DK156445B - PROCEDURE FOR COVERING GALVANIZED METAL WITH AN ORGANIC POWDER AND GALVANIZED METAL WITH SUCH COATING - Google Patents
PROCEDURE FOR COVERING GALVANIZED METAL WITH AN ORGANIC POWDER AND GALVANIZED METAL WITH SUCH COATING Download PDFInfo
- Publication number
- DK156445B DK156445B DK145181A DK145181A DK156445B DK 156445 B DK156445 B DK 156445B DK 145181 A DK145181 A DK 145181A DK 145181 A DK145181 A DK 145181A DK 156445 B DK156445 B DK 156445B
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- DK
- Denmark
- Prior art keywords
- metal
- galvanized metal
- coating
- galvanized
- powder
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2350/00—Pretreatment of the substrate
- B05D2350/60—Adding a layer before coating
- B05D2350/65—Adding a layer before coating metal layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
- B05D2401/30—Form of the coating product, e.g. solution, water dispersion, powders or the like the coating being applied in other forms than involving eliminable solvent, diluent or dispersant
- B05D2401/32—Form of the coating product, e.g. solution, water dispersion, powders or the like the coating being applied in other forms than involving eliminable solvent, diluent or dispersant applied as powders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/102—Pretreatment of metallic substrates
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
- Laminated Bodies (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- ing And Chemical Polishing (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Coating With Molten Metal (AREA)
Abstract
Description
iin
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Opfindelsen omhandler en fremgangsmâde til overtræk-ning af galvaniseret métal med et organisk pulver samt galvaniseret métal med et sâdant overtrsek.The invention relates to a method for coating galvanized metal with an organic powder and galvanized metal with such a coating section.
Undersogelser, der har fort til nærværende opfindelse, 5 har vist, at det er muligt at præparere zinkoverfladen af det galvaniserede stâl sâledes, at adhæsionen af det virksomme pulver overtrsek pâ zirikbeklædningen er ækvivalent med adhæsionen til omhyggeligt præpare-ret blodt stâl. Dette betyder, at det er muligt at 10 anvende galvaniseret stâl som bæremateriale og drage fordel af den overlegne korrosionsbestandighed af zinkbeklædningen uden at miste den gode adhæsion af det virksomme pulverovertræk til bæremateria-· let.Studies which have advanced the present invention have shown that it is possible to prepare the zinc surface of the galvanized steel so that the adhesion of the active powder to the zircon coating is equivalent to the adhesion to carefully prepared blood steel. This means that it is possible to use galvanized steel as a carrier material and to take advantage of the superior corrosion resistance of the zinc coating without losing the good adhesion of the active powder coating to the carrier material.
15 En væsentlig fordel ved at anvende galvaniseret stâl fremfor blodt stâl som bæremateriale opnâs, nâr pul-verovertrækket bliver fysisk beskadiget, som det kan ske under transport, tilrigning eller installation af industrielt udstyr. I denne situation bestemmes kor-20 rosionsbestandigheden kun af bærematerialet, og zinkbeklædningen af det galvaniserede stâl tilvejebringer en væsentlig storre korrosionsbeskyttelse end muligt ved brugen af en passiverende skylning som typisk an-vendt ved blodtstâl.15 A significant advantage of using galvanized steel rather than blood steel as a carrier material is obtained when the powder coating is physically damaged, as can be done during transport, alignment or installation of industrial equipment. In this situation, the corrosion resistance is determined only by the support material, and the zinc coating of the galvanized steel provides substantially greater corrosion protection than is possible by the use of a passivating rinse typically used in blood steel.
25 Tidligere anvendtes en forbehandling af galvaniseret métal omfattende otte eller mindst seks arbejdstrin forud for overtrækningen med det organiske pulver.In the past, a preprocessing of galvanized metal comprising eight or at least six working steps was used prior to coating with the organic powder.
Opfindelsen tilvejebringer en forbehandling af et galvaniseret métal som bæremateriale, som ikke kræver 30 nogen passivering til at beskytte stâlet imod korro-sion, og som kun omfatter fire arbejdstrin, og som tilvejebrînger en foroget adhæsion af det virksomme organiske pulver ved den pâfolgende overtrækning end 2The invention provides a pretreatment of a galvanized metal as a carrier material which requires no passivation to protect the steel against corrosion, and which comprises only four working steps, and which provides for increased adhesion of the effective organic powder by the subsequent coating than 2
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mulig ved de konventionelle forbehandlingsfremgangs-mâder.possible by the conventional pre-treatment methods.
Fremgangsmâdén ifolge opfindelsen er af den i krav l's indledning angivne art og er ejendommelig ved det i 5 krav l's kendetegnende del angivne.The method according to the invention is of the nature specified in the preamble of claim 1 and is peculiar to the characterizing part of claim 1.
Stâlets metalliske zinklag anvendes direkte til at tilvejebringe en offerkorrosionsbeskytte3.se af métal 1 et fremfor anvendelsen af mindre virksomme 10 kemiske skylninger, sâsom en zinkphosphatskylning, til aflejring af et korrosionsbeskyttende lag pâ overfladen. Endvidere slipper man for at anvende chromforbindelse og fjerner herved risikoen for skadelige affaldsstoffer. Der aflejres et minimalt 15 zink phosphatlag pâ métal1et, hvilket sikrer en bedre adhæsion af det organiske pulver til métallet.The metallic zinc layer of the steel is used directly to provide a sacrificial corrosion protection of metal 1, rather than the use of less effective 10 chemical rinses, such as a zinc phosphate rinse, to deposit a corrosion-protective layer on the surface. Furthermore, the use of chromium compound is avoided, thereby eliminating the risk of harmful waste. A minimum of 15 zinc phosphate layers are deposited on the metal, which ensures a better adhesion of the organic powder to the metal.
Det med pulver overtrukne galvaniserede métal er ejendommeligt ved det i den kendetegnende del af krav 7 angivne.The powder coated galvanized metal is peculiar to that of the characterizing part of claim 7.
20 Fremgangsmâden med fire arbejdstrin ifelge opfindel- sen er soin felger:The four-step process according to the invention is soin rims:
Trin 1. Det ferste trin omfatter en rensning og æts-ning med phosphorsyre. Fedt og snavs fjernes derved, og samtidigt ætses det galvaniserede métal af phos-25 phorsyren, hvilket resulterer i smâ mængder af zink- phosphatkrystaller fordelt tilfældigt over bæremate-rialets overflade.Step 1. The first step comprises a purification and etching with phosphoric acid. Grease and dirt are thereby removed and at the same time the galvanized metal of the phosphoric acid is etched, resulting in small amounts of zinc phosphate crystals distributed randomly over the surface of the carrier material.
Trin 2. Det andet trin er en vandskylning, der f jerner overskud af rense- og ætseoplosning fra trin 1 3 q samt aile salte (chlorider, nitrater, sulfater og lignende), som mâtte være pâ overf laden af bærema-terialet. Som folge af syreoverforing fra trin 1 er derme Rkvlnine· er» mi 1 ri Rvreskvlninff.Step 2. The second step is a water rinse which removes excess cleaning and etching solution from step 13 3 q and all salts (chlorides, nitrates, sulfates and the like) which must be on the surface of the carrier material. As a result of acid transfer from step 1, there is a Rvlnine · er »mi 1 ri Rvreskvlninff.
33
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Trin 3. Det tredje trin er en vandskylning, der an-vendes til fuldstændig fjernelse af rester af blode syre-, sait- eller mineralske rester forblevet pâ overfladen efter trin 2. Dette trin krsever mindre tid, 5 sâfremt vandet opvarmes.Step 3. The third step is a water rinse which is used to completely remove any residual blood acid, sait or mineral residue remaining on the surface after step 2. This step requires less time if the water is heated.
Trin 4. Det fjerde trin omfatter en grundig torring af det galvaniserede métal ved pâfering af varme.Step 4. The fourth step involves a thorough drying of the galvanized metal by the application of heat.
Nedenfor gives en nærmere beskrivelse af hvert af disse arbejdstrin samt af fremgangsmâdeme til ud0velse af 1 o arbejdstrinnene.A detailed description of each of these work steps is provided below as well as the procedures for performing the work steps.
Det forste arbejdstrin til forberedelse af det galva-niserede métal til overtrækning omfatter en rensning og syreætsning til at tilvejebringe en ren og oxid-fri overflade. Dette opnâs ved at anvende en typisk 15 biodegradabel oplosning (en flydende syreoplasning) indeholdende phosphorsyre, oplosningsmidler og over-fladeaktive stoffer, og som kan kebes i handelen til at fjerne let fraktioneret fedt, værkstedssnavs, svej-seflusmidler, oxider og bearbejdningsskæl fra det gal-20 vaniserede métal og i almindelighed ætser metallet mikroskopisk forud for overtrækningen med det organiske pulver. Da rense- og ætsemidler indeholder phosphorsyre, sker der en tilfældig fordeling af en lille mængde zinkphosphatkrystaller resulterende fra den 25 kemiske reaktion af phosphorsyren med zinken over me-tallets overflade. Typisk anvendes der en 3-20 volu-menprocent oplosning af denne syresammensætning ved 45-65°C. Den nejagtige temperaturkoncentration mâ ju-steres til at opnâ en grundig rensning med et mini-30 malt angreb pâ zinken. Oplesningen rummes normalt i et kar, der er sâ stort, at hele emnet af galvaniseret métal kan dyppes ned i den. Det har vist sig, at den minimale dyppetid i denne oplesning er 1,5-5,5 min med et storre tidsbehov, nâr det galvaniserede métal 35 er stærkt forurenet med snavs eller olie eller er ble- 4The first step of preparing the galvanized metal for coating comprises a purification and acid etching to provide a clean and oxide-free surface. This is achieved by using a typical biodegradable solution (a liquid acid solution) containing phosphoric acid, solvents and surfactants, and which can be purchased commercially to remove lightly fractionated grease, workshop dirt, welding fluxes, oxides and working dandruff. -20 vanished metals and generally the metal is etched microscopically prior to coating with the organic powder. Since detergents and etchants contain phosphoric acid, a random distribution of a small amount of zinc phosphate crystals results from the chemical reaction of the phosphoric acid with the zinc over the metal surface. Typically, a 3-20 volume percent solution of this acid composition is used at 45-65 ° C. The exact temperature concentration must be adjusted to achieve a thorough cleaning with a minimal attack on the zinc. The solution is usually housed in a vessel so large that the whole galvanized metal can be immersed into it. It has been found that the minimum dipping time in this readout is 1.5-5.5 minutes with a greater time requirement when the galvanized metal 35 is heavily contaminated with dirt or oil or has become pale.
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vet behandlet med specielle rensemidler af metalhand-leren. I stedet for ved dypning kan rense- og ætseop-lesningen sprejtes pâ det galvaniserede métal.treated with special detergents by the metal dealer. Instead of dipping, the cleaning and etching readings can be sprayed on the galvanized metal.
Det andet arbejdstrin omfatter en vandskylning, der 5 kræves til at f jerne overskydende rensemiddel fra det ferste arbejdstrin samt resterende salte, sâsom chlorider, nitrater eller sulfater, pâ overf laden af bæremateri- alet. Typisk anvendes der postevand, men i. omrâder, hvor vandet har et sterre mineralindhold, kan af-10 ioniseret vand være mere egnet. Det i dette trin benyttede vand bliver let forurenet med det i det tredje arbejdstrin anvendte syrerensemiddel som felge af overferingen af rensemidlet til overfladen af det galvaniserede stâl.The second working step comprises a water rinse required to remove excess detergent from the first working step and residual salts, such as chlorides, nitrates or sulfates, on the surface of the support material. Typically, tap water is used, but in areas where the water has a higher mineral content, deionized water may be more suitable. The water used in this step is easily contaminated with the acid detergent used in the third working step as rims of the transfer of the detergent to the surface of the galvanized steel.
15 Det tredje arbejdstrin omfatter ogsâ en vandskylning.15 The third working step also includes a water rinse.
Som tidligere nævnt kræves der en sâdan vandskylning til at sikre, at hele det opl0ste rensemiddel plus aile tilstedeværende salte og aile salte og minera-ler, som er forblevet pâ overfladen efter det andet 20 arbejdstrin, bliver fjernet.As previously mentioned, such water rinsing is required to ensure that all of the dissolved detergent plus all the salts present and all salts and minerals that remain on the surface after the second 20 working steps are removed.
I det fjerde arbejdstrin skal det behandlede galvaniserede métal terres forud for dets overtrækning med det organiske pulver. Denne terring foretages sædvanligvis ved at indfere det forbehandlede og 25 skyllede galvaniserede métal i en ovn ved en tempe-ratur pâ 55-2.00°C i 2-10 min. til en grundig terring. T3φiske talværdier kan være 120°C i ca. 5 min.In the fourth working step, the treated galvanized metal must be ground prior to its coating with the organic powder. This ring is usually made by inserting the pretreated and rinsed galvanized metal into an oven at a temperature of 55-2.00 ° C for 2-10 minutes. to a thorough ring. T3φ numerical values can be 120 ° C for approx. 5 min.
Efter afslutningen af denne forbehandling i fire ar-20 bejdstrin skal det galvaniserede métal overtrækkes med pulver inden for et kort tidsforl0b eller i det mindste fer der udvikler sig en mængde zinkoxid pâ det galvaniserede métal som folge af andre oxiderings-midlers udsættelse over for atmosfæren. Dette skyl- 5At the end of this pretreatment in four working steps, the galvanized metal must be coated with powder within a short period of time or at least a quantity of zinc oxide in the galvanized metal will develop as a result of exposure to other atmospheric oxidants. This is due 5
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des, at der ifelge opfindelsen ikke aflejres noget passiverende overtræk, og teoretisk skulle det galva-niserede métal overtrækkes med pulveret umiddelbart efter t0rringen. Som felge af begrænsninger i værk-5 stedet og personalekrav har det i praksis dog vist sig, at tidsforsinkelsen imellem terringen (arbejdstrin nr. 4) og pülverovertrækningen af det galvaniserede métal kan spænde fra ca. 5 min til 6 h med en gennemsnit-lig'tidsforsinkelse pà ca. 10 min. Sëlv om 6 h har 110 vist 'sig som værende en overgrænse, er dette en til-nærmëise, idet det er konstateret, sttssâfremt der forldfeer 2 eller 3 dage imellem terringen (det fjarde serbejdstrin ifelge opfindelsen) og pulver-.oveitbr^mingen, vil adhæsionen af overtrækslaget :15 iikies 'vasre ssâ god som ved en tidsforsinkelse pâ fra nmin itü ‘6 h. Indvirkningen af tidsforsinkelsen pâ caveitbrsÊkkets adhæsion vil variera med udsættelsen af ',det gâlvariiserede métal over for temperatur og fug-itighed ((jàksaipelvis inden i en Æygrïing eller uden 20 fer at Usager cqg .lignende).that, according to the invention, no passivating coatings are deposited, and theoretically the galvanized metal should be coated with the powder immediately after drying. However, as rims of limitations in the workshop 5 and personnel requirements, it has been found in practice that the time delay between the ringing (work step # 4) and the powder coating of the galvanized metal can range from approx. 5 minutes to 6 hours with an average delay time of approx. 10 min. Although about 6 hours, 110 has proved to be an upper limit, this is an approximation, as it is found, if there are two or three days between the turret (the fourth working step according to the invention) and the powder coating, the adhesion of the coating layer: 15 iikies 'wash is as good as at a time delay of nmin itü' 6 h. in an Æggrïing or without 20 fer to Usager cqg .like).
Det overtrsèksmaiteriale, der rskal anvendes, er typisk et organisk puiver sâsom epoxy, polyester, acryl eller hybrider, -sorn er blandinger af polyestre og epoxy-pulvere. De typiske epoxyovertrækspulvere er 25 homogène, smelteblandede 100% faststoffer udformet til pâfering pâ metaller.The coating material to be used is typically an organic powder such as epoxy, polyester, acrylic or hybrids, which are mixtures of polyesters and epoxy powders. The typical epoxy coating powders are 25 homogeneous, melt-blended 100% solids designed for metal application.
Det organiske pulverovertræk pâferes typisk ved elek-trostatisk pâsprejtning, men kan ogsâ pâf0res ved at dyppe det behandlede, skyllede og terrede galvanise-30 rede métal i et fluidiseret lag af pulveret. Ved pâ- fering med en elektrostatisk sprejte udsendes pulveret fra en dispersion, som tildeler pulveret en elek-trisk positiv ladning. Da det galvanîserede métal er negativt ladet, tiltrækkes pulveret og bringes til at 35 klæbe til metallet. Den særskilte tykkelse af overtrækslaget er ikke kritisk, men en typisk tykkelse, der harThe organic powder coating is typically applied by electrostatic spraying, but can also be applied by dipping the treated, rinsed and grounded galvanized metal into a fluidized layer of the powder. When applied to an electrostatic syringe, the powder is emitted from a dispersion which imparts an electrically positive charge to the powder. Since the galvanized metal is negatively charged, the powder is attracted and caused to adhere to the metal. The distinct thickness of the coating layer is not critical, but a typical thickness that has
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US22117680A | 1980-12-29 | 1980-12-29 | |
| US22117680 | 1980-12-29 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK145181A DK145181A (en) | 1982-06-30 |
| DK156445B true DK156445B (en) | 1989-08-21 |
| DK156445C DK156445C (en) | 1990-01-22 |
Family
ID=22826681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK145181A DK156445C (en) | 1980-12-29 | 1981-03-31 | PROCEDURE FOR COVERING GALVANIZED METAL WITH AN ORGANIC POWDER AND GALVANIZED METAL WITH SUCH COATING |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0057334B1 (en) |
| JP (1) | JPS57116777A (en) |
| AT (1) | ATE15775T1 (en) |
| AU (1) | AU548696B2 (en) |
| BR (1) | BR8101935A (en) |
| CA (1) | CA1185841A (en) |
| DE (1) | DE3172403D1 (en) |
| DK (1) | DK156445C (en) |
| ES (1) | ES500918A0 (en) |
| GR (1) | GR75616B (en) |
| IE (1) | IE51072B1 (en) |
| MX (1) | MX155753A (en) |
| PT (1) | PT72784B (en) |
| ZA (1) | ZA812177B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19743151A1 (en) | 1997-09-30 | 1999-04-01 | Herberts Pulverlack Gmbh | Powder coating composition, process for its preparation and its use |
| CN114107969A (en) * | 2021-11-26 | 2022-03-01 | 山西汾西重工有限责任公司 | Passivation solution and preparation method of blue-white passivation film |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3674445A (en) * | 1968-05-13 | 1972-07-04 | Jones & Laughlin Steel Corp | Vapor deposited zinc coated metallic substrates having organic coatings |
| JPS4930343B1 (en) * | 1969-12-27 | 1974-08-12 | ||
| JPS4990643A (en) * | 1972-12-29 | 1974-08-29 | ||
| DE2522136A1 (en) * | 1975-05-17 | 1976-11-25 | Goldschmidt Ag Th | Coating dipmetallised articles - with drying or hardening resin coating compns. applied directly after metallising to utilise residual heat |
| JPS5552352U (en) * | 1978-10-02 | 1980-04-07 | ||
| JPS55148177A (en) * | 1979-05-08 | 1980-11-18 | Nec Corp | Printing head for matrix printer |
| JPS5637176A (en) * | 1979-09-03 | 1981-04-10 | Oki Electric Ind Co Ltd | Printing head for dot printer |
-
1981
- 1981-03-31 AT AT81400514T patent/ATE15775T1/en active
- 1981-03-31 ES ES500918A patent/ES500918A0/en active Granted
- 1981-03-31 DK DK145181A patent/DK156445C/en not_active IP Right Cessation
- 1981-03-31 DE DE8181400514T patent/DE3172403D1/en not_active Expired
- 1981-03-31 BR BR8101935A patent/BR8101935A/en unknown
- 1981-03-31 IE IE735/81A patent/IE51072B1/en unknown
- 1981-03-31 EP EP81400514A patent/EP0057334B1/en not_active Expired
- 1981-04-01 GR GR64548A patent/GR75616B/el unknown
- 1981-04-01 PT PT72784A patent/PT72784B/en unknown
- 1981-04-01 AU AU68987/81A patent/AU548696B2/en not_active Ceased
- 1981-04-01 ZA ZA00812177A patent/ZA812177B/en unknown
- 1981-04-01 MX MX186672A patent/MX155753A/en unknown
- 1981-04-01 JP JP56047326A patent/JPS57116777A/en active Granted
- 1981-04-03 CA CA000374660A patent/CA1185841A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| MX155753A (en) | 1988-04-22 |
| AU6898781A (en) | 1982-07-08 |
| GR75616B (en) | 1984-08-01 |
| EP0057334A3 (en) | 1982-12-08 |
| JPH0242906B2 (en) | 1990-09-26 |
| DK145181A (en) | 1982-06-30 |
| BR8101935A (en) | 1982-11-03 |
| DK156445C (en) | 1990-01-22 |
| PT72784B (en) | 1983-01-10 |
| ES8205884A1 (en) | 1982-07-16 |
| CA1185841A (en) | 1985-04-23 |
| PT72784A (en) | 1981-05-01 |
| JPS57116777A (en) | 1982-07-20 |
| ATE15775T1 (en) | 1985-10-15 |
| AU548696B2 (en) | 1986-01-02 |
| ZA812177B (en) | 1982-12-29 |
| ES500918A0 (en) | 1982-07-16 |
| EP0057334A2 (en) | 1982-08-11 |
| IE51072B1 (en) | 1986-09-17 |
| EP0057334B1 (en) | 1985-09-25 |
| DE3172403D1 (en) | 1985-10-31 |
| IE810735L (en) | 1982-06-29 |
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