EP1032474A1 - Method for multi-layered repair coating of substrates - Google Patents

Method for multi-layered repair coating of substrates

Info

Publication number
EP1032474A1
EP1032474A1 EP98955544A EP98955544A EP1032474A1 EP 1032474 A1 EP1032474 A1 EP 1032474A1 EP 98955544 A EP98955544 A EP 98955544A EP 98955544 A EP98955544 A EP 98955544A EP 1032474 A1 EP1032474 A1 EP 1032474A1
Authority
EP
European Patent Office
Prior art keywords
binders
layer
radiation
curable
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.)
Granted
Application number
EP98955544A
Other languages
German (de)
French (fr)
Other versions
EP1032474B1 (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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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 multi-layer painting, in particular refinishing of substrates with a filler layer and a top coat layer, which is used in particular in the field of vehicle and vehicle parts painting.
  • Multilayer vehicle refinish coatings generally consist of a filler layer applied to optionally precoated substrates and a top coat of a color and / or effect basecoat layer and a transparent clearcoat layer. However, it can also be a top coat made from a pigmented single-layer top coat.
  • aqueous or so-called high-solid coating agents have already been developed for almost all paint layers.
  • two-component water-based paints based on hydroxy-functional binders and polyisocyanate hardeners and on the basis of epoxy / polyamine systems are known.
  • the coatings obtained with these varnishes do not yet correspond to the level of properties of conventional solvent-based fillers or primers in several respects.
  • the sandability of water fillers is still insufficient, and there are problems to ensure bubble-free application at higher layer thicknesses.
  • an extended drying time must generally be accepted, which impairs the effectiveness, for example, in a paint shop.
  • EP-A-000 407 describes radiation-curable coating compositions based on an OH-functional polyester resin esterified with acrylic acid, a vinyl compound, a photoinitiator and a polyisocyanate.
  • acrylic acid a vinyl compound
  • photoinitiator a photoinitiator
  • polyisocyanate a polyisocyanate
  • the curing step is followed by radiation curing using UV light and in a second curing step the coating is given its final hardness by the OH / NCO crosslinking.
  • the second curing step can take place at 130 - 200 ° C or over several days at room temperature. The final hardness is only reached after several days.
  • EP-A-247 563 describes clearcoats curable by means of UV radiation based on a poly (meth) acryloyl-functional compound, a polyolmono (meth) acrylate, a polyisocyanate, a light stabilizer and a photoinitiator.
  • Some of the radiation-curable binders here also contain hydroxyl functions which can react with the polyisocyanate present and offer an additional curing option.
  • EP-A-540 884 describes a method for producing a multi-layer coating for automotive OEM painting by applying a clear coat on a dried or crosslinked basecoat, the
  • the object of the invention was to provide a method for producing a multi-layer coating, in particular refinishing coating, which makes it possible.
  • Environmentally friendly coating agents can be applied easily even in high layer thicknesses and with high pigmentation.
  • the coatings obtained should cure quickly and completely and be easy to sand after a short drying time, and should ensure very good interlayer adhesion, good topcoat level and satisfactory resistance to chemicals, petrol and water.
  • the object is achieved by a method for producing a multi-layer coating, in which a surface coating agent is applied to a substrate which may have been pre-coated with a primer and / or further coating agents, and then a top coat comprising a coloring and / or effect base coat layer and a transparent clear coat layer or a topcoat made of a pigmented single-layer topcoat is applied, characterized in that the coating agent used is one which contains binders which can be cured exclusively by radical and / or cationic polymerization, these binders being cured by means of high-energy radiation, or by radicals and / or cationic polymerization contains curable binders, these binders being cured by means of high-energy radiation and additionally containing chemically crosslinking binders.
  • the multilayer structure according to the invention is still superior to a conventional refinish coating structure with regard to interlayer adhesion and rapid and complete curing even in high layer thicknesses and with high pigmentation.
  • coating agents which crosslink by means of high-energy radiation via a radical and / or cationic polymerization.
  • These can be high-solids aqueous or solvent-containing systems, for example with a solids content of 50 to 95% by weight (in both aqueous and conventional, solvent-containing systems).
  • the systems can also be used as
  • 100% coating agents are available, which can be applied without solvents and without water.
  • binders curable by means of high-energy radiation all conventional radiation-curable binders or their binders can be used in the process according to the invention
  • Mixtures are used which are known to the person skilled in the art and are described in the literature. They are either binders which can be crosslinked by free-radical polymerization or by cationic polymerization. In the former, radicals are generated by the action of high-energy radiation on the photoinitiators, which then trigger the crosslinking reaction. In the case of the cationically curing systems, Lewis acids are formed by the irradiation from initiators, which in turn trigger the crosslinking reaction.
  • the free-radically curing binders can e.g. are prepolymers, such as poly- or oligomers, which have free-radically polymerizable olefinic double bonds in the molecule.
  • 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 polyurethanes or unsaturated polyesters.
  • Mn number average molecular weight
  • Compounds are preferably from 200 to 10,000.
  • the molecule preferably contains an average of 2-20 free-radically polymerizable olefinic double bonds.
  • Aliphatic and / or cycloaliphatic (meth) acrylates are preferably used in each case.
  • (Cyclo) aliphatic polyurethane (meth) acrylates, polyester (meth) acrylates and epoxy (meth) acrylates are particularly preferred.
  • the binders can be used individually or in a mixture.
  • the prepolymers can be in combination with reactive diluents, ie reactive polymerizable liquid monomers.
  • the reactive diluents are generally used in amounts of 1-50% by weight, preferably 5-30% by weight, based on the total weight of the prepolymer and reactive diluent.
  • the reactive diluents can be mono-, di- or polyunsaturated. Examples of 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 diluents 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,
  • polyunsaturated reactive diluents 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.
  • Preferred reactive diluents are diacrylates such as e.g.
  • Dipropylene glycol diacrylate, tripropylene glycol diacrylate and / or hexanediol diacrylate are used.
  • binders for cationically polymerizable systems. It can be, for example, poly unfunctional epoxy oligomers which contain more than two epoxy groups in the molecule. Examples include polyalkylene glycol diglycidyl ether, hydrogenated bisphenol A glycidyl ether, epoxy urethane resins, glycerol triglycidyl ether, diglycidyl hexahydrophthalate, diglycidyl ester of dimer acids, epoxidized derivatives of (methyl) cyclohexene, such as e.g.
  • the number average molecular weight of the polyepoxide compounds is preferably less than 10,000.
  • Reactive diluents such as e.g. Cyclohexene oxide, butene oxide, butanediol diglycidyl ether or hexanediol diglycidyl ether can be used.
  • Suitable photoinitiators are, for example, those which absorb in the 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,
  • Benzoylcyclohexanol, organophosphorus compounds e.g.
  • the photoinitiators are used, for example, in amounts of 0.1 to 7
  • % By weight, preferably 0.5-5% by weight, based on the sum of free-radically polymerizable prepolymers, reactive diluents and photoinitiators.
  • the photoinitiators can be used individually or in combination.
  • synergistic components e.g. tertiary amines can be used.
  • Photoinitiators for cationic curing systems are substances known as onium salts, which release Lewis acids photolytically under the action of radiation. Examples include diazonium salts, sulfonium salts or iodonium salts. Triarylsulfonium salts are preferred.
  • the photoinitiators for cationically curing systems can be used in amounts of 0.5 to 5% by weight, based on the sum of cationically polymerizable prepolymers, reactive diluents and initiators, individually or as
  • binders are epoxy (meth) acrylates, polyurethane (meth) acrylates, polyester (meth) acrylates and (meth) acrylic-functional poly (meth) acrylates.
  • Aromatic epoxy (meth) acrylates are particularly preferred.
  • the binders exemplified by means of high-energy radiation are generally available as commercial products.
  • the coating materials curable by means of high-energy radiation can only contain binders curable by means of high-energy radiation, but they can also contain other chemically crosslinking binders in addition to the binders curable by means of high-energy radiation.
  • Any two-component binder systems based on a hydroxy-functional and an isocyanate-functional component, a hydroxy-functional and an anhydride component, a polyamine and an epoxy component or a polyamine and an acryloyl-functional component can be used, for example, as chemical crosslinking binders.
  • the binders which can also be used may be those based on aqueous or
  • Binders can be, for example, up to 50% by weight, based on the UV-curable binder.
  • the 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 process according to the invention.
  • Fillers that can be used in the paint industry and organic or inorganic coloring and / or corrosion protection pigments.
  • pigments are titanium dioxide, micronized titanium dioxide, iron oxide pigments, carbon black, azo pigments, zinc phosphate.
  • fillers are silicon dioxide, aluminum silicate, barium sulfate and talc.
  • UV-curable pigments and / or fillers can also advantageously be used. These are pigments and / or fillers which are mixed with compounds curable by means of UV radiation, e.g. with acrylic-functional silanes, are coated and included in the radiation curing process.
  • the coating compositions which can be used in the process according to the invention can contain customary paint additives.
  • the additives are the usual ones additives that can be used in the paint sector. Examples of such additives are leveling agents, for example based on (meth) acrylic homopolymers or silicone oils, anti-cratering agents, anti-foaming agents, catalysts, adhesion promoters.
  • the additives are used in customary amounts known to the person skilled in the art.
  • the fillers which can be used in the process according to the invention can be formulated without solvents. Their solids content is then 100% by weight. However, the fillers can 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.
  • solvents are monohydric or polyhydric alcohols, e.g. Propanol, butanol, hexanol; Glycol ethers or esters, e.g. butyl glycol, butyl diglycol, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, ethyl glycol acetate, butyl glycol acetate, butyl diglycol acetate, esters, e.g. Butyl acetate, isobutyl acetate, amyl acetate, glycols, e.g. Ethylene glycol, propylene glycol and their oligomers,
  • monohydric or polyhydric alcohols e.g. Propanol, butanol, hexanol
  • Glycol ethers or esters e.g. butyl glycol, butyl diglycol, diethylene glycol dialkyl ether, dipropylene glycol dialkyl
  • 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.
  • the filler layer is applied in the method according to the invention to an optionally precoated substrate.
  • Preferred substrates are metal or plastic substrates.
  • the fillers can be applied to customary primer or other intermediate layers, such as those used for multi-layer painting in the motor vehicle sector. You can use a coating that has already been pre-coated or pre-treated as part of vehicle refinishing
  • Vehicle body or parts thereof are applied, but they can also be applied to old paintwork.
  • the application can be carried out according to 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 as are common for vehicle refinishing, or on old paintwork, such as KTL- Substrates to be applied.
  • the substrates or lacquer layers to which the filler layer is applied can already have hardened or pre-dried.
  • Suitable spatulas, primers or primers for refinishing are, for example, those based on peroxide-curing unsaturated polyesters, acid-curing polyvinyl butyrals, physically drying binders, for example polyurethanes or acrylates, and two-component crosslinking binders, for example based on an epoxy and a polyamine component or polyisocyanate. and a hydroxy component.
  • the filler layer is exposed to high-energy radiation, preferably UV radiation, if necessary after a short flash-off phase.
  • high-energy radiation preferably UV radiation
  • UV radiation sources with emissions in the wavelength range from 180 to 420 nm, in particular from 200 to 400 nm, are preferred.
  • UV radiation sources are optionally doped high-pressure mercury, medium-pressure and low-pressure lamps, gas discharge tubes, such as e.g. Xenon low pressure lamps, pulsed and non-pulsed UV lasers, UV spot lamps, such as UV emitting diodes and black light tubes. Irradiation is preferably carried out with pulsed UV radiation.
  • So-called high-energy electron flash devices in short: UV flash lamps) are then particularly preferably used as the radiation source.
  • 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 preferably contain a plurality of flash tubes, for example quartz tubes filled with inert gas, such as xenon.
  • the UV flash lamps should have an illuminance of at least 10 megalux, preferably 10 to 80 megalux per flash discharge on the surface of the coating to be cured.
  • the energy per flash discharge should preferably be 1 to 10 kJoules.
  • the UV flash lamps are preferably portable devices that can be positioned directly in front of a damaged area to be repaired. Depending on the circumstances, one or more UV flash lamps can be used. UV flash lamps that can be used for example described in WO-A-9411123 and in EP-A-525 340. UV flash lamps are commercially available.
  • the filler layer can be dried or hardened by a plurality of successive lightning discharges. 1 to 40 successive lightning discharges are preferably triggered.
  • the distance between the UV flash lamp and the substrate surface to be irradiated can be 5-50 cm, preferably 10-25 cm, particularly preferably 15-20 cm.
  • the shielding of the UV lamps to prevent radiation leakage can be e.g. by using an appropriately lined protective housing around the transportable 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 flash discharges selected.
  • the flashes can be triggered, for example, every 4 s.
  • the UV flash lamps are ready for use at any time, i.e. they do not require a baking time and can remain switched off between two somewhat different curing or irradiation processes without the loss of time resulting from the baking phase during the renewed irradiation process.
  • a particular advantage of the method according to the invention lies in the fact that high layer thicknesses can be applied in one operation (without intermediate sanding) and that even with high pigmentation, the filler, for example in the case of a pigment
  • PVD Physical Vinyl vapor deposition
  • coatings with layer thicknesses of, for example, 200 to 400, preferably 300 to 400 ⁇ m can be applied, which harden quickly and completely and are easy to sand.
  • the procedure can be such that the surface coating agent is used in several, preferably two,
  • Spraying is applied and after the first spraying or after each further spraying, if there are more than two spraying, one each Intermediate radiation is triggered.
  • a layer thickness of 100 to 200 ⁇ m is applied in a first spraying cycle.
  • Intermediate curing is carried out with, for example, 2 to 5 flashes, then another layer of, for example, 100-200 ⁇ m is applied in a second spraying cycle and the required number of Lightning discharges the complete hardening.
  • the filler coating compositions which can be used according to the invention contain further chemically crosslinkable binders, the temperatures generated on the coating by means of UV radiation (UV flash lamp) are generally sufficient to harden the additional crosslinkable binders. A separate hardening process is not necessary.
  • the coating compositions which can be used in the process according to the invention can be formulated or used as abrasive fillers, primer fillers or wet-on-wet fillers.
  • a top coat consisting of a color and / or effect basecoat layer and a transparent KJar lacquer layer or a top coat made of a pigmented single-layer topcoat is applied to the filler layer.
  • Coloring and / or effect-imparting basecoats which can be used for the basecoat / clearcoat topcoat are all suitable in vehicle painting, in particular repair painting, customary solvent-based or water-based basecoats known to the person skilled in the art.
  • solvent-based basecoats are those based on
  • Polyacrylate and / or polyester resins optionally in combination with melamine resins and cellulose esters.
  • water-based paints are those based on physically drying polyurethane, polyurethane / urea, polyester, polyester urethane and / or polyacrylate resins and their modifications, such as, for example, acrylated or silicon-modified polyurethane and / or polyester resins.
  • waterborne basecoats made from chemically crosslinking binder components, for example from hydroxyl-containing binders and polyisocyanate crosslinkers, are also suitable.
  • the basecoat film can be cured at room temperature or forced at 40-80 ° C, for example. However, the basecoat film can also be coated wet-on-wet, if necessary after a brief flash-off phase, with a clear coat and then cured together with the clear coat.
  • An embodiment of the method according to the invention consists in using as base lacquer one which contains binders curable by means of high-energy radiation.
  • the binders curable by means of high-energy radiation are, for example, the binders already mentioned above in the description of the coating compositions.
  • aliphatic polyurethane (meth) acrylates and / or aliphatic (meth) acrylic-functional poly (meth) arylates are preferably used in the basecoat.
  • Curing can then be carried out with a UV radiation source, as described above for the filler.
  • the basecoat can be applied wet-on-wet to the filler layer
  • the filler layer can first be completely cured by means of UV radiation (abrasive filler), optionally in several irradiation steps, and then the basecoat film can be separately cured with UV radiation.
  • UV radiation abrasive filler
  • Clearcoats which can be used for the basecoat / clearcoat topcoat are all customary in vehicle painting, in particular repair painting
  • Suitable solvent-based or water-based clearcoats known to those skilled in the art. Examples of these are solvent-based or aqueous clear lacquers based on binders containing hydroxyl groups and / or amino groups and polyisocyanate crosslinkers and on binders containing binders containing amino groups and acryloyl groups.
  • the hardening of the clear coat can be
  • 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 basecoat which is not based on radiation-curable binders, and a clearcoat 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 usual radiation-curable binders, as already described above in the description of
  • Polyurethane (meth) acrylates and / or aliphatic acrylic-functional poly (meth) acrylates are used.
  • binders based on aromatic substances which are curable by means of high-energy radiation are particularly preferred in this embodiment
  • Epoxy (meth) acrylates and binders based on aliphatic polyurethane (meth) acrylates and / or aliphatic (meth) acrylic-functional poly (meth) acrylates which are curable in the clear coat by means of high-energy radiation.
  • a customary solvent-based or water-based pigmented single-layer topcoat to the hardened or intermediate-hardened filler layer, or else wet-on-wet.
  • 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.
  • filler Even very thick layers of filler can be applied in one spray phase without bubbles 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 meet the requirements for a paint system, for example a repair paint system, in the field of vehicle painting, the Drying or hardening of the coatings can take place in a very short time compared to lacquer structures which have been dried or hardened in the customary manner.
  • the method according to the invention can advantageously be used in vehicle refinishing, in particular for refinishing
  • the invention is illustrated by the following example.
  • the filler produced above is applied to KTL-coated sheets.
  • a filler layer with a resulting dry film layer thickness of approximately 300 ⁇ m is applied in one operation and after a brief flashing off at room temperature, the filler layer is exposed to radiation from a UV flash lamp (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.
  • the multilayer structure according to the invention in terms of sandability and topcoat level corresponds to the good level of a conventional repair lacquer structure with a solvent-based 2-component filler.
  • the multi-layer structure according to the invention is even significantly superior to a conventional refinish coating structure with solvent-based two-component filler with regard to adhesion to different substrates.

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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)
  • Manufacture Or Reproduction Of Printing Formes (AREA)
  • Production Of Multi-Layered Print Wiring Board (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

Verfahren zur mehrschichtigen Lackierung von SubstratenProcess for multi-layer painting of substrates
Die Erfindung betrifft ein Verfahren zur mehrschichtigen Lackierung, insbesondere Reparaturlackierung von Substraten mit einer Füllerschicht und einer Decklackschicht, welches insbesondere Anwendung findet auf dem Gebiet der Fahrzeug- und Fahrzeugteilelackierung .The invention relates to a method for multi-layer painting, in particular refinishing of substrates with a filler layer and a top coat layer, which is used in particular 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 färb- und/oder effektgebenden Basislackschicht und einer transparenten Klarlackschicht. Es kann sich jedoch auch um eine Deckbeschichtung aus einem pigmentierten Einschichtdecklack handeln.Multilayer vehicle refinish coatings generally consist of a filler layer applied to optionally precoated substrates and a top coat of a color and / or effect basecoat layer and a transparent clearcoat layer. However, it can also be a top coat made from a pigmented single-layer top coat.
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.For ecological reasons, efforts are also being made to reduce the solvent emissions of the coating agents in vehicle refinishing. For example, aqueous or so-called high-solid coating agents have already been developed for almost all paint layers. For the filler and primer area, for example, two-component water-based paints based on hydroxy-functional binders and polyisocyanate hardeners and on the basis of epoxy / polyamine systems are known. However, the coatings obtained with these varnishes do not yet correspond to the level of properties of conventional solvent-based fillers or primers in several respects. For example, the sandability of water fillers is still insufficient, and there are problems to ensure bubble-free application at higher layer thicknesses. In addition, when using water-based paints, an extended drying time must generally be accepted, which impairs the effectiveness, for example, in a paint shop.
Es ist bereits bekannt, in der Fahrzeuglackierung mittels energiereicher Strahlung härtbare Beschichtungsmittel einzusetzen. 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-It is already known to use coating agents which can be hardened in vehicle painting by means of high-energy radiation. For example, US Pat. No. 4,668,529 describes a one-component (IC) filler coating composition for refinishing which is curable by means of UV radiation. Only so-called reactive thinners are used as UV-curable components. It is tripropylene glycol triacrylate and trimethylpropane triacrylate. In addition, a physically drying epoxy resin based on a bisphenol A-
Diglycidy lethers enthalten.Diglycidy lethers included.
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.EP-A-000 407 describes radiation-curable coating compositions based on an OH-functional polyester resin esterified with acrylic acid, a vinyl compound, a photoinitiator and a polyisocyanate. In a 1st
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.The curing step is followed by radiation curing using UV light and in a second curing step the coating is given its final hardness by the OH / NCO crosslinking. The second curing step can take place at 130 - 200 ° C or over several days at 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 based on a poly (meth) acryloyl-functional compound, a polyolmono (meth) acrylate, a polyisocyanate, a light stabilizer and a photoinitiator. Some of the radiation-curable binders here also contain hydroxyl functions which can react with the polyisocyanate present and offer an additional curing 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 dasEP-A-540 884 describes a method for producing a multi-layer coating for automotive OEM painting by applying a clear coat on a dried or crosslinked basecoat, the
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.Contains clear coat coating agent by radical and / or cationic polymerization curable binder, and the curing is carried out by means of high-energy radiation. After the clearcoat layer has been irradiated, the stoving process takes place, with the basecoat and clearcoat together in e.g. 80 - 160 C.
Aufgabe der Erfindung war es, ein Verfahren zur Herstellung einer mehrschichtigen Lackierung, insbesondere Reparaturlackierung bereitzustellen, welches es ermöglicht. umweltfreundliche FüUerbeschichtungsmittel 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 multi-layer coating, in particular refinishing coating, which makes it possible. Environmentally friendly coating agents can be applied easily even in high layer thicknesses and with high pigmentation. The coatings obtained should cure quickly and completely and be easy to sand after a short drying time, and should ensure very good interlayer adhesion, good topcoat level and satisfactory resistance to chemicals, petrol and water.
Die Aufgabe wird gelöst durch ein Verfahren zur Herstellung einer mehrschichtigen Lackierung, bei dem auf ein gegebenenfalls mit einem Grundierungs- und/oder weiteren Beschichtungsmitteln vorbeschichtetes Substrat ein FüUerbeschichtungsmittel aufgebracht und anschließend eine Deckbeschichtung aus einer färb- und/ oder effektgebenden Basislackschicht und einer transparenten Klarlackschicht oder eine Deckbeschichtung aus einem pigmentierten Einschichtdecklack appliziert wird, dadurch gekennzeichnet, daß als FüUerbeschichtungsmittel 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 multi-layer coating, in which a surface coating agent is applied to a substrate which may have been pre-coated with a primer and / or further coating agents, and then a top coat comprising a coloring and / or effect base coat layer and a transparent clear coat layer or a topcoat made of a pigmented single-layer topcoat is applied, characterized in that the coating agent used is one which contains binders which can be cured exclusively by radical and / or cationic polymerization, these binders being cured by means of high-energy radiation, or by radicals and / or cationic polymerization contains curable binders, these binders being cured by means of high-energy radiation and additionally containing chemically 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,It was surprising and cannot be deduced from the prior art that the multi-layer coatings obtained with the process according to the invention have the same high level of properties required for painting as has hitherto been achieved with the customary but solvent-based paints, in particular repair paints. This applies in particular to properties such as sandability,
Decklackstand, Wasser- und Chemikalienbeständigkeit. Außerdem wurde überraschend gefunden, daß der erfmdungsgemäße Mehrschichtaufbau bezüglich Zwischenschichthaftung sowie rascher und vollständiger Durchhärtung auch in hohen Schichtdicken und bei hoher Pigmentierung einem üblichen Reparaturlackaufbau noch überlegen ist.Top coat level, water and chemical resistance. In addition, it was surprisingly found that the multilayer structure according to the invention is still superior to a conventional refinish coating structure with regard to interlayer adhesion and rapid and complete curing even in high layer thicknesses and with high pigmentation.
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, beispielsweise mit einem Festkörpergehalt von 50 bis 95 Gew.-% (bei wäßrigen wie auch konventionellen, lösemittelhaltigen Systemen). Die Systeme können jedoch auch alsWith the filler coating compositions which can be used in the process according to the invention are coating agents which crosslink by means of high-energy radiation via a radical and / or cationic polymerization. These can be high-solids aqueous or solvent-containing systems, for example with a solids content of 50 to 95% by weight (in both aqueous and conventional, solvent-containing systems). However, the systems can also be used as
100 %ige Beschichtungsmittel, die ohne Lösungsmittel und ohne Wasser appliziert werden können, vorliegen.100% coating agents are available, which can be applied without solvents and without water.
Als mittels energiereicher Strahlung härtbare Bindemittel können im erfmdungsgemäßen Verfahren alle üblichen strahlenhärtbaren Bindemittel oder derenAs binders curable by means of high-energy radiation, all conventional radiation-curable binders or their binders can be used in the process according to the invention
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.Mixtures are used which are known to the person skilled in the art and are described in the literature. They are either binders which can be crosslinked by free-radical polymerization or by cationic polymerization. In the former, radicals are generated by the action of high-energy radiation on the photoinitiators, which then trigger the crosslinking reaction. In the case of the cationically curing systems, Lewis acids are formed by the irradiation from initiators, which in turn trigger the 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) dieserThe free-radically curing binders can e.g. are prepolymers, such as poly- or oligomers, which have free-radically polymerizable olefinic double bonds in the molecule. 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 polyurethanes or unsaturated polyesters. The number average molecular weight (Mn) of this
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. 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 Reaktiv Verdünner, 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, Polyethylenglykol- di(meth)acrylat, l,3-Butandiol-di(meth)acrylat, Vinyl(meth)acrylat, Allyl(meth)acrylat,Compounds are preferably from 200 to 10,000. The molecule preferably contains an average of 2-20 free-radically polymerizable olefinic double bonds. Aliphatic and / or cycloaliphatic (meth) acrylates are preferably used in each case. (Cyclo) aliphatic polyurethane (meth) acrylates, polyester (meth) acrylates and epoxy (meth) acrylates are particularly preferred. The binders can be used individually or in a mixture. The prepolymers can be in combination with reactive diluents, ie reactive polymerizable liquid monomers. The reactive diluents are generally used in amounts of 1-50% by weight, preferably 5-30% by weight, based on the total weight of the prepolymer and reactive diluent. The reactive diluents can be mono-, di- or polyunsaturated. Examples of 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 diluents 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,
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, Pentaerythrit- tetra(meth)acrylat. Die Reaktivverdünner können einzeln oder im Gemisch eingesetzt werden. Bevorzugt werden als Reaktiwerdünner Diacrylate wie z.B.Divinylbenzene, dipropylene glycol di (meth) acrylate, hexanediol di (meth) acrylate. Examples of polyunsaturated reactive diluents 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. Preferred reactive diluents are diacrylates such as e.g.
Dipropylenglykoldiacrylat, Tripropylenglykoldiacrylat und/oder Hexandioldiacrylat eingesetzt.Dipropylene glycol diacrylate, tripropylene glycol diacrylate and / or hexanediol diacrylate are 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 poly unktioneile Epoxy oligomere, 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.The usual binders known to the person skilled in the art and described in the literature can be used as binders for cationically polymerizable systems. It can be, for example, poly unfunctional epoxy oligomers which contain more than two epoxy groups in the molecule. Examples include polyalkylene glycol diglycidyl ether, hydrogenated bisphenol A glycidyl ether, epoxy urethane resins, glycerol triglycidyl ether, diglycidyl hexahydrophthalate, diglycidyl ester of dimer acids, epoxidized derivatives of (methyl) cyclohexene, such as e.g. 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate or epoxidized polybutadiene. The number average molecular weight of the polyepoxide compounds is preferably less than 10,000. Reactive diluents, such as 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 in the 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,Examples of photoinitiators for radical curing systems are benzoin and derivatives, acetophenone and derivatives, such as e.g. 2,2-diacetoxyacetophenone,
Benzophenon und -derivate, Thioxanthon und -derivate, Anthrachinon, 1-Benzophenone and derivatives, thioxanthone and derivatives, anthraquinone, 1-
Benzoylcyclohexanol, phosphororganische Verbindungen, wie z.B.Benzoylcyclohexanol, organophosphorus compounds, e.g.
Acylphosphinoxide. Die Photoinitiatoren werden beispielsweise in Mengen von 0, 1 - 7Acylphosphine oxides. The photoinitiators are used, for example, in amounts of 0.1 to 7
Gew.-%, bevorzugt 0,5 - 5 Gew.-% eingesetzt, bezogen auf die Summe von radikalisch polymerisierbaren Prepolymeren, Reaktivverdünnern und Photoinitiatoren.% By weight, preferably 0.5-5% by weight, based on the sum of free-radically polymerizable prepolymers, reactive diluents and photoinitiators.
Die Photoinitiatoren können einzeln oder in Kombination eingesetzt werden.The photoinitiators can be used individually or in combination.
Außerdem können weitere synergistische Komponenten, z.B. tertiäre Amine, eingesetzt werden.In addition, other synergistic components, e.g. tertiary amines can 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 alsPhotoinitiators for cationic curing systems are substances known as onium salts, which release Lewis acids photolytically under the action of radiation. Examples include diazonium salts, sulfonium salts or iodonium salts. Triarylsulfonium salts are preferred. The photoinitiators for cationically curing systems can be used in amounts of 0.5 to 5% by weight, based on the sum of cationically polymerizable prepolymers, reactive diluents and initiators, individually or as
Gemische eingesetzt werden.Mixtures are used.
Zur Herstellung der mittels energiereicher Strahlung, beispielsweise gepulster Strahlung, härtbaren FüUerbeschichtungsmittel 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. Erfindungsgemäß können die mittels energiereicher Strahlung härtbaren FüUerbeschichtungsmittel 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 acryloylfunktionellen Komponente eingesetzt werden. Bei den zusätzlich einsetzbaren Bindemitteln kann es sich um solche auf wäßriger oderVarious free-radically curing systems, various cationically curing systems or free-radically and cationically curing systems can be combined with one another to produce the coating compositions curable by means of high-energy radiation, for example pulsed radiation. Radically curing systems are preferably used. Preferred free-radically curing binders are epoxy (meth) acrylates, polyurethane (meth) acrylates, polyester (meth) acrylates and (meth) acrylic-functional poly (meth) acrylates. Aromatic epoxy (meth) acrylates are particularly preferred. The binders exemplified by means of high-energy radiation are generally available as commercial products. According to the invention, the coating materials curable by means of high-energy radiation can only contain binders curable by means of high-energy radiation, but they can also contain other chemically crosslinking binders in addition to the binders curable by means of high-energy radiation. Any two-component binder systems based on a hydroxy-functional and an isocyanate-functional component, a hydroxy-functional and an anhydride component, a polyamine and an epoxy component or a polyamine and an acryloyl-functional component can be used, for example, as chemical crosslinking binders. The binders which can also be used may be those based on aqueous or
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 vernetzendenAct solvent based. If, in addition to the radiation-curing binders, other chemically crosslinking binders are used in the filler coating compositions, then those based on a hydroxy-functional and an isocyanate-functional component or a polyamine and an epoxy component can preferably be used. The proportion of chemically cross-linking
Bindemitteln kann beispielsweise bis zu 50 Gew.-%, bezogen auf das UV-härtbare Bindemittel, betragen.Binders can be, for example, up to 50% by weight, based on the UV-curable binder.
Die im erfindungsgemäßen Verfahren einsetzbaren FüUerbeschichtungsmittel können Füllstoffe und Pigmente enthalten. Es handelt sich dabei um die üblichen in derThe 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
Lackindustrie einsetzbaren Füllstoffe und organischen oder anorganischen f arbgebenden 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 Schleifbarkeit 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.Fillers that can be used in the paint industry and organic or inorganic coloring and / or corrosion protection 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. To improve hardness and grindability, UV-curable pigments and / or fillers can also advantageously be used. These are pigments and / or fillers which are mixed with compounds curable by means of UV radiation, e.g. with acrylic-functional silanes, are coated and included in the radiation curing process.
Die im erfindungsgemäßen Verfahren einsetzbaren FüUerbeschichtungsmittel 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 coating compositions which can be used in the process according to the invention can contain customary paint additives. The additives are the usual ones additives that can be used in the paint sector. Examples of such additives are leveling agents, for example based on (meth) acrylic homopolymers or silicone oils, anti-cratering agents, anti-foaming agents, catalysts, adhesion promoters. The additives are used in customary amounts known 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.The fillers which can be used in the process according to the invention can be formulated without solvents. Their solids content is then 100% by weight. However, the fillers can 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.
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,Examples of such solvents are monohydric or polyhydric alcohols, e.g. Propanol, butanol, hexanol; Glycol ethers or esters, e.g. butyl glycol, butyl diglycol, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, ethyl glycol acetate, butyl glycol acetate, butyl diglycol acetate, esters, e.g. Butyl acetate, isobutyl acetate, amyl acetate, glycols, e.g. Ethylene glycol, propylene glycol and their oligomers,
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.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. vorbehandelteThe filler layer is applied in the method according to the invention to an optionally precoated substrate. Preferred substrates are metal or plastic substrates. The fillers can be applied to customary primer or other intermediate layers, such as those used for multi-layer painting in the motor vehicle sector. You can use a coating that has already been pre-coated or pre-treated as part of vehicle refinishing
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.Vehicle body or parts thereof are applied, but they can also be applied to old paintwork. The application can be carried out according to the known methods, preferably by spray application.
Die Füller können beispielsweise auf übliche lösemittel- oder wasserbasierendeThe fillers can be based, for example, on conventional solvent- or water-based
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.Spatulas, primers, adhesive primers or other intermediate layers, as are common for vehicle refinishing, or on old paintwork, such as KTL- Substrates to be applied. The substrates or lacquer layers to which the filler layer is applied can already have hardened or pre-dried. Suitable spatulas, primers or primers for refinishing are, for example, those based on peroxide-curing unsaturated polyesters, acid-curing polyvinyl butyrals, physically drying binders, for example polyurethanes or acrylates, and two-component crosslinking binders, for example 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 to one of the above-mentioned substrates, the filler layer is exposed to high-energy radiation, preferably UV radiation, if necessary after a short flash-off phase. UV radiation sources with emissions in the wavelength range from 180 to 420 nm, in particular from 200 to 400 nm, are preferred. Examples of such UV radiation sources are optionally doped high-pressure mercury, medium-pressure and low-pressure lamps, gas discharge tubes, such as e.g. Xenon low pressure lamps, pulsed and non-pulsed UV lasers, UV spot lamps, such as UV emitting diodes and black light tubes. Irradiation is preferably carried out with pulsed UV radiation. So-called high-energy electron flash devices (in short: UV flash lamps) are then particularly preferably used as the radiation source.
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 preferably contain a plurality of flash tubes, for example quartz tubes filled with inert gas, such as xenon. The UV flash lamps should have an illuminance of at least 10 megalux, preferably 10 to 80 megalux per flash discharge on the surface of the coating to be cured. The energy per flash discharge should preferably be 1 to 10 kJoules. The UV flash lamps are preferably portable devices that can be positioned directly in front of a damaged area to be repaired. Depending on the circumstances, one or more UV flash lamps can be used. UV flash lamps that can be used for example described 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 filler layer can be dried or hardened by a plurality of successive lightning discharges. 1 to 40 successive lightning discharges are preferably triggered. The distance between the UV flash lamp and the substrate surface to be irradiated can be 5-50 cm, preferably 10-25 cm, particularly preferably 15-20 cm. The shielding of the UV lamps to prevent radiation leakage can be e.g. by using an appropriately lined protective housing around the transportable 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 flash discharges selected. The flashes can be triggered, for example, every 4 s. The UV flash lamps are ready for use at any time, i.e. they do not require a baking time and can remain switched off between two somewhat different curing or irradiation processes without the loss of time resulting from the baking phase during the renewed irradiation process.
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-A particular advantage of the method according to the invention lies in the fact that high layer thicknesses can be applied in one operation (without intermediate sanding) and that even with high pigmentation, the filler, for example in the case of a 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 FüUerbeschichtungsmittel in mehreren, bevorzugt zwei,Volume concentration (PVC) of 30 to 45% and more, coatings with layer thicknesses of, for example, 200 to 400, preferably 300 to 400 μm can be applied, which harden quickly and completely and are easy to sand. In order to ensure rapid hardening even with high pigmentation, the procedure can be such that the surface coating agent is used in several, preferably two,
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.Spraying is applied and after the first spraying or after each further spraying, if there are more than two spraying, one each Intermediate radiation is triggered. For example, a layer thickness of 100 to 200 μm is applied in a first spraying cycle. Intermediate curing is carried out with, for example, 2 to 5 flashes, then another layer of, for example, 100-200 μm is applied in a second spraying cycle and the required number of Lightning discharges the 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.If, in addition to the radiation-curable binders, the filler coating compositions which can be used according to the invention contain further chemically crosslinkable binders, the temperatures generated on the coating by means of UV radiation (UV flash lamp) are generally sufficient to harden the additional crosslinkable binders. A separate hardening process is not necessary.
Die im erfindungsgemäßen Verfahren einsetzbaren FüUerbeschichtungsmittel können als Schleiffüller, Grundierfüller oder naß-in-naß-Füller formuliert bzw. eingesetzt werden.The coating compositions which can be used in the process according to the invention can be formulated or used as abrasive fillers, primer fillers or wet-on-wet fillers.
Nach teilweiser oder vollständiger Härtung der Füllerschicht oder naß-in-naß wird im erfindungsgemäßen Verfahren auf die Füllerschicht eine Deckbeschichtung aus einer färb- und/oder effektgebenden Basislackschicht und einer transparenten KJarlackschicht oder eine Deckbeschichtung aus einem pigmentierten Einschichtdecklack aufgebracht.After partial or complete hardening of the filler layer or wet-on-wet, in the process according to the invention, a top coat consisting of a color and / or effect basecoat layer and a transparent KJar lacquer layer or a top coat made of a pigmented single-layer topcoat is applied to the filler layer.
Für die Basislack/Klarlack-Deckbeschichtung einsetzbare färb- 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 vonColoring and / or effect-imparting basecoats which can be used for the basecoat / clearcoat topcoat are all suitable in vehicle painting, in particular repair painting, customary solvent-based or water-based basecoats known to the person skilled in the art. Examples of solvent-based basecoats are those based on
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. Die Härtung der Basislackschicht kann bei Raumtemperatur oder forciert bei 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.Polyacrylate and / or polyester resins, optionally in combination with melamine resins and cellulose esters. Examples of water-based paints are those based on physically drying polyurethane, polyurethane / urea, polyester, polyester urethane and / or polyacrylate resins and their modifications, such as, for example, acrylated or silicon-modified polyurethane and / or polyester resins. Furthermore, waterborne basecoats made from chemically crosslinking binder components, for example from hydroxyl-containing binders and polyisocyanate crosslinkers, are also suitable. The basecoat film can be cured at room temperature or forced at 40-80 ° C, for example. However, the basecoat film can also be coated wet-on-wet, if necessary after a brief flash-off phase, with a clear coat and then cured together with the clear coat.
Eine Ausfuhrungsform 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 FüUerbeschichtungsmittel bereits genannten Bindemittel. Bevorzugt werden im Basislack in diesem Fall jedoch aliphatische Polyurethan(meth)acrylate und/oder aliphatische (meth)acrylfunktionelle Poly(meth)arylate eingesetzt.An embodiment of the method according to the invention consists in using as base lacquer one which contains binders curable by means of high-energy radiation. The binders curable by means of high-energy radiation are, for example, the binders already mentioned above in the description of the coating compositions. In this case, however, aliphatic polyurethane (meth) acrylates and / or aliphatic (meth) acrylic-functional poly (meth) arylates are preferably used in the basecoat.
Eine Härtung kann dann, wie vorstehend für den Füller beschrieben, mit einer UV- Strahlungsquelle erfolgen. Dabei kann der Basislack naß-in-naß auf die FüllerschichtCuring can then be carried out with a UV radiation source, as described above for the filler. The basecoat can be applied wet-on-wet to the filler layer
(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.(wet-on-wet filler) and filler and basecoat are exposed to the radiation in one step. If necessary, the intermediate layer can be briefly irradiated. However, especially with high layer thicknesses and high pigmentation of the filler, the filler layer can first be completely cured by means of UV radiation (abrasive filler), optionally in several irradiation steps, and then the basecoat film can be separately cured with UV radiation.
Für die Basislack/Klarlack-Deckbeschichtung einsetzbare Klarlacke sind alle in der Fahrzeuglackierung, insbesondere der Reparaturlackierung üblichen und demClearcoats which can be used for the basecoat / clearcoat topcoat are all customary in vehicle painting, in particular repair painting
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 beiSuitable solvent-based or water-based clearcoats known to those skilled in the art. Examples of these are solvent-based or aqueous clear lacquers based on binders containing hydroxyl groups and / or amino groups and polyisocyanate crosslinkers and on binders containing binders containing amino groups and acryloyl groups. The hardening of the clear coat can
Raumtemperatur oder forciert bei beispielsweise 40 - 80 °C erfolgen. 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 derRoom 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 basecoat which is not based on radiation-curable binders, and a clearcoat 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 usual radiation-curable binders, as already described above in the description of
FüUerbeschichtungsmittel genannt wurden. Bevorzugt werden dabei aliphatischeFor coating agents have been mentioned. Aliphatic are preferred
Polyurethan(meth)acrylate und/oder aliphatische acrylfunktionelle Poly(meth)acrylate eingesetzt.Polyurethane (meth) acrylates and / or aliphatic acrylic-functional poly (meth) acrylates are used.
Besonders bevorzugt werden in dieser Ausführungsform im Füller mittels energiereicher Strahlung härtbare Bindemittel auf Basis von aromatischenIn this embodiment, binders based on aromatic substances which are curable by means of high-energy radiation are particularly preferred in this embodiment
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.Epoxy (meth) acrylates and binders based on aliphatic polyurethane (meth) acrylates and / or aliphatic (meth) acrylic-functional poly (meth) acrylates which are curable in the clear coat by means of high-energy radiation. There is still the possibility of applying a customary solvent-based or water-based pigmented single-layer topcoat to the hardened or intermediate-hardened filler layer, or else wet-on-wet. 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 layers of filler can be applied in one spray phase without bubbles 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.
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.The coatings otherwise meet the requirements for a paint system, for example a repair paint system, in the field of vehicle painting, the Drying or hardening of the coatings can take place in a very short time compared to lacquer structures which have been dried or hardened in the customary manner.
Das erfindungsgemäße Verfahren kann vorteilhaft eingesetzt werden in der Fahrzeugreparaturlackierung, insbesondere zur Reparaturlackierung vonThe method according to the invention can advantageously be used in vehicle refinishing, in particular for refinishing
Fahrzeugteilen, kleineren Schadstellen und zum Spotrepair.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):The following components were mixed together and dispersed for a few minutes using a high-speed stirrer (all information relates to the weight):
131 Teile eines handelsüblichen aromatischen Epoxyacrylates131 parts of a commercially available aromatic epoxy acrylate
56 Teile Hexandioldiacrylat 9 Teile eines handelsüblichen Haftvermittlers 127 Teile handelsüblicher Schwerspat 126 Teile handelsübliches Kaolin 6, 1 Teile einer Mischung handelsüblicher Photoinitiatoren (Arylphosphinoxid- und56 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
Acetophenonderivat) 113 Teile ButylacetatAcetophenone derivative) 113 parts of butyl acetate
Erstellung eines Mehrschichtaufbaus 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. Eigenschaft erfindungsgemäßer Vergleichs-Creation of a multilayer structure The filler produced above is applied to KTL-coated sheets. A filler layer with a resulting dry film layer thickness of approximately 300 μm is applied in one operation and after a brief flashing off at room temperature, the filler layer is exposed to radiation from a UV flash lamp (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. Property of comparative invention
Mehrschichtaufbau Mehrschichtaufbau (1)Multi-layer structure Multi-layer structure (1)
Feucht/Warm-Test (2) (3) 0/0Wet / warm test (2) (3) 0/0
Haftung (4) 0-1Liability (4) 0-1
Haftung (4) nachLiability (4) after
Feucht/Warm-Test (2) 0-1Wet / warm test (2) 0-1
Schleifbarkeit LO. i.O. des FüllersSandability LO. OK of the fountain pen
Decklackstand i.O. i.O.Topcoat level ok OK
(1) Zum Vergleich wurde in dem oben beschriebenen Reparaturlackaufbau der UV-Füller durch einen üblichen lösemittelbasierenden 2K-Polyurethan-Füller ersetzt.(1) For comparison, the UV filler in the repair paint system described above was replaced by a conventional solvent-based two-component polyurethane filler.
(2) Feucht/Warm-Test nach DIN 50017(2) Wet / warm test according to DIN 50017
(3) Beurteilung der Blasenbildung nach DIN 53209(3) Assessment of blistering according to DIN 53209
(4) Gitterschnitt in Anlehnung an DIN 53151(4) Cross-cut based on DIN 53151
i.O. : in OrdnungOK : okay
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 in terms of sandability and topcoat level corresponds to the good level of a conventional repair lacquer structure with a solvent-based 2-component filler. With comparable high filler layer thicknesses of, for example, 300 μm and without intermediate sanding, the multi-layer structure according to the invention is even significantly superior to a conventional refinish coating structure with solvent-based two-component filler with regard to adhesion to different substrates.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung einer mehrschichtigen Lackierung, bei dem auf ein gegebenenfalls mit einem Grundierungs- und/oder weiteren Beschichtungsmitteln vorbeschichtetes Substrat ein FüUerbeschichtungsmittel aufgebracht und anschließend eine Deckbeschichtung aus einer färb- und/oder effektgebenden1. A process for producing a multilayer coating, in which a surface coating agent is applied to a substrate which may have been pre-coated with a primer and / or further coating agents, and then a top coating comprising a coloring and / or effect agent
Basislackschicht und einer transparenten Klarlackschicht oder eine Deckbeschichtung aus einem pigmentierten Einschichtdecklack appliziert wird, dadurch gekennzeichnet, daß als FüUerbeschichtungsmittel ein solches verwendet wird, das entwederBasecoat layer and a transparent clearcoat layer or a top coat of a pigmented single-layer topcoat is applied, characterized in that one is used as a coating agent that either
a) ausschließlich durch radikalische und/oder kationische Polymerisation härtbare Bindemittel enthält, oder dasa) contains only binders curable by radical and / or cationic polymerization, or that
b) durch radikalische und/oder kationische Polymerisation härtbare Bindemittel ausschließlich zusammen mit chemisch vernetzenden Bindemitteln enthält, wobei mittels energiereicher Strahlung gehärtet wird.b) contains binders curable by free-radical and / or cationic polymerization exclusively together with chemically crosslinking binders, with curing using high-energy radiation.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Härtung mittels gepulster UV-Strahlung erfolgt.2. The method according to claim 1, characterized in that the curing is carried out by means of pulsed UV radiation.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß als durch radikalische Polymerisation härtbare Bindemittel aromatische Epoxidharz(meth)acrylate verwendet werden.3. The method according to claim 1 or 2, characterized in that aromatic epoxy resin (meth) acrylates are used as binders curable by radical polymerization.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß für die Herstellung der Basislackschicht ein durch UV-Strahlung härtbarer Lack verwendet wird. 4. The method according to any one of claims 1 to 3, characterized in that a lacquer curable by UV radiation is used for the production of the base lacquer layer.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß als Basislack ein üblicher chemisch vernetzender und/oder physikalisch trocknender Basislack und als Klarlack ein durch UV-Strahlung härtbarer Klarlack verwendet werden.5. The method according to any one of claims 1 to 4, characterized in that a conventional chemically crosslinking and / or physically drying basecoat is used as the basecoat and a clearcoat which is curable by UV radiation is used as the clearcoat.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Füllerschicht in einem Arbeitsgang in Schichtdicken von bis zu 400 μm aufgebracht wird.6. The method according to any one of claims 1 to 5, characterized in that the filler layer is applied in one operation in layer thicknesses of up to 400 microns.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es zur Reparaturlackierung von Substraten durchgeführt wird.7. The method according to any one of claims 1 to 6, characterized in that it is carried out for refinishing substrates.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß es zur8. The method according to claim 7, characterized in that it for
Reparaturlackierung von Kraftfahrzeugkarossen oder deren Teilen durchgeführt wird. Refinishing of vehicle bodies or their parts is carried out.
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
DE19757082 1997-12-20
DE1997157082 DE19757082A1 (en) 1997-12-20 1997-12-20 Multilayer coating system containing a filler coating cured by high energy radiation
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 true EP1032474A1 (en) 2000-09-06
EP1032474B1 EP1032474B1 (en) 2001-10-17

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EP98955544A Revoked EP1032474B1 (en) 1997-11-20 1998-11-05 Method for multi-layered repair coating of substrates

Country Status (10)

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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)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE0003245L (en) * 2000-09-13 2002-03-14 Tetra Laval Holdings & Finance Packaging laminate for an autoclavable packaging container
MXPA03004310A (en) * 2000-11-15 2004-09-10 Ssw Holding Co 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
US20070065584A1 (en) * 2003-11-03 2007-03-22 Ryan John F 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.
JP5518736B2 (en) 2007-12-20 2014-06-11 コーティングス フォーリン アイピー カンパニー， エルエルシー Method 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
CA2882194C (en) * 2012-09-21 2021-01-05 Basf Coatings Gmbh Method for producing and repairing a multicoat color 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

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7707669A (en) 1977-07-08 1979-01-10 Akzo Nv METHOD OF COVERING A SUBSTRATE WITH A RADIATION HARDABLE COATING COMPOSITION.
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
GB2262055A (en) * 1991-11-28 1993-06-09 Tudor Hart George Henry Distressed paint finishes
DE19510363C1 (en) * 1995-03-22 1996-10-17 Herberts Gmbh Coating plastic substrates
DE19635447C1 (en) * 1996-08-31 1997-11-20 Herberts Gmbh Multilayer repair painting process, especially for car repairs
AU721046B2 (en) * 1996-12-19 2000-06-22 Rohm And Haas Company Coating substrates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9926733A1 *

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Publication number Publication date
CA2310716C (en) 2007-05-22
CA2310716A1 (en) 1999-06-03
ATE206960T1 (en) 2001-11-15
ES2167953T3 (en) 2002-05-16
DE59801811D1 (en) 2001-11-22
US6531188B1 (en) 2003-03-11
JP2001523573A (en) 2001-11-27
PT1032474E (en) 2002-04-29
WO1999026733A1 (en) 1999-06-03
JP4439726B2 (en) 2010-03-24
DK1032474T3 (en) 2001-11-19
EP1032474B1 (en) 2001-10-17

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