EP0871802A1 - Procede permettant d'eliminer l'acide degage pendant le trempage electrophoretique cathodique - Google Patents

Procede permettant d'eliminer l'acide degage pendant le trempage electrophoretique cathodique

Info

Publication number
EP0871802A1
EP0871802A1 EP96930151A EP96930151A EP0871802A1 EP 0871802 A1 EP0871802 A1 EP 0871802A1 EP 96930151 A EP96930151 A EP 96930151A EP 96930151 A EP96930151 A EP 96930151A EP 0871802 A1 EP0871802 A1 EP 0871802A1
Authority
EP
European Patent Office
Prior art keywords
acid
anode
oxidation
mixture
electrocoating
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.)
Granted
Application number
EP96930151A
Other languages
German (de)
English (en)
Other versions
EP0871802B1 (fr
Inventor
Klaus Arlt
Udo Heil
Karl-Heinz Grosse-Brinkhaus
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.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP0871802A1 publication Critical patent/EP0871802A1/fr
Application granted granted Critical
Publication of EP0871802B1 publication Critical patent/EP0871802B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • C25D21/18—Regeneration of process solutions of electrolytes

Definitions

  • the present invention relates to a method for removing the acid released during cathodic electrocoating during the deposition of the paint film from the electrocoating bath.
  • the substrate to be painted is immersed in an aqueous electrocoating bath and switched as a cathode. After the voltage is applied, paint film is deposited on the substrate.
  • the lacquers used are polymers which have been converted into a water-dispersible form by protonation. Protonation is mainly achieved by adding weak organic acids. These acids accumulate in the anode area if the cationic paint binder is neutralized during the paint deposition and the used paint is gradually replaced by new, protonated paint. The acid must therefore be removed from the bath in order to control the pH of the electro-immersion bath. This is usually done via the so-called anolyte cycle.
  • the anolyte circuit first assumes that the anode is separated from the rest of the electrodeposition bath by a diaphragm or a membrane.
  • This membrane is typically an anion exchange membrane that only has a flow of anions, i.e. in the present case acid residues, in the direction of the anode.
  • paint binders and pigments are retained.
  • the anolyte circuit removes acid-enriched electrolyte from the anode compartment, generally discards it as waste water, and replaces it with water.
  • electro-immersion baths usually contain an ultrafiltration circuit. This removes bath liquid directly and feeds it to ultrafiltration in order to separate solvents and other low-molecular components of the paint that accumulate in the bath.
  • DE-4409270 also proposes the anodic oxidation of the acid used.
  • formic acid is also used here essentially, ie over 90%, as the acid.
  • anode materials are called platinum or platinized stainless steel electrodes, platinized titanium electrodes, platinized graphite electrodes, ruthenium-doped stainless steel electrodes or mixed oxide-doped electrodes made of stainless steel, titanium or graphite.
  • no measurement results and no numerical values for the degradation rates achieved are mentioned.
  • electrodes are known from German patent 15 71 721, which among other things. can be used as an anode for carrying out the chlor-alkali electrolysis.
  • oxides of platinum, iridium, rhodium, palladium, ruthenium, manganese, lead, chromium, cobalt, iron, titanium, tantalum, zirconium or silicon are used.
  • Other areas of application for the electrodes mentioned are electrodialysis and electrocoating.
  • German patent 1671 422 also discloses the use of an anode consisting of a titanium core and a mixed coating of at least part of the core surface made of a material made of ruthenium oxide and titanium oxide which is resistant to the electrolyte and the electrolysis products for alkali chloride electrolysis.
  • These anodes show a significantly lower overvoltage and are also dimensionally stable. Due to these properties, cell constructions, e.g. Membrane cells were developed, thus increasing the performance of the previously known mercury and diaphragm cells.
  • German published patent application 3423605 describes composite electrodes made of electrically conductive plastic and catalytic particles partially pressed therein (carrier particles with applied catalyst) and processes for their production. You can use it as an oxygen anode, for example, in the electrolytic extraction of metals from aqueous Solutions are used. Electrodialysis and electrodeposition are mentioned as further areas of application.
  • European patent 0296 167 also describes the use of comparable electrodes (so-called “dimensionally stable anodes DSA”) in cathodic electrodeposition coating. These are neither dissolved nor destroyed during the electrophoretic coating process under the conditions of the electrodeposition process there, ie in relation to Lacquer formulation, current density, pH value and the decomposing influence of chlorine.
  • DSA dimensionally stable anodes
  • Electrodes for oxidative degradation were also tested and used in the field of wastewater treatment. It was found in particular that electrodes with a coating of tin oxide (Sn0 2 ) have a high efficiency in the electrochemical degradation of organic substances. These electrodes were tested in particular in comparison to conventional electrodes, for example the above-mentioned DSA electrodes (Stucki, Kötz, Carcer, Suter: "Electrochemical waste water treatment using high overvoltage anodes, Part II: Anode Performance and applications", Journal of Applied Electrochemistry 21 (1991), 99-104; Comninellis: “Traitment des eaux residuaires par intens electrochimique", gwa 11/92, 792-797; Comninellis: “Electrochemical treatment of waste water containing phenol", Electrochemical Engineering and the Environment 92, Symposium Series No. 127, 189-201).
  • the object of the present invention is to provide a process for removing the acid released during cathodic electrocoating during the deposition of the paint film, which process reduces the number of rinsing processes required via the anolyte circuit to remove acid and possible degradation products of the acid or that works entirely without the anolyte cycle.
  • This object could surprisingly be achieved in that the released acid, preferably formic acid, is removed by oxidation on anodes which are coated with a layer of ruthenium, iridium or tin oxide or a mixture of these oxides.
  • acids other than formic acid are generally less favorable for electrochemical degradability.
  • Lactic acid can only be broken down electrochemically to approx. 35%.
  • the anolyte circuit can even be completely dispensed with, ie the electrodes according to the invention can be inserted directly into the electrodeposition bath and the anode and cathode compartments no longer have to be separated from one another by a membrane.
  • additional methods for reducing the acid content are used according to the invention.
  • membrane processes known per se These preferably start with the ultrafiltrate, because the higher molecular paint components are no longer present here. Examples of suitable membrane processes are processes using dialysis, osmosis, reverse osmosis, electrodialysis or a further ultrafiltration.
  • electrocoating baths which contain synthetic resins containing cationic groups as binders. They are preferably protonated reaction products made from synthetic resins and amines containing epoxy groups. These are preferably formic acid, acetic acid, lactic acid and dimethylolpropionic acid. The use of formic acid is very preferred. The acids mentioned are oxidized to water and carbon dioxide at the anode.
  • the substrate of the electrodes according to the invention can consist of metal or conductive plastic.
  • the metals are preferably titanium, tantalum, niobium or an alloy of these metals.
  • an alloy of titanium and 1 to 15% by weight of molybdenum. Titanium is particularly preferred as the substrate.
  • the layer of ruthenium, iridium or tin oxide or a mixture of these oxides applied to the anodes used according to the invention preferably has a layer thickness of 0.01 to 10 ⁇ m. A particularly preferred range is 0.1-7 ⁇ m.
  • Binder dispersion (cf. EP 074634, example C, but neutralized with formic acid)
  • the following example shows the preparation of a cationic resin which is neutralized by formic acid.
  • Bisphenol A, bisphenol A diglycidyl ether and a bisphenol A-ethylene oxide adduct are heated together and form a modified polyepoxy resin.
  • a blocked isocyanate is given as a crosslinker.
  • a reaction with a mixture of secondary amines then takes place.
  • the resin is partially neutralized with formic acid and dispersed in water.
  • Demineralized water 3026.63 Liquid epoxy resin produced by reacting bisphenol A and epichlorohydrin with an epoxide equivalent weight of 188. (Manufacturer: Shell Chemicals)
  • polyurethane crosslinker made from diphenylmethane diisocyanate, in which 4.3 of 6 moles of isocyanate are first reacted with butyl diglycol and the remaining 1.7 moles with trimethylol propane.
  • the crosslinker is present in an 80% solution of methyl isobutyl ketone and isobutanol (weight ratio 9: 1).
  • the Epikote 828, bisphenol A and Dianol 265 are heated to 130 ° C. in a reactor with nitrogen blanketing. Then 1.6 parts of the benzyldimethylamine (catalyst) are added, the reaction mixture is heated to 150 ° C. and kept between 150 and 190 ° C. for about half an hour and then cooled down to 140 ° C. The remaining amount of benzyldimethylamine is then added and the temperature is kept at 140 ° C. until an epoxide equivalent weight of 1120 is established after about 2.5 hours. Immediately afterwards, the polyurethane crosslinker is added and the temperature is reduced to 100.degree. The mixture of secondary amines is then added and the reaction is held at 115 ° C.
  • the resin is dispersed in the water in which the formic acid and the emulsifier mixture are dissolved.
  • the solid is 35% after this step, and increases to 37% after stripping off the low-boiling solvents.
  • the dispersion is characterized by a particle size of approx. 150 nm.
  • the EEW of the reaction mixture is then 860.
  • the mixture is cooled and 9.91 parts of butyl glycol and 17.88 parts of a propylene glycol diglycidyl ether with EEW 333 (DER 732, Dow Chemical) are added.
  • EEW 333 propylene glycol diglycidyl ether with EEW 333
  • EEW 333 a propylene glycol diglycidyl ether with EEW 333
  • the resin has a solids content of 69.8% (measured for 1 hour at 130 ° C) and a viscosity of 5.5 dPas (40% in Solvenon PM; cone-plate viscometer at 23 ° C).
  • C. pigment paste (cf. EP 505 445, example: pigment paste B 3, but neutralized with formic acid)
  • To prepare the pigment paste 34.34 parts of deionized water, 0.38 part of formic acid (85% strength) and 18.5 parts of rubbing resin were premixed. Then 0.5 parts of carbon black, 6.75 parts of extender (ASP 200), 37.28 parts of titanium dioxide (R 900) and 2.25 parts of crosslinking catalyst (DBTO) are added and the mixture is mixed for 30 minutes under a high-speed dissolver stirrer. The mixture is then dispersed in a laboratory stirred ball mill for 1 to 1.5 h to a Hegman fineness of less than 12 and adjusted to the desired processing viscosity with further water, if necessary.
  • ASP 200 extender
  • R 900 titanium dioxide
  • DBTO crosslinking catalyst
  • binder dispersion A For the cathodically depositable electrocoat material, 36.81 parts of binder dispersion A are diluted with 52.5 parts of deionized water and 10.69 parts of pigment paste C are added to this mixture with stirring.
  • the paint has a solids content of approx. 20% with an ash content of 25%.
  • a titanium electrode coated with iridium oxide (dimensions 10 x 10 cm) serves as the anode and is immersed directly in the electrocoating material.
  • steel sheets (dimensions approx. 10 x 20 cm) are coated automatically at 28 ° C with 280 V for 2 min.
  • the layer thickness is approx. 20 ⁇ m.
  • the sheets are immersed in the ultrafiltrate to rinse off adhering paint material and thus return it to the plunge pool.
  • the KTL material is analyzed and compensated with binder and pigment paste.
  • the meq acid analyzes show the development of the acidity in
  • Figure 1 shows the plot of the meq-acid content against the "turnover" of the KTL bath (a turnover value of 1 means a complete
  • Acid discharge 100 constant meq acid value
  • Figure 2 shows the acid discharge based on the meq acid value after 0.3 turnover (the basis 0.3 turnover was chosen because the equilibrium between bath and ultrafiltrate has almost been reached at this point). .

Landscapes

  • 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)
  • Prevention Of Electric Corrosion (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne un procédé permettant d'éliminer l'acide dégagé lors du trempage électrophorétique cathodique, pendant le dépôt du film de peinture, par oxydation au niveau de l'anode, selon lequel on utilise des anodes recouvertes d'oxyde de ruthénium, d'iridium ou d'étain ou d'un mélange desdits oxydes.
EP96930151A 1995-09-18 1996-09-02 Procede permettant d'eliminer l'acide degage pendant le trempage electrophoretique cathodique Expired - Lifetime EP0871802B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19534534 1995-09-18
DE19534534A DE19534534A1 (de) 1995-09-18 1995-09-18 Verfahren zur Entfernung der bei der kathodischen Elektrotauchlackierung freigesetzten Säure
PCT/EP1996/003845 WO1997011211A1 (fr) 1995-09-18 1996-09-02 Procede permettant d'eliminer l'acide degage pendant le trempage electrophoretique cathodique

Publications (2)

Publication Number Publication Date
EP0871802A1 true EP0871802A1 (fr) 1998-10-21
EP0871802B1 EP0871802B1 (fr) 2000-01-05

Family

ID=7772455

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96930151A Expired - Lifetime EP0871802B1 (fr) 1995-09-18 1996-09-02 Procede permettant d'eliminer l'acide degage pendant le trempage electrophoretique cathodique

Country Status (6)

Country Link
US (2) US6398944B1 (fr)
EP (1) EP0871802B1 (fr)
AT (1) ATE188518T1 (fr)
DE (2) DE19534534A1 (fr)
ES (1) ES2143778T3 (fr)
WO (1) WO1997011211A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19938886C1 (de) * 1999-08-17 2001-02-01 Dupont Automotive Coatings Gmb Reinigungsmittel und Verfahren zur Reinigung von Ultrafiltrationsmembranen in Elektrotauchlackierungsanlagen
DE10235117B3 (de) * 2002-08-01 2004-02-12 EISENMANN Maschinenbau KG (Komplementär: Eisenmann-Stiftung) Anlage zur kataphoretischen Tauchlackierung von Gegenständen
US20170096742A1 (en) * 2015-10-02 2017-04-06 Waste Hub Electrochemical processes for acid whey treatment and reuse

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL128866C (fr) 1965-05-12
GB1195871A (en) 1967-02-10 1970-06-24 Chemnor Ag Improvements in or relating to the Manufacture of Electrodes.
US3682814A (en) * 1970-09-25 1972-08-08 Scm Corp Cathodic electrocoating process
DE3423605A1 (de) 1984-06-27 1986-01-09 W.C. Heraeus Gmbh, 6450 Hanau Verbundelektrode, verfahren zu ihrer herstellung und ihre anwendung
KR900006661B1 (ko) 1986-03-03 1990-09-17 피이피이지이 인더스트리이즈 인코포레이팃드 내용해성 양극을 사용하는 양이온 전착방법
US4879013A (en) * 1986-03-03 1989-11-07 Ppg Industries, Inc. Method of cationic electrodeposition using dissolution resistant anodes
DE3642164A1 (de) 1986-12-10 1988-06-23 Basf Ag Verfahren zum entfernen von saeure aus kathodischen elektrotauchlackier-baedern mittels elektrodialyse
DE4409270C1 (de) 1994-03-18 1995-03-30 Herberts Gmbh Verfahren zur abwasserfreien kataphoretischen Tauchlackierung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9711211A1 *

Also Published As

Publication number Publication date
ES2143778T3 (es) 2000-05-16
ATE188518T1 (de) 2000-01-15
DE59604138D1 (de) 2000-02-10
DE19534534A1 (de) 1997-03-20
US20020060155A1 (en) 2002-05-23
WO1997011211A1 (fr) 1997-03-27
EP0871802B1 (fr) 2000-01-05
US6398944B1 (en) 2002-06-04

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