EP0385806B1 - Phosphatbeschichtungen für Metalloberflächen - Google Patents

Phosphatbeschichtungen für Metalloberflächen Download PDF

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Publication number
EP0385806B1
EP0385806B1 EP90302271A EP90302271A EP0385806B1 EP 0385806 B1 EP0385806 B1 EP 0385806B1 EP 90302271 A EP90302271 A EP 90302271A EP 90302271 A EP90302271 A EP 90302271A EP 0385806 B1 EP0385806 B1 EP 0385806B1
Authority
EP
European Patent Office
Prior art keywords
ion
phosphate
particles
phosphate solution
acidic aqueous
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 - Lifetime
Application number
EP90302271A
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English (en)
French (fr)
Other versions
EP0385806A1 (de
Inventor
Koetu Endo
Akio Tokuyama
Tamotsu Sobata
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.)
Nippon Paint Co Ltd
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Nippon Paint Co Ltd
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Filing date
Publication date
Application filed by Nippon Paint Co Ltd filed Critical Nippon Paint Co Ltd
Publication of EP0385806A1 publication Critical patent/EP0385806A1/de
Application granted granted Critical
Publication of EP0385806B1 publication Critical patent/EP0385806B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/14—Orthophosphates containing zinc cations containing also chlorate anions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/16—Orthophosphates containing zinc cations containing also peroxy-compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/362—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations

Definitions

  • the present invention relates to a process for phosphating a metal surface to be coated with a coating composition. More particularly, it relates to a process for forming a phosphate film on a metal surface, which is specifically suitable for cationic electro-coating and is excellent in film adhesion, corrosion resistance and especially hot brine resistance, and scab corrosion resistance.
  • phosphate coating by dipping the desired phosphating is only obtained by treating a metal with a phosphate solution containing a higher concentration, i.e. about 2 to 4g/l, of zinc ion, at a higher temperature (60 to 90°C) for a comparatively longer duration of time (3 ⁇ 10 minutes), and further more, thus obtained coating, having a comparatively high coating weight (3 ⁇ 5g/m2) and bad quality, is believed to be unsuitable as a base coat and especially a base coat for electrodeposition coating because of its poor adhesion , corrosion resistance, coating appearance or the like.
  • JP-A-55107784 a novel technique has been proposed in JP-A-55107784, in which a metal surface is treated by dipping means with an acidic aqueous phospate solution containing controlled amounts of zinc ion, phosphate ion and phosphating accelerator as nitrite ion, at a lower temperature for a short period of time, obtaining a uniform dense phosphating coating having a comparatively low coating weight, being excellent in adhesion and anticorrosion properties and being specifically useful as an under coat for electrodeposition coating. Since then, such a dipping method has again moved into the limelight in the related technical fields.
  • a metal surface is first treated by dipping with an acidic aqueous phosphate solution containing from 0.5 to 1.5g/l of zinc ion, from 5 to 30g/l of phosphate ion, and from 0.01 to 0.2g/l nitrite ion as main ingredients, at 40 ⁇ 70°C for 15 to 120 seconds and then treated, for the purpose of removing the remained sludge, by spraying with the same phosphate solution at 40 ⁇ 70°C for 2 to 60 seconds, to obtain a uniform and dense phosphate film with a low coating weight of 1.5 ⁇ 3g/m2, which is useful as an under coat for electrodeposition coating.
  • This technique is very useful for the treatment of iron-based surface and however, is not for the treatment of zinc-based surface because of resulting a phosphate coating having inferior secondary adhesion for intermediate and top coats and brine-spraying resistance of the electrodeposited coating.
  • a far improved phosphating process applicable to not only iron-based surface, but also to a zinc-based surface or a metal surface including both iron-based and zinc-based surfaces has been a pressing need.
  • EP-A-201228 discloses a stress coating composition containing colloidal silica, a metal phosphate, and hexavalent chromium, in which 5-50% of the colloidal silica is replaced by powdered silica of the general particle size 0.001 - 0.1 ⁇ m.
  • scab corrosion resistance i.e. resistance to the formation of scabby rusts formed on iron-based surface when injured coating is repeatedly subjected to brine or dry-wet climatical changes
  • hot brine resistance i.e. resistance to the formation of scabby rusts formed on iron-based surface when injured coating is repeatedly subjected to brine or dry-wet climatical changes
  • no good solution has been found out in having a higher degree of scab corrosion resistance and hot brine resistance as desired.
  • steel had once been the major substrate, which had been customarily phosphated by spraying treatment. Even it that area, galvanized steel is increasing a share of the substrate material, because of its excellent corrosion resistance.
  • an object of the invention to provide a process for forming a phosphate film on both iron-based surface and a metal surface including iron-based surface and zinc-based surface. Another object of the invention is to provide a process for forming a phosphate film which is suitable for coating and especially electrodeposition coating. A further object of the invention is to provide a process for forming a phosphate film which is excellent in scab resistance when applied on iron-based surface, excellent in hot brine resistance when applied on iron-based surface or zinc-based surface, and is excellent in secondary adhesion when applied with an intermediate or top coat thereupon.
  • the abovementioned and other objects can be attained with a process for phosphating a metal surface with an acidic aqueous phosphate solution containing 0.01 to 10g/l of colloidal particles having an isoelectric point of 3 or less and an average particle diameter of 0.1 ⁇ or less.
  • the invention had been made on the basis of our novel finding that the desired effects of such colloidal particles are fully attained when zinc ion, nickel ion, manganese ion and fluoride ion are present each in defined concentration range in an acidic aqueous phosphate solution.
  • the advantage of the present invention is most prominently exhibited when the treatment is carried out on metal surfaces which include both an iron-based surface and a zinc-based surface, or an iron-based surface alone. However, it is likewise useful for a zinc-based surface, and thus, the present process in widely applicable to various metal surfaces, including galvanized steel plate, galvanealed steel plate, electro galvanized steel plate, electro zinc-alloy plated steel plate, complex electro galvanized steel plate and the like.
  • a metal surface is first subjected to a spray treatment and/or a dip treatment with an alkaline degreasing agent at 20 ⁇ 60°C for about 2 minutes and washed with tap-water.
  • the washed metal is treated with a surface conditioner by spraying and/or dipping in the surface conditioner solution at a room temperature for 10 ⁇ 30 seconds, and subsequently, thus treated metal is subjected to the present process, i.e. treating the metal surface with the present acidic aqueous phosphate solution at 20 ⁇ 70°C for 15 seconds or more, by dipping and/or spraying means, and finally washed with tap-water and then with a deionized water.
  • the zinc ion concentration in the present phosphate solution should be in a range of 0.1 to 2.0g/l and more preferably 0.3 to 1.5g/l.
  • the zinc ion content in said acidic phosphate solution is less than 0.1g/l, an even phosphate film cannot be formed on the iron-based surfaces, resulting an uneven, partly blue-colored film.
  • the zinc ion content exceeds over 2.0g/l, there indeed results an even phosphate film but since the formed film is liable to be easily dissolved in an alkaline solution and especially in an alkaline atmosphere exposed at the time of cationic electrodeposition, it is unable to use the phosphated substrate for electrodeposition coating and especially for cationic electrodeposition coating. At that time, there is an undesired decrease in hot brine resistance in general, and scab resistance in the case of iron-based surface.
  • the content of phosphate ion in the present acidic phosphate solution should be limited in a range of 5 to 40g/l, and preferably 10 to 30g/l.
  • the content of phosphate ion in the above solution is less than 5g/l, an uneven phosphate film is apt to be formed.
  • the phosphate content is more than 40g/l, no further benefits result, and it is therefore economically disadvantageous to use additional quantities of phosphate chemicals.
  • the content of colloidal particles having an isoelectric point of 3 or less and an average particle diameter of 0.1 ⁇ or less should be selected in a range of 0.01 to 10g/l, preferably 0.05 to 5g/l.
  • Average diameter of such particles should be in a range of 0.001 ⁇ to 0.1 ⁇ , the ,lower limit being the minimum diameter for colloidal dispersion and the upper limit being fixed for the intended objects and effects of improvements in scab resistance, hot brine resistance and the like.
  • the isolectric point of such particles is one of the characteristics showing an electrification tendency of the particles, and electrification may vary with pH of the aqueous dispersion of said particles.
  • the colloidal particles used in the present invention are acidic particles capable of being electrified in negative in an acidic aqueous phosphate solution.
  • the colloidal particles having an isoelectric point of more than 3 are used in the present phosphate solution, these particles are aggregated, resulting sludges, and the intended objects of modification of phosphate film can not be attained therewith.
  • a phosphating accelerator the following are used:
  • Test results The test results are shown in Table 2.
  • the test methods used are as follows:
  • Example 3 The similar coated plates were prepared as in Example 1 excepting adding a post-treatment after washing step (e) and before pure water washing step (f), the post-treatment comprising dipping the washed plate into Surflite 41 (chromic post-treating agent, 0.4wt% content, made by Nippon Paint Co.) at 50°C for 15 seconds.
  • Surflite 41 chromic post-treating agent, 0.4wt% content, made by Nippon Paint Co.
  • Example 7 The similar procedures as stated in Example 7 were repeated excepting substituting Surflite 70AN-1 (zirconium base post-treating agent, 1.0wt% content, made by Nippon Paint Co.) for Surflite 41.
  • the test results with thus obtained coated plates were shown in Table 3.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Claims (7)

  1. Verfahren zum Phosphatieren einer Metalloberfläche, umfassend Kontaktieren der Metalloberfläche mit einer sauren wäßrigen Phosphatlösung, welche enthält:
    (a) von 0,1 bis 2,0 g/l Zink-Ion;
    (b) von 5 bis 40 g/l Phosphat-Ion;
    (c) einen Phosphatierungsbeschleuniger, enthaltend:
    (i) von 0,01 bis 0,5 g/l Nitrit-Ion,
    (ii) von 0,05 bis 5 g/l m-Nitrobenzolsulfonat-Ion, oder
    (iii) von 0,5 bis 10 g/l Wasserstoffperoxid (bezogen auf 100 % H₂O₂); sowie
    (d) von 0,01 bis 10 g/l kolloidale Teilchen mit einem isoelektrischen Punkt von 3 oder weniger und einem mittleren Teilchendurchmesser von 0,1 Mikrometer oder weniger; und
    nachfolgendem Abspülen der Lösen von der Oberfläche.
  2. Verfahren nach Anspruch 1, bei welchem die kolloidalen Teilchen ein oder mehrere Silica-Teilchen, Silica-Aluminiumoxid-Teilchen, Silica-Titandioxid-Teilchen, Silica-Zirconiumdioxid-Teilchen, Antimonoxid-Teilchen und Acrylharz-Teilchen umfassen.
  3. Verfahren nach Anspruch 1 oder 2, bei welchem die saure wäßrige Phosphatlösung ferner bis zu 3 g/l Mangan-Ion enthält.
  4. Verfahren nach Anspruch 1 oder 2, bei welchem die saure wäßrige Phosphatlösung ferner bis zu 6 g/l Nickel-Ion enthält.
  5. Verfahren nach Anspruch 1 oder 2, bei welchem die saure wäßrige Phosphatlösung ferner bis zu 4 g/l Fluorid-Ion enthält.
  6. Verfahren nach Anspruch 1 oder 2, bei welchem die saure wäßrige Phosphatlösung ferner bis zu 15 g/l Nitrat-Ion und/oder weniger als 2 g/l Chlorat-Ion enthält.
  7. Verfahren nach einem der vorhergehenden Ansprüche oder nach Anspruch 2, bei welchem die Behandlung bei einer Temperatur von 20-70°C ausgeführt wird.
EP90302271A 1989-03-02 1990-03-02 Phosphatbeschichtungen für Metalloberflächen Expired - Lifetime EP0385806B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP1050567A JPH0819531B2 (ja) 1989-03-02 1989-03-02 金属表面のリン酸亜鉛処理方法
JP50567/89 1989-03-02

Publications (2)

Publication Number Publication Date
EP0385806A1 EP0385806A1 (de) 1990-09-05
EP0385806B1 true EP0385806B1 (de) 1994-09-14

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ID=12862581

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90302271A Expired - Lifetime EP0385806B1 (de) 1989-03-02 1990-03-02 Phosphatbeschichtungen für Metalloberflächen

Country Status (3)

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EP (1) EP0385806B1 (de)
JP (1) JPH0819531B2 (de)
DE (1) DE69012374T2 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4029956A1 (de) * 1990-09-21 1992-03-26 Metallgesellschaft Ag Phosphatierverfahren
DE19621184A1 (de) * 1996-05-28 1997-12-04 Henkel Kgaa Zinkphosphatierung mit integrierter Nachpassivierung
JP3669844B2 (ja) * 1998-08-13 2005-07-13 日本ペイント株式会社 リン酸系前処理を含むノンクロム防錆方法
US6743302B2 (en) 2000-01-28 2004-06-01 Henkel Corporation Dry-in-place zinc phosphating compositions including adhesion-promoting polymers
JP4727840B2 (ja) * 2001-04-19 2011-07-20 株式会社神戸製鋼所 加工性及び耐食性に優れた被覆鋼板、並びにその製造方法
RU2510432C1 (ru) * 2012-09-12 2014-03-27 Открытое акционерное общество "Сибнефтепровод" (ОАО "Сибнефтепровод") Состав для удаления коррозии и консервации поверхностей металлоконструкций и труб перед их покраской
DE102013107505A1 (de) * 2013-07-16 2015-01-22 Thyssenkrupp Rasselstein Gmbh Verfahren zum Auftragen einer wässrigen Behandlungslösung auf die Oberfläche eines bewegten Stahlbands
CN103695881B (zh) * 2013-12-19 2016-08-24 湖南金裕化工有限公司 常温无渣快速磷化液及其制备方法
CN103668149B (zh) * 2013-12-19 2016-08-24 湖南金裕化工有限公司 常温快速磷化液及其制备方法
CN111321397B (zh) * 2020-04-14 2023-08-04 安徽江南泵阀集团有限公司 一种提高不锈钢泵表面磷化性能的方法
WO2022135778A1 (de) * 2020-12-22 2022-06-30 M-M-Morant-Gmbh Chrom(vi)-freies beschichtungsmittel für metalle

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0201228A2 (de) * 1985-04-30 1986-11-12 Allegheny Ludlum Steel Corporation Kornorientierter Siliziumstahl und Spannungsdeckschicht dafür

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4673444A (en) * 1981-03-16 1987-06-16 Koichi Saito Process for phosphating metal surfaces
JPS57152472A (en) * 1981-03-16 1982-09-20 Nippon Paint Co Ltd Phosphating method for metallic surface for cation type electrodeposition painting
DE3712339A1 (de) * 1987-04-11 1988-10-20 Metallgesellschaft Ag Verfahren zur phosphatierung vor der elektrotauchlackierung

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0201228A2 (de) * 1985-04-30 1986-11-12 Allegheny Ludlum Steel Corporation Kornorientierter Siliziumstahl und Spannungsdeckschicht dafür

Also Published As

Publication number Publication date
JPH02228482A (ja) 1990-09-11
EP0385806A1 (de) 1990-09-05
DE69012374T2 (de) 1995-03-30
DE69012374D1 (de) 1994-10-20
JPH0819531B2 (ja) 1996-02-28

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