EP0828568A1 - Procede de peinture multicouche - Google Patents

Procede de peinture multicouche

Info

Publication number
EP0828568A1
EP0828568A1 EP96917417A EP96917417A EP0828568A1 EP 0828568 A1 EP0828568 A1 EP 0828568A1 EP 96917417 A EP96917417 A EP 96917417A EP 96917417 A EP96917417 A EP 96917417A EP 0828568 A1 EP0828568 A1 EP 0828568A1
Authority
EP
European Patent Office
Prior art keywords
layer
coating
coating agent
clear lacquer
electrophoretically
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
EP96917417A
Other languages
German (de)
English (en)
Other versions
EP0828568B1 (fr
Inventor
Joachim Blum
Dieter STRANGHÖNER
Dieter Engel
Klausjörg Klein
Walter KÜHHIRT
Matthias Kimpel
Friedrich-Ludwig Siever
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
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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Application filed by Herberts GmbH filed Critical Herberts GmbH
Publication of EP0828568A1 publication Critical patent/EP0828568A1/fr
Application granted granted Critical
Publication of EP0828568B1 publication Critical patent/EP0828568B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/576—Three layers or more the last layer being a clear coat each layer being cured, at least partially, separately
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/577—Three layers or more the last layer being a clear coat some layers being coated "wet-on-wet", the others not
    • 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 invention relates to a method for producing a multilayer coating of conductive, in particular metallic substrates, which is particularly suitable for automotive coating.
  • Today's high-quality automotive OEM coatings generally consist of an electrophoretically applied primer that protects against corrosion and subsequently spray-applied subsequent layers consisting of a filler layer and a subsequently applied decorative coating of coloring and / or effect basecoat and a protective clearcoat layer that seals the surface.
  • the total layer thickness of such automotive coatings is in practice between 90 and 130 ⁇ m, which is the sum of 15 to 25 ⁇ m layer thickness for the primer, 30 to 40 ⁇ m for the filler layer, 10 to 25 ⁇ m for the basecoat layer and 30 to 40 ⁇ m for the Clear coat results.
  • layer thicknesses are considerably exceeded if paintwork with a particularly good visual appearance, i.e. with outstanding gloss and top coat level, for example, in the painting of motor vehicles of the luxury and luxury class.
  • DE-A-42 15070 and DE-A-3839905 describe the application of several layers of clear lacquer to one basecoat. This then results in layer thicknesses of 120 ⁇ m and above, e.g. up to 170 ⁇ m, which is undesirable for reasons of material savings and weight savings on the finished vehicle.
  • the object of the invention is to provide multi-layer paints, in particular motor vehicle paints, which meet the requirements of an outstanding gloss and topcoat level without exceeding the normal level of the total layer thicknesses of motor vehicle paints and without disadvantages in the process To have to accept the level of property.
  • this object can surprisingly be achieved by a process for producing a multilayer coating, in which a primer from an electrophoretically separable aqueous coating composition (I) is applied electrophoretically and then baked on an electrically conductive substrate, whereupon a color and / or effect basecoat is applied from an aqueous coating agent (II) and baked, and this is provided with one or more clearcoat coatings, which is characterized in that a) the coating agent (I) used is one which is electrically baked to a baked state leads conductive primer layer, b) the basecoat is formed from an electrophoretically depositable aqueous coating agent (II) by electrophoretic deposition, c) the total dry film thickness of the clearcoat or clearcoat layers is 40 to 80 ⁇ m and d) the total the dry layer thickness of the multi-layer coating is 80 to 110 ⁇ m.
  • the clear lacquer layer can consist of one or more layers, the first clear lacquer layer preferably being stoved before application of the further clear lacquer layers. Several layers of clear lacquer can be created from the same or from different clear lacquer coatings.
  • electroplating (I) and (II) known per se, anodically or cathodically depositable electrodeposition lacquers (ETL), which can be deposited electrophoretically but differ from one another, can be used to produce the first and second coating layers, it being true that this is electrophoretic depositable coating agent (I) contains constituents which, in the baked state, impart to the first coating layer a sufficiently low specific resistance for the electrophoretic deposition of a further coating layer from a coating agent (II) different from (I), and that the electrophoretically depositable coating agent (II) contains coloring and / or effect pigments.
  • ETL cathodically depositable electrodeposition lacquers
  • the coating compositions (I) and (II) are aqueous coating compositions with a solids content of, for example, 10 to 20% by weight.
  • This consists of conventional binders, at least some of the binders carrying ionic and / or substitutable substituents and groups which may be capable of chemical crosslinking, as well as any crosslinking agents, electrically conductive constituents, fillers, pigments and conventional lacquer additives.
  • the ionic groups or groups of the binders which can be converted into ionic groups can be anionic or groups which can be converted into anionic groups, for example acidic groups such as -C00H, -S0 3 H and / or -P0 3 H 2 and the corresponding anionic groups neutralized with bases . They can also be cationic or convertible into cationic groups, for example basic groups, preferably nitrogen-containing basic groups; these groups can be present in quaternized form or they are converted into ionic groups using a conventional neutralizing agent, for example an organic monocarboxylic acid, such as, for example, formic acid or acetic acid. Examples are amino, ammonium, for example quaternary ammonium, phosphonium and / or sulfonium groups.
  • the conventional anionic group-containing anodically depositable electrocoat binders and paints can be used to produce the first and / or second coating layer.
  • examples are those as described in DE-A-28 24418. These are, for example, binders based on polyesters, epoxy resin esters, resin (meth) acrylic copoly, maleate oils or polybutadiene oils with a weight average molecular weight (Mw) of for example 300-10000 and an acid number of 35-300 mg KOH / g.
  • binders based on polyesters or (meth) acrylic copolymer resins are preferably used as anodically depositable binders.
  • the binders carry -C00H, -S0 3 H and / or -P0 3 H 2 groups. After neutralization of at least some of the acidic groups, the resins can be converted into the water phase.
  • the binders can be self-crosslinking or externally crosslinking.
  • the lacquers can therefore also contain customary crosslinking agents, for example triazine resins, crosslinking agents which contain groups capable of esterification or blocked polyisocyanates.
  • the usual cathodic electrocoat materials (KTL) based on cationic or basic binders can also be used in the process according to the invention for producing the first and / or second coating layer.
  • Such basic resins are, for example, primary, secondary and / or tertiary amino group-containing resins, the amine numbers of which are e.g. are 20 to 250 mg KOH / g.
  • the weight average molecular weight (Mw) of the base resins is preferably 300 to 10,000.
  • base resins examples include amino epoxy resins, amino epoxy resins with terminal double bonds, amino epoxy resins with primary 0H groups, aminopolyurethane resins, amino group-containing polybutadiene resins or modified epoxy resin-carbon dioxide products amino (meth) acrylate resins preferably used in the production of the second coating layer.
  • These base resins can be self-crosslinking or they are used in a mixture with known crosslinking agents.
  • crosslinkers are aminoplast resins, blocked polyisocyanates, crosslinkers with terminal double bonds, polyepoxide compounds or crosslinkers which contain groups capable of transesterification.
  • base resins and crosslinking agents which can be used in cathodic dip lacquer (KTL) baths are described in EP-A-0082 291, EP-A-0 234 395, EP-A-0227975, EP-A-0 178531, EP-A-0 333 327, EP-A-0310 971, EP-A-0 456270, US 3922 253, EP-A-0 261 385, EP-A-0 245 786, DE-A-33 24211, EP-A-0414 199 , EP-A-0476514. These resins can be used alone or in a mixture.
  • Non-yellowing CTL systems are preferably used, which cause yellowing or discoloration Avoid the multi-layer coatings produced by the process according to the invention when baking.
  • KTL systems that crosslink using specially selected blocked polyisocyanates, as described, for example, in EP-A-0 265 363.
  • the electrocoat (ETL) coating agent (I) contains components that impart electrical conductivity. They should give the first coating layer in the baked state a resistivity which is sufficiently low for the electrophoretic deposition of a further coating layer from the electrophoretically depositable coating agent (II), for example between 10 3 and 10 8 ohm.cm.
  • examples of such ingredients are teilchenför strength inorganic or organic electrical conductors or semiconductors, such as iron oxide black, graphite, conductive carbon black, metal powders such as aluminum, copper or stainless steel, Molybdändi 'sulfide or polymers having electrical conductivity, such as preferably polyaniline.
  • Electrodeposition paints containing such constituents which can be used according to the invention can be found in US 3,674,671, GB 2,129,807, EP-A-0409821 and EP-A-0426327.
  • the electrical conductivity-imparting constituents are contained in the ETL coating agent (I) in such an amount that the desired specific resistance of the coating layer deposited therefrom is achieved in the baked state.
  • the proportion of the constituent (s) which confer electrical conductivity is, for example, between 1 and 30% by weight.
  • the proportion can easily be determined by a specialist; it depends, for example, on the specific weight, the specific electrical conductivity and the particle size of the components imparting electrical conductivity. One or more of these components can be present in combination.
  • ETL- Coating agents (I) and (II) contain fillers and / or conventional paint additives.
  • the ETL coating agent (I) can also contain pigments.
  • Pigments include, for example, the customary inorganic and / or organic colored pigments and / or effect pigments, such as, for example, titanium dioxide, iron oxide pigments, phthalocyanine pigments, quinacridone pigments, metal pigments, for example made of titanium, aluminum or copper, interference pigments such as, for example, titanium dioxide-coated aluminum, coated mica, coated mica, graphite Iron oxide, platelet-shaped copper phthalocyanine pigments in question.
  • black pigments are coarse coal, coarse soot produced by incomplete combustion, coarse soot obtained by catalytic or thermal decomposition of liquid or gaseous hydrocarbons.
  • fillers are kaolin, talc or silicon dioxide.
  • the pigments can be dispersed into pigment pastes, e.g. using known paste resins. Resins of this type are familiar to the person skilled in the art. Examples of paste resins that can be used in KTL baths are described in EP-A-0 183025 and in EP-A-0469497. In particular in the case of the ATL coating agents which are preferably used for the production of the second coating layer, it is possible to use pigment pastes as are used in the water-based lacquers which are known to the person skilled in the art and are suitable for producing two-layer lacquers of the basecoat / clearcoat type. Such pigment pastes can be obtained by rubbing the pigments in a special water-thinnable paste resin. An example of such a paste resin, which can preferably be used, based on an anionically stabilized polyurethane resin can be found in DE-A-40 00889.
  • additives as are known in particular for ETL coating agents, are possible as additives.
  • these are wetting agents, neutralizing agents, leveling agents, catalysts, corrosion inhibitors, antifoams, solvents, but in particular light stabilizers, if appropriate in combination with antioxidants.
  • an ETL coating agent (I) it is preferred in the process according to the invention as an ETL coating agent (I) to use a KTL coating agent and as an ETL coating agent (II) an ATL coating agent.
  • all customary clear lacquers or transparent colored or colorless pigmented coating compositions are suitable as clear coating compositions for the production of the third and possibly further coating layers.
  • These can be single-component or multi-component clear lacquer coating compositions. They can be solvent-free (liquid or as a powder clearcoat), or they can be systems based on solvents, or they can be water-dilutable clearcoats, the binder systems of which are suitable, e.g. anionic, cationic or non-ionic, are stabilized.
  • the water-dilutable clear lacquer systems can be water-soluble or water-dispersed systems, for example emulsion systems or powder slurry systems.
  • the clear lacquer coating agents harden when stoved to form covalent bonds as a result of chemical crosslinking.
  • the clearcoats which can be used in the process according to the invention are customary clearcoat coating compositions which contain one or more customary base resins as film-forming binders. If the base resins are not self-crosslinking, they may also contain crosslinking agents. Both the base resin component and the crosslinker component are not subject to any limitation. Polyester, polyurethane and / or (meth) acrylic copolymer resins, for example, can be used as film-forming binders (base resins).
  • base resins polyester, polyurethane and / or (meth) acrylic copolymer resins, for example, can be used as film-forming binders (base resins).
  • the selection of the crosslinking agents which may be present is not critical, it depends on the functionality of the base resins, ie the crosslinking agents are selected such that they have a reactive functionality which is complementary to the functionality of the base resins.
  • complementary functionalities between base resin and crosslinker are: carboxyl / epoxy, hydroxyl / methylol ether directly bonded to carbon or silicon, hydroxyl / free and / or blocked isocyanate directly bonded to carbon or silicon, (meth) acryloyl / CH-acidic group.
  • hydroxyl groups bonded directly to silicon are also to be understood as latent silanol groups, such as alkoxysilane groups.
  • Several such complementary functionalities can also be present side by side in a clear lacquer.
  • the crosslinking agents optionally used in the clear lacquers can be present individually or in a mixture.
  • Examples of one- (1K) and two-component (2K) non-aqueous clearcoat systems which can be used as clearcoat in the process according to the invention can be found in DE-A-38 26693, DE-A-40 17 075, DE-A-41 24 167, DE-A-41 33704, DE-A-42 04 518, DE-A-42 04611, EP-A-0 257 513, EP-A-0408858, EP-A-0 523 267, EP-A -0 557 822, W0-92 11 327.
  • Examples of one (1K) or two-component (2K) water-based clearcoat systems which can be used as clearcoat in the process according to the invention can be found in DE-A-39 10829, DE-A-40 09931, DE-A-4009932, DE-A -41 01 696, DE-A-41 32 430, DE-A-41 34 290, DE-A-42 03510, EP-A-0365098, EP-A-0365 775, EP-A-0 496079, EP- A-0 546640.
  • Examples of the powder clearcoat systems preferably used in the process according to the invention for producing the transparent coating layer can be found in EP-A-0 509 392, EP-A-0509 393, EP-A-0 522648, EP-A-0 544 206, EP-A -0 555 705, DE-A-42 22 194, DE-A-42 27 580.
  • the transparent coating can be applied in a single layer or in the form of several layers from the same or from several different transparent coating agents.
  • the transparent coating layer is expediently applied as a third layer comprising only one clear lacquer coating agent.
  • Clearcoat compositions which have the lowest possible drainage tendency are preferably used, for example solid-state clearcoats according to adjusted rheological behavior. Powder clearcoats are particularly preferred.
  • Electrically conductive materials such as metals are suitable as the substrate for the method according to the invention.
  • Particularly suitable are e.g. Automotive bodies or parts thereof, they can consist of pretreated or untreated metal or electrically conductive or plastic provided with an electrically conductive layer.
  • the first coating layer from the aqueous coating agent (I) is deposited electrophoretically on these substrates in a customary manner in a dry layer thickness of, for example, 5 to 15 ⁇ m and, for example, baked at temperatures between 130 and 180 ° C.
  • the second coating layer made of a second color and / or effect coating agent (II) different from (I) which can be deposited by electrophoresis is applied to the substrate thus obtained, which has an ETL layer with a specific resistance of in particular 10 3 to 10 s Ohm.cm. a dry layer thickness of, for example, 10 to 45 ⁇ m, preferably applied between 15 and 30 ⁇ m and likewise baked, for example, at temperatures between 130 and 180 ° C.
  • the second coating layer generally has virtually no electrical conductivity, that is, it has a resistivity of, generally, about 10 to ⁇ Ohm.cm in the stoved state.
  • the coating obtained by electrocoating from the coating agent (I) serves in particular to protect against chemical and corrosive attack, so that it is advantageous to coat the entire surface of a three-dimensional substrate, for example a body, if possible.
  • the coloring and / or effect-giving coating which is obtained by electrocoating from the coating composition (II) and which is electrically insulating in the baked state can, but does not have to extend over the entire surface of the three-dimensional substrate; a possible double coating is accordingly, for example, an entire surface first coating by electrocoating from the coating agent (I) and a coloring and / or effect coating from the coating agent (II) by electrocoating, for example essentially only on outer areas, in particular visible surfaces of a three-dimensional substrate, that is to say for example not in narrow cavities of a body .
  • the third coating layer is applied from a conventional liquid or powder clearcoat, and baked for example at temperatures from 80 to 160 ⁇ C. If necessary, further layers of clear lacquer can be applied from the same or different clear lacquer coating compositions. According to the invention, work is preferably carried out in such a way that the layer thickness of the transparent coating layer or the total layer thickness of a plurality of transparent coating layers is between 40 and 80 ⁇ m, particularly preferably between 50 and 60 ⁇ m.
  • the method according to the invention allows the production of multi-layer coatings, in particular automotive coatings with something comparable in comparison to the prior art

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un procédé d'une peinture multicouche, qui consiste à appliquer par électrophorèse sur un substrat électroconducteur, un apprêt composé d'un produit de revêtement (I) aqueux, pouvant être déposé électrophorèse puis cuit sur lequel on applique une couche de peinture de base colorante et/ou à effet, composée d'un produit de revêtement (II) aqueux et qui est ensuite cuite. Cette couche de base est ensuite revêtue d'une ou plusieurs couches de vernis. Dans ce procédé: a) le produit de revêtement (I) utilisé donne, une fois cuit, une couche d'apprêt électroconductrice, b) la couche de peinture de base est composée d'un produit de revêtement (II) aqueux et pouvant être déposé par électrophorèse c) l'épaisseur totale de la couche ou des couches de vernis sèches se situe entre 40 et 80 mu m et d) l'épaisseur totale des couches sèches de la peinture multicouche se situe entre 80 et 110 mu m.
EP96917417A 1995-05-30 1996-05-24 Procede de peinture multicouche Expired - Lifetime EP0828568B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19519667 1995-05-30
DE19519667A DE19519667C1 (de) 1995-05-30 1995-05-30 Verfahren zur Mehrschichtlackierung
PCT/EP1996/002233 WO1996038234A1 (fr) 1995-05-30 1996-05-24 Procede de peinture multicouche

Publications (2)

Publication Number Publication Date
EP0828568A1 true EP0828568A1 (fr) 1998-03-18
EP0828568B1 EP0828568B1 (fr) 1999-02-03

Family

ID=7763139

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96917417A Expired - Lifetime EP0828568B1 (fr) 1995-05-30 1996-05-24 Procede de peinture multicouche

Country Status (13)

Country Link
US (1) US5908667A (fr)
EP (1) EP0828568B1 (fr)
JP (1) JPH11505886A (fr)
KR (1) KR100398465B1 (fr)
AT (1) ATE176408T1 (fr)
BR (1) BR9608599A (fr)
CA (1) CA2222798A1 (fr)
DE (2) DE19519667C1 (fr)
ES (1) ES2129971T3 (fr)
MX (1) MX9709223A (fr)
PL (1) PL323599A1 (fr)
WO (1) WO1996038234A1 (fr)
ZA (1) ZA964395B (fr)

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Publication number Publication date
US5908667A (en) 1999-06-01
EP0828568B1 (fr) 1999-02-03
MX9709223A (es) 1998-03-31
KR100398465B1 (ko) 2004-01-28
DE19519667C1 (de) 1997-02-06
ZA964395B (en) 1996-12-09
ATE176408T1 (de) 1999-02-15
JPH11505886A (ja) 1999-05-25
KR19990022091A (ko) 1999-03-25
BR9608599A (pt) 1999-01-05
CA2222798A1 (fr) 1996-12-05
ES2129971T3 (es) 1999-06-16
WO1996038234A1 (fr) 1996-12-05
PL323599A1 (en) 1998-04-14
DE59601270D1 (de) 1999-03-18

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