EP0131282B1 - Procédé de revêtement de boites ouvertes à une extrémité - Google Patents

Procédé de revêtement de boites ouvertes à une extrémité Download PDF

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Publication number
EP0131282B1
EP0131282B1 EP84107925A EP84107925A EP0131282B1 EP 0131282 B1 EP0131282 B1 EP 0131282B1 EP 84107925 A EP84107925 A EP 84107925A EP 84107925 A EP84107925 A EP 84107925A EP 0131282 B1 EP0131282 B1 EP 0131282B1
Authority
EP
European Patent Office
Prior art keywords
cans
bath
coating
paint
electrodeposition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP84107925A
Other languages
German (de)
English (en)
Other versions
EP0131282A2 (fr
EP0131282A3 (en
Inventor
Horst Buchholz
Gerhard F. Dr. Ottmann
Hans-Peter Dr. Patzschke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Axalta Coating Systems Germany GmbH and Co KG
Original Assignee
Herberts GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6203753&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0131282(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Herberts GmbH filed Critical Herberts GmbH
Priority to AT84107925T priority Critical patent/ATE46370T1/de
Publication of EP0131282A2 publication Critical patent/EP0131282A2/fr
Publication of EP0131282A3 publication Critical patent/EP0131282A3/de
Application granted granted Critical
Publication of EP0131282B1 publication Critical patent/EP0131282B1/fr
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00Electrophoretic coating characterised by the process
    • C25D13/12Electrophoretic coating characterised by the process characterised by the article coated
    • C25D13/14Tubes; Rings; Hollow bodies

Definitions

  • the invention relates to a method for coating one-sided open cans such as metallic cans by means of the immersion lacquer process with lacquer, in which the individual cans are washed, coated on the outside and inside, the cans being coated with an anionic ETL lacquer as the anode and when coating with cationic ETL lacquer can be switched as a cathode, dried and then optionally printed and dried again.
  • the cans treated in this way can also be crimped at the open end.
  • ETL electro dip painting process
  • Cans which are closed on one side cannot simply be coated electrophoretically, because it is necessary for a uniform coating that the air in the can completely escapes. Therefore, the mechanical engineering industry has developed special methods that are carried out step by step, i.e. it is painted in individual successive steps, for example first on the inside.
  • the cans for the interior painting are kept on the floor and at the same time the necessary electrical contacts are made.
  • a counter electrode is inserted into the can from the open end, which must be at a short distance of 0.25 to 5 mm from the inner wall of the can, so that the shape of the electrode has to be adapted very precisely to that of the can.
  • the cans Because of the complicated structure of the corresponding system, the cans have to be coated individually one after the other, so that only very short coating times of 10 to 500 msec are available if one wants to achieve a high can throughput.
  • liquid In closed systems, for example in a vertical arrangement (EP-50 045, EP-19 669, GB-PS-1 117 831, US-PS-3 922 213 and DE-OS-2 929 570), liquid must be pumped at high speeds, in order to be able to alternately carry out ETL liquid and water rinsing in short periods of time and to remove the gases (oxygen or hydrogen, depending on the polarity) that arise during the ETL coating.
  • the approximately horizontally arranged cans must be rotated in order to achieve an even coating. (DE-OS-2 633 179 and US-PS-4 107 016). When blowing out the cans, there is a great risk of contamination.
  • the older EP-A-118 756 (Art 54 (3) and (4)) describes a process in which the cans are immersed at an angle in the electro-immersion bath. In the process described in US-A-2,362,474, the cans can only be coated individually and in succession.
  • the object of the invention is to simplify the coating of metal cans which are open on one side in such a way that coating can be carried out on the outside as well as on the inside in one continuous operation.
  • the cans are passed through the immersion bath at the same time to a plurality of them, wherein for the coating they are immersed vertically and with the bottom closed in the electrodeposition bath, filled with bath liquid from above by means of a filler neck and for lifting out of the immersion bath be tilted so that their opening is facing downward and that the counter electrode is outside the cans in the electro-immersion bath.
  • the invention makes it possible to coat metal cans which are open on one side at the same time on the outside and inside in one work step and to dry immediately thereafter and, if appropriate, to print or label them.
  • the mechanical effort and space requirements are relatively low, so that an economical mode of operation is possible. For example, up to 16 cans at the same time, i.e. passed side by side through an electro-dip bath and thereby coated with lacquer.
  • the trimmed or untrimmed cans are vertical, i.e. pressed with the bottom down into the ETL basin or - more advantageously, faster - filled with bath liquid through a filler neck.
  • the cans When transporting through the ETL basin, the cans are either immersed under the bath surface or, particularly with untrimmed cans, advantageously guided so that the can opening is above the bath liquid surface.
  • they To lift the cans out of the immersion bath, they are tilted again so that their opening lies downwards so that the liquid in the cans can drain off completely.
  • the transport element can be an endless conveyor belt or an endless chain on which the cans hang practically vertically or stand on it, ie the conveyor belt can run above the surface of the bath or be guided through the ETL immersion bath.
  • the cans for coating are passed through an immersion bath and it is also possible to pass several cans next to one another through the immersion bath at the same time, even with mass production with high throughput, sufficiently long coating times can be achieved in order to be able to apply even higher-quality paint coatings properly .
  • a coating time of 1 to 120 seconds a pigmented or unpigmented lacquer is applied electrophoretically using direct current, the wet film deposited on the cans having a sheet resistance of at least 0.6 x 108 ohms. cm.
  • the cans to be coated are switched via the holding device when using an anionic ETL lacquer as an anode and when using a cationic ETL lacquer as a cathode.
  • the counter electrode is located at a distance from the cans in the immersion bath.
  • the inner coating is carried out with the aid of a so-called wrap-around, which achieves the coating in the deposited film because of its maximum insulating effect, or with the aid of an inner electrode inserted into the can.
  • the electrophoretic coating is such that the wall opposite the counterelectrode, i.e. the outer wall of the can is coated.
  • the wet wall that builds up initially isolates the outer wall.
  • the electric field lines then migrate into the interior of the can, where the deposition continues.
  • the deposition time and the insulating effect of the material, characterized by the sheet resistance must be coordinated in order to achieve a good grip. The longer the coating time, the higher the layer resistance due to the increase in the layer thickness and through electro-osmotic processes which are used to reduce the content of neutralizing agent or for electrochemical dewatering.
  • the lower limit of the coating time should therefore be over 3 seconds, in particular over 5 seconds and particularly suitably over 10 seconds.
  • the upper limit is determined by the length of the immersion bath, the transport speed and the amount of hollow bodies to be coated to be managed. In order to achieve an economically acceptable level, the upper limit should expediently be less than 60 seconds and preferably less than 30 seconds of coating time.
  • the amount of film applied depends on the deposition voltage, which is between 50 and 400 volts. With increasing tension, the wrap is improved. In order to avoid electrical breakdowns, the voltage is either continuously increased or a short bias is used, i.e. Before the actual coating, voltages of less than 100 volts are used for 0.1 to 0.5 seconds.
  • the wet film resistance required for good insulation should be as high as possible.
  • its lower limit is limited by the desired short coating time.
  • the lower limit should be at least 1 x 10 8 ohm-cm, expediently above 1.5 x 10 8 ohm-cm and preferably above 2 x 10 8 ohm-cm.
  • the upper limit is therefore below 10 x 10 8 , suitably below 7 x 10 8 and preferably below 4 x 10 8 ohm-cm.
  • the bath conductivity which is determined by the degree of neutralization of the binder, is above 800 gScm- 1 , expediently above 1200 and preferably above 1600 gScm- 1 lies.
  • Both anionic and cationic resins can be used as binders, the anionic ones being preferred for acidic and the cationic ones for basic fillings.
  • the anionic resins such as maleinized or acrylated butadiene oils, maleinized natural oils, epoxy esters and acrylate resins containing carboxyl groups, acrylic epoxy resins, unmodified or modified with fatty acids have an acid number of 30 to 180, in particular between 40 and 80, and are at least partially neutralized with ammonia, amines or amino alcohols . Easily volatile amines are produced so that they can be removed from the film as completely as possible with the desired short burn-in times of 30 seconds to 300 seconds. Ammonia is particularly preferred.
  • crosslinking takes place either oxidatively via unsaturated double bonds or by thermal reaction with corresponding crosslinking agents such as phenolic resins or amine-formaldehyde resins.
  • corresponding crosslinking agents such as phenolic resins or amine-formaldehyde resins.
  • External or self-crosslinking acrylate resins are preferred for the production of white lacquer coatings.
  • Acrylated or maleinized epoxy esters or epoxy acrylates are preferred for coating with clear lacquers.
  • the cationic resins such as butadiene oil aminoalkylimides, Mannich bases of phenolic resins, Michael addition products of primary and / or secondary amines and / or alkanolamines on resins with unsaturated double bonds or amino epoxy resins have an amine number of 30 to 120 mg KOH / g / solid resin, preferably from 50 to 90, and are at least partially neutralized with organic monocarboxylic acids such as carbonic acid, formic acid, acetic acid, lactic acid etc.
  • Blocked isocyanates or resins which contain ester groups capable of transesterification are preferably used as crosslinking agents.
  • the binders are neutralized with the neutralizing agents and, if appropriate, diluted with deionized or distilled water in the presence of solvents.
  • Suitable solvents are primary, secondary and / or tertiary alcohols, ethylene or propylene glycol mono- or diether, diacetone alcohol or even small amounts of non-water-dilutable solvents such as petroleum hydrocarbon.
  • the lowest possible solvent content is desirable, advantageously below 15% by weight and preferably less than 5 wt .-%, the worsens with increasing solvent content.
  • the bath solid is generally between 5 and 30% by weight, in particular over 10 and under 20% by weight. With increasing solids, the bath conductivity is increased and the deposition equivalent (amperes x sec / g) is reduced, whereby the wrap can be increased. Due to the high concentration of layer-forming ions, the layer resistance goes through a maximum.
  • the bath temperature is between 20 and 35 ° C. As the temperature drops, the wrap increases. Temperatures below 20 ° C are uneconomical because the heat generated by the ETL coating has to be dissipated again by plenty of cooling water. Temperatures above 35 ° C make it difficult to run the bath because too much solvent evaporates and hydrolysis on the binder system produces fluctuations in the electrical data.
  • the coating agent can additionally contain customary lacquer aids such as catalysts, leveling agents, anti-foaming agents, lubricants, etc.
  • additives should be selected that do not interfere with water at the pH of the bath, do not carry in any interfering foreign ions, and do not turn out to be irreversible when standing for a long time.
  • the binders can be used pigmented or unpigmented. Such materials can be used as pigments and fillers which, owing to their small particle size below 10 ⁇ m, particularly below 5 ⁇ m, can be stably dispersed into the lacquer and can be stirred up again when standing. They must not contain any interfering foreign ions and must not react chemically with water or the neutralizing agent.
  • the pigmentation can be both white and colored; white is preferred. With the additional incorporation of interference pigments, it is possible to apply metal effect coatings such as B. aluminum, gold, etc. to achieve.
  • the pigments such as B. Titanium dioxide are ground in a concentrated regrind and then adjusted with a further binder to a pigment-binder ratio of about 0.1: 1 to 0.7: 1.
  • the wrap is increased by the incorporation of pigments.
  • pigments it is also possible to use finely powdered, insoluble resins, such as powdered polycarbonates, epoxy resins or blocked polyisocyanates, the amounts added being chosen so that they do not exceed the maximum sheet resistance.
  • the binder, pigment content, bath solids content, solvent content, choice of neutralizing agent and the degree of neutralization are coordinated with the coating conditions such as bath temperature, deposition voltage and deposition time in such a way that a complete full coating takes place in the electrocoating bath (ETL bath), which after baking inside the can Layer thicknesses of at least 3 microns, preferably at least 4 microns, most preferably at least 5 microns and at most 10 microns, especially at most 7 microns is pore-free.
  • the electrodeposition is done in an immersion bath.
  • the cans which are closed on one side can be practically vertical, i.e. with the aid of a magnetic, electromagnetic or mechanical holding device, which also means vacuum holding. with the opening facing upwards, under the bath surface of the ETL basin.
  • the filling of the can is supported by pumping in additional bath material via a filler neck, which can also be designed as a hollow electrode. Direct current is used as the current source.
  • the cans are electrically connected via the holding device as an anode or as a cathode.
  • the counter electrode is always outside in the electro-immersion bath.
  • the can Due to the encapsulation of the paint and the deposition voltage and coating time required for the respective can shape, the can is completely coated on the inside and outside.
  • This process has the advantage that the entire coating is carried out in a single process step and, due to the low mechanical expenditure on the hanger, many cans can be coated side by side at the same time.
  • An auxiliary electrode can also be inserted into the box to provide support, especially when high throughput speeds are required.
  • the immersion electrode has a shape not determined by the can and is less than half the diameter of the can. It is preferably arranged so that it is inserted into the interior of the cans at the same time as the can holder.
  • the auxiliary electrode can be made hollow. Filtered varnish is pumped into the can through this feed line.
  • the inner coating is carried out after filling the vertical cans with an inner electrode and the outer coating is carried out in the usual way with a second counter electrode in the ETL bath.
  • the untrimmed cans are only so far immersed that they are completely coated after trimming. On the other hand, it must be ensured that the edges of the can do not dip under the surface of the bath. This makes it possible to coat the outside with a different paint first on the inside and then in a further step in a second ETL basin.
  • the coating can also be carried out simultaneously on the inside and outside with two different paint qualities,
  • the cans are emptied by rotating the cans, with the can bottom being raised.
  • the hanger When the hanger is extended, it is rinsed together with the cans first with ultrafiltrate and then with water, to which an emulsifier can optionally be added to avoid wetting problems.
  • the paint is baked in at times of 1 to 300 seconds at temperatures of 180 to 250 ° C.
  • the conveyor belt with buckets and cans is fed through the furnace.
  • the can bottom can be predried and provided with a protective auxiliary layer. Afterwards, the transfer can take place on a conveyor belt leading through the drying oven.
  • the opening of the can can be directed downwards or preferably upwards.
  • Continuous coating in the ETL tank enriches the amine with an anionic binder and carboxylic acid with a cationic one.
  • the refill materials are either neutralized correspondingly lower or the excess neutralizing agents are removed by electrodialysis.
  • the rinsing water is enriched by ultrafiltration and returned to the paint basin, which increases the degree of utilization of the paint and removes unwanted foreign ions.
  • An anionic, self-crosslinking acrylate resin according to DE-AS-1 669 107 was neutralized with ammonia and diluted to a solids content of 15% by weight with deionized water.
  • a flanged can (diameter 56 mm, length 116 mm) was held at the flanged edge with an electrically conductive clamp and carefully immersed completely in a conductive container insulated against earth and filled with diluted lacquer with a diameter of 19 cm.
  • the direct current from a voltage source was connected to the socket and the other pole to the outer vessel.
  • the coating was carried out with an auxiliary electrode with a diameter of 1 cm, which was immersed in the can 8 cm deep.
  • the can was baked for 3 minutes at 215 ° C in a convection oven. The can was completely covered on the inside and outside with a thin and pore-tight clear lacquer. For measured values, see Table 1.
  • the binder from Example 1 was pigmented with 0.4 part by weight of titanium dioxide to 1 part by weight of binder and, after neutralization with ammonia, diluted to a solids content of 9% by weight.
  • the coating was carried out without an auxiliary electrode.
  • the can was completely covered with a white varnish.
  • the porosity, measured in an electrolyte solution at 4 volts, is 5 mA after 30 seconds.Measured values see Table 1.
  • a cationic amino epoxy resin according to DE-OS-3 122 641 was pigmented with 0.4 part by weight of a mixture of 99 parts by weight of titanium dioxide and 1 part by weight of carbon black and, after neutralization with formic acid, to a solids content of 15 parts by weight. % diluted with deionized water. The coating was carried out without an auxiliary electrode. The can was completely covered with a gray varnish. For measured values, see Table 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Materials For Medical Uses (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)
  • Orthopedics, Nursing, And Contraception (AREA)
  • Pens And Brushes (AREA)

Claims (5)

1. Procédé pour revêtir de laque au moyen du procédé de laquage par immersion des boîtes ouvertes d'un côté, dans lequel les boîtes individuelles sont lavées, revêtues extérieurement et intérieurement dans un bain d'immersion électrolytique, les boîtes étant reliées comme anode lors d'un revêtement à l'aide d'une laque anionique de laquage électrolytique par immersion (ou LEI) et comme cathode lors d'un revêtement à l'aide d'une laque cationique par LEI, séchées et ensuite éventuellement imprimées et à nouveau séchées, caractérisé en ce que les boîtes sont guidées simultanément à plusieurs côte à côte à travers le bain d'immersion, en étant immergées verticalement pour le revêtement, les fonds fermés tournés vers le bas dans le bain d'immersion, en étant remplies de liquide du bain par le haut au moyen d'une tubulure de remplissage et en étant basculés lorsqu'elles sont relevées hors du bain d'immersion de telle façon que leur ouverture soit orientée vers le bas, et en ce que la contre-électrode se trouve dans le bain d'immersion en dehors des boîtes.
2. Procédé selon la revendication 1, caractérisé en ce que les boîtes sont guidées à travers le bain d'immersion en y étant plongées de façon incomplète, de façon que leur ouverture soit située au-dessus de la surface de liquide du bain.
3. Procédé selon le revendication 1 ou 2, caractérisé en ce que les boîtes sont guidées par un élément de transport.
4. Procédé selon la revendication 3, caractérisé en ce que l'on emploie comme élément de transport un convoyeur à bande sans fin ou une chaîne sans fin guidée à travers le bain d'immersion.
5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que les boîtes sont guidées par l'élément de transport à travers la bain d'immersion et le four de séchage.
EP84107925A 1983-07-12 1984-07-06 Procédé de revêtement de boites ouvertes à une extrémité Expired EP0131282B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84107925T ATE46370T1 (de) 1983-07-12 1984-07-06 Verfahren zum beschichten einseitig offener dosen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3325068 1983-07-12
DE19833325068 DE3325068A1 (de) 1983-07-12 1983-07-12 Verfahren zum beschichten einseitig offener hohlkoerper

Publications (3)

Publication Number Publication Date
EP0131282A2 EP0131282A2 (fr) 1985-01-16
EP0131282A3 EP0131282A3 (en) 1985-09-11
EP0131282B1 true EP0131282B1 (fr) 1989-09-13

Family

ID=6203753

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84107925A Expired EP0131282B1 (fr) 1983-07-12 1984-07-06 Procédé de revêtement de boites ouvertes à une extrémité

Country Status (8)

Country Link
US (1) US4529492A (fr)
EP (1) EP0131282B1 (fr)
JP (1) JPS6039199A (fr)
AT (1) ATE46370T1 (fr)
CA (1) CA1227161A (fr)
DE (2) DE3325068A1 (fr)
ES (1) ES534164A0 (fr)
ZA (1) ZA845310B (fr)

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GB2192407B (en) * 1986-07-07 1990-12-19 Metal Box Plc Electro-coating apparatus and method
DE3728762A1 (de) * 1987-08-28 1989-03-09 Basf Lacke & Farben Bindemittel fuer die kathodische elektrotauchlackierung
ATE96476T1 (de) * 1989-11-16 1993-11-15 Plm Berlin Dosenwerk Gmbh Verfahren und vorrichtungen zum anodischen oder kathodischen elektrolackieren von hohlkoerpern, insbesondere von dosen.
US7943028B2 (en) * 2004-08-13 2011-05-17 Ppg Industries Ohio, Inc. Method for coating objects
US20060051511A1 (en) * 2004-08-13 2006-03-09 Orosz Gary R Apparatus and systems for coating objects
US7947160B2 (en) * 2004-08-13 2011-05-24 Ppg Industries Ohio, Inc. System for coating objects
US20060032730A1 (en) * 2004-08-13 2006-02-16 Kaufman Paul J Belt conveyor apparatus
CA2905575C (fr) 2013-03-15 2022-07-12 Modumetal, Inc. Procede et appareil d'application en continu de revetements metalliques nanostratifies
AR102068A1 (es) 2014-09-18 2017-02-01 Modumetal Inc Métodos de preparación de artículos por electrodeposición y procesos de fabricación aditiva
BR112017005464A2 (pt) 2014-09-18 2017-12-05 Modumetal Inc método e aparelho para aplicar continuamente revestimentos de metal nanolaminado
DE102015122467A1 (de) * 2015-12-21 2017-06-22 Dürr Systems Ag Anlage und Verfahren zum Behandeln von Werkstücken
EP3612669A1 (fr) * 2017-04-21 2020-02-26 Modumetal, Inc. Articles tubulaires dotés de revêtements déposés par électrodéposition et systèmes et procédés de production desdits articles
WO2019210264A1 (fr) 2018-04-27 2019-10-31 Modumetal, Inc. Appareils, systèmes et procédés de production d'une pluralité d'articles pourvus de revêtements nano-stratifiés à l'aide d'une rotation

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US2215166A (en) * 1937-02-15 1940-09-17 Crosse & Blackwell Ltd Method of coating metal for foodstuff containers
US2362474A (en) * 1941-07-25 1944-11-14 Manning Bowman & Co Electroplating apparatus
US3253943A (en) * 1963-03-04 1966-05-31 Union Carbide Corp Bottle coating machine
AT294278B (de) * 1967-09-08 1971-11-10 Stolllack Ag Verfahren zur Elektrobeschichtung von Höhlkorpern
US3483907A (en) * 1967-10-02 1969-12-16 Juliana M Corridon Tote bag
US3660266A (en) * 1968-02-12 1972-05-02 Ashdee Corp Electrocoating equipment accessory
US3620952A (en) * 1969-06-02 1971-11-16 Continental Can Co Mechanical apparatus for electrodeposition of cans
US3694336A (en) * 1969-06-02 1972-09-26 Continental Can Co Method for can electrodeposition
US3801485A (en) * 1972-09-01 1974-04-02 American Can Co Apparatus and method for electrodepositing a coating on interior surfaces of container bodies
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DE3304940A1 (de) * 1983-02-12 1984-08-16 Herberts Gmbh, 5600 Wuppertal Verfahren zum beschichten einseitig offener hohlkoerper

Also Published As

Publication number Publication date
ES8504275A1 (es) 1985-04-01
US4529492A (en) 1985-07-16
CA1227161A (fr) 1987-09-22
ES534164A0 (es) 1985-04-01
ZA845310B (en) 1985-03-27
DE3479747D1 (en) 1989-10-19
JPS6039199A (ja) 1985-02-28
EP0131282A2 (fr) 1985-01-16
ATE46370T1 (de) 1989-09-15
EP0131282A3 (en) 1985-09-11
DE3325068A1 (de) 1985-01-24
JPH0440440B2 (fr) 1992-07-02

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