EP1152841B2 - Method for multi-layer varnishing - Google Patents

Method for multi-layer varnishing Download PDF

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Publication number
EP1152841B2
EP1152841B2 EP99962155A EP99962155A EP1152841B2 EP 1152841 B2 EP1152841 B2 EP 1152841B2 EP 99962155 A EP99962155 A EP 99962155A EP 99962155 A EP99962155 A EP 99962155A EP 1152841 B2 EP1152841 B2 EP 1152841B2
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EP
European Patent Office
Prior art keywords
radiation
irradiation
energy radiation
coat
coating
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.)
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EP99962155A
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German (de)
French (fr)
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EP1152841A1 (en
EP1152841B1 (en
Inventor
Helmut Löffler
Karin Maag
Wolfgang Feyrer
Christine Kimpel
Jens Zeyen
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EIDP Inc
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EI Du Pont de Nemours and Co
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/574—Three layers or more the last layer being a clear coat at least some layers being let to dry at least partially before applying the next layer
    • 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
    • B05D3/02—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 baking
    • B05D3/0209—Multistage baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/577—Three layers or more the last layer being a clear coat some layers being coated "wet-on-wet", the others not
    • 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
    • B05D3/02—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 baking
    • B05D3/0254—After-treatment
    • B05D3/0263—After-treatment with IR heaters
    • 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
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/544—No clear coat specified the first layer is let to dry at least partially before applying the second layer

Definitions

  • the invention relates to a method for vehicle refinishing.
  • the EP-A-0 540 884 describes a process for the production of a multicoat paint system for motor vehicle finishing by applying a clearcoat to a cured basecoat, wherein the clearcoat film comprises free radical curable binders and curing of the clearcoat is carried out by UV radiation.
  • the application of the clearcoat takes place when illuminated with light of a wavelength of more than 550 nm or in the absence of light.
  • high energy radiation curable binders based on an NCO and acryloyl functional urethane compound prepared from a hydroxyalkyl ester of (meth) acrylic acid and a polyisocyanate and based on a polyfunctional hydroxyl compound.
  • the EP-A-0 000 407 describes curable by high-energy radiation coating compositions based on an esterified with acrylic acid OH-functional polyester resin, a vinyl compound and a polyisocyanate.
  • a first curing step the irradiation with UV light and a second curing step, the final curing takes place at temperatures of 130 to 200 ° C.
  • German Patent Application P 198 18 735 are proposed by means of high-energy radiation coating compositions containing as binders compounds A) with free-radically polymerizable double bonds and other in the sense of an addition and / or condensation reaction functional groups and compounds B) with free-radically polymerizable double bonds and others in terms of addition and / or condensation reaction reactive functional groups, the latter to be reactive with the additional reactive groups of the compounds A).
  • the coatings obtained after UV irradiation can be exposed to higher temperatures, for example 30 to 120 ° C.
  • the object of the invention was therefore to provide a process for multi-layer vehicle refinishing, using at least partially radiation-curable coating compositions, with which coatings are obtained, which are free from cracking and have good adhesion to the ground.
  • the resulting coatings are said to have very good resistance to chemicals and weathering as well as good sandability. They should also show sufficient flexibility at high crosslinking density.
  • the coatings should also show a perfect optical appearance.
  • the object is achieved by the subject of the invention forming method according to claim 1.
  • UV radiation in particular UV radiation, but also, for example, electron radiation can be used.
  • At least partially curable coating agent (s) a Ablmediaphase granted. It may, for example, be a flash-off of 5 to 15 minutes, preferably 5 to 10 minutes at room temperature. Only then does the irradiation with IR radiation take place.
  • the coating compositions which are at least partly curable by means of high-energy radiation in the process according to the invention can be aqueous, diluted with solvents or be free from solvents and water. It may be by means of high-energy radiation, preferably by means of UV radiation, completely or only partially curable coating agent: curable by high-energy radiation coating agents are in particular known in the art cationic and / or free-radically curing coating compositions. Preference is given to free-radically curing coating compositions. Upon action of high-energy radiation on these coating compositions, free radicals are produced in the coating agent, which initiate crosslinking by radical polymerization of olefinic double bonds.
  • the preferred radically curing coating compositions contain conventional prepolymers of the type defined in claim 1.
  • the prepolymers may be used in combination with conventional reactive diluents, i. reactive liquid monomers.
  • reactive diluents are used, for example, in amounts of from 1 to 50% by weight, preferably from 5 to 30% by weight, based on the total weight of prepolymers and reactive diluents. These are low molecular weight defined compounds which may be mono-, di- or polyunsaturated.
  • reactive diluents are: (meth) acrylic acid and its esters, maleic acid and its half esters, vinyl acetate, vinyl ethers, substituted vinylureas, ethylene and propylene glycol di (meth) acrylate, 1,3- and 1,4-butanediol di (meth) acrylate, Vinyl (meth) acrylate, allyl (meth) acrylate, glycerol tri-, di- and mono (meth) acrylate, trimethylolpropane tri-, di- and mono (meth) acrylate, styrene, vinyltoluene, divinylbenzene, pentaerythritol tri- and tetra (meth) acrylate, di- and tripropylene glycol di (meth) acrylate, hexanediol di (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 used.
  • the radically curing coating compositions contain photoinitiators, e.g. in amounts of 0.1 to 5 wt .-%, preferably from 0.5 to 3 wt .-%, based on the sum of radically polymerizable prepolymers, reactive diluents and photoinitiators.
  • photoinitiators such as benzoin and derivatives, acetophenone and derivatives, e.g. 2,2-diacetoxyacetophenone, benzophenone and derivatives, thioxanthone and derivatives, anthraquinone, 1-benzoylcyclohexanol, organophosphorus compounds, e.g. Acyl phosphine oxides.
  • the photoinitiators can be used alone or in combination.
  • other synergistic components e.g. tertiary amines used.
  • the coating compositions which can be used by means of high-energy radiation and which are at least partially curable in the process according to the invention preferably contain one or more further binders in addition to the high-energy radiation-curable binder system.
  • the further binders which may additionally be present, are preferably conventional binder systems curable by means of addition and / or condensation reactions. However, they can also be conventional physically drying binder systems or combinations of both named binder systems.
  • the coating compositions which can be at least partially curable by means of high-energy radiation in the process according to the invention may contain additional components customary for the paint formulation.
  • the additives are the usual additives which can be used in the coatings sector. Examples of such additives are flow control agents, anticratering agents, antifoams, catalysts, adhesion promoters, rheology-influencing additives, thickeners, light stabilizers and emulsifiers.
  • the additives are used in customary quantities known to the person skilled in the art.
  • the coating compositions which can be used in the process according to the invention may contain proportions of organic solvents and / or water.
  • the solvents are conventional lacquer-based solvents. These may come from the manufacture of the binders or may be added separately.
  • Examples of such solvents are monohydric or polyhydric alcohols, for example: Propanol, butanol, hexanol; Glycol ethers or esters, e.g. Diethylene glycol dialkyl ethers, dipropylene glycol dialkyl ethers, each with C1 to C6 alkyl, ethoxypropanol, butyl glycol; Glycols, e.g.
  • the coating compositions which can be used in the process according to the invention can contain pigments and / or fillers. These are the usual fillers which can be used in the coatings industry and organic or inorganic color and / or effect pigments and anticorrosive pigments. Examples of inorganic or organic color pigments are titanium dioxide, micronized titanium dioxide, iron oxide pigments, carbon black, azo pigments, phthalocyanine pigments, quinacridone and pyrrolopyrrole pigments.
  • effect pigments are: metal pigments, eg of aluminum, copper or other metals; Interference pigments, such as metal oxide-coated metal pigments, eg titanium dioxide-coated or mixed oxide-coated aluminum, coated mica, such as titanium dioxide-coated mica and graphite effect pigments.
  • fillers are silicon dioxide, aluminum silicate, barium sulfate and talc.
  • special coated fillers for increasing the scratch resistance can advantageously be contained in the coating compositions. Suitable fillers are, for example, micronized aluminum oxide or micronized silicon oxides. These fillers are coated with compounds containing W-curable groups, eg, with acrylic-functional silanes, and are thus included in radiation curing of the coating composition.
  • Such transparent fillers which are particularly suitable for clearcoats are available as commercial products, for example under the name AKTISIL®.
  • the general composition of the coating materials that can be used depends on which layer of the multi-layer structure is to be produced with the respective coating agent, ie. H. whether it is for example a clearcoat, a basecoat or a filler or another common intermediate layer.
  • the application of the coating compositions in the process according to the invention can be carried out on various substrates.
  • Preferred substrates are metal or plastic substrates.
  • the application in the multi-layer structure by conventional methods, preferably by means of spray application.
  • the substrates can be precoated, for example provided with a conventional primer layer.
  • the irradiation with IR radiation takes place. It can be used to those skilled and used for paint drying IR emitters.
  • the IR emitter is positioned in front of the substrate surface to be irradiated, for example at a distance of 20 to 70 cm.
  • the irradiation time with IR radiation can be, for example, 1 to 20 minutes.
  • temperatures of, for example, 40 to 200 ° C. can be achieved at the substrate surface.
  • the settings should be made so that temperatures of, for example, 40 to 100 ° C are reached at the substrate surface.
  • Particularly good results are achieved if the application is not directly irradiated with IR radiation, but followed by a Ablstructurephase. It may, for example, be a flash-off of 5 to 15 minutes, preferably 5 to 10 minutes at room temperature.
  • the irradiation can be carried out with high-energy radiation, preferably with UV radiation.
  • UV radiation coating can preferably be done with UV radiation sources with emissions in the wavelength range of 180 to 420 nm, in particular from 200 to 400 nm.
  • Examples of usable UV radiation sources are e.g. High pressure mercury, medium pressure and low pressure radiator.
  • the lamp length can vary. For example, lamps between 5 and 200 cm in length are commonly used. Depending on the specific application and the required radiation energy lamp and reflector geometry can be matched to each other in the usual way.
  • the respective lamp power can vary, for example, between 20 and 250 W / cm (watts per cm lamp length). Preferably lamps with powers between 80 and 120 W / cm are used.
  • the mercury lamps may also be doped by introducing metal halides. Examples of doped radiators are iron or gallium mercury lamps.
  • W radiation sources are gas discharge tubes, e.g. Xenon low pressure lamps, W-lasers, UV spotlights, e.g. UV emitting diodes and black light tubes.
  • discontinuous UV radiation sources can also be used.
  • the W-type blowers may include a plurality of flash tubes, for example, with inert gas, such as xenon, filled quartz tubes.
  • the UV flash lamps have an illuminance of at least 10 megalux, preferably from 10 to 80 megalux per flash discharge.
  • the energy per flash discharge can be, for example, 1 to 10 kJoule.
  • the UV radiation sources are generally integrated into a UV system, which usually consists of the UV radiation sources, the reflector system, the power supply, electrical controls, the shielding, the cooling system and the ozone extraction. Other arrangements are of course also possible, as well as individual components can be omitted.
  • the exposure time with UV radiation can be, for example, in the range from 1 millisecond to 400 seconds, preferably from 4 to 160 seconds, depending on the number of selected lightning discharges when UV flash lamps are used as the UV radiation source.
  • the flashes can be triggered, for example, every 4 seconds. Curing can be done, for example, by 1 to 40 consecutive flash discharges.
  • the irradiation time can be, for example, in the range of a few seconds to about 5 minutes, preferably less than 5 minutes.
  • the distance of the UV radiation sources to the substrate surface to be irradiated may be for example 5 to 60 cm.
  • the shielding of the UV radiation sources to prevent radiation leakage may e.g. by using a suitably lined protective housing around a transportable lamp unit or with the aid of other safety measures known to those skilled in the art.
  • the refinish process according to the invention can be carried out in various embodiments.
  • IR and UV irradiation phases can partially or completely overlap, ie the IR irradiation phase can be completed before or simultaneously with termination of the UV irradiation phase.
  • IR irradiation phase it is likewise possible to connect a further IR irradiation phase to the completed UV irradiation phase.
  • the downstream IR irradiation phase can be, for example, 0.5 to 30 minutes. Otherwise, the statements made above concerning IR radiation apply.
  • IR, UV and IR irradiation may be sequentially performed in sequence, or the IR irradiation phase may extend over the entire irradiation time, i. the IR irradiation is carried out before, during and also after the UV irradiation phase.
  • the irradiation phases IR irradiation and subsequent UV irradiation can also be repeated several times as required.
  • the irradiation time per irradiation interval and the total irradiation time can be varied.
  • the coating agent is applied in one or more further spray passes and again an IR and then UV are applied irradiation.
  • This procedure is useful, for example, in the application of higher layer thicknesses, e.g. to 400 microns, desired filler layers particularly advantageous.
  • the multilayer structure it is possible in the multilayer structure to first apply an at least partially radiation-curable basecoat and first to subject it to an IR and subsequently to a UV irradiation. Thereafter, an at least partially radiation-curable clearcoat can be applied and again subjected first to IR and subsequently to UV irradiation. Optionally, in both cases, a further IR irradiation can follow the UV irradiation.
  • the radiation curing of the individual layers of the multi-layer structure as well as the layers applied by means of several spray paths can be carried out in each case with different radiation intensity and different irradiation time for each layer individually or for two or more layers together.
  • IR emitters and UV emitters For irradiation of the painted substrate surfaces according to the invention, it is possible, for example, to position IR emitters and UV emitters side by side and to switch them accordingly or, if appropriate, to position the emitters mutually in front of the substrate surface to be irradiated. It is also possible to use a so-called combined emitter, which includes IR and UV radiation source in a device. For example, in the latter case, IR and UV lamps can be alternately arranged side by side in the device.
  • one or more at least partially curable by means of high-energy radiation layers of a conventional multi-layer structure in the vehicle paint can be cured.
  • This may be, for example, a multi-layer structure of primer, filler, basecoat and clearcoat or of primer, filler and monolayer topcoat.
  • one or more layers of the multi-layer structure can be produced from at least partially radiation-curable coating compositions.
  • a filler layer (binder base: 2-component polyurethane, solvent-based) was applied to a cathodic electrodeposition coating (KTL) in a resulting dry film thickness of about 80 microns and cured after a short flash-off time at room temperature for 30 minutes at 60 ° C.
  • KTL cathodic electrodeposition coating
  • the filler layer was a water-based paint (prepared according to DE-A-196 43 802 , Preparation Example 4) in a resulting dry film thickness of 13 to 15 microns applied. After a flash-off phase of 20 minutes at room temperature, the UV-radiation-curable clearcoat prepared as described above was applied in a resulting dry film thickness of 40-50 ⁇ m.
  • Example 2 The procedure was analogous to Example 1 with the difference that after application of the clearcoat after a Ablrangephase of 30 minutes at room temperature directly the UV irradiation with a UV flash lamp (power 3500 Ws) was carried out.
  • the UV irradiation was carried out with 30 flashes, which were triggered at intervals of about 4 s, with an object distance of about 20 cm.
  • Example 2 Comp. 1 Wet / warm test (1) (2) 1.1 1.1 3.1 Liability (3) 0-1 1 1-2 Adhesion (3) after wet / warm test (1) 2 2-3 3 optics I.O. I.O. lightweight microstructure (1) Wet / warm test according to DIN 50017 (2) Evaluation of bubble formation according to DIN 53209 (3) cross-hatching in accordance with DIN 53151 OK, okay

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Medicinal Preparation (AREA)

Abstract

The invention relates to a method for multi-layer varnishing by applying filler layers and/or additional coating agent layers and by subsequently applying a coating layer of base coat/clear lacquer texture or of a pigmented finishing coat consisting of one layer onto a substrate. At least one of the layers is produced by a coating agent which is at least partially hardenable by means of radiation of high energy. After application of said coating agent, exposure to IR radiation and then to radiation of high energy are carried out.

Description

Die Erfindung betrifft ein Verfahren zur Fahrzeugreparaturlackierung.The invention relates to a method for vehicle refinishing.

Die UV-Technologie bei der Beschichtung und Härtung ist insbesondere in der Holzbeschichtungsindustrie seit längerem Stand der Technik. Aber auch in anderen Anwendungsgebieten, so auch in der Fahrzeuglackierung, ist es bekannt geworden, mittels energiereicher Strahlung härtbare Beschichtungsmittel einzusetzen. Man nutzt auch hier die Vorteile strahlungshärtbarer Beschichtungsmittel, wie z.B. die sehr kurzen Härtungszeiten, die geringe Lösemittelemission der Beschichtungsmittel sowie die sehr gute Härte der daraus erhaltenen Beschichtungen.The UV technology in the coating and curing has long been state of the art, especially in the wood coating industry. But also in other fields of application, such as in vehicle painting, it has become known to use curable coating by means of high-energy radiation. Here too, the advantages of radiation-curable coating compositions, such as e.g. the very short curing times, the low solvent emission of the coating materials and the very good hardness of the coatings obtained therefrom.

Neben geeigneten strahlungshärtbaren Bindemitteln und Photoinitiatoren sind auch verschiedene Arten von Strahlungsquellen bekannt worden.In addition to suitable radiation-curable binders and photoinitiators, various types of radiation sources have also become known.

So beschreibt beispielsweise die DE-A- 196 35 447 ein Verfahren zur Herstellung einer mehrschichtigen Reparaturlackierung, wobei als Klarlack oder pigmentierter Decklack ein Beschichtungsmittel appliziert wird, das auschließlich durch UV-Strahlung radikalisch polymerisierbare Bindemittel enthält. Die UV-Bestrahlung des applizierten Beschichtungsmittels erfolgt mit UV-Blitzlampen.For example, describes the DE-A-196 35 447 a method for producing a multi-layer refinish, wherein a clearcoat or pigmented topcoat a coating agent is applied, which contains exclusively by UV radiation radically polymerizable binder. The UV irradiation of the applied coating agent is carried out with UV flash lamps.

Die EP-A-0 540 884 beschreibt ein Verfahren zur Herstellung einer Mehrschichtlackierung für die Kraftfahrzeugserienlackierung durch Auftrag einer Klarlackschicht auf eine getrocknete bzw. gehärtete Basislackschicht, wobei das Klarlackbeschichtungsmittel durch radikalische Polymerisation härtbare Bindemittel enthält und die Härtung der Klarlackschicht mittels UV- Strahlung durchgeführt wird. Der Auftrag des Klarlackes erfolgt bei Beleuchtung mit Licht einer Wellenlänge von über 550 nm oder unter Ausschluß von Licht.The EP-A-0 540 884 describes a process for the production of a multicoat paint system for motor vehicle finishing by applying a clearcoat to a cured basecoat, wherein the clearcoat film comprises free radical curable binders and curing of the clearcoat is carried out by UV radiation. The application of the clearcoat takes place when illuminated with light of a wavelength of more than 550 nm or in the absence of light.

Es sind auch mittels energiereicher Strahlung härtbare Beschichtungsmittel beschrieben worden, welche Bindemittel enthalten, die mittels energiereicher Strahlung und zusätzlich über einen weiteren Vernetzungsmechanismus aushärten können.There have also been described by means of high-energy radiation curable coating compositions containing binders which can cure by means of high-energy radiation and additionally via a further crosslinking mechanism.

Zum Beispiel werden in der DE-A-28 09 715 mittels energiereicher Strahlung härtbare Bindemittel genannt, die auf einer NCO- und acryloylfunktionellen Urethanverbindung, hergestellt aus einem Hydroxyalkylester der (Meth)acrylsäure und einem Polyisocyanat, und auf einer polyfunktionellen Hydroxylverbindung basieren.For example, in the DE-A-28 09 715 high energy radiation curable binders based on an NCO and acryloyl functional urethane compound prepared from a hydroxyalkyl ester of (meth) acrylic acid and a polyisocyanate and based on a polyfunctional hydroxyl compound.

Die EP-A-0 000 407 beschreibt mittels energiereicher Strahlung härtbare Beschichtungsmittel auf Basis eines mit Acrylsäure veresterten OH-funktionellen Polyesterharzes, einer Vinylverbindung und eines Polyisocyanates. In einem ersten Härtungsschritt erfolgt die Bestrahlung mit UV-Licht und einem zweiten Härtungsschritt erfolgt die Endhärtung bei Temperaturen von 130 bis 200°C.The EP-A-0 000 407 describes curable by high-energy radiation coating compositions based on an esterified with acrylic acid OH-functional polyester resin, a vinyl compound and a polyisocyanate. In a first curing step, the irradiation with UV light and a second curing step, the final curing takes place at temperatures of 130 to 200 ° C.

In der noch nicht offengelegten deutschen Patentanmeldung P 198 18 735 werden mittels energiereicher Strahlung härtbare Beschichtungsmittel vorgeschlagen, die als Bindemittel Verbindungen A) mit radikalisch polymerisierbaren Doppelbindungen und weiteren im Sinne einer Additions- und/oder Kondensationsreaktion reaktiven funktionellen Gruppen enthalten sowie Verbindungen B) mit radikalisch polymerisierbaren Doppelbindungen und weiteren im Sinne einer Additions- und/oder Kondensationsreaktion reaktiven funktionellen Gruppen, wobei letztere reaktiv sein sollen gegenüber den zusätzlichen reaktiven Gruppen der Verbindungen A). Zur vollständigen Aushärtung können die erhaltenen Beschichtungen nach der UV-Bestrahlung höheren Temperaturen von z.B. 30 bis 120°C ausgesetzt werden.In the not yet revealed German Patent Application P 198 18 735 are proposed by means of high-energy radiation coating compositions containing as binders compounds A) with free-radically polymerizable double bonds and other in the sense of an addition and / or condensation reaction functional groups and compounds B) with free-radically polymerizable double bonds and others in terms of addition and / or condensation reaction reactive functional groups, the latter to be reactive with the additional reactive groups of the compounds A). For complete curing, the coatings obtained after UV irradiation can be exposed to higher temperatures, for example 30 to 120 ° C.

Mit den vorstehend genannten Verfahren zur mehrschichtigen Fahrzeuglackierung unter Verwendung mittels energiereicher Strahlung härtbarer Bindemittel werden jedoch Beschichtungen erhalten, die in verschiedener Hinsicht noch verbesserungsbedürftig sind. Die Beschichtungen zeigen noch Schwächen bezüglich Bewitterungs- und Chemikalienbeständigkeit und weisen eine unbefriedigende Schleifbarkeit auf. Des Weiteren kommt es bei den mittels energiereicher Strahlung härtbaren Beschichtungsmitteln durch den Härtungsprozeß zu einem Volumenschrumpf der aufgebrachten Beschichtung, was zu Spannungen und Rißbildung im Film führt. Enthaftungserscheinungen zum Untergrund können die Folge sein. Das Problem der Rißbildung und mangelnden Zwischenschichthaftung ist noch nicht zufriedenstellend gelöst worden.However, with the above-mentioned multi-layer vehicle painting processes using high-energy-radiation-curable binders, coatings are obtained which are still in need of improvement in various respects. The coatings still show weaknesses in terms of weathering and chemical resistance and have an unsatisfactory sandability. Furthermore, in the case of the coating compositions curable by means of high-energy radiation, the hardening process leads to a volume shrinkage of the applied coating, which leads to tensions and cracking in the film. Enthaftungserscheinungen to the underground can be the result. The problem of cracking and lack of intercoat adhesion has not yet been satisfactorily resolved.

Aufgabe der Erfindung war es daher, ein Verfahren zur mehrschichtigen Fahrzeugreparaturlackierung, unter Verwendung zumindest teilweise strahlungshärtbarer Beschichtungsmittel bereitzustellen, mit welchem Beschichtungen erhalten werden, die frei sind von Rißbildungen und eine gute Haftung zum Untergrund aufweisen. Die erhaltenen Beschichtungen sollen eine sehr gute Chemikalien- und Witterungsbeständigkeit sowie eine gute Schleifbarkeit aufweisen. Sie sollen auch bei hoher Vernetzungsdichte eine ausreichende Flexibilität zeigen. Die Beschichtungen sollen außerdem ein einwandfreies optisches Aussehen zeigen.The object of the invention was therefore to provide a process for multi-layer vehicle refinishing, using at least partially radiation-curable coating compositions, with which coatings are obtained, which are free from cracking and have good adhesion to the ground. The resulting coatings are said to have very good resistance to chemicals and weathering as well as good sandability. They should also show sufficient flexibility at high crosslinking density. The coatings should also show a perfect optical appearance.

Die Aufgabe wird gelöst durch das einen Gegenstand der Erfindung bildende Verfahren gemäß Anspruch 1.The object is achieved by the subject of the invention forming method according to claim 1.

Als energiereiche Strahlung kann insbesondere UV-Strahlung, aber auch beispielsweise Elektronenstrahlung eingesetzt werden.As high-energy radiation, in particular UV radiation, but also, for example, electron radiation can be used.

Bevorzugt wird nach Applikation des oder der mittels energiereicher Strahlung zumindest teilweise härtbaren Beschichtungsmittel(s) eine Ablüftphase gewährt. Es kann sich beispielsweise um ein Ablüften von 5 bis 15 Minuten, bevorzugt 5 bis 10 Minuten bei Raumtemperatur handeln. Erst anschließend erfolgt die Bestrahlung mit IR-Strahlung.Preferably, after application of the or by means of high-energy radiation at least partially curable coating agent (s) a Ablüftphase granted. It may, for example, be a flash-off of 5 to 15 minutes, preferably 5 to 10 minutes at room temperature. Only then does the irradiation with IR radiation take place.

Die im erfindungsgemäßen Verfahren verwendeten mittels energiereicher Strahlung zumindest teilweise aushärtbaren Beschichtungsmittel können wäßrig, mit Lösemitteln verdünnt oder frei von Lösemitteln und Wasser sein. Es kann sich um mittels energiereicher Strahlung, bevorzugt mittels UV-Strahlung, vollständig oder nur teilweise aushärtbare Beschichtungsmittel handeln: Bei mittels energiereicher Strahlung aushärtbaren Beschichtungsmitteln handelt es sich insbesondere um dem Fachmann bekannte kationisch und/oder radikalisch härtende Beschichtungsmittel. Bevorzugt sind radikalisch härtende Beschichtungsmittel. Bei Einwirkung energiereicher Strahlung auf diese Beschichtungsmittel entstehen im Beschichtungsmittel Radikale, die eine Vernetzung durch radikalische Polymerisation olefinischer Doppelbindungen auslösen.The coating compositions which are at least partly curable by means of high-energy radiation in the process according to the invention can be aqueous, diluted with solvents or be free from solvents and water. It may be by means of high-energy radiation, preferably by means of UV radiation, completely or only partially curable coating agent: curable by high-energy radiation coating agents are in particular known in the art cationic and / or free-radically curing coating compositions. Preference is given to free-radically curing coating compositions. Upon action of high-energy radiation on these coating compositions, free radicals are produced in the coating agent, which initiate crosslinking by radical polymerization of olefinic double bonds.

Die bevorzugt einsetzbaren radikalisch härtenden Beschichtungsmittel enthalten übliche Prepolymere, der im Anspruch 1 definierten Art. Die Prepolymere können in Kombination mit üblichen Reaktiwerdünnern, d.h. reaktiven flüssigen Monomeren, vorliegen.The preferred radically curing coating compositions contain conventional prepolymers of the type defined in claim 1. The prepolymers may be used in combination with conventional reactive diluents, i. reactive liquid monomers.

Unter (Meth)acryl ist hier Acryl und/oder Methacryl zu verstehen.Under (meth) acrylic is to be understood here as acrylic and / or methacrylic.

Werden Reaktiwerdünner verwendet, so werden sie beispielsweise in Mengen von 1 bis 50 Gew.-%, bevorzugt von 5 bis 30 Gew.-%, bezogen auf das Gesamtgewicht von Prepolymeren und Reaktiwerdünnern, eingesetzt. Es handelt sich um niedermolekulare definierte Verbindungen, die mono-, di- oder polyungesättigt sein können. Beispiele für solche Reaktiwerdünner sind: (Meth)acrylsäure und deren Ester, Maleinsäure und deren Halbester, Vinylacetat, Vinylether, substituierte Vinylhamstoffe, Ethylen- und Propylenglykoldi(meth)acrylat, 1,3- und 1,4-Butandioldi(meth)acrylat, Vinyl(meth)acrylat, Allyl(meth)acrylat, Glycerintri-, -di- und -mono(meth)acrylat, Trimethylolpropantri-, -di- und -mono(meth)acrylat, Styrol, Vinyltoluol, Divinylbenzol, Pentaerythrittri- und - tetra(meth)acrylat, Di- und Tripropylenglykoldi(meth)acrylat, Hexandioldi(meth)acrylat. Die Reaktiwerdünner können einzeln oder im Gemisch eingesetzt werden. Bevorzugt werden als Reaktiwerdünner Diacrylate wie z.B. Dipropylenglykoldiacrylat, Tripropylenglykoldiacrylat und/oder Hexandioldiacrylat eingesetzt.If reactive diluents are used, they are used, for example, in amounts of from 1 to 50% by weight, preferably from 5 to 30% by weight, based on the total weight of prepolymers and reactive diluents. These are low molecular weight defined compounds which may be mono-, di- or polyunsaturated. Examples of such reactive diluents are: (meth) acrylic acid and its esters, maleic acid and its half esters, vinyl acetate, vinyl ethers, substituted vinylureas, ethylene and propylene glycol di (meth) acrylate, 1,3- and 1,4-butanediol di (meth) acrylate, Vinyl (meth) acrylate, allyl (meth) acrylate, glycerol tri-, di- and mono (meth) acrylate, trimethylolpropane tri-, di- and mono (meth) acrylate, styrene, vinyltoluene, divinylbenzene, pentaerythritol tri- and tetra (meth) acrylate, di- and tripropylene glycol di (meth) acrylate, hexanediol di (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 used.

Die radikalisch härtenden Beschichtungsmittel enthalten Photoinitiatoren, z.B. in Mengen von 0,1 bis 5 Gew.-%, bevorzugt von 0,5 bis 3 Gew.-%, bezogen auf die Summe von radikalisch polymerisierbaren Prepolymeren, Reaktiwerdünnern und Photoinitiatoren. Geeignet sind die üblichen Photoinitiatoren, wie beispielsweise Benzoin und -derivate, Acetophenon und -derivate, z.B. 2,2-Diacetoxyacetophenon, Benzophenon und -derivate, Thioxanthon und -derivate, Anthrachinon, 1-Benzoylcyclohexanol, phosphororganische Verbindungen, wie z.B. Acylphospinoxide. Die Photoinitiatoren können allein oder in Kombination eingesetzt werden. Außerdem können weitere synergistische Komponenten, z.B. tertiäre Amine, eingesetzt werden.The radically curing coating compositions contain photoinitiators, e.g. in amounts of 0.1 to 5 wt .-%, preferably from 0.5 to 3 wt .-%, based on the sum of radically polymerizable prepolymers, reactive diluents and photoinitiators. Suitable are the usual photoinitiators, such as benzoin and derivatives, acetophenone and derivatives, e.g. 2,2-diacetoxyacetophenone, benzophenone and derivatives, thioxanthone and derivatives, anthraquinone, 1-benzoylcyclohexanol, organophosphorus compounds, e.g. Acyl phosphine oxides. The photoinitiators can be used alone or in combination. In addition, other synergistic components, e.g. tertiary amines used.

Die im erfindungsgemäßen Verfahren, wie im Anspruch 1 definiert, einsetzbaren mittels energiereicher Strahlung zumindest teilweise härtbaren Beschichtungsmittel enthalten bevorzugt neben dem mittels energiereicher Strahlung härtbaren Bindemittelsystem ein oder mehrere weitere Bindemittel. Bei den weiteren Bindemitteln, die zusätzlich vorliegen können, handelt es sich bevorzugt um übliche mittels Additions- und/oder Kondensationsreaktionen aushärtbare Bindemittelsysteme. Es kann sich aber auch um übliche physikalisch trocknende Bindemittelsysteme oder um Kombinationen beider genannter Bindemittelsysteme handeln.The coating compositions which can be used by means of high-energy radiation and which are at least partially curable in the process according to the invention preferably contain one or more further binders in addition to the high-energy radiation-curable binder system. The further binders, which may additionally be present, are preferably conventional binder systems curable by means of addition and / or condensation reactions. However, they can also be conventional physically drying binder systems or combinations of both named binder systems.

Bei den Additions- und/oder Kondensationsreaktionen im vorstehend genannten Sinne handelt es sich um dem Fachmann bekannte lackchemische Vernetzungsreaktionen wie beispielsweise die ringöffnende Addition einer Epoxidgruppe an eine Carboxylgruppe unter Bildung einer Ester- und einer Hydroxylgruppe, die Addition einer Hydroxylgruppe an eine Isocyanatgruppe unter Bildung einer Urethangruppe, die Reaktion einer Hydroxylgruppe mit einer blockierten Isocyanatgruppe unter Ausbildung einer Urethangruppe und Abspaltung des Blockierungsmittels, die Reaktion einer Hydroxylgruppe mit einer N-Methylolgruppe unter Wasserabspaltung, die Reaktion einer Hydroxylgruppe mit einer N-Methylolethergruppe unter Abspaltung des Veretherungsalkohols, die Umesterungsreaktion einer Hydroxylgruppe mit einer Estergruppe unter Abspaltung des Veresterungsalkohols, die Umurethanisierungsreaktion einer Hydroxylgruppe mit einer Carbamatgruppe unter Alkoholabspaltung, die Reaktion einer Carbamatgruppe mit einer N-Methylolethergruppe unter Abspaltung des Veretherungsalkohols.The addition and / or condensation reactions in the abovementioned sense are known to those skilled paint chemical crosslinking reactions such as the ring-opening addition of an epoxide group to a carboxyl group to form an ester and a hydroxyl group, the addition of a hydroxyl group to an isocyanate group to form a Urethane group, the reaction of a hydroxyl group with a blocked isocyanate group to form a urethane group and cleavage of the blocking agent, the Reaction of a hydroxyl group with an N-methylol group with elimination of water, the reaction of a hydroxyl group with an N-methylol ether group with elimination of the etherification alcohol, the transesterification reaction of a hydroxyl group with an ester group with elimination of the esterification alcohol, the Umurethanisierungsreaktion a hydroxyl group with a carbamate group with elimination of alcohol, the reaction of a Carbamate group with an N-methylol ether group with elimination of the etherification alcohol.

Es ist zu beachten, daß die jeweiligen Komponenten mit Hydroxylgruppen und die jeweiligen Komponenten mit Isocyanatgruppen getrennt gelagert werden müssen und erst kurz vor der Applikation miteinander vermischt werden dürfen.It should be noted that the respective components must be stored separately with hydroxyl groups and the respective components with isocyanate groups and may only be mixed together shortly before application.

Die im erfindungsgemäßen Verfahren einsetzbaren mittels energiereicher Strahlung zumindest teilweise härtbaren Beschichtungsmittel können zusätzliche, für die Lackformulierung übliche Komponenten enthalten. Sie können z.B. lackübliche Additive enthalten. Bei den Additiven handelt es sich um die üblichen auf dem Lacksektor einsetzbaren Additive. Beispiele für solche Additive sind Verlaufsmittel, Antikratermittel, Antischaummittel, Katalysatoren, Haftvermittler, rheologiebeeinflussende Additive, Verdicker, Lichtschutzmittel und Emulgatoren. Die Additive werden in üblichen, dem Fachmann geläufigen Mengen eingesetzt.The coating compositions which can be at least partially curable by means of high-energy radiation in the process according to the invention may contain additional components customary for the paint formulation. You can e.g. customary paint additives. The additives are the usual additives which can be used in the coatings sector. Examples of such additives are flow control agents, anticratering agents, antifoams, catalysts, adhesion promoters, rheology-influencing additives, thickeners, light stabilizers and emulsifiers. The additives are used in customary quantities known to the person skilled in the art.

Die im erfindungsgemäßen Verfahren einsetzbaren Beschichtungsmittel können Anteile an organischen Lösemitteln und/oder Wasser enthalten. Bei den Lösemitteln handelt es sich um übliche lacktechnische Lösemittel. Diese können aus der Herstellung der Bindemittel stammen oder werden separat zugegeben. Beispiele für solche Lösemittel sind ein- oder mehrwertige Alkohole, z:B. Propanol, Butanol, Hexanol; Glykolether oder -ester, z.B. Diethylenglykoldialkylether, Dipropylenglykoldialkylether, jeweils mit C1- bis C6-Alkyl, Ethoxypropanol, Butylglykol; Glykole, z.B. Ethylenglykol, Propylenglykol und deren Oligomere, Ester, wie z.B. Butylacetat und Amylacetat, N-Methylpyrrolidon sowie Ketone, z.B. Methylethylketon, Aceton, Cyclohexanon; aromatische oder aliphatische Kohlenwasserstoffe, z.B. Toluol, Xylol oder lineare oder verzweigte aliphatische C6-C12-Kohlenwasserstoffe.The coating compositions which can be used in the process according to the invention may contain proportions of organic solvents and / or water. The solvents are conventional lacquer-based solvents. These may come from the manufacture of the binders or may be added separately. Examples of such solvents are monohydric or polyhydric alcohols, for example: Propanol, butanol, hexanol; Glycol ethers or esters, e.g. Diethylene glycol dialkyl ethers, dipropylene glycol dialkyl ethers, each with C1 to C6 alkyl, ethoxypropanol, butyl glycol; Glycols, e.g. Ethylene glycol, propylene glycol and their oligomers, esters, e.g. Butyl acetate and amyl acetate, 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.

Die im erfindungsgemäßen Verfahren einsetzbaren Beschichtungsmittel können Pigmente und/oder Füllstoffe enthalten. Es handelt sich dabei um die üblichen in der Lackindustrie einsetzbaren Füllstoffe und organischen oder anorganischen farb- und/oder effektgebenden Pigmente und Korrosionsschutzpigmente. Beispiele für anorganische oder organische Farbpigmente sind Titandioxid, mikronisiertes Titandioxid, Eisenoxidpigmente, Ruß, Azopigmente, Phthalocyaninpigmente, Chinacridon- und Pyrrolopyrrolpigmente. Beispiele für Effektpigmente sind: Metallpigmente, z.B. aus Aluminium, Kupfer oder anderen Metallen; Interferenzpigmente, wie z.B. metalloxidbeschichtete Metallpigmente, z.B. titandioxidbeschichtetes oder mischoxidbeschichtetes Aluminium, beschichteter Glimmer, wie z.B. titandioxidbeschichteter Glimmer und Graphiteffektpigmente. Beispiele für Füllstoffe sind Siliciumdioxid, Aluminiumsilikat, Bariumsulfat und Talkum. In den Beschichtungsmitteln können vorteilhafterweise neben den üblichen Additiven spezielle gecoatete Füllstoffe zur Erhöhung der Kratzfestigkeit enthalten sein. Als Füllstoffe kommen hier z.B. micronisiertes Aluminiumoxid oder micronisierte Siliciumoxide in Frage. Diese Füllstoffe sind mit Verbindungen gecoatet, die W-härtbare Gruppen enthalten, z.B. mit acrylfunktionellen Silanen, und werden somit bei der Strahlenhärtung des Beschichtungsmittels mit einbezogen. Derartige besonders für Klarlacke geeignete transparente Füllstoffe sind als Handelsprodukte, z.B. unter dem Namen AKTISIL®, erhältlich.The coating compositions which can be used in the process according to the invention can contain pigments and / or fillers. These are the usual fillers which can be used in the coatings industry and organic or inorganic color and / or effect pigments and anticorrosive pigments. Examples of inorganic or organic color pigments are titanium dioxide, micronized titanium dioxide, iron oxide pigments, carbon black, azo pigments, phthalocyanine pigments, quinacridone and pyrrolopyrrole pigments. Examples of effect pigments are: metal pigments, eg of aluminum, copper or other metals; Interference pigments, such as metal oxide-coated metal pigments, eg titanium dioxide-coated or mixed oxide-coated aluminum, coated mica, such as titanium dioxide-coated mica and graphite effect pigments. Examples of fillers are silicon dioxide, aluminum silicate, barium sulfate and talc. In addition to the customary additives, special coated fillers for increasing the scratch resistance can advantageously be contained in the coating compositions. Suitable fillers are, for example, micronized aluminum oxide or micronized silicon oxides. These fillers are coated with compounds containing W-curable groups, eg, with acrylic-functional silanes, and are thus included in radiation curing of the coating composition. Such transparent fillers which are particularly suitable for clearcoats are available as commercial products, for example under the name AKTISIL®.

Die generelle Zusammensetzung der einsetzbaren Beschichtungsmittel, beispielsweise die Art der Pigmentierung, richtet sich danach, welche Schicht des Mehrschichtaufbaus mit dem jeweiligen Beschichtungsmittel erstellt werden soll, d. h. ob es sich beispielsweise um einen Klarlack, einen Basislack oder einen Füller oder eine weitere übliche Zwischenschicht handelt.The general composition of the coating materials that can be used, for example the type of pigmentation, depends on which layer of the multi-layer structure is to be produced with the respective coating agent, ie. H. whether it is for example a clearcoat, a basecoat or a filler or another common intermediate layer.

Der Auftrag der Beschichtungsmittel im erfindungsgemäßen Verfahren kann auf verschiedene Substrate erfolgen. Bevorzugte Substrate sind Metall- oder Kunststoffsubstrate. Die Applikation im Mehrschichtaufbau erfolgt nach üblichen Verfahren, bevorzugt mittels Spritzauftrag. Die Substrate können vorbeschichtet, beispielsweise mit einer üblichen Grundierungsschicht versehen sein.The application of the coating compositions in the process according to the invention can be carried out on various substrates. Preferred substrates are metal or plastic substrates. The application in the multi-layer structure by conventional methods, preferably by means of spray application. The substrates can be precoated, for example provided with a conventional primer layer.

Nach Applikation des oder der mittels energiereicher Strahlung zumindest teilweise härtbaren Beschichtungsmittel erfolgt die Bestrahlung mit IR-Strahlung. Es können dem Fachmann bekannte und für die Lacktrocknung übliche IR-Strahler eingesetzt werden. Der IR-Strahler wird vor der zu bestrahlenden Substratoberfläche, beispielsweise in einem Abstand von 20 bis 70 cm, positioniert. Die Bestrahlungsdauer mit IR-Strahlung kann beispielsweise 1 bis 20 min betragen. In Abhängigkeit von Bestrahlungsdauer und Leistung der Strahlungsquelle können dabei an der Substratoberfläche Temperaturen von beispielsweise 40 bis 200°C erreicht werden. Günstigerweise sollten die Einstellungen so vorgenommen werden, daß Temperaturen von beispielsweise von 40 bis 100°C an der Substratoberfläche erreicht werden. Besonders gute Resultate werden erzielt, wenn nach der Applikation nicht direkt mit IR-Strahlung bestrahlt wird, sondern sich eine Ablüftphase anschließt. Es kann sich beispielsweise um ein Ablüften von 5 bis 15 Minuten, bevorzugt 5 bis 10 Minuten bei Raumtemperatur handeln.After application of the or by means of high-energy radiation at least partially curable coating agent, the irradiation with IR radiation takes place. It can be used to those skilled and used for paint drying IR emitters. The IR emitter is positioned in front of the substrate surface to be irradiated, for example at a distance of 20 to 70 cm. The irradiation time with IR radiation can be, for example, 1 to 20 minutes. Depending on the duration of irradiation and the power of the radiation source, temperatures of, for example, 40 to 200 ° C. can be achieved at the substrate surface. Conveniently, the settings should be made so that temperatures of, for example, 40 to 100 ° C are reached at the substrate surface. Particularly good results are achieved if the application is not directly irradiated with IR radiation, but followed by a Ablüftphase. It may, for example, be a flash-off of 5 to 15 minutes, preferably 5 to 10 minutes at room temperature.

Wenn mittels der IR-Bestrahlung die gewünschte Temperatur der Substratoberfläche erreicht bzw. die vorgesehene Bestrahlungsdauer abgelaufen ist, kann die Bestrahlung mit energiereicher Strahlung, bevorzugt mit W-Strahlung erfolgen.If the desired temperature of the substrate surface is reached by means of the IR irradiation or the intended irradiation time has elapsed, the irradiation can be carried out with high-energy radiation, preferably with UV radiation.

Die Härtung der zumindest teilweise mittels energiereicher Strahlung, bevorzugt UV-Strahlung härtbaren Beschichtung kann bevorzugt mit UV-Strahlungsquellen mit Emissionen im Wellenlängenbereich von 180 bis 420 nm, insbesondere von 200 bis 400 nm erfolgen.The curing of the at least partially curable by means of high-energy radiation, preferably UV radiation coating can preferably be done with UV radiation sources with emissions in the wavelength range of 180 to 420 nm, in particular from 200 to 400 nm.

Beipiele für einsetzbare UV-Strahlungsquellen sind z.B. Quecksilberhochdruck-, mitteldruck- und -niederdruckstrahler. Die Lampenlänge kann variieren. Gebräuchlich sind beispielsweise Lampen zwischen 5 und 200 cm Lampenlänge. In Abhängigkeit vom speziellen Anwendungsfall und von der benötigten Strahlungsenergie können Lampen- und Reflektorgeometrie in üblicher Weise aufeinander abgestimmt sein. Die jeweilige Lampenleistung kann beispielsweise zwischen 20 und 250 W/cm (Watt pro cm Lampenlänge) variieren. Bevorzugt werden Lampen mit Leistungen zwischen 80 und 120 W/cm eingesetzt. Gegebenenfalls können die Quecksilberlampen durch Einbringen von Metallhalogeniden auch dotiert sein. Beispiele dotierter Strahler sind Eisen- oder Galliumquecksilberlampen.Examples of usable UV radiation sources are e.g. High pressure mercury, medium pressure and low pressure radiator. The lamp length can vary. For example, lamps between 5 and 200 cm in length are commonly used. Depending on the specific application and the required radiation energy lamp and reflector geometry can be matched to each other in the usual way. The respective lamp power can vary, for example, between 20 and 250 W / cm (watts per cm lamp length). Preferably lamps with powers between 80 and 120 W / cm are used. Optionally, the mercury lamps may also be doped by introducing metal halides. Examples of doped radiators are iron or gallium mercury lamps.

Weitere Beispiele für W-Strahlungsquellen sind Gasentladungsröhren, wie z.B. Xenonniederdrucklampen, W-Laser, UV-Punktstrahler, wie z.B. UV-emittierende Dioden und Schwarzlichtröhren. Neben diesen kontinuierlich arbeitenden UV-Strahlungsquellen können jedoch auch diskontinuierliche UV-Strahlungsquellen eingesetzt werden. Bevorzugt handelt es sich hierbei um sogenannte Hochenergieblitzeinrichtungen (kurz: UV-Blitzlampen). Die W-Blitzlarnpen können eine Mehrzahl von Blitzröhren, beispielsweise mit inertem Gas, wie Xenon, gefüllte Quarzröhren, enthalten. Die UV-Blitzlampen weisen beispielsweise eine Beleuchtungsstärke von mindestens 10 Megalux, bevorzugt von 10 bis 80 Megalux pro Blitzentladung auf. Die Energie pro Blitzentladung kann beispielsweise 1 bis 10 kJoule betragen.Further examples of W radiation sources are gas discharge tubes, e.g. Xenon low pressure lamps, W-lasers, UV spotlights, e.g. UV emitting diodes and black light tubes. In addition to these continuously operating UV radiation sources, however, discontinuous UV radiation sources can also be used. These are preferably so-called high-energy-jet devices (in short: UV flash lamps). The W-type blowers may include a plurality of flash tubes, for example, with inert gas, such as xenon, filled quartz tubes. For example, the UV flash lamps have an illuminance of at least 10 megalux, preferably from 10 to 80 megalux per flash discharge. The energy per flash discharge can be, for example, 1 to 10 kJoule.

Die UV-Strahlungsquellen sind im allgemeinen in eine UV-Anlage integriert, die normalerweise aus den UV-Strahlungsquellen, dem Reflektorsystem, der Stromversorgung, elektrischen Steuerungen, der Abschirmung, dem Kühlsystem und der Ozonabsaugung besteht. Andere Anordnungen sind natürlich auch möglich, ebenso können einzelne der genannten Bestandteile weggelassen werden.The UV radiation sources are generally integrated into a UV system, which usually consists of the UV radiation sources, the reflector system, the power supply, electrical controls, the shielding, the cooling system and the ozone extraction. Other arrangements are of course also possible, as well as individual components can be omitted.

Die Betrahlungsdauer mit UV-Strahlung kann beim Einsatz von UV-Blitzlampen als UV-Strahlungsquelle beispielsweise im Bereich von 1 Millisekunde bis 400 Sekunden, bevorzugt von 4 bis 160 Sekunden, je nach Anzahl der gewählten Blitzentladungen, liegen. Die Blitze können beispielsweise etwa alle 4 Sekunden ausgelöst werden. Die Härtung kann beispielsweise durch 1 bis 40 aufeinanderfolgende Blitzentladungen erfolgen.The exposure time with UV radiation can be, for example, in the range from 1 millisecond to 400 seconds, preferably from 4 to 160 seconds, depending on the number of selected lightning discharges when UV flash lamps are used as the UV radiation source. The flashes can be triggered, for example, every 4 seconds. Curing can be done, for example, by 1 to 40 consecutive flash discharges.

Beim Einsatz kontinuierlicher UV-Strahlungsquellen kann die Bestrahlungsdauer beispielsweise im Bereich von einigen Sekunden bis etwa 5 Minuten, bevorzugt unter 5 Minuten liegen.When using continuous UV radiation sources, the irradiation time can be, for example, in the range of a few seconds to about 5 minutes, preferably less than 5 minutes.

Der Abstand der UV-Strahlungsquellen zur zu bestrahlenden Substratoberfläche kann beispielsweise 5 bis 60 cm betragen. Die Abschirmung der UV-Strahlungsquellen zur Vermeidung von Strahlungsaustritt kann z.B. durch Verwendung eines entsprechend ausgekleideten Schutzgehäuses um eine transportable Lampeneinheit oder mit Hilfe anderer, dem Fachmann bekannter Sicherheitsmaßnahmen, erfolgen.The distance of the UV radiation sources to the substrate surface to be irradiated may be for example 5 to 60 cm. The shielding of the UV radiation sources to prevent radiation leakage may e.g. by using a suitably lined protective housing around a transportable lamp unit or with the aid of other safety measures known to those skilled in the art.

Das erfindungsgemäße Verfahren zur Reparaturlackierung kann in verschiedenen Ausführungsformen durchgeführt werden.The refinish process according to the invention can be carried out in various embodiments.

So ist es beispielsweise möglich, die UV-Bestrahlungsphase an die beendete IR-Bestrahlungsphase anzuschließen oder die UV-Bestrahlung bei fortlaufender IR-Bestrahlung zu beginnen. Im letzteren Fall können IR- und UV-Bestrahlungsphase teilweise oder ganz überlappen, d.h. die IR-Bestrahlungsphase kann vor oder gleichzeitig mit Beendigung der UV-Bestrahlungsphase abgeschlossen werden.For example, it is possible to apply the UV irradiation phase to the completed IR irradiation phase or to start the UV irradiation with continuous IR irradiation. In the latter case, IR and UV irradiation phases can partially or completely overlap, ie the IR irradiation phase can be completed before or simultaneously with termination of the UV irradiation phase.

Ebenso ist es möglich, an die abgeschlossene UV-Bestrahlungsphase eine weitere IR-Bestrahlungsphase anzuschließen. Die nachgeschaltete IR-Bestrahlungsphase kann beispielsweise 0,5 bis 30 Minuten betragen. Ansonsten gelten die vorstehend bereits gemachten Aussagen bezüglich der IR-Bestrahlung. Im Falle einer sich an die UV-Bestrahlungsphase anschließenden IR-Bestrahlungsphase können in Reihenfolge IR-, UV- und IR-Bestrahlung nacheinander durchgeführt werden oder die IR-Bestrahlungsphase erstreckt sich über die gesamte Bestrahlungszeit, d.h. die IR-Bestrahlung wird vor, während und auch nach der W-Bestrahlungsphase durchgeführt.It is likewise possible to connect a further IR irradiation phase to the completed UV irradiation phase. The downstream IR irradiation phase can be, for example, 0.5 to 30 minutes. Otherwise, the statements made above concerning IR radiation apply. In the case of an IR irradiation phase subsequent to the UV irradiation phase, IR, UV and IR irradiation may be sequentially performed in sequence, or the IR irradiation phase may extend over the entire irradiation time, i. the IR irradiation is carried out before, during and also after the UV irradiation phase.

Die Bestrahlungsphasen IR-Bestrahlung und anschließende UV-Bestrahlung können je nach Bedarf auch mehrmals hintereinander wiederholt werden.The irradiation phases IR irradiation and subsequent UV irradiation can also be repeated several times as required.

Bei jeder der genannten Ausführungsformen können die Bestrahlungsdauer pro Bestrahlungsintervall und die Gesamtbestrahlungsdauer variiert werden.In each of the mentioned embodiments, the irradiation time per irradiation interval and the total irradiation time can be varied.

Desweiteren ist es auch möglich die miteinander gekoppelten Bestrahlungsintervalle IR- und UV-Bestrahlung im Zusammenhang mit der Durchführung mehrerer Spritzgänge, mehrerer Arbeitsgänge oder im Zusammenhang mit der Strahlungshärtung mehrerer aufeinander folgender Schichten des Mehrschichtaufbaues anzuwenden.Furthermore, it is also possible to apply the coupled IR and UV radiation irradiation intervals in connection with the execution of several spray passes, several operations or in connection with the radiation curing of several successive layers of the multilayer structure.

Beispielsweise kann nach Applikation des zumindest teilweise strahlungshärtbaren Beschichtungsmittels in einem Spritzgang zunächst eine Zwischenhärtung mit IR-Bestrahlung und eine anschließende W-Bestrahlung erfolgen, nachfolgend wird das Beschichtungsmittel in einem oder mehreren weiteren Spritzgängen aufgebracht und es erfolgt wiederum zunächst eine IR- und anschließend eine UV-Bestrahlung. Diese Arbeitsweise ist beispielsweise bei der Applikation von in höheren Schichtdicken, z.B. bis 400 µm, gewünschten Füllerschichten besonders vorteilhaft.For example, after application of the at least partially radiation-curable coating composition in one spray pass, intermediate curing with IR irradiation followed by UV irradiation takes place. Subsequently, the coating agent is applied in one or more further spray passes and again an IR and then UV are applied irradiation. This procedure is useful, for example, in the application of higher layer thicknesses, e.g. to 400 microns, desired filler layers particularly advantageous.

Ebenso ist es möglich, im Mehrschichtaufbau zunächst einen zumindest teilweise strahlungshärtbaren Basislack zu applizieren und zunächst einer IR- und nachfolgend einer UV-Bestrahlung zu unterwerfen. Danach kann ein zumindest teilweise strahlungshärtbarer Klarlack appliziert und wieder zunächst einer IR- und nachfolgend einer UV-Bestrahlung unterworfen werden. Gegebenenfalls kann sich in beiden Fällen eine weitere IR-Bestrahlung an die UV-Bestrahlung anschließen. Die Strahlungshärtung der einzelnen Schichten des Mehrschichtaufbaues sowie der mittels mehrerer Spritzgänge aufgetragenen Schichten kann dabei jeweils mit unterschiedlicher Strahlungsintensität und unterschiedlicher Bestrahlungsdauer für jede Schicht einzeln oder für zwei oder mehrere Schichten gemeinsam erfolgen.Likewise, it is possible in the multilayer structure to first apply an at least partially radiation-curable basecoat and first to subject it to an IR and subsequently to a UV irradiation. Thereafter, an at least partially radiation-curable clearcoat can be applied and again subjected first to IR and subsequently to UV irradiation. Optionally, in both cases, a further IR irradiation can follow the UV irradiation. The radiation curing of the individual layers of the multi-layer structure as well as the layers applied by means of several spray paths can be carried out in each case with different radiation intensity and different irradiation time for each layer individually or for two or more layers together.

Zur erfindungsgemäßen Bestrahlung der lackierten Substratoberflächen ist es beispielsweise möglich, IR-Strahler und UV-Strahler nebeneinander zu positionieren und entsprechend zu schalten oder die Strahler gegebenenfalls wechselseitig vor der zu bestrahlenden Substratoberfläche zu positionieren. Es besteht auch die Möglichkeit einen sogenannten Kombi-Strahler einzusetzen, der IR- und UV-Strahlungsquelle in einem Gerät beinhaltet. Beispielsweise können in letzterem Fall IR- und UV-Lampen in dem Gerät abwechselnd nebeneinander angeordnet sein.For irradiation of the painted substrate surfaces according to the invention, it is possible, for example, to position IR emitters and UV emitters side by side and to switch them accordingly or, if appropriate, to position the emitters mutually in front of the substrate surface to be irradiated. It is also possible to use a so-called combined emitter, which includes IR and UV radiation source in a device. For example, in the latter case, IR and UV lamps can be alternately arranged side by side in the device.

Mit dem erfindungsgemäßen Verfahren können ein oder mehrere zumindest teilweise mittels energiereicher Strahlung aushärtbare Schichten eines üblichen Mehrschichtaufbaus in der Fahrzeuglackierung gehärtet werden. Dabei kann es sich beispielsweise um einen Mehrschichtaufbau aus Grundierung, Füller, Basislack und Klarlack oder aus Grundierung, Füller und Einschichtdecklack handeln. Es können dabei ein oder mehrere Schichten des Mehrschichtaufbaus aus zumindest teilweise strahlungshärtbaren Beschichtungsmitteln erstellt werden.With the method according to the invention, one or more at least partially curable by means of high-energy radiation layers of a conventional multi-layer structure in the vehicle paint can be cured. This may be, for example, a multi-layer structure of primer, filler, basecoat and clearcoat or of primer, filler and monolayer topcoat. In this case, one or more layers of the multi-layer structure can be produced from at least partially radiation-curable coating compositions.

Mit dem erfindungsgemäßen Verfahren werden rißbildungsfreie Beschichtungen mit sehr guter Haftung zum Untergrund und sehr guter Zwischenschichthaftung erhalten. Die applizierten Beschichtungen zeigen eine ausreichende Standfestigkeit und nach Härtung ein einwandfreies optisches Aussehen. Chemikalien-und Bewitterungsbeständigkeit sind sehr gut. Die erhaltenen Beschichtungen zeigen bei hoher Vemetzungsdichte gleichzeitig eine ausreichende Flexibilität. Mit dem erfindungsgemäßen Vefahren erstellte Füllerbeschichtungen sind sehr gut schleifbar.With the method according to the invention, crack-free coatings with very good adhesion to the substrate and very good intercoat adhesion are obtained. The applied coatings show sufficient stability and after curing a perfect optical appearance. Chemical and weathering resistance are very good. The coatings obtained simultaneously show sufficient flexibility at high crosslinking density. Filler coatings produced with the method according to the invention are very easy to sand.

Die Erfindung soll an Hand der folgenden Beispiele näher erläutert werden.The invention will be explained in more detail with reference to the following examples.

Beispiel 1example 1

Zunächst wurde ein mittels UV-Strahlung härtbarer Klarlack hergestellt. Dazu wurden folgende Komponenten miteinander vermischt und mittels Schnellrührer einige Minuten homogenisiert:

  • 55 g eines handelsüblichen OH- und acryloyifünktionellen Bindemittels (Jägalux 5154)
  • 10 g eines handelsüblichen Polyisocyanates (Desmodur N 75)
  • 3,8 g eines handelsüblichen Photoinitiators auf Basis Arylphosphinoxid (Lucirin TPO)
  • 0,5 g eines handelsüblichen Verlaufsmittels (Byketol OK)
  • 2,5 g Butylacetat
First, a UV-curable clearcoat was prepared. For this purpose, the following components were mixed together and homogenized using a high-speed stirrer for a few minutes:
  • 55 g of a commercially available OH and acryloyifunktionellen binder (Jägalux 5154)
  • 10 g of a commercially available polyisocyanate (Desmodur N 75)
  • 3.8 g of a commercially available photoinitiator based on arylphosphine oxide (Lucirin TPO)
  • 0.5 g of a commercial leveling agent (Byketol OK)
  • 2.5 g of butyl acetate

Erstellung eines MehrschichtaufbausCreation of a multi-layer structure

Auf ein durch kathodische Elektrotauchlackierung (KTL) beschichtetes Blech wurde eine Füllerschicht (Bindemittelbasis: 2K-Polyurethan, lösemittelbasierend) in einer resultierenden Trockenfilmschichtdicke von ca. 80 µm aufgebracht und nach kurzer Ablüftzeit bei Raumtemperatur 30 Minuten bei 60°C gehärtet.A filler layer (binder base: 2-component polyurethane, solvent-based) was applied to a cathodic electrodeposition coating (KTL) in a resulting dry film thickness of about 80 microns and cured after a short flash-off time at room temperature for 30 minutes at 60 ° C.

Auf die Füllerschicht wurde ein Wasserbasislack (hergestellt entsprechend DE-A-196 43 802 , Herstellungsbeispiel 4 ) in einer resultierenden Trockenfilmschichtdicke von 13 bis 15 µm appliziert. Nach einer Ablüftphase von 20 Minuten bei Raumtemperatur, wurde der wie vorstehend beschrieben hergestellte mittels UV-Strahlung härtbare Klarlack in einer resultierenden Trockenfilmschichtdicke von 40-50 µm appliziert.On the filler layer was a water-based paint (prepared according to DE-A-196 43 802 , Preparation Example 4) in a resulting dry film thickness of 13 to 15 microns applied. After a flash-off phase of 20 minutes at room temperature, the UV-radiation-curable clearcoat prepared as described above was applied in a resulting dry film thickness of 40-50 μm.

Nach einer Ablüftphase von 5 Minuten bei Raumtemperatur erfolgte eine IR-Bestrahlung des applizierten Klarlackes. Die Bestrahlungszeit betrug 5 Minuten. Anschließend erfolgte die UV-Bestrahlung mit einer UV-Blitzlampe (Leistung 3500 Ws). Die Bestrahlung erfolgte mit 30 Blitzen, die im Abstand von etwa 4 s ausgelöst wurden, bei einem Objektabstand von ca. 20 cm.After a flash-off phase of 5 minutes at room temperature, an IR irradiation of the applied clearcoat took place. The irradiation time was 5 minutes. Subsequently, the UV irradiation was carried out with a UV flash lamp (power 3500 Ws). The irradiation took place with 30 flashes, which were triggered at a distance of about 4 s, with an object distance of about 20 cm.

Beipiel 2Example 2

Es wurde analog Beispiel 1 vorgegangen, nur mit dem Unterschied, daß an die UV-Bestrahlung eine weitere IR-Bestrahlung (5 Minuten Bestrahlungszeit) angeschlossen wurde.The procedure was analogous to Example 1, but with the difference that a further IR irradiation (5 minutes irradiation time) was connected to the UV irradiation.

Vergleichsbeispiel 1Comparative Example 1

Es wurde analog Beispiel 1 vorgegangen mit dem Unterschied, daß nach Applikation des Klarlackes nach einer Ablüftphase von 30 Minuten bei Raumtemperatur direkt die UV-Bestrahlung mit einer UV-Blitzlampe (Leistung 3500 Ws) erfolgte. Die UV-Bestrahlung erfolgte mit 30 Blitzen, die im Abstand von ca. 4 s ausgelöst wurden, bei einem Objektabstand von ca. 20 cm.The procedure was analogous to Example 1 with the difference that after application of the clearcoat after a Ablüftphase of 30 minutes at room temperature directly the UV irradiation with a UV flash lamp (power 3500 Ws) was carried out. The UV irradiation was carried out with 30 flashes, which were triggered at intervals of about 4 s, with an object distance of about 20 cm.

Vergleich der lacktechnischen ErgebnisseComparison of technical results

Beispiel 1example 1 Beispiel 2Example 2 Vgl.-Bsp. 1Comp. 1 Feucht/Warm-Test (1)(2)Wet / warm test (1) (2) 1/11.1 1/11.1 1/33.1 Haftung (3)Liability (3) 0-10-1 11 1-21-2 Haftung (3) nach Feucht/Warm-Test (1)Adhesion (3) after wet / warm test (1) 22 2-32-3 33 Optikoptics i.O.I.O. i.O.I.O. leichte Mikrostrukturlightweight microstructure (1) Feucht/Warm-Test nach DIN 50017
(2) Beurteilung der Blasenbildung nach DIN 53209
(3) Gitterschnitt in Anlehnung an DIN 53151
i.O. in Ordnung(1) Wet / warm test according to DIN 50017
(2) Evaluation of bubble formation according to DIN 53209
(3) cross-hatching in accordance with DIN 53151
OK, okay

Claims (4)

  1. A method of lacquer coating vehicles for repair purposes by the application of one or more primer surface coats and/or coats of further coating media to an optionally precoated substrate, and the subsequent application of a covering lacquer coat comprising a base lacquer/clear lacquer structure or comprising a pigmented single-coat covering lacquer, wherein at least one of the coats of the multi-coat structure is produced from a coating medium which can be at least partially hardened by means of high-energy radiation, characterised in that the application of the coating medium or coating media which can be at least partially hardened by means of high-energy radiation is followed firstly by irradiation with IR radiation and subsequently by irradiation with high-energy radiation, wherein the irradiation with IR radiation can overlap, at least partly, the subsequent irradiation with high-energy radiation, and that the coating medium or coating media which can be at least partially hardened by means of high-energy radiation contains/contain (meth)acryloyl-functional binders which additionally comprise OH groups and polyisocyanates.
  2. A method according to claim 1, characterised in that after the application of the coating media which can be at least partially hardened by means of high-energy radiation, an aeration phase is carried out at room temperature, whereupon irradiation with IR radiation is effected.
  3. A method according to claims 1 or 2, characterised in that a primer surface coat, a pigmented covering lacquer coat, a base lacquer coat and/or a clear lacquer coat is applied as a coat which can be at least partially hardened by high-energy radiation.
  4. A method according to any one of the preceding claims, characterised in that another IR irradiation step is performed following irradiation with high-energy radiation.
EP99962155A 1998-12-16 1999-11-24 Method for multi-layer varnishing Expired - Lifetime EP1152841B2 (en)

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DE19857941 1998-12-16
DE19857941A DE19857941C2 (en) 1998-12-16 1998-12-16 Process for multi-layer painting
PCT/EP1999/009064 WO2000035598A1 (en) 1998-12-16 1999-11-24 Method for multi-layer varnishing

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DE19857940C1 (en) 1998-12-16 2000-07-27 Herberts Gmbh Process for multi-layer painting with radiation-curable coating agents
DE10100170A1 (en) * 2001-01-04 2002-07-11 Basf Ag coating agents
JP5133481B2 (en) * 2001-09-25 2013-01-30 関西ペイント株式会社 Repair painting method
AU2008343024B2 (en) 2007-12-20 2013-10-24 Coatings Foreign Ip Co. Llc Process for producing a multilayer coating
WO2010144903A1 (en) * 2009-06-12 2010-12-16 E. I. Du Pont De Nemours And Company Process for multilayer coating
JP6540178B2 (en) * 2015-04-13 2019-07-10 コニカミノルタ株式会社 Method of manufacturing electrophotographic photosensitive member
PL233241B1 (en) * 2017-09-06 2019-09-30 Politech Spolka Z Ograniczona Odpowiedzialnoscia Method for decoration of cosmetic package elements, made from plastics

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NL7707669A (en) * 1977-07-08 1979-01-10 Akzo Nv METHOD OF COVERING A SUBSTRATE WITH A RADIATION HARDABLE COATING COMPOSITION.
DE4122743C1 (en) * 1991-07-10 1992-11-26 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung Ev, 8000 Muenchen, De
DE4133290A1 (en) * 1991-10-08 1993-04-15 Herberts Gmbh METHOD FOR PRODUCING MULTILAYER LACQUERING USING RADICALLY AND / OR CATIONICALLY POLYMERIZABLE CLEAR VARNISHES
DE4421558C2 (en) * 1994-06-20 2000-02-03 Maximilian Zaher Process for coating metal substrates and metal products coated with the process
DE19533858B4 (en) * 1995-09-13 2005-09-22 IHD Institut für Holztechnologie Dresden gGmbH Process for the electrostatic coating of wood and wood-based materials
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PT1152841E (en) 2002-11-29
EP1152841B1 (en) 2002-06-19
DE59901829D1 (en) 2002-07-25
DK1152841T3 (en) 2002-07-29
ATE219392T1 (en) 2002-07-15
DE19857941C2 (en) 2002-08-29
DE19857941A1 (en) 2000-06-21
CA2347868A1 (en) 2000-06-22
ES2176040T5 (en) 2008-07-01
ES2176040T3 (en) 2002-11-16
CA2347868C (en) 2009-07-14
JP2002532234A (en) 2002-10-02
WO2000035598A1 (en) 2000-06-22

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