EP0964751B1 - Procede de production d'enduits resistants aux egratignures, en particulier des peintures a plusieurs couches - Google Patents

Procede de production d'enduits resistants aux egratignures, en particulier des peintures a plusieurs couches Download PDF

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Publication number
EP0964751B1
EP0964751B1 EP98910675A EP98910675A EP0964751B1 EP 0964751 B1 EP0964751 B1 EP 0964751B1 EP 98910675 A EP98910675 A EP 98910675A EP 98910675 A EP98910675 A EP 98910675A EP 0964751 B1 EP0964751 B1 EP 0964751B1
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EP
European Patent Office
Prior art keywords
coating composition
meth
loss factor
coating
storage modulus
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EP98910675A
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German (de)
English (en)
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EP0964751A1 (fr
Inventor
Peter Betz
Rainer Kleimann
Uwe Meisenburg
Karl-Heinz Joost
Andrea Hesselmaier
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BASF Coatings GmbH
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BASF Coatings GmbH
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • 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
    • B05D7/53—Base coat plus clear coat type
    • B05D7/534—Base coat plus clear coat type the first layer being let to dry at least partially before applying the second layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • 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
    • B05D7/53—Base coat plus clear coat type
    • B05D7/536—Base coat plus clear coat type each layer being cured, at least partially, separately

Definitions

  • the present invention relates to a method for producing scratch-resistant coatings, especially scratch-resistant Coating systems.
  • the present invention also relates to methods suitable for this method Coating agents.
  • This article suggests the scratch resistance of the clear coat by incorporating siloxane macromonomers because these siloxane macromonomers lead to an increased homogeneity of the clear lacquer surface and above 60 ° C for an improved plastic flow to lead.
  • EP-A-540 884 describes a method for producing Multicoat paint systems in particular in the automotive sector Use of free-radically and / or cationically polymerizable, silicone-containing Clear varnishes known, in which the application of the clear varnish under lighting with light of a wavelength of over 550 nm or in the absence of light takes place and then the clearcoat layer using high-energy Radiation is hardened.
  • the surfaces obtained in this way should have a good visual appearance Behavior and have good scratch resistance. Details of the Amount of scratch resistance and information on how the scratch resistance was determined, however, are not included in EP-A-540 884.
  • EP-A-568 967 also describes a process for the preparation of Multicoat paint systems in particular in the automotive sector Use of radiation-curable clearcoats known. According to EP-A-568 In 967, however, it is essential to the invention that in order to achieve Clear lacquer layers with a high optical quality are initially a thermal curing clearcoat and then a radiation-curable clearcoat is applied.
  • the present invention is therefore based on the object of a method for To provide manufacture of scratch-resistant coatings.
  • the coating agents used in this process be a have good storage stability (at least 8 weeks when stored at 50 ° C) and lead to coatings which at the same time lead to a high scratch resistance Chemical resistance, good moisture resistance and good polishability.
  • These coating agents should also be used as a clear coat and / or top coat for the production of a multi-layer coating, especially in the motor vehicle sector, be suitable.
  • the cured coating compositions should be one good weather resistance, good acid / base resistance and good Resistance to bird droppings, etc., a high gloss and a good Appearance.
  • the objective assessment of the scratch resistance of the hardened Coating based on the test method selected physical parameters. This procedure should Determination of the physical parameters can be used practically and with Adequate accuracy is as adequate as possible for the visual assessment Enable characterization of scratch resistance.
  • a method for producing scratch-resistant coatings which is characterized in that a coating agent is used which, after curing, has a storage module E 'in the rubber-elastic range of at least 10 7.6 Pa and a loss factor tan ⁇ at 20 ° C. of at most 0.10, the storage module E 'and the loss factor tan ⁇ having been measured using dynamic mechanical thermal analysis on homogeneous free films with a layer thickness of 40 ⁇ 10 ⁇ m.
  • the present application also relates to the use of the Process for producing a multi-layer coating and for this process suitable coating agents.
  • varnishes that only have one at the test temperature medium or even a small plastic part, but a very high one Have memory module in the rubber-elastic area, nevertheless coatings with a high scratch resistance. It is particularly advantageous that these coating compositions of the invention lead to coatings that at the same time as the high scratch resistance, good polishability, good Moisture resistance, good weather resistance, good chemicals as well Acid / base resistance and high gloss. Furthermore, the invention Coating agent with a good storage stability of 8 weeks Storage at 50 ° C.
  • the coating agent is selected such that the cured coating agent in the rubber-elastic region has a storage modulus E 'of at least 10 7.6 Pa, preferably of at least 10 8.0 Pa, particularly preferably of at least 10 8.3 Pa, and has a loss factor at 20 ° C of a maximum of 0.10, preferably of a maximum of 0.06, the memory module E 'and the loss factor tan ⁇ using dynamic mechanical thermal analysis on homogeneous free films with a layer thickness of 40 ⁇ 10 ⁇ m have been measured.
  • the loss factor tan ⁇ is defined as the quotient of the loss module E "and the memory module E '.
  • Dynamic mechanical thermal analysis is a well known Measuring method for determining the viscoelastic properties of Coatings and described for example in Murayama, T., Dynamic Mechanical Analysis of Polymeric Material, Esevier, New York, 1978 and Loren W. Hill, Journal of Coatings Technology, Vol. 64, No. 808, May 1992, pages 31 to 33rd
  • the measurements can be carried out, for example, using the MK II, MK devices III or MK IV from Rheometrics Scientific.
  • the memory module E 'and the loss factor tan ⁇ are free on homogeneous Films measured.
  • the free films are produced in a known manner by that the coating agent is applied and cured on substrates on which the coating agent is not liable.
  • suitable substrates Glass, Teflon and especially called polypropylene.
  • Polypropylene has the Advantage of good availability and is therefore usually considered Carrier material used.
  • the layer thickness of the free films used for the measurement is generally 40 ⁇ 10 ⁇ m.
  • the special selection of the coating agent based on the value of the memory module in the rubber-elastic range and the loss factor at 20 ° C the cured Coating agent enables the provision of Coating agents with the desired property profile of a good one Scratch resistance with good polishability, chemicals and Moisture resistance as well as weather resistance, because both parameters by simple DMTA measurements can be determined. Furthermore, the resulting Coatings have a high gloss and an acid and base resistance that is comparable to the corresponding values of conventional, thermal hardened paints.
  • the paint surface is covered with a sieve fabric a mass is damaged.
  • the screen mesh and the lacquer surface are thoroughly wetted with a detergent solution.
  • the test board is by means of a motor drive in lifting movements under the screen fabric pushed back.
  • the boards are at least 2 after application of the paints Stored for weeks at room temperature before the test is carried out.
  • the test specimen is made of nylon mesh (No. 11, 31 ⁇ m mesh size, Tg 50 ° C) covered eraser (4.5 x 2.0 cm, wide side perpendicular to the direction of scratching).
  • the coating weight is 2000 g.
  • the direction of rotation is Fabric stitches parallel to the direction of scratching.
  • a pipette approx. 1 ml of one freshly stirred 0.25% Persil solution applied in front of the eraser.
  • the number of revolutions of the motor is set so that 80 in a time of 80 s Double strokes can be carried out.
  • the remaining one Washing liquid rinsed with cold tap water and the test board with Blown compressed air dry.
  • the gloss is measured according to DIN 67530 before and after damage (measuring direction perpendicular to the scratch direction).
  • the coating compositions of the invention have a clear improved scratch resistance in the BASF brush test. This preferably indicates Coating agents according to the invention in the cured state Scratch resistance that the delta gloss value after the BASF brush test of cured coating agent applied over a basecoat maximum 8, is preferably at most 4 and particularly preferably 0.
  • the acid / base resistance is checked using the so-called BART test ( B ASF A CID R ESISTANCE T EST):
  • B ASF A CID R ESISTANCE T EST The above-described steel sheets coated with ETL, filler, basecoat and topcoat are exposed to further temperature loads on a gradient oven (30 min 40 ° C, 50 ° C, 60 ° C and 70 ° C).
  • the test substances sulfuric acid 1%, 10%, 36%; sulfurous acid 6%; hydrochloric acid 10%; sodium hydroxide solution 5%
  • Coating agents with the corresponding viscoelastic properties mentioned above are preferably curable coating agents by means of UV or electron radiation, in particular by means of UV radiation.
  • coating compositions based on Ormocer are also suitable, for example.
  • These radiation-curable coating compositions usually contain at least one, preferably several radiation-curable binders, in particular based on ethylenic unsaturated prepolymer and / or ethylenically unsaturated oligomer, possibly one or more reactive diluents, possibly one or more Photoinitiators and, if applicable, customary auxiliaries and additives,
  • Radiation-curable coating compositions are preferably used, the Viscosity at 23 ° C less than 100 s flow time in a DIN 4 cup, especially preferably less than 80 s run-out time in the DIN 4 cup.
  • the binders used in these radiation-curable coating compositions are, for example, (meth) acrylic-functional (meth) acrylic copolymers, polyether acrylates, polyester acrylates, unsaturated polyesters, epoxy acrylates, urethane acrylates, amino acrylates, melamine acrylates, silicone acrylates and the corresponding methacrylates. It is preferred to use binders which are free from aromatic structural units.
  • the use of epoxy acrylates leads to hard, scratch-resistant coatings, but they generally show weather resistance in need of improvement.
  • Urethane (meth) acrylates and / or polyester (meth) acrylates are therefore preferably used, particularly preferably aliphatic urethane acrylates.
  • Aqueous dispersions of the radiation-curable binders mentioned are also suitable as binders in the coating compositions according to the invention.
  • essentially silicone-free, particularly preferably silicone-free binders are preferably used, since the resulting coating compositions have an improved overcoatability compared to silicone-containing coating compositions.
  • the polymers or oligomers used as binders usually have a number average molecular weight from 500 to 50,000, preferably from 1,000 to 5,000.
  • Polymers are preferred in the coating compositions according to the invention and / or oligomers used, at least 2, especially per molecule preferably have 3 to 6 double bonds.
  • the ones used Binder also has a double bond equivalent weight of 400 to 2,000, particularly preferably from 500 to 900.
  • the binders also prove 23 ° C preferably has a viscosity of 250 to 11,000 mPa.s.
  • Polyester (meth) acrylates are known in principle to the person skilled in the art. you are through different methods can be produced. For example, acrylic acid and / or Methacrylic acid used directly as an acid component in the construction of the polyester become. There is also the possibility of hydroxyalkyl esters Use (meth) acrylic acid as alcohol component directly in the construction of the polyester. However, the polyester (meth) acrylates are preferred by acrylating Polyesters made. For example, those containing hydroxyl groups can initially Polyesters are built up, which are then reacted with acrylic or methacrylic acid become. It is also possible first to build up polyesters containing carboxyl groups be then with a hydroxyalkyl ester of acrylic or methacrylic acid be implemented.
  • Unreacted (meth) acrylic acid can be washed out, Distill or preferably by reacting with an equivalent amount of one Mono- or diepoxide compound using suitable catalysts, such as e.g. Triphenylphosphine, are removed from the reaction mixture.
  • suitable catalysts such as e.g. Triphenylphosphine
  • Polyether (meth) acrylates are also known in principle to the person skilled in the art. They are can be produced by various methods. For example, those containing hydroxyl groups Polyether esterified with acrylic acid and / or methacrylic acid be, by reacting di- and / or polyhydric alcohols with various amounts of ethylene oxide and / or propylene oxide according to well known Methods (see e.g. Houben-Weyl, Volume XIV, 2, Macromolecular Substances II, (1963)) can be obtained. Polymerization products of tetrahydrofuran can also be used or butylene oxide.
  • epoxy (meth) acrylates are also well known to and need for the skilled worker therefore not to be explained in more detail. They are usually made by by adding acrylic acid to epoxy resins, for example to epoxy resins based on bisphenol A or other commercially available epoxy resins.
  • Flexibility of the epoxy (meth) acrylates is analogous, for example possible that corresponding epoxy-functional prepolymers or oligomers with longer-chain, aliphatic dicarboxylic acids, especially aliphatic Dicarboxylic acids with at least 6 carbon atoms, such as adipic acid, Sebacic acid, dodecanedioic acid and / or dimer fatty acids are implemented.
  • This The flexibility reaction can take place before or after the addition of acrylic or Methacrylic acid can be carried out on the oligomers or prepolymers.
  • Urethane (meth) acrylates are also well known to those skilled in the art and require therefore not to be explained in more detail. They can be obtained through Implementation of a di- or polyisocyanate with a chain extender from the group of the diols / polyols and / or diamines / polyamines and / or Dithiols / polythiols and / or alkanolamines and subsequent implementation of the remaining free isocyanate groups with at least one Hydroxyalkyl (meth) acrylate or hydroxyalkyl esters of other ethylenic unsaturated carboxylic acids.
  • the polyurethane acrylates by first a Part of the isocyanate groups of a di- or polyisocyanate with at least one Hydroxyalkyl ester is implemented and the remaining isocyanate groups then reacted with a chain extender. Also in this case, the amounts of chain extender, isocyanate and Hydroxyalkyl esters are chosen so that the equivalent ratio of the NCO groups the reactive groups of the chain extender between 3: 1 and 1: 2, is preferably 2: 1 and the equivalent ratio of the remaining NCO groups to the OH groups of the hydroxyalkyl ester is 1: 1. Of course all intermediate forms of these two processes are also possible.
  • isocyanate groups of a diisocyanate can first be mixed with a diol implemented, then another part of the isocyanate groups with the hydroxyalkyl ester and subsequent to it the rest Isocyanate groups are reacted with a diamine.
  • the urethane (meth) acrylates can be made more flexible, for example, by that corresponding isocyanate-functional prepolymers or oligomers with longer-chain, aliphatic diols and / or diamines, especially aliphatic Diols and / or diamines with at least 6 carbon atoms are implemented. This The flexibility reaction can take place before or after the addition of acrylic or Methacrylic acid can be carried out on the oligomers or prepolymers.
  • the binder is preferably used in the coating compositions according to the invention in an amount of 5 to 90% by weight, particularly preferably 20 to 70% by weight, each based on the total weight of the coating agent in the case of Clear lacquers or the weight of the coating agent without pigments and Fillers used in the case of pigmented systems.
  • the coating compositions according to the invention can optionally also have one or more Contain reactive thinners.
  • the reactive diluents can be ethylenic be unsaturated compounds.
  • the reactive diluents can be mono-, di- or be polyunsaturated. They usually serve to influence the viscosity and the paint properties, such as the crosslink density.
  • the reactive diluent (s) are used in the inventive Coating agents preferably in an amount of 0 to 70 wt .-%, particularly preferably from 15 to 65% by weight, in each case based on the total weight of the coating composition in the case of clear coats or on the weight of the Coating agent without pigments and fillers in the case of pigmented systems, used.
  • Examples of reactive diluents are (meth) acrylic acid and its esters, Maleic acid and its esters or half esters, vinyl acetate, vinyl ether, Vinyl ureas and the like used.
  • Examples include alkylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, Vinyl (meth) acrylate, allyl (meth) acrylate, glycerol tri (meth) acrylate, Trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, styrene, Vinyl toluene, divinylbenzene, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipropylene glycol di (meth) acrylate, hexanediol di (
  • the two acrylate groups can be separated by a polyoxibutylene structure.
  • 1,12-Dodecyl diacrylate and the reaction product of can also be used 2 moles of acrylic acid with one mole of a dimer fatty alcohol, which is generally 36 C atoms. Mixtures of the monomers mentioned are also suitable.
  • Mono- and / or diacrylates such as e.g. Isobornyl acrylate, hexanediol diacrylate, tripropylene glycol diacrylate, Laromer® 8887 from BASF AG and Actilane® 423 from Akcros Chemicals Ltd., GB, used. Isobornyl acrylate, hexanediol diacrylate and Tripropylene glycol diacrylate used.
  • the coating compositions according to the invention optionally contain, preferably in Proportions of 0 to 10 wt .-%, preferably in UV-cured Preparations 2 to 6 wt .-%, based on the weight of the coating agent without pigments and fillers, usual, in radiation-curable coating agents Photoinitiators used, for example benzophenones, benzoins or Benzoin ether, preferably benzophenone in UV preparations. It can too for example those commercially available under the names Irgacure® 184, Irgacure® 1800 and Irgacure® 500 from Ciba Geigy, Grenocure® MBF from Rahn and Products available from Lucirin® TPO from BASF AG are used.
  • the coating compositions of the invention may also contain usual auxiliaries and / or additives, for example light stabilizers (e.g. HALS compounds, benzotriazoles, oxalanilide, etc.), slip additives, Polymerization inhibitors, matting agents, defoamers, leveling agents and film-forming aids, e.g. Cellulose derivatives, or others, in top coats additives usually used.
  • light stabilizers e.g. HALS compounds, benzotriazoles, oxalanilide, etc.
  • slip additives e.g. HALS compounds, benzotriazoles, oxalanilide, etc.
  • Polymerization inhibitors e.g. HALS compounds, benzotriazoles, oxalanilide, etc.
  • matting agents e.g. Cellulose derivatives, or others
  • film-forming aids e.g. Cellulose derivatives, or others
  • the coating compositions according to the invention come in particular as clear lacquers used, so that they usually no or only transparent fillers and does not contain opaque pigments. But it is also the use of pigmented coating agents possible.
  • the Coating agent in this case still 1 to 20 wt .-%, based on the Total weight of the coating agent, one or more fillers included.
  • the coating compositions of the invention can on glass and various metal substrates, such as Aluminum, steel, various Iron alloys, etc., are applied. They are preferred as clear or Topcoat in the field of automotive painting (automobile series and Automotive refinishing) used. Of course they can Coating agent in addition to application on a wide variety of metals also on other substrates, such as wood, paper, plastics, mineral substrates or similar be applied. They are also in the area the coating of packaging containers and in the area of the coating of films for the furniture industry and the like used.
  • the Coating agents according to the invention preferably on primed or with a Base coat coated metal sheets or metal strips applied.
  • Primers can use the primers commonly used become.
  • Both conventional and aqueous basecoats come as basecoats for use.
  • inventive To apply coating agents to metal substrates initially with a Electrocoating and then with a functional layer and wet-in-wet were coated with a basecoat. With the procedures mentioned it is however, generally required that the basecoat and the filler or Functional layer before application of the coating agent according to the invention be branded.
  • the coating compositions of the invention are particularly suitable as Topcoat for producing a multi-layer coating in the field of automotive series and / or automotive refinishing of automobile bodies and their parts as well as truck bodies etc.
  • the coating films are cured by means of radiation, preferably by means of UV radiation.
  • radiation preferably by means of UV radiation.
  • the facilities and conditions for these hardening methods are known from the literature (see e.g. R. Holmes, U.V. and E.B. Curing Formulations for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, United Kindom 1984) and need no further description.
  • the coating compositions 1 to 4 are prepared from the components listed in Table 1 with vigorous stirring using a dissolver or a stirrer. A free film applied over polypropylene with a layer thickness of 40 ⁇ 10 ⁇ m was produced from each of these clearcoats 1 to 4 and examined by means of DMTA. The film is cured with 2 Hg UV lamps. The irradiated dose is approximately 1800 mJ / cm 2 . The viscoelastic parameters of the homogeneous, hardened free films were determined by means of DMTA measurements. The storage module E 'determined in this way in the rubber-elastic range and the loss factor tan ⁇ at 20 ° C. are each given in Table 2.
  • the scratch resistance of the cured coating of these coating compositions of Examples 1 to 4 was determined using the BASF brush test by measuring the drop in gloss.
  • the respective coating agent was burned onto a metal sheet, which had previously been baked with a commercially available electrocoating from BASF Lacke + Maschinen AG, Weg (layer thickness 18-22 ⁇ m), with the commercially available filler Ecoprime 130 from BASF Lacke + Maschinen AG, Weg (30 min 130 ° C; dry film thickness 35 - 40 ⁇ m) and with a commercially available aqueous basecoat from BASF Lacke + Weg (baked 30 min 130 ° C; dry film thickness 20 - 25 ⁇ m), with a dry film thickness of 40 - 45 ⁇ m applied and hardened by means of UV radiation (radiated energy 1800 mJ / cm 2 ).
  • the resulting polymer solution has one Solids content of 62% (determined in a forced air oven at 130 ° C. for 1 h), a Acid number of 9 and a viscosity of 21 dPas (measured on a 60% Dissolving the polymer solution in the aromatic solvent described below Use an ICI-plate-cone viscometer at 23 ° C).
  • the blocked isocyanate 2 is prepared analogously to the preparation of the blocked isocyanates 1 with the only difference that instead of 504.0 g of the hexamethylene diisocyanate trimere now 666.1 g of a commercially available Isocyanurate trimers of isophorone diisocyanate are used.
  • this coating agent V1 became a homogeneous one free film applied over polypropylene with a layer thickness of 40 ⁇ 10 ⁇ m manufactured and examined by means of DMTA (curing conditions 20 min / 140 ° C).
  • Table 2 also shows the storage stability of the coating material and the results of testing the cured coating for Polishability, moisture resistance, acid / base resistance and paintability specified.
  • the scratch resistance of the coating agent V1 cured coating analogous to Example 1 using the BASF brush test determined by measuring the drop in gloss.
  • the coating agent V1 to that described in Example 1 with an electrocoat, filler and metal sheet provided with a basecoat with a dry film layer thickness of 40 - 45 ⁇ m applied and thermally hardened together with the basecoat (20 min 140 ° C).
  • the BASF brush test was then used to determine this overall structure Scratch resistance determined.
  • the ⁇ Glanz values determined are also in Table 2 shown.
  • a coating agent V2 is produced from the following components with intensive stirring using a dissolver or a stirrer: 44.5 parts Novacure 3200 (aliphatic epoxy acrylate from Interorgana) 32.2 parts Ebecryl 264 (aliphatic urethane acrylate from UCB) 3.0 parts Irgacure 184 (photoinitiator from CIBA GEIGY) 10.0 parts Dirpopylenglykoldiacrylat 10.0 parts trimethylolpropane 0.3 parts Ebecryl 350 (silicone acrylate from UCB)
  • this coating agent V2 was used to produce a free film applied over polypropylene with a layer thickness of 40 ⁇ 10 ⁇ m, hardened by means of UV radiation (radiated energy 1800 mJ / cm 2 ) and examined by means of DMTA.
  • the values of the memory module E 'determined in this way in the rubber-elastic range and of the loss factor tan ⁇ at 20 ° C. are shown in Table 2.
  • Table 2 is also the result of testing the cured Coating specified with regard to paintability.
  • the scratch resistance of the cured coating of this coating agent V2 was determined analogously to Example 1 using the BASF brush test by measuring the drop in gloss.
  • the coating agent V2 was applied to the metal sheet described in Example 1, provided with an electrocoat, filler and basecoat, with a dry film thickness of 40-45 ⁇ m and cured by means of UV radiation (radiated energy 1800 mJ / cm 2 ).
  • the scratch resistance of this overall structure was then determined using the BASF brush test.
  • the determined ⁇ gloss values are also shown in Table 2.
  • the initiator mixture is a monomer mixture of 819 g butyl methacrylate, 145 g of methyl methacrylate and 484 g of hydroxypropyl methacrylate within 4 Hours dosed.
  • the reaction mixture kept at 140 ° C for two more hours and then cooled.
  • the resulting polymer solution has a solids content of 60% (determined in a convection oven for 1 h at 130 ° C) and an OH number of 130 (based on Solid content).
  • this coating agent V3 was a free, over Polypropylene applied film with a layer thickness of 40 ⁇ 10 microns and examined using DMTA (curing conditions 20 min / 140 ° C).
  • Table 2 also shows the storage stability of coating material V3 and the results of the test of the cured coating with regard to the Polishability, moisture resistance and chemical resistance specified.
  • the scratch resistance of the coating agent V3 cured coating analogous to Example 1 using the BASF brush test determined by measuring the drop in gloss.
  • the coating agent V3 to that described in Example 1 with an electrocoat, filler and metal sheet provided with a basecoat with a dry film layer thickness of 40 - 45 ⁇ m applied and thermally hardened together with the basecoat (20 min 140 ° C).
  • the BASF brush test was then used to determine this overall structure Scratch resistance determined.
  • the ⁇ Glanz values determined are also in Table 2 shown.
  • the coating agent of comparative example V2 is characterized by a high tan ⁇ at 20 ° C and good scratch resistance, but at the same time poor paintability.
  • the very scratch-sensitive two-component clearcoat (comparative example 3), the but is also characterized by good acid resistance in contrast, a late increase in the tan ⁇ value and a low value of the Storage module E 'in the rubber-elastic area.
  • the coating composition according to the invention is distinguished by a higher storage modulus E 'in the rubber-elastic range of at least 10 7.6 Pa and a later increase in the loss factor tan ⁇ and a correspondingly low tan ⁇ value at 20 ° C. off.
  • This makes it possible to provide a coating agent that leads to coatings with excellent scratch resistance (e.g. little or no scratching in the BASF brush test, ⁇ gloss less than or equal to 8, improved scratch resistance in the AMTEC brush test) with good polishability and good resistance to chemicals and moisture
  • the coating compositions of the invention are distinguished by an improved storage stability compared to the conventional clearcoat of comparative example 1 which has been optimized for scratch resistance.

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

Claims (16)

  1. Composition de revêtement, caractérisée en ce qu'elle présente à l'état durci un module de mémoire E', dans le domaine élastique, d'au moins 107,6 Pa et un facteur de perte tanδ à 20°C d'au maximum 0,10, le module de mémoire E' et le facteur de perte ayant été mesurés par la thermo-analyse dynamique-mécanique sur des feuils libres ayant une épaisseur de couche de 40 ± 10 µm.
  2. Composition de revêtement selon la revendication 1, caractérisée en ce que la composition de revêtement présente à l'état durci un module de mémoire E' dans le domaine élastique d'au moins 108,0 Pa, de préférence d'au moins 108,3 Pa, et/ou un facteur de perte tanδ à 20°C d'au maximum 0,06.
  3. Composition de revêtement selon la revendication 1 ou 2, caractérisée en ce que la composition de revêtement présente à l'état durci une résistance à la rayure telle que la valeur de la différence (Δ) de brillant après l'essai aux brosses BASF de la composition de revêtement durcie, appliquée sur une peinture de base, est égale au maximum à 8, de préférence au maximum à 4, et, de façon particulièrement préférée, égale à 0.
  4. Composition de revêtement selon l'une quelconque des revendications 1 à 3, caractérisée en ce que la composition de revêtement est durcissable par rayonnement UV ou par faisceau d'électrons.
  5. Composition de revêtement selon la revendication 4, caractérisée en ce que la composition de revêtement présente à 23°C une viscosité de moins de 100 s, de préférence de moins de 80 s, de temps d'écoulement dans le godet DIN 4.
  6. Composition de revêtement selon la revendication 4 ou 5, caractérisée en ce que la composition de revêtement contient en tant que liant un ou plusieurs polyester(méth)acrylates et/ou polyuréthanne(méth)acrylates et/ou en ce que le liant utilisé est pratiquement exempt de silicone.
  7. Composition de revêtement selon l'une quelconque des revendications 4 à 6, caractérisée en ce qu'elle contient en tant que diluant réactif un ou plusieurs mono- et/ou diacrylates.
  8. Procédé pour la production de revêtements résistants à la rayure, caractérisé en ce qu'on utilise une composition de revêtement qui, après durcissement, présente un module de mémoire E' dans le domaine élastique d'au moins 107,6 Pa et un facteur de perte tanδ à 20°C d'au maximum 0,10, le module de mémoire E' et le facteur de perte ayant été mesurés par la thermo-analyse dynamique-mécanique sur des feuils libres ayant une épaisseur de couche de 40 ± 10 µm.
  9. Procédé selon la revendication 8, caractérisé en ce que la composition de revêtement à l'état durci présente un module de mémoire E' dans le domaine élastique d'au moins 108,0 Pa, de préférence d'au moins 108,3 Pa, et/ou un facteur de perte tanδ à 20°C d'au maximum 0,06.
  10. Procédé selon la revendication 8 ou 9, caractérisé en ce que la composition de revêtement présente à l'état durci une résistance à la rayure telle que la valeur de la différence (Δ) de brillant selon l'essai aux brosses BASF de la composition de revêtement durcie, appliquée sur une peinture de base est d'au maximum 8, de préférence d'au maximum 4, et, de façon particulièrement préférée, égale à 0.
  11. Procédé selon l'une quelconque des revendications 8 à 10, caractérisé en ce que la composition de revêtement est durcissable par rayonnement UV ou par faisceau d'électrons.
  12. Procédé selon la revendication 11, caractérisé en ce que la composition de revêtement présente à 23°C une viscosité de moins de 100 s, de préférence de moins de 80 s, de temps d'écoulement dans le godet DIN 4.
  13. Procédé selon la revendication 11 ou 12, caractérisé en ce que la composition de revêtement contient en tant que liant un ou plusieurs polyester(méth)acrylates et/ou polyuréthanne(méth)acrylates et/ou en ce que le liant utilisé est pratiquement exempt de silicone.
  14. Procédé selon l'une quelconque des revendications 11 à 13, caractérisé en ce que la composition de revêtement contient en tant que diluant réactif un ou plusieurs mono- et/ou diacrylates.
  15. Procédé pour la production de revêtements de peinture multicouches, dans lequel
    (1) une peinture de base pigmentée est appliquée à la surface d'un subjectile,
    (2) la couche de peinture de base est séchée ou réticulée,
    (3) un vernis transparent de finition est appliqué sur la couche de peinture de base ainsi obtenue, et ensuite
    (4) la couche de vernis de finition est durcie,
    caractérisé en ce qu'on utilise en tant que vernis de finition, une composition de revêtement selon l'une quelconque des revendications 1 à 7.
  16. Procédé selon la revendication 15, caractérisé en ce qu'on l'utilise pour la production de revêtements de peinture multicouches dans le secteur de l'automobile.
EP98910675A 1997-03-07 1998-02-16 Procede de production d'enduits resistants aux egratignures, en particulier des peintures a plusieurs couches Revoked EP0964751B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19709467 1997-03-07
DE19709467A DE19709467C1 (de) 1997-03-07 1997-03-07 Beschichtungsmittel sowie Verfahren zur Herstellung von Mehrschichtlackierungen
PCT/EP1998/000860 WO1998040171A1 (fr) 1997-03-07 1998-02-16 Procede de production d'enduits resistants aux egratignures, en particulier des peintures a plusieurs couches

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Publication Number Publication Date
EP0964751A1 EP0964751A1 (fr) 1999-12-22
EP0964751B1 true EP0964751B1 (fr) 2002-10-02

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EP98910675A Revoked EP0964751B1 (fr) 1997-03-07 1998-02-16 Procede de production d'enduits resistants aux egratignures, en particulier des peintures a plusieurs couches

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US (1) US6261645B1 (fr)
EP (1) EP0964751B1 (fr)
JP (1) JP2001522297A (fr)
KR (1) KR20000076029A (fr)
CN (1) CN1255075A (fr)
AT (1) ATE225214T1 (fr)
AU (1) AU743304B2 (fr)
BR (1) BR9810860A (fr)
CA (1) CA2283419A1 (fr)
DE (2) DE19709467C1 (fr)
ES (1) ES2185152T3 (fr)
PL (1) PL187077B1 (fr)
WO (1) WO1998040171A1 (fr)

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KR20000076029A (ko) 2000-12-26
DE19709467C1 (de) 1998-10-15
WO1998040171A1 (fr) 1998-09-17
DE59805797D1 (de) 2002-11-07
BR9810860A (pt) 2000-09-12
AU743304B2 (en) 2002-01-24
PL335728A1 (en) 2000-05-08
ATE225214T1 (de) 2002-10-15
CA2283419A1 (fr) 1998-09-17
ES2185152T3 (es) 2003-04-16
JP2001522297A (ja) 2001-11-13
US6261645B1 (en) 2001-07-17
PL187077B1 (pl) 2004-05-31
CN1255075A (zh) 2000-05-31
AU6497598A (en) 1998-09-29
EP0964751A1 (fr) 1999-12-22

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