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
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
  • C04B24/42—Organo-silicon compounds
• • 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
  • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B14/02—Granular materials, e.g. microballoons
• • 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
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/005—Halogen-containing compounds
• • 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
  • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
  • C04B26/30—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Other silicon-containing organic compounds; Boron-organic compounds
• • 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
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/02—Compositions 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
• • 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
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/20—Resistance against chemical, physical or biological attack
  • C04B2111/203—Oil-proof or grease-repellant materials
• • 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
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/20—Resistance against chemical, physical or biological attack
  • C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials

Definitions

• the present invention relates to a special hydraulically setting mixture, wherein a produced therefrom, set or hardened workpiece on the surface has dirt-repellent properties.
• Hydraulically setting materials such as cementitious materials
• pollution of the surfaces of such concrete paving stones by a variety of materials, such as traffic and industrial emissions, especially carbon blacks, pollen, grass stains, oils, especially engine oils, beverage and food residues, especially cola, coffee, red wine or ketchup, and by
• the growth of microorganisms, such as algae or fungi is an aesthetically significant problem.
• the equipment of hydraulically set materials in such applications with dirt-repellent properties [hereinafter also "easy-to-clean" or ETC called] is therefore desirable.
• dirt-repellent properties is meant the property of the surface to prevent the penetration of both aqueous and oily substances into the material and to facilitate the removal of these substances from the surface.
• EP 0 838 467 teaches the use of a fluorine-containing silane or silane system
• EP 0 913 370 teaches the use of aqueous, silane-containing emulsions to obtain water-repellent (hydrophobic) properties of such materials. Unfortunately, the teaching does not lead to the desired "easy-to-clean" surfaces.
• EP 1 445 242 discloses non-cement-based plasters or coatings for facades which have dirt-repellent properties.
• the dirt-repellent properties are achieved by the microroughness is reduced so that dirt particles can not penetrate into the pore space and set.
• the disadvantage here is that kaliwasserglasbasêt, non-cementitious plaster mixtures are modified as such.
• the present invention thus relates to a hydraulically setting mixture, in particular for materials with "easy-to-clean" properties, comprising:
• mixture components or components used in each case give a total of 100% by weight. It is envisaged that, depending on the concrete selection of the constituents of the mixture, the general quantity limits mentioned under a), b) and c) will always be complied with.
• the fluoro-organyl-substituted silicon compounds used according to the invention are preferably selected from the series of fluorinated organyl-substituted silanes and fluorinated organyl-substituted siloxanes or mixtures thereof. In particular, they are preferably selected from the series of monomeric fluoroalkyl-substituted silanes and fluoroalkyl-substituted siloxanes or mixtures thereof.
• Preferred examples of monomeric fluoroalkyl-substituted silanes are 3,3,4,4,5,5,6,6,7,7,8,8,8- Tridecafluorooctyl-triethoxysilane and 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl-trimethoxysilane.
• Preferred examples of monomeric fluoroalkyl-substituted silanes are 3,3,4,4,5,5,6,6,7,7,8,8,8- Tridecafluorooctyl-triethoxysilane and 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl-trimethoxysilane.
• organosilane or organosiloxane in particular a C 1 -C 16 -alkyltrialkoxysilane, for example methyl, propyl, butyl, octyl, hexadecyltrimethoxysilane or trie
• Such preparations are, for example, but not exclusively, from DE 196 06 01 1, EP 0 538 555, EP 0 675 128, EP 0 716 127, EP 0 716 128, EP 0 832 91 1, EP 0 846 717, EP 0 953 591, EP 0 960 921, EP 1 033 395,
• a hydraulically setting mixture according to the invention may be advantageous as additional components in addition
• Pozzolans such as fly ash or microsilica, and blast furnace cements are selected and used or contained. So is in an inventive
• additives in a mixture according to the invention can be, for example, aggregates according to EN 206-1: 2000.
• aggregates may be aggregates, sands, gravels, chippings, porphyry, quartz, lime and rock flour or mixtures thereof, but also flyash, microsilica and other silicate additives or mixtures thereof.
• Sands can be, for example, quartz sands or river sands. Gravel, chippings, crushed sands, porphyry, quartz, lime and rock flour or mixtures thereof are preferred.
• a mixture according to the invention may advantageously contain additives which preferably contain a maximum particle size of 8 to 63 mm, particularly preferably 8 mm, 16 mm, 32 mm or 63 mm, in particular aggregates with a maximum particle size of 32 mm, in accordance with the specifications of DIN 1045 -2. It is particularly preferred if the aggregate (s) is / are an aggregate with 32 mm largest grain and / or sand with 5 mm maximum grain size.
• a mixture according to the invention can be prepared in a simple and economical manner by combining and mixing the claimed components. So you can typically add a mixture of the invention with water and mix in a mixing apparatus.
• C is an alkyl radical R 5 in the structural element derived from general formula IV
• R 1 in the formulas II, III, IV, V and / or VI independently of one another is a linear, branched or cyclic alkyl group having 1 to 8 C atoms or an aryl group, preferably R 1 is independently methyl, ethyl or propyl; with R 2 , R 3 and / or R 5 in the abovementioned formulas independently of a linear or
• branched alkyl having 1 to 4 carbon atoms, preferably independently of one another methyl or ethyl, and
• HX is an acid, where X is an inorganic or organic acid radical, where x, y and u are independently 0 or 1 and a, b, c, d and e are each independently integer with a> 0 , b> 0, c> 0, d> 0, e> 0 and (a + b + c + d)> 2, preferably (a + b + c + d)> 4, particularly preferably (a + b + c + d)> 10, with X comprises, for example, chloride, nitrate, formate or acetate, or (ii) compounds wherein the organosiloxanes are co-condensates or block co-condensates or mixtures thereof derived from at least two of the aforementioned alkoxysilanes of the general Formulas II, III, IV and V are, preferably in a molar ratio of the formulas II and III 1: ⁇ 3.5 derived or with a, b, c and
• said fluorinated organo-substituted silicon compounds may also be in the form of an aqueous preparation, e.g. as an aqueous solution,
• Dispersion or emulsion can be used.
• aqueous preparations may in particular be aqueous dispersions or
• Emulsions of a fluoroorganyl-substituted silane and / or siloxane which has a content of fluorinated organyl-substituted silicon compound of from 1, 5 wt .-% to 90 wt .-%, preferably 2 wt .-% to 80 wt .-%, particularly preferably 2 , 5% by weight to 70% by weight, very particularly preferably 5% by weight to 60% by weight (in each case based on the total mass of the aqueous formulations).
• inventively used fluorine-organyl-substituted silicon compounds in the form of an aqueous emulsion may contain at least one emulsifier, which advantageously from the series of alkyl sulfates with Cs-Cis-alkyl, alkyl and alkaryl ether with Cs-Cis-alkyl in the hydrophobic radical and 1 to 40
• Ethylene oxide (EO) or propylene oxide (PO) units alkylsulfonates with Cs-Cis-alkyl, alkarylsulfonates with Cs-Cis-alkyl, and half esters of sulfosuccinic acid with monohydric alcohols or alkylphenols having 5 to 15 carbon atoms, alkali metal and ammonium salts of carboxylic acids having 8 to 20 carbon atoms in the alkyl, aryl, alkaryl or aralkyl radical, alkyl and alkaryl phosphates having 8 to 20 carbon atoms in the organic radical, alkyl ether or alkaryl ether phosphates having 8 to 20 carbon atoms in the alkyl or alkaryl radical and 1 up to 40 EO units,
• EO / PO ethylene oxide / propylene oxide
• Emulsifier in such an emulsion is preferably 0.01 to 5 wt .-%, based on the total weight of the emulsion.
• an aqueous composition of a fluorine-organyl-substituted silicon compound used according to the invention may advantageously also contain customary auxiliaries selected from inorganic or organic acids,
• Buffer substances fungicides, bactericides, algicides, microbicides,
• the fluoro-organyl-substituted silicon compounds used according to the invention can be present in solid or liquid form. So it is also possible that they are in free-flowing, especially powdery form and in water
• the fluorine-organyl-substituted silicon compound can thus advantageously be in a solid, free-flowing form and on a
• inorganic material in particular a porous or absorbent material, supported or sorbed, in particular absorbed, are present; it may preferably be in solid, free-flowing form and also be dispersible in water.
• fluoroorganyl-substituted silicon compound is present as a particulate or pulverulent formulation, these can be used as such or in the form of a dispersion in the preparation of a mixture according to the invention.
• Such particulate or fluorinated fluorine organyl-substituted silicon compounds can be obtained by using the fluoroorganylsubstituABLE invention
• metal oxides may be oxides, hydroxides or hydrated oxides of the elements of the main groups I, II, III and / or IV and of the
• Subgroups IV, VI, Villa and / or VIIIc of the Periodic Table of the Elements (PSE) and / or cerium be.
• silicas such as flame silicas, d. H. pyrogenic silicas, precipitated silicas, crystalline silicas, or zeolites used.
• carbonates and / or bicarbonates and sulfates and / or hydrogen sulfates but also phosphates, hydrogen phosphates and / or
• Dihydrogenphosphate the said metals or elements are used as support materials.
• Carrier materials are used. Such materials are, for example, clays, expanded clay, limestone, chalk, plaster and / or minerals such as slate flour.
• Suitable particulate or pulverulent, in particular free-flowing, formulations can be obtained, for example, by treating at least one of the said support materials with at least one of the above-mentioned liquid fluorine-organyl-substituted silicon compounds or preparations according to the invention.
• the treatment may be, for example, by wetting (mixing, kneading, milling, dipping, flooding) said support materials with at least one of said fluorine organyl-substituted silicon compounds or said
• the treatment can also be carried out by spraying the carrier material with a fluoroorganyl-substituted
• the treatment is preferably carried out in an internal mixer, for example a Lödigemischer. Also, grinding and / or sifting of the powders may be carried out before or after.
• the preparation of suitable particle or pulverulent formulations can be carried out, for example, as described in the example of EP 0466958. Furthermore, can the preparation of suitable particle or pulverulent formulations, for example as described in US Pat. No. 7,514,494.
• the average particle size of the carrier materials used according to the invention is advantageously 1 nm to 100 ⁇ m, including all intervening numbers, preferably 2 nm to 10 ⁇ m, more preferably 3 nm to 1 ⁇ m, very particularly preferably 5 nm to 500 nm.
• the average particle size can be determined, for example, by transmission electron microscopy (TEM) can be determined.
• the specific surface area of the carrier materials used according to the invention is advantageously 20 to 800 m 2 / g including all numbers lying therebetween, preferably 25 to 600 m 2 / g, particularly preferably 50 to 500 m 2 / g, very particularly preferably 60 to 400 m 2 / g , in particular 70 and 300 m 2 / g.
• the specific surface area (BET) can be determined, for example, on the basis of DIN 66131.
• carrier materials used according to the invention may preferably have a pore volume of from 0.1 to 10 cm 3 / g.
• the pore volume can be calculated from the sum of micro, meso and macro pore volumes. The determination of the micro- and mesopores is carried out by recording an N2 isotherm and its evaluation according to BET, de Boer and Barret, Joyner,
• the determination of the macropores D> 30 nm is carried out by Hg porosimetry.
• the sample is dried for 15 hours at 100 ° C in a drying oven and degassed at room temperature in vacuo.
• the sample is added for 15 hours
• carbon blacks can also be used as support materials.
• carbon blacks carbon blacks having an average primary particle size of 8 to 80 nm, preferably 10 to 35 nm and a DBP number of 40 to 200 ml / 100 g,
• DBP dibutyl phthalate
• Pigment blacks made by furnace, gas black, channel or flame black examples include carbon black FW 200, Carbon black FW 2, carbon black FW 2 V, carbon black FW 1, carbon black FW 18, carbon black S 170, carbon black S 160, special carbon black 6, special carbon black 5, special carbon black 4, special carbon black 4A, Printex 150 T, Printex U, Printex V, Printex 140 U Printex 140, Printex 95, Printex 90, Printex 85, Printex 80, Printex 75, Printex 55, Printex 45, Printex 40, Printex P, Printex 60, Printex XE 2, Printex L 6, Printex L, Printex 300, Printex 30, Printex 3, Printex 35, Printex 25, Printex 200, Printex A, Printex G, special black 550, special black 350,
• Preferred embodiments of the invention can be used gas soot.
• Fluororganylsubstitu lying on silicon compounds or corresponding preparations, in particular a fluoroalkylalkoxysilane or liquid fluoralkylsilanbas founded system, as mentioned above, can be adjusted by grinding, for example in a ball mill, bead mill or counter-jet mill and / or in a suitable mixing unit, for example a ploughshare mixer ,
• the particle size can be increased by suitable agglomeration.
• silicatic additives can advantageously be selected from the series of microsilica, fly ash,
• Water is preferably 1 to 20 wt .-%. If the fluoro-organyl-substituted silicon compound used according to the invention is used in the form of its aqueous preparation, then it is advantageous for the fluoro-organyl-substituted silicon compound used according to the invention.
• Condensers may be all common flow aids, in particular polycarboxylate ethers (PCEs) and / or polymethyl methacrylates and lignosulfonates or naphthalene-formaldehyde sulfonates.
• PCEs polycarboxylate ethers
• Condensers may be all common flow aids, in particular polycarboxylate ethers (PCEs) and / or polymethyl methacrylates and lignosulfonates or naphthalene-formaldehyde sulfonates.
• Hydraulically setting mixtures according to the invention can be used as further
• Adjuvants for example, dispersants and wetting aids, such as, for example, siliconates or alkyl phosphonates, defoamers, such as, for example, trialkyl phosphates, air entraining agents, such as saponified resin acids, retarders and
• Accelerators such as formates, and / or water reducers.
• hydraulically setting mixtures according to the invention can be used in the concrete industry, these being mixed in conventional compulsory mixers.
• Pulverform ige formulations may be advantageous in
• Mixing water are predispersed.
• the content of additionally introduced water can be advantageous in setting the desired w / c value be taken into account.
• the processability of the mixtures according to the invention is advantageously unchanged in comparison with unmodified mixtures.
• Such a solid mixture according to the invention of a hydraulically setting mixture can be obtained, for example, by adding cement [component according to feature a], aggregate [component according to feature b] and a free-flowing carrier material containing at least one organosilicon-substituted silicon compound [component according to feature c] is treated in one
• Mixing container mixes, mixes, if necessary filled in a transport container and provides for the application. Furthermore, you can such a
• Solids mixture optional Condenser [component according to feature d] and / or other auxiliaries [component according to feature e] add or mix, provided that these components are powdery or giant-shaped. If these components are liquid according to d) or e), they can likewise be applied to one of the said support materials, thus converting into a free-flowing form and mixing in or mixing in with a mixture according to the invention.
• a hydraulically setting mixture obtained in accordance with the invention can be subjected to shaping and curing known per se to a person skilled in the art, whose surfaces advantageously have a lower tendency to become soiled ("easy-to-clean” property) even when attrition occurs.
• the present invention thus also provides materials, in particular components, concrete products or moldings, which are obtainable using a hydraulically setting mixture according to the invention.
• Next object of the present invention is the use of a
• a fluorine-organyl-substituted silicon compound for the mass modification of a hydraulically setting mixture, in particular a mixture containing 6 to 25% by weight of cement, 50 to 90% by weight of at least one Aggregate and 0.001 to 8 wt .-% of at least one fluorine-organyl-substituted silicon compound and optionally 1 to 20 wt .-% of water and / or 0.01 to 2 wt .-% of plasticizer and / or 0.01 to 1 wt .-% contains at least one further adjuvant, wherein the components used in each case add up to 100 wt .-%.
• cleaning and cleaning processes can be carried out on account of the newly achieved "easy-to-clean" properties of hydraulically hardened workpieces, in spite of abrasion and weathering
• compositions of the invention can be prepared and used advantageously.
• the mortar test specimens used were prepared from a commercially available universal mortar (mortar group II according to DIN V 18580, mortar group P II according to DIN V 18550) from Quick-Mix. For this purpose, about 100 g of the mortar were thoroughly stirred with about 24 ml of water. The additives listed in the examples were each predispersed in the mixing water. The resulting mixture was filled in PE formwork, dried for 24 h at 25 ° C, then disconnected and cured for a further 28 days at 25 ° C. The contamination properties were determined on the basis of DIN EN ISO 10545-14, the test is described in more detail below.
• Example 1 (Comparative Example) A mortar specimen was prepared as described above. No additives were used.
• Example 2 A mortar specimen was prepared as described above. In the mixing water, 3% by weight of the aqueous fluoroalkylsilane formulation prepared according to Example 1 of DE 19955047 were dispersed before addition.
• Example 3 A mortar specimen was prepared as described above. In the mixing water, 3% by weight of the aqueous fluoroalkylsilane formulation prepared according to Example 1 of DE 19955047 were dispersed before addition.
• a mortar specimen was prepared as described above. In the mixing water before addition 5 wt .-% of a powder prepared as in the example of
• EP 0 466 958 B1 containing 6% by mass 3,3,4,4,5,5,6,6,7,7,8,8,8- Tridecafluoroctyl-triethoxy-silane, dispersed.
• a mortar specimen was prepared as described above.
• 10% by weight of a powder prepared as described in the example of EP 0 466 958 B1, containing 6% by mass 3,3,4,4,5,5,6,6,7,7, 8,8,8-tridecafluorooctyl-triethoxy-silane, dispersed.
• Example 6 (comparative example)
• a mortar specimen was prepared as described above. In the mixing water, 2% by weight of an o / w emulsion which contains 50% by weight (based on the total amount of the emulsion) of an octyltriethoxysilane were dispersed before addition.
• aqueous polluting agents (coffee, cola, red wine) each achieve a 4 or 5 and at the same time a significant improvement over one olive oil

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• 2011
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