EP0964751A1 - 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

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Publication number
EP0964751A1
EP0964751A1 EP98910675A EP98910675A EP0964751A1 EP 0964751 A1 EP0964751 A1 EP 0964751A1 EP 98910675 A EP98910675 A EP 98910675A EP 98910675 A EP98910675 A EP 98910675A EP 0964751 A1 EP0964751 A1 EP 0964751A1
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EP
European Patent Office
Prior art keywords
coating agent
coating
loss factor
coatings
meth
Prior art date
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Application number
EP98910675A
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German (de)
English (en)
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EP0964751B1 (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, in particular scratch-resistant
  • the present invention also relates to coating compositions suitable for this process
  • This article proposes to increase the scratch resistance of the clearcoat coatings by incorporating siloxane macromonomers, since these siloxane macromonomers lead to an increased homogeneity of the clearcoat surface and above 60 ° C. to an improved plastic flow.
  • EP-A-540 884 discloses a process for the production of multi-layer coatings, in particular in the motor vehicle sector, using free-radically and / or cationically polymerizable, silicone-containing clearcoats, in which the clearcoat is applied when illuminated with light of a wavelength of more than 550 nm or in the absence of light and then the clearcoat layer by means of high-energy
  • EP-A-568 967 also discloses a process for producing multi-layer coatings, in particular in the motor vehicle sector, using radiation-curable clearcoats. According to EP-A-568 967, however, it is essential to the invention that, in order to achieve clear lacquer layers with a high optical quality, first a thermally curing clear lacquer and then a radiation-curable clear lacquer are applied.
  • the present invention is therefore based on the object of providing a method for producing scratch-resistant coatings.
  • the coating agents used in this process should at the same time have good storage stability (at least 8 weeks when stored at 50 ° C.) and lead to coatings which, at the same time, have high chemical resistance, good moisture resistance and good polishability in addition to the high scratch resistance.
  • These coating compositions should also be suitable as clearcoat and / or topcoat for producing a multi-layer coating, in particular in the motor vehicle sector.
  • the cured coating compositions should have good weather resistance, good acid / base resistance and good resistance to bird droppings, etc., high gloss and good appearance.
  • the objective assessment of the scratch resistance of the hardened coating should be possible based on physical parameters, regardless of the test method selected. This method should be practically applicable for determining the physical parameters and should enable the character of the scratch resistance to be characterized as adequately as possible with sufficient accuracy.
  • 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 " ° " Pa and a loss factor tan ⁇ at 20 ° C has a maximum of 0, 10, the memory module E 'and the loss factor tan ⁇ using the dynamic mechanical thermal analysis homogeneous free films with a layer thickness of 40 + 10 ⁇ m have been measured.
  • the present application also relates to the use of the process for producing a multilayer coating and to coating compositions suitable for this process.
  • DMTA dynamic mechanical thermal analysis
  • lacquers which have only a medium or even a small plastic portion at the test temperature, but which have a very high storage modulus in the rubber-elastic range, nevertheless produce coatings with a high scratch resistance. It is particularly advantageous that these coating compositions according to the invention lead to coatings which, in addition to the high scratch resistance, have good polishability, good moisture resistance, good weather resistance, good chemical and acid / base resistance and a high gloss. Furthermore, the coating compositions according to the invention have a good storage stability of 8 weeks when stored at 50 ° C.
  • the coating agent is selected so that the cured coating compositions in the gurnrnielastischen area has a storage modulus E 'of at least 10 ⁇ 6 p a preferably at least 10 8> ° Pa, particularly preferably at least l ⁇ 8,3 p a un ( j has a loss factor at 20 ° C.
  • the loss factor tan ⁇ is defined as the quotient of the loss module E "and the storage module E '.
  • Dynamic mechanical thermal analysis is a generally known measurement method for determining the viscoelastic properties of coatings and is 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 33.
  • the measurements can be carried out, for example, using the MK II, MK III or MK IV devices from Rheometrics Scientific.
  • the storage module E 'and the loss factor tan ⁇ are measured on homogeneous free films.
  • the free films are produced in a known manner by applying and curing the coating agent on substrates to which the coating agent does not adhere. Glass, Teflon and in particular polypropylene may be mentioned as examples of suitable substrates. Polypropylene has the
  • the layer thickness of the free films used for the measurement is generally 40 + 10 ⁇ m.
  • the special selection of the coating compositions based on the value of the storage module in the rubber-elastic range and the loss factor at 20 ° C. of the cured coating compositions enables the provision of Coating agents with the desired property profile of good scratch resistance with good polishability, chemical and moisture resistance as well as weather resistance, since both parameters can be determined by simple DMTA measurements.
  • the resulting coatings also have a high gloss and an acid and base resistance that is comparable to the corresponding values of conventional, thermally hardened paints.
  • lacquers which have only a medium or even a small plastic component at the test temperature, but which have a high to very high storage modulus in the rubber-elastic range, also give coatings with a high scratch resistance
  • the varnish surface is damaged with a sieve fabric that is loaded with a mass.
  • the sieve fabric and the varnish surface are adequately wetted with a detergent solution.
  • the test panel is pushed back and forth under the sieve fabric by means of a motor drive
  • an ETL with a layer thickness of 18 - 22 ⁇ m first a filler with a layer thickness of 35 - 40 ⁇ m, then a black basecoat with a layer thickness of 20 - 25 ⁇ m and finally the coating agent to be tested with a layer thickness from 40 - 45 ⁇ m applied and harded in each case
  • test specimen Stored for weeks at room temperature before the test is carried out
  • the test specimen is eraser (4.5 x 2.0 cm, wide side perpendicular to the direction of scratching) covered with nylon sieve mesh (No. 11, 31 ⁇ m mesh size, Tg 50 ° C).
  • the coating weight is 2000 g.
  • the screen mesh is renewed before each test, whereby the running direction of the mesh is parallel to the scratch direction.
  • a pipette approx. 1 ml of a freshly stirred 0.25% Persil solution is applied in front of the eraser.
  • the number of revolutions of the motor is set so that 80 double strokes are carried out in a time of 80 s.
  • the remaining washing liquid is rinsed off with cold tap water and the test panel is blown dry with compressed air.
  • the gloss is measured according to DIN 67530 before and after damage (measuring direction perpendicular to the scratch direction).
  • the coating compositions according to the invention have a significantly improved scratch resistance in the BASF brush test.
  • the coating composition according to the invention preferably has such a scratch resistance that the delta gloss value after the BASF brush test of the cured coating agent applied over a basecoat is a maximum of 8, preferably a maximum of 4 and particularly preferably 0.
  • the acid / base resistance is checked using the so-called BART test (BASF ACID RESISTANCE TEST):
  • Viscoelastic properties are preferably curable by means of UV or electron radiation, in particular by means of UV radiation.
  • coating agents based on Ormoceren are among others. suitable.
  • These radiation-curable coating compositions usually contain at least one, preferably a plurality of radiation-curable binders, in particular based on ethylenically unsaturated prepolymers and / or ethylenically unsaturated oligomers, optionally one or more reactive diluents, optionally one or more photoinitiators and optionally conventional auxiliaries and additives.
  • Radiation-curable coating compositions are preferably used, the viscosity of which at 23 ° C. is less than 100 s run-out time in the DLN 4 cup, particularly preferably less than 80 s run-out time in the DLN 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 a have improved paintability compared to silicone-containing coating agents.
  • the polymers or oligomers used as binders usually have a number average molecular weight of 500 to 50,000, preferably 1,000 to 5,000.
  • Polymers and / or oligomers which have at least 2, particularly preferably 3 to 6, double bonds per molecule are preferably used in the coating compositions according to the invention.
  • the binders used preferably also have a double bond equivalent weight of 400 to 2,000, particularly preferably 500 to 900.
  • the binders at 23 ° C. preferably have a viscosity of 250 to 1,000 mPa.s.
  • Polyester (meth) acrylates are known in principle to the person skilled in the art. They can be produced by various methods. For example, acrylic acid and / or methacrylic acid can be used directly as an acid component in the construction of the polyester. There is also the option of using hydroxyalkyl esters of (meth) acrylic acid as the alcohol component directly in the construction of the polyester.
  • the polyester (meth) acrylates are preferably prepared by acrylating polyesters. For example, polyesters containing hydroxyl groups can first be built up, which are then reacted with acrylic or methacrylic acid. It is also possible first to build up polyesters containing carboxyl groups, which are then reacted with a hydroxyalkyl ester of acrylic or methacrylic acid.
  • Unreacted (meth) acrylic acid can be obtained by washing, distilling, or preferably by reacting with an equivalent amount of a mono- or diepoxide compound using suitable catalysts, e.g. Triphenylphosphine, are removed from the reaction mixture.
  • suitable catalysts e.g. Triphenylphosphine
  • Polyether (meth) acrylates are also known in principle to the person skilled in the art. They can be produced by various methods. For example, hydroxyl group-containing polyethers which are esterified with acrylic acid and / or methacrylic acid, by reacting dihydric and / or polyhydric alcohols with different amounts of ethylene oxide and / or propylene oxide according to well-known methods (see, for example, Houben-Weyl, volume XIV, 2, macromolecules Substances II, (1963)) can be obtained. Polymerization products of tetrahydrofuran or butylene oxide can also be used.
  • the polyether (meth) acrylates and the polyester (meth) acrylates can be made more flexible, for example, by using corresponding OH-functional prepolymers or oligomers (based on polyether or polyester) with longer-chain, aliphatic dicarboxylic acids, in particular aliphatic dicarboxylic acids with at least 6 ° C. -Atoms, such as adipic acid, sebacic acid, dodecanedioic acid and / or dimer fatty acids, are reacted.
  • This flexibilization reaction can be carried out before or after the addition of acrylic or methacrylic acid to the oligomers or prepolymers.
  • epoxy (meth) acrylates are also well known to the person skilled in the art and therefore do not need to be explained in more detail. They are usually produced by adding acrylic acid to epoxy resins, for example to epoxy resins based on bisphenol A or other commercially available epoxy resins.
  • the epoxy (meth) acrylates can be made more flexible, for example, by using corresponding epoxy-functional prepolymers or oligomers with longer-chain, aliphatic dicarboxylic acids, in particular 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 flexibilization reaction can be carried out before or after the addition of acrylic or methacrylic acid to the oligomers or prepolymers.
  • Urethane (meth) acrylates are also well known to the person skilled in the art and therefore do not need to be explained in more detail. They can be obtained by reacting 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 reaction of the remaining free isocyanate groups with at least one
  • chain extender di- or polyisocyanate and hydroxyalkyl ester
  • the polyurethane acrylates by first reacting some of the isocyanate groups of a di- or polyisocyanate with at least one hydroxyalkyl ester and then reacting the remaining isocyanate groups with a chain-lengthening agent.
  • the amounts of chain-lengthening agent, isocyanate and hydroxyalkyl ester are so chosen that the equivalent ratio of the NCO groups to the reactive groups of the chain extender between 3 1 and 1 2, preferably at 2.
  • the urethane (meth) acrylates can be made more flexible, for example, by reacting corresponding isocyanate-functional prepolymers or oligomers with longer-chain, aliphatic diols and / or diamines, in particular aliphatic diols and / or diamines with at least 6 carbon atoms.
  • This flexibilization reaction can be carried out before or after the addition of acrylic or methacrylic acid to the oligomers or prepolymers.
  • the binder is used in the coating compositions according to the invention preferably in an amount of 5 to 90% by weight, particularly preferably 20 to 70% by weight, in each case based on the total weight of the coating composition in the case of clearcoats or on the weight of the coating composition without Pigments and fillers are used in the case of pigmented systems.
  • the coating compositions of the invention may optionally also contain one or more reactive diluents.
  • the reactive diluents can be ethylenically unsaturated compounds.
  • the reactive diluents can be mono-, di- or polyunsaturated. They usually serve to influence the viscosity and the paint properties, such as the crosslinking density.
  • the reactive diluent (s) in the coating compositions according to the invention are preferably present in an amount of 0 to 70% by weight, particularly preferably 15 to 65% by weight, in each case based on the total weight of the coating composition in the case of clearcoats or on the weight of the coating agent without pigments and fillers in the case of pigmented systems.
  • reactive diluents are (meth) acrylic acid and its esters, maleic acid and its esters or half-esters, vinyl acetate, vinyl ether, vinyl ureas and others. used.
  • examples include alkylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate,
  • the two acrylate groups can be separated by a polyoxibutylene structure. It is also possible to use 1, 12-dodecyl diacrylate and the reaction product of 2 moles of acrylic acid with one mole of a dimer fatty alcohol, which generally has 36 carbon atoms. Mixtures of the monomers mentioned are also suitable.
  • Preferred reactive diluents are 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. Isobornyl acrylate, hexanediol diacrylate and tripropylene glycol diacrylate are particularly preferably used.
  • the coating compositions according to the invention optionally contain, preferably in proportions of 0 to 10% by weight, preferably in preparations cured by means of UV rays, 2 to 6% by weight, based on the weight of the coating composition
  • customary photoinitiators used in radiation-curable coating agents for example benzophenones, benzoins or benzoin ethers, preferably benzophenone in UN preparations Ciba Geigy, Grenocure® MBF from Rahn and Lucirin® TPO from BASF AG
  • the coating compositions according to the invention optionally also contain customary auxiliaries and / or additives, for example light stabilizers (for example HALS compounds, benzotriazoles, oxalanilide etc.), slip additives, polymerization inhibitors, matting agents, defoamers, leveling agents and film-forming auxiliaries, for example cellulose derivatives, or others Additives usually used in topcoats These customary auxiliaries and / or additives are usually used in an amount of up to 15% by weight, preferably 2 to 9% by weight, based on the weight of the coating composition without pigments and without fillers
  • customary auxiliaries and / or additives for example light stabilizers (for example HALS compounds, benzotriazoles, oxalanilide etc.), slip additives, polymerization inhibitors, matting agents, defoamers, leveling agents and film-forming auxiliaries, for example cellulose derivatives, or others Additives usually used in topcoats
  • the coating compositions of the invention are used in particular as clear lacquers, so that they usually contain no or only transparent fillers and no opaque pigments. However, use in the form of pigmented coating compositions is also possible.
  • the coating compositions contain 2 to 40% by weight, based on based on the total weight of the coating agent, one or more pigments.
  • the coating agents may also contain 1 to 20% by weight, based on the total weight of the coating agent, of one or more fillers
  • the coating compositions according to the invention can be applied to glass and a wide variety of metal substrates, such as aluminum, steel, various iron alloys and the like. They are preferred as clear or topcoat in the field of automotive painting (automobile series and
  • the coating compositions can also be applied to other substrates, such as wood, paper, plastics, mineral substrates or the like. They are also in the field the coating of packaging containers and in the field of coating films for the furniture industry, among others.
  • the coating compositions according to the invention are preferably applied to primed metal sheets or metal strips or coated with a basecoat.
  • the primers commonly used can be used as primers.
  • Both conventional and aqueous basecoats are used as the basecoat.
  • the present invention therefore also relates to a process for the production of multi-layer coatings, in which
  • a coating agent according to the invention is used as the topcoat.
  • the coating compositions according to the invention are suitable as topcoats for producing a multi-layer coating in the field of motor vehicles.
  • the coating films are cured by means of radiation, preferably by means of UV radiation.
  • radiation preferably by means of UV radiation.
  • the systems and conditions for these curing methods are known from the literature (see, for example, R. Holmes, UV and EB Curing Formulations for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, United Kindom 1984) and do not require any 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 clear coats 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 ⁇ .
  • 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 that 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 + Maschinen AG, Munster (baked for 30 min 130 ° C, dry film thickness 20 - 25 ⁇ m) was coated, applied with a dry film thickness of 40 - 45 ⁇ m and hardened by UV radiation (radiated energy 1800 mJ / cm ⁇ )
  • a monomer mixture of 1 108 g of ethyl hexyl acrylate, 55 g of styrene, 404 g of 4-hydroxibutyl acrylate and 16 g of acrylic acid are added within 4 hours, and an initiator solution of 63 g of t-butyl perethyl hexanoate 95 g of the aromatic solvent described are metered uniformly into the reactor over the course of 4.5 hours.
  • the metering of the monomer mixture and the initiator solution is started simultaneously. After the initiator metering has ended, the reaction mixture is kept at 140 ° C. for two hours and then cooled.
  • the resulting polymer solution has a solids content of 62% (best immed in a convection oven at 130 ° C for 1 h), an acid number of 9 and a viscosity of 21 dPas (measured on a 60% solution of the polymer solution in the aromatic solvent described, using an ICI plate cone viscometer at 23 ° C)
  • the blocked isocyanate 2 is prepared analogously to the preparation of the blocked isocyanate 1 with the only difference that instead of 504.0 g of the hexamethylene diisocyanate trimers, 666.1 g of a commercially available isocyanurate trimer of isophorone diisocyanate are now used.
  • the transparent topcoat is produced by weighing acrylate resin, isocyanate 1, isocyanate 2 and aminoplast resin in the order given below and mixing well by stirring with a laboratory turbine stirrer, then adding the first amount of xylene and also stirring well.
  • the UV absorber and the radical scavenger are separately premixed with (the second amount) xylene until they are completely dissolved and then added to the first part of the formulation and likewise stirred well. Then n-butanol and the leveling agent are added and mixed in well.
  • the paint obtained is optionally adjusted for application with xylene to a viscosity of 23 seconds, measured in a DIN-4 cup at 20 ° C.
  • this coating agent VI was used to produce a homogeneous free film applied over polypropylene with a layer thickness of 40 + 10 ⁇ m and examined by means of DMTA (curing conditions 20 min / 140 ° C.).
  • Table 2 also shows the storage stability of the coating composition and the results of the test of the cured coating with regard to polishability, moisture resistance, acid / base resistance and ability to be repacked.
  • the scratch resistance of the cured coating of this coating agent VI was determined analogously to Example 1 using the BASF brush test by measuring the drop in gloss.
  • coating agent VI 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 thermally cured together with the basecoat (20 min 140 ° C.).
  • 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.
  • a coating agent V2 is produced from the following components with intensive stirring using a dissolver or a stirrer
  • Irgacure 184 photoinitiator from CIBA GEIGY
  • 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 ⁇ ) and by means of
  • the scratch resistance of the hardened coating of this coating agent V2 was determined analogously to example 1 with the help of the BASF brush test by measuring the drop in gloss.
  • the coating agent V2 was applied to the metal sheet described in example 1, which was provided with an electrocoat, filler and a basecoat and had a dry film layer thickness from 40 - 45 ⁇ m applied and hardened by means of UV radiation (radiated energy 1800 mJ / cm ⁇ ).
  • the scratch resistance of this total structure was then determined by means of the BASF brush test.
  • the ⁇ gloss values determined are also shown in Table 2
  • a monomer mixture of 819 g of butyl methacrylate, 145 g of methyl methacrylate and 484 g of hydroxypropyl methacrylate is metered in over the course of 4 hours.
  • the reaction mixture is kept at 140 ° C. for a further two hours and then cooled.
  • the resulting polymer solution has a solids content of 60% (determined in a forced air oven at 130 ° C. for 1 h) and an OH number of 130 (based on the solids content).
  • the transparent topcoat is produced by weighing the acrylic resin and mixing it well by stirring with a laboratory turbine stirrer, then adding the solvents other than xylene and the leveling agent and also stirring them in well.
  • the UV absorber and the radical scavenger are separately premixed with xylene until they are completely dissolved and then added to the first part of the formulation and also stirred well.
  • the isocyanate is added shortly before application.
  • the paint obtained is optionally adjusted for application with xylene to a viscosity of 23 seconds, measured in a DIN-4 cup at 20 ° C.
  • leveling agent 5% solution of a polyether substituted
  • Table 2 also shows the storage stability of coating agent V3 and the results of the test of the hardened coating with regard to polishability, moisture resistance and chemical resistance.
  • the scratch resistance of the cured coating of this coating agent V3 was determined analogously to Example 1 using the BASF brush test by measuring the drop in gloss.
  • the coating agent V3 was applied to the metal sheet described in Example 1, provided with an electrocoat, filler and a basecoat, with a dry film thickness of 40-45 ⁇ m and thermally cured together with the basecoat (20 min 140 ° C.).
  • 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 high scratch resistance of the conventional clearcoat (comparative example 1) optimized for scratch resistance is achieved with an early increase in the tan ⁇ value.
  • this has other disadvantages, e.g. lower storage stability, poor polishability and poor chemical resistance.
  • the coating composition of comparative example V2 is distinguished by a high tan ⁇ value at 20 ° C. and by good scratch resistance, but at the same time by poor ability to be repacked.
  • the very scratch-sensitive two-component clearcoat (comparative example 3), which is also characterized by good acid resistance, on the other hand, shows a late increase in the tan ⁇ value and a low value of the storage module E 'in the rubber-elastic range.
  • the coating composition according to the invention is distinguished by a higher storage module E 'in the rubber-elastic range of at least 10'> 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.
  • 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.
  • Table 1 Composition of the coating compositions of Examples 1 to 4
  • Viaktin VTE 6160 commercially available aliphatic, hexafunctional
  • Laromer® 8777 commercially available difunctional epoxy acrylate from BASF
  • Laomer® PO84F commercially available amine-modified, polyether acrylate from
  • Ebecryl® 5129 commercially available aliphatic, hexafunctional urethane acrylate from UCB
  • Polishability visual assessment of the paint surface after polishing with polishing paste with regard to the appearance of grinding marks
  • Moisture resistance measured using the constant climate test by storing for 10 days at 40 ° C and 100% relative humidity

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Glass Compositions (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
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
DE19709467A DE19709467C1 (de) 1997-03-07 1997-03-07 Beschichtungsmittel sowie Verfahren zur Herstellung von Mehrschichtlackierungen
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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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JP (1) JP2001522297A (fr)
KR (1) KR20000076029A (fr)
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AU (1) AU743304B2 (fr)
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Families Citing this family (77)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6258918B1 (en) 1998-04-22 2001-07-10 3M Innovative Properties Company Flexible polyurethane material
US6423425B1 (en) 1998-05-26 2002-07-23 Ppg Industries Ohio, Inc. Article having a chip-resistant electrodeposited coating and a process for forming an electrodeposited coating
DE19856990A1 (de) * 1998-12-10 2000-06-15 Herberts & Co Gmbh Wäßrige Elektrotauchlacke, deren Herstellung und Verwendung
US7157507B2 (en) * 1999-04-14 2007-01-02 Allied Photochemical, Inc. Ultraviolet curable silver composition and related method
DE19920799A1 (de) 1999-05-06 2000-11-16 Basf Coatings Ag Thermisch und mit aktinischer Strahlung härtbarer Beschichtungsstoff und seine Verwendung
DE19928253C2 (de) * 1999-06-21 2001-07-12 Basf Coatings Ag Folie und ihre Verwendung zur Beschichtung von Gegenständen
US6623791B2 (en) 1999-07-30 2003-09-23 Ppg Industries Ohio, Inc. Coating compositions having improved adhesion, coated substrates and methods related thereto
CN1209427C (zh) 1999-07-30 2005-07-06 匹兹堡玻璃板工业俄亥俄股份有限公司 具有改进抗刮性的涂料组合物、涂覆基材及其有关方法
US6610777B1 (en) 1999-07-30 2003-08-26 Ppg Industries Ohio, Inc. Flexible coating compositions having improved scratch resistance, coated substrates and methods related thereto
PT1204709E (pt) 1999-07-30 2007-05-31 Ppg Ind Ohio Inc Composições de revestimento que têm resistência ao arranhão melhorada, substratos revestidos e métodos relacionados com eles
BR0012882A (pt) 1999-07-30 2002-04-09 Ppg Ind Ohio Inc Revestimentos curados tendo resistência ao risco melhorada, substratos revestidos e métodos a eles relacionados
ATE283117T1 (de) * 1999-10-02 2004-12-15 Du Pont Verfahren zur herstellung von basislack/klarlack- zweischichtlackierungen und/oder transparenten versiegelungsschichten
DE60020859T2 (de) 1999-10-06 2006-05-11 Allied Photochemical, Inc., Kimball UV-Härtbare Zusammensetzungen zur Herstellung von Elektrolumineszenzbeschichtungen
US6767577B1 (en) 1999-10-06 2004-07-27 Allied Photochemical, Inc. Uv curable compositions for producing electroluminescent coatings
US6509389B1 (en) * 1999-11-05 2003-01-21 Uv Specialties, Inc. UV curable compositions for producing mar resistant coatings and method for depositing same
US6500877B1 (en) * 1999-11-05 2002-12-31 Krohn Industries, Inc. UV curable paint compositions and method of making and applying same
DE19956483A1 (de) * 1999-11-24 2001-06-28 Basf Coatings Ag Lackierte Kunststoffformteile, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19958488A1 (de) * 1999-12-04 2001-06-21 Dupont Performance Coatings Wäßrige Elektrotauchlacke, deren Herstellung und Verwendung
WO2001040385A2 (fr) * 1999-12-06 2001-06-07 Slidekote, Inc. Compositions de lubrifiants durcissables par u.v.
US20060100302A1 (en) * 1999-12-06 2006-05-11 Krohn Roy C UV curable compositions for producing multilayer paint coatings
WO2001040386A2 (fr) * 1999-12-06 2001-06-07 Krohn Industries, Inc. Compositions reticulables sous l'effet des uv pour la production de peintures multicouches
US6805917B1 (en) 1999-12-06 2004-10-19 Roy C. Krohn UV curable compositions for producing decorative metallic coatings
WO2001051567A1 (fr) 2000-01-13 2001-07-19 Uv Specialties, Inc. Compositions conductibles transparentes qui peut secher aux u.v.
WO2001051568A1 (fr) * 2000-01-13 2001-07-19 Uv Specialties, Inc. Compositions ferromagnetiques durcissables aux uv
DE10009822C1 (de) * 2000-03-01 2001-12-06 Basf Coatings Ag Verfahren zur Herstellung von Beschichtungen, Klebschichten oder Dichtungen für grundierte oder ungrundierte Substrate und Substrate
DE10021139B4 (de) * 2000-04-29 2005-06-30 Basf Coatings Ag Mehrkomponentenbeschichtungsstoffe, -klebstoffe und -dichtungsmassen und ihre Verwendung
US6579914B1 (en) * 2000-07-14 2003-06-17 Alcatel Coating compositions for optical waveguides and optical waveguides coated therewith
US6635341B1 (en) 2000-07-31 2003-10-21 Ppg Industries Ohio, Inc. Coating compositions comprising silyl blocked components, coating, coated substrates and methods related thereto
US7323499B2 (en) 2000-09-06 2008-01-29 Allied Photochemical, Inc. UV curable silver chloride compositions for producing silver coatings
EP1325171A2 (fr) * 2000-09-06 2003-07-09 Allied Photochemical, Inc. Composition de chlorure d'argent durcissable aux uv pour la production de rev tements d'argent
DE10047989A1 (de) * 2000-09-28 2002-04-18 Basf Coatings Ag Thermisch und mit aktinischer Strahlung härtbare Mehrkomponentenbeschichtungsstoffe, -klebstoffe und -dichtungsmassen und ihre Verwendung
DE10126651A1 (de) 2001-06-01 2002-12-12 Basf Coatings Ag Pulverlacksuspensionen (Pulverslurries) und Pulverlacke, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10130972C1 (de) 2001-06-27 2002-11-07 Basf Coatings Ag Verfahren zur Herstellung von Beschichtungen aus thermisch und mit aktinischer Strahlung härtbaren Beschichtungsstoffen und mit dem Verfahren herstellbare Lackierungen
DE10140769A1 (de) * 2001-08-20 2003-03-06 Basf Ag Mit Lack beschichtete Folien
DE10153645A1 (de) * 2001-10-31 2003-05-22 Basf Coatings Ag Härtbares Stoffgemisch, Verfahren zu seiner Herstellung und seine Verwendung
DE10202565A1 (de) * 2002-01-24 2003-08-07 Basf Coatings Ag Gehärtete Materialien, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10221007B4 (de) * 2002-05-11 2016-10-13 Basf Coatings Gmbh Wässrige Dispersion von anorganischen Nanopartikeln, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10221010A1 (de) * 2002-05-11 2003-11-27 Basf Coatings Ag Wässrige Dispersion von anorganischen Nanopartikeln, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10221009B4 (de) * 2002-05-11 2016-10-13 Basf Coatings Gmbh Beschichtungsstoffe, deren Verwendung, Verfahren zur Herstellung von Beschichtungen und transparente Beschichtungen
DE10224381A1 (de) * 2002-06-01 2003-12-24 Basf Coatings Ag Kratzfest beschichtete Substrate, Verfahren zu Ihrer Herstellung und ihre Verwendung
DE10245029B4 (de) * 2002-09-25 2005-02-03 Bollig & Kemper Gmbh & Co. Kg Kratzfester Klarlack
US20040071978A1 (en) * 2002-10-15 2004-04-15 Omnova Solutions Inc. Laminate and method of production
DE10316890A1 (de) * 2003-04-12 2004-11-04 Basf Coatings Ag Mit aktinischer Strahlung aktivierbare Initiatoren enthaltende Mischungen sowie Zwei- und Mehrkomponentensysteme, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10335620A1 (de) 2003-08-04 2005-03-03 Basf Coatings Ag Verfahren zur Herstellung von Kunststoffformteilen mit funktionalen Oberflächen
US20050244587A1 (en) * 2003-09-09 2005-11-03 Shirlin Jack W Heating elements deposited on a substrate and related method
US6946628B2 (en) * 2003-09-09 2005-09-20 Klai Enterprises, Inc. Heating elements deposited on a substrate and related method
US20050109623A1 (en) * 2003-09-10 2005-05-26 Bao Sheng Corporation Multi-color anodizing processes
US7399793B2 (en) * 2003-10-31 2008-07-15 Basf Corporation Coating composition curable with ultraviolet radiation
US20050101685A1 (en) * 2003-11-07 2005-05-12 Allied Photochemical, Inc. UV curable composition for forming dielectric coatings and related method
US20050101686A1 (en) * 2003-11-07 2005-05-12 Krohn Roy C. UV curable composition for forming dielectric coatings and related method
DE10353638A1 (de) 2003-11-17 2005-06-23 Basf Coatings Ag Strukturviskose, wässrige Dispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung
US20050176841A1 (en) * 2003-12-30 2005-08-11 Krohn Roy C. UV curable ink compositions
JP4726437B2 (ja) * 2004-06-04 2011-07-20 旭化成ホームズ株式会社 基礎コンクリートの改善方法
US7268172B2 (en) * 2004-10-15 2007-09-11 Bayer Materialscience Llc Radiation curable compositions
EP1809462B1 (fr) * 2004-11-04 2010-08-25 BASF Coatings GmbH Procede de fabrication de corps moules notamment destines a l'industrie automobile et pellicules destinees a cet effet presentant un revetement
US20060173122A1 (en) * 2005-02-01 2006-08-03 Carmen Flosbach Non-aqueous, liquid coating compositions curable by free-radical polymerization of olefinic double bonds
DE102005012589B4 (de) 2005-03-18 2007-06-14 Basf Coatings Ag Mit UV-A-Strahlung härtbares, lösemittelhaltiges Gemisch, Verfahren zu seiner Herstellung und seine Verwendung
US7375144B2 (en) * 2005-06-16 2008-05-20 Eastman Chemical Company Abrasion resistant coatings
US20070048441A1 (en) * 2005-08-31 2007-03-01 Basf Corporation Radiation curable clearcoat repair system and method for obtaining film build in thin film areas using the system
DE102006002596A1 (de) * 2006-01-18 2007-07-19 Tesa Ag Verbundfolie
US20070185266A1 (en) * 2006-02-07 2007-08-09 Carmen Flosbach Non-aqueous, liquid coating compositions curable by free-radical polymerization of olefinic double bonds
GB2447741B (en) * 2007-03-12 2009-06-17 Kansai Paint Co Ltd Method for making multilayer coating film
US7569160B2 (en) * 2007-04-10 2009-08-04 Henkel Ag & Co. Kgaa Electrically conductive UV-curable ink
US9207373B2 (en) 2007-04-10 2015-12-08 Stoncor Group, Inc. Methods for fabrication and highway marking usage of agglomerated retroreflective beads
DE102007031594A1 (de) 2007-07-06 2009-01-08 Basf Coatings Ag Universeller Spotblender für Einkomponenten- und Zweikomponentenklarlacke
US20090176907A1 (en) * 2008-01-08 2009-07-09 Ramesh Subramanian Direct-to-metal radiation curable compositions
DE102008010346B4 (de) 2008-02-14 2019-05-09 Karl Wörwag Lack- Und Farbenfabrik Gmbh & Co. Kg UV-härtbare Zusammensetzung, ihre Verwendung als Beschichtungsmittel und Verfahren zur Lackierung von Fahrzeugachsen
CA2719573A1 (fr) * 2008-04-01 2009-10-08 The Sherwin-Williams Company Compositions pouvant durcir
DE102008051472A1 (de) 2008-10-14 2010-04-15 Basf Coatings Ag Kratz- und witterungsbeständiger, mit aktinischer Strahlung oder thermisch und mit aktinischer Strahlung härtbarer Lack
KR20100053094A (ko) * 2008-11-12 2010-05-20 삼성전자주식회사 금속 질감을 표현한 사출 모재 및 제조방법
KR101234851B1 (ko) * 2009-12-31 2013-02-19 제일모직주식회사 하드 코팅 조성물 및 하드코트층을 포함하는 적층체
US10487233B2 (en) 2011-04-12 2019-11-26 Basf Coatings Gmbh Solvent-borne clearcoat coating composition, method for producing it and use thereof
JP5845126B2 (ja) * 2012-03-29 2016-01-20 日新製鋼株式会社 塗装金属板およびその製造方法
KR20160099715A (ko) 2013-12-20 2016-08-22 바스프 코팅스 게엠베하 안료 및 충전제 함유 제형
DE102014007805A1 (de) 2014-05-27 2015-12-03 WindplusSonne GmbH Solarabsorber, Verfahren zu seiner Herstellung und seine Verwendung
CN104140724B (zh) * 2014-07-23 2016-06-08 Ppg涂料(天津)有限公司 多层涂层体系、涂覆方法和经其涂覆的基底
CN106802969B (zh) * 2015-11-26 2020-08-07 英业达科技有限公司 阻尼材料动态特性的验证系统及其验证方法

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS534020B2 (fr) * 1974-09-05 1978-02-13
NL7714169A (nl) 1977-12-21 1979-06-25 Akzo Nv Werkwijze voor het bekleden van een substraat met een stralingshardbare bekledingscompositie.
AT368179B (de) 1980-12-10 1982-09-27 Vianova Kunstharz Ag Verfahren zur herstellung von (meth)acrylsaeuremodifiziertenpolyerstern
DE8200357U1 (de) 1982-01-09 1982-06-16 Hans Esser Automaten-Esser, 5400 Koblenz Sicherheits-schliesseinrichtung
DE3316593A1 (de) 1983-05-06 1984-11-08 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von (meth)-acrylsaeureestern und deren verwendung
US4609718A (en) 1985-05-08 1986-09-02 Desoto, Inc. Ultraviolet curable buffer coatings for optical glass fiber based on long chain oxyalkylene diamines
DE3836370A1 (de) 1988-10-26 1990-05-17 Basf Lacke & Farben Verfahren zum beschichten von holz, holzwerkstoffen und papier
DE4133290A1 (de) * 1991-10-08 1993-04-15 Herberts Gmbh Verfahren zur herstellung von mehrschichtlackierungen unter verwendung von radikalisch und/oder kationisch polymerisierbaren klarlacken
DE4215070A1 (de) 1992-05-07 1993-11-11 Herberts Gmbh Verfahren zur Herstellung von Mehrschichtlackierungen
DE4310414A1 (de) * 1993-03-31 1994-10-06 Basf Lacke & Farben Verfahren zur Herstellung einer zweischichtigen Decklackierung auf einer Substratoberfläche
DE4341235A1 (de) * 1993-12-03 1995-06-08 Basf Lacke & Farben Zur Lackierung von Automobilkarosserien geeignete Pulverlacke
US5609918A (en) * 1994-06-13 1997-03-11 Kansai Paint Company Limited Method of forming a top coat
JPH07331165A (ja) * 1994-06-13 1995-12-19 Kansai Paint Co Ltd 上塗り塗膜形成方法
JPH0812931A (ja) * 1994-06-28 1996-01-16 Kansai Paint Co Ltd 上塗り塗膜形成方法
US6040009A (en) * 1994-06-23 2000-03-21 Mazda Motor Corporation Low solvent content type-resin composition, coating composition containing such resin composition and process for coating such coating composition
JP3286747B2 (ja) * 1995-02-20 2002-05-27 関西ペイント株式会社 塗料用硬化性組成物及び上塗り塗膜形成方法
US5565243A (en) * 1995-05-01 1996-10-15 Ppg Industries, Inc. Color-clear composite coatings having improved hardness, acid etch resistance, and mar and abrasion resistance
JP3458205B2 (ja) * 1995-11-20 2003-10-20 関西ペイント株式会社 高固形分塗料組成物及びそれを用いる上塗り塗膜形成方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9840171A1 *

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DE19709467C1 (de) 1998-10-15
KR20000076029A (ko) 2000-12-26
BR9810860A (pt) 2000-09-12
AU6497598A (en) 1998-09-29
EP0964751B1 (fr) 2002-10-02
DE59805797D1 (de) 2002-11-07
WO1998040171A1 (fr) 1998-09-17
ES2185152T3 (es) 2003-04-16
JP2001522297A (ja) 2001-11-13
CN1255075A (zh) 2000-05-31
ATE225214T1 (de) 2002-10-15
AU743304B2 (en) 2002-01-24
CA2283419A1 (fr) 1998-09-17
PL335728A1 (en) 2000-05-08
US6261645B1 (en) 2001-07-17
PL187077B1 (pl) 2004-05-31

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