EP0367653B1 - Verfahren zur Beschichtung eines Metallsubstrats mit Pulvergrundierungsschicht und mittels Tauchen angebrachte Oberflächenbeschichtung, Grundierungszusammensetzung und so erhaltene Materialien - Google Patents

Verfahren zur Beschichtung eines Metallsubstrats mit Pulvergrundierungsschicht und mittels Tauchen angebrachte Oberflächenbeschichtung, Grundierungszusammensetzung und so erhaltene Materialien Download PDF

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Publication number
EP0367653B1
EP0367653B1 EP89402897A EP89402897A EP0367653B1 EP 0367653 B1 EP0367653 B1 EP 0367653B1 EP 89402897 A EP89402897 A EP 89402897A EP 89402897 A EP89402897 A EP 89402897A EP 0367653 B1 EP0367653 B1 EP 0367653B1
Authority
EP
European Patent Office
Prior art keywords
powder
primer
substrate
coating
dipping
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
EP89402897A
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English (en)
French (fr)
Other versions
EP0367653A1 (de
EP0367653B2 (de
Inventor
Jean-Yves Dutheil
Eric Perraud
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.)
Arkema France SA
Original Assignee
Elf Atochem SA
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 Elf Atochem SA filed Critical Elf Atochem SA
Publication of EP0367653A1 publication Critical patent/EP0367653A1/de
Publication of EP0367653B1 publication Critical patent/EP0367653B1/de
Application granted granted Critical
Publication of EP0367653B2 publication Critical patent/EP0367653B2/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/546—No clear coat specified 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B05D1/22—Processes for applying liquids or other fluent materials performed by dipping using fluidised-bed technique
    • B05D1/24—Applying particulate 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
    • B05D7/58—No clear coat specified
    • B05D7/587—No clear coat specified some layers being coated "wet-on-wet", the others not
    • 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
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • 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
    • B05D2451/00—Type of carrier, type of coating (Multilayers)

Definitions

  • the present invention relates to a method for coating a metal substrate using a surface coating applied by dipping after coating said substrate with a powdered primer.
  • the soaking process in a fluidized bed requires prior preheating of the metal part to be coated before its immersion in the tank with a porous bottom in which the powder of the suspension coating is kept in suspension by air circulation: the powder then melts at contact with hot metal surfaces and forms a deposit, the thickness of which depends on the temperature of the substrate and its duration of immersion in the powder.
  • the part is preheated in an oven at a temperature determined according to the nature and thickness of the part to be coated.
  • an excessively high preheating temperature can be harmful, more particularly in the case where the metal part has previously been coated with an adhesion primer which can deteriorate during the passage of the part in the oven and / or no longer ensuring adhesion with the surface coating and the metal substrate.
  • the adhesion primers for surface coatings applied by dipping are exclusively in liquid form, that is to say the resins of the primer are either in suspension or in solution in one or more solvents.
  • the coating of metal substrates with these liquid primers is done for example using a pneumatic gun.
  • adhesion primers developed by the applicant are in the form of powder compositions, which can be applied as they are to metallic substrates.
  • the metal substrate which has previously been able to undergo one or more surface treatments such as alkaline degreasing, brushing, shot blasting, hot rinsing, etc., is coated with one or more layers of powder adhesion primer.
  • the metal substrate can be chosen from a wide range of products. These can be ordinary or galvanized steel parts, aluminum or aluminum alloy parts, the steel parts being more particularly targeted for the invention.
  • the thickness of the metal substrate is not critical in itself, it will most often be between 1 and 50 mm.
  • the application of the powder primer composition according to the invention can be carried out according to the powder application techniques usually used.
  • the powder application techniques there may be mentioned electrostatic spraying, a technique particularly preferred for the application of primer according to the invention, soaking in a fluidized bed.
  • the powder is introduced into a gun where it is conveyed by compressed air and passes through a nozzle brought to a high potential, generally between ten and one hundred kilovolts.
  • the applied voltage can be of positive or negative polarity, negative polarity being generally preferred.
  • the powder flow in the gun is generally between 10 and 200 g / min.
  • powders with an average particle size of between 5 and 100 ⁇ m, and preferably between 5 and 80 ⁇ m.
  • the average thickness of the primer can be between 5 and 60 ⁇ m, and preferably between 10 and 20 ⁇ m.
  • the powder compositions which constitute the adhesion primer according to the invention are based on solid thermosetting resins and preferably based on epoxy resins and epoxy resin hardener (s).
  • thermosetting resin is meant in the present description epoxy resins, phenolic resins, epoxyphenolic precondensates, alone or as a mixture.
  • epoxy resins By way of example of advantageously preferred epoxy resins, mention may be made of the products obtained by reaction of bisphenol-A and of epichlorohydrin and the degree of polymerization of which is greater than two, as well as the high molecular weight polycondensates of phenoxy type without free reactive group.
  • phenolic resins examples include the resins obtained by polycondensation of formaldehyde and of a phenol.
  • amine-type compound means aliphatic or aromatic amines and their derivatives, such as dicyandiamide, benzyldimethylamine, boron trifluoride monoethylamine.
  • acid anhydride By way of example of acid anhydride, mention may be made of aromatic anhydrides such as phthalic anhydride or cycloaliphtalic anhydrides such as hexahydrophthalic anhydride.
  • isocyanate type compound means a monomer, prepolymer or polymer compound containing at least two free or blocked isocyanate groups.
  • Polyisocyanate compounds with an aromatic or aliphatic structure whose isocyanate groups are blocked by condensation with phenol or caprolactam are particularly preferred.
  • the proportion of epoxy resin (s) and hardener (s) of the amine, acid anhydride or isocyanate type must be such that the number of epoxy functions is equal to the number of reactive functions of the amine of the acid anhydride or isocyanate compound.
  • the primers in accordance with the invention may also contain various additives and agents, alone or as a mixture, such as pigments, fillers, corrosion inhibiting agents, etc.
  • additives and agents such as pigments, fillers, corrosion inhibiting agents, etc.
  • strontium chromate such as strontium chromate.
  • zinc phosphate titanium dioxide
  • silica such as silica
  • the substrate is placed in an oven where it is heated to a determined temperature depending in particular on the nature of said substrate, its shape and the desired coating thickness.
  • the energy stored during the passage through the oven of the substrate coated with primer allows, in addition to the crosslinking of the primer, the melting and the adhesion of the surface coating applied by dipping on the substrate as soon as it leaves the oven.
  • the powder adhesion primers developed by the applicant resist particularly well at the high temperatures which may be necessary to ensure effective preheating of the substrate to be coated.
  • the powder primers according to the invention can not only be heated to 270-320 ° C, but they can, without damage to the quality of the final coating, undergo heating at higher temperatures, such as for example between 320 and 380 ° C, when necessary.
  • the average residence time of the substrate in the oven is generally between 1 and 30 min and preferably between 3 and 10 min.
  • the substrate is immersed in a soaking tank containing the surface coating as defined above.
  • the surface coatings in powder form, applied by dipping and in accordance with the invention are preferably based on polyamide and / or polyetheresteramide.
  • polyamide entering the powder surface coating is meant the aliphatic polyamides obtained from lactams or amino acids whose hydrocarbon chain has a number of carbon atoms between 4 and 20 such as, for example, caprolactam, enantholactam, dodecalactam, undecanolactam, amino 11-undecanoic acid, amino 12-dodecanoic acid, the condensation products of a dicarboxylic acid with a diamine such as, for example, polyamides 6.6 , 6.10, 6.12, 9.6, (products of the condensation of hexamethylene diamine with adipic acid, azelaic acid, sebacic acid, dodecanedioic acid-1,12 and nonamethylene diamine with acid adipic), the copolyamides resulting from the polymerization of the various monomers mentioned above or the mixtures of several polyamides mentioned above.
  • the inherent viscosity (measured at 20 ° C for a solution of 0.5 g per 100 g of metacresol) of the polyamides can be between 0.20 and 2.0, and preferably between 0.60 and 1.30 dlg- 1 .
  • polyamides also means semi-aromatic amorphous polyamides, and in particular as defined in French patents FR 1,588,130, 2,324,672 and 2,575,756, in European patent EP 53,876, in Japanese patents 59,015,447 and 60,217,237.
  • polyetheresteramides is intended to mean both the random polyetheresteramides (that is to say formed by the random sequence of the various monomer components) and the block polyetheresteramides, that is to say formed from blocks having a certain length of chain. their various constituents.
  • the number-average molecular mass of these polyamide blocks is generally between 500 and 10,000 and more particularly between 600 and 5,000.
  • the polyamide blocks of the polyetheresteramides are preferably formed from polyamide 6, 6.6, 6.12, 11 or 12 or from copolyamides resulting from the polycondensation of their monomers.
  • the number average molecular weight of the polyethers is generally between 200 and 6000 and more particularly between 600 and 3000.
  • the polyether blocks preferably consist of polytetramethylene glycol (PTMG), polypropylene glycol (PPG), or polyethylene glycol (PEG).
  • PTMG polytetramethylene glycol
  • PPG polypropylene glycol
  • PEG polyethylene glycol
  • the inherent viscosity of polyetheresteramides is advantageously between 0.8 and 2.05, and preferably between 0.80 and 1.20.
  • the inherent viscosity is measured in metacresol at 25 ° C with an initial concentration of 0.5 g per 100 g of metacresol. It is expressed in dlg- 1 .
  • the polyetheresteramides according to the invention can be formed from 5 to 85% by weight of polyether and from 95 to 15% by weight of polyamide, and preferably from 30 to 80% by weight of polyether and from 70 to 20% by weight of polyamide.
  • the particle size of the surface coating powders can be between 20 and 300 ⁇ m, and preferably between 40 and 200 ⁇ m.
  • the soaking technique according to the invention is carried out in a non-electrostatic fluidized bed, the electrostatic fluidized beds being unsuitable and difficult to use for soaking in powders based on polyamide and / or polyetheresteramide which are particularly preferred by the plaintiff.
  • the thickness of the surface coating can be between 150 and 600 ⁇ m, and preferably between 200 and 400 ⁇ m.
  • the substrate is cooled, for example with ambient air, by immersion in water or in any other suitable solvent, after having possibly undergone a post-melting.
  • the inherent viscosity of PA-11 measured at 20 ° C for a solution of 0.5 g of polymer in 100 g of m-cresol, is equal to 1.
  • the powdered primer composition as described in A. 2 °) is deposited at room temperature on the steel plate by electrostatic spraying under a negative electrostatic charge of 40 kV, the metal surface being at potential O.
  • the substrate thus coated passes through an oven maintained at 380 ° C where it remains for 3 min.
  • the substrate thus coated is removed from the soaking tank and then cooled in air after post-melting.
  • the metal substrate is a sandblasted steel plate and the surface coating has the same characteristics as those of EXAMPLE 1.
  • the substrate is coated with the primer by electrostatic spraying under the same conditions as in 1.B.
  • the materials undergo an adhesion test carried out in accordance with standard NF T 58-112 and a salt spray aging test carried out in accordance with standard NF X 41-002.
  • the metal substrate and the surface coating have the same characteristics as in EXAMPLE 2 and the conditions for processing and evaluating the materials obtained are identical to those described in EXAMPLE 2.
  • the metal substrate and the surface coating have the same characteristics as those of EXAMPLE 1.
  • the material obtained is such that the initial adhesion of the coating is zero (Class O) and the corrosion path is complete in a few hours.
  • the surface appearance of the coating is quite poor with in particular bubbling on the edges corresponding to degradation of the primer.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Claims (6)

1. Verfahren zur Beschichtung von metallischen Trägermaterialien mittels einer Grundierungssubstanz und eines Oberflächenbelags, dadurch gekennzeichnet, daß es die folgenden Verfahrensschritte beinhaltet:
a) Beschichtung des Trägermaterials mit einer oder mehreren pulverförmigen Grundierungssubstanzen auf Basis thermohärtbarer Kunstharze gemäß einer Auftragungstechnik für Pulver,
b) Erwärmung des so beschichteten Trägermaterials und unmittelbar danach:
c) Tauchauftragung des pulverförmigen Oberflächenbelags in einem Fließbett.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Temperatur zur Erwärmung des Trägermaterials in der Stufe b) 380°C erreichen kann.
3. Verfahren nach Anspruch 1 oder 2, in dem der Oberflächenbelag auf Polyamidbasis, vorzugsweise PA-11 und/oder PA-12, und/oder auf Polyetheresteramidbasis ist.
4. Zusammensetzung der pulverförmigen Grundierung auf Basis von Epoxydharz(en) und von Härter(n) aus Epoxydharz(en), die wie in den Ansprüchen 1, 2 oder 3 definiert in dem Verfahren eingesetzt werden.
5. Zusammensetzung nach Anspruch 4, dadurch gekennzeichnet, daß die Härter aus Epoxydharz(en) unter den Harzen des Amin-, Säureanhydrid- oder Isocyanattyps ausgewählt werden.
6. Verbundwerkstoff bestehend aus:
- einem metallischen Trägermaterial,
- einer oder mehreren Grundierungslagen wie in den Ansprüchen 1 bis 5 definiert, deren mittlere Schichtdicke vorzugsweise 10 bis 20 µm beträgt,
- einem Oberflächenbelag wie in den Ansprüchen 1 bis 3 definiert, deren mittlere Schichtdicke vorzugsweise 200 bis 400 µm beträgt.
EP89402897A 1988-11-03 1989-10-20 Verfahren zur Beschichtung eines Metallsubstrats mit Pulvergrundierungsschicht und mittels Tauchen angebrachte Oberflächenbeschichtung und so erhaltene Materialien Expired - Lifetime EP0367653B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8814332A FR2638466B1 (fr) 1988-11-03 1988-11-03 Procede pour revetir des substrats metalliques a l'aide d'un primaire en poudre et d'un revetement superficiel applique par trempage, compositions de primaire en poudre utilisees et materiaux composites obtenus
FR8814332 1988-11-03

Publications (3)

Publication Number Publication Date
EP0367653A1 EP0367653A1 (de) 1990-05-09
EP0367653B1 true EP0367653B1 (de) 1993-05-19
EP0367653B2 EP0367653B2 (de) 2001-11-21

Family

ID=9371527

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89402897A Expired - Lifetime EP0367653B2 (de) 1988-11-03 1989-10-20 Verfahren zur Beschichtung eines Metallsubstrats mit Pulvergrundierungsschicht und mittels Tauchen angebrachte Oberflächenbeschichtung und so erhaltene Materialien

Country Status (14)

Country Link
US (1) US5891515A (de)
EP (1) EP0367653B2 (de)
JP (1) JPH0755306B2 (de)
AT (1) ATE89496T1 (de)
AU (1) AU628877B2 (de)
CA (1) CA2002109C (de)
DE (1) DE68906643T3 (de)
DK (1) DK174338B1 (de)
ES (1) ES2055133T5 (de)
FI (1) FI100661B (de)
FR (1) FR2638466B1 (de)
IE (1) IE63336B1 (de)
NO (1) NO306956B1 (de)
PT (1) PT92182B (de)

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JP4907054B2 (ja) * 2003-12-09 2012-03-28 中央発條株式会社 高耐久性ばねおよびその塗装方法
US7235278B2 (en) * 2004-03-31 2007-06-26 Mcneil-Ppc, Inc. Method and apparatus for applying particulate material to a substrate
ATE513025T1 (de) * 2004-10-20 2011-07-15 Valspar Sourcing Inc Beschichtungszusammensetzungen für dosen und beschichtungsverfahren
US7507440B2 (en) * 2005-02-23 2009-03-24 Ppg Industries Ohio, Inc. Methods of forming composite coatings
GB2428395B (en) * 2005-07-19 2007-09-05 Ian Webb A process of powder coating and a powder coating apparatus
CA2622550C (en) * 2005-10-18 2014-03-25 Valspar Sourcing, Inc. Coating compositions for containers and methods of coating
EP2366810B1 (de) 2008-11-27 2019-08-21 Nippon Steel Corporation Elektrostahlblech und herstellungsverfahren dafür
JP5721330B2 (ja) * 2010-01-27 2015-05-20 藤倉化成株式会社 ベースコート塗料組成物、および複合塗膜とその製造方法
FR2955864B1 (fr) 2010-02-01 2012-03-23 Arkema France Poudre a base de polyamide et procede de revetement d'objet par fusion de ladite poudre
JP5606807B2 (ja) * 2010-06-14 2014-10-15 中央発條株式会社 粉体塗装方法
CN103143488B (zh) * 2011-12-06 2014-10-22 苏州汉扬精密电子有限公司 塑胶与金属结合件的表面涂装方法
JP6132153B2 (ja) * 2013-07-18 2017-05-24 株式会社ジェイテクト 摺動軸およびステアリング装置
IT201900007422A1 (it) * 2019-05-28 2020-11-28 Sercolor Srl Un metodo e relativo macchinario per la realizzazione di un effetto di corrosione su pezzi metallici
EP3851211A1 (de) * 2020-01-14 2021-07-21 Triarca A/S Oberflächenbeschichtung von elektrischen gehäusen

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Also Published As

Publication number Publication date
DK546089A (da) 1990-05-04
FR2638466B1 (fr) 1993-05-07
DE68906643T3 (de) 2002-05-29
IE63336B1 (en) 1995-04-19
FR2638466A1 (fr) 1990-05-04
EP0367653A1 (de) 1990-05-09
AU628877B2 (en) 1992-09-24
NO894344D0 (no) 1989-11-01
FI895222A0 (fi) 1989-11-02
NO894344L (no) 1990-05-04
EP0367653B2 (de) 2001-11-21
JPH02258084A (ja) 1990-10-18
ES2055133T5 (es) 2002-05-01
CA2002109A1 (fr) 1990-05-03
JPH0755306B2 (ja) 1995-06-14
PT92182B (pt) 2001-05-31
PT92182A (pt) 1990-05-31
DE68906643D1 (de) 1993-06-24
US5891515A (en) 1999-04-06
IE893536L (en) 1990-05-03
NO306956B1 (no) 2000-01-17
ATE89496T1 (de) 1993-06-15
DE68906643T2 (de) 1993-10-07
DK546089D0 (da) 1989-11-02
AU4397989A (en) 1990-05-10
DK174338B1 (da) 2002-12-16
CA2002109C (fr) 1999-02-16
ES2055133T3 (es) 1994-08-16
FI100661B (fi) 1998-01-30

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