AU600357B2 - Process for protection, reconstitution and restoration of stone buildings, monuments and similar - Google Patents
Process for protection, reconstitution and restoration of stone buildings, monuments and similar Download PDFInfo
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- AU600357B2 AU600357B2 AU15479/88A AU1547988A AU600357B2 AU 600357 B2 AU600357 B2 AU 600357B2 AU 15479/88 A AU15479/88 A AU 15479/88A AU 1547988 A AU1547988 A AU 1547988A AU 600357 B2 AU600357 B2 AU 600357B2
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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
- C04B41/45—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
- C04B41/48—Macromolecular compounds
- C04B41/488—Other macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C04B41/4884—Polyurethanes; Polyisocyanates
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Polyurethanes Or Polyureas (AREA)
- Tents Or Canopies (AREA)
- Compounds Of Unknown Constitution (AREA)
- Finishing Walls (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Glass Compositions (AREA)
Abstract
According to a process for protection, reconstruction and restoration of stone buildings, the building is treated with a solution composed of an aliphatic isocyanate and one or more organic solvents inert to the isocyanate, and the isocyanate is then hardened in the presence of moisture. The means for carrying out the process consists of a solution of aliphatic isocyanate in one or more organic solvents inert to the isocyanate.
Description
-aal WV- IU s16 appiicatlon~s) madie in a Uonvention country in respect of the invention (si' the subject of the application.
Declared at Aschaffenburg9 this SF114 Tro: The Comimissioner of Patents 11 /81 AU-AI-i15479/88 pc7WELTORGAN1I'TON FOR 21ST! El UM INTERNATIONALE ANMELDUGR I C N CDE~ VERTRAG OBER DIE INTERNATIONALE ZUSAMMEA F B5DE SENTES PT (51) Internationale Patentkclassifikatlon 4 C04B 41/48 (11) Internationale Verdffentlichungsnummer: WO088/ 07982 Al (43) Internationales Verdffentlichungsdatum: 20. Oktober 1988 (20.10.88) (21) Internationales Aktenzeichen: PCT/DE88/00226 Verdffentlicht Mit internationalem Recherchenbericht.
(22) Internationales Anmeldedatum: 12. April 1988 (12.04.88) (31) Priorititsaktenzeichen: (32) Prioritatsdatumn: (33) Prioritiitsland: P 37 12967.8 16. April 1987 (16.04.87)
DE
(71)(72) Anmielder und Erfinder: RABE, Jilrgen, Walter [DE/ DE]; Bessenibacher Weg 70, D-8750 Aschaffenburg
(DE),
(74) Anwiilte: BECKER, Thomas, U. usw,; Eisenhi1tcn:tAa- B~e 2, D-4030 Ratingen I (DE).
(81) Bestimmungsskaaten: AU, BR, Fl, JF, SU, 2 %':Lnc fo1 A.Q.J. P 8 D EC 1988
AUSTRALIAN
4 NOV\988 PATENT OFFICE~ (54) Title: PROCESS FOR PROTECTION, I ECONSTITUTION AND RESTORATION OF STONE BUILDINGS, MONUMENTS AND SIMILAR (54) Bezeichnung: VERFAHREN ZUM SCHUTZ, ZUR SANIERUNG UND RESTAURIERUNG VON STEINER- NEN BAUWERKEN, DENKMALERN UND DEROLEICHEN (57) Abstract Accoraing to a process for protection, reconstruction and restoration of stone buildings, the building is treated with a solution composed of an aliphatic isocyanate arid one or more organic solvents Inert to the isocyanate, and the isocyapate is then hardened in the presence of moisture, The means Cor carrying out the process consists of a solution of aliphatic isocyanate in one or more organic solvents inert to the isocyanate, (57) Zusamnmenfassung Die Erfindung betrifft emn Verfabren mim Schutz, zur Sanierung oder Restaurierung von steinernen Bauwerken, bei dem das Bauwerk mit elner L8.sung behandelt wird, die, aus einem aliphatischen Isocyanat und einern oder mehreren damit inerten organischen Lbsungsmitteln besteht und dann das Isocyanat unter der EinWirkung von Feuchtigkeit ausgehtlrtet wird. Dlvi Erfindung betrifft weiterhin die Mittel zur Durchfilhrung des 'Verfahrens aus einer Lbsung aus a),ph,'Atischem Isocyanat in einem oder rrehreren damit, inerten organi'schen Lbsungsmitteln.
Method for protecting, renovating and restoring stone structures, monuments and the Like Stone structures, monuments and the Like, hereinafter designated for the sake of simplicity as structures, are subjected in the course of years to a constant exposure to the atmosphere. The surface -of the structures is constantly exposed to the harmful substances contained in the atmosphere, such as carbon dioxide, carbon monoxide, sulfur dioxide, nitrogen oxides etc., along with the moisture deposited by rain and fog. Dirt is deposited in the pores and together with metabolic products produced by the microorganisms, and the stone texture of the structure is destroyed, thus bringing about a more or less rapid errosion of the stone material used in the structure.
In the course of the years, this results in a continuously progressing destruction of the structure.
In the case of historical structur'es, monuments and the like, in particular, this continuous process of destruction proves to be extremely unpleasant because irreplaceable assets are always lost as a result.
Great efforts have already been made to stop this process of destruction and, in addition, to renovate the damage which has already occurred.
c -a -2- For this purpose, stone materials are treated with solutions of silicic-acid ester. A part of its natural binder 'is therefore returned to the stone.
This known silicic-acid ester method iL however, applicable to Lime-bound materials only to a limited extent.
In addition, a further disadvantage can be seen in the Sfact that the pores present in the stone material are LargeLy sealed so that the natural breathing of the stone material is impaired by the treatment.
Starting from this known prior art, it is therefore the object of the present invention to provide a new method for protecting, renovating and restoring stone structures, monuments and the like which can be applied to all stone materials and which retains, in particular, the capillary texture present in the stone material.
This object is achieved according to the invention with a method of the type defined above, wherein the structure is treated with a solution which consists of an aliphatic isocyanate and one or more organic solvents inert thereto, and then the isocyanate is cured by exposure to moisture.
The isocyanate used in the method according to the invention is preferably a polyisocyanate prepolymer which is commercially obtainable, for example, under the designation Desmodur E. Such a polyisocyanate prepolymer has reactive isocyanate groups which are able to react with the moisture of the air and form polymers in doing so.
The content of reactive NCO groups is preferably approx.
and the equivalent weight is preferably in the range of 500.
It may be remarked, however, that other polyisocyanate prepolymers, which polymerize and consequently cure after
A
3 introduction into the texture of the stone, may aL o be used in the method according to the invention.
The solvents used in the method according to the invention should be solvents which are inert in relation to the polyisocyanate prepolymer.
Accordingly, a multiplicity of solvents is available.
The preferred solvents are chosen in accordance with aspects such as low toxicity, inexpensiveness, good solution properties, good wetting of the stone material etc.
Preferred solvents are xylene, methyl isobutyl ketone, solvent naphtha, toluene, ethyl acetate, isobutyl acetate, acetone and methoxypropyl acetate.
Solvent combinations can, of course, also be used for the treatment with the aliphatic isocyanate.
Preferred solvent mixtures are the following examples: 1) 30 parts by weight of xylene, 100 parts by weight of methyl isobutyl ketone.
2) 250 parts by weight of isobutyl acetate, 180 parts by weight of xylene, 350 parts by weight of solvent naphtha.
3) 250 parts by weight of methyl isobutyl ketone, 180 parts by weight of xylene, 350 parts by weight of solvent naphtha.
4) 30 parts by weight of xylene, 80 parts by weight of acetone, 80 parts by weight of isobutyl acetate.
100 parts by weight of ethyl acetate, 70 parts by weight of toluene, 30 parts by weight of acetone.
6) 100 parts by weight of toluene, 30 parts by weight of acetone, 30 part3 by weight of methoxypropyl acetate.
The method according to the invention for treating structures can be subdivided into those methods which are L used exclusively for protecting as yet undamaged
C
-4 structures, furthermore into those for the renovation of already damaged structures and finally into methods for restoring heavily damaged structures.
According to this classification, the method according to the invention comprises, on the one hand, the so-called hydrophobizing of the structure in which hydrophobizing is carried out superficially by appl'ying a solution of 1 to 10 parts by weight of the aliphatic isocyanate and 99 to 90 parts by weight of the solvent inert thereto or the solvent combination inert thereto.
As a result of this measure of the method, the isocyanate solution penetrates a few mm into the stone material.
The solvent evaporates and the isocyanate reacts with the moisture to form a polymer film which coats the surface of the stone and the entire capillary system, and specifically, the capillary walls to the depth specified above, with a polymer film.
The capillaries themselves, however, remain open and, consequently, the vapor diffusion capability of the stone material remains intact to the greatest possible extent.
In this manner, a hydrophobizing of the surface is achieved which has the effect that the stone becomes water-repellent. The rain and the dirt applied with it therefore trickle off the stone and the dirt is no longer deposited on the stone. Consequently, there is no longer any habitat for the microorganisms which, as a consequence of their metabolic products, cause an initial incipient solution of the stone texture and as a result, provide the condition for the penetration of further moisture and further dirt and for exposure to the harmful substances contained in the atmosphere.
The concentration of the isocyanate in the soLvent necessary for the hydrophobizing depends on the size of the ct\ capillary system of the stone material. A quite coarse 5 structure of the stone requires a substantially higher proportion of isocyanate in the solution than a fine Scapillary structure.
The concentration of the solution is therefore expedient- I Ly determined on the basis of empirical tests.
For the renovation of structures which are already dama- I ged, according to the method according to the invention, a solution of 3 to 15% by weight of aliphatic isocyanate and 97 to 35% by weight of the solvent inert thereto or the solvent mixtures inert thereto are applied.
This solution penetrates into the pores, coats the capillary walls with a polymer film and thus consolidates the already damaged stone texture. The capillaries themselves, however, remain intact and continue to be available for the vapor diffusion of the stone.
In the method according to the invention, no closed surface layer is produced and no direct chemical reaction takes place with the stone material itself. No crust is formed.
The consolidation by the method according to the invention takes place, on the contrary, only as a result of the penetration into the capillary spaces and the lining of the walls of the capillaries wIth the polymer film, which has the result that the nature of the stone is completely irrelevant for the method according to the invention and, accordingly, also in contrast to the known silicic acid ester method, does not present any limitation for the method according to the invention.
The restoration of heavily damaged structures is carried out by the method according to the invention by applying a moldable compound from a solution of 3 to 70% by weight of aliphatic isocyanate in 97 to 30% by weight of solvent S inert thereto or of solvent mixture inert thereto and
U
s^r j Vi Q 0 -i 6 mineraL constituents. A preferred concentration range is 8 to 30% by weight of isocyanate and 92 to 70% by weight of solvent mixture.
In the case of a moldable stone replacement compound applied in such a manner, the solvent evaporates and the isocyanate left behind cures under the influence of moisture and the cured compound thus replaces the stone substance already lost, suitable choice of the mineral constituents used in the moldable compound expediently ensuring that the stone parts replaced in this manner have the same appearance as the remaining stone.
Process techniques usual per se can be applied for the application of the solutions in the method according to the invention. For hydrophobizing, a spraying on, brushing on or flooding may expediently be used. At the same time, for the renovation of already damaged structures, an impregnation in the solution, or if this is not possible because of th: size of the structure, a multiple brushing on or spra/ing on or application by means of a flowing film (flooding) is suitable.
The invention is explained in more detail on the basis of the examples below and at the same time the stone samples obtained, treated with the method according to the invention, are tested in comparison with untreated stone samples for their properties and the results are compared.
Example 1 Mechanicat rupture tests For the rupture tests, prisms measuring 4 x 4 x 16 cm were cut from Soskut soft lime quarrystone. The test specimens were saturated by absorption from a solvent Z© layer as a consequence of capillary activity and tested after the treatment in a comparison with the untreated 4~ specimens. I n t h is pr oc es s 0 t he following re s u Lts w e re obta ined: Soskut quarrystone test Untreated test Treatment with the polyisocyanate prepotymer specimen solution in a mixture of 50% by weight of xyLene and 50% by weight of methyl isobuty, ketone Concentration Increase in of the soLution in Y by 6 a weight6 8.1 325 30,2 47.6 273 46 Chipped stone from the surface (ayer of the Soskut quarry Untreated test Treatment with the poLyisocyanate prepoLymer specimen soI~ution I Concentration Increase in 7 of the sotution in 7byba aweight6a 30 10 '32 48 300 6 =tensi~e strength in. bending N/mm 2 Example 2 a =compression strength N/mm 2 wear-res istance test of weathered Soskut soft Lime quar rYstone The surface of quarrys tone blanks was impregnated with a 12% poLyisocyanate prepoLymer solution in a mixture of by weight of xyLene and 50% by weight of methyl isobuty( ketonie, the solution being drawn into the stone under the irftLuence of capiL~ary activity* The Stone specimen treated in this manner was subjected to th~e 8O0hm wear-res istance test along with an untreated stone specimen. Ini this process, the foL~owing results were obtained: I ~C _I 8 Before the After the Difference Increase wear test wear test Mass Thick- Mass Thick- Mass Thick- ness ness ness g mm g mm g mm Untreated 382.7 41.3 285.8 31.2 96.9 10.1 Treated 332.4 40.6 275.8 34.0 56.6 6.6 Example 3 Vapor diffusion test of Soskut soft Lime quarrystone The tests were determined on the basis of the binding to CaCL 2 of quantities of moisture which were absorbed from the air and which had diffused through disk-shaped test specimens having a diameter of 7 cm. The concentration of the poLyisocyanate prepolymer solutions used for treating the specimens in a mixture of 50% by weight of xylene and 50% by weight of methyl isobutyl ketone was by weight. The quarrystone disk had absorbed the solution as a consequence of the capillary activity.
The following results were obtained! Parameter Increase in Decrease in the Test time Thickness weight of the vapor diffusion quantity of in CaCl h cm g Untreated 984 2.20 19.5 Treated 984 2.23 15.9 18.5 Example 4 Frost resistance test Prisms measuring 4 x 4 x 16 cm were manufactured from the Soskut soft lime quarrystone and similar test 9 specimens were produced to test the stone substitute material.
The polyisocyanate prepolymer solution in a mixture of by weight of xylene and 50% by weight of methyl isobutyl ketone used for the treatment was a 12% by weight solution which the test specimen absorbed from a solution as a result of the capillary activity.
Test method: The number of cycles between freezing to -200C and breakdown in water at +200C was tested. The number of cycles which the specimen passed through without damage was compared.
The increase in frost resistance of the Soskut soft limestone as a consequence of treatment with the solut ion according to the invention was Example Water absorption test In each case 5 pieces of the lhrl sandstone and of the Udelfang sandstone cut to the same size were subjected to storage in water in the untreated state and after impregnation with the 6% by weight polyisocyanate prepolymer solution according to the invention in a mixture of by weight xylene and 50% by weight methyl isobutyl ketone.
The results are Listed below: i 10 Ihrt sandstone (untreated) Specimen Weight, g Dimensions, mm No. Days of storage in water After Length Width Height 6 7 8 drying 1 314.33 314.40 314.54 314.54 294.10 52 52 52 2 312.63 312.73 312.82 312.82 292.05 52 52 51 3 310.98 311.09 311.22 311.22 290.73 51 51 52 4 310.17 310.33 310.39 310.39 289.51 51 51 52 309.47 309.66 309.78 309.78 289.58 51 51 52 Specimen Weight per Water absorp- No. Weight, 9 unit volume tion Dry Saturated Water ab- kg/dm 3 by by with water sorption mass volume _Wa.
1 294,10 314.54 20.44 2.09 6,95 14,54 2 292.05 312.82 20 ,77 2.12 7.11 15.06 1 290,73 311.22 20.49 2.15 7.05 15.15 4 289,51 310.39 20.88 2,14 7,21 15.44 289.58 309.78 20.20 2,14 6.98 14.94 Average 7.06 15,.02 thrl sandstone (mpregnated with the solution according to the invent ion) Specimen Weight, 9 Dimensions, mm No. Days of storage in water After Length Width Height 5 6 7 8 drying 1a 29 2a 29 3a 29 4a 29 Sa 29 7,.49 297.67 297.86 297.86 7,65 297.84 298.02 298.02 p7.04 297.18 297.31 297.31 3.$8 293.70 .34 293.85 2.39 292,54 292.66 292.66 292.88 292.93 292.72 289,40 288.14 iNw r~
I
11 Spec imen No. Weight, Saturated with water 9 Water absorption Weigh Water absorpunit volume tion.
kg/din 3 by %by mass voLume la 292.88 297.86 4.98 2.17 1.70 3.68 2a 292.93 298.02 5.09 2.17 1,74 3.76 3a 292.72 297.31 4.59 2.16 1.57 3.39 4a 289.46 293.85 4.45 2.18 1.54 3.36 a 288.14 292.66 4'.52 2.17 1.57 3.41 Average; 1.62 3.52 LQdeI~fang sandstone (untreated) Specimen Weight, g Dimensions, mm No. Days of storage in water Af ter Length Width Height 6 7 8 drying 1 277.61 277.90 278,07 2-78.07 256.11 51 51 2 277.37 277.60 277.77 277.77 256.47 51 51 3 281.17 281. 41 281.66 281.66 261.53 51 51 4 274.53 274,85 275.05 275.05 251.95 51 51 269.33 269.61 269.81 269.81 245.43 51 51 Specimen Weight per Water ab~sorp- No, Weight, g wni t vo~tme t ion.
Dr>y saturated Water ab- kg/din 3 X< by X~ by with water sorptioni mass voLume W'a 1 256.11 278.0 21.96 1.97 8.5? 16i87 2 2-56.47 277.77 21.30 1,97 8.31 16.38 3 261 .53 Z8 20,13 2.01 7.70 15.48 4 251195 275,05 3.10 1.914 9,17 17.76 24$5,43 269.81 24.38 1,39 9,13 18.75 Average,, 1'?1Q5 r I r" 12 Odelfang sandstnne (impregnated with the solution according to the invention Specimen Weight, g Dimensions, mm No. Days of storage in water After Length Width Height 6 7 8 drying la 270.09 270.49 270.85 271.10 267.12 50 50 51 2a 248.19 248.95 249.61 250.47 243.10 50 50 51 3a 251.81 252.38 252.80 253.20 248.26 50 50 51 4a 250.56 250.92 251.14 251.50 247.89 50 50 51 250.01 250.80 251.38 252.08 245.25 50 50 51 Specitmen Weight per Water absorp- No. Weight, g unit volume tion Dry Saturated Water ab- kg/dm 3 by by with water sorption mass volume __Wa_ la 267.12 2a 243.10 3a 248.26 4a 247.89 245,25 271.10 250.47 253.20 251.50 252.00 3.98 7.37 4.94 3.61 6.75 2.10 1.91 1.95 1.94 1,92 1.49 3.03 1.99 1.46 2.75 3.12 5.78 3.87 2.83 5.29 Average: E'ampLe 6 Modified Quervain crystallization test 2.14 4.18 The same Ildelfang sandstone test specimens were used as in Example 5 (5 pieces untreated and 5 pieces treated with the, solution according to the invention as in Exampie 5) The specimens were subjected to the Quervain crysta L ization test using 10% sodium sulfate solution.
After 10 cycles sand formation was observed in the untreated test specimens, white, in the case of the treated test specimens, there was still no change even after 20 cycles.
/A
ICE
Claims (2)
1. Process of hydrophobizing as by pnirnnmpntnml inf linrp nninr micrccrgonicms yet undamaged stone structures of open porosity with the following steps:
11. a solution of an aliphatic isocyanate and one or more solvents, inert to said isocyanate is applied to said stone structure by spraying, brushing or flooding, 1.2. the concentration of said isocyanate in said solvent being in the range of 1 to 10 by wheight, corresponding to 99 to 90 by wheight of said solvent(s), the amount having chosen, depending on the size of the open capil- lary structure of said stone structure, such as the solu- tion hardens upon reaction with moisture while forming a polymeric film on the surface of the cappilary walls while maintaining vapor diffu-sion capability within said capillary system. 2. Process for consolidation of stone structures with open poro- sity, damaged by environmental influence and/or microorganisms with the following steps: 2.1, a solution of an aliphatic isocyanate and one or more sol- vents, inert to said isocyanate, is applied to said stone structure by impregnating, flooding or multiple spraying or brushing 2,2. the concentration of said isocyanate in said solvent(s) being in the range of 3 to 15 by wheight, corresponding Sto 97 to 85 by wheight of said solvent(s), the amount having chosen, depending on the size of the open capil- lary structure of said stone structure such as the solu- tion covers the capillary walls with a polymeric film upon reaction with moisture hardens and consolidates the da- /C IA maged stone structure while maintaining vapor diffusion c-~ I /1- capability within said capillary system. 3. Process for restoring stone structures with open porosity heavily damaged by environmental influence and/or microorga- nisms with loss of stone with the following steps: 3.1. a moldable mass which consists of an aliphatic isocyanate and one or more solvents, inert to said isocyanate and mineral constituents is applied to the damaged parts of said stone structure 3.2. the concentration of said isocyanate being 8 to 30 by weight, related to said solutions of isocyanate and sol- vent(s), corresponding to 92 to 70 by wheight of said solvent(s), and 3.3. hardening of said mass under moisture influence while re- placing lost stonec os c\5 c. e r\ 4. Process according to one of claims 1 to 3, using a polyisocy- anate-prepolymer as aliphatic isocyanate. Process according to claim 4 using a polyisocyanate-prepolymer with a content of reactive NCO groups being approximately by wheight. 6. Process according to one of claim-s 1 to 5 using xylene, methyl -isobutyl ketone, solvent naphta, toluene, ethyl acetate, isobutyl acetate, acetone or methoxypropyl acetate alone or as a mixture as solvent. 7. Process according to claim 6 using one of the following mix- /tures of said solvents: 30 parts by weight of xylene, 100 parts by weight of methyl isobutyl ,etone. 250 parts by weight of isobutyl acetate, 180 parts by weight of xylene, 350 parts by weight of solvent naphta. 250 parts by weight of methyl isobutyl ketone, 180 parts by weight of xylene, 350 parts by weight of solvent naphta, 30 parts by weight of xylene, 80 parts by weight of acetone, parts by weight of isobutyl acetate, 100 parts by weight of ethyl acetate, 'O0 parts by weight of toluene, 30 parts by weight of acatc?. 100 parts by weight of toluene, 30 parts by-weight of ace- tone, 30 parts by weight of methoxypropyl acetate. 7 Method for protecting, renovating and restoring stone structures, monuments and the like. Abstract The invention relates to a method for protecting, reno- vating or restoring stone structures in which the struc- ture is treated with a solution which consists of an aLiphatic isocyanate and one or more organic solvents inert thereto and then the isocyanate is cured by expo- sure to moisture. The invention furthermore relates to the agents for carrying out the method consisting of a solution of aliphatic isocyanate in one or more organic solvents inert thereto. INTERNATIONAL SEARCH REPORT International Application No PCT/DE 88/00226 I. CLASSIFICATION OF SUBJECT MATTER (If several classification symbols apply, Indicate all) According to International Patent Classification (IPC) or to both National Classification and IPC Int.Cl 4 C 04 B 41/48 II, FIELDS SEARCHED Minimum Documentation Searched 7 Classification System Classficatlon Symbols Int.Cl C 04 B 41/00; C 04 B 26/00 Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields Searched a III, DOCUMENTS CONSIDERED TO BE RELEVANT' Category Citation of Document, 11 with Indication, where appropriate, of the relevant passages 12 Relevant to Claim No. 13 X Chemical Abstracts, volume 88, No 22, 29 1,4,6,9,11 May 1978, (Columbus, Ohio, US), see page 318, abstract 157472v, JP, A, 77109518 (KOWA CHEMICAL INDU- STRIES CO, LTD) 13 September 1977 X DE, A, 3135941 (MISAWA HOMES 1,6,11 24 March 1983 see abstract; page 6, lines 5-7 X DE, A, 2713857 (SAGER WOERNER) 1,6 12 October 1978 see claim 1 A FR, A, 2410709 BARTAK) 29 June 1979 1-3,6-8 see page 1, lines 5-10; claim 1 A Chemical Abstracts, volume 100, No 10, 1-3,6-8 March 1984, (Columbus, Ohio, US), see page 295, abstract 73078z, JP, A, 58172281 (MATSUSHITA ELECTRIC WORKS, LTD) 11 October 1983 SSpecial categories of cited documents: 10 later document published after the International filng date document denning the general state of the art which s not or priority date and not in conflict with the application but considered to be of particular relevance cited to understand the principle or theory underlying the invention earlier document but published on or after the international document of particular relevance the claimed invention Scannot be considered novel or cannot be considered to document which may throw doubts on prority claim(s) or involve an inventive step which is cited to establish the publicatlol date of another document of particular relevance;' the claimed Inventior clain or other special reason (as specinied) cannot be considered to involve an Inventive step when the document referring to an oral disclosure, use, exhibition or document Is combined with one or more other fuch docu- other means ments, such combination being obvious to a pelon skllllid document published prior to the internatlona filing date but in the art, later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Search Report 31 May 1988(31.05.88) 129 June 1988(29.06.88) International Searching Authority Signature of Authorized Officer European Patent Office Form PCT/ISA210 (second sheet) (January 1985) ANNEX TO THE INTERNATIONAL SEARCH- REPORT ON INTERNATIONAL PATENT APPLICATION INO. DE 8800226 SA 21584 This annex lists the patent family members relating to ihe patent docunments cited in thc aho'.e-mentioned international search report. The members arc as contained in the Europeamn Paitent Office E11 file on l7/tJ6/8i The European Pautent Office is in no vtay lible for these particulars lihich are merely -,ken for thc purpose of information. Paen ocmnt Publication llatcnt faniily Publication cited in search report date miembler(,;) date LiE-A- 3135941 24-03-83 Keine OE-A- 2713857 12-10-78 Keine FR-A- 2410709 29-06-79 BE-A- 872406 30-05-79 GB-A,B 2010871 04-07-79 NL-A- 7811685 06-0U6-79 D E-A- 2851313 07-06-79 AT-A,B 351997 27-08-79 US-A- 4263161 21-04-81 CA-A- 1121108 06-04-82 SE-B- 425083 30-08-82 SE-A- 78122-44 02-06-79 CH-A- 638475 30-09-83 For more detatls about this annex see official Journal of the ,uropcun Patent O)ffitc. No, I 118,,
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873712967 DE3712967A1 (en) | 1987-04-16 | 1987-04-16 | METHOD FOR PROTECTING, RENOVATING AND RESTORING STONE CONSTRUCTIONS, MONUMENTS AND THE LIKE |
| DE3712967 | 1987-04-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU1547988A AU1547988A (en) | 1988-11-04 |
| AU600357B2 true AU600357B2 (en) | 1990-08-09 |
Family
ID=6325787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU15479/88A Ceased AU600357B2 (en) | 1987-04-16 | 1988-04-12 | Process for protection, reconstitution and restoration of stone buildings, monuments and similar |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0287026B1 (en) |
| AT (1) | ATE58365T1 (en) |
| AU (1) | AU600357B2 (en) |
| CA (1) | CA1314361C (en) |
| CS (1) | CS270584B2 (en) |
| DD (1) | DD281216A5 (en) |
| DE (2) | DE3712967A1 (en) |
| ES (1) | ES2019117B3 (en) |
| FI (1) | FI94127C (en) |
| PL (1) | PL150756B1 (en) |
| WO (1) | WO1988007982A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2643899B1 (en) * | 1989-03-01 | 1992-11-20 | Crea Eric | Renovation of external marble and stone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU1202388A (en) * | 1987-02-20 | 1988-08-25 | Ube Industries, Ltd. | High strength cured cement article and process for manufacturing the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1194754B (en) * | 1963-10-09 | 1965-06-10 | Hoechst Ag | Water repellent for building protection |
| FI237174A (en) * | 1973-08-10 | 1975-02-11 | Nya Asfalt Ab | |
| DE2713857A1 (en) * | 1977-03-29 | 1978-10-12 | Sager & Woerner | Surface impregnation of concrete, plaster, bricks, natural stone etc. - using compsn. contg. epoxide, isocyanate and opt. organo-silicon cpd. |
| AT351997B (en) * | 1977-12-01 | 1979-08-27 | Bartak Gottlieb | INSULATING LIQUID FOR NIGHTLY INSULATING MASONRY AGAINST RISING LIQUID |
| DE3135941A1 (en) * | 1981-09-10 | 1983-03-24 | Misawa Homes K.K., Tokyo | Process for the surface treatment of components consisting of lightweight aerated concrete |
| DE3629061A1 (en) * | 1986-08-27 | 1988-03-03 | Bayer Ag | IMPREGNANT AND ITS USE |
-
1987
- 1987-04-16 DE DE19873712967 patent/DE3712967A1/en active Granted
-
1988
- 1988-04-11 CA CA000563773A patent/CA1314361C/en not_active Expired - Fee Related
- 1988-04-12 ES ES88105787T patent/ES2019117B3/en not_active Expired - Lifetime
- 1988-04-12 AT AT88105787T patent/ATE58365T1/en not_active IP Right Cessation
- 1988-04-12 AU AU15479/88A patent/AU600357B2/en not_active Ceased
- 1988-04-12 EP EP88105787A patent/EP0287026B1/en not_active Expired - Lifetime
- 1988-04-12 DE DE8888105787T patent/DE3861045D1/en not_active Expired - Lifetime
- 1988-04-12 WO PCT/DE1988/000226 patent/WO1988007982A1/en active IP Right Grant
- 1988-04-15 CS CS882587A patent/CS270584B2/en unknown
- 1988-04-15 DD DD88314798A patent/DD281216A5/en not_active IP Right Cessation
- 1988-04-15 PL PL1988271855A patent/PL150756B1/en unknown
-
1989
- 1989-10-12 FI FI894835A patent/FI94127C/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU1202388A (en) * | 1987-02-20 | 1988-08-25 | Ube Industries, Ltd. | High strength cured cement article and process for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CS258788A2 (en) | 1989-11-14 |
| FI94127C (en) | 1995-07-25 |
| EP0287026B1 (en) | 1990-11-14 |
| FI94127B (en) | 1995-04-13 |
| WO1988007982A1 (en) | 1988-10-20 |
| EP0287026A1 (en) | 1988-10-19 |
| DD281216A5 (en) | 1990-08-01 |
| PL271855A1 (en) | 1989-02-06 |
| ATE58365T1 (en) | 1990-11-15 |
| PL150756B1 (en) | 1990-06-30 |
| CA1314361C (en) | 1993-03-16 |
| ES2019117B3 (en) | 1991-06-01 |
| DE3712967A1 (en) | 1988-12-22 |
| CS270584B2 (en) | 1990-07-12 |
| FI894835A0 (en) | 1989-10-12 |
| AU1547988A (en) | 1988-11-04 |
| DE3712967C2 (en) | 1989-04-13 |
| DE3861045D1 (en) | 1990-12-20 |
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