AU667927B2 - Method of increasing the viscosity of water, and use of the method - Google Patents

Abstract

The prepn. of thickened water comprises slurrying 1-9 wt.% highly dispersed synthetic esp. pyrogenic silica acid in water, adding only a small amt. of additives, the additive being 0.05-0.5 wt.% poly(N-vinyl-2-pyrrolidone) (PVP).

Description

ACJP DATE 24/03/94 PCT NUMBER PCT/DE93/00512IAIIifhlIIHd OPT ATE04/0/94 APPN. I 4367/9 I~I N ~I~IIII AU9343067 (51) Internationale Patentklassifikation 5 (11) Internationale Veroffentlichungsnummer: WO 93/25474 C01IB 33/193, BO IF 17/00 C09D 7/00, CI ID 3/60 Al (43) Internationales A01IN 25/04, C09K 7/02 Veriiffentlichungsdatum: 23. Dezember 1993 (23.12.93) A62D 1 /00, A47C 27/08 (21) Internationales Aktenzeichen: PCT/DE93/00512 (81) Bestimmungsstaaten: AU, CA, Fl, HU, JP, NO, PL, RU, US, europtiisches Patent (AT, BE, CH, DE, DK, ES, FR, (22) Internationales Anmeldedatum: 11. Juni 1993 (11.06.93) GB, GR, IE, IT, LU, MC, NL, PT, SE).

Prioritiitsdaten: Veriiffentlicht P 42 19 266,8 12. Juni 1992 (12.06.92) DE Mit imternationalemn Recherczenbericit P 42 25584.8 4. August 1992 (04.08.92) DE A'it gelinderten Ansprii c/en.

P 43 14 749.6 5. Mai 1993 (05.05.93) DE (71)(72) Anmelder und Ertinder: LORNERT, Gernot [DE/DE]; Rottweg 16, D-4236 Hamminkein BUlL, J~rgen [DE/DE]; Heldstralge 19~, D-4190 Kleve LOH- NERT, Katharina [DE/DE]; Rottweg 16, D-4236 Hamminkeln (DE).

(74)Anwalt: PFENNING, MEINIG PARTNER; Mozartstrasse 17, D-80336 Mflnchen (DE).

(54)Title: METHOD OF INCREASING THE VISCOSITY OF WATER, AND USE OF THE METHOD (54) Bezeichnung: VERFAHREN ZUR VERDICKUNG VON WASSER UND SEINE VERWENDUNG (57) Abstract The method proposed for increasing the viscosity of water is charcterized in that, for the instantaneous production of increased-viscosity water which does not lose its viscosity characteristics on storage, a slurry is prepared containing 1-9 preferably 2-5 of high-disperse synthetic, preferably pyrogenic, silicic acid in water with only a small amount of added ethers of fatty alcohols or sacoaric alcoohols or esters of fatty acids with poly(ethylene glycol) or poly(propylene glycol) with a molecular wveight between 250 and 50,000, at a concentration of 0.005 to 1.5 poly(ethylene glycol) or poly(propylene glycol) with a molecular weight between 600 and 50,000 at a concentration of 0.05 to 1.5 poly(ethylenimine) at a concentration 0.003 or poly(N-vi-, niyl-2-pyrrolidone) at a concentration of 0.05 to 0.5 0A., Characteristic of this system is its marked rheopexic properties which are s,-own instantaneously under the action of shear forces. Under such conditions, the viscosity increases and a stable, homogeneous terminal state is produced. The increased-viscosity water thus produced can be used as, for instance, a fire extinguishant, a carrier (57) Zusammenfassung Verfahren zur Verdickung 'von Wasser dadurch gekennzeichnet, dags zur momentanen Bereitung von haltbar verdicktemn Wasser eine Aufschifimmung von 1-9 vorzugsweise 2-5 an hochdisperser synthetischer, bevorzu.gt pyrogener, Kieselsflure in Wasser mit einem nur geringen Zusatz von Ethern mit Fettalkoholen, Zuckeralkoholen, oder Estern mit Fettsiluren des Polyethylenglykols oder Polypropylenglykols, der Molmassen 250-50.000, in Konzentrationen von 0,005 von Polyethylenglykol oder Polyp ropylIenglykolI der Moiriassen 600-50.000 in Konzentrationen von 0,05 %a bis 1,5 von Polyethylenimin in Konzentrationen von 0,003 oder von Poly(N-vinyl-2-pyrrolidon) in Konzentrationen von 0,05 zur dauerhaften Verdikkung gebracht werden kann. Kennzeichnend ist das ausgepriigt rheopexe Verhalten dieses Systems, welches sich durch Einwirkung von Schereinflflssen momentan zeigt. Dabei erh6ht sich die Verdickung und es wird emn homogener und haltbarer Endzustand erreicht. Da~s so verdickte Wasser ist z.B. als Lbschmittel, als Trilger f~r Pflanzenschutz- und Reinigungsmittel oder als Fflllmedium for Wasserbettmatratzen einsetzbar.

I PCT/DE93/00512 LOHNERT, BUIL Method of Thickening of Water, and its Use.

Thickening of liquids is of technological significance for controlling flow properties, for instance, for avoiding losses and running when employed as a means of depositing or transport,for retaining sedimentable particles in a homogeneous mixture, for fixing the liquids to surfaces in order to obtain longer lasting effectivity or in order to improve the behavior of the liquids as hydrostatic media for pressure distribution, for example, by reducing or eliminating wave propagation.

Due to its non-toxicity, capacity as a solvent, compatibility, low cost and good availability, water is an excellent liquid medium. On the other hand, its quick, uncontrollable avd sOye-ldirunnin^, its adhesion to surfaces as only thin films of a RPY water, theeYsedimentation of solids if present and its strong wave propagation are often disadvantageous for technological application. This is the case when it is used as a fire extinguishant, as a liquid carrier of cleansing or plant protection agents but also in exploiting its very good pressure distribution properties.

The production of thickened water to fulfill the mentioned technological objects, in particular, in a lasting, controllable manner and in order to avoid diminishing its advantageous properties by adding minimal amounts of ,cessory agents is, therefore, often a challenge. -r this purpose, various technological paths reflecting the respective specific needs have been embarked upon.

Organic viscosity-increasing agents, such as gelatin, starches or cellulose derivatives, natural polysaccharides (gums) or synthetic, water-soluble high polymers alter the properties of water in a manner that is disadvantageous for the mentioned technological applications by producing sticky or thread-drawing properties, or due to poor stability (oxidative or microbial decomposition, cf. Kirk- Othmer, Encyclopedia of Chemical Technology, 3rd. ed., vol. 18, p. 623).

If on the other hand, inorganic viscosity-increasing agents such as crystalline silicates (bentonite, attapulgite or mica) are solely utilized as a stable viscosity-increasing agent for water, the required concentrations are distinctly above 10% in order to obtain technologically exploitable viscosity-increasing results as is known from the forest-fire-fighting application of thickened water using bentonite or attapulgite (lit., C.E. Hardy, Chemicals for Forest Fire -Y l -2- Fighting, 3rd. ed., Boston, 1977). Crystalline layered silicates, such as bentonite often form undesirable, difficult-to-remove residues after evaporation of the water.

All mentioned viscosity-increasing agents for water have in common that they require considerable time (ranging from hours to days), due to their swelling behavior, to achieve the desired maximum viscosity, which is difficult to control by outside influences and which requires handling that is often complicated. Silicic gels produced by the gelling of unstabilized silicic sols or by neutralization of water glass can generate a thickening effect even in low concentrations, however, they continuously separate water from the gel (syneresis) due to polycondensation of the silicic acids resulting from neutralization, causing the gel to shrink. Evaporation of the water results in a hardened residue which is very difficult to remove from surfaces, vessels or devices, pipes or the like consequently eliminating the use of water the viscosity of which has been increased in this manner, for fire extinguishers, plant-protection sprayers or as a filling medium, for waterbeds. Moreove., the gelling time of silicic acid in low concentrations in watr: is difficult to control even when auxiliary agents such as salts are added.

Although highly-disperse, amorphous, synthetic silicic acid does not show the latter-mentioned disadvantageous properties, they are employed as viscosity-increasing agents predominantly for organic, hydrophobic fluids, because due to their hydrophilic properties, they show a distinctly weaker effect as a viscosity-increasing agent in low concentrations in water. This also is true for other liquid hydrophilic media, such as, glycerin.

R.K. Iler also confirms, in "The Chemistry of Silica", Wiley, New York, 1979, p. 336, that dispersions of pyrogenically produced silicic acid form sols in an aqueous so'ution, which do not form strong gels an, therefore, are only of little use as inorganic binders.

The present invention found as a solution to the object of instantaneous production of stable, thickened water, that the viscosity of a lowly-concentrated silicic ool which can be prepared from highly-disperse synthetic, preferably from pyrogenic silicic acid in water by slurrying in water, slurries of preferably 2pyrogenic silicic acid in water with only a small amount of added specific water soluble organic compounds, notably ethers of fatty alcohols or saccharic alcohols or 41 x I i locr~-~- I -3esters of fatty acids with poly(ethylene glycol) or poly (propylene glycol) with a molecular weight of >250 50,000, in a concentration from 0.005 to poly(ethylene glycol) or poly(propylene glycol) with a molecular weight of >600 50,000 in a concentration from 0.05% to of poly(ethylenimine) in a concentration from >0.003 or of poly(N-vinyl-2-pyrrolidone) in a concentration from 0.05 to can be instantaneously and stably increased. Characterizing and differing from the other mentioned thickening methods for water is that in this thickening method, in particulir, the marked rheopexicbehavior of the system which are shown instantaneously under the action of shear forces, such as, being stirred with an electric stirrer (800-1600 rpm), passing through centrifugal pumps or being sprayed through nozzles. Thickening and a homogeneous and a very stable thickening effect is produced.

The mentioned organic compounds can be employed in SO/ely the mentioned concentrationsf6r in combination. The range of application for poly(ethylene glycol) or its mentioned derivatives is limited to a pH-range of 1-9. If the pHvalues are higher, dilution to a thin watery consistency prior to being added occurs. In the case of poly(ethylenimine), this dilution can be detected below a pH-value of 3. A combination of the two additives permits increasing the viscosity in a correspondingly larger pHrange. The synthetic amorphous silicic acid can also be mixed dry with the mentioned organic compounds prior to adding the water. This mixture can be stored until use and then mixed with the amount of water required to reach the needed concentration. The silicic acid and the mentioned organic additivies can also be mixed directly with the water.

The thickened slurry of synthetic, amorphous silicic acid of low concentration in water ("thickened water") produced in this manner can, be very successfully utilized as a fire-extinguishant for class A fires (in particular for hard-to-extinquish fires of tires or other synthetic materials), because they massively adhere to hydrophobes or hot surfaces and thus permit keeping thick water layers at disposal on horizontal, vertical or even downward showing surfaces of any kind. It is suited as a drilling fluid, because it is stable against shear forces under pressure and at high temperatures. It can also be used as a carrier for cleaning agents, such as antiliming agents, because, e.g., organic acids such as citric, tartaric or malic acids can be dissolved in it, which can be applied to calcified surfaces to produce a lasting effect.

rar la -r-u.

-4- The use of the invented viscosity-increased water is also very advantageous as a hydrostatic, pressure-equalizing filling for waterbeds or cushions or gel saddles with the advantage of eliminating wave reflections. Development of microorganisms in the thickened water is not observed in theflexible cushions even over a period of several months, whereas similar cushions filled with water had slimey deposits, probably algae, on the inner walls after the same period of time.

The invented thickened water demonstrates compatibility with the salts of anorganic and organic acids dissolved in it even in higher concentrations an addition of 30% of potassium acetate or potassium lactate) so that frost resistance at -30C) is achieved. Sugar or its derivatives such as sorbitol; glycol orglycerol can also be dissolved in any concentration in viscosity-increased water without diminishing the viscosity. Therefore, the viscosityincreased water can also be employed as a reuseable, liquid filling for cooling pillows, cooling cells or cooling bags. Due to the good handling properties, these mixtures can be refilled as desired and thus reused. This is usually not possible with fillings of this type produced with organic gel formers.

Moreover, the stable thickening permits the incorporation and stable suspension of sedimentable mineral or organic insoluble materials, even proteins, which is useful for analytic, but also synthetically preparative purposes, such as separation of materials.

For the use as fire-extinguishants, from concentrats can be added to the viscosity-increased water of the AFFF type), with thethickening as well as foamability being retained. A thickened foam is produced that contrary to foam which is only made with AFFF has considerably better adhesion-to-surface properties so that uncontrollable running of the foam is avoided and fighting fires of solid materials (class A) and of flammable liquids (class B) is permitted.

The following exAmples make the present invention more apparent without the intention of limiting the spirit or scope of the invention:

%I.

ii ~i Example 1 2.2 liters of a 15% dispersion of an amorphous, synthetic silicic acid (Wacker HDK KD 150, reg. trademark, Wacker Chemie GmbH, Munich) are mixed with 7.8 liters of water. 20 grams of poly(oxyethylene lauryl ether) with a molecular weight of approximately 380 (Mulsifan CPA, reg. trademark, of Zschimmer and Schwarz, Lahnstein) are mixed with the watery dispersion which has a flow time of 10 seconds in a DIN 53 211 cup. The mixture has a flow viscosity of 11 seconds immediately following the addition. A 500 ml part of the mixture is filled into a spray-pump bottle and is sprayed onto a vertical, smooth aluminum surface. The thickeninqof the mixture increases immediately due to the spraying forces so that the mixture remains sticking completely to the metal surface.

Another 500 ml part of the thinly liquid mixture is stirred in a vessel for a few seconds with an electric stirrer (Philips Elektroquirl, 800/1600 rpm, cutting knife diameter approx.

4 cm). The mixture continues to thicken instantaneously and then a flow viscosity of approximately 29 seconds is measured in the flow beaker. (A small part of the mixture does not flow out of the cone of the beaker).

Similar thickening can be obtained by pumping the mixture through an electric centrifugal pump (flow rate: 68 liter/min). (Flow viscosity approx. 26 sec.).

Instantaneous thickening and very good adhesion of the thickened l.dter to surfaces of any kind is also found when spraying with plant-protection agent "sprayers"(Gloria, types 172 RTG and 176 T, various spray nozzles). Good adhesion to plants is also found, in particular, where water pearls off the surface of the plants due to surface hydrophobicity. Thus, for example, use for low-loss application of water in thick layers onto plants, is also possible which may contain other additives which leads to improved prevention of frost damage or can be utilized for applying plant-protection agents. By spraying with water the applied layers can be removed again, if need be.

Instead of poly(oxyethylene lauryl ethers), poly(ethylen glycol) with a molecular weight of approximately 4220 or poly(oxyethylene sorbitan monostearate) with a molecular weight of approximately 1200 or PEG-120 jojoba alcohol and PEG-120 jojoba acid (molecular weight approx. 5400) or poly(ethylenimine) or poly(N-vinyl-2-pyrrolidone) were tried and yielded the same results. A viscosity-increasing effect which increases due to the influence of shear forces can already be found with added amounts of only 0.05% of the mentioned low-molecular poly(oxyethylene) derivates, poly(ethylene glycol), poly(N-vinyl-2pyrrolidone), or only 0.003% of poly(oxyethylenimine), -6and the viscosity is correspondingly lower. The polyethers have an upper action limit of approximately poly(Nvinylpyrrolidone) one of approximately 1% with regard to the overall mixture, above which slurries of the silicic acid in water return to their initial thinly liquid state.

Example 2 Thickened water produced according to example 1 is employed to extinguish a fully developed fire with 6 burning automobile tires. It is applied using a commercial liter water-fire extinguisher according to DIN. The fire was completely extinguished with 5 liters of the viscosity-increased water, without rekindling. On the other hand, the same fire could not be extinguished using 12 kg quenching powder, because rekindling recurred after temporary extinguishing of the flames with the powder.

Example 3 Thickened water produced according to example 1 was filled into a cushion holding 5 liters and another cushion of the same type was filled with pure water. The filling with the thickened water completely avoided wave reflections, whereas in the cushion that was only filled with pure water long-lasting "wave motion" occurred. Comparison also revealed distinctly improved sitting comfort due to the avoidance of "wave motion" Both cushions were emptied after 6 months, and examination of the interior revealed formation of slimey, greenish deposits only in the cushion that was filled with pure water, whereas the interior of the cushion filled with viscosity-increased water showed no changes.

A waterbed Prod. "Kuss", DLM Mfg. Co, Findlay, Oh., unstabilized) was filled with approximately 500 1 of the thickened water according to example i.

Solely by this means, 100% stabilization of the waterbed was achieved, which is indicated by a reflection period of <1 second following a shock impulse at the edge of the waterbed. An unstabilized waterbed only filled with water has, on the other hand, a reflection period of seconds. Thus, considerable improvement of reclining comfort is obtained without the mechanical stabilizing systems that are commonly used with waterbeds.

*1 -7- Example 4 Viscosity-increased water produced according to example 1 was mixed with 30 weight per cent of potassium acetate, which dissolves in it. Potassium acetate is described as so-called "loaded stream agent" in Ki.rk-Othmers Encyclopedia of Chemical technology, Supplement, p. 454, 1985 for use as an antifreeze in loaded stream water fire extinguishers and for little effective class B fires.

The thickening effect is retained even with this additive. The mixture was cooled for 24 hours to with the homogeneous, thick-flowing consistency being retained. Freezing was not observed. After warming, the thickened starting consistency was retained, decomposition or coagulation was not observed. The procedure can be multiply rereated.

In a small-scale extinguishing test using pine roof slates, very good flame extinguishing properties were determined with this viscosity-increased mixture, also indicated by the good adhesion on the inflammable surfaces. The test was repeated with potassium acetate being replaced by potassium lactate and yielded corresponding results.

In other tests, it was discovered that a high concentrated, approximately 30% solution of potassium acetate or potassium lactate in water without the additives described in example 1 can increase the viscosity of this mixture by adding approximately 3.3 .7eight in per cent of synthetic amorphous silicic acid, with adhesion to flat surfaces (plastic, rubber) not being as good as with the same mixture with the addition of the organic compounds mentioned in example I. Contrary to the organic additives in example 1, this increase in viscosity occurs only if high concentrations of both mentioned organic salts are employed.

Example Thickened water produced according to example 1 is mixed in 3 tests with 3% and 6% of a commercial AFFF foam concentrate without the synergists contained in it of the poly(oxyethylene fatty alcohol ether) type. The mixtures proved to be foamable with a foam nozzle, yielding, in comparison to foam formation with nonthickened water or to the non-thickened slurry of silicic acid in water, without the thickening additive a thickened foamis.

Contrary to the aforem.ntioned "non-thickened" foams,this foam adheres to surfaces.These "thickened" foams obtained in this manner are suited for -8extinguishing fires of liquid hydrocarbons. Moreover, they are also very effective in fighting fires of solid materials as they adhere to the latter.

With approximately 5 liters of a foam thickened in this manner coritaining 6% of the AFFF foam concentrates permits extinguishing a fire of pine slates measuring 270cm x 50 cm (7 layers respectively, cross-section 2cm x 4cm). Practically no rekindling was discovered.

Example 6 A slurry of 150g pyrogenic silicic acid (Aerosil 200, reg.

trademark, Dagussa) in 4850ml of water is mixed with of poly(N-vinvyl-2-pyrrolidone) (Sokalan HP 50 or HP 53, reg. trademark, BASF) and stirred with a glass rod. A slight increase in viscosity occurs, indicated by a flow period in a DIN 53 211 cup from 9 seconds (without Sokalan) to 20 seconds (with Sokalan). If the mixture is subsequently briefly sheared (1 sec.) with a stirrer (Philips Elektroquirl, 800/1600 rpm, diameter of the cutting knife 4cm), the viscosity increases to a value at which a pastelike consistency is obtained which has a strong property to form layers on wall and sticks to the cone of the flow beaker and thus no longer permits determining the viscosity in the cup. The mixture shows very good stability of the homogeneity, adhesion to surfaces, such as poly(ethylene), glass, metal, as well as lasting stability against shearing forces even at However, it still can be sprayed very well through nozzles of commercial fire extinguishers or plantprotection agent sprayers.The mixture shows a much delayed release of water when coming into direct contact with sucking substrates, such as, soil.

This is advantageous in the use of water whose viscosity has been increased in this manner for extinguishing garabage dump fires, because application of the extinguishant by injection is possible without uncontrolled penetration. Unthickened water, on the other hand, penetrates quickly and uncontrollably and, therefore, is quickly lost as an extinguishant for the fire-endangered zones.

'srr Irm -9- Example 7 An amount of 30g of pyrogenic silicic acid is mixed with 500ml of water and 470g of a solution of sorbitol syrup in water). Adding 2g of poly(N-vinyl-2-pyrrolidone) and blending with an electric stirrer at 800 rpm yields a pourable paste which can be utililzed as a filling for cooling bags. fhe mass is sufficiently mouldable to conform to uneven surfaces even at -20°C. It can be repeatedly frozen and thawed, and therefor can be multiply reused.

Example 8 A visocisty-increased slurry of pyrogenic silicic acid such as described in example 1 is mixed with 2% of citric or tartaric or malic acid, and 500ml of this mixture is used to clean calcified stone or plastic surfaces.

Thorough material-saving cleaning of the calcified surfaces is achieved due to the adhesive effect.

It

Claims (4)

1. 2. A method for thickening of water quickly and stably according to claim 1, characterized by an intensification of the thickening effect being achieved by vigorous stirring, shear force action or pumping processes or by spraying processes.
2. 3. Use of thickened water according to claims 1 -2 as a binding medium or carrier substance for pigments, cleaning agents, plant-protection agents, drilling fluids, extinguishants or as filling for waterbeds or cushions. P d' z r r -11- AMENDED CLAIMS [(filed with the International Office on 22 November 1993 (22/11/93); original claims 1-3 replaced by amended claims (2pages)] 1. A method for the production of thickened water by preparing a slurry of 1 9% weight per cent of high-disperse synthetic, preferably pyrogenic silicic acid in water with a only small amount of additives, characterized by providing 0.05 0.5 weight per cent of poly(N-vinyl-2-pyrrolidone) (PVP) as said additive. 2. A method according to claim 1, characterized by using PVP in mixture with the state- of-the-art additives of ethers of fatty alcohols, saccharic alcohols, or esters of fatty acids of poly(ethylene glycols) or poly(prolylene glycol) of molecular weights from >6000 50,000 or of poly(ethylenimine). 3. A method according to claim 1 or 2, characterized by achieving intensification of the thickening effect by vigorous stirring, shearing action or by spraying processes.
3. 4. Thickened water, characterized by being obtained according to at least one of the claims 1 to 3. Use of said thickened water according to claim 4 as a binding medium or carrier substance for pigments, cleaning agents, plant-protection agents, drilling fluids, extinguishants or as a filling for waterbeds or cushions. SA,' .f i1 r l l _I II c- INTERNATIONAL SEARCH REPORT International application No. PCT/DE 93/00512 A. CLASSIFICATION OF SUBJECT MATTER 5 C01B 33/193, B01F 17/00, C09D 7/00, C11D 3/60, A01N 25/04,C09K 7/02, Int.C A62D 1/00, A47C 27/08 According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system Collowed by classification symbols) Int.C1' C01B, B01F, C09D, C11D, A01N,C09K, A62D, A47C Documenlntion searched other than minimum documentation to the extent that such documents are included in the fields searched Electronic data base consulted during the international search (name of data base and, where practicable, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation of document. with indication, where appropriate, of the relevant passages Relevant to claim No. X DE, B2, 2524309 (LIEPMANN, 9 December 1976 1,3 (09.12.76), column l,line 27, claims 1-2 X EP, Al, 0407003 (HAMILTON LABORATORIES PTY.) 1,2 9 January 1991 (09.01.91) claims 5,10 X DE, Al, 2104061 (IMPERIAL CHEMICAL INDUSTRIES LTD.) 1,3 19 August 1971 (19.08.71) claims 1,48,49,51 X DE, Al, 1542748 (DEUTSCHE GOLD- U. SILBER-SCHEI- DEANSTALT) 30 July 1970 (30.07.70) claims 1-3,5 1,3 P,X WO, Al, 9213602 (BUIL, J. ET AL.) 20 August 1992 1,3 (20.08.92) page 10,line 20 page 11,line 28, claim 2 A US, A, 4321157 (HARRIS, R.G. ET AL.) 23 March 1982 1,3 (23.03.82) claim l,abstract SFurther documents are listed in the continuation of Box C. See patent family annex. Special categories of cited documents: laterdocumentpublishedaftertheintemational filingdateorpriority "A document defining the general state of the art which is not considered date and not in conflict with the application but cited to understand to b denngthe general stae of theparticular relevanceart whh is not consiered the principle or theory underlying the invention earlier document but published on or after the international filing date document of particular relevance; the claimed invention cannot be considered novel or cannot be considered to involve an inventive document which may throw doubts on priority claim(s) or which is step when the document is taken alone cited to establish the publication date of another citation or other special reason (as specified) document of particular relevance the claimed invention cannot be document referring to an oral disclosure, use, exhibition or other considered to involve an inventive step when the document is means combined with oneor more othersuch documents,such combination being obvious to a person skilled in the art document published prior to the International filing date but later than n obou to se n te a the priority date claimed document member of the same patent family Date of the actual completion of the international search Date of mailing of the international search report 31 August 1993 (31.08.93) 23 September 1993 (23.09.93) Name and mailing address of the ISA/ Authorized officer EUROPEAN PATENT OFFICE FacsI'ile No. Telephone No. Form PCT/ISA/210 (second sheet) (July 1992) IAN41kKNAI INAL SEARCH REPORT International application No. PCT/DE 93/00512 fC (Continuation j. DOCUMfENTS CONSIDERED TO BE RELEVANT Caiegor Citation of document, with indication. wnere appropriate. of the relevant passages Relevant to claim No, A EP, Al, 0432271 (KUMIAI CHEMICAL INDUJSTRY CO.) 1,3 19 June 1991 (19.06.91) page 4,line 50 line 54; page 8,line 52 line 55,claims 1,4 A Patent Abstracts of Japan, vol. 3,No. 97, M-69, 17 August 1979 (17.08.79) abstract of JP, A, 1,3
4. 54-71900 (ONODA CEMENT CO LTD) 8 June 1979 (8.06.79) A GB, A, 2099296 (JOUBERT AND JOUBERT PROPRIETARY LIMITED) 8 December 1982 (08.12.82) 1,3 claims 1,2 Farm PCI'/ISA/210 (cntinuation of second snect) (July 1992) SP '5926 INTERNATIONAL SEARCH REPORT International application No. Information on patent family members 30/07/93 PCT/DE 93/00512 Patent document Publication Patent family Publication cited in search report date member(s) date DE-B2- 2524309 09/12/76 NONE EP-A1- 0407003 09/01/91 AU-B- 622999 30/04/92 AU-A- 5308490 25/10/90 DE-Al- 2104061 19/08/71 BE-A- 762320 29/07/71 FR-A- 2078186 05/11/71 GB-A- 1349508 03/04/74 NL-A- 7101477 09/08/71 DE-A1- 1542748 30/07/70 BE-A- 674442 15/04/66 CH-A- 487595 31/03/70 FR-A- 1481063 00/00/00 GB-A- 1133210 0G/00/00 NL-A- 6517174 01/07/66 WO-Al- 9213602 20/08/92 AU-A- 1184392 07/09/92 DE-A- 4103388 06/08/92 DE-A- 4118888 17/12/92 DE-A- 4134870 29/04/93 US-A- 4321157 23/03/82 AT-E,T- 5896 15/02/84 CA-A- 1152845 30/08/83 EP-A,B- 0028432 13/05/81 JP-B- 4002640 20/01/92 JP-A- 56139595 31/10/81 EP-A1- 0432271 19/06/91 AU-B- 628178 10/09/92 AU-A- 5634390 18/12/90 JP-A- 2306903 20/12/90 US-A- 5180416 19/01/93 WO-A- 9014010 29/11/90 GB-A- 2099296 08/12/82 AU-A- 8241082 28/10/82 fr Form PCT/ISA/210 (patent family annex) (July 1992) ITRNATIONALER RECHERCHENBERICHT Internationales Aktenzeichen PCT/DE 93/00512 A. KLASSIFIZIERUNG DES ANMELDUNGSGEGEN~STANDES C018 33/193, B01F 17/00, C09D 7/00, C11D 3/60, AOlN 25/04, C09K 7/02, A62D 1/00 A47C 27/08 Nach der Internaijonalen ?'aientkassifikation (IPK) oder nach der nationalen Klassifikation und der IpX B. RECHERCHIERTE GEBIETE Recherchierter lMindestprofsLofT (Kiassifikaionssystem und Klassifikadionssymnbole) C0iB, BOYF, CO9D, C11D, A0iN, CO9K, A62D, A47C 4 Recherte, aber nicht zumn Mindestprilfstoff gehbrende Ver8ffentichungen, soweil. diese unter die recherchierten Gebiete fallen W~hrend der inwernafionalen Recherche konsultierte elektronische Dasenbank (Name der Dasenbank und evtL verwendete Suchbegri~e) EDOC, WPI, USPM C. ALS WESENTLICH ANGESSHENE UNTERLAGEN Kategorie* Bezelichning der Ver~ffenflichung, soweit erforderlich unter Angabe der in Betracht Batr. Anspruch Nr. kommenden Teile X DE, B2, 2524309 (LIEPMANN, 9 Dezember 1976 1,3 (09.12.76), Spalte 1, Zeile 27, AnsprUiche 1-2 EP, Al, 0407003 (HAMILTON LABORATORIES PTY.), 1,2 9 Januar 1991 (09.01.91), Anspr~che 5,10 X DE, Al, 2104061 (IMPERIAL CHEMICAL INDUSTRIES 1,3 LTD.), 19 August 1971 (19.08.71), Ansprt~che 1,48, 49,51 x DE, Al, 1542748 (DEUTSCHE GOLD- U. 1-3 SILBER-SCHEIDEANSTALT), 30 Juli 1970 (30.07.70), AnsprUche 1-3,5 F1 Weitere Ver6ffentlichungen sind der Fortsetzung von r1 h nagPaetanle L.JFel d C zu entnehmen. ieh nagPtnfmle Besondere Kategorien von angegebenen Verbffendichungen: Spierc VerMbfcnliung. die ac demn internitiionilen Anmeldedatuc ader demn Ver~tenticiiung, die den mulgennelnen Stand der Technik definlert, abr sien Priorititsdaiumn vcctffc-nuici warden ist und mit der AnMeldung nuit kallidieni, sic besonderi bedeutsarn antuiehen ist canderri nur zurri Versiadnue duc der Maindung 2ugrundeliegenden Prinzips ader der ihr zuurundeliegendcn Tlieorle jngegeben let lterce Dalcument, du ledadic Le ader cnch dccii iniernaianijen Verbffentlliung van bemanderer Bedeutung: die beaneprudite Frijindung bann Anmneideditumn vertttentlicdt worcien is dlie autgrund dicier Verfifentlichung nicht Cli neu eder aut ecilindenidier 'L Verdirentlichung, die gecigiet isi, einen Prioritlitcapruch twelfelhisf arichiiemen Tititkat beruhterd betracitct warden zu I asn, dureli die dui Veretfcailichungsditumn einer anderen im Redcertie. Vertffentlcuag von besonderer BedeuuunK: die beic pruchte Erindung hann benit gen inanten Ver ifentlichung belegt warden gall cider die &usi cinemn anderen nicii its cuf erfindeclidier Titlgkemi beruhen4 1eirncfiet warden, wenn die besanderen GCmsnd angcgabca let (vie augelflbrt) Verdttcallichung mit einer Ode! mebreren Verelfenhhcungen dicier Kategone in 00 Verbtentlichuag, die id cuf cune mOndlicie Oftenbarruag, elne Bcautzung, tine Verbiadung gebradit wird und diese Verbindung (Or ein~n Fcdmin ncheliegend Auctellung oder adere Maflaimren befahi lit Veretllcitung, die var dami intcradonulen Aknmeldestumn, &ar ncci dcii Vereftcatlliuag, die Mltgtied dertelben Pctentfatlce i beinepruchten Prioritsdatum vertlfentlitct warden iii Datumn des Abschiusses der internationalen Recherche Absendedatumn des internationalen Recherche n berch Ls 31 August 1993 23 1~ M' Name und Postanschrift der irtternationalen Recherchenbeharde Bevollmlichtigter Bediensteter 9 Europasches Patentamt, P.B. 5818 Patenlaa 2 0NL-2280 HV Rijswijk Tel. 31-70) 340.2040, Tx. 31 651 epo rdi, INGA-KARIN PETERSSON Formblatt PCT/ISA/210 (Blaut 2) (Juli 1992) ii I I INTERNATIONALER RECHERCHEN13ERICHT Internaionales Aktenzeichen PCT/DE 93/00512 C (Fortsetzung). ALS WESENTLICH ANCESEHENE UNTERLAGEN Kategrie*Bezeichnung der Veroffentlichung, soweit erforderlich unter Angabe der in Betracht Mer. Asrc r KaeoIe kormnenden Teile F npuc r WO, Al, 9213602 (BUlL, J. ET 20 August 1992 (20.08.92), Seite 10, Zeile 20 Seite 11, Zeile 28, Anspruch 2 UaS, A, 4321157 (HARRIS, R.G. ET 23 M~rz 1982 (23.03.82), Anspruch 1, Zusammer-~assung EP, Al, 0432271 (KUMIAI CHEMICAL INDUSTRY CO.), 19 Juni 1991 (19.06.91), Seite 4, Zeile 50 Zeile 54; Seite 8, Zeile 52 Zeile Anspriiche 1,4 Patent Abstracts of Japan, Band 3,Nr 97, M-69, 17 August 1979 (17.08.79), abstract of JP, A, 54-71900 (ONODA CEMENT CO LTD), 8 Juni 1979 (08.06.79) GB, A, 2099296 (JOUBERT AND JOUBERT PROPRIETARY LIMITED), 8 Dezember 1982 (08.12.82), Ansprdche 1, 2 1,3 1,3 1,3 1,3 1,3 Formbltrt PC f/ISA/210 (Fortsetzung von Blaut 2) (Juli 1992) S, '5926 UNTERNATIONALER RECHERCHENBERICHT -Internationales Aktenzeichen Angaben zu Verolfentlichungen, die zur selben Patentfamiliegehoren 30/07/93 PCT/DE 93/00512 Im Recherchenbericht Datum der Mtglied(er) der Datum der angefurtes Paientdokument V er Wentlichung -P .tentfamilie Verbffentlichung DE-B2- 2524309 09/12/76 KEINE EP-Al- 0407003 09/01/91 AU-B- 622999 30/04/92 AU-A- 5308490 25/10/90 DE-Al- 2104061 19/08/71 BE-A- 762320 29/07/71 FR-A- 2078186 05/11/71 GB-A- 1349508 03/04/74 NL-A- 7101477 09/08/71 DE-Al- 1542748 30/07/70 BE-A- 674442 15/04/66 CH-A- 487595 31/03/70 FR-A- 1481063 00/00/00 GB-A- 1133210 00/00/00 NL-A- 6517174 01/07/66 WO-AI- 9213602 20/08/92 AU-A- 1184392 07/09/92 DE-A- 4103388 06/08/92 DE-A- 4118888 17/12/92 DE-A- 4134870 29/04/93 US-A- 4321157 23/03/82 AT-E,T- 5896 15/02/84 CA-A- 1152845 30/08/83 EP-A,B- 0028432 13/05/81 OP-B- 4002640 20/01/92 OP-A- 56139595 31/10/81 EP-Al- 0432271 19/06/91 AU-B- 628178 10/09/92 AU-A- 5634390 18/12/90 OP-A- 2306903 20/12/90 US-A- 5180416 19/01/93 WO-A- 9014010 29/11/90 GB-A- 2099296 08/12/82 AU-A- 8241082 28/10/82 Formblatt PCT/ISA/2 1 0 (Anhang Patentfamille) (Juli 1992)