EP0828568B1 - Procede de peinture multicouche - Google Patents

Procede de peinture multicouche Download PDF

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Publication number
EP0828568B1
EP0828568B1 EP96917417A EP96917417A EP0828568B1 EP 0828568 B1 EP0828568 B1 EP 0828568B1 EP 96917417 A EP96917417 A EP 96917417A EP 96917417 A EP96917417 A EP 96917417A EP 0828568 B1 EP0828568 B1 EP 0828568B1
Authority
EP
European Patent Office
Prior art keywords
coat
lacquer
coating
coating agent
clear
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP96917417A
Other languages
German (de)
English (en)
Other versions
EP0828568A1 (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
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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 multi-layer paint conductive, especially metallic Substrates that are particularly suitable for automotive painting.
  • the total layer thickness of such automotive paintwork 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 and 30 to 40 ⁇ m for the Clear coat results.
  • These layer thicknesses become significant exceeded if paintwork with particularly good optical Appearance, i.e. with outstanding gloss and top coat for example in the painting of motor vehicles of the upper and luxury class should be achieved.
  • DE-A-42 15 070 in DE-A-38 39 905 or in US-A-5203975
  • Layer thicknesses 120 ⁇ m and above, e.g. up to 170 ⁇ m, what from Saving material and saving weight on the finished Vehicle is undesirable.
  • the object of the invention is to provide multi-layer coatings, in particular automotive paintwork, the Requirements of an outstanding gloss and topcoat level are sufficient, without the normal measure of the total layer thickness of automotive paintwork to exceed and without disadvantages in To have to accept overall property level.
  • a Clear coat with a high thickness of 40 to 80 microns, preferably from 50 to 60 ⁇ m provided. This is applied to the baked basecoat be applied.
  • the clear coat can consist of one or more Layers exist, the first clear lacquer layer preferably before Application of the further layers of clear lacquer is baked.
  • Several Clearcoat layers can be the same or different Clear coating agents are created.
  • the electrophoretic separable coating agent (I) contains components that the first Coating layer in the baked state one for electrophoretic Depositing another coating layer from one of (I) various electrophoretically depositable coating agents (II) give sufficiently low resistivity, and that the electrophoretically depositable coating agent (II) color and / or contains effect pigments.
  • the coating agents (I) and (II) are aqueous Coating agents with a solids content of, for example, 10 to 20% by weight.
  • This consists of conventional binders, with at least a part the binder ionic and / or convertible into ionic groups Substituents and possibly capable of chemical crosslinking Groups carries, as well as any existing crosslinkers, electrically conductive components, fillers, pigments and paint 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 -COOH, -SO 3 H and / or -PO 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 quaternized 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 usual 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 24 418. These are, for example, binders based on polyesters, epoxy resin esters, (meth) acrylic copolymer resins, 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.
  • Mw weight average molecular weight
  • binders based on polyesters or (meth) acrylic copolymer resins are preferably used as anodically depositable binders.
  • the binders carry -COOH, -SO 3 H and / or -PO 3 H 2 groups. After neutralization of at least some of the acidic groups, the resins can be converted into the water phase.
  • the 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 transesterification or blocked polyisocyanates.
  • the first and / or second coating layers are the usual cathodic ones Electrophoretic coatings (KTL) based on cationic or basic Binder.
  • KTL Electrophoretic coatings
  • Such basic resins are, for example, primary, resins containing secondary and / or tertiary amino groups, the Amine numbers e.g. are 20 to 250 mg KOH / g.
  • the weight average of the Molar mass (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 OH groups, Aminopolyurethane resins, amino group-containing polybutadiene resins or modified epoxy resin-carbon dioxide-amine reaction products as well which is preferred in the production of the second coating layer Amino (meth) acrylate resins used.
  • base resins can be self-crosslinking or they are used with known crosslinkers Mixture used.
  • crosslinkers examples include Aminoplast resins, blocked polyisocyanates, crosslinkers with terminal Double bonds, polyepoxide compounds or crosslinkers Contain transesterifiable groups.
  • non-yellowing CTL systems are preferred used a yellowing or discoloration of those produced by the process according to the invention Avoid multi-layer painting when baking. For example it is blocked by means of specially selected KTL systems crosslinking polyisocyanates, such as 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.
  • Such constituents are particulate inorganic or organic electrical conductors or semiconductors, such as, for example, iron oxide black, graphite, carbon black, metal powder, for example made of aluminum, copper or stainless steel, molybdenum disulfide or polymers with electrical conductivity, such as, for example, preferably polyaniline.
  • electrodeposition paints containing such constituents, which can be used according to the invention, can be found in US Pat.
  • ETL coating agent (I) Coating layer in the baked state electrical conductivity components and in the case of the ETL coating agent (II) Color and / or effect pigments contained in the ETL coating agents (I) and (II) fillers and / or additives customary in paint contain.
  • the usual pigments are used, for example inorganic and / or organic colored pigments and / or Effect pigments, e.g. Titanium dioxide, iron oxide pigments, Phthalocyanine pigments, quinacridone pigments, metal pigments, e.g. out Titanium, aluminum or copper, interference pigments, such as e.g.
  • black pigments are coarse coal, generated by incomplete combustion carbon black, by catalytic or thermal decomposition of coarse particles obtained from liquid or gaseous hydrocarbons Soot.
  • fillers are kaolin, talc or silicon dioxide.
  • the pigments can be dispersed into pigment pastes, e.g. under Use of known paste resins.
  • paste resins are known to the person skilled in the art common.
  • paste resins that can be used in KTL baths are in EP-A-0 183 025 and EP-A-0 469 497.
  • pigment pastes use as in the known to those skilled in the manufacture of Suitable for two-coat finishes of the basecoat / clearcoat type Waterborne basecoats are used.
  • Such pigment pastes can are obtained by grinding the pigments in a special water-thinnable paste resin.
  • An example of such preferred paste resin based on an anionic Stabilized polyurethane resin can be found in DE-A-40 00 889.
  • additives are known for ETL coating agents.
  • examples include wetting agents, Neutralizing agents, leveling agents, catalysts, Corrosion inhibitors, anti-foaming agents, solvents, in particular however, light protection agents if necessary in combination with Antioxidants.
  • ETL coating agent (I) a KTL coating agent and as an ETL coating agent (II) an ATL coating agent to use.
  • a clear coat for the production of the third and any additional coating layers are in principle all usual clear coats or transparent colored or colorless pigmented Coating agent suitable. It can be one or act multi-component clear lacquer coating agents. You can be solvent-free (liquid or as a powder clear coat), or it can are systems based on solvents or are are water-thinnable clear coats, whose binder systems in suitably, e.g. anionic, cationic or non-ionic, are stabilized. With the water-borne clear lacquer systems it can are water-soluble or water-dispersed systems, act, for example, emulsion systems or powder slurry systems. The Clear lacquer coating agents harden during baking under training covalent bonds due to chemical cross-linking.
  • the clear lacquers which can be used in the process according to the invention are concerned it is usual clearcoat coating agents, the one or more usual Contain base resins as film-forming binders. You can if the base resins are not self-crosslinking, if necessary also Crosslinker included. Both the base resin component and the Crosslinker components are not subject to any restrictions.
  • Film-forming binders (base resins) can, for example, be polyester, Polyurethane and / or (meth) acrylic copolymer resins can be used. The Selection of any crosslinker that is included is not critical to them depends on the functionality of the base resins, i.e. the crosslinker are selected so that they are one for the functionality of the base resins have complementary, reactive functionality.
  • Complementary functionalities between base resin and crosslinker are: Carboxyl / epoxy, directly bound to carbon or silicon Hydroxyl / methylol ether, directly bound to carbon or silicon Hydroxyl / free and / or blocked isocyanate, (meth) acryloyl / CH-acidic Group.
  • are directly bound to silicon Hydroxyl groups also latent silanol groups, e.g. Alkoxysilane groups to understand. If compatible with each other, can also combine several such complementary functionalities in one Clear varnish side by side.
  • the possibly in the clear coats Crosslinkers used can be present individually or in a mixture.
  • Examples of one (1K) and two-component (2K) non-aqueous Clear lacquer systems used as clear lacquer in the process according to the invention can be used can be found in DE-A-38 26 693, DE-A-40 17 075, DE-A-41 24 167, DE-A-41 33 704, DE-A-42 04 518, DE-A-42 04 611, EP-A-0 257 513, EP-A-0 408 858, EP-A-0 523 267, EP-A-0 557 822, WO-92 11 327.
  • Examples of one (1K) or two-component (2K) Water-clear lacquer systems used as clear lacquer in the process according to the invention can be used can be found in DE-A-39 10 829, DE-A-40 09 931, DE-A-40 09 932, DE-A-41 01 696, DE-A-41 32 430, DE-A-41 34 290, DE-A-42 03 510, EP-A-0 365 098, EP-A-0 365 775, EP-A-0 496 079, EP-A-0 546 640.
  • Powder clearcoat systems can be found in EP-A-0 509 392, EP-A-0 509 393, EP-A-0 522 648, 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 in a single layer or in shape of multiple layers from the same or from several different transparent coating agents can be applied.
  • a substrate for the method according to the invention are electrical conductive materials, such as metals. Particularly suitable are e.g. Automobile bodies or parts of them, them can be made of pretreated or untreated metal or electrical conductive or provided with an electrically conductive layer Plastic.
  • the first coating layer is applied to these substrates from the aqueous coating agent (I) electrophoretically in a conventional manner in a dry layer thickness of, for example, 5 to 15 ⁇ m deposited and for example at temperatures between 130 and 180 ° C. branded.
  • the second coating layer made of a second color and / or effect coating agent (II) which is different from (I) and which can be deposited electrophoretically is applied to the substrate thus obtained, which has an ETL layer having a specific resistance of in particular 10 3 to 10 8 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 practically no electrical conductivity, ie it has a specific resistance of more than 10 9 ohm.cm in the baked state.
  • the one obtained by electrodeposition from the coating agent (I) Coating serves in particular to protect against chemical and corrosive attack, so it is advantageous to try the whole Surface of a three-dimensional substrate, for example one To coat the body.
  • the one obtained by electrodeposition from the coating agent (II) color and / or effect and in the baked state electrical Insulating coating can, but does not have to cover the entire surface extend across the three-dimensional substrate; a possible Accordingly, double coating is, for example, an entire surface first coating by electrocoating from the coating agent (I) and a color and / or effect coating from the Coating agent (II) by electrocoating, for example in essential only on outer areas, especially visible surfaces a three-dimensional substrate, i.e. for example not in narrow Cavities in a body.
  • the third Coating layer is made from a common liquid or powder clear coat applied and for example at temperatures of 80 to 160 ° C. branded. If necessary, further layers of clear lacquer from the the same or different clear lacquer coating agents applied become. According to the invention is preferably carried out so that the Layer thickness of the transparent coating layer or the Total layer thickness of several transparent coating layers between 40 and 80 microns, particularly preferably between 50 and 60 microns.
  • the method according to the invention allows the production of Multi-layer paintwork, in particular of automotive paintwork with comparable to the prior art Overall property level as well as improved gloss and top coat level. It has been shown that excellent properties through the Procedure according to the invention can be achieved, although the Elimination of filler layers enables.
  • the high layer thickness at Clear coat application is the total layer thickness after the Multi-layer coatings produced according to the method of the invention low. They are in particular 80 to 110 ⁇ m and below comparable to the area of usual automotive OEM paintwork high clear coat thickness.

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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)
  • Laminated Bodies (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Claims (6)

  1. Procédé de fabrication d'une peinture multicouche, dans lequel on dépose puis on cuit sur un substrat électriquement conducteur une couche de base constituée d'un revêtement aqueux (I) séparable par électrophorèse, puis on la fait cuire, opération dans laquelle on dépose et on fait cuire une couche de vernis de base produisant une couleur et/ou un effet et constituée d'un revêtement aqueux (II), et l'on munit celle-ci d'un ou plusieurs revêtements de vernis transparent,
    caractérisé en ce que
    (a) on utilise comme revêtement (I) un revêtement qui conduit à l'état cuit à une couche de base électriquement conductrice,
    (b) on forme par séparation électrophorétique la couche de vernis de base est formée à partir d'un revêtement aqueux (II) séparable par électrophorèse (II),
    (c) l'épaisseur totale de la ou des couches sèches de vernis transparent est comprise entre 40 et 80 µm et
    (d) l'épaisseur totale de la couche sèche du revêtement à plusieurs couches se situe entre 80 et 110 µm.
  2. Procédé selon la revendication 1, caractérisé en ce que l'épaisseur totale de couche sèche de la couche ou les couches de vernis transparent est comprise entre 50 et 60 µm.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'on le réalise pour vernir des véhicules automobiles et des pièces de véhicule automobiles.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'on utilise comme revêtement (II) pour produire la couche de vernis de base un revêtement séparable à l'anode.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'on dépose la couche de fond en une épaisseur de couches sèches de 5 à 15 µm, et en ce qu'on dépose la couche de base en une épaisseur de couche sèche de 10 à 45 µm.
  6. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'on produit la ou les couches de vernis transparentes en utilisant un vernis pulvérulent.
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 EP0828568A1 (fr) 1998-03-18
EP0828568B1 true 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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US6423425B1 (en) 1998-05-26 2002-07-23 Ppg Industries Ohio, Inc. Article having a chip-resistant electrodeposited coating and a process for forming an electrodeposited coating

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CA2222798A1 (fr) 1996-12-05
MX9709223A (es) 1998-03-31
DE59601270D1 (de) 1999-03-18
DE19519667C1 (de) 1997-02-06
BR9608599A (pt) 1999-01-05
ES2129971T3 (es) 1999-06-16
EP0828568A1 (fr) 1998-03-18
KR19990022091A (ko) 1999-03-25
WO1996038234A1 (fr) 1996-12-05
JPH11505886A (ja) 1999-05-25
KR100398465B1 (ko) 2004-01-28
ZA964395B (en) 1996-12-09
PL323599A1 (en) 1998-04-14
ATE176408T1 (de) 1999-02-15
US5908667A (en) 1999-06-01

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