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EP1032474B1 - Method for multi-layered repair coating of substrates - Google Patents

Method for multi-layered repair coating of substrates Download PDF

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Publication number
EP1032474B1
EP1032474B1 EP98955544A EP98955544A EP1032474B1 EP 1032474 B1 EP1032474 B1 EP 1032474B1 EP 98955544 A EP98955544 A EP 98955544A EP 98955544 A EP98955544 A EP 98955544A EP 1032474 B1 EP1032474 B1 EP 1032474B1
Authority
EP
European Patent Office
Prior art keywords
lacquer
coat
radiation
binders
meth
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.)
Revoked
Application number
EP98955544A
Other languages
German (de)
French (fr)
Other versions
EP1032474A1 (en
Inventor
Karin Maag
Helmut Löffler
Werner Lenhard
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
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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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=26041766&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1032474(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from DE1997151478 external-priority patent/DE19751478A1/en
Priority claimed from DE1997157082 external-priority patent/DE19757082A1/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1032474A1 publication Critical patent/EP1032474A1/en
Application granted granted Critical
Publication of EP1032474B1 publication Critical patent/EP1032474B1/en
Anticipated expiration legal-status Critical
Revoked 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
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/005—Repairing damaged coatings
    • 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

Definitions

  • the invention relates to a method for multilayer Refinishing of substrates with a filler layer and a top coat layer, which application is in the field of vehicle and Vehicle parts painting.
  • Multi-layer vehicle refinishes generally consist of one optionally pre-coated substrates applied filler layer and one Top coat consisting of a color and / or effect basecoat and one transparent clear coat. However, it can also be a top coat act from a pigmented one-coat topcoat.
  • UV curable One-component (IC) filler coating agent for refinishing.
  • IC UV radiation curable One-component
  • UV curable Components are only used in so-called reactive thinners. It is tripropylene glycol triacrylate and trimethylpropane triacrylate.
  • EP-A-000 407 describes radiation-curable coating compositions based on an OH-functional polyester resin esterified with acrylic acid, one Vinyl compound, a photoinitiator and a polyisocyanate.
  • a 1st Curing step the radiation is cured by means of UV light and in a second
  • the OH / NCO crosslinking gives the coating its final hardness.
  • the second hardening step can take place at 130 - 200 ° C or over several days Room temperature. The final hardness is only reached after several days.
  • EP-A-247 563 describes clearcoats curable by means of UV radiation Basis of a poly (meth) acryloyl functional compound, one Polyolmono (meth) acrylates, a polyisocyanate, a light stabilizer and one Photoinitiators. Some of the radiation-curable binders still contain here Hydroxy functions that can react with the existing polyisocyanate and offer an additional hardening option.
  • EP-A-540 884 describes a method for producing a Multi-layer painting for automotive serial painting by application of a Clear coat on a dried or crosslinked basecoat, the Clear lacquer coating agent by radical and / or cationic polymerization contains curable binders, and curing by means of high-energy radiation is carried out. After the clear coat has been irradiated, the stoving process takes place. where basecoat and clearcoat together in e.g. Be baked at 80 - 160 ° C.
  • the object of the invention was to provide a method for producing a multilayer To provide painting, in particular refinishing, which makes it possible to Environmentally friendly filler coating, even in high layer thicknesses and with high pigmentation easy to apply.
  • the coatings obtained are said to harden quickly and completely and be easy to sand after a short drying time as well as very good interlayer adhesion, good topcoat level and satisfactory Ensure chemical, gasoline and water resistance.
  • the object is achieved by a method for producing a multilayer Repair painting, in which, if necessary, with a primer and / or other coating agents precoated substrate a filler coating agent applied and then a top coat of a color and / or effect basecoat and a transparent clearcoat or a Top coat is applied from a pigmented single-layer top coat, characterized in that such a filler is used is either exclusively through radical and / or cationic Contains polymerization curable binders, these binders by means of high-energy radiation can be cured, or by radical and / or contains cationic polymerization curable binders, these binders can be cured by means of high-energy radiation and additionally chemically contains crosslinking binders.
  • Multicoat paint systems obtained according to the invention do the same for a high level of properties required for painting, as was previously the case with usual proven but solvent-based paints, especially repair paints, was achieved. This applies in particular to properties such as sandability, Top coat level, water and chemical resistance. It also became surprising found that the multilayer structure according to the invention with respect Interlayer adhesion as well as quick and complete hardening even in high Layer thicknesses and with high pigmentation a usual refinish build-up is superior.
  • the filler coating compositions which can be used in the process according to the invention are coating agents which are emitted by means of high-energy radiation crosslink radical and / or cationic polymerization. It can be about Act high-solids aqueous or solvent-containing systems, for example with a solids content of 50 to 95 wt .-% (with aqueous as well conventional, solvent-based systems). However, the systems can also be used as 100% coating agent that is applied without solvent and without water can be present.
  • curable by means of high-energy radiation binders can Process according to the invention all conventional radiation-curable binders or their Mixtures are used that are known to the person skilled in the art and in the literature are described. It is either through radical or through cationic polymerization crosslinkable binders. With the former arise through Exposure to high-energy radiation on the photoinitiators radicals, which then trigger the crosslinking reaction. With the cationic curing systems formed by radiation from initiators Lewis acids, which in turn the Trigger crosslinking reaction.
  • the free-radically curing binders can e.g. to prepolymers like Poly- or oligomers, the radical polymerizable olefinic double bonds have in the molecule, act.
  • prepolymers or oligomers are (meth) acrylic functional (meth) acrylic copolymers, epoxy resin (meth) acrylates, Polyester (meth) acrylates, polyether (meth) acrylates, polyurethane (meth) acrylates ,, Amino (meth) acrylates, silicone (meth) acrylates, melamine (meth) acrylates, unsaturated Polyurethane or unsaturated polyester.
  • the number average molecular weight (Mn) of this Compounds is preferably 200 to 10,000.
  • Aliphatic and / or cycloaliphatic (meth) acrylates are preferred in each case used.
  • (Cyclo) aliphatic polyurethane (meth) acrylates are particularly preferred, Polyester (meth) acrylates and epoxy (meth) acrylates.
  • the binders can be used individually or used in a mixture.
  • the prepolymers can be used in combination with reactive diluents, i.e. reactive polymerizable liquid monomers.
  • the reactive thinners are in generally in amounts of 1-50% by weight, preferably 5-30% by weight, based on the total weight of prepolymer and reactive diluent used.
  • the Reactive diluents can be mono-, di- or polyunsaturated. Examples for monounsaturated reactive diluents are: (meth) acrylic acid and its esters, Maleic acid and its half esters, vinyl acetate, vinyl ether, substituted Vinyl ureas, styrene, vinyl toluene.
  • unsaturated reactive thinners are: di (meth) acrylates such as alkylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, Divinylbenzene, dipropylene glycol di (meth) acrylate, hexanediol di (meth) acrylate.
  • di (meth) acrylates such as alkylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, Divinylbenzene, dipropylene glycol di (meth) acrylate, hexanediol di (meth) acrylate.
  • polyunsaturated reactive thinners examples include: glycerol tri (meth) acrylate, Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate.
  • the reactive diluents can be used individually or in a mixture become.
  • Preferred reactive diluents are diacrylates such as e.g. Dipropylene glycol diacrylate, tripropylene glycol diacrylate and / or hexanediol diacrylate used.
  • Binders known to those skilled in the art and described in the literature are used become. These can be, for example, polyfunctional epoxy oligomers which contain more than two epoxy groups in the molecule. It is about for example polyalkylene glycol diglycidyl ether, hydrogenated bisphenol A glycidyl ether, Epoxy urethane resins, glycerol triglycidyl ether, Diglycidyl hexahydrophthalate, diglycidyl ester of dimer acids, epoxidized derivatives des (methyl) cyclohexene, e.g.
  • the number average of Molar mass of the polyepoxide compounds is preferably less than 10,000. It can also Reactive thinners, e.g. Cyclohexene oxide, butene oxide, butanediol diglycidyl ether or Hexanediol diglycidyl ether can be used.
  • Suitable photoinitiators are, for example, those which Absorb wavelength range from 190 to 600 nm.
  • photoinitiators for radical curing systems are benzoin and derivatives, acetophenone and derivatives such as e.g. 2,2-diacetoxyacetophenone, Benzophenone and derivatives, thioxanthone and derivatives, anthraquinone, 1-benzoylcyclohexanol, organophosphorus compounds, e.g. Acylphosphine oxides.
  • the photoinitiators are used, for example, in amounts of 0.1-7 % By weight, preferably 0.5-5% by weight, based on the sum of radical polymerizable prepolymers, reactive thinners and photoinitiators.
  • the photoinitiators can be used individually or in combination.
  • other synergistic components e.g. tertiary amines, be used.
  • Photoinitiators for cationic curing systems are substances that act as onium salts are known which photolytically release Lewis acids under the action of radiation. Examples include diazonium salts, sulfonium salts or iodonium salts. Prefers are triarylsulfonium salts.
  • the photoinitiators for cationic curing systems can be in amounts of 0.5 to 5 wt .-%, based on the sum of cationic polymerizable prepolymers, reactive diluents and initiators, individually or as Mixtures are used.
  • curable filler coatings can be various free radicals curing systems, various cationic curing systems or radical and cationic curing systems can be combined.
  • Preferred free radical curing binders are epoxy (meth) acrylates, polyurethane (meth) acrylates, polyester (meth) acrylates and (meth) acrylic functional poly (meth) acrylates.
  • Aromatic are particularly preferred Epoxy (meth) acrylates.
  • the examples mentioned using high-energy radiation curable binders are generally available as commercial products.
  • those curable by means of high-energy radiation Filler coating agents can only be hardened using high-energy radiation Contain binders, but they can also be used in addition to those with high energy Radiation-curable binders and other chemically crosslinking binders contain.
  • any chemically crosslinking binder two-component binder systems based on one hydroxy functional and one isocyanate-functional component, a hydroxy-functional and one Anhydride component, a polyamine and an epoxy component or one Polyamine and an acryloyifunctional component can be used.
  • Both additionally usable binders can be those on aqueous or Act solvent based.
  • the proportion of chemically cross-linking Binders can, for example, up to 50 wt .-%, based on the UV-curable Binders.
  • the filler coating compositions which can be used in the process according to the invention can Contain fillers and pigments. These are the usual ones in the Paint industry usable fillers and organic or inorganic coloring and / or anti-corrosion pigments. Examples of pigments are Titanium dioxide, micronized titanium dioxide, iron oxide pigments, carbon black, azo pigments, Zinc phosphate. Examples of fillers are silicon dioxide, aluminum silicate, Barium sulfate and talc. Can improve hardness and ductility UV-curable pigments and / or fillers are also advantageously used. It These are pigments and / or fillers that are used by means of UV radiation curable compounds, e.g. are coated with acrylic functional silanes and in the Radiation curing process should be included.
  • the filler coating compositions which can be used in the process according to the invention can customary paint additives included.
  • the additives are the usual ones additives that can be used in the paint sector. Examples of such additives are Leveling agents, e.g. based on (meth) acrylic homopolymers or Silicone oils, anti-cratering agents, anti-foaming agents, catalysts, adhesion promoters.
  • the Additives are used in the usual amounts familiar to the person skilled in the art.
  • the fillers which can be used in the process according to the invention can be solvent-free be formulated. Their solids content is then 100% by weight.
  • the fillers can however also contain small amounts of organic solvents and / or water.
  • the solvents are common paint solvents. these can originate from the production of the binders or are added separately. Examples of such solvents are monohydric or polyhydric alcohols, e.g. Propanol, Butanol, hexanol; Glycol ether or ester, e.g.
  • Methyl ethyl ketone Acetone, cyclohexanone; aromatic or aliphatic hydrocarbons, e.g. Toluene, xylene or linear or branched aliphatic C6-C12 hydrocarbons.
  • the filler layer is applied to one in the process according to the invention optionally precoated substrate.
  • Preferred substrates are metal or Plastic substrates.
  • the fillers can be applied to conventional primers or others Intermediate layers, such as those for the multi-layer coating on the Motor vehicle sector are used to be applied. You can click on an im Pre-coated or pre-treated as part of vehicle refinishing Vehicle body or parts thereof are applied, but they can also be on Old paintwork can be applied.
  • the application can be based on the known Methods, preferably by spray application.
  • the fillers can be based, for example, on conventional solvent- or water-based Spatulas, primers, adhesive primers or other intermediate layers, such as for the Vehicle refinishing is common, or on old paintwork such as KTL substrates, be applied.
  • the substrates or layers of paint. on the the Filler layer is applied, can be cured or pre-dried his.
  • primer or primer for refinishing For example, those based on peroxide-curing unsaturated are suitable Polyester, acid-curing polyvinyl butyral, physically drying binder, e.g. Polyurethanes or acrylates, as well as two-component crosslinking Binders, e.g. based on an epoxy and a polyamine component or Polyisocyanate and a hydroxy component.
  • UV radiation sources are preferred with emissions in the wavelength range from 180 to 420 nm, in particular from 200 up to 400 nm.
  • UV radiation sources may be doped High-pressure mercury, medium-pressure and low-pressure lamps, gas discharge tubes, such as. Xenon low pressure lamps, pulsed and unpulsed UV lasers, UV spotlights, such as. UV emitting diodes and black light tubes.
  • As a radiation source then particularly preferred so-called high-energy electron flash devices (in short: UV flash lamps).
  • Preferred UV flash lamps emit light with a wavelength of 200 to 900 nm with a maximum at about 300 to 500 nm.
  • the UV flash lamps contain preferably a plurality of flash tubes, for example with inert gas, such as Xenon, filled quartz tubes.
  • the UV flash lamps are said to be on the surface of the curing coating an illuminance of at least 10 megalux, preferred effect from 10 to 80 Megalux per lightning discharge.
  • the energy per flash discharge should preferably be 1 to 10 kJoules.
  • the UV flash lamps are preferred to transportable facilities that are in front of a mending Damage point can be positioned. Depending on the circumstances, one or several UV flash lamps can be used. UV flash lamps that can be used described, for example, in WO-A-9411123 and in EP-A-525 340. UV flash lamps are commercially available.
  • the drying or hardening of the filler layer can be carried out by a plurality successive lightning discharges occur. 1 to 40 are preferred successive lightning discharges triggered.
  • the distance of the UV flash lamp to substrate surface to be irradiated can be 5 - 50 cm, preferably 10 - 25 cm, are particularly preferably 15-20 cm.
  • the shielding of the UV lamps Avoiding radiation leakage can e.g. by using a appropriately lined protective housing around the portable lamp unit or with the help of other safety measures known to the person skilled in the art.
  • the total irradiation time is in the range of a few seconds, for example in the range from 3 milliseconds to 400 seconds, preferably from 4 to 160 seconds, depending on the number of selected lightning discharges.
  • the flashes can be approx. triggered every 4 s.
  • the UV flash lamps are ready for use at any time, i.e. they do not require a burn-in time and can do something between two times separate curing or radiation processes remain switched off, without losing time in the re-irradiation process due to the stoving phase occur.
  • a particular advantage of the method according to the invention is that high layer thicknesses can be applied in one operation (without intermediate sanding) and that even with high pigmentation of the filler, for example with a pigment volume concentration (PVC) of 30 to 45% and more, coatings with layer thicknesses of, for example, 200 to 400, preferably 300 to 400 ⁇ m can be applied by the cure rapidly and completely and are easy to sand.
  • the procedure can be such that the filler coating agent is applied in several, preferably two, spray passes, and after the first spray pass or after each further spray pass, if a total of more than two spray passes, there is intermediate radiation is triggered.
  • a first spray pass for example, 100 to 200 ⁇ m thickness with for example 2 to 5 flashes carried out an intermediate curing
  • a further layer of, for example 100 is in a second spray pass - 200 ⁇ m is applied and it is carried out with the required Number of lightning discharges complete hardening.
  • filler coating compositions which can be used in the process according to the invention can Formulated or used as a sanding filler, primer filler or wet-on-wet filler become.
  • a top coating from a color and / or effect basecoat and a transparent clearcoat or a top coat made of a pigmented single-layer topcoat is in method according to the invention on the filler layer a top coating from a color and / or effect basecoat and a transparent clearcoat or a top coat made of a pigmented single-layer topcoat.
  • Basecoats are all in vehicle painting, especially refinishing, usual solvent-based or water-based basecoats known to those skilled in the art suitable.
  • solvent-based basecoats are those based on Polyacrylate and / or polyester resins, optionally in combination with Melamine resins and cellulose esters.
  • waterborne basecoats are such Based on physically drying polyurethane, polyurethane / urea, polyester, Polyester urethane and / or polyacrylate resins and their modifications, such as e.g. acrylated or silicon-modified polyurethane and / or polyester resins.
  • the hardening of the basecoat can be hot or at room temperature for example, 40-80 ° C.
  • the basecoat can also be wet-on-wet, if necessary after a short flash-off phase with a clear varnish and then be cured together with the clear coat.
  • One embodiment of the method according to the invention is as a basecoat to use such a binder that can be hardened by means of high-energy radiation contains.
  • the binders curable by means of high-energy radiation are for example, the above in the description of the filler coating compositions binder already mentioned. In this case, however, are preferred in the basecoat aliphatic polyurethane (meth) acrylates and / or aliphatic (meth) acrylic functional Poly (meth) arylates used.
  • the basecoat can be applied wet-on-wet to the filler layer (wet-on-wet filler) and filler and basecoat layers exposed to radiation together in one work step. If necessary there is a short interim exposure of the filler layer. However, it can also especially with high layer thicknesses and high pigmentation of the filler, initially the filler layer is completely hardened using UV radiation (abrasive filler), possibly in several irradiation steps, and then the separate one The basecoat film is cured with UV radiation.
  • UV radiation abrasive filler
  • Clearcoats that can be used for the basecoat / clearcoat topcoat are all in the Vehicle painting, especially the usual repair painting and the Suitable solvent-based or water-based clearcoats known to those skilled in the art. Examples this is based on solvent-based or aqueous clear lacquers binders containing hydroxyl groups and / or amino groups and Polyisocyanate crosslinkers and based on amino groups and binder containing acryloyl groups.
  • the hardening of the clear coat can Room temperature or forced at 40 - 80 ° C, for example.
  • a further embodiment of the method according to the invention consists in creating a multilayer structure which is based on a radiation-curable filler, a physically drying or chemically crosslinking base coat which is not based on radiation-curable binders, and a clear coat which contains binders curable by means of high-energy radiation.
  • the basecoat can be applied to the fully cured filler and after curing the basecoat or after briefly drying the basecoat, the radiation-curing clearcoat can be applied. Then UV radiation is applied.
  • the clear lacquer can contain the customary radiation-curable binders, as already mentioned above in the description of the filler coating compositions.
  • Aliphatic polyurethane (meth) acrylates and / or aliphatic acrylic-functional poly (meth) acrylates are preferably used. Particularly preferred in this embodiment are binders curable by means of high-energy radiation based on aromatic epoxy (meth) acrylates and binders curable by means of high-energy radiation based on aliphatic polyurethane (meth) acrylates and / or aliphatic (meth) acrylic-functional poly (meth) in the filler ) acrylates used. There is still the possibility of applying the hardened or intermediate hardened filler layer. or wet-on-wet, to apply a customary solvent- or water-based pigmented single-coat topcoat.
  • multilayer coatings with great hardness, high scratch resistance and very good chemical and water resistance are obtained in a short time.
  • the individual layers of paint show very good interlayer adhesion and resistance to dissolving of the paint layers below or above. Even very thick filler layers can be applied without bubbles in one spray cycle and dry quickly. Highly pigmented fillers can also be applied in high layer thicknesses and show rapid and complete hardening.
  • the filler coatings are easy to sand after a short drying time. They show a very good topcoat level.
  • the coatings otherwise correspond to the requirements for a paint structure, for example a refinish structure, in the field of vehicle painting, with the drying or curing of the coatings being able to be carried out in a very short time in comparison with the paint structures which have been dried or hardened in the customary manner.
  • the method according to the invention can advantageously be used in the Vehicle refinishing, in particular for refinishing Vehicle parts, smaller damaged areas and for spot repair.
  • the invention is illustrated by the following example.
  • the filler produced above is applied to KTL-coated sheets.
  • a filler layer in a resulting dry film layer thickness of about 300 ⁇ m is applied and after a brief flash-off at room temperature, the filler layer to irradiation by a UV flash lamp is exposed (3500 Ws). It is irradiated with 30 flashes (about 120 s).
  • the filler is then sanded and a solvent-based, customary pigmented two-pack topcoat based on acrylate / polyisocyanate is overpainted.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)
  • Paints Or Removers (AREA)

Abstract

Process for producing a multi-layer lacquer finish, in which a surfacer coating compound is applied to a substrate optionally pre-coated with a priming layer and/or further coating layers, and a top coating comprising a color-imparting and/or special-effect-imparting base lacquer layer and a transparent clear lacquer layer, or a top coating comprising a pigmented one-layer top lacquer, is then applied, in which the surfacer coating compound which is used is one which either contains binders which are curable exclusively by free radical and/or cationic polymerization, wherein the said binders are cured by means of high-energy radiation, or is one which contains binders which are curable by free radical and/or cationic polymerization, wherein the said binders are cured by means of high-energy radiation, and additionally contains chemically cross-linking binders.

Description

Die Erfindung betrifft ein Verfahren zur mehrschichtigen Reparaturlackierung von Substraten mit einer Füllerschicht und einer Decklackschicht, welches Anwendung findet auf dem Gebiet der Fahrzeug- und Fahrzeugteilelackierung.The invention relates to a method for multilayer Refinishing of substrates with a filler layer and a top coat layer, which application is in the field of vehicle and Vehicle parts painting.

Mehrschichtige Fahrzeugreparaturlackierungen bestehen im allgemeinen aus einer auf gegebenfalls vorbeschichtete Substrate aufgebrachten Füllerschicht und einer Deckbeschichtung aus einer farb- und/oder effektgebenden Basislackschicht und einer transparenten Klarlackschicht. Es kann sich jedoch auch um eine Deckbeschichtung aus einem pigmentierten Einschichtdecklack handeln.Multi-layer vehicle refinishes generally consist of one optionally pre-coated substrates applied filler layer and one Top coat consisting of a color and / or effect basecoat and one transparent clear coat. However, it can also be a top coat act from a pigmented one-coat topcoat.

Aus ökologischen Gründen ist man bestrebt, auch in der Fahrzeugreparaturlackierung die Lösemittelemission der Beschichtungsmittel zu reduzieren. So sind bereits für nahezu alle Lackschichten wäßrige oder sogenannte High-solid-Beschichtungsmittel entwickelt worden. Für den Füller- und Grundierungsbereich sind beispielsweise zweikomponentige Wasserlacke auf Basis von hydroxyfunktionellen Bindemitteln und Polyisocyanathärtern sowie auf Basis von Epoxid/Polyamin-Systemen bekannt. Die mit diesen Lacken erhaltenen Beschichtungen entsprechen jedoch in mehreren Punkten noch nicht dem Eigenschaftsniveau konventioneller lösemittelbasierender Füller bzw. Grundierungen. Beispielsweise ist bei den Wasserfüllern die Schleifbarkeit noch unzureichend, und es gibt Probleme, bei höheren Schichtdicken eine blasenfreie Applikation zu gewährleisten. Außerdem muß beim Einsatz von Wasserlacken generell eine verlängerte Trockenzeit in Kauf genommen werden, was die Effektivität beispielsweise in einer Lackierwerkstatt beeinträchtigt.Efforts are made for ecological reasons, including in vehicle refinishing to reduce the solvent emissions of the coating agents. So are already for Almost all layers of paint are aqueous or so-called high-solid coating agents has been developed. For example, for the filler and primer area two component water based paints based on hydroxy functional binders and Polyisocyanate hardeners and based on epoxy / polyamine systems known. The Coatings obtained with these varnishes, however, correspond in several points not yet the level of properties of conventional solvent-based fillers or Primers. For example, the sandability is still with the water fillers insufficient, and there are problems with a bubble-free layer thickness To ensure application. In addition, when using water-based paints in general an extended drying time can be accepted, which is the effectiveness impaired in a paint shop, for example.

Es ist bereits bekannt, in der Fahrzeuglackierung mittels energiereicher Strahlung härtbare Beschichtungsmittel einzusetzen. It is already known in vehicle painting using high-energy radiation use curable coating agents.

So beschreibt die US-A-4 668 529 ein mittels UV-Strahlung härtbares Einkomponenten (lK)-Füllerbeschichtungsmittel für die Reparaturlackierung. Als UV-härtbare Komponenten werden lediglich sogenannte Reaktivverdünner eingesetzt. Es handelt sich um Tripropylenglykoltriacrylat und Trimethylpropantriacrylat. Zusätzlich ist ein physikalisch trocknendes Epoxidharz auf Basis eines Bisphenol A-Diglycidylethers enthalten.For example, US Pat. No. 4,668,529 describes a UV radiation curable One-component (IC) filler coating agent for refinishing. As UV curable Components are only used in so-called reactive thinners. It is tripropylene glycol triacrylate and trimethylpropane triacrylate. In addition is a physically drying epoxy resin based on a bisphenol A diglycidyl ether contain.

In der EP-A-000 407 werden strahlenhärtbare Überzugsmittel beschrieben auf Basis eines mit Acrylsäure veresterten OH-funktionellen Polyesterharzes, einer Vinylverbindung, eines Photoinitiators und eines Polyisocyanates. In einem 1. Härtungsschritt erfolgt die Strahlenhärtung mittels UV-Licht und in einem 2. Härtungsschritt erhält der Überzug durch die OH/NCO-Vernetzung seine Endhärte. Der 2. Härtungsschritt kann bei 130 - 200°C oder über mehrere Tage bei Raumtemperatur erfolgen. Die Endhärte wird erst nach mehreren Tagen erreicht.EP-A-000 407 describes radiation-curable coating compositions based on an OH-functional polyester resin esterified with acrylic acid, one Vinyl compound, a photoinitiator and a polyisocyanate. In a 1st Curing step, the radiation is cured by means of UV light and in a second The OH / NCO crosslinking gives the coating its final hardness. The second hardening step can take place at 130 - 200 ° C or over several days Room temperature. The final hardness is only reached after several days.

In der EP-A-247 563 werden mittels UV-Strahlung härtbare Klarlacke beschrieben auf Basis einer poly(meth)acryloylfunktionellen Verbindung, eines Polyolmono(meth)acrylates, eines Polyisocyanates, eines Lichtstabilisators und eines Photoinitiators. Ein Teil der strahlenhärtbaren Bindemittel enthält hier noch Hydroxyfunktionen, die mit dem vorhandenen Polyisocyanat reagieren können und eine zusätzliche Härtungsmöglichkeit bieten.EP-A-247 563 describes clearcoats curable by means of UV radiation Basis of a poly (meth) acryloyl functional compound, one Polyolmono (meth) acrylates, a polyisocyanate, a light stabilizer and one Photoinitiators. Some of the radiation-curable binders still contain here Hydroxy functions that can react with the existing polyisocyanate and offer an additional hardening option.

Die EP-A-540 884 beschreibt ein Verfahren zur Herstellung einer Mehrschichtlackierung für die Kraftfahrzeugserienlackierung durch Auftrag einer Klarlackschicht auf eine getrocknete oder vernetzte Basislackschicht, wobei das Klarlackbeschichtungsmittel durch radikalische und/oder kationische Polymerisation härtbare Bindemittel enthält, und die Härtung mittels energiereicher Strahlung durchgeführt wird. Nach Bestrahlung der Klarlackschicht erfolgt der Einbrennprozeß, wobei Basislack und Klarlack gemeinsam bei z.B. 80 - 160°C eingebrannt werden.EP-A-540 884 describes a method for producing a Multi-layer painting for automotive serial painting by application of a Clear coat on a dried or crosslinked basecoat, the Clear lacquer coating agent by radical and / or cationic polymerization contains curable binders, and curing by means of high-energy radiation is carried out. After the clear coat has been irradiated, the stoving process takes place. where basecoat and clearcoat together in e.g. Be baked at 80 - 160 ° C.

Aufgabe der Erfindung war es, ein Verfahren zur Herstellung einer mehrschichtigen Lackierung, insbesondere Reparaturlackierung bereitzustellen, welches es ermöglicht, umweltfreundliche Füllerbeschichtungsmittel auch in hohen Schichtdicken und mit hoher Pigmentierung problemlos zu applizieren. Die erhaltenen Beschichtungen sollen rasch und vollständig durchhärten und nach kurzer Trockenzeit gut schleifbar sein sowie sehr gute Zwischenschichthaftung, guten Decklackstand und zufriedenstellende Chemikalien-, Benzin- und Wasserfestigkeit gewährleisten.The object of the invention was to provide a method for producing a multilayer To provide painting, in particular refinishing, which makes it possible to Environmentally friendly filler coating, even in high layer thicknesses and with high pigmentation easy to apply. The coatings obtained are said to harden quickly and completely and be easy to sand after a short drying time as well as very good interlayer adhesion, good topcoat level and satisfactory Ensure chemical, gasoline and water resistance.

Die Aufgabe wird gelöst durch ein Verfahren zur Herstellung einer mehrschichtigen Reparatur-Lackierung, bei dem auf ein gegebenenfalls mit einem Grundierungs- und/oder weiteren Beschichtungsmitteln vorbeschichtetes Substrat ein Füllerbeschichtungsmittel aufgebracht und anschließend eine Deckbeschichtung aus einer farb- und/oder effektgebenden Basislackschicht und einer transparenten Klarlackschicht oder eine Deckbeschichtung aus einem pigmentierten Einschichtdecklack appliziert wird, dadurch gekennzeichnet, daß als Füllerbeschichtungsmittel ein solches verwendet wird, das entweder ausschließlich durch radikalische und/oder kationische Polymerisation härtbare Bindemittel enthält, wobei diese Bindemittel mittels energiereicher Strahlung gehärtet werden, oder das durch radikalische und/oder kationische Polymerisation härtbare Bindemittel enthält, wobei diese Bindemittel mittels energiereicher Strahlung gehärtet werden und das zusätzlich chemisch vernetzende Bindemittel enthält.The object is achieved by a method for producing a multilayer Repair painting, in which, if necessary, with a primer and / or other coating agents precoated substrate a filler coating agent applied and then a top coat of a color and / or effect basecoat and a transparent clearcoat or a Top coat is applied from a pigmented single-layer top coat, characterized in that such a filler is used is either exclusively through radical and / or cationic Contains polymerization curable binders, these binders by means of high-energy radiation can be cured, or by radical and / or contains cationic polymerization curable binders, these binders can be cured by means of high-energy radiation and additionally chemically contains crosslinking binders.

Es war überraschend und aus dem Stand der Technik nicht herleitbar, daß die mit dem erfindungsgemäßen Verfahren erhaltenen Mehrschichtlackierungen das gleiche, für eine Lackierung erforderliche, hohe Eigenschaftsniveau zeigen, wie es bisher mit den üblichen bewährten aber lösemittelbasierenden Lacken, insbesondere Reparaturlacken, erzielt wurde. Das betrifft insbesondere solche Eigenschaften wie Schleifbarkeit, Decklackstand, Wasser- und Chemikalienbeständigkeit. Außerdem wurde überraschend gefunden, daß der erfindungsgemäße Mehrschichtaufbau bezüglich Zwischenschichthaftung sowie rascher und vollständiger Durchhärtung auch in hohen Schichtdicken und bei hoher Pigmentierung einem üblichen Reparaturlackaufbau noch überlegen ist.It was surprising and cannot be deduced from the prior art that the Multicoat paint systems obtained according to the invention do the same for a high level of properties required for painting, as was previously the case with usual proven but solvent-based paints, especially repair paints, was achieved. This applies in particular to properties such as sandability, Top coat level, water and chemical resistance. It also became surprising found that the multilayer structure according to the invention with respect Interlayer adhesion as well as quick and complete hardening even in high Layer thicknesses and with high pigmentation a usual refinish build-up is superior.

Bei den im erfindungsgemäßen Verfahren einsetzbaren Füllerbeschichtungsmitteln handelt es sich um Beschichtungsmittel, die mittels energiereicher Strahlung über eine radikalische und/oder kationische Polymerisation vernetzen. Es kann sich dabei um festkörperreiche wäßrige oder lösemittelhaltige Systeme handeln, heispielsweise mit einem Festkörpergehalt von 50 bis 95 Gew.-% (bei wäßrigen wie auch konventionellen, lösemittelhaltigen Systemen). Die Systeme können jedoch auch als 100 %ige Beschichtungsmittel, die ohne Lösungsmittel und ohne Wasser appliziert werden können, vorliegen.With the filler coating compositions which can be used in the process according to the invention are coating agents which are emitted by means of high-energy radiation crosslink radical and / or cationic polymerization. It can be about Act high-solids aqueous or solvent-containing systems, for example with a solids content of 50 to 95 wt .-% (with aqueous as well conventional, solvent-based systems). However, the systems can also be used as 100% coating agent that is applied without solvent and without water can be present.

Als mittels energiereicher Strahlung härtbare Bindemittel können im erfindungsgemäßen Verfahren alle üblichen strahlenhärtbaren Bindemittel oder deren Mischungen eingesetzt werden, die dem Fachmann bekannt und in der Literatur beschrieben sind. Es handelt sich entweder um durch radikalische oder durch kationische Polymerisation vernetzbare Bindemittel. Bei ersteren entstehen durch Einwirkung von energiereicher Strahlung auf die Photoinitiatoren Radikale, die dann die Vernetzungsreaktion auslösen. Bei den kationisch härtenden Systemen werden durch die Bestrahlung aus Initiatoren Lewis-Säuren gebildet, die dann ihrerseits die Vernetzungsreaktion auslösen.As a curable by means of high-energy radiation binders can Process according to the invention all conventional radiation-curable binders or their Mixtures are used that are known to the person skilled in the art and in the literature are described. It is either through radical or through cationic polymerization crosslinkable binders. With the former arise through Exposure to high-energy radiation on the photoinitiators radicals, which then trigger the crosslinking reaction. With the cationic curing systems formed by radiation from initiators Lewis acids, which in turn the Trigger crosslinking reaction.

Bei den radikalisch härtenden Bindemitteln kann es sich z.B. um Prepolymere, wie Poly- oder Oligomere, die radikalisch polymerisierbare olefinische Doppelbindungen im Molekül aufweisen, handeln. Beispiele für Prepolymere oder Oligomere sind (meth)acrylfunktionelle (Meth)acrylcopolymere, Epoxidharz(meth)acrylate, Polyester(meth)acrylate, Polyether(meth)acrylate, Polyurethan(meth)acrylate,, Amino(meth)acrylate, Silikon(meth)acrylate, Melamin(meth)acrylate, ungesättigte Polyurethane oder ungesättigte Polyester. Die zahlenmittlere Molmasse (Mn) dieser Verbindungen liegt bevorzugt bei 200 bis 10000. Bevorzugt sind durchschnittlich 2-20 radikalisch polymerisierbare olefinische Doppelbindungen im Molekül enthalten. Bevorzugt werden jeweils aliphatische und/oder cycloaliphatische (Meth)acrylate eingesetzt. Besonders bevorzugt sind (cyclo)aliphatische Polyurethan(meth)acrylate, Polyester(meth)acrylate und Epoxy(meth)acrylate. Die Bindemittel können einzeln oder im Gemisch eingesetzt werden. The free-radically curing binders can e.g. to prepolymers like Poly- or oligomers, the radical polymerizable olefinic double bonds have in the molecule, act. Examples of prepolymers or oligomers are (meth) acrylic functional (meth) acrylic copolymers, epoxy resin (meth) acrylates, Polyester (meth) acrylates, polyether (meth) acrylates, polyurethane (meth) acrylates ,, Amino (meth) acrylates, silicone (meth) acrylates, melamine (meth) acrylates, unsaturated Polyurethane or unsaturated polyester. The number average molecular weight (Mn) of this Compounds is preferably 200 to 10,000. 2-20 on average are preferred contain radically polymerizable olefinic double bonds in the molecule. Aliphatic and / or cycloaliphatic (meth) acrylates are preferred in each case used. (Cyclo) aliphatic polyurethane (meth) acrylates are particularly preferred, Polyester (meth) acrylates and epoxy (meth) acrylates. The binders can be used individually or used in a mixture.

Die Prepolymere können in Kombination mit Reaktivverdünnern, d.h. reaktiven polymerisierbaren flüssigen Monomeren, vorliegen. Die Reaktivverdünner werden im allgemeinen in Mengen von 1 - 50 Gew.-%, bevorzugt 5 - 30 Gew.-%, bezogen auf das Gesamtgewicht von Prepolymer und Reaktivverdünner, eingesetzt. Die Reaktivverdünner können mono-, di- oder polyungesättigt sein. Beispiele für monoungesättigte Reaktivverdünner sind: (Meth)acrylsäure und deren Ester, Maleinsäure und deren Halbester, Vinylacetat, Vinylether, substituierte Vinylharnstoffe, Styrol, Vinyltoluol. Beispiele für diungesättigte Reaktivverdünner sind: Di(meth)acrylate wie Alkylenglykol-di(meth)acrylat, Polyethylenglykoldi(meth)acrylat, 1,3-Butandiol-di(meth)acrylat, Vinyl(meth)acrylat, Allyl(meth)acrylat, Divinylbenzol, Dipropylenglykol-di(meth)acrylat, Hexandiol-di(meth)acrylat. Beispiele für polyungesättigte Reaktivverdünner sind: Glycerin-tri(meth)acrylat, Trimethylolpropan-tri(meth)acrylat, Pentaerythrit-tri(meth)acrylat, Pentaerythrittetra(meth)acrylat. Die Reaktivverdünner können einzeln oder im Gemisch eingesetzt werden. Bevorzugt werden als Reaktivverdünner Diacrylate wie z.B. Dipropylenglykoldiacrylat, Tripropylenglykoldiacrylat und/oder Hexandioldiacrylat eingesetzt.The prepolymers can be used in combination with reactive diluents, i.e. reactive polymerizable liquid monomers. The reactive thinners are in generally in amounts of 1-50% by weight, preferably 5-30% by weight, based on the total weight of prepolymer and reactive diluent used. The Reactive diluents can be mono-, di- or polyunsaturated. examples for monounsaturated reactive diluents are: (meth) acrylic acid and its esters, Maleic acid and its half esters, vinyl acetate, vinyl ether, substituted Vinyl ureas, styrene, vinyl toluene. Examples of unsaturated reactive thinners are: di (meth) acrylates such as alkylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, Divinylbenzene, dipropylene glycol di (meth) acrylate, hexanediol di (meth) acrylate. Examples for polyunsaturated reactive thinners are: glycerol tri (meth) acrylate, Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate. The reactive diluents can be used individually or in a mixture become. Preferred reactive diluents are diacrylates such as e.g. Dipropylene glycol diacrylate, tripropylene glycol diacrylate and / or hexanediol diacrylate used.

Als Bindemittel für kationisch polymerisierbare Systeme können die üblichen dem Fachmann bekannten und in der Literatur beschriebenen Bindemittel eingesetzt werden. Es kann sich dabei beispielsweise um polyfunktionelle Epoxyoligomere, die mehr als zwei Epoxygruppen im Molekül enthalten, handeln. Es handelt sich beispielsweise um Polyalkylenglykoldiglycidylether, hydrierte Bisphenol-A-Glycidylether, Epoxyurethanharze, Glycerintriglycidylether, Diglycidylhexahydrophthalat, Diglycidylester von Dimersäuren, epoxidierte Derivate des (Methyl)cyclohexens, wie z.B. 3,4-Epoxycyclohexyl-methyl(3,4-epoxycyclohexan)carboxylat oder epoxidiertes Polybutadien. Das Zahlenmittel der Molmasse der Polyepoxidverbindungen liegt bevorzugt unter 10000. Es können auch Reaktivverdünner, wie z.B. Cyclohexenoxid, Butenoxid, Butandioldiglycidylether oder Hexandioldiglycidylether, eingesetzt werden.As a binder for cationically polymerizable systems, the usual ones Binders known to those skilled in the art and described in the literature are used become. These can be, for example, polyfunctional epoxy oligomers which contain more than two epoxy groups in the molecule. It is about for example polyalkylene glycol diglycidyl ether, hydrogenated bisphenol A glycidyl ether, Epoxy urethane resins, glycerol triglycidyl ether, Diglycidyl hexahydrophthalate, diglycidyl ester of dimer acids, epoxidized derivatives des (methyl) cyclohexene, e.g. 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate or epoxidized polybutadiene. The number average of Molar mass of the polyepoxide compounds is preferably less than 10,000. It can also Reactive thinners, e.g. Cyclohexene oxide, butene oxide, butanediol diglycidyl ether or Hexanediol diglycidyl ether can be used.

Die unter Strahleneinwirkung härtenden Bindemittelsysteme enthalten Photoinitiatoren. Geeignete Photoinitiatoren sind beispielsweise solche, die im Wellenlängenbereich von 190 bis 600 nm absorbieren.Contain the binder systems that harden under the influence of radiation Photoinitiators. Suitable photoinitiators are, for example, those which Absorb wavelength range from 190 to 600 nm.

Beispiele für Photoinitiatoren für radikalisch härtende Systeme sind Benzoin und -derivate, Acetophenon, und -derivate, wie z.B. 2,2-Diacetoxyacetophenon, Benzophenon und -derivate, Thioxanthon und -derivate, Anthrachinon, 1-Benzoylcyclohexanol, phosphororganische Verbindungen, wie z.B. Acylphosphinoxide. Die Photoinitiatoren werden beispielsweise in Mengen von 0,1 - 7 Gew.-%, bevorzugt 0,5 - 5 Gew.-% eingesetzt, bezogen auf die Summe von radikalisch polymerisierbaren Prepolymeren, Reaktivverdünnern und Photoinitiatoren. Die Photoinitiatoren können einzeln oder in Kombination eingesetzt werden. Außerdem können weitere synergistische Komponenten, z.B. tertiäre Amine, eingesetzt werden.Examples of photoinitiators for radical curing systems are benzoin and derivatives, acetophenone and derivatives such as e.g. 2,2-diacetoxyacetophenone, Benzophenone and derivatives, thioxanthone and derivatives, anthraquinone, 1-benzoylcyclohexanol, organophosphorus compounds, e.g. Acylphosphine oxides. The photoinitiators are used, for example, in amounts of 0.1-7 % By weight, preferably 0.5-5% by weight, based on the sum of radical polymerizable prepolymers, reactive thinners and photoinitiators. The photoinitiators can be used individually or in combination. In addition, other synergistic components, e.g. tertiary amines, be used.

Photoinitiatoren für kationisch härtende Systeme sind Substanzen, die als Oniumsalze bekannt sind, welche unter Strahleneinwirkung photolytisch Lewis-Säuren freisetzen. Beispiele hierfür sind Diazoniumsalze, Sulfoniumsalze oder Jodoniumsalze. Bevorzugt sind Triarylsulfoniumsalze. Die Photoinitiatoren für kationisch härtende Systeme können in Mengen von 0,5 bis 5 Gew.-%, bezogen auf die Summe von kationisch polymerisierbaren Prepolymeren, Reaktivverdünnern und Initiatoren, einzeln oder als Gemische eingesetzt werden.Photoinitiators for cationic curing systems are substances that act as onium salts are known which photolytically release Lewis acids under the action of radiation. Examples include diazonium salts, sulfonium salts or iodonium salts. Prefers are triarylsulfonium salts. The photoinitiators for cationic curing systems can be in amounts of 0.5 to 5 wt .-%, based on the sum of cationic polymerizable prepolymers, reactive diluents and initiators, individually or as Mixtures are used.

Zur Herstellung der mittels energiereicher Strahlung, beispielsweise gepulster Strahlung, härtbaren Füllerbeschichtungsmittel können verschiedene radikalisch härtende Systeme, verschiedene kationisch härtende Systeme oder radikalisch und kationisch härtende Systeme miteinander kombiniert werden. Bevorzugt werden radikalisch härtende Systeme eingesetzt. Bevorzugte radikalisch härtende Bindemittel sind Epoxid(meth)acrylate, Polyurethan(meth)acrylate, Polyester(meth)acrylate und (meth)acrylfunktionelle Poly(meth)acrylate. Besonders bevorzugt sind aromatische Epoxid(meth)acrylate. Die beispielhaft genannten mittels energiereicher Strahlung härtbaren Bindemittel sind im allgemeinen als Handelsprodukte erhältlich. For the production of high-energy radiation, for example pulsed Radiation, curable filler coatings can be various free radicals curing systems, various cationic curing systems or radical and cationic curing systems can be combined. To be favoured radical curing systems used. Preferred free radical curing binders are epoxy (meth) acrylates, polyurethane (meth) acrylates, polyester (meth) acrylates and (meth) acrylic functional poly (meth) acrylates. Aromatic are particularly preferred Epoxy (meth) acrylates. The examples mentioned using high-energy radiation curable binders are generally available as commercial products.

Erfindungsgemäß können die mittels energiereicher Strahlung härtbaren Füllerbeschichtungsmittel ausschließlich mittels energiereicher Strahlung härtbare Bindemittel enthalten, sie können jedoch auch neben den mittels energiereicher Strahlung härtbaren Bindemitteln noch andere chemisch vernetzende Bindemittel enthalten. Als chemisch vernetzende Bindemittel können beispielsweise beliebige zweikomponentige Bindemittelsysteme auf Basis einer hydroxyfunktionellen und einer isocyanatfunktionellen Komponente, einer hydroxyfunktionellen und einer Anhydridkomponente, einer Polyamin- und einer Epoxidkomponente oder einer Polyamin- und einer acryloyifunktionellen Komponente eingesetzt werden. Bei den zusätzlich einsetzbaren Bindemitteln kann es sich um solche auf wäßriger oder Lösemittelbasis handeln. Werden in den Füllerbeschichtungsmitteln neben den strahlenhärtenden Bindemitteln noch andere chemisch vernetzende Bindemittel eingesetzt, dann können bevorzugt solche auf Basis einer hydroxyfunktionellen und einer isocyanatfunktionellen Komponente oder einer Polyamin- und einer Epoxidkomponente eingesetzt werden. Der Anteil an chemisch vernetzenden Bindemitteln kann beispielsweise bis zu 50 Gew.-%, bezogen auf das UV-härtbare Bindemittel, betragen.According to the invention, those curable by means of high-energy radiation Filler coating agents can only be hardened using high-energy radiation Contain binders, but they can also be used in addition to those with high energy Radiation-curable binders and other chemically crosslinking binders contain. For example, any chemically crosslinking binder two-component binder systems based on one hydroxy functional and one isocyanate-functional component, a hydroxy-functional and one Anhydride component, a polyamine and an epoxy component or one Polyamine and an acryloyifunctional component can be used. Both additionally usable binders can be those on aqueous or Act solvent based. Are used in the filler coatings in addition to the radiation-curing binders and other chemically crosslinking binders used, then those based on a hydroxy-functional and an isocyanate-functional component or a polyamine and one Epoxy component are used. The proportion of chemically cross-linking Binders can, for example, up to 50 wt .-%, based on the UV-curable Binders.

Die im erfindungsgemäßen Verfahren einsetzbaren Füllerbeschichtungsmittel können Füllstoffe und Pigmente enthalten. Es handelt sich dabei um die üblichen in der Lackindustrie einsetzbaren Füllstoffe und organischen oder anorganischen farbgebenden und/oder Korrosionsschutzpigmente. Beispiele für Pigmente sind Titandioxid, mikronisiertes Titandioxid, Eisenoxidpigmente, Ruß, Azopigmente, Zinkphosphat. Beispiele für Füllstoffe sind Siliciumdioxid, Aluminiumsilikat, Bariumsulfat und Talkum. Zur Verbesserung von Härte und Schleitbarkeit können vorteilhaft auch UV-härtbare Pigmente und/oder Füllstoffe eingesetzt werden. Es handelt sich hierbei um Pigmente und/oder Füllstoffe, die mit mittels UV-Strahlung härtbaren Verbindungen, z.B. mit acrylfunktionellen Silanen, gecoated sind und in den Strahlenhärtungsprozeß mit einbezogen werden.The filler coating compositions which can be used in the process according to the invention can Contain fillers and pigments. These are the usual ones in the Paint industry usable fillers and organic or inorganic coloring and / or anti-corrosion pigments. Examples of pigments are Titanium dioxide, micronized titanium dioxide, iron oxide pigments, carbon black, azo pigments, Zinc phosphate. Examples of fillers are silicon dioxide, aluminum silicate, Barium sulfate and talc. Can improve hardness and ductility UV-curable pigments and / or fillers are also advantageously used. It These are pigments and / or fillers that are used by means of UV radiation curable compounds, e.g. are coated with acrylic functional silanes and in the Radiation curing process should be included.

Die im erfindungsgemäßen Verfahren einsetzbaren Füllerbeschichtungsmittel können lackübliche Additive enthalten. Bei den Additiven handelt es sich um die üblichen auf dem Lacksektor einsetzbaren Additive. Beispiele für solche Additive sind Verlaufsmittel, z.B. auf der Basis von (Meth)acryl-Homopolymerisaten oder Silikonölen, Antikratermittel, Antischaummittel, Katalysatoren, Haftvermittler. Die Additive werden in üblichen, dem Fachmann geläufigen Mengen eingesetzt.The filler coating compositions which can be used in the process according to the invention can customary paint additives included. The additives are the usual ones additives that can be used in the paint sector. Examples of such additives are Leveling agents, e.g. based on (meth) acrylic homopolymers or Silicone oils, anti-cratering agents, anti-foaming agents, catalysts, adhesion promoters. The Additives are used in the usual amounts familiar to the person skilled in the art.

Die im erfindungsgemäßen Verfahren einsetzbaren Füller können lösemittelfrei formuliert werden. Ihr Festkörpergehalt beträgt dann 100 Gew.-%. Die Füller können jedoch auch geringe Mengen organische Lösemittel und/oder Wasser enthalten. Bei den Lösemitteln handelt es sich um übliche lacktechnische Lösemittel. Diese können aus der Herstellung der Bindemittel stammen oder werden separat zugegeben. Beispiele für solche Lösemittel sind ein- oder mehrwertige Alkohole, z.B. Propanol, Butanol, Hexanol; Glykolether oder -ester, z.B.Butylglykol, Butyldiglykol, Diethylenglykoldialkylether, Dipropylenglykoldialkylether, Ethylglykolacetat, Butylglykolacetat, Butyldiglykolacetat, Ester, wie z.B. Butylacetat, Isobutylacetat, Amylacetat, Glykole, z.B. Ethylenglykol, Propylenglykol und deren Oligomere, Alkyl-Pyrrolidone, z.B. N-Methylpyrrolidon sowie Ketone, z.B. Methylethylketon, Aceton, Cyclohexanon; aromatische oder aliphatische Kohlenwasserstoffe, z.B. Toluol, Xylol oder lineare oder verzweigte aliphatische C6-C12-Kohlenwasserstoffe.The fillers which can be used in the process according to the invention can be solvent-free be formulated. Their solids content is then 100% by weight. The fillers can however also contain small amounts of organic solvents and / or water. At The solvents are common paint solvents. these can originate from the production of the binders or are added separately. Examples of such solvents are monohydric or polyhydric alcohols, e.g. Propanol, Butanol, hexanol; Glycol ether or ester, e.g. butyl glycol, butyl diglycol, Diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, ethyl glycol acetate, Butyl glycol acetate, butyl diglycol acetate, esters such as e.g. Butyl acetate, isobutyl acetate, Amyl acetate, glycols, e.g. Ethylene glycol, propylene glycol and their oligomers, Alkyl pyrrolidones, e.g. N-methylpyrrolidone and ketones, e.g. Methyl ethyl ketone, Acetone, cyclohexanone; aromatic or aliphatic hydrocarbons, e.g. Toluene, xylene or linear or branched aliphatic C6-C12 hydrocarbons.

Der Auftrag der Füllerschicht erfolgt im erfindungsgemäßen Verfahren auf ein gegebenenfalls vorbeschichtetes Substrat. Bevorzugte Substrate sind Metall- oder Kunststoffsubstrate. Die Füller können auf übliche Grundierungs- oder weitere Zwischenschichten, wie sie für die Mehrschichtlackierung auf dem Kraftfahrzeugsektor verwendet werden, appliziert werden. Sie können auf eine im Rahmen der Fahrzeugreparaturlackierung bereits vorbeschichtete bzw. vorbehandelte Fahrzeugkarosse bzw. deren Teile aufgebracht werden, sie können jedoch auch auf Altlackierungen aufgebracht werden. Die Applikation kann nach den bekannten Methoden, bevorzugt mittels Spritzauftrag, erfolgen.The filler layer is applied to one in the process according to the invention optionally precoated substrate. Preferred substrates are metal or Plastic substrates. The fillers can be applied to conventional primers or others Intermediate layers, such as those for the multi-layer coating on the Motor vehicle sector are used to be applied. You can click on an im Pre-coated or pre-treated as part of vehicle refinishing Vehicle body or parts thereof are applied, but they can also be on Old paintwork can be applied. The application can be based on the known Methods, preferably by spray application.

Die Füller können beispielsweise auf übliche lösemittel- oder wasserbasierende Spachtel, Grundierungen, Haftprimer oder weitere Zwischenschichten, wie sie für die Fahrzeugreparaturlackierung üblich sind, oder auf Altlackierungen, wie z.B. KTL-Untergründe, aufgebracht werden. Die Untergründe bzw. Lackschichten. auf die die Füllerschicht aufgebracht wird, können dabei bereits ausgehärtet oder vorgetrocknet sein. Als für die Reparaturlackierung übliche Spachtel, Grundierungen oder Primer kommen beispielsweise solche in Frage auf Basis peroxidhärtender ungesättigter Polyester, säurehärtender Polyvinylbutyrale, physikalisch trocknender Bindemittel, z.B. Polyurethane oder Arcrylate, sowie zweikomponentiger vernetzender Bindemittel, z.B. auf Basis einer Epoxid- und einer Polyaminkomponente oder Polyisocyanat- und einer Hydroxykomponente.The fillers can be based, for example, on conventional solvent- or water-based Spatulas, primers, adhesive primers or other intermediate layers, such as for the Vehicle refinishing is common, or on old paintwork such as KTL substrates, be applied. The substrates or layers of paint. on the the Filler layer is applied, can be cured or pre-dried his. As a standard spatula, primer or primer for refinishing For example, those based on peroxide-curing unsaturated are suitable Polyester, acid-curing polyvinyl butyral, physically drying binder, e.g. Polyurethanes or acrylates, as well as two-component crosslinking Binders, e.g. based on an epoxy and a polyamine component or Polyisocyanate and a hydroxy component.

Nach Applikation des Füllers auf einen der vorstehend genannten Untergründe wird die Füllerschicht, gegebenenfalls nach einer kurzen Ablüftphase, energiereicher Strahlung, bevorzugt UV-Strahlung, ausgesetzt. Bevorzugt sind UV-Strahlungsquellen mit Emissionen im Wellenlängenbereich von 180 bis 420 nm, insbesondere von 200 bis 400 nm. Beispiele für derartige UV-Strahlungsquellen sind gegebenenfalls dotierte Quecksilberhochdruck-, mitteldruck- und niederdruckstrahler, Gasentladungsröhren, wie z.B. Xenonniedrdrucklampen, gepulste und ungepulste UV-Laser, UV-Punktstrahler, wie z.B. UV-emittierende Dioden und Schwarzlichtröhren. Bevorzugt erfolgt die Bestrahlung mit gepulster UV-Strahlung. Als Strahlungsquelle werden dann besonders bevorzugt sogenannte Hochenergieelektronen-Blitzeinrichtungen (kurz: UV-Blitzlampen) eingesetzt.After application of the filler on one of the above-mentioned substrates the filler layer, possibly after a short flash-off phase, is more energetic Radiation, preferably UV radiation, exposed. UV radiation sources are preferred with emissions in the wavelength range from 180 to 420 nm, in particular from 200 up to 400 nm. Examples of such UV radiation sources may be doped High-pressure mercury, medium-pressure and low-pressure lamps, gas discharge tubes, such as. Xenon low pressure lamps, pulsed and unpulsed UV lasers, UV spotlights, such as. UV emitting diodes and black light tubes. Prefers the irradiation takes place with pulsed UV radiation. As a radiation source then particularly preferred so-called high-energy electron flash devices (in short: UV flash lamps).

Bevorzugte UV-Blitzlampen emittieren Licht einer Wellenlänge von 200 bis 900 nm mit einem Maximum bei etwa 300 bis 500 nm. Die UV-Blitzlampen enthalten bevorzugt eine Mehrzahl von Blitzröhren, beispielsweise mit inertem Gas, wie Xenon, gefüllte Quarzröhren. Die UV-Blitzlampen sollen an der Oberfläche des zu härtenden Überzuges eine Beleuchtungsstärke von mindestens 10 Megalux, bevorzugt von 10 bis 80 Megalux pro Blitzentladung bewirken. Die Energie pro Blitzentladung soll bevorzugt 1 bis 10 kJoule betragen. Bei den UV-Blitzlampen handelt es sich bevorzugt um transportable Einrichtungen, die direkt vor einer auszubessernden Schadstelle positioniert werden können. Je nach den Gegebenheiten können ein oder mehrere UV-Blitzlampen eingesetzt werden. Einsetzbare UV-Blitzlampen sind beispielsweise beschrieben in den WO-A-9411123 und in der EP-A-525 340. UV-Blitzlampen sind im Handel erhältlich.Preferred UV flash lamps emit light with a wavelength of 200 to 900 nm with a maximum at about 300 to 500 nm. The UV flash lamps contain preferably a plurality of flash tubes, for example with inert gas, such as Xenon, filled quartz tubes. The UV flash lamps are said to be on the surface of the curing coating an illuminance of at least 10 megalux, preferred effect from 10 to 80 Megalux per lightning discharge. The energy per flash discharge should preferably be 1 to 10 kJoules. The UV flash lamps are preferred to transportable facilities that are in front of a mending Damage point can be positioned. Depending on the circumstances, one or several UV flash lamps can be used. UV flash lamps that can be used described, for example, in WO-A-9411123 and in EP-A-525 340. UV flash lamps are commercially available.

Die Trocknung bzw. Härtung der Füllerschicht kann durch eine Mehrzahl aufeinanderfolgender Blitzentladungen erfolgen. Bevorzugt werden 1 bis 40 aufeinanderfolgende Blitzentladungen ausgelöst. Der Abstand der UV-Blitzlampe zur zu bestrahlenden Substratoberfläche kann dabei 5 - 50 cm, bevorzugt 10 - 25 cm, besonders bevorzugt 15 - 20 cm betragen. Die Abschirmung der UV-Lampen zur Vermeidung von Strahlungsaustritt kann dabei z.B. durch Verwendung eines entsprechend ausgekleideten Schutzgehäuses um die transportable Lampeneinheit oder mit Hilfe anderer, dem Fachmann bekannter Sicherheitsmaßnahmen, erfolgen.The drying or hardening of the filler layer can be carried out by a plurality successive lightning discharges occur. 1 to 40 are preferred successive lightning discharges triggered. The distance of the UV flash lamp to substrate surface to be irradiated can be 5 - 50 cm, preferably 10 - 25 cm, are particularly preferably 15-20 cm. The shielding of the UV lamps Avoiding radiation leakage can e.g. by using a appropriately lined protective housing around the portable lamp unit or with the help of other safety measures known to the person skilled in the art.

Die Bestrahlungsdauer liegt insgesamt im Bereich weniger Sekunden, beispielsweise im Bereich von 3 Millisekunden bis 400 Sekunden, bevorzugt von 4 - 160 Sekunden, je nach Anzahl der gewählten Blitzentladungen. Die Blitze können beispielsweise ca. alle 4 s ausgelöst werden. Die UV-Blitzlampen sind jederzeit sofort einsetzbereit, d.h. sie bedürfen keiner Einbrennzeit und können zwischen zwei zeitlich etwas auseinanderliegenden Härtungs- bzw. Bestrahlungsvorgängen ausgeschaltet bleiben, ohne daß beim erneuten Bestrahlungsvorgang durch die Einbrennphase Zeiteinbußen auftreten.The total irradiation time is in the range of a few seconds, for example in the range from 3 milliseconds to 400 seconds, preferably from 4 to 160 seconds, depending on the number of selected lightning discharges. The flashes can be approx. triggered every 4 s. The UV flash lamps are ready for use at any time, i.e. they do not require a burn-in time and can do something between two times separate curing or radiation processes remain switched off, without losing time in the re-irradiation process due to the stoving phase occur.

Ein besonderer Vorteil des erfindungsgemäßen Verfahrens liegt, darin, daß in einem Arbeitsgang hohe Schichtdicken aufgebracht werden können (ohne Zwischenschleifen) und daß auch bei hoher Pigmentierung der Füller, beispielsweise bei einer Pigment-Volumenkonzentration (PVK) von 30 bis 45 % und mehr, Überzüge mit Schichtdicken von beispielsweise 200 bis 400, bevorzugt 300 bis 400 µm aufgebracht werden können, die schnell und vollständig durchhärten und gut schleifbar sind. Um die rasche Durchhärtung auch bei hoher Pigmentierung zu gewährleisten kann so vorgegangen werden, daß das Füllerbeschichtungsmittel in mehreren, bevorzugt zwei, Spritzgängen appliziert wird und nach dem ersten Spritzgang bzw. nach jedem weiteren Spritzgang, wenn insgesamt mehr als zwei Spritzgänge erfolgen, jeweils eine Zwischenbestrahlung ausgelöst wird. So werden z.B. in einem 1. Spritzgang beispielsweise 100 bis 200 µm Schichtdicke aufgebracht Mit z.B. 2 bis 5 Blitzen erfolgt eine Zwischenhärtung, anschließend wird in einem 2. Spritzgang eine weitere Schicht von z.B. 100 - 200 µm aufgebracht und es erfolgt mit der erforderlichen Anzahl von Blitzentladungen die vollständige Härtung.A particular advantage of the method according to the invention is that high layer thicknesses can be applied in one operation (without intermediate sanding) and that even with high pigmentation of the filler, for example with a pigment volume concentration (PVC) of 30 to 45% and more, coatings with layer thicknesses of, for example, 200 to 400, preferably 300 to 400 μ m can be applied by the cure rapidly and completely and are easy to sand. In order to ensure the rapid hardening even with high pigmentation, the procedure can be such that the filler coating agent is applied in several, preferably two, spray passes, and after the first spray pass or after each further spray pass, if a total of more than two spray passes, there is intermediate radiation is triggered. Thus, for example be applied in a first spray pass, for example, 100 to 200 μ m thickness with for example 2 to 5 flashes carried out an intermediate curing, then a further layer of, for example 100 is in a second spray pass - 200 μ m is applied and it is carried out with the required Number of lightning discharges complete hardening.

Sind in den erfindungsgemäß einsetzbaren Füllerbeschichtungsmitteln neben den strahlenhärtbaren Bindemitteln weitere chemisch vernetzbare Bindemittel enthalten, so reichen die mittels der UV-Bestrahlung (UV-Blitzlampe) erzeugten Temperaturen auf der Beschichtung im allgemeinen aus, die zusätzlichen vernetzbaren Bindemittel zu härten. Ein separater Härtungsvorgang ist nicht erforderlich.Are in the filler coating compositions used according to the invention in addition to radiation-curable binders contain further chemically crosslinkable binders, so the temperatures generated by means of UV radiation (UV flash lamp) are sufficient the coating in general, the additional crosslinkable binders harden. A separate hardening process is not necessary.

Die im erfindungsgemäßen Verfahren einsetzbaren Füllerbeschichtungsmittel können als Schleiffüller, Grundierfüller oder naß-in-naß-Füller formuliert bzw. eingesetzt werden.The filler coating compositions which can be used in the process according to the invention can Formulated or used as a sanding filler, primer filler or wet-on-wet filler become.

Nach teilweiser oder vollständiger Härtung der Füllerschicht oder naß-in-naß wird im erfindungsgemäßen Verfahren auf die Füllerschicht eine Deckbeschichtung aus einer farb- und/oder effektgebenden Basislackschicht und einer transparenten Klarlackschicht oder eine Deckbeschichtung aus einem pigmentierten Einschichtdecklack aufgebracht.After partial or complete hardening of the filler layer or wet-on-wet is in method according to the invention on the filler layer a top coating from a color and / or effect basecoat and a transparent clearcoat or a top coat made of a pigmented single-layer topcoat.

Für die Basislack/Klarlack-Deckbeschichtung einsetzbare farb- und/oder effektgebende Basislacke sind alle in der Fahrzeuglackierung, insbesondere der Reparaturlackierung, üblichen und dem Fachmann bekannten lösemittel- oder wasserbasierenden Basislacke geeignet. Beispiele für lösemittelbasierende Basislacke sind solche auf Basis von Polyacrylat- und/oder Polyesterharzen, gegebenenfalls in Kombination mit Melaminharzen und Celluloseestern. Beispiele für Wasserbasislacke sind solche auf Basis physikalisch trocknender Polyurethan-, Polyurethan/harnstoff-, Polyester-, Polyesterurethan- und/oder Polyacrylatharze sowie deren Modifizierungen, wie z.B. acrylierter oder siliziummodifizierter Polyurethan- und/oder Polyesterharze. Weiterhin kommen Wasserbasislacke aus chemisch vernetzenden Bindemittelkomponenten, z.B. aus hydroxylgruppenhaltigen Bindemitteln und Polyisocyanatvernetzern, in Frage. Color and / or effect paint can be used for the basecoat / clearcoat topcoat Basecoats are all in vehicle painting, especially refinishing, usual solvent-based or water-based basecoats known to those skilled in the art suitable. Examples of solvent-based basecoats are those based on Polyacrylate and / or polyester resins, optionally in combination with Melamine resins and cellulose esters. Examples of waterborne basecoats are such Based on physically drying polyurethane, polyurethane / urea, polyester, Polyester urethane and / or polyacrylate resins and their modifications, such as e.g. acrylated or silicon-modified polyurethane and / or polyester resins. Farther come waterborne basecoats from chemically crosslinking binder components, e.g. from binders containing hydroxyl groups and polyisocyanate crosslinkers.

Die Härtung der Basislackschicht kann bei Raumtemperatur oder forciert hei beispielsweise 40 - 80°C erfolgen. Die Basislackschicht kann jedoch auch naß-in-naß, gegebenenfalls nach einer kurzen Ablüftphase mit einem Klarlack überlackiert und dann gemeinsam mit dem Klarlack gehärtet werden.The hardening of the basecoat can be hot or at room temperature for example, 40-80 ° C. However, the basecoat can also be wet-on-wet, if necessary after a short flash-off phase with a clear varnish and then be cured together with the clear coat.

Eine Ausführungsform des erfindungsgemäßen Verfahrens besteht darin, als Basislack einen solchen einzusetzen, der mittels energiereicher Strahlung härtbare Bindemittel enthält. Bei den mittels energiereicher Strahlung härtbaren Bindemittel handelt es sich beispielsweise um die vorstehend bei der Beschreibung der Füllerbeschichtungsmittel bereits genannten Bindemittel. Bevorzugt werden im Basislack in diesem Fall jedoch aliphatische Polyurethan(meth)acrylate und/oder aliphatische (meth)acrylfunktionelle Poly(meth)arylate eingesetzt.One embodiment of the method according to the invention is as a basecoat to use such a binder that can be hardened by means of high-energy radiation contains. The binders curable by means of high-energy radiation are for example, the above in the description of the filler coating compositions binder already mentioned. In this case, however, are preferred in the basecoat aliphatic polyurethane (meth) acrylates and / or aliphatic (meth) acrylic functional Poly (meth) arylates used.

Eine Härtung kann dann, wie vorstehend für den Füller beschrieben, mit einer UV-Strahlungsquelle erfolgen. Dabei kann der Basislack naß-in-naß auf die Füllerschicht (naß-in-naß-Füller) aufgebracht werden und Füller- und Basislackschicht werden gemeinsam in einem Arbeitsschritt der Strahlung ausgesetzt. Gegebenenfalls kann eine kurze Zwischenbestrahlung der Füllerschicht erfolgen. Es kann jedoch auch, insbesondere bei hohen Schichtdicken und hoher Pigmentierung des Füllers, zunächst die Füllerschicht vollständig mittels UV-Strahlung ausgehärtet werden (Schleiffüller), gegebenenfalls in mehreren Bestrahlungsschritten, und anschließend die separate Härtung der Basislackschicht mit UV-Strahlung erfolgen.Curing can then, as described above for the filler, with a UV radiation source respectively. The basecoat can be applied wet-on-wet to the filler layer (wet-on-wet filler) and filler and basecoat layers exposed to radiation together in one work step. If necessary there is a short interim exposure of the filler layer. However, it can also especially with high layer thicknesses and high pigmentation of the filler, initially the filler layer is completely hardened using UV radiation (abrasive filler), possibly in several irradiation steps, and then the separate one The basecoat film is cured with UV radiation.

Für die Basislack/Klarlack-Deckbeschichtung einsetzbare Klarlacke sind alle in der Fahrzeuglackierung, insbesondere der Reparaturlackierung üblichen und dem Fachmann bekannten lösemittel- oder wasserbasierenden Klarlacke geeignet. Beispiele hierfür sind lösemittelbasierende oder wäßrige Klarlacke auf Basis hydroxylgruppenhaltiger und/oder aminogruppenhaltiger Bindemittel und Polyisocyanatvernetzer sowie auf Basis aminogruppenhaltiger und acryloylgruppenhaltiger Bindemittel. Die Härtung der Klarlackschicht kann bei Raumtemperatur oder forciert bei beispielsweise 40 - 80°C erfolgen. Clearcoats that can be used for the basecoat / clearcoat topcoat are all in the Vehicle painting, especially the usual repair painting and the Suitable solvent-based or water-based clearcoats known to those skilled in the art. Examples this is based on solvent-based or aqueous clear lacquers binders containing hydroxyl groups and / or amino groups and Polyisocyanate crosslinkers and based on amino groups and binder containing acryloyl groups. The hardening of the clear coat can Room temperature or forced at 40 - 80 ° C, for example.

Eine weitere Ausführungsform des erfindungsgemäßen Verfahrens besteht darin, einen Mehrschichtaufbau zu erstellen, der auf einem strahlenhärtbaren Füller, einem physikalisch trocknenden oder chemisch vernetzenden, nicht auf strahlenhärtbaren Bindemitteln basierenden, Basislack und einem Klarlack der mittels energiereicher Strahlung härtbare Bindemittel enthält, basiert. In diesem Fall kann der Basislack auf den vollständig ausgehärteten Füller aufgebracht werden und nach Härtung des Basislackes oder nach kurzer Zwischentrocknung des Basislackes, kann der strahlenhärtende Klarlack aufgebracht werden. Anschließend erfolgt die Bestrahlung mit UV-Strahlen. Der Klarlack kann in diesem Fall die üblichen strahlenhärtbaren Bindemittel enthalten, wie sie vorstehend bereits bei der Beschreibung der Füllerbeschichtungsmittel genannt wurden. Bevorzugt werden dabei aliphatische Polyurethan(meth)acrylate und/oder aliphatische acrylfunktionelle Poly(meth)acrylate eingesetzt.
Besonders bevorzugt werden in dieser Ausführungsform im Füller mittels energiereicher Strahlung härtbare Bindemittel auf Basis von aromatischen Epoxid(meth)acrylaten und im Klarlack mittels energiereicher Strahlung härtbare Bindemittel auf Basis von aliphatischen Polyurethan(meth)acrylaten und/oder aliphatischen (meth)acrylfunktionellen Poly(meth)acrylaten eingesetzt. Es besteht weiterhin noch die Möglichkeit, auf die gehärtete oder zwischengehärtete Füllerschicht. oder auch naß-in-naß, einen üblichen lösemittel- oder wasserbasierenden pigmentierten Einschichtdecklack aufzubringen.
Mit dem erfindungsgemäßen Verfahren erhält man in kurzer Zeit Mehrschichtüberzüge mit großer Härte, hoher Kratzfestigkeit sowie sehr guter Chemikalien- und Wasserbeständigkeit. Die einzelnen Lackschichten zeigen eine sehr gute Zwischenschichthaftung, und Anlöseresistenz gegenüber darunter bzw. darüberliegenden Lackschichten. Auch sehr dicke Füllerschichten können in einem Spritzgang blasenfrei appliziert werden und trocknen rasch. Auch hoch pigmentierte Füller können in hohen Schichtdicken aufgebracht werden und zeigen eine rasche und vollständige Durchhärtung. Die Füllerbeschichtungen sind nach kurzer Trockenzeit gut schleifbar. Sie zeigen einen sehr guten Decklackstand.
Die Überzüge entsprechen ansonsten den Anforderungen an einen Lackaufbau, z.B. einen Reparaturlackaufbau, auf dem Gebiet der Fahrzeuglackierung, wobei die Trocknung bzw. Härtung der Überzüge im Vergleich zu in üblicher Weise getrockneten bzw. gehärteten Lackaufbauten in sehr verkürzter Zeit erfolgen kann.A further embodiment of the method according to the invention consists in creating a multilayer structure which is based on a radiation-curable filler, a physically drying or chemically crosslinking base coat which is not based on radiation-curable binders, and a clear coat which contains binders curable by means of high-energy radiation. In this case the basecoat can be applied to the fully cured filler and after curing the basecoat or after briefly drying the basecoat, the radiation-curing clearcoat can be applied. Then UV radiation is applied. In this case, the clear lacquer can contain the customary radiation-curable binders, as already mentioned above in the description of the filler coating compositions. Aliphatic polyurethane (meth) acrylates and / or aliphatic acrylic-functional poly (meth) acrylates are preferably used.
Particularly preferred in this embodiment are binders curable by means of high-energy radiation based on aromatic epoxy (meth) acrylates and binders curable by means of high-energy radiation based on aliphatic polyurethane (meth) acrylates and / or aliphatic (meth) acrylic-functional poly (meth) in the filler ) acrylates used. There is still the possibility of applying the hardened or intermediate hardened filler layer. or wet-on-wet, to apply a customary solvent- or water-based pigmented single-coat topcoat.
With the process according to the invention, multilayer coatings with great hardness, high scratch resistance and very good chemical and water resistance are obtained in a short time. The individual layers of paint show very good interlayer adhesion and resistance to dissolving of the paint layers below or above. Even very thick filler layers can be applied without bubbles in one spray cycle and dry quickly. Highly pigmented fillers can also be applied in high layer thicknesses and show rapid and complete hardening. The filler coatings are easy to sand after a short drying time. They show a very good topcoat level.
The coatings otherwise correspond to the requirements for a paint structure, for example a refinish structure, in the field of vehicle painting, with the drying or curing of the coatings being able to be carried out in a very short time in comparison with the paint structures which have been dried or hardened in the customary manner.

Das erfindungsgemäße Verfahren kann vorteilhaft eingesetzt werden in der Fahrzeugreparaturlackierung, insbesondere zur Reparaturlackierung von Fahrzeugteilen, kleineren Schadstellen und zum Spotrepair.The method according to the invention can advantageously be used in the Vehicle refinishing, in particular for refinishing Vehicle parts, smaller damaged areas and for spot repair.

Die Erfindung soll an Hand des folgenden Beispiels erläutert werden.The invention is illustrated by the following example.

Beispielexample Herstellung eines FüllersProduction of a filler

Folgende Komponenten wurden miteinander vermischt und mittels Schnellrührer einige Minuten dispergiert (alle Angaben beziehen sich auf das Gewicht):

  • 131 Teile eines handelsüblichen aromatischen Epoxyacrylates
  • 56 Teile Hexandioldiacrylat
  • 9 Teile eines handelsüblichen Haftvermittlers
  • 127 Teile handelsüblicher Schwerspat
  • 126 Teile handelsübliches Kaolin
  • 6.1 Teile einer Mischung handelsüblicher Photoinitiatoren (Arylphosphinoxid- und Acetophenonderivat)
  • 113 Teile Butylacecat
    • The following components were mixed together and dispersed for a few minutes using a high-speed stirrer (all information relates to the weight):
  • 131 parts of a commercially available aromatic epoxy acrylate
  • 56 parts of hexanediol diacrylate
  • 9 parts of a commercially available adhesion promoter
  • 127 parts of commercially available heavy spar
  • 126 parts of commercially available kaolin
  • 6.1 parts of a mixture of commercially available photoinitiators (arylphosphine oxide and acetophenone derivative)
  • 113 parts of Butylacecat

    • Erstellung eines MehrschichtaufbausCreation of a multilayer structure

    Der vorstehend hergestelte Füller wird auf KTL-beschichtete Bleche aufgebracht. In einem Arbeitsgang wird eine Füllerschicht in einer resultierenden Trockenfilmschichtdicke von etwa 300 µm aufgebracht und nach kurzem Ablüften bei Raumtemperatur wird die Füllerschicht der Bestrahlung durch eine UV-Blitzlampe (3500 Ws) ausgesetzt. Es wird mit 30 Blitzen (etwa 120 s) bestrahlt. Anschließend wird der Füller geschliffen und ein lösemittelbasierender üblicher pigmentierter 2K-Decklack auf Basis Acrylat/Polyisocyanat überlackiert. The filler produced above is applied to KTL-coated sheets. In one operation, a filler layer in a resulting dry film layer thickness of about 300 μ m is applied and after a brief flash-off at room temperature, the filler layer to irradiation by a UV flash lamp is exposed (3500 Ws). It is irradiated with 30 flashes (about 120 s). The filler is then sanded and a solvent-based, customary pigmented two-pack topcoat based on acrylate / polyisocyanate is overpainted.

    Ergebnisse der lacktechnischen UntersuchungenResults of the paint tests

    Eigenschaftproperty erfindungsgemäßer MehrschichtaufbauMulti-layer structure according to the invention Veraleichs-Mehrschichtaufbau Veraleichs multilayer construction Feucht/Warm-Test Wet / warm test 0/00/0 Haftung liability 0-10-1 Haftung nach Feucht/Warm-Test liability after wet / warm test 0-10-1 Schleifbarkeit des FüllersSandability of the filler i.O.OK i.O.OK DecklackstandTop coat stand i.O.OK i.O.OK

    Die Ergebnisse zeigen, daß der erfindungsgemäße Mehrschichtaufbau bezüglich Schleifbarkeit und Decklackstand dem guten Niveau eines üblichen Reparaturlackaufbaus mit einem lösemittelbasierenden 2K-Füller entspricht. Bei vergleichbaren hohen Füllerschichtdicken von beispielsweise 300 µm und ohne Zwischenschleifen ist der erfindungsgemäße Mehrschichtaufbau bezüglich der Haftung auf verschiedenen Untergründen einem üblichen Reparaturlackaufbau mit lösemittelbasierendem 2K-Füller sogar deutlich überlegen.The results show that the multilayer structure according to the invention with regard to sandability and top coat level the good level of a conventional repair paint system with a solvent-based 2-component filler. With comparable high filler layer thicknesses of for example 300 microns and without intermediate grinding is the invention Multi-layer construction with regard to the adhesion on different substrates a usual Repair lacquer build-up with solvent-based 2K filler is even clearly superior.

    Claims (6)

    1. A method for the lacquer coating, for repair purposes, of motor vehicle bodies or parts thereof, by the application of a multi-coat lacquer coating, wherein a primer surfacer coating medium is applied to a substrate, which is optionally pre-coated with a primer coating medium and/or with further coating media, and a covering coat comprising a colour- and effect-imparting base lacquer coat or a transparent clear lacquer coat or a covering coat comprising a pigmented, single-coat covering lacquer is subsequently applied, characterised in that the primer surfacer coating medium which is used is one which either
      a) contains binder vehicles which can be cured solely by radical and/or cationic polymerisation, or which
      b) contains binder vehicles which can be cured solely by radical and/or cationic polymerisation, together with chemically crosslinking binder vehicles, wherein curing is effected by means of high-energy radiation.
    2. A method according to claim 1, characterised in that curing is effected by means of pulsed UV radiation.
    3. A method according to claims 1 or 2, characterised in that aromatic epoxy resin (meth)acrylates are used as binder vehicles which can be cured by radical polymerisation.
    4. A method according to any one of claims 1 to 3, characterised in that a lacquer which can be cured by UV radiation is used for the production of the base lacquer coat.
    5. A method according to any one of claims 1 to 4, characterised in that a customary chemically crosslinking and/or physically drying base lacquer is used as a base lacquer, and a clear lacquer which can be cured by UV radiation is used as a clear lacquer.
    6. A method according to any one of claims 1 to 5, characterised in that the primer surfacer coat is applied in one operation at coat thicknesses up to 400 µm.
    EP98955544A 1997-11-20 1998-11-05 Method for multi-layered repair coating of substrates Revoked EP1032474B1 (en)

    Applications Claiming Priority (5)

    Application Number Priority Date Filing Date Title
    DE1997151478 DE19751478A1 (en) 1997-11-20 1997-11-20 Multilayer coating system containing a filler coating cured by high energy radiation
    DE19751478 1997-11-20
    DE1997157082 DE19757082A1 (en) 1997-12-20 1997-12-20 Multilayer coating system containing a filler coating cured by high energy radiation
    DE19757082 1997-12-20
    PCT/EP1998/007082 WO1999026733A1 (en) 1997-11-20 1998-11-05 Method for multi-layered coating of substrates

    Publications (2)

    Publication Number Publication Date
    EP1032474A1 EP1032474A1 (en) 2000-09-06
    EP1032474B1 true EP1032474B1 (en) 2001-10-17

    Family

    ID=26041766

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP98955544A Revoked EP1032474B1 (en) 1997-11-20 1998-11-05 Method for multi-layered repair coating of substrates

    Country Status (10)

    Country Link
    US (1) US6531188B1 (en)
    EP (1) EP1032474B1 (en)
    JP (1) JP4439726B2 (en)
    AT (1) ATE206960T1 (en)
    CA (1) CA2310716C (en)
    DE (1) DE59801811D1 (en)
    DK (1) DK1032474T3 (en)
    ES (1) ES2167953T3 (en)
    PT (1) PT1032474E (en)
    WO (1) WO1999026733A1 (en)

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    SE0003245L (en) * 2000-09-13 2002-03-14 Tetra Laval Holdings & Finance Packaging laminate for an autoclavable packaging container
    CA2428594C (en) * 2000-11-15 2011-01-25 Ssw Holding Company, Inc. Coating with anti-microbial agent for refrigerator shelving
    US7361383B2 (en) 2001-06-04 2008-04-22 E.I. Dupont De Nemours & Company Process for multilayer coating of substrates
    EP1354640A1 (en) 2002-04-19 2003-10-22 Dürr Systems GmbH Process and apparatus for hardening a coating
    WO2005044668A1 (en) * 2003-11-03 2005-05-19 M I 6 Technologies, Inc. Spray-on paint protection film and method of applying same
    US7185982B2 (en) * 2004-05-04 2007-03-06 Gripping Eyewear, Inc. Multiple piece eyeglasses temple tip
    US7335402B2 (en) * 2005-03-09 2008-02-26 Ppg Industries Ohio, Inc. Radiation curable putty compositions and methods for refinishing a substrate using such compositions
    FR2899502B1 (en) * 2006-04-06 2009-04-10 Macdermid Printing Solutions E EMBOSSING DEVICE, SUCH AS A CYLINDER OR SLEEVE
    ES2326301B1 (en) * 2007-08-09 2010-06-29 Bulma Tecnologia, S.L. PROCEDURE FOR REPAIR OF PAINT DEFECTS IN THE AUTOMOTIVE SECTOR BY ULTRAVIOLET DRYING.
    CA2708277A1 (en) 2007-12-20 2009-07-09 E. I. Dupont De Nemours And Company Process for producing a multilayer coating
    US9102785B2 (en) * 2008-04-11 2015-08-11 Ppg Industries Ohio, Inc. Curable compositions based on polyuretidiones, polythiols and photoactivable bases and generation of isocyanates from uretidiones
    DE102010012047A1 (en) * 2010-03-19 2011-09-22 Basf Coatings Gmbh Process for coating a metal or plastic substrate, coating obtainable therefrom and coated substrate
    EP2898023B1 (en) * 2012-09-21 2016-11-09 BASF Coatings GmbH Method for producing and repairing a multi-coat colour and/or effect paint system
    CN106221459B (en) * 2016-08-31 2018-05-11 长沙松润新材料有限公司 The coating of imitative anodic oxidation and CNC effects, the base material having that effect and preparation method

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    US4668529A (en) 1985-04-12 1987-05-26 Ronald L. Berry Filler composition and method
    EP0202803A3 (en) * 1985-05-14 1987-06-03 Commonwealth Of Australia Department Of Industry Technology And Commerce Laser curing of coatings and inks
    US4960611A (en) * 1987-09-30 1990-10-02 Kansai Paint Company, Limited Method of remedying coating
    DE4133290A1 (en) 1991-10-08 1993-04-15 Herberts Gmbh METHOD FOR PRODUCING MULTILAYER LACQUERING USING RADICALLY AND / OR CATIONICALLY POLYMERIZABLE CLEAR VARNISHES
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    Also Published As

    Publication number Publication date
    JP4439726B2 (en) 2010-03-24
    DK1032474T3 (en) 2001-11-19
    ATE206960T1 (en) 2001-11-15
    EP1032474A1 (en) 2000-09-06
    JP2001523573A (en) 2001-11-27
    PT1032474E (en) 2002-04-29
    CA2310716C (en) 2007-05-22
    WO1999026733A1 (en) 1999-06-03
    DE59801811D1 (en) 2001-11-22
    CA2310716A1 (en) 1999-06-03
    ES2167953T3 (en) 2002-05-16
    US6531188B1 (en) 2003-03-11

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