DE102009045112A1 - Mixture for cementitious materials with easy-to-clean properties - Google Patents

Mixture for cementitious materials with easy-to-clean properties

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Publication number
DE102009045112A1
DE102009045112A1 DE200910045112 DE102009045112A DE102009045112A1 DE 102009045112 A1 DE102009045112 A1 DE 102009045112A1 DE 200910045112 DE200910045112 DE 200910045112 DE 102009045112 A DE102009045112 A DE 102009045112A DE 102009045112 A1 DE102009045112 A1 DE 102009045112A1
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DE
Germany
Prior art keywords
weight
parts
hydraulically setting
silane
mixture according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
DE200910045112
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German (de)
Inventor
Manuel Dr. Friedel
Spomenko Ljesic
Wolfgang Dr. Lortz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Degussa GmbH
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Evonik Degussa GmbH
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Filing date
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Priority to DE200910045112 priority Critical patent/DE102009045112A1/en
Publication of DE102009045112A1 publication Critical patent/DE102009045112A1/en
Application status is Withdrawn legal-status Critical

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Classifications

    • 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
    • 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
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/46Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
    • C09K8/467Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
    • C09K8/473Density reducing additives, e.g. for obtaining foamed cement compositions
    • 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
    • C04B2111/2038Resistance against physical degradation
    • C04B2111/2069Self cleaning materials, e.g. using lotus effect
    • 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
    • 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
    • Y02W30/92Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • 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
    • Y02W30/94Use of waste materials as fillers for mortars or concrete from metallurgical processes

Abstract

The present invention relates to a hydraulically setting mixture which
- 6 to 25 parts by weight of cement,
- 50 to 90 parts by weight of at least one additional charge,
0.01 to 3 parts by weight of at least one silane-based or siloxane-based hydrophobizing agent,
0.01 to 3 parts by weight of at least one siliceous additive having an average particle size of 1 nm to 20 μm and an inner surface area (BET) of 20 to 800 m 2 / g, and
optionally as further components at least 1 to 20 parts by weight of water, 0.05 to 0.5 parts by weight of plasticizer and 0.01 to 1 part by weight of at least one further auxiliary
contains and building materials made from it, components, concrete goods or moldings.
Furthermore, the invention relates to the use of a hydraulically setting mixture according to the invention for the production of building materials, components, concrete goods or moldings, for example as facing concrete, wherein the surface of corresponding body even with abrasion only a lower tendency to fouling ("easy-to-clean" property) having.

Description

  • The present invention relates to a special hydraulically setting mixture, wherein a hardened or hardened material surface produced therefrom has dirt-repellent properties.
  • Hydraulically setting materials, such as cementitious materials, are used in modern construction in many relevant places, such as for the application of concrete paving stones for driveways, sidewalks or terraces. Especially in the outdoors, the 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, from a aesthetic point of view is a major 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.
  • By 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.
  • It is known to produce "easy-to-clean" properties by aftertreatment of finished, cured surfaces with various materials. So teaches others EP 0 838 467 the use of a fluorine-containing silane or silane system for surface treatment. Disadvantage of such systems for the aftertreatment of a surface is, on the one hand, the need for a further process step after the production of such materials or materials, on the other hand, the durability of such coatings is often too low, since they are removed by weathering and abrasion.
  • It is also known to improve hydraulically hardening materials, in particular cement-bonded materials, by the addition of mass modifiers. That's how it teaches EP 0 913 370 the use of aqueous, silane-containing emulsions to obtain water-repellent (hydrophobic) properties of such materials. Unfortunately, teaching does not lead to the desired "easy-to-clean" surfaces.
  • Out US 5,650,004 is a cement-based plaster mixture is known, which is used for the sealing of swimming pools. The water-repellent properties and improved durability of the plaster mixture are achieved by the addition of silane-modified powders and pozzolanic fillers. Disadvantage of this plaster mixture is that although permanently water-repellent properties can be achieved, so even aqueous contaminants can be rejected, but no dirt-repellent properties are achieved in the sense described above.
  • Out DE 10 346 082 Hydraulically hardening mixtures are known whose special composition leads to a changed structure. As a result, wear-resistant workpieces with conditionally dirt-repellent surfaces are obtained.
  • Out EP 1 445 242 are non-cement-based plasters or coatings for facades are known that 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 kaliwasserglasbasierte, non-cementitious plaster mixtures are modified as such.
  • It is an object of the present invention to provide a further hydraulically setting mixture, in particular a cement-bound mixture, wherein the surface of a material produced therefrom after setting or hardening has sufficiently good dirt-repellent properties and these are as long-lasting as possible.
  • This object is achieved according to the features of the claims.
  • Surprisingly, it has now been found that by adding at least one silane-based and / or siloxane-based hydrophobing agent together with at least one silicatic additive, in particular a well-defined fumed or precipitated silica, to a hydraulically setting mixture, in particular an otherwise conventional concrete mixture, permanent ETC- Characteristics of a produced therefrom, hydraulically set and hardened material can be achieved.
  • Furthermore, it has surprisingly been found that it may be advantageous to premix said silicate additive, especially if it is precipitated silica, together with the other solids of the mixture according to the invention, such as cement and aggregates in a suitable mixing units.
  • The subject of the present invention is thus a hydraulically setting mixture which
    • 6-25 parts by weight of cement,
    • - 50-90 parts by weight of at least one additional charge,
    • 0.01-3 parts by weight of at least one silane-based or siloxane-based hydrophobing agent,
    • 0.01-3 parts by weight of at least one siliceous additive having an average particle size of 1 nm to 20 μm and an inner surface area (BET) of 20 to 800 m 2 / g,
    contains.
  • In addition, a hydraulically setting mixture according to the invention can be advantageously used as further components at least
    • - 1-20 parts by weight of water, and
    • Optionally 0.05-0.5 parts by weight of plasticizer, preferably selected from the group of polycarboxylate ethers (PCEs), polymethyl methacrylates and lignosulfonates or naphthalene-formaldehyde sulfonates, and
    • Optionally 0.01-1 parts by weight of at least one further adjuvant, preferably selected from the group of dispersing aids and wetting aids, such as siliconates or alkyl phosphonates, defoamers, such as trialkyl phosphates, air entraining agents, such as saponified resin acids, retarders and accelerators, such as formates, and / or water reducer
    contain.
  • Preference is given to mixtures according to the invention, in particular cement-bound mixtures which
    • 7-24, in particular 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 or 23 parts by weight of cement,
    • - 55-85, in particular 60, 65, 70, 75 or 80 parts by weight of at least one aggregate,
    • 0.05-2.5, in particular 0.5, 1, 1.5 or 2 parts by weight of at least one silane-based or siloxane-based hydrophobizing agent,
    • 0.05-2.5, in particular 0.5, 1, 1.5 or 2 parts by weight of at least one siliceous additive having an average particle size of 2 nm to 20 μm, in particular 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 130, 150, 170, 190, 210, 230, 250 and 270 nm and 0.3, 0.5, 0.75, 1, 1.25, 1.5, 2, 2.5, 3, 4, 5, 10, 12, 15, 18, 19 and 20 μm, and an inner surface (BET) of 20 to 800 m 2 / g, in particular 40, 60, 80, 100, 120, 150, 175, 180, 200, 250, 300, 350, 400, 500, 600 and 700 m 2 / g, and optionally as further components at least
    • - 2-10, in particular 3, 4, 5, 6, 7, 8 and 9 parts by weight of water, and
    • Optionally 0.05 to 0.5, in particular 0.1, 0.2, 0.3 or 0.4 parts by weight of plasticizer, preferably selected from the series of polycarboxylate ethers (PCEs), polymethyl methacrylates and lignosulfonates or naphthalene-formaldehyde sulfonates
    • Optionally 0.05-0.9, in particular 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8 parts by weight of at least one further auxiliary, preferably selected from the group of dispersing aids and wetting aids, such as, for example, siliconates or alkylphosphonates, defoamers, such as, for example, trialkyl phosphates, air-entraining agents, such as saponified resin acids, retarders and accelerators, such as, for example, formates, and / or water reducers
    contain.
  • Cements in a mixture according to the invention, all customary Portland cements and Portland composite cements and blast furnace cements can be used or contained. Thus, in a blend according to the invention, the cement is preferably, but not exclusively, selected from the Portland Cement range, Portland composite cements and blast furnace cements.
  • So-called additives in a mixture according to the invention can be, for example, aggregates, such as sands, gravels or grit. Sands may be, for example, quartz sands, river sands and / or fly ash. Thus, a mixture according to the invention may advantageously contain additives which are preferably selected from the series of sands, gravel and chippings, preferably such aggregates with a maximum particle size from 8 to 63 mm, more preferably those of 8 mm, 16 mm, 32 mm or 63 mm, in particular aggregates of a maximum grain size of 32 mm, in accordance with the specifications of DIN 1045-2 ,
  • Furthermore, mixtures according to the invention are preferably based on at least one silane-based or siloxane-based hydrophobizing agent selected from the series of aqueous silane- and / or siloxane-based compositions, silane and / or siloxane-based emulsions, wherein the silane and / or siloxane-based composition or emulsion preferably has an active ingredient content Silane and / or siloxane of 2.5 to 90 wt .-%, based on the composition or emulsion.
  • Water repellents in the context of the present invention may be alkyl-substituted silanes of the general formula I.
    Figure 00060001
    in which R 1 is linear or branched C 1 -C 18 -alkyl, groups R 2 are identical or different and R 2 is a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms, preferably having 1 or 2 carbon atoms. Preferred examples are those with radicals:
    R 1 = CH 3 -, C 2 H 5 -, C 3 H 7 -, C 4 H 9 -, iC 4 H 9 -, C 6 H 13 -, iC 6 H 13 , C 8 H 16 -, iC 8 H 16 - and
    R 2 = H, methyl or ethyl.
  • In addition, hydrophobicizing agents according to the invention may be oligomeric siloxanes of the general formula II
    Figure 00060002
    in the groups R 1 and R 3 are independently C 1 -C 18 alkyl, which may contain one or more heteroatoms such as N, O, F, Cl, P or S, groups R 2 are the same or different and R 2 a Is hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably 1 or 2 carbon atoms, and n + m is the degree of oligomerization as being 2 to 50, preferably 2 to 30, determined. These are advantageously oligomer mixtures having a mean degree of oligomerization of from 2 to 50, preferably from 2 to 30, the average molecular weight preferably being from 300 to 10 000 g / mol. The silanoligomers of the general formula II can be present as linear, cyclic and / or branched units. The determination of the molar mass can be determined, for example, by means of GPC by methods familiar to the person skilled in the art.
  • Preferred examples of silanoligomers are those having radicals:
    R 1 = CH 3 -, C 2 H 5 -, C 3 H 7 -, C 4 H 9 -, iC 4 H 9 -, C 6 H 13 -, iC 6 H 13 , C 8 H 16 -, iC 8 H 16 - and
    R 2 = H, methyl or ethyl
    R 3 = CH 3 -, C 2 H 5 -, C 3 H 7 -, C 4 H 9 -, iC 4 H 9 -, C 6 H 13 -, iC 6 H 13 , C 8 H 16 -, iC 8 H 16 -, NH 2 -C 3 H 6 -, NH 2 -C 2 H 4 -NH-C 3 H 6 -, NH 2 -C 2 H 4 -NH-C 2 H 4 -NH-C 3 H 6 .
    Figure 00070001
  • In addition, mixtures of said hydrophobing agents of the general formulas I and II can be used or used according to the invention. In this case, each of the hydrophobizing agents I and II independently account for between 0% and 100% of the total amount of hydrophobizing agent (proportion of total hydrophobing agent).
  • Suitable silane or siloxane-based water repellents and their preparation can be, for example, but not exclusively EP 0 838 467 . EP 0 814 110 . EP 0 960 921 . EP 1 205 481 . EP 1 099 703 and or EP 1 306 381 remove. Thus, the entire contents of the aforementioned documents are to be considered as fully within the scope of the present disclosure.
  • As a rule, a mixture according to the invention can be prepared in a simple and economical manner by combining and mixing the claimed components.
  • Thus, in general, by mixing the components according to the present main claim, one can first provide a hydraulic setting mixture. This can, if one then together when applied with a claimed amount of water, optionally with good mixing with or in the skilled person known devices or containers, other components that are listed above, enforce and the thus obtained Bring the mixture or a mass produced in this way to a desired shape and allow it to set hydraulically or harden.
  • Advantageously, the said silane / siloxane-containing hydrophobizing agents can be used in the form of an aqueous preparation. As a result, the incorporation into the aqueous, cement-containing mixtures can be additionally simplified. Such aqueous preparations may, in particular, be aqueous emulsions which have a content of hydrophobizing agent of the formula I and / or II of in total 2.5% by weight to 90% by weight, preferably 5% by weight to 80% by weight, particularly preferably from 5% by weight to 70% by weight, very particularly preferably from 10% by weight to 60% by weight (in each case based on the total mass of the aqueous emulsion).
  • If water repellents used according to the invention are present in the form of an aqueous emulsion, they may contain at least one emulsifier which advantageously comprises a series of alkyl sulfates with C 8 -C 18 -alkyl, alkyl and alkaryl ether sulfates with C 8 -C 18 -alkyl in the hydrophobic radical and with 1 to 40 ethylene oxide (EO) or propylene oxide (PO) units, alkyl sulfonates with C 8 -C 18 alkyl, alkaryl sulfonates with C 8 -C 18 alkyl, and half esters of sulfosuccinic acid with monohydric alcohols or alkylphenols with 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 to 40 EO units, alkyl polyglycol ethers and alkaryl polyglycol ethers having 8 to 40 EO units and C 8 -C 20 -carbon atoms in the alkyl l- or aryl radicals, ethylene oxide / propylene oxide (EO / PO) block copolymer having 8 to 40 EO or PO units, addition products of alkylamines having C 8 -C 22 -alkyl radicals with ethylene oxide or propylene oxide, alkyl polyglycosides with linear or branched saturated or unsaturated C 8 -C 24 -alkyl radicals and Oligoglykosidresten with 1 to 10 hexose or pentose units, silicon-functional surfactants or mixtures of these emulsifiers is selected.
  • The content of emulsifier in such an emulsion is preferably 0.01 to 5 wt .-%, based on the total weight of the emulsion.
  • In addition, an aqueous composition of a hydrophobizing agent used according to the invention can advantageously also comprise customary auxiliaries selected from inorganic or organic acids, buffer substances, fungicides, bactericides, algicides, microbicides, odorous substances, corrosion inhibitors, preservatives, rheology aids.
  • Furthermore, silicatic additives according to the invention are advantageously selected from the series of microsilica, fly ash, flame silicic acids, precipitated silicas, zeolites, crystalline silicas, silica sols, kaolin, mica, kieselguhr, diatomaceous earth, talc, wollastonite or clay or from a mixture of corresponding silicates Microsilica, fly ash, flame silicic acids, precipitated silicas, zeolites, crystalline silicas, silica sols, kaolin, mica, kieselguhr, diatomaceous earth, talc, wollastonite or clay, or from an aqueous dispersion of at least one pyrogenic silica or at least one precipitated silica or a mixture of pyrogenically prepared and precipitated silicas.
  • The silicatic additives advantageously used in the present application, d. H. which are used for the preparation of a hydraulically setting mixture according to the invention or are present in the mixture according to the invention can be oxides, hydroxides or oxide hydrates of the silicon. These may contain other elements, such as. As lithium, sodium, potassium, magnesium, calcium, boron, aluminum, carbon, phosphorus, sulfur, halogens, titanium, chromium, iron, nickel, copper, zinc, zirconium, molybdenum, silver preferably in ionized form, optionally also in Form of oxides, included. Such siliceous fillers may be microsilica, fly ash, flame silicas, precipitated silicas, silica sols, kaolin, mica, diatomaceous earth, diatomaceous earth, talc, wollastonite or clay or even silicates inter alia in the form of glass beads, ground glass splinters (glass powder), glass fibers or glass fabrics.
  • Silica acids, such as flame silicic acids, precipitated silicas, crystalline silicic acids or zeolites are preferably used. Particularly preferred flame silicas and / or precipitated silicas. Silicate fillers used according to the invention may be pulverulent solids, but they are preferably in the form of aqueous dispersions. Also, grinding and / or sifting of the powders may be carried out before or after.
  • The average particle size used according to the invention or present in a mixture according to the invention silicate additives is advantageously 1 nm to 20 microns including all intervening numbers, preferably 2 nm to 10 .mu.m, more preferably 3 nm to 5 microns. The average particle size can be determined, for example, by means of transmission electron microscopy (TEM).
  • The specific surface area of siliceous additives used according to the invention or present in a mixture according to the invention is advantageously 20 to 800 g / m 2 including all numbers lying therebetween, preferably 25 to 600 g / m 2 , particularly preferably 50 to 500 g / m 2 preferably 60 to 400 g / m 2 , in particular 70 and 300 g / m 2 . The specific surface area (BET) can, for example, be based on DIN 66131 be determined.
  • If the silicatic additives according to the invention are used in the form of aqueous dispersions or a mixture according to the invention contains an aqueous dispersion of silicate additives, these advantageously have a content of at least one of said silicatic additives of from 2% by weight to 80% by weight, preferably 2 Wt .-% to 60 wt .-%, more preferably 5 wt .-% to 50 wt .-%, most preferably 10 wt .-% to 40 wt .-% (each based on the total mass of the aqueous dispersion) , Thus, the content of silicate additive in an aqueous dispersion used in the context of the present invention is preferably from 2 to 80% by weight.
  • Aqueous dispersions of silicate additives used according to the invention can be stabilized by salts of elements of main groups I and II of the Periodic Table of the Elements (PSE) and by salts of compounds of main group V of PSE, in particular by oxides, hydroxides, nitrates, nitrites, sulfates , Sulfites, sulfides, halides, phosphates, hydrogen phosphates, dihydrogen phosphates, carbonates, bicarbonates of sodium, potassium and / or ammonium.
  • If precipitated silicas are used as additives in the present invention, they can advantageously be premixed in suitable mixing units. Suitable mixing units are, for example, Lödige type mixers.
  • Advantageously precipitated silicas are premixed at 100 to 1000, in particular at 150 to 500 revolutions using a ploughshare mixer for a period of 30 minutes.
  • The silicate additive used according to the invention or present in the mixture according to the invention can have a content of carbon in pure or chemically bound form of between 0.1 and 25% by weight, preferably between 0.1 and 10% by weight, more preferably between 0 and 0 , 1 and 5 wt .-% (based on the total mass of the siliceous filler) have.
  • The silicate additive used according to the invention or present in the mixture according to the invention can furthermore contain a content of physically and chemically bound alcohol between 0 and 25% by weight, preferably between 0 and 15% by weight, particularly preferably between 0 and 10% by weight. %, (based on the total mass of the siliceous filler).
  • A silane-modified oxidic or siliceous additive used in the context of the invention can be predominantly homogeneous or inhomogeneous.
  • Silane-modified silicate additives are obtainable by mixing at least one microbeaded or microgranular silicate additive according to the invention in a compressed gas with at least one silane from the series of organosilicon compounds of general formula I and / or II and / or an organosilicon compound, as in US Pat DE 198 44 607 described, implemented. Furthermore, suitable silane-modified silicate additives can be obtained, for example, by treating silicate additives with a silanizing reagent. The treatment can be carried out, for example, by wetting (mixing, kneading, grinding, dipping, flooding) said silicate additives with the silanizing reagent and subsequent thermal aftertreatment, for example in a drying cabinet. However, the treatment can also be carried out by spraying the silicatic additives with a silanizing reagent, optionally under the influence of a higher temperature and optionally in vapor form.
  • A silicate, silane-modified additive used according to the invention may contain from 0.1 to 50% by weight, preferably from 0.1 to 25.0% by weight, particularly preferably from 0.1 to 10% by weight, of silane in a tethered or unbonded form contain.
  • A silane-modified, siliceous additive used according to the invention may further contain from 50 to 99.9% by weight of microbeaded or microgranular, siliceous filler.
  • In this case, the silane-modified silicate additive may have a pearl fraction greater than 1000 μm of less than 30% by weight, preferably less than 20% by weight, particularly preferably less than 10% by weight, and / or a bead fraction greater than 500 μm of less than 30 Wt .-%, preferably less than 20 wt .-%, more preferably less than 10 wt .-%, have.
  • The above-mentioned silane may be chemically and / or physically linked to the surface of the additives.
  • The silane used may in particular be an organosilicon compound or mixtures of organosilicon compounds of the general formula I and / or II.
  • As silane may also be advantageous compounds such as described in DE 198 44 607 , be used.
  • As silanes in the sense of the present invention for the modification of silicatic additives, it is also possible to use mixtures of silanes, for example mixtures of different silanes of the general formula I and / or II or mixtures of the oligomeric or polymeric siloxanes of the general formula II with silanes of the general formula I or Mixtures of silanes of the general formula I with mixtures of the oligomeric or polymeric siloxanes of the general formula II.
  • A silicate additive used in accordance with the invention and / or the silane which can be used to modify the additive can be admixed with additives before the reaction.
  • Also, the siliceous additive may be contacted with additional additives during the implementation of the silane modification.
  • Water, short-chain or long-chain alcohols, for example dodecanol, tetradecanol, hexadecanol, octadecanol, or other alcohols with molecular weights> 50 g / mol, short-chain or long-chain polyethers or polyether alcohols, for example diethylene glycol, triethylene glycol or others with molecular weights> 100 g / can be used as additives. mol, short-chain or long-chain amines having molecular weights> 50 g / mol, emulsion formers or else short-chain or long-chain silicone oils, for example silicone oils with molecular weights> 100 g / mol, or mixtures of the abovementioned compounds.
  • The modification reaction can be carried out at temperatures between 1 and 300 ° C, preferably between 1 and 200 ° C, more preferably between 1 and 150 ° C, and most preferably at temperatures between 1 and 130 ° C.
  • A silane-modified silicate additive to be used according to the invention can additionally be subjected to a compaction or processing step.
  • Finally, mixtures of at least two of the aforementioned silicate, optionally silanized, additives can be used.
  • If the hydrophobizing agents of the general formula I and / or II according to the invention and / or the silicatic additives according to the invention are used in the form of their aqueous preparations, then it is advantageous for the calculation of the total composition of the cement-bound mixture to use only the proportion of active substance in the respective aqueous composition as inventive Silane / siloxane-containing hydrophobing agent or inventive silicate additive, considered. Advantageously, the water content of these aqueous preparations is taken into account in the calculation of the necessary amount of water added.
  • All the usual flow aids, in particular polycarboxylate ethers (PCEs) and / or polymethyl methacrylates and also lignosulfonates or naphthalene-formaldehyde sulfonates, can be liquefied.
  • Hydraulically setting mixtures according to the invention may contain, for example, dispersants and wetting aids such as siliconates or alkyl phosphonates, defoamers such as trialkyl phosphates, air entrainers such as saponified resin acids, retarders and accelerators such as formates and / or water reducers.
  • Advantageously, hydraulically setting mixtures according to the invention can be used in the concrete industry, these being mixed in conventional compulsory mixers.
  • In this case, one can advantageously proceed by premixing powdery silicate additives with the cement and the other solid additives, liquid, non-aqueous water repellents of the general formulas I and / or II. Also premixed with the cement, aqueous formulations, such as the novel aqueous By contrast, emulsions of hydrophobizing agents and / or said aqueous dispersions of the well-defined silicate additives are added together with the mixing water. The content of additionally introduced water can advantageously be taken into account when setting the desired w / c value. The processability of the mixtures according to the invention is advantageously unchanged in comparison with unmodified mixtures.
  • However, it is also possible to submit a mixture of solids of a hydraulically setting mixture according to the invention in a compulsory mixer and to add and mix a defined amount of water in one batch or portionwise.
  • A hydraulically setting mixture obtained in accordance with the invention can subsequently be subjected to shaping and curing known per se to the person skilled in the art whose surfaces in the sense of the invention advantageously also have a lower tendency to become soiled ("easy-to-clean" property).
  • The present invention thus also relates to components, concrete products or molded articles obtainable using a hydraulically setting mixture according to the invention.
  • Next object of the present invention is the use of a hydraulically setting mixture according to the invention for the production of components, concrete products or moldings, the surface of which, even with abrasion has only a lower tendency to fouling ("easy-to-clean" property).
  • Thus, it is advantageously possible to use a hydraulically setting mixture according to the invention in the construction sector, in particular for the production of workpieces, for concrete paving stones, or else as facing concrete.
  • It should be noted that for the manufacturers of cement-bonded workpieces, in particular for the manufacturers of concrete blocks, it was until today of great interest to sustainably modify hydraulically setting, especially cement-bonded workpieces and despite abrasion and weathering easy-to-clean properties to ensure the surface.
  • By providing and using mixtures according to the invention, cleaning and maintenance costs can be significantly reduced by prolonged cleaning cycles due to the newly achieved, despite abrasion and weathering permanent easy-to-clean properties of hydraulically hardened workpieces. Such mass modifications can advantageously be carried out in particular during operation of a production plant and the workpieces can already be delivered completely protected. Additional effort on the site is eliminated.
  • But also on site an application compositions of the invention can be prepared and used advantageously.
  • The invention will be explained in more detail with reference to the following examples, without, however, limiting the scope of the invention.
  • Examples
  • The mortar test specimens used were made of a commercially available universal mortar (mortar group II according to DIN V 18580 , Mortar group P II according to DIN V 18550 ) made by Quick-Mix. For this purpose, about 90 g of the mortar were thoroughly stirred with about 13 ml of water. Each of the water repellents and additives listed in the examples were each predispersed in the mixing water. The resulting Mixture was filled in PE cups, dried for 24 days at 25 ° C, then disconnected from the PE beaker and cured for a further 28 days at 25 ° C. The pollution properties were based on DIN EN ISO 10545-14 determined, the test is described in more detail below.
  • Data in% by weight relate in each case to the weight of the mortar used, d. H. the complete dry mix.
  • Example 1 (comparative example)
  • A mortar specimen was prepared as described above. However, no silane-based or siloxane-based water repellents, silicate additives or other auxiliaries were used.
  • Example 2
  • A mortar specimen was prepared as described above. In the mixing water before addition 2 wt .-% of an aqueous emulsion containing 50 wt .-% of a Propylethoxyoligosiloxans having an average molecular weight of about 700 g / mol, and 3 wt .-% of a finely divided precipitated silica having a specific surface of 175 m 2 / g and an average particle size of 5 microns, dispersed.
  • Example 3
  • A mortar specimen was prepared as described above. In the mixing water before addition 2 wt .-% of an aqueous emulsion containing 50 wt .-% of an octyltriethoxysilane and 5 wt .-% of an aqueous dispersion containing 20 wt .-% of a fumed silica and is stabilized with KOH and characterized is dispersed by an average aggregate size of 0.12 μm and a pH of 9.0 to 10.0.
  • Example 4
  • A mortar specimen was prepared as described above. 2% by weight of an aqueous emulsion comprising 50% by weight of an octyltriethoxysilane and 1% by weight of a hydrophilic fumed silica having a specific surface area of 200 m 2 / g and a mean primary particle size of 12 nm, dispersed.
  • Example 5 (Comparative Example)
  • A mortar specimen was prepared as described above. In the mixing water, 2% by weight of an aqueous emulsion containing 50% by weight of an octyltriethoxysilane were dispersed before addition.
  • Example 6 (comparative example)
  • A mortar specimen was prepared as described above. In the mixing water before addition 5 wt .-% of an aqueous dispersion containing 20 wt .-% of a fumed silica and is stabilized with KOH and which is characterized by an average aggregate size of 0.12 microns and a pH of 9 , 0 to 10.0, dispersed.
  • Example 7 (comparative example)
  • A mortar specimen was prepared as described above. 3% by weight of a finely divided precipitated silica having a specific surface area of 175 m 2 / g and an average particle size of 5 μm were dispersed in the mixing water prior to addition.
  • evaluation
  • On the surface of the hardened mortar test specimens (not on the formwork side), one drop each (about 0.5 ml) of the soiling agents coffee (sweetened), cola, red wine, and olive oil was applied. After 1 hour reaction time at 25 ° C, the surface was blotted with a soft cloth and charged with deionized water for 3 min. Finally, the water is blotted with a soft cloth and visually assessed the contamination of the surface after drying. 5 means that no soiling is visible, 4 means that soiling is poorly visible, 3 means soiling 2 means that dirt is clearly visible and 1 means that dirt is very visible. Good easy-to-clean properties can only be mentioned if a clear improvement compared to an untreated control sample is achieved. Very good easy-to-clean properties can be used when the 3 aqueous pollution agents (coffee, cola, red wine) each achieve a 4 or 5 and at the same time olive oil achieves a significant improvement compared to an untreated control sample.
  • Table 1 below shows the results of the soiling test. example Pollution with coffee (sweetened) Pollution with coke Pollution with red wine Pollution with olive oil 1 1 5 1 1 2 4 5 4 3 3 4 5 4 1 4 4 5 4 1 5 2 4 1 1 6 2 2 1 1 7 2 2 1 1
    Tab. 1: Results of the contamination test
  • It is clear that according to the definition above with the mixture according to the invention from Example 2, very good easy-to-clean properties are achieved, and that with the mixtures 3 and 4 according to the invention, good easy-to-clean properties are still achieved. Comparative blends 5, 6 and 7 show no such clear improvement in cleaning properties
  • QUOTES INCLUDE IN THE DESCRIPTION
  • This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.
  • Cited patent literature
    • EP 0838467 [0004, 0023]
    • EP 0913370 [0005]
    • US 5650004 [0006]
    • DE 10346082 [0007]
    • EP 1445242 [0008]
    • EP 0814110 [0023]
    • EP 0960921 [0023]
    • EP 1205481 [0023]
    • EP 1099703 [0023]
    • EP 1306381 [0023]
    • DE 19844607 [0042, 0048]
  • Cited non-patent literature
    • DIN 1045-2 [0017]
    • DIN 66131 [0034]
    • DIN V 18580 [0070]
    • DIN V 18550 [0070]
    • DIN EN ISO 10545-14 [0070]

Claims (10)

  1. A hydraulically setting mixture comprising: - 6-25 parts by weight of cement, - 50-90 parts by weight of at least one aggregate, - 0,01-3 parts by weight of at least one silane- or siloxane-based hydrophobing agent, - 0,01-3 parts by weight of at least one siliceous additive, which has an average particle size of 1 nm to 20 μm and an inner surface area (BET) of 20 to 800 m 2 / g.
  2. Hydraulically setting mixture according to claim 1, characterized, that the mixture as further components at least 1-20 parts by weight of water, - If necessary, 0.05-0.5 parts by weight of plasticizer as well Optionally 0.01-1 parts by weight of at least one further auxiliary contains.
  3. Hydraulically setting mixture according to claim 1 or 2, characterized in that the cement from the series of Portland cements, Portland composite cements and blast furnace cements is selected.
  4. Hydraulically setting mixture according to one of claims 1 to 3, characterized in that aggregates are selected from the series sands, gravels and chippings, in particular those with 32 mm largest grain.
  5. Hydraulically setting mixture according to one of claims 1 to 4, characterized in that a silane or siloxane-based hydrophobing agent is selected from the series of aqueous silane and / or siloxane-based compositions, silane and / or siloxane-based emulsions, silane and / or siloxane-based Compositions or emulsion having an active ingredient content of silane and / or siloxane of from 2.5 to 90% by weight, based on the composition or emulsion.
  6. Hydraulically setting mixture according to one of claims 1 to 5, characterized in that silicate additives are selected from the series of microsilica, fly ash, flame silicas, precipitated silicas, zeolites, crystalline silicas, silica sols, kaolin, mica, kieselguhr, diatomaceous earth, talc, wollastonite or Clay a mixture of microsilica, fly ash, flame silicic acids, precipitated silicas, zeolites, crystalline silicas, silica sols, kaolin, mica, kieselguhr, diatomaceous earth, talc, wollastonite or clay, an aqueous dispersion of at least one pyrogenic silica or at least one precipitated silica or a mixture of pyrogenic and precipitated silicas.
  7. Hydraulically setting mixture according to claim 6, characterized in that the content of silicate additive in the aqueous dispersion is 2 to 80 wt .-%.
  8. Components, concrete products or moldings, obtainable using a hydraulically setting mixture according to one of claims 1 to 7.
  9. Use of a hydraulically setting mixture according to any one of claims 1 to 7 for the production of components, concrete products or moldings according to claim 8, wherein the surface also has a lower tendency to fouling even when attrition ("easy-to-clean" property).
  10. Use of a hydraulically setting mixture according to at least one of claims 1 to 9 as facing concrete.
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DE102018100354A1 (en) * 2018-01-09 2019-07-11 Braun Steine Gmbh Concrete block and method for producing a concrete block

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RU2577864C2 (en) 2010-04-01 2016-03-20 Эвоник Дегусса Гмбх Curable mixture
DE102011086362A1 (en) 2011-11-15 2013-05-16 Evonik Industries Ag A composition comprising block co-condensates of propyl-functional alkali silicates and silicates and processes for their preparation
DE102014206359A1 (en) 2014-04-03 2015-10-08 Evonik Degussa Gmbh Low-VOC dialkyl-functional alkoxysiloxanes, processes and their use as hydrophobizing impregnating agents for mineral building materials

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