AU615293B2 - Latex-bound fire protection compound - Google Patents

Abstract

Thermally-expandable fireproofing material containing expanded graphite, an aqueous chloroprenlatex containing carboxyl groups and substances which form a paracrystalline carbon network in the event of fire.

Description

AOJP DATE 30/11/89 (51) Internationale Patentkassifikatio, 4 C09K 21/00 APPLN. I D 34119 89 OBER DIE PCI NUMBER PCT/EP89/00371 S ENS(PCT) (11) Internationale Veriffentlichungstiummer: WVO 89/09808 Al (43) Internationales Veriiffe[.~Iichungsdatum: 19. Oktober 1989 (19,10,89) (71) Internaionales Aktenzeichen: PCT/EP89/0037 I (22) Intern ationtl es Anmeldedatum: 7. April 1989l (07.04,89) Priori titsd aten: A 889/88 7. April 1988 (07.04.88) (81, Bestimiungsstaaten: AT (europfiisches Patent), AU, BB.

BE (europ~iisches Patent), BF (OAPI Patenti), BG, BJ (OAPI Patent), BR, CF (OAPI Patent), CG (OAPI Patent), CH (europaiisches Patent), CM (OAPI Patent), DE (europtiisches Patent), DK, Fl, FR (europ~isches Patent), GA (QAPI Patent), GB (europtiisches Patent), H U, 11T (europiiisches Patent), JP', KP, KR, LK, LU Ceuropliisches Patent), MC, MG, ML (OAPI Patent), MR (OAPI Patent), MW, NL (t.uroptiisches Patent), NO, RO, SD, SE (europfiisches 'Patent), SN (QAPI Patent).

SU, TD (OAPI Patent), TGi (GAP! Patent), US.

X'ertiffentlicht Alit interiationalecm Rechcrclwetbericht, (71) Anmelder (fair alle Bestimnuungssiaailen ausser US): CHE- M IE LINZ GES ELLSC-HA FT M, B, H. [AT/AT]; St.- Peter-Strale 25, A-4021 Linz (AT), (72) Erfinder;und lrinder/Anmelder (nurfiar U3) HORACEK, Heinz [AT' AT]4; Bockgasse 43, A-4020 Linz WUDY, Herma~nn [AT/AT]; Prey~gasse 274, A-15ll1 Pfaffstitten (AT).

(74) Anwalt: KUNZ, Ekketiard; Chemie Holding AG, Patentwesen, St.- Peter- Strasse 25, A-4021 Linz (54) Title: LATEX-BOUND FIREPROOFING MATERIAL (54) Bezeichnung: LATEXGEBUNI)ENE BRAN DSCH UTZMASSE (57) Abstract Thermally-expandable fireproofing material containing expanded graphite, an aqueous chioroprenlatex containing carboxy] groups and substances which form a paracrystalline carbon network in the event of fire.

(57) Zusammenfassung Thermisch expandierbare Brandschutzmasse be5tehend aus Bl3hgraphit, einem Carbo~vlgruppen enthaltenden .agiirigen Chloroprenlatex und Substanzen, die im Brandfall r-in parakristallines Kohlenstoffgerflst bilden.

r Latex-bonded fire-protection compound Description The invention relates to thermally expandable fire-protection compounds or fire-protection laminates, which comprise expandable graphite, a chloroprene latex containing carboxyl groups and substances from the group comprising polyacrylonitrile, cellulose or derivatives thereof, phenol/formaldehyde resins, polyfurfuryl alcohol and polyimides, and to a process for the production thereof.

Thermally expandable fire-protection compounds, which consist of expandable graphite, chloroprene rubber, a phenolic resin, an organic solvent and, if appropriate, additionally of hydrated alumina and inorganic fibers, have been described,' for example, in Austrian Patent 360,130. In preventive fire protection, they prove to be particularly effective above all because of their excellent resistance to moisture, frc it, heat, light and industrial climates, and because of their high expansion pressure. Under the action of heat and fire, they expand in the event of fire in the opening which is to be protected, at a relatively low flowability. As a result, the expanding compound also does not avoid obstacles in an opening which is not completely sealed and, dule to its high expansion pressure or extension pressure, which normAlly is above 2 bar, forms a tightly sealing barrier layer, whereby a further spread of heat, fire and smoke gases is reduced or delayed, or completely prevented.

This sealing material has a high mechanical strength even in the expanded state. A disadvantage in the production, processing and application of such compounds is, however, their brittleness and low flexibility. A further disadvantage is that, in producing them, organic solvents are used which require a greater expenditure on equipment and a greater labor effort for solvent recovery and for minimizing any environmental pollution and health hazard v caused by solvents.

o v ,.f II I I I 1 2 The use of solvent-free fire-protection compounds consisting of expandable graphite and a polymeric binder has been described in WO 88/02,019. The polymeric binder can be either a flexible binder, for example polyvinyl acetate, an elastomeric binder, for example a chloroprene polymer, a thermosetting binder, for example a formaldehyde resin, or a thermosetting binder with an addition of a flexible binder. However, the disadvantage of these fire-protection compounds is that, in the case of using flexible or elastomeric binders, although they have a sufficient flexibility which is required for easy handling, the stability and hardness, which are necessary for perfect sealing against further spreading of the fire, of the barrier layer formed after the expansion in the event of fire is too low. Because of their high hardness, fire-protection compounds based on thermosetting binders can be processed only with great difficulty, and although the crust formed after the expansion in the event of fire is hard, it is also cracked and brittle and does not form a sufficiently stable and tight barrier layer.

It was the object of the invention to eliminate these disadvantages arising with the known fireprotection compounds and, above all, to obtain less brittle compounds which form a sufficiently stable and hard barrier layer in the event of fire and do not require any organic solvents in the production thereof.

It was possible to achieve the object by means of a fireprotection compound which was obtained by the combination of three defined components.

The subject of the present invention is accordingly a thermally expandable fire-protection compound, which comprises 25 to 60% by weight of expandable graphite, 5 to 25% by weight, calculated as solids, of a chloroprene latex with at least 0.3 mole of carboxyl groups per 1 kg of latex solids, 3 to 25% by weight of substances from the group comprising polyacrylonitrile, cellulose or derivatives thereof, phenol/formaldehyde resins, polyfurfuryl alcohol and polyimides, and, if

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It proves here to be particularly advantageous if the fire-protection compounds do not contain any organic solvents but, instead, if latex dispersions on an exclusively aqueous basis are used. Because of the residual water content present, these fire-protection compounds show a more favorable fire behavior than in the case of the use of organic solvents. Because of the absence of organic solvents, they can be produced and processed with substantially greater ease and substantially less pollution of the environment. Above all because of the content of elastomeric chloroprene polymer, the fire-rrotection compounds according to the invention show good elasticity and flexibility so that they, or laminates or boards produced from them, can easily be applied, processed and handled. Depending on the particular composition of the fire-protection compound, very high expansion pressures, preferably more than 5 bar, and hence particularly effective sealing can be achieved in the event of fire. The barrier layer formed after the expansion is distinguished by its strength, hardness and stability, so that it does not form cracks and is not destroyed by the thermal, mechanical and aerodynamical stresses and fire turbulence in the event of fire.

The expandable graphite used can be produced, for example, by acid treatment of a natural graphite with fuming nitric acid, as described in US Patent 3,574,644 or by H. Spatzek, Carbon 86 (1986).

The chloroprene latex is usually produced by copolymerization of chloroprene with acrylic acid or methacrylic acid. Such latices are, for example, commercially available as Skyprene* (Toyo Soda), Bayprene" (Bayer), Butaclor® (Distugil), Denka Chloroprene® (Druki Kagaku Kogyo), Nairite (USSR) or Neoprene® (Du Pont).

The substances from the group comprising polyacrylonitrile, cellulose or derivatives thereof, phenol/ formaldehyde resins, polyfurfuryl alcohol and polyiiaides S form a paracrystalline carbon skeleton in the event of

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0)° -I 1 4 fire. When they are heated in the event of fire, these substances first crosslink, and the strong intermolecular bonds are preserved even during further thermal stress, which leads to pyrolytic decomposition and finally to the formation of the paracrystalline carbon skeleton (Chemie-Ing.-Techn. 42 No. 9/10 (1970), pages 659-669).

Three-dimensionally crosslinked thermosets such as, for example, phenol/formaldehyde resins prove to be particularly suitable in this case. Phenolic resins with tertiary butyl groups such as, for example, p-tertbutylphenol/formaldehyde resin 7520E or 7522E made by Rousselot, show particularly good results.

Examples of additives which modify the fire behavior are melamine and its derivatives, various graphite salts, cyanuric acid derivatives, dicyandiamide, halogenated hydrocarbons, polyammonium phosphates and guanidine salts. These substances also expand with decomposition under the action of heat. Since they have a decomposition temperature which differs from that of expandable graphite, the expansion pressure also increases with rising temperature in the event of fire, so that more complete sealing of the opening takes place.

Moreover, further additives, which above all improve the strength of the sealing compound in the expanded state, consolidate the crust and increase the cohesion, such as, for example, inorganic fibers, for example mineral fibers or glass fibers, glass powders, vermiculites, bentonites, silica, silicates, borax, starch, sugar, chloroparaffins, aluminum sulfate, hydrated alumina or magnesium hydroxide, can also be used.

Furthermore, flame-proofing agents can be added, for example halogenated or phosphorus-containing hydrocarbons such as, for example, tris-chloropropyl phosphate, dibromoneopentyl glycol or antimony trioxide. Moreover, those additives can also be used which assi.st in increasing the foam formation in the event of flame action.

Examples of these are salicylic acid, p-hydroxybenzoic '1 acid, PVC and also nitrogen hydrazides or sulfo hydra- SA j zides, triazoles, urea-dicarboxylic anhydride and <v 0 ammonium carbonate.

The fire-protection compound according to the invention can be used both as a paste and in the form of boards, strips, tapes or moldings. Fire-protection laminates, in which the fire-protection compound has been laminated to a carrier web, for example a glass fiber mat, are particularly advantageous and easy to apply. For decorative reasons or, for example, for protecting the fire-protection compound, the laminates or boards can be covered by a covering layer, for example a plastic film, e.g. a PVC film, paper or aluminum sheet, on one side or both sides. It is also possible to finish the fireprotection laminates or boards with an adhesive layer which is then advantageously covered by a backing film.

The fire-protection compounds according to the invention are produced by mixing and homogenizing expandable graphite, a latex dispersion which contains carboxyl groups and is preferably aqueous, substances from the group comprising polyacrylonitrile, cellulose or derivatives thereof, phenol/formaldehyde resins, po1yfurfuryl alcohol and polyimides, preferably a phenol/ formaldehyde resin or polylinide resin, and, if appropriate, further additives which modify the fire behavior, for example in a kneader, dissolver or mixer. The cornmpound thus obtained can either be used as such or it can be applied to a carrier web, for example a sheet or a nonwoven (for example by means of a blade). After drying, the laminate can be compressed on a calender, if appropriate with an embossing roller, and if appropriate with simultaneous lamination to a covering layer, for example of PVC or aluminum.

The fire-protection compounds according to the invention are used for fire-protecting sealing or isolation of openings in building components which form a fire section, such as, for example, gaps between walls, cavities or interspaces, wall breaks, cable ducts or the like. Likewise, door seals, window seals or other seals can be produced which foam up in the event of fire and i seal the slot or the opening located in front. The joint 'i)U: 6 between glass and frame in fire-protection glazing by means of the fire-protection compounds or laminates according to the invention also gives perfect fire protection. The fabrication of complete bricks, with which breakthroughs for cables or pipes are lined and which form a barrier under the action of fire, is also possible. In the event of fire, these compounds foam up under the action of heat and seal the opening, so that the further passage of fire and smoke and hence further spreading of the fire are prevented.

Examples 1-15 and Comparison Example 16 P-o-0p The raw materials (stated in parts by weight) listed in Tables 1 and 2 are added in a stirred vessel in the following order: additives, Al(OH) 3 phenolic resin, 50% aqueous chloroprene latex dispersion, expandable graphite, mineral fibers (Inorphil® 061-60, made by G.M.

Langer, Federal Republic of Germany). The compound was in each case homogenized for 1 hour by means of a dissolver with a toothed disk at 30 0 C and at a pH of 10 (adjusted by means of KOH). The viscosity was about 4 Pas, measured at 30 0 C in a Brookfield viscometer (spindle 7, 20 rpio).

The fire-protection compound obtained was then applied by means of a blade to a glass mat having a weight per unit area of 50 g/m 2 and dried at 190 0

C.

The expandable graphite was obtained by acid treatment of a natural graphite with fuming nitric acid.

The phenolic resin used was a tert-butylphenol/ formaldehyde resin, type 7520E made by Rousselot, France.

Commercially available latex dispersions based on a copolymer of chloroprene and methacrylic acid were Sused. The carboxyl group content indicated in each case in Tables 1 and 2 was adjusted by mixing the following latices of different carboxyl group contents: Neoprene 115 (Du Pont): 0.33 mole of COOH per 1 kg of latex solids, Neoprene" 750 and Neoprene® 824A: no COOH content, Bayprene® 4R (Bayer): 0.23 mol of COOH per 1 kg of latex solids. In Comparison Example V 16, a 10% chloroprene t'L, solution in toluene was used in place of the aqueous I latex dispersion, under otherwise the same conditions.

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1 7 The properties of the fire-protection laminates are also listed in Tables 1 and 2. The expansion pressure was measured at 250°C on samples having a diameter of 113 mm and inserted between two heatable metal plates.

The pressure generated on expansion was transmitted from the lower plate to a force transducer with pressure indication. The expanding material was here not delimited sideways and was able to spread unhindered in the plane.

The expansion height was measured on samples having a diameter of 50 mm and inserted into a metal cylinder of 100 mm height and an internal diameter of 50 mm. The cylinder with the sample, preloaded with 100 g via a ram, was heated for 10 minutes in an oven at 300°C.

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I ~U11 8 Table 1 (Raw materials in parts by weight) Example Moles of carboxyl per 1 kg of latex solids Latex Phenolic resin Inorphil® Expandable graphite Al(OH) 3 Additives 3 Properties Unexpanded 1 Expanded 2 Thickness (mm) Weight per unit area (kg/m 2 2xpansion pressure (bar) Expansion height (mm) 1 2 3 4 5 6 7 8 0.33 21 3 57 0.33 30 4 2 53 0.05 30 4 2 53 0.33 27 4 57 0.05 21 10 2.1 57 0.33 27 10 48 0.33 27 4 57 0.33 27 12 57 4 1- 11 19/A 9.9 11/B 12/B 12/B 12/C 2.4 2.56 2.5 2.02 2.8 2.16 2.5 2.50 2.5 2.50 2.4 2.43 2.6 2.47 2.2 2.05 12.5 6.8 7 8 6 8.5 9.6 8.7 19 17 20 20 13 15 13 17 1 flexible, brittle 2 stable and hard, unstable A aluminum sulfate B dicyandiamide C melamine <T 0 1 9 Table 2 (Raw materials in parts by weight) Example Mole of carboxyl per 1 kg of latex solids Latex Phenolic resin Inorphil* Expandable graphite Al(OH) 3 Additives 3 Properties Unexpanded l Expanded 2 Thickness (mm) Weight per unit area (kg/m 2 Expansion pressure (bar) Expansion height (mm) 9 10 li 12 13 14 15 V16 0.33 27 0.17 27 0.23 27 0.33 25 0.33 0.23 0 40 22 (toluene) 7 6.5 1.5 1.3 37 42 29.3 4 4 4 4 6 S 1.4 57 57 57 57 54.6 12/D 12/E 12/F 12/G 13 5 11/H 14 9.4 14/H 2.3 2.79 2.5 3.53 2.2 2.47 2.2 1.84 2.5 3.6 2.6 2.8 2.5 3.0 12 13 8.6 8.8 13 10 8 3 12 19 13 17.5 19 17 12 18 1 2 3 flexible, brittle, a little flexible stable and hard, unstable D starch E borax F guanylurea sulfate G guanidine phosphate H guanidine carbonate

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Example 17: Small-fire test with laminates according to Examples 13 and V16 In order to prove effective sealing of an opening by the fire-protection compound according to the invention in the event of fire, two 20 cm long PVC pipes having an external diameter of 16 cm and a wall thickness of 3.5 mm were each wound with 230 g of 15 cm wide fireprotection laminate according to Example 13, which was also laminated on the mat side to a 0.05 mm thick aluminum foil, so that the expandable graphite was located on the pipe side. The wound pipes were each packaged in a zinc sheet sleeve and each inserted into a bore (22 cm diameter) in a 10 cm thick light concrete slab (Ytong®).

The pipes protruded for 5 cm from the bore on both sides of the slab.

Two analogously wound pipes were inserted into two further, similar bores of the light concrete slab, but a fire-protection laminate according to Comparison Example V16 was used in place of the fire-protection laminate according to the invention. The laminate, which was slightly less flexible, showed small cracks and points of easy fracture during winding.

The light concrete slab was then installed analogously to DIN 4102 in a small fire chamber and subjected to a flame from one side up to a temperature of about 1,000°C in accordance with the standard temperature curve. The fire-protection compounds started to expand after about 4 minutes as a result of the heat, all 4 PVC pipes being softened and compressed. The isolations with the laminates according to Example 13 were completely sealed after 13 or 14 minutes respectively, and those with the laminates according to Comparison Example V16 after 13 or 17 minutes respectively, so that smoke gases, fire or soot no longer penetrated outwards. After minutes, the outward-protruding pipe ends of the isolation according to the invention started to break apart, whereas the pipe ends of the isolations according to the Comparison Example started to melt off. After 60 minutes, I- 11 the pipe ends had fully broken off or melted off, and the temperature of the expanded foam according to Example 13 was 290°C, and that of the expanded foam according to Comparison Example V16 was 310 or 370°C.

After 80 minutes, the test was terminated, without breakthroughs of flames or smoke gas being detectable. It was also found that, when the fire-protection compound according to Example 13 is used, the temperature on the side facing away from the fire was 80°C lower during the fire test than in the case of using the conventional fire-protection compound according to Comparison Example V16.

The hardness of the expanded foam according to Example 13 was measured after cooling by means of a compressive strength test on a pinching device 4045 according to DIN 53,421 and was 0.2 N/mm 2 (60% compression).

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Claims (11)

1. A thermally expandable fire-protection compound, which comprises 25 to 60% by weight of expandable graphite, 5 to 25% by weight, calculated as solids, of a chloroprene latex with at least 0.3 mol of carboxyl groups per 1 kg of latex solids, 3 to 25% by weight of substances from the group comprising polyacrylonitrile, cellulose or derivatives thereof, phenol/formaldehyde resins, polyfurfuryl alcohol and polyimides, and, if appropriate, further additives.

2. A fire-protection compound as claimed in claim 1, wherein the latex employed is exclusively an aqueous based latex.

3. A fire-protection compound as claimed in claim 1 or 2, wherein the chioroprene latex is composed of a copolymer of essentially chloroprene and acrylic acid or methacrylic acid. *o a

4. A fire-protection compound as claimed in any one of laims 1 to 3, which contains a phenol/formaldehyde resin.

5. A fire-protection lainate, wherein a fire-protection compound as claimed in any one of claims 1 to 4 is applied to a carrier web. 6 A fire-protection laminate as claimed in claim wherein the fire-protection compound is covered by a covering layer.

7. A process for producing a fire-protection compound or a fire-protection laminate as claimed in any one of claims 1 to 6, which comprises mixing expandable graphite, a latex dispersion which contains carboxyl groups and is preferably aqueous, substances from the group comprising 87 3S/MS -I i I I I 13 polyacrylonitrile, cellulose or derivatives thereof, phenol/formaldehyde resins, polyfurfuryl alcohol, polyimides and, if appropriate, further additives, with one another with good homogenization, if desired applying the compound obtained to a carrier web and, if desired, laminating the resulting laminate to a covering layer.

8. A thermally expandable fire-protection compound substantially as herein described with reference to any one of the Examples excluding Example 16.

9. A process for producing a fire-protection compound or a fire-protection laminate substantially as herein described with reference to the section Prociss. DATED this 4th day of July 1991 a *e CHEMIE LINZ GESELLSCHAFT MBH by their Patent Attorneys GRIFFITH HACK CO. 879 3S/MS -e _T Abstract A thermally expandable fire-protection compound consisting of expandable graphite, an aqueous chloroprene latex containing carboxyl groups, and substances from the group comprising polyacrylonitrile, cellulose or deriva- tives thereof, phenol/formaldehyde resins, polyfurfuryl alcohol and polyimides. N1' NT i, 11 I- INTERNATIONAL SEARCH REPORT International Application NOP C T/EP 8 9/00 37 1 1. CLASSIFICATION OF SUBJECT MATTER (if severalI ciasaication symoola apply, Indicate all) According to international Patent Claaaiflcalion (IPC) or to both National Classification and IPC Int.C1 4:C 09 K 21/00 i1. FIELDS SEARCHED Minimum Documentation Searchiec Clasification System i Classification Symbols Int. Cl 4C09 K; C 09 D Documentation Searchad other than Minimum Documentation to the Extant that such Documents are Included In "tia Fleira Searched Ill. DOCUMENTS CONSIDERED TO BE RELEVANT'$ Category *I Citation ot Document, 11with Indication, wre apororiato, of the reievant vassaoea 13 Rlevant to Claim No, 13 X WO,A,88/02019 (DIXON) 24 March 1988, see 1,2,3,5,6,8 claims l,6,12,13;page 2,lines 25-27;page 14,15 Y see claims 1,16;page 4,line 27 1,3.-8 Y FR,A,2265838 (CHEMIE LINZ) 24 October 1975, 1,3-8 see claims 1,3, 11 Special categories of cited doccimenta; ia later document published atter the international filing date A doumet dfinng he gner~l tet ofthe rt hic isnotor Priority date ano not in conflict with the application btil "Aldcunit e to e partia releaefteatwihont cited to underatand the pnncitplo or theory underlying the consderd t beOf artiula retysiceInvention earlier document but published on or after the international document of Particular relevance, the cleimed invention filing dais cannot be considered novel or cannot be considered to 110 document which may throw doubts on prioriy claim)s) or involve an inventive step which is cited to establish the publication date of another document of Particular relevance; the claimed Inventiont citation or other sptecial reason tes specified) cannot be considered to involii an inventive ase when the 0'D document ref errtng to an oral dieilosure, use, exhibition or document is combined with one or more other such docil. other insane ments, such combination being obvious to a person skiled "Fil document Published prior to the international iting date but in the art. loit than the priority date claimed 11" document member of the same atent family IV. CERTIFICATION Dates of the Actual Completion of the International Search Date of Meiling of this International Search Report 07 June 1989 (07.06.89) I12 July 1989 (12.07.89) International Seerching Authority Signature of Authorixed Otticer tJROPEAN PATENT OFFICE Form PCTItSAi2t0 #secoind sheet) (January too$)t ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. EP 8900371 SA 27793 This annex lists the patent family rnemberm -bz~aing to the patent documents cited in the above-mentioned international search report. The members are as contained in the Eurf~pean Patent Office EDP file on 23/06/89 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. WO-A- 8802019 24-03-88 AU-A- 7913287 07-04-88 FR-A- 2265838 24-10-75 AT-A,B 330320 25-06-76 BE-A- 827342 29-09-75 CA-A- 1058455 17-07-79 CH'-A- 596292 15-03-78 DE-AB,C 2421332 02-10-75 GB-A- 1497118 05-01-78 JP-A- 51098736 31-08-76 LU-A- 72151 04-02-76 NL-A- 7503 719 01-10-75 SE-B- 418752 22-06-81 SE-A- /503272 30-09-75 C A. w For more details about this annex see Official Journal of the European Patent Menc, No. 12/82 II :~Jj INTERNATIONALER RECHERCLHENBERICHT Internationale$ Akterizeichen PCT/EP 89/00371 IKLASSIFIKATION DES ANMELDUNGSGEG ENSTANDS lbei Mahreren Klassifikatlanssymbalon find alle anzuge~anl 6 Nach der Internationalen Patentklassifikation (IPC) oder nach der natianalen Kiassifikation und der IPC In C C 09 K 21/00

11. RECHERCH-IERTE SACHGEBIETE Recherchierter Mindlestprufstoff 7 Recherchierte nicht zumn Mlndlestprufstoff gehorende Veroffentlichungen, saweijthese unter die recherchierien Sachgebiete fallen 8 III. EINSCHLAGIGE VEROFFENTLICHUNGEN 9 Art* Kennzeichnung der Veraffentllchungll t soweit erfarderlich unter Angabe der malgeblichen Teile t 2 1Beir. Anspruch Nr. 13 X WO, A, 88/02019 (DIXON) 24. marz 1988, siehe 1,2,3,5,6,8 Anspriche 1,6,12,13; Seite 2, Zeilen 25-27; Seite 5, Zeilen 14,15 y siehe AnsprLche 1,16; Seite 4, Zeile 27 1,3-8 Y FR, A, 2265838 (CHEM'IE LINZ) 24. Oktober 1975, 1,3-8 siehe Anspr~che 1,3,11 Besondere Kategorien qon angegebenen Veraffentlichungen 1 Veroffentlichung, dit: den ailgemneinen Stand der Technik Spatere Veroffentlichung, die nach dem inrernatlonalen An- definleri, aber nlcht alW besanders bedeutsam anzusehen ist meldedlatumn ader dem Prlorititsdatum veraf-fentlicht warden 5Iteres Dakcument, das jedach enst am ader nach dem Interna- ist und mit der Anmeldung nicht kallidiert, sondern nur zurn tianalen Anmeldedlatumn veraf-fentlicht warden Is Verstindnis des der Ertindlung zugrundeliegendlen Prinzips oder der ihr zugrundeliegenden Thearie angegeben ist Ver~ffentlichung, die geeignet it, einen Prlorititsanspruch Verdflentlichung von besanderer Bedleutung: die beanspruch- zweifeihaft erschelnen zu lassen, oder durch die dlas Verdf. to Erfindung kann nicht eli neu oder auf erfindelischer Tatig- fentllchungsdatum einer anderen im Recherchenberichi goi brhn btahenwre narsisen \kr6ffentlichung belegt wes-den soil ader die aus elnom ki euednercttwre anderen besonderen Grund angeeben ist We ausgefuhrt) Veroffentlichung von besonderer Bedeutung; die beanspruch. "OV Veffnihug ioscau iemnlhe fenen, to Erfindung kann nicht all aul erfinderischer Tatigkeit be. erdfenlicung di sih af ene ~ndich Ofenb r u g, ruhend betrachtet werden, wenn die Veroffentlichung mit emse Benutzung, sine Ausstellung oden andere Maalnahmen cnrae errnaiee eofnlcugndce ae bezehigonie in Verbindlung gsbracht wind und diese Verbindung fur Verdffsntlichung, die var dem internetionalen Anmeldedla- sinen Fachmann naheliegend Ist turn. aber nach dem beansnruchien Pfioritascdatum veroffent- Veratfentlichung, die Mitglied derselben Patentfamilie ist licht warden ust IV, BESCHEINIGUNG Datum des Abschiusise der internationalen Recherche Absendledatumn des Internatianalen Rechsnchenberichti 7. Juni 1989 12 J UL IS89 Internationale Recherchenbehorde Unterschr 1 tigten Bedleniteten Europaiches Patentamnt DER PUTTEN Farmblatt PCT,'ISA/21 0 (Blats 2) (JanUar 1985f I', ANHANG ZUM INTERNATIONALEN RECHERCHENBERIGHT OBER DIE INTERNATIONALE PATENTANMELDUNG NR. EP 8900371 SA 27793 In diesem Anhang sind die Mitglieder der Patentfamilien der im obengenannten internationalen Recherchenbericht angefuhrten Patentdokumente angegeben. Die Angaben uber die Famiiienmitglieder entsprechen dem Stand der Datei des Europaiischen Patent2mtS am 23/06/89 Diese Angaben dienen nur zur Unterrichtung und erfolgen ohne Gewahr. Im Recherchenbericht Datum der Mitglied(er) der Datum der angefuhrtes Patentdokument T ,erdffentlichung P'atentfamilie Verdffentlichung WO-A- 8802019 24-03-88 AU-A- 7913287 07-04-88 FR-A- 2265838 24-10-75 AT-A,B 330320 BE-A- 827342 CA-A- 1058455 CH-A- 596292 DE-A,BC 2421332 GB-A- 1497118 JP-A- 51098736 LU-A- 72151 NL-A- 7503719 SE-B- 418752 SE-A- 7503272 2 5-06-7 6

29-00-75 17-07 -7 9 15-03- 78 02-10 -7 05-011-78 3 1-08-76 04-02 -7 6 0 1-10-7 22-06 -8 1

30-09-7 Fflr nahere Einzclheiten zu diesem Anhat siche Amtsblatt des Europaischcn Patentamnts, Nr.12/82