EP0760871B1 - Procede de revetement de substrats metalliques phosphates - Google Patents

Procede de revetement de substrats metalliques phosphates Download PDF

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Publication number
EP0760871B1
EP0760871B1 EP95920868A EP95920868A EP0760871B1 EP 0760871 B1 EP0760871 B1 EP 0760871B1 EP 95920868 A EP95920868 A EP 95920868A EP 95920868 A EP95920868 A EP 95920868A EP 0760871 B1 EP0760871 B1 EP 0760871B1
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EP
European Patent Office
Prior art keywords
organic
coating
metal substrates
phosphating
process according
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
EP95920868A
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German (de)
English (en)
Other versions
EP0760871A1 (fr
Inventor
Gabriele Büttner
Matthias Kimpel
Klausjörg Klein
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
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Publication date
Application filed by Herberts GmbH filed Critical Herberts GmbH
Publication of EP0760871A1 publication Critical patent/EP0760871A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • 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
    • 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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment

Definitions

  • the invention relates to a method for coating phosphated Metal substrates with organic coatings, in particular Electrocoat coatings.
  • Pretreatment of metallic substrates e.g. made of aluminium, but especially from galvanized or non-galvanized steel, for one Painting, in particular for an electrophoretically to be applied Dip painting, exists when good corrosion protection is desired and good substrate adhesion by electrophoretic deposition generated coating layer should be achieved from a phosphating and a passivating rinse. Then on this surface the electrocoat is applied and baked.
  • JP-A-58 130 282 describes the treatment of phosphated surfaces with aqueous, Fe, Zn, Ni, Mo, Co, W, Mg, Mn or Si solutions described before coating the surfaces receive.
  • the SU-A-914652 describes the increase in wear resistance and the electrical conductivity of castings by treating a porous Phosphate coating with aqueous solutions of the formates and / or oxalates of Ag, Cu, Pb and / or Bi and then heating the treated surfaces to the Decomposition temperature of the salts.
  • the object of the present invention is a coating method to provide for phosphated metal substrates, which the Corrosion protection increases beyond the level reached.
  • the Coating method should preferably be composed with simple and ecologically and health-friendly after-treatment materials be feasible. It should also allow a high one Generate level of corrosion protection if the previous one Phosphating is based on a concept for ecological reasons, which leads to only moderate corrosion protection. In particular, should the coating process allow chrome, nickel and nitrite free work.
  • this object can be achieved by a method for coating phosphated metal substrates with one or more organic coatings, which is characterized in that the phosphated metal substrates are free of nickel after phosphating in a phosphating solution and before application of the first organic coating can be treated with an aqueous solution which contains 5 to 10,000 ppm of dissolved bismuth in the form of inorganic and / or organic compounds, and deposits the element in a total amount of 5 to 100 mg / m 2 .
  • the phosphated metal substrates are preferred throughout or part of the Treatment time switched additionally as cathode.
  • metal parts can be used as metallic substrates, as they are common in the automotive industry, for example.
  • metallic substrates can be used as metallic substrates, as they are common in the automotive industry, for example.
  • components made of aluminum, magnesium or their alloys, iron and especially steel, e.g. non-galvanized or with pure zinc, zinc-nickel alloy or zinc-iron alloy galvanized.
  • the different Substrates can coexist on a workpiece (Mixed construction).
  • the metallic substrates are phosphated in the usual way, i.e. using phosphating solutions known per se. It can for example, such as those used by Horst Gehmecker in JOT, No. 5, 1992 pages 42 to 46. It is e.g. around Contains zinc, manganese, iron and / or nickel Phosphating materials.
  • Nickel ions proved to be particularly advantageous with regard to Generation of a high level of corrosion protection.
  • the Phosphating layers can be sprayed or immersed be applied.
  • the solutions become on the surface of the Metal substrate deposited a thin layer of phosphate crystals. This should be as dense and fine-grained as possible.
  • After phosphating the metal substrate is rinsed and optionally dried before it according to the invention before application of the organic coating with a aqueous solution containing 5 to 10,000 ppm of bismuth dissolved in Contains form of inorganic and / or organic compounds treated becomes.
  • the treatment with the aqueous solution can, for example, in Dipping method with an exposure time of, for example, between 1 and 120 seconds.
  • Dipping method with an exposure time of, for example, between 1 and 120 seconds.
  • the immersion process prefers.
  • the dipping process is particularly preferably carried out in such a way that aqueous solutions which contain 5 to 10,000 ppm of dissolved bismuth in the form of inorganic and / or organic compounds are used, the phosphated metal substrate being additionally connected as a cathode in a DC circuit during the treatment.
  • the treatment vessel can serve as an anode, and a counter electrode can be inserted.
  • This procedure also leads to the removal of interfering anions from the phosphate layer.
  • a DC voltage in the range from 3 to 100 V, preferably 5 to 50 V, is preferably used, current densities of 0.1 to 10 A / m 2 being used, the current flow being able to exist during the entire immersion period or the current only flows during part of the immersion period.
  • the current strength can be kept constant during the current flow or the current strength is varied.
  • aqueous solutions that can be used in the process according to the invention those containing 5 to 10,000 ppm, preferably above 10 and below 6000 ppm, dissolved bismuth in the form of inorganic and / or organic compounds included, calculated as an element.
  • the inorganic and / or organic compounds of the above Elements bismuth mentioned are readily water-soluble or they have one sufficient water solubility to maintain as a source a concentration of 5 to 10,000 ppm of the above Elements bismuth can be used in the aqueous solutions.
  • those used in the aqueous solutions Compounds as a finely divided colloidal solution or dispersion and have a depot effect for the element bismuth.
  • Inorganic or organic compounds are inorganic or organic complex compounds of bismuth.
  • An example of a chelating ligand is acetylacetone called.
  • Preferred inorganic or however, organic compounds are the corresponding salts inorganic or preferably organic acids.
  • salts inorganic acids are chlorides, sulfates and nitrates.
  • organic Acids serve, for example, mono- or polycarboxylic acids, e.g.
  • the salts of monocarboxylic acids such as, for example, are preferred Benzoates, formates, acetates, propionates, octoates, neodecanoates.
  • aqueous media which are 5 to 10000 ppm, preferably between 10 and 6000 ppm, of dissolved bismuth included, most preferred.
  • Bismuth is preferred in form a salt of a mono- or polycarboxylic acid.
  • suitable organic carboxylic acids of which in the invention Bismuth salts that can be used are aromatic, araliphatic and aliphatic mono- or dicarboxylic acids.
  • Prefers are the bismuth salts of organic monocarboxylic acids, especially with more than two carbon atoms, such as bismuth benzoate, propionate, -octoate, -neodecanoate.
  • the bismuth salts of are particularly preferred "Hydroxycarboxylic acids. Examples are bismuth salicylate, -4-hydroxybenzoate, lactate, dimethylol propionate.
  • aqueous solutions contain customary auxiliaries, e.g. Surfactants.
  • the phosphated metal substrates During the treatment of the phosphated metal substrates with the aqueous solution, the latter is depleted of the corresponding element by incorporating an appropriate amount of the same on the surface of the phosphated metal substrate. This does not result in galvanic deposition of the corresponding element or elements on the phosphate layer in the form of a closed coating, but rather the method according to the invention is carried out in such a way that the element is present in a total amount of 5 to 100 mg / m 2 on the surface of the phosphated one Deposit metal substrate.
  • the phosphate layer is doped with the element.
  • EDX energy-dispersive X-ray analysis
  • the composition of the aqueous solution is preferably continuous monitored analytically, for example using appropriate ion selective electrodes. According to the measured consumption Element in the aqueous solution must be replenished, for example by adding an appropriate aqueous concentrate. If you work with salt solutions of the element, see above the counter anion accumulates as a free acid in the consumption of Elements corresponding way. By dragging out when diving However, the substrates from the solution will accumulate free acid withdrawn from the system in sufficient quantities and it sets in Balance one. This dragging effect occurs in particular Wear when the phosphated metal substrates are concerned three-dimensional and thus creating objects.
  • the immersion bath with the aqueous solution can also with a Electrodialysis circuit to be coupled, which serves the purpose to remove enriching free acid from the immersion bath.
  • the substrates can be rinsed with solution, e.g. with deionized water, and dried before using according to the invention can be provided with an organic coating.
  • the Organic coatings can be made from aqueous or non-aqueous Coating agents, preferably stoving coating agents, are applied, for example by spraying, dipping or rolling. To be favoured the organic coatings by electrocoating (ETL), especially preferably applied by cataphoretic dip painting (KTL).
  • ETL electrocoating
  • KTL cataphoretic dip painting
  • electrodeposition paints in the process according to the invention per se known electrodeposition lacquers which can be deposited on the anode or are preferred cathodic electrodeposition coatings can be used. she are not subject to any limitation. You can use the usual additives and Contain catalysts.
  • Electrocoating paints are aqueous coating compositions with a solids content of for example 10-20% by weight.
  • the solids content consists of usual binders that are ionic or in ionic groups transferable substituents and those capable of chemical crosslinking Wear groups, and optionally pigments and / or fillers and other additives.
  • the ionic groups can be anionic or in groups convertible to anionic groups, e.g. -COOH groups or cationic or convertible basic groups, e.g. Amino, ammonium, e.g. quaternary ammonium, phosphonium and / or Be sulfonium groups. Binders with basic are preferred Groups.
  • Nitrogen-containing basic groups are particularly preferred. These groups can be quaternized or they can be combined with a usual neutralizing agents, e.g. an organic monocarboxylic acid, such as. Lactic acid, formic acid, acetic acid, as the expert common, converted into ionic groups.
  • a neutralizing agents e.g. an organic monocarboxylic acid, such as. Lactic acid, formic acid, acetic acid, as the expert common, converted into ionic groups.
  • anionic groups containing anodic electrodeposition paint binders and paints are described in DE-A-28 24 418. These are, for example, binders based on polyesters, epoxy resin esters, (meth) acrylic copolymers, maleate oils or polybutadiene oils with a weight average molecular weight of, for example, 300-10000 and an acid number of 35-300 mg KOH / g.
  • the binders carry -COOH, -SO 3 H and / or -PO 3 H 2 groups. After neutralization of at least some of the acidic groups, the resins can be converted into the water phase.
  • the lacquers can also contain customary crosslinking agents, for example triazine resins, crosslinking agents which contain groups capable of transesterification and / or transamidation, or blocked polyisocyanates.
  • cathodic electrocoat materials are preferred cationic or basic binders.
  • Such basic resins are for example primary, secondary and / or tertiary amino groups resins containing, the amine numbers e.g. at 20 to 250 mg KOH / g lie.
  • the weight average molecular weight (Mw) of the base resins is preferably from 300 to 10,000.
  • Examples of such base resins are Amino (meth) acrylic copolymer resins, amino epoxy resins, amino epoxy resins with terminal double bonds, amino epoxy resins with primary OH groups, Aminopolyurethane resins, amino group-containing polybutadiene resins or modified epoxy resin-carbon dioxide-amine reaction products.
  • This Base resins can be self-crosslinking or they are known Crosslinkers used in the mixture.
  • crosslinkers are Aminoplast resins, blocked polyisocyanates, crosslinkers with terminal Double bonds, polyepoxide compounds or crosslinkers contain groups capable of transesterification and / or transamidation.
  • Examples of cathodic dip lacquer (KTL) baths Base resins and crosslinking agents which can be used according to the invention, are in EP-A-0 082 291, EP-A-0 234 395, EP-A-0 209 857, EP-A-0 227 975, EP-A-0 178 531, EP-A-0 333 327, EP-A-0 310 971, EP-A-0 456 270, US 3,922,253, EP-A-0 261 385, EP-A-0 245 786, DE-33 24 211, EP-A-0 414 199, EP-A-0 476 514. These resins can be used alone or in Mixture can be used.
  • ETL coating agent pigments In addition to the base resins and any crosslinking agents present can the electrocoat (ETL) coating agent pigments, fillers and / or conventional paint additives. They come as pigments usual inorganic and / or organic pigments in question. Examples are carbon black, titanium dioxide, iron oxide, kaolin, talc or Silicon dioxide. It is also possible to use common anti-corrosion pigments to use. Examples include zinc phosphate, lead silicate or organic corrosion inhibitors. The type and amount of pigments depends on the intended use of the coating agent. Should be clear Coatings are obtained, so no or only transparent Pigments such as micronized titanium dioxide or silicon dioxide used. If opaque coatings are to be applied, so are preferably contain coloring pigments in the electrocoating bath.
  • the pigments can be dispersed into pigment pastes, e.g. under Use of known paste resins. Such resins are known to the person skilled in the art common. Examples of paste resins that can be used in KTL baths are in EP-A-0 183 025 and EP-A-0 469 497.
  • ETL coating agents include wetting agents, neutralizing agents, leveling agents, Catalysts, anti-foaming agents and conventional ones in coating agents solvents used.
  • the coating is applied Branding networked. If it is a primer, you can Subsequent layers are applied.
  • a coating is obtained with the process according to the invention excellent adhesion to the substrate and excellent Corrosion protection, which is the level of previously known coatings from phosphating, usual passivation and organic coating, exceed.
  • the method according to the invention avoids the use of Nickel, chrome and nitrite.
  • the phosphating agent can work free of environmental and metal compounds that are hazardous to health.
  • the invention allows the after-treatment of the phosphate layer with simple to carry out aqueous solutions.
  • Example 1 To 223 parts of the paste resin according to EP-A-0 469 497 Al Example 1 (55%) 15 parts of acetic acid (50%) are 30 parts of a commercial wetting agent (50%) and 374 parts given deionized water.
  • Example 3 4.5 parts are added to 815.5 parts of the dispersion from Example 2 Formic acid (50%) and 1760 parts of deionized water. Under 420 parts of pigment paste according to Example 3 are added with thorough stirring.
  • a non-galvanized steel sheet (ST 1405) Bonder R 26/60 / 0C (for testing purposes, a so-called “Bonder” sheet sold by Chemetall with a pretreatment of nickel-containing trication phosphating and chromic acid passivation) is coated with the KTL from Example 4 in a 20 ⁇ m dry layer thickness and Baked for 10 min at 175 ° C (object temperature).
  • a commercially available filler is then sprayed on in a 35 ⁇ m dry layer and baked for 15 minutes at 165 ° C (object temperature).
  • a single-coat topcoat suitable for automotive serial painting is applied by spraying in a thickness of 40 ⁇ m and baked for 30 minutes at 130 ° C (object temperature).
  • Example 5a is repeated, however, using a steel sheet (ST 1405) Bonder R 2640 / W / OC ("bonder" sheet sold for experimental purposes by Chemetall with a pretreatment consisting of nickel-free trication phosphating without passivation).
  • Bonder R 2640 / W / OC (“bonder” sheet sold for experimental purposes by Chemetall with a pretreatment consisting of nickel-free trication phosphating without passivation).
  • Example 5c (example according to the invention)
  • Example 5b is repeated with the difference that before the KTL is applied, the sheet is immersed for 10 seconds at room temperature in an aqueous solution of the bismuth salt from Example 1 with a bismuth content of 1000 ppm and then rinsed with deionized water and dried. During the immersion, the sheet is switched as a cathode at a voltage of 10 volts and a current density of 1.5 A / m 2 .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Insulated Metal Substrates For Printed Circuits (AREA)

Claims (7)

  1. Procédé de revêtement de substrats métalliques avec une ou plusieurs couches organiques, dans lequel on phosphate ies substrats métalliques dans une solution de phosphatation qui est dépourvue de nickel et on traite les substrats ainsi phosphatés après la phosphatation et avant le dépôt de la première couche organique avec une solution aqueuse, caractérisé en ce qu'on traite avec une solution aqueuse qui contient entre 5 et 10000 ppm de bismuth dissous sous forme de composés minéraux ou organiques et extrait l'élément en une quantité totale comprise entre 5 et 100 mg/m3.
  2. Procédé selon la revendication 1, caractérisé en ce que les substrats métalliques phosphatés pendant le traitement global ou une partie de la durée de traitement sont de plus connectés en tant que cathode.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la solution aqueuse contient un ou plusieurs sels d'acides organiques et/ou minéraux de bismuth.
  4. Procédé selon la revendication 3, caractérisé en ce qu'on utilise comme acides organiques des acides mono ou polycarboxyliques.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution aqueuse contient des sels de bismuth d'acides hydroxycarboxyliques.
  6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les couches organiques sont déposées en utilisant des moyens de revêtement par recuit.
  7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que comme couche organique, on dépose par trempage électrophorétique une laque électrophorétique,
EP95920868A 1994-05-27 1995-05-23 Procede de revetement de substrats metalliques phosphates Expired - Lifetime EP0760871B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4418491 1994-05-27
DE4418491 1994-05-27
PCT/EP1995/001957 WO1995033083A1 (fr) 1994-05-27 1995-05-23 Procede de revetement de substrats metalliques phosphates

Publications (2)

Publication Number Publication Date
EP0760871A1 EP0760871A1 (fr) 1997-03-12
EP0760871B1 true EP0760871B1 (fr) 1998-05-06

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EP95920868A Expired - Lifetime EP0760871B1 (fr) 1994-05-27 1995-05-23 Procede de revetement de substrats metalliques phosphates

Country Status (10)

Country Link
US (1) US5773090A (fr)
EP (1) EP0760871B1 (fr)
JP (1) JPH10501027A (fr)
KR (1) KR970703447A (fr)
AT (1) ATE165874T1 (fr)
BR (1) BR9507776A (fr)
CA (1) CA2190945A1 (fr)
DE (1) DE59502118D1 (fr)
MX (1) MX9605901A (fr)
WO (1) WO1995033083A1 (fr)

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DE10010758A1 (de) * 2000-03-04 2001-09-06 Henkel Kgaa Korrosionsschutzverfahren für Metalloberflächen
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EP1302566B1 (fr) * 2001-10-11 2004-02-04 FRANZ Oberflächentechnik GmbH & Co KG Production d'une région de surface métalliquement conductive sur des alliages Al-Mg oxydés
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US20090169903A1 (en) * 2007-12-27 2009-07-02 Kansai Paint Co., Ltd. Process for producing metal substrate with multilayer film, metal substrate with multilayer film obtained by the process, and coated article
US8192801B2 (en) * 2008-04-25 2012-06-05 GM Global Technology Operations LLC Self-deposited coatings on magnesium alloys
BRPI0912295A2 (pt) * 2008-05-29 2015-10-20 Nihon Parkerizing material metálico com uma película de bismuto aplicada e método para a produção do mesmo, líquido para o tratamento da superfície usado no método, e material metálico revestido por eletrodeposição catiônica e método para a produção do mesmo
US8187439B2 (en) * 2009-08-05 2012-05-29 GM Global Technology Operations LLC Electrocoating process for mixed-metal automotive bodies-in-white
US10766821B2 (en) 2014-06-16 2020-09-08 Latitude 18, Inc. Inorganic-organic phosphate ceramics and coatings
US20160229386A1 (en) * 2015-02-06 2016-08-11 GM Global Technology Operations LLC Transmission assembly with electrical noise reduction and method of making and using the same
BR112017021409B1 (pt) * 2015-04-07 2023-02-28 Chemetall Gmbh Método para fosfatação de uma superfície metálica, e, superfície metálica revestida com fosfato
EP3659998B1 (fr) 2017-07-27 2021-05-19 Tokyo Ohka Kogyo Co., Ltd. Composé amine aromatique ainsi que procédé de fabrication de celui-ci, agent de durcissement pour composé époxy, composition durcissable, et objet durci ainsi que procédé de fabrication de celui-ci

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Also Published As

Publication number Publication date
DE59502118D1 (de) 1998-06-10
MX9605901A (es) 1997-12-31
US5773090A (en) 1998-06-30
CA2190945A1 (fr) 1995-12-07
ATE165874T1 (de) 1998-05-15
WO1995033083A1 (fr) 1995-12-07
JPH10501027A (ja) 1998-01-27
EP0760871A1 (fr) 1997-03-12
KR970703447A (ko) 1997-07-03
BR9507776A (pt) 1997-08-19

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