DK153322B - PROCEDURES FOR HYDROPHOBATION OF BUILDING MATERIALS, IN PARTICULAR POROUS MATERIALS. - Google Patents
PROCEDURES FOR HYDROPHOBATION OF BUILDING MATERIALS, IN PARTICULAR POROUS MATERIALS. Download PDFInfo
- Publication number
- DK153322B DK153322B DK511177AA DK511177A DK153322B DK 153322 B DK153322 B DK 153322B DK 511177A A DK511177A A DK 511177AA DK 511177 A DK511177 A DK 511177A DK 153322 B DK153322 B DK 153322B
- Authority
- DK
- Denmark
- Prior art keywords
- water
- surfactant
- emulsion
- alcohol
- silanes
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 21
- 239000004566 building material Substances 0.000 title claims description 12
- 239000011148 porous material Substances 0.000 title claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000839 emulsion Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- 150000004756 silanes Chemical class 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 239000007859 condensation product Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 description 26
- 238000011282 treatment Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 12
- 230000002209 hydrophobic effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000004567 concrete Substances 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- -1 fatty acid esters Chemical class 0.000 description 3
- ZBJVLWIYKOAYQH-UHFFFAOYSA-N naphthalen-2-yl 2-hydroxybenzoate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=C(C=CC=C2)C2=C1 ZBJVLWIYKOAYQH-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011111 cardboard Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- ZMRUPTIKESYGQW-UHFFFAOYSA-N propranolol hydrochloride Chemical compound [H+].[Cl-].C1=CC=C2C(OCC(O)CNC(C)C)=CC=CC2=C1 ZMRUPTIKESYGQW-UHFFFAOYSA-N 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 125000005625 siliconate group Chemical group 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds 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
- C04B41/4905—Compounds 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
- C04B41/4922—Compounds 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds 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
- C04B41/4905—Compounds 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
- C04B41/495—Compounds 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 oligomers or polymers
- C04B41/4961—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/62—Coating or impregnation with organic materials
- C04B41/64—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
Landscapes
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
iin
DK 153322 BDK 153322 B
Den foreliggende opfindelse angår en fremgangsmåde til hydrofobering af byggematerialer, især porøse materialer.The present invention relates to a method for hydrophobizing building materials, especially porous materials.
Det er kendt at hydrofobere bygningsoverflader, dvs. gøre 5 dem vandafvisende. Hensigten med denne behandling er at hindre først og fremmest regnvand i at trænge ind i bygningens overflader og disses pore- og kapillarsystem og medbringe i regnvandet opløste aggressive stoffer.It is known to hydrophobic building surfaces, ie. make 5 them water resistant. The purpose of this treatment is to prevent, first and foremost, rainwater from entering the building's surfaces and their pore and capillary system and to bring into the rainwater dissolved aggressive substances.
Til dette formål er det kendt at blande forskellige 10 overfladeaktive stoffer - eksempelvis stearater eller silikoner, altså stoffer med en vis grænsevinkel i forhold til vand . - i byggematerialets bestanddele under fabrikationen eller at behandle færdige konstruktioner med sådanne præparater eller opløsninger og emulsioner deraf.For this purpose, it is known to mix different surfactants - for example stearates or silicones, ie substances with a certain boundary angle to water. - in the constituents of the building material during manufacture or to treat finished structures with such preparations or solutions and emulsions thereof.
15 Fra SE-patentskrift nr. 367.616 og nr. 381.453 er det kendt at benytte silaner af en særlig type. På basis af silanop-løsninger i organiske opløsningsmidler kan der naturligvis fremstilles emulsioner, men indtrængningen af disse emulsioner i materialet er begrænset. Fra SE-patentskrift 20 nr. 372.930 er det endvidere kendt at anvende de i SE-patentskrift nr. 367.616 benyttede silaner, dog ikke i form af emulsioner, på en specielt renset overflade.15 From SE Patent Nos. 367,616 and 381,453, it is known to use silanes of a particular type. Of course, based on silane solutions in organic solvents, emulsions can be prepared, but the penetration of these emulsions into the material is limited. Furthermore, SE patent application No. 372,930 discloses using the silanes used in SE patent no. 367,616, however not in the form of emulsions, on a specially cleaned surface.
Emulsioner dannet direkte med hydrolyserende silaner i vand eller vand/alkohol som emulgeringsvæske har ikke denne 25 ulempe.Emulsions formed directly with hydrolyzing silanes in water or water / alcohol as emulsifying liquid do not have this disadvantage.
Fremstilling af et imprægneret byggemateriale ved hjælp af sådanne emulsioner er kendt fra beskrivelsen til DK-patent-ansøgning nr. 434/75. Det fremgår heraf, at man kan fremstille hydrofoberingsmidler for byggematerialer direkte 30 af visse silaner eller silanopløsninger i alkohol og vand ved mekanisk dispergering. Imidlertid udviser sådanne emulsioner forøget tendens til separering ved tiltagende vandindhold. Den mekaniske behandling af emulsionen skal iPreparation of an impregnated building material by means of such emulsions is known from the specification of DK Patent Application No. 434/75. It can be seen from this that hydrophobic agents for building materials can be prepared directly from certain silanes or silane solutions in alcohol and water by mechanical dispersion. However, such emulsions exhibit an increased tendency for separation at increasing water content. The mechanical treatment of the emulsion must i
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2 visse tilfælde gentages under imprægneringsprocessen.2 certain cases are repeated during the impregnation process.
I byggeindustrien er der behov for i visse tilfælde at beskytte porøse (mineralske) byggematerialer midlertidigt 5 mod fugtindtrængning, fortrinsvis nedbør, dels ved lagring umiddelbart efter fremstillingen, under transport og dels under montagen. Endvidere er der naturligvis behov for beskyttelse af den færdige bygnings overflader. Dette gælder eksempelvis produkter af beton, gasbeton, natursten, asbest, 10 tegl af forskellig art og kalksandsten samt produkter af eksempelvis pap, træ eller cellulose.In the construction industry, it is necessary in some cases to temporarily protect porous (mineral) building materials from moisture penetration, preferably precipitation, partly by storage immediately after manufacture, during transport and partly during assembly. Furthermore, there is of course a need for protection of the finished building's surfaces. This applies, for example, to products made of concrete, gas concrete, natural stone, asbestos, 10 bricks of various kinds and limestone sand as well as products of eg cardboard, wood or cellulose.
Påføring af beskyttelsesmidler kan ske allerede på fabrikationsstedet i mere eller mindre lukkede lokaler. Det er da nødvendigt at tage størst muligt hensyn til arbejdshygiejne 15 ved sammensætning af hydrofoberingsmidlet og ved tilrettelæggelse af påføringsarbejdet.The application of protective agents can already be done at the manufacturing site in more or less closed rooms. It is then necessary to take the utmost account of occupational hygiene 15 in the composition of the hydrophobic agent and in the organization of the application work.
På grund af den store mængde af behandlede overflader skal midlet og fremgangsmåden, hvorved det påføres byggematerialerne, være billig. Behandlingen skal kunne forstærkes, 20 gentages og kompletteres, og den må ikke forhindre efterfølgende behandlinger af overfladelaget.Because of the large amount of surface treated, the agent and the method by which it is applied to the building materials must be inexpensive. The treatment must be reinforced, repeated and supplemented, and must not prevent subsequent treatments of the surface layer.
Det er kendt, at kravet til en acceptabel økonomi opfyldes ved anvendelse af vandopløsninger af silikonater og først og fremmest methylsilikonater. Til disse vandige opløsninger må 25 der af reaktionstekniske årsager tilsættes forholdsvis store mængder natriumhydroxid- eller kaliumhydroxidopløs- ning. Sådanne opløsninger med en pH-værdi over 13 udgør en arbej dsmedicinsk risiko.It is known that the requirement for an acceptable economy is met by using aqueous solutions of siliconates and, first of all, methyl siliconates. For these aqueous solutions, relatively large amounts of sodium hydroxide or potassium hydroxide solution must be added. Such solutions with a pH value above 13 pose an occupational medical risk.
Det er en fordel ved hydrofoberingsbehandlingen, hvis den 30 forbedrer vedhæftningen mellem det mineralske underlag og organiske belægninger, farver af varierende type baseret på opløsningsmidler, eller dispergeringsfarver eller asfalt, der benyttes som fugtbeskyttende afdækning eller som 3It is an advantage of the hydrophobic treatment if it improves the adhesion between the mineral substrate and organic coatings, colors of varying type based on solvents, or dispersion paints or asphalt used as a moisture-protective cover or as 3
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bindelag mellem underlaget og en papbelægning.bonding layer between the substrate and a cardboard coating.
Formålet med den foreliggende opfindelse er at anvise en hydrofoberingsfremgangsmåde, som er økonomisk og risikofri 5 og giver en effektiv og enkel beskyttelse af byggematerialer.The object of the present invention is to provide a hydrophobic process which is economical and risk-free and provides an effective and simple protection of building materials.
Dette opnås ifølge opfindelsen ved, at man bringer materialet i kontakt med et middel i form af en emulsion fremstillet af vand eller vand/alkoholbiåndinger som 10 kontinuerlig fase og alkyltrialkoxysilaner eller kondensationsprodukter deraf som dispers fase, hvorhos midlet som dispergeringsmiddel indeholder et nedbrydeligt tensid, idet emulsionen fremstilles ved, at en blanding af silaner og det nedbrydelige tensid og eventuelt alkohol sættes til vand 15 eller en vand/alkoholblanding, og idet silanindholdet i emulsionen udgør 1-50% af emulsionens rumfang, og tensidindholdet udgør højst ca. 1% af emulsionens rumfang.This is achieved according to the invention by contacting the material with an agent in the form of an emulsion made of water or water / alcohol mixtures as a continuous phase and alkyl trialkoxysilanes or condensation products thereof as a dispersing phase, wherein the agent as a dispersant contains a degradable surfactant. the emulsion is prepared by adding a mixture of silanes and the degradable surfactant and optionally alcohol to water or a water / alcohol mixture, the silane content of the emulsion being 1-50% of the volume of the emulsion, and the surfactant content not exceeding approx. 1% of the volume of the emulsion.
Det har overraskende vist sig, at fordelene ved tilsætning af tensider kan opnås uden modsvarende ulemper, hvis man 20 benytter tensider, som mister de overfladeaktive egenskaber ved passende foranstaltninger ved fremstillingen af midlet eller ved påføringen. Dette kan ske ved, at man i blandingen af silaner, hydrolyseprodukter og/eller kondensationsprodukter deraf, vand og alkohol, tilsætter 25 tensider, som kan nedbrydes, og som mister de overfladeaktive egenskaber enten ved materialeegenskaber eller ved reaktioner med andre i fremstillingsprocessen for et hydrofoberet overfladelag deltagende materialer, eller ved reaktioner, som imitieres efter fremstillingen af 30 materialet eller efter behandling med imprægneringsmidlet.Surprisingly, it has been found that the advantages of adding surfactants can be obtained without corresponding disadvantages if surfactants are used which lose the surfactant properties by appropriate measures in the preparation of the agent or in the application. This can be done by adding in the mixture of silanes, hydrolysis products and / or condensation products, water and alcohol, decomposable surfactants which lose the surfactant properties either by material properties or by reactions with others in the hydrophobic production process. materials, or by reactions imitated after the preparation of the material or after treatment with the impregnating agent.
Ved fremgangsmåden ifølge opfindelsen anvendes ingen helbredsskadelige eller giftige opløsningsmidler. Anvendelsen af alkyltrialkoxysilanerne er risikofrit, da de kun i stor koncentration er lettere hud- og øjenirriterende.In the process of the invention, no harmful or toxic solvents are used. The use of the alkyl trialkoxysilanes is risk-free as they are only slightly skin and eye irritant to a high concentration.
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44
Bearbejdning af midlets bestanddele kræver ikke større fagkundskaber eller indsats af beskyttelsesudstyr og apparatur. Blandingen kan ske umiddelbart inden 5 behandlingen, eventuelt i et særligt blandemundstykke, eller en passende tid forud for behandlingen, hvorved blandingen skal opvise en passende stabilitet.The machining of the constituents of the agent does not require major technical knowledge or the insertion of protective equipment and apparatus. The mixing can be done immediately before the treatment, possibly in a special mixing nozzle, or a suitable time prior to the treatment, whereby the mixture must exhibit a suitable stability.
Det er kendt, at emulsioner med silaner og deres hydrolyseprodukter direkte i vand eller en vand/alkoholblanding kan 10 frembringes ved højeffektiv mekanisk emulgering. Det har vist sig, at store fordele med hensyn til blandt andet stabilitet af emulsionen og en mindskning af partikelstørrelsen kan opnås ved tilsætning til emulsionsmidlet. Det har imidlertid også beklageligvis vist sig, at 15 hydrofoberingseffekten af sådanne emulsioner mindskes eller helt går tabt ved generel tilsætning af sådanne overfladeaktive stoffer.It is known that emulsions with silanes and their hydrolysis products directly in water or a water / alcohol mixture can be produced by high-efficiency mechanical emulsification. It has been found that great advantages in, inter alia, stability of the emulsion and a reduction in particle size can be obtained by addition to the emulsion agent. However, it has also unfortunately been found that the hydrophobic effect of such emulsions is diminished or completely lost by the general addition of such surfactants.
Ved fremgangsmåden ifølge opfindelsen kræves ingen højeffektiv mekanisk emulgering. Der foretages eksempelvis 20 simpel omrøring eller direkte blanding i ledninger i eller udenfor et særligt mundstykke. Emulsionen kan påføres og eventuelt også blandes ved alle sædvanlige påføringsmetoder, eksempelvis med pensel eller malerulle eller ved sprøjtning.In the process of the invention, no highly efficient mechanical emulsification is required. For example, 20 simple stirring or direct mixing is performed in conduits inside or outside a particular nozzle. The emulsion can be applied and possibly mixed with all usual application methods, for example with a brush or paint roller or by spraying.
25 De anvendte alkyltrialkoxysilaner er kendt fra SE-patentskrift nr. 367.616. Som anvendelige tensider kan nævnes bl.a. estere af forskellig sammensætning, eksempelvis phosphorsyreestere eller siliciumsyreestere og fremfor alt fedtsyreestere samt forskellige alkoholalkylenoxidaddukter.The alkyltrialkoxysilanes used are known from SE Patent No. 367,616. Useful surfactants include: esters of various compositions, for example phosphoric acid esters or silicic acid esters and above all fatty acid esters and various alcohol alkylene oxide adducts.
30 Blandingen kan ske på forskellige måder og i forskellige trin. Eksempelvis kan man opløse silaner i alkohol og emulgere i vand, hvorved blandingen med vand resulterer i hydrolyse- og kondensationsprodukter i vand eller vand/alkoholblanding. Man kan også emulgere silaner og deres hydro- 5The mixing can be done in different ways and in different steps. For example, silanes can be dissolved in alcohol and emulsified in water, whereby mixing with water results in hydrolysis and condensation products in water or water / alcohol mixture. It is also possible to emulsify silanes and their hydrogels
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lyse- og kondensationsprodukter eller eventuelt opløsninger deraf i organiske opløsningsmidler i vand med tilsætning af ovennævnte tensider. Nedbrydningen af tensider til 5 ikke-overfladeaktivt stof sker siden, enten i forbindelse og i reaktion med i det behandlede materiale indgående bestanddele eller efter imprægneringspåføringen med en nedbrydende komponent i et efterfølgende behandlingstrin.light and condensation products or optionally solutions thereof in organic solvents in water with the addition of the above surfactants. The decomposition of surfactants to 5 non-surfactants then occurs, either in conjunction and in reaction with constituents contained in the treated material, or after the impregnation application with a degrading component in a subsequent treatment step.
Emulsionerne af silan og hydrolyse- og kondensationspro-10 dukter deraf i vand eller en vand/alkoholbiånding kan fremstilles med såvel yderst stort som yderst lille silan-indhold, dvs. fra 1 til 50% af emulsionens rumfang. Tensidindholdet udgør som anført ovenfor højst ca. 1% af emulsionens rumfang, fortrinsvis 0,01-1,0%. Indtrængnings-15 dybden for det anvendte middel er betydeligt større end for de kendte midler af denne art.The emulsions of silane and its hydrolysis and condensation products in water or a water / alcohol blend can be prepared with both extremely high and very low silane content, ie. from 1 to 50% of the volume of the emulsion. The surfactant content, as stated above, does not exceed approx. 1% of the volume of the emulsion, preferably 0.01-1.0%. The depth of penetration of the agent used is considerably greater than that of the known agents of this kind.
Nedbrydningen af tensidet sker i de fleste tilfælde ved påvirkning af byggematerialets basicitet, reaktion med eksempelvis metaloxider i eller umiddelbart efter 20 fabrikations- eller monteringsprocessen, men den kan også ske på grund af samtidig eller efterfølgende imprægnerings-behandling med væsker, først og fremmest vand eller vand/alkoholblandinger indeholdende basiske eller sure stoffer eller indeholdende oxidations- eller reduktionsmidler 25 eller gasser bestående af eller indeholdende og blandede med sådanne stoffer.In most cases, the decomposition of the surfactant occurs by affecting the basicity of the building material, reaction with, for example, metal oxides in or immediately after the manufacturing or assembly process, but it can also occur due to simultaneous or subsequent impregnation treatment with liquids, primarily water or water / alcohol mixtures containing basic or acidic substances or containing oxidizing or reducing agents or gases consisting of or containing and mixed with such substances.
Emulsionerne anvendt ved fremgangsmåden ifølge opfindelsen har en væsentligt større stabilitet end emulsioner fremstillet med silaner i henhold til beskrivelsen til 30 DK-patentansøgning nr. 434/75.The emulsions used in the process of the invention have a substantially greater stability than emulsions made with silanes according to the description of DK patent application No. 434/75.
En yderligere fordel ved midlet anvendt ved fremgangsmåden ifølge den foreliggende opfindelse er, at det kan påføres allerede hydrofobe overflader, selv om det indeholder væsentlige mængder af vand. Indholdet af tensider elimine 6A further advantage of the agent used in the process of the present invention is that it can already be applied to hydrophobic surfaces, although it contains significant amounts of water. The content of surfactants eliminates 6
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rer midlertidigt det tidligere overfladelags vandafvisende egenskab, indtil tensidet er nedbrudt.temporarily retains the water repellent property of the former surface layer until the surfactant is degraded.
Med det anvendte imprægneringsmiddel kan byggematerialer 5 eller andre materialer, som består af eller indeholder bestanddele, som kan reagere med silaner, hydrofoberes. Disse bestanddele kan være hydroxylholdige grupper, eksempelvis kalk eller metaloxider, eller stoffer, der reagerer med silaner på anden måde, således at en 10 siloxanfilm kan dannes på overfladen.With the impregnating agent used, building materials 5 or other materials consisting of or containing components which can react with silanes can be hydrophobized. These constituents may be hydroxyl-containing groups, for example, lime or metal oxides, or substances which react with silanes in another way, so that a siloxane film can be formed on the surface.
Til nærmere belysning af opfindelsens egenskaber og virkningsmåde i forhold til den kendte teknik gennemføres nogle sammenligningsforsøg.In order to elucidate the properties and mode of operation of the invention in relation to the prior art, some comparative experiments are carried out.
Blandinger af hydrofoberende stoffer, tensider, alkohol og 15 vand fremstilles. Den trådskurede ydre overflade af en letbetonblok med en rumvægt på 0,5 behandles med disse blandinger. Letbetonen har en pH-værdi på ca. 8.Mixtures of hydrophobic substances, surfactants, alcohol and water are prepared. The wire-cut outer surface of a lightweight concrete block with a space weight of 0.5 is treated with these mixtures. The lightweight concrete has a pH of approx. 8th
1. Prøvelegemer og imprægneringsmetode1. Sample bodies and impregnation method
Som prøvelegemer anvendes letbetonplader med en diameter på 20 80 mm og en tykkelse på 10 mm, som i princippet er frem stillet ifølge det svenske ER-nævns anbefalinger med hensyn til difussionstest af puds.As test bodies, lightweight concrete slabs with a diameter of 20 80 mm and a thickness of 10 mm are used, which are in principle made according to the recommendations of the Swedish ER in respect of the diffusion test of plaster.
Imprægneringen gennemføres ved at dyppe prøvelegemet i væskeoverfladen, hvorved opsugningen af imprægnerings-25 væsken sker gennem såkaldt "kapillar selvsugning".The impregnation is carried out by dipping the sample body into the liquid surface, whereby the impregnation liquid is aspirated through so-called "capillary self suction".
Imprægneringsvirkningen konstateres efter indtrådt hydrofo-bering gennem mætning af et ikke-fugtbart tværsnit efter befugtning af brudte prøvelegemer.The impregnation effect is ascertained after hydrophobization occurs by saturating a non-wettable cross section after wetting fractured sample bodies.
77
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2. Behandlingsvæsker2. Treatment fluids
Blandingsbetegnelse ifølge opfindelsenMixture designation according to the invention
ABCABC
5 Vand ml 1.000 1.000 1.0005 Water ml 1,000 1,000 1,000
Ethylalkohol ml 50 50 50Ethyl alcohol ml 50 50 50
Blanding af alkyltrialkoxy- silaner ml 50 50 50Mixture of alkyl trialkoxy silanes ml 50 50 50
Tensid 1, ml 0,25 0 0 10 Tensid 2, ml 0 0,25 0Surfactant 1, ml 0.25 0 0 10 surfactant 2, ml 0 0.25 0
Blandingsmetode I omrøringMixing method In stirring
Blandingsmetode II Blanding i højeffektiv blandeapparatur 80.000 o/m.Mixing method II Mixing in high-efficiency mixing equipment 80,000 rpm.
15 3. Anvendt præparat15 3. Preparation used
Som silanpræparat anvendes en alkyltrialkoxysilan, som forhandles under varemærket "Transilan" af firmaet BINAB, Gøteborg.As the silane preparation is used an alkyl trialkoxy silane, which is marketed under the trademark "Transilan" by the company BINAB, Gothenburg.
Som ethylalkohol anvendes en industrialkohol.As ethyl alcohol, an industrial alcohol is used.
20 Som tensid 1 anvendes et tensid, der forhandles under varemærket "Berol 08" af Berol Kemi, Stennungsund, Sverige, opløst i ethylalkohol. Tensid 1 er et ikke-ionisk tensid baseret på normal primær alkohol, er meget kraftigt hydrofilt og betegnes som et alkoholalkylenoxidaddukt.20 As surfactant 1, a surfactant sold under the trademark "Berol 08" is used by Berol Kemi, Stennungsund, Sweden, dissolved in ethyl alcohol. Surfactant 1 is a nonionic surfactant based on normal primary alcohol, is very strongly hydrophilic and is termed an alcohol alkylene oxide adduct.
25 Tensidet er ikke bestandigt mod baser og syrer, oxidationsmidler og reduktionsmidler.The surfactant is not resistant to bases and acids, oxidizing agents and reducing agents.
Som tensid 2 anvendes et tensid, som forhandles under varemærket "Berol 452" af Berol Kemi, Stennungsund, Sverige. Tensidet er flydende og er et anionisk tensid af alkyl- 8As surfactant 2 is used a surfactant which is marketed under the trademark "Berol 452" by Berol Kemi, Stennungsund, Sweden. The surfactant is liquid and is an anionic surfactant of alkyl 8
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ethersulfattypen. Dette tensid er bestandigt mod baser med en pH-værdi op til ca. 13,0.ethersulfattypen. This surfactant is resistant to bases with a pH up to approx. 13.0.
4. Fremstillingsalternativ 5 Fremstillingen sker i princippet efter forskellige alternativer, idet der dog ikke kan påvises forskelle med hensyn til egenskaber eller virkningsmåde af det anvendte middel og behandlingsresultatet.4. Manufacturing alternative 5 Manufacturing is in principle based on different alternatives, however, no differences in the properties or mode of action of the agent used and the treatment result can be detected.
Alternativerne kan i princippet vælges under hensyntagen til 10 f.eks. produkternes anvendelsesområde eller til opbevaringstekniske synspunkter.The alternatives can in principle be selected taking into account 10 e.g. the scope of the products or for storage technical points of view.
Alternativ a Blanding af vand og opløsningsmiddel (alkohol), hvorpå der tilsættes tensider. Derefter tilsættes silan (even-15 tuelt blandet med opløsningsmiddelalkohol).Alternative a Mixture of water and solvent (alcohol) to which surfactants are added. Then silane is added (optionally mixed with solvent alcohol).
b Blanding af silan og alkohol, tilsæt til vand og tensid (og eventuel alkohol).b Mix silane and alcohol, add to water and surfactant (and any alcohol).
c Blanding af silan, alkohol og tensid, tilsæt til vand (og eventuelt alkohol).c Mix silane, alcohol and surfactant, add to water (and optionally alcohol).
20 d Blanding af silan og tensid, som derpå sættes til vand og alkohol.20 d Mixture of silane and surfactant which is then added to water and alcohol.
e Forsøg udføres selv efter varierende opbevaringstider med hensyn til blandingerne, hvorved de nedenfor under 5. beskrevne reaktioner helt eller delvis udvikles.e Experiments are carried out even after varying storage times with respect to the mixtures, whereby the reactions described below under 5. are developed in whole or in part.
25 Der gennemføres forskellige forsøg med forskellige blandinger med hensyn til rumfangsfordeling af de i blandingen indgående bestanddele, nemlig silan, alkohol, vand og tensider i de forhold, som fremgår af beskrivelsen.25 Various experiments are carried out with different mixtures in terms of volume distribution of the constituents of the mixture, namely silane, alcohol, water and surfactants in the conditions shown in the description.
Der kunne ikke konstateres nogen afvigelser fra de neden-30 for beskrevne forhold.No deviations from the conditions described below were found.
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9 5. Reaktioner i blandingen9 5. Reactions in the mixture
Silaner hydrolyserer efter kontakt med vand til silanoler, som efter kondensation danner vandafvisende siloxaner.Silanes hydrolyze upon contact with water for silanols, which after condensation form water-repellent siloxanes.
5 Reaktioner kan forekomme mellem siloxanerne samt mellem disse og det behandlede underlag.Reactions may occur between the siloxanes as well as between these and the treated substrate.
Disse reaktioner er tidsbestemte og kan indtræde efter blanding af væsken, under opbevaring eller ved umiddelbar behandling af et materiale.These reactions are timed and may occur after mixing of the liquid, during storage or upon immediate processing of a material.
10 6. Sammenligning mellem behandling og mellem fremgangs måden ifølge opfindelsen og kendte teknikker10 6. Comparison between treatment and between the method according to the invention and known techniques
Behandlingstype AB CType of treatment AB C
Blandbarhed ved omrøring let let svær 15 Stabilitet af blanding, separering efter nogle nogle omgående dage timer ifølge opfindelsenStability of mixing, separation after some instantaneous hours according to the invention
Blandbarhed ved blanding 20 med hurtigblander let let letMixability of blend 20 with quick blender lightly lightweight
Stabilitet af blanding, separering efter efter 1 år måneder nogle kan der timer ikke konsta- 25 teres sepa- tionStability of mixing, separation after 1 year months some hours can not be separated
Indtrængningsdybde af behandling efter kontakttid på 300 sek. 6 mm 5 mm 2 mm 30 Hydrofoberingseffekt dråbetest med dråbe på 0,05 ml dråben forsvinderDepth of treatment after contact time of 300 sec. 6 mm 5 mm 2 mm 30 Hydrophobic effect drop test with drop of 0.05 ml drop disappears
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ίο efter antal sek. mere end 3600 sek. 0 3.600 sek.ίο by number of sec. more than 3600 sec. 0 3,600 sec.
Indtrængningsdybde ved 5 behandling af overflade, som allerede er hydrofob t = 1 mm efter kontakttid 300 sek. 3 mm 3 mm 0 mmDepth of penetration at surface treatment already hydrophobic t = 1 mm after contact time 300 sec. 3 mm 3 mm 0 mm
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE7613507 | 1976-12-02 | ||
| SE7613507A SE404358C (en) | 1976-12-02 | 1976-12-02 | PROCEDURE FOR HYDROPHOBOUS TREATMENT OF BUILDING MATERIAL, IN PARTICULAR POROSA SADANA |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK511177A DK511177A (en) | 1978-06-03 |
| DK153322B true DK153322B (en) | 1988-07-04 |
| DK153322C DK153322C (en) | 1988-12-27 |
Family
ID=20329631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK511177A DK153322C (en) | 1976-12-02 | 1977-11-18 | PROCEDURES FOR HYDROPHOBATION OF BUILDING MATERIALS, IN PARTICULAR POROUS MATERIALS. |
Country Status (7)
| Country | Link |
|---|---|
| AT (1) | AT371791B (en) |
| DE (1) | DE2751714A1 (en) |
| DK (1) | DK153322C (en) |
| FI (1) | FI64564C (en) |
| GB (1) | GB1592569A (en) |
| NO (1) | NO154701C (en) |
| SE (1) | SE404358C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0075962A1 (en) * | 1981-09-30 | 1983-04-06 | Josef Dr. PÜHRINGER | Impregnation agent for porous building materials |
| US4648904A (en) * | 1986-02-14 | 1987-03-10 | Scm Corporation | Aqueous systems containing silanes for rendering masonry surfaces water repellant |
| DE3635260A1 (en) * | 1986-10-16 | 1988-04-28 | Wacker Chemie Gmbh | METHOD FOR MAKING WATER REPELLENT OF SUCTIONABLE INORGANIC CONSTRUCTION MATERIALS |
| DE4029640A1 (en) * | 1990-09-19 | 1992-03-26 | Goldschmidt Ag Th | PREPARATION FOR WATER REPELLENT IMPREGNATION OF POROESER MINERAL BUILDING MATERIALS |
| FR2674862B1 (en) * | 1991-04-05 | 1994-09-09 | Corning France | COMPOSITION AND METHOD FOR TREATING ARTICLES TO PROVIDE SUSTAINABLE ADHESIVE AND WATER REPELLENT PROPERTIES. |
| DE4122263C1 (en) * | 1991-07-05 | 1993-02-25 | Degussa Ag, 6000 Frankfurt, De | |
| DE4309971A1 (en) * | 1993-03-26 | 1994-09-29 | Bayer Ag | Impregnation emulsion for mineral building materials |
| DE4409141A1 (en) * | 1994-03-17 | 1995-09-21 | Degussa | Process for the treatment of mineral building materials |
| DE19747794A1 (en) * | 1997-10-30 | 1999-05-06 | Degussa | Process for the production of concrete which has been rendered hydrophobic in the mass |
| DE19904496A1 (en) * | 1999-02-04 | 2000-08-10 | Wacker Chemie Gmbh | Aqueous creams of organosilicon compounds |
| FR2918660B1 (en) * | 2007-07-13 | 2010-10-01 | Edouard Serras | METHOD FOR MANUFACTURING A BUILDING ELEMENT FROM A MIXTURE OF PLASTER, WATER AND A LOAD |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1246516B (en) * | 1957-04-08 | 1967-08-03 | Ucb Sa | Water-repellent pigmented coatings for porous or fibrous building materials |
| US3567492A (en) * | 1968-06-24 | 1971-03-02 | Midland Silicones Ltd | Method for treating stone to obtain improved bonding to bituminous material |
| DE1595471B2 (en) * | 1965-01-21 | 1972-05-10 | Dow Corning Corp., Midland, Mich. (V.StA.) | PROCESS FOR PRODUCING COLLOIDAL SUSPENSIONS OF SILSESQUIOXANES |
| SE372930B (en) * | 1970-10-29 | 1975-01-20 | Dynamit Nobel Ag | |
| SE381453B (en) * | 1972-12-01 | 1975-12-08 | Dynamit Nobel Ag | METHOD OF IMPREGNATING MASURES WITH NEUTRAL OR WEAKLY ACID REACTIVE SURFACE BY TREATMENT WITH ALCOHOLIC OR PETROL SOLUTIONS OF ALKYLTRIAL COXISILAN OR CONDENSATION PRODUCTS THEREOF |
| DK43475A (en) * | 1975-02-07 | 1976-08-08 | Nya Asfalt Ab | PROCEDURE AND AGENT FOR IMPREGNATION OF BUILDING MATERIALS |
-
1976
- 1976-12-02 SE SE7613507A patent/SE404358C/en not_active IP Right Cessation
-
1977
- 1977-11-18 DK DK511177A patent/DK153322C/en not_active IP Right Cessation
- 1977-11-19 DE DE19772751714 patent/DE2751714A1/en active Granted
- 1977-11-21 FI FI773505A patent/FI64564C/en not_active IP Right Cessation
- 1977-11-29 AT AT0852777A patent/AT371791B/en not_active IP Right Cessation
- 1977-11-30 NO NO774088A patent/NO154701C/en unknown
- 1977-12-01 GB GB50011/77A patent/GB1592569A/en not_active Expired
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1246516B (en) * | 1957-04-08 | 1967-08-03 | Ucb Sa | Water-repellent pigmented coatings for porous or fibrous building materials |
| DE1595471B2 (en) * | 1965-01-21 | 1972-05-10 | Dow Corning Corp., Midland, Mich. (V.StA.) | PROCESS FOR PRODUCING COLLOIDAL SUSPENSIONS OF SILSESQUIOXANES |
| US3567492A (en) * | 1968-06-24 | 1971-03-02 | Midland Silicones Ltd | Method for treating stone to obtain improved bonding to bituminous material |
| SE372930B (en) * | 1970-10-29 | 1975-01-20 | Dynamit Nobel Ag | |
| SE381453B (en) * | 1972-12-01 | 1975-12-08 | Dynamit Nobel Ag | METHOD OF IMPREGNATING MASURES WITH NEUTRAL OR WEAKLY ACID REACTIVE SURFACE BY TREATMENT WITH ALCOHOLIC OR PETROL SOLUTIONS OF ALKYLTRIAL COXISILAN OR CONDENSATION PRODUCTS THEREOF |
| DK43475A (en) * | 1975-02-07 | 1976-08-08 | Nya Asfalt Ab | PROCEDURE AND AGENT FOR IMPREGNATION OF BUILDING MATERIALS |
Also Published As
| Publication number | Publication date |
|---|---|
| FI64564C (en) | 1983-12-12 |
| ATA852777A (en) | 1982-12-15 |
| NO154701B (en) | 1986-08-25 |
| DE2751714A1 (en) | 1979-02-08 |
| NO154701C (en) | 1986-12-03 |
| DE2751714C2 (en) | 1990-10-31 |
| GB1592569A (en) | 1981-07-08 |
| FI773505A (en) | 1978-06-03 |
| SE404358B (en) | 1978-10-02 |
| DK511177A (en) | 1978-06-03 |
| NO774088L (en) | 1978-06-05 |
| FI64564B (en) | 1983-08-31 |
| SE7613507L (en) | 1978-06-03 |
| SE404358C (en) | 1984-10-15 |
| AT371791B (en) | 1983-07-25 |
| DK153322C (en) | 1988-12-27 |
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| PBP | Patent lapsed |