e. the carrier comprising the adsorbed fluoroorganic-substituted silicon compound, possesses free-flowing properties and thus it can easily be transported and mixed into mixtures of different composition. The free-flowing properties in most cases can easily be determined optically by pouring the powder from e.g. a container onto a flat surface. However, for more critical cases, or if an exact rating is required, it can be determined in accordance with ISO 4342 by using the pourability tester according to Dr. Pfrengle (sold e.g. by Karg-lndustrietechnik). In that case, a given amount of powder is poured through a defined orifice onto a slightly roughened surface. By measuring the height of the obtained cone formed by the powder, the pouring angle can be determined according to a reference list. The lower the pouring angle, expressed in degrees, the better the pourability and the free-flowing characteristics of the powder. Hence, the inventive free-flowing powder has typically a pouring angle of about 70° or less, preferably of about 60° or less, and in particular of about 50° or less.