AU642394B2 - Process for producing relief formes - Google Patents

Description

OP! DATE 29/11/90 INT AOJP DATE 10/01/91

INI

APPF 'LN. ID 35196 89 rNUMBER PCT/EP89/00478 )BER DIE .NS (PCT) 11) Intiernationale Veriiffentlichungsnummer: WO 90/13853 43) Internationales Verdffentlichungsditum: 15, November 1990 (15.11.90) (51) Internationale Patentkiassifikation 5 G03F 7/32 Al (21) Internationales Aktenzeichen: PCT/EP89/00478 (22) Internationales Anmeldedatum: 29. April 1989 (29.04.89) (71)Annielder: BASF AKTIENGESELLSCH~AFZT [DE/DEl; Patentabteilung ZSP-C6, Carl- Bosch-Stra~e 38, D-6700 Ludwigshafen (DE).

(72) Emfinder: TELSER, Thimas Seilerstrage 26, D-6700 Ludwigshafen KOCH, Horst Tiefenthalerstrage 47, D-6718 Grtinstadt KURTZ, Karl-Rudolf Schlog6- Wolfs-Brunnen-Weg 62, D-6900 Heidelberg (DE).

BACH, Helmut Dahlienstrate 7, D-6704 Mutterstadt WERTHER, Heinz-Ulrich Hans-Hoffmann- Strage 12. D-6706 Wachenheim (DE).

(81) Bestimmungsstaaten: AT (europalisches Patent), AU, BE (europ~Iisches Patent), CH (europltisches Patent), DE (europ~isches Patent), DK, Fl, FR (europllisches Patent), GB (europaisches Patent), IT (europ~isches Patent), LU (europtiisches Patent), NL (europdisches Patent), NO, SE (europ~iisches Patent).

Veiiiffentlicht AM internationalem Reclierchenberich.

642394 (54)Title: PROCESS FOR PRODUCING RELIEF FORMES (54) Bezeichnung: VERFANREN ZUR HERSTELLUNG VON RELIEFFORMEN (57) Abstract The invention concerns a process for the production of relief printing formes. After exposure, using actinic rays, of layers crosslinked by photopolymerization, thus producing an image, the uncrosslinked parts of the layers are washed out with hydrocarbon solvents or mixtures of hydrocarbon solvents and alcohols, specified hydrogenated oil fractions being used as the hydrocarbon solvents. The process is particularly suitable for the production of flexographic printing formes.

(57) Zusainmenfassung Die Erfindung betrifft emn Verfahren zur Herstellung von Reliefformen. Nach bildm~igemn Belichten von durch Photopolymerisation vernetzbaren Schichten mit aktinischemn Licht werden die unvemnetzten Anteile der Schichten mit Kohl enwasserstoffl6sungsmitteln oder Gemischen aus Kohlenwasserstoffi~sungsmitteln und Alkoholen ausgewaschen, wobei als KohlenwasserstoffU~sungsmittel bestimmte hydrierte Erd~5lfraktionen verwendet werden. Das Verfahren eignet sich besonders zur Herstellung von Flexodruckformen.

Siehe Rickseite O.Z. 0050/39792 Preparation of relief printina plates The present invention relates to a process for preparing relief printing plates crosslinked by photopolymerization, wherein certain developers are used for washing out the non-crosslinked parts of the layers.

The preparation of printing plates and photoresists, by imagewise exposure of photopolymerizable or photocrosslinkable relief-forming layers to actinic light, with crosslinking of the exposed parts of the layer, and subsequent washing out of the non-crosslinked parts of the layers in developers is known. The developers usually used are chlorohydrocarbons, eg.

trichloroethylene or tetrachloroethylene, aromatic hydrocarbons, such as benzene or toluene, saturated cyclic and acyclic hydrocarbons, such as hexane or cyclohexane, unsaturated cyclic hydrocarbons, eg. terpenoid compounds, limonene, pinene, and lower aliphatic ketones, such as acetone or methyl ethyl ketone, if necessary as a mixture with an alcohol (for example butanol having a content of about 20% by volume).

The washout solution frequently used commercially for flexographic printing plates and photoresists, consisting of about 80 parts by volume of tetrachloroethylene and 20 parts by volume of n-butanol or trichloroethane, is toxic and therefore gives rise to problems during operation of the washout apparatuses.

Thus, operation in conformity of the regulations requires extraction, and the waste air must be freed from the chlorohydrocarbons before being released. Disposal of the washout solution used also presents problems. Other problems arise as a result of the pronounced swelling which the exposed layer undergoes during the washout process. The pronounced swelling of the layer causes damage to the photopolymerized structures (fragmentation, detachment of fine elements, etc.) and low resistance to overwashing.

Combustibility problems are encountered when Ir r.lr~ r I, -2- O.Z. 0050/39792 alternative washout agents, such as the aromatic and aliphatic hydrocarbons, are used. These solvents have flashpoints below 21'C and would therefore have to be used in explosion-proof systems. This also applies to the low molecular weight solvents from the group consisting of the ketones.

Terpenoid hydrocarbons, eg. limonene, have sufficiently high flashpoints; however, their use as a washout solution is restricted by their intense, frequently irritating odor.

It is an object of the present invention to provide a washout agent whose flashpoint is substantially above room temperature and which requires only a short washout time for printing plates and photoresists, causes only slight swelling of the printing plate and has low toxicity and only a slight or pleasant odor.

We have found that this object is achieved and that, surprisingly, these properties can be obtained with washout agents which contain certain hydrogenated petroleum fractions as hydrocarbon solvents.

The present invention relates to a process for preparing a relief printing plate, which is crosslinked by photopolymerization, by imagewise exposing a layer which can be crosslinked by photopolymerization to actinic light, with crosslinking of the exposed parts of the layer, and washing out the non-crosslinked parts of the layer with a hydrocarbon solvent or a mixture of a hydrocarbon solvent and an alcohol, wherein a hydrogenated petroleum fraction which has a flashpoint 45"C and a Loiling range of from 160 to 220*C is used as the hydrocarbon solvent.

The hydrogenated petroleum fractions generally have an aromatics content of according to DIN 51,378. Preferred hydrogenated petroleum fractions are those which contain from 0.5 to 50%, likewise determined according to DIN 51,378, of naphthenic compounds.

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'4tc- 4 3 O.Z. 0050/39792 The novel washout agents may also contain added odor improvers and/or surface active compounds.

Hydrocarbon solvents containing aromatics (aromatics content 10%) are also suitable as washout agents for printing plates or resists but have substantially lower OEL values (OEL occupational exposure limit) and an unpleasant odor.

On the other hand, purely paraffinic solvents, for example the synthetic isoparaffins, are hardly suitable for washing out printing plates and resists. The same applies to high boiling n-paraffin mixtures.

Because of excessively long washout times, dearomatized hydrocarbon solvents having a boiling range above 230 C are also unsuitable as washout agents for printing plates or resists.

Hydrogenated petroleum fractions which are particularly preferred according to the invention are those which, in addition to an aromatics content of 1% and a flashpoint of 45°C, have a boiling range of from 170 to 220'C, in particular from 180 to 210°C, and a content of naphthenic hydrocarbons of from 0.5 to 50%, in particular from 10 to 40% (according to DIN 51 378).

Examples of suitable hydrogenated petroleum fractions are Shellsol®D 60 from Shell and Exxsol®D from Esso, which have a boiling range of about 180 to 210"C, a flashpoint of about 60°C and an aromatics content of 0.5% and contain about 30% of naphthenic hydrocarbons. These products are also virtually completely odorless and have high OEL values.

Since flexographic printing plates generally have a multilayer structure (frequently a thin, about 5 pm thick top layer of polyamide is present on the relief layer, which is about 3,000 pm thick), it may be Sadvantageous to add an alcohol component to the 35 hydrogenated petroleum fractions to be used according to the invention.

Alcohols of 4 to 8 carbon atoms (eg. n-butanol, Ao.: 't tv SI- at. -4- O.Z. 0050/39792 n-pentanol, isobutanol, hexanol, etc.) have proven suitable for this purpose. In order to ensure that the top layer of polyamide is sufficiently soluble, the content of the alcohol component should be not less than 5, preferably 20, by volume. The presence of the alcohol lowers the flashpoint of the pure hydrocarbon solvent by 10-20°C. The flashpoints of the formulated washout solutions are then about 40"C. The washout solutions can therefore be used in apparatuses which are not explosion-proof.

As stated above, the washout solutions may also contain surface active compounds which accelerate dissolution of the unexposed material, and odor-improving substances.

Examples of suitable surface active compounds are alkyl-sulfonates and their salts, alkylammonium salts or oxyethylated fatty alcohols, fatty alcohol ether sulfates and their salts and fatty alcohol phosphorus esters and their salts. The surface active compounds can usually be added to the washout solution in an amount of from 0 to 2% by weight.

Examples of suitable odor-improving additives are the naturally occurring terpenoid compounds, limonene, pinene, citronellol, etc. They can be added to the washout solution in an amount of from 0 to not more than by weight, depending on the desired intensity of the aromatic odor.

Developing and washout of the imagewise exposed photopolymeric layers are carried out in a conventional 30 manner in the known spray brush or friction washers at from 20 to 50"C. It was found that the washout time required for a certain washout depth is only insignificantly longer in the case of the novel washout solutions than in the case of the conventional washout agents, but that the solvent absorption of the exposed parts of the relief layer is dramatically reduced in the case of the novel washout solutions. This results in a very

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S L-2 L~ 'i lht;l~r~- ~Y ".Vfjt'' 5 O.Z. 0050/39792 considerable improvement in the overwashing resistance of the structures produced by imagewise exposure, ie. even if the washout time required for a certain relief height is exceeded, defect-free structures are obtained. This is important in particular for thin layers (thickness 0.7 mm), which are used in photoresists and increas- .ingly also in high quality halftone flexographic printing.

The stability to fragmentation of the structures produced by imagewise exposure is also considerably improved by the use, according to the invention, of the hydrogenated petroleum fractions described above. This is particularly important in the case of thick, flexible and resilient printing plates which have a high relief (about 3 mm) and are used, for example, for printing cartons and corrugated board.

Another surprising advantage of the washout solutions to be used according to the invention relates to the surface' quality of the imagewise exposed and washed out layers. Particularly when flexographic printing plates are washed out in the solvents conventionally used in flexographic printing, the result is frequently an undesirable surface structure in the form of wrinkles (orange peel), which is not observed when washout is effected in the novel solvents, so that the relief printing plates prepared according to the invention have a uniformly smooth surface.

Another surprising advantage of the washout solutions to be used according to the invention is the fact that, in spite of the high boiling range of the hydrogenated petroleum fractions under discussion in comparison with the washout solutions containing tetrachloroethylene, longer drying times are not required ee. after the washout process.

35 Another advantage is that the washout agents according to the present invention can be used in washout apparatuses which are not explosion-proof. Because of the 6 O.Z. 0050/39792 slight intrinsic order of the hydrogenated petroleum fractions to be used according to the invention, extraction in the washout apparatuses can be greatly reduced. After preparation, the relief printing plates are odorless.

A further advantage is the fact that the novel washout solutions can be successfully used on a large number of known layers which can be crosslinked by photopolymerization.

For example, short washout times are found in the case of photopolymerizable layers which contain vinylaromatic/alkadiene block copolymers (styrene-isoprenestyrene, styrene-butadiene-styrene, styrene-isoprenestyrene/butadiene, etc.) as binders, and in the case of layers which contain alkadiene/acrylonitrile copolymers (butadiene-acrylonitrile), fluorine rubbers (vinylidene chloride-hexafluoropropylene copolymers), natural rubber, silicone polymers and polysulfide rubbers as binders.

Short washout times are also found in the case of recording materials which contain ethylene-propylenediene terpolymers as binders.

The examples and comparative examples which follow illustrate the advantages of the novel washout agents for flexographic printing plates.

The raw layers used had the following compositions (amounts in by weight) 1. Plate type 1 (single -layer plate) 1* 3-block rubber of styrene/isoprene/styrenebutadiene according to EP-A-27 612, Example 2 87.592 30 Liquid paraffin 5 Hexanediol diacrylate 5 Benzil dimethyl ketal 1.2 2,6-di-tert-butyl-p-cresol 1.2 Solvent Black 26,150) dye 0.008 35 2,700 pm thick layer on 125 pm thick polyethylene

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7 O.Z. 0050/39792 terephthalate film which was coated with a polyurethane adhesion promoter.

2. Plate type 2 (multilayer plate) 3-block rubber as for plate type 1 Hexanediol diacrylate Benzil dimethyl ketal 2,6-di-tert-butyl-p-cresol Solvent Black 26,150) dye t? 93.596 5 0.4 1.0 0.004 700 pm thick layer on 125 pm thick polyethylene terephthalate film which had been coated with a polyurethane adhesion promoter. The base used was a photocrosslinkable layer which was likewise based on an elastomeric binder (thickness 2,000 pm).

3. Plate type 3 Terpolymer of ethylene/propylene/ethylidenenorbornene (containing 50% of ethylene and 8 double bonds per 1,000 carbon atoms) 78 Dioctyl adipate 10 Dihydrocyclopentadienyl acrylate 6 Isobornyl acrylate 4 Benzil dimethyl ketal 2 I 4 I 4 Si 2,700 pm thick layer on 125 pm thick polyethylene terephthalate film which was coated with a polyurethane adhesion promoter.

EXAMPLE 1 A flexographic printing plate (plate type 1) was prepared in a conventional manner.

The flexographic printing plate was first preexposed uniformly for 65 seconds from the back in a tube exposure unit, and subjected to stepwise imagewise exposure through a photographic negative (exposure times per copy of the negative from 6 to 20 minutes) and washed out at room temperature in a brush washer which was not

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#P r .r St 8 O.Z. 0050/39792 explosion proofed and had a low rate of air extraction (about 10 The washer contained a washout solution consisting of 80 parts by volume of a hydrogenated petroleum fraction (naphthene content 35%, boiling range 186-217*C) and 20 parts by volume of n-butanol.

For a desired relief height of 700 pm, the optimum washout time was 6 minutes.

After an exposure time of only 6 minutes, all test elements of the resulting flexographic printing plate have been completely and correctly formed.

The fleyographic printing plate, was dried for 2 hours at 65"C, stored for 15 hours at room temperature, subjected to a conventional aftertreatment with an aqueous bromine solution and dried again.

After preparation, the printing plate had a uniformly smooth surface and was odorless, and no orange peel was observed.

The aftertreated flexographic printing plate was clamped on a printing cylinder in a flexographic printing unit and gave excellent printed copies which showed no information loss at all compared with the photographic negative.

EXAMPLE 2 The procedure was similar to that in Example 1, except that the alcohol component added to the washout solution was n-pentanol (20 parts by volume) instead of n-butanol. The washout tests were once again carried out in a brush washer which was not explosion-proof and had a low extraction rate (about 10 m 3 /hour).

The optimum washout time was 6 minutes. All test elements had been completely and correctly formed after S an exposure time of only 6 minutes.

Following the aftertreatment, this printing plate o' too had a uniformly smooth surface and good printing 35 properties and was odorless.

COMPARATIVE EXAMPLE 1 The procedure was similar to that in Example 1, 'o.

a i Ar.~&4~ 9- O.Z. 0050/39792 except that the washout solution used was a mixture of parts by volume of tetrachioroethylene and 20 parts by volume of n-butanol.

The washout tests were carried out in a brush washer which was not explosion-proof but had a high air extraction rate (about 100 m 3 I/h).

The optimum washout time was 5 minutes. The test elements were correctly formed o~nly after an exposure time of 12 minutes. With shorter exposure times, fragzentation was observed in the test elements, in particular in screen elements and dots.

After drying and after treatment, the printing plates had a nonuniform structured surface (orange peel).

COMPARATIVE EXAMPLE 2 The procedure was similar to that in Example 1, except that the washout solution used was a mixture of parts by volume of mineral spirit (aromatics content boiling range 187-2160C) and 20 parts by volume of n-butanol. The washout tests were carried out in a washer which was explosion-proof and had a high extraction rate (about 100 m 3 The optimum washout time was 5 minutes. After their preparation, the printing plates had an unpleasant odor.

COMPARATIVE EXAMPLE 3 The procedure was similar to that in Example 1, except that the washout solution used was a mixture of parts by volume of mineral spirit (aromatics content 25%, boiling range 155-185*C) and 20 parts by volume of 30 n-butanol. The tests was (sic] carried out in a washer which was explosion-proof and had a high extraction rate (about 100 m 3 The optimum washout time for a 700 pm relief was 6 minutes. After their preparation, the printing plates had an unpleasant odor.

COMPARATIVE EXAMPLE 4 The procedure was similar to that in Example 1, I I 4 4 4 0 444 0 4* 00 4 4 4 00 4 0

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10 O.Z. 0050/39792 except that the washout agent used was a mixture of parts by volume of a hydrogenated mineral oil (boiling range 220-255*C, content of naphthenic compounds about and 20 parts by volume of n-butanol. The tests was [sic] carried out in a brush washer which was not explosion-proof and had a low extraction rate (about m/h).

The washout time for a 700 pm high relief was 17 minutes.

EXAMPLE 3 The procedure was similar to that in Example 2, except that, instead of plate type 1, the multilayer plate type 2 having a fixed relief height of 700 pm was used. The tests were carried out in a washer which was not explosion-proof and had a low extraction rate (about m 3 The optimum washout time was 6 minutes. With 100% overwashing, ie. with a total washout time of 12 minutes, no damage to the relief structure or lacking test elements could be observed. The printing plates were odorless.

COMPARATIVE EXAMPLE The procedure was similar to that in Example 3, except that in this case a washout solution consisting of 80 parts by volume of tetrachloroethylene and 20 parts by volume of n-butanol was used. The tests were carried out in a washer which was not explosion-proof and had a high extraction rate (about 100 m/h).

The* optimum washout time was 5 minutes. 100% overwashing was evident in this case from the lack of critical test elements (isolated dots and lines) and from fragmentation of dots and screen elements.

EXAMPLE 4 .For a plate of type 1 prepared as in Example 1, 35 drying was determined as a function of time in a throughcirculation drier at Directly after the washout process, the increase .4 11 O.Z. 0050/39792 in we.Ight due to swelling was After a drying time of 2 hours at 65"C, this figure had decreased to based on the initial weight. The extracted proportion determined after a drying time of 24 hours was 0.3%, based on the initial weight.

COMPARATIVE EXAMPLE 6 The procedure was similar to that in Example 4, except that the washout solvent used was a mixture of parts,,by volume of tetrachloroethylene and 20 parts by volume of n-butanol.

Directly after the washout process, the increase in weight due to swelling was After a drying time of 2 hours, this figrre had likewise decreased to but the extracted proportion was based on the initial weight.

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5 EXAMPLE The flexographic printing plate used was plate type 3. After preexposure through the back, the printing plate was exposed imagewise from the front for 20 minutes through a test negative and then developed in a brush washer to give the plate. The washout solution used was a mixture of 80 parts by volume of a hydrogenated mineral oil fraction (naphthene content 35%, paraffin content boiling range 186-217*C, aromatics content 1% according to DIN 51,378) and 20 parts by volume of n-butanol.

The optimum washout time for a relief height of 700 pm was 12 minutes. All test elements were satisfactorily and correctly formed. Aftertreatment gave plates which had a uniformly smooth surface.

COMPARATIVE EXAMPLE 7 The procedure was similar to that in Example except that the washout agent used was a mixture of parts by volume of tetrachloroethylene and 20 parts by volume of n-butanol.

The optimum washout time for a relief height of 700 pm was once again 12 minutes. Fragmentation was 044 49/~ 12 O.Z. 0050/39792 observed at edges and in dots. The aftertreatment gave plates which had a nonuniform surface which had been destroyed.

EXAMPLE 6 The procedure was similar to that in Example 1, except that the washout solution used was a mixture of parts by volume of hydrogenated petroleum fraction (boiling range 160-195"C, naphthene content parts by volume of n-butanol and 5 parts by volume of limonene.

The washout tests were carried out in a brush washer which was not explosion-proof and had a low extraction rate (about 10 m 3 The optimum washout time for a 700 pm relief was 5 minutes. The plates had a pleasant orange-like odor.

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Claims (7)

1. A process for preparing a flexographic printing plate, which is crosslinked by photopolymerization, by imagewise exposing a layer which can be crosslinked by photopolymerization to actinic light, with crosslinking of the exposed parts of the layer, and washing out the non-crosslinked parts of the layer with a hydrocarbon solvent or a mixture of a hydrocarbon solvent and an alcohol, wherein a hydrogenated petroleum fraction which has a flashpoint 450C and a boiling range of from 160 to 220°C is used as the hydrocarbon solvent.

2. A process as claimed in claim 1, wherein the hydrogenated petroleum fraction has an aromatics content of as defined in DIN 51, 378.

3. A process as claimed in any one of the preceding claims, wherein the hydrogenated petroleum fraction contains from 0.5 to 50% of the naphthenic compounds, as defined in DIN 51, 378.

4. A process as claimed in any one of the preceding claims, wherein the hydrogenated petroleum fraction contains an added odor improver. i

5. A process as claimed in any one of the preceding claims, wherein the hydrogenated petroleum fraction contains an added surface-active compound. DATED this 6th day of August, 1993 BASF AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS THE ATRIUM i. 290 BURWOOD ROAD HAWTHOHN VICTORIA 3122 AUSTRALIA O.Z. 0050/39792 Abstract of the Disclosures The present invention relates to a process for preparing relief plates. After imagewise exposure of layers which can be crosslinked by photopolymerization to actinic light, the non-crosslinked parts of the layers are washed out with a hydrocarbon solvent or a mixture of a hydrocarbon solvent and an alcohol, certain hydrogenated petroleum fractions being used as hydrocarbon solvents. The process is particularly suitable for pre- paring printing plates. a* 4 Is at 1 r INTERNATIONAL SEARCH REPORT International Application No PCT/EP 89/00478 I. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, Indicate all) According to International Patent Classification (IPC) or to both National Classification and IPC Int.Cl. GO3F 7/32 II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System Classification Symbols Int.Cl 5 GO3F Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included in the Fields Searched Ill. DOCUMENTS CONSIDERED TO BE RELEVANT' Category Citation of Document, 11 with Indication, where appropriate, of the relevant passages 12 Relevant to Claim No., X,Y US, A, 3887373 HAYS) 3 June 1975 see the whole document Y GB, A, 1189944 DU PONT DE NEMOURS) 29 April 1970, see page 2,line 43 page 2, line 46;page 1,line 80 page 1,line 86; claims 1-23 A Patent Abstracts of Japan, vol. 8,No. 278 (P-322)(1715), 19 December 1984; JP, A, 59146054 (TORAY) 21 August 1984 see the whole document Special categories of cited documents: 'i later document published alter the International filing date document defining the geniral state to the art which is not or priority date and not In conflict with the application but considered to be of particuiar relevance cited to understand the principle or theory underlying the invention earlier document but published on or after the international document of particular relevance; the claimed invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step 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 ments, 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 IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Search Report 8 November 1989 (08.11.89) 05 December 1989 (05.12.89) International Searching Authority Signature of Authorized Officer EUROPEAN PATENT OFFICE Form PCTiISAI210 (second sheet) iJanuary 1985) ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. EP 8900478 SA 28601 Tbis annex lists the patent family memnbers relating to the patent documents cited in the above-nientioned international search report. The members are as contained in the European Patent Office EDP ile on 28111189 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent document Publication Patent family I Publication cited in search report I date Imember(s) date US-A- 3887373 03-06-75 JP-A- 50013029 10-02-75 GB-A- 1189944 29-04-70 BE-A- 709435 16-07-68 For more details about this annex -see Official Journal of the European Patent Office, ;No, 12182 INTERNATIONALER RECHERCHENBERICHT Internationales Aktenzeichen PCT /EP 89 /00478 1. KIASSIFIKATION DES ANMELOUNGSGEGENSTANOS (be( M413faen Klassif atlontsymtoolan sind aile anzugsban) 6 Nach der Intcrnationaten Patentkiassifikation (IPC) ader nach der nationalen Kiessifikation und der [PC In 15:G 03 F 7/32

11. RECHERCHIERTE SACHGEBIETE Recherchierter MindlestorustoWf Klassifikationssystem Klassit ikationssyrnbale Recherchierte nicht Zumn Mindestprufstoff gehdrende Veroffentlichungen, soweit diese unter die recherchierien Sachgebiete f allen 8 IIL.EINSCHILAGIGEVEROFFENTLICHUNGEN 9 Art. Kennzeschnung der Verdffentlichungll,soweit erfordearlich unter Angabe der maageblichen Teile 12 Betr, Ansoruch Nr. 1 3 X,Y US, A, 3887373 HAYS) 3. Juni 1975, siehe das ganze Dokument Y 1189944 DU PONT DE NEMOURS)

29. April1 1970, siehe Seite 2, ZeiJle 43 Seite 2, Zeile 46; Seite 1, Zeile 80 Seite 1, Zeile 86, Anspr~iche 1-23 A Patent Abstracts of Japan, Band 8, Nr. 278 (P-322)(1715), 19. Dezemnber 1984; JP, A, 59146054 (TORAY) 21. August 1984, siehe die ganze Zusamrnenfassung B esondere Kategorien von angaebenen Verdffentlichungeni a Verdffentlichung, die den allgemeinen Stand der Technik Spatere Vertiffentlichung, die nach dem internationalen An- definiert. abet nicht als besonders bedleutseam anzusahen ist muldedlaturn odor dem PrIoritatsdaturn verdffentlicht worden Siteres Dokcument, des jecloch ers am odor nasch dem inrne. ist und mit der Anmeldlung nicht kollidiert. soirtdrn nur zum tionlen nmedecltur verffetlict wrdenistVeruandnls des der Erfindcung zugrundeliaeandeon Prinzips tionlenAnmldedtumvetffetlici wrde Stodor dler ihr zugrundeliepondon Theorie aiineben ist Veroffentlichung, die Meignet ist, eamen Prioritatsanspruch Verbff entichung von besonderer Bedleutung: die banspnjch. zwalfelhaft erscheinen zu lessen. odor durch die des Verdf. t ridn anncteinuoe u rdrthr~tg fentlichungsaetumn einer anderen im Recherchenibericht ge t Erfnund bsannchtt war de u r neice narwuen Nkrdffentlichung beWTg warden sili oder die aus eitnr etbrhn ercttwre anderan besondhren Grund angegeben ist (wyie ausgefi~hrt) Veroffentlichung von besonderer Bedeautung; die beanipruch- "0"Verifenticung de schauf eine mijndflcho Offenbarung. to Erfindung kann nicht als auf eriinderischer Titigkoit be- erofentichng. ie ichruhend betrachtet warden, wenn die Varotfentlichung mit eine Sanutzung, sine Ausatellung oder andere Mal~nahmen einer odor mehreren anderen Veroffentlichungan dieser Kate. bezieht gorie in Verbindlung 9pbracht wvird und diese Verbindlung fir Veroffentlichung. die var dam internationelen Anmeldedla- amnen Fachmann neheliegand ist turn. aber nach dem beanspruchtefl PrioritAudatumn varotfent- Veriff entlichung. die Mitglied derselben Petentf amilia it llcht worden iat IV. BESCHEINIGILNG Internationale Recherchenbehorde neshitd bvlmcitn Europiisches Patentamt T.K. WILLIS Forvnblort PCT/ISA/210 lStart 2) (Januar 1985) ANHANG ZUM INTERNATIONALEN RECHERCHENBERJCHT OBER DIE INTERNATIONALE PATENTANMELDUNG NR. EP 8900478 SA 28601 In diesern Anhang vind die M4itglieder der Patentfamilien der ins obengenannten internationalen Recherchenbcricht angefiffhrten Patentdokumente angegeben. Die Angaben Ober die Familienmitgiiedcr entsprechen dem; Stand der Datei des Europatachen, Patentautts am 28/11/89 Diese Angaben dienen nur zur Unterriebtung und erfolgen ohnc Gewahr. tIm Recherchenbericht Datum der Mitglied(er) der Datum der angefuhrtes Patentdokument Verbffentlichung Patentfamiei Verbffentlichung US-A- 3887373 03-06-75 JP-A- 50013029 10-02-75 GB-A- 1189944 29-04-70 BE-A- 709435 16-07-68 Fur nahere Einzelheiten zu diesem Anhang siehe Amtsbtatt des Europfiischen Patentaints, Nr.1 2/82