Radiation-curable paint systems having a lower layer with low-temperature elasticity

Translation of description of equivalent WO 2004009251 A2

p0001A radiation-curable coating systems with low temperature elastic underlayer

p0002description

p0003The present invention relates to a method for improving the fracture mechanical properties of highly scratch-resistant radiation-curable coating systems, according to this method erhältli- before painting and the use of such sprays.

p0004A high scratch resistance is a widespread demand for paintwork. These plastic parts are, for example, in the automobile industry coated with a scratch-resistant clearcoat, which are firstly to thermosetting, so-called. Once or can act two-component PU coatings, or other preferably clearcoats that upon irradiation with actinic radiation cure. For hard coatings, however, often the problem arises that a initierter in the paint microcrack very locally defined by the painting in the substrate to which the paint is applied, propagates, as described for example in DE-Al 199 56 483 ,

p0005DE-Al 199 56 483 describes lacquered plastic moldings that on a plastic layer of at least one graft polymer of an elastomeric grafting base having a glass transition temperature T_G below 10 ° C and a graft with a T_G of more than 30 ° C, having at least one coating with specific properties. A rubber phase is thus distributed in the substrate.

p0006A disadvantage of the process described, to enable such graft polymers only insufficiently can bind covalently to the topcoat, as can be grafted only on the volume fraction of the elastomeric component of the blend. In particular, it is important for a high shatterproof coating system to prevent small microcracks through a continuous elastomer layer from spreading. DE-Al 199 20 801 describes special multilayer Klarlackie- ments in which each clearcoat film is radiation is equipped whereby scratch by inorganic nanoparticles with a layer.

p0007DE-Al 100 27 268 describes special multilayer Klarlackie- ments, in which curing in one step by means of thermal crosslinking of polyols based on acrylic copolymers with Triazinvernetzer takes place, this can be done simultaneously or sequentially.

p0008WO 99/26732 describes a method for preparing a multilayer coating, in which, on an optionally precoated substrate, a coating agent and a clear lacquer layer are applied.

p0009A disadvantage of these documents mentioned that even with application of the technical teaching disclosed there fertil scratch resistance, in particular the problem of cracks in the paint, is not able to meet today's requirements.

p0010It was therefore the object to develop a paint that has a very high scratch resistance with good adhesion to the substrate as well as reduced crack propagation in the substrate.

p0011The object was achieved by a multi-layer coating on a substrate, comprising at least one radiation-curable coating system (F) and at least one between the substrate and radiation-curable coating system (F) located elastic intermediate layer (D) having a glass transition temperature (T_G) Of -20 ° C or lower (as measured in the frequency range up to 1000 Hz).

p0012One in a multilayer coating according to the invention in an outboard paint system (F) arising crack propagates in the uses described typical loads not by the elastic intermediate layer (D) passed away, so that the substrate on which the multi-layer coating is applied, is not damaged and its mechanical characteristics reserves.

p0013Such a multi-layer coating according to the invention may comprise further layers. For example, a multi-layer coating according to the invention of the following layers, which may be arranged as follows typically consists of:

p0014(F) at least one radiation-curable coating system, (E) optionally at least one pigmented and / or provided with effect substances layer, (D) at least one elastic intermediate layer (D) having a

p0015Glass transition temperature (T_G) Of -20 ° C or lower, (C) optionally at least one layer selected from the group primer, basecoat, undercoat, pigmented or with effect substances PROVIDED paint and substrate 2, (B) optionally at least an elastic intermediate layer, if layer (C), a substrate 2 is, as well as (A) substrate 1 having a toughness in accordance with DIN EN ISO 179 / lfü at 23 ° C and 50% humidity of at least 20 kJ / m.

p0016The construction of such a multi-layer coating is usually in the order given, so that the substrate 1 (A) as agreed below, the radiation-curable coating system (F) above and the elastic intermediate layer (D) therebetween resides.

p0017Substrates 1 and / or 2 in the layers (A) and / or (C) may be for example wood, wood veneer, paper, cardboard, textile, leather, nonwoven, plastics surfaces, metals or particular coated metals, preferred are paper, plastics or metals, particularly preferred are plastics / and very particularly preferably transparent plastics.

p0018are understood with toughness gem known by the person skilled in the engineering plastics as plastics. DIN EN ISO 179 / LFU at 23 ° C and 50% humidity of at least 20, preferably at least 25 kJ / m², For example, polymers and copolymers containing (meth) acrylic esters, vinyl aromatic compounds such as styrene, divinylbenzene, vinyl esters such as vinyl acetate, halogenated ethylenically unsaturated compounds, for example vinyl chloride,

p0019Vinylidene chloride, conjugated unsaturated compounds, such as butadiene, isoprene, chloroprene, α, ß-unsaturated nitrites, such as acrylonitrile, monounsaturated compounds such as ethylene, propylene, 1-butene, 2-butene, isobutene, simple cyclic unsaturated compounds , for example, cyclopentene, cyclohexene, N-pyrrolidone Vinylpyr-, N-Vinyllactarne such as N-vinylcaprolactam, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl, iso- propyl ynyl ether, n-butyl vinyl ether, in copolymerized form.

p0020named are polyethylene, polypropylene, polystyrene, polybutadiene, polyesters, polyamides, polyethers, polyvinyl chloride, polycarbonate, polyvinyl acetal, polyacrylonitrile, polyacetal, polyvinyl alcohol, polyvinyl acetate, phenolic resins, urea arze, melamine minharze, alkyd resins, epoxy resins or polyurethanes, block, or graft copolymers and blends thereof.

p0021Particular mention may be ABS, AES, AMMA, ASA, EP, EPS, EVA, EVAL, HDPE, LDPE, MABS, MBS, MF, PA, PA6, PA66, PAN, PB, PBT, PBTP, PC, PE, PEC, PEEK , PEI, PEK, PEP, PES, PET, PETP, PF, PI, PIB, PMMA, POM, PP, PPS, PS, PSU, PUR, PVAC, PVOH, PVC, PVDC, PVP, SAN, SB, SMS, UF, UP plastics (abbreviations according to DIN 7728) and aliphatic polyketones.

p0022The plastics mentioned may be preferred coronisiert. The substrates may optionally be pigmented or unpigmented.

p0023Preferred substrates are polyolefins, such as PP (polypropylene), which can be oriented either isotactic, syndiotactic or atactic and optionally may be unoriented or uni- or bisaxiales stretching, SAN (styrene-acrylonitrile copolymers), PC (Polycarbonate), PMMA (polymethylmethacrylate), PBT (poly (butylated terephthalate) s), PA (Polyamide), ASA (acrylonitrile-styrene-acrylate esters copolymers) and ABS (acrylonitrile-butadiene-styrene copolymers), and their physical mixtures (blends). Particular preference is given to PP, SAN, ABS, ASA and blends of ABS or ASA with PA or PBT or PC.

p0024Substrates 1 in layer (A) can be identical or different Liehe, successive laminated substrates such as laminated plastics.

p0025The substrates 1 and 2 in the layers (A) and (C) may be the same or different.

p0026It may be present in each case one or more substrates 1 and / or 2 in the layers (A) and / or (C), for example 1 to 3, preferably 1 to 2, and particularly preferably one.

p0027Contains layer (C) at least one substrate 2, so this may be preferably be a film, such as a plastic or metal or particularly preferably be a plastic film which can be made from the specified plastics.

p0028Such a film can have a thickness of 1 .mu.m to 2 mm, preferably 5 .mu.m to 1000 .mu.m, more preferably from 5 microns to 750 microns, most preferably from 10 microns to 500 microns and especially from 25 to 300 microns.

p0029If layer (C) comprises a substrate 2, this can usefully with a further elastic intermediate layer (B) with the substrate (A) to be connected. Such an intermediate layer has the same characteristics as the intermediate layer (D) (see below) and may be identical or different from this.

p0030Typical thicknesses of layer (B) ranging from 0.1 to 1000 microns, preferably from 0.5 to 500 .mu.m, particularly preferably from 1 to 250 microns and most preferably from 1 to 100 microns.

p0031There may be used one or more resilient couplings in the layer (B), for example 1 to 3, preferably 1 to 2, and particularly preferably one.

p0032Layer (C) may, for example, at least one primer, base coat, primer, contain pigmented or provided with effect substances, paint, and / or optionally at least a substrate 2, which has already been described above.

p0033As color and / or effect coating materials in the layer (C) and / or (E) are basically all the usual for this purpose and known to those skilled paints into consideration. This may be curable physically, thermally, with actinic radiation or both thermally and with actinic radiation (dual-cure). It may be conventional base coats, waterborne basecoats, substantially solvent, ttel- and water-free liquid basecoats (100% systems), substantially solvent edium and water-free solid basecoats (pigmented powder coating materials) or substantially solvent-free pigmented powder coating dispersions (powder slurry basecoats) act. They may be thermally or dual cure-curable, and self- or externally crosslinking.

p0034This may be one or several, preferably 1 to 3, particularly preferably 1 to 2 and very particularly preferably a f Rb and / or effect paint be.

p0035In the present invention, essentially solvent-free, that the coating material concerned has a residual content of volatile solvents of <2.0 wt .-%, preferably <1.5 wt .-% and particularly preferred <1.0 wt .-% has , It is especially advantageous if the residual content lies below the gas-chromatographic detection limit.

p0036paint systems water based paints are particularly preferred in the multilayer according to the invention applied as from patent applications EP 0089497 Al, EP 0256540 Al, EP 0260447 Al, EP 0297576 Al, WO 96/12747, EP 0523610 AI, EP 0228003 Al, EP 0397806 Al, EP 0574417 Al, EP 0531510 Al, EP 0 581 211 Al, EP 0708788 Al, EP 0593454 Al, DE-A-43 28 092 AI, EP 0299148 AI, EP 0394737 Al, EP 0590484 Al, EP 0234362 Al, EP 0234361 Al, EP 0543817 AI, W095 / 14721, EP 0521928 Al, EP 0522420 Al, EP 0 522 419 Al, EP 0649865 Al, EP 0536712 Al, EP 0596460 Al, EP 0596461 Al, EP 0584818 Al, EP 0669356 Al, EP 0669356 Al, EP 0634431 AI, EP 0678536 Al, EP 0354261 Al, EP 0424705 Al, WO 97/49745, WO 97/49747, EP 0401565 AI or EP 0,817,684, column 5, lines 31 to 45, known are.

p0037The f RB- described above and / or effect coatings can not only of producing color and / or effect basecoats, but also by color and / or effect combination effect coats serve. In the present invention hereunder is to understand a painting, the at in a color and / or effect coating system fulfills least two functions. Functions of this kind are in particular the protection against corrosion, promotion of adhesion, absorption of mechanical energy and the color and / or effectors tender. In particular, the combination effect coat serves to absorb mechanical energy and to color and / or effect at the same time; therefore fulfills the functions of a primer coat or protective primer and a basecoat. Preferably, the combination effect coat also has a corrosion protection effect and / or adhesion-promoting effect.

p0038Typical thicknesses of layer (C) and / or (E) ranging from 0.1 to 2000 μ, preferably 0.5 to 1000 .mu.m, more preferably from 1 to 500 microns, most preferably from 1 to 250 microns and especially from 10 to 100 microns.

p0039The usable in the multi-layer coatings paints may contain color and / or effect pigments. As color pigments all coatings pigments of organic or inorganic nature. Examples of inorganic or organic color pigments are titanium dioxide, micronized titanium dioxide, iron oxide pigments, carbon black, azo pigments, phthalocyanine pigments, quinacridone and pyrrolopyrrole pigments.

p0040The effect pigments are characterized in particular by a platelet chenartigen construction. Examples of effect pigments are metal pigments, for example made of aluminum, copper or other metals; Interference pigments, such as etalloxidbeschichtete metal pigments, for example titanium dioxide coated or mischoxidbeschichte- tes aluminum, coated mica, such as titanium dioxide-coated mica and graphite effect pigments. Advantageously can nen, for example, to improve the hardness, UV-curable pigments and possibly fillers. This is to deal with radiation-curable compounds, eg acrylic-functional silanes, coated pigments / fillers, which may be included in the radiation curing process with thus.

p0041In the intermediate layer (D) is according to the invention at least one compound having a glass transition temperature (T_G) Include lower, preferably of respectively -20 ° C or - 30 ° C or lower, particularly preferably -40 ° C or lower, most preferably -50 ° C or lower, and particularly -60 ° C or lower.

p0042The glass transition temperature Tg was bending vibration tests (according to DIN 53440 Tl to T3) at a frequency from 0 to 1000 Hz, preferably from 100 to 1000 Hz determined. The bending vibration provides the important of fracture mechanical perspective Tg at high strain rates (frequencies).

p0043The thickness ZS of the intermediate layer according to the invention contained in the multi-layer coating (D), for example, from 0.1 to 1000 microns, preferably 0.5 to 500 .mu.m, more preferably from 1 to 250 microns, most preferably from 5 to 50 microns, particularly 10 to 50 microns.

p0044usable example, as compounds in the elastic intermediate layer are rubber-containing polymers, ac-Resins, polyacrylates having a T_G as indicated, and poly-iso-butylenes. As rubber-containing polymers, for example thermoplastic elastomers are contemplated. Such thermoplastic elastomers usually contain at least one elastomeric component (soft domain) and at least one thermoplastic component (hard domain), which may be joined together as a blend or vulcanizate block polymer, preferably as a block polymer.

p0045When the elastomeric component may be styrene-butadiene (SBR), polyisoprene (IR), polybutadiene (BR), chloroprene (CR) acrylonitrile-butadiene (NBR), butyl (isobutene / isoprene copolymer, IIR), butyl / α-methylstyrene terpolymer, ethylene / propylene (EPM), ethylene / propylene / diene (EPDM), epichlorohydrin (CO), epichlorohydrin / ethylene oxide (ECO) or ethylene / vinyl acetate rubber ( EVA / EVM) act, preferably polybutadiene, polyisoprene, ethylene / propylene or ethylene / propylene / diene rubber, more preferably polybutadiene or polyisoprene and very particularly preferably polybutadiene act.

p0046The elastomeric component comprises (based polymer in a block on the block) usually have molecular weights of at least 80,000 g / mol, preferably at least 100,000, particularly preferably 100,000 to 250,000 and most preferably 120,000 to 230,000 g / mol.

p0047When the thermoplastic component may be, for example, polypropylene, preferably isotactic polypropylene, a random or block copolymer of propylene and ethylene, HDPE, LDPE, LLDPE, EVA, ethylene / methacrylate copolymers, ethylene / ethylamine methacrylate copolymers, SAN, ABS, ASA, PMMA or polystyrene act, preferred are polystyrene and polypropylene and particularly preferred is polystyrene.

p0048The thermoplastic component comprises (based polymer in a block on the block) to generally have molecular weights of up to 50,000 g / mol, preferably from 5,000 to 40,000 and more preferably 6000 to 20000 g / mol.

p0049In general, the proportion of the thermoplastic component of the total thermoplastic elastomer up to 50% by weight, preferably up to 40 and more preferably up to 35 wt%. The minimum amount of thermoplastic component is generally at least 8% by weight, preferably at least 20 and particularly preferably at least 25 wt%.

p0050Preferred thermoplastic elastomers are those having at least one elastomeric block Y and at least one thermoplastic block Z of the general form Z (-YZ) m, wherein m is a positive integer from 1 to 10, preferably 1 to 5, particularly preferably 1 to 3, most more preferably 1 or 2 and in particular 1 means. In the latter case we speak of so-called. Triblock polymers. The polymers may, for example, linear or branched, eg star-shaped, constructed, preferably linear.

p0051Particularly preferred thermoplastic elastomers are Styrololi- goblockpolyere, most preferably styrene-Triblockpo- are mers, in which the thermoplastic block predominantly, preferably completely consists of styrene. especially preferred are the so-called. styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-ethylene / butylene-styrene (SEBS) and styrene-ethylene / propylene-styrene (SEPS) block polymers, which optionally also with reactive comonomers such as maleic anhydride may be nktionalisiert f. The thermoplastic elastomers may further be hydrogenated completely or partially.

p0052The inventively employable thermoplastic elastomers can moreover also a so-called. Diblock fraction (ZY) m include, the preferably up to 50% by weight, more preferably up to 40, very particularly preferably up to 30% by weight and in particular up to 20% by weight may be.

p0053Furthermore, the invention can be used according thermoplastic elastomers with mineral oil, polystyrene, poly olefins can, fillers or additives such as antioxidants, UV-stabilizers or antiozonants are added.

p0054Very particular preference as thermoplastic elastomers the Kraton® grades from Kraton Polymers US LLC, Houston, Texas, USA and Vector® trademarks of Dexco polymer, Houston, Texas, USA in question. Particularly preferred are the Kraton D and G brands, preferably the Kraton D-marks and particularly preferably Kraton D1101, D1118, D4150, D1112, D-KS 225 ES, D1102, D1116, D1186 and D4123, and Vector- brands 7400, 8508 and 2518th

p0055Polyacrylates (co) polymers with a T_G as indicated in question.

p0056This set is usually as follows:

p0057Main monomer 50-98% by weight secondary monomer 10-40% by weight of functionalized monomer 0-20% by weight,

p0058with the proviso that the sum is always 100% by weight.

p0059Therein are principal monomers such as (meth) acrylic acid methyl ester, (meth) acrylate, (meth) acrylic acid-n-propyle- esters, (meth) acrylic acid n-butyl ester, (meth) acrylic acid-iso-butylene ster, (meth) acrylic acid SEj-butyl ester, (meth) acrylic acid-n-penty- esters, (meth) acrylic acid iso-pentyl ester, (meth) acrylic acid-2-methyl-butyl ester, (meth) acrylsäureamylester, (meth) acrylic acid-n - hexyl ester, (meth) acrylic acid-2-ethylbutyl, (meth) acrylic acid pentyl ester, (meth) acrylic acid n-heptyl ester, (meth) acrylic acid n-octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid - n-decyl ester, (meth) acrylsäureundecylester, (meth) acrylic acid n-dodecyl ester, (meth) acrylic acid 2-methoxyethyl ester, (meth) acrylic acid-2-ethoxyethyl, (meth) acrylic acid 4-methoxy-butyl ester, (meth ) acrylic acid 2- (2 '-methoxyethoxy-) ethyl ester, (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid-2-hydroxy-propyl ester, (meth) acrylic acid 3-hydroxypropyl ester, (meth) acrylic acid 4-hydroxybutyl, ethylene glycol (meth) acrylate, propylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 2-ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di ( meth) acrylate, tetraethylene glycol di (meth) acrylate, tri- methylolpropantri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol and tetra (meth) acrylate, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, vinyl butyrate, methyl vinyl ketone, vinyl toluene, vinylnaphthalene, methyl vinyl ether, ethyl vinyl ether, n-propyl, iso-propyl, n-butyl vinyl ether, SEj-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl tylvinylether, 4-hydroxybutyl vinyl ether, n-octyl vinyl ether, ethylene, propylene, 1-butene, 2-butene, iso-butene, cyclopentene, cyclohexene, cyclododecene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, divinylbenzene, tert-butylstyrene and mixtures thereof.

p0060Suitable secondary monomers include

p0061(Meth) acrylic acid-iso-bornylester, (meth) acrylsäuretridecylester, (meth) lauryl acrylate, (meth) stearyl acrylate, (meth) acrylic acid 10-cyclohexylundecylester, (meth) acrylic acid-2-cyanethylester, (meth) acrylic acid-2 -dimethylaminoethyle- esters, (meth) glycidyl acrylate, (meth) acrylic acid-3- (trimeth- oxysilyl) propyl ester, (meth) acrylic acid-2- (trimethoxysilyl) ethyl ester, N- (2-hydroxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-octyl tyl (meth) acrylamide, acrolein, (meth) acrylonitrile, fumarate iso-propyl fumarate-n butyl fumarate-SEJ-butyl tylester, Fumarsäurediamylester, fumarate-2-ethylbutyl, fumarate n-octyl ester, fumarate, 2-ethylhexyl, fumaric säuredidodecylester, bis (2-hydroxyethyl) fumarate, Maleinsäuredi- butyl Maleinsäuredi- 2-ethylhexyl Maleinsäuredi- (2-hydroxyethyl) ester, Maleinsäurenitril, Maleinsäuredi- nitrile, vinyl valerate, divinyl ether, 2-chloroethyl vinyl ether, α-propiolactone, δ-valerolactone, ε-caprolactone, N-vinylformamide, N-vinylacetamide, N-vinyl -N-methylformamide, N-vinyl-N-methylaceta- mid, allylacetic acid, vinylacetic acid, and mixtures thereof.

p0062Functionalized monomers are, for example, the

p0063carry carboxyl, hydroxyl, epoxy, allyl, carboxamide, A domestic, isocyanate, hydroxymethyl, methoxymethyl or silyloxy. This may for example be (meth) acrylic acid, (meth) acrylic acid formal, (meth) acrylsäurehydroxymethylester, (meth) acrylsäurebenzophenonglycidylester, (meth) acrylic acid-2-sulfonic foethylester, (meth) acrylamide, N-methylol (meth) crylamid, fumaric acid, fumaric acid iso-propyl ester, fumaric acid n-hexyl ester, fumaric acid amide, fumaric acid diamide, fumaronitrile, fumaric säuredinitril, crotonic acid, Crotonsäureglycidylester, itaconic acid, itaconic acid, itaconic anhydride, citraconic acid, Citraconsäurehalbester, citraconic anhydride, succinic acid, maleic acid, monomethyl maleate, Maleinsäuremonoethyl- ester, monobutyl maleate, maleic anhydride, maleic acid amide, maleic acid diamide, N-Methylolmaleinsäureamid, vinyl succinimide, vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, sodium vinylsulfonate, tetraallyloxyethane, diallyl phthalate, Diallylsucci- nat, Tetraallylethan, tetraallyloxysilane, allyl, triallyl, triallyl, diketene, monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and their water-soluble alkali metal, alkaline earth metal or ammonium salts, such as: acrylic acid, methacrylic acid, Dimethylacryl- acid, ethacrylic acid, maleic acid, citraconic acid, methylenemalonic acid, crotonic acid, fumaric acid, mesaconic acid or itaconic acid and mixtures thereof.

p0064To the specified T_G to obtain, these have a high proportion of n-butyl acrylate or 2-ethylhexyl acrylate on a rule, preferably at least 50% by weight.

p0065The weight average molecular weight of the useful (co) polymers, optionally prior to further crosslinking (determined by gel permeation chromatography using polystyrene as standard and tetrahydrofuran as eluent) is, for example 200000-1500000 g / mol, preferably from 250,000 to 1,200,000, especially preferably from 300,000 to 900,000.

p0066The gel content of the useful (co) polymers, ie of at 24stün- ended storage soluble at room temperature under THF proportion of an adhesive film, is from 30 to 70, preferably between 30 and 60 and particularly preferably between 40 and 60 wt%.

p0067According to the invention are particularly suitable radiation-polyacrylates.

p0068These are polyacrylates, which are by active energy gieeinstrahlung networked. These adhesives usually contain poly (meth) acrylate, preferably polyacrylate resins optionally in combination with aliphatic or aromatic epoxy, urethanes, polyesters or polyethers. Epoxy resins, aliphatic, aromatic or mixed aliphatic-aromatic urethanes are preferably used.

p0069The network is active energy radiation, but it can also be networked via a second curing or further curing mechanisms (dual cure), for example by moisture, oxidation or heat, preferably by heat, for example at the specified curing temperature. Furthermore, cross-linking monomers may be added, for example 1, 3-butylene glycol di (meth) acrylate, tripropylene KOLDI (meth) acrylate, trimethylolpropane triacrylate or hritoltetraacrylat Pentaeryt-.

p0070For crosslinking by UV light, a photoinitiator may be added.

p0071The photoinitiator can be bound to the well to the poly (meth) acrylate. The photoinitiator may then be eg cyclic imide structures, eg maleimide or maleimide derivatives, benzo or Acetophenongruppen. The latter are for example in EP-Bl 377 199, page 3, line 14 to page 13, line 45, and described in EP-A 395 987 page 3, line 24 to page 5, line 42, and are hereby incorporated by reference takeover inserted.

p0072Particularly suitable are the UV acrylates acResin^® A 203 UV and acResin^® A 258 UV from BASF AG, Ludwigshafen.

p0073When poly-iso-butene (PIB) or modified poly-iso-butene, for example, the reaction products of PIB with maleic anhydride PIB hydroformylated, hydroformylated and subsequently hydrogenated PIB and hydroformylated and subsequently hydrogenated aminatingly PIB, come Glissopal.RTM or Oppanol® brands BASF AG, Polybutene® grades from BP, the Infineum®-C series from Infineu Int. Ltd., Lubrizol® LZ brands Lubrizol, Vistanex® brands from ExxonMobil Chemical Corp. , Te trox® brands Nippon Petrochemicals and Efrolen® brands from Efrimov. in question, which have a molecular weight of about 200 to 1,000,000, preferably the Oppanole® BIO, B10N, B10SFN, B100, B100G, B12N, B12SF, B12SFN, B15, B15 BULK, B15N, B15SF, B15SFN, B150, B150G , B200, B200G, B246, B250, B30SF, B50, B50SF, B80, NTK and NTS, and Glissopale® 1300, 2300, 550, 750, ES 3252, M 1600 OS, SA, V 1500, V 220, V 230, V33, V 500, V640, V700, V90 and 1000, Infineum® C9945, C9925, C9950, C9970, C9980, C9983, C9984, C9913, C9922, C9907, C9924 and C9995 and Vista nex® L-80, L -100, L-120, L-140, LM-MS, LM-MH, LM-MS-LC, LM-MH-LC and LM-H-LC.

p0074Of course, also a mixture of different

p0075Compounds are used lower, for example 1 to 5, preferably 1 to 4, particularly preferably 1 to 3 and most preferably 1 to 2, compounds having a glass transition temperature of -20 ° C or lower. In particular, a compound is used. The invention in radiation-curable coating systems (F) usable radiation-curable materials are known per se and not restricted, it may be, for example, the radiation-curable clearcoat or topcoat materials to the expert for such purposes known. They generally contain at least one radically and / or cationically polymerizable group, preferably, they are radically polymerizable.

p0076Polymerizable groups may be those which have unsaturated bonds, preferably carbon-carbon double bonds.

p0077Radical polymerizable groups are, for example, isolated ethylenically unsaturated groups, conjugated unsaturated groups, vinyl aromatic groups, vinyl chloride and vinylidene chloride groups, N-vinylamides, vinyl pyrrolidones, Vinyllactarne, vinyl ester, (meth) acrylic ester or acrylonitrile.

p0078Cationic polymerizable groups are, for example leneinheiten isobutylene or vinyl ethers.

p0079The preferred radiation-curable compositions contain as polymerizable groups preferably acrylate, methacrylate or vinyl ether functions.

p0080Usually contains a radiation-curable composition used in the invention

p0081(Fl) at least one polymerizable compound having a plurality of copolymerizable, ethylenically unsaturated groups, (F2), if appropriate, reactive diluents, (F3) optionally, photoinitiator, and (F4) optionally further typical coatings additives.

p0082As the compounds (Fl) radiation-curable, free-radically polymerizable compounds having a plurality, ie at least two copolymerizable ethylenically unsaturated groups.

p0083It is preferable that in compounds (Fl) vinyl ether or (meth) acrylate, particularly preferably in each case are the acrylate compounds, ie the derivatives of acrylic acid. Preferred vinyl ether and (meth) acrylate compounds (Fl) contain 2 to 20, preferably 2 to 10 and very particularly preferably 2 to 6, copolymerizable, ethylenically unsaturated double bonds.

p0084Particularly preferred are those compounds (Fl) having a content of ethylenically unsaturated double bonds are of 0.1 - 0.7 ol / 100 g, most preferably 0.2 to 0.6 mol / 100 g, the number average molecular weight M._n the compounds (Fl) is, if not stated otherwise, preferably below 15,000, more preferably from 300 to 12,000, most preferably from 400 to 5000 and especially from 500 to 3000 g / mol (determined by gel permeation chromatography using polystyrene as standard and tetrahydrofuran as eluent).

p0085mentioned acrylate compounds are (meth) (meth) acrylic esters and especially acrylic esters and vinyl ethers of polyfunctional alcohols, especially those which at best contain ether groups contain no further functional groups apart from the hydroxyl or. Examples of such alcohols include bifunktioneile alcohols such as ethylene glycol, propylene glycol and their more highly condensed, such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene etc., 1,2-, 1,3- or 1, 4-butanediol, 1, 5- pentanediol, 1, 6-hexanediol, 3-methyl-l, 5-pentanediol, neopentyl glycol, alkoxylated phenolic compounds, such as ethoxylated or propoxylated bisphenols, 1,2-, 1,3- or 1, 4-cyclohexanedimethanol, trifunctional nelle and higher alcohols such as glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, Ditrimethy- lolpropan, dipentaerythritol, sorbitol, mannitol and the corresponding alkoxylated, especially ethoxylated and / or propoxylated alcohols.

p0086The alkoxylation products are obtainable conventionally by reacting the above alcohols with alkylene oxides, especially ethylene oxide or Propyle monoxide obtainable. The degree of alkoxylation per hydroxyl group is preferably from 0 to 10, that is, 1 mol of hydroxyl group may be alkoxylated with up to 10 mol of alkylene oxides.

p0087(Meth) acrylate compounds include polyester (meth) acrylates mentioned among others, it is the (meth) acrylic esters or vinyl ethers of polyesterols.

p0088Examples of suitable polyesterols are those which, as they can be prepared by esterification of polycarboxylic acids, preferably dicarboxylic acids, with polyols, preferably diols. The starting materials for such hydroxyl-containing polyesters are known in the art. Preferably have the dicarboxylic acids succinic acid, adipic acid, sebacic acid, o-phthalic acid, tetrahydrophthalic acid, terephthalic their isomers and hydrogenation products and also esterifiable derivatives, such as anhydrides or dialkyl esters of said acids. Suitable polyols include the abovementioned alcohols, preferably ethylene glycol, propylene glycol-1,2 and 1,3, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, 2, 2-bis (4- hydroxycyclohexyl) propane and polyglycols of the type of ethylene glycol and propylene glycol into consideration.

p0089Radiation-curable compounds (Fl) are, for example, unsaturated polyester resins into consideration, which consist essentially of polyols, especially diols, and polycarboxylic acids, especially dicarboxylic acids, one of the esterification contains a copolymerizable, ethylenically unsaturated group. For example, it involves maleic acid, fumaric acid or maleic anhydride.

p0090Polyester (meth) acrylates can be prepared in a plurality of stages or else in one stage, as described for example in EP-A 279 303, from (meth) acrylic, polycarboxylic acid and polyol.

p0091It may be, for compounds (Fl) for example, urethane or epoxy (meth) acrylates or vinyl ethers.

p0092Urethanes (meth) acrylates, for example by reacting polyisocyanates with hydroxyalkyl (meth) acrylates or vinyl ethers available and optionally chain extenders such as diols, polyols, diamines, polyamines or dithiols or polythiols. In water without addition of emulsifiers dispersible urethane (meth) acrylates additional ionic and / or nonionic hydrophilic groups are introduced by synthesis components such as hydroxycarboxylic into the urethane contain, for example.

p0093The invention as a binder (Fl) used include polyurethanes as constituent components substantially:

p0094(Fl-a) at least one organic aliphatic, aromatic or cycloaliphatisch.es di- or polyisocyanate,

p0095(Fl-b) and at least one compound having at least one isocyanate-reactive group and at least one radically polymerizable unsaturated group

p0096(Fl-c) optionally at least one compound having at least two isocyanate-reactive groups. As component (Fl-a) for example, aliphatic, aromatic and cycloaliphatic di- and polyisocyanates having an NCO functionality of at least 1.8, preferably 1.8 to 5 and more preferably 2 to 4, and also their isocyanurates, biurets, allophanates and uretdiones.

p0097The diisocyanates are preferably isocyanates having 4 to 20 carbon atoms. Examples of customary diisocyanates are aliphatic diisocyanates such as tetramethylene, hexamethylene diisocyanate (1, 6-diisocyanatohexane), Octamethylendiiso- diisocyanate, decamethylene, dodecamethylene Tetradecamethylendiisocyanat, derivatives of Lysindiisocyanates, tetramethyl, trimethylhexanediisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1,4, 1 , 3- or 1, 2-diisocyanatocyclohexane, 4,4' or

p00982, 4 '-di (isocyanatocyclohexyl) methane, l-isocyanato-3, 3, 5- trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate), 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or 2,4, or 2, 6-diisocyanato-l-methyl cyclohexane and aromatic diisocyanates such as 2,4- or 2, 6-toluene diisocyanate and the isomer mixtures thereof, m- or p-xylylene diisocyanate, 2,4'- or 4, 4'-diisocyanatodiphenylmethane and the isomer mixtures thereof, 1,3- or 1, -Phenylendiisocyanat, l-chloro-2, 4-phenylene diisocyanate, 1, 5-naphthylene diisocyanate, diphenylene, 4-diisocyanate, 4, 4'-diisocyanato -3, 3 '-dimethyldiphenyl, 3-Methyldiphenyl- methane-4,4'-diisocyanate, tetramethylxylylene diisocyanate, 1, 4-diisocyanatobenzene or diphenyl ether-4, 4-diisocyanate.

p0099There may also be mixtures of said diisocyanates.

p0100Preferably, hexamethylene diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and di (isocyanatocyclohexyl) methane are.

p0101Suitable polyisocyanates include polyisocyanates, uretdione, biuret, urethane or allophanate groups, polyisocyanates containing oxadiazinetrione, uretonimine-modified polyisocyanates of linear or branched C4-co-alkylene, cycloaliphatic diisocyanates having 6 to 20 C -atoms or aromatic diisocyanates having 8 to 20 carbon atoms or their mixtures.

p0102The di- and polyisocyanates which can be used preferably have a

p0103Isocyanate group content (calculated as NCO, molecular weight = 42) of 10 to 60% by weight based on the di- and polyisocyanates diisocyanate (mixture), preferably 15 to 60% by weight and particularly preferably 20 to 55 wt%.

p0104Preferred are aliphatic or cycloaliphatic di- and poly-isocyanates are, for example, the abovementioned aliphatic or cycloaliphatic diisocyanates, or mixtures thereof.

p0105Furthermore, preferred

p01061) Polyisocyanates containing isocyanurate groups of aromatic, aliphatic and / or cycloaliphatic diisocyanates. Particularly preferred here to the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanate are nurate and especially the diisocyanate based on hexamethylene diisocyanate and isophorone diisocyanate. The isocyanurates present are, in particular, tris or tris isocyanatoalkyl isocyanurates, which constitute cyclic trimers of the diisocyanates, or mixtures with their higher, more than one isocyanurate ring homologs. The isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average NCO functionality of 3 to 4.5.

p01072) uretdione with aromatic, aliphatic and / or cycloaliphatically bonded isocyanate groups, preferably aliphatically and / or cycloaliphatically attached, and in particular those derived from hexamethylene diisocyanate or isophorone. Uretdione cyclic dimerization of diisocyanates. The uretdione diisocyanates can be present in the preparations cyanates as a sole component or in a mixture with other polyisocyanates, in particular those mentioned under 1), used.

p01083) biuret groups and having aromatically, cycloaliphatically or aliphatically attached, preferably cycloaliphatically or aliphatically bonded isocyanate groups, especially tris (δ-isocyanatohexyl) biuret or whose mixtures with its higher homologs. These polyisocyanates containing biuret groups generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 3 to 4.5.

p01094) urethane and / or allophanate groups and having aromatically, aliphatically or cycloaliphatically attached, preferably aliphatically or cycloaliphatically bound which isocyanate groups such as, for example, by reacting excess quantities of hexamethylene diisocyanate or of isophorone diisocyanate with polyhydric alcohols such as trimethylolpropane, neopentyl glycol, pentaerythritol, 1,4-butanediol, 1, 6-hexanediol, 1,3-propanediol, ethylene glycol, diethylene glycol, glycerol , 1,2-dihydroxypropane or mixtures thereof can be obtained. These urethane and / or allophanate-containing polyisocyanates generally have an NCO content of 12 to 20 wt .-% and a medium-sized NCO functionality of 2.5 to. 3

p01105 containing) oxadiazinetrione polyisocyanates, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such oxadiazinetrione-containing polyisocyanates can be prepared from diisocyanate and carbon dioxide.

p01116) uretonimine modified polyisocyanates.

p0112The polyisocyanates 1) to 6) can be optionally in a mixture with diisocyanates, used in a mixture.

p0113As component (Fl-b) are compounds which carry an isocyanate-reactive group and at least one radical polymerizable group at least.

p0114Isocyanate-reactive groups include -OH, -SH, -NH and -NHR¹, Wherein R¹ Hydrogen or a group containing 1 to 4 carbon atoms, alkyl group such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl or seJc-butyl tyl means.

p0115Components (Fl-b) can, for example, monoesters of α, ß-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, acrylamidoglycolic acid, methacrylamidoglycolic acid or vinyl ethers with di- or polyols be, preferably 2 to 20 C-atoms and comprise at least two hydroxy groups, such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1,3-propylene glycol, 1, 1-dimethyl-l, 2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol,

p01161, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 2-methyl-l, 5-pentanediol, 2-ethyl-l, 4-butanediol, 1, 4-dimethylol cyclohexane, 2, 2-bis (4-hydroxycyclohexyl) propane, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, ditrimethylolpropane, erythritol, sorbitol, poly-THF with a molecular weight from 162 to 2000, poly-1, 3-propanediol having a molecular weight from 134 to 400 or polyethylene glycol a molecular weight between 238 and 458. In addition, esters or aide the (meth) acrylic acid with amino alcohols such. B. 2-aminoethanol, 2- (methylamino) ethanol, 3-amino-l-propanol, l-amino-2-propanol or 2- (2-aminoethoxy) ethanol, 2-mercapto ethanol or polyaminoalkanes such as ethylene diamine or diethylene triamine, or vinyl acetic acid.

p0117Unsaturated polyetherols or polyesterols or polyacrylate polyols are suitable with an average OH functionality 2 to 10

p0118Examples of amides of ethylenically unsaturated carboxylic acids with amino alcohols are hydroxyalkyl (meth) acrylamides such as N-hydroxymethyl thylacrylamid, N-hydroxymethylmethacrylamide, N-Hydroxyethy- lacrylamid, N-Hydroyxethylmethacrylamid, 5-hydroxy-3-oxa-pentyl (meth) acrylamide, N -Hydroxyalkylcrotonamide as N-hydroxymethyl or N-thylcrotonamid Hydroxyalkylmaleinimide as N-hydroxyethyl maleimide.

p0119Preferably used are 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 1, 4-butanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, 1, 5-pentanediol mono (meth) acrylate, 1, 6-hexanediol mono (meth) acrylate, glycerol mono- and di (meth) acrylate, trimethylolpropane mono- and di (meth) acrylate, pentaerythritol mono-, di- and tri (meth) acrylate and 4-hydroxybutyl tylvinylether, 2- aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 4-amino-butyl (meth) acrylate, 6-aminohexyl (meth) acrylate, 2-methyl thioether (meth) acrylate, 2-aminoethyl (meth) acrylamide, 2-amino-propyl (meth) acrylamide, 3-aminopropyl (meth) acrylamide, 2-hydroxy ethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide or 3-Hydrσxypropyl ( meth) acrylamide. Particularly preferred are 2-hydroxyethyl acrylate, 2-hydroxyethyl, 2- or 3-hydroxypropyl acrylate, 1, 4-butanediol monoacrylate and 3- (acryloyl oxy) -2-hydroxypropyl methacrylate.

p0120As component (Fl-c) are compounds which contain at least two isocyanate-reactive groups, such as -OH, -SH, -NH or -NHR²Wherein R² is independently hydrogen, methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso- butyl, seJc-butyl or tert-butyl can mean comprise.

p0121These are preferably diols or polyols, such as 2 to 20 carbon atoms which Kohlenwasserstoffdiole, eg ethylene glycol, 1,2-propanediol, 1, 3-propanediol, 1, l-dimethylethane-l, 2-diol, 1, 6-hexanediol, 1, 10-decanediol, bis- (4-hydroxycyclohexane) iso- propylidene, tetramethylcyclobutanediol, 1,2-, 1,3- or 1,4-cyclo- hexanediol, cyclooctanediol, norbornanediol, pinanediol, decalindiol, etc. esters thereof with short chain dicarboxylic acids such as adipic acid, cyclohexanedicarboxylic acid, their carbonates, prepared by the reaction of diols with phosgene or by transesterification with dialkyl or diaryl carbonates, or aliphatic diamines, such as methylene -, and isopropylidene-bis (cyclohexylamine), piperazine, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-cyclohexane-bis- ( methylamine), etc., dithiols or polyfunctional alcohols, secondary or primary amino alcohols such as ethanolamine, diethanolamine, monopropanolamine, dipropanolamine, etc., or thio alcohols such as Thioethylenglykol.

p0122Furthermore conceivable are diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, pentaerythritol, 1,2- and 1, 4-butanediol, 1, 5-pentanediol,

p01232-methyl-l, 5-pentanediol, 2-ethyl-l, 4-butanediol, 1,2-, 1,3- and 1, 4-dimethylol cyclohexane, 2, 2-bis (4-hydroxycyclohexyl) propane, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, dipentaerythritol, ditrimethylolpropane, erythritol and sorbitol, 2-aminoethanol, 3-amino-l-propanol, l-amino-2-propanol or 2- (2-aminoethoxy) ethanol, bisphenol A, or butanetriol.

p0124Unsaturated polyetherols or polyesterols or polyacrylate polyols are suitable with an average OH functionality of from 2 to 10, and polyamines such as polyethyleneimine or free amine group-containing polymers, of poly-N-vinylfor- formamide.

p0125Particularly suitable here are the cycloaliphatic diols such as bis isopropylidene (4-hydroxycyclohexane), Tetramethylcyclobu- tandiol, 1,2-, 1,3- or 1,4-cyclohexanediol, cyclooctanediol or norbornanediol.

p0126The inventively useable polyurethanes tion by reaction of components (Fl-a), (Fl-b) and (Fl-c) with one another.

p0127Here, the molar composition (Fl-a): (Fl-b): (Fl-c) per 3 mol of reactive Isocycanatgrüppen in (Fl-a) generally as follows: (Fl-b) 1,5 - 3, 0, preferably 2.0 to 2.9, particularly preferably 2.0 to 2, 5, and especially 2.0 to 2.3 mol of isocyanate-reactive groups, and

p0128(Fl-c) from 0 to 1.5, preferably 0.1 to 1.0, particularly preferably 0.5 to 1.0 and in particular 0.7 to 1.0 mol of isocyanate-reactive groups. When the polyurethanes in aqueous systems are preferably substantially all isocyanate groups reacted.

p0129The formation of the adduct of isocyanate-functional compound and the compound comprising isocyanate-reactive groups is generally carried out by mixing the components in any order, optionally at elevated temperature.

p0130Preference is given, the compound comprising isocyanate reactive groups added to the isocyanate group-containing compound, preferably in several steps.

p0131Particularly preferably, the compound containing isocyanate groups is initially taken and the compounds which contain groups reactive toward isocyanate added. In particular, the compound containing isocyanate groups (Fl-a) is initially taken and then (Fl-b) were added. Subsequently desired, additional components can be optionally added.

p0132In general, the reaction at temperatures between 5 and 100 ° C, preferably between 20 to 90 ° C. and more preferably between 40 and 80 ° C and in particular between 60 and 80 ° C.

p0133Is preferably carried out under anhydrous conditions.

p0134Anhydrous means that the water content in the reaction system% by weight is not more than 5, preferably not more than 3 wt% and particularly preferably not more than 1% by weight.

p0135Preferably, the reaction is carried out in the presence of at least one suitable inert gas, for example nitrogen, argon, helium, carbon dioxide or the like.

p0136The reaction may also be carried out in the presence of an inert solvent, such as acetone, iso-butyl methyl ketone, toluene, xylene, butyl acetate or ethoxyethyl acetate. Preferably, the reaction is carried out in the absence of a solvent.

p0137The urethane (meth) acrylates preferably have a number average molecular weight M_n 500 to 20,000, in particular 750 to 10000 more preferably between 750 and 3000 g / mol (determined by gel permeation chromatography using polystyrene as the standard and tetrahydrofuran). The urethane (meth) acrylates preferably have a content of 1 to 5, particularly preferably from 2 to 4 moles of (meth) acrylic groups per 1000 g of urethane (meth) acrylate.

p0138The urethane preferably have a content of 1 to 5, particularly preferably from 2 to 4 moles of vinyl ether groups per 1,000 g of urethane.

p0139Epoxy (meth) acrylates are obtainable by reaction of epoxides with (meth) acrylic acid. Suitable epoxides are, for example, epoxidized olefins, aromatic glycidyl ethers or aliphatic glycidyl ethers, preferably those of aromatic or aliphatic glycidyl ethers.

p0140Epoxidized olefins, for example, ethylene oxide,

p0141Propylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, vinyl oxirane, styrene oxide or epichlorohydrin, preferred are ethylene oxide, propylene oxide, isobutylene oxide, vinyloxirane or epichlorohydrin, styrene oxide, particularly preferably ethylene oxide, propylene oxide or epichlorohydrin, and very particularly preferably ethylene oxide and epichlorohydrin.

p0142Aromatic glycidyl ethers such as bisphenol-A diglycidyl ether, bisphenol F diglycidyl ether, Bisphenόl-B diglycidyl ether, bisphenol S diglycidyl ether, hydroquinone diglycidyl ether, Alkylierung- sprodukte of phenol / dicyclopentadiene, eg, 2, 5-bis [(2, 3-epoxy propoxy) phenyl] octahydro-4, 7-methano-5H-indene) (CAS-No. [13446-85-0]), tris [4- (2, 3-epoxypropoxy) phenyl] methane isomers ( CAS-No. [66072-39-7]), phenol-based epoxy novolaks (CAS-Nr. [9003-35-4]) and cresol-based epoxy novolaks (CAS-No. [37382-79-9]).

p0143Aliphatic glycidyl ethers include for example 1, 4-Butandioldig- lycidether, 1, 6-hexanediol, Trimethylolpropantrig- lycidylether, pentaerythritol tetraglycidyl, 1, 1,2,2-tetra kis [4- (2, 3-epoxypropoxy) phenyl] ethane (CAS -No. [27043-37-4]), diglycidyl ether of polypropylene glycol (α, ω-bis poxy (2, 3-epoxypro-) poly (oxypropylene) (CAS-No. [16096-30-3]) and hydrogenated bisphenol A (2, 2-bis [4- (2, 3-epoxypropoxy) cyclohexyl] propane, CAS-No. [13410-58-7]).

p0144The epoxy (meth) acrylates and vinyl ethers preferably have a number average molecular weight M_n 340 to 20,000, particularly preferably from 500 to 10,000 g / mol and very particularly preferably between 750 and 3000 g / mol; the content of (meth) acrylic or vinyl ether groups is preferably from 1 to 5, more preferably 2 to 4 per 1,000 grams of epoxide (meth) acrylate or vinyl ether epoxide (determined by Gel permeation chromatography using polystyrene as standard and tetrahydrofuran as eluent).

p0145Other suitable radiation-curable compounds (Fl) are the carbonate (meth) acrylates, the acrylic groups on average preferably 1 to 5, in particular 2 to 4, particularly preferably 2 to 3 (meth) and most preferably 2 (meth) acrylic groups.

p0146The number average molecular weight M_n of the carbonate (meth) acrylates is preferably less than 3000 g / mol, particularly preferably less than 1500 g / mol, more preferably less than 800 g / mol (determined by gel permeation chromatography using polystyrene as standard, tetrahydrofuran as solvent).

p0147The carbonate (meth) acrylates are obtainable in a simple manner by transesterification of carbonic esters with polyhydric, preferably dihydric, alcohols (diols, eg hexanediol) and subsequent esterification of the free OH groups with (meth) acrylic acid or else transesterification with (meth) acrylic acid esters as it is described for example in EP-A 92 269th They are also obtainable by reacting phosgene, urea derivatives with polyhydric, eg, dihydric alcohols.

p0148Analogously, Vinylethercarbonate are obtainable by reacting a hydroxyalkyl with carbonic esters and, if appropriate, dihydric alcohols.

p0149Also conceivable are (meth) acrylates or vinyl ethers of polycarbonate natpolyolen as the reaction product of one of said di- or polyols and a carbonic ester and also a hydroxyl-containing (meth) acrylate or vinyl ether.

p0150Suitable carbonic esters include ethylene carbonate, 1,2- or 1, 3-propylene carbonate, diethyl or di- ester.

p0151Suitable hydroxyl-containing (meth) acrylates are for instance 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxy propyl (meth) acrylate, 1, 4-butanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, glycerol and di (meth) acrylate, tri- methylolpropanmono- and di (meth) acrylate, and pentaerythritol mono-, di- and tri (meth) acrylate.

p0152Suitable hydroxyl vinyl ethers include 2-hydroxy ethyl vinyl ether and 4-hydroxybutyl. Particularly preferred carbonate (meth) acrylates are those of the formula:

p0153<img id="imgf000025_0001" he="23" wi="86" file="imgf000025_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0154wherein R is H or CH₃, X is a C₂-C_8th Alkylene group and n is an integer from 1 to 5, preferably 1 stands to third

p0155R is preferably H and X preferably represents C₂- To Cio-alkylene, for example 1,2-ethylene, 1, 2-propylene,

p01561,3-propylene, 1,4-butylene or 1,6-hexylene, more preferably C₄- To -alkylene. Very particularly preferably, X is C₆Alkylene.

p0157Preferably, aliphatic carbonate (meth) acrylates.

p0158Other suitable radiation-curable compounds (Fl) and (meth) acrylates or vinyl ethers of polyether polyols can be used. This may be one or preferably polyhydric, in statistical

p0159Means 2 to 70, preferably 2 to 60 per molecule polyalkylene polyether alcohols, as are obtainable by Alkoxlyierung suitable Startermolküle in a conventional manner. To produce these polyether alcohols, any monohydric or polyhydric alcohols may be mono- getzt as starter molecules.

p0160Alkylene oxides suitable for the alkoxylation are ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide and vinyl oxirane that can be used in any order or as a mixture in the alkoxylation reaction.

p0161Suitable starter molecules are, for example, trimethylolpropane, trimethylolethane, neopentylglycol, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, 1, 2-propanediol, ethylene glycol, 2, 2-dimethyl-l, 2-ethanediol, neopentylglycol , 1, 3-propanediol, 1, 2-butanediol or 1, 4-butanediol. Vinylethergruppenhaltige polyether for example be obtained by reaction of hydroxyalkyl with alkylene oxides.

p0162(Meth) acrylic acid-containing polyether can as described above under (Fl-b), for example, by transesterification of (meth) crylsäureestern acrylates with the polyether alcohols, acrylic acid by esterification of the polyether with (meth), or by use of hydroxyl-containing (meth) obtained th will.

p0163Preferred polyether alcohols are polyethylene glycols having a molar mass between 106 and 2000 preferably 106-898 more preferably 238-678.

p0164Other suitable polyether poly-THF having a molar mass 162-2000 and poly-l, 3-propanediol having a molar mass between 134 and 1178th

p0165Particularly preferred as compounds (Fl) are urethane or carbonate (meth) acrylates or vinyl ethers, especially urethane (meth) acrylates.

p0166Compounds (Fl) are often in admixture with compounds (F2), which serve as reactive diluents, are used.

p0167Suitable reactive diluents (compounds (F2)) include radiation-curable, free-radically or cationically polymerizable compounds having only one ethylenically unsaturated, copolymerizable group.

p0168may be mentioned include -C-C₂o-alkyl (meth) acrylates, vinylaromatics having up to 20 carbon atoms, vinyl esters of up to 20 carbon atoms, carboxylic acids containing, ethylenically unsaturated nitriles, vinyl ethers of 1 to 10 carbon atoms containing alcohols, α, ß-unge - saturated carboxylic acids and their anhydrides and aliphatic hydrocarbons having 2 to 8 carbon atoms and 1 or 2 double bonds.

p0169The term (meth) acrylic acid is used in the context of this document for acrylic acid and methacrylic acid.

p0170As the (meth) acrylic acid alkyl esters are those having a -C-Cιo-alkyl, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate. In particular, mixtures of the (meth) acrylates are also suitable.

p0171Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are vinyl laurate, vinyl stearate, vinyl propionate and vinyl acetate.

p0172α, ß-unsaturated carboxylic acids and anhydrides thereof may for example be acrylic acid, methacrylic acid, fumaric acid, crotonic acid, itaconic acid, maleic acid or maleic anhydride, preferably acrylic acid.

p0173Suitable vinylaromatic compounds include vinyltoluene, α-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.

p0174Examples of nitriles are acrylonitrile and methacrylonitrile.

p0175Suitable vinyl ethers include vinyl methyl ether Vinylisobutyl-, Vinylhexylether and Vinyloctylether.

p0176As nonaromatic hydrocarbons having 2 to 8 carbon atoms and one or two olefinic double bonds are butadiene, isoprene, and called ethylene, propylene and isobutylene.

p0177Further, N-vinylformamide, N-vinylpyrrolidone, and N-vinylcaprolactam.

p0178Photoinitiators (F3) to the expert, known photoinitiators are used, for example those mentioned in "Advances in Polymer Science", Volume 14, Springer Berlin 1974 or in KK Dietli- ker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Ra dical and Cationic Polymerization, PKT Oldring (Eds), SITA Technology Ltd, London, said.

p0179For example, mono- or bisacylphosphine oxides as Irga- CURE® come 819 (bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide), as described for example in EP-A 7508, EP-A 57 474, DE-A 196 18 720 , EP-A are described 495 751 or EP-A 615 980, for example, 2,4,6-tri- methylbenzoyldiphenylphosphinoxid (Lucirin^® TPO)

p0180Ethyl-2, 4, 6-trimethylbenzoylphenylphosphinate, benzophenones, hydroxy droxyacetophenone, phenylglyoxylic and its derivatives or mixtures of these photoinitiators. As examples may be mentioned benzophenone, acetophenone, Acetonaphthochinon, methyl ethyl ketone, valerophenone, hexanophenone, α-Phenylbutyrophenon, p-morpholino propiophenone, dibenzosuberone, 4-morpholinobenzophenone, 4-morpholine linodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-Metho - xyacetophenon, ß-Methylanthraquinone, terfc-butyl anthraquinone, answer hrachinoncarbonysäureester, benzaldehyde, α-tetralone, 9-nanthren Acetylphe-, 2-acetylphenanthrene, 10-thioxanthenone, lead 3-Acetylphenant-, 3-acetylindole, 9-fluorenone, 1- indanone, 1, 3, 4-Triacetylben- benzene, thioxanthen-9-one, xanthene-9-one, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2, 4-di-isopropylthioxanthone, 2,4- sealing lorthioxanthon, benzoin, benzoin isobutyl ether, Chloroxanthenon, benzoin tetrahydropyranyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin-iso-propyl ether, 7-H-benzoin methyl ether, benz [de] anthracene-7-one, 1-naphthaldehyde,

p01814,4 '-bis (imethylamino) benzophenone, 4-phenylbenzophenone, 4-chloro benzophenone, Michler's ketone, 1-acetonaphthone, 2-acetonaphthone, 1-Benzoylcyclohexan-l-ol, 2-hydroxy-2, 2-dimethylacetophenone, 2, 2-dimethoxy-2-pb.enylacetoph.enon, 2, 2-diethoxy-2-phenylaceto- phenone, 1, 1-dichloroacetophenone, 1-hydroxyacetophenone, acetophenone nondimethylketal, o-methoxybenzophenone, triphenylphosphine, tri- o tolylphosphine, benz [a] anthracene-7, 12-dione, 2, 2-Diethoxyaceto- benzophenone, benzil ketals, such as benzil dimethyl ketal, 2-methyl-l- [4- (methylthio) phenyl] -2-morpholinopropan-l-on, anthraquinones such as 2-methyl anthraquinone, 2-ethyl anthraquinone,

p01822- ert-butyl anthraquinone, 1-chloroanthraquinone, 2-Amylanthraquinone and 2, 3-butanedione.

p0183Also suitable are non- or low-yellowing photoinitiators of the phenylglyoxalic ester, as described in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761 are described.

p0184Among said photoinitiators phosphine oxides, α-hydroxy ketones and benzophenones are preferred.

p0185In particular, mixtures of different photoinitiators may be used.

p0186The photoinitiators can be used alone or in combination with a photopolymerization promoter, of the benzoic acid, amine or similar type.

p0187Further, typical coatings additives (F4), for example, antioxidants, antioxidants, stabilizers, activators (accelerators), fillers, pigments, dyes, degassing agents, luster agents, antistatic agents, flame retardants, thickeners, thixotropic agents, leveling assistants, binders, antifoam agents, perfumes, surface active agents , viscosity modifiers, plasticizers plasticizing Decorators, tackifying resins (tackifiers), chelating agents or compatibilizers (compatibilizer) are used. As accelerators for the thermal postcuring eg tin can octoate, zinc octoate, dibutyltin diazabicyclo [2.2.2] octane can be used.

p0188Furthermore, one or more photochemically and / or thermally activatable initiators can be added, such as potassium permanganate peroxodisulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-tert-butyl tylperoxid, azobis-isobutyronitrile, Cyclohexylsulfonylacetylpe- peroxide, di-iso-propylpercarbonat, tert -Butylperoktoat or Benzpi- nakol, for example, those thermally activatable initiators which have a half-life at 80 ° C of more than 100 hours, such as di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, t-butyl perbenzoate, silylated pinacols that z . B. under the trade name ADDID 600 from Wacker, are commercially available, or hydroxyl-containing amine N-oxides, such as 2,2,6,6-Te tramethylpiperidin-N-oxyl, 4-hydroxy-2, 2,6 , 6-tetramethylpiperidinyl din-N-oxyl etc.

p0189Further examples of suitable initiators are described in "Polymer Handbook", 2nd Ed., Wiley &amp; Sons, New York.

p0190Suitable thickeners, besides free-radically (co) polymerized (co) polymers include customary organic and inorganic thickeners such as hydroxymethylcellulose or bentonite.

p0191Chelating agents such as ethylenediamine acetic acid and its salts and also .beta.-diketones can be used.

p0192Suitable fillers include silicates, for. Example, by hydrolysis of silicon tetrachloride, such as Aerosil silicates obtainable^® . from Degussa, silica, talc, aluminum silicates, calcium carbonates, etc.

p0193Suitable stabilizers comprise typical UV absorbers such Oxani- lide, triazines and benzotriazole (the latter available as Tinuvin^® Grades from Ciba-Spezialitätenche ie) and benzophenones. These can be used alone or together with suitable free-radical scavengers, examples being sterically hindered amines such as 2, 2, 6, 6-tetramethylpiperidine, 2, 6-di-tert. -butylpiperidin or its deriva- tives, z. B. Bis- (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate are used. Stabilizers are usually used in amounts of from 0.1 to 5.0 wt .-%, based on the solid components present in the preparation.

p0194Other suitable stabilizers are for example N-oxyls such as 4-hydroxy-2, 2,6, 6-tetramethyl-piperidine-N-oxyl, 4-oxo-2, 2,6, 6-tetramethyl-piperidine-N-oxyl , 4-acetoxy-2, 2,6, 6-te- tramethyl-piperidin-N-oxyl, 2,2,6, 6-tetramethyl-piperidine-N-oxyl, 4, 4 ', 4' '-tris (2,2,6, 6-tetramethyl-piperidine-N-oxyl ) phosphite or 3-oxo-2,2,5,5-tetramethyl-pyrrolidin-N-oxyl, phenols and naphthols, such as p-aminophenol, p-nitrosophenol, 2-tert-Butylphe- nol, 4 -terfc.-Butylph.enol, 2, 4-di-fcerfc.-butylphenol,

p01952-methyl-4-fcerfc.-butylphenol, 4-methyl-2, 6-terfc.-butylphenol (2, 6-terfc. Butyl-p-cresol) or 4-terfc. Butyl-2, 6-dimethylphenol, quinones, such as hydroquinone or hydroquinone monomethyl ether, aromatic amines such as N, N-diphenylamine, N-nitroso-diphenyl-amine, phenylenediamines such as N, N'-dialkyl-para-phenylene - diamine, wherein the alkyl groups may be the same or different and each independently consist of 1-4 carbon atoms and may be straight or branched, hydroxyl amines such as N, N-diethylhydroxylamine, urea derivatives such as urea or thiourea, phosphorus-containing compounds such as triphenylphosphine, triphenyl phosphite or triethyl phosphite or sulfur-containing compounds such as diphenyl sulfide or phenothiazine.

p0196Typical compositions for radiation-curable compositions are, for example,

p0197(Fl) 0 - 100% by weight, preferably 50 - 90, more preferably 60 - 90 and in particular 60 - 80% by weight, (F2) 0 - 60 wt%, preferably 5 - 50, particularly preferably 6 - 40 and in particular 10 - 30% by weight, (F3) from 0 to 20% by weight, preferably from 0.5 to 15, particularly preferably 1 - 10 and in particular 2-5% by weight, and (F4) 0 - 50% by weight, preferably 2-40, more preferably 3 - 30 and in particular 5 - 20% by weight,

p0198with the proviso that (Fl), (F2), (F3) and (F4) together give 100% by weight.

p0199In particularly preferred radiation-curable compositions, the connection (Fl) to 10 to 100 wt .-%, based on the total amount of the compound (Fl), urethane (meth) acrylate (s), Epoxyacryla- th, polyether acrylates or polyester acrylates.

p0200Particularly suitable as layers (F) usable radiation-curable compositions are described in EP-AI 942 022, particularly from page

p02014, line 18 to page 18, Z.31 described in DE-Al 199 44 156,

p02025. 1, Z. 26 to page 6, line 63 and described in DE-Al 199 56 231, page 2, lines 33 to page 4, line 65, and the registration with the German Patent the application number 101 40 769.6 and the filing date of 20.08.2001 described. The coating of the substrates takes place after usual, the specialist admitted procedures, which involve applying at least one coating composition to the substrate to be coated in the desired thickness and any volatile components in the coating material, optionally with heating, away. This process can be optionally repeated one or more times. Application to the substrate may take place extrude in a known manner, eg., By spraying, troweling, knife coating, brushing, rolling, pouring, laminating, back injection or co. The coating thickness is generally in a range from about 3 to 1000 g / m² and preferably 10 to 200 g / m²,

p0203Furthermore, a method of coating substrates is fenbart of-, which comprises applying the coating composition to the substrate, and optionally dried, cured with electron beams or UV light under an oxygen atmosphere or preferably under inert gas, optionally at temperatures up to the level of the drying temperature, and then at temperatures up to 160 ° C, preferably between 60 and 160 ° C, thermally treated.

p0204The method of coating of substrates can also be carried out such that after application of the coating composition up to 160 ° C, preferably between 60 and 160 ° C, thermally treated first at temperatures and then treated with electron beams or UV light under oxygen or, preferably, under inert gas is cured.

p0205Curing of the films formed on the substrate may if desired take place exclusively by thermal means. In general, however, the coatings are cured both by exposure to high-energy radiation and thermally.

p0206Curing may also take place in addition to or instead of thermal curing by NIR radiation, with NIR radiation is electromagnetic radiation in the wavelength range from 760 nm to 2.5 .mu.m, preferably from 900 to 1500 n is referred to herein.

p0207Optionally, when multiple layers of coating compositions are applied one above the other means, after each coating operation a thermal, NIR and / or radiation cure.

p0208Suitable radiation sources for the radiation cure are low-pressure mercury lamps, -Mitteldruckstrahler high-pressure jet and also fluorescent Impulsstrahier, metal tallhalogenidstrahler, electronic flash devices, which allow Radiation curing without a photoinitiator, or excimer emitters. Radiation curing is accomplished using high energy radiation, ie UV radiation or daylight, preferably light in the wavelength range of λ = 200 to 700 nm, more preferably from λ = 200 to 500 nm and very particularly preferably λ = 250 to 400 nm, or by irradiation with high-energy electrons (electron beams; 150 to 300 keV). Radiation sources used cimerstrahler example high-pressure mercury vapor lamps, lasers, pulsed lamps (flashlight), halogen lamps or explosion. The normally sufficient for crosslinking radiation dose in UV curing is in the range of 80 to 3000 mJ / cm.

p0209Of course, multiple radiation sources for curing, eg two to four.

p0210These may also emit each in different wavelength ranges.

p0211The irradiation may be optionally under an inert gas atmosphere, carried out with exclusion of oxygen, for. Example. Suitable inert gases are preferably nitrogen, noble gases, carbon dioxide, or combustion gases. Irradiation may also take place with the coating composition covered with transparent media. Transparent media are,. As plastic films, glass or liquids, eg., Water. Particularly preferred is irradiation in the manner as described in DE-Al 199 57 900th

p0212Another object of the invention is a method for the coating of substrates which comprises

p0213i) a substrate with a coating composition as described above is coated,

p0214ii) removing volatile constituents of the coating composition to form a film, under conditions in which the photoinitiator (C) as yet essentially forms no free radicals,

p0215iii) optionally subjecting the film formed in step ii) with high-energy radiation, the film being precured, and then, if appropriate, the article coated with the precured film or contacting the surface of the precured film into contact with another substrate, iv) the film thermally or with NIR radiation completing curing Steps iv) and iii) can also be performed in reverse order, ie, the film may be first thermally or by NIR-radiation and then cured with high-energy radiation. 5

p0216Furthermore, substrates coated with an inventive multilayer paint system of the present invention.

p021710

p0218Also subject of the present invention, a method for coating substrates with at least one radiation-curable coating system (F), in which between the substrate and the at least one radiation-curable coating system (F), an elastic

p021915 intermediate layer (D) having a glass transition temperature (T_G) Is applied low of -20 ° C or.

p0220The coating can be carried out and for the radiation-curable coating systems (F) and 20 elastic intermediate layer (D), the above statements by one of the aforementioned methods.

p0221The thickness of such a layer as described for curing may be from 0.1 micron to several mm, preferably from 1 to 2000 microns, more preferably 5 to 1000 microns, most preferably from 25 10 to 500 microns and especially from 10 to 250 microns ,

p0222For a given system, the fracture-mechanical behavior of the ratio V of the intermediate layer thickness is ZS (layer (D)) to the total thickness of the intermediate layer plus the thickness DL of the topcoat,

p022330 ie, the sum of the thickness of the layers (E) and (F), determined V = ZS / (ZS + DL). The lower the temperatures to which are exposed to the systems, and the higher the strain rates are, the larger V must be chosen so that it does not come to breakage upon mechanical stress. According betra-

p022435 gen values ​​V at least 0.05 at temperatures of at least 25 ° C, preferably at least 0.1 at temperatures of at least 0 ° C, more preferably at least 0.2 at temperatures of at least -20 ° C and very particularly preferably 0 minimum 3 at temperatures of -50 ° C.

p022540

p0226The multi-layer coatings provide improved adhesion, especially in engineering plastics and improved hardness, elasticity, abrasion resistance and chemical resistance compared to known UV-curable coatings.

p022745 Particularly preferably multicoat systems of the invention are suitable as or in exterior coatings, ie, those applications which are exposed to daylight, preferably of buildings or parts thereof, interior coatings, road markings, coatings on vehicles and aircraft. In particular, multi-layer coatings of the invention are used as or in automotive clearcoat and topcoat material (s), both for the Automobilaußen- and for the -innenbereich.

p0228The Mehschichtlackierungen invention can trap so that these do not propagate into the substrate in the outer layer of lacquer cracks which occur by the present invention interlayer (D). For this purpose, several elastic intermediate layers in a multilayer painting course be incorporated, for example, between the layers (E) and (F) and / or between (A) and (C), provided that these layers are included in the multi-layer coating.

p0229With the multi-layer coatings can be achieved high scratch resistance.

p0230In this font used ppm and percentage data relate, unless indicated otherwise, percentages by weight and ppm.

p0231Examples

p0232The scratch resistance was determined as determined by the Scotch Brite test, as it is, Z. 5 described in DE-Al 199 40 312, page 8, line 64 to page 9:

p0233The test specimen is a 3 X 3 cm, silicon-on modified nonwoven (Scotch Brite SUFN, 3M Germany, 41453 Neuss) is attached to a cylinder. This cylinder presses the fiber web of 750 g of the coating and is moved over the coating pneumatically. The distance of displacement is 7 cm. After 10 or 50 double strokes (DH) is measured in the central region of the stress of the gloss (sixfold determination) according to DIN 67530, ISO 2813 at an incident angle of 60 °. From the gloss values ​​of the coatings before and after the mechanical stresses the difference is formed. The loss of gloss is inversely proportional to the scratch resistance.

p0234The strength a_cu was in accordance with DIN EN ISO 179 / lfü at -50 ° C measured. The topcoat was prepared from 1 Laromer® LR 8987 from BASF AG, Ludwigshafen and additives.

p0235The topcoat was prepared from 2 Laromer® LR 8949 from BASF AG, Ludwigshafen and additives.

p0236The following substrates were used:

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