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US20030144364A1 - Water-in-oil creams of organosilicon compounds - Google Patents

Water-in-oil creams of organosilicon compounds Download PDF

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Publication number
US20030144364A1
US20030144364A1 US10/351,786 US35178603A US2003144364A1 US 20030144364 A1 US20030144364 A1 US 20030144364A1 US 35178603 A US35178603 A US 35178603A US 2003144364 A1 US2003144364 A1 US 2003144364A1
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United States
Prior art keywords
cream
radicals
amount
organopolysiloxanes
emulsifiers
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.)
Abandoned
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US10/351,786
Inventor
Manfred Schmuck
Roland Sucker
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Evonik Operations GmbH
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Individual
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Publication date
Priority claimed from DE10203247A external-priority patent/DE10203247A1/en
Application filed by Individual filed Critical Individual
Assigned to GOLDSCHMIDT AG reassignment GOLDSCHMIDT AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SCHMUCK, MANFRED, SUCKER, ROLAND
Publication of US20030144364A1 publication Critical patent/US20030144364A1/en
Assigned to GOLDSCHMIDT GMBH reassignment GOLDSCHMIDT GMBH CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: GOLDSCHMIDT AG
Priority to US11/623,781 priority Critical patent/US8075998B2/en
Abandoned legal-status Critical Current

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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
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/4922Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
    • 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
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61Coating or impregnation
    • C04B41/62Coating or impregnation with organic materials
    • C04B41/64Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991Coated
    • Y10T428/2993Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y10T428/2995Silane, siloxane or silicone coating

Definitions

  • the invention relates to hydrocarbon-free aqueous creams of organosilicon compounds, their preparation and their use.
  • Organosilicon compounds have been used for many years for the impregnation of inorganic and organic building materials in order to protect them against penetration of water. These silanes/siloxanes are employed as such, as solutions in solvents or in the form of emulsions. Aqueous hydrophilic emulsions of solvent-free organosilicon compounds are prior art and can be regarded as a substitute of equivalent value for solvent-based systems.
  • DE-A-199 45 305 relates to an impregnation cream for the waterproofing of building materials, which consists of a water-in-oil emulsion of hydrophobicizing organosilicon compounds, a nonactive hydrocarbon component, water, emulsifer and, if desired, auxiliaries and additives.
  • the creams are prepared by blending two intermediate products in the form of creams.
  • Hydrocarbons include, in particular, aliphatic and/or dearomatized petroleum spirit hydrocarbons, petroleum spirit hydrocarbons having from 9 to 12 carbon atoms and small proportions of aromatics, isoparaffinic hydrocarbons having from 11 to 15 carbon atoms and mixtures thereof.
  • EP-B-0 819 665 describes the preparation and use of an aqueous cream having a nonfluid consistency which penetrates into the building material after application and can be applied to the surfaces to be impregnated by blade coating and spraying.
  • the cream-like consistency is based on the high active ingredient content of from about 65 to 90% by weight in the emulsion.
  • DE-C-40 29 640 describes the preparation of an emulsion having a low viscosity and a lower active ingredient content than that described in EP-B-0 819 665, which can be applied by rolling, spraying or flooding.
  • the use concentration of this type of emulsions is generally 5-10%.
  • the emulsions described are water-dilutable oil-in-water systems (O/W).
  • Cream-like emulsions also have the advantage that they do not form harmful aerosols on spray application. Creams can, inter alia, be applied to the surfaces to be impregnated by rolling, so that covering of, for example, windows becomes unnecessary.
  • This invention provides for, inter alia, a hydrocarbon-free water-in-oil cream of organosilicon compounds, which comprises the components
  • the invention provides, in a first embodiment, hydrocarbon-free water-in-oil creams of organosilicon compounds, which comprise the components
  • An advantage of these novel emulsions is that they do not require an uneconomically high solids content in order to have a cream-like consistency. Owing to their freedom from hydrocarbons, penetration of the emulsions of the invention does not damage the environment.
  • creams are paste-like, water-containing preparations which are emulsion systems comprising active ingredient, water and emulsifiers.
  • the aqueous creams of the invention penetrate completely into the building material. As a result, a water-repellent effect is obtained quickly after application.
  • the aqueous creams are virtually solvent-free.
  • the creams preferably contain no organic solvents such as hydrocarbons.
  • the aqueous creams are preferably nonfluid spreadable, sprayable and rollable, preferably colorless, coatings having a cream-like consistency.
  • the cream is applied in a thickness of 1 mm by spraying or blade coating onto a vertical concrete or lime-sand brick surface.
  • Nonfluidity then means that this cream descends by no more than 5 cm, preferably no more than 1 cm, particularly preferably not at all, after application before it is completely absorbed by the substrate.
  • the C 1 -C 20 -alkyl-C 1 -C 6 -alkoxysilanes (A1) preferably have 1 or 2 identical or different, unsubstituted or halogen-substituted, SiC-bonded monovalent C 1 -C 20 -alkyl radicals and the other radicals are identical or different C 2 -C 6 -alkoxy radicals.
  • C 1 -C 20 -alkyl radicals are the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl radicals; hexyl radicals such as the n-hexyl radical; heptyl radicals such as the n-heptyl radical; octyl radicals such as the n-octyl radical and isooctyl radicals such as the 2,2,4-trimethylpentyl radical; nonyl radicals such as the n-nonyl radical; decyl radicals such as the n-decyl radical and dodecyl radicals such as the n-dodecyl radical; cycloalkyl radicals such as cyclopentyl, cycl
  • halogen-substituted C 1 -C 20 -alkyl radicals are alkyl radicals substituted by fluorine, chlorine, bromine or iodine atoms, e.g. the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2′,2′,2′hexafluoroisopropyl radical and the heptafluoroisopropyl radical.
  • C 1 -C 6 -alkoxy radicals are the methoxy, ethoxy, n-propoxy, isopropoxy, n-butyoxy, isobutoxy, sec-butoxy, tert-butoxy radicals; pentyloxy radicals such as the n-pentyloxy radical and hexyloxy radicals such as the n-hexyloxy radical. Ethoxy radicals are particularly preferred.
  • alkoxy radicals can be substituted by halogen atoms, but this is not preferred.
  • the aqueous cream can contain one alkoxy-containing organopolysiloxane (A2) or a mixture of a plurality of organopolysiloxanes.
  • the organopolysiloxanes (A2) can additionally contain hydroxyl groups which aid binding to the building materials.
  • the organopolysiloxanes (A2) preferably have a viscosity of, for example, about 2000 mPa ⁇ s in order to achieve particularly good distribution on the pore surfaces in the wall. It is also possible to use relatively high viscosity organopolysiloxanes (A2) right up to solid resins, for example solid methylsilicone resins having a molar mass of from about 2000 to about 10,000 g/mol and, for example, a glass transition temperature range of about 40-50° C. However, these have to be dissolved in the silanes before preparation of the creams of the invention.
  • organopolysiloxanes (A2) are organopolysiloxanes comprising units of the formula (I)
  • R are identical or different monovalent, unsubstituted or halogen-substituted, SiC-bonded C 1 -C 20 -hydrocarbon radicals,
  • R 1 are identical or different monovalent C 1 -C 6 -alkyl radicals
  • x is 0, 1, 2 or 3, on average from 0.8 to 1.8,
  • y is 0, 1, 2 or 3, on average from 0.01 to 2.0
  • z is 0, 1, 2 or 3, on average from 0.0 to 0.5, with the proviso that the sum of x, y and z is not more than 3.5.
  • the organopolysiloxane (A2) preferably has a viscosity of from about 10 mPa ⁇ s to about 50 000 mPa ⁇ s, in particular from about 50 mPa ⁇ s to about 5000 mPa ⁇ s, at 25° C.
  • C 1 -C 20 -hydrocarbon radicals are the C 1 -C 20 -alkyl radicals and halogen-substituted C 1 -C 20 -alkyl radicals listed above in the case of the organoalkoxysilanes, alkenyl radicals such as the vinyl, allyl, n-5-hexenyl, 4-vinylcyclohexyl and 3-norbornenyl radicals; aryl radicals such as the phenyl, biphenylyl, naphthyl, anthryl and phenanthryl radicals; alkaryl radicals such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals; aralkyl radicals such as the benzyl radical and the alpha- and ⁇ -phenylethyl radicals. Particular preference is given to unsubstituted C 1 -C 12 -alkyl
  • part of the radical R can be replaced by hydrogen atoms bound directly to silicon atoms. However, this is not preferred.
  • radicals R 1 are the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl radicals; pentyl radicals such as the n-pentyl radical and hexyl radicals such as the n-hexyl radical, with ethyl radicals being particularly preferred.
  • x preferably has an average value of from 0.9 to 1.1.
  • y preferably has an average value of from 0.4 to 1.2.
  • z preferably has an average value of from 0.0 to 0.2.
  • organosiloxanes (A2) are organosiloxanes which are obtainable by reaction of methyltrichlorosilane and, if desired, a C 1 -C 8 -alkyltrichlorosilane, or phenyltrichlorosilane with ethanol in water, e.g. the organopolysiloxanes of the empirical formulae
  • organopolysiloxanes (A3) which may be used in addition to component (A2) are preferably organopolysiloxanes comprising units of the formula (II)
  • R 2 are identical or different monovalent, unsubstituted or halogen-substituted, SiC-bonded C 1 -C 20 -hydrocarbon radicals which are free of basic nitrogen,
  • R 3 are identical or different monovalent, unsubstituted or halogen-substituted, SiC-bonded C 1 -C 30 -hydrocarbon radicals which contain basic nitrogen,
  • R 4 may be identical or different and are each a hydrogen atom or a C 1 -C 6 -alkyl radical
  • a is 0, 1, 2 or 3
  • b is 0, 1, 2 or 3, on average at least 0.05
  • c is 0, 1, 2 or 3
  • the amine number is the number of ml of 1N HCl required to neutralize 1 g of organopolysiloxane (A3).
  • the amine number of the organopolysiloxane (A3) is preferably at least about 0.1, in particular at least about 0.2, and preferably not more than about 8, in particular not more than about 4.
  • radicals R 2 have been given above in the case of the radical R. Particular preference is given to the methyl radical and the isooctyl radical.
  • each silicon atom to which a hydrogen atom is bound also bears a hydrocarbon radical, in particular a methyl radical.
  • the radical R 3 is preferably a radical of the formula (III)
  • R 5 may be identical or different and are each hydrogen or a monovalent, substituted or unsubstituted C 1 -C 10 -hydrocarbon radical or C 1 -C 10 -aminohydrocarbon radical and R 6 is a divalent C 1 -C 15 -hydrocarbon radical.
  • radicals R 5 are the examples of hydrocarbon radicals given above for the radical R and also hydrocarbon radicals substituted by amino groups, e.g. aminoalkyl radicals, with particular preference being given to the aminoethyl radical.
  • the radical R 6 is preferably a divalent hydrocarbon radical having from about 1 to 10 carbon atoms, particularly preferably from about 1 to 4 carbon atoms, in particular the n-propylene radical.
  • radicals R 6 are the methylene, ethylene, propylene, butylene, cyclohexylene, octadecylene, phenylene and butenylene radicals.
  • alkyl radicals R 1 all apply analogously to the radical R 6 .
  • radical R 4 examples and preferred examples of the radical R 4 are given above in the case of the radical R 1 . Particular preference is given to the methyl and ethyl radicals.
  • the preferred average value of a is from 0 to 2, in particular from 0 to 1.8.
  • the preferred average value of b is from about 0.1 to 0.6, in particular from 0.15 to 0.30.
  • the preferred average value of c is from 0 to 0.8, in particular from 0.01 to 0.6.
  • the organopolysiloxanes (A3) preferably have a viscosity of from about 5 to about 5000 mPa ⁇ s, in particular from about 100 to about 3000 mPa ⁇ s, at 25° C.
  • Organopolysiloxanes (A3) can be prepared in a known manner, for example by equilibration or condensation of amino-functional silanes with organopolysiloxanes (A2) which contain alkoxy groups and/or hydroxyl groups and are free of basic nitrogen.
  • the creams of the invention can further comprise hydrophobic solids having a large surface area, as are known, for example, from DE-A-39 11 479, in order to improve the water-repellent effect.
  • the creams particularly preferably contain from about 5 to 100% by weight of C 1 -C 20 -alkyl-C 1 -C 6 -alkoxysilanes (A1), based on the amount of active ingredients (A1), (A2) and/or (A3).
  • organopolysiloxanes (A2) being present in an amount of from about 5 to 100% by weight, based on the amount of active ingredients (A1) and/or (A3).
  • organopolysiloxanes (A3) which comprise siloxane units containing basic nitrogen in addition to other organosiloxane units being present in an amount of from about 5 to 100% by weight, based on the amount of active ingredients (A1), (A2) and/or (A3).
  • the aqueous creams comprise at least one emulsifier known per se.
  • the amount of emulsifiers depends on the desired properties.
  • the creams particularly preferably contain from about 1 to about 40% by weight, more preferably from about 5 to about 20% by weight, of the emulsifiers, based on the amount of active ingredients (A2), (A2) and/or (A3).
  • Suitable W/O emulsifiers generally have an HLB of from 2 to 5 and may be found among the following classes of substances: sorbitan esters, fatty alcohol ethoxylates, lanolin derivatives, fatty acid esters, glucose esters, emulsifiers based on polyglycerol or pentaerythritol and also organosiloxanes such as cetyl dimethicone copolyol.
  • the water-in-oil creams of the invention can be prepared by methods known per se from the prior art.
  • the waterproofing creams of the invention are preferably applied in a thickness of from about 0.1 mm to about 3 mm, in particular from about 0.2 mm to about 1.5 mm, particularly preferably from about 0.3 mm to about 1.1 mm.
  • the aqueous creams are suitable for waterproofing of mineral building materials, in particular for post-installation hydrophobicizing impregnation of natural or artificial stone, facing masonry, concrete, cement, lime-sand brick and porous concrete, building materials made from clay minerals, e.g. bricks, as waterproofing additive, which may also have a binding effect, to plaster of Paris, renders and in coatings for buildings, e.g. mineral paints, silicone resin emulsion paints and renders, paints containing dispersed silicate, emulsion paints, spreadable fillers, reinforcing compositions and primers.
  • the early rain resistance of coating compositions for buildings is improved.
  • the aqueous creams are thus also suitable for the treatment of organic building materials such as wood.
  • the aqueous creams are also suitable for hydrophobicizing finely divided inorganic materials such as perlite, vermiculite and thermal insulation materials.
  • a lime-sand brick having dimensions of 7 cm ⁇ 5 cm ⁇ 2 cm was coated on all sides in the laboratory with the cream described in Example 2. The amount applied was 160 g/m 2 , corresponding to about 40 g/m 2 of active ingredient. Immediately after coating had been carried out, the lime-sand brick was subjected to artificial rain. It was found that during the approximately 50 minute penetration time of the cream or the active ingredient therefrom, the water raining onto the surface was repelled as beads without washing off even tiny amounts of the cream. Even after the active ingredient of the cream had been completely absorbed the water was still repelled as beads.
  • the brick After having been subjected to the artificial rain, the brick was stored at room temperature for 14 days and the water absorption was determined in accordance with DIN 52103.
  • Example 2 A concrete cube having dimensions of 6 cm ⁇ 6 cm ⁇ 6 cm was impregnated on all sides with the cream descrbed in Example 1. The amount of cream applied was 300 g/m 2 , corresponding to an amount of active ingredient of 45 g/m 2 . During the 60 minute penetration time, the coated concrete cube was subjected to artificial rain. No removal of the coating occurred.
  • An impregnation cream was prepared as described in DE-199 45 305, Example 1. Based on the total composition, 40% by weight of an isoparaffinic hydrocarbon mixture having a boiling range from 185 to 213° C. and a flashpoint of above 60° C. and 40% by weight of a 1:1 mixture of an alkylalkoxysilane and an alkylalkoxysiloxane were combined and homogenized. 19.3% by weight of water and 0.7% by weight of emulsifier Marlipal® were subsequently added a little at a time and emulsification was carried out in a customary manner until a cream-like consistency had been obtained. The inert cream was thus ready to apply.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Cosmetics (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Fats And Perfumes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)

Abstract

The invention relates to hydrocarbon-free aqueous creams of organosilicon compounds, their preparation and their use. The hydrocarbon-free water-in-oil creams of organosilicon compounds comprise the components:
(A) one or more C1-C20-alkyl-C1-C6-alkoxysilanes (A1), alkoxy-containing organopolysiloxanes (A2) and/or organopolysiloxanes (A3) which comprise, in addition to other organosiloxane units, siloxane units which bear Si—C-bonded radicals containing basic nitrogen, with the proviso that the amine number of the organopolysiloxane is at least 0.01,
(B) one or more emulsifiers and
(C) water.

Description

    RELATED APPLICATIONS
  • This application claims priority under 35 U.S.C. § 119 to German application 102 03 247.5, filed Jan. 29, 2002, herein incorporated by reference. [0001]
  • BACKGROUND OF THE INVENTION
  • 1. Field of the Invention [0002]
  • The invention relates to hydrocarbon-free aqueous creams of organosilicon compounds, their preparation and their use. [0003]
  • 2. Description of the Related Art [0004]
  • Organosilicon compounds have been used for many years for the impregnation of inorganic and organic building materials in order to protect them against penetration of water. These silanes/siloxanes are employed as such, as solutions in solvents or in the form of emulsions. Aqueous hydrophilic emulsions of solvent-free organosilicon compounds are prior art and can be regarded as a substitute of equivalent value for solvent-based systems. [0005]
  • DE-A-199 45 305 relates to an impregnation cream for the waterproofing of building materials, which consists of a water-in-oil emulsion of hydrophobicizing organosilicon compounds, a nonactive hydrocarbon component, water, emulsifer and, if desired, auxiliaries and additives. The creams are prepared by blending two intermediate products in the form of creams. Hydrocarbons include, in particular, aliphatic and/or dearomatized petroleum spirit hydrocarbons, petroleum spirit hydrocarbons having from 9 to 12 carbon atoms and small proportions of aromatics, isoparaffinic hydrocarbons having from 11 to 15 carbon atoms and mixtures thereof. [0006]
  • EP-B-0 819 665 describes the preparation and use of an aqueous cream having a nonfluid consistency which penetrates into the building material after application and can be applied to the surfaces to be impregnated by blade coating and spraying. The cream-like consistency is based on the high active ingredient content of from about 65 to 90% by weight in the emulsion. [0007]
  • DE-C-40 29 640 describes the preparation of an emulsion having a low viscosity and a lower active ingredient content than that described in EP-B-0 819 665, which can be applied by rolling, spraying or flooding. The use concentration of this type of emulsions is generally 5-10%. [0008]
  • The emulsions described are water-dilutable oil-in-water systems (O/W). [0009]
  • However, these water-dilutable systems have a critical disadvantage. The application is very strongly influenced by the weather. If it starts to rain after application, the impregnated material is washed off from the exterior wall or washed out of the region close to the surface of the wall. [0010]
  • This applies particularly in the case of building protection systems which have a cream-like consistency and are applied in correspondingly high thicknesses. Since immediate penetration of the surface does not occur in the case of such systems, the cream remains on the building material surface before it is finally absorbed, so that this layer can be washed off more or less completely by rain and can get into the ground, which is ecologically and economically undesirable. Such an occurrence requires a second application. [0011]
  • Building protection emulsions having a low active content and a correspondingly low viscosity are washed out of the surface by rain after application. It is precisely in the region close to the surface where the water-repellent active ingredient should be located that impregnation has to be carried out again after rain. [0012]
  • Dong Hwang et al, Journal of the Korean Ceramic Society, Volume 37, No. 8, pp. 760 to 767, 2000, describe the emulsification of silanes as waterproofing agents for concrete. It is stated here that emulsions of silanes which require use of O/W and W/O emulsifiers are stabilized with the aid of polyvinyl alcohol (PVA). [0013]
  • OBJECT OF THE INVENTION
  • It is an object of the invention to find an environmentally friendly system which, firstly, penetrates well into a mineral or organic building material and, secondly, is rain-resistant immediately after application and is not washed off. Furthermore, a cream-like consistency is desired so as to prevent the composition running off vertical surfaces and ceilings which are to be impregnated. Cream-like emulsions also have the advantage that they do not form harmful aerosols on spray application. Creams can, inter alia, be applied to the surfaces to be impregnated by rolling, so that covering of, for example, windows becomes unnecessary. [0014]
  • SUMMARY OF THE INVENTION
  • This invention provides for, inter alia, a hydrocarbon-free water-in-oil cream of organosilicon compounds, which comprises the components [0015]
  • (A) one or more alkyl-alkoxysilanes (A1), alkoxy-containing organopolysiloxanes (A2) and/or organopolysiloxanes (A3) which comprise, in addition to other organosiloxane units, siloxane units which bear Si—C-bonded radicals containing basic nitrogen, with the proviso that the amine number of the organopolysiloxane is about at least 0.01, [0016]
  • (B) one or more emulsifiers and [0017]
  • (C) water. [0018]
  • It has surprisingly been found that hydrocarbon-free W/O emulsions of silanes and/or polysiloxanes meet these requirements. This form of emulsion is rain-resistant immediately after application. [0019]
  • DETAILED DESCRIPTION OF THE INVENTION
  • The invention provides, in a first embodiment, hydrocarbon-free water-in-oil creams of organosilicon compounds, which comprise the components [0020]
  • (A) one or more C[0021] 1-C20-alkyl-C1-C6-alkoxysilanes (A1), alkoxy-containing organopolysiloxanes (A2) and/or organopolysiloxanes (A3) which comprise, in addition to other organosiloxane units, siloxane units which bear Si—C-bonded radicals containing basic nitrogen, with the proviso that the amine number of the organopolysiloxane is at least about 0.01,
  • (B) one or more emulsifiers and [0022]
  • (C) water. [0023]
  • An advantage of these novel emulsions is that they do not require an uneconomically high solids content in order to have a cream-like consistency. Owing to their freedom from hydrocarbons, penetration of the emulsions of the invention does not damage the environment. [0024]
  • For the purposes of the present invention, creams are paste-like, water-containing preparations which are emulsion systems comprising active ingredient, water and emulsifiers. [0025]
  • The aqueous creams of the invention penetrate completely into the building material. As a result, a water-repellent effect is obtained quickly after application. The aqueous creams are virtually solvent-free. The creams preferably contain no organic solvents such as hydrocarbons. [0026]
  • The aqueous creams are preferably nonfluid spreadable, sprayable and rollable, preferably colorless, coatings having a cream-like consistency. [0027]
  • The nonfluidity of the creams is defined as follows: [0028]
  • The cream is applied in a thickness of 1 mm by spraying or blade coating onto a vertical concrete or lime-sand brick surface. Nonfluidity then means that this cream descends by no more than 5 cm, preferably no more than 1 cm, particularly preferably not at all, after application before it is completely absorbed by the substrate. [0029]
  • The C[0030] 1-C20-alkyl-C1-C6-alkoxysilanes (A1) preferably have 1 or 2 identical or different, unsubstituted or halogen-substituted, SiC-bonded monovalent C1-C20-alkyl radicals and the other radicals are identical or different C2-C6-alkoxy radicals.
  • Examples of C[0031] 1-C20-alkyl radicals are the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl radicals; hexyl radicals such as the n-hexyl radical; heptyl radicals such as the n-heptyl radical; octyl radicals such as the n-octyl radical and isooctyl radicals such as the 2,2,4-trimethylpentyl radical; nonyl radicals such as the n-nonyl radical; decyl radicals such as the n-decyl radical and dodecyl radicals such as the n-dodecyl radical; cycloalkyl radicals such as cyclopentyl, cyclohexyl, 4-ethylcyclohexyl, cycloheptyl, norbornyl and methylcyclohexyl radicals.
  • Examples of halogen-substituted C[0032] 1-C20-alkyl radicals are alkyl radicals substituted by fluorine, chlorine, bromine or iodine atoms, e.g. the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2′,2′,2′hexafluoroisopropyl radical and the heptafluoroisopropyl radical.
  • Particular preference is given to unsubstituted C[0033] 1-C12-alkyl radicals.
  • Examples of C[0034] 1-C6-alkoxy radicals are the methoxy, ethoxy, n-propoxy, isopropoxy, n-butyoxy, isobutoxy, sec-butoxy, tert-butoxy radicals; pentyloxy radicals such as the n-pentyloxy radical and hexyloxy radicals such as the n-hexyloxy radical. Ethoxy radicals are particularly preferred.
  • The alkoxy radicals can be substituted by halogen atoms, but this is not preferred. [0035]
  • The aqueous cream can contain one alkoxy-containing organopolysiloxane (A2) or a mixture of a plurality of organopolysiloxanes. The organopolysiloxanes (A2) can additionally contain hydroxyl groups which aid binding to the building materials. [0036]
  • The organopolysiloxanes (A2) preferably have a viscosity of, for example, about 2000 mPa·s in order to achieve particularly good distribution on the pore surfaces in the wall. It is also possible to use relatively high viscosity organopolysiloxanes (A2) right up to solid resins, for example solid methylsilicone resins having a molar mass of from about 2000 to about 10,000 g/mol and, for example, a glass transition temperature range of about 40-50° C. However, these have to be dissolved in the silanes before preparation of the creams of the invention. [0037]
  • Particularly useful organopolysiloxanes (A2) are organopolysiloxanes comprising units of the formula (I) [0038]
  • RxSi(OR1)ySi(OH)zO4-x-y-z/2   (I)
  • where [0039]
  • R are identical or different monovalent, unsubstituted or halogen-substituted, SiC-bonded C[0040] 1-C20-hydrocarbon radicals,
  • R[0041] 1 are identical or different monovalent C1-C6-alkyl radicals,
  • x is 0, 1, 2 or 3, on average from 0.8 to 1.8, [0042]
  • y is 0, 1, 2 or 3, on average from 0.01 to 2.0, and [0043]
  • z is 0, 1, 2 or 3, on average from 0.0 to 0.5, with the proviso that the sum of x, y and z is not more than 3.5. [0044]
  • The organopolysiloxane (A2) preferably has a viscosity of from about 10 mPa·s to about 50 000 mPa·s, in particular from about 50 mPa·s to about 5000 mPa·s, at 25° C. [0045]
  • Examples of C[0046] 1-C20-hydrocarbon radicals are the C1-C20-alkyl radicals and halogen-substituted C1-C20-alkyl radicals listed above in the case of the organoalkoxysilanes, alkenyl radicals such as the vinyl, allyl, n-5-hexenyl, 4-vinylcyclohexyl and 3-norbornenyl radicals; aryl radicals such as the phenyl, biphenylyl, naphthyl, anthryl and phenanthryl radicals; alkaryl radicals such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals; aralkyl radicals such as the benzyl radical and the alpha- and β-phenylethyl radicals. Particular preference is given to unsubstituted C1-C12-alkyl radicals and the phenyl radicals.
  • Although not indicated in the formula shown above, part of the radical R can be replaced by hydrogen atoms bound directly to silicon atoms. However, this is not preferred. [0047]
  • Examples of radicals R[0048] 1 are the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl radicals; pentyl radicals such as the n-pentyl radical and hexyl radicals such as the n-hexyl radical, with ethyl radicals being particularly preferred.
  • x preferably has an average value of from 0.9 to 1.1. y preferably has an average value of from 0.4 to 1.2. z preferably has an average value of from 0.0 to 0.2. [0049]
  • Examples of organosiloxanes (A2) are organosiloxanes which are obtainable by reaction of methyltrichlorosilane and, if desired, a C[0050] 1-C8-alkyltrichlorosilane, or phenyltrichlorosilane with ethanol in water, e.g. the organopolysiloxanes of the empirical formulae
  • CH3Si(OC2H5)0.8O1.1 or
  • C6H5Si(OC2H5)0.72O1.14.
  • The organopolysiloxanes (A3) which may be used in addition to component (A2) are preferably organopolysiloxanes comprising units of the formula (II) [0051]
  • R2 aR3 b(OR4)cSiO4-a-b-C/2   (II)
  • where [0052]
  • R[0053] 2 are identical or different monovalent, unsubstituted or halogen-substituted, SiC-bonded C1-C20-hydrocarbon radicals which are free of basic nitrogen,
  • R[0054] 3 are identical or different monovalent, unsubstituted or halogen-substituted, SiC-bonded C1-C30-hydrocarbon radicals which contain basic nitrogen,
  • R[0055] 4 may be identical or different and are each a hydrogen atom or a C1-C6-alkyl radical,
  • a is 0, 1, 2 or 3, [0056]
  • b is 0, 1, 2 or 3, on average at least 0.05, and [0057]
  • c is 0, 1, 2 or 3, [0058]
  • with the proviso that the sum of a, b and c is less than or equal to 3 and the amine number of the organopolysiloxane (A3) is at least 0.01. [0059]
  • The amine number is the number of ml of 1N HCl required to neutralize 1 g of organopolysiloxane (A3). The amine number of the organopolysiloxane (A3) is preferably at least about 0.1, in particular at least about 0.2, and preferably not more than about 8, in particular not more than about 4. [0060]
  • Examples and preferred examples of radicals R[0061] 2 have been given above in the case of the radical R. Particular preference is given to the methyl radical and the isooctyl radical.
  • It is preferred that each silicon atom to which a hydrogen atom is bound also bears a hydrocarbon radical, in particular a methyl radical. [0062]
  • The radical R[0063] 3is preferably a radical of the formula (III)
  • R5 2NR6—  (III),
  • where [0064]
  • R[0065] 5 may be identical or different and are each hydrogen or a monovalent, substituted or unsubstituted C1-C10-hydrocarbon radical or C1-C10-aminohydrocarbon radical and R6 is a divalent C1-C15-hydrocarbon radical.
  • Examples of radicals R[0066] 5 are the examples of hydrocarbon radicals given above for the radical R and also hydrocarbon radicals substituted by amino groups, e.g. aminoalkyl radicals, with particular preference being given to the aminoethyl radical.
  • Preference is given to at least one hydrogen atom being bound to each nitrogen atom in the radicals of the formula (III). [0067]
  • The radical R[0068] 6 is preferably a divalent hydrocarbon radical having from about 1 to 10 carbon atoms, particularly preferably from about 1 to 4 carbon atoms, in particular the n-propylene radical.
  • Examples of radicals R[0069] 6 are the methylene, ethylene, propylene, butylene, cyclohexylene, octadecylene, phenylene and butenylene radicals.
  • Preferred examples of radicals R[0070] 3 are
  • H[0071] 2N(CH2)3—,
  • H[0072] 2N(CH2)2NH(CH2)2—,
  • H[0073] 2N(CH2)2NH(CH2)3—,
  • H[0074] 2N(CH2)2—,
  • H[0075] 3CNH(CH2)3—,
  • C[0076] 2H5NH(CH2)3—,
  • H[0077] 3CNH(CH2)2—,
  • C[0078] 2H5NH(CH2)2—,
  • H[0079] 2N(CH2)4—,
  • H[0080] 2N(CH2)5—,
  • H(NHCH[0081] 2CH2)3—,
  • C[0082] 4H9NH(CH2)2NH(CH2)2—,
  • cyclo-C[0083] 6H11NH(CH2)3—,
  • cyclo-C[0084] 6H11NH(CH2)2—,
  • (CH[0085] 3)2N(CH2)3—,
  • (CH[0086] 3)2N(CH2)2—,
  • (C[0087] 2H5)2N(CH2)3— and
  • (C[0088] 2H5)2N(CH2)2—.
  • The examples of alkyl radicals R[0089] 1 all apply analogously to the radical R6.
  • Examples and preferred examples of the radical R[0090] 4 are given above in the case of the radical R1. Particular preference is given to the methyl and ethyl radicals.
  • The preferred average value of a is from 0 to 2, in particular from 0 to 1.8. [0091]
  • The preferred average value of b is from about 0.1 to 0.6, in particular from 0.15 to 0.30. [0092]
  • The preferred average value of c is from 0 to 0.8, in particular from 0.01 to 0.6. [0093]
  • The organopolysiloxanes (A3) preferably have a viscosity of from about 5 to about 5000 mPa·s, in particular from about 100 to about 3000 mPa·s, at 25° C. [0094]
  • Organopolysiloxanes (A3) can be prepared in a known manner, for example by equilibration or condensation of amino-functional silanes with organopolysiloxanes (A2) which contain alkoxy groups and/or hydroxyl groups and are free of basic nitrogen. [0095]
  • The creams of the invention can further comprise hydrophobic solids having a large surface area, as are known, for example, from DE-A-39 11 479, in order to improve the water-repellent effect. [0096]
  • For the purposes of the present invention, the creams particularly preferably contain from about 5 to 100% by weight of C[0097] 1-C20-alkyl-C1-C6-alkoxysilanes (A1), based on the amount of active ingredients (A1), (A2) and/or (A3).
  • In the same way, preference is given according to the invention to the organopolysiloxanes (A2) being present in an amount of from about 5 to 100% by weight, based on the amount of active ingredients (A1) and/or (A3). [0098]
  • In the same way, particular preference is given according to the invention to the organopolysiloxanes (A3) which comprise siloxane units containing basic nitrogen in addition to other organosiloxane units being present in an amount of from about 5 to 100% by weight, based on the amount of active ingredients (A1), (A2) and/or (A3). [0099]
  • The aqueous creams comprise at least one emulsifier known per se. [0100]
  • The amount of emulsifiers depends on the desired properties. For the purposes of the present invention, the creams particularly preferably contain from about 1 to about 40% by weight, more preferably from about 5 to about 20% by weight, of the emulsifiers, based on the amount of active ingredients (A2), (A2) and/or (A3). [0101]
  • It has been found that it is possible to obtain paste-like emulsions having active contents of from about 5 to about 50% by weight, preferably from about 20 to about 40% by weight, when suitable W/O emulsifiers are used. Suitable W/O emulsifiers generally have an HLB of from 2 to 5 and may be found among the following classes of substances: sorbitan esters, fatty alcohol ethoxylates, lanolin derivatives, fatty acid esters, glucose esters, emulsifiers based on polyglycerol or pentaerythritol and also organosiloxanes such as cetyl dimethicone copolyol. [0102]
  • The water-in-oil creams of the invention can be prepared by methods known per se from the prior art. [0103]
  • The waterproofing creams of the invention are preferably applied in a thickness of from about 0.1 mm to about 3 mm, in particular from about 0.2 mm to about 1.5 mm, particularly preferably from about 0.3 mm to about 1.1 mm. [0104]
  • Furthermore, the aqueous creams are suitable for waterproofing of mineral building materials, in particular for post-installation hydrophobicizing impregnation of natural or artificial stone, facing masonry, concrete, cement, lime-sand brick and porous concrete, building materials made from clay minerals, e.g. bricks, as waterproofing additive, which may also have a binding effect, to plaster of Paris, renders and in coatings for buildings, e.g. mineral paints, silicone resin emulsion paints and renders, paints containing dispersed silicate, emulsion paints, spreadable fillers, reinforcing compositions and primers. In particular, the early rain resistance of coating compositions for buildings is improved. The aqueous creams are thus also suitable for the treatment of organic building materials such as wood. [0105]
  • The aqueous creams are also suitable for hydrophobicizing finely divided inorganic materials such as perlite, vermiculite and thermal insulation materials.[0106]
  • EXAMPLES Example 1
  • 150 g of octyltriethoxysilane and 15 g of cetyl dimethicone polyol were placed in a 2 l glass beaker and 835 ml of water were added while stirring with a high-speed stirrer. The addition time was 10 minutes. [0107]
  • A stable cream had formed. [0108]
  • Example 2
  • 250 g of a mixture consisting of 60% of octyltriethoxysilane and 40% of a reaction product of 93 g of α,ω-polysiloxanediol and 7 g of γ-aminopropyltriethoxysilane (cf. DE-C-40 29 640) and 25 g of emulsifier (cetyl dimethicone polyol) were placed in a glass beaker of the same size as in Example 1 and 725 g of water were added dropwise. As emulsifying apparatus, an Ultraturrax was used. [0109]
  • A stable cream was formed. [0110]
  • Example 3
  • 200 g of an organopolysiloxane as described in DE-A-196 28 035, example on page 6, lines 60 to 64, comprising siloxane units which bear SiC-bonded radicals containing basic nitrogen were placed in a glass beaker of the same size as in Example 1. The amine number of the polysiloxane was at least 0.01. 20 g of emulsifier (sorbitan monooleate) were added to the initial charge, and 780 g of water were emulsified in with the aid of a Mizer disk. The addition of water took 20 minutes. A stable cream had formed. [0111]
  • Use tests: [0112]
  • A) A lime-sand brick having dimensions of 7 cm×5 cm×2 cm was coated on all sides in the laboratory with the cream described in Example 2. The amount applied was 160 g/m[0113] 2, corresponding to about 40 g/m2 of active ingredient. Immediately after coating had been carried out, the lime-sand brick was subjected to artificial rain. It was found that during the approximately 50 minute penetration time of the cream or the active ingredient therefrom, the water raining onto the surface was repelled as beads without washing off even tiny amounts of the cream. Even after the active ingredient of the cream had been completely absorbed the water was still repelled as beads.
  • After having been subjected to the artificial rain, the brick was stored at room temperature for 14 days and the water absorption was determined in accordance with DIN 52103. [0114]
  • Untreated lime-sand brick: 12.7% [0115]
  • Treated lime-sand brick: 0.9% [0116]
  • Reduction in the water absorption: 93% [0117]
  • B) A concrete cube having dimensions of 6 cm×6 cm×6 cm was impregnated on all sides with the cream descrbed in Example 1. The amount of cream applied was 300 g/m[0118] 2, corresponding to an amount of active ingredient of 45 g/m2. During the 60 minute penetration time, the coated concrete cube was subjected to artificial rain. No removal of the coating occurred.
  • After storage at room temperature for 14 days, the reduction in the water absorption was determined in accordance with DIN 52103. [0119]
  • Concrete cube not impregnated 6% water absorption [0120]
  • Concrete cube impregnated 0.6% water absorption [0121]
  • Reduction in the water absorption 90% [0122]
  • C) A wooden cuboid having dimensions of 5 cm×7 cm×2 cm was coated with the cream from Example 3. The amount applied was 100 g/m[0123] 2, corresponding to an amount of active ingredient of 25 g/m2. The treatment with artificial rain carried out subsequently removed no emulsion.
  • After storage at room temperature for 14 days, the water absorption was determined in accordance with ASTM D 5401. [0124]
  • Reduction in the water absorption 84% [0125]
  • Comparative Example
  • An impregnation cream was prepared as described in DE-199 45 305, Example 1. Based on the total composition, 40% by weight of an isoparaffinic hydrocarbon mixture having a boiling range from 185 to 213° C. and a flashpoint of above 60° C. and 40% by weight of a 1:1 mixture of an alkylalkoxysilane and an alkylalkoxysiloxane were combined and homogenized. 19.3% by weight of water and 0.7% by weight of emulsifier Marlipal® were subsequently added a little at a time and emulsification was carried out in a customary manner until a cream-like consistency had been obtained. The inert cream was thus ready to apply. [0126]
  • The emulsifier Marlipal® contained 9 EO units (HLB=13.7). After application to a mineral substrate, the cream could be rinsed off completely with water (rain). It was clearly an O/W emulsion. [0127]
  • The above description is intended to be illustrative and not limiting. Various changes or modifications in the embodiments described herein may occur to those skilled in the art. These changes can be made without departing from the scope or spirit of the invention. [0128]

Claims (20)

1. A hydrocarbon-free water-in-oil cream of organosilicon compounds, which comprises the components
(A) one or more optionally halogen-substituted alkyl-alkoxysilanes (A1), alkoxy-containing organopolysiloxanes (A2) and/or organopolysiloxanes (A3) which comprise, in addition to other organosiloxane units, siloxane units which bear Si—C-bonded radicals containing basic nitrogen, with the proviso that the amine number of the organopolysiloxane is at least about 0.01,
(B) one or more emulsifiers and
(C) water.
2. A hydrocarbon-free water-in-oil cream of organosilicon compounds, which comprises the components
(A) one or more optimally halogen-substituted C1-C20-alkyl-C1-C6-alkoxysilanes (A1), alkoxy-containing organopolysiloxanes (A2) and/or organopolysiloxanes (A3) which comprise, in addition to other organosiloxane units, siloxane units which bear Si—C-bonded radicals containing basic nitrogen, with the proviso that the amine number of the organopolysiloxane is at least 0.01,
(B) one or more emulsifiers and
(C) water.
3. The cream as claimed in claim 2, wherein the C2-C20-alkyl-C2-C6-alkoxysilanes (A1) have 1 or 2 identical or different, unsubstituted or halogen-substituted, SiC-bonded monovalent C1-C20-alkyl radicals and the other radicals are identical or different C2-C6-alkoxy radicals.
4. The cream as claimed in claim 2, wherein the C1-C20-alkyl-C1-C6-alkoxysilanes (A1) are present in an amount of from about 5 to 100% by weight, based on the amount of active ingredients (A1), (A2) and/or (A3).
5. The cream as claimed in claim 1, wherein the alkoxy-containing organopolysiloxanes (A2) comprise units of the formula (I)
RxSi(OR1)ySi(OH)zO4-x-y-z/2   (I)
where
R are identical or different monovalent, unsubstituted or halogen-substituted, SiC-bonded C1-C20-hydrocarbon radicals,
R1 are identical or different monovalent C1-C6-alkyl radicals,
x is 0, 1, 2 or 3, on average from 0.8 to 1.8,
y is 0, 1, 2 or 3, on average from 0.01 to 2.0, and
z is 0, 1, 2 or 3, on average from 0.0 to 0.5, with the proviso that the sum of x, y and z is not more than 3.5.
6. The cream as claimed in claim 2, wherein the alkoxy-containing organopolysiloxanes (A2) are present in an amount of from about 5 to 100% by weight, based on the amount of active ingredients (A1), (A2) and/or (A3).
7. The cream as claimed in claim 2, wherein the organopolysiloxanes (A3) which comprise, in addition to other organosiloxane units, siloxane units comprising units of the formula (II)
R2 aR3 b(OR4)cSiO4-a-b-c/2   (II)
where
R2 are identical or different monovalent, unsubstituted or halogen-substituted, SiC-bonded C1-C20-hydrocarbon radicals which are free of basic nitrogen,
R3 are identical or different monovalent, unsubstituted or halogen-substituted, SiC-bonded C1-C30-hydrocarbon radicals which contain basic nitrogen,
R4 may be identical or different and are each a hydrogen atom or a C1-C6-alkyl radical,
a is 0, 1, 2 or 3,
b is 0, 1, 2 or 3, on average at least 0.05, and
c is 0, 1, 2 or 3,
with the proviso that the sum of a, b and c is less than or equal to 3.
8. The cream as claimed in claim 2, wherein the organopolysiloxanes (A3) which comprise, in addition to other organosiloxane units, siloxane units containing basic nitrogen are present in an amount of from about 5 to 100% by weight, based on the amount of active ingredients (A1), (A2) and/or (A3).
9. The cream as claimed in claim 2, wherein the emulsifiers (B) have an HLB of from about 2 to 5.
10. The cream as claimed in claim 2, wherein the emulsifiers (B) are selected from the group consisting of sorbitan esters, fatty alcohol ethoxylates, lanolin derivatives, fatty acid esters, glucose esters and emulsifiers based on polyglycerol or pentaerythritol.
11. The cream according to claim 2, wherein the emulsifier is cetyl dimethicone copolyol.
12. The cream as claimed in claim 2, wherein the emulsifiers (B) are present in an amount of from about 1 to about 40% by weight, based on the amount of active ingredients (A1), (A2) and/or (A3).
13. The cream according to claim 2, wherein the emulsifiers (B) are present in an amount from about 5 to about 40% by weight, based upon the amount fo active ingredients (A1), (A2) and/or (A3).
14. The cream as claimed in claim 2, wherein the amount of the components (A)+(B) is from about 5 to about 50% by weight, based upon total weight of the cream.
15. The cream as claimed in claim 2, wherein the amount of the components (A) and (B) is from 20 to 40% by weight, based upon total weight of the cream.
16. A method for waterproofing building materials which comprises applying a cream according to claim 1 to said building materials.
17. A coating composition which comprises a cream according to claim 1.
18. A process for hydrophobing finely divided inorganic materials which comprises contacting a cream according to claim 1 with said materials.
19. The process according to claim 18 wherein the finely divided inorganic materials are perlite, vermiculite, or a thermal insulation material.
20. A finely divided hydrophobized inorganic material is obtained by the process according to claim 18.
US10/351,786 2002-01-29 2003-01-27 Water-in-oil creams of organosilicon compounds Abandoned US20030144364A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090030111A1 (en) * 2005-04-18 2009-01-29 Dow Corning Corporation Architectural Coating Compositions Containing Silicone Resins

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201703823D0 (en) 2017-03-09 2017-04-26 Safeguard Europe Ltd Water-in-oil emulsion compositions

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5091002A (en) * 1989-04-08 1992-02-25 Th. Goldschmidt Ag Preparation for the water-repellent impregnation of porous mineral building materials
US5196054A (en) * 1990-09-19 1993-03-23 Th. Goldschmidt Ag Preparation for the water-repellant impregnation of porous, mineral building materials
US5264027A (en) * 1992-08-11 1993-11-23 Wacker Silicones Corporation Detergent resistant compositions
US5962585A (en) * 1996-07-11 1999-10-05 Wacker-Chemie Gmbh Aqueous creams of organosilicon compounds for hydrophobicizing building materials
US20020031488A1 (en) * 2000-06-19 2002-03-14 Mohamed Kanji Cosmetic compositions comprising at least one polymethylsilsesquioxane film former

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4990377A (en) * 1988-05-02 1991-02-05 Pcr Group, Inc. Buffered silane emulsions having low volatile organic compounds when cured
JPH0824616A (en) 1994-07-20 1996-01-30 Nippon Saafuakutanto Kogyo Kk W / O emulsifier composition
DE19945305A1 (en) 1999-07-20 2001-01-25 Remmers Bauchemie Gmbh Facade cream and process for its manufacture
US6543646B2 (en) 2000-06-19 2003-04-08 Food Cart Systems, Inc. Method and apparatus for remotely dispensing beverages

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5091002A (en) * 1989-04-08 1992-02-25 Th. Goldschmidt Ag Preparation for the water-repellent impregnation of porous mineral building materials
US5196054A (en) * 1990-09-19 1993-03-23 Th. Goldschmidt Ag Preparation for the water-repellant impregnation of porous, mineral building materials
US5264027A (en) * 1992-08-11 1993-11-23 Wacker Silicones Corporation Detergent resistant compositions
US5962585A (en) * 1996-07-11 1999-10-05 Wacker-Chemie Gmbh Aqueous creams of organosilicon compounds for hydrophobicizing building materials
US20020031488A1 (en) * 2000-06-19 2002-03-14 Mohamed Kanji Cosmetic compositions comprising at least one polymethylsilsesquioxane film former

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090030111A1 (en) * 2005-04-18 2009-01-29 Dow Corning Corporation Architectural Coating Compositions Containing Silicone Resins
US7807744B2 (en) 2005-04-18 2010-10-05 Dow Corning Corporation Architectural coating compositions containing silicone resins

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