[go: up one dir, main page]

EP1594629B1 - Use of a process for making a multilayer coating for making and/or repairing a (serial) car paint - Google Patents

Use of a process for making a multilayer coating for making and/or repairing a (serial) car paint Download PDF

Info

Publication number
EP1594629B1
EP1594629B1 EP04706659A EP04706659A EP1594629B1 EP 1594629 B1 EP1594629 B1 EP 1594629B1 EP 04706659 A EP04706659 A EP 04706659A EP 04706659 A EP04706659 A EP 04706659A EP 1594629 B1 EP1594629 B1 EP 1594629B1
Authority
EP
European Patent Office
Prior art keywords
coating
quotient
surface energy
acrylates
use according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP04706659A
Other languages
German (de)
French (fr)
Other versions
EP1594629A2 (en
Inventor
Klaus Holzapfel
Peter Mayenfels
Hubert Baumgart
Theodora Dirking
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.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP1594629A2 publication Critical patent/EP1594629A2/en
Application granted granted Critical
Publication of EP1594629B1 publication Critical patent/EP1594629B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/546—No clear coat specified each layer being cured, at least partially, separately
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • 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
    • B05D7/14—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 to metal, e.g. car bodies
    • 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
    • B05D3/08—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 flames
    • 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
    • B05D3/10—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 other chemical means
    • B05D3/107—Post-treatment of applied 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
    • 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
    • B05D3/14—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 electrical means
    • B05D3/141—Plasma treatment
    • 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

Definitions

  • the present invention relates to the use of a method for producing a multi-layer coating, for example multicoat paint system, for the production and / or repair of an automobile (series) coating in which a subsequent coating material (B) is applied to a first coating (A) and cured.
  • a method for producing a multi-layer coating for example multicoat paint system
  • a subsequent coating material (B) is applied to a first coating (A) and cured.
  • the same requirements regarding the properties of a refinish are applied as for the original finish, ie high resistance to atmospheric agents, chemicals and mechanical loads are expected (see above).
  • the repair coatings are a repainting or overpainting of either an example damaged by an accident body of a car or a finish or a complete repainting of an already painted automobile due to paint damage, color differences or other undesirable disturbances in the already applied paint.
  • the paint used for the repair must adhere to the top coat of the original paint finish (standard finish) and wet it completely. In this case, a complex mechanical pretreatment such as grinding should be avoided.
  • the lacquers used can be the lower ones Layer and the upper layer are already coordinated during their production, so that a good wetting and adhesion is usually guaranteed.
  • the refinish must also adhere to the lower layers at the same time, if the overlying layers have flaked off.
  • the curing of the refinish paints must be done at relatively low temperatures, otherwise plastic and rubber parts on the vehicle suffer.
  • the curable with actinic radiation or with actinic and thermal radiation coatings for such tasks would be preferred since their curing can be carried out at low temperatures.
  • Example 10 discloses a method of coating a magnet with a first coating of parylene. This coating is modified prior to application of an acrylic resin coating by a low pressure plasma technique.
  • GB 1 218 042 A discloses a method of coating a tape with a first polyethylene coating. This coating is modified by a corona discharge before applying a second coating.
  • US 4,980,196 A in claims 11 and 12 discloses a method of coating steel with a first organosilane coating. This coating is modified prior to the application of a second coating by a plasma treatment step.
  • US 4,567,106 A discloses a process for coating polyolefin with a coating of polyurethane.
  • the substrate is modified before the application of the coating by a treatment technique (flaming or corona discharge process).
  • the polyethylene substrate may itself be a coating on a metallic substrate.
  • the object of the present invention is therefore the use of a new process for the production of multi-layer coatings for the manufacture and / or repair of an automotive (series) paint available to provide that no longer has the disadvantages of the prior art, but the largely independent of the prevailing conditions, especially as regards temperature and humidity, and also under extreme conditions. In this case, each subsequently applied layer should adhere well to the previous layer and also completely wet it.
  • the repair of the coating by the new method is to be made possible and the repair site thus obtained at high and low temperatures, high and low humidity and under rapidly changing conditions between these extremes, as prevail in the tropical climate and Wüsbenmony, at high radiation intensity and undergo no damage under intense mechanical and chemical stress or a consistent Reparatudacktechnik high quality result, regardless of which of the layers of the multi-layer coating of the used for repair coating material is applied.
  • the novel process should be reliably applicable to the widest possible selection of coatings and coating materials, with particular attention being paid to the coatings or curable coating materials cured with the aid of actinic radiation.
  • a method for producing a multi-layer coating is based on a first coating (A) applying and curing a subsequent coating material (B), wherein the first coating (A) is modified and the coating material (B) is counted such that the quotient (Q) of surface energy of the second coating (B) and surface energy of the first Coating (A) is less than or equal to 1, wherein the quotient (Q) is adjusted by modifying the surface of the coating (A) by reducing the surface energy of the first coating (A) by one or a combination of the methods of low pressure plasma technique, atmospheric pressure plasma technique, Flaming, fluorinating and silicating, and wherein the first coating (A) is a radiation curable binder selected from the group consisting of (meth) acrylic functional (meth) acrylic copolymers, polyether acrylates, polyester acrylates, unsaturated polyesters, epoxy acrylates, urethane acrylates, aminoacrylates, melamine acrylates, silicone acryl
  • the quotient Q is calculated by dividing the surface energy of the second coating (B) by the surface energy of the coating (A).
  • the process according to the invention makes the production of a multilayer coating largely independent of the prevailing conditions, in particular as regards temperature and atmospheric humidity, and can also be used under extreme conditions. In this case, each subsequent applied layer adheres well to the previous layer and wets them completely.
  • the repairability of the coating is improved by the new use.
  • the repair site obtained in this way is stable at high and low temperatures, high and low humidity and rapidly changing conditions between these extremes, as in the tropical climate and in the desert climate and suffers no damage at high radiation intensity and under intense mechanical and chemical stress, but gives a consistent repair coating high Quality regardless of which layer of the multi-layer coating the coating material is applied.
  • the use according to the invention results in the success of overcoating or repair coating since wettability and subsequently adhesion are guaranteed.
  • the painter is instructed by the teaching of the invention namely that he can ensure the success of its coating with respect to wetting and adhesion by the quotient Q to a value less than or equal to 1, preferably less than or equal 0.95, in particular 0.9 sets
  • the adjustment of the quotient Q is carried out by modifying the coating (A) and selecting the coating material (B) as is customarily carried out in the case of a first series coating of basecoat and clearcoat.
  • the coating (A), in particular the surface of the coating (A) is modified because z. B. otherwise creates a different visual impression or a Kochlacklerung is necessary with itself.
  • one or a combination of the following surface treatment methods is used: low-pressure plasma technique, atmospheric pressure plasma technique, flaming, fluorination, silicating.
  • the coating (A) with liquid primers z. B. be treated by dipping, spraying and brushing.
  • the dielectric barrier discharge (corona) can be used for surface treatment.
  • the surface energy of the first coating (A) for adjusting the quotient Q is modified such that it is> 30, preferably> 40 and in particular> 50 mJ / m 2 . Then a particularly good wetting and subsequent adhesion are also achieved.
  • the surface tension is a term for the interfacial tension of solids and liquids against the vapor phase or air. It is defined as force per unit length, has the dimension mN / m and is dimensional and value equal to the surface work that is necessary to either fully form or increase the surface under reversible conditions and isothermal. Under certain conditions, the surface tension corresponds to the free energy of the surface per unit area (Surface energy in mJ / m 2 ).
  • the surface energy of solids can be determined inter alia by determining the contact angle of liquid droplets of known surface tension and polarity and by evaluating the measurements according to Kaelble or Zismann ( Römpp Lexikon Lacke and printing inks, Georg Thieme publishing house Stuttgart, 1998, page 416 "Surface tension”; CD Römpp Chemie Lexikon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995 “Wetting”). Other methods are " Paint Additives ", Johan Bieleman, Weinheim, WILEY-VCH 1998, page 133ff , known.
  • the use can be carried out with the customary coatings and coating materials known to the person skilled in the art. Examples include alkyd resin paints, Dispersons paints, epoxy paints, polyurethane paints and acrylic resin paints.
  • the coating materials can be used in liquid, paste or powder form. Also, no special requirements are placed on the type of application. The coating materials may, for. B. by spraying, knife coating, brushing, pouring, dipping or rolling.
  • actinic radiation cured coatings (A), although they are particularly highly cross-linked, non-polar, non-reactive and inert and therefore difficult to coat without the inventive method.
  • actinic radiation is electromagnetic radiation and corpuscular radiation into consideration
  • the electromagnetic radiation includes near infrared (NIR), visible light, UV radiation, X-rays and gamma rays, in particular UV radiation.
  • the corpuscular radiation comprises Electron radiation, alpha radiation, proton radiation and neutron radiation, in particular electron radiation.
  • Actinic radiation cured coatings (A) are prepared from actinic radiation curable coating materials (A) selected from the group consisting of (meth) acrylic functional (meth) acyl copolymers, polyether acrylates, polyester acrylates, unsaturated polyesters, epoxy acrylates, urethane acrylates, amino acrylates, Melamine acrylates, silicone acrylates and the corresponding methacrylates. Binders are preferably used which are free of aromatic structural units.
  • Such UV-curable coating materials (A) go, for example, from the patents EP-A-0 540 884 .
  • Further examples of such actinic radiation-curable coating materials which are suitable are, for example, from the German patent DE 197 09 467C1 , Page 4, line 30, to page 6, cell 30, or the German patent application DE 199 47 523 A1 known
  • the coating material used (A) in addition to curing with actinic radiation also thermally curable, ie dual-cure, it preferably also contains conventional and known thermally curing binders and crosslinking agents and / or thermally curing reactive diluents, and this example in the German patent applications DE 198 187 735 A1 and DE 199 20 799 A1 or the European patent application EP 0 928 800 A1 is described.
  • thermal curing is understood to mean the heat-initiated curing of a coating material coating which usually employs a separately present crosslinking agent. This is usually referred to by experts as extraneous networking. If the crosslinking agents are already incorporated into the binders, this is also called self-crosslinking. According to the invention, the crosslinking is advantageous and is therefore preferred.
  • the coating materials used to produce the coatings (A) can also be used as coating materials (B). Otherwise it is also possible to use coating materials curable thermally and / or with actinic radiation. Preferably, the coating materials (A) are used.
  • a per se known UV radiation curable lacquer consisting of: 35.31% by weight Ebecryl® 1290 (Hexafunctional aliphatic urethane acrylate) 35.31% by weight Sartomer® 494 (Ethyoxlated pentaerythritol tetraacrylate) 8.65% by weight hydroxypropyl acrylate 0.98% by weight Actilane ® 800 (radiation curing silicone acrylate from Akcros Chemie) 0.14% Dow Corning® PA 57 (silicone additive from Dow Coming) 0.42% by weight Irgacure® 819 (bisacylphosphine photoinitiator) 2.65% by weight Genocure® MBF (photoinitiator) 1.12% by weight Tinuvin® 123 (Aminoether HALS from Ciba Specialty Chemicals) 1.40% by weight Tinuvin® 400 (UV absorber from Ciba Specialty Chemicals) 5.09% by weight methyl acetate 5.72% Butyl acetate
  • a per se known by UV radiation and heat curable lacquer consisting of the following components: Master batch: Methacrylate copolymer a) 9 dipentaerythritol 20 UV absorber (substituted hydroxyphenyltriazine) 1.0 HALS (N-methyl-2,2,6,6-tetramethylpiperidinyl ester) 1.0 Wetting agent (Byk® 306 from Byk Chemie) 0.4 butyl 27.4 Solvent naphtha® 12.8 Irgacure® 184 (commercial photoinitiator from Ciba Specialty Chemicals) 1.0 Lucirin® TPO (commercial photoinitiator BASF AG) 0.5 Total: 100 Crosslinking agent 1: Total: 38.28 Crosslinking agent 1: Isocyanatoacrylate Roskydal® UA VPLS 2337 from Bayer AG (based on trimeric hexamethylene diisocyanate, content of isocyanate groups: 12% by weight) 27.84 Crosslink
  • the metering of the monomer mixture and the initiator solution was started simultaneously. After completion of the Initiatorzulaufs the resulting reaction mixture was heated for a further two hours at 140 ° C with stirring and then cooled.
  • the resulting solution of the methacrylate copolymer (A) was diluted with a mixture of 1-methoxypropylacetate-2, butylglycolacetate and butylacetate. was first at RT for 5 min, then 10 min. at 80 ° C and then 20 min. cured at 140 ° C in an IST Inert plant at 14 m / s with a capacity of 1500 mJ / cm 2 . This resulted in a coating (AII).
  • Both coatings (AI) and (AII) were subjected to a measurement of the contact angle according to the manual of Krüss GmbH, Hamburg, "Drop Shape Analysis” according to the method of Owens, Wendt, Rabel and Kaeble at 23 ° C. and 50% relative humidity the following measuring liquids: H 2 O bidist., 1,5-pentanediol, diiodomethane, ethylene glycol and glycerol, each without and with flame treatment, measuring in each case immediately, after one day or four days. The surface energy was calculated from the determined contact angles.
  • Table 1 lists the contact angles measured on the coatings (AI) and (AII) treated as indicated below. In it is: sample coating 1 AII 5 min. RT, without flame 2 AII, with flame, measurement immediately 3 AII, with flame treatment, measurement after 1 day 4 AII, with flame, measurement after 4 days 5 AI without flaming 6 AI with flame treatment, measurement immediately 7 AI with flame treatment, measurement after 1 day 8th AI with flame treatment, measurement after 4 days
  • the flame treatment was carried out using a type S 4-S 300/2000 automatic flame dispenser manufactured by Friedrich Shufer Maschinenbaugelischaft mbH, Sprendlingen, Germany. with a propane gas flame of 10 cm width from a distance of 10 cm to the substrate in one pass at 150 mm / s feed rate.
  • Table 2 lists the surface energies of the correspondingly treated coatings (AI) and (AII) calculated therefrom.
  • Table 1 contact angle Contact angle [°] sample H 2 O ethylene glycol 1,5-pentanediol CH 2 l 2 glycerin 1 93 ⁇ 0.4 75 ⁇ 0.4 66 ⁇ 0.2 61 ⁇ 0.2 89 ⁇ 1.4 2 42 ⁇ 0.9 16 ⁇ 4.4 19 ⁇ 4,2 39 ⁇ 1.3 43 ⁇ 0.8 3 48 ⁇ 1.3 22 ⁇ 1.7 21 ⁇ 1.6 40 ⁇ 1.9 57 ⁇ 1.4 4 57 ⁇ 1.0 32 ⁇ 1.0 32 ⁇ 1.0 43 ⁇ 0.9 61 ⁇ 1.1 5 96 ⁇ 0.8 84 ⁇ 0.4 77 ⁇ 0.2 70 ⁇ 0.3 96 ⁇ 0.5 6 44 ⁇ 4.6 29 ⁇ 4.3 35 ⁇ 3.7 50 ⁇ 1.3 49 ⁇ 3.3 7 60 ⁇ 9.5 41 ⁇ 2.3 36 ⁇ 1.0 52 ⁇ 1.4
  • the results show an increase in the surface energy of the coatings (AI) and (AII), d. H. the coating (A) by the flame treatment, regardless of whether it was only a curable with actinic radiation or a thermally and UV-curable coating material.
  • the increase is achieved by increasing the polar fraction of the surface energy.
  • Example 2 recoatability of the coating (AI), production of a multiple coating
  • the recoatability of the coating (AI) with itself was checked by means of a cross-cut test in accordance with DIN ISO 2409: 1994-10.
  • the cured paint 1 (coating (AI)) (becomes the coating B) had a surface energy of 19.4 mJ / m 2 .
  • the flame treatment was carried out as indicated above. Now, the surface energy of the coating (AI) (becomes the coating A) was 48.0 mJ / cm 2 .
  • the coating (AI) prepared above was in each case covered with a further layer of lacquer (AI) (coating material (B)) with a layer thickness of 40 + 10 ⁇ m.
  • the curing of the upper layer was carried out, as above, first at RT for 20 min., Then 1 min, with a UV-H 250 hand lamp from Kühnast Strahlenstechnik, Wambatersbach, at a distance of 30 cm and then in an IST Inert plant 14 m / s with an output of 4x500 mJ / m 2 .
  • Example 3 recoatability of the coating (AII), production of a multiple coating
  • the recoatability of the coating (AII) with itself was tested analogously to the preceding Example 2 by means of a cross-cut test in accordance with DIN ISO 2409: 1994-10.
  • the coating (AII) after both as well as without flaming with the paint (AII), ie with itself, painted over.
  • the cured paint All (coating (AII) (becomes the coating B) had a surface tension of 25.1 mJ / m 2 .
  • the coating (AII) prepared above was covered in each case with a further layer of lacquer (AII) (coating material (B)) with a layer thickness of 40 ⁇ 10 ⁇ m.
  • the curing of the upper layer was carried out, as above, first at RT for 5 min., Then 10 min. at 80 ° C and then 20 min. at 140 ° C In an IST inert plant at 14 m / s with a capacity of 1500 mJ / cm 2 .

Landscapes

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

Abstract

Process for producing a multilayer coating, in which a first coating (A) has applied to it a subsequent coating material (B) which is then cured involves selecting and/or modifying the first coating (A) and/or selecting the coating material (B) in such a way that the quotient (Q) formed from the surface energy of the second coating (B) and the surface energy of the first coating (A) is less than or equal to 1, and its use.

Description

Die vorliegende Erfindung betrifft die Verwendung eines Verfahrens zur Herstellung einer Mehrschichtbeschichtung, z B. Mehrschichtlackierung, zur Herstellung und/oder Reparatur einer Automobil (serien) lackierung bei dem auf eine erste Beschichtung (A) ein nachfolgender Beschichtungsstoff (B) aufgebracht und gehärtet wird.The present invention relates to the use of a method for producing a multi-layer coating, for example multicoat paint system, for the production and / or repair of an automobile (series) coating in which a subsequent coating material (B) is applied to a first coating (A) and cured.

Für eine Kraftfahrzeugserienlackierung, insbesondere eine Automobilserienlackierung von hoher Qualität, werden bekanntermaßen Farbe und/oder Effekt gebende Mehrwhichdacklerungen aus Primer, Elektrotauchlackierung, Füllerlackierung oder Steinselagschutzgrundierung, Basislackierung und kariackierung verwendet Die Klariackierungen müssen hohe Anforderungen hinsichtlich der optischen und ästhetischen Eigenschaften (Appearance) sowie der Härte, Kratzfestigkeit, Chemikalienbeständigkeit, Etch-Beständigkeit und Witterungsstabilität erfüllen.For a motor vehicle series painting, in particular a high-quality automotive OEM coating, it is known to use multicolour and / or effect multi-layer dacings of primer, electrodeposition coating, surfacer coat or stone antiscalant primer, base coat and varnish. The varnish finishes must meet high requirements in terms of visual and aesthetic properties (appearance) and hardness , Scratch resistance, chemical resistance, etch resistance and weathering stability.

An eine Reparaturlackierung werden die gleichen Anforderungen in Bezug auf die Eigenschaften gestellt wie an die Serienlackierung, d. h. es werden hohe Beständigkeiten gegen Witterungseinflüsse, Chemikalien und mechanische Belastungen erwartet (vgl. oben). Bei den Reparaturiackierungen handelt es sich um eine Nach- bzw. Überlackierung entweder einer beispielsweise durch einen Unfall beschädigten Stelle eines Automobils oder eine Verlaufslackierung oder eine vollständige Überlackierung eines bereits lackierten Automobils aufgrund von Lackschäden, Farbtonunterschieden oder sonstigen unerwünschten Störungen im bereits aufgebrachten Lack. Der für die Reparatur eingesetzte Lack muss auf der obersten Schicht der ursprünglichen Lackierung (Serienlackierung) haften und diese vollständig benetzen. Dabei soll eine aufwändige mechanische Vorbehandlung wie Anschleifen vermieden werden. Bei der Serienlackierung können die eingesetzten Lacke der unteren Schicht und der oberen Schicht bereits bei deren Herstellung aufeinander abgestimmt werden, so dass eine gute Benetzung und Haftung üblicherweise gewährleistet ist. Eine solche Abstimmung ist bei der Reparatur nicht möglich. Zum einen ist eine Benetzung/Haftung auf der obersten Decklackschicht der Serienlackierung durch den Reparaturlack schwer aufgrund der (benötigten) Eigenschaften der Deckschicht zu erreichen. Diese ist nämlich stark vernetzt, unpolar, nicht reaktiv und inert.The same requirements regarding the properties of a refinish are applied as for the original finish, ie high resistance to atmospheric agents, chemicals and mechanical loads are expected (see above). The repair coatings are a repainting or overpainting of either an example damaged by an accident body of a car or a finish or a complete repainting of an already painted automobile due to paint damage, color differences or other undesirable disturbances in the already applied paint. The paint used for the repair must adhere to the top coat of the original paint finish (standard finish) and wet it completely. In this case, a complex mechanical pretreatment such as grinding should be avoided. In the case of series painting, the lacquers used can be the lower ones Layer and the upper layer are already coordinated during their production, so that a good wetting and adhesion is usually guaranteed. Such a vote is not possible during the repair. On the one hand, wetting / adhesion on the uppermost topcoat of the series finish by the refinish is difficult to achieve due to the (required) properties of the topcoat. It is highly cross-linked, non-polar, non-reactive and inert.

Andererseits muss der Reparaturlack auch gleichzeitig auf den unteren Schichten haften, falls die darüberliegenden Schichten abgeplatzt sind. Hinzu kommt, dass die Härtung der Reparaturlacke bei relativ geringen Temperaturen erfolgen muss, da sonst Kunststoff- und Gummiteile am Fahrzeug leiden. Somit wären die mit aktinischer Strahlung oder mit aktinischer und thermischer Strahlung härtbaren Lacke für solche Aufgaben bevorzugt, da deren Härtung bei niedrigen Temperaturen erfolgen kann.On the other hand, the refinish must also adhere to the lower layers at the same time, if the overlying layers have flaked off. In addition, the curing of the refinish paints must be done at relatively low temperatures, otherwise plastic and rubber parts on the vehicle suffer. Thus, the curable with actinic radiation or with actinic and thermal radiation coatings for such tasks would be preferred since their curing can be carried out at low temperatures.

Auf Grund ihrer besonderen Eigenschaften ist die Anwendung dieser Lacke in der Automobilindustrie besonders erwünscht. Sie weisen einen besonders guten Glanz, eine hohe Härte, eine ausgezeichnete Bewitterungsstabilität und gute Kratzbeständigkeit auf.Due to their special properties, the use of these paints in the automotive industry is particularly desirable. They have a particularly good gloss, high hardness, excellent weathering stability and good scratch resistance.

Allerdings ist der Einsatz dieser Lacke als Serienlacke in der Automobilindustrie bisher erschwert, da die Haftung einer darauf nachfolgend aufzutragenden Lackschicht schlecht ist und eine nur unzureichende Benetzung der mit diesen Lacken hergestellten Beschichtungen erfolgt.However, the use of these paints as series paints in the automotive industry has hitherto been difficult because the adhesion of a subsequently applied lacquer layer is poor and there is only insufficient wetting of the coatings produced with these paints.

Eine gute Benetzung der (unteren) Beschichtung durch den nachfolgend aufgetragenen Beschichtungsstoff und eine anschließende ausgezeichnete Haftung des ausgehärteten Lackes auf der Beschichtung ist jedoch notwendig, um auf der unteren Beschichtung einen weiteren Lack, z. B. Decklack aufzutragen oder um eine Reparaturlackierung durchzuführen und eine dauerhafte Verbindung der Schichten und somit eine Mehrschichtbeschichtung hoher Qualität und Beständigkeit zu erhalten.However, good wetting of the (lower) coating by the subsequently applied coating material and subsequent excellent adhesion of the cured coating to the coating is necessary in order to deposit on the lower coating another coating, e.g. B. apply topcoat or to perform a refinish and to obtain a permanent connection of the layers and thus a multi-layer coating high quality and durability.

Dies gilt auch für Reparaturlackierungen. Insbesondere bei der Reparatur von Mehrschichtlackierungen bestehend aus Primer, Elektrotauchlackierung, Füllerlackierung oder Steinschlagschutzgrundierung, Basislackierung und Klariackierung. So muss z. B. bei einer nur geringfügigen Beschädigung des Klarlacks dieser zur Reparatur mit sich selbst überlackiert werden, wobei es durch die unterschiedlichen Eigenschaften des ausgehärteten Klarlacks und der des noch aufzutragenden flüssigen Klarlacks zu Probleme der Benetzung und der anschließenden Haftung kommt (vgl. oben). Diese Probleme verstärken sich weiter, wenn nicht nur die Klariackierung, sondern noch weitere darunterliegende Schichten abgeplatzt sind und diese zur Erhaltung des optischen Gesamteindrucks ebenfalls repariert bzw. neu aufgebaut werden müssen.This also applies to refinish. In particular, in the repair of multi-layer coatings consisting of primer, electrocoating, surfacer or stone chip protection primer, base coat and Klariackierung. So z. B. in the case of only minor damage to the clearcoat for repair with himself over-painted, whereby it comes through the different properties of the cured clearcoat and the still to be applied liquid clearcoat problems of wetting and subsequent adhesion (see above). These problems continue to increase when not only the Klariackierung, but also more underlying layers have flaked off and this must also be repaired or rebuilt to maintain the overall visual impression.

Aus der EP 0349749A1 ist die Verwendung einer Plasma-Vorbehandlung von lackierten Bauteilen zur Erhöhung der Haftfähigkeit einer nachfolgend aufzubringenden zweiten Lackschicht bekannt. Wie das Verhältnis der Oberflächenspannungen sein soll, wird nicht angegeben. Ferner geht eine Anwendung auf mit aktinischer Strahlung oder mit aktinischer Strahlung und thermisch gehärtete Beschichtungen nicht hervor.From the EP 0349749A1 is the use of a plasma pretreatment of painted components to increase the adhesion of a subsequently applied second coat of paint known. How the ratio of surface tensions should be is not stated. Further, an application to actinic radiation or actinic radiation and thermally cured coatings is not apparent.

Aus DE101 07 613 und De 101 08 723 ist es darüber hinaus bekannt, mittels Beeinflussung der Oberflächenenergie gezielte Oberftachenbeschichtungen durchzuführen.Out DE101 07 613 and De 101 08 723 In addition, it is known to carry out targeted Oberftachenbeschichtung by influencing the surface energy.

US 5,154,978 A offenbart in Beispiel 10 ein Verfahren zur Beschichtung eines Magnets mit einer ersten Beschichtung von Parylene. Diese Beschichtung wird vor dem Auftragen einer Acrylharz-Beschichtung durch eine Niederdruckplasmatechnik modifiziert. US 5,154,978 A in Example 10 discloses a method of coating a magnet with a first coating of parylene. This coating is modified prior to application of an acrylic resin coating by a low pressure plasma technique.

GB 1 218 042 A offenbart ein Verfahren zur Beschichtung eines Bandes mit einer ersten Polyäthylenbeschichtung. Diese Beschichtung wird vor dem Auftragen einer zweiten Beschichtung durch eine Coronaentladung modifiziert. GB 1 218 042 A discloses a method of coating a tape with a first polyethylene coating. This coating is modified by a corona discharge before applying a second coating.

US 4,980,196 A offenbart in Ansprüchen 11 und 12 ein Verfahren zur Beschichtung von Stahl mit einer ersten Organosilanbeschichtung. Diese Beschichtung wird vor dem Auftragen einer zweiten Beschichtung durch einen Plasmabehandlungsschritt modifiziert. US 4,980,196 A in claims 11 and 12 discloses a method of coating steel with a first organosilane coating. This coating is modified prior to the application of a second coating by a plasma treatment step.

US 4,567,106 A offenbart ein Verfahren zur Beschichtung von Polyolefin mit einer Beschichtung von Polyurethan. Das Substrat wird vor dem Auftragen der Beschichtung durch eine Behandlungstechnik (o.a. Beflammen oder Coronaentladungsprozess) modifiziert. Das Polyäthylen-Substrat kann selbst eine Beschichtung auf einem metallischen Substrat sein. US 4,567,106 A discloses a process for coating polyolefin with a coating of polyurethane. The substrate is modified before the application of the coating by a treatment technique (flaming or corona discharge process). The polyethylene substrate may itself be a coating on a metallic substrate.

Aufgabe der vorliegenden Erfindung ist es daher die Verwendung, eines neuen Verfahrens zur Herstellung von Mehrschichtbeschichtungen zur Herstellung und/oder Reparatur einer Automobil (serien) lackierung zur Verfügung zu stellen, das die Nachteile des Standes der Technik nicht mehr aufweist, sondern das weitgehend unabhängig von den herrschenden Bedingungen, insbesondere was Temperatur und Luftfeuchtigkeit betrifft, und auch unter extremen Bedingungen anwendbar ist. Dabei soll jede nachfolgend aufzubringende Schicht auf der vorherigen Schicht gut haften und diese ferner vollständig benetzen.The object of the present invention is therefore the use of a new process for the production of multi-layer coatings for the manufacture and / or repair of an automotive (series) paint available to provide that no longer has the disadvantages of the prior art, but the largely independent of the prevailing conditions, especially as regards temperature and humidity, and also under extreme conditions. In this case, each subsequently applied layer should adhere well to the previous layer and also completely wet it.

Insbesondere soll die Reparatur der Beschichtung durch das neue Verfahren ermöglicht werden und die so erhaltene reparierte Stelle soll bei hohen und niederen Temperaturen, hoher und niedriger Luftfeuchtigkeit sowie unter rasch zwischen diesen Extremen wechselnden Bedingungen, wie sie im Tropenklima und im Wüsbenklima herrschen, bei hoher Strahlungsintensität und bei intensiver mechanischer und chemischer Belastung keine Beschädigung erleiden bzw. eine beständige Reparatudackierung hoher Qualität ergeben, unabhängig davon auf welchen der Schichten der Mehrschichtbeschichtung der zur Reparatur eingesetzte Beschichtungsstoff aufgebracht wird.In particular, the repair of the coating by the new method is to be made possible and the repair site thus obtained at high and low temperatures, high and low humidity and under rapidly changing conditions between these extremes, as prevail in the tropical climate and Wüsbenklima, at high radiation intensity and undergo no damage under intense mechanical and chemical stress or a consistent Reparatudackierung high quality result, regardless of which of the layers of the multi-layer coating of the used for repair coating material is applied.

Insbesondere soll das neue Verfahren zuverlässig bei einer möglichst großen Auswahl an Beschichtungen und Beschichtungsstoffen anwendbar sein, wobei besonderes Augenmerk auf die mit Hilfe von aktinischer Strahlung gehärteten Beschichtungen bzw. härtbaren Beschichtungsstoffe gelegt wurde.In particular, the novel process should be reliably applicable to the widest possible selection of coatings and coating materials, with particular attention being paid to the coatings or curable coating materials cured with the aid of actinic radiation.

Demgemäß wurde die erfindungsgemäße Verwendung eines Verfahrens zur Herstellung einer Mehrschichtbeschichtung gefunden, bei dem man auf eine erste Beschichtung (A) einen nachfolgenden Beschichtungsstoff (B) aufbringt und härtet wird, wobei man die erste Beschichtung (A) modifiziert und den Beschichtungsstoff (B) derart auszählt, dass der Quotient (Q) aus Oberflächenenergie der zweiten Beschichtung (B) und Oberflächenenergie der ersten Beschichtung (A) kleiner oder gleich 1 ist, wobei der Quotient (Q) eingestellt wird, indem die Oberfläche der Beschichtung (A) modifiziert wird, indem die Oberflächenenergie der ersten Beschichtung (A) durch eine oder eine Kombination der Methoden Niederdruckplasmatechnik, Atmosphärendruckplasmatechnik, Beflammen, Fluorieren und Silikatisieren erhöht wird, und wobei die erste Beschichtung (A) ein strahlenhärtbares Bindemittel gewählt aus der Gruppe bestehend aus (meth)acrylfunktionellen (Meth)Acrylcopolymeren, Polyetheracrylaten, Polyesteracrylaten, ungesättigten Polyestern, Epoxyacrylaten, Urethanacrylaten, Aminoacrylaten, Melaminacrylaten, Silikonacrylaten und deren entsprechenden Methacrylaten umfasst.Accordingly, the inventive use of a method for producing a multi-layer coating was found, which is based on a first coating (A) applying and curing a subsequent coating material (B), wherein the first coating (A) is modified and the coating material (B) is counted such that the quotient (Q) of surface energy of the second coating (B) and surface energy of the first Coating (A) is less than or equal to 1, wherein the quotient (Q) is adjusted by modifying the surface of the coating (A) by reducing the surface energy of the first coating (A) by one or a combination of the methods of low pressure plasma technique, atmospheric pressure plasma technique, Flaming, fluorinating and silicating, and wherein the first coating (A) is a radiation curable binder selected from the group consisting of (meth) acrylic functional (meth) acrylic copolymers, polyether acrylates, polyester acrylates, unsaturated polyesters, epoxy acrylates, urethane acrylates, aminoacrylates, melamine acrylates, silicone acrylates and their corresponding methacrylates sst.

Der Quotient Q berechnet sich indem man die Oberflächenenergie der zweiten Beschichtung (B) durch die Oberflächenenergie der Beschichtung (A) teilt.The quotient Q is calculated by dividing the surface energy of the second coating (B) by the surface energy of the coating (A).

Durch die erfindungsgemäße Verwendung ist eine gute Benetzung der unteren Beschichtung (A) durch den nachfolgend aufgetragenen Beschichtungsstoff (B) und eine anschließende ausgezeichnete Haftung der Beschichtung (B) auf der Beschichtung (A) möglich.By the use according to the invention a good wetting of the lower coating (A) by the subsequently applied coating material (B) and a subsequent excellent adhesion of the coating (B) on the coating (A) is possible.

Weiterhin wird durch das erfindungsgemäße Verfahren die Herstellung einer Mehrschichtbeschichtung weitgehend unabhängig von den herrschenden Bedingungen, insbesondere was Temperatur und Luftfeuchtigkeit betrifft und ist auch unter extremen Bedingungen anwendbar. Dabei haftet jede nachfolgend aufzubringende Schicht gut auf der vorherigen Schicht und benetzt diese vollständig.Furthermore, the process according to the invention makes the production of a multilayer coating largely independent of the prevailing conditions, in particular as regards temperature and atmospheric humidity, and can also be used under extreme conditions. In this case, each subsequent applied layer adheres well to the previous layer and wets them completely.

Auch wird die Reparaturfähigkeit der Beschichtung durch die neue Verwendung verbessert. Die so erhaltene reparierte Stelle ist bei hohen und niederen Temperaturen, hoher und niedriger Luftfeuchtigkeit sowie unter rasch zwischen diesen Extremen wechselnden Bedingungen, wie sie im Tropenklima und im Wüstenklima herrschen, haltbar und erleidet bei hoher Strahlungsintensität und bei intensiver mechanischer und chemischer Belastung keine Beschädigung, sondern ergibt eine beständige Reparaturiackierung hoher Qualität unabhängig davon auf welcher Schicht der Mehrschichtbeschichtung der Beschichtungsstoff aufgebracht wird.Also, the repairability of the coating is improved by the new use. The repair site obtained in this way is stable at high and low temperatures, high and low humidity and rapidly changing conditions between these extremes, as in the tropical climate and in the desert climate and suffers no damage at high radiation intensity and under intense mechanical and chemical stress, but gives a consistent repair coating high Quality regardless of which layer of the multi-layer coating the coating material is applied.

Ferner ist durch die erfindungsgemäße Verwendung der Erfolg einer Überlackierung oder Reparaturiackierung gegeben, da eine Benetzbarkeit und anschließend Haftung garantiert wird. Der Lackierer wird durch die erfindungsgemäße Lehre nämlich angeleitet, dass er den Erfolg seiner Lackierung hinsichtlich Benetzung und Haftung sicherstellen kann, indem er den Quotienten Q auf einen Wert kleiner gleich 1, vorzugsweise kleiner gleich 0,95 und insbesondere 0,9 einstelltFurthermore, the use according to the invention results in the success of overcoating or repair coating since wettability and subsequently adhesion are guaranteed. The painter is instructed by the teaching of the invention namely that he can ensure the success of its coating with respect to wetting and adhesion by the quotient Q to a value less than or equal to 1, preferably less than or equal 0.95, in particular 0.9 sets

Die Einstellung des Quotienten Q erfolgt durch Modifizierung der Beschichtung (A) und Auswahl des Beschichtungsstoffs (B) so wie dies üblicherweise bei einer ersten Serienlackierung aus Basislack und Klariack vorgenommen wird.The adjustment of the quotient Q is carried out by modifying the coating (A) and selecting the coating material (B) as is customarily carried out in the case of a first series coating of basecoat and clearcoat.

Zur Einstellung des Quotienten Q wird die Beschichtung (A), insbesondere die Oberfläche der Beschichtung (A) modifiziert, weil z. B. sonst ein anderer optischer Eindruck entsteht oder eine Überlacklerung mit sich selbst nötig ist. Dazu wird eine oder eine Kombination der folgenden Methoden zur Oberflächenbehandlung der eingesetzt : Niederdnrckplasmatechnik, Atmosphärendruckpiasmatechnik, Beflammen, Fluorieren, Silikatisieren.To set the quotient Q, the coating (A), in particular the surface of the coating (A) is modified because z. B. otherwise creates a different visual impression or a Überlacklerung is necessary with itself. For this purpose, one or a combination of the following surface treatment methods is used: low-pressure plasma technique, atmospheric pressure plasma technique, flaming, fluorination, silicating.

Ferner kann die Beschichtung (A) mit flüssigen Primern z. B. durch Tauchen, Besprühen und Bepinseln behandelt werden. Auch kann die dielektrische Barriereentladung (Corona) zur Oberflächenbehandlung verwendet werden.Furthermore, the coating (A) with liquid primers z. B. be treated by dipping, spraying and brushing. Also, the dielectric barrier discharge (corona) can be used for surface treatment.

Die genannten Methoden sind dem Fachmann geläufig und können den nachfolgenden Zitaten entnommen werden ( Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag Stuttgart, 1998, Seite 416 "Oberflächenspannung"), Plasmabehandlung ( Römpp Lexikon Lacke und Druckfarben, . Georg Thieme Verlag Stuttgart, 1998, Seite 455 "Plasmabehandlung", PLASMA-TREAT®, Firmenschrift AGRODYN Hochspannungstechnik GmbH), Beflammen ( Römpp Lexikon Lacke und Druckfarben, Georg Thieme Veriag Stuttgart, 1998, Seite 59 "Beflammen"; Abflammautomat Typ S 4-S 300/2000 der Firma Friedrich Schäfer Maschinenbaugesellschaft mbH, Sprendlingen), Fluorieren ( Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag Stuttgart, 1998, Seite 244 "Fluorieren"), Silikatisieren, Primerbeschichtung ( Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag Stuttgart, 1998, Seite 472 "Primer"), dielektrische Barriereentladung ( Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag Stuttgart, 1998, Seite 117 "Corona".The methods mentioned are familiar to the person skilled in the art and can be taken from the following citations ( Römpp Lexikon Lacke and printing inks, Georg Thieme publishing house Stuttgart, 1998, page 416 "Surface tension"), plasma treatment ( Römpp Lexikon Lacke and printing inks,. Georg Thieme Verlag Stuttgart, 1998, page 455 "Plasma treatment", PLASMA-TREAT®, company publication AGRODYN Hochspannungstechnik GmbH), flaming ( Römpp Lexikon Lacke und Druckfarben, Georg Thieme Veriag Stuttgart, 1998, page 59 "Flaming"; Automatic fire extinguisher type S 4-S 300/2000 of Friedrich Schäfer Maschinenbaugesellschaft mbH, Sprendlingen), fluorination ( Römpp Lexikon Lacke and printing inks, Georg Thieme publishing house Stuttgart, 1998, page 244 "Fluorinating"), silicating, primer coating ( Römpp Lexikon Lacke and printing inks, Georg Thieme publishing house Stuttgart, 1998, page 472 "Primer"), dielectric barrier discharge ( Römpp Lexikon Lacke and Printing inks, Georg Thieme Verlag Stuttgart, 1998, page 117 "Corona".

Bei einer besonders bevorzugten Variante der Verwendung wird die Oberflächenenergie der ersten Beschichtung (A) zur Einstellung des Quotienten Q derart modifiziert, dass sie > 30, bevorzugt > 40 und insbesondere > 50 mJ/m2 beträgt. Dann werden ebenfalls eine besonders gute Benetzung und anschließende Haftung erreicht.In a particularly preferred variant of the use, the surface energy of the first coating (A) for adjusting the quotient Q is modified such that it is> 30, preferably> 40 and in particular> 50 mJ / m 2 . Then a particularly good wetting and subsequent adhesion are also achieved.

Die Oberflächenspannung ist eine Bezeichnung für die Grenzflächenspannung von Feststoffen und Flüssigkeiten gegenüber der Dampfphase bzw. Luft. Sie ist definiert als Kraft pro Längeneinheit, hat die Dimension mN/m und ist dimensions- und wertmäßig gleich der Oberflächenarbeit, die nötig ist, um unter reversiblen Bedingungen und isotherm die Oberfläche entweder über haupt zu bilden oder sie zu vergrößert. Unter bestimmten Bedingungen entspricht die Oberflächenspannung der freien Energie der Oberfläche pro Flächeneinheit (Oberflächenenergie in mJ/m2). Die Oberflächenenergie von Feststoffen kann u. a. durch Bestimmung der Randwinkel von Flüssigkeitstropfen bekannter Oberflächenspannung und Polarität und durch Auswertung der Messungen nach Kaelble oder Zismann ermittelt werden ( Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag Stuttgart, 1998, Seite 416 "Oberflächenspannung"; CD Römpp Chemie Lexikon - Version 1.0, Stuttgart/New York: Georg Thieme Verlag 1995 "Benetzung"). Weitere Verfahren sind aus " Lackadditive", Johan Bieleman, Weinheim, WILEY-VCH 1998, Seite 133ff . bekannt.The surface tension is a term for the interfacial tension of solids and liquids against the vapor phase or air. It is defined as force per unit length, has the dimension mN / m and is dimensional and value equal to the surface work that is necessary to either fully form or increase the surface under reversible conditions and isothermal. Under certain conditions, the surface tension corresponds to the free energy of the surface per unit area (Surface energy in mJ / m 2 ). The surface energy of solids can be determined inter alia by determining the contact angle of liquid droplets of known surface tension and polarity and by evaluating the measurements according to Kaelble or Zismann ( Römpp Lexikon Lacke and printing inks, Georg Thieme publishing house Stuttgart, 1998, page 416 "Surface tension"; CD Römpp Chemie Lexikon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995 "Wetting"). Other methods are " Paint Additives ", Johan Bieleman, Weinheim, WILEY-VCH 1998, page 133ff , known.

Die Verwendung ist mit den üblichen, dem Fachmann bekannten Beschichtungen und Beschichtungsstoffen durchführbar. Beispielhaft genannt seien AIkydharz-Lacke, Dispersons-Lacke, Epoxidharz-Lacke, Polyurethan-Lacke und Acrylharz-Lacke. Die Beschichtungsstoffe können in flüssiger, pasten- oder pulverförmiger Form eingesetzt werden. Auch sind an die Art der Auftragung keine besonderen Anforderungen gestellt. Die Beschichtungsstoffe können z. B. durch Spritzen, Rakeln, Streichen, Gießen, Tauchen oder Walzen aufgebracht werden.The use can be carried out with the customary coatings and coating materials known to the person skilled in the art. Examples include alkyd resin paints, Dispersons paints, epoxy paints, polyurethane paints and acrylic resin paints. The coating materials can be used in liquid, paste or powder form. Also, no special requirements are placed on the type of application. The coating materials may, for. B. by spraying, knife coating, brushing, pouring, dipping or rolling.

Die Verwendung wird mit aktinischer Strahlung gehärteten Beschichtungen (A) durch geführt obwohl diese besonders stark vernetzt, unpolar, nicht reaktiv und inert sind und sich daher ohne das erfindungsgemäße Verfahren nur schwer beschichten lassen.The use is carried out with actinic radiation cured coatings (A), although they are particularly highly cross-linked, non-polar, non-reactive and inert and therefore difficult to coat without the inventive method.

Als aktinische Strahlung kommt elektromagnetische Strahlung und Korpuskularstrahlung in Betracht Die elektromagnetische Strahlung umfasst nahes infrarot (NIR), sichtbares Licht, UV-Strahlung, Röntgenstrahlung und Gammastrahlung, insbesondere UV-Strahlung. Die Korpuskularstrahlung umfasst Elektronenstrahlung, Alphastrahlung, Protonenstrahlung und Neutronenstrahlung, Insbesondere Elektronenstrahlung.
Mit aktinischer Strahlung gehärtete Beschichtungen (A) werden aus mit aktinischer Strahlung härtbaren Beschichtungsstoffen (A) hergestellt, die ausgewählt sind aus der Gruppe bestehend aus (meth)acrylfunktionellen (Meth)Acylcopolymeren, Polyetheracrylaten, Polyesteracrylaten, ungesättigte Polyestern, Epoxyacrylaten, Urethanacrylaten, Aminoacrylaten, Melaminacrylaten, Silikonacrylaten und den entsprechenden Methacrylaten. Bevorzugt werden Bindemittel eingesetzt, die frei von aromatischen Struktureinhelten sind.As actinic radiation is electromagnetic radiation and corpuscular radiation into consideration The electromagnetic radiation includes near infrared (NIR), visible light, UV radiation, X-rays and gamma rays, in particular UV radiation. The corpuscular radiation comprises Electron radiation, alpha radiation, proton radiation and neutron radiation, in particular electron radiation.
Actinic radiation cured coatings (A) are prepared from actinic radiation curable coating materials (A) selected from the group consisting of (meth) acrylic functional (meth) acyl copolymers, polyether acrylates, polyester acrylates, unsaturated polyesters, epoxy acrylates, urethane acrylates, amino acrylates, Melamine acrylates, silicone acrylates and the corresponding methacrylates. Binders are preferably used which are free of aromatic structural units.

Solche UV-härtbaren Beschichtungsstoffe (A) gehen beispielsweise aus den Patentschriften EP-A-0 540 884 , EP-A- 0 568 967 oder US-A-4,675,234 hervor. Weitere Beispiele solcher mit aktinischer Strahlung härtbarer Beschichtungsstoffe, die in Betracht kommen, sind beispielsweise aus dem deutschen Patent DE 197 09 467C1 , Seite 4, Zeile 30, bis Seite 6, Zelle 30, oder der deutschen Patentanmeldung DE 199 47 523 A1 bekanntSuch UV-curable coating materials (A) go, for example, from the patents EP-A-0 540 884 . EP-A-0 568 967 or US-A-4,675,234 out. Further examples of such actinic radiation-curable coating materials which are suitable are, for example, from the German patent DE 197 09 467C1 , Page 4, line 30, to page 6, cell 30, or the German patent application DE 199 47 523 A1 known

Ist der eingesetzte Beschichtungsstoff (A) zusätzlich zu der Härtung mit aktinischer Strahlung auch noch thermisch härtbar, d. h. Dual-Cure-härtbar, enthält sie/er vorzugsweise noch übliche und bekannte thermisch härtende Bindemittel und Vernetzungsmittel und/oder thermisch härtende Reaktiwerdünner, sowie dies beispielsweise in den deutschen Patentanmeldungen DE 198 187 735 A1 und DE 199 20 799 A1 oder der europäischen Patentanmeldung EP 0 928 800 A1 beschrieben wird.If the coating material used (A) in addition to curing with actinic radiation also thermally curable, ie dual-cure, it preferably also contains conventional and known thermally curing binders and crosslinking agents and / or thermally curing reactive diluents, and this example in the German patent applications DE 198 187 735 A1 and DE 199 20 799 A1 or the European patent application EP 0 928 800 A1 is described.

Im Rahmen der vorliegenden Erfindung wird unter "thermische Härtung" die durch Hitze initiierte Härtung einer Schicht aus einem Beschichtungsstoff, bei der üblicherweise ein separat vorliegendes Vernetzungsmittel angewandt wird, verstanden. Üblicherweise wird dies von der Fachwelt als Fremdvernetzung bezeichnet. Sind die Vernetzungsmittel in die Bindemittel bereits eingebaut, spricht man auch von Selbstvernetzung. Erfindungsgemäß ist die Fremdvernetzung von Vorteil und wird deshalb bevorzugt angewandt.In the context of the present invention, the term "thermal curing" is understood to mean the heat-initiated curing of a coating material coating which usually employs a separately present crosslinking agent. This is usually referred to by experts as extraneous networking. If the crosslinking agents are already incorporated into the binders, this is also called self-crosslinking. According to the invention, the crosslinking is advantageous and is therefore preferred.

Die zur Herstellung der Beschichtungen (A) verwendeten Beschichtungsstoffe können auch als Beschichtungsstoffe (B) eingesetzt werden. Ansonsten können auch thermisch und/oder mit aktinischer Strahlung härtbare Beschichtungsstoffe eingesetzt werden. Vorzugsweise werden die Beschichtungsstoffe (A) eingesetzt.The coating materials used to produce the coatings (A) can also be used as coating materials (B). Otherwise it is also possible to use coating materials curable thermally and / or with actinic radiation. Preferably, the coating materials (A) are used.

BeispieleExamples Beispiel1: Herstellung von Beschichtungen (A) und OberflächenspannungsbestimmungExample 1: Preparation of Coatings (A) and Surface Tension Determination

Ein an sich bekannter mittels UV-Strahlung härtbarer Lack (AI), bestehend aus: 35,31 Gew.-% Ebecryl ® 1290 (Hexafunktionales aliphatisches Urethanacriat) 35,31 Gew.-% Sartomer ® 494 (Ethyoxliertes Pentaerythritol Tetraacrylat) 8,65 Gew.% Hydroxypropylacrylat 0,98 Gew.-% Actilane ® 800 (strahlenhärtendes Silikonacrylat der Firma Akcros Chemie) 0,14 Ges.-% Dow Corning ® PA 57 (Silikonadditiv der Firma Dow Coming) 0,42 Gew.-% Irgacure ® 819 (Bisacylphosphin-Photoinitiator) 2,65 Gew.-% Genocure ® MBF (Photoinitiator) 1,12 Gew.-% Tinuvin ® 123 (Aminoether-HALS der Firma Ciba Specialty Chemicals) 1,40 Gew.-% Tinuvin ® 400 (UV-Absorber der Firma Ciba Specialty Chemicals) 5,09 Gew.% Methylacetat 5,72 Ges.-% Buthylacetat 98/100% 3,21 Gew.-% Isopropanol wurde zunächst bei RT 20 min., dann 1 min. mit Handlampe (Handlampe UV-H 250 der Firma Kühnast Strahlungstechnik, Wächtersbach) im Abstand von 30 cm und anschließend in einer IST Inert-Anlage mit 14 m/s mit einer Leistung von 4x500 mJ/cm2 gehärtet. Es resultierte eine Beschichtung (AI).A per se known UV radiation curable lacquer (AI), consisting of: 35.31% by weight Ebecryl® 1290 (Hexafunctional aliphatic urethane acrylate) 35.31% by weight Sartomer® 494 (Ethyoxlated pentaerythritol tetraacrylate) 8.65% by weight hydroxypropyl acrylate 0.98% by weight Actilane ® 800 (radiation curing silicone acrylate from Akcros Chemie) 0.14% Dow Corning® PA 57 (silicone additive from Dow Coming) 0.42% by weight Irgacure® 819 (bisacylphosphine photoinitiator) 2.65% by weight Genocure® MBF (photoinitiator) 1.12% by weight Tinuvin® 123 (Aminoether HALS from Ciba Specialty Chemicals) 1.40% by weight Tinuvin® 400 (UV absorber from Ciba Specialty Chemicals) 5.09% by weight methyl acetate 5.72% Butyl acetate 98/100% 3.21% by weight isopropanol was first at RT 20 min., Then 1 min. with hand lamp (hand lamp UV-H 250 from Kühnast Strahlenstechnik, Wächtersbach) at a distance of 30 cm and then hardened in an IST inert system with 14 m / s with a power of 4x500 mJ / cm 2 . This resulted in a coating (AI).

Ein an sich bekannter mittels UV-Strahlung und Wärme härtbarer Lack (AII), bestehend aus den folgenden Bestandteilen: Stammlack: Methacrylatcopolymerisat a) 9 Dipentaerythritpentaacrylat 20 UV-Absorber (substituiertes Hydroxyphenyltriazin) 1,0 HALS (N-Methyl-2,2,6,6-tetramethylpiperidinylester) 1,0 Netzmittel (Byk ® 306 der Firma Byk Chemie) 0,4 Butylacetat 27,4 Solventnaphtha ® 12,8 Irgacure ® 184 (handelsüblicher Fotoinitiator der Firma Ciba Specialty Chemicals) 1,0 Lucirin ® TPO (handelsüblicher Photoinitiator der Firma BASF AG) 0,5 Summe: 100 Vernetzungsmittel 1: Summe: 38,28 Vernetzungsmittel 1: Isocyanatoacrylat Roskydal ® UA VPLS 2337 der Firma Bayer AG (Basis: Trimeres Hexamethylen-diisocyanat; Gehalt an Isocyanatgruppen: 12 Gew.-%) 27,84 Vernetzungsmittel 2: Isocyanatoacrylat Roskydal ® UA VP FWO 3003-77 der Firma Bayer AG (Basis; Trimeres von Isophorondiisocyanat (70,5 %ig in Butylacetat; Viskosität: 1.500 mPas; Gehalt an Isocyanatgruppen: 6,7 Gew.-%) 6,96 Verdünner 3,48 A per se known by UV radiation and heat curable lacquer (AII), consisting of the following components: Master batch: Methacrylate copolymer a) 9 dipentaerythritol 20 UV absorber (substituted hydroxyphenyltriazine) 1.0 HALS (N-methyl-2,2,6,6-tetramethylpiperidinyl ester) 1.0 Wetting agent (Byk® 306 from Byk Chemie) 0.4 butyl 27.4 Solvent naphtha® 12.8 Irgacure® 184 (commercial photoinitiator from Ciba Specialty Chemicals) 1.0 Lucirin® TPO (commercial photoinitiator BASF AG) 0.5 Total: 100 Crosslinking agent 1: Total: 38.28 Crosslinking agent 1: Isocyanatoacrylate Roskydal® UA VPLS 2337 from Bayer AG (based on trimeric hexamethylene diisocyanate, content of isocyanate groups: 12% by weight) 27.84 Crosslinking agent 2: Isocyanatoacrylate Roskydal® UA VP FWO 3003-77 from Bayer AG (basis; trimer of isophorone diisocyanate (70.5% in butyl acetate, viscosity: 1500 mPas; content of isocyanate groups: 6.7% by weight) 6.96 thinner 3.48

a) Das Methacrylatcopolymerisat wurden nach der folgenden Vorschrift hergestellt:a) The methacrylate copolymer was prepared according to the following procedure:

In einem geeigneten Reaktor, ausgerüstet mit einem Rührer, zwei Tropftrichtern für die Monomermischung und die Initiatorlösung, Stickstoffeinleitungsrohr, Thermometer, Heizung und Rückflußkühler, wurde 650 Gewichtsteile einer Fraktion aromatischer Kohlenwasserstoffe mit einem Siedebereich von 158 bis 172 °C eingewogen. Das Lösemittel wurde auf 140 °C erhitzt. Hiernach wurden eine Monomermischung aus 652 Gewichtsteilen Ethylhexylacrylat, 383 Gewichtsteilen 2-Hydroxyethylmethacrylat, 143 Gewichtsteilen Styrol, 212 Gewichtsteilen 4-Hydroxybutylacrylat und 21 Gewichtsteile Acrylsäure innerhalb von vier Stunden und eine Initiatorlösung aus 113 Gewichtsteilen des aromatischen Lösemittels und 113 Gewichtsteilen test.-Butylperethylhexanoat innerhalb von 4, 5 Stunden gleichmäßig in die Vorlage zudosiert. Mit der Dosierung der Monomermischung und der Initiatorlösung wurde gleichzeitig begonnen. Nach der Beendigung des Initiatorzulaufs wurde die resultierend Reaktionsmischung während weiterer zwei Stunden auf 140 °C unter Rühren erhitzt und anschließend abgekühlt. Die resultierende Lösung des Methacrylatcopolymerisats (A) wurde mit einem Gemisch aus 1-Methoxypropylacetat-2, Butylglykolacetat und Butylacetat verdünnt. wurde zunächst bei RT 5 min., dann 10 min. bei 80 °C und anschließend 20 min. bei 140 °C in einer IST Inert-Anlage mit 14 m/s mit einer Leistung von 1500 mJ/cm2 gehärtet. Es resultierte eine Beschichtung (AII).In a suitable reactor equipped with a stirrer, two dropping funnels for the monomer mixture and the initiator solution, nitrogen inlet tube, thermometer, heater and reflux condenser, 650 parts by weight of a fraction of aromatic hydrocarbons having a boiling range of 158 to 172 ° C was weighed. The solvent was heated to 140 ° C. Thereafter, a monomer mixture of 652 parts by weight of ethylhexyl acrylate, 383 parts by weight of 2-hydroxyethyl methacrylate, 143 parts by weight of styrene, 212 parts by weight of 4-hydroxybutyl acrylate and 21 parts by weight of acrylic acid within four hours and an initiator solution of 113 parts by weight of the aromatic solvent and 113 parts by weight of test butyl peroxyhexanoate within 4, 5 hours evenly dosed into the template. The metering of the monomer mixture and the initiator solution was started simultaneously. After completion of the Initiatorzulaufs the resulting reaction mixture was heated for a further two hours at 140 ° C with stirring and then cooled. The resulting solution of the methacrylate copolymer (A) was diluted with a mixture of 1-methoxypropylacetate-2, butylglycolacetate and butylacetate. was first at RT for 5 min, then 10 min. at 80 ° C and then 20 min. cured at 140 ° C in an IST Inert plant at 14 m / s with a capacity of 1500 mJ / cm 2 . This resulted in a coating (AII).

Beide Beschichtungen (AI) und (AII) wurden einer Messung der Randwinkel nach dem Handbuch der Firma Krüss GmbH, Hamburg, »Drop Shape Analysis« gemäß dem Verfahren von Owens, Wendt, Rabel und Kaeble bei 23 °C und 50% relative Luftfeuchte mit den- folgenden Messflüssigkeiten: H2O bidest., 1,5-Pentandiol, Diiodmethan, Ethylenglykol und Glycerin jeweils ohne und mit Beflammung unterzogen, wobei jeweils sofort, nach einem Tag oder nach vier Tagen gemessen wurde. Die Berechnung der Oberflächenenergie erfolgte aus den ermittelten Randwinkeln.Both coatings (AI) and (AII) were subjected to a measurement of the contact angle according to the manual of Krüss GmbH, Hamburg, "Drop Shape Analysis" according to the method of Owens, Wendt, Rabel and Kaeble at 23 ° C. and 50% relative humidity the following measuring liquids: H 2 O bidist., 1,5-pentanediol, diiodomethane, ethylene glycol and glycerol, each without and with flame treatment, measuring in each case immediately, after one day or four days. The surface energy was calculated from the determined contact angles.

In Tabelle 1 sind die, an den, wie nachfolgend angegeben, behandelten Beschichtungen (AI) und (AII) gemessenen Randwinkel aufgeführt. Darin ist: Probe Beschichtung 1 AII 5 min. RT, ohne Beflammung 2 AII, mit Beflammung, Messung sofort 3 AII, mit Beflammung, Messung nach 1 Tag 4 AII, mit Beflammung, Messung nach 4 Tagen 5 AI ohne Beflammung 6 AI mit Beflammung, Messung sofort 7 AI mit Beflammung, Messung nach 1 Tag 8 AI mit Beflammung, Messung nach 4 Tagen Table 1 lists the contact angles measured on the coatings (AI) and (AII) treated as indicated below. In it is: sample coating 1 AII 5 min. RT, without flame 2 AII, with flame, measurement immediately 3 AII, with flame treatment, measurement after 1 day 4 AII, with flame, measurement after 4 days 5 AI without flaming 6 AI with flame treatment, measurement immediately 7 AI with flame treatment, measurement after 1 day 8th AI with flame treatment, measurement after 4 days

Die Beflammung erfolgte mit einem Abflammautomaten Typ S 4-S 300/2000 der Firma Friedrich Schäfer Maschinenbaugeselischaft mbH, Sprendlingen, mit einer Propangasflamme von 10 cm Breite aus einem Abstand von 10 cm zum Substrat in einem Durchlauf mit 150 mm/s Vorschubgeschwindigkeit.The flame treatment was carried out using a type S 4-S 300/2000 automatic flame dispenser manufactured by Friedrich Schäfer Maschinenbaugelischaft mbH, Sprendlingen, Germany. with a propane gas flame of 10 cm width from a distance of 10 cm to the substrate in one pass at 150 mm / s feed rate.

In. Tabelle 2 sind die daraus berechneten Oberflächenenergien der entsprechend behandelten Beschichtungen (AI) und (AII) aufgeführt. Tabelle 1: Randwinkel Randwinkel [°] Probe H2O Ethylenglykol 1,5-Pentandiol CH2l2 Glycerin 1 93 ± 0,4 75 ± 0,4 66 ± 0,2 61 ± 0,2 89 ± 1,4 2 42 ± 0,9 16 ± 4,4 19 ± 4,2 39 ± 1,3 43 ± 0,8 3 48 ± 1,3 22 ± 1,7 21 ± 1,6 40 ± 1,9 57 ± 1,4 4 57 ± 1,0 32 ± 1,0 32 ± 1,0 43 ± 0,9 61 ± 1,1 5 96 ± 0,8 84 ± 0,4 77 ± 0,2 70 ± 0,3 96 ± 0,5 6 44 ± 4,6 29 ± 4,3 35 ± 3,7 50 ± 1,3 49 ± 3,3 7 60 ± 9,5 41 ± 2,3 36 ± 1,0 52 ± 1,4 55 ± 6,3 8 66 ± 3,1 49 ± 1,2 49 ± 3,7 55 ± 0,8 59 ± 6,4 Tabelle 2: Oberflächenenergien Oberflächenenergie [mJ/m2] Probe Disperser Anteil Polarer Anteil Gesamt 1 23,4 1,7 25,1 2 29,4 22,4 51,8 3 28,9 18,5 47,4 4 29,0 14,2 43,2 5 17,4 2,0 19,4 6 24,0 24,0 48,0 7 6,5 14,7 41,2 8 25,0 12,0 37,0 In. Table 2 lists the surface energies of the correspondingly treated coatings (AI) and (AII) calculated therefrom. Table 1: contact angle Contact angle [°] sample H 2 O ethylene glycol 1,5-pentanediol CH 2 l 2 glycerin 1 93 ± 0.4 75 ± 0.4 66 ± 0.2 61 ± 0.2 89 ± 1.4 2 42 ± 0.9 16 ± 4.4 19 ± 4,2 39 ± 1.3 43 ± 0.8 3 48 ± 1.3 22 ± 1.7 21 ± 1.6 40 ± 1.9 57 ± 1.4 4 57 ± 1.0 32 ± 1.0 32 ± 1.0 43 ± 0.9 61 ± 1.1 5 96 ± 0.8 84 ± 0.4 77 ± 0.2 70 ± 0.3 96 ± 0.5 6 44 ± 4.6 29 ± 4.3 35 ± 3.7 50 ± 1.3 49 ± 3.3 7 60 ± 9.5 41 ± 2.3 36 ± 1.0 52 ± 1.4 55 ± 6.3 8th 66 ± 3.1 49 ± 1.2 49 ± 3.7 55 ± 0.8 59 ± 6.4 Surface energy [mJ / m 2 ] sample Disperser share Polar component total 1 23.4 1.7 25.1 2 29.4 22.4 51.8 3 28.9 18.5 47.4 4 29.0 14.2 43.2 5 17.4 2.0 19.4 6 24.0 24.0 48.0 7 6.5 14.7 41.2 8th 25.0 12.0 37.0

Die Ergebnisse zeigen eine Erhöhung der Oberflächenenergie der Beschichtungen (AI) und (AII), d. h. der Beschichtung (A) durch die Beflammung unabhängig davon, ob es sich nur um einen mit aktinischer Strahlung oder einen thermisch und mit UV-Strahlung härtbaren Beschichtungsstoff handelte. Insbesondere wird die Erhöhung durch Anhebung des polaren Anteiles der Oberflächenenergie erreicht.The results show an increase in the surface energy of the coatings (AI) and (AII), d. H. the coating (A) by the flame treatment, regardless of whether it was only a curable with actinic radiation or a thermally and UV-curable coating material. In particular, the increase is achieved by increasing the polar fraction of the surface energy.

Beispiel2: Überlackierbarkeit der Beschichtung (AI), Herstellung einer MehrfachbeschichtungExample 2: recoatability of the coating (AI), production of a multiple coating

Die Überlackierbarkeit der Beschichtung (AI) mit sich selbst wurde mittels einer Gitterschnittprüfung gemäß DIN ISO 2409:1994-10 überprüft. Dazu wurde die Beschichtung (AI) sowohl nach als auch ohne Beflammung mit dem Lack (AI), d. h. mit sich selbst überlackiert.The recoatability of the coating (AI) with itself was checked by means of a cross-cut test in accordance with DIN ISO 2409: 1994-10. For this purpose, the coating (AI) both after and without flame treatment with the paint (AI), d. H. overpainted with itself.

Die oben angegeben, den UV-härtbaren Lack. (AI) bildenden Komponenten werden unter intensivem Rühren mittels eines Dissolvers oder eines Rührers vermischt, um den entsprechenden Lack (AI) herzustellen. Von diesem Lack (AI) wurde jeweils ein applizierter Film mit einer Schichtdicke von 40 ± 10 µm auf einer geeigneten Prüftafel hergestellt. Die Aushärtung des Films erfolgt zunächst bei RT für 20 min., dann 1 min. mit einer Handlampe UV-H 250 der Firma Kühnast Strahlungstechnik, Wächtersbach, im Abstand von 30 cm und anschließend in einer IST Inert-Anlage mit 14 m/s mit einer Leistung von 4x500 mJ/cm2.The above given, the UV-curable varnish. (AI) forming components are mixed with vigorous stirring by means of a dissolver or a stirrer to produce the corresponding paint (AI). An applied film with a layer thickness of 40 ± 10 μm was produced from this paint (AI) on a suitable test panel. The film is first cured at RT for 20 min, then 1 min. with a UV-H 250 hand-held lamp from Kühnast Strahlenstechnik, Wächtersbach, at a distance of 30 cm and then in an IST inert system at 14 m / s with an output of 4x500 mJ / cm 2 .

Der ausgehärtete Lack 1 (Beschichtung (AI)) (wird zur Beschichtung B) besaß eine Oberflächenenergie von 19,4 mJ/m2.The cured paint 1 (coating (AI)) (becomes the coating B) had a surface energy of 19.4 mJ / m 2 .

Die Beflammung erfolgte, wie vorstehend angegeben. Nun betrug die Oberflächenenergie der Beschichtung (AI) (wird zur Beschichtung A) 48,0 mJ/cm2.The flame treatment was carried out as indicated above. Now, the surface energy of the coating (AI) (becomes the coating A) was 48.0 mJ / cm 2 .

Der Quotient Q = B/A betrug somit 0,41.The quotient Q = B / A was thus 0.41.

Anschließend wurde die oben hergestellte Beschichtung (AI) jeweils mit einer weiteren Schicht Lack (AI) (Beschichtungsstoff (B)) mit einer Schichtdicke von 40 + 10 µm bedeckt. Die Aushärtung der oberen Schicht erfolgte, wie oben, zunächst bei RT für 20 min., dann 1 min, mit einer Handlampe UV-H 250 der Firma Kühnast Strahlungstechnik, Wächtersbach, im Abstand von 30 cm und anschließend in einer IST Inert-Anlage mit 14 m/s mit einer Leistung von 4x500 mJ/m2.Subsequently, the coating (AI) prepared above was in each case covered with a further layer of lacquer (AI) (coating material (B)) with a layer thickness of 40 + 10 μm. The curing of the upper layer was carried out, as above, first at RT for 20 min., Then 1 min, with a UV-H 250 hand lamp from Kühnast Strahlenstechnik, Wächtersbach, at a distance of 30 cm and then in an IST Inert plant 14 m / s with an output of 4x500 mJ / m 2 .

Bei den untersuchten Prüftafeln ohne Beflammen wurden Gitterschnitt-Kennwerte von GT 4 oder GT 5 erhalten. Demgegenüber zeigten die mittels Beflammung behandelten Prüftafeln Gitterschnitt-Kennwerte von GT 0 oder GT 1.Cross-hatch characteristics of GT 4 or GT 5 were obtained in the examined test panels without flaming. In contrast, the test panels treated by flame treatment showed cross-hatch characteristics of GT 0 or GT 1.

Beispiel 3: Überlackierbarkeit der Beschichtung (AII), Herstellung einer MehrfachbeschichtungExample 3: recoatability of the coating (AII), production of a multiple coating

Die Überlackierbarkeit der Beschichtung (AII) mit sich selbst wurde analog zum vorhergehenden Beispiel 2 mittels einer Gitterschnittprüfung gemäß DIN ISO 2409:1994-10 überprüft. Dazu wurde die Beschichtung (AII) sowohl nach als auch ohne Beflammung mit dem Lack (AII), d. h. mit sich selbst, überlackiert.The recoatability of the coating (AII) with itself was tested analogously to the preceding Example 2 by means of a cross-cut test in accordance with DIN ISO 2409: 1994-10. For this purpose, the coating (AII) after both as well as without flaming with the paint (AII), ie with itself, painted over.

Der ausgehärtete Lack All (Beschichtung (AII) (wird zur Beschichtung B) besaß eine Oberflächenspannung von 25,1 mJ/m2.The cured paint All (coating (AII) (becomes the coating B) had a surface tension of 25.1 mJ / m 2 .

Die Beflammung erfolgte wie vorstehend beschrieben. Nun betrug die Oberflächenenergie der Beschichtung (AII) (wird zur Beschichtung A) 51,8 mJ/cm2.
Der Quotient (Q) = B/A betrug somit 0,5.The flame treatment was carried out as described above. Now, the surface energy of the coating (AII) (for coating A) was 51.8 mJ / cm 2 .
The quotient (Q) = B / A was thus 0.5.

Anschließend wurde die oben hergestellte Beschichtung (AII) jeweils mit einer weiteren Schicht Lack (AII) (Beschichtungsstoff (B)) mit einer Schichtdicke von 40 ± 10 µm bedeckt. Die Aushärtung der oberen Schicht erfolgte, wie oben, zunächst bei RT für 5 min., dann 10 min. bei 80 °C und anschließend 20 min. bei 140 °C In einer IST Inert-Anlage mit 14 m/s mit einer Leistung von 1500 mJ/cm2.Subsequently, the coating (AII) prepared above was covered in each case with a further layer of lacquer (AII) (coating material (B)) with a layer thickness of 40 ± 10 μm. The curing of the upper layer was carried out, as above, first at RT for 5 min., Then 10 min. at 80 ° C and then 20 min. at 140 ° C In an IST inert plant at 14 m / s with a capacity of 1500 mJ / cm 2 .

Bei den untersuchten Prüftafeln ohne Beflammen wurden Gitterschnitt-Kennwerte von GT 4 oder GT 5 erhalten. Demgegenüber zeigten die mittels Beflammung behandelten Prüftafeln Gitterschnitt-Kennwerte von GT 0 oder GT 1.Cross-hatch characteristics of GT 4 or GT 5 were obtained in the examined test panels without flaming. In contrast, the test panels treated by flame treatment showed cross-hatch characteristics of GT 0 or GT 1.

Somit wurde gezeigt, dass es überraschenderweise mittels der erfindungsgemäßen Verwendung möglich ist, durch Einstellung des Quotienten Q eine Vorhersage über den Erfolg der Herstellung der Mehrschichtbeschichtung zu treffen.Thus, it has been shown that it is surprisingly possible by means of the use according to the invention to make a prediction about the success of the production of the multilayer coating by setting the quotient Q.

Claims (7)

  1. Use of a process for producing a multilayer coating for producing and/or refinishing an automotive (OEM) finish, in which a first coating (A) has applied to it a subsequent coating material (B) which is then cured, characterized in that the first coating (A) is modified and the coating material (B) is selected in such a way that the quotient (Q) formed from the surface energy of the second coating (B) and the surface energy of the first coating (A) is less than or equal to 1, the quotient (Q) being set by modifying the surface of the coating (A), by raising the surface energy of the first coating (A) by means of one or a combination of the methods low-pressure plasma technology, atmospheric-pressure plasma technology, flaming, fluorinating and silicatization, and the first coating (A) comprising a radiation-curable binder selected from the group consisting of (meth)acryloyl-functional (meth)acrylic copolymers, polyether acrylates, polyester acrylates, unsaturated polyesters, epoxy acrylates, urethane acrylates, amino acrylates, melamine acrylates, silicone acrylates, and the corresponding methacrylates thereof.
  2. Use according to Claim 1, characterized in that the quotient (Q) is set such that it is less than or equal to 0.95.
  3. Use according to any of the preceding claims, characterized in that the quotient (Q) is set such that it is less than or equal to 0.90.
  4. Use according to any of the preceding claims, characterized in that to set the quotient (Q) the surface energy of the first coating (A) is selected or changed such that it is > 30 mi/m2
  5. Use according to any of the preceding claims, characterized in that to set the quotient (Q) the surface energy of the first coating (A) is selected or changed such that it is > 40 mJ/m2.
  6. Use according to any of the preceding claims, characterized in that to set the quotient (Q) the surface energy of the first coating (A) is selected or changed such that it is > 50 mJ/m2
  7. Use according to any of the preceding claims, characterized in that the coating (A) is cured by means of actinic radiation and/or the coating material (B) is curable by means of actinic radiation.
EP04706659A 2003-02-15 2004-01-30 Use of a process for making a multilayer coating for making and/or repairing a (serial) car paint Expired - Lifetime EP1594629B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10306357 2003-02-15
DE10306357A DE10306357B4 (en) 2003-02-15 2003-02-15 Method for producing a multilayer coating and its use
PCT/EP2004/000851 WO2004071678A2 (en) 2003-02-15 2004-01-30 Method for producing a multilayer coating

Publications (2)

Publication Number Publication Date
EP1594629A2 EP1594629A2 (en) 2005-11-16
EP1594629B1 true EP1594629B1 (en) 2009-07-08

Family

ID=32797432

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04706659A Expired - Lifetime EP1594629B1 (en) 2003-02-15 2004-01-30 Use of a process for making a multilayer coating for making and/or repairing a (serial) car paint

Country Status (5)

Country Link
US (1) US7399503B2 (en)
EP (1) EP1594629B1 (en)
AT (1) ATE435708T1 (en)
DE (2) DE10306357B4 (en)
WO (1) WO2004071678A2 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005013975A1 (en) * 2005-03-26 2006-09-28 Krauss-Maffei Kunststofftechnik Gmbh Apparatus and method for the production of optical data carriers and optical data carriers
DE102006021410B4 (en) * 2006-05-09 2009-07-16 Leonhard Kurz Gmbh & Co. Kg Method for producing a multilayer structure and use of the method
DE102009022238A1 (en) * 2009-05-20 2010-11-25 Kraussmaffei Technologies Gmbh Process for the production of plastic molded parts with an integrated conductor track
EP2666544B1 (en) * 2012-05-24 2017-11-01 Vito NV Process for deposition and characterization of a coating
EP3934917B1 (en) * 2019-03-06 2025-06-25 Axalta Coating Systems IP Co. LLC Controlled surface wetting resulting in improved digital print edge acuity and resolution

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1218042A (en) 1968-01-30 1971-01-06 St Annes Board Mill Co Ltd Laminate
JPS60186538A (en) * 1984-03-07 1985-09-24 Dai Ichi Kogyo Seiyaku Co Ltd Primer for polyolefin
US5154978A (en) * 1989-03-22 1992-10-13 Tdk Corporation Highly corrosion-resistant rare-earth-iron magnets
US4980196A (en) * 1990-02-14 1990-12-25 E. I. Du Pont De Nemours And Company Method of coating steel substrate using low temperature plasma processes and priming
US6083628A (en) 1994-11-04 2000-07-04 Sigma Laboratories Of Arizona, Inc. Hybrid polymer film
DE10107613A1 (en) * 2001-02-17 2002-09-05 Kluthe Gmbh Chem Werke Liquid strippable film for protection of newly-painted cars during transport comprises an aqueous dispersion of two different plastics, preferably hard and soft polyester-polyurethane plastics, with no release agent
DE10108723A1 (en) * 2001-02-23 2002-09-12 Messer Griesheim Gmbh Process for the treatment of plastic surfaces
DE10242177A1 (en) 2002-09-10 2004-03-18 Volkswagen Ag Coating a lacquered surface, e.g. for applying scratch-resistant coating to car body part, includes initial corona discharge treatment
DE10245726A1 (en) 2002-10-01 2004-04-15 Bayer Ag Process for producing a scratch-resistant coating system

Also Published As

Publication number Publication date
DE502004009716D1 (en) 2009-08-20
EP1594629A2 (en) 2005-11-16
WO2004071678A3 (en) 2005-04-07
DE10306357A1 (en) 2004-09-02
DE10306357B4 (en) 2006-01-12
US20060083860A1 (en) 2006-04-20
US7399503B2 (en) 2008-07-15
ATE435708T1 (en) 2009-07-15
WO2004071678A2 (en) 2004-08-26

Similar Documents

Publication Publication Date Title
EP1015131B1 (en) Method for producing multi-layer paints
DE60110775T2 (en) Process for repair coating
DE19709560C1 (en) Clearcoat paint composition for wet-in-wet application before stoving
EP0964751B1 (en) Process for producing scratch resistant coatings and its use, in particular for producing multilayered coats of enamel
EP1337350B2 (en) Colour- and/or effect-producing multicoat lacquer, method for production and use thereof
EP1658146B1 (en) Method for producing chromophore and/or effect-producing multilayer varnishes
EP1261524B1 (en) Method for producing multilayer paint coatings on electrically conductive substrates
EP1341833B1 (en) Acrylate-based coating composition containing fluoromodified polymers
EP2342253A1 (en) Scratch- and weather-resistant varnish curable by means of actinic radiation or curable by heat and by means of actinic radiation
DE102004028368A1 (en) Process for producing multicoat color and / or effect paint systems
EP1594629B1 (en) Use of a process for making a multilayer coating for making and/or repairing a (serial) car paint
EP1348001A1 (en) Clear lacquer coat
EP2588545A1 (en) Method for producing a multi-coat colour and/or effect paint system, the colour-forming coating composition comprising a ketone for reducing the pinhole count
EP3325176B1 (en) Method for manufacturing a coating made of a filler and covering varnish layer
EP2245099B1 (en) Aqueous coating material, a method for the production thereof and the use thereof
EP4186951A1 (en) Method for producing a multilayer coating
DE10129660C1 (en) Repairing or double-coating of paintwork on vehicle bodywork or components employs coatings hardened successively by light, with a final heat treatment
DE102012215127A1 (en) Producing color- and/or effect-producing multilayer coating, useful in automobile industry, comprises applying pigmented aqueous basecoat containing e.g. acrylic polymer, on substrate, forming polymer film, applying clear-coat, and curing
DE102010025769A1 (en) Process for the preparation of a color and / or effect multilayer coating
DE4409478C2 (en) Method for producing a decorative multicoat paint system
DE10356034A1 (en) Thermally cured, transparent topcoat, method of manufacture and its use
DE102012209486A1 (en) Producing color and/or effect-imparting multi-layer coating, useful e.g. for increasing needle stick limit, comprises e.g. applying pigmented aqueous basecoat to substrate, forming polymer film, and applying clear coat to basecoat layer

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20050428

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RTI1 Title (correction)

Free format text: USE OF A PROCESS FOR MAKING A MULTILAYER COATING FOR MAKING AND/OR REPAIRING A (SERIAL) CAR PAINT

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 502004009716

Country of ref document: DE

Date of ref document: 20090820

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090708

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20091019

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090708

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090708

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20091008

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20091109

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: BASF COATINGS GMBH

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090708

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090708

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090708

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090708

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090708

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090708

26N No opposition filed

Effective date: 20100409

BERE Be: lapsed

Owner name: BASF COATINGS A.G.

Effective date: 20100131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100131

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20100130

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20100930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100131

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100131

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100201

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20091009

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090708

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090708

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090708

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100130

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100109

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090708

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20170331

Year of fee payment: 14

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502004009716

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180801