EP1047812A2 - Procede de trempage electrophoretique anodique - Google Patents

Procede de trempage electrophoretique anodique

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Publication number
EP1047812A2
EP1047812A2 EP99902531A EP99902531A EP1047812A2 EP 1047812 A2 EP1047812 A2 EP 1047812A2 EP 99902531 A EP99902531 A EP 99902531A EP 99902531 A EP99902531 A EP 99902531A EP 1047812 A2 EP1047812 A2 EP 1047812A2
Authority
EP
European Patent Office
Prior art keywords
weight
component
acid
bath
groups
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
EP99902531A
Other languages
German (de)
English (en)
Other versions
EP1047812B1 (fr
Inventor
Eduard Ehmann
Manfred Evers
Armin Göbel
Bettina Vogt-Birnbrich
Konstadinos Markou
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to SI9930064T priority Critical patent/SI1047812T1/xx
Publication of EP1047812A2 publication Critical patent/EP1047812A2/fr
Application granted granted Critical
Publication of EP1047812B1 publication Critical patent/EP1047812B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C25D1/00—Electroforming
    • 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
    • C25D13/04—Electrophoretic coating characterised by the process with organic material
    • 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
    • C25D13/24—Regeneration of process liquids
    • 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
    • C25D13/10—Electrophoretic coating characterised by the process characterised by the additives used
    • 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 for producing an anodic electrodeposition coating (ATL) using a low-solvent / free electrodeposition coating bath (ATL bath), wherein electrodialysis in the ETL bath is not required to maintain the bath and coating parameters. It is also not necessary to regularly discard ultrafiltrate.
  • ATL bath low-solvent / free electrodeposition coating bath
  • Electrodeposition coating is used to bring a workpiece with an electrically conductive surface made of metal or from electrically conductive plastic or from a substrate provided with an electrically conductive coating into an aqueous ATL bath and connected as an anode to a direct current source.
  • the ATL bath consists of an aqueous dispersion, e.g. Suspension or emulsion or from an aqueous solution of one or more binders which have been made at least partially water-dispersible or water-soluble by salt formation with organic or inorganic neutralizing agents, from pigments, fillers, additives and other auxiliaries dispersed therein.
  • aqueous dispersion e.g. Suspension or emulsion or from an aqueous solution of one or more binders which have been made at least partially water-dispersible or water-soluble by salt formation with organic or inorganic neutralizing agents, from pigments, fillers, additives and other auxiliaries dispersed therein.
  • the usual ATL baths are operated continuously, i.e.
  • the substrates described above are immersed and coated in an electrodeposition basin filled with the coating agent. This removes solid matter from the ATL bath and at the same time releases neutralizing agent in the ATL bath.
  • the supplied refill material with an increased solid content is neutralized less than the ATL bath, and the released neutralizing agent is required to disperse / homogenize the refill material in the ATL bath and is consumed in the process.
  • the compensation can also be done with fully neutralized refill material.
  • the expenditure on equipment is then greater, however, since the released neutralizing agent has to be removed by means of (electro) dialysis (Glasurit Manual 1984, page 377 and Willibald Machu "Electrocoating", Verlag Chemie GmbH Weinheim / Bergstrasse, 1974, page 166).
  • the neutralizing agent released during the coating can also be removed by regularly discarding ultrafluidate.
  • Electro-dip coating which still contains 6% organic solvent in the refill paste form and 0.5% in the running bath.
  • the cathodes can also be placed in the ATL bath in washable dialysis cells (electrodialysis) and the neutralizing agent obtained there discarded, or the coating material can be subjected to ultrafiltration continuously or discontinuously and the ultrafiltrate obtained at least partially at regular intervals discard. Because of the higher investment costs and a higher maintenance and monitoring effort, such electrodialysis devices are not available in most ATL baths. The regular discarding of ultrafiltrate or dialysate also requires more effort in the treatment of water and is therefore undesirable.
  • the object was therefore to provide a process for the preparation of an aqueous, low-solvent or solvent-free coating composition for anodic electrocoating, when used to coat conductive substrates in an ATL bath to maintain the
  • Bath and coating parameters do not mean removal of the neutralizing agent released during coating by an electrodialysis device is required and a large amount of ultrafiltrate does not have to be regularly discarded.
  • an anodic refill material consisting of a pigment-free aqueous binder component and a pigment-containing aqueous paste resin component, is used to compensate for the coating material used in the electro-dip coating and the neutralizing agent released, which is so low that it is under-neutralized so that when it is added to the ATL bath compensates the neutralizing agent released there and still contains only small amounts of organic solvents.
  • the invention therefore relates to a process for anodic electrodeposition in which the coating agent used in an anodic electrodeposition bath is compensated for by a neutralized anodic refill material, which is characterized in that the refill material consists of
  • A) to B) are present in a weight ratio of 1: 1 to 4: 1 and the mixture of A) and B) has a solids content of 45 to 73% by weight, a solvent content of ⁇ 0.75% by weight and one MEQ value that is 50 to 70% lower than the MEQ value of the electro-dip.
  • components A) and B) can, for example, according to DIN EN
  • the solids content of component A) is preferably 45 to 65% by weight.
  • the solids content of component B) is preferably 60 to 73% by weight.
  • the MEQ value of component A) is preferably 20 to 35, the MEQ value of component B) is preferably 5 to 10.
  • the MEQ value is a measure of the content of neutralizing agent in a water-based paint. It is defined as the amount of milliequivalents of the neutralizing agent based on 100 g solids.
  • the organic solvent content of component A) is preferably ⁇ 0.4% by weight, that of component B) is preferably ⁇ 0.5% by weight.
  • the mixing ratio of component (A) to component (B) is 1: 1 to 4: 1, preferably from 2: 1 to 3.5: 1, based on the weight of the respective aqueous component.
  • the mixture has a solids content of 45 to 73 wt .-%, a
  • Solvent content of at most 0.75% by weight and an MEQ value which is 50 to 70%, preferably 60 to 70% lower than the MEQ value of the ATL bath in the coatable state.
  • Component (A) contains the binder or binders of the aqueous coating agent, and optionally a biocidal component and, if necessary, crosslinking agents and, if appropriate, emulsifiers, layering agents, further additives such as e.g. Neutral resins, common paint additives such as light stabilizers and optical brighteners.
  • Component (B) contains one or more paste resin (s), pigments and / or fillers, if appropriate a biocidal component and, if necessary, crosslinking agents, and if appropriate layering agents and customary paint additives and further additives, for example as they are also present in component (A) can.
  • binder systems can be used as suitable binders of component (A) an acid number from 20 to 150, preferably from 20 to 120 and a hydroxyl number from 20 to 150, preferably from 60 to 120, such as are known for aqueous coating systems, especially for anodic electrocoat coatings.
  • polyester, polyacrylate and polyurethane resins include, for example, polyester, polyacrylate and polyurethane resins; modified polyester or polyurethane resins, e.g. Alkyd resins, urethanized polyester resins or acrylated polyester or polyurethane resins, as well as mixtures of these resins. Polyester resins are preferred.
  • Suitable polyester resins in component (A) are, for example, carboxyl-containing and hydroxyl-containing polyesters having an acid number of 20 to 150 and a hydroxyl number of 20 to 150. They are obtained by the processes known to the person skilled in the art by reacting polyhydric alcohols and polyhydric carboxylic acids or carboxylic acid anhydrides, and optionally aromatic and / or aliphatic monocarboxylic acids. The required hydroxyl group content is set in a manner known per se by suitable choice of the type and proportions of the starting components.
  • the carboxyl groups can be introduced, for example, by half-ester formation from a prefabricated, hydroxyl-containing polyester resin with acid anhydrides. Carboxyl groups can also be incorporated, for example, by using hydroxycarboxylic acids in the polycondensation reaction.
  • the dicarboxylic acids and the polyols can be aliphatic or aromatic
  • the low molecular weight polyols used to produce the polyesters are, for example, diols such as alkylene glycols, for example ethylene glycol, butylene glycol, hexanediol, hydrogenated bisphenol A and 2,2-butylethyl propanediol, neopentyl glycol and / or other glycols such as dimethylolcyclohexane.
  • diols such as alkylene glycols, for example ethylene glycol, butylene glycol, hexanediol, hydrogenated bisphenol A and 2,2-butylethyl propanediol, neopentyl glycol and / or other glycols such as dimethylolcyclohexane.
  • higher functional or mixtures of higher and monofunctional OH components such as tri- methylolpropane, pentaerythritol, glycerin, hexanetriol; Polyethers that are condensates of glycols with alkylene oxides; Monoethers of such glycols, such as diethylene glycol monoethyl ether, tripropylene glycol onomethyl ether, are used.
  • the acid component of the polyester preferably consists of low molecular weight
  • Dicarboxylic acids or their anhydrides with 2 to 18 carbon atoms in the molecule Dicarboxylic acids or their anhydrides with 2 to 18 carbon atoms in the molecule.
  • Suitable acids are, for example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, adipic acid, azeleic acid, sebacic acid, fumaric acid, maleic acid, glutaric acid, succinic acid, itaconic acid and / or
  • 1,4-cyclohexanedicarboxylic acid instead of these acids, their methyl esters or anhydrides, if they exist, can also be used.
  • higher-functional carboxylic acids such as trifunctional carboxylic acids, trimellitic acid, malic acid, aconitic acid, bishydroxyethyl taurine and dimethylolpropionic acid, dimethylolbutyric acid or bisanhydrides.
  • Polycarboxylic acids that do not form cyclic anhydrides are preferred.
  • polyester resins can, for example, also by incorporating unsaturated compounds, compounds containing isocyanate groups or by lap or
  • Graft polymerization can be modified with ethylenically unsaturated compounds.
  • Preferred polyesters in component (A) are, for example, carboxyl-containing polyesters with an acid number from 20 to 120, a hydroxyl number from 20 to 150, preferably from 60 to 120. They are for example
  • the quantitative ratios of the starting components are calculated from the molar ratios to the desired acid numbers and hydroxyl numbers of the Lead resin.
  • the selection of the individual starting components is known to the person skilled in the art, taking into account the objective.
  • the number average molecular weight Mn, measured against polystyrene as calibration substance, is for example 1000 to 6000, preferably 2000 to 4000.
  • Oil-free polyesters containing carboxyl groups such as those e.g. are described in DE-A-32 47 756.
  • polyesters preferably contain 0.3 to 3.0, particularly preferably 0.5 to 2.5 milliequivalents of aliphatic, cycloaliphatic and / or monocyclic aromatic
  • Dicarboxylic acids condensed per gram of resin.
  • tri- or polybasic cyclic carboxylic acids 0.8 to 2.0, preferably 0.9 to 1.8, particularly preferably 1.1 to 1.5 millimoles per gram of resin are expediently bound to the polyester via only one carboxyl group.
  • Three- and / or polybasic polycarboxylic acids are used as polycarboxylic acids, preferably three- and / or four-basic acids.
  • the esterification of preferably aromatic and cycloaliphatic dicarboxylic acids, which cannot form an intramolecular anhydride, is preferably carried out with dialcohols which either contain secondary OH groups or contain sterically hindered primary OH groups by substitution with JS, an OH group-containing polyester being formed by excess alcohol.
  • the alcohols preferably contain 2 to 21, particularly preferably 4 to 8 carbon atoms.
  • the dicarboxylic acids preferably contain 5 to 10 carbon atoms, particularly preferably 6 carbon atoms.
  • Examples include isophthalic acid, terephthalic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid or alkyl-substituted dicarboxylic acids
  • butyl isophthalic acid is particularly preferred.
  • a corresponding one can be used instead of some of the dicarboxylic acids
  • Amount of tricarboxylic acid such as trimellitic anhydride can be condensed into the resin molecule.
  • dimethyl esters such as dimethyl terephthalate or dimethyl 1,4-cyclohexanedicarboxylate can also be introduced into the polyester by transesterification, if appropriate in the presence of transesterification catalysts.
  • Preferred dialcohols are neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, hexanediol-2,5, 1,4-bis (hydroxymethyl) cyclohexane, 1 J-isopyrilidine-bis- (p-phenoxy) -2-propanol, 2,2,4-trimethylpentanediol. 1,3, as well as mixtures thereof.
  • the glycidyl ester of ⁇ -branched fatty acids can also be used as dialcohol, for example, because the fatty acid is incorporated into the molecule in a manner which is stable to hydrolysis.
  • a partial use of polyols with more than two OH groups such as trimethylolpropane or pentaerythritol is possible to set suitable OH numbers and viscosities. The same applies to a minor modification to
  • This esterification (first stage) is carried out azeotropically in a known manner or in the melt at elevated temperature (above 190 ° C.) and gives a clear result
  • carboxyl groups must also be introduced into the OH group-containing polyesters.
  • a reaction takes place at temperatures below 190 ° C. with an aromatic or cycloaliphatic dicarboxylic acid, which is preferably carried out by defunctionalization a long-chain, aliphatic hydrophobic monoalcohol from a polycarboxylic acid with three or four carboxyl groups such as trimesic acid, hemellitic acid, pragmatic acid and mellophanic acid.
  • the process is particularly simple when using anhydride-containing compounds such as trimellitic anhydride, pyromellitic anhydride or corresponding hydrogenated ring systems, and also cyclopentanetetracarboxylic anhydride or pyrazine tetracarboxylic anhydride.
  • anhydride-containing compounds such as trimellitic anhydride, pyromellitic anhydride or corresponding hydrogenated ring systems, and also cyclopentanetetracarboxylic anhydride or pyrazine tetracarboxylic anhydride.
  • the polycarboxylic acids can, for example, be reacted stoichiometrically with so much monoalcohol in a two-pot process that a dicarboxylic acid is retained, which is then added to the OH group-containing polyester at temperatures of about 150 to 190 ° C.
  • Step 2 the approximately stoichiometric amounts of monoalcohol and trimellitic anhydride are added in the order given.
  • Straight-chain and / or branched saturated and / or unsaturated, primary, secondary and / or tertiary, preferably primary and / or secondary alcohols can, for example, be used as monoalcohols. Mixtures, in particular isomeric mixtures, of these alcohols can also be used. Aliphatic C6 to C18 monoalcohols and benzyl alcohol and its alkyl substitution products are preferred. Branched-chain C8 to C13 iso-monoalcohols are particularly preferred. Particularly half-esters that are stable to hydrolysis are produced by
  • carboxyl groups can also, for example, by using Hydroxycarboxylic acids such as dimethylolpropionic acid take place in the polycondensation reaction, the free carboxyl group of which generally does not participate in the polycondensation reaction because of the steric hindrance, so that this acid is incorporated exclusively via the hydroxyl groups.
  • Hydroxycarboxylic acids such as dimethylolpropionic acid
  • the molar ratios of the overall formulation for the production of the polyester are chosen so that a viscosity suitable for the respective application is achieved. It is, for example, about 200 to 3000, preferably 250 to 2000 and particularly preferably 300 to 1500 mPas, measured 50% in butyl glycol at 25 ° C. Like the molecular weight, it can be adjusted by mixing resins with higher and lower viscosity, or higher and lower molecular weight.
  • the upper limit of the acid number is preferably below 100, particularly preferably below 60; the lower limit of the acid number is preferably above 35, particularly preferably above 40.
  • the carboxyl-containing polyester contains at least one, preferably at least two, carboxyl groups per molecule, by which
  • the selected excess of alcohol gives a hydroxyl number of about 20 to 150, preferably from 60 to 120, in the finished resin
  • Resins preferred which have a relatively high hydroxyl number with a low acid number are preferred.
  • the polycondensation takes place, for example, azeotropically or in the melt, for example at reaction temperatures between 160 to 240 ° C., preferably between 160 to 210 ° C.
  • the mixture is cooled to a temperature such that a product with a viscosity is obtained which ensures that water is incorporated.
  • this means that the melt viscosity achieved should not exceed 40,000 mPa.s. This can be achieved by cooling to a suitable temperature.
  • the polycondensation product is neutralized for transfer into an aqueous solution or dispersion.
  • the neutralizing agent can be added to the polycondensation resin before or during the addition of water, but it can also be placed in the water in which the polycondensation resin is dispersed.
  • high-speed stirring disc devices for example, high-speed stirring disc devices,
  • Rotor / stator mixers or high pressure homogenizers are used. During or after the transfer into the aqueous solution or dispersion, organic solvents can optionally be removed by distillation.
  • Suitable bases such as ammonia, are suitable as neutralizing agents for this purpose; primary, secondary and tertiary amines such as diethylamine, triethylamine, morpholine; Alkanolamines such as diisopropanolamine, dimethylaminoethanol, triisopropanolamine, dimethylamino-2-methylpropanol; quaternary ammonium hydroxides or optionally also small amounts of alkylene polyamines such as ethylenediamine. Mixtures of these can also be used
  • Neutralizing agents can be used.
  • the stability of the aqueous dispersion can be influenced by the choice of the neutralizing agent.
  • the amount of neutralizing agent is chosen so that the MEQ value of the mixture of component (A) and component (B) is 50 to 70% below the MEQ value of the ATL bath.
  • Suitable polyacrylate resins in component (A) are, for example, copolymers containing carboxyl groups and / or sulfonic acid groups with an acid number of 20 to 150 and a number-average molecular weight Mn of 1,000 to 10,000.
  • the monomers containing acid groups are also used for the purpose of incorporating carboxyl and / or sulfonic acid groups into the copolymers, which, owing to their hydrophilicity, have the effect of Ensure water solubility or water dispersibility of the copolymers, especially after the at least partial neutralization of the acid groups.
  • Suitable monomers containing acid groups are in principle all olefinically unsaturated polymerizable compounds which have at least one carboxyl and / or sulfone group, such as, for example, olefinically unsaturated mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid or the half esters of fumaric acid, Maleic acid and itaconic acid or olefinically unsaturated compounds containing sulfonic acid groups, such as, for example, 2-acrylamido-2-methylpropanesulfonic acid or any mixtures of such olefinically unsaturated acids.
  • Acrylic acid and methacrylic acid are particularly preferred.
  • the copolymers may contain, in addition to the monomers containing acid groups, further functional monomers with which e.g. Have cross-linking reactions carried out. Both self-crosslinking of the copolymers and external crosslinking with other components additionally incorporated into the lacquer can take place.
  • Examples of such functional groups are hydroxyl, amino, amido, keto, aldehyde, lactam, lactone, isocyanate, epoxy and silane groups.
  • Olefinically unsaturated monomers which carry such functional groupings are known. Hydroxy and epoxy groups are particularly preferred.
  • all non-functional olefinically unsaturated monomers can be used in the preparation of the copolymers.
  • Suitable non-functional monomers are, for example, esters of acrylic and methacrylic acid, the alcohol components of which contain 1 to 18 carbon atoms, vinyl aromatics, vinyl esters of aliphatic monocarboxylic acids, acrylic and
  • the copolymers can be prepared by polymerization using customary processes.
  • the copolymers are preferably prepared in organic solution. Continuous or discontinuous polymerization processes are possible.
  • Aromatics, esters, ethers and ketones can be used as solvents. Glycol ethers are preferably used.
  • the copolymerization is generally carried out at temperatures between 80 to 180 ° C using conventional initiators such as aliphatic
  • the copolymers as described for the polycondensation resins, can be neutralized and converted into an aqueous solution or dispersion, the organic solvent optionally being able to be removed by distillation.
  • Suitable polyurethane resins in component (A) are, for example, anionic polyurethane resins which contain carboxyl, sulfonic acid and / or phosphonic acid groups in salt form. They are produced in a manner known per se from polyols, polyisocyanates and optionally chain extenders.
  • the polyurethane resins can be produced both in bulk and in organic solvents which cannot react with isocyanates. As described for the polycondensation resins, they are converted into the aqueous phase by neutralizing the acid groups. In many cases, it is useful to
  • a prepolymer with acid groups and terminal isocyanate groups in organic solvents, which, after neutralization of the acid groups with tertiary amines, is chain-extended and transferred into the aqueous phase, the organic solvents being able to be removed by distillation.
  • the polyols used to prepare the prepolymer can be low and / or high molecular weight and can also contain anionic groups.
  • Low molecular weight polyols preferably have a number average molecular weight Mn of 60 to 400 and can contain aliphatic, alicyclic or aromatic groups. You can use up to 30 wt .-% of the total polyol components.
  • Suitable low molecular weight polyols are, for example, diols, triols and polyols, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-
  • High molecular weight polyols consist of linear or branched polyols with an OH number of 30 to 150. You can use up to 97 wt .-% of the total polyol components. These are preferably saturated or unsaturated polyester and / or polyether diols and / or polycarbonate diols with a molecular weight Mn of 400 to 5000 or mixtures thereof.
  • Suitable linear or branched polyether diols are, for example, poly (oxyethylene) glycols, poly (oxypropylene) glycols and / or poly (oxybutylene) glycols.
  • Polyesters are preferred and are prepared in a known manner by esterification of dicarboxylic acids or their anhydrides with diols.
  • polyols or polycarboxylic acids with a higher functionality can also be used to a small extent.
  • the groups capable of forming anions can originate from the polyester or they are introduced into the prepolymer by using compounds which contain two H-active groups which react with isocyanate groups and at least one group which is capable of forming anions.
  • Suitable groups which react with isocyanate groups are, in particular, hydroxyl groups and primary and / or secondary amino groups.
  • Groups which are capable of forming anions are, for example, carboxyl, sulfonic acid and / or phosphonic acid groups.
  • dihydroxycarboxylic acids such as dihydroxypropionic acid, dihydroxybutyric acid, dihydroxysuccinic acid, diaminobenzoic acid and preferably ⁇ , ⁇ -dimethylolalkanoic acid such as dimethylolpropionic acid.
  • Suitable polyisocyanates are aliphatic, cycloaliphatic and / or aromatic polyisocyanates with at least two isocyanate groups per molecule and the known biuret, AUophanat, urethane and / or isocyanurate group derivatives of these diisocyanates and mixtures of these polyisocyanates.
  • the isomers or isomer mixtures of organic diisocyanates are preferably used.
  • the polyisocyanate component used to prepare the prepolymer can also contain small amounts of higher-functionality polyisocyanates.
  • the preparation of the prepolymer is expediently carried out in the presence of catalysts, e.g. Organotin compounds or tertiary amines performed.
  • catalysts e.g. Organotin compounds or tertiary amines performed.
  • the polyurethane resin is converted into the aqueous phase, as described for the polyester resins, by neutralizing the acid group
  • Polyurethane resin with a basic neutralizing agent Polyurethane resin with a basic neutralizing agent.
  • basic neutralizing agents are those described above for neutralizing the polyester resins.
  • the coating composition according to the invention is preferably crosslinked when baked by reaction with a crosslinking component.
  • Crosslinking components are familiar to the person skilled in the art. examples are Aminoplast resins, in particular melamine-formaldehyde resins; Phenolic resins; blocked polyisocyanates or transesterification crosslinking agents such as polyesters or polyurethane esters with hydroxyalkyl ester groups, acetoacetic acid or malonic acid alkyl ester derivatives, tris (alkoxycarbonylamino) triazine derivatives and mixtures of these crosslinking components which can give highly crosslinked coatings with or without the action of catalysts. Blocked polyisocyanates are preferred.
  • the blocked polyisocyanates contain on average more than one isocyanate group, preferably at least two isocyanate groups per molecule. They are said to be in the watery
  • Phase stable at about neutral to weakly basic pH split when exposed to heat from about 100 ° C to 200 ° C and crosslink with the reactive hydroxyl and / or carboxyl groups present in the resin dressing.
  • Blocked polyisocyanates are obtained by reacting polyisocyanates with monofunctional compounds with active hydrogen.
  • Any organic di- and / or polyisocyanates with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound free isocyanate groups are suitable as polyisocyanates, which can be used individually or in a mixture in a blocked form as crosslinking agents.
  • Polyisocyanates containing about 3 to 36, particularly preferably 8 to 15, carbon atoms are preferred.
  • suitable diisocyanates are tolylene diisocyanate, diphenylmethane diisocyanate and in particular
  • Dicyclohexylmethane diisocyanate which are the known biuret, urethane, uretdione and / or isocyanurate group derivatives these diisocyanates.
  • Monofunctional compounds with active hydrogen that can be used to block the polyisocyanates are common.
  • CH-acidic compounds such as acetylacetone
  • CH-acidic esters such as alkyl acetoacetate
  • Dialkyl malonate (cyclo) aliphatic alcohols such as n-butanol, 2-ethylhexanol, cyclohexanone; Glycol ethers such as butyl glycol, butyl diglycol; Phenols such as cresol, tert-butylphenol; Diamino alcohols such as dimethylaminoethanol; Oximes such as butanone oxime, acetone oxime, cyclohexanone oxime; Lactams such as e-caprolactam or pyrrolidone-2; Imides; Hydroxyalkyl esters; Hydroxamic acids and their esters; Pyrazoles.
  • aliphatic alcohols such as n-butanol, 2-ethylhexanol, cyclohexanone
  • Glycol ethers such as butyl glycol, butyl diglycol
  • Phenols such as cresol, tert-buty
  • the polyisocyanates can be blocked within a molecule with the same or different blocking agents. Mixtures of polyisocyanates blocked the same or different can also be used.
  • the melamine-formaldehyde resins crosslink with the hydroxyl groups of the polyester resin to form ether groups.
  • these crosslinkers are triazines such as melamine or benzoguanamine, which are condensed by known technical processes in the presence of alcohols such as methanol, ethanol, propanol, butanol or hexanol with aldehydes, in particular formaldehyde.
  • alcohols such as methanol, ethanol, propanol, butanol or hexanol with aldehydes, in particular formaldehyde.
  • methanol-etherified melamine resins such as Cymel 325, Cymel 327, Cymel 350, Cymel 370, Maprenal MF 927; Butanol or isobutanol etherified melamine resins such as e.g. Setamin US 138 or Maprenal MF 610; mixed etherified melamine resins, and in particular um
  • Hexamethylol melamine resins such as e.g. Cymel 301 or Cymel 303.
  • component (A) Because of the low content of organic solvent in component (A), it is advantageous to use component (A) as a conventional biocidal component to prevent infestation with microorganisms such as bacteria, yeasts, algae or
  • Add mushrooms such as formaldehyde depot products, phenolic compounds, organic sulfur compounds or oxidizing agents.
  • Commercially available anionically and / or non-ionically stabilized emulsifiers can also be used in quantities of up to 3% by weight, based on solid resin, for the production of component (A).
  • auxiliaries and additives customary in lacquer can also be added in the customary amounts, for example optical brighteners such as derivatives of stilbene, coumarin, 1,3-diphenylpyrazoline, naphthalimide, benzoxazole and thiophenbenzoxazole, customary catalysts, such as them are known to the person skilled in the art for the respective crosslinking systems; ethoxylated or propoxylated derivatives of substituted phenols or fatty alcohols with more than 10 C atoms as layer formers.
  • optical brighteners such as derivatives of stilbene, coumarin, 1,3-diphenylpyrazoline, naphthalimide, benzoxazole and thiophenbenzoxazole
  • customary catalysts such as them are known to the person skilled in the art for the respective crosslinking systems
  • the aqueous pigmented component (B) contains one or more paste resins, pigments and / or fillers, neutralizing agents, water and expediently a biocidal component and, if appropriate, crosslinking agents and / or additives customary in lacquers, as described, for example, for component (A).
  • the layer formers can e.g. in amounts up to 10% by weight, based on the solids of the components, components (A) and / or (B) are added.
  • the addition can take place to the components (A) / or (B) or in the aqueous components (A) and / or (B) or in the coatable electrocoating bath.
  • the layer formers are preferably added to the binders of components (A) and / or (B) before they are converted into the aqueous dispersion.
  • Suitable paste resins are polyester resins, polyurethane resins, polyacrylate resins and aminoplast resins, as are described in component (A). Polyester urethane resins are preferred.
  • a particularly preferred embodiment is, for example, OH group-containing urethanized oil-free polyesters with an acid number of 10 to 50 and a number average molecular weight (Mn) of 2,000 to 20,000.
  • Such polyester urethane resins are obtained, for example, by reacting one or more polyester polyol (s) free of carboxyl groups and having an OH number of 35 to 200 and a number average molecular weight of 500 to 5000 with 2 to 30% by weight, based on the polyester polyol low molecular weight diols with a molecular weight of 60 to 350, some of the low molecular weight diols containing at least one acid group capable of forming anions, and with 0 to 6% by weight, based on the polyester polyol, of low molecular weight triols with a molecular weight of 60 to 350 one or more diisocyanates, in the ratio of the OH groups of polyester polyol, diol and triol to the NCO groups of the diisocyanate of more
  • Isocyanate groups are implemented.
  • the reaction can also be carried out in stages. Depending on the use of diols or higher functional polyols, one or more hydroxyl groups are obtained at the chain end.
  • the anionic-forming diol such as dimethylolpropionic acid
  • organic solvent which does not react with the isocyanate groups can first be reacted with one or more diisocyanates, followed by further reaction with polyester and low molecular weight diol and / or triol free of anion groups.
  • the polyaddition can be terminated by monofunctional additives such as butanone oxime, dibutylamine or alcoholic solvents.
  • monofunctional additives such as butanone oxime, dibutylamine or alcoholic solvents.
  • the solvents which do not react with the isocyanate groups are intended to keep the reactants in a liquid state and to enable better temperature control during the reaction. Suitable solvents are, for example, dimethylformamide, dimethylacetamide, l-methyl-2-pyrrolidone, acetonitrile, tetrahydrofuran, dioxane,
  • Esters such as ethyl acetate, but also ketones such as acetone, fully etherified mono- or diglycols of ethylene glycol or propylene glycol, and with methoxy groups substituted ketones.
  • the aforementioned biocides, crosslinking agents and / or conventional lacquer additives are added to it. Then the transfer into the aqueous takes place
  • Customary pigments, fillers, corrosion inhibitors and paint auxiliaries can be used for pigmenting the aqueous component (B), as long as they do not enter into interfering reactions with water in a weakly basic to neutral pH value and do not introduce water-soluble interfering foreign ions.
  • Suitable pigments are, for example, inorganic pigments, e.g. White pigments such as titanium dioxide, zinc sulfide, lithopone, lead carbonate, lead sulfate, tin oxide, antimony oxide; colored inorganic pigments such as chrome yellow, nickel titanium yellow,
  • Effect pigments such as aluminum bronzes, pearlescent pigments or interference pigments can also be used.
  • Barium sulfate, aluminum hydroxide and silicas can be used.
  • the aqueous pigmented component (B) can also be admixed with conventional auxiliaries, such as anti-foaming agents, dispersing aids and rheology control agents.
  • the aqueous pigmented component (B) is prepared in the usual manner, the A person skilled in the art by dispersing the pigments and auxiliaries in the paste resin.
  • the composition of the ingredients for optimal dispersion is determined separately for each dispersing unit. Suitable dispersing units are, for example, stirring disc devices, three-roll mills, ball mills or, preferably, sand or pearl mills.
  • Components (A) and (B) are used for coating in a mixing ratio of 1: 1 to 4: 1, based on the weight of the respective aqueous components.
  • the two components are mixed with the bath material in the specified mixing ratio.
  • both components can be added to the bath at the same time or in succession.
  • the components are preferably premixed with part of the bath material in a conventional mixing device.
  • a mixing element can be, for example, a stirred tank, a static mixer or a rotor / stator mixer.
  • Components (A) and (B) can also be mixed beforehand in the desired ratio and used as a one-component material for post-compensation.
  • component (A) is mixed with additional neutralizing agent in order to obtain the desired MEQ value of the ATL bath and, if appropriate, prediluted with water. Then component (B) is fed in in the manner described above and the mixture is adjusted to the desired final solid for the coating.
  • the first step is to present the required amount of water with the neutralizing agent and to supply components (A) and (B) in the manner described above.
  • the ATL bath has a solids content of 8 to 25% by weight, preferably 10 to 15% by weight, an MEQ value of 50 to 90, preferably 60 to 70 and an organic solvent content of less 0.3% by weight.
  • the deposition is carried out by applying a DC voltage of 50 to 500 volts with a coating time of 0.5 to 5 minutes at a temperature of the ATL bath of 18 to 35 ° C.
  • the coating material is suitable for coating workpieces with an electrically conductive surface, in particular for priming and single-layer coating of household and electrical appliances, steel furniture, components, construction and agricultural machinery, automobile bodies and automotive accessories.
  • a polyester resin with an acid number of 49 and a hydroxyl number of 60 made from 26.17 parts by weight of neopentyl glycol, 5.43 parts by weight of trimethylolpropane, 10.83 parts by weight of isophthalic acid, 21.45 parts by weight of isodecanol and 36.12 parts by weight of trimellitic anhydride
  • a mixture of 2.55 parts by weight of dimethylethanolamine (50%) and 3 parts by weight of deionized water is added in a reaction vessel with stirrer, thermometer and reflux condenser, at 100 ° C.
  • Hexamethylene diisocyanate, blocked with butanone oxime are previously heated to 70 to 80 ° C, added to the mixture and stirred homogeneously for 15 minutes.
  • a mixture of 1.38 parts by weight of diisopropanolamine (50%), 0.7 parts by weight of ammonia spirit and 2.60 parts by weight of completely deionized water is then added and the mixture is stirred in homogeneously for 10 minutes.
  • Dissolver mixer 9.40 kg of a melamine resin of the hexamethylol melamine resin type are added with stirring and the mixture is stirred at 40 ° C. for 30 minutes. Solid 30 minutes 180 ° C: 60.8%
  • the mixture is then neutralized with 30.0 g of 50% dimethylethanolamine solution and an aqueous dispersion is prepared with 1450 g of water.
  • the acetone is removed from the reaction mixture by distillation, so that a solvent-free aqueous polyurethane dispersion is obtained.
  • Paste resin placed in a dissolver mixer and sprinkled in the order given 41.70 kg titanium dioxide, 7.00 kg aluminum hydrosilicate, 7.00 kg post-treated aluminum hydrosilicate, 1.80 kg silicon dioxide and 0.50 kg of a polybutylene with stirring.
  • the regrind prepared in this way is stirred for 20 minutes at 50 to 60 ° C. and then dispersed on a Coball mill under specified conditions.
  • Aqueous pigmented component (B2) Aqueous pigmented component (B2)

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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)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Peptides Or Proteins (AREA)
  • Apparatuses And Processes For Manufacturing Resistors (AREA)
  • Saccharide Compounds (AREA)
EP99902531A 1998-01-17 1999-01-11 Procede de trempage electrophoretique anodique Expired - Lifetime EP1047812B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SI9930064T SI1047812T1 (en) 1998-01-17 1999-01-11 Anodic electrophoretic coating method

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19801605 1998-01-17
DE19801605A DE19801605C1 (de) 1998-01-17 1998-01-17 Verfahren zur anodischen Elektrotauchlackierung
PCT/EP1999/000118 WO1999036597A2 (fr) 1998-01-17 1999-01-11 Procede de trempage electrophoretique anodique

Publications (2)

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EP1047812A2 true EP1047812A2 (fr) 2000-11-02
EP1047812B1 EP1047812B1 (fr) 2002-05-08

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US (1) US6350358B1 (fr)
EP (1) EP1047812B1 (fr)
JP (1) JP3694459B2 (fr)
KR (1) KR100585502B1 (fr)
CN (1) CN1191393C (fr)
AT (1) ATE217367T1 (fr)
BR (1) BR9907006B1 (fr)
CA (1) CA2318202C (fr)
DE (2) DE19801605C1 (fr)
ES (1) ES2177225T3 (fr)
MX (1) MXPA00006988A (fr)
PT (1) PT1047812E (fr)
WO (1) WO1999036597A2 (fr)
ZA (1) ZA99250B (fr)

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CA2517550C (fr) * 2003-03-04 2009-09-08 Valspar Sourcing Inc. Methode de traitement d'un equipement de revetement electrolytique contamine
CA2518053C (fr) * 2003-03-04 2012-10-30 Valspar Sourcing, Inc. Detection de micro-organismes dans une operation de revetement electrolytique
CA2518051A1 (fr) * 2003-03-04 2004-09-16 Valspar Sourcing, Inc. Systeme de gestion d'electrorevetement
DE10318481B4 (de) * 2003-04-16 2006-09-07 Ami-Agrolinz Melamine International Gmbh Verfahren zur kontinuierlichen Synthese eines Melaminflüssigharzes

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DE3247756A1 (de) * 1982-12-23 1984-06-28 Herberts Gmbh, 5600 Wuppertal Waessriges ueberzugsmittel
DE4223181A1 (de) * 1992-07-15 1994-01-20 Herberts Gmbh Verfahren zur Wiederaufbereitung von Elektrotauchlackbädern

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See references of WO9936597A2 *

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KR100585502B1 (ko) 2006-06-02
DE59901390D1 (de) 2002-06-13
MXPA00006988A (es) 2003-07-14
ATE217367T1 (de) 2002-05-15
ZA99250B (en) 1999-07-14
CA2318202C (fr) 2008-11-18
JP2002509197A (ja) 2002-03-26
WO1999036597A3 (fr) 1999-09-30
HK1035006A1 (en) 2001-11-09
ES2177225T3 (es) 2002-12-01
CN1293721A (zh) 2001-05-02
DE19801605C1 (de) 1999-03-18
CN1191393C (zh) 2005-03-02
JP3694459B2 (ja) 2005-09-14
US6350358B1 (en) 2002-02-26
BR9907006B1 (pt) 2008-11-18
KR20010034197A (ko) 2001-04-25
WO1999036597A2 (fr) 1999-07-22
BR9907006A (pt) 2000-10-17
EP1047812B1 (fr) 2002-05-08
CA2318202A1 (fr) 1999-07-22
PT1047812E (pt) 2002-10-31

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