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EP0296167B1 - Procede de depot electrolytique cationique utilisant des anodes resistant a la dissolution - Google Patents

Procede de depot electrolytique cationique utilisant des anodes resistant a la dissolution Download PDF

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Publication number
EP0296167B1
EP0296167B1 EP87901876A EP87901876A EP0296167B1 EP 0296167 B1 EP0296167 B1 EP 0296167B1 EP 87901876 A EP87901876 A EP 87901876A EP 87901876 A EP87901876 A EP 87901876A EP 0296167 B1 EP0296167 B1 EP 0296167B1
Authority
EP
European Patent Office
Prior art keywords
anode
cathode
aqueous dispersion
electrodeposition
anodes
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.)
Revoked
Application number
EP87901876A
Other languages
German (de)
English (en)
Other versions
EP0296167A1 (fr
Inventor
Henry T. Austin
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.)
PPG Industries Inc
Original Assignee
PPG Industries Inc
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=25268719&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0296167(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by PPG Industries Inc filed Critical PPG Industries Inc
Priority to AT87901876T priority Critical patent/ATE90117T1/de
Publication of EP0296167A1 publication Critical patent/EP0296167A1/fr
Application granted granted Critical
Publication of EP0296167B1 publication Critical patent/EP0296167B1/fr
Anticipated expiration legal-status Critical
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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
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes

Definitions

  • the present invention relates to a method of cationic electrodeposition of aqueous dispersions of cationic resinous compositions using an anode which does not dissolve nor deteriorate during the process.
  • Cationic electrodeposition has been used industrially since 1972.
  • the early cationic electrodeposition compositions comprised quaternary ammonium salt group-containing resins in combination with aminoplast curing agents.
  • cationic compositions comprising amine salt group-containing resins in combination with blocked isocyanate curing agents were introduced for priming automobile bodies.
  • Today, over 90 percent of the automobile bodies are primed by cationic electrodeposition and practically all of the cationic compositions use the amine salt-blocked isocyanate resins.
  • the part being coated is of course the cathode.
  • the counter-electrode or anode is usually made of a corrosion-resistant material such as stainless steel since most cationic electrodeposition baths are acidic in nature. Because of the electrochemical reactions which occur at the anode, the stainless steel electrode slowly dissolves during the cationic electrodeposition process. The rate of dissolution depends principally on the current density, temperature of the electrodeposition bath to which the anode is exposed; the greater the current density and the higher the temperature, the faster the rate of ion dissolution. Also, the composition to which the electrode is exposed can affect the rate of dissolution. The presence of chloride ion greatly accelerates dissolution, and other unknown constituents of the electrodeposition bath can also affect dissolution.
  • electrodeposition baths in one location may be relatively passive to the stainless steel anodes, whereas electrodepositon baths in another location employing the same cationic paint may be very aggressive towards the stainless steel anode.
  • the dissolution of the anode results in low film builds and poor appearance. Eventually, if the dissolution is great enough, the anode must be replaced resulting in a time-consuming and expensive shut down of the electrodeposition process.
  • the anodes comprise a metal support of titanium with a ruthenium oxide coating thereon.
  • the anodes are commercially available as DSA-electrodes.
  • Chlorine generation at the anode requires a high concentration of chloride salts and the solution is subjected low voltages.
  • the steel anodes may be coated with an oxidation catalyst to assist controlling of the oxidation conditions.
  • an oxidation catalyst As catalysts are disclosed platinum, other precious metals, chromates, manganates, vandates, molybdates, cobalt, nickel, chromium and various oxides of the metals or other heavy metals which do not materially suppress the passage of electric current.
  • the object is attained by a method of electrocoating an electrically conductive surface serving as a cathode in an electrical circuit comprising said cathode and an anode having a conductive coating adhered to a substrate immersed in an aqueous dispersion of a cationic resinous composition which will dissolve stainless steel anodes by passing electric current between said cathode and anode at a constant voltage of from 50 to 500 volts to cause a coating to deposit on the cathode characterized by using an anode which does not dissolve nor deteriorate during the electrocoating process and comprises a titanium including alloys of titanium substrate and a coating of a material selected from the group consisting of ruthenium oxide, iridium oxide and mixtures thereof and operating at a current density of from 0.5 to 10 amperes per 929.034 cm2 (square foot).
  • the aqueous dispersion can contain chloride ion in amounts of at least 10 parts, preferably 10 to 200 parts per million based on the weight of the aqueous dispersion.
  • the electrode does not dissolve nor deteriorate in the cationic electrodeposition environment, provides for consistent quality coatings, and provides for considerable maintenance savings associated with not having to replace the dissolved stainless steel electrodes because of dissolution.
  • an aqueous electrodeposition bath containing an electrodepositable paint is placed in contact with an electrically conductive anode and an electrically conductive cathode and upon passage of an electric current, usually direct current, between the anode and cathode while immersed in the electrodepositon bath, an adherent film of paint is deposited on the cathode.
  • the electrodeposition of the paint occurs at a constant voltage between 50 and 500 volts, and at a current density of 0.5 to 10 amperes per 929.03 cm2 (square foot) with higher current densities being used during the initial stages of the electrodeposition and the current density gradually decreasing as the deposited coating insulates the cathode.
  • the cathode such as a series of automobile bodies
  • the cathode passes through the bath where it passes a series of anodes arranged from the beginning to the end.
  • the anodes first in line or towards the entrance end of the tank are subjected to the greatest current flows, and in the case of the stainless steel electrodes, dissolve the fastest. It is these anodes which are preferably replaced with the anodes to be used according to the present invention.
  • the stainless steel anodes may be replaced with the specific electrodes, it may not be necessary to replace the stainless steel anodes which are positioned more towards the exit end of the tank since these electrodes may not have that great a current flow (due to the insulating effect of the deposited coating) and may not significantly dissolve in the bath. Therefore, the electrodes in the bath towards the entrance end of the tank should be those of the invention, whereas the other electrodes more towards the exit end of the tank may be of the conventional stainless steel type.
  • the anodes may be exposed directly to the electrodeposition paint or as is more usually the case, they may be part of an electrodialysis cell positioned within the electrodeposition bath, in which instance, the anodes are separated from the electrodeposition paint by semi-permeable membranes which are permeable to ionic materials such as acid anion and water-soluble anionic impurities such as chloride ion but impermeable to resin and pigment of the paint.
  • ionic materials which are attracted to the anode and pass through the membrane can then be removed from the bath by periodically flushing the anode area with water.
  • the anode area is commonly referred to as the anolyte cell and the liquid in which the anode is in contact the anolyte solution.
  • Using the anodes in this manner is particularly desirable when the buildup of excess acid from the cationic electrodeposition resin is a particular problem.
  • the electrodeposition paints which are used in the process of electrodeposition comprise cationic resins, pigments, crosslinkers and adjuvant materials such as flow control agents, inhibitors, organic co-solvents and of course the dispersing medium, water.
  • cationic electrodeposition compositions are those based on cationic resins which contain active hydrogens and include amine salt groups, for example, the acid-solubilized reaction products of epoxy resins and primary or secondary amines in combination with capped isocyanate curing agents.
  • Cationic electrodeposition paints employing these resinous ingredients are described in U S -A-4,031,050 to Jerabek.
  • Specially modified cationic resins such as those containing primary amine groups formed from reacting polyepoxides with diketimines containing at least one secondary amine group, for example, the methyl isobutyl diketimine of diethylene triamine, are also well known electrodeposition resins and cationic paints employing these resinous ingredients are described in U S -A-4,017,438 to Jerabek et al.
  • Modified cationic resins such as those obtained by chain extending the polyepoxide to increase its molecular weight can also be used in the method of the invention. Such resins are described in U S Patent No.
  • the cationic electrodeposition paints preferably contain capped isocyanate curing agents because these curing agents provide for low temperature cure and the development of optimum cured coating properties.
  • cationic electrodeposition paints based on epoxy resins and capped polyisocyanates are often contaminated with chloride ion which is a by-product of the method of preparation of the epoxy resins and capped polyisocyanates.
  • chloride ion is a by-product of the method of preparation of the epoxy resins and capped polyisocyanates.
  • Many epoxy resins are made from epichlorohydrin and certain polyisocyanates are made from phosgene.
  • Chloride has a very adverse effect on the dissolution of the conventional stainless steel electrodes. It is therefore with cationic paints containing chloride ion that the invention is particularly useful.
  • Such paints typically have a chloride ion concentration of at least 10, usually 10 to 200 parts per million (ppm) based on total weight of the aqueous dispersion.
  • the anodes which are useful in the process of the invention comprise a substrate of titanium including titanium alloys as self-supporting material which is chemically resistant and to which the coating of the specific metal oxides described below will adhere.
  • chemically resistant is meant the substrate is resistant to the surrounding electrolyte, that is, the electrodeposition paint or the anolyte solution, and is not subject to an appreciable extent to erosion, deterioration or to electrolyte attack.
  • suitable titanium alloys include titanium, alloys with tantalum, niobium and titanium with 1 to 15 percent by weight molybdenum.
  • the entire substrate be of the titanium or alloy. Rather, a core of metal such as copper or aluminum may be cladded or coated with the titanium or alloy.
  • the suitable materials are selected from, oxides of ruthenium oxide and iridium oxide and mixtures of two or more oxides. Because of cost and performance in an electrodeposition environment, ruthenium oxide and iridium oxide are the selected oxides with ruthenium oxide being the most preferred.
  • the thickness of the substrate and the outer layer of the metal oxide is not critical. It only is necessary that the thickness of the substrate furnish a self-supporting structure and the metal oxide layer be present in an amount sufficient to function as an anode, that is, to be able to combine current density requirements with corrosion resistance.
  • the substrate is from 1270 ⁇ m to 12 700 ⁇ m (50 to 500 mils) in thickness and the metal oxide layer is from 0.254 ⁇ m to 254 ⁇ m (0.01 to 10 mils) in thickness.
  • the coating of the metal oxide layer can be on both sides of the substrate or on one side, that is, the side facing the cathode.
  • the substrate is entirely covered with a metal oxide layer.
  • the configurations of the anodes are not particularly critical but for use in electrodeposition tanks, they are usually square or rectangular.
  • electrodes having an area of from 9290 cm2 to 46 450 cm2 (10 to 50 square feet) are used, and as mentioned above, usually a series of electrodes are positioned in the tank extending from the entrance to the exit end of the tank.
  • the procedure for making the electrodes is generally a proprietary process with the manufacturers.
  • the metal oxide can be applied by evaporative techniques, thermal decomposition of suitable metal oxides in organic medium, and by electroplating. is In the instance the oxide is desired, the oxide is precipitated by chemical, thermal or electrical means. Oxides of the group of metals can also be applied directly to the titanium support in a molten bath of the oxide.
  • One cationic electrodeposition paint was based on an acid-solubilized epichlorohydrin-bisphenol A type epoxy resin-amine reaction product and a capped isocyanate curing agent.
  • the epoxy resin was an epichlorohydrin-bisphenol A type.
  • the paint was available from PPG Industries, Inc. under the trademark UNI-PRIME®.
  • the second paint was a cationic acrylic prepared from glycidyl methacrylate and contained a capped polyisocyanate curing agent.
  • the paint was available from PPG as ED-4000.
  • Samples of anolyte solutions from the paints were collected and used for testing.
  • the anodes being tested were 1524 mm by 25.4 mm (6 inches by 1 inch) and were made part of an electrical circuit inserted between two 1524 mm by 25.4 mm (6 inch by 1 inch) steel cathodes.
  • the electrode spacing was about 50.8 mm (2 inches) and the electrodes were immersed to a 50.8 mm (2-inch) depth in the anolyte solutions.
  • the effects of temperature, amperage and time on the loss of weight of the electrodes was measured and is reported in Table I below.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Claims (4)

  1. Procédé de peinture par électrodéposition d'une surface conductrice de l'électricité, servant de cathode dans un circuit électrique comprenant ladite cathode et une anode, possédant un revêtement conducteur qui adhère à un subjectile ou support plongé dans une dispersion aqueuse d'une composition résineuse cationique, qui va dissoudre des anodes en acier inoxydable en faisant passer un courant électrique entre la cathode et l'anode à une tension constante de 50 à 500 volts, de manière à amener un revêtement ou une peinture à se déposer sur la cathode,
    caractérisé en ce que
    on utilise une anode qui ne se dissout ni ne s'altère pas au cours du processus d'électrodéposition de la peinture et est constituée d'un subjectile ou support en titane, y compris en alliages du titane et d'un revêtement d'une matière choisie dans le groupe formé par l'oxyde de ruténium, l'oxyde d'iridium et leurs mélanges et fonctionant à une densité de courant de 0,5 à 10 ampères par 929,034 cm² (pied carré).
  2. Procédé suivant la revendication 1,
    caractérisé en ce que
    la matière de revêtement conductrice est l'oxyde de ruténium.
  3. Procédé suivant la revendication 1, caractérisé en ce que
    la dispersion aqueuse contient l'ion chlorure en des proportions d'au moins 10 parties par million sur base du poids de la dispersion aqueuse.
  4. Procédé suivant la revendication 1,
    caractérisé en ce que
    la dispersion aqueuse contient l'ion chlorure en des proportions de 10 à 200 parties par million sur base du poids de la dispersion aqueuse.
EP87901876A 1986-03-03 1987-02-18 Procede de depot electrolytique cationique utilisant des anodes resistant a la dissolution Revoked EP0296167B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87901876T ATE90117T1 (de) 1986-03-03 1987-02-18 Schwerloesliche anode fuer die kathodische elektrolytische abscheidung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US83514886A 1986-03-03 1986-03-03
US835148 2001-04-13

Publications (2)

Publication Number Publication Date
EP0296167A1 EP0296167A1 (fr) 1988-12-28
EP0296167B1 true EP0296167B1 (fr) 1993-06-02

Family

ID=25268719

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87901876A Revoked EP0296167B1 (fr) 1986-03-03 1987-02-18 Procede de depot electrolytique cationique utilisant des anodes resistant a la dissolution

Country Status (9)

Country Link
EP (1) EP0296167B1 (fr)
JP (1) JPH01501488A (fr)
KR (1) KR900006661B1 (fr)
AT (1) ATE90117T1 (fr)
AU (1) AU580475B2 (fr)
CA (1) CA1308058C (fr)
DE (1) DE3786079T2 (fr)
MX (1) MX164828B (fr)
WO (1) WO1987005340A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6398944B1 (en) 1995-09-18 2002-06-04 Basf Coatings Ag Method of removing acid formed during cathodic electrodip coating

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4997534A (en) * 1989-02-13 1991-03-05 General Electric Company Electrochemical machining with avoidance of erosion
DE10235117B3 (de) * 2002-08-01 2004-02-12 EISENMANN Maschinenbau KG (Komplementär: Eisenmann-Stiftung) Anlage zur kataphoretischen Tauchlackierung von Gegenständen
DE102014004292B4 (de) 2014-03-26 2016-09-01 Ekk Anlagentechnik Gmbh & Co. Kg Anodenzelle zur Verwendung in einem elektrophoretischen Beschichtungsverfahren

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1571721C3 (de) 1965-05-12 1980-03-06 Diamond Shamrock Technologies, S.A., Genf (Schweiz) Elektrode zur Verwendung in elektrolytischen Prozessen
DE3342713A1 (de) 1982-11-25 1984-09-27 Oronzio De Nora S.A., Lugano Elektrolytisches verfahren und elektrolysezelle zur herstellung organischer verbindungen
DE3423605A1 (de) 1984-06-27 1986-01-09 W.C. Heraeus Gmbh, 6450 Hanau Verbundelektrode, verfahren zu ihrer herstellung und ihre anwendung

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL126074C (fr) * 1957-07-17
US3682814A (en) * 1970-09-25 1972-08-08 Scm Corp Cathodic electrocoating process
GB1457511A (en) * 1973-02-08 1976-12-01 Imp Metal Ind Kynoch Ltd Composite body electrodes for electrolytic processes
JPS5139900B2 (fr) * 1973-10-20 1976-10-30
JPS58171589A (ja) * 1982-03-31 1983-10-08 Ishifuku Kinzoku Kogyo Kk 電解用電極及びその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1571721C3 (de) 1965-05-12 1980-03-06 Diamond Shamrock Technologies, S.A., Genf (Schweiz) Elektrode zur Verwendung in elektrolytischen Prozessen
DE3342713A1 (de) 1982-11-25 1984-09-27 Oronzio De Nora S.A., Lugano Elektrolytisches verfahren und elektrolysezelle zur herstellung organischer verbindungen
DE3423605A1 (de) 1984-06-27 1986-01-09 W.C. Heraeus Gmbh, 6450 Hanau Verbundelektrode, verfahren zu ihrer herstellung und ihre anwendung

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6398944B1 (en) 1995-09-18 2002-06-04 Basf Coatings Ag Method of removing acid formed during cathodic electrodip coating

Also Published As

Publication number Publication date
ATE90117T1 (de) 1993-06-15
KR900006661B1 (ko) 1990-09-17
JPH01501488A (ja) 1989-05-25
EP0296167A1 (fr) 1988-12-28
DE3786079D1 (de) 1993-07-08
AU7085987A (en) 1987-09-28
JPH0572480B2 (fr) 1993-10-12
DE3786079T2 (de) 1993-12-09
KR880700870A (ko) 1988-04-13
AU580475B2 (en) 1989-01-12
MX164828B (es) 1992-09-28
WO1987005340A1 (fr) 1987-09-11
CA1308058C (fr) 1992-09-29

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