AU688905B2

AU688905B2 - Use of molding materials for the production of moldings having good resistance to partly halogenated chlorofluorocarbons

Info

Publication number: AU688905B2
Application number: AU24478/95A
Authority: AU
Inventors: Franz Brandstetter; Gerhard Lindenschmidt; Herbert Morgenstern; Doris Zeltner
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1994-04-25
Filing date: 1995-04-24
Publication date: 1998-03-19
Anticipated expiration: 2015-04-24
Also published as: ES2119439T3; CN1054388C; WO1995029204A1; CA2188896A1; EP0757706A1; ZA953281B; AU2447895A; JPH09512293A; TW282483B; DE59503174D1; CN1149306A; KR970702322A; MY130535A; EP0757706B1

Description

0050/44830 Use of molding materials for the production of moldings having good resistance to partly halogenated chlorofluorocarbons The present invention relates to the use of certain polymers for the production of moldings which are in contact with partly halogenated CFCs.

Stress crack-resistant polystyrene and ABS polymers have resistance to CFCs which is sufficient for most applications in which corresponding moldings come into direct contact with CFCs.

Refrigerators as used in the private and commercial sectors have, as a rule, a sandwich structure comprising a plastic inner container/insulating layer/metal housing. The plastic inner containers of these refrigerators are predominantly produced from stress crack-resistant polystyrene or ABS polymers. ABS polymers are to be understood as meaning very generally blends of styrene/acrylonitrile (SAN) polymers on the one hand and graft copolymers haying a grafting base comprising butadiene rubbers, onto which the SAN polymers have been grafted.

The plastic inner containers are produced in general by extrusion and subsequent thermoforming; both processes are known to a person skilled in the art and are described in the literature. The plastic inner container is in direct contact with the insulating layer, which as a rule consists of polyurethane foam (PUR foam) which is produced using certain blowing agents. While in the past predominantly chlorofluorocarbons (CFCs) were used as blowing agents, recently partly halogenated CFCs (HCFCs), eg. l,l-dichloro-l-fluoroethane (HCFC-141 have increasingly been used since they have a less adverse effect on the protective ozone layer.

However, these novel blowing agents lead to stress cracks, partial dissolution effects and blisters in the case of stress crack-resistant polystyrene as well as ABS polymers, presenting a considerable problem.

JP-A 25227/93 describes thermoplastic molding materials for use as inner lining of refrigaesitors, which materials contain graft polymers which are based on acrylate rubbers and whose average particle size is at least 150 nm. These are not completely satisfactory with respect to the weight increase under the action of partly halogenated CFCs.

AMENDED SHEET 0050/44830 2 It is an object of the present invention to provide products which are suitable for the production of moldings which are in contact with HCFCs, and which have better resistance to these HCFCs than the polymers used to date for such applications.

We have found that this object is achieved, according to the invention, by the use as claimed in claim 1.

Preferred embodiments of the invention are described in the subclaims.

Molding materials which can be used according to the invention are those which contain, in component A, a blend of two polymers all) and a 12 as the grafting base.

The mixing ratio of polymer all) to a 12 is not critical but is in general from 4:1 to 1:4, in particular from 1:2 to 2:1.

The acrylate polymers anl) are composed of a,1 1 from 50 to 99.9, preferably from 55 to 98, by weight of an alkyl acrylate where the alkyl radical is of 1 to carbon atoms. Preferred acrylates are those where the alkyl radical is of 2 to 10 carbon atoms, in particular ethyl acrylate, tert-butyl acrylate, isobutyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, among which the two last-mentioned are very particularly preferred.

Examples of crosslinking monomers all 2 which are used in amounts of from 0.1 to 5, preferably from 0.25 to 4, in particular from to 3, by weight, based on a 11 are polyfunctional monomers having at least two olefinic, unconjugated double bonds, specific examples of which are divinylbenzene, dialkyl fumarate, diallyl phthalate, triallyl cyanurate, trialkyl isocyanurate, tricyclodecenyl acrylate and dihydrodicyclopentadienyl acrylate. Tricyclodecenyl acrylate and dihydrodicyclopentadienyl acrylate are particularly preferred.

Up to 49.9, preferably from 5 to 45, in particular from 10 to 40, by weight of monomers which are copolymerizable and [sic] a 111 and are selected from the group consisting of the vinyl alkyl ethers where the alkyl radical is of 1 to 8 carbon atoms (eg. vinyl methyl ether, vinyl propyl ether, vinyl ethyl ether), butadiene, isoprene, styrene, acrylonitrile, methacrylonitrile and/or [sic] may be used as further monomers a11 3 in the preparation of all).

AMENDED SHEET 0050/44830 3 By using such comonomers, it is possible to control the property profile of the polymers all), for example with regard to the degree of crosslinking, which may be desirable in some cases.

Processes for the preparation of polymers all) are known to a person skilled in the art and are described in the literature, for example in German Patent 1,260,135. Corresponding products are also commercially available.

Carrying out the preparation by emulsion polymerization has proven particularly advantageous in some cases.

The exact polymerization conditions, in particular the type, dosage and amount of the emulsifier, are preferably chosen so that the latex of the acrylate, which is at least partly crosslinked, has a weight average particle size (d 50 of from about 50 to 700 nm, in particular from 100 to 600 nm. The latex preferably has a narrow particle size distribution, ie. the quotient d 90 dio Q d 5 o is preferably less than 0.5, in particular less than 0.35.

If the grafting base of component A consists exclusively of all), the average particle size of a 1 is less than 150 nm, preferably from 50 to 140 nm, particularly preferably from 50 to 120 nm.

In addition to the polymers anl), the graft copolymers A) contain butadiene polymers al2) as a second grafting base. The polymers a 12 are butadiene copolymers which may also contain to [sic] to preferably from 2 to 30, by weight of further copolymerizable monomers in addition to 60-100, preferably 70-99 by weight of butadiene. The alkyl acrylates described above under alll) as well as the monomers a 113 are suitable as such further copolymerizable monomers; reference may be made to the description there for details.

The amount of the grafting base all) with a 12 in the graft polymer A) is from 50 to 90, preferably from 55 to 85, in particular from 60 to 80, by weight, based on the total weight of A).

cm \0 to 50% zy 6 \xi'ac,1 o^ A A graft a2) which is obtained by copolymerization of AMENDED SHEET 0050/44830 4 a 21 from 60 to 90, in particular from 65 to 80, by weight of a vinylaromatic monomer, preferably styrene or a substituted styrene of the general formula I

CH

2 (RI)n where R is alkyl of 1 to 8 carbon atoms, hydrogen or halogen,

R

1 is alkyl of 1 to 8 carbon atoms or halogen and n is 0, 1, 2 or 3, and a 22 from 10 to 40, in particular from 20 to 35, by weight of polar, copolymerizable monomers [lacuna] acrylonitrile, methacrylonitrile, esters of (meth)acrylic acid where the alkyl radical is of 1 to 4 carbon atoms, maleic anhydride, (meth)acrylamide and/or vinyl alkyl ethers where the alkyl radical is of 1 to 8 carbon atoms, or of a mixture thereof, is grafted onto the grafting base all) and ai2).

The graft a 22 may be prepared in one or more, for example two or three, process steps, and the overall composition is not affected thereby.

The graft is preferably prepared in emulsion, as described, for example, in German Patent 1,260,135 and German Laid-Open Applications DOS 3,227,555, DOS 3,149,357, DOS 3,149,358 and DOS 3,414,118.

Depending on the conditions chosen, a certain amount of free copolymers of styrene and acrylonitrile is formed in the graft copolymerization.

The graft copolymer (al a 2 generally has an average particle size of, preferably, from 50 to 1000 nm, in particular from 100 to 700 nm (dso weight average). The conditions in the preparation of the elastomer bl) and in the grafting are therefore chosen so that particle sizes in this range result. Relevant measures are known and are described, for example, in German Patent 1,260,135 and German Laid-Open Application DOS 2,826,925, as well as in J.

Appi. Polym. Sci. 9 (1965), 2929-2938. The particle size of the latex of the elastomer can be increased, for example, by means of agglomeration.

AMENDED SHEET 0050/44830 In some cases, blends or a plurality of acrylate polymers which have different particle sizes have also proven useful. Corresponding products are described in German Laid-Open Application DOS 2,826,925 and U.S. Patent 5,196,480, to which reference is made here for further details.

Accordingly, preferably used blends of acrylate polymers are those in which a first polymer has a particle size dso of from to 150 nm and a second polymer has a particle size of from 200 to 700 nm, as described in the abovementioned U.S. Patent 5,196,480.

In the blends of polymers all) (as described in German Published Application DAS 1,164,080, German Patent 1,911,882 and German Laid-Open Application DOS 3,149,358) and polymers al2), the polymers a 12 in general have an average particle size of from to 1000 nm, preferably from 100 to 700 nm.

Some preferred graft polymers all) are shown below: a 2 60 by weight of grafting base a 21 comprising a 2 11) 98 by weight of n-butyl acrylate and a21 2 2 by weight of dihydrodicyclopentadienyl acrylate and 40 by weight of graft a 22 comprising a 221 75 by weight of styrene and a22 2 25 by weight of acrylonitrile a 2 grafting base as in a 2 /1 with 5 by weight of a graft comprising a 2 21) 12.5 by weight of styrene (1st graft stage) and 40 by weight of a second graft stage comprising a 2 2 1 75 by weight of styrene and a22 2 25 by weight of acrylonitrile a 3 grafting base as in a 2 /1 with 13 by weight of a first graft stage comprising styrene and 27 by weight of a second graft stage comprising styrene and acrylonitrile in a weight ratio 3:1.

The novel molding materials contain, as component from 30 to 99, preferably from 40 to 80, by weight of a copolymer of 99 bl) from 50 toA94, preferably from 55 to 90, in particular from to 85, by weight of vinylaromatic monomers, preferably styrene and/or substituted styrenes of the general formula I and Li. AMENDED 3HEET r, 0 0050/44830 6 b 2 from 1 to 50, preferably from 10 to 45, in particular from to 35, by weight of the monomers described for a 22 Such products can be prepared, for example, by the process descriLed in German Published Applications DAS 1,001,001 and DAS 1,003,436. Such copolymers are also commercially available.

The weight average molecular weight determined by light scattering is preferably from 50,000 to 500,000, in particular from 100,000 to 250,000, corresponding to viscosity numbers of from 30 to 130, preferably from 30 to 100 (measured in 0.5 strength by weight solution in dimethylformamide at 25 0

C).

Up to 20, preferably from 0.5 to 10, by weight of conventional additives and processing assistants ray be present as component C.

Conventional additives are, for example, stabilizers and antioxidants, heat stabilizers and UV stabilizers, lubricants and mold release agents, colorants, such as dyes and pigments, pulverulent fillers and reinforcing agents, and plasticizers. Such additives are used in the conventional effective amounts.

The stabilizers may be added to the materials at any stage of the preparation of the thermoplastic materials. The stabilizers are preferably added at an early stage in order to prevent decomposition from beginning before the material can be protected. Such stabilizers must be compatible with the material.

The antioxidants and heat stabilizers which may be added to the thermoplastic materials according to the invention include those which are generally added to polymers, such as halides of metals of group I of the Periodic Table, for example sodium halides, potassium halides and lithium halides in combination with copper(I) halides, for example chloride, bromide or iodide. Other suitable stabilizers are sterically hindered phenols, hydroquinones, various substituted members of this group around [sic] combinations thereof, in concentrations of up to 1 by weight, based on the weight of the mixture.

Stabilizers which are generally added to polymers may also be used as stabilizers, in amounts of up 2.0 by weight, [lacuna] on the mixture.

AMENDED SHEET 0050/44830 Examples of stabilizers are various substituted resorcinols, salicylates, benzotriazoles, benzophenones, HALS stabilizers and the like, as commercially available under the tradenames Topanol®, Irganox® and Tinuvin®.

Suitable lubricants and mold release agents, which are added, for example, in amounts of up to 1 by weight of the thermoplastic material, are stearic acids, stearyl alcohol, stearic esters and stearamides.

Further possible additives are silicone oils, preferably in amounts of from 0.05 to 1 by weight.

Organic dyes, such as nigrosine, and pigments, eg. titanium dioxide, cadmium sulfide, cadmium sulfide selenide, phthalocyanines, ultramarine blue or carbon black, may also be added.

According to the invention, the molding materials described above are used for the production of moldings which come into contact with partly halogenated CFCs (ie. HCFCs). Two known members of this class of substances are 1,l-dichloro-l-fluoroethane (HCFC 141 b) and 1,l-dichloro-2,2,2-trifluoroetbane (HCFC 123).

The moldings can be produced by methods which are known per se to a person skilled in the art and are described in the literature, such as extrusion, injection molding, blow molding and thermoforming, to mention but a few.

The moldings obtainable according to the invention possess good stress cracking resistance and good resistance to complete [sic] dissolution by HCFCs in addition to good processability and are therefore suitable for all applications in contact with HCFCs, in particular for the production of inner containers in refrigerators.

Examples The following components were used: AI: graft polymer of by weight of a grafting base comprising 98 by weight of n-butyl acrylate and 2 by weight of dihydrodicyclopentadienyl acrylate and 40 by weight of a graft comprising a copolymer AMENDED SHEET 0050/44830 8 of 75 by weight of styrene and 25 by weight of acrylonitrile having an average particle diameter d 50 of 100 nm

A

2 graft copolymer of by weight of a grafting base as in Al and by weight of a graft comprising by weight of styrene and 30 by weight of acrylonitrile, having an average particle diameter dso of 250-350 nm

A

3 graft copolymer of by weight of a grafting base as in A 1 and A 2 13 by weight of a first graft comprising styrene and 27 by weight of a second graft comprising a copolymer of 75 by weight of styrene and 25 by weight of acrylonitrile, having an average particle diameter d 5 o of 500 nm

A

4 graft copolymer of 62 by weight of a grafting base comprising butadiene and 38 by weight of a graft comprising 70 by weight of styrene and 30 by weight of acrylonitrile

A

5 graft copolymer containing 62 by weight of a grafting base as in A 5 13 by weight of a first graft comprising styrene and 25 by weight of a second graft comprising 70 by weight of styrene and 30 by weight of acrylonitrile BI: copolymer of 65 by weight of styrene and 35 by weight of acrylonitrile, having a viscosity number (VN) of 80 ml/g, measured in 0.5 strength by weight solution in dimethylformamide at 25 0

C

B

2 copolymer having the same composition as BI, but a viscosity number of 60 ml/g

C

1 diisodecyl phthalate (Palatinol®Z from BASF Aktiengesellschaft)

C

2 1,,3-tri(2' [sic] (Topanol® CA from ICI) AMENDED SHEET 0050/44830 9

C

3 dilauryl P,P-thiodipropionate (Irganox® PS 800 from Ciba- Geigy AG)

C

4 n-octadecyl-3-(3' 5'-di-tert-butyl-4'-hydroxyphenyl) propane (Irganox® 1076 from Ciba-Geigy AG) Components A, B and C were mixed in an extruder in the amounts stated in the table, the mixture was extruded and the extrudate granulated. In order to determine the stress cracking resistance and the partial dissolution behavior, test specimens and sheets were produced from the granules by compression molding or by injection molding.

The Steinle test is used for determining the stress cracking resistance of the products with respect to HCFC 123. To carry out the test, compression molded or injection molded dumbbells are clamped over a bending radius of 170 mm and stored in an HCFC 123 atmosphere at 0.5 bar for 10 minutes and 50 minutes. The tensile test according to DIN 53 455 is carried out immediately thereafter. Any stress cracks which occur in the material manifest themselves in a sharp decrease in the elongation at break. The corresponding values are shown in the table.

In order to test the resistance of the materials to partial dissolution, a special test was developed. The test specimens used are compression molded sheets having a thickness of about 0.5 mm.

These are fastened, with a 2 mm thick intermediate polythene layer, to a metal sheet. The arrangement, with the test sheet facing downward, is placed on a vessel which is filled with the blowing agent (HCFC). Solid carbon dioxide is present on the metal sheet, so that the rising HCFC 123 vapors condense on t he plastic sheet. The intermediate polyethylene layer prevents the presence of a diffusion barrier behind the test specimen.

After an action time of 1 hour, disks having a diameter of about 2.7 cm are punched out of the plastic sheet, dried in the air for minutes and then weighed. The drying time in the air ensures that blowing agent present on the sheet can evaporate off. The sheets are dried for 24 hours at 40°C and then weighed again. The difference gives the amount of blowing agent absorbed.

Thn blistering is assessed visually.

The results are shown in the table.

AMENDED SHEET Table Ex- Composition Decrease in elon- Weight increase [Blistering ample A (parts by B (parts by (parts by gation at break by weight] j(visual) weight) weight) weight) [in based on starting value] IV 42 Al 58 B 1 -0 11 none 2V1) 47 A 3 53 B 1 0 none 3 L7.5 Al :36.05 B1 1 C1 0 5 none 15.8 A 4 30.65 B 2 f0.1 C 2 0.2 C 3 41.Al 6.BI1 C, 0 3 none 17.5 A4 6 7 B 0.1 C 2 158 0.2 C 3 28 A 4 72 B 1 -73-100 1 none 6 17.5 Al 66.7 B 1 1 0 3nn 15.8 AS 0.1 C 2 7V pLystyrene* 65 T severe v Comparative example Commercial stress crack-resistant polystyrene AMENDED SHEET

Claims

1. Use of a molding material containing, as essential compo- nents, A) from 1 to 50 by weight, based on the total weight of the molding material, of a graft copolymer composed of 0 al) from 50 to 90 by weight, based on of a grafting base composed of all) a partially or completely crosslinked acrylate polymer formed from al 1 1 from 50 to 99.9 by weight, based on all), of at least one alkyl acrylate where the alkyl radical is of 1 to 10 carbon atoms, a 112 from 0.1 to 5 by weight, based on all), of a polyfunctional, crosslinking monomer and a 113 from 0 to 49.9 by weight, based on all), of a further monomer which is copolymeriz- able with a lll and is selected from the group consisting of the vinyl alkyl ethers where the alkyl radical is of 1 to 8 car- bon atoms, butadiane, isoprene, styrene, acrylonitrile, methacrylonitrile and methyl methacrylate and a 12 a butadiene polymer composed of ,121) from 60 to 100 by weight, based on a 12 of butadiene, and a 12 2) from 0 to 40 by weight, based on a 12 of further copolymerizable monomers selected from the group consisting of the vinyl alkyl ethers where the alkyl group is of 1 to 8 carbon atoms, alkyl acrylates where the alkyl group is of 1 to 10 carbon atoms, isoprene, styrene, acrylonitrile, AMENDED SHEET SR4?!, R.4 >4/iE C) O 0050/44830 12 methacrylonitrile and methyl methacrylate and a 2 from 10 to 50 by weight, based on of a shell grafted onto the graft copolymer and composed of a 21 from Xto by weight, based on a 21 of a vinylaromatic monomer and \o LC a 22 from '5to 51% by weight of polar, copolymeriz- able comonomers selected from the group consis- ting of acrylonitrile, methacrylonitrile, esters of (meth)acrylic acid where the alkyl radical is of 1 to 4 carbon atoms, maleic anhydride, (meth)acrylamide and vinyl alkyl ethers where the alkyl radical is of 1 to 8 carbon atoms, B) from 30 to 99 by weight, based on the total weight of the molding material, of a copolymer of bl) from 50 to 99 by weight of a vinylaromatic monomer and b 2 from 1 to 50 by weight of monomers as described for a22) and C) from 0 to 20 by weight of conventional additives and processing assistants foz the production of moldings which come into contact with partly halogenated CFCs (HCFCs), with the proviso that the weight average particle size (dso) of the component anl) is less than 150 nm if the component A contains only all) as the grafting base.

2. Use as claimed in claim 1 for the production of inner con- tainers in refrigerators. AMENDED SHEET L~I LL: 0050/44830 Use of molding materials for the production of moldings having good resistance to partly halogenated chlorofluorocarbons Abstract Molding materials are used for the production of moldings which come into contact with partly halogenated chlorofluorocarbons. INTERNATIONAL SEARCH REPORT ntemato \ppication No PCT/EP 95/01535 A. CLASSIFICATION OFSUBJECT MATTER IPC 6 C08L51/04 C08L55/02 C08L25/08 According to Intematonal Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Mimnmum documentation searched (classification system followed by classification symbols) IPC 6 C08L Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched Electronic data base consulted during the international iearch (name of data base and, where practcal, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category' Citation of document, with indication, where appropnate, of the relevant passages Relevant to claim No. X EP,A,O 483 832 (MONSANTO KASEI CO.) 6 May 1,2 1992 see page 28, line 52 page 29, line claims; examples; tables X DATABASE WPI 1,2 Week 9310 Derwent Publications Ltd., London, GB; AN 93-080445 'freon resistant thermoplastic resins for mfg. refrigerators...' JP,A,05 025 227 (MITSUBISHI RAYON CO. LTD) 2 February 1993 cited in the application see abstract Further documents are listed in the continuation of box C. Patent family members are listed in annex. SSpecial categories of cited documents -T later document published alter the international filing date or pnority date and not in conflict with the application but document defining the general state of the art which is not ted to understand the principle or theory underlying the considered to be of particular relevance invention earlier document but published on or after the international document of particular relevance; the claimed invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on ponity claim(s) or involve an inventive step when the document is taken alone which is cited to establish the publication date of another document of particular relevance; the claimed invention citation or other special reason (as specified) 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 such docu. other means mcnts, such combination being obvious to a person skilled document published prior to the international filing date but in the art. later than 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 July 1995 3 08.95 Name and mailing address of the ISA Authorized offic European Patent Office, P.B. 5818 Patentlaan 2 NL 2280 HV Rijswijk Tel. (+31-70)340-2040, Tx 3 651 eponl, Loiselet-Taisne, S Fax: (+31-70)

340.3016 Form PCT/ISA/210 (second she*t) (July 1992) INTERNATIONAL SEARCH REPORT Internatc %pplication No lnz,,.itauon an patent famiuly members PCT/EP 95/01535 Patent document Publication Patent family duliatio cited in search report date member(s) Idt EP-A-483832 06-05-92 JP-A- 4170460 18-06-92 AU-B- 636254 22-04-93 AU-A- 8685591 07-05-92 US-A- 5229457 20-07-93 Fenm PCT/ISA/210 (patent rmiy annex) (July 1992) INTERNATIONALER RECHERCIIENBERICHT Intcmzut es Aktenzechen IPCT/EP 95/01535 A. KLASSII17IARUNG DE.S ANMELDUNOSGI:GENSTANDES IPK 6 C08L51/04 C08L55/02 C08L25/08 Nach der lnternauonalen Patentlasmflnkation(IPK) Oder nach der nationalen Klasikation und der IPK Bi. K1ECHERCH1ERTE GEI3IETE Reeherchierter Mindestpnifstoff (Klasstikationssystem und Klassikationssymbole) IPK 6 C08L Recherchierte abcr nicht zum Mindcstprufistoff gehorende Ver~ffeniehungen, soweit diee unter die reehcrchierten Gebietc fallen WAhrend der intemnationalen Rccherchec konsultierte elektronische Datcnbank (Name dcr Datenbanc und evtI. verwendete Suchibcgniffe) C ALS WESENTLICH ANGESEHIENE UNTERLAGEN Kategoie* Bezeuchnung der Verfffentlichung, soweit erfordertch tinter Angabe der in Belracht kormenden Talce Mer. Anspruch Nr. X EP,A,O 483 832 (MONSANTO KASEI CO.) 6.Mai 1,2 1992 siehe Seite 28, Zeile 52 Seite 29, Zeile AnsprUche; Beispiele; Tabellen X DATABASE WPI 1,2 Week 9310 Derwent Publications Ltd., London, GB; AN 93-080445 'freon resistant thermoplastic resins for mfg. refrigerators 'I JP,A,05 025 227 (MITSUBISHI RAYON CO. LTD) 2.Februar 1993 in der Anmeldung erw~hnt siehe Zusammenfassung Weitr Verdfentichungen eund der FarLsetzung von Feld C zu MV Siehe Ahn itnail Besondere Kategorien von angegebenen Ver6ffentlichungen T Sptre Verorfentlichung, die niich dcm internattionaien Anmeldedatumn Verdflenlielung di e lgeennSad e ehi dfnet dedm PriontAtsdatum ver6ffentlicht warden ist und mit der abrnctasbgsnesbduemazee Anmeldung nicht kollidiert, sondem nur zutnVersthndrus des der be nits Doul ods edch er a odene dis t eaoln Erindung zugrundeliegenden Priumps Oder der ihr zugrundeliegendt- E'Anmdedotumen veroffenlllch t am de rc en inentoae Theone angegeben it Anmededtum erdfenfich worcn stX Verdienliuchung von besonderer Bedeutung; die beansprucbte Erindun W Ver~ffentlichung, die geelgnet ist, eanen Pnioritftsanspruch zweilelhaft Cr- kann illein aufgrud dieser Verafffenliachung nicht als neu Oder Auf scheinena zu laeaen, Oder durch die dna Veri~ffendichungsdatum caner erfindcrischc 'rti ct benihend betrachtet werden anderen inm Rechechenbencht genannten Ver8(fentlichung becgt Werden Vcrdflenlitchung van besonderer Bedcutumg; die bcanspnuchte ErfindunE soil Oder die aus cinern anderen besonderen Grund angegeben ist (ie kasus nucht als auf erfindenischer Tiigkeat berithend betrachtet agef-diet) wertien, wenn die Vcwflentlichunr, nut aner Oder mchreren anderen 0'Verolentiehung, die ich auf cane mulndliche Offenbarung, Vcr~ffntlichungen dieter Kategonc in Verbindung gebracht ward und cine Benutzung, eine Ausstellung Oder- andere Mallnahrnen be2ht diese Verbindung fur cinen Fachmann naheliegeni It Vcr~lTcntlichung, die var demn internationalen Anmneldedatum, aber nach Ver~fren ichndeMtld rsbnPanfmicit dem beanspnschten Priantiasatumn verdffentlicht warden ist 9 ug i igaddrcbnPtalau~ i Datum des Absehiusses der intemalianalen Recherche Absendedatum des inlenalianalen Rccherchenberichts; 1995 30 (0 9 Name unrd Postansh-ift der Internationale Recherehenbeh6rde Bevollmlehiigter Bediensleter Europasches Patentamt, P.B. 58 IS Patentlaan 2 NL 2280 1-I Rijswijk Tel. 31-70) 340-2D0, Ty-31651epo ni, Liee-ase Faxc 31.70) 340-3016 Liee -a se Formbltit PC7/1SA1210 (latt 2) (Jull 1992) tNTERNATIONALER RECIIERCHENBERICJJT Angaben zu Ver6ffentlichungen, -c zur relb~n Patentfuruic gchdrcn Inwtmc i Aktcnzcichcn PICT/EP 95/01535 Im Rechcrcheribericht Datum der I Mitglied(er) dcr I Datum der angerolhrtes Patentdokument Verdfrentlichun Patentfamilic Verorfenlhichung EP-A-483832 06-05-92 JP-A- 4170460 18-06-91' AU-B- 636254 22-04-93 AU-A- 8685591 07-05-92 US-A- 5229457 20-07-9% Formblatt PCT/ISA,'210 (Anhang Patentfamille)(Juli 1992)